Pvd metal effect pigment having gradient on nanoscale metal particles, method for the production thereof and use thereof

The present invention relates to a the outside of the 1st and 2nd PVD metal effect pigments lamellar crystal , the PVD metal effect pigments states the lamellar crystal has at least one PVD layer, and the at least one PVD layer comprising metal oxide and elemental metal cluster, metal effect pigments PVD of the 1st and 2nd in the outside elements of the amount of metal clusters are different from each other, and the difference of at least 10 atomic %. The invention further relates to the use of PVD metal effect pigments and method for producing them.

Metal effect pigments have been used for many years in order to produce in the coating of metal effect.

Traditional metal effect pigments a metal pigment by a sheet form, derived from the effect of the incident light in the corresponding application medium in the parallel orientation in the plane of the metal in the form of direct reflection of the pigment.

The typical metal effect pigments application field is the coating industry, especially in the automotive industry, plastics industry and printing industry.

Metal effect through certain parameter description. These parameters include a characteristic the flash and metal gloss luster, brightness, and the angular heterochromic (flop), that is, the brightness changes with the incident angle and/or visual angle, and refers. In the case of non-ferrous metal coating, the chromaticity and the other parameters of angular heterochromic ("two-color"). Gloss by with respect to the standard, the ratio of the reflected light to scattered light.

Metal effect of the impact of key factors, including particle shape and form factor, that is, the average particle diameter of the pigment the ratio of thickness of the average particles, particle thickness, and their surface roughness, particle size, particle size distribution, and pigment parallel to the orientation of the coating or plastic surface.

While having a relatively large diameter and uniform shape in metallic effect pigment particles to, reflection relatively high, this shows that the high metal gloss, improved brightness and strong along with angle heterochromic, with a relatively low particle size of the pigment, scattering portion is very high, refers to the good.

However, by first refers to the thickness of the metallic pigment. The thinner the metal pigments, their than the material of the covered force, that is, per unit weight, the better refers.

In the printing, coating, plastics and cosmetic industries, dark metal effect pigments to the metal with a large interest.

Application of the relatively high value, has been the development of the special thin aluminum effect pigment, by PVD technology and production.

Known for a long time by a PVD metal effect pigments technical production, as a result of their extremely high gloss, great and refers are known for their unique optical properties. Because they about 30-70nm and their low thickness of the very smooth surface, after the application of them having very close in accordance with the tendency of the substrate. If the matrix is very smooth, the result is the basic such as mirror appearance.

In the pure metal effect pigments, commercial so far only discloses aluminum effect pigment. In fact, example is (By Avery   Dennison production, sale by Eckart), (Schlenk) or (Ciba).

This kind of pigment in its highest embodiment display the "silver" tone.

Based on that the metal layer by PVD technology to produce the pigment is described in more detail in US   2,839,378 in. In the description the production has extremely thin layer thickness manufacturing such as the mirror of the pigment, through vapor phase deposition is applied to having the "release layer" on a substrate. In the application of the metal layer after removing moving, will be through the mechanical action to the desired particle size of pigment grinding.

In this way the production of pigment in the coating formulation described in detail in US application of   2,941,894 in. The Patent emphasizes the high-reflectivity, low-pigmented level, that is, the application medium pigment concentration in the low level, and of the pigment hiding power or refers ratio.

Thickness by vapor-phase deposition technique for 35-45nm method for the metal of the pigment more accurately described in US   4,321,087 in, and calls for the application of the release layer, the metallization operation, the removal of the procedures in solvent bath , concentrated and removing particles by ultrasonic crushing the particles to the required pigment size.

WO99/35194 described pigment has a three-layer structure, wherein the metal layer is positioned in the middle of the the inherent color is not affected by two external dielectric carrier layer change. The production method to be adopted is that it includes three layers of vapor phase deposition in the application of multi-layer structure can be produced, therefore, the production cost is extremely greatly improved.

EP   1   522   606   A1 describes the production of black alumina sheet. In this case, not only did not disclose effect pigment, did not disclose a multi-layer structure. The flake as disclosed herein has the advantages of not having a gloss and along with angle heterochromic metal effect.

US   4,430,366 described comprising metal and metal oxide mixture of the production of flake. There is also no relates to effect pigment.

WO   2007093401   A2 described having a oxygen and the metal in the composition of the extremely homogeneous dark metal effect pigments layer. A method for producing these effects of the pigment costly and inconvenient.

DE   69601432   T2 relates to an Image on the matrix method for heat generation, wherein the oxygen-containing black aluminum application in such a way, so that it is in 200-1100nm under the wavelength of the light transmission ratio of at least 0.3. The document provides no relates to effect of the pigment.

EP   1   144   711   B1 discloses a method for reflecting color of the pigment, wherein the reflecting layer on the top of the color change of a application generates at least one layer, said layer comprising a refractive index greater than 1.8 transparent material, usually a metal oxide, and the light absorption metal, when the evaporation of the accompanying application, and the light absorbing metal different from the metal oxide of the metal. In the craft project, the method is very difficult to control.

DE   10   2007   007   908   A1 discloses by PVD technology to produce dark metal effect pigments. They have a very homogeneous composition and having 25-58 relatively high oxygen content of atomic %. Because the metal is dispersed in the metal oxide in the form of small metal clusters, has a dark color of the layer. This kind of effect pigment produces a prominent bright/dark along with angle heterochromic dark, but high-gloss effect pigment. The production of these has a uniform PVD metal effect pigments of the process engineering aspects of the method of the same expensive and inconvenient, and only allow low-productivity.

In order to ensure that the high-oxygen-content and uniform chemical composition, the need to play in the coating operation with the width and length of the coated metal gasification rate and the oxygen supply rate monitoring. This requires in particular in the production equipment is very high level of cost and complexity of:on the tape, for example, may, for example, the transmitted ratio measurement in-situ measurement and adjustment of the thickness of the metal layer. However, very difficult to monitor the entire vapor deposition zone, that is, with the width and length of the the operation of the on.

The purpose of this invention is to provide a very high up to occasionally, preferably is easy to produce bright/dark along with angle heterochromic neutral, covering, metal, black colored or non-colored caution metal effect pigments such as the mirror.

Another aim is to find a production of this kind of metal effect pigments cost-effective and simple method. Pigment can be can be easily monitoring method for the production. The method also preferably allows a high productivity.

The invention is based on the purpose by providing a 1st and 2nd with the outside of the PVD lamellar crystal metal effect pigments, metal effect pigments states the lamellar crystal by the PVD has at least one PVD layer, the at least one PVD layer includes metal clusters with elements of the elemental metal and metal oxide, metal effect pigments PVD of the 1st and 2nd in the outside of the amount of elemental metal are different from each other, and the difference of at least 10 atomic %.

PVD metal effect pigments of the present invention the preferred development claim described 2-11 in.

PVD metal effect pigments of the present invention can comprise or by one or more PVD layer.

PVD metal effect pigments lamellar crystal preferably the diameter is at least 10 times the thickness of the metal effect pigments PVD metal effect pigments. Preferably the diameter is at least 20 times, preferably at least 50 times, more preferably at least 80 times, even more preferably at least 100 times the thickness. Very suitable also for an aggregate of 200 times, 400 times, 500 times or 1000 times the diameter of the thickness.

The outside of the PVD metal effect pigments lamellar crystal metal PVD meant that the top and the bottom surface of the effect pigments, metal effect pigments PVD can comprise 1, 2, 3 or more PVD layer. PVD metal effect pigments is applied to the outside of the finger for example, the PVD metal effect pigments anti-corrosion layer.

Statements "atomic %" relates to all component, in other words the elemental metal, metal oxide and oxygen, wherein the oxidized metal and oxygen of the metal oxide present in the form of a (number: 1) in the PVD layer.

Through deformation of the ground to obtain a contrast metal effect pigments, metal effect pigments PVD of this invention is extremely smooth surface of the, more particularly no recesses and/or projections are known. By deformation of the metal effect pigments ground to obtain a contrast, the boundary region is not tear or wear, but typically has a linear fracture edge.

PVD metal effect pigments of the present invention the specific characteristic is that it has an asymmetric structure. Asymmetry in the PVD layer thickness is characterized in that the elements of a different metal. According to the invention, the PVD layer is by physical vapor deposition (PVD) in a (number: 1) applied in the PVD deposition operation a layer of (number: 1). The asymmetry of the PVD layer therefore can be attributed to the nonuniform a PVD layer, PVD is in the present invention the metal effect of the pigment on the PVD layer thickness of the elemental metal and metal oxide having a non-uniform distribution of results.

lamellar crystal PVD metal effect of the pigment between 1st and 2nd metal elements of the differing by at least 10 atomic %, preferably at least 14 atomic %, more preferably at least 17 atomic %. According to the present invention one preferred development, the poor 21-96 atomic %, more preferably 24-87 atomic %, and even more preferably of 27-76 within the range of atomic %. Also has proved to be very appropriate 31-68 atom % or 37-46 the difference of atomic %.

In addition to elemental metal outer, PVD metal effect pigments of the present invention also contains metal oxide. Here the one in the (number: 1) PVD layer thickness in the upper curve, the amount of elemental metal with elemental metal oxide is greatly correlated to the amount of opposite, preferably on the contrary, and vice versa.

According to the present invention, in the PVD layer, to form a metal oxide of the metal with the PVD layer of the same metal as the element in the. Expressed in a different way, the elements in the PVD layer of metal and metal oxide metal and preferably are different from each other. Therefore, the metal elements can be distributed in a metal oxide, or metal oxide may be present in the metal in the distribution, depending on the elemental metal and the metal oxide of the respective fraction.

