DE19639229A1 - Composition with matrix containing pigment with angle-dependent colour in different matrix - Google Patents

Abstract

A composition is claimed, which contains at least one matrix (M1) containing pigment with colour depending on the viewing angle, in structural elements structurised spatially or in areas, in at least one other matrix (M2). Either M1 and M2 are not identical or they contain identical concentrations of non-identical pigments with colour depending on the viewing angle. Also claimed are (i) a composition with numerous matrices (1a-1x) containing pigment with angle-dependent colour bound to M2; and (ii) a method of producing the composition.

Description

The invention relates to compositions containing platelets shaped pigments with depending on the viewing angle Colourfulness.

Pigments with color depending on the viewing angle, which oriented three-dimensionally cross-linked substances flow contain sigcrystalline structure with a chiral phase for example from EP-B-601 483 corresponds to US-A-5,362,315 or EP-A-686 674 known. These registrations disclose inter alia rem the use of such pigments for coloring plastic fen and compositions containing such pigments. Also a variety of color effects that can be achieved with the pigments ten is mentioned in the patents or patent applications mentioned wrote. All the compositions and described Applications common that these pigments alone, in combination with one another or with other color carriers in a matrix works and used. This is a targeted structure Turization of any matrix with pigments with a Be Viewing angle depending on color is not possible.

The present invention relates to a composition which characterized in that at least one matrix ("Ma trix 1 "), which pigments depend on the viewing angle contains colorfulness, spatial or flat structure in the form of structural elements in at least one width ren matrix ("Matrix 2") is present, with matrix 1 and matrix 2 are not identical or are not identical in both matrices Pigments with a color depending on the viewing angle in identical concentrations are included.  

The composition according to the invention can contain several pigments matrices 1 included.

It preferably contains 1 to 100 pigment-containing matrices 1, be particularly preferably 1 to 20 pigment-containing matrices 1.

For the purposes of the invention, the pigment-containing matrix is too understand that in the matrix pigments from the observation win depending on the color.

A composition according to the invention can in turn itself spatially or flatly structured in at least one additional matrix must be incorporated.

The composition according to the invention enables each selectively adjustable spatial or flat structure tion of materials by means of pigments angle-dependent color instead of statistical, from Processing process or interactions between pigment and matrix caused pigment distribution in the matrix known compositions containing pigments with the Be viewing angle dependent color.

For example, the three-dimensional depth effect, the structuring of the colors, the color brilliance, the pig ment size or the direction of polarization of the reflected Light individually or in the composition according to the invention can also be set very precisely in combination.

