SURFACE-MODIFIED EMBOSSED EFFECT PIGMENTS

Description

[0001] The present invention relates to a surface-modified effect pigment and a process for producing the same, as well as nail varnish compositions containing this surface-modified effect pigment.

[0002] WO 2005 / 055965 A1 discloses cosmetic compositions such as nail polishes containing embossed aluminum pigments with a rainbow effect. However, binders based on hydrocarbon resins are not disclosed.

[0003] EP 1 462 085 A1 discloses a nail polish composition with a mirror effect, comprising particles with a metallic luster in a proportion of ≥ 2 wt. %, based on the total weight of the nail polish composition, as well as texturizing agents. EP 1 462 085 A1 does not disclose surface-modified effect pigments. Furthermore, this patent does not disclose diffractive effect pigments.

[0004] EP 1 299 066 A2 describes a nail polish containing aluminum flakes with a mirror-like appearance. According to EP 1 299 066 A2, the nail polish must contain nitrocellulose with a molecular weight of > 56,000 g / mol as a film former to achieve a mirror-like effect on a fingernail. This patent does not disclose any diffractive effect pigments.

[0005] EP 1 796 794 A1 discloses a cosmetic composition comprising a PVD aluminum pigment in a pigmentation level of 0.05 to 5.0 wt. %, based on the total weight of the cosmetic composition, and at least one leafing additive. Long-chain phosphoric acid esters or a mixture of several long-chain phosphoric acid esters serve as the leafing additive. However, in most nail polishes, the leafing effect is not fully realized. Furthermore, this patent does not disclose any diffractive effect pigments.

[0006] EP 2 248 514 A2 describes nitrocellulose-free nail polish compositions comprising at least one styrene / maleic anhydride copolymer as a high-gloss film former, at least one epoxy resin as a co-film former, at least one reactive component, and at least one solvent. The nitrocellulose-free nail polish composition is said to have comparable or better adhesion properties than nitrocellulose-containing nail polish compositions. EP 2 248 514 A2 discloses only pearlescent pigments as effect pigments.

[0007] US 6692830 B2 fundamentally discloses diffractive metallic effect pigments with a rainbow effect, which can also be coated with various interference layers. The pigments exhibit different line densities.

[0008] EP 1901870 B1 describes the production of diffractive metallic effect pigments with an average size d 50 of more than 75 µm.

[0009] EP 2598578 B1 discloses dark embossed metallic effect pigments.

[0010] Embossed metallic effect pigments are well known and are also used in nail polishes. However, there is still a need to improve the rainbow effect in nail polishes.

[0011] It has been shown that the surface-modified effect pigments according to the invention do not produce good results in all nail polish systems, such as those disclosed in EP 1796794 B2. The leafing effect is often lost during or after application, and consequently, the optical properties of the effect pigments are not fully realized.

[0012] The object of the present invention is to provide a nail polish composition containing embossed effect pigments that exhibits an improved rainbow effect and improved chroma. Furthermore, the brilliance should also be improved, if possible.

[0013] A further object is to provide a process for producing the nail polish according to the invention.

[0014] Furthermore, a method for coating keratin-containing substrates with a nail varnish is to be provided.

[0015] The object underlying the invention is achieved by providing a nail polish composition containing a) an embossed effect pigment comprising a platelet-shaped metallic substrate with an embossed structure which has a periodic pattern with diffractive elements and which is produced by PVD processes and optionally at least one coating applied to the substrate, wherein the substrate has an elemental metal content of 80 to 100 wt.%, based on the substrate, and wherein the effect pigment has been treated with a leafing additive for surface modification, b) at least one hydrocarbon resin as binder, c) at least one solvent or solvent mixture and d) optionally further auxiliaries.

[0016] The object of the underlying invention is also achieved by a process for producing the nail varnish composition according to the invention comprising the steps i) Surface modification of the effect pigment by a leafing additive in a dispersion in a solvent, ii) Dissolving the hydrocarbon resin in a solvent or solvent mixture iii) Mixing and homogenizing the dispersion according to i) with the binder solution according to ii), and iv) if necessary supplementing with further solvent or solvent mixture. Inventive nail polish composition:

[0017] The invention is directed to a nail polish composition that enables and maintains the leafing effect of the effect pigments in an excellent manner.

[0018] This nail polish composition according to the invention contains: a) an effect pigment comprising a platelet-shaped metallic substrate with an embossed structure which has a periodic pattern with diffractive elements and which is produced by PVD processes and optionally at least one coating applied to the substrate, wherein the substrate has an elemental metal content of 80 to 100 wt.%, based on the substrate, and wherein the effect pigment has been treated with a leafing additive for surface modification, b) at least one hydrocarbon resin as a binder, c) at least one solvent or solvent mixture and d) optionally further auxiliaries.