Because metal layer utilizes PVD reactive gasification and oxygen in the presence of application, a (number: 1) PVD layer of metal and the elements of the same metal as the metal oxide. Therefore, in the present invention the production of PVD in metal effect pigments, metal or metal oxide does not exist the gasification side by side each other.

According to the present invention, metal can be a single metal or metal alloy, or a single metal oxide or metal alloy oxide.

In PVD metal clusters of this invention are present in the form of the elements in the metal effect pigments of the present invention metal obviously decided the coloring of PVD metal effect pigments. As part of the presence of metal oxide in the present invention the coloring of PVD metal effect pigments do not have part or only the part of the very much smaller.

Surprisingly the PVD metal effect pigments of the present invention has the optical performance of the surprising. Has higher the face of the metal element of the PVD metal effect pigments of the present invention actually serve as the metal reflector part or actually serve as the metal absorber. Has higher elemental metal is in the form of metal clusters of PVD metal effect pigments of the present invention part actually have a coloring effect.

Furthermore, surprisingly, the original such that: in the application, the present invention asymmetric PVD metal effect pigments of generating uniform and attractive visual impression. In the application, such as, for example, in coating such as ink, printing ink, paint, cosmetics and the like, about 50% has the advantages of a relatively high amount of elemental metal in the form of metal clusters of PVD metal effect pigments of the present invention, and about 50% with the elemental metal in the form of metal clusters wherein the PVD metal effect pigments of the present invention facing the observer's eyes. Surprisingly, the observer cannot see the irregular color impression, but homogeneous color impression. The effect of having a continuous metal layer for a PVD metal effect pigments provided is particularly surprising.

Furthermore, surprisingly, PVD metal effect pigments of the present invention with the in one (number: 1) having a very homogeneous in the PVD layer of metal oxide and metal clusters form of elemental metal distribution compared with PVD metal effect pigments and a lower pigment dark tone the thickness of the produce.

Furthermore, surprisingly, the original is PVD metal effect pigments of the present invention provides a display to the bright/dark grey heterochromic along with angle, metal effect pigments is preferably dark gray PVD. Consider the optical effect of the present invention is attributable to the asymmetry of the PVD metal effect pigments, metal effect pigments depends on the PVD which surface faces the viewer, thereby generate asymmetric colored. Because the viewer receives the average of the color, can be obtained with still can be obtained/dark dark grey heterochromic along with angle metal effect pigments of the range.

According to a development of the invention, sheet crystalline PVD is provided with a layer of metal effect pigments are arranged in the top of another layer of the two PVD layer, said layer comprising metal clusters with elements of the respective elemental metal and metal oxide, wherein the PVD metal effect of the pigment the 1st and 2nd in the outside of the amount of elemental metal are different from each other, and the difference of at least 10 atomic %.

According to the invention the change programme, two PVD layer by vapor deposition directly applied to the each other. Here, elements in the two layers of the metal of metal and metal oxide can be the same or different from each other.

For example, the 1st PVD layer of metal can be aluminum or alumina, metal can be 2nd PVD layer of the chromium or chromium oxide, or titanium or titanium dioxide.

However, according to the present invention, the metal also 1st PVD layer can be aluminum or alumina, 2nd PVD layer of metal can also be aluminum or alumina, wherein the 1st and 2nd PVD layer of alumina in the corresponding fraction of aluminum or elements preferably are different from each other.

According to the present invention, the metal also 1st PVD layer can be chromium or chromium oxide, 2nd PVD layer of metal can also be a chromium or chromium oxide, wherein the 1st and 2nd PVD layer of chromium oxide or chromium elements in the corresponding fraction preferably are different from each other.

According to the present invention, the metal also 1st PVD layer can be titanium or titanium dioxide, 2nd PVD layer of metal can also be titanium or titanium dioxide, wherein the 1st and 2nd PVD layer of titanium dioxide or prepared in the corresponding fraction preferably are different from each other.

According to the present invention especially preferably has two PVD layer of metal effect pigments PVD metal or metal oxide in the above combination.

1st PVD layer and 2nd PVD layer regardless of the metal in the same or different from each other, the PVD metal effect pigments of the metal element in 1st and 2nd the amount of the metal element in the amount of the difference of at least 10 atomic %.

According to the invention another change programme, PVD lamellar crystal is provided with a layer of metal effect pigments on a layer arranged on the other of the three or more of the PVD layer, all PVD layers each contain metal clusters with elements of the elemental metal and metal oxide, and elemental metal of highest quantity PVD metal effect of the pigment present in the 1st or 2nd in the outside, the PVD metal effect pigments and 1st 2nd in the outside of the outer surface and the amount of metal elements are different from each other, and the difference of at least 10 atomic %.

In three-layer or multi-layer structure, PVD metal effect pigments of the present invention preferably has the highest quantity outside of the elemental metal.

It is essential to one outside of the outside of the metal element in the 2nd at least 10 atomic % of the metal content of the element.

The outside of the containing two outer PVD layer of between 3rd, 4th, 5th, a PVD layer of course can be lower than or higher than the outside of the metal element in the content of the elemental metal, the outside than the amount of the other elemental metal highest quantity the outside of the metal element in a low amount of at least 10 atomic %.

Between the outside of the-containing PVD PVD layer of elemental metal in the interlayer can be therefore the amount of fluctuation in the horizontal aspect, highest quantity element metal is preferably present in one of the two outside.

According to the present invention, preferably at least one PVD layer the amount of elemental metal in the PVD layer are preferably at least in part on the thickness of 0.1-4 atom % / nmPVD layer thickness gradient change continuously.

The elements of the continuous metal elemental metal phosphor is not a sudden change in the amount of the, but by curved linear or closer to the linear manner to the change in the layer thickness of the PVD. According to one preferred change programme, change with the change of the amount of the elements is approximately linear, change with the change of the amount of elemental metal, that is, increase or decrease in gradient of 0.1-4 atom % / nm thickness, more preferably 0.2-2 atom % / nm thickness, still more preferably 0.4-1.5 atom % / nm within the range of the thickness.

Elemental metal, the amount of metal oxide and oxygen by ESCA (electron spectroscopy for chemical analysis) measurement. ESCA determination of the elemental metal, the amount of the metal oxide and oxygen usually in about 20 nanometer of averaging on the PVD layer thickness. In atomic % ± 1 that with a measured value of the precision of the atomic %.

The thickness of the metal effect pigments PVD by SEM (scanning electron microscope) determination.

According to the present invention another change of the programme, element in two successive metal PVD layer does not change continuously.

If arrangement two or more continuous PVD layer, the mutant of the metal elements. Therefore, no matter the same each other or different metal elements, can be in a layer is arranged in another layer between the two PVD layer 1-10nm to the change in the thickness of several atomic %, for example greater than 5 atomic % or more than 10 atomic % or more than 15 atomic %, wherein the elements changed significantly changes the gradient of the metal.

According to the invention another change programme, the 1st of metallic pigment in the amount of elemental metal 0-60 atomic %, the 2nd metal of the pigment in the amount of elemental metal is preferably 30-95 atomic %, conditions of PVD metal effect pigments is 1st and 2nd between the metal elements of the difference of at least 10 atomic %.

If a in the outside element metal such as the amount of 50 atomic %, the outside of the metal element in the 2nd amount is less than 40 atom % or at least 60 atomic %. On the other hand, if a in the outside element metal such as the amount of 20 atom %, such as 2nd in the outside element metal amount is at least 30 atom %.

Preferably, the content of the elemental metal having a relatively high the outside of the metal element in the amount of at least 40 atom %, preferably at least 45 atomic %, more preferably at least 50 atomic %, even more preferably at least 55 atom %, or at least 60 atomic %. Have proven very suitable are also the amount of elemental metal 65-95 atom %, or 70-90 atomic %.

According to the present invention, preferably a layer arranged on the other of the at least two layer on the PVD layers of the same metal as or different, and preferably selected from the group consisting of aluminum, magnesium, chromium, silver, copper, gold, zinc, tin, manganese, iron, cobalt, nickel, titanium, tantalum, molybdenum, mixtures thereof and alloys thereof.

Has proved that aluminum, chromium, and titanium alloy is the preferred metal.

Furthermore, preferably, one or more for the thickness of the layer of PVD 10-500nm, preferably 20-280nm. One or more of the PVD can also be the thickness of the layer of 30-170nm, more preferably 50-110nm, still more preferably 60-90nm.

In a preferred variation in the programme, in the 2, 3 or more of the PVD layer of metal effect pigments PVD under the condition, with the highest elemental metal content of the layer thickness of the layer for PVD 10-40nm, more preferably 15-35nm, and even more preferably of 20-30nm. In particular, when the thickness is 10-40nm, preferably 15-30nm time, the PVD layer absorbs incident light, the PVD metal effect pigments of the present invention show strong dark. Under these layer thickness of the, PVD layer has strong absorption performance.

Having the highest metal content if the PVD layer of the layer thickness is 40 nanometer the above, such as 50-500nm, 80-280 nanometer, or 100-170nm, the PVD layer has a stronger reflection effect.

According to the present invention is preferably elemental metal is in the form of at least part of the said cluster is taken, the cluster preferably has 1-10nm is of an average particle size. Furthermore, elemental metal the bunch has preferably 1.5-8 nanometer, preferably 2-6nm particle size.

