RU2803616C2 - Sequence of color-changing layers containing pigments creating the effect of shape of plates - Google Patents

Abstract

FIELD: paints.

SUBSTANCE: present invention relates to a sequence of layers of paints, films, coatings or varnishes, which comprises: b) at least one first colour layer comprising a dye and/or pigment, c) creating an effect layer above at least one first colour layer containing at least one platelet effect pigment, wherein at least one platelet effect pigment comprises particles having an average length of 2 to 500 µm, an average width of 2 to 500 µm, and an average thickness of not more than 1 µm , and d) at least one second colour layer above the effect layer comprising a dye and/or pigment, each of at least one first colour layer and at least one second colour layer comprising a dye and/or pigment that is not a pigment that creates the effect of shape of plates, while at least one dye and/or at least one pigment comprised in at least one first colour layer differs from at least one dye and/or at least one pigment comprised in at least one second colour layer, whereas if at least one first colour layer has the sum of the reflection coefficient and the scattering coefficient, which is less than 40%, the system further comprises: a) under at least one lower a layer comprising a pigment and having the sum of the first colour layer of the reflectance and scattering coefficient of at least 40%.

EFFECT: providing such a sequence of paints, varnishes or films/foils, which gives the object covered with it the effect of changing and, in particular, the effect of changing the colour shade and/or the effect of changing the brightness, without the need to include any interfered pigment, whereas easily adjustable for any desired shade changing effect and/or brightness changing effect.

15 cl, 9 dwg, 8 tbl, 5 ex

Description

The present invention relates to a system, such as a system of layers of paints, films, coatings or varnishes, or a system containing a substrate which is covered by a system of layers of paints, films, coatings or varnishes, the system exhibiting a color changing effect even though the system does not contain any one interference pigment.

Systems such as objects or substrates, respectively, coated, for example, with paints, the paints imparting a color changing effect, suitably exhibit a change in color properties when viewed from different angles or viewing angles. These effects are called color changing effects. A color property that changes when viewed from different angles may be the brightness or hue of a paint. More specifically, a change in the brightness of a printed object depending on the viewing angle is generally called a luminance change effect, while a change in the color tone of a printed object depending on the viewing angle is called a color change effect or a color transition effect.

Inks that impart such a transformative effect to the object coated with them are of interest, for example, for coating objects used for security purposes, such as counterfeit-proof securities such as banknotes, credit cards, postage stamps, telephone cards and identity cards, while while varnishes that give such a changing effect to the object they cover are of interest, for example, for coating cars in order to give them a characteristic appearance.

To give the system a color changing effect, holographic foils are often used. In addition, interference pigments are usually added to paint, varnish or film, respectively, for the same purpose. Such interference pigments contain at least two different layers that cause partial reflection of light waves in different planes and partial refraction of light waves such that light waves reflected from different planes travel different distances, resulting in interference. Interference is a phenomenon in which two waves superimpose to produce a resulting wave of greater, lesser, or the same amplitude. Interference usually means the interaction of waves that are correlated or coherent with each other because they come from the same source, or because they have the same or nearly the same frequency. Interference effects can be observed for all types of waves, including, for example, light waves, radio waves, sound waves, waves on the surface of water, or waves of matter. Examples of such interference pigments are, for example, carrier flakes such as aluminum oxide flakes or silicon dioxide flakes on which highly refractive metal oxides such as titanium dioxide and iron(III) oxide are applied.

US 7,077,897 B2 describes a multilayer interference pigment for safety applications which consists of a transparent support material supported by alternating layers of colorless, non-absorbent metal oxides with high and low refractive indices, the difference between the refractive indices being at least 0.1 . The corresponding pigment is produced by alternately applying a high refractive index metal oxide and a low refractive index metal oxide to a transparent support material in a wet hydrolysis process of the respective water-soluble inorganic metal compounds, followed by separation, drying and optional calcination of the resulting pigment.

However, known systems based on interference pigments have a high cost due to the complex structure of the interference pigments and the labor-intensive production process for synthesizing the interference pigments. Another significant disadvantage of known systems based on interference pigments is that each of these inks can only be used for one specific color transition, for example, red-green.

In view of the above, it is an object of the present invention to provide a system, such as a sequence of paints, a sequence of varnishes or a sequence of films/foils, which imparts a changing effect to an object coated therewith and, in particular, a color tone changing effect and/or a brightness changing effect , but which is nevertheless economical because there is no need to include any interference pigment. In addition, the system must be easily adjustable for any desired color change effect and/or brightness change effect.

According to the present invention, this object is achieved by providing a system, such as a series of paints or varnishes, which contains:

b) at least one first color layer containing a dye and/or pigment,

c) an effect layer above the at least one first color layer comprising at least one platelet effect pigment, wherein the at least one platelet effect pigment consists of particles having an average length of from 2 to 500 μm , an average width from 2 to 500 µm and an average thickness of not more than 1 µm, and

d) at least one second color layer above the effect layer containing a dye and/or pigment,

wherein each of the at least one first color layer and the at least one second color layer contains a dye and/or a pigment other than a platelet effect pigment, wherein the at least one dye and/or the at least one pigment, contained in the at least one first color layer is not at least one dye and/or at least one pigment contained in the at least one second color layer, and

wherein at least if the at least one first color layer has a sum of reflectance and scattering coefficient of less than 40%, the system further comprises:

a) below the at least one first color layer, a lower layer containing pigment and having a sum of reflectance and scattering coefficient of at least 40%.

The basis of this solution is the unexpected discovery that when an effect-creating layer (c) containing at least one platelet-shaped effect-producing pigment consisting of particles having the particular above-mentioned values of average length, average width and average thickness is located between one or several first color layers (b) containing a dye and/or a pigment other than a platelet effect pigment, and one or more second color layers (d) containing a dye and/or a pigment other than a platelet effect pigment platelet shapes, wherein the at least one dye and/or the at least one pigment contained in the at least one first color layer is not the at least one dye and/or the at least one pigment contained in the at least one one second color layer, wherein at least one first color layer (b) has a sum of reflectance and scattering coefficient of at least 40%, and/or a lower layer containing pigment and having a sum of reflectance and scattering coefficient, a component of at least 40% is located under the first color layer (b), resulting in a system, such as a paint system, a varnish system or a film/foil system, which exhibits a color tone changing effect, i.e. which provides a change in color tone depending on the viewing angle, and/or which exhibits the effect of changing brightness, i.e. which demonstrates the change in brightness depending on the viewing angle. In accordance with the present invention, the respective layers preferably have a composition such that the system delta a/b is at least 15, which characterizes the color changing effect, and/or the system delta L is at least 10, which characterizes the brightness changing effect. The parameters a, b and L mean the L*a*b* color space as defined by the International Commission on Illumination (CIE), according to the standard DIN EN ISO 11664-4 “Colorimetry - Part 4: L*a*b* color space CIE 1976 ", and which mathematically describes all perceived colors in three coordinates, including the L value for lightness or brightness, respectively, the a value for the opposite colors green-red, and the value b for the opposite colors blue-yellow. Since there is no need to contain interference pigments and only standard dyes and pigments are present, the system according to the present invention is therefore economical. Moreover, since any known dye and/or pigment can be used for at least one first color layer (b), for at least one second color layer (d), and for any possible additional optional color layer, the color tint effect can be adjust to obtain the desired color tint effect. As a result, the present invention provides a system that provides any desired color change effect and/or brightness change effect. Even different changes in color tone can be made on different areas of the same substrate.

To measure the effect of change in accordance with the present invention, visible light is directed onto the system (ie, the surface of the upper layer of the system) in a dark environment at an incidence angle of 45° with respect to the horizontal direction. The light is at least partially reflected and scattered by the system, and the color of the reflected and scattered light is measured from various viewing angles. Traditionally, color measurements at five or six angles provide a satisfactory solution. Examples of angles at which the color of reflected and scattered light is measured are shown below. Changes at more or less different angles are also useful for determining color transitions. In addition to sunlight, other standard light sources can be used, for example A, C, D50, D65, F2, F7, F11 or F12, with D50 being particularly preferred.

In accordance with the present invention, an effect pigment is defined as consisting of particles of pigment that create a platelet-shaped effect that are capable of reflecting incident light, but which do not provide any effect of changing color tone, and interference pigments according to the present invention are expressly excluded from the definition of an effect pigment. pigment effect. Interference pigments typically consist of thin, highly refractive layers that interfere with light waves.

In principle, the present invention is not limited to the specific kind of effect pigment contained in the effect layer (c) as long as it sufficiently reflects the incident light. Preferably, the effect-producing pigment is selected from the group consisting of a metal or a mineral. Suitable examples are therefore pigments which consist of silver, gold, aluminum, alloys such as brass bronzes, copper-zinc alloys and aluminum bronzes, mica, metal oxide-doped alpha iron oxides such as manganese oxide-doped alpha -iron oxides, alumina-doped alpha-iron oxides and silica-doped alpha-iron oxides, as well as arbitrary combinations of two or more of the foregoing. More preferably, the effect pigment contained in the effect layer (c) is a metallic effect pigment, i.e. effect-creating pigment consisting of metal.

Most preferably, the platelet effect pigment contained in the platelet effect layer (c) is a platelet pigment composed of metal particles selected from the group consisting of silver, gold, aluminum, copper, brass bronzes, copper zinc alloys or other alloys such as Stapa AE 8 NL/80 Aluminium, Metalstar 07 0095 Silver, Aluminum Stapa AE Reflexal VIII/80, Stapa Reflexal 88 NL/80, Metalstar 06 7000 Silver, Rotoflex XA 6-203 Bleichgold, Rotoflex XA 6-206 Reichbleichgold, Rotoflex XA 6-209 Reichgold, Roto Vario 530080 Silver, Rotovario 500 042 Silver, Rotovario 500022 Silber, Hydro Pellet 1300, Rotovario 500001 Silber from Eckart, or Decomet 1010/10, Grander 4140 Reichg old, Grander 4140 Reichbleichgold , Grander 4140 Bleichgold from Schlenk, or Silvet ET 2016 from Silberline, as well as arbitrary combinations of two or more of the above substances.

In addition to the effect pigment, the effect layer (c) may also contain one or more non-effect pigments or dyes.

In accordance with the present invention, a platelet effect pigment is defined as an effect pigment consisting of particles having an average length of 2 to 500 μm, an average width of 2 to 500 μm, and an average thickness of not more than 1 μm. Particularly good results are obtained when the platelet effect pigment consists of particles having an average length of from 2 to 40 µm, and more preferably from 2 to 20 µm, or from 2 to 500 µm, and more preferably from 2 to 100 µm. Particle length is defined in this regard as the greatest extent of the particle, while average particle length means the average of the lengths of at least 600 measured particles and preferably at least 1000 measured particles. For example, 1000 particles of platelet effect pigment are optically characterized as detailed below, and as a result, the lengths of the 1000 particles are determined. Then the sum of 1000 length values is calculated and divided by 1000.

