WO1998049243A1 - Colorant organique multiphase a effet, et mode de fabrication - Google Patents

Colorant organique multiphase a effet, et mode de fabrication Download PDF

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Publication number
WO1998049243A1
WO1998049243A1 PCT/EP1998/002430 EP9802430W WO9849243A1 WO 1998049243 A1 WO1998049243 A1 WO 1998049243A1 EP 9802430 W EP9802430 W EP 9802430W WO 9849243 A1 WO9849243 A1 WO 9849243A1
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phase
polymers
weight
effect
polymer
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PCT/EP1998/002430
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German (de)
English (en)
Inventor
Robert Rupaner
Reinhold J. Leyrer
Peter Schuhmacher
Karl Siemensmeyer
Heinrich Johann Eilingsfeld
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Basf Aktiengesellschaft
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Publication of WO1998049243A1 publication Critical patent/WO1998049243A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre

Definitions

  • 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 Patoscuro 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).
  • a method for coating and printing substrates, in which cholesteric liquid crystals are used, is known from WO 96/02597.
  • 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.
  • 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.
  • highly charged polystyrene particles which form a space lattice, are embedded in a poly (N-isopropylacrylamide) hydrogel.
  • 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.
  • 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.
  • 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.
  • the matrix will more or less completely fill the space between the particles of the disperse phase.
  • a matrix defined in the sense of the present invention can also be regarded as a continuous phase.
  • 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 ⁇ n 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.
  • 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 ⁇ m, preferably 0.1 to 2 ⁇ m, in particular 0.15 to 1.0 ⁇ m. Particles with a particle size of 0.2 to 0.7 ⁇ m 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:
  • 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
  • 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. Gurchtle, 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.
  • an analytical ultracentrifuge see, for example, W. Gurchtle, Makromol. Chem. 185 (1984), pp. 1025 to 1039
  • a commercial CHDF device are calculated from the PI values obtained.
  • 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.
  • 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.
  • the matrix phase (phase 2) also contains or consists of one or more polymers and / or copolymers.
  • 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.
  • phase 2 polymers 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).
  • 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.
  • 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.
  • the polymer material of the matrix phase is an elastically deformable polymer, e.g. consists essentially of natural rubber or a synthetic rubber.
  • the color of a layer of the colorant according to the invention varies with stretching and compression.
  • 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.
  • 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.
  • 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.
  • phase 2 polymers 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.
  • 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, polyacryl
  • 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,
  • coloring additives for example organic dyes or organic or inorganic pigments which are soluble in water or organic media
  • 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.
  • stabilizers against UV radiation and weather influences can also be added to the polymers, in particular the phase mixture.
  • stabilizers against UV radiation and weather influences can also be added to the polymers, in particular the phase mixture.
  • 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.
  • the forms mentioned can also be in a mixture with solid or liquid additives such as solvents, dispersants, diluents, auxiliaries or extenders.
  • 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 ⁇ m, preferably 1 to 100 ⁇ m, in particular 10 to 100 ⁇ m.
  • the lateral extent is 5 to 5000 ⁇ m, preferably 20 to 3000 ⁇ m, in particular 50 to 1000 ⁇ m. 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 depends on the type of preparation and can be carried out routinely.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • phase 1 and phase 2 are 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.
  • thermally activatable polymerization initiators preference is given to those which decompose between 20 and 180 ° C., in particular between 50 and 80 ° C.
  • photoinitiators and their mixtures can be used for photochemical curing.
  • photoinitiators examples include 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.
  • 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
  • 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-tetraphe ⁇ yl-butane or the corresponding lithium compound, diphenylmethyl sodium, di - phenylmethyl potassium, 1-methylstyryllithium or potassium tert-butoxide.
  • 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.
  • reactive groups such as epoxy, cyanate, isocyanate or isothiocyanate groups
  • 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.