Here, elements embedded metal clusters in successive layers of metal oxide, the element metal of the metal and the metal oxide of the same. Therefore, preferably the element having a lower element metal clusters exist in the PVD layer of metal content in the outside.

The PVD layer has only one PVD of the present invention under the condition of metal effect pigments, are present in the form of elemental metal preferably said cluster is taken and one outside embedded with metal oxide. Elemental metal having a relatively high content of outside the 2nd, said cluster is taken may also be an elemental metal form.

According to the present invention, metal effect pigments lamellar crystal PVD can be optionally modified surface of the encapsulated anti-corrosion layer.

Anti-corrosion layer can be the application does not need to be encapsulated. In particular, if the anti-corrosion layer by PVD application of the same, because there is no cover edge, encapsulated anti-corrosion layer does not exist, of the present invention to protect the edge of the PVD metal effect pigments influence to anti-corrosion, anti-corrosion layer is preferably encapsulated application. Encapsulated anti-corrosion layer can be, for example, by wet-chemical coating or the coated in a fluidized bed application.

Furthermore, the surface of the PVD metal effect pigments can have organic modified phosphoric acid and/or phosphoric acid and/or its derivatives. Furthermore, the surface of the pigment can be a vanadium compound and/or molybdenum compounds, and combinations thereof. Furthermore, the invention can be coated on the pigment organic polymer and/or metal oxide. The metal oxide preferably comprises SiO₂, boron oxide, alumina, molybdate, vanadate, and include their hydroxide and oxide hydrate or mixtures thereof.

In one particularly preferred embodiment, the preferred anti-corrosion layer contains encapsulated SiO₂ or by SiO₂ composition. Particularly preferred SiO₂ layer by the sol-gel method on encapsulated applied to effect pigments. In this case, it is preferred to use a tetra alkoxy silane, such as tetramethoxy silane or tetra ethoxy silane.

In another preferred embodiment, anti-corrosion layer of the PVD metal effect pigments of the present invention can be, for example, silane, titanate or aluminate organic chemical surface modification. The effect of organic chemical surface modification with application medium around such as paint or ink of the compatibilized binder systems. This kind of organic chemical the coating may be, for example, so that the chemical is attached to the paint or ink on the base, thereby to allow PVD metal effect pigments of the present invention the covalently attached. PVD metal effect pigments attached to the base price of a total system improves the coating medium such as ink and paint for example after solidifying anti-condensed and resistance to mechanical.

In this case, organic chemical surface modification can be if DE   10   2006   009   130   A1 discloses, by one or more organic functional silane, aluminate, titanate zirconate and/or realizing, or if DE   10   2005   037   612   A1 discloses, by at least one organic phosphorus-containing compound to achieve. DE by a reference to the   10   2006   009   130   A1 and DE   10   2005   037   612   A1 in the content of the combination herein.

In fact very advantageously, preferably contains or is made of silicon oxide of the metal oxide coating is also extensible PVD metal effect pigments in order to prevent mechanical impact on stability. Therefore, metal effect pigments PVD the mechanical stability is improved to a certain degree, the PVD metal effect pigments of the present invention can be even in order to relatively harsh mechanical stress, for example, by extrusion into such as polymer application medium, in the base material, and the like.

Therefore, PVD metal effect pigments of the present invention can also be extruded through the in the base material in the production of powder coatings, wherein the PVD metal effect pigments used is destroyed or damaged PVD metal effect pigments non-coated or coated with pure organic protective layer with much less degree the situation.

The metal oxide layer, more particularly protection of silicon oxide, aluminum oxide and/or inorganic/organic hybrid located in the layer thickness of the layer is preferably 5-60nm, more preferably 10-50nm range.

According to one preferred variation of the programme, in particular when the PVD metal effect pigments is used for powder coating, the surface of the metal oxide, preferably silicon oxide is organic chemical modification of the surface. In this case, the metal oxide surface is preferably at least one kind of organic silane-modified, it is preferably used in the still after the metal oxide surface having at least one reactive organic groups and so that the chemical is attached to the application medium, more particularly on the base material.

PVD found metal effect pigments of the present invention is preferably used for PVD metal effect pigments based on content of the total powder coating weight 0.1-20 weight %, preferably 0.2-10% by weight, more preferably 0.5-6% in the weight of the powder coating.

The invention preferably lamellar crystal PVD metal effect pigments in order to dust-free or low-dust presentation forms, for example in particulate, granular, briquetting, debris, or the small cylinder is provided in the form of tablets.

In the corresponding presentation form, preferably the value of the residual moisture content 0-15 weight %, more preferably 0.05-10 weight %, and even more preferably of 1-5 weight % of water and/or organic solvent or solvent mixture, under each kind of situation PVD metal effect pigments based on the total weight of the preparation.

In particular, the rules-compacted under the condition of particle in the shape of, the residual moisture content is positioned in a high range, such as 5-15 weight %, preferably 6-10 within the range of % by weight, in each case based on the total weight of the particles.

The shape of the rules to the commercial forms of granular, briquetting, debris, small cylindrical object or tablet under the condition of, preferably 0-10 weight %, more preferably 0.05-3% by weight, very preferably 0.1-1% of the weight of the lower residual moisture content, under each kind of situation PVD metal effect pigments based on the total weight of the preparation.

Under the condition of the water-bearing application, particularly the invention preferably PVD metal effect pigment preparation of the organic solvent in the amount of 2 weight % or less, preferably 1 weight % or less, more preferably 0.5 weight % the following in order to make the VOC and/or odor load is minimized.

According to a further preferred form of, the invention as a PVD metal effect pigments in the solvent or as a dispersion of the sticks the existence.

The invention is based on the purpose by also lamellar crystal according to any one of the PVD coating of metal effect pigments according to Claim 1-11, paint, automobile finish, powder coating, printing ink, conductive paint formulation, digital printing ink, plastic, or the use of the cosmetic formulations.

The aim of the invention is to through the provision according to claim a 1-11 lamellar crystal any one of metal effect pigments PVD coating composition.

Coating composition preferably is selected from the group consisting of paint, paint, automobile finish, powder coating, printing ink, digital printing inks, plastics and cosmetic formulation.

The aim of the invention is to through the provision according to claim with a 1-11 lamellar crystal any one of PVD or metal effect pigments according to claim 13 or 14 of the products of the coating composition.

Article may include a coating film, which is more particularly a greenhouse film, paper, cardboard, fabric, furniture, vertical component, plastic component, and the like of the car body.

The invention is based on the purpose of production further by providing a metal effect pigments lamellar crystal of the PVD method to realize, the method comprises the following steps:

(A) in a gas-phase deposition in vacuum chamber of the vacuum section by reactive physical vapor deposition (PVD) in the presence of oxygen of the linear movement of the substrate is coated with at least one metal, part of the metal and oxygen reaction to form a metal oxide, the unreacted metal and the metal oxide formed relative to the direction of movement of the linear moving substrate for asymmetric distribution of deposited on the gas-phase deposition, in order to get a PVD layer and a layer on another layer are arranged in a plurality of PVD layer,

(B) the application of one or more PVD layer is removed,

(C) will remove one or more of the PVD layer crushing,

(D) optionally one or more of the PVD layer transform component of a dispersion or paste.

According to the present invention a preferred embodiment, in step (a) in, in a vacuum chamber by a physical vapor deposition (PVD) coating the linear moving substrate presence of oxygen of at least one metal, wherein the oxygen by and relative to the direction of movement of the substrate relative to the one or a plurality of metal vapor source in quantity and/or space to introduce asymmetric distribution in the vacuum chamber, in order to get a PVD layer and a layer on another layer are arranged in a plurality of PVD layer.

According to the present invention another change of the programme, in step (a) in, device for adding oxygen through the introduction substantially in the center of at least one metal vapor source in a metal vapor, wherein in one aspect the linear moving matrix and the metal vapor source device, on the other hand and between the hydrogen to provide one or a plurality of defined vapor deposition section and form the shutter aperture of the shutter (shutter   aperture), wherein the shutter aperture with respect to the one or a plurality of metal vapor source and one or a plurality of hydrogen device is not symmetrically arranged.

According to the invention another change programme, the stated purpose is also achieved by an initial inspection method to realize unsymmertry of, said method is according to the 1st and 2nd in the outside elements produce different PVD layer of metal, the method comprises the following steps: in a pound bB and the length of the width of the vapor in the coating in a single vacuum chamber method of at least one of the oxygen supply source from the presence of at least one carburetor source VQ_A of at least one metal M_A circulation or movement of the coating, the linear moving substrate or belt, to produce in the length is Δ l_B1 matrix or belt in subparagraph 1st with the resulting transmission ratio T1 quality coverage m_MA1 (the quality of metal A 1) and m_o1 (provide metal A1 the quality of the oxygen), and then in the length is Δ l_B2 matrix or belt in subparagraph 2nd with the resulting transmission ratio T2 quality coverage m_MA2 (the quality of metal A 2) and m_O2 (provide metal A2 the quality of the oxygen), wherein on the belt, 1st and 2nd segmented non-overlapping, and wherein the T1 and T2 has mutually independent 0-95% the value of between, and 5-90% ΔT the difference, and wherein the metal M and oxygen in the circulation or movement of the quality of the substrate or tape coverage extremely constant.

Transmission ratio can determine to the conventional method.

Because this method, produced in the matrix or belt of the side by side each other are separated from each other or PVD layer, which is to be produced are respectively equivalent to the PVD of metal effect pigments are as follows and 2nd 1st example for example on the outside. Transmission ratio measurement may then be separated in the space on the lower and upper. Therefore the obtained result according to the different transmission ratio to allow a preliminary check to be produced in the PVD metal effect pigments or PVD layer or generated in the 1st or 2nd between on the asymmetry of the outside.

The above related to the present invention the corresponding metal effect pigments suitable for the observation of the method of the invention.

In the method of the invention, a portion of gasified metal and for into oxygen reaction in order to form the metal oxide. In the method of the invention, is not an essential element of the reaction of metal and oxygen and the metal forming the metal oxide is not symmetrical in the linear movement of the deposited on the substrate, in order to get the asymmetric structure of the PVD layer.

Programme change according to 1st, elemental metal and metal oxide can be asymmetrical deposition of the metal vapor and oxygen in quantity and/or space symmetrically not introduced in the PVD apparatus.

In the metal vapor and space and/or symmetrically introduced within the PVD apparatus, according to the 2nd change programme, in a linear movement of the asymmetric deposition on the substrate in a linear movement of the substrate and the metal vapor source and disposed between the hydrogen and the shutter, wherein the shutter to one or more of metal vapor source and one or a plurality of hydrogen device is not symmetrically configuration.

With the substrates are preferably linear movement, it can also take the form of a circulating belt. With can be a metal strip or by a plastic film. Under the condition of the metal bars, stainless steel, preferably of stainless steel has proved to be suitable. In the case of plastic tape, with may be, for example, from polyethylene terephthalate, other polyester or polypropylene ester form. According to one preferred embodiment, the linear moving substrate with a release coating, the promotion, or practical application of the steam to remove layer PVD or remove the.

As a release coating, can use the water-soluble salt or can be dissolved in a solvent such as acetone, the film-forming material in ethyl acetate and the like.

Is applied to a linear moving matrix, such as single metal or metal alloy of the metal, for example, a metal carburetor source, also known as the metal source through the vapor deposition application. Metal or may comprise a heating crucible to be gasified metal resistance heating small boat type carburetor. Metal gasification can also be generated by the electron beam vaporizer.

According to the method of the invention 1st change programme, relative to the linear movement of the linear moving direction of the substrate, can be used in metal vaporizer for into oxygen before and/or after.

According to the present invention a preferred embodiment, the method of the invention in the context of the programme change 1st, linear oxygen radical in after the moving direction is arranged in the metal carburetor. Therefore, first of all the linear mobile matrix directed through the metal vapor cone, then through oxygen circular cone. Because the metal vapor and the superimposed oxygen circular cone , first metal, and then increasingly and metal oxides are deposited on the substrate in a linear movement. Before the deposition on a substrate, through the metal of the metal oxide formed by the reaction of steam with oxygen. Therefore, in the method of the invention, there are reactive gasification.

The method of the invention in the programme of the change, because the metal vapor and the superimposed oxygen circular cone , linear movement of the linear moving direction of the substrate on a reduced content of an elemental metal, and metal oxide therefore includes the element in the metal cluster. Furthermore, the final substantially metal oxide and a relatively small extent of the elemental metal is deposited as a metal cluster. The resulting a (number: 1) of the element layer, PVD metal clusters asymmetric in relation to the amount of.

With regard to linear movement of the linear moving matrix, in the method of the invention in the 1st change programme, oxygen origin , of course, also can configure first, then dispose the metal vapor sources or metal vaporizer. In this embodiment, first guide linear moving substrate is passed through oxygen circular cone , then through the metal vapor cone. The superposition of the two conical, first-time deposition of the metal oxide, metal cluster increasingly include the form of the elemental metal. Finally, substantially metal, and metal oxides are deposited of the minimum degree. The resulting a (number: 1) PVD layer of the element is also in relation to the amount of the metal clusters is not symmetrical.

The invention it has been found that through the metal gasifier and oxygen origin the linear moving the substrate relative to the direction of movement of the non-symmetrical configuration, can be surprisingly provide the simplicity of the innovation with the above-mentioned performance of metal effect pigments PVD.

According to another embodiment, the method of the invention under the condition of 1st change programme, oxygen origin relative to the moving direction of the linear moving substrate before and after the metal of the gasifier, but through oxygen quantity each provided by the source is different. In this case, in the metal vapor sources provided in front of or after oxygen quantity can be bigger or smaller.

In order to the method of the invention 1st change programme of this embodiment, the element having the included in the metal oxide of the metal clusters on the two sides of this floor PVD, wherein two in the outside elements of the amount of metal clusters are different.

If in a linear moving direction, of the metal vapor sources provide oxygen origin in front of and after the metal vapor sources of oxygen compared with oxygen originlower quantity , a relatively high content of elemental metal and a relatively low level of metal oxide is first deposited, then is increasingly more elemental metal. Subsequently, the content of metal oxide, the metal oxide in the content of the elemental metal. In this way, the core is able to generate a a (number: 1) PVD layer, any of the metal oxide, which is mainly composed of elements with the different metal and a metal oxide and/or the outside of the element metal, therefore, the PVD layer is not symmetrical. Of course, can also be the reverse configuration, wherein the linear movement of the linear moving substrate, than 1st 2nd oxygen originoxygen origin a large amount of oxygen.

According to the method of the invention changes in 2nd programme, the metal vapor and unreliable for linear moving matrix symmetrically or symmetrically introduced. By configuring a symmetrically spaced apart from the metal vapor oxygen introduced into the part of the matrix and linear moving the shutter, the matrix in the moving direction of the linear moving substrate by elemental metal and the metal oxide is not symmetrically vapor coating. Preferably configuration shutter so that only about half of the metal vapor gasification cone and oxygen circular cone reaches the linear moving substrate, where it to elemental metal and deposited in the form of metal oxide.

In the 2nd change programme of the method of the invention, metal vapor cone and oxygen circular cone aperture angle of preferably set differently. According to the method of the invention such a 2nd change programme of a preferred embodiment of the, oxygen circular cone smaller than the aperture angle of the cone, the aperture angle of the metal vapor.

oxygen circular cone the aperture angle of the hydrogen can be, for example, by the geometrical shape of the device design setting. Metal vapor cone aperture angle of the same through the metal of the gasifier can be the geometrical shape of the opening of the set.

If the given hydrogen and metal vaporizer opening device for the geometric shape of the same, according to the method of the invention changes in 2nd programme, can also be through metal gasifier and a hydrogen device and linear movement of the distance difference is not symmetry. Preferably the metal of the gasifier compared to oxygen increase device from the substrate at a greater distance. Therefore, changes to the method of the invention of the programme 2nd this embodiment, the centre oxygen extremely , preferably in the center has been introduced in the form of conical metal vapors.

Surprisingly, with the metal and oxygen in the case of vapor coating procedures, the linear speed of the linear movable matrix is at most 1000m/min. According to one preferred development, the linear velocity is at least 10m/min, preferably at least 60m/min, more preferably at least 120m/min. Has proved to be very appropriate 200-950m/min, more preferably 450-850m/min, and even more preferably of 620-780m/min the linear speed of the.

Due to the need for the metal effect pigments PVD or not of the inhomogeneity of the symmetry and therefore not requiring any expensive and inconvenient in order to get the homogeneous prevention layer PVD, the method of the invention is simple in process engineering.

As oxygen origin , can use the oxygen-supplying compound and/or water-supplying compound and/or water. Used in the present invention the "oxygen" also includes an oxygen atom, such as oxygen atom of a OH group compound, or water, of course, and molecular oxygen.

According to one preferred embodiment, using molecular oxygen (O₂). According to another preferred embodiment, the use of water and/or air.

If the PVD metal effect pigments of the present invention with more than one (number: 1) PVD layer, it can be used, for example, the two or more of the PVD coating apparatus one on top of the other disposed after and provide correspondingly has two or more of the PVD layer into a linear movement of the substrate, wherein each of the asymmetric form of PVD layer as described above. A kind of optional may also there is linear mobile matrix and in the same PVD coated again in the coating equipment, wherein each of the asymmetric form of PVD layer as described above.

In this kind of situation can use different metal and/or metal oxide application 2nd, 3rd, 4th, and 5th PVD layer. Of course, various PVD layer formed of the same metal can also be used, wherein the proportion of only oxygen PVD layer by PVD layer to change, so that the element ratio of metal and metal oxide by the PVD layer changes to the PVD layer, wherein each of the asymmetric form of PVD layer as described above.

The width of the linear movement of the substrate, there may be of the two or more metal vapor sources and/or two or more oxygen origin , wherein the source is formed by the corresponding of the mid-point of the longitudinal axis of these sources is preferably arranged laterally relative to the moving direction. Therefore, metal vapor sources flush andoxygen origin each other and with the linear matrix into a right angle to the moving direction of the configuration, therefore, in a linear movement on the cross section of the substrate, the corresponding elemental metal and/or the concentration of metallic oxide is constant.

According to the present invention one preferred development, the linear moving substrate has a width of 0.1-5m, preferably 0.5-4m, more preferably 1-3m.

According to the present invention, vaporizer sources with resistance heating and/or through electron beam gasification operation.

In the vacuum chamber, preferably prevalance 10^-4 -10^-1 of the pressure.

If molecular the oxygen uses as an oxygen source, with one-half meters in the case of coating width, flow rate is preferably located 1-15slm, more preferably 2-10slm (slm: standard liters/minute) in the range of.

Conversion of relatively large metal and oxygen, the formation of a metal oxide through the metal vapor-conical or more densely populated oxygen origin configuration is realized.

According to the present invention a preferred development of the method, step (a) into a linear movement of the substrate for use in a physical vapor deposition (PVD), preferably by application of the metal layer, or a metal foil.