[0019] The nail polish composition according to the invention, which comprises at least one surface-modified effect pigment, preferably contains no nitrocellulose or cellulose acetate butyrate, unlike most commercially available nail polish compositions. The visual appearance of the nail polish composition according to the invention, after application and drying, is largely determined by the at least one surface-modified embossed effect pigment.

[0020] The nail polish composition according to the invention comprises the at least one surface-modified embossed effect pigment preferably in a proportion from a range of 0.2 wt.% to 7.0 wt.%, more preferably from a range of 0.3 wt.% to 5.0 wt.%, particularly preferably from a range of 0.35 wt.% to 3.0 wt.% and very particularly preferably from a range of 0.4 wt.% to 2.0 wt.%, in each case based on the total weight of the nail polish composition.

[0021] In the nail polish compositions according to the invention, the surface-modified embossed effect pigments are preferably arranged on the surface of the applied nail polish. "Arranging on the surface" is understood according to the invention to mean that the surface-modified effect pigments are located on the nail polish base and / or, starting from the nail polish composition / air or nail polish composition / topcoat interface, in the direction of the painted substrate in the third of the nail polish composition adjacent to this interface. The surface-modified effect pigments preferably float in the nail polish and align themselves with the nail polish surface. The surface-modified effect pigments are therefore characterized by pronounced leafing behavior in the nail polish composition according to the invention.

[0022] Due to this pronounced leafing behavior of the surface-modified effect pigments, nail polish compositions can be produced according to the invention that owe their visual appearance primarily to the at least one surface-modified effect pigment added to the nail polish base. The rainbow effect and the chroma of the embossed effect pigments are therefore much more effectively emphasized.

[0023] In further embodiments, depending on the desired optical effect, additional surface-modified, preferably non-diffractive, effect pigments can also be added to the nail polish composition, whereby both the surface modification and the effect pigments can be different from one another. Conventional organic and / or inorganic pigments can also be added to the nail polish composition according to the invention. Embossed effect pigments:

[0024] According to the invention, the nail polish composition according to the invention contains an effect pigment comprising a platelet-shaped metallic substrate with an embossed structure having a periodic pattern with diffractive elements, which is produced by PVD processes and has a line density of 5,000 to 20,000 lines / cm, and optionally at least one coating applied to the substrate, wherein the substrate has an elemental metal content of 80 to 100 wt.%, based on the substrate.

[0025] According to the invention, the embossed structure has a periodic pattern with diffractive elements. The periodic pattern refers to the smallest unit of diffractive elements. The periodic diffractive structure preferably has 5,000 to 20,000 diffractive elements / cm, particularly preferably 9,000 to 18,000 diffractive elements / cm, and most preferably 12,000 to 16,000 diffractive elements / cm. Within this range, predominantly visible light (approximately 400 to 800 nm wavelength) is diffracted by the diffractive elements according to the known principle of a diffraction grating, whereby the observer perceives a rainbow effect. However, portions of the IR radiation and / or UV radiation can also be diffracted.

[0026] The periodicity essentially determines the diffracted wavelengths of the incident light. This can be calculated in detail using known formulas, such as those found in US Pat. No. 6,692,830 B2.

[0027] Examples of diffractive elements that can be considered are symmetrical triangles, asymmetrical triangles, grooves of various shapes, rectangular functions, circles, wavy lines, cones, truncated cones, knobs, prisms, pyramids, truncated pyramids, cylinders, hemispheres, etc. as well as combinations of these geometric shapes and bodies.

[0028] Geometric bodies with one or more surfaces arranged parallel to the pigment surface, such as truncated cones, truncated pyramids, cylinders or rectangular functions, have a higher reflectivity due to these surfaces.

[0029] Geometric bodies that have slanted side surfaces relative to the pigment surface enhance the rainbow effect. Slanted side surfaces are understood to be side surfaces that, relative to the substrate, have an angle of 5 to 89°, preferably 15 to 84°, even more preferably 27 to 80°, and even more preferably 43 to 74°. Suitable geometric bodies include, for example, cones, truncated cones, pyramids, truncated pyramids, etc.

[0030] For example, with truncated cones, reflection occurs both at the top surface parallel to the pigment surface and the rainbow effect is enhanced at the lateral surface. Similarly, with truncated pyramids, reflection occurs at the top surface and the rainbow effect is enhanced at the slanted side surfaces.

[0031] Of course, in the case of truncated cones or truncated pyramids, it is also possible to arrange the cover surface not parallel to the pigment surface, but diagonally to the pigment surface.