The matrices into which the one from EP-B-601 483 (corresponds US-A-5,362,315) or EP-A-686 674 known pigments with from Viewing angles depending on the color,  are preferably selected from the group water-based paints aq ge dispersions such as PMA, SA, polyvinyl derivatives te, PVC, polyvinylidene chloride, SB copolymers, PV-AC copolymer resins, ACR, EVA, ACR / PVC graft polymers or EVA / PVC graft polymeric, water-soluble binders such as Schel lacquer, maleic resins, rosin-modified phenolic resins, left linear and branched saturated polyesters, aminoplast crosslinked zende saturated polyester, fatty acid modified alkyd resins or plasticized urea resins, water-thinnable bandage agents such as PU dispersions, EP resins, urine fabric resins, melamine resins, phenolic resins, alkyd resins, alkyd resins emulsions or silicone resin emulsions, powder coatings as for for example powder coatings for TRIBO / ES, polyester coating coating powder resins, PUR coating powder resins, EP coating powder resins, EP / SP hybrid coating powder resins, PMA coating powder resins Powder coatings for fluidized bed sintering such as for example thermoplastic EPS, LD-PE, LLD-PE, HD-PE, PVC or PVC co- and graft polymers are also soluble lacquers containing tel. B. one- and two-component paints as in for example shellac, rosin rosin esters, maleate resins, Nitrocelluloses, rosin-modified phenolic resins, physics Lish drying saturated polyester, aminoplast crosslinking saturated polyesters, isocyanate-crosslinking saturated poly esters, self-crosslinking saturated polyesters, alkyds with ge saturated fatty acids, linseed oil alkyd resins, soybean oil resins, suns flower oil alkyd resins, safflower oil alkyd resins, ricinenalkyd resins, Wood oil / linseed oil alkyd resins, mixed oil alkyd resins, resin modified Alkyd resins, styrene / vinyl toluene modified alkyd resins, acry lated alkyd resins, urethane-modified alkyd resins, siliconmo differentiated alkyd resins, epoxy-modified alkyd resins, Isophthalic acid alkyd resins, non-plasticized urea resins, plasticized urea resins, melamine resins, polyvinyl acetals, non-crosslinking P (M) A homopolymers or copolymers,  non-crosslinking P (M) A homopolymers or copolymers with non acrylic monomers, self-crosslinking P (M) A homo- or copolymers sate, P (M) A copolymers with other non-acrylic monomers, externally crosslinking P (M) A homopolymers or copolymers, externally crosslinked zende P (M) A copolymers with other non-acrylic monomers, cross-linking P (M) A copolymers with non-acrylic monomers, Acrylate copolymerization resins, unsaturated hydrocarbons fabric resins, organically soluble cellulose compounds, silicone combination resins, PUR resins, EP resins, peroxide-curing unsaturated Synthetic resins, radiation-curing synthetic resins containing photoinitiator, or radiation-curing synthetic resins photoinitiator-free, solvent-free non-lacquers such as isocyanate-crosslinking ge saturated polyester, PUR 2K resin systems, PUR 1K resin systems moisture-curing or EP resins, plastics, e.g. B. not networked, partially networked and networked or networked art fabrics such as AAS - methacrylate-acrylic-styrene, ABS - acrylonitrile-butadiene-styrene, ACM - acrylic ester rubber, AES - acrylonitrile-ethylene-propylene-styrene, AMMA - acrylonitrile thyl methacrylate, ANM - acrylic ester rubber, APP - atactic Polypropylene, ASA - acrylonitrile styrene acrylic ester, BR - Cis-1,4-polybutadiene, BS - butadiene styrene, CA - Celluloseace tat, CAB - cellulose acetobutyrate, CAP - cellulose acetopropio nat, CF - cresol formaldehyde, CM - chlorinated polyethylene chew Tschuk, CMC - carboxymethyl cellulose, CN - cellulose nitrate, CO - epichlorohydrin rubber, CP - cellulose propionate, CR - Chloropen rubber, CSM - chlorosulfonyl polyethylene, CTA - Cellulose triacetate, DAIP - diallyl isophthalate, DAP - Dial lylphthalate, EC - ethyl cellulose, ECB - ethylene cop. bitumen, ECTFE - ethylene chlorotrifluoroethylene, EEA - ethylene ethyl acre lat, EMA - ethylene methacrylate, EP - epoxy, -EPDM - ethylene pro pilen terpolymer, EPE - epoxy resin ester, EPM - ethylene propy len rubber, EPS - expanded polystyrene, ETFE - ethylene tetrafluoroetylene, EVA, EVAC - ethylene vinyl acetate, EVAL, EVOH -  Ethylene vinyl alcohol, FEP - perfluoroethylene propylene, FF -Furan resins, FMQ - fluorine modified silicone rubber, FPM - fluorine rubber, Hgw - hard tissue, Hm - hard mats, Hp - hard paper, IIR - butyl rubber, IPDI - isophorone diisocyanate, IR - Cis-1,4-polyisoprene rubber, MBS - methyl methacrylate buta diene rubber, MC - methyl cellulose, MDI - diphenylmethane iii sociant, MF - melanin formaldehyde, MMA - methyl methacrylate, MPF - Melanin-phenol-formaldehyde, MQ - methyl silicone rubber, NBR - Nitrile rubber, NCR - Acrylonitrile chloroprene rubber, NC - nitrocellulose, NDI - naphthylene diisocyanate, NR - natural chew Tschuk, PA - polyamides, PAI - polyamide imides, PAN - polyacrylics nitrile, PBT (P) - polybutylene terephthalate, PC - polycarbonate, PCD - polycarbodiimide, PCTFE - polychlorotrifluoroethelen, PDAP - polydiallyl phthalate, PE - polyethylene, PEBA - polyether Block amides, PEC - polyester carbonate, PE-C - chlorinated Po polyethylene, PEEK - polyacryletherketone, PEI - polyetherimide, PEO, PEOX - polyethylene oxide, PEP - polyethylene polyamides, PES - Polyethersulfphone, PET (P) - polyethylene terephthalate, PEV, PEX - cross-linked polyethylene, PF - phenol-formaldehyde, PFA - Perflu oralkoxy cop., PFEP - polytetrafluoroethylene perfluoropropylene, PHA - phenacrylic resins, PI - polyimide, PIB - polyisobutylene, PIR - polyisocyanurate, PMI - polymethacrylimide, PMMA - polymetyl methacrylate, PMP - poly-4-methylpentene-1, PMQ - phenylmodifi Ornamental silicone rubber, PMS - poly-methylstyrene, PO - polyo lefine, POM - polyoxymethylene, PP - polypropylene, PP-C - chlo polypropylene, PPE - polyphenylene ether, PPMS - polypa ramethylstyrene, PPO - polyphenyl oxide, PPOX - polypropylene oxide, PPS - polyphenylene sulfide, PPSU - polyphenylene sulfone, PS - polystyrene, PSBR - pyridine-styrene-butadiene rubber, PSU - Polysulfone, PTFE - polytetrafluoroethylene, PTP - polyterephtha latex, PUR - Polyurethane, PVAC - Polyvinylacetet, PVAL - Po lyvinyl alcohol, PVB - polyvinyl butyral, PVC - polyvinyl chloride rid, PVC-C - chlorinated polyvinyl chloride, PVDC -  Polyvinylidene chloride, PVDF - polyvinylidene fluoride, PVE - Po lyvinylether, PVF - polyvinyl fluoride, PVFM - polyvinyl formal, PVK - polyvinyl carbazole, PVP - polyvinyl pyrrolidone, RF - Re sorcinol-formaldehyde, SAN - styrene-acrylonitrile, SB - styrene-but adien, SBR - styrene-butadiene rubber, SI - silicone, SMA - Styrene maleic anhydride cop., SMS styrene methyl styrene, SP - Ge saturated polyester, TAC - triallyl cyanurate, TDI - tolueneii socyanate, TFA - fluoro-alkoxy terpolymer, TMDI - trimethylhexa methylene diisocyanate, TPU - thermoplastic polyurethanes, UF - Urea-formaldehyde, UP - Unsaturated polyester, VAC - Vinyl acetate, VC - vinyl chloride, VCE - vinil chloride-ethylene - Cop., VCEVA - vinyl chloride-ethylene-vinyl acetate, VCOA - Vinylchloridoctylacetate, VCVDC - vinyl chloride-vinylidene chloride rid, VMQ - vinyl-modified silicone rubber, PU - cross-linked Polyethylene, VF - volcanic fever, XPS - extruded, expan dated polystyrene, co- and graft polymers, rubbers such. B. Silicone rubber, liquids such as B. org. Solvents, like THF; Oils such as silicone oil; inorg. Liquids such as B. Water.

Plastics are preferably used as matrix materials used.

Transparent materials are particularly preferred as matrix materials Plastics used.

The pigments with colors depending on the viewing angle are in amounts of 0.01-70, preferably 0.1 to 20 wt .-% (based on the total weight of the pigment-containing compound settlement), particularly preferably 1 to 10 wt .-% in the respective Matrix incorporated.  

Pigments with a platelet-like structure are preferred a thickness of 1 µm to 20 µm containing oriented crosslinking substances with a liquid crystalline structure with chiral Phase used. Depending on the effects you want Grain sizes with a diameter of about 10 mm to 1 µm be used. Pigments with a grain size are preferred between 5 mm and 3 µm, particularly preferably between 4 mm and 5 µm used. The pigments are preferably thick from 2 to 15 µm, particularly preferably 3 to 10 µm.

However, other interference pigments can also be used will.

Incorporation of the pigments from the viewing angle dependent color in the matrices is also used in practice usual methods.

The production of the first matrix can also be done, for example described in EP-B-601 483.