According to one preferred embodiment, Precoatd substrate used as the linear moving substrate.

According to one embodiment of the invention, the metallized substrate is used as a host, it is preferably on a substrate surface between the metal layer with a release coating. The system can be used, for example, is provided with a release coating and aluminum layer subsequently, a chromium layer or a titanium layer the plastic strip. The metal layer also preferably by PVD application. The metal layer having a small content of natural have corresponding metal oxide.

As an alternative, metal foil can be used as the linear moving substrate. As a metal foil, can be used, for example, using aluminum-metallized thread, it has been the commercial. In on the aluminum metallized foil , the average thickness of the aluminum is preferably located 10-50nm, more preferably 20-40nm in the range of.

In the Precoatd, metallized linear movement of the metal roof or substrate on the foil goes against , as described above may then be applied in a asymmetric PVD layer or 2, 3, 4, 5 and the like so as to obtain an asymmetric PVD layer metal effect pigments asymmetric PVD.

Step (b) in one or more of the PVD layer can be removed by making the coated substrate is passed through a linear movement of the solvent or solvent mixture. Can also be removed by exposing to the mechanical energy, in which the substrate for example by deflection rollers, as a result, removing metal film rupture and stand.

Step (c) of removing the metal film debris through the mechanical and it may be exposed, for example by stirring and/or by ultrasonic irradiation until reaching the required PVD metal effect pigments of small and large.

Optionally, then can the solvent in step (d) the separation and/or conversion, in order to get, have metal effect pigments of the present invention of the PVD dispersion or paste.

Optionally, the metal effect pigments PVD can have anti-corrosion layer. Anti-corrosion layer is preferably wet-chemical or in the fluidized bed to the envelopment of the PVD metal effect pigments. Subsequently, organic chemical surface modification can be applied to anti-corrosion protective layer. In this text, PVD metal effect pigments reference on the above observation value.

In another step, may then be the dispersion or by compacting with sticks the transformation optionally with anti-corrosion layer, a dense metal effect pigments of the presentation forms. For example, by pelletizing, granulating, the group is solid , production and/or extrusion, PVD metal effect pigments can be converted into particles, granules, lumps, tablets or a small cylindrical object.

Figure description

Figure 1 the display has a (number: 1) PVD layer multi-layer of the present invention metal effect pigments PVD the illustrative structure, wherein the top surface of the metal element in the amount of A greater than the bottom surface of the metal element in the amount of B.

Figure 2 has described source roller 1 belt type of PVD coating unit in the form of a basic structure of the apparatus, wherein the linear moving substrate (12) by the states the source roller 1 unfolded. Then means of deflection rollers (2) and (3) the matrix is guided to the winding roller (4). Transmission ratio measurement (5) and (6) and quartz oscillation measurement (7) and the deposition of a metal oxide dissolved in determining the amount of elemental metal. The shutter (9) and (10) will have a small boat type vaporizer (8) (metal vaporizer) coating unit the vapor separation with the outside world. The shutter (9) and (10) defining a vapor deposition section (16), in which the linear moving substrate by PVD vapor coating. Belt coating unit is located in a vacuum chamber (11) in.

Fig. 3 display oxygen entrance (13), metal vaporizer (8) and having a shutter aperture (18) of the shutter length L (14) and (15) of the geometric configuration. By the shutter (14) and (15) defined by the substrate shutter aperture limit of the vapor deposition. Shutter (14) and (15) in the substrate and metal vaporizer (8) and oxygen entrance (13) between. Illustrative configuration also display shutter aperture (18) of the mid-point of the length L and the gasifier oxygen entrance the horizontal distance between the mid-point of the Δ l   17.

Figure 4 configuration of the display order of the shutter aperture a plan view of the longitudinal direction, it also can be placed in the Figure 3 configuration shown, subdivided into the PVD layer and "bottom" layer A1, "intermediate" layer A2 and "top" layer A3. The width of the lower part of the shutter is then opened to the present invention, on the whole, PVD metal effect pigments PVD layer of "sequential overall level ".

Fig. 5 display oxygen entrance , metal vaporizer (8), oxygen supply apparatus (13) and the shutter asymmetric configuration (14) and (15) of the geometric configuration. The illustrative configuration also demonstrates by the shutter (14) and (15) defining the length of the diaphragm L of the shutter (18). Shutter aperture defining a matrix (12) of the vapour deposition of the 18. The horizontal distance is defined "y" metal vaporizer (8) with the mid-point of the shutter aperture (18) between the beginning of the length of the vapor coating (18) of the mid-point. In this configuration, oxygen entrance (13) metal is located directly in the gasifier 8 above the mid-point of. Therefore, in this situation the lower evaporator mid-point between the middle point of the Δ l oxygen entrance (17) to 0.

Figure 6 shows the disposition of the shutter aperture a plan view of the longitudinal direction, it also can be placed in fig. 5 in the configuration shown, subdivided into the PVD layer and "bottom" layer C3, "intermediate" layer C2 and "top" layer C1. The width of the lower part of the shutter is then opened to the present invention, on the whole, PVD metal effect pigments PVD layer of "sequential overall level ".

Fig. 7 display is directly mounted on a linear moving substrate (12) on the width of two or more of a plurality of gasifier sources of illustrative configuration. oxygen entrance (13) are arranged in parallel through the bore of tube display. Discharged oxygen by hole , shown by an arrow, such as small. Illustrative configuration also display by the shutter (9) and (10) length of the diaphragm to limit L of the shutter (18). The shutter (9) and (10) of the vapour deposition of the defined matrix. Metal vaporizer and oxygen supply apparatus (13) for the horizontal distance between Δ l (17) expressed.

Figure 8 diagrammatically shows two rotary crucible gasifier 8. The rotary crucible gasifier (8) by the electron beam in the linear spectrum generated on gasification material, and the vaporous material therefore gasification. A linear movement of the substrate with respect to the rotary crucible gasifier (8) of the front and rear tube oxygen supply (13) in the hole in the then enters into the vacuum chamber discharges the oxygen , wherein the different symbol length the arrow of the different levels of air flow. Illustrative configuration also display by the shutter (9) and (10) defining the aperture of the shutter (18) liter the length of the The shutter (9) and (10) of the vapour deposition of the defined matrix. Rotary crucible gasifier (8) with the mid-point of the shutter aperture (18) the oxygen entrance (13) the mid-point of the horizontal distance between each case by Δ l (17) expressed.

Fig. 9 display from the embodiment 1a TEM PVD layer of the Image. Dematiaceous plaque is a metal cluster.

Figure 10 the display from the embodiment 1a of the PVD layer 9 related electronic diffractogram like. Diffraction reflection in a concentric ring arrangement. The zero-order reflection become blank. Concentric rings display from Figure 9 black plaque is a metal cluster.

Fig. 11 is displayed in the form of a from the embodiment of the invention 1a, 1b, 4a and 4c PVD layer of metal clusters in the size distribution. The cumulative frequency with respect to the cluster size.

Figure 12 the display from the embodiment of the invention 1a, 1b and 1c of the aluminum oxide layer electronic diffraction reflection of the intensity distribution. The reciprocal lattice distance relative to the emission intensity.

Figure 13 the embodiment of the invention from 4a, 4b and 4c of the chromium oxide electronic diffraction reflection of the intensity distribution. The reciprocal lattice distance relative to the emission intensity.

Figure 14a, 15a, 16a, 17a, 18a, 19a and 20a display each case by sputtering XPS/ESCA curve determination, for the embodiment of the invention 1-6 and comparative example 8, element carbon (C), oxygen (O) of the concentration distribution, the total concentration of the Cr (tot) and Al (tot), and the associated elemental metal Al (0) and Cr (0) of the concentration distribution.

Figure 14b, 15b, 16b, 17b, 18b, 19b and 20b display each case on the layer thickness of the element in atomic % that the ratio of the metal and the metal oxide, oxygen not these respectively corresponding to part of Figure 14a, 15a, 16a, 17a, 18a and 19a.

Figure 21 display for the embodiment of the invention and comparison example, a^*, b^* colorimetric in the plane of the CIELAB data.

Embodiment

In the below, described reference embodiment of the present invention the production of PVD metal effect pigments, but not to impose any restriction of this invention.

Part A: and on the comparative example of the prior art 1-8 compared with, reference the embodiment of the invention 1-10 PVD production of metal effect pigments of the present invention.

Part B: measuring TEM-based (transmission light, diffraction), embodiment 1 and 1a, 1b and 1c, and embodiment 4 and 4a, 4b and 4c of the invention metal effect pigments PVD is characterized in the structure.

C part: measuring EDX-based, the invention is characterized in the structure of the pigment.

Part D: based on the embodiment of the invention 1, 2 and 3 (Al-based) and the embodiment of the invention 4, 5 and 6 (Cr-based), B A from the top surface to the bottom surface of the layer thickness and/or metal on oxygen the curve characteristic. Compared with the prior art based on the comparison example 8 a, corresponding to the same DE   10   2007   007   908   A1 embodiment 1.

E part: of the embodiment of the invention from the PVD metal effect pigments of the present invention, with respect to the from the comparison example 1-8 of metal effect pigments PVD (no gradient having a very uniform of metal effect pigments PVD) colorimetric assessment.

Part A: according to the embodiment of the invention 1-10 PVD production of metal effect pigments of the present invention

Step 1 : coating of the carrier film

According to the embodiment of the invention 1-10 PVD metal effect pigments of the general production for each kind of situation according to the schematic 2, 7 and 8 with unit different PVD.