[0032] The rainbow effect and / or the reflectivity of the effect pigment can be enhanced or the relative ratio of rainbow effect to reflection can be changed via the geometric bodies arranged on the surface of the platelet-shaped metallic substrate by embossing and / or shaping.

[0033] The geometric bodies can be presented separately or mixed together. It is also possible, of course, to arrange the geometric shapes and geometric bodies in a superimposed manner, so that, for example, additional geometric bodies are arranged on top of a wave-like structure.

[0034] According to a further variant of the invention, unembossed or unshaped, i.e. smooth, sections can be present on the platelet-shaped metallic substrate surface alongside embossed and / or shaped sections. This can also change the relative ratio of rainbow effect to reflection.

[0035] Preferably, the entire surface of the platelet-shaped metallic substrate is provided with the diffractive structure, preferably embossed. However, only a portion of the metallic effect pigment surface can be provided with the diffractive structure, preferably embossed, or formed into a diffractive structure. Preferably, at least 60%, particularly preferably at least 75%, and most particularly preferably at least 90% of the metallic effect pigment surface will be embossed with a diffractive structure or formed into a diffractive structure.

[0036] In a particularly preferred embodiment, the diffractive structure comprises or consists of wave-shaped, for example sinusoidal, lines, cones, or truncated cones. In a very particularly preferred embodiment, the diffractive structure comprises or consists of sinusoidal lines, since this shape is particularly easy to emboss and, in addition, produces a very strong diffraction effect. With these sinusoidal lines, the diffractive structure is preferably embossed over the entire platelet-shaped metallic substrate.

[0037] According to a preferred embodiment, the nail polish composition according to the invention contains an effect pigment comprising a platelet-shaped, metallic substrate with an embossed structure, wherein the metal is taken from the group consisting of aluminum, copper, chromium, iron or alloys thereof.

[0038] Particularly preferably, the platelet-shaped, metallic substrate with an embossed structure contains or consists of a metal made of aluminum, which reflects particularly well and is easy to produce by PVD processes.

[0039] To achieve a clearly perceptible effect, the diffractive structure, preferably a line structure, preferably has a certain minimum depth, since otherwise the physical effect of diffraction may be insufficiently developed. Therefore, the diffractive structure should preferably have a depth (measured as "peak to valley" according to WO 2005 / 055965 A1) of at least 40 nm, preferably 40 nm to 600 nm, more preferably 50 nm to 400 nm, and most preferably 100 nm to 250 nm.

[0040] Above 600 nm, the stability of the structure as a whole may no longer be present. Below 40 nm, the diffractive effect is too weak.

[0041] The platelet-shaped metallic embossed substrates are manufactured by PVD processes.

[0042] Preferably, the metallic platelet-shaped, engraved substrate has an average thickness h 50 (median value) from a range of 20 nm to 80 nm, particularly preferably from a range of 30 to 60 nm.

[0043] The determination of the median value h 50 was preferably carried out according to the method described in WO 2004 / 087816 A2 (pages 24 and 25) using SEM.

[0044] Below 20 nm, the substrate may become too dark and may lose the necessary mechanical strength required to maintain the imprinted structure.

[0045] Above 80 nm, the metallic substrate becomes too thick to produce the necessary brilliance and opacity.

[0046] The depth of the diffractive structure can therefore exceed the average layer thickness h 50 of the platelet-shaped metallic substrate.

[0047] The mean size d 50 (median) of the effect pigments with embossed structure is in a range of 5 - 120 µm, preferably in a range of 10 - 75 µm and very particularly preferably in a range of 15 - 40 µm.

[0048] The d50 value is determined using laser diffraction methods as a volume-averaged cumulative cross-section curve of the size distribution (Fraunhofer diffraction) in a manner customary for those skilled in the art. The Horiba LA-950 instrument from Horiba is used as the measuring device.

[0049] The h 50 value of the cumulative frequency distribution of the size distribution function indicates that 50% of the measured effect pigments have a size that is equal to or smaller than the specified value.

[0050] Below 5 µm, the number of diffractive structures per pigment particle is too small to produce an effective rainbow effect. Above 120 µm, the effect pigment is too large to align sufficiently plane-parallel to the surface of the nail polish after application to an artificial or natural finger. Poor orientation also disrupts the rainbow effect and the chroma due to a partially canceling superposition of the diffracted light emitted by differently oriented effect pigment particles.

[0051] If metallic effect pigments are used in cosmetic formulations, they must meet certain purity requirements such as EU Cosmetic Regulation 1223 / 2009 or FDA 21CFR part 73.

