Classifications

• • 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
  • C09D11/00—Inks
• • 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
  • C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
  • B05D5/065—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
• • 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
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • 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
  • C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
• • 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
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/68—Particle size between 100-1000 nm
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/69—Particle size larger than 1000 nm
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/28—Colorants ; Pigments or opacifying agents
  • D21H21/285—Colorants ; Pigments or opacifying agents insoluble
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
  • C09C2200/305—Thickness of intermediate layers within the stack
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
  • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
  • C09C2200/308—Total thickness of the pigment particle
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H2250/00—Laminate comprising a hologram layer
  • G03H2250/34—Colour layer

Definitions

• the present invention relates to a system, such as a system of layers of inks, foils, coatings or lacquers or a system comprising a substrate which is coated with a system of layers of inks, foils or lacquers, wherein the system exhibits a colour flop effect, even if the system does not contain any interference pigment.
• Systems such as objects or substrates, respectively, coated for instance with inks, wherein the inks impart a colour flop effect show a change of a coiouristic property under different viewing angles or observation angles, respectively.
• Such effects are called flop effects or flip-flop effects, respectively.
• the coiouristic property, which changes under different observation angles, may be the brightness or colour shade of the ink. More specifically, a change of the brightness of a printed object in dependency of the observation angle is typically called brightness flop effect, whereas a change of the colour shade of a printed object in dependency of the observation angle is referred to as colour shade flip-flop effect or a colour travel effect.
• Inks imparting an object coated therewith with such a flip-flop effect are for instance interesting for coating objects used for safety applications, such as for forgery-proof security papers, such as banknotes, credit cards, postage stamps, telephone cards and identity cards, whereas lacquers imparting an object coated therewith with such a flip-flop effect are for instance interesting for coating automobiles in order to impart them a specific outer appearance.
• holographic foils are often used.
• interference pigments are added into the system like e.g. an ink or coating.
• Such interference pigments comprise at least two different layers, which cause a reflection of parts of the light waves at different planes and a refraction of a part of the light waves, so that the light waves reflected from the different planes travel different distances leading to an interference.
• Interference is a phenomenon in which two waves superpose to form a resultant wave of greater, lower or the same amplitude.
• Interference usually refers to the interaction of waves that are correlated or coherent with each other, either because they come from the same source or because they have the same or nearly the same frequency. Interference effects can be observed with all types of waves, for example, light, radio, acoustic, surface water waves or matter waves.
• Examples for such interference pigments are for instance carrier platelets, such as alumina platelets or silica platelets, which are coated with high-refractive metal oxides, such as with titanium dioxide and iron(ill)oxide.
• US 7,077,897 B2 describes a multilayer interference pigment for security applications, which consists of a transparent support material which is coated with alternating layers of colourless, non-absorbent metal oxides of high and low refractive indices, with the difference between the refractive indices being at least 0.1.
• the respective pigment is obtainable by alternate coating of the transparent support material with a metal oxide of high refractive index and a metal oxide of low refractive index by a wet process by hydrolysis of the corresponding, water-soluble, inorganic metal compounds, and separating off, drying and optionally calcining the resultant pigment.
• known inks based on interference pigments are expensive due to the complex structure of the interference pigments and the laborious production process for synthesizing the interference pigments.
• Another important disadvantage of known inks based on interference pigments is that each of these inks can only be used for one specific colour shade flip-flop, for example red-green.
• the object underlying the present invention is to provide a system, such as an ink sequence, which imparts an object coated therewith with a flip-flop effect and particularly a colour shade flip-flop effect and/or with a brightness flip- flop effect, but which is nevertheless cost efficient, because it does not need to include any interference pigment.
• the system, such as the ink sequence, respectively shall be easily adjustable for any desired colour shade flip- flop effect and/or brightness flip-flop effect.
• this object is satisfied by providing a system, such as an ink sequence, which comprises:
• pigment being different from the white pigment contained in the lower layer and being no metal effect pigment
• the respective layers are composed so that the delta a/b of the system is at least 15, which characterizes a colour flip-flop effect, and/or so that the delta L of the system is at least 10, which characterizes as brightness flip-flop effect.
• the parameters a, b and L refer to the CIE L * a*b* colour space, which is standardized in the DIN EN ISO 11664-4 threadCo!orimetry - Part 4: CIE 1976 L*a*b* Colour space 11 , and which describes mathematically all perceivable colours in the three dimensions L for lightness or brightness, respectively, and a and b for the colour opponents green-red and blue-yellow.
• the system according to the present invention is cost efficient Moreover, since any known dye and/or pigment may be used for the at least one first colour layer b), for the at least one second colour layer d) and for any possible further optional colour layer, the colour shade effect can be tailored upon desire to a desired colour shade. All in all, the present invention allows formulating a system, such as an ink sequence showing any desired colour shade flip-flop effect and/or brightness flip-flop effect. Even different colour shade flip-flops can be realized in different areas on the same substrate.
• the delta a/b measured as set out above is at least 30 and more preferably at least 38.
• the delta L measured as set out above is at least 20 and more preferably at least 30.
• the metallic layer c) may have in the vertical direction a transparency defined as ratio of visible light passing through the metallic layer c) divided by the intensity of incident visible light entering the metallic layer c) in the vertical direction of 40 to 90%, In other words, 10 to 60% of the visible light entering the metallic layer c) in the vertical direction is reflected and scattered by the metallic layer c), i.e. in particular by the metallic pigment(s) contained in the metallic layer c).
• the percentage of reflectance and scattering is defined as ( /lio)*100, wherein ho is the intensity of visible light entering into the metallic layer c) in the vertical direction and H is the intensity of visible light having been entered into the metallic layer c) in the vertical direction which has been reflected and scattered by the metallic layer c).
• the percentage of reflectance and scattering of the metallic layer c) at an angle of 25° with respect to the horizontal direction may be higher than the percentage of reflectance and scattering of the metallic layer c) at an angle of 45° with respect to the horizontal direction and the percentage of reflectance and scattering of the metallic layer c) in the vertical direction may be lower than the percentage of reflectance and scattering of the metallic layer c) at an angle of 45° with respect to the horizontal direction.
• the difference between the sum of reflectance and scattering of the metallic layer c) at an angle of 25° and that of the metallic layer c) at an angle of 45° may be at least 5% and preferably at least 10%.
• the difference between the sum of reflectance and scattering of the metallic layer c) at an angle of 45° and that of the metallic layer c) in the vertical direction is at least 5% and preferably at least 10%.