  • polyaddition reactions can also advantageously be carried out in an inert solvent or dispersant.
  • 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.
  • 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 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.
  • 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 ⁇ LP values, ie different polarity.
  • the solubility parameters ⁇ 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 ⁇ y ? - values between phase 1 and matrix phase 2, the lower the tendency towards molecular mixing or swelling.
  • 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.
  • polystyrene resin polycondensates and cocondensates of aliphatic dicarboxylic acids having 4 to 12 carbon atoms with aliphatic diamines of approximately the same chain length
  • PA 6.6 polyhexamethylene diadipamide
  • alicyclic polyamides alicyclic polyamides
  • PA 6.6 polyhexamethylene diadipamide
  • PA 6.6 polyhexamethylene diadipamide
  • alicyclic polyamides 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.
  • 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.
  • dicarboxylic acid units are residues of isophthalic acid or of aliphatic dicarboxylic acid such as glutaric acid, adipic acid, sebacic acid;
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A21, page 169.
  • 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
  • R represents hydrogen or methyl
  • the phenyl rings of these monomers can carry further substituents.
  • 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.
  • 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.
  • 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.
  • At least the polymers of dispersed phase 1, preferably the polymers of both phases, are crosslinked.
  • the crosslinking can take place at the same time as the polymerization, or can be connected to the polymerization in a separate step (postcrosslinking).
  • postcrosslinking it is advantageous to crosslink the phase 1 polymers already during the polymerization, and to subsequently crosslink the phase 2 polymers.
  • 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.
  • 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.
  • Group 1 bisacrylates, bismethacrylates, bis- ⁇ -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:
  • 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
  • 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).
  • N-methylol- (meth) acrylamide acrylamidoglycolic acid and their ethers and / or esters with C j to C 6 alcohols
  • AA-EM acetacetoxyethyl methacrylamide
  • DAAM diacetone acrylamide
  • GMA g
  • 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.
  • 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.
  • 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
  • the polymer particles of the disperse phase 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 ⁇ m, preferably from 0.1 to 2 ⁇ m, in particular 0.15 to 1.0 ⁇ m and specifically from 0.2 to 0.7 ⁇ m 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • suitable substrates are e.g. Glass or hard rubber plates or polyolefin or PTFE plates or foils.
  • films can also be produced in analogy to the process described above for producing pigments according to the invention.
  • the hardened layer of the effect colorant according to the invention is separated from the substrate and the comminution is omitted.
  • All methods known from the prior art are suitable as application methods.
  • the application can be carried out by pouring, dipping, knife coating, brushing, brushing, roll coating, spraying or spraying.
  • 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.
  • 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.
  • solutions are aqueous solutions.
  • 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 Composition of the monomer emulsion ME 1:
  • 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 ⁇ m 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).
  • CHDF 440 nm
  • 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 ⁇ m 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 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).
  • CHDF maximum at 258 nm
  • 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).
  • CHDF maximum at 233 nm
  • 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.
  • 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).
  • CHDF 242 nm
  • 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 7 is carried out analogously with the dispersion from example 2.
  • the filming forms a homogeneous, transparent filming with no visible color effects.
  • Example 1 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 11 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 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 1 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.
  • 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
  • 0.1 g of a potassium salt of a perfluorocarboxylic acid with 12 carbon atoms 50% by
  • Example 11 The mixture of Example 11 is allowed to film on a polyethylene film. The result does not differ from that of Example 11.
  • Example 11 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 4a 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.
  • a PEO-PPO block copolymer ® Pluronic PE 6400 from BASF AG
  • Example 1 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 6 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.
  • 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 9 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.
  • a high-pressure spray gun Proxon, Gala 500
  • 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.