[0052] If, for example, aluminum platelets are used as a metallic platelet-shaped substrate, they preferably have an aluminum content of ≥ 97 wt.%, more preferably ≥ 98 wt.%, particularly preferably ≥ 99 wt.% and most preferably ≥ 99.7 wt.%, in each case based on the total weight of the aluminum platelet. In a preferred embodiment, the aluminum flakes further have a mercury content of preferably ≤ 1 ppm, an arsenic content of preferably ≤ 2 ppm, a lead content of preferably ≤ 10 ppm, a cadmium content of preferably ≤ 1 ppm, a barium content of preferably ≤ 10 ppm, a chromium content of preferably ≤ 20 ppm, a nickel content of preferably ≤ 20 ppm, a copper content of preferably ≤ 20 ppm, a cobalt content of preferably ≤ 20 ppm, an antimony content of preferably ≤ 2 ppm, a selenium content of preferably ≤ 10 ppm and a zinc content of preferably ≤ 20 ppm.

[0053] In particular, it is preferred that the aluminum platelets have a mercury content of preferably ≤ 1 ppm, an arsenic content of preferably ≤ 2 ppm, a lead content of preferably ≤ 10 ppm and a cadmium content of preferably ≤ 1 ppm.

[0054] If copper platelets are used as a metallic platelet-shaped substrate, they preferably have a copper content of >_ 95 wt.%, more preferably ≥ 96 wt.%, particularly preferably ≥ 97 wt.% and very particularly preferably ≥ 98 wt.%, in each case based on the total weight of the copper platelet. In a preferred embodiment, the copper platelets further have a mercury content preferably of ≤ 1 ppm, an arsenic content preferably of ≤ 3 ppm, a lead content preferably of ≤ 20 ppm, a cadmium content preferably of ≤ 15 ppm, a barium content preferably of ≤ 10 ppm, a chromium content preferably of ≤ 20 ppm, a nickel content preferably of ≤ 20 ppm, a cobalt content preferably of ≤ 20 ppm, an antimony content preferably of ≤ 2 ppm and a selenium content preferably of ≤ 10 ppm.

[0055] If gold bronze platelets are used as a metallic platelet-shaped substrate, they preferably have a copper content in a range from 70 wt.% to 95 wt.%, a zinc content in a range from < 5 wt.% to < 30 wt.%, an aluminum content in a range from 0.01 wt.% to ≤ 1.5 wt.%, a tin content in a range from 0.001 wt.% to ≤ 0.5 wt.%, in each case based on the total weight of the gold bronze platelets. In a preferred embodiment, the gold bronze flakes further have a mercury content preferably of ≤ 1 ppm, an arsenic content preferably of ≤ 3 ppm, a lead content preferably of ≤ 20 ppm, a cadmium content preferably of ≤ 15 ppm, a barium content preferably of ≤ 10 ppm, a chromium content preferably of ≤ 20 ppm, a nickel content preferably of ≤ 20 ppm, a cobalt content preferably of ≤ 20 ppm, an antimony content preferably of ≤ 2 ppm and a selenium content preferably of ≤ 10 ppm.

[0056] According to one embodiment, the nail polish composition according to the invention contains, as an effect pigment, a metallic platelet-shaped, metallic engraved substrate with diffractive elements, which has no further optically active coatings. This substrate is preferably made of aluminum.

[0057] According to a further preferred embodiment, the metallic, platelet-shaped embossed substrates to be used according to the invention are not further coated, apart from the coating with a leafing additive required according to the invention. Metal oxide layers that naturally form in air, such as an aluminum oxide layer, are not considered a coating.

[0058] In this case, the effect pigment consists only of a metallic layer into which the embossed structure, preferably a linear structure, is embossed. Such effect pigments are particularly preferred because their overall thickness is minimal due to the lack of additional coatings. Such pigments are particularly easy to incorporate into nail polishes.

[0059] The production of such effect pigments is described, for example, in EP 643745 B1 or EP 1901870 B1.

[0060] Such pigments are commercially available, for example, under the trade names Metalure ®< Prismatic and Silverdream Prismatic from Eckart America.

[0061] In a further embodiment of the invention, the metallic platelet-shaped, engraved substrate, preferably an aluminum substrate, has optically active coatings containing at least one layer package of: A) a low-index layer with a refractive index < 1.8 and B) a high-index layer with a refractive index of over 2.0 on.

[0062] These layers are also preferably produced using PVD processes.

[0063] The low-refractive-index layer preferably consists of SiO 2 , Al 2 O 3 , B 2 O 3 or MgF 2 .

[0064] The high-index coating present in this embodiment can comprise at least one high-index layer made of or with at least one metal oxide, metal hydroxide and / or metal oxide hydrate, wherein the metal ion is preferably selected from the group of metals consisting of Ti, Fe, Sn, Mn, Zr, Sr, Ba, Ni, Ag, Zn, Cu, Cr and Co, and more preferably selected from the group of metals consisting of Ti, Fe, Sn, Zr, Zn and Cr, and particularly preferably selected from the group of metals consisting of Ti and Fe.