The thickness of the coated with the release coating 23 the polyethylene terephthalate of   m (Peru Time) film is used as a substrate. Release coating by the acetone soluble methyl methacrylate resin and usually pre-in the independent application in the working steps.

Gasification technology is used for electron beam gasification technology or resistance heating gasification technology.

Furthermore, single-section and the two sections there are differences between the coating method.

Single-stage method describes a single coating step production according to the embodiment of the invention the metal effect pigments PVD.

For describing two sections of the method for two consecutive independent coating step production according to the embodiment of the invention the metal effect pigments PVD.

Vapor PVD metal layer the application of the layer thickness of the quality of the coverage of the monitoring. The coverage of a substrate, the quality of the distance between the metal of the gasifier, the length of the shutter aperture L, substrate tape speed and the corresponding gasifying rate determination.

Embodiment through the required flow of gas from MKS, Munich, German Corporation gas flow adjuster provided (mass flow controller). Oxygen supply device position each case diagrammatically shown in Figure 3, 5, 7 and 8 in.

For the embodiment of the invention 1-3, usually using oscillating quartz testing quality coverage. In the embodiment of the invention 4-6 and comparative example under the condition of, the coverage from the film quality after determining by weighing removed.

Steps 2 : is separated from the carrier film and

After the physical vapor deposition, according to a corresponding embodiment, each of the carrier film PVD layer or PVD layer stack by solvent from the release coating on a substrate, is removed. In the resulting suspension, for the release coating solvent and removing the residue of the PVD layer or PVD layer stack separation, and washing, crushing tool to subsequently use PVD layer or PVD layer stack crushing to the desired particle size.

E according to the procedures as described in part, in the preparation of color master batch colorimetric assessment of the embodiment of the invention and comparative example.

The embodiment of the invention 1-10 to the corresponding method for the parameter record in table 1a in.

According to the comparison example 1-8 production of metal effect pigments PVD process parameters are recorded in table 1b in.

In the comparison example * 1-8 does not exist in other oxygen supply device. Operation than the embodiment of the invention in significantly more weak under vacuum to the chamber. Chamber remaining oxygen in order to produce a sufficiently high content of reactive gasification, in other words by the presence of oxygen and gasification elemental metal to form a metal oxide.

Comparison example 1-8 of metal effect pigments can be only PVD 0.5m/min low speed of production.

By contrast, according to the embodiment of the invention producing PVD under the condition of metal effect pigments, a sufficiently high speed, is located in 4-60m/min range.

According to the embodiment of the invention 1, 3, 4 and 6 the PVD layer production single stage belt law :

The elaboration of single-stage gasification method according to the embodiment of the invention the metal effect pigments PVD of a PVD layer of the asymmetric structure, the procedure is as follows:

In order to be able to display according to the embodiment of the invention 1 and 4 of the structure of the PVD layer, coating with a metal the gasifier, oxygen supply device and the shutter configuration of the configuration of the equipment to PVD, in embodiment 1, as shown in Figure 3 in illustrative display, for the implementation of example 4, as shown in Figure 5 in illustrative display.

PVD layer thickness of the layer is divided into each section or slice through the vapor phase deposition of the substrate shutter aperture configuration of the longitudinal direction, as shown in Figure 4 and as shown in Figure 3 with configuration, and as shown in Figure 6 and as shown in Figure 5 disposed binding. In the schematic 4 and 6 in, for embodiment 1, layer section A2 (the embodiment of the invention 1a), A1 (embodiment of this invention, 1b) and A3 (the embodiment of the invention 1c), and in embodiment 4, layers of section C2 (embodiment of this invention, 4a), C3 (embodiment of this invention, 4b) and C1 (the embodiment of the invention 4c) shown in each case in plan view.

Therefore, schematic 4 shown in the floorplan display for the embodiment 1, the following coating sequence mechanism: on with the direction A1, then A2, and A3.

Embodiment 1a: from the embodiment 1 of the 2nd layer layer A2

Embodiment 1b: from the embodiment 1 of the 1st layer layer of A1

Embodiment 1c: from embodiment 1 3rd layer section layer A3

Section (in table 1a is called in) by the oxygen content of the A1 to A2 to A3 improved. This is vapor deposition section of the shutter aperture with respect to the oxygen supply device and the metal of the gasifier a result of the asymmetric configuration, as shown in Figure 3. Subsequent off-line transmission ratio measurement has been proved that this result.

In section A1 under the condition of, measured 32% transmittance; in the layer section A2 under the condition of, 46% of the transmission ratio; in the layer section A3 under the condition of, 86% of the transmission ratio. The greater the transmission ratio, the transparent metal oxide content of the large.

Therefore, schematically 5 shown in the floorplan display for the embodiment 4, the following coating sequence mechanism: on the belt direction, C3, then C2, then C1.

Embodiment 4a: from embodiment 4 2nd layer of layer C2

Embodiment 4b: from the embodiment 4 of the 1st layer layer C3

Embodiment 4c: from embodiment 4 3rd layer of layer C1

Section (in table 1a is called in) by the oxygen content in the C1 to C2 to C3 improve. This is the shutter aperture and gas phase deposition section relative to the oxygen supply device and the metal of the gasifier a result of the asymmetric configuration, as shown in Figure 5. Subsequent off-line transmission ratio measurement has been proved that this result.

In section C1 under the condition of, measured 54% transmittance; section of the layer C2 under the condition of, 77% transmittance; section of the layer C3 under the condition of, 92% transmittance. The greater the transmission ratio, the transparent metal oxide content of the large.

In the embodiment of the invention 3 under the condition of, the use of as shown in Figure 7 illustrative display of the PVD metal gasifier and the configuration. In the embodiment of the invention 6 in, the use of as shown in Figure 8 illustrative display of the PVD metal gasifier and the configuration. As these PVD configuration, the use of each kind of situation with the advancing direction of the substrate the other vaporizer sources horizontally, in order to realize the deposition of the coating are of the width of the film in Peru Time (approximately 50 centimeter coating width) on.

In the embodiment of the invention 2, 5, 7, 8, 9 and 10 through the two sections in the PVD layer production belt law :

The XPS analysis shows EDAX and method for single-stage and two-stage belt law two PVD layer between the changes, as through the two-section belt law according to embodiment 2 and 5 production PVD layer.

The production according to the embodiment of the invention 2 the PVD metal effect pigments of the present invention, first of all according to fig. 4 the plan view of the cover used for producing the section A2 and A3 of the shutter aperture, layer section A1 (example 2a) produced by vapor phase deposition of aluminum. In this case, the gas is not provided, in order to produce the metal layer. After the the first-coated substrate, with the substrate wound, and open the shutter aperture in order to produce the section A2 and A3, but cover section A1 of the shutter aperture. Then according to the table 1a the method parameter the 2nd layer 2b with oxygen vapor supply of the application, in order to produce the comprises a PVD metal layer and the metal oxide coating of PVD PVD layer structure.

The production according to the embodiment of the invention 5 PVD of metal effect pigments of the present invention, first of all according to fig. 6 in plan view of the cover used for producing the section C2 and C3 of the shutter aperture, of containing layer C1 embodiment 5a. In this case, the gas is not provided, in order to produce the metal layer. After the the first-coated substrate, with the substrate wound, and open the shutter aperture in order to produce the-containing layer section C2 and C3 embodiment 5b, but covering the produce section C1 of the shutter aperture. Then according to the table 1a the method parameter the 2nd layer 5b of the supply with oxygen more oxidation application.

In order to produce the embodiment of the invention 7, choose to be correspondent to Figure 7 the illustrative configuration in PVD configuration. With the embodiment of the invention 3 on the contrary, each of the oxygen supply device along each of the resistance heating boat gasifier (metal vaporizer) very close configuration.

As the oxygen supply device configuration result, produce very rich in oxide of aluminum layer PVD (example 7b). In 2nd coating step, according to fig. 2 has no oxygen supply device to use resistance heating PVD gasification method of the aluminum oxide-rich for very 2nd PVD of metal aluminum layer, embodiment 7b coating.

The elaboration of the layer thickness of the metal colored the independence of the aluminum, producing the embodiment of the invention 8, 9 and 10.

In this case, according to fig. 2 by electron beam evaporation method to produce three aluminum-based coating. By changing the belt speed, produces three the aluminum layer having different layer thickness, according to 8a, 9a and 10a. At the end of the coating, the coating with the substrate wound, subsequent oxidation under each kind of situation Cr layer (embodiment 8b, 9b and 10b) are coated, in the embodiment 8, 9 and 10 in the three under the condition of having different thickness of a large scale Al layer on the blue coloring.

Therefore, as the effect of the individual embodiment the gold is brown 8b, 9b and 10b of the Cr layer in each case generated on the aluminum layer the same as the thickness of the blue coloring. The advantages of this is critical, that is, under the condition of the effect pigments, coloring only depends on the metal chromium/chromium oxide layer thickness. Therefore, with two of them contribute to the color effect of the layer thickness compared with the effect pigments, fully improve the tone reproducibility is possible.

Part B: through TEM (electron diffraction, transmission) to clarify the structure of the pigment of the invention

The present invention is analyzed the structure of the PVD a metal effect pigments, through the transmission electron microscope studies (TEM) lifts PVD metal effect pigments. The instrument used is a Zeiss   922   Omega (from Zeiss). It is equipped with Ultrascan   1000 (from Gatan)   CCD detector. The imaging medium for the electron beam, illuminate at very uniform and the same PVD metal effect pigments in parallel and their section. Accelerating voltage for 200kV. Electronic in the sample in order to non-uniformity of the crystal lattice structure and to proliferation of diffraction. After the to disengage, electronic through the electronic optical system focusing in the intermediate Image plane, in the after another amplification stage, through electronic CCD camera imaging. Lighting layer obtained in this way the true drawing. Figure 9 such as the display from the embodiment of the invention 1a TEM of a layer of the Image.