• the lower layer a has a sum of reflectance and scattering defined as (I2/I20 IOO of more than 50%, or of at least 75%, or of at least 90% or of at least 95%, such as of 100%, wherein I20 is the intensity of visible light entering into the lower layer a) in the vertical direction and I2 is the intensity of visible light being reflected and scattered by the lower layer a).
• the sum of total reflectance and scattering of the metallic layer c) and of the lower layer a) defined as ( ⁇ h+l2)/lio)*100 is at least 50%, or of at least 75% or of at least 85%, wherein ho, h and h are as defined above.
• visible light is irradiated in accordance with the present invention on the system (i.e, onto the surface of the uppermost layer of the at least one second colour layer d) or, if further layer(s) are arranged above it onto the surface of the uppermost layer above the at least one second colour layer d)) in a dark environment at an incident angle of 45° with regard to the horizontal direction.
• At least a part of the light is reflected and scattered by the system and the colour of the reflected and scattered light is measured at different viewing angles.
• a five or six angle colour measurement offers a convenient solution. Examples for the angles at which the colour of the reflected and scattered light is measured are defined further below.
• Measurements at more or less different angles are also suitable for detection of the colour travel.
• Besides visual light other standardized light types can be used, e.g. A, C, D50, D65, F2, F7, F11 or F12, wherein D50 is particularly preferred.
• the present invention is not specifically limited to the kind of white pigment, which is included in the lower layer a), as long as it has good reflectance and scattering properties. Good results are in particular obtained, when the white pigment included in the lower layer a) is selected from the group consisting of tita- nium dioxide, barium sulfate, zinc oxide, zinc sulfide, lead carbonate, calcium car- bonate, aluminium oxide, aluminium silicate and arbitrary combinations of two or more of the aforementioned substances.
• the substrate (onto which the system is arranged) can be any substrate with a white surface, such as paper, cardboard, white foiSs/fiims, white glass, white textiles, white nonwovens, white silicone substrates or white wood substrates.
• a white coating may be applied onto the substrate.
• the surface of a substrate is not white by nature it can be coated with a white coating, wherein then the coating is the lower layer a) according to the present invention.
• the lower layer a) is a white film.
• the lower layer a), i.e. the film preferably contains 0.1 to 10% by weight, more preferably 0.25 to 4% by weight and still more preferably 0.75 to 1.5% by weight of white pigment based on the total weight of the lower layer a). Good results are in particular obtained, when the film has a thickness of preferably 1 to 100 pm, more preferably of 2 to 50 pm and most preferably of 10 to 30 pm. Thicker films or even plastic boards are also suitable.
• the lower layer a) is a paper.
• the lower layer a), i.e. the paper preferably contains 0.1 to 50% by weight, more preferably 1 to 10% by weight and still more preferably 3 to 7% by weight of white pigment based on the total weight of the lower layer a). Good results are in particular obtained, when the paper has a thickness of at least 10 p . Thicker papers or even cardboards are also most suitable.
• the lower layer a) is an ink or a lacquer. In this embodiment, the lower layer a), i.e.
• the ink or a lacquer preferably contains 10 to 90% by weight and preferably 30 to 90% by weight of white pigment based on the total weight of the lower layer a). Good results are in particular obtained, when the ink or lacquer has a thickness of preferably 1 to 1 ,000 pm or 0.5 to 1 ,000 pm wherein in the case of an ink a thickness of 0.5 to 10 pm is preferred and in the case of a lacquer a thickness of 0.5 to 1000 pm is preferred.
• the white pigment included in the lower layer a) is titanium oxide and most preferably rutile.
• the titanium oxide and preferably rutile is present in the form of particles having an average dso particle size of 0.1 to 50 pm, preferably of 0.1 to 10 pm and more preferably of 0.2 to 0.5 pm.
• the lower layer a) is a substrate like cardboard or glass, the pigment particles can be bigger; for thin films, white inks or lacquers and coatings a smaller particle size is more preferred.
• the Dso is the diameter of the particle that 50% of a sample's mass is smaller than Deo and 50% of a sample's mass is larger than Dso.
• the lower layer a) has a sum of reflectance and scattering of at least 40%, more preferably of at least 50%, even more preferably of at least 60%, still preferably of at least 70%, still preferably of at least 80%, still preferably of at least 90% and most preferably of at least 95%.
• the sum of reflectance and scattering of a layer, such as of the metallic layer, is measured in accordance with the present invention preferably by using a Haze- Gloss instrument from Byk Garnder, Geretsried, Germany.
• a piece of the prepared layer with or without being attached to other layers and having for instance an area of 10 cm 2 is cut out of the system and placed in the apparatus.
• Norm light D65 is irradiated in a defined ang!e, e.g. 20°, 60° or 85° and preferably 20°, from the vertical direction onto the surface of the layer to be analyzed and the reflected (which corresponds to gloss, as defined in DIN 67530) as well as the scattered light (which corresponds to haze) is detected.
• the measurement principle is shown in figure 6,
• the remainder of the lower layer a) - in case the lower layer a) is an ink layer or a lacquer layer - may be composed of binder, solvent, and/or additives.
• the lower layer a) of the system in accordance with the present invention is an ink layer or a lacquer, it contains, depending on the ink film thickness and the type of ink, 10 to 90% by weight of binder based on the total weight of the lower layer a).
• the present invention is not particularly limited concerning the kind of binder included in the lower layer a).
• the binder is selected from the group consisting of polyesters, polyethers, polyurethanes, polyamides, polyacrylates, maleinate resins, collophonium resins, ketone resins, alkyd resins, collophonium modified phenolic resins, hydrocarbon resins, silicates, silicones, silanes, phenolic resins, urea resins, melamine resins, polyter- pene resins, polyvinylalcohois, polyvinylacetates, polyvinylchloride, polyvinyleth- ers, polyvinyipropionates, polymethacrylates, polystyrenes, polyolefines, couma- rone-indene resins, aromatic formaldehydre resins, carbamide acid resins, sulfonamide resins, chlorinated resins, nitrocellulose, CAB (cellulose acetate butyrate), CAP (cellulose acetate propionate), cellulose compounds, rubbers, radiation cubeame resins
• the lower layer a) of the system in accordance with the present invention may contain more than 0 to 100% by weight of solvent, based on the total weight of the lower layer a).