If the system is produced using printing technology, i.e. if the layers of the system are layers of paint, the average length of the pigment particles creating the platelet effect is preferably from 2 to 40 μm, and more preferably from 2 to 20 μm. If the system is produced, for example, by spray technology, i.e. if the layers of the system are layers of coating or varnish, the average particle length of the platelet effect pigment is preferably from 2 to 500 µm and more preferably from 2 to 100 µm. This is preferred when the system is a hybrid system in which one or more, but not all, of the layers are layers of paint while the other layers, including at least the effect layer (c), are layers coating or varnish. If the system is obtained by laminating foils or films, i.e. If the layers of the system are layers of foil or film, the average particle length of the platelet effect pigment is preferably from 2 to 40 µm and more preferably from 2 to 20 µm in the corresponding layer of foil or film. In accordance with the present invention, foils mean aluminum foils, while films mean plastic films.

According to a further preferred embodiment of the present invention, the platelet effect pigment consists of particles having an average width of 2 to 40 µm, and more preferably 2 to 20 µm, or 2 to 500 µm, and more preferably 2 to 100 microns. Particle width is defined in this regard as the greatest extent of a particle in a direction that is perpendicular to the length of the particle, while average particle width means the average width of at least 600 measured particles and preferably at least 1000 measured particles.

If the system is produced by printing technology, i.e. if the layers of the system are layers of paint, the average particle width of the platelet effect pigment is preferably from 2 to 40 µm, and more preferably from 2 to 20 µm. If the system is produced, for example, by spray technology, i.e. if the layers of the system are layers of coating or varnish, the average particle width of the platelet effect pigment is preferably from 2 to 500 µm and more preferably from 2 to 100 µm. This is preferred when the system is a hybrid system in which one or more, but not all, of the layers are layers of paint while the other layers, including at least the effect layer (c), are layers coating or varnish. If the system is obtained by laminating foils or films, i.e. if the layers of the system are layers of foil or film, the average particle width of the platelet effect pigment is preferably from 2 to 40 µm and more preferably from 2 to 20 µm.

The length and width of particles in general and specifically of platelet effect pigment particles are preferably measured in accordance with the present invention as follows. To obtain a sample, the pigment particles are washed with acetone, then a few drops of a dispersion of the pigment particles in acetone are applied, for example, to a polymethyl methacrylate (PMMA) or glass plate or mica substrate attached to a rotating table and dried at room temperature. Thus, most of the pigment particles are oriented parallel to the surface of the substrate. By selecting an appropriate dilution factor, the individual pigment particles can be prevented from overlapping on the substrate, and the length and width of the individual pigment particles can be determined optically. The length and width are then determined optically, preferably using scanning electron microscopy, which is carried out using a Phenom Pro XL instrument from Thermo Fisher Scientific, Phenom World BV (Eindhoven, The Netherlands) measured in backscatter electron (BSE) mode using a voltage of 15 kV and beam current strength of 1.7 nanoamperes. Particle length and width values are then obtained from image analysis using the ParticleMetric toolkit contained in ProSuite software supplied by Phenom-World BV (Eindhoven, The Netherlands). More specifically, the images are preferably enlarged so that between 20 and 80 particles can be examined. The particle length and width are then determined for individual particles. To calculate the average length and width, respectively, as described above, at least 600 and preferably at least 1000 particles are measured, then the sums of the measured lengths and widths, respectively, are calculated and divided by the number of particles measured.

The platelet effect pigment particles may have a regular cross-sectional shape, such as a circular cross-sectional shape. However, the pigment particles that create the platelet effect may have a regular or any irregular cross-sectional shape. Regardless of whether the platelet effect pigment particles have a regular or irregular cross-sectional shape, according to the present invention, they can be further characterized by calculating the average diameter. More specifically, the average diameter is calculated according to the equation (L+W)/2, in which L represents the average length of the particles and W represents the average width of the particles. Preferably, the average particle diameter of the platelet effect pigment is from 2 to 500 µm, more preferably from 2 to 40 µm and even more preferably from 2 to 20 µm or from 2 to 500 µm and more preferably from 2 to 100 µm, in including from 2 to 100 microns or from 2 to 50 microns. If the system is produced using printing technology, i.e. if the layers of the system are layers of paint, the average particle diameter of the platelet effect pigment is preferably 2 to 40 µm, and more preferably 2 to 20 µm. If the system is produced by, for example, spray technology, i.e. if the layers of the system are layers of coating or varnish, the average particle diameter of the platelet effect pigment is preferably from 2 to 500 µm and more preferably from 2 to 100 µm. This is preferred when the system is a hybrid system in which one or more, but not all, of the layers are paint layers, while the other layers, including at least the effect layer (c), are selected from the group , which consists of layers of coating, varnish, film and foil. If the system is obtained by laminating foils or films, i.e. if the layers of the system are foil or film layers, the average particle diameter of the platelet effect pigment is preferably 2 to 40 µm, and more preferably 2 to 20 µm.

Taking the present invention further, it is proposed that the at least one platelet-shaped effect pigment be composed of particles having an average thickness of from 0.01 to no more than 1 µm, more preferably from 0.05 to 1 µm and even more preferably from 0.05 to 0.5 µm, in particular when the system consists of paints. When the system consists of coatings or varnishes, it is proposed that the at least one pigment creating the platelet effect be composed of particles having an average thickness of from 0.01 to 1 μm. This is preferred when the system is a hybrid system in which one or more, but not all, of the layers are layers of paint, while the other layers, including at least the effect layer (c), are layers coating or varnish. Particle thickness is defined in this regard as the shortest extent of a particle in a direction that is perpendicular to a two-dimensional plane defined by particle length and particle width, while average particle thickness means the average thickness of at least 600 measured particles and preferably at least at least 1000 measured particles. The specified particle thicknesses apply to all systems based on paints, coatings, varnishes, films and foils.

The thickness of the particles in general and specifically of the platelet effect pigment particles is measured in accordance with the present invention preferably as follows. A resin commonly used in electron microscopy, such as TEMPFIX resin available from Gerhard Neubauer Chemikalien (Münster, Germany), is applied to the sample in the form of a plate and heated on a hotplate until softened. The plate-shaped sample is then removed from the hot plate and appropriate pigment particles are sprayed or applied onto the softened resin. The resin hardens again when cooled, and the pigment particles are oriented almost vertically due to the interaction between adhesion and gravity and are attached to the sample in the form of a platelet. This makes it easier to measure pigments in the transverse direction using an electron microscope. The resulting sample is placed on a sample holder and scanning electron microscopy is performed using a Phenom Pro XL instrument from Thermo Fisher Scientific, Phenom World BV (Eindhoven, The Netherlands) in backscatter electron (BSE) mode using a voltage of 15 kV and force beam current 1.7 nanoamperes. Particle thickness values are then obtained from image analysis using the ParticleMetric toolkit contained in ProSuite software supplied by Phenom-World BV (Eindhoven, The Netherlands). More specifically, the images are preferably enlarged so that between 20 and 80 particles can be examined. The particle thickness is then determined for individual particles. When thickness is determined, the azimuthal angle α of the pigment particle with respect to a plane perpendicular to the surface is evaluated and taken into account to calculate the thickness according to the T _{effect formula.} =T _measured. /cos α, in which T represents the thickness of the particle. To determine the average thickness, as described above, measure the thickness values of at least 600 measured particles and preferably at least 1000 measured particles, sum the resulting values, and then divide the sum by the number of measured particles.

The length, width and thickness of the particles in the final multilayer system can be determined accordingly. More specifically, several sample fragments, each having an area of, for example, approximately 1 cm ² , can be cut from the multilayer system, for example, using a laser. Samples can then be embedded in a conventional electron microscopy resin, such as packaging media such as epoxy resins such as Araldite 502 or 6005, which are available from Electron Microscopy Sciences (Hatfield, PA, USA). One or more microtome longitudinal sections of the layer of the analyzed system and/or one or more microtome cross sections of the layer of the analyzed system can then be made, each of the sections having a thickness of, for example, 5 mm. One or more microtome sections can be obtained, for example, by using an electrically driven industrial rotary microtome type RM 2155, supplied by Leica Mikrosysteme (Bensheim, Germany). Before taking sections, the desired thickness is set and then the appropriate metal panels are installed and in the actual working stage the rotary microtome is passed over the appropriate sample. One or more samples are then placed on a sample holder. For example, one or more longitudinal sections may be mounted on the sample holder shown in FIG. 4a, and the cross sections can be mounted on the sample holder shown in FIG. 4b. Scanning electron microscopy is performed on each of the resulting thin sections, whereby particle length, particle width, particle thickness, average particle length, average particle width, and average particle thickness are determined as described above.

According to a further preferred embodiment of the present invention, the at least one platelet-shaped effect pigment consists of particles having a first aspect ratio, determined by dividing the average length by the average particle width, and being from 1 to 20, and preferably from 1 to 2 or 2 to 5. The numerical ranges indicated are preferred for all paint, coating, varnish and film systems.

It is further preferred that the at least one platelet effect pigment is composed of particles having a second aspect ratio, determined by dividing the average particle length by the average particle thickness and ranging from 1 to 75,000, preferably from 1 to 1000, more preferably from 1 to 200, even more preferably from 1 to 100 and most preferably from 1 to 60. The particles of such metallic effect pigments are generally oriented such that their two-dimensional plane, defined by the length of the particle and the width of the particle, is oriented in generally parallel to the longitudinal section of the effect-producing layer.

In further developing the idea of the present invention, it has been proposed that the average relative particle area of the effect-creating layer (c) is from 5 to 75%, more preferably from 10 to 55%, and most preferably from 15 to 35%. According to the present invention, the average relative particle area of the effect layer (c) means the result of dividing the total longitudinal sectional area of the effect layer (c) covered by the plate shape effect pigment particles by the total longitudinal sectional area of the effect layer. The measuring principle is shown in Fig. 5a and 5b.

The average relative particle area of any of the individual layers and, in particular, the effect-producing layer is measured in accordance with the present invention, preferably by scanning electron microscopy on the surface of the layer in question of the system obtained as described above, or on a longitudinal section of the layer in question of the system obtained as described above . The particles are stained using ParticleMetric instrumentation software, and then the total longitudinal sectional area that is covered by the particles is estimated and divided by the total longitudinal sectional area analyzed by scanning electron microscopy to yield a percentage mean relative particle area.

According to a further preferred embodiment of the present invention, the effect layer (c) of the system according to the present invention has an average thickness of 0.1 to 50 μm, more preferably 0.1 to 30 μm, and most preferably 0. 2 to 20 µm, in particular when the system consists of paints or films. When the system consists of coatings or varnishes, the effect layer (c) of the system according to the present invention has an average thickness of 0.1 to 150 μm, more preferably 1 to 100 μm, and even more preferably 10 to 50 μm. This is preferred when the system is a hybrid system in which one or more, but not all, of the layers are paint layers while the other layers, including at least the effect layer (c) are coating layers or varnish.

Preferably, the effect layer (c) of the system according to the present invention comprises, preferably when it is a paint layer, a coating layer or a varnish layer, depending on the effect layer thickness, viscosity and application method, from 10 to 95% by weight of the binder relative to the total weight of the composition applied to form the effect layer, wherein the binder is preferably selected from the group consisting of polyesters, polyethers, polyurethanes, polyamides, polyacrylates, maleate resins, rosin resins, ketone resins, aldehydes resins, alkyd resins, rosin-modified phenolic resins, hydrocarbon resins, silicates, organosilicon compounds, phenolic resins, urea resins, melamine resins, epoxy resins, polyterpene resins, shellac, copal, dammar, lignin derivative, natural resins, polyvinyl alcohols, simple polyvinyl ether, polyvinyl acetates, polyvinyl chloride, polyvinyl ethers, polyvinyl propionates, polyvinyl butyrates, polymethacrylates, polystyrenes, polyolefins, hydrocarbon resins, coumaron-indene resins, aromatic formaldehyde resins, urea acid resins, sulfonamide resins, chlorinated resins, nitrocellulose, CAB (acetate butyrate cellulose), CAP (cellulose acetate propionate), cellulose compounds, rubbers, polysaccharides, radiation-curable resins, thermoset resins and arbitrary combinations of two or more of the above binders.

In addition to the binder or instead of the binder, the effect-creating layer (c) may contain, depending on the nature and viscosity of the paint and the method of application, from more than 0 to 95% by weight of solvent, relative to the total weight of the composition applied to form the effect-creating layer (c). Good results are obtained in particular when the solvent is selected from the group consisting of mineral oils, vegetable oils, fatty acid esters, alcohols, esters, ethers, glycols, water, cyclic or linear hydrocarbons, ketones, lactones, alkanes, aromatics hydrocarbons, monomers and oligomers, including hydroxyl, carboxyl, alkoxy, amine, acrylic or vinyl aromatic compounds, and arbitrary combinations of two or more of the above solvents.

In addition, the effect-creating layer (c) may contain one or more additives. Examples of such additives are substances selected from the group consisting of rheological additives, binders, defoamers, glidants, anticorrosion additives, gloss additives, waxes, wetting agents, curing agents, chelating agents, photoinitiators, inhibitors, drying agents, stabilizers, emulsifiers, pH adjusting additives, abrasion resistant additives, plasticizers, antistatic additives, preservatives, light protective agents, matting agents, fillers and arbitrary combinations of two or more of the above additives.

Within the scope of the present invention, it has been discovered that the degree of effect obtained by changing the system can be influenced, if the system is a paint system, by means of the hiding power of the paint. If the system is a paint system, it is preferred that the paint hiding power of the dry effect layer (c) is above the at least one first color layer (b), i.e. above the top of one or more first color layers is from 25 to 100%, more preferably from 40 to 100%, even more preferably from 50 to 100% and most preferably from 60 to 100%. The hiding power of a paint is the percentage of the area of the top one or more first color layers that is covered by the effect layer (c). Ink coverage refers to the actual coverage area when printing halftones. Likewise, it is preferable that the ink hiding power of the dry effect layer (c) on the substrate is 25 to 100%, more preferably 40 to 100%, even more preferably 50 to 100%, and most preferably 60 to 100%.

If the system is a varnish system, a coating or a film/foil system, the hiding power of the effect layer (c) above at least one first color layer (b), i.e. above the top of one or more first color layers is complete, i.e. is 100% or at least 90%. In any case, the effect layer (c) completely covers at least one first color layer (b). Likewise, it is preferable that the effect layer (c) completely covers the substrate.

Taking the present invention further, it is proposed that the surface density of the dry effect layer (c) be from 0.2 to 15 g/cm ² , more preferably from 0.3 to 10 g/cm ² and most preferably from 0.4 to 7.5 g/cm ² , in particular when the system consists of paints. When the system is a coating or varnish system, the dry surface density of the effect layer (c ⁾ is from 0.1 to 60 g/cm2 and more preferably from 1 to 30 g/ ^cm2 and even more preferably from 1 to 20 g/cm2 cm ² . This is preferred when the system is a hybrid system in which one or more, but not all, of the layers are paint layers while the other layers, including at least the effect layer (c), are coating layers , varnish or film.

Further, it is preferable that the weight ratio of pigment to binder in the dry effect layer is from 0.02:1 to 2:1, more preferably from 0.1 to 2:1, and even more preferably from 0.2:1 to 1.8:1. More specifically, it is preferable that the weight ratio of pigment to binder in the dry effect layer (c) is from 0.3:1 to 2:1, more preferably from 0.7:1 to 2:1, and most preferably from 0. 7:1 to 1.8:1 when the system consists of paints. When the system consists of varnishes or coatings, it is preferable that the weight ratio of pigment to binder in the dry effect layer (c) is from 0.02:1 to 2:1, more preferably from 0.2:1 to 1.5: 1 and most preferably from 0.2:1 to 1:1. This is preferred when the system is a hybrid system in which one or more, but not all, of the layers are paint layers while the other layers, including at least the effect layer (c), are coating layers , varnish or film/foil.

Developing further the ideas of the present invention, it is proposed that the effect-creating layer (c) of the system in accordance with the present invention is a system of paints or films/foils that contains from 10 to 70% by weight, preferably from 20 to 70% by weight, yet more preferably 30 to 70% by weight and more preferably 40 to 70% by weight of platelet effect pigment, based on the total weight of the dry effect layer. When the system is a coating or varnish system, it is preferred that the effect layer contains from 1 to 30% by weight, and more preferably from 2 to 25% by weight, platelet effect pigment, based on the total weight of the dry effect layer. This is preferred when the system is a hybrid system in which one or more, but not all, of the layers are layers of paint while the other layers, including at least the effect layer (c), are layers coating, varnish or film/foil. It is particularly preferred that the effect layer (c) has the above-mentioned metallic effect pigment content.

Further, it is preferable that the effect-producing layer (c) of the system according to the present invention has a sum of reflectance and scattering coefficient of 20 to 100%, more preferably 30 to 100%, and most preferably 40 to 100%.

The sum of the reflectance and scattering coefficient of a layer, such as an effect layer, is measured in accordance with the present invention, preferably using a haze and gloss measuring instrument from Byk Garnder (Geretsried, Germany). A fragment of the resulting layer, whether or not containing other layers attached to it and having an area of, for example, 10 cm ² , is cut out from the system and placed in the device. A standard D65 light source is directed to irradiate at a specific angle, for example 20°, 60° or 85° and preferably 20° with respect to the vertical direction, onto the surface of the layer to be analyzed and the reflected light (which corresponds to gloss as described in the standard) is measured DIN 67530) as well as diffuse light (which corresponds to turbidity). The measuring principle is shown in Fig. 6.

In accordance with the present invention, the system necessarily contains, under at least one first color layer (b), a lower layer (a), which may, but must, contain pigment and has a sum of reflectance and scattering coefficient of at least 40%, if the at least one first color layer (b) has a sum of reflectance and scattering coefficient of less than 40%, while the bottom layer (a) may or may not be present if the at least one first color layer (b) has a sum of reflectance and scattering coefficient of at least 40%. If more than one first color layer (b) is present, the statement "at least one first color layer (b) has a sum of reflectance and scattering coefficient of less than 40%" means that the totality of all first color layers (b) has the sum of the reflection coefficient and the scattering coefficient being at least 40%.

Preferably there is a bottom layer (a) which has a sum of reflectance and scattering coefficient of at least 50%, preferably at least 60%, more preferably at least 70%, even more preferably at least 80% and most preferably at least 90%.

In principle, the present invention is not limited to a particular kind of pigment that is contained in the bottom layer (a), provided that it has good reflectance and scattering coefficient. However, good results are obtained in particular when the bottom layer (a) contains a white pigment, and more preferably the white pigment is selected from the group consisting of titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, lead carbonate, calcium carbonate, oxide aluminum, aluminum silicate and arbitrary combinations of two or more of the above.

For example, the bottom layer (a) may be a substrate on which the system is applied, if the substrate is a substrate with a sum of reflectance and scattering coefficient of at least 40%, such as suitable highly reflective paper, cardboard, foil, white film, white glass, white textile substrate, white non-woven substrate, white silicon substrate, white ceramic substrate, white mineral substrate or white wood substrate. Alternatively, the bottom layer (a) is a layer between the substrate and the at least one first color layer (b).

According to a first particularly preferred embodiment of the present invention, the bottom layer (a) is a white film. According to this embodiment, the bottom layer (a) which is a film preferably contains from 0.1 to 10% by weight, more preferably from 0.25 to 4% by weight and even more preferably from 0.75 to 1.5% by mass of white pigment in relation to the total mass of the lower layer (a). Good results are obtained in particular when the film has a thickness of preferably from 1 to 100 µm, more preferably from 2 to 50 µm and most preferably from 10 to 30 µm. Thicker films or even plastic sheets or molded products are also most suitable.

According to a second particularly preferred embodiment of the present invention, the bottom layer (a) is paper. According to this embodiment, the bottom layer (a), which is paper, preferably contains from 1 to 50% by weight, more preferably from 1 to 10% by weight, and even more preferably from 3 to 7% by weight of white pigment, based on the total mass of the lower layer (a). Good results are obtained in particular when the paper has a thickness of at least 10 µm. Thicker paper or even cardboard materials are also most suitable.

According to a third particularly preferred embodiment of the present invention, the bottom layer (a) is a paint, enamel, coating or varnish. According to this embodiment, the base layer (a), which is a paint, enamel, coating or varnish, preferably contains from 10 to 90% by weight and preferably from 30 to 90% by weight of white pigment, based on the total weight of the dry base layer (a). ). Good results are obtained in particular when the paint, enamel, coating or varnish has a thickness of preferably from 1 to 10,000 µm, wherein in the case of paint a thickness of from 0.5 to 100 µm is particularly preferred, in the case of enamel , coating or varnish, a thickness of 0.5 to 1000 µm, and more preferably 0.5 to 500 µm, is particularly preferred, and in the case of enamel, a thickness of 0.1 to 2 mm is particularly preferred.

Preferably, a bottom layer (a) is present, and the dye and/or pigment contained in each of the at least one first color layer (b) and at least one second color layer (d) is not the pigment contained in the bottom layer ( A).

Particularly good results are obtained when the white pigment contained in the lower layer (a) is titanium dioxide and most preferably rutile. According to this embodiment, titanium dioxide, and preferably rutile, is present in the form of particles having an average particle size d50 of _0.1 to 50 μm, preferably 0.1 to 10 μm, and more preferably 0.2 to 1 μm. If the bottom layer(s) is a thicker substrate such as cardboard or glass, the pigment particles may be larger; For thin films, white inks and coatings containing smaller particles are preferred.

The remaining mass of the lower layer (a) is preferably in the case where the lower layer (a) is a layer of paint, varnish or enamel, it may consist of a binder, solvent and/or additives.

Preferably, when the bottom layer(s) of the system according to the present invention is a layer of paint, coating or varnish, it contains, depending on the thickness of the paint film and the type of paint, from 10 to 90% by weight of binder relative to to the total mass of liquid paint, coating, varnish or enamel that forms the bottom layer(s). In the case where the lower layer (a) is enamel, this enamel preferably consists of silicates and oxides. The present invention is not particularly limited with respect to the type of binder contained in the bottom layer (a). However, it is preferred that the binder is selected from the group consisting of polyesters, polyethers, polyurethanes, polyamides, polyacrylates, maleate resins, rosin resins, ketone resins, aldehyde resins, alkyd resins, rosin-modified phenolic resins, hydrocarbon resins, silicates, organosilicon resins compounds, phenolic resins, urea resins, melamine resins, epoxy resins, polyterpene resins, shellac, copal, dammar, lignin derivative, natural resins, polyvinyl alcohols, polyvinyl ether, polyvinyl acetates, polyvinyl chloride, polyvinyl ethers, polyvinyl propionates, polyvinyl butyrates, polymethacrylates, polystyrenes, polyolefins, hydrocarbon resins, coumaron-indene resins, aromatic formaldehyde resins, urea resins, sulfonamide resins, chlorinated resins, nitrocellulose, CAB (cellulose acetate butyrate), CAP (cellulose acetate propionate), cellulose compounds, rubbers, polysaccharides, radiation-curable resins, thermo-curable resins, and arbitrary combinations of two or more of the above binders.

In addition to or instead of a binder, the composition applied to form the bottom layer(s) of the system in accordance with the present invention may contain from more than 0 to 95% by weight of solvent, based on the total weight of the liquid paint, coating, varnish or enamel used to form the lower layer (a). The amount of solvent depends on the paint system, application and pigment content. Good results are obtained in particular when the solvent is selected from the group consisting of mineral oils, vegetable oils, fatty acid esters, alcohols, esters, ethers, glycols, water, cyclic or linear hydrocarbons, ketones, lactones, alkanes, aromatics hydrocarbons, monomers and oligomers, including hydroxyl, carboxyl, alkoxy, amine, acrylic or vinyl aromatic compounds, and arbitrary combinations of two or more of the above solvents.

In addition, the liquid paint, coating, varnish or enamel used to form the base layer(s) may contain one or more additives. Examples of such additives are substances selected from the group consisting of rheological additives, binders, defoamers, glidants, anticorrosion additives, gloss additives, waxes, wetting agents, curing agents, chelating agents, photoinitiators, inhibitors, drying agents, stabilizers, emulsifiers, pH adjusting additives, abrasion resistant additives, plasticizers, antistatic additives, preservatives, light protective agents, matting agents, fillers and arbitrary combinations of two or more of the above additives.

The at least one first color layer (b) may have a sum of reflectance and scattering coefficient of less than 40% or at least 40%. As described above, if the at least one first color layer (b) has a sum of reflectance and scattering coefficient of less than 40%, then the system necessarily includes a bottom layer (a), while the bottom layer (a) is optional , i.e. it may or may not be present if the at least one first color layer (b) has a sum of reflectance and scattering coefficient of at least 40%.

If the at least one first color layer (b) has a sum of reflectance and scattering coefficient of at least 40%, then the sum of the reflectance and scattering coefficient of the at least one first color layer (b) is more preferably at least 50 %, even more preferably at least 60%, even more preferably at least 70%, even more preferably at least 80%, even more preferably at least 90% and most preferably at least 99%.

According to the present invention, at least one dye and/or at least one pigment contained in the first color layer (b) is different from at least one dye and/or at least one pigment contained in at least one second color layer (d). This provides a particularly distinctive change effect. In particular, it is preferable that the at least one dye and/or the at least one pigment contained in the first color layer (b) has a different color or hue, respectively, and/or a different lightness than the at least one dye and/or at least one pigment contained in at least one second color layer (d), i.e. the hue and/or lightness of the first color layer (b) is different from the hue and/or lightness of one second color layer (d).

In accordance with another specific preferred embodiment of the present invention, any of the first color layer (b) and at least one second color layer (d) of the system in accordance with the present invention contains from 0.001 to 5% by weight of at least one dye and /or from 0.1 to 60% by weight or preferably from 0.1 to 50% by weight of at least one pigment that is neither a platelet effect pigment nor preferably also a white pigment, based on the total dry weight the first color layer (b) and the second color layer (d), respectively. The pigments are preferably organic or inorganic pigments having a characteristic color. Each of the at least one first color layer (b) and each of the at least one second color layer (d) may contain one or more white pigments and/or one or more platelet effect pigments and/or fillers that complement the pigment/pigments that are neither a white pigment nor a plate-shaped pigment. However, it is preferred that each of the at least one first color layer (b) as well as each of the at least one second color layer (d) does not contain any platelet effect pigment, nor any white pigment.

Taking the present invention further, it is proposed that the at least one first color layer (b) has a higher pigment content than the at least one second color layer (d).

When the system is a coating or varnish system, it is preferred that the pigment content of the at least one dry second color layer (d) is from 2 to 30%, more preferably from 2 to 25%, and most preferably from 2 to 20%. When the system is a paint system, it is preferred that the pigment content of the at least one dry second color layer (d) is from 0.1 to 50%, more preferably from 1 to 50%, and most preferably from 2 to 50%.

Taking the idea of the present invention further, it is proposed that the second color layer (d) and, if more than one second color layer (d) is present, the sum of all second color layers (d) has a sum of reflectance and scattering coefficient of from 1 to 80 %, more preferably from 5 to 60% and most preferably from 5 to 40%.

Moreover, in particular, any of the paints, coatings or varnishes used to form the first color layer (b) and at least one second color layer (d) preferably contain, depending on the paint, coating or varnish system, viscosity and application method, from 10 to 99.9% by weight of the binder relative to the total weight of the first color layer (b) and at least one second color layer (d), the binder being preferably selected from the group consisting of polyesters, polyethers, polyurethanes, polyamides, polyacrylates, maleate resins, rosin resins, ketone resins, aldehyde resins, alkyd resins, rosin-modified phenolic resins, hydrocarbon resins, silicates, organosilicon compounds, phenolic resins, urea resins, melamine resins, epoxy resins, polyterpene resins, shellac, copal, dammar, lignin derivative, natural resins, polyvinyl alcohols, polyvinyl ether, polyvinyl acetates, polyvinyl chloride, polyvinyl ethers, polyvinyl propionates, polyvinyl butyrates, polymethacrylates, polystyrenes, polyolefins, hydrocarbon resins, coumaron-indene resins, aromatic formaldehyde resins s , urea resins, sulfonamide resins, chlorinated resins, nitrocellulose, CAB (cellulose acetate butyrate), CAP (cellulose acetate propionate), cellulose compounds, rubbers, polysaccharides, radiation-curing resins, thermosetting resins and arbitrary combinations of two or more from the above mentioned binders.

In addition to or instead of a binder, any of the paints, coatings or varnishes used to form the first color layer (b) and at least one second color layer (d) of the system in accordance with the present invention may contain, depending on the system paints, coatings or varnishes, viscosity and method of application, from more than 0 to 90% by weight of solvent based on the total weight of the liquid paint, coating or varnish used to form the first color layer (b) and/or one or more liquid paints , coatings or varnishes used to form at least one second color 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 , cyclic or linear hydrocarbons, ketones, lactones, alkanes, aromatic hydrocarbons, monomers and oligomers including hydroxyl, carboxyl, alkoxy, amine, acrylic or vinyl aromatic compounds, and arbitrary combinations of two or more of the above solvents.

In addition, any of the liquid paints, coatings or varnishes used to form the first color layer (b) and at least one second color layer (d) of the system in accordance with the present invention may also contain one or more additives. Examples of such additives are substances selected from the group consisting of rheological additives, binders, defoamers, glidants, anticorrosion additives, gloss additives, waxes, wetting agents, curing agents, chelating agents, photoinitiators, inhibitors, drying agents, stabilizers, emulsifiers, pH adjusting additives, abrasion resistant additives, plasticizers, antistatic additives, preservatives, light protective agents, matting agents, fillers and arbitrary combinations of two or more of the above additives.

Preferably the system contains from one to three, more preferably one or two and most preferably one first color layer (b) below the effect layer (c).

According to a further preferred embodiment of the present invention, the system comprises one to three, and more preferably one or two, second color layers (d) above the effect layer (c).

Particularly preferred is the arrangement of one or more first color layers (b) in direct contact with the effect layer (c) and, if present, with the lower layer (a), i.e. there is no intermediate layer between the first color layer (b) and the effect layer (c), and there is no intermediate layer between the first color layer (b) and the bottom layer (a), if present. In the case where more than one first color layer (b) is present, the upper color layer is in direct contact with the effect-creating layer (c), and the lower first color layer (b) is in direct contact with the lower layer (a), if present, all colored layers (b) are in direct contact with each other and are located one above the other. These embodiments are particularly preferred if the system is a paint system, a coating system or a varnish system. If the system is a foil/film system, then one or more adhesive layers may be present between one or more of layers (a), (b), (c) and (d).

Likewise, it is particularly preferred to arrange one or more second color layers (d) in direct contact with the effect layer (c), i.e. there is no intermediate layer between the effect layer (c) and the second color layer (b). In the case of more than one second color layer (d), the lower color layer (d) is preferably in direct contact with the effect layer (c), with all color layers (d) preferably being in direct contact with each other and located one above the other . These options are particularly preferred if the system is a paint system, a coating system or a varnish system. If the system is a foil/film system, then one or more adhesive layers may be present between one or more layers.