In addition to. the outer, electronic diffractogram like of the sample is also provided important information on the nature of the layer. Diffraction Image of the intermediate Image plane is not, and is amplified by the diffraction plane imaging. From the diffraction of the reflected intensity and position, on of the pigment may be made clearly the internal structure of a structural state. Figure 10 such as the display from the embodiment 1a of a layer of electronic diffractogram like.

In the embodiment of the invention 1a, 1b, 1c and 4a, 4b and 4c of the present invention in the PVD metal effect pigments, the real Image and electronic diffractogram like TEM recording. Found that material is not uniform, but basic by a minute metal clusters the oxidation matrix embedded therein (see Figure 9 the black plaque in). In accordance with the embodiment of the invention in all PVD metal effect pigments, the size can be detected a number of nanometers of metal cluster. For more accurately determining the size of the metal clusters, in according to the embodiment of the invention 1a, 1b, 4a and 4c under the condition of, based on each case about 100 metal clusters, the diameter of the measuring their, generated by these measurement value of the statistical size analysis (fig. 11). Sample 1c and 4b of the size of the small bunch so that they can not be determined with sufficient accuracy. Assessment of the display when the oxide content, the size of the metal clusters, rather than reduce the amount of them. The average size of the metal clusters 5 nanometer the following, the overall aluminum bunchchromium bunch slightly greater size.

Recording embodiment 1a, 1b, 1c, 4a, 4b and 4c of the pigment of electronic diffractogram like. CCD camera of the Image as the result of the presence in electronic form, may be reflected not only the position of the evaluation, the evaluation of their intensity distribution. On the basis of their position and intensity distribution, respectively, are found in the metal aluminum and chromium on just fit fire diffraction maximum value. Therefore, reliable evidence of the existence of these metal clusters. For all sample, reflection significantly widened. This display of the metal crystallites diffraction is only a few nanometer size. At the same time, can be recognized that when the oxide content rises, the reflection intensity is reduced, and the approximate stoichiometric oxide content becomes very small under the condition of. This with this kind of situation no longer exists any active metal of this fact the same. Reflective disperse acyclic, interfere with other has been found. In particular, with the metal oxide does not exist the various crystal modified fitting of the line. However, the presence of continuous wide maximum of the intensity of the background. This is the typical intensity distribution of an amorphous solid. Therefore, these layers can be displayed in the presence of the oxide in an amorphous form.

Therefore, the embodiment of the invention 1a, 1b, 1c, 4a, 4b and 4c having embedded therein a layer is formed of the basic metal clusters nanometer size amorphous metal oxide. When the oxide content rises, the average size of these bunches drop, is usually 5 nanometer the following.

C part: by SEM and EDX characterization

Measured by EDX measuring analysis oxygen :

According to the embodiment of the invention 1a, 1b, 1c, 4a, 4b and 4c oxygen and of a layer of metal using the above-mentioned measuring method by EDX (instrument:   Gemini EDAX;   Incorp from the EDEX. , The United States) measurement.

Sample preparation:

Dispersed in the solvent in the layer and crushing. The few drops of dispersion applied to the sample plate, the solvent is slowly evaporated at room temperature. Layer substantially parallel to the orientation of the surface of the connecting plate.

Measurement:

The embodiment of the invention for determining the level oxygen the average atomic ratio of the metal.

To this end, first of all a scanning electron microscope to find wherein at least 4-5 independent of the area of the mutual superposition PVD layer. On measurement at these positions. The aluminum/alumina layer in order to measure, select 5kV the accelerating voltage; the chromium/chromium oxide, operation 8kV voltage. This effectively averages to ensure that, at the same time total is stimulated of two or more multi-layer, wherein the different measuring substrate background. Excitation regarding oxygen , in the K-line (excitation can be: about 0.5keV), the chromium, in the K-line (excitation can be: about 5.4keV), for the aluminum, in the K-line (excitation can be: about 1.5keV) carried out under the condition of. The excited X-ray spectrum is subjected to measurement, the content of oxygen and metal by means of the software program to determine the peak height ratio.

On embodiment 7-10 and comparative example 1-8 physical data report in table 2a and 2b in.

Table 2a:on the embodiment of the invention 7-10 and the oxygen content of the layer thickness of the physical data

Table 2b:on the present invention is relatively example 1-8 and the oxygen content of the layer thickness of the physical data

Part D : (XPS/ESCA) and sputtering through the photoelectron spectrum characterization curve measurement of the

Structural characterization to a more accurate, of the present invention through the ESCA analysis 1-6 and comparative example 8 the coating film. In order to better analyze the composition of the inner layer, so that they each case subjected to a continuous sputtering (Ar⁺ ion) and re-measurement. Here, measurement on feed under each kind of situation, metal (Al or Cr), nitrogen and carbon. Measuring ESALAB VG   Scientific from the use of the   250 instrument. Using monochromatic excitation   KαX-ray radiation Al (exciting voltage: 15kV ; power: 150W ; spot size: the 500  m). The transmission function of the instrument on the copper sample. Charge compensation with 6eV/0 . 05mA beam current of the electron energy to "electron gun pan-shoots the type ". The set level in order to assess in such a manner that: the carbon main 285eV lower.

First of all, to 80eV passes energy record of the total spectrum. From these in the spectrum, the use of the so-called Scofield Factors to quantitative determination of atomic % more than that of a surface of four elements, measuring the error is about 10%. Assessment is based on the assumption that all: analysis of volume is inherent. Photoelectron spectroscopy depth of the information is usually 5-10nm sensitive method for the surface of the.

Subsequently, using 30eV passes energy of, recording each elemental high resolution spectrum. In particular in the case of metal spectrum, to different this distinction between metal oxidation state. The aluminum sample (embodiment 1-3) under the condition of, each case quantitatively measuring element (metal) the content of aluminum and Al (III). The chromium sample (embodiment 4-6, comparative example 8) under the condition of, on the one hand elements from chromium, Cr (III) oxidation state and, and Cr (VI) Cr (IV). The standardization of the known technical adjustment and more of the partially overlapping spectrum. The possessive sample, the presence of the detectable not the measurable content of chromium (VI).

According to the manufacturers instructions, through sputtering, PVD determining corresponding to the thickness of the layer of metal effect pigments. Under each kind of situation of that of the standard is a metal such as aluminum or chromium or their oxide. Certain system error can be obtained, that is, the sputtering removal performance according to their, the PVD layer does not necessarily have a standard nature of the material.

For the embodiment of the invention 1-6 and comparative example 8 in the steam is applied to the carrier film on the PVD layer, the layer thickness of the sputter rate measuring on oxygen , metal and carbon content of the concentration curve is shown in Figure 14a, 15a, 16a, 17a, 18a, 19a and 20a in. If sputtering through the steam application coating, from the carbon content of the surface of the pollution or matrix film. Because it is always lower than 2 atomic % and does not have any gradient, the concentration of the nitrogen not displayed.

On the one hand, the metal concentration, has been reported in atomic % of the total metal content. From the high-resolution spectral assessment of view, the content of the measuring element metal, expressed as the same of another parameter in the Figure. The concentration of the shown here each case relates to the measured feed of, metal, carbon and nitrogen and of the concentrations of.

Table 3 display in the layer thickness of the results of the evaluation on the curve. The following more detailed explanation of these results.

All chart share initially (before the sputtering) on carbon signal of a certain value. The signal from the organic material pollution to the surface of the pigment, the importance of and has no analysis. From the 1st initial area, it is clear that there is always the same the oxygen content of the relatively high, and the corresponding relatively low metal content. The discovery is attributable to the metal oxide layer is naturally formed. In the subsequent assessment without further consider these values, in particular in in considering the concentration gradient.

As the material, within the PVD metal effect pigments, carbon signal is very small (<1 atom %), suddenly very strongly in this previous growth. Here, the steam application of the metal/metal oxide layer through sputtering erosion, and accordingly, the measurement detection of the polymer film. Carbon-based signal corresponding to the rising and the falling of the metal signal, in particular, can be based on the best to determine the intersection of the line thickness total level (such as the display in Figure 14a in). These the value draws Yu Biao 3 in. Here again measurement REM is given by the value of the pigment layer thickness. Because the reflected electron microscope measurement display (REM) the relatively high accuracy, determine the correction factor. In table 3 the analysis involved in PVD coating film of each layer of the layer thickness and/or the concentration gradient always relates to all other details of the correction value by the factor. Therefore, will always through the sputtering rate to the standardization of the measuring layer thickness measuring REM of those.

Furthermore, in the PVD layer determining the average of the oxygen. This method on the one hand, by EDX, the method also been described for DE   10   2007   007   908   A1 in. On the other hand, an average of the ESCA data. Two display the value of the relatively good and consistent 40-46 within the range of atomic %.

Also each PVD layer or PVD layer stack structure. The parameter for the first oxygen concentration of the concentration curve, the second curve is the concentration of the elemental metal. Figure 14 and 15 such as a display with different gradient through each region between the best-fit line. Based on this point, with different gradient of the section of each region can be the best to be the best and line to the intersection of the slope of the line, to determine the concentration gradient.

For certain PVD layer or PVD layer stack, a large number of possible explanations exist. For example, the embodiment of the invention 1 the single-layer of oxygen concentration in the PVD layer has a continuous very linear gradient, or three slightly different gradient. Has adopted a table 3 in the corresponding on two kinds of explanation. The small difference in the gradient, the interpretation of a single gradient in the form of the fitting of the display the maximum. According to the embodiment of the invention 2 and 5 of the two layer structure of the PVD metal effect pigments are respectively in Figure 15a and 18a is easy to pass through the element metal in (are respectively Al (0) and Cr (0)) the amount of the (improve) the slope of the significant change and the layer thickness of the oxygen (O) (reducing) the amount of the slope of the that significantly change.

In according to the embodiment of the invention 4 and 6 in the PVD layer, the explanation of each of the three gradient.

According to the steam intaking the highest metric is all gradient slope each case marked in bold in table 3 in; the gradient of the elemental metal, under each kind of situation the only record.

Through the two-stage process of preparing the embodiment of the invention 2 and 5 PVD layer contains the PVD metal layer. In Figure 15 and 18 in, can be seen a sharp increase of the concentration of elemental metal. However, this value will not rise to 100%, and still obviously always exists in the residual oxygen content.

Comparison example 8 corresponding to the DE   10   2007   007   908   A1 embodiment 1 (fig. 20), with the basic constant oxygen concentration and elemental metal (Cr (0)) concentration of large layer thickness within the range. The end of the only in the PVD layer, in about 110-120nm under the layer thickness, with the parallel signal C therefore in order to achieve improved and the tail end of the pigment, the value slightly increased, this is why metal concentration of the artificial factors representative of such an increase.

For the sake of completeness, also assessed the arrow end region and determining the resulting artificial slight oxygen concentration gradient. Therefore, the PVD layer to have the constant oxygen concentration, such as DE   10   2007   007   908   A1 stated.

From table 3 that the according to the embodiment of the invention one or more of the PVD layer (metal effect pigments PVD) under the condition of, the maximum oxygen concentration gradient is always higher than comparative example 8 the situation.

The above-mentioned through TEM measuring and displaying the elemental metal is embedded with metal oxide matrix in the form of small nanoparticles. The PVD the optical performance of the metal effect pigments, metal effect pigments PVD these metal nano particles in particular key of the asymmetric concentration distribution.

In addition the gradient slope, in the PVD layer to determine the maximum and the minimum concentration of these concentrations and different ΔCM (0) (centimeter (0): elemental metal concentration). In particular in the maximum concentration centimeter (0) and in case of under the condition of the difference, with respect to the according to the comparison example 8 the PVD layer, in accordance with the significant difference of the embodiment of the invention is obvious in the PVD layer.

According to the embodiment of the invention of uniform compared to extremely layer is PVD according to the comparison example 8 PVD layer of actual higher maximum concentration centimeter (0) and actual higher concentration difference ΔCM (0). According to the comparison example of the 8 PVD layer of, artificial concentration difference ΔCM (0) to 5 atom % (see table 3).

And according to the prior art a very uniform structure compared with PVD metal effect pigments, metal effect pigments of the present invention by PVD greater layer thickness the concentration difference, PVD metal effect pigments of the present invention the difference between the outside the ΔCM (0) is at least 10 atomic %, preferably at least 15 atom %, more preferably at least 20 atomic % (see table 3).

According to the present invention, in the PVD layer, whether there is one or more associated with elemental metal concentration gradient is not critical. However, the key is the layer thickness of the whole PVD whether there is a concentration gradient of the elemental metal. There may be in the middle having a constant concentration or even minor paragraph which reduces the concentration. Part E: according to the embodiment of the invention of the PVD layer with respect to the according to the comparison example (having a very homogeneous and does not have the element metal gradient embodiments) colorimetric assessment of the PVD layer

The following statements according to the present invention embodiment and according to the comparison example of the PVD metal effect pigments of colorimetric nature.

Therefore, through the stirred 2g conventional nitro-cellulose varnish (Dr.Renger   Bronzemischlack 2615e   Erco; from Morton) incorporated in the metal effect pigments PVD. PVD metal effect pigments introduce, in brush then dispersed in the varnish.

The use of scraper blows the type device will complete varnish in order to 50 the thickness of wet film   m of from # 2853 to Byk Gardner test (black/white according to the paper) is.

Selection of coloring level (PVD the amount of metal effect pigments) in order to get the hidden layer. Therefore, the effect of the substrate does not form a part of the colorimetric data.

According to the manufacturers instructions (Optronic   Multiflash   instrument, Berlin, Germany), the scraper blows the type subjected to colorimetric. Illuminated in order to carry on the 45° chang Jia , CIELAB   L^*, a^* and b^* value of the angle with respect to the mirror surface 15 °, 20 °, 25 °, 45 °, 55 °, 70 °, 75° and 110° observation angle measuring (light source: D65).

Table 4a and 4b are summarized according to the embodiment of the invention 1-10 and according to the comparison example 1-8 PVD metal effect of the pigment of the colorimetric data.

Table 4a: scraper sweep of the embodiment of the invention metal effect pigments PVD the colorimetric data

Table 4b: scraper is provided of the example of the PVD metal effect pigments colorimetric data

According to the luminance with angle heterochromic, the embodiment of the invention and a comparison example of the PVD metal effect pigments of colorimetric performance is fully comparable. However, PVD metal effect pigments of the present invention display the grey metal is strong. However, this characteristic has interesting not so far can be obtained in the prior art of a very high luminance with angle heterochromic.

PVD according to the comparison example of the metallic effect pigment on the contrary, all PVD metal effect pigments of the present invention to fully higher tape speed and a considerable greater reproducibility production. Because the metal effect pigments in order to be able to represent a large and with good production of a product reproducibility, the invention presents the obvious economic progress. Furthermore, it can provide grey and light metal effect pigments PVD, some of them are so far not possible.

Figure 21 display in CIELAB   a^*, b^* in said method, PVD metal effect pigments of the present invention and from the comparative example of the PVD metal effect pigments of the color display.

In Figure 21 in, it is clear that according to the embodiment of the invention 8, 9 and 10 of the present invention metal effect pigments PVD regardless of their specific, the total layer thickness of the color in the same position. For their respective has only a layer having a very homogeneous composition of a layer of metal PVD according to the comparison example of the effect pigment, the change of the layer thickness of the entire color space through-igur 21.

According to the embodiment of the invention 8 PVD metal effect pigments of the comparison example 8 comparison of metal effect pigments PVD display color position approximately the same, the difference lies in the embodiment of the invention 8 of the PVD metal effect pigments than thickness total level according to the comparison example 8 low PVD metal effect pigments of 45 nanometer.

PVD metal effect pigments of the present invention the advantages of

PVD metal effect pigments of the present invention usually has surprising advantages as follows:

Can use cheap coating and/or of the single-side or double-side coated metallized sheet, for example aluminum foil, it is preferably in metal level like aluminum level with the matrix, preferably of between the form of polymeric film having a release coating.

On the top of the the metal level like aluminum level , can then be coated with, for example, a layer for PVD application characteristic operation according to the present invention metal gradient of the elements of another metal/metal oxide layer. On the top of the aluminum layer, for example, may exist, or has been applied in a layer of the chromium oxide with asymmetric element chromium of the chromium layer structure.

The designated only use on the aluminum foil 60 nanometer chromium/chromium oxide, productivity to two times; the material cost of the Cr is reduced by half. These can make the double-coating method for belt law cheaper than that of a single coating, which need to be 130 nanometer having a very uniform layer thickness of a Cr oxide.

Generating another process engineering advantages of use of metal/metal oxide, such as chromium/chromium oxide coating on the sheet, for example, during operation of the heat load is low, this is because the coating operation since the tape speed increasing and to reduce the heat load. Under the condition of the double speed, for example, or on half the thermal load on the substrate.

Of course, this advantage is not limited to chromium/chromium oxide of aluminum foil and the special combined. Therefore, generally speaking, the substrate has been coated with metal, preferably plastic strip, can subsequently through PVD the Precoatd substrate is not symmetrical for metal oxide and elemental metal in the PVD layer of a coating.

Because of having more metallic 1st and 2nd more rich oxide asymmetric structure of the outside, in a application is in particular the required grey within the range of the tone more cautious, wherein the statistically 50% more metallic the outside of a PVD metal effect pigments and 50% rich oxide of a PVD metal effect pigments the outside of the eyes of the observer, in spite of this, these tone has a dark color/dark along with angle. Asymmetric PVD metal effect pigments because of this the concrete distribution, to be embedded metal oxide in any of the elements of the color of the metal clusters undulating phenomenon due to the asymmetry of the PVD metal effect pigments is compensation or weaken, wherein some of the pigment having symmetrical PVD is not possible.

The PVD metal effect pigments of the present invention the more metallic the outside, they have significant than the material of the covered force, per unit weight of the pigment is high matrix misprision of horizontal.

The method of the invention can be very advantageously drunkard procedure of advancing, application of one or a plurality of asymmetric PVD layer of the monitoring can be very effectively achieved by a reflection coefficient measurement. Since the optically active asymmetric PVD layer of the pole does not depend on metal PVD layer 2nd layer thickness, even when the production of two layers of PVD metal effect pigments of this is possible.

In the aqueous coating applications, for example, and compared with the traditional PVD metal effect pigments, metal effect pigments of the present invention can be not only PVD at a relatively high-level thickness production, and the quality of on greater, display a better the nature of the application.