The pigment-containing matrix produced in this way, for example (Matrix 1) is brought into a desired form. This can depending on the matrix material used and the desired shape happen in many different ways. So it is with possible for example, the matrix 1 by spraying, spraying, Ra rolling, rolling, pouring, flooding, air brushing, sprinkling, Dipping, coil coating, printing (e.g. screen printing, gravure printing, Pad printing, flexo printing, offset printing), casting (e.g. Rotati onsguß, injection molding), extrusion (e.g. single screw extrusion extrusion, twin-screw extrusion, co-extrusion), blowing (e.g. Film blowing, blow molding, injection blowing), calendering, Laminating, duplicating, tribulating, dry coating, swirls sintering, electrostatic coating, TRIBO, ESTA or Lami to bring the kidneys into the desired shape, possibly with a  further comminution by, for example, cutting, grinding, Breaking can take place.

To shape the pigment-containing matrix 1 when using Plastics as matrix material is, for example, rolls, Ra keln, spraying, splashing, dipping, pouring, extruding, blowing, Calendering, coating, laminating when using Plastics advantageous, possibly with subsequent cutting, Grinding, breaking.

When using lacquers as matrix 1, the pigment-containing matrix 1, for example spraying, spraying, Ra celn, rolls, printing advantageous, if necessary with subsequent Cut, grind, break after removing one if necessary auxiliary carrier.

The structured pigment-containing first matrix (matrix 1) is into a second matrix (Ma trix 2) incorporated.

As a second matrix, they are suitable for the first time materials mentioned trix with the restriction that as Ma trix 2 does not use the material already used as Matrix 1 may be used if pigments, which are identical to those in Matrix 1, in the same concentra tration or the same shape or color or pigments that light reflect the same direction of polarization, who introduced the. Among identical pigments is in the sense of the present Invention to understand that the pigments have the same shape and color are and reflect light of the same polarization direction. In Matrix 2 can also use pigments from the viewing angle dependent colors. The training As already described in general for Matrix 1,  respectively. When using liquid materials is on it to ensure that a flat or spatial structure tion of the matrix 1 is retained, as is the case, for example, with Droplets due to phase separation of the liquids used can be observed as material for matrix 1 and 2.

Plastics are preferred, particularly preferably transparent annuity plastics used as matrix 2.

The composition according to the invention preferably comprises com combinations of pigment-containing transparent plastics (Ma trix 1) in transparent plastics (matrix 2).

The incorporation of the matrix 1 containing pigments with the Be viewing angle dependent color in the second matrix takes place in a manner known per se. It can vary which material is used as matrix 1 or as matrix 2 will be very different. However, it is Expert in the field of processing the respective mate rialien familiar.

In addition to compositions consisting of a matrix 1 containing pigments with the viewing angle dependent color in another matrix 2, also together solutions in which several matrices (1a to 1x) contain tend pigments with a color that depends on the viewing angle are present in a matrix 2.

The invention further relates to compositions in which several matrices (1a to 1x) containing pigments with from Be viewing angle dependent color to a matrix 2 ver are bound.  

Through a targeted combination of matrix material and pig ment to different matrices 1a to 1x and structure Formation of the respective matrices into a desired shape and subsequent incorporation of the structured matrices 1a up to 1x in a matrix 2 can be the diversity of the structure tion of the multi-component system according to the invention is still almost increase arbitrarily. For example, color tones (e.g. due to different colors of the pigments in each Single structure element), color brilliance (e.g. by difference pigment concentration in the matrix of the individual structure lements), "Sparkle effects" (e.g. through different pig target size per individual structural element) and so on achieve a targeted three-dimensional depth effect.

The compositions according to the invention can only be found under Use of pigments depending on the viewing angle Create color and high transparency. The pigments must a wide range of visible light spectra have sufficient transparency to create a spatial Structuring without covering those lower in matrix 2 Make structures visible.

The compositions according to the invention can, like that the following non-exhaustive list shows on the below different areas or to make the difference use the most diverse objects:

Construction (interiors, facades, wallpapers, doors, windows, interior ver clothing), gifts, writing utensils, packaging, Glasses frame, vehicles (motor vehicle, rail vehicle, Aircraft, two-wheeled vehicle), vehicle accessories, sporting goods, Game objects, textile, buttons, leather, cosmetics, jewelry, house halt (dishes, furniture, household appliances), printed matter (e.g. cardboard boxes, packaging, carrier bags,  Papers, labels, foils), documents, check cards, cash loose means of payment, banknotes, decorative foils or elements, Advertising media, furniture foils, phono foils, office supplies, (e.g. Spine of folders, document folders), photo albums, phone cards, Check and credit cards, business cards, key cards, ID cards, Air tickets, tickets, seals, floor coverings (paste and thermoplastic technology) tiles, stamping foils, sheet metal shaving foils, laminating foils for window profiles, label foils s, coatings, casting compounds, pebble coverings, foils or Coatings for e.g. B. Boats, surfboards, snowboard, skis, Glass coatings, printing on glass, conservatories, sails or inserts for sails, cast foils, mirror foils, lamps screen foils, synthetic leather, decorative foils for motor vehicles inside and outside (e.g. root wood replacement, crash pad foils, door side covering dung, moldings), textile construction, tents, tent windows, pla NEN, awnings, housing, for. B. telephones, computer systems, Modesek gate, e.g. B. glasses, jewelry, watches, watch straps, impact resistance, weather-resistant film for skis, sports and leisure activities clothing and equipment, e.g. B. use in sports shoes, Rain protection, sun protection (umbrellas, awnings), swimming caps, Packaging, self-adhesive films, floppy sleeves, toys, Building boards, carpets, wallpaper, wall coatings, sanitary ware rich, e.g. B. shower cubicles, hollow body, housing.

In addition to the decorative structure of the combination according to the invention a protective function (copy protection) occur. The compositions according to the invention are therefore particularly suitable for hedging and / or Authenticity identification of data carriers such as securities, ID cards or the like.

The following drawings serve to further explain the Invention.  

Fig. 1 shows schematically the preparation of the composition according to the invention. Pigments with color ( 1 ) depending on the viewing angle are incorporated into a matrix (2) (matrix 1). A pigment matrix system ( 3 ) was created. This is then converted into the desired geometric shape ( 4 ) and then incorporated as a structural element ( 4 ) in a second matrix (“matrix 2”) ( 5 ), the composition ( 6 ) according to the invention is obtained.

Fig. 2-4 show various ways in which the structural elements can be constructed.