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Abstract

La présente invention porte sur un colorant organique à effet, à base d'un mélange multiphase comprenant au moins deux substances organiques, avec une ou plusieurs phases dispersées, qualifiées conjointement de phase 1, et avec une phase matricielle continue (phase 2), et présentant les caractéristiques suivantes: la phase dispersée (phase 1) ne gonfle pas dans la phase matricielle (phase 2), sinon en très faible proportion; dans la phase 2, la phase 1 forme au moins des domaines de structure régulière; il existe une différence entre les indices de réfraction des phases 1 et 2. L'invention concerne également le mode de fabrication de ces colorants à effet, des préparations solides, pâteuses ou fluides nécessaires à base de polymères monodispersés de phase 1 contenus dans un mélange de substances qui est liquide à température normale ou ne le devient qu'à une température élevée et qui contient des précurseurs de polymères de phase 2 convertibles en polymères de phase 2, et/ou des polymères de phase 2 dispersée, ainsi que des polymères monodispersés connus. Par ailleurs, l'invention concerne l'utilisation des colorants à effet selon l'invention ou les préparations susmentionnées nécessaires à la fabrication de revêtements décoratifs et/ou protecteurs, ainsi que la fabrication de laques, de couleurs d'imprimerie et d'encres impliquant l'utilisation desdits colorants à effet.
PCT/EP1998/002430 1997-04-28 1998-04-24 Colorant organique multiphase a effet, et mode de fabrication WO1998049243A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997117879 DE19717879A1 (de) 1997-04-28 1997-04-28 Organisches, mehrphasiges Effektfarbmittel, seine Herstellung und seine Verwendung
DE19717879.0 1997-04-28

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WO2005095495A1 (fr) * 2004-03-31 2005-10-13 Basf Aktiengesellschaft Dispersions aqueuses a compatibilite ionique amelioree et leur utilisation dans des pates de couchage de papier

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Publication number Priority date Publication date Assignee Title
DE10321083A1 (de) 2003-05-09 2004-11-25 Basf Ag Polymerdispersion mit Farbeffekt
EP2108463B8 (fr) 2008-04-11 2019-10-09 BASF Coatings GmbH Procédé de fabrication de peintures fantaisie et leur utilisation

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US3969433A (en) * 1973-05-11 1976-07-13 Akira Kose Iridescent composition and the process of preparing the same
US3992486A (en) * 1971-02-09 1976-11-16 Rohm And Haas Company Process for altering appearance of polymer by incorporating therein crosslinked particulate polymers prepared by endopolymerization
EP0171955A2 (fr) * 1984-07-27 1986-02-19 Inax Corporation Objet en imitation de marbre
JPH04106171A (ja) * 1990-08-27 1992-04-08 Kansai Paint Co Ltd 上塗用塗料組成物
EP0590471A2 (fr) * 1992-09-24 1994-04-06 Röhm Gmbh Composition de moulage de polystyrène diffusant la lumière et articles moulés de celle-ci
WO1997032223A1 (fr) * 1996-02-29 1997-09-04 Minnesota Mining And Manufacturing Company Film optique a continuite reciproque des phases

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US3992486A (en) * 1971-02-09 1976-11-16 Rohm And Haas Company Process for altering appearance of polymer by incorporating therein crosslinked particulate polymers prepared by endopolymerization
US3969433A (en) * 1973-05-11 1976-07-13 Akira Kose Iridescent composition and the process of preparing the same
EP0171955A2 (fr) * 1984-07-27 1986-02-19 Inax Corporation Objet en imitation de marbre
JPH04106171A (ja) * 1990-08-27 1992-04-08 Kansai Paint Co Ltd 上塗用塗料組成物
EP0590471A2 (fr) * 1992-09-24 1994-04-06 Röhm Gmbh Composition de moulage de polystyrène diffusant la lumière et articles moulés de celle-ci
WO1997032223A1 (fr) * 1996-02-29 1997-09-04 Minnesota Mining And Manufacturing Company Film optique a continuite reciproque des phases

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Publication number Priority date Publication date Assignee Title
WO2005095495A1 (fr) * 2004-03-31 2005-10-13 Basf Aktiengesellschaft Dispersions aqueuses a compatibilite ionique amelioree et leur utilisation dans des pates de couchage de papier

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