• the solvent amount depends on the ink system, the application and the pigment content. Good results are in particular obtained, when the solvent is selected from the group consisting of mineral oils, vegetable oils, fatty acid esters, alcohols, esters, ethers, glycols, water, aromatic compounds, water, monomers and oligomers with hydroxy, car- boxy, alkoxy, amino, acrylic or vinyl functionality and arbitrary combinations of two or more of the aforementioned solvents.
• the lower layer a) may contain one or more additives.
• additives are those selected from the group consisting of rheological additives, adhesives, defoamers, slip additives, anti-corrosion additives, gloss additives, waxes, wetting agents, curing agents, chelating agents, photoinitiators, inhibitors, desiccants, stabilizers, emulsifiers, pH adjustment additives, abrasion resistance additives, plasticizers, antistatic additives, preservatives, light protection agents, matting agents and arbitrary combinations of two or more of the aforementioned additives.
• the metallic layer c) of the system in accordance with the present invention is an ink, a foil, a film or a lacquer, which contains 10 to 70% by weight, preferably 20 to 70% by weight, still preferably 30 to 70% by weight and more preferably 40 to 70% by weight of metallic pigment and/or a platelet-shaped effect pigment based on the total weight of the dry metallic layer. If a metallic pigment is included, it is preferred that the metallic pigment is a metal effect pigment.
• the weight ratio of pigment to binder in the dry metallic layer c) is 0.3:1 to 2:1 , more preferably 0.7:1 to 2:1 and most preferably 0.7:1 to 1.8:1.
• the metallic layer c) is an ink or lacquer having a weight ratio of sum of metallic pigment and platelet-shaped effect pigment to binder of 0.3:1 to 2:1 , more preferably of 0.7:1 to 2:1 and even more preferably of 0.7:1 to 1.8:1.
• the metallic pigment included in the metallic layer c) is selected from the group consisting of silver, gold and aluminium pigments, e.g.
• the metallic layer c) can also contain one or more non-metallic pigments or dyes.
• the metallic pigment included in the metallic layer c) is present in the form of platelets having an average dso size of 2 to 3,000 pm. Bigger particles are preferred for higher lacquer film thicknesses and smaller particles are preferred for printing inks.
• the platelet-shaped effect pigment is preferably selected from the group consisting of silver, gold, aluminium, alloys, such as brass bronzes, copper- zinc alloys and aluminium bronzes, mica, metal oxide doped alpha-iron oxides, such as manganese doped alpha-iron oxides, aluminium oxide doped alpha-iron oxides and silicium dioxide doped alpha-iron oxides, and arbitrary combinations of two or more of the aforementioned substances.
• the plateletshaped effect pigment is composed of silver, gold or aluminium particles.
• an effect pigment is defined to be composed of platelet-shaped effect pigment particles, which are able to reflect incident light but which do not exhibit any colour shade flop effect, wherein interference pigments are according to the present invention explicitly excluded from the definition of the effect pigment.
• Interference pigments are typically composed of thin, highly refractive layers, which produce an interference of light waves.
• metallic pigments fulfil these requirements, they are also considered as platelet-shaped effect pigment particles.
• platelet-shaped means according to the present invention that the particles, of which the pigment is composed, has a second aspect ratio as specified further below.
• the platelet-shaped effect pigment is composed of particles having an average length of 2 to 500 pm, preferably of 2 to 75 pm, more preferably of 2 to 40 pm or of 2 to 500 pm and most preferably of 2 to 20 pm or of 2 to 100 pm.
• the particle length is defined in this connection as the longest extension of the particle, whereas average particle length means the average of the lengths of at least 600 measured particles and preferably of at least 1 ,000 measured particles.
• 1 ,000 of the plateletshaped effect pigment particles are optically characterized as set out in further detail below, whereby the lengths of the 1 ,000 particles are determined. Then, the sum of the 1 ,000 lengths is calculated, which is divided by 1 ,000.
• the average length of the platelet-shaped effect pigment particles is preferably 2 to 40 pm and more preferably 2 to 20 pm.
• the system is prepared by e.g. a spraying technique, i.e. if the layers of the system are coating or lacquer layers, the average length of the platelet-shaped effect pigment particles is preferably 2 to 500 pm and more preferably 2 to 100 pm.
• the system is a hybrid system, in which one or more, but not all of the layers are ink layers, whereas the other layers including at least the metallic layer c) are coating or lacquer layers.
• the average length of the plateletshaped effect pigment particles is preferably 2 to 40 pm and more preferably 2 to 20 pm in the respective foil or film layer.
• Foils are meant in accordance with the present invention to be aluminium foils, whereas films are meant to be plastic films.
• the platelet-shaped effect pigment is composed of particles having an average width of 2 to 500 pm, preferably of 2 to 75 pm, more preferably of 2 to 40 pm or of 2 to 500 pm and most preferably of 2 to 20 pm or of 2 to 100 pm.
• the particle width is defined in this connection as the longest extension of the particle in the direction being perpendicular to the particle length, whereas average particle width means the average of the widths of at least 600 measured particles and preferably of at least 1 ,000 measured particles.
• the average width of the platelet-shaped effect pigment particles is preferably 2 to 40 pm and more preferably 2 to 20 pm.
• the system is prepared by e.g. a spraying technique, i.e. if the layers of the system are coating or lacquer layers, the average width of the platelet-shaped effect pigment particles is preferably 2 to 500 pm and more preferably 2 to 100 pm.
• the system is a hybrid system, in which one or more, but not all of the layers are ink layers, whereas the other layers including at least the metallic layer c) are coating or lacquer layers.
• the average width of the platelet-shaped effect pigment particles is preferably 2 to 40 pm and more preferably 2 to 20 pm.
• the length and width of particles in general and specifically of platelet-shaped effect pigment particles are measured in accordance with the present invention preferably as follows:
• the pigment particles are washed out with acetone, then a few drops of the dispersion of pigment particles in acetone are applied to e.g. a PMMA (po!ymethyl methacrylate) or glass pane, or a mica substrate fixed on a turntable and dried at room temperature, in this way, most of the pigment particles orient themselves parallel to the surface of the substrate.
• a PMMA po!ymethyl methacrylate
• mica substrate fixed on a turntable and dried at room temperature
• the length and width is then determined optically, preferably by means of scanning electron microscopy, which is performed with a Phe- nom Pro XL from Thermo Fisher Scientific, Phenom World BV, Eindhoven ,The Netherlands, in the measurement modus BSE (back scattered electrons) using a voltage of 15 kV and using a beam current of 1 ,7 Nanoampere.
