DE19639179C2 - Translucent substrates with brilliant colors depending on the viewing angle - Google Patents

Description

The invention relates to translucent substrates with high brilliant color effects depending on the viewing angle.

Compositions containing pigments with the consideration Color-dependent colors are for example from EP-686 674 A1 known. This application discloses the Kombina in Example 26 tion of pigments with color depending on the viewing angle with soot in a matrix system (paint binder) an opaque overall system.

The present invention relates to a translucent zu composition according to claim 1.

The term "specular angle configuration" is, for example, in H.-J. Eberle, A. Miller and F.-H. Cruiser, "Liquid Crystals, 1989 (5), 907-916 ". In the gloss angle configuration the angle of illumination of the surface corresponds to the view angle of the surface.

Are preferably translucent in the invention Composition in the visible wavelength range absorptive Colorants included.  

As absorptive colorants in the visible wavelength range For example, inorganic pigments such as inorganic Colored, black or luminous pigments or organic pigments such as organic colored, black or luminous pigments. Inorganic or organic black pig are preferred mente or dark colored pigments with a small L-value (Lab system) carbon black or inorganic are particularly preferred or organic black pigments.

The colorants are in amounts of 0.01 to 5% by weight, preferably from 0.02 to 3, particularly preferably from 0.05 to 1 wt .-% present.

The composition according to the invention combines the EP-686 674 A1 known color effects with a pronounced Translucency of the composition.

The composition according to the invention consists of translucent casual material in which pigments and absorptive colors tel. Examples of translucent materials are water-based paints, aqueous dispersions such as PMA, SA, polyvinyl derivatives, PVC, polyvinylidene chloride, SB-Co po, PV-AC-Copo-resins, ACR, EVA, ACR / PVC graft polymers, EVA / PVC graft polymers, water-soluble binders, as with for example shellac, male resins, rosin mod. phenol resins, linear and branched saturated polyesters, amino plastic cross-linking saturated polyester, fatty acid mod. al kyd resins or plasticized urea resins, water-dilutable Binders such as PU dispersions, EP resins, Urea resins, melamine resins, phenolic resins, alkyd resins, Al kydharzemulsionen or silicone resin emulsions, powder coatings, such as powder coatings for TRIBO / ES polyester be layering powder resins, PUR coating powder resins,  EP coating powder resins, EP / SP hybrid coating powder resinify, PMA coating powder resins, powder coatings for us internally, such as thermoplastic EPS, LD PE, LLD-PE, HD-PE, PVC, PVC co- and graft polymers, solvent lacquers containing tel. B. One- and two-component paints Schel varnish, rosin resin esters, maleate resins, nitrocelluloses, rosin-modified phenolic resins, physically drying saturated polyester, aminoplast crosslinking saturated poly esters, isocyanate-crosslinking saturated polyesters, self-ver wetting saturated polyesters, alkyds with saturated fatty acids ren, linseed oil alkyd resins, soybean oil resins, sunflower oil alkyd resins, Safflower oil alkyd resins, ricinen alkyd resins, wood oil / linseed oil kydharze, mixed oil alkyd resins, resin-modified alkyd resins, sty rol / vinyl toluene modified alkyd resins, acrylated alkyd resins, urethane-modified alkyd resins, silicone-modified alkydhar ze, 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 homopolymers or copolymers, P (M) A copolymers with an their non-acrylic monomers, externally cross-linking P (M) A homo- or Copolymers, externally crosslinking P (M) A copolymers their non-acrylic monomers, cross-linking P (M) A copolymers sate with non-acrylic monomers, acrylate copolymerization resins, unsaturated hydrocarbon resins, organically soluble cellu loose compounds, silicone combination resins, PUR resins, EP resins, peroxide-curing unsaturated synthetic resins, radiation-curing Resins containing photoinitiator, or radiation-curing art Resins free of photoinitiators, solvent-free paints, isocyanate crosslinking saturated polyester PUR 2K resin systems, PUR 1K resin systems moisture curing, EP resins, plastics z. B. networked, partially networked and networked or crosslinking  Plastics such as AAS - methacrylate-acrylic-styrene, ABS - Acrylni tril-butadiene-styrene, ACM - acrylic ester rubber, AES - acrylic nitrile-ethylene-propylene-styrene, AMMA - acrylonitrile-methyl methacrylate, ANM - acrylic ester rubber, APP - atactic butt lypropylene, 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 - diphenylmethandii 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 - polyamideimides, 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  Polyethylene, PEEK - polyacryletherketone, PEI - polyetherimide, PEO, PEOX - polyethylene oxide, PEP - polyethylene polyamides, PES - Polyethersullphone, 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-methyl styrene, 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 - polyvinyli denchloride, PVDF - polivinylidene fluoride, PVE - polyvinyl ether, PVF - polyvinyl fluoride, PVFM - polyvinyl formal, PVK - Po lyvinylcarbazol, PVP - polyvinylpyrrolidone, RF - resorcinol Formaldehyde, SAN - styrene-acrylonitrile, SB - styrene-butadiene, SBR - styrene-butadiene rubber, SI - silicone, SMA - styrene maleic anhydride cop., SMS - styrene-methylstyrene, SP - saturated Polyester, TAC - triallyl cyanurate, TDI - toluene diisocyanate, TFA - fluoroalkoxy terpolymer, TMDI - trimethylhexamethylene di isocyanate, TPU - thermoplastic polyurethane, UF - urine Fabric formaldehyde, UP - Unsaturated polyester, VAC - Viny lacetate, VC - vinyl chloride, VCE - vinil chloride-ethylene cop., VCEVA - vinyl chloride-ethylene vinyl acetate, VCOA - vinyl chlori doctylacetate, VCVDC - vinyl chloride-vinylidene chloride, VMQ - vinyl modified silicone rubber, XLPE - cross-linked polyethylene,  VF - volcanic fever, XPS - extruded, expanded Polystyrene, copolymers and graft polymers, rubbers e.g. B. silicone Rubber, liquids e.g. B. org. Solvents such as THF; oils such as silicone oil; anorg. Liquids like water.