Further developing the idea of the present invention, it is proposed that at least one first dry color layer (b) and/or at least one second dry color layer (d) has a thickness ranging from 0.3 to 100 μm, preferably from 0. 5 to 10 µm and more preferably 1 to 10 µm, in particular if the system is a paint system. If more than one first color layer (b) is present, then preferably the total thickness of all first color layers (b) is from 0.3 to 100 μm, and more preferably from 0.5 to 10 μm. Likewise, if more than one second color layer (d) is present, then preferably the total thickness of all dry second color layers (d) is from 0.3 to 100 μm, and more preferably from 0.5 to 10 μm. When the system is a coating or varnish system, the at least one first dry color layer (b) has a thickness of from 1 to 500 μm. If more than one first color layer (b) is present, then preferably the total thickness of all dry first color layers (b) is from 1 to 500 μm. The at least one second dry color layer (d) has a thickness preferably from 10 to 80 µm, more preferably from 10 to 70 µm and even more preferably from 10 to 50 µm. If more than one second color layer (d) is present, then the total thickness of all dry second color layers (d) is preferably 10 to 80 μm, more preferably 10 to 70 μm, and most preferably 10 to 50 μm.

If the system is a paint system, particularly good results are obtained when the paint coverage of each of the at least one first color layer (b) above the bottom layer (a), if present, or above the substrate, respectively, is from 50 to 100%, more preferably 75 to 100% and most preferably 90 to 100%. It is further preferred that the total paint coverage of all of the at least one first color layer (b) above the bottom layer (a), if present, or above the substrate, respectively, is, if the system is a paint system, from 50 to 200%, more preferably 50 to 150%, and most preferably 50 to 100%.

If the system is a coating system, a varnish system or a film/foil system, the covering power of all of the at least one first color layer (b) above the bottom layer (a), if present, or above the substrate, respectively, is maximum, those. is 100% or at least 95%.

Likewise, it is preferable that the hiding power of each of the at least one second color layer (d) above the effect layer (c) is from 10 to 90%, more preferably from 30 to 80%, and most preferably from 40 to 60% . It is further preferred that the total paint coverage of all of the at least one second color layer (d) above the effect layer (c) is from 30 to 200%, and more preferably from 60 to 180%.

If the system is a coating system, a varnish system, or a film/foil system, the covering power of the sum of all of the at least one second color layer (d) above the effect layer (c) is maximum, i.e. is 100% or at least 95%.

In addition to the layers described above, the system may contain one or more additional layers. For example, the system may comprise above the at least one second color layer (d) a second effect layer and above it at least one third color layer. The at least one third layer is, in principle, similar in composition compared to the at least one first color layer (b) and the at least one second color layer (d), i.e. at least one third color layer contains at least one dye and/or pigment, wherein the dye and/or pigment is not a platelet shape effect pigment. According to this embodiment, it is preferable that the at least one dye and/or at least one pigment contained in the third color layer is different from the at least one dye and/or at least one pigment contained in the at least one first color layer. layer, and also differs from at least one dye and/or at least one pigment contained in at least one second color layer. Thus, the at least one third color layer has a different color or hue, respectively, and/or a different lightness than the at least one dye and/or at least one pigment contained in the at least one first color layer (b ), and also has a different color or hue, respectively, and/or a different lightness than at least one dye and/or at least one pigment contained in at least one second color layer (d), i.e. . the color tone and/or lightness of the at least one third color layer is different from the color tone and/or lightness of the first and second color layers (b) and (d).

In particular, if the system is a coating system or varnish system, such as a coating system for an automobile, it is preferred that a layer of clear varnish is disposed above the top second color layer (d) or above the top third color layer, if present, for protection. systems from mechanical stress and destruction. Any known clearcoat, such as one-component or two-component clear coats, can be used for this purpose. By way of example only, the clear coat may contain as a binder acrylates, polyesters, polyurethanes, all containing OH functionality in the case of two-component systems, or suitable mixtures. In addition, the coating may contain water or organic solvents as a solvent, isocyanates or amines containing two or more functional groups as a hardener, and rheological additives, binders, defoamers, slip agents, plasticizers, anticorrosive additives, and gloss additives as additives. , waxes, wetting agents, curing agents, chelating agents, photoinitiators, inhibitors, drying agents, stabilizers, emulsifiers, pH adjusting additives, abrasion resistant additives, antistatic additives, preservatives, light protective agents, matting agents and arbitrary combinations of two or more of the above additives The thickness of this clear varnish layer is preferably at least 50 µm.

In particular, if the system is an ink system, such as for example an ink system for packaging applications, it may be advantageous that a printing coating varnish is located above the top second color layer (d) or above the top third color layer, if present. to protect the system from mechanical stress and to regulate the gloss level. Such printing coating varnish may be a one-component or two-component system and may contain as binders polyesters, polyethers, polyurethanes, polyamides, polyacrylates, maleate resins, rosin resins, ketone resins, aldehyde resins, alkyd resins, rosin-modified phenolic resins, hydrocarbon resins, silicates, organosilicon compounds, phenolic resins, urea resins, melamine resins, epoxy resins, polyterpene resins, shellac, copal, dammar, lignin derivative, natural resins, polyvinyl alcohols, polyvinyl ether, polyvinyl acetates, polyvinyl chloride, polyvinyl ethers, polyvinylpropionates, polyvinyl butyrates, polymethacrylates, polystyrenes, polyolefins, hydrocarbon resins, coumaron-indene resins, aromatic formaldehyde resins, urea resins, sulfonamide resins, chlorinated resins, nitrocellulose, CAB (cellulose acetate butyrate), APP (propio acetate nate cellulose) , cellulose compounds, rubbers, polysaccharides, radiation-curable resins, thermoset resins and optional combinations of two or more of the above binders, and may contain mineral oils, vegetable oils, fatty acid esters, alcohols, esters, ethers as solvents , glycols, water, cyclic or linear hydrocarbons, ketones, lactones, alkanes, aromatic hydrocarbons, monomers and oligomers including hydroxyl, carboxyl, alkoxy, amine, acrylic or vinyl aromatic compounds, and arbitrary combinations of two or more of the above solvents as solvents , and may also contain isocyanates, amines or photoinitiators containing two or more functional groups as a hardener.

It is further preferred that the system does not (with the exception of one or more possible adhesive layers) between the bottom layer (a) and the effect layer (c) have any additional layer besides the at least one first color layer (b). In addition, it is also preferred that above the effect layer (c) (excluding one or more possible adhesion layers) only at least one second color layer (d) and optionally one or more additional color layers and/or pigment-free layers are present varnishes and/or coatings covering the print.

As described above, a particular advantage of the present invention is that the alteration effect is obtained even without introducing any interference pigment into any layer of the system. Accordingly, in accordance with the present invention, in the system, i.e. in the above layers (a)-(d), no interference pigment is contained.

The effect of the change can be calculated using color data measured from different viewing angles. This calculation measures the values of a and b, which means that the L*a*b* (CIELAB) color space can be used. The color space L*a*b* mathematically describes all perceived colors in three coordinates, where L stands for lightness, a and b stand for the opposite colors green-red and blue-yellow, the color transition can be described as delta a/b between dimensions under different viewing angles. Another suitable color space for color transition studies is the HCL (hue-chrominance-luminescence) color space. HCL space uses the CIELAB model, which was defined by the International Commission on Illumination (CIE) in 1976, translated into polar coordinates. The L axis is the same as in the CIELAB system, but the a and b coordinates are converted to polar coordinates, where the distance from zero represents the chroma C and the angle represents the hue or hue. In this color space, delta values for hue and chrominance can be analyzed to describe color transitions.

According to the present invention, it is preferable that delta a/b is at least 15, where delta a/b is determined according to the equation delta a/b=((a[15°]-a[110°]) ² +( b[15°]-b[110°])2)1/2, where a[15°] is the a value of the L*a*b* color space, measured when observed at an angle of 15°, a[110°] represents the a value measured at an angle of 110°, b[15°] represents the b value of the L*a*b* color space measured at an angle of 15°, and b[110°] represents the b value measured by viewing at an angle of 110°, wherein the measurement is made by irradiating the system in a dark environment with a standard light source at an angle of incidence of 45° with respect to the horizontal direction, with a reflection angle of 135° with respect to the horizontal direction being defined as the viewing angle , which is 0°. Viewing angles can be seen in Fig. 2. The higher the numerical value of delta a/b, the stronger the effect of the change.

According to the embodiment described above, the delta a/b value between the 15° and 110° measurements was selected as a means to describe the color transition. However, in other embodiments, other angles may also be suitable to describe the effect of the change.

According to a particularly preferred embodiment of the present invention, the delta a/b value measured as described above is at least 30 and more preferably at least 38.

As an alternative to the above-mentioned delta a/b value or in addition to the above-mentioned delta a/b value, the system in accordance with the present invention may have a delta L value of at least 10, wherein delta L is determined according to the equation delta |L[ 15°]-L[110°]| (| | means the absolute difference of two values), in which L[15°] is the L value of the L*a*b* color space measured at an angle of 15°, and L[110°] is the L value measured when observed at an angle of 110°, wherein the measurement is carried out by irradiating the system in a dark environment with a standard light source at an incidence angle of 45° with respect to the horizontal direction, and a reflection angle of 135° with respect to the horizontal direction is defined as the viewing angle, component 0°.

According to a particularly preferred embodiment of the present invention, the delta L value measured as described above is at least 20 and more preferably at least 30.

As an alternative to the above delta a/b and/or delta L values, or in addition to the above delta a/b and/or delta L values, the system in accordance with the present invention may have a delta h° value of at least 15 , while delta h° is determined according to the equation delta |h°[15°]-h°[110°]| (| | means the absolute difference of two values), in which h°[15°] represents the h° value in the HCL color space measured at an angle of 15° and h°[110°] represents the h° value measured at observed at an angle of 110°, the measurement being carried out by irradiating the system in a dark environment with a standard light source at an angle of incidence of 45° with respect to the horizontal direction, the angle of reflection being 135° with respect to the horizontal direction being defined as the viewing angle of 0°.

According to a particular preferred embodiment of the present invention, the delta h° is at least 30.

As stated above, if present, the bottom layer (a) may be a support such as film, paper or the like, or the bottom layer (a) may be located on a support, the bottom layer (a) being, for example , paint, enamel, coating or varnish. If the bottom layer (a) is not present, then the bottom of the at least one first color layer (b) may be directly disposed on the substrate or may even form a substrate, for example in the case where the at least one first color layer (b ) is a plastic, glass or ceramic sheet. Whether the bottom layer (a) is a substrate, or the bottom layer (a) or the bottom of at least one first color layer (b) is located on the substrate, the substrate can be any material to which the bottom layer can be applied system layer. For example, the substrate may be a material selected from the group consisting of films, metals, glazes, paper, cardboard, paperboard, glass, wood, textile, non-woven, silicone, ceramic, mineral materials, labels, rubbers, and arbitrary combinations of two or more of the above materials.