[0065] In further embodiments, high-index metal sulfides such as MoS 2 can also be used.

[0066] In a further embodiment, the optionally present high-index coating can comprise, alternatively or in addition to the layer comprising at least one metal oxide, metal hydroxide and / or metal oxide hydrate, at least one semitransparent metal layer. The metals of the semitransparent metal layer can be selected from the group consisting of Ag, Al, Cr, Ni, Au, Pt, Pd, Cu, Zn and Ti, preferably selected from the group consisting of Ag, Au and Cu. Of course, the semitransparent metal layer can also comprise alloys or mixtures of the metals listed above. The average thickness of the semitransparent metal layer is preferably in a range from 1 nm to 30 nm, more preferably in a range from 4 nm to 26 nm and particularly preferably in a range from 7 nm to 21 nm.

[0067] In further embodiments, the metallic platelet-shaped, engraved substrate, preferably an aluminum substrate, has only one layer applied to both sides by PVD processes, which layer preferably has a low refractive index. Such layers are not intended to contribute to the optical activity of the effect pigment, but merely to impart mechanical stability. Such effect pigments are described, for example, in WO 2000 / 34395.

[0068] For example, Viavi (Santa Rosa, California, USA) offers embossed effect pigments with corresponding coatings under the trade name SpectraFlair ®<.

[0069] Further examples of such effect pigments have the following layer structures. Al / SiO 2 / Al / SiO 2 / Al Cr / MgF 2 / Al / MgF 2 / Cr MoS 2 / SiO 2 / Al / SiO 2 / MoS 2 Fe 2 O 3 / SiO 2 / Al / SiO 2 / Fe 2 O 3

[0070] The production of such effect pigments is described, for example, in US 6,749,777 B2.

[0071] With these effect pigments, the color impression is influenced not only by diffraction due to the diffractive structure but also by interference phenomena from the additional coatings. This can result in a "disturbance" of the pure rainbow effect. For the purposes of this invention, the resulting effect is nevertheless also referred to as the "rainbow effect."

[0072] In a further embodiment, the platelet-shaped, metallic embossed substrate consists of a mixed layer of metal, which is preferably present predominantly as a nanometal, and a metal oxide, wherein the metal and the metal oxide contain the same metal. Such PVD effect pigments are described in EP 2598578 B1 and are characterized by the very low reflection of these pigments. They are essentially black effect pigments, but nevertheless exhibit a rainbow effect due to their embossing. The metal used here is preferably aluminum or chromium. The average thicknesses of such embossed effect pigments range from 40 to 130 nm.

[0073] In a further embodiment, the surface-modified effect pigments according to the invention, to be used in a nail polish composition, based on metallic platelet-shaped substrates with coatings, preferably have an average total thickness h 50 from a range of 20 nm to 4000 nm, more preferably from a range of 30 nm to 3000 nm, particularly preferably from a range of 70 nm to 2000 nm, and most preferably from a range of 230 nm to 1300 nm. Average total thickness is understood to mean the complete average thickness of the surface-modified effect pigment, i.e. metallic platelet-shaped substrate plus optional coating plus surface modification. Leafing additive:

[0074] An essential component of the present invention is the provision of a nail polish in which the leafing properties of the surface-modified effect pigments are very well emphasized.

[0075] According to the invention, the leafing additives used for surface modification are those made from phosphoric acid esters of the general formula: (RO) x -P(O)(OR 1< ) (3-x) (I). Where x = 1 to 3 and the radicals R, R 1< , R 2< , and R 3< have the following meanings: R = linear and / or branched alkyl radical having a carbon chain from a range of C 8 to C 20 ) and R 1< = H. In the phosphoric acid esters according to formula (I), x is 1 or 2 in preferred embodiments, although mixtures of the mono- and diphosphoric acid ester are also possible. R is more preferably C 10 to C 20 and more preferably C 12 to C 18 and most preferably C 12 to C 16 . In further preferred embodiments, R = C 12 to C 18 and R 1< = H.

[0076] Monocetylphosphoric acid ester, dicetylphosphoric acid ester, and mixtures thereof are particularly preferred as leafing additives.

[0077] It is particularly preferred that the embossed effect pigments are coated with the additive in a separate step before being incorporated into the nail polish system.

[0078] A process according to the invention for the surface modification of the embossed effect pigments comprises the following steps: i. Suspending the embossed effect pigment comprising a platelet-shaped metallic substrate with an embossed structure in at least one solvent; ii. Adding the leafing additive, optionally at elevated temperature, to the suspension from step i. and stirring the resulting suspension; iii. Separating and optionally drying the surface-modified effect pigment obtained according to step ii. from the solvent.