Fig. 2 shows different types of pigments that can be incorporated into a matrix to form a structural element. Distinguishable structural elements can be achieved by different pigment concentrations of identical pigments in identical matrix material ( 7 a, b) or by different pigment sizes of same color and equally polarized light reflecting pigments in identical matrix material ( 8 a, b) or by pigments of different color and equal size and equally polarized light reflective ( 9 a, b) or by pigments of identical color and size that reflect differently polarized light, ( 10 a, b). 11 a, b shows an example of a structural element which differs according to more than one of the criteria described above (pigment-containing matrix 1).

Fig. 3 shows schematically possible geometric shapes of the structural elements. In principle, the pigment matrix systems can be converted into thread-like shapes ( 12 ), into sheet-like shapes ( 13 ) or into spatially extensive (three-dimensional) shapes ( 14 ).

FIG. 4 schematically shows structural elements that are constructed from different optical properties of the matrix (2). With a transparent matrix, the incident light is almost completely transmitted ( 15 ), with a translucent matrix to a certain extent reflected ( 16 ), with an opaque matrix almost completely reflected ( 17 ) and with an opaque matrix completely reflected ( 18 ).

Fig. 5-7 show examples of how that can be arranged in Fig. 2-4 is described structural elements in a further matrix (5). Here, in Fig. 5, the structural turelemente (19) of sheet-like manner while they are spatially structured in Fig. 6. In FIG. 5 and FIG. 6 have the structure elements (19) are oriented uniformly, while zusätz in Fig. 7 Lich tilting of the individual structure elements (19) are shown.

In contrast, a pigment matrix system is shown in FIG. 8, which was formed by incorporating pigments 1 into a matrix 2 according to EP-A-686 674. Structuring as described in Fig. 5-7 is not possible in this case.

Fig. 9-10 schematically show the achievable with structural elements combined on the viewing angle dependent color effects to the spatial low-effects. In Fig. 9, two different structural elements ( 20 ), ( 21 ) are arranged in a matrix (5) so that they are partially overlapping when viewed from above. The structural elements differ as follows: ( 20 ) is formed from a transparent matrix (2) and red pigments with a color ( 22 ) depending on the viewing angle, ( 21 ) consists of a substance-identical matrix (2) and green pigments ( 23 ) with a Viewing angle dependent color; ( 22 ) and ( 23 ) are incorporated into the matrix (2) in identical concentrations, reflect polarized light in the same direction and have the same particle size. The optical effects which can be achieved with the arrangement described in FIG. 9 are described in FIG. 10:
The light ( 24 ) striking the structural element ( 20 ) is emitted according to the method described in H.-J. Eberle, A. Miller and F.-H. Kreuzer, Liquid Crystals, 1989 (5), 907-916 reflects the physical relationship described and, depending on the angle of illumination and observation, leads to a red to green color change ( 24 a).

The same applies to the light ( 25 ) striking structure element ( 21 ), the color appearance changing from green to blue ( 25 a). In contrast, light ( 26 ) striking both structure elements is first reflected by structure element ( 20 ) in a wavelength-selective manner ( 26 a) while the rest of the light ( 26 b) is transmitted. When this "light residue" strikes structural element ( 21 ), part of the light spectrum is again reflected ( 26 c) and the remaining spectral residue ( 26 d) is transmitted. In the angular configuration shown in Fig. 10, the light ( 24 a) reflected by structure element ( 20 ) is orange and the light ( 25 a) reflected by ( 21 ) is turquoise. The eye that is fixed at position ( 27 ) thus perceives an orange color, the eye in position ( 28 ) perceives a turquoise hue. The eye in position ( 29 ) perceives an orange and a turquoise color at the same time, whereby due to the high transparency of the structural element, the turquoise color appears deeper and a terrace-like structure can be observed at the boundary line ( 30 ) between the overlapping and non-overlapping structural element .

Fig. 11 shows diagrammatically how a plurality of structural elements (4 a, 4 b, 4 c) in a matrix 5 as shown in Fig. 1 are transferred. In a first step, as described in FIG. 1, structural elements ( 4 a), ( 4 b), ( 4 c) are formed which consist of identical matrix 2 and distinguishable pigment species ( 1 a), ( 1 b), ( 1 c) are formed. In the second step, the structural elements ( 4 a), ( 4 b), ( 4 c) are converted into a uniform matrix without using a further matrix ( 31 ).

Fig. 12 is explained in Example 4.

Fig. 13 is explained in Example 4.

The following examples serve to further explain the invention:
In Example 1, three structural elements ( 1 a, 1 b, 1 c) are produced and converted into a matrix 2. In Example 2, who described smaller structural elements compared to Example 1. Example 3 describes the production of 3 structural elements which, in contrast to the two previous examples, are incorporated into a further matrix. Example 4 describes how stacked structural elements are incorporated into a matrix and thus lead to terraced structures with color effects depending on the viewing angle. In Example 5, the hard matrices used in Example 1-4 are replaced by a soft film, where the structural elements are formed by grinding the film. In Example 6, the structural elements are already brought into the desired shape by granulation during their production. In Example 7, liquid structural elements are described, which are converted into a further matrix. Example 8 describes how spatially dimensioned structural elements are incorporated into a further matrix.

example 1 Composition based on rigid PVC as matrix 1a, 1b, 1c and matrix 2

Recipe:

1a) 100 parts S-PVC K value 60 commercially available under the name Vinnolit H 60 DS from Vinnolit Kunststoff GmbH, Ismaning,
1.3 parts of octyltin compound commercially available under the name Hostastab SnS 10 from Hoechst AG,
0.5 parts of glycerin fatty acid internal lubricant commercially available under the name Loxiol G 16 from Henkel KGaA, Düsseldorf,
0.5 parts ester wax external lubricant commercially available under the name wax E from Hoechst AG,
1 tsp. Platelet-shaped pigments with color depending on the viewing angle (grain diameter 10 to 45 µm).

The platelet-shaped pigments from the viewing angle dependent colors were produced as in Example 4 described in EP-A-686 674, with the difference that the pigment fraction used by grinding for five minutes in a universal mill and then sieving with one Test sieve with a mesh size of 40 µm obtained has been.