• the particle lengths and widths are then analyzed from the obtained images with the software too!“ParticleMetric” which is included in the software ProSuite distributed by Phe- nom-World BV, Eindhoven, The Netherlands. More specifically, the images are preferably enlarged so that 20 to 80 particles may be examined.
• the particle length and width are determined for single particles in order to calculate the average length and width, respectively, as set out above at least 600 and preferably of at least 1 ,000 particles are measured, then the sum of the measured lengths and width, respectively, is calculated, which is divided by the number of measured particles.
• the platelet-shaped effect pigment particles may have a regular cross-sectional form, such as a circular cross-sectional form. However, the platelet-shaped effect pigment particles may have a regular or any irregular cross-sectional form. Irrespective of whether the platelet-shaped effect pigment particles have a regular or irregular cross-sectional form, according to the present invention they may be further characterized by a calculated average diameter. More specifically, the average diameter is calculated according the equation (L+W)/2, in which L is the average length of the particles and W is the average width of the particles. Preferably, the average diameter of the platelet-shaped effect pigment particles is 2 to
• the average diameter of the platelet-shaped effect pigment particles is preferably 2 to 40 pm and more preferably 2 to 20 pm.
• the average diameter of the platelet-shaped effect pigment particles is preferably 2 to 500 pm and more preferably 2 to 100 pm.
• the system is a hybrid system, in which one or more, but not all of the layers are ink layers, whereas the other layers including at least the metallic layer c) are coating or lacquer layers.
• the system is prepared by laminating foils or films, i.e. if the layers of the system are foil or film layers, the average diameter of the plate- let-shaped effect pigment particles is preferably 2 to 40 pm and more preferably 2 to 20 pm.
• the at least one platelet-shaped effect pigment is composed of particles having an av- erage thickness of 0.01 to at most 1 pm, more preferably of 0.05 to 1 pm and even more preferably of 0.05 to 0.5 pm, in particular when the system is composed of inks.
• the at least one platelet shaped effect pigment is composed of particles having an average thickness of 0.01 to 1 pm.
• the system is a hy- brid system, in which one or more, but not all of the layers are ink layers, whereas the other layers including at least the metallic layer c) are coating or lacquer layers.
• the particle thickness is defined in this connection as the shortest extension of the particle in the direction being perpendicular to the two-dimensional plane being defined by the particle length and the particle width, whereas average parti- cle thickness means the average of the thicknesses of at least 600 measured particles and preferably of at least 1 ,000 measured particles. These numbers for the particle thickness apply to all systems based on inks, coatings, lacquers, films and foils.
• the thickness of particles in general and specifically of platelet-shaped effect pigment particles is measured in accordance with the present invention preferably as follows: A resin commonly used in electron microscopy, for example TEMPFIX distributed by Gerhard Neubauer Chemikalien, Munster, Germany, is applied to a sample plate and heated on a heating plate until softened.
• the sample plate is removed from the heating plate and the respective pigment particles are sprinkled or spread onto the softened resin.
• the resin becomes solid again as it cools and the pigment particles arrange - due to the interplay between adhesion and gravity - almost vertically and are fixed on the sample plate. This makes it easy to measure the pigment’s lateral extension in the electron microscope.
• the resulting sample is placed on a sample holder and scanning electron microscopy is performed with a Phenom Pro XL from Thermo Fisher Scientific, Phenom World BV, Eindhoven ,The Netherlands, in the measurement modus BSE (back scattered electrons) using a voltage of 15 kV and using a beam current of 1 ,7 Nanoampere.
• the length, width and thickness of the particles in the final layer system may be determined accordingly. More specifically, several sample pieces having each for instance an area of about 1 cm 2 may be cut out of the layer system for example with a laser. The samples may then be embedded in a resin common for electron microscopy, such as embedding media like epoxy resins, e.g. Araldite 502 or 6005, supplied by Electron Microscopy Sciences, Hatfield, Pennsylvania. Thereafter, one or more microtome longitudinal sections of the layer of the system to be analyzed and/or one or more microtome cross-sections of the layer of the system to be analyzed may be made, each of the sections having for instance a thickness of 5 mm.
• the microtome section(s) may be prepared for instance by using a motorized commercial rotary microtome of type RM 2155 available from Leica
• the desired thickness Prior to sectioning, the desired thickness is set and then, the respective metal panels are fixed and in the actual operational step, the rotary microtome is run over the respective sample. Subsequently, the sample(s) are fixed on a sample holder.
• the longitudinal section(s) may be fixed on sample holder shown in figure 4a and cross-sections may be fixed on sample holder shown in figure 4b.
• the at least one platelet-shaped effect pigment is composed of particles having a first aspect ratio of the average particle length divided by the average particle width of 1 to 20 and preferably of 1 to 2 or of 2 to 5 These numeric value ranges are preferred for all systems, i.e. for on inks, coatings, lacquers, films and foils.
• the at least one platelet-shaped effect pigment is composed of particles having a second aspect ratio of the average particle length divided by the average particle thickness of 1 to 75,000, preferably of 1 to 1 ,000, more preferably of 1 to 200, even more preferably of 1 to 100 and most preferably of 1 to 60.
• Such metal effect pigments are mostly oriented so that their two- dimensional plane being defined by the particle length and the particle width is oriented basically parallel to the longitudinal section of the metallic layer.
• the average particle area ratio of the metallic layer c) is 5 to 75%, more preferably 10 to 55% and most preferably 15 to 35%.
• the average particle area ratio of the metallic iayer c) means in accordance with the present invention the sum of the area in the longitudinal section of the metallic Iayer c) which is covered by the plateletshaped effect pigment particles divided by the total area of the longitudinal section of the metallic Iayer. The measurement principle is shown in figures 5a and 5b.
• the average particle area ratio of any of the single layers and particularly of the metallic layer is measured in accordance with the present invention preferably by scanning electron microscopy from the surface of the concerned Iayer of the system being prepared as described above or from a longitudinal section of the concerned Iayer of the system being prepared as described above.
• the particles are colored with the software tool“ParticieMetric” and then the sum of the area in the longitudinal section which is covered by particles is evaluated and divided by the total area of the longitudinal section analyzed by scanning electron microscopy so as to obtain the average particle area ratio in percent.
• the aforementioned parameters mentioned for the platelet-shaped effect pigments are also preferred for the metallic pigment, if present, in addition to the other parameters mentioned above for the metallic pigment.
• the layer c) is mentioned for the ease of nomenclature in the present patent application metallic Iayer, even in the case that it only includes platelet-shaped effect pigments, which are no metallic pigments.
• the metallic Iayer can be also designated as effect layer c) in the present invention.
• the metallic layer c) of the system in accordance with the present invention may have a thickness of 0.1 to 50 pm, more preferably of 0.5 to 20 pm and most preferably of 1 to 10 pm.
• the metallic layer c) of the system in accordance with the present invention contains, depending on the metallic layer thickness, the viscosity and the application method, 10 to 95% by weight of binder based on the total weight of the composition applied to form the metallic layer, wherein the binder is preferably selected from the group consisting of polyesters, polyethers, polyurethanes, polyamides, polyacrylates, ma!einate resins, collophonium resins, ketone resins, alkyd resins, collophonium modified phenolic resins, hydrocarbon resins, silicates, silicones, phenolic resins, urea resins, melamine resins, poiyterpene resins, po!yvi- nylalcohols, polyvinyiacetates, polyvinylchloride, polyvinylethers, polyvinyipropio- nates, polymethacrylates, polystyrenes, polyolefines, coumarone-indene resins,
• the metallic layer c) may contain, depending on the nature and the viscosity of the ink and the application method, more than 0 to 95% by weight of solvent based on the total weight of the composition applied to form the metallic layer c). Good results are in particular obtained, when the solvent is selected from the group consisting of mineral oils, vegetable oils, fatty acid esters, alcohols, esters, ethers, glycols, water, monomers and oligomers with hydroxy, carboxy, aikoxy, amino, acrylic or vinyl functionality aromatic compounds and arbitrary combinations of two or more of the aforementioned solvents.
• the composition applied to form the metallic layer c) may contain one or more additives.
• additives examples include those selected from the group consisting of rheological additives, adhesives, defoamers, slip additives, anticorrosion additives, gloss additives, waxes, wetting agents, curing agents, chelating agents, photoinitiators, inhibitors, desiccants, stabilizers, emulsifiers, pH adjustment additives, abrasions resistance additives, plasticizers, antistatic additives, preservatives, light protection agents, matting agents, fillers and arbitrary combinations of two or more of the aforementioned additives.
• the degree of the obtained flip- flop effect of the system is influenced, if the system is an ink system, by the ink coverage.
• Ink coverage refers to the real area coverage when halftones are printed. Since the colour pigments that are used in printing inks are basically transparent or semi-transparent, the most impact on the colour travel is due to the metallic ink.
• the metallic layer c) contains metallic pigments having an average dso particle size of 5 to 15 pm, and/or a platelet-shaped effect pigment having a first aspect ratio of the average particle length divided by the average particle width of the platelet-shaped effect pigment particles of 1 to 20 and more preferably of 1 to 2 or 2 to 5.
• the coverage of the metallic layer c) on the at least one first colour layer b), i.e. on the uppermost of the first colour layer(s), is complete, i.e. 100% or at least 95%.
• the grammage of the dry metallic layer c) is 0.2 to 2 gsm, more preferably 0.3 to 1.5 gsm and most preferably 0.4 to 1.2 gsm.
• the metallic layer c) contains metallic pigments having an average dso particle size of 5 to 15 pm, and/or a platelet-shaped effect pigment having a first aspect ratio of the average particle length divided by the average particle width of the platelet-shaped effect pigment particles is 1 to 20 and more preferably 1 to 2 or 2 to 5.
• the weight ratio of pigment to binder in the dry metallic layer c) is 0.3:1 to 2:1 , more preferably 0.7:1 to 2:1 and most preferably 0.7:1 to 1.8:1. Also this embodiment is particularly suitable, if the metallic layer c) contains metallic pigments having an average dso particle size of 5 to 15 pm, and/or a platelet-shaped effect pigment having a first aspect ratio of the average particle length divided by the average particle width of the platelet-shaped effect pigment particles is 1 to 20 and more preferably 1 to 2 or 2 to 5.
• any of the first colour layer b) and of the at least one second colour layer d) of the system in accordance with the present invention contains 0.001 to 5% by weight of at least one dye and/or 0.1 to 50% by weight of at least one pigment being no white pigment, no platelet-shaped effect pigment and no metallic pigment, based on the total dry weight of the first colour layer b) and/or second colour layer d).
• the pigments are preferably organic or inorganic pigments with a specific colour.
• Each of the at least one first colour layer b) as well as each of the at least one second colour layer d) may comprise one or more white pigments and/or one or more platelet-shaped effect pigments and/or one or more metallic pigments in addition to or as substitute for that/those being no white pigment, no platelet-shaped effect pigment and no metallic pigment.
• each of the at least one first colour layer b) as well as each of the at least one second colour layer d) does not comprises any white pigment, no platelet-shaped effect pigment as well as not any metallic pigment.
• any of the first colour layer b) and of the at least one second colour layer d) preferably contains, depending on the ink system, the viscosity and the application method, 10 to 95% by weight of binder based on the total weight of composition applied to form the at least one first colour layer b) and/or of the composition applied to form the at least one second colour layer d), wherein the binder is preferably selected from the group consisting of polyesters, polyethers, polyurethanes, polyamides, polyacrylates, maleinate resins, coliophonium resins, ketone resins, alkyd resins, coliophonium modified phenolic resins, hydrocarbon resins, silicates, silicones, phenolic resins, urea resins, melamine resins, polyterpene resins, poly- vinylalcohols, polyvinylacetates, polyvinylchloride, polyvinylethers, polyvtnylpropi- onates, polymethacrylates, polystyre
• any of the first colour layer b) and of the at least one second colour layer d) of the system in accordance with the present invention contains, depending on the ink system, the viscosity and the application method, more than 0 to 90% by weight of solvent based on the total weight of the composition applied to form the first colour layer b) and/or of the at least one second colour layer d), wherein the solvent is preferably selected from the group consisting of mineral oils, vegetable oils, fatty acid esters, alcohols, esters, ethers, glycols, water, aromatic compounds, monomers and oligomers with hydroxy-, amino-, alkoxy-, carboxy-, acrylic or vinyl functionality and arbitrary combinations of two or more of the aforementioned solvents.
• any of the compositions applied to form the first colour layer b) and of the at least one second colour layer d) of the system in accordance with the present invention may contain one or more additives.