The composition according to the invention preferably contains translucent material selected from the group of Plastics.

The composition according to the invention particularly preferably contains tongue translucent material, selected from the group of transparent plastics.

In the translucent material there are pigments as in for example from EP-A-686 674 or from EP-601483 B1 (corresponds US-5,362,315) are known, in a known manner incorporated.

The pigments with colors depending on the viewing angle are in the composition according to the invention in Amounts of 0.01-70, particularly preferably 0.1 to 20% by weight (based on the total weight of the composition) present.

The processing of the composition according to the invention can for example by spraying, spraying, knife coating, rolling, whale zen, pouring, flooding, air brushing, sprinkling, diving, coil Coating, printing (e.g. screen printing, gravure printing, tampon printing, Felxo printing, offset printing), casting (e.g. rotary casting, spraying cast), extrusion (e.g. single-screw extrusion, two-screw core extruding, coextruding) blowing (e.g. film blowing, Blow molding, injection blowing), calendering, laminating, dublie ren, triblieren, dry coating, sintering, electro static coating, TRIBO, ESTA, or laminating.  

The incorporation of the absorptive colorants into the Invention appropriate composition is as described in EP-686 674 A1 ben, or known in the art.

The materials of the invention can be followed as follows de non-exhaustive list of possible application areas offer shows, use in different fields: Construction (interiors, facades, wallpaper, 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 (e.g. dishes, furniture, household appliances), printed matter (e.g. cardboard boxes, packaging, carrier bags, papers, labels ten, foils), documents, check cards, cashless payment medium, banknotes, decorative foils or elements, advertising media, furniture belfoils, phono foils, office supplies, (e.g. file spine, Document folders), photo albums, phone cards, check and Kre dit cards, business cards, key cards, ID cards, air cards, a tickets, seals, floor coverings (paste and thermopla st technology) tiles, embossing foils, sheet metal laminating foils, Laminating film for window profiles, label films, coating tion, casting compounds, pebble coverings, foils or coatings for z. B. boats, surfboards, snowboard, skis, glass coatings printing on glass, conservatories, sails or inserts for Sails, cast films, mirror films, lampshade films, plastics the, decorative films for cars inside and outside (e.g. burl wood Er set, crash pad foils, door side cladding, decorative strips), Textile construction, tents, tent windows, tarpaulins, awnings, housings, z. B. telephones, computer systems, fashion sector, for. B. glasses, Jewelry, watches, watch straps, impact resistant, weatherproof Foil for skis, sports and leisure clothing as well  Equipment, e.g. B. Use in sports shoes, rain protection, Son protection (umbrellas, awnings), bathing caps, packaging, Self-adhesive films, disk sleeves, toys, building boards, Carpets, wallpapers, wall coatings, sanitary areas, e.g. B. Shower cubicles, hollow bodies, housings.