1b) 100 parts S-PVC K value 60, Vinnolit H 60 DS, Vinnolit Kunststoff GmbH, Ismaning,
1.3 parts octyltin compound, Hostastab SnS 10, Hoechst AG,
0.5 parts glycerol fatty acid ester, Loxiol G 16, Henkel KGaA, Düsseldorf,
0.5 parts ester wax, wax E, Hoechst AG,
1 tsp. Platelet-shaped pigments with color depending on the viewing angle (grain diameter 10 to 45 µm).

The platelet-shaped pigments from the viewing angle dependent colors were produced as in Example 3 described in EP-A-686 674, with the difference that the pigment fraction used by grinding for five minutes in a universal mill and then sieving with one Test sieve with a mesh size of 40 µm obtained has been.

1c) 100 parts S-PVC K-value 60, Vinnolit H 60 DS, Vinnolit Kunststoff GmbH, Ismaning,
1.3 parts octyltin compound, Hostastab SnS 10, Hoechst AG,
0.5 parts glycerol fatty acid ester, Loxiol G 16, Henkel Düsseldorf,
0.5 parts ester wax, wax E, Hoechst AG, Gersthoven,
1 tsp. Pigment platelet-shaped pigments with color depending on the viewing angle (grain diameter 10 to 45 µm).

The platelet-shaped pigments from the viewing angle dependent colors were produced as in Example 4 described in EP-A-686 674, with the difference that 3.4 g instead of 2.8 g of the red color mixture and 0.6 g instead of 1.2 g the blue color mixture was used and the used pigment fraction by grinding for five minutes in one Universal grinder and subsequent sieving with an analy sieve with a mesh size of 40 µm was obtained.

2) 100 parts S-PVC K-value 60, Vinnolit H 60 DS, Vinnolit Kunststoff GmbH, Ismaning,
1.3 parts octyltin compound, Hostastab SnS 10, Hoechst AG,
0.5 parts glycerol fatty acid ester, Loxiol G 16, Henkel Düsseldorf,
0.5 parts ester wax, wax E, Hoechst AG, Gersthoven,
0.5 parts of carbon black pigments commercially available under the name Printex V.

Mixing preparation: The components of recipes 1a, 1b, 1c, were each with an IKA laboratory stirrer 500 rpm 3 min, mixed cold.

The production of the matrix 1a, 1b, 1c in the form of rolled skins was done by rolling each mixture in 5 minutes  Tröster mixing mill at 20 rpm at 185 ° C. The rolled skin thickness was 0.6 mm.

Subsequently, the rolled skins 1 a, 1 b, 1 c were cut into pieces with a side scissors with a side length of about 0.5 to 5 cm, mixed for 1 min with an IKA laboratory stirrer, sprinkled onto an aluminum plate to a layer thickness of about 2 mm. The matrices 1a, 1b, 1c are then converted into matrix 2 by pressing on a Werner & Pfleiderer laboratory press with a pressing pressure of 10 N / mm² (185 ° C., 10 min.).

The partially overlaid different colored structural elements result in a play of colors with great depth and brilliance, if there is a dark background. This effect can be reinforced by

100 parts S-PVC K-value 60, Vinnolit H 60 DS, Vinnolit Kunststoff GmbH, Ismaning,
1.3 parts octyltin compound, Hostastab SnS 10, Hoechst AG,
0.5 parts glycerol fatty acid ester, Loxiol G 16, Henkel Düsseldorf,
0.5 parts ester wax, wax E, Hoechst AG,
0.5 parts Amorphous carbon commercially available under the name Printex V,
using an IKA laboratory stirrer at 500 rpm for 3 min. cold mixed and on a Tröster mixer mill at 20 rpm / 185 ° C for 5 min. be rolled (rolled skin thickness 0.6 mm). A black rolled skin is obtained. The matrix 2 is then with the black rolled skin at 185 ° C for 10 min. pressed on a Werner & Pfleiderer laboratory press (pressing pressure 10 N / mm²). Such compositions can be used, for example, as floor tiles.

Example 2 Composition based on rigid PVC

In this example a composition is described which contains smaller structural elements than in example 1. For this, the procedure is as in Example 1, with the difference that the rolled skins 1 a, 1 b, 1 c are ground to pieces with a side length of 0.1 to 0.5 cm using a mill. In contrast to Example 1, the partially superimposed different colored structural elements lead to a finer structured appearance, so that even for small-format applications, such as. B. bracelet, clock face, a play of colors with great depth fen fencing and brilliance can be achieved.

Example 3 Furniture foils or tiles made of hard PVC

Recipe:

1a) 100 parts S-PVC K value 60, Vinnolit H 60 DS, Vinnolit Kunststoff GmbH, Ismaning,
1.3 parts octyltin compound, Hostastab SnS 10, Hoechst AG,
0.5 parts glycerol fatty acid ester, Loxiol G 16, Henkel Düsseldorf,
0.5 parts ester wax, wax E, Hoechst AG,
1 tsp. Platelet-shaped pigments with color depending on the viewing angle (grain diameter 10 to 55 µm).

The platelet-shaped pigments with from the viewing angle Pending colors were produced as in Example 4 of EP-A-686 674 described, with the difference that the turned set pigment fraction by grinding for five minutes in one Universal mill and subsequent sieving with one analysis sieve with a mesh size of 50 microns was obtained.

1b) 100 parts S-PVC K-value 60 DS, Vinnolit H 60 DS, Vinno lit Kunststoff GmbH, Ismaning,
1.3 parts octyltin compound, Hostastab SnS 10, Hoechst AG,
0.5 parts glycerol fatty acid ester, Loxiol G 16, Henkel Düsseldorf,
0.5 parts ester wax, wax E, Hoechst AG,
1 tsp. Platelet-shaped pigments with color depending on the viewing angle (grain diameter 10 to 55 µm).

The platelet-shaped pigments depend on the viewing angle pending colors were prepared as in Example 3 of EP-A-686 674 described, with the difference that the turned set pigment fraction by grinding for five minutes in one Universal mill and subsequent sieving with one analysis sieve with a mesh size of 50 microns was obtained.