Moreover, as stated above, according to a particularly preferred embodiment of the present invention, the system is a paint system, coating or varnish system. In the case of the ink system, any known printing technology can be used, such as offset printing, lithography, gravure printing, flexographic printing, gravure printing, silk-screen printing, digital printing, inkjet printing, pad printing, transfer printing, relief printing, etc. . In the case of a varnish system, any known application technology can be used, such as electrostatic spray coating, air and airless electrostatic systems, dip coating, electrophoresis, anodic electrodeposition (anaphoresis), cathodic electrodeposition (cataphoresis), autophoresis, pour-on, cast coating, drum coating , rotary coating, deep coating, roller coating, roll coating, powder coating, swirl sintering, flame spray or electrostatic powder spray.

Furthermore, the present invention relates to the use of a system and preferably a system of inks, coatings or varnishes according to the present invention for applying and in particular printing or spraying onto a substrate. Such systems can be used on (internal and external) surfaces of cars, computer cases, passports, banknotes, food packaging, magazines, beer cans, clothing items, furniture items, floor panels, wallpaper, cosmetic packaging, spare parts labels, protective features in general, mobile phone cases or on any architectural surfaces.

In accordance with the second aspect of the present invention, the present invention relates to a system comprising:

b) at least one first color layer containing a dye and/or pigment,

c) an effect layer above the at least one first color layer comprising at least one effect pigment, and

d) at least one second color layer above the effect layer containing a dye and/or pigment,

wherein each of the at least one first color layer and at least one second color layer contains a dye and/or pigment that is not an effect-producing pigment, wherein the at least one dye and/or at least one pigment contained in the at least one first color layer is not at least one dye and/or at least one pigment contained in the at least one second color layer, and

wherein at least if the at least one first color layer has a sum of reflectance and scattering coefficient of less than 40%, the system further comprises:

a) below the at least one first color layer, a lower layer containing pigment and having a sum of reflectance and scattering coefficient of at least 40%, wherein:

i) delta a/b of the system is at least 15, wherein delta a/b is determined according to the equation delta a/b=((a[15°]-a[110°])2+(b[15°]- b[110°])2)1/2, in which a[15°] is the a value of the L*a*b* color space measured at an angle of 15°, and a[110°] is the a value, measured at 110°, b[15°] is the b value measured at 15°, and b[110°] is the b value measured at 110°, where the measurement is carried out by irradiation systems in a dark environment with a standard light source at an incidence angle of 45° with respect to the horizontal direction, with a reflection angle of 135° with respect to the horizontal direction being defined as a viewing angle of 0° and/or

ii) the delta L of the system is at least 10, where delta L is determined according to the equation delta L=|L[15°]-L[110°]|, in which L[15°] is the value of L measured during observation at an angle of 15° and L[110°] is the L value of the L*a*b* color space measured at an angle of 110°, the measurement being made by irradiating the system in a dark environment with a standard light source at an incident angle of 45° with respect to the horizontal direction, wherein a reflection angle of 135° with respect to the horizontal direction is defined as an observation angle of 0° and/or

iii) the delta h° of the system is at least 15, wherein the delta h° is determined according to the equation delta h°=|h°[15°]-h°[110°]|, in which h°[15°] is the h° value measured at an angle of 15° and h°[110°] is the color space h° value measured at an angle of 110°, the measurement being made by irradiating the system in a dark environment with a standard light source at an incident angle 45° with respect to the horizontal direction, wherein a reflection angle of 135° with respect to the horizontal direction is defined as a viewing angle of 0°, and preferably no interference pigment is present in the system.

All features described above as preferred, and in particular all features described above as preferred with respect to the nature and composition of the layers and corresponding components, are also preferred for this second aspect of the present invention. In particular, any of layers (a), (b), (c) and (d) may have a composition as described above.

The present invention will now be described by means of the following illustrative, non-limiting figures.

In FIG. 1 shows an object containing a substrate that is coated with an ink system in accordance with one embodiment of the present invention.

In FIG. 2 is a schematic diagram of a method for performing an angle dependent color measurement system in accordance with one embodiment of the present invention.

In FIG. 3 shows angle-dependent color measurement results for four different systems in accordance with one embodiment of the present invention.

In FIG. 4a, b show sample holders that are suitable for holding longitudinal sections or cross sections of a system in accordance with the present invention or a layer thereof for scanning electron microscopy (SEM) analysis to determine particle length, particle width and particle thickness.

In FIG. 4c is a schematic diagram of an exemplary pigment particle having a particle length and a particle width.

In FIG. 5 a, b shows the principle of determining the average relative particle area of a layer of a system in accordance with the present invention.

In FIG. 6 shows the principle of determining the reflectance coefficient and scattering coefficient of a layer of a system in accordance with the present invention.

In FIG. 1 shows a system 10 that includes a substrate 12 that is coated with a series of inks 14 in accordance with one embodiment of the present invention. The ink sequence 14 comprises (from bottom to top) a bottom layer 16, a first color layer 18, an effect layer 20, and a second color layer 22. The bottom layer 16 contains a white pigment 24, preferably consisting of titanium dioxide having an average particle diameter of from 0.1 to 50 μm, at a concentration of from about 30 to 90% by weight of white pigment based on the total weight of the dried bottom layer 16. In addition, the first color layer 18 contains from about 0.001 to 5% by weight of dye 26 and/or from about 0.1 to 50% pigment based on the total dry weight of the first color layer 18, while the effect layer 20 contains from 10 to 70% by weight pigment creating a metallic effect, for example, aluminum particles creating the effect of the shape of the plates 28, consisting of aluminum and having an average particle length of approximately 10 μm, an average particle width of approximately 5 μm, an average particle thickness of approximately 0.5 μm, and thus a first aspect ratio of 2 and a second aspect ratio 20, based on the total weight of the dried effect layer 20, and the second color layer 22 contains from about 0.001 to 5% by weight of dye 30 and/or from 0.1 to 50% pigment, based on the total weight of the dried second color layer 22.

In FIG. 2 is a schematic diagram of a method for performing an angle dependent color measurement system in accordance with one embodiment of the present invention. In a dark environment, a beam of visible light 40 of adjustable intensity and wavelength within a predetermined range is directed to the system 10, which is described, for example, with respect to FIG. 1, at an angle of 45° with respect to the horizontal direction. Since the angle of incidence of the irradiating light beam with respect to the horizontal direction is the same as the angle of reflection 42, the angle of reflection 42 is 135° with respect to the horizontal direction. This reflection angle 42 is determined to measure the angle-dependent visible color of the system in accordance with the present invention when the viewing angle is 0°. To measure the angle-dependent apparent color of the system 10, the sum of the reflectance coefficient and the scattering coefficient is measured when viewed at different angles 44, 44', 44'', for example, as shown in FIG. 2, at viewing angles of -15°, 15°, 25°, 45°, 75° and 110°. Of course, it is also possible to measure visible color when viewed from more than six different angles or when observed from less than six different angles, for example when viewed from five different angles, for example when observed from angles of 15°, 25°, 45 °, 75° and 110°. For these measurements, for example, a BYK-mac i spectrophotometer from Byk Garnder (Geretsried, Germany) with a D50 light source can be used, performing six-angle measurements as described above. This instrument appears to be most suitable for measuring rectangular samples having a minimum width of 2 cm and a minimum length of 5 cm. Measuring at least 10 samples is particularly preferred, and even more preferable is measuring 100 or even 600 samples.

In FIG. 3 shows the results of measuring angle-dependent color of four different systems in accordance with one embodiment of the present invention. Angle-dependent color measurements of four different systems were carried out as described above in relation to FIG. 2, at viewing angles of -15°, 15°, 25°, 45°, 75° and 110°. At each viewing angle, the a-value and b-value of each system were determined. The corresponding values are graphically presented in Fig. 3 for any of the four systems, with the largest triangle in each graph representing the value measured at an viewing angle of -15°. Additional marks on each graph, starting from the largest triangle, represent the corresponding values determined when observed at angles of 15°, 25°, 45°, 75° and 110°. The horizontal axis in Fig. 3 represents the measured values of a, while the vertical axis in FIG. 3 represents the measured values b. As can be seen in FIG. 3, the a-values and b-values of all four samples differ depending on the viewing angles at which they were determined. This shows that the effect of change occurs in all four systems.

In FIG. 4a and 4b illustrate sample holders that are suitable for holding longitudinal sections or cross sections of a system in accordance with the present invention or a layer thereof for scanning electron microscopy (SEM) analysis to determine particle length, particle width and particle thickness. The sample holder shown in Fig. 4a is suitable for longitudinal sections of a layer or system (from the front view), while the sample holder shown in FIG. 4b is suitable for cross sections of a layer or system. Sections are placed on the appropriate area of the sample holders as represented by the blue arrow.

In FIG. 4c is a schematic representation of an exemplary pigment particle 46 having a particle length 48 and a particle width 50. Particle length 48 represents the greatest extent of particle 46, while particle width 50 is defined in this regard as the greatest extent of particle 46 in a direction that is perpendicular to particle length 48. Particle thickness is the shortest extent of particle 46 in a direction that is perpendicular to the two-dimensional plane defined by particle length 48 and particle width 50, i.e. the extent of a particle in a direction perpendicular to the plane of the paper.

In FIG. 5a and 5b show the principle of determining the average relative particle area of a system layer in accordance with the present invention by SEM using a longitudinal section of the system layer in question, obtained as described above. Particles 46 are colored using ParticleMetric tooling software as shown in FIG. 5a, and then the total longitudinal sectional area that is covered by particles 46, as shown in FIG. 5b are evaluated and divided by the total area of the longitudinal section analyzed by scanning electron microscopy to obtain the average relative particle area as a percentage.

In FIG. 6 shows the principle of determining the reflectance coefficient and scattering coefficient of a layer of a system in accordance with the present invention. A sample of the resulting layer, such as a corresponding longitudinal section, or the layer itself, having an area of, for example, 10 cm ² , is cut from the system and placed in a measuring device, which is preferably a turbidity and gloss tester from Byk Garnder (Geretsried). , Germany). The standard light source D65, represented by the reference number 52, irradiates the surface of the analyzed layer 54 at a certain angle β of 20° with respect to the vertical direction, and reflects light (which corresponds to gloss 56, as described in DIN 67530) as well as diffuse light (which corresponds to turbidity 58) is measured using sensor 60.

The present invention will now be described by way of the following illustrative but non-limiting examples.

Example 1

Solvent-containing nitrocellulose-polyurethane (NC/PU) flexographic inks were printed onto 30-μm-thick oriented polypropylene (OPP) films. The following inks are from hubergroup Deutschland GmbH: 61GU336812 (yellow; hereafter abbreviated as Y), 62GU336816 (magenta; hereinafter abbreviated as M), 63GU336821 (blue; hereinafter abbreviated as C), 69GU336827 (black; hereinafter abbreviated as M) designated as Bk), 77GU289376 (white color; hereinafter abbreviated as W) and 76GU318960 (silver color; hereinafter abbreviated as S) were printed onto the films at an ink viscosity of 20 s for a 4 mm DIN nozzle. diluted with a mixture of ethanol and ethyl acetate in a ratio of 9: 1. The ratio of pigment to binder in the dry paint film ranged from 0.9: 1 to 1.5: 1 for Y, M, C and Bk paints, 1: 0.3 for paint W and 0.9:1 for ink S, with dry ink densities ranging from 0.7 to 1.5 g/m ² for each ink.The following color sequences were printed (from bottom to top):

The layers corresponding to the printing plates were as follows:

Color changing effects for each system were measured using a BYK-mac i spectrophotometer. The color transition was assessed by measuring the a/b ratio when observed at five angles, which were -15°, 15°, 25°, 45°, 75° and 110°. To evaluate the extent of the color changing effect for each system, the a and b values of the L*a*b* color space were measured at viewing angles of 15° and 110°, and as a result, the delta a/b ratio was determined according to the following equation:

delta a/b=a/b=((a[15°]-a[110°]) ² +(b[15°]-b[110°]) ² ) ^1/2

The higher the numerical value of delta a/b, the stronger the effect of the change.

For seven different experiments the following results were obtained:

Thus, the greatest color changing effects were achieved for ink hiding power from 90 to 100% in the case of color printing ink between white and silver layers, for ink hiding power from 80 to 100% in the case of the silver layer, for ink hiding power from 0 to 10% in the case of an optional black layer and for the total hiding power of the ink from 40 to 60% in the case of applying all printing inks over silver, i.e. creating the effect layer.

In an additional experiment, Y, M and C paints were thinned 100% using 60GU319987 thinner, resulting in pigment to binder ratios ranging from 0.9:2 to 1.5:2. The effect of color change was also observed in the case of using these paints.

Example 2

In another gravure experiment, solvent-based NC/PU flexographic inks were tested in the following colors: cyan 63GU514973, magenta 62GU514969, yellow 61GU515076, black 69GU515074, white 67GU515182, silver 66GU515184, and 70GU50 thinner was used. 4288 from hubergroup Deutschland GmbH.

The cyan and magenta inks were thinned 120%. Yellow, silver and white inks were used for printing without thinner. The paints were further thinned to a viscosity of 20 s for a 4 mm DIN nozzle using a 9:1 mixture of ethanol and ethyl acetate. Inks were applied to corona treated OPP film using a Roto Hand Proofer from Pamarco. The following color sequences were examined (from bottom to top):

W-Y-S-M-C-Bk, W-S-Y-M-C, W-Y-S-M-Bk and W-S-Y-M-C-Bk.

Abbreviations for colors: W - white, Y - yellow, S - silver, M - magenta, C - cyan and Bk - black.

In this experiment, it was observed that inks having higher pigment content exhibited a less pronounced color change effect, indicating that transparency was insufficient at the ink film thickness achieved by intaglio printing at standard pigment content. The paint application density ranged from 0.7 to 1.5 g/m ² for each paint. The pigment to binder ratio ranged from 1.5:2 to 3:2 for yellow, cyan, magenta and silver and 2:3 for white. Delta a/b values of 15°/110° up to 40 have been achieved when printing yellow ink between white and silver ink and when printing other inks above or below the silver ink.

Example 3

In the third experiment, the inks from Example 2 were applied using a K Printing Proofer from RK Print Coat Instruments. The same inks and color sequences as in Example 2 were used and resulted in ink films having a density of 0.13 to 0.8 g/m ² . It has been observed that additional dilution of the inks by 100% was required to obtain the optimum color changing effect, resulting in pigment to binder ratios of 1:2 to 1:6 for yellow, 1:8 to 1:10 for cyan and magenta. paints, 1:1.5 for silver paint and 1:0.7 for white paint. The achieved delta a/b 15°/110° was 27 for the white-yellow-silver-cyan color sequence and 35 for the white-yellow-silver-magenta color sequence.

In addition, the present invention relates to the following combinations of features or aspects, respectively. Each of the following aspects can be combined with the above options.

Example 4

Solvent-based NC/PU flexographic inks were printed onto 30 μm thick white oriented polypropylene (OPP) films. The following inks are from hubergroup Deutschland GmbH: 61GU336812 (yellow; hereafter abbreviated as Y), 62GU336816 (magenta; hereinafter abbreviated as M), 63GU336821 (blue; hereinafter abbreviated as C and 76GU318960 (silver; hereinafter abbreviated as M) designated as S) were applied by printing on films with an ink viscosity of 20 s for a 4 mm DIN nozzle. The inks were diluted with a mixture of ethanol and ethyl acetate in a ratio of 9: 1. The pigment to binder ratio of the dry ink film was from 0. 9:1 to 1.5:1 for Y, M and C inks and 0.9:1 for S inks, with dry ink densities ranging from 0.7 to 1.5 g/ ^m2 for each ink. the following sequences of colors (from bottom to top):

Color changing effects for each system were measured using a BYK-mac i spectrophotometer. The color transition was assessed by measuring the a/b ratio when observed at five angles, which were -15°, 15°, 25°, 45°, 75° and 110°. To evaluate the extent of the color shift effect for each system, the h° values of the HCL color space were measured at viewing angles of 15° and 110°, resulting in the delta h value being determined according to the following equation:

Δh°=delta h°=|h°[15°]-h°[110°]|,

which is the absolute difference between the corresponding two values of h°.

For different sequences of paints and covering abilities of the coating, the following results were obtained:

Note: h° values are polar coordinates from 0 to 360°.

Example 5

In this experiment, automotive coatings were applied to sheet metal substrates. The following formulations were used, based on standard products from the Nexa Autocolor Aquabase paint mixing system:

The D ₁₀ and D ₉₀ values represent cutoffs for 10% and 90% of the total particle mass.

The varnishes were applied using a Sata Jet 5000 at 1.6 bar for the first color (red) and 1.9 bar for the silver, blue and green.

The following sequences of layers were applied:

In the final step, a clear coat was applied to the substrates using a solvent-containing product from Nexa.

The coatings had the following thicknesses:

red coating: double application, final thickness of the red layer was approximately 30 µm;

silver coating: single/double application, final silver layer thickness was approximately 15/30 µm;

blue/green coating: single/twice application, final blue/green layer thickness was approximately 20/40 µm;

clear coat: double application, final clear coat layer thickness was 90 to 100 µm. The clear coat used was 2K HS Plus Clear Coat P190-6570 (2 parts) plus Hardener P210-8645 (1 part), both under the Autocolor brand from PPG Industries, Ohio.

The coated substrates were measured using a BYK-mac i spectrophotometer as described above, some example measurement results are presented in the following table:

ΔL=delta L=|L[15°]-L[110°]|

Δh°=delta h°=|h°[15°]-h°[110°]|

Color changes were observed for all combinations tested. The use of small and medium-sized aluminum pigment particles provides a more pronounced effect of change. When larger aluminum particles are used, the color change is quite visible on the particles themselves, but it cannot be properly measured and assessed.

Additional aspects of the present invention are described below.

Aspect 1. System containing:

a) bottom layer (16) containing white pigment (24),

b) above the bottom layer (16) at least one first color layer (18) containing a dye (24) and/or pigment that is different from the white pigment (24) contained in the bottom layer (16) and is not metallic pigment,

c) a metal layer (20) above at least one first color layer (18) containing at least one metal pigment (28) and

d) at least one second color layer (22) above the metal layer (20) containing a dye (30) and/or pigment that is not the white pigment (24) contained in the lower layer (16) and does not represent a pigment that creates a metallic effect.

Aspect 2. The system according to aspect 1, wherein at an angle of at least 0 to 45° with respect to the horizontal direction, the color hue of the visible light (34) reflected and scattered by the metal layer (20) is different from the hue of the visible light ( 38), reflected by the bottom layer (16).

Aspect 3. The system according to aspect 1 or 2, wherein the white pigment (24) contained in the bottom layer (16) is selected from the group consisting of titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, lead carbonate, carbonate calcium, alumina, aluminum silicate and arbitrary combinations of two or more of the above.

Aspect 4. A system according to any of the preceding aspects, wherein the bottom layer (16):

i) is a foil/film and contains from 0.1 to 10% by weight, preferably from 0.25 to 4% by weight and more preferably from 0.75 to 1.5% by weight of white pigment (24) relative to to the total weight of the lower layer (16), the foil/film having a thickness preferably from 1 to 100 µm, more preferably from 2 to 50 µm and most preferably from 10 to 30 µm, or

ii) is paper or paperboard and contains from 0.1 to 50% by weight, preferably from 1 to 10% by weight and more preferably from 3 to 7% by weight of white pigment (24) relative to the total weight of the lower layer ( 16), or

iii) is a paint and contains from 10 to 90% by weight and preferably from 30 to 90% by weight of white pigment (24) relative to the total weight of the lower layer (16), the paint having a thickness of preferably from 1 to 10,000 µm.

Aspect 5. A system according to any of the preceding aspects, wherein the white pigment (24) contained in the bottom layer (16) is titanium dioxide and preferably rutile and is present in the form of particles having an average particle size d ₅₀ of 0.1 to 50 µm, preferably 0.1 to 10 µm and more preferably 0.2 to 0.5 µm.

Aspect 6. A system according to any of the preceding aspects, wherein the metal layer (20) is a paint having a pigment to binder ratio in the metal layer (20) of from 0.3:1 to 2:1, preferably from 0.7:1 to 2:1 and more preferably 0.7:1 to 1.8:1.

Aspect 7. A system according to any of the preceding aspects, wherein the metal pigment (28) contained in the metal layer (20) is present in the form of platelets having an average size d ₅₀ of 2 μm to 3000 μm.

Aspect 8. A system according to any of the preceding aspects, wherein the metal layer (20) has a thickness of 0.1 to 50 μm, more preferably 0.5 to 20 μm, and most preferably 1 to 10 μm.

Aspect 9. A system according to any of the preceding aspects, wherein the paint hiding power of the metal layer (20) over the at least one first color layer (18) is from 40 to 100%, more preferably from 70 to 100%, even more preferably from 80 to 100% and most preferably from 90 to 100%, the hiding power of the paint being the percentage of the area of the top one or more first color layers (18) that is covered by the metal layer (20).

Aspect 10. A system according to any of the preceding aspects, wherein the dry areal density of the metal layer (20) is from 0.2 to 2 g/cm ² , more preferably from 0.3 to 1.5 g/cm ² and most preferably from 0.4 to 1.2 g/cm ² .

Aspect 11. A system according to any of the preceding aspects, wherein the weight ratio of pigment to binder in the metal layer (20) is from 0.3:1 to 2:1, more preferably from 0.7:1 to 2:1 and most preferably from 0.7:1 to 1.8:1.

Aspect 12. A system according to any of the preceding aspects, wherein any of the first color layer (18) and at least one second color layer (22) contains from 0.001 to 5% by weight of at least one dye (26, 30 ) and/or from 0.1 to 50% by weight of at least one pigment that is neither a white pigment nor a metallic pigment, relative to the total dry weight of the first color layer (18) and/or the second color layer (22) .

Aspect 13. A system according to any of the preceding aspects, wherein the at least one dye (26) and/or the at least one pigment contained in the first color layer (18) is different from the at least one dye (30) and/or at least one pigment contained in at least one second color layer (22).

Aspect 14. A system according to any of the preceding aspects that does not contain any interference pigment.

Aspect 15. A system according to any of the preceding aspects, wherein delta a/b is at least 15, more preferably at least 30, and most preferably at least 38, wherein delta a/b is determined according to the equation delta a/ b=((a[15°]-a[110°])2+(b[15°]-b[110°]) ² ) ^1/2 , in which a[15°] represents the value of a measured when observed at an angle of 15°, a[110°] represents the value of a measured when observed at an angle of 110°, b[15°] represents the value of b measured when observed at an angle of 15°, and b[110°] represents is the b-value measured when viewed at an angle of 110°, the measurement being carried out by irradiating the system in a dark environment with a standard light source at an incidence angle of 45° with respect to the horizontal direction, with a reflection angle of 135° with respect to the horizontal direction, defined as an observation angle of 0°.

List of reference designations

10 - Coated system/object

12 - Backing

14 - Sequence of colors

16 - Bottom layer

18 - First color layer

20 - Effect layer

22 - Second color layer

24 - White pigment

26 - First dye

28 - Pigment that creates the effect of the shape of plates

30 - Second dye

40 - Irradiating light beam

42 - Angle of reflection of the irradiating light beam

44, 44', 44'' - Reflectance/scattering coefficient/color tint measurement angle

46 - Pigment particle

48 - Particle length

50 - Particle width

52 - Standard light source

54 - Layer surface

56 - Shine

58 - Turbidity

60 - Sensor

β - Angle of incidence of light from a standard source

Claims (37)

1. A sequence of layers with a color changing effect, containing: b) at least one first color layer (18) containing a dye (26) and/or pigment, c) an effect layer (20) above the at least one first color layer (18), comprising at least one platelet effect pigment (28), wherein the at least one platelet effect pigment (28), consists of particles (46) having an average length (48) from 2 to 500 μm, an average width (50) from 2 to 500 μm, and an average thickness of not more than 1 μm, and d) at least one second color layer (22) above the effect layer (20), containing a dye (30) and/or pigment, wherein each of the at least one first color layer (18) and at least one second color layer (22) contains a dye (26, 30) and/or a pigment that is not a platelet effect pigment, wherein at least at least one dye (26) and/or at least one pigment contained in at least one first color layer (18) is different from at least one dye (30) and/or at least one pigment contained in at least one second color layer (22), and wherein at least if at least one first color layer (18) has a sum of reflectance and scattering coefficient of less than 40%, the system further comprises: a) under at least one first color layer (18) a lower layer (16) containing a pigment (24) and having a sum of reflectance and scattering coefficient of at least 40%, wherein the system does not contain interference pigments, with an interference pigment being defined as a pigment that creates interference of light waves. 2. The sequence according to claim 1, wherein the at least one platelet effect pigment (28) is a metal platelet effect pigment, and preferably a silver platelet effect pigment, the effect pigment gold flake effect pigment, aluminum flake effect pigment, copper flake effect pigment, copper-zinc alloy flake effect pigment, or brass bronze flake effect pigment. 3. The sequence according to claim 1 or 2, wherein the at least one platelet-shaped effect pigment (28) consists of particles (46) having an average thickness of from 0.01 to 1 μm, preferably from 0. 05 to 1 µm and more preferably from 0.05 to 0.5 µm. 4. Sequence according to any one of paragraphs. 1-3, wherein the at least one platelet-shaped effect pigment (28) is composed of particles (46) having a first aspect ratio being the ratio of the average particle length (48) and the average particle width (50), and being from 1 to 20 and preferably from 1 to 2 or from 2 to 5. 5. Sequence according to any one of paragraphs. 1-4, in which at least one platelet-shaped effect pigment (28) consists of particles (46) having a second aspect ratio, which is the ratio of the average length of the particle (48) and the average thickness of the particle, and is between 1 to 75,000, preferably from 1 to 1000, more preferably from 1 to 200, even more preferably from 1 to 100 and most preferably from 1 to 60. 6. Sequence according to any one of paragraphs. 1-5, in which the average relative particle area of the effect-creating layer (20) is from 5 to 75%, preferably from 10 to 55%, and most preferably from 15 to 35%. 7. Sequence according to any one of paragraphs. 1-6, in which the effect-creating layer (20) has a thickness of from 0.1 to 50 μm, preferably from 0.1 to 30 μm and most preferably from 0.2 to 20 μm or from 0.1 to 150 μm , preferably from 1 to 100 µm and more preferably from 10 to 50 µm. 8. Sequence according to any one of paragraphs. 1-7, in which the weight ratio of pigment and binder in the dry effect layer (20) is from 0.02:1 to 2:1, preferably from 0.1 to 2:1, and more preferably from 0.2:1 up to 1.8:1. 9. Sequence according to any one of paragraphs. 1-8, wherein the effect-creating layer (20) has a sum of reflectance and scattering coefficient of 20 to 100%, more preferably 30 to 100%, and most preferably 40 to 100%. 10. Sequence according to any one of paragraphs. 1-9, in which the bottom layer (16) is present and: i) is a film and contains from 0.1 to 10 wt. %, preferably from 0.25 to 4 wt. % and more preferably from 0.75 to 1.5 wt. % white pigment (24) based on the total weight of the lower layer (16), the film having a thickness of preferably 1 to 100 μm, more preferably 2 to 50 μm, and most preferably 10 to 30 μm, or ii) is paper or cardboard and contains from 0.1 to 50 wt. %, preferably from 1 to 10 wt. % and more preferably from 3 to 7 wt. % white pigment (24) relative to the total weight of the lower layer (16), or iii) is a paint and contains from 10 to 90 wt. % and preferably from 30 to 90 wt. % of white pigment (24) based on the total weight of the dry base layer (16), in which the paint has a thickness preferably from 0.5 to 100 μm, or iv) is a coating or varnish and contains from 10 to 90 wt. % and preferably from 30 to 90 wt. % white pigment (24) based on the total weight of the dry base layer (16), the coating or varnish having a thickness preferably from 0.5 to 1000 μm. 11. Sequence according to any one of paragraphs. 1-10, in which there is a bottom layer (16), and a dye (26, 30) and/or pigment contained in each of at least one first color layer (18) and at least one second color layer (22) , different from the pigment (24) contained in the lower layer (16). 12. Sequence according to any one of paragraphs. 1-11, in which any of at least one first color layer (18) and at least one second color layer (22) contains from 0.001 to 5 wt. % of at least one dye (26, 30) and/or from 0.1 to 50 wt. % of at least one non-white pigment and non-metallic pigment, based on the total dry weight of the first color layer (18) and/or the second color layer (22). 13. Sequence according to any one of paragraphs. 1-12, wherein delta a/b is at least 15, more preferably at least 30, and most preferably at least 38, wherein delta a/b is determined according to the delta equation in which a[15°] is the a value measured at an angle of 15°, a[110°] is a value measured at an angle of 110°, b[15°] is a b value measured at observed at an angle of 15°, and b[110°] is the value of b measured when observed at an angle of 110°, the measurement being carried out by irradiating the system in a dark environment with a standard light source at an incidence angle of 45° with respect to the horizontal direction, wherein a reflection angle of 135° with respect to the horizontal direction is defined as an observation angle of 0°. 14. A sequence of layers with a color changing effect, containing: b) at least one first color layer (18) containing a dye (26) and/or pigment, c) an effect layer (20) above at least one first color layer (18) containing at least one effect pigment (28) and d) at least one second color layer (22) above the effect layer (20), containing a dye (30) and/or pigment, wherein each of at least one first color layer (18) and at least one second color layer (22) contains a dye (26, 30) and/or a pigment that is not an effect pigment, wherein the at least one dye ( 26) and/or at least one pigment contained in at least one first color layer (18) is at least different from at least one dye (30) and/or at least one pigment contained in at least at least one second color layer (22), and wherein at least if at least one first color layer (18) has a sum of reflectance and scattering coefficient of less than 40%, the system further comprises: a) under at least one first color layer (18) a lower layer (16) containing a pigment (24) and having a sum of reflectance and scattering coefficient of at least 40%, and: i) the delta a/b of the system is at least 15, where the delta a/b is determined according to the delta equation in which a[15°] is the a value measured at an angle of 15°, a[110°] is a value measured at an angle of 110°, b[15°] is a b value measured at observed at an angle of 15°, and b[110°] is the value of b measured when observed at an angle of 110°, the measurement being carried out by irradiating the system in a dark environment with a standard light source at an incidence angle of 45° with respect to the horizontal direction, wherein a reflection angle of 135° with respect to the horizontal direction is defined as an observation angle of 0° and/or ii) the delta L of the system is at least 10, where delta L is determined according to the delta equation wherein L[15°] is the L value measured at an angle of 15°, and L[110°] is the value of L measured at an angle of 110°, the measurement being carried out by irradiating the system in a dark environment with a standard source light at an angle of incidence of 45° with respect to the horizontal direction, wherein an angle of reflection of 135° with respect to the horizontal direction is defined as a viewing angle of 0° and/or iii) the delta h° of the system is at least 15, where the delta h° is determined according to the delta equation in which h°[15°] is the value of h° measured at an angle of 15°, and h°[110°] is the value of h° measured when observed at an angle of 110°, the measurement being carried out by irradiating the system at dark environment with a standard light source at an angle of incidence of 45° with respect to the horizontal direction, with a reflection angle of 135° with respect to the horizontal direction being defined as an viewing angle of 0°, and wherein the system does not contain interference pigments, with an interference pigment being defined as a pigment that creates interference of light waves. 15. The sequence of claim 14, wherein the system delta a/b is at least 15, preferably at least 30, and more preferably at least 38.