The following examples serve to further explain the Invention:

example 1 Preparation of a composition according to the invention, for. B. ge suitable as thermoplastic, self-adhesive film, mirror film, tent window recipe

100 parts Vinnolit® H 70 DF
55 parts Vinnolit® DOP
2.5 parts Irgastab® BZ 555
0.2 parts Sandufor VSU
0.05 tle.Sicotop® black
5 parts of pigment with a color depending on the viewing angle, produced according to EP-686 674 A1, Example 4, but without grinding and without screening.

mixture preparation

10 l Henschel mixer, final mixing temperature 120 ° C, discharge temperature tur 40 ° C, pigment with color depending on the viewing angle shortly before lowering at low speed (e.g. 500 rpm) to admit.

processing

Preplasticization on a planetary roller extruder at 185 ° C film Position on the Berstorff L - Laboratory calender at 190/190 ° C Kalan speed 2 m / min, film thickness 0.3 mm.  

effect Description

Self-adhesive films adhere to smooth surfaces without glue, such as glass panes. The most printed foils serve preferably as an advertising medium.

Follow self-adhesive films based on the above recipe of behavior: A film applied to a window pane appears transparent under a light background. dark Background causes the slide to appear covered and one pronounced color flop from green to blue. This ver holding opens up a number of possible uses, e.g. B. "Mirror Film"; Advertising media for shop windows, shading systems lay, umbrellas, umbrellas. For example, if the The rear window of a motor vehicle is used as advertising space See the driver out through the film, causing the ver road safety is increased.

Comparative Example 1

Procedure as in Example 1, but with 10 parts instead of 0.05 Share Sicotop® black

effect Description

The film appears in the review no longer transparent, the color effect is on top strongly weakened green-blue.

Example 2 Rigid PVC / thermoplastic example Lampshade foil recipe

70 parts PVC-Vinnolit® H 60 DS (Vinnolit Kunststoff GmbH)
15 parts PVC-EVA, copolymerized (plasticizer free) Vinnolit® VK 801 (Vinnolit Kunststoff GmbH)
15 parts Modifier Baymod® A 95 (Bayer AG)
1.3 parts octyltin compound Hostastab® SnS 10 (Hoechst AG)
0.5 parts Loxiol® G 16
0.5 parts lubricant wax E (Hoechst AG)
3 parts pigment with dependence on the viewing angle colored, produced as described in EP-686 674 A1, Example A.
0.05 parts soot paste (Sicotop® black)

mixture preparation

Mix the component without pigments in a 10 l Henschelmi shear up to a final mixing temperature of 120 ° C. drain Tempe temperature 40 ° C, add pigment at 40 ° C at the end of the mixing time.

processing

Preplasticization of the mixture thus produced on the planet whale Zen extruder at 185 ° C. Then from the plasticized Bulk film production on the Berstorff L laboratory calender 190 ° C, calender speed 2 m / min. A film is obtained with a film thickness of 0.3 mm.

effect Description

A lamp covered with such a film shows one pronounced color flop from green to blue on the edges can be observed particularly well. The foil appears to the Be Trachten with the light source switched off, i.e. dark behind reason, as opaque. The pigments from the viewing angle-dependent colors are transparent, so that a ho he luminous efficacy is reached.

Comparative Example 2

Carried out as in example 2, but with 0.001 parts instead of 3 parts Pigment.  

The film appears transparent when the light source is switched on rent, dark when the light source is switched off without an obs respectable color effect.

Example 3 polymethylmethacrylate example Covers for light sources description

1.4 parts of pigment were added to Degalan® P 6 (PMMA, Degussa) color, depending on the viewing angle, produced as in EP-686 674 A1, Example 4 and 0.05 parts Sico top® black carbon black paste mixed and injection molded on an angel machine ES 600/125 sprayed at 230 ° C. The so made The cover caps show a pronounced color flop of green to blue. A light source attached behind it (e.g. glass fiber cable as an optical fiber) loses only slightly Luminosity, since the pigments used with the viewing angle-dependent color and transparent The amount of soot is correspondingly low.

Comparative Example 3

Carried out as in Example 3, but with 75 parts instead of 1.4 parts len pigment with color depending on the viewing angle. The light source almost completely loses its luminosity, because due to the high pigment concentration an even The pigments are not aligned and are therefore light scattering effects dominate.

Example 4 example Lacquer for car lights

10 g of the pigments prepared according to Example 3, EP-A-686 674 were 5 min. with stirring in 20 g of thinner (Permacron® Super cryl, thinner 3054, from Spies and Hecker, Cologne)  dispersed. This dispersion was poured into a mixture of 50 g Lacquer (Permacron® MS Klarlack 8010, Spies and Hecker) and 25 g Hardener (Permacron® MS Special Hardener 3368, Spiel and Hecker) added.

The paint formulation thus obtained was colored spray gun (Sata-Farb Spritztechnik GmbH, Ludwigsburg) in the form of fine droplets on a black primed model to (Bauer, model Mercedes 300 S, year of construction 1955, scale 1:18) sprayed evenly. After painting was 30 Mi pre-dried at 80 ° C and as a protective layer Clearcoat (paint formulation as described, but without Pig elements). Relative depending on the position of the light source to the object are in different places of the model car continuously changing color impressions throughout Observe the spectral range between red and green.

The described color impression is too on a black background observe. Is this LC pigment-containing paint on one Car headlights applied, so is the desired color flop not attainable or only in a weakened form.

By adding 0.1 part Printex V (Degussa) to the in This paint system described above is also based on a headlamp a pronounced color flop from red to green achieved.

Comparative Example 4

Carried out as in Example 4, but with 6 parts Printex® V instead of 0.1 parts. The headlight appears black, the color flop from red to green has weakened sharply.

Example 5 PET example hollow body

Kodak PETG copolyester 6763 (Eastman Chemical Internatio nal A.G./Zug, Switzerland) 2 parts of pigment were included Color angle dependent, produced according to EP-686 674 A1, Example 3 and 0.1 part PV real blue A2R (Hoechst, Frankfurt) admixed and on a Fischer Extrusionblasan blown into bottles.

effect Description

The bottle shows a color gradient from violet to turquoise and the color flop is also in the case of light-colored fillings (e.g. body milk) very pronounced. At the same time, the possibility remains that Fill level to be recognized from the outside.

Comparative Example 5

Carried out as in example 5, but with 6 parts PV real blue A2R instead of 0.1 parts. The color flop is greatly weakened and the Level in the bottle no longer recognizable.

Claims (4)

1. Translucent composition containing pigments with a color dependent on the viewing angle, characterized in that it contains absorptive colorants in an amount in which the angle-dependent color effect occurring with the gloss angle configuration is enhanced without the transparency of the composition for all other angle configurations the human eye is decisively impaired, the colorants being present in amounts of 0.01 to 5% by weight and the pigments having a color depending on the viewing angle being present in amounts of 0.01 to 70% by weight. 2. Composition according to claim 1, characterized in that that the absorptive colorants in the visible wavelength be absorb richly. 3. Composition according to claim 1 or 2, characterized records that inorganic or or as absorptive colorants ganic colored, black or luminous pigments are present. 4. Composition according to claim 1 or 2, characterized indicates that the absorptive colorants are carbon black or black organic or organic pigments or organic colored pigments elements are present.