1c) 100 parts S-PVC K-value 60 DS, Vinnolit H 60 DS, Vinnolit Kunststoff GmbH, Ismaning,
1.3 parts octyltin compound, Hostastab SnS 10, Hoechst AG,
0.5 parts glycerol fatty acid ester, Loxiol G 16, Henkel Düsseldorf,
0.5 parts ester wax, wax E, Hoechst AG,
1 tsp. Platelet-shaped pigments with color depending on the viewing angle (grain diameter 10 to 55 µm).

The platelet-shaped pigments depend on the viewing angle Pending colors were produced as in Example 4 of EP-A-686 674, with the difference that 3.4 g instead 2.8 g of the red color mixture and 0.6 g instead of 1.2 g of the blue Color mixture was used and the pigment fracture used by grinding for five minutes in a universal mill and  then sieving with an analytical sieve with a Ma width of 50 µm was obtained.

2) 100 parts S-PVC K-value 60 Vinnolit H 60 DS, Vinnolit Kunststoff GmbH, Ismaning,
1.3 Tle.Sn - stabilizer Hostastab SnS 10 , Hoechst AG,
0.5 parts glycerol fatty acid ester, Loxiol G 16, Henkel Düsseldorf,
0.5 parts ester wax, wax E, Hoechst AG.

Mixing preparation: The components of recipes 1a, 1b, 1c, 2 were each individually using an IKA laboratory stirrer at 500 rpm for 3 minutes, mixed cold.

The production of the matrix 1a, 1b, 1c in the form of rolled skins was carried out by rolling mixture 1a for five minutes each, 1b, 1c in a Tröster mixing mill at 20 rpm and 185 ° C.

The rolled skins 1 a, 1 b, 1 c were then cut into strips of 2 × 30 cm. The composition according to the invention is prepared by rolling mixture 2 on the Tröster mixing rolling mill at 20 rpm and 185 ° C. for 4 minutes. After a rolling time of 4 minutes, the rolled skins 1 a, 1 b, 1 c are each 10% (wt. ) added. After a further minute of rolling, the composition thus produced is removed.

By adding 10% (by weight) of the rolled skins 1 a, 1 b, 1 c to the mixture 2, in contrast to Example 1, colored, partially overlapping and colorless transparent structures are produced next to one another in matrix 2.

By limiting the rolling time to one minute position of the composition according to the invention remain Structures of the matrices 1a, 1b, 1c largely preserved. Analogous for example 1, the color can be stored with a black background can be increased significantly.

Comparative Example 1

Comparative example 1 corresponds to example 3 with the difference that the rolling time for the preparation of the invention together seating 10 min. is.

In contrast to Example 3, the structural elements of the individual matrices 1a, 1b, 1c dissolved and lead to a uniform appearance with a mixed color from 1a, 1b, 1c diluted by the colorless mixture 2.

Example 4

Cards made of hard PV copolymer with security feature, suitable e.g. B. as ID cards, phone cards, key cards, lift cards, seals
80 parts copolymer PVC / PVAC, Vinnolit SA 3060/10, Vinnolit Kunststoff GmbH, Ismaning,
15 parts MBS; Kane B 22, Kanika Düsseldorf,
5 parts S-PVC K-value 100, Vinnolit C 100 V, Vinnolit Kunststoff GmbH, Ismaning,
1.5 parts octyltin compound, Hostastab SnS 10, Hoechst AG,
0.6 parts fatty acid ester, Hostastat FE 20, Hoechst AG,
0.5 parts ester wax, Hostalub WE 4, Hoechst AG,
0.1 parts soot paste, Sicotop black 00 6307 C2, BASF Ludwigshafen,
1 part of platelet-shaped pigments with a color depending on the viewing angle (grain diameter 10 to 55 µm).

The platelet-shaped pigments depend on the viewing angle Pending colors were produced as in Example 4 of EP-A-686 674 described, with the difference that the turned set pigment fraction by grinding for five minutes in a university Versalmühle and subsequent sieving with an analytical sieve was obtained with a mesh size of 50 microns.

Mixing preparation: The Individual components of the recipe abandoned and on a Mi final temperature of 100 ° C heated with stirring The mixture thus produced was cooled to 40 ° C. and drained.

The mixture was applied to an IDE single screw extruder Pre-plasticized melt temperature of 180 ° C. The melt was on a Berstorff 4-roll L-calender at one temperature of 175 ° C and a calender speed of 2 m / min a film thickness of 0.2 mm is formed.

The films obtained in this way are on a Herbold cutting mill (Type SMS 30/50-H5-3) for pieces with a side length of 1-8 mm ground.

In an analog production step, pieces as above are wrote produced with the difference that as a platelet shaped pigments with colors depending on the viewing angle speed were used instead of Example 4 in EP-A-686 674 were prepared according to Example 3.

The pieces produced in this way with a color change from red to green or from green to blue were measured using a IKA laboratory stirrer cold stirred at 500 rpm for 1 minute.  

(Quantity ratio of the pieces 1: 1). This mixture was then pressed on a Werner & Pfleiderer laboratory press with a pressure of 10 N / mm² at 185 ° C. for 10 minutes to form a 0.3 mm thick plate. One observes terrace-shaped color effects depending on the viewing angle as described in FIG. 9, FIG. 10.

As variant 1, the films provided with pigments with a color dependent on the viewing angle were punched out with a punch (side length 4 × 40 cm) instead of grinding on a cutting mill using a punch from Zwick (model 7101) with a punch (side length 4 × 40 cm). The punching pattern of the foils is shown in FIG. 12a.

The punched-out foils thus obtained were then superimposed in such a way that the punched-out openings of the first foil were only partially identical to those of the second foil ( FIG. 12b).

The two films arranged according to FIG. 12b were then pressed on a Werner & Pfleiderer laboratory press with a pressing pressure of 10 N / mm 2 at 185 ° C. for 10 minutes to form a 0.3 mm thick plate.

The observable color effects are in principle those described in FIG. 10, the following differences occurring if, in a first example, the film below is that with green ( FIG. 13a) and in a second example, the film below is that with red ( FIG. 13b) pigments is:

In a second variant, the foils produced as described were cut into 4 mm wide strips with pigments with a coloration depending on the viewing angle and superimposed as shown in FIG. 12c.

The two films arranged according to FIG. 12c were then pressed (see above). The following colors can be observed at the points designated in FIG. 13 c:

The terrace effects also occur at the interfaces on. Accordingly, there are targeted structuring in the variants  described, while in the first part of Example 4 statistical Distributions of the structural elements occur.