[0079] Solvents used here are those which, on the one hand, are as compatible as possible with the nail polish system according to the invention and are physiologically acceptable, and, on the other hand, are able to sufficiently dissolve the leafing additive.

[0080] When using the phosphoric acid esters as leafing additives, preferred solvents are ethyl acetate and butyl acetate and their mixtures and most preferred is butyl acetate.

[0081] The optionally elevated temperature serves to improve the solubility of the additive in the solvent and is preferably in a range from 40 to 100 °C or up to the boiling temperature of the solvent and particularly preferably in a range from 50 to 90 °C.

[0082] The leafing additive for surface modification is preferably used in an amount from a range of 5 wt.% to 50 wt.%, particularly preferably from a range of 10 wt.% to 40 wt.% and very particularly preferably from a range of 15 wt.% to 35 wt.%, in each case based on the total weight of the embossed effect pigment used.

[0083] Since the additive amounts stated here refer to the starting material, the actual additive amount in the finished coated embossed effect pigment may be lower, since, for example, at an amount of 50 wt.%, not all of the additive can be absorbed onto the pigment surface. Accordingly, smaller amounts of the leafing additives may be found in the nail polish according to the invention containing the embossed effect pigments.

[0084] However, the relatively high additive quantities in the starting material result in a very high and dense coating of the effect pigment surface with the additive.

[0085] In particularly preferred embodiments, at least one phosphoric acid ester of the formula (I), where in each case R is a linear alkyl radical with preferably C 10 to C 20 , particularly preferably C 12 to C 18 and R 1< = H, is used as leafing additive in the process according to the invention in a total amount from a range of 15 wt.% to 40 wt.%, more preferably a range of 20 wt.% to 35 wt.%, based on the total weight of the embossed effect pigment used.

[0086] Below the amounts of the specific substances to be used as starting material for surface modification specified for the various effect pigment types in the embossed effect pigments surface-modified according to the invention or the various effect pigment / additive combinations described above, sufficient leafing of the effect pigments does not occur. Exceeding the specified amounts of additives may result in excessive amounts of additives being incorporated into the finished nail polish composition, causing disruptive effects.

[0087] At the higher baseline values ​​of the initial concentration ranges specified above, some of the leafing additives used will not adhere to the surface of the embossed effect pigment because its surface is already saturated. However, for high and even coverage, sufficient amounts of additive, which may include a significant excess, are necessary, as only then can a strong leafing effect be expected.

[0088] Naturally, the amount of leafing additive can be reduced the smaller the specific surface area of ​​the embossed effect pigment, and vice versa. A lower specific surface area is found in very large and / or thick embossed effect pigments. Thick embossed effect pigments are particularly obtained in those where the metallic embossed substrate is coated with additional layers.

[0089] According to the invention, "total amount" means the complete amount of starting material of the leafing additive, regardless of whether it is exclusively at least one phosphoric acid ester.

[0090] The embossed effect pigments surface-modified with the leafing additive according to the invention can be used not only in the nail polish according to the invention but also in other cosmetic formulations. The surface-modified effect pigments are distinguished by their excellent leafing behavior in nail polish compositions, and in particular in the nail polish composition according to the invention. Binder:

[0091] The nail polish compositions according to the invention comprise at least one hydrocarbon resin as a binder, wherein the binder preferably has a binder solids content from a range of 25 wt.% to 64 wt.%, more preferably from a range of 25 wt.% to 60 wt.%, more preferably from a range of 28 wt.% to 55 wt.%, particularly preferably from a range of 29 wt.% to 50 wt.% and very particularly preferably from a range of 35 wt.% to 43 wt.%, in each case based on the total weight of the nail polish composition.

[0092] Below a binder content of 25 wt.%, no good optical effects could be seen from the effect pigments in the applied nail polish.

[0093] Above 63 wt.%, the optical quality of the effect pigments also decreases and the viscosity of the nail polish compositions according to the invention becomes increasingly too high.

[0094] Hydrocarbon resins are synthetic resins formed by the reaction of hydrocarbons (except olefins) with themselves in the presence of aluminum chloride or sulfuric acid as a catalyst (see https: / / www.spektrum.de / lexikon / chemie / kohlenwasserstoffharze / 4959). Hydrocarbon resins are divided into three groups according to their structure: petroleum resins, coal tar resins, and terpene resins. Coumaron-indene resins are the most important group of coal tar resins. The reaction products of xylene and formaldehyde, the xylene-formaldehyde resins, are also considered hydrocarbon resins. In preferred embodiments, nail polish compositions containing aromatic hydrocarbon resins are used.