• additives are those selected from the group consisting of rheological additives, adhesives, defoamers, slip additives, plasticizers, anti-corrosion additives, gloss additives, waxes, wetting agents, curing agents, chelating agents, photoinitiators, inhibitors, desiccants, stabilizers, emulsifiers, pH adjustment additives, abrasions resistance additives, antistatic additives, preservatives, light protection agents, matting agents, fillers and arbitrary combinations of two or more of the aforementioned additives.
• the at least one dye and/or at least one pigment included in the first colour layer b) is different from the at least one dye and/or at least one pigment included in the at least one second colour layer d).
• at least one dye and/or at least one pigment included in the first colour layer b) has a different colour or colour shade, respectively, and/or lightness than at least one dye and/or at least one pigment included in the at least one second colour layer d), i.e. the colour shade and/or lightness of the first colour layer b) is different to the colour shade and/or lightness of the at one second colour layer d).
• the system includes 1 to 3, more preferably 1 or 2 and most preferably 1 first colour layer b) between the lower layer (16) and the metallic layer c).
• the system includes 1 to 3 and more preferably 1 or 2 second colour layers d) on the metallic layer c). It is particularly preferred that the first colour !ayer(s) b) are arranged in direct contact with the lower layer a) and the metallic layer c), i.e. that there is no intermediate layer between the lower layer a) and the first colour layer b) and no intermediate layer between the first colour layer b) and the metallic layer c).
• the lowest colour layer b) is in direct contact with the lower layer a) and the uppermost colour layer b) is in direct contact with the metallic layer c), wherein all the colour layers b) are arranged in direct contact with each other one above another.
• the system is an ink system, a coating system or a lacquer system. If the system is a foil / film system, then one or more adhesive layers may be present between one or more of the layers a), b), c) and d).
• the second colour layer ⁇ s) d) are arranged in direct contact with the metallic layer c), i.e. that there is no intermediate layer between the metallic layer c) and the second colour layer d). in case of more than one second colour layers d), the lowest colour layer d) is in direct contact with the metallic layer c), wherein all the colour layers d) are arranged in direct contact with each other one above another.
• the system is an ink system, a coating system or a lacquer system. If the system is a foil / film system, then one or more adhesive layers may be present between one or more of the layers.
• the first colour layer b) and/or the at least one second colour layer d) has a thickness of 0.3 to 100 pm, preferably of 0.5 to 10 pm and more preferably of 1 to 10 pm. If more than one first colour layer b) is contained, then preferably the sum of the thicknesses of all first colour layers b) is 0.3 to 100 pm and more preferably of 0.5 to 10 pm. Likewise thereto, if more than one second colour layer d) is contained, then preferably the sum of the thicknesses of all second colour layers d) is 0.3 to 100 pm and more preferably of 0.5 to 10 pm.
• the at least one first colour layer b) is an ink layer
• the ink coverage of each of the at least one first colour layers b) on the lower layer a) is 70 to 100%, more preferably 80 to 100% and most preferably 90 to 100% or is 50 to 100%, more preferably 75 to 100% and most preferably 90 to 100%.
• the ink coverage of the sum of all of the at least one first colour layers b) on the lower layer a) is, if the system is an ink system, 70 to 100%, more preferably 80 to 100% and most preferably 90 to 100% or is 50 to 200%, more preferably 50 to 150% and most preferably 50 to 100%.
• the coverage of the sum of all of the at least one first colour layers b) on the lower layer a) is complete, i.e. 100% or at least 95%, and the first colour layers b) completely covers the lower layer a).
• the at least one second colour layer d) is an ink layer it is preferred that the ink coverage of each of the at least one second colour layers d) on the metallic layer c) is 10 to 90%, more preferably 30 to 80% and most preferably 40 to 60%. Also it is preferred that the ink coverage of the sum of all of the at least one second colour layers d) on the metallic layer c) is 10 to 90%, more preferably 30 to 80% and most preferably 40 to 60% or is 30 to 200% and more preferably 60 to 180%.
• the system is a lacquer system, film system or foil system
• the coverage of the sum of all of the at least one second colour layers c) on the metallic layer c) is complete, i.e. 100% or at least 95.
• the system may comprise one or more further layers.
• the system may comprise above the metallic layer c) one further white layer with a transparency in vertical direction of at least 50%.
• a second metallic layer being composed as the metallic layer described above on the at least one second colour layer d).
• the system does not comprise any further metallic layer in addition to the metallic layer c). in addition, it is preferred that the system does not comprise (except possible adhesive layer(s)) between the lower layer a) and the metallic layer c) any further layer in addition to the at least one first colour layer b). Moreover, it is also preferred that above the metallic layer c) (except possible adhesive layer(s)) only the at least one second colour layer d) and optionally one or more non-coloured !ayer(s) with a transparency in vertical direction of at least 50% is/are arranged.
• an interference pigment comprises at least two different layers, which cause a reflection of parts of the light waves at different planes and a refraction of a part of the light waves, so that the light waves reflected from the different planes travel different distances leading to an interference.
• the flop effect can be calculated with the colour data measured at different viewing angles.
• the measured a and b values that refer to the CIE L*a*b* colour space can be used.
• the L*a*b* colour space describes mathemati- caiiy all perceivable colours in the three dimensions L for lightness and a and b for the colour opponents green-red and btue-yellow.
• the colour travel can be described as delta a/b between measurements at different viewing angles.
• the delta a/b between the measurement at 15° and 110° was chosen as a means to describe the colour travel.
• other angles might also be suitable to describe the flop effect.
• the delta L measured as set out above is at least 20 and more preferably at least 30.
• the delta h° is at least 30.
• the lower layer a) may be the substrate, such as a foil/film, a paper or the like, or the lower layer a) may be arranged on the substrate, wherein the lower layer a) is for instance an ink or a lacquer.
• the substrate may be made of a material being selected from the group consisting of foils/films, metals, glazings, papers, cardboards, cartons, glasses, woods, textiles, nonwovens, silicones, rubbers and arbitrary combinations of two or more of the aforementioned materials.
• the system is an ink system or a lacquer system.
• any known printing technique may be used, such as offset, lithography, intaglio printing, flexographic printing, gravure printing, screen printing, digital printing, inkjet printing, pad printing, transfer printing, letter printing and the like.
• any known application technique may be used, such as electrostatic spray coating, air and airless electrostatic systems, dip coating, electrophoresis, anodic electrodeposition (anaphoresis), cathodic electrodeposition (cathaphoresis), autophoresis, flooding, casting, drum coating, spin coating, intaglio coating, roiling, coil coating, powder coating, whirl-sintering, flame spraying or electrostatic powder spraying.
• the present invention relates to the use of a system and preferably an ink or lacquer system according to the present invention for coating and in particular printing or spraying a substrate.
• the present invention relates to a system comprising:
• pigment being different from the white pigment contained in the lower layer and being no metal effect pigment
• any of the layers a), b), c) and d) may be composed as described above.
• Fig. 1 shows an object comprising a substrate, which is coated with an ink system in accordance with one embodiment of the present invention.
• Fig. 2 shows schematically a method for measuring the angle dependent colour measurement of a system in accordance with one embodiment of the present invention.
• Fig. 3 shows the results of angle dependent colour measurements of four different systems in accordance with one embodiment of the present invention.
• Fig. 4a, b show sample holders, which are suitable for carrying longitudinal sections or cross-sectional section for SEM analysis for determining the particle length, particle width and particle thickness.
• Fig. 4c shows an exemplary schematic pigment particle showing the particle length and particle width.
• Fig. 5a, b show the principle of the determination of the average particle area ratio.
• Fig. 6 shows the principle of the determination of the reflectance and scattering of a layer.
• Fig. 1 shows a system 10, which comprises a substrate 12, which is coated with an ink sequence 14 in accordance with one embodiment of the present invention.
• the ink sequence 14 comprises from the bottom up a lower layer 16, a first colour layer 18, a metallic layer 20 and a second colour layer 22.
• the lower layer 16 contains white pigment 24 preferably consisting of titanium oxide having an average diameter of 0.1 to 50 pm in a concentration of about 30 to 90 % by weight of white pigment based on the total weight of the dried lower layer 16.
• the first colour layer 18 contains about 1 to 15 % by weight of dye 26 or pigment, based on the total weight of the dry first colour layer 18, whereas the metallic layer 20 includes 30 to 60 % by weight of metallic effect pigment, e.g.
• Fig. 2 shows schematically a method for measuring the angle dependent colour appearance of a system in accordance with one embodiment of the present invention.
• a visible light beam 40 with an adjusted intensity and wavelength range is irradiated onto a system 10 as described for instance with regard to Fig. 1 at an angle of 45° with respect to the horizontal direction. Since the angle of incidence with regard to the horizontal direction is the same as the angle of reflection 42 of the irradiated light beam, the angle of reflection 42 is 135° with respect to the horizontal direction.
• This angle of reflection 42 is defined for the measurement of the angle dependent colour appearance of the system in accordance with the present invention as an observation angle of 0°.
• the sum of reflectance and scattering is measured at different observation angles 44, 44', 44”, for instance - as shown in fig 2 - at observation angles of -15°, 15°, 25°, 45°, 75° and 110°.
• a Byk mac i instrument from Byk Garnder, Geretsried, Germany can be used, with D50 light incidence and a six angle measurement at the observation angles describes above. It is most suitable to measure rectangular samples with a minimum width of 3 cm and a minimum length of 5 cm. It is especially preferred that at least 10 samples are measured, even more preferred is the measurement of 100 or even 600 samples.
• Fig. 3 shows the results of angle dependent colour measurements of four different systems in accordance with one embodiment of the present invention.
• the angle dependent colour measurements of the four different systems have been performed as described above with regard to figure 2 at observation angles of -15°, 15°, 25°, 45°, 75° and 110°.
• the a-value as well as the b-vaiue of each system have been determined.
• the respective values are plotted in figure 3 for any of the four systems, wherein the largest triangle of each graph represents the value measured at an observation angle of -15°.
• the further markers in each graph starting from the largest triangle represent the respective values determined at observation angles of 15°, 25°, 45°, 75° and 110°.
• the horizontal axis of figure 3 shows the measured a-values, whereas the vertical axis of figure 3 shows the measured b-values.
• the a-values and b- vaiues of ail four samples differ depending of the observation angle at which they have been determined. This shows, that all four systems showed a flip-flop effect.
• Figures 4a and 4b show sample holders, which are suitable for fixing longitudinal sections or cross-sectional section for SEM analysis for determining the particle length, particle width and particle thickness.
• the sample holdersshown in Figure 4a is suitable for longitudinal sections of a layer or a system (for frontal view), whereas the sample hoSdersshown in Figure 4b is suitable for cross-sectional sections of a layer or a system. The sections are placed onto the respective sample holder area as shown by the blue arrow.
• Fig. 4c shows an exemplary schematic pigment particle 46 showing the particle length 48 and particle width 50.
• the particle length 48 is the longest extension of the particle 46, whereas the particle width 50 is defined in this connection as the longest extension of the particle 46 in the direction being perpendicular to the particle length 48.
• the particle thickness is the shortest extension of the particle 46 in the direction being perpendicular to the two-dimensional plane being defined by the particle length 48 and the particle width 50, i.e. the extension of the particle perpendicular to the paper plane.
• Figures 5a and 5b show the principle of the determination of the average particle area ratio by SEM from a longitudinal section of the concerned layer of the system being prepared as described above.
• the particles 46 are colored with the software tool“ParticIeMetric” as shown in figure 5a and then the sum of the area in the longitudinal section which is covered by particles 46 as shown in figure 5b is evaluated and divided by the total area of the longitudinal section analyzed by scanning electron microscopy so as to obtain the average particle area ratio in percent.
• Figure 6 shows the principle of the determination of the reflectance and scattering of a layer.
• a part of the prepared layer such as a longitudinal section thereof or the layer itself, having for instance an area of 10 cm 2 is cut out of the system and placed in the measurement apparatus, which is preferably the Haze-Gloss instrument from Byk Garnder, Geretsried, Germany.
• Norm light D65 shown by the reference number 52 is irradiated in defined angle b of 20° from the vertical direction onto the surface of the layer 54 to be analyzed and the reflected (which corresponds to gloss 56, as described in DIN 67530) as well as the scattered light (which corresponds to haze 58) is detected by a sensor 60.
• the present invention is described by means of illustrating, but not limiting examples.
• Example 1 Example 1
• Solvent-based flexographic inks based on NC/PU have been printed on 30pm thick foils of oriented polypropylene (OPP).
• OPP oriented polypropylene
• the inks have been diluted with ethanol/ethyl acetate 9:1.
• the pigment-binder ratio in the dry ink film was 0.9: 1 to 1 ,5:1 for the in
• the flip-flop effects for each system were measured with a Byk mac I instrument. A five angle measurement for a/b travel evaluation was carried out at observation angles of -15 157257457757110°.
• the highest colour flip-flop effects have been achieved for 90 to 100% ink coverage for the colour ink printed between the white and silver layers, for 80 to 100% ink coverage for the silver layer, for 0 to 10% coverage for the optional black layer and sum of ink coverage of 40 to 60% for all inks printed on the side above the silver, i.e. metallic layer.
• solvent-based inks based on NC/PU have been tested in gravure printing: Cyan 63GU514973, Magenta 62GU514969, Yellow 61GU515076, Black 69GU515074, White 67GU515182, Silver 66GU515184, and Extender
• Cyan and Magenta were extended by 120% Yellow, Silver and white were printed without extender.
• the inks have again been diluted to 20s in a DIN 4 cup with eth- anol/ethylacetate 9:1.
• the inks were applied on corona treated OPP film with a Ro- to Hand Proofer (Pamarco).
• the following ink sequences have been investigated from bottom to up:
• W-Y-S-M-C-Bk W-S-Y-M-C, W-Y-S-M-Bk and W-S-Y-M-C-Bk.
• Solvent-based flexographic inks based on NC/PU have been printed on 30pm thick foils of white oriented polypropylene (OPP).
• OPP white oriented polypropylene
• the following inks from the hu- bergroup GmbH: 61GU336812 (Yellow; abbreviated subsequently as Y), 62GU336816 (Magenta; abbreviated subsequently as M), 63GU336821 (Cyan; abbreviated subsequently as C), and 76GU318960 (Silver; abbreviated subsequently as S) were printed onto the foils at a print viscosity 20s in a DIN 4 cup.
• the inks have been diluted with ethanol/ethyl acetate 9:1.
• the pigment-binder ratio in the dry ink film was 0.9: 1 to 1 ,5:1 for the inks Y, M, C and Bk, 1 :0.3 for W and 0.9:1 for S, wherein between 0.7 and 1 ,5 g/m 2 of dry ink (for each ink) have been applied.
• the following ink sequences have been printed, from the bottom up:
• the h° values are polar coordinates of between 0 and 360°.
• the present invention refers to the following feature combinations or aspects, respectively. Each of the following aspects may be combined with the aforementioned embodiments.
• a system comprising:
• Aspect 2 The system in accordance with aspect 1 , wherein at least at an angle of 0 to 45° with respect to the horizontal direction the colour shade of the visible light (34) being reflected and scattered by the metallic layer (20) is different to the colour shade of the visible light (38) being reflected by the lower layer (16).
• Aspect 3 The system in accordance with aspect 1 or 2, wherein the white pigment (24) included in the lower layer (16) is selected from the group consisting of titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, lead carbonate, calcium carbonate, aluminium oxide, aluminium silicate and arbitrary combinations of two or more of the aforementioned substances.
• i) is a foii/film and contains 0,1 to 10% by weight, preferably 0.25 to 4% by weight and more preferably 0.75 to 1.5% by weight of white pigment (24) based on the total weight of the lower layer (16), wherein the foil/film has preferably a thickness of 1 to 100 pm, more preferably of 2 to 50 pm and most preferably of 10 to 30 pm, or
• ii) is a paper or cardboard and contains 0.1 to 50% by weight, preferably 1 to 10% by weight and more preferably 3 to 7% by weight of white pigment (24) based on the total weight of the lower layer (16) or
• iii) is an ink and contains 10 to 90% by weight and preferably 30 to 90% by weight of white pigment (24) based on the total weight of the lower layer (16), wherein the ink has preferably a thickness of 1 to 10,000 pm.
• Aspect 5 The system in accordance with any of the preceding aspects, wherein the white pigment (24) included in the lower layer (16) is titanium oxide and preferably rutile and present in the form of particles having an average dso particle size of 0.1 to 50 pm, preferably of 0.1 to 10 pm and more preferably of 0 2 to 0.5 pm.
• Aspect 6 The system in accordance with any of the preceding aspects, wherein the metallic layer (20) is an ink having a ratio of pigment to binder in the metallic layer (20) is 0,3:1 to 2:1 , preferably 0,7:1 to 2:1 and more preferably 0,7:1 to 1,8:1.
• Aspect 7 The system in accordance with any of the preceding aspects, wherein the metallic pigment (28) included in the metallic layer (20) is present in the form of platelets having an average dso size of 2 pm to 3000 pm.
• Aspect 8 The system in accordance with any of the preceding aspects, wherein the metallic layer (20) has a thickness of 0.1 to 50 pm, more preferably of 0.5 to 20 pm and most preferably of 1 to 10 pm.
• Aspect 9 The system in accordance with any of the preceding aspects, wherein the ink coverage of the metallic layer (20) on the at least one first colour layer (18) is 40 to 100%, more preferably 70 to 100%, even more preferably 80 to 100% and most preferably 90 to 100%, wherein the ink coverage is the percentage of the area of the upperst of the first colour layer(s) (18), which is covered by the metallic layer (20).
• Aspect 10 The system in accordance with any of the preceding aspects, wherein the dry laydown of the metallic iayer (20) is 0.2 to 2 gsm, more preferably 0.3 to 1.5 gsm and most preferably 0.4 to 1.2 gsm.
• Aspect 11 The system in accordance with any of the preceding aspects, wherein the weight ratio of pigment to binder in the metafile layer (20) is 0.3:1 to 2:1 , more preferably 0.7:1 to 2:1 and most preferably 0.7:1 to 1.8:1.
• any of the first colour Iayer (18) and of the at least one second colour iayer (22) contains 0.001 to 5% by weight of at least one dye (26, 30) and/or 0.1 to 50% by weight of at least one pigment being no white pigment and no metallic pigment, based on the total dry weight of the first colour Iayer (18) and/or second colour Iayer (22).
• Aspect 13 The system in accordance with any of the preceding aspects, where- in the at least one dye (26) and/or at least one pigment included in the first colour Iayer (18) is different from the at least one dye (30) and/or at least one pigment included in the at least one second colour Iayer (22).
• Aspect 14 The system in accordance with any of the preceding aspects, which does not contain any interference pigment.

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• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
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• Wood Science & Technology (AREA)
• Nanotechnology (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Laminated Bodies (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paints Or Removers (AREA)
• Cosmetics (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

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• 2018
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