To enhance the color effects described
40 parts S-PVC K-value 60, Vinnolit S 3160,
40 parts copolymer PVC / PVAC, Vinnolit SA 3060/10,
15 parts EVA / PVC graft polymer, Vinnolit VK 802,
5 parts S-PVC K-value 100, Vinnolit C 100 V,
0.5 parts fatty acid ester, Hostastat FE 20,
0.4 parts ester wax, Hostalub WE 4,
2 parts titanium dioxide, Kronos Cl 2220,
1.5 parts Ovtylzinnverb., Hostastab SnS 10,
1 teaspoon of amorphous carbon, Printex V,
placed in a 10 l Henschel mixer and heated to a final mixing temperature of 100 ° C with stirring, then cooled to 40 ° C and drained. A mixture is obtained for a black base film.

Was analog with
80 parts copolymer PVC / PVAC, Vinnolit SA 3060/10,
15 parts MBS, Kane B 22,
5 parts S-PVC K-value 100, Vinnolit C 100 V,
1.5 parts octyltin compound, Hostastab Sns 10,
0.6 parts fatty acid ester, Hostastat FE 20,
0.5 parts ester wax, Hostalub WE 4
method. A mixture for a transparent overlay film was obtained.

The resulting mixtures for the black base film and the transparent overlay film were each separated on one  IDE single-screw extruders to a melt temperature of 180 ° C pre-plasticized. The melt was then on a Berstorff 4 Rolling L calenders at a temperature of 175 ° C and a Ka Landing speed of 2 m / min to a film thickness of 0.2 5 mm shaped.

Then those described above in the production were Pattern with pigments with color depending on the viewing angle between the base film and the over lay film and placed on a Werner & Pfleiderer laboratory press with a pressing pressure of 10 N / mm² at 185 ° C for 10 minutes 0.6 mm thick plate pressed.

Such compositions according to the invention are particularly suitable especially as security elements for data carriers. The fall Protection against pollution is compared, for example, from DE 39 42 663 known security elements increased significantly.

The one for the respective films with pigments from view Color angle described dependent color effects were reinforced by the black background film, the Overlay film has a protective function.

Example 5

PVC / EVA graft polymers for flexible plasticizers free of monomer plasticizers layers the z. B. for decorative, weatherproof Be layers for tarpaulins, "textile construction", tents, clothing, Rain protection are suitable.

Recipe:
100 parts Vinnolit VK 802,
2.5 parts CaZn stabilizer (Bärostab NT 521 X, Bärlocher, Munich),
3 parts plasticizer, (Edenol D81, Fa. Henkel, Düsseldorf),
2 parts processing aid (Paraloid K 175, Rohm & Haas, Frankfurt),
50.5 parts of lubricant (Loxiol G 70, Henkel),
0.05 parts soot paste (Sicotop black, from BASF, Ludwigshafen),
0.3 parts Antioxidant (Irganox 10 10, Ciba-Additi ve, Bensheim),
0.2 parts UV absorber (Tinuvin 312, Ciba-Additive),
10 parts of platelet-shaped pigments with colors depending on the viewing angle (grain diameter 0.1 to 10 mm).

The platelet-shaped pigments depend on the viewing angle Pending colors were produced as in Example 4 described in EP-A-686 674, with the difference that the pigment fraction used was not ground and not sieved has been.

Mixing preparation: The Individual components of the recipe abandoned and on a Mi heated to a final temperature of 100 ° C with stirring. Then The mixture thus produced was cooled to 40 ° C. and drained.

The mixture was applied to an IDE single screw extruder Pre-plasticized melt temperature of 180 ° C. The melt was on a Berstorff 4-roll L-calender at one temperature of 175 ° C and a calender speed of 2 m / min a film thickness of 0.15 mm is formed. The so made After cooling to room temperature, the film is placed on a diamond ZKM mill ground.  

Then another film, as described above in of a thickness of 0.3 mm, by instead of 10 parts of Pig elements with colors depending on the viewing angle Grain diameter 0.1 to 10 mm 1 part of pigments with the view Color angle dependent colouration were used, the platelet-shaped pigments with depending on the viewing angle eng color were produced as in Example 4 of EP-A-686 674 described, with the difference that the turned set pigment fraction by grinding for five minutes in a university Versalmühle and subsequent sieving with an analytical sieve was obtained with a mesh size of 40 microns. The slide will not cooled, but in the still hot melt sprinkled ground shredded film of the first film and pressed in by means of a smoothing roller and onto a with adhesive laminated medium pretreated polyester fabric.

The carrier is selected depending on the area of application (tarpaulin, poly ester, rainwear, cotton) and was made in a known manner pretreated with adhesion promoter.

Effect description: Those places with pigments Grain diameters 0.1 to 10 mm are shown strong glitter effect with color change from green to blue, whereas the other parts of the matrix have a pronounced one Color flop with color change from green to blue shows.

Example 6

Composition based on soft PVC, suitable for. B. for self-adhesive films, housings, packaging.
Recipe:
1. 60 parts PVC (Vinnolit H 70 DF),
40 parts of plasticizer commercially available under the designation DOP from Vinnolit GmbH,
2.5 parts stabilizer, (bar NT521 X commercially available from Bärlocher),
3 parts of plasticizer Edenol D81 (from Henkel),
0.5 parts stabilizer Irgastab CH55 (from Ciba-Additive),
0.4 parts of Loxiol G70 lubricant (from Henkel),
1 part of platelet-shaped pigments with color depending on the viewing angle (grain diameter 0.1 to 10 mm).

The platelet-shaped pigments with a coloration dependent on the viewing angle were prepared as described in Example 4 of EP-A-686 674, with the difference that no grinding and no screening took place.
2. 70 parts Vinnolit H70 DF,
30 parts DOP,
2.5 pcs.bar stick NT521 X,
3 parts Edenol D81,
0.5 parts Igrastab CH 55,
0.4 parts Loxiol G70,
2 parts of platelet-shaped pigments with color depending on the viewing angle (grain diameter 10 to 45 µm).