[0095] Other particularly preferred aromatic hydrocarbon resins are resins obtained predominantly or entirely by polymerizing various purified styrene monomers. The styrene monomers are preferably largely optically transparent ("water-clear").

[0096] Hydrocarbon resins represent a specific group of resins used for paints and printing inks.

[0097] This special class of resins is by no means a general term for resins that are based solely on hydrocarbons.

[0098] The hydrocarbon resins are produced in a conventional manner by heating high-boiling fractions from gasoline pyrolysis (pyrolysis oil) or the isoprene-free C5 fraction from gasoline pyrolysis in the presence of aluminum chloride. The hydrocarbon resins are soluble in most organic solvents, e.g., esters, ethers, chlorinated hydrocarbons, and aromatics.

[0099] Without being bound by theory, the inventors suspect that when using polar binders, the effect pigments coated with suitable additives are still partially wetted by the binder and therefore do not exhibit the desired leafing effect. In contrast, the resins of the nail polish composition according to the invention are unusually non-polar for nail polish compositions and therefore do not wet the effect pigments. This presumably allows the embossed effect pigments to better develop the leafing effect.

[0100] Typically, "hydrocarbon resins" are understood to be very low-molecular-weight polymers with molecular weights below 2,000 g / mol. However, it has surprisingly been shown that hydrocarbon resins with higher molecular weights can also be used in accordance with the invention.

[0101] The nail polish compositions according to the invention preferably comprise, as binders, hydrocarbon resins having an average molecular weight (M w ) in a range from 800 to 6,500 g / mol, preferably in a range from 900 to 6,000 g / mol or in a range from 1,200 to 5,500 g / mol. The average molecular weight M w was determined by gel permeation chromatography (GPC) using a polystyrene standard.

[0102] In a preferred embodiment, the nail varnish compositions according to the invention comprise at least two different hydrocarbon resins having a first average molecular weight M w from a range of 1,000 to 2,000 g / mol and a second average molecular weight M w from a range of 4,000 to 5,900 g / mol in a weight ratio of 1:1 to 1:10, preferably 1:1 to 1:8, particularly preferably 1:1 to 1:4 and very particularly preferably 1:1 to 1:2 of the two different hydrocarbon resins.

[0103] In a particularly preferred embodiment, the nail varnish compositions according to the invention comprise at least two different hydrocarbon resins having a first average molecular weight M w from a range of 1,200 to 1,600 g / mol and a second average molecular weight M w from a range of 4,500 to 5,500 g / mol in a weight ratio of 1:1 to 1:10, preferably 1:1 to 1:8, particularly preferably 1:1 to 1:4 and very particularly preferably 1:1 to 1:2 of the two different hydrocarbon resins.

[0104] These mixtures preferably relate to aromatic hydrocarbon resins which are obtained predominantly or entirely by polymerization of various purified styrene monomers.

[0105] The nail polish compositions according to the invention can comprise hydrocarbon resins as binders, such as Kristalex F100 Hydrocarbon Resin, Kristalex 5140 Hydrocarbon Resin, Kristalex 3070 Hydrocarbon Resin, Kristalex 3085 Hydrocarbon Resin, and Kristalex F115 Hydrocarbon Resin, all from Eastman. These resins are obtained predominantly or entirely by polymerizing various purified styrene monomers.

[0106] The nail varnish compositions according to the invention preferably comprise the hydrocarbon resins Kristalex F100 Hydrocarbon Resin and Kristalex 5140 Hydrocarbon Resin as binders.

[0107] In particularly preferred embodiments, the nail polish composition according to the invention contains hydrocarbon-containing resin in an amount which constitutes 80 to 100 wt.%, more preferably 90 to 100 wt.% and particularly preferably 95 to 100 wt.% of the total organic binder.

[0108] To the inventors' knowledge, the use of hydrocarbon resins in nail polishes as the main component of the binder is not common. Hydrocarbon resins are usually very rarely used as components of nail polishes, and when they are, they are used in relatively small amounts together with other binders.

[0109] In further embodiments, the nail polish composition according to the invention therefore contains no or virtually no additional binders from the group consisting of nitrocellulose, polyester resins, polyvinyl resins, alkyd resins, epoxy resins, or cellulose acetate butyrate. These binders are preferably present in proportions of less than 10 wt. %, more preferably less than 5 wt. %, particularly preferably less than 1 wt. %, and most preferably less than 0.1 wt. %, each based on the total weight of the hydrocarbon resins and additional binders. These binders have proven to be rather detrimental to achieving a truly strong rainbow effect.

[0110] Without being bound to any theory, the inventors suspect that in nail polish compositions containing the above-mentioned binders, these at least partially wet the effect pigments due to their stronger polarity and thus have poorer leafing properties. Solvent:

[0111] The nail polish compositions according to the invention preferably contain certain solvents. For example, ethyl acetate, butyl acetate, or isopropanol can be added as solvents to the nail polish compositions according to the invention.

[0112] The nail varnish composition according to the invention preferably contains a mixture of isopropanol, ethyl acetate and butyl acetate as solvent.

[0113] The nail varnish composition according to the invention particularly preferably contains the solvent mixture of isopropanol, ethyl acetate and butyl acetate in an amount of 70 to 100 wt.%, more preferably 75 to 98 wt.%, based on the total solvent of the nail varnish composition.

[0114] It is irrelevant whether these preferred solvents are introduced via the binders or the effect pigment dispersion.

[0115] In further preferred embodiments, the proportion of butyl acetate in this solvent mixture is 30 to 60 wt.% and particularly preferably 35 to 55 wt.%, based on the total solvent.

[0116] In a further particularly preferred embodiment, the proportion of isopropanol is below 20% by weight, preferably below 15% by weight, and more preferably below 10% by weight, in each case based on the total solvent.

[0117] Excessive amounts of isopropanol in the nail polish composition according to the invention lead to a poor visual appearance of the effect pigments. This is presumably due to the nail polishes drying too quickly after application.

[0118] The nail polish compositions according to the invention are extremely easy to apply to human or artificial fingernails and / or toenails. They are characterized by good flow during application and, after subsequent drying, form a homogeneous film on human or artificial fingernails and / or toenails.

[0119] In preferred embodiments, the nail polish according to the invention contains 50% by weight to 70% by weight, preferably 55% by weight to 68% by weight and particularly preferably 57 to 65% by weight of solvent, in each case based on the weight of the total nail polish.

[0120] Below a solvent content of 55 wt.%, the viscosity of the nail polish increases too much and the effect pigments cannot orient themselves optimally, which leads to a reduction or loss of the rainbow effect.

[0121] Above a solvent content of 70 wt.%, the viscosity of the nail polish decreases too much, which leads to poorly controlled application of the nail polish to the fingernail. Other ingredients:

[0122] The nail polish compositions according to the invention may additionally contain one or more other ingredients. These include, in particular, plasticizers and antioxidants.

[0123] As plasticizers, for example, glycols and their derivatives such as diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether or furthermore diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, glycol esters, derivatives of propylene glycol and in particular propylene glycol phenyl ether, propylene glycol diacetates, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether and diethylene glycol methyl ether, propylene glycol butyl ether, or mixtures thereof, can be used.

[0124] Furthermore, esters of carboxylic acids, such as citrates, in particular trimethyl citrate, tributyl citrate, trimethyl acetyl citrate, tributyl acetyl citrate, triethyl 2-hexyl acetyl citrate or phthalates, in particular dimethoxyethyl phthalate; or phosphates, in particular tricresyl phosphate, tributyl phosphate, triphenyl phosphate, tributoxyethyl phosphate or tartrates, in particular dibutoxy tartrate; adipates, carbonates, sebacates; benzyl benzoate, butyl acetyl ricinoleate, glyceryl acetyl ricinoleate, butyl glycolate, camphor, glycerol triacetates, N-ethyl-o,p-toluenesulfonamide, oxyethylene compounds such as oxyethylene oils, in particular vegetable oils, such as castor oil, hydrocarbon oils and mixtures thereof.

[0125] Preferred plasticizers are particularly hydrocarbon oils.

[0126] The weight proportions of the plasticizers in the total nail polish composition are preferably in a range from 0 to 15 wt.%, more preferably from 1 to 10 wt.%, and particularly preferably from 5 to 10 wt.%.

[0127] The nail polish composition according to the invention may further contain one or more antioxidants.

[0128] "Antioxidants" are understood to mean compounds that protect the components of the nail polish according to the invention, in particular the hydrocarbon binders, from the effects of oxygen, heat, ozone, and / or UV radiation. One or more such compounds can be used.

[0129] Examples of such compounds are IRGANOX ®< 1010, IRGANOX ®< 565, IRGANOX ®< 1076 (BASF) or sulfur-containing antioxidants such as zinc dibutyldithiocarbamate (PERKACIT ZDBC. (Performance additives Italy SpA). The antioxidants are preferably used in amounts from a range of 0 to 5 wt.%, more preferably from a range of 0.05 to 1 wt.%, based on the total nail polish composition. Other additives:

[0130] The nail polish composition according to the invention may further contain other conventional additives as are known to the person skilled in the art.

[0131] Such further additives include, for example, anti-settling agents, preservatives, oils, waxes, radical scavengers, wetting additives, dispersing agents, wