Patent Grant
11299636
The present application is a 35 U.S.C. § 371 National Phase conversion of PCT/EP2008/009993, filed Nov. 25, 2008, which claims benefit of European Application No. 08003114.9, filed Feb. 20, 2008, the disclosure of which is incorporated herein by reference. The PCT International Application was published in the German language.
The present invention relates to new effect pigments which are based on artificial substrates and which feature improved optical properties.
The present invention further relates to a new process for producing these effect pigments and also to their use in cosmetics, paints, printing inks, varnishes, powder coating materials, and plastics.
The optical effect of effect pigments is based on the directed reflection of light at predominantly planar, light-refracting pigment particles which are aligned substantially parallel to one another. These pigments particles generally have a substantially transparent substrate and one or more coatings on the substrate. Depending on the composition of the coating(s) of the pigment particles, interference, reflection, and absorption phenomena produce perceptions of color and lightness. Irregularities in the substrate surface to be coated, or colored impurities in the substrate, can lead to unwanted scattered-light effects or instances of unclean color in the end product. These unwanted scattered-light effects and/or color impurities occur particularly when natural substrate materials are used, such as natural mica. In circumventing the aforementioned drawbacks, artificial substrates afford new opportunities for high-quality pigments with new color and luster effects.
U.S. Pat. No. 3,331,699 A describes pearlescent pigments based on glass flakes with interference colors and an intense sparkle effect. The glass flakes are coated with a translucent metal oxide layer of high index. The color of the pigments is dependent on the selected metal oxide and on the thickness of the metal oxide layer.
The metal-coated glass flakes coated to counter corrosive effects with an additional protective layer of metal oxides such as SiO2, Al2O3 or TiO2 are described in U.S. Pat. No. 5,436,077 A. These coated glass flakes are comparable in terms of their appearance with metal foils.
Glass flakes coated with titanium oxides and/or iron oxides are known from U.S. Pat. No. 6,045,914 A. The average particle size of the glass flakes is situated in a range from approximately 1 to 250 μm, the thickness being around 0.1 to 10 μm.
WO 2004/055119 A1 describes interference pigments which are based on coated platelet-shaped substrates. The substrates in this case are covered with a first layer of SiO2 to which is applied subsequently a high-index layer consisting, for example, of TiO2, ZrO2, SnO2, Cr2O3, Fe2O3 or Fe3O4, or an interference system comprising alternating high-index and low-index layers. Optionally the pigments may further have an outer protective layer.
Thermally and mechanically stable, metal oxide-coated effect pigments based on thin glass flakes with a thickness≤1.0 μm are known from WO 2002/090448 A2.
The optical properties of effect pigments can be influenced, in accordance with WO 2006/110359 A2, by an appropriate particle size distribution. The classified, metal oxide-coated glass flakes described therein have a D10 of at least 9.5 μm, preferably of 9.5 μm. A drawback is that the pigments have to have a size range with a D90 value of not more than 85 μm, preferably of about 45 μm. Consequently, in accordance with the teaching of WO 2006/110359 A2, only small-particle effect pigments with enhanced sparkle effect can be provided.
Performance drawbacks, such as the clogging of filters, for example, can be prevented in accordance with the teaching of WO 2007/114442 A1 by an appropriate particle size distribution, in which the D10 is between 4.7 and 25 μm and the ratio of D90 to D10 is between 2 and 3.
A drawback of the effect pigments known to date in the prior art is that their color purity is low. Hence a viewer viewing a plurality of effect pigments from one batch under a light microscope will see effect pigments having a variety of colors—that is, colors which are different from one another.
It is an object of the present invention to provide new effect pigments having improved optical properties, more particularly having a color purity which is increased relative to the prior art, at a constant angle of light incidence and angle of viewing. It is a further object of the invention to provide a process for producing these effect pigments.
This object has been achieved by a provision of effect pigments comprising artificial platelet-shaped substrates which have at least one optically active coating, where the effect pigments have a volume-averaged cumulative undersize distribution curve with the characteristic numbers D10, D50 and D90, said cumulative undersize distribution curve having a span ΔD of 0.7-1.4, and the span ΔD being calculated in accordance with formula (I):
ΔD=(D90−D10)/D50 (I),
and the average thickness of the artificial platelet-shaped substrates being 500 nm to 2000 nm.
Preferred developments are specified in dependent claims 2 to 10.
The object has further been achieved through the provision of a process for producing the effect pigments of the invention, comprising the following steps:
a) size-classifying the artificial substrates,
b) coating the artificial substrates.
The coating of substrates in step b) takes place preferably after the size-classifying in step a).
Further provided by the invention is the use of the effect pigments of the invention in cosmetics, plastics, and coating compositions, such as paints, printing inks, varnishes, powder coating materials, and electrocoat materials. The invention accordingly provides compositions which comprise the effect pigments of the invention.
Effect pigments having improved optical properties are, for the purposes of this invention, effect pigments notable in particular for their high color purity at a constant angle of light incidence and angle of viewing. In their respective entirety, then, the effect pigments of the invention have a uniform color or a uniform hue. For a viewer, therefore, there are no marked color differences from one effect pigment of the invention to the next effect pigment of the invention in an entirety.
Surprisingly it has been found that substrates having a narrow span in the particle size distribution and coated with at least one optically active coating exhibit a markedly higher color purity than effect pigments having a broader span, as is the case in the prior art.
The invention characterizes the particle size distribution using the span ΔD, defined as ΔD=(D90−D10)/D50. The smaller the span, the narrower the particle size distribution.
The D10 value indicates the value of the longitudinal dimension of the effect pigments, as determined by means of laser granulometry in the form of the sphere equivalent, which 10% of the pigment particles attain at most, or fall below, out of the entirety of all the particles. Correspondingly, the D50 value and the D90 value, respectively, indicate the maximum longitudinal dimensions of the effect pigments, as determined by means of laser granulometry in the form of sphere equivalents, which 50% or 90% of the particles attain at maximum, or fall below, out of the entirety of all the particles.
The effect pigments of the invention possess a span ΔD in a range from 0.7 to 1.4, preferably from 0.7 to 1.3, more preferably from 0.8 to 1.2, very preferably from 0.8 to 1.1.
Above a span ΔD of 1.4, the effect pigments obtained lack color purity. Effect pigments below a size distribution span of 0.7 are very costly and inconvenient to produce by the usual methods, and hence can no longer be produced economically.
The effect pigments of the invention may have any desired median particle size (D50). The D50 values of the effect pigments of the invention encompass a range from 3 to 350 μm. The effect pigments of the invention preferably have a D50 value in a range of 3-15 μm or 10-35 μm or 25-45 μm or 30-65 μm or 40-140 μm or 135-250 μm.
The D10 values of the effect pigments of the invention encompass preferably a range from 1 to 120 μm. Preferably the effect pigments of the invention have the combinations of D90, D50 and D10 values as specified in Table 2. In the present case, the D10, D50, and D90 values of Table 2 are combined only in such a way as to produce a span ΔD of 0.7-1.4. Combinations of D10, D50, and D90 values that lead to a span which is not within the ΔD range of 0.7-1.4 are not inventive embodiments.
It has surprisingly been found that the combinations of ranges of D90, D50 and D10 values as specified in Table 2 produce effect pigments of extremely high color purity.
In this context it has surprisingly emerged that it is not the absolute size of the effect pigments that is critical but rather the proportion of the sizes to one another. It is critical that the span ΔD=(D90−D10)/D50 is situated within a narrow range from 0.7 to 1.4. Within this range, for example, the D50 values of the effect pigments may be 15, 20, 25, 30 μm or else 50, 80, 100, 150, 200, 250, 300 or 350 μm. It has been found that surprisingly, even in the case of a majority of relatively large effect pigments, effect pigments of color purity are obtained if the span ΔD is situated in a range from 0.7 to 1.4.
The average thickness of the artificial platelet-shaped substrates is 500 nm to 2000 nm and preferably 750 to 1500 nm.
The aspect ratio of the effect pigments of the invention, calculated from the quotient of particle diameter to thickness, is preferably 2-980, more preferably 5-950, and very preferably 10-920.
If substrates below an average thickness of 500 nm are coated with high-index metal oxides, then the substrate has a marked optical influence on the interference color of the system as a whole. The effect pigments obtained, consequently, no longer have the desired high color purity. Moreover, there is a marked decrease in the mechanical stability of these effect pigments with respect, for example, to shearing forces. Furthermore, the times taken to coat these thin substrates with, for example, high-index metal oxides or semi-transparent metals, owing to the high specific surface areas of these pigments, are very long, resulting in high production costs.
Above an average substrate layer thickness of 2000 nm, the effect pigments become too thick overall. This entails a poorer opacity and also a lower level of plane-parallel orientation within the application medium. The poorer orientation results in turn in a reduced luster.
In one preferred embodiment the standard deviation of the thickness of the artificial substrates is 15% to 100% and more preferably 20% to 70%.
The average thickness is determined on the basis of a cured paint film in which the effect pigments are oriented substantially plane-parallel to the substrate. For this purpose a transverse section of the cured paint film is examined under a scanning electron microscope (SEM), the thickness of 100 effect pigments being ascertained and statistically averaged.
Below a standard deviation of 15%, the effect pigments obtained exhibit color flop. Above a standard deviation of 100%, the collective of pigments as a whole contains so many relatively thick pigments that orientation is then poorer and hence luster is lost.
It has surprisingly been found that effect pigments whose artificial substrates have an average thickness of 500 to 2000 nm and also a span ΔD of 0.7 to 1.4 exhibit the desired extraordinary color purity at a constant angle of light incidence and angle of viewing.
The effect pigments are preferably pearlescent pigments or optically variable pigments.
The effect pigments of the invention may also be present here in a mixture with other effect pigments.
Effect pigments based on natural mica have been known for some considerable time. When using natural mica as a substrate, however, it is necessary to accept that its surface is not ideally smooth but instead has irregularities, such as steps, for example. These irregularities limit the quality of the resultant effect pigments, since they often lead to different colors within the same pigment platelet. This considerably reduces the color purity in particular. Furthermore, the foreign ion impurities that are present in natural mica may alter the perceived color of the effect pigments, with the consequence that a plurality of effect pigments originating from one production batch have differing colors or hues, thus giving the pigment mixture a low color purity.
These disadvantages of natural mica can be circumvented through the use of artificial substrates. Artificial substrates are substrates which do not occur as such in nature but instead must be synthesized. Suitable base substrates for the effect pigments of the invention are, for example, synthetic, nonmetallic, platelet-shaped substrates. The substrates are preferably substantially transparent, more preferably transparent.
One preferred variant of the invention uses as substrates glass platelets (i.e., glass flakes), platelets of synthetic mica, SiO2 platelets, polymer platelets, platelet-shaped bismuth oxychloride and/or platelet-shaped aluminum oxides or mixtures thereof. For the effect pigments of the invention it is preferred to use substrates consisting of glass platelets or synthetic mica.
The effect pigments of the invention may be substrates provided with one or more optically active layers or coatings. An optically active layer or coating is a layer or coating at which incident light gives rise to perceptible color effects by virtue of physical effects such as reflection, interference, absorption, refraction, etc.
As optically active layers or coatings it is preferred to apply layers which comprise metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or mixtures thereof. In one preferred variant the optically active layers or coatings are composed of the aforementioned materials.
Unless indicated otherwise, the terms “layers” or “coatings” are used interchangeably for the purposes of this invention.
In one preferred variant of the invention a coating or two or more coatings may have a refractive index n≥1.9, and hence are high-index.
If the effect pigments of the invention have two or more layers, these layers, in relation to refractive index, are preferably arranged in alternation, so that a high-index layer having a refractive index of n≥1.9 is followed preferably by a low-index layer having a refractive index n<1.9, or vice versa.
The coating in this case may either surround the entire substrate or be present only partially on the substrate. The metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride or metal oxynitride layers, or layers with mixtures of the aforementioned compounds, may be low-index (refractive index<1.9) or high-index (refractive index n≥1.9).
In one preferred embodiment the substrate is or comprises a low-index platelet-shaped substrate and the coating has at least one high-index layer (n≥1.9). Substrate platelets used with preference are glass platelets, synthetic mica platelets and/or SiO2 platelets.
Metal oxides and/or metal oxide hydrates used are preferably titanium oxide, titanium dioxide, titanium oxide hydrate, aluminum oxide, aluminum oxide hydrate, silicon oxide, silicon dioxide, iron oxide, iron hydroxide, tin oxide, chromium oxide, antimony oxide, cerium oxide or their mixed oxides.
In a further inventive embodiment of the invention the substrates are coated with metal layers. In this case it is preferred to apply semitransparent metal layers in order to provide effect pigments having interference colors in accordance with the Fabry-Perot effect.
Suitable metals for generating the semitransparent metal layers are, for example, aluminum, chromium, nickel, silver, gold, titanium, copper or their alloys.
The thickness of the semitransparent metal layers is situated preferably in a range from 4 to 40 nm and more preferably 5 to 30 nm.
As a metal fluoride, one variant applies magnesium fluoride as a coating. As metal nitrides or metal oxynitrides it is possible, for example, to use those of the metals titanium, zirconium and/or tantalum.
The substrate is coated preferably with metal oxide layers and/or metal oxide hydrate layers.
Examples of low-index layers include aluminum oxide, aluminum oxide hydrate, silicon oxide, silicon oxide hydrate and/or magnesium fluoride.
Examples of high-index layers used are titanium dioxide, titanium suboxides, iron oxide, iron hydroxide, tin oxide, zinc oxide, zirconium oxide, cerium oxide, cobalt oxide, chromium oxide, antimony oxide or their mixed oxides.
Different colors in the effect pigments of the invention can be set here through the choice of layer material and layer thickness, as shown for example by Table 1.
Where the effect pigments of the invention have a coating with titanium dioxide, the titanium dioxide may be present in the rutile or anatase crystal polymorph. The best-quality and most stable pearlescent pigments are obtained when the titanium dioxide layer is in the rutile form. The rutile form can be obtained by, for example, applying a layer of SnO2 to the substrate or the pigment before the titanium dioxide layer is applied. Applied to a layer of SnO2, TiO2 crystallizes in the rutile polymorph.
The thickness of the metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride or metal nitride layers or of layers with a mixture of the aforementioned compounds is situated typically in a range of 30-350 nm, more preferably of 50-300 nm.
The metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride and/or metal nitride layers may contain or comprise colorants such as Prussian Blue, ultramarine, carmine red, azopigments, phthalocyanines or FD & C dyes/lakes. These colorants may be present in the coating and/or applied to this coating and if necessary fixed thereon by adhesion promoters.
In order to provide better protection from weathering effects to the effect pigments of the invention they may additionally be coated with an outer protective layer. This layer comprises or is composed preferably of one or two metal oxide layers of the elements Si, Al or Ce. Particular preference is given here to a sequence in which first of all a cerium oxide layer is applied and is then followed by an SiO2 layer, as described in WO 2006/021386 A1, hereby incorporated by reference.
The outer protective layer may also be organic-chemically modified on the surface. By way of example, one or more silanes may be applied to this outer protective layer. The silanes may be alkylsilanes having branched-chain or unbranched alkyl radicals of 1 to 24 C atoms, preferably 6 to 18 C atoms.
The silanes may alternatively be organofunctional silanes which allow chemical attachment to a plastic, a binder of a paint or of an ink, etc.
The organofunctional silanes which are used preferably as surface modifiers and which contain suitable functional groups are available commercially and are produced, for example, by Degussa, Rheinfelden, Germany and sold under the trade name “Dynasylan®”. Other products can be acquired from OSi Specialties (Silquest® silanes) or from Wacker, examples being standard silanes and α silanes from the GENIOSIL® product group.
Examples thereof are 3-methacryloyloxypropyltrimethoxysilane (Dynasylan MEMO, Silquest A-174NT), vinyltri(m)ethoxysilane (Dynasylan VTMO or VTEO, Silquest A-151 or A-171), 3-mercaptopropyltri(m)ethoxysilane (Dynasylan MTMO or 3201; Silquest A-189), 3-glycidoxypropyltrimethoxysilane (Dynasylan GLYMO, Silquest A-187), tris-(3-trimethoxysilylpropyl)isocyanurate (Silquest Y-11597), gamma-mercaptopropyltrimethoxysilane (Silquest A-189), bis-(3-triethoxysilylpropyl) polysulfide (Silquest A-1289), bis-(3-triethoxysilyl) disulfide (Silquest A-1589), beta-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Silquest A-186), bis(triethoxysilyl)ethane (Silquest Y-9805), gamma-isocyanatopropyltrimethoxysilane (Silquest A-Link 35, GENIOSIL GF40), (methacryloyloxymethyl)tri(m)ethoxysilane (GENIOSIL XL 33, XL 36), (methacryloyloxymethyl)(m)ethyldimethoxysilane (GENIOSIL XL 32, XL 34), isocyanatomethyl)trimethoxysilane (GENIOSIL XL 43), (isocyanatomethyl)methyldimethoxysilane (GENIOSIL XL 42), (isocyanatomethyl)trimethoxysilane (GENIOSIL XL 43), 3-(triethoxysilyl)propylsuccinic anhydride (GENIOSIL GF 20), (methacryloyloxymethyl)methyldiethoxysilane, 2-acryloyloxyethylmethyldimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltripropoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriacetoxysilane, 3-methacryloyloxypropymethyldimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane (GENIOSIL XL 10), vinyltris(2-methoxyethoxy)silane (GENIOSIL GF 58) and vinyltriacetoxysilane.
It is also possible, however, to use other organofunctional silanes on the effect pigments of the invention.
Additionally it is possible to use aqueous prehydrolyzates which are obtainable commercially, for example, from Degussa. These include, among others, aqueous, alcohol-free aminosilane hydrolyzate (Dynasylan Hydrosil 1151), aqueous, alcohol-free, amino/alkyl-functional siloxane cooligomer (Dynasylan Hydrosil 2627), aqueous, alcohol-free diamino/alkyl-functional siloxane cooligomer (Dynasylan Hydrosil 2776), aqueous, alcohol-free amino/vinyl-functional siloxane cooligomer (Dynasylan Hydrosil 2907), aqueous, alcohol-free amino/alkyl-functional siloxane cooligomer (Dynasylan Hydrosil 2909), aqueous, alcohol-free epoxy-functional siloxane oligomer (Dynasylan Hydrosil 2926) or aqueous, alcohol-free amino/methacrylate-functional siloxane cooligomer (Dynasylan Hydrosil 2929), oligomeric diaminosilane system (Dynasylan 1146), vinyl/alkyl-functional siloxane cooligomer (Dynasylan 6598), vinyl- and methoxy-containing vinylsilane concentrate (oligomeric siloxane) (Dynasylan 6490) or oligomeric short-chain alkyl-functional silane (Dynasylan 9896).
In one preferred embodiment the organofunctional silane mixture, in addition to at least one silane without a functional binding group, comprises at least one amino-functional silane. The amino function is a functional group which is able to enter into one or more chemical interactions with the majority of groups present in binders. Said interactions may involve a covalent bond, such as with isocyanate or carboxylate functions of the binder, for example, or hydrogen bonds, such as with OH or COOR functions, or else ionic interactions. An amino function is therefore very suitable indeed for the purpose of the chemical attachment of the effect pigment to different kinds of binders.
The following compounds are taken preferably for this purpose:
Aminopropyltrimethoxysilane (Dynasylan AMMO; Silquest A-1110), aminopropyltriethoxysilane (Dynasylan AMEO) or N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Dynasylan DAMO, Silquest A-1120) or N-(2-aminoethyl)-3-aminopropyltriethoxysilane, triamino-functional trimethoxysilane (Silquest A-1130), bis(gamma-trimethoxysilylpropyl)amine (Silquest A-1170), N-ethyl-gamma-aminoisobutyltrimethoxysilane (Silquest A-Link 15), N-phenyl-gamma-aminopropyltrimethoxysilane (Silquest Y-9669), 4-amino-3,3-dimethylbutyltrimethoxysilane (Silquest Y-11637), N-cyclohexylaminomethylmethyldiethoxysilane (GENIOSIL XL 924), (N-cyclohexylaminomethyl)triethoxysilane (GENIOSIL XL 926), (N-phenylaminomethyl)trimethoxysilane (GENIOSIL XL 973), and mixtures thereof.
In one further-preferred embodiment the silane without a functional binding group is an alkyl silane. The alkyl silane preferably has the formula (A):
R(4-z)Si(X)z (A)
In this formula z is an integer from 1 to 3, R is a substituted or unsubstituted, unbranched or branched alkyl chain having 10 to 22 C atoms, and X is a halogen and/or alkoxy group. Preferred alkyl silanes have alkyl chains with at least 12 C atoms. R may also be connected cyclically to Si, in which case z is typically 2.
A silane of this kind has the effect of strong hydrophobicization of the pigment surface. This in turn leads to the pearlescent pigment thus coated having a tendency to float upward in the surface coating. In the case of platelet-shaped effect pigments, behavior of this kind is referred to as “leafing”.
A silane mixture composed of at least one silane which possesses at least one functional group allowing attachment to the binder, and an alkyl silane which does not have an amino group and which is insoluble or virtually insoluble in water permits optimum performance properties on the part of the pearlescent pigments.
An organic-chemical surface modification of this kind means that the effect pigments exhibit excellent orientation in a paint or ink film, i.e., are oriented substantially plane-parallel with respect to the painted or coated substrate, and at the same time react chemically with the binder system of the paint or ink and hence are bound covalently in the paint or ink film. Paint or ink films of this kind exhibit enhanced mechanical and chemical resistance toward environmental effects, such as weather, etc.
When the effect pigments of the invention in an applicator drawdown (e.g., in a nitrocellulose varnish) are viewed in transmission under a light microscope, the effect pigments of the invention are seen to have a very uniform color. The individual pigments have largely the same color, preferably the same color.
The color imparted by effect pigments, such as pearlescent pigments, is as a result of interference phenomena. In the context of these phenomena, interference colors which are complementary to one another are mutually extinguished: thus, for example, a mixture of blue and yellow pearlescent pigments produces a silver or grey color. It is well known that mixtures of different-colored pearlescent pigments always produce a less pure hue with a lower luster, owing to the ever-present mutual extinction or attenuation of certain color fractions.
In order, therefore, to obtain effect pigments, preferably pearlescent pigments, having a high color purity, it is necessary for the hues of the individual pigments to be as uniform as possible. The purity of hue can be represented quantitatively by the following method in accordance with a statistical evaluation.
The starting point for determining the color purity of the effect pigments of the invention are digital color microscope images of applicator drawdowns. Applicator drawdown is carried out with a paint comprising 6% by weight effect pigments in a colorless nitrocellulose varnish. The percent by weight quantities here are based on the total weight of the paint. The paint is applied in a wet film thickness of 76 μm to a BYK-Gardner black-white drawdown chart (byko-chart 2853) and subsequently dried. Within these dried applicator drawdowns, the platelet-shaped effect pigments have a largely plane-parallel orientation. The microscope images are taken preferably using the Axioskop 2 microscope and the AxioCam digital camera from Zeiss, Germany. From the resulting digital images, the AxioVision 4.6 image-recording and image-processing software from Zeiss is then used to prepare color-neutral digital images with a 12-bit depth of color. When the applicator drawdowns are observed through the microscope, the irradiated light is incident vertically from above onto the applicator drawdown. In the applicator drawdown, in turn, the effect pigments have a largely plane-parallel orientation, and hence the incident light falls perpendicularly onto the pigment platelets. The viewing angle is in this case likewise perpendicular to the surface of the pigment platelets.
In order to obtain undistorted statistical data, around 20 individual micrographs were produced at randomly selected points on the black substrate of the applicator drawdowns. This constituted the imaging of more than 100 individual evaluable pigments.
Since the image-processing software is unable to recognize the pigments automatically, they are marked manually. In the marking of the individual pigment area fractions, care should be taken to ensure that there is no recording of pigment marginal regions or regions in which the pigments overlap, since in this case the perceived color of the individual pigment particles is immediately distorted by the overlap (see also
For the areas thus marked, the image-processing software calculates the respective area means of the red, green, and blue fractions. For meaningful statistics, the color fractions of at least 100 evaluable pigment particles are determined from the various micrographs.
The image-processing software uses the sRGB color model. Conversion to the XYZ color space is accomplished via the well-known transformation matrix (II) (IEC 61966-2-1:1999).
The resulting X, Y, and Z values are then converted into the customary CIE (1976) Lab values:
The calculation for Y* and Z* is made in a manner similar to that for the calculation of X*. The tristimulus values used were Xn=94.81, Yn=100 and Zn=107.34 for the D65 illuminant and the 10° standard observer.
This produces a distribution of measurement points in the a*-b* color space (see also
The scattering is quantified by first calculating the common middle point (ā,
Subsequently, for each measurement point (a,b), its distance from the middle point (ā,
ΔC*=√{square root over ((a−ā)2+(b−
This gives a color difference distribution in the a*-b* color space. This distribution may likewise be represented in the form of a cumulative undersize distribution curve. The 90% quantile (ΔC*90) of this color difference distribution is a suitable measure for characterizing the size of the color scattering (see
The effect pigments of the invention preferably have a 90% quantile of the color difference distribution ΔC*90 of 0.2 to 8.0 and more preferably of 0.5 to 6.0; with further preference, of 0.6 to 5.0; with particular preference of 0.7 to 4.0, and with very particular preference of 0.7 to 3.0.
The inventors have not as yet found any scientifically meaningful explanation for this surprising effect. It is, however, thought that the pigment substrates which are largely the same in their size are coated substantially more uniformly with the coloring layers—as, for example, high-index metal oxides or semitransparent metals—than is the case for substrates having a greater span ΔD. As a result, coatings with a substantially more homogeneous layer thickness are formed on the substrates. Since the color is imparted as a result of interference phenomena, and in the case of the substrates used is determined critically by the layer thickness of the high-index coating, the more uniform layer thicknesses give rise to a purer hue or a greater color purity in the case of the effect pigments of the invention.
The present invention encompasses pearlescent pigments without color flop and also effect pigments with a high color flop in multilayer systems.
The critical factor, however, is that, at constant angle of incidence and angle of viewing in an applicator drawdown, with largely plane-parallel orientation of the platelet-shaped effect pigments of the invention, the hue observed is always largely the same in the sense of the present description. It is not necessary here for the angle of incidence and angle of viewing always to be perpendicular to the pigment platelets, although such a case is preferred.
The effect pigments of the invention are suitable more particularly for application in cosmetics, such as, for example, body powder, face powder, compact and loose powder, face makeup, powder cream, cream makeup, emulsion makeup, wax makeup, foundation, mousse makeup, blusher, eye makeup such as eye shadow, mascara, eyeliner, liquid eyeliner, eyebrow pencil, lip care stick, lipstick, lip gloss, lip liner, hair-styling compositions such as hairspray, hair mousse, hair gel, hair wax, hair mascara, permanent or semi-permanent hair colors, temporary hair colors, skin care compositions such as lotions, gels, and emulsions, and nail varnish compositions.
In order to obtain specific color effects in the cosmetic applications it is possible to use not only the effect pigments of the invention but also other colorants and/or conventional effect pigments or mixtures thereof, in variable proportions. Conventional effect pigments used may be, for example, commercial pearlescent pigments based on natural mica coated with high-index metal oxides (such as the Prestige® product group from Eckart, for example), BiOCl platelets, TiO2 platelets, pearlescent pigments based on synthetic mica coated with high-index metal oxides or based on glass flakes or Al2O3, SiO2 or TiO2 platelets coated with high-index metal oxides. In addition it is also possible to add metallic effect pigments, such as the Visionaire® product group from Eckart, for example. The colorants may be selected from inorganic or organic pigments.
Preferred effect pigments for the purposes of the present invention possess a span ΔD of 0.7-1.4, preferably 0.7-1.3, more preferably 0.8-1.2, and very preferably 0.8-1.1, and a D50 value of 3-350 μm. Their average thickness is 500-2000 nm; the standard deviation in the thickness is 15%-100%.
Further-preferred effect pigments for the purposes of the present invention possess a span ΔD of 0.8-1.2, a D50 value of in each case preferably 3-15 μm, 10-35 μm, 25-45 μm, 30-65 μm, 40-140 μm or 135-250 μm. Their average thickness is 500-2000 nm, and the standard deviation in the thickness is 15%-100%.
Further-preferred effect pigments for the purposes of the present invention possess a span ΔD of 0.8-1.2 and an average thickness of 500-2000 nm, more preferably of 750-1500 nm. The standard deviation in the thickness is 15%-100%, and the effect pigments have a D50 value of 3-350 μm.
Further-preferred effect pigments for the purposes of the present invention possess a span ΔD of 0.8-1.2 and a standard deviation in the thickness of 20%-70%. The average thickness of the effect pigments is 500-2000 nm, preferably 750-1500 nm. They have a D50 value of 3-350 μm.
A process for producing the effect pigments of the invention comprises the following steps:
a) size-classifying the artificial substrates
b) coating the artificial substrates.
If the starting substrates are too large, it is possible optionally to carry out a comminuting step prior to the size-classifying.
The size classification may take place before or after the coating of the substrates. Advantageously, however, the substrate is first classified and then coated. The size classification is carried out and repeated as and where necessary, until the pearlescent pigments have the inventive particle size distribution.
A narrow span ΔD of the substrates can be achieved through suitable comminuting and/or classifying operations on the artificial substrates to be coated. The artificial substrates to be coated may be comminuted using, for example, a ball mill, jet or agitator ball mill, edge runner mill or dissolver. The span ΔD of the final fraction can be set by means of appropriate classification, such as by multiple wet sieving, for example. Further classification methods include centrifugation in cyclones or sedimentation from a dispersion.
The comminuting and classifying operations may take place in succession and as and where necessary may be combined with one another. For instance, a classifying operation may follow a comminuting operation, which is followed by a further comminuting operation on the fine fraction, and so on.
The object on which the invention is based is achieved, additionally, by the provision of a coating composition which comprises the effect pigments of any of claims 1 to 10. In one preferred variant the coating composition is selected from the group consisting of cosmetics, paint, printing ink, varnish, powder coating material, and electrocoat material.
The object on which the invention is based is further achieved by the provision of a plastic which comprises the effect pigments of any of claims 1 to 10.
In the text below, the invention is elucidated in more detail by a number of examples and figures, without being confined thereto.
The examples below are intended to elucidate the invention in more detail, but without restricting it thereto.
A suspension of 200 g of glass flakes (average thickness: 1 μm, standard deviation of the thickness: around 40%) in DI water (around 3% by weight) (DI: deionized water: fully demineralized) is classified on a 100 μm sieve, and the sieve undersize is sieved in turn on a 63 μm sieve. This sieving procedure is repeated twice with the residue obtained on the 63 μm sieve, to give a glass flake fraction whose particle size distribution (MALVERN Mastersizer MS 2000) is as follows: D10=50 μm, D50=82 μm, D90=132 μm, Span ΔD=1.00.
200 g of glass flakes from example 1 are suspended in 2000 ml of deionized water and the suspension is heated to 80° C. with turbulent stirring. The pH of the suspension is adjusted to 1.9 using dilute HCl and then a first layer of “SnO2” is precipitated onto the glass flakes. This layer is formed by addition of a solution consisting of 3 g of SnCl4×5H2O (in 10 ml of concentrated HCl plus 50 ml of deionized water), with simultaneous metering of 10% NaOH in order to keep the pH constant, over a period of 1 hour. In order to complete the precipitation, the suspension is stirred for a further 15 minutes. Thereafter the pH is lowered to 1.6 using dilute HCl, and a solution of 200 ml of TiCl4 (400 g TiCl4/l deionized water) is then metered into this suspension. The pH is kept at a constant 1.6 by counter-addition of 10% NaOH. This is followed by stirring for 15 minutes more and by filtration, the filter cake being rinsed with deionized water. The filter cake is then subjected to initial drying at 100° C. and to calcining at 750° C. for 30 minutes. A highly lustrous effect pigment is obtained which shows a red interference color. Microscopic investigation of the coated pigments shows extraordinary consistency in the color of the pigments.
200 g of glass flakes from example 1 are coated by the method of example 2 with TiO2, but with metered addition of only 167 ml of TiCl4. The product after calcining is a highly lustrous effect pigment having a golden interference color. Microscopic investigation, in the same way as in example 2, shows an extraordinary consistency in color of the pigments.
Commercially available golden pearlescent “Reflecks Dimension Sparkling Gold” pigments from BASF Catalysts.
Commercially available golden pearlescent “RonaStar Golden Sparks” pigments from Merck.
Below, the inventive effect pigments of example 3, with a narrow span and high color purity, were compared in a detailed analysis with the commercially available pearlescent pigments of the comparative examples. All of the pearlescent pigments in the form of an applicator drawdown have a golden interference color which is perceptible visually to the observer.
The starting point for the determination of the color purity of the inventive effect pigments were digital color microscope images of dried applicator drawdowns (produced with a paint containing 6% by weight pigments in nicrocellulose varnish (% by weight figure is based on the total weight of the paint) and knife-coated in a wet film thickness of 76 μm onto a BYK-Gardner black-white drawdown chart (byko-chart 2853), and subsequently dried at room temperature). These images were recorded using the Axioskop 2 microscope and the AxioCam digital camera from Zeiss. This equipment allowed the preparation, with the aid of the AxioVision 4.6 image-recording and image-processing software, of color-neutral digital images with a 12-bit depth of color.
In order to obtain distortion-free statistical data, around 20 individual micrographs were taken at randomly selected locations on the applicator drawdowns. Over 100 individual evaluable pigments were imaged in this procedure.
In
The 90% quantile of the color difference distribution is the lowest for the inventive effect pigments of inventive example 3, whereas the commercially available comparison products exhibit significantly higher values.
200 g of glass flakes from example 1 are suspended in 2000 ml of deionized water and the suspension is heated to 80° C. with turbulent stirring. The pH of the suspension is adjusted to 1.9 using dilute HCl and then a first layer of “SnO2” is precipitated onto the glass flakes. This layer is formed by addition of a solution consisting of 3 g of SnCl4×5H2O (in 10 ml of concentrated HCl plus 50 ml of deionized water), with simultaneous metering of 10% NaOH in order to keep the pH constant, over a period of 1 hour. In order to complete the precipitation, the suspension is stirred for a further 15 minutes. Thereafter the pH is lowered to 1.6 using dilute HCl, and a solution of 185 ml of TiCl4 (400 g TiCl4/l deionized water) is then metered into this suspension. The pH is kept at a constant 1.6 by counter-addition of 10% NaOH. Thereafter the pH is raised to 7.5 using 5% NaOH, and stirring takes place for 15 minutes. A waterglass solution (207 g of waterglass solution, 27% SiO2, mixed with 207 g of deionized water) is then introduced slowly into the suspension, and the pH is kept constant at 7.5. This is followed by stirring for 20 minutes more, and the pH is lowered again to 1.9. Then a second layer of “SnO2” is deposited on the SiO2 surface. This layer is formed by addition of a solution consisting of 3 g of SnCl4×5H2O (in 10 ml of concentrated HCl plus 50 ml of deionized water), with simultaneous metered addition of a 10% NaOH, in order to keep the pH constant, over a period of 1 hour. In order to complete the precipitation, the suspension is stirred for a further 15 minutes. After that the pH is lowered to 1.6 using dilute HCl, and a solution of 189 ml of TiCl4 (400 g TiCl4/l deionized water) is then metered into the suspension. In the course of this procedure, the pH is kept constant at 1.6 by counter-addition of 10% NaOH. This is followed by stirring for 15 minutes more and by filtration, the filter cake being rinsed with deionized water. The filter cake is then subjected to initial drying at 100° C. and to calcining at 750° C. for 30 minutes. An extremely highly lustrous effect pigment is obtained which exhibits a color flop, with a change from a green interference color for steep viewing angles into a blue interference color at a shallow viewing angle.
Presented below are cosmetic applications with the inventive effect pigments:
Preparation:
1. Mix components of phase A
2. Add phase B to phase A
3. Mix and dispense into suitable container
Cocos Nucifera (Coconut) Oil
Persea Gratissima (Avocado) Oil and
Preparation:
1. Mix phase A and heat to 85° C.
2. Mix phase B
3. Add phase B to phase A with stirring
4. In suitable container, allow to cool to room temperature
Prunus Amygdalus Dulcis (Sweet
Preparation:
1. Heat phase A to 70° C. with stirring
2. Add components of phase B to phase A
3. Mix phase C until Aristoflex is dissolved
4. Heat the mixture to 70° C.
5. Add phase C to phase AB
6. Allow to cool to 40° C., and add phase D
Simmondsia Chinensis (Jojoba) Seed Oil
Preparation:
1. Heat phase A to 85° C.
2. Add phase B to phase A, mix and then dispense into suitable container
Parkii
Preparation:
1. Heat phase A to 85° C.
2. Add phase B to phase A, mix and then dispense into suitable container
Preparation:
1. Heat phase A to 85° C.
2. Add phase B to phase A; after mixing at 75° C. dispense into suitable container
Preparation:
1. Disperse Veegum into phase A
2. Stir for 15 minutes
3. Add phase B to phase A
4. Add phase C to phase AB
5. Stir for 10 minutes
6. Add phase D to phase ABC and heat to 75° C.
7. Heat phase E to 75° C.
8. Add phase E to phase ABCD
9. Allow to cool to 60° C., and add phase F
Preparation:
1. Heat phase A to 85° C. with stirring
2. Heat phase B to 85° C.
3. Add phase B to phase A
4. Allow to cool to 55° C. with stirring
5. Add phase C, mix, dispense into suitable container
Preparation:
1. Mix phase A, heat until all is melted
2. Premix phase B with speed mixer (2400 rpm, 1 min)
3. Add half of melted phase A to phase B, mix in speed mixer (2400 rpm, 30 s)
4. Add remainder of phase A to phase B and mix in speed mixer (2400 rpm, 30 s)
5. Add phase C, mix in speed mixer (2400 rpm, 30 s), allow to cool to room temperature
Preparation:
1. Mix phases A and B with stirring
2. Dispense into suitable container
Preparation:
1. Mix phase A
2. Add phase B and homogenize
3. Press eyeshadow at 150 bar for 30 minutes
Preparation:
1. Mix phase A
2. Add phase B and homogenize
3. Press eyeshadow at 150 bar for 30 minutes
Preparation:
1. Disperse Carbopol in phase A
2. Heat to 65° C.
3. Gradually add ingredients from phase B
4. Allow to cool with stirring, at 40-45° C. add phase C
Preparation:
1. Heat phases A and B separately to 90° C.
2. Add phase B to phase A with stirring
3. Allow to cool to 55° C.
4. Add phase C and dispense into a suitable container
Macadamia ternifolia Seed Oil
Preparation:
1. Heat phases A and B separately to 80° C.
2. Add phase A to phase B with stirring
3. Allow to cool to 45° C.
4. Add phase C
Macadamia Integrifolia Seed Oil
Preparation:
1. Heat phase A to 85° C.
2. Add phase B to phase A and mix
3. Dispense into lipstick mold at 75° C.
Preparation:
1. Mix phase A and heat to 75° C.
2. Mix phase B and heat to 70° C.
3. Add phase B slowly to phase A, with homogenization, and allow to cool with stirring
Butyrospernum Parkii (Shea Butter)
Preparation:
1. Mix phase A, disperse Keltrol
2. Heat to 80° C.
3. Heat phase B to 80° C.
4. Add phase B slowly to phase A
5. Allow to cool to 40° C., and add phase C
Preparation:
1. Heat phases A and B separately to 80° C.
2. Add phase B slowly to phase A
3. In separate vessel, stir Klucel and Veegum into the water of phase C
4. Allow phase AB to cool to 40° C.
5. Add phases C and D
Preparation:
1. Mix phase A in speed mixer (30 s/2000 rpm)
2. Add phase B to phase A and mix in speed mixer (30 s/2500 rpm)
3. Dispense into suitable container
Preparation:
1. Mix phase A
2. Add phase B and homogenize
3. Press blush at 150 bar for 30 s
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|---|---|---|---|---|
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|---|---|---|---|
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| Number | Date | Country | |
|---|---|---|---|
| 20100297045 A1 | Nov 2010 | US |