The platelet-shaped pigments with a coloration dependent on the viewing angle were prepared as described in Example 3 of EP-A-686 674, with the difference that the pigment fraction used was ground for five minutes in a universal mill and then sieved with an analytical sieve with a mesh size of 40 µm was obtained.
3. 70 parts Vinnolit H70 DF,
30 parts DOP,
2.5 pcs.bar stick NT521 X,
3 parts Edenol D81,
0.5 parts Igrastab CH 55,
0.4 parts Loxiol G70,
0.5 parts of carbon black pigment.

Mixing preparation: The Individual components of the recipe are given up for themselves and heated to a final mixing temperature of 120 ° C with stirring. The mixtures thus prepared were then at 40 ° C. cooled and drained. The cooled mixture became 1 Granules made by mixing 1 on a granule machine (Reifenhäuser, screw diameter 45 mm) at 170 ° C was processed into granules. Then the Granules cooled to 20 ° C. Mix 2 was also used method.

The granules thus obtained from mixture 1 and mixture 2 were then mixed at 20 ° C. in a Henschel mixer in a ratio of 1: 1 and applied to a black film which was produced from mixture 3 (preparation as in Example 5). Finally, the film with the granules was pressed at 170 ° C. for 5 minutes with N / mm² pressure and cooled to room temperature. The pressing creates partially overlapping matrix systems that show a pronounced color flop and extreme depth effect with terrace effects.

Example 7

Composition suitable for coatings, boats, surfboards, facades, floors or potting compounds based on epoxy resin.
Recipe:
a) 100 parts of epoxy resin commercially available under the name Epikote 215 from Shell (Hoogvliet),
65 parts hardener commercially available under the name Epikure 205 (Shell),
2 parts of silica (HDK N20, from Wacker-Chemie, Munich),
3 parts of platelet-shaped pigments with color depending on the viewing angle (grain diameter 0.1 to 10 µm).

The platelet-shaped pigments with a coloration that was dependent on the viewing angle were produced as described in Example 4 of EP-A-686 674, with the difference that no grinding or screening took place.
b) 100 parts of Epikote 215,
65 parts Epicure 205,
2 parts HDK N20,
3 parts of platelet-shaped pigments with a color depending on the viewing angle (grain diameter 0.1 to 10 µm).

The platelet-shaped pigments with from the viewing angle Pending colors were produced as in Example 4 described in EP-A-686 674, with the difference that 3.4 g instead of 2.8 g of the red color mixture and 0.6 g instead of 1.2 g of the  blue color mixture was used and used in the Pigment fraction no grinding and sieving took place.

Mixing preparation: The components of the respective recipe were each separately stirred in an IKA stirrer at 50 rpm 3 '. The two mixtures were then degassed individually in a laboratory desiccator for 10 minutes under vacuum.

Processing: Mass a) was in a thickness of 200 microns a black phono housing (PVC film) applied.

Mass b) was then structured using a pipette applied to the not yet hardened coating (mass a) brings and smoothed out. The resulting coating hardens in about 2 hours.

Effect description: Show the masses that flow into each other a glitter effect with a distinctive color flop between gold, green and blue.

Example 8

Incorporation of spatially dimensioned structural elements made of epoxy resin into a further matrix made of epoxy
100 parts epoxy resin Epikote 215, Shell, Hoogvliet 25 (NL),
65 parts hardener Epikure F 205, Shell Hoogvliet (NL),
3 parts of platelet-shaped pigments (grain diameter 0.1-10 µm).

The platelet-shaped pigments depend on the viewing angle Pending colors were produced as in Example 4 of EP-A-686 674, wherein no grinding and screening took place.  

The ingredients were in an IKA laboratory stirrer at 50 rpm min. touched. The mixture was then placed in a desiccator cator 10 min. degassed. Then the degassed mass was turned into one cast hemispherical shape cast from silicone mass and cured for one day at room temperature. You get after Take out a hemisphere with various from the silicone mold shades of color between green and blue.

In a second step, hemispheres with red pigments manufactured with color depending on the viewing angle, by proceeding as described above with the sub decided that instead of according to Example 4 from EP-A-686 674 manufactured ten pigments pigments were used, which according to Example 3 were produced from EP-A-686 674. The resulting half balls have shades of color between red and green.

The hemispherical structural elements produced by the methods described were incorporated into a second matrix as follows:
Preparation of the mixture:
100 parts of epoxy resin and
65 parts hardener
were in an IKA laboratory stirrer at 50 rpm for 3 min. touched.

After evacuation (desiccator, 10 min.) The mass was converted into a Cube mold made of silicone mass up to a fill level of 1/3 of the cube edge length cast after using structural elements green pigments (prepared as described above) on the Bottom of the cube. The structural elements were completely covered by the epoxy resin. The mass was en hardened for 5 hours at room temperature. In a second The same procedure was followed with the difference that instead of which uses green red hemispherical structural elements (preparation as described above). After curing was done the cube shape 2/3 filled with resin. In a third Step, the rest of the cube shape was filled up with resin,  whereby both color types, produced like described above were used. After this 3. Resin layer, the cube was removed from the silicone mass. The color effects of the cube can be as follows write: Depending on the perspective and the superimposition of the structure elements are observed in shades of color between red-green-blue-turquoise and purple with a pronounced spatial effect.

Claims (8)

1. Composition characterized in that at least ei ne matrix ("Matrix 1"), which contains pigments with coloration depending on the viewing angle, is spatially or areal structured in the form of structural elements in at least one further matrix ("Matrix 2"), where Matrix 1 and Matrix 2 are not identical or in both matrices non-identical pigments with colors depending on the viewing angle are contained in identical concentrations. 2. Composition characterized in that several Ma trices (1a to 1x) containing pigments with a view Color angle dependent on a matrix 2 ver are bound. 3. Composition according to claim 1, characterized in that they contain several pigment-containing matrices 1. 4. Composition according to one or more of claims 1 to 3, characterized in that they have 1 to 100 matrices 1, contains. 5. Composition according to one or more of claims 1 to 3, characterized in that they have 1 to 20 matrices 1, contains. 6. Composition according to claims 1-5, characterized net that the matrices are plastics. 7. Process for the preparation of compositions according to ei nem or more of claims 1 or 3 to 6, characterized characterized in that at least one pigment-containing matrix 1 into a matrix 2 in a manner known per se is worked. 8. Use of the composition according to claims 1-6 for Protection and / or authentication of  Data carriers such as securities, ID cards or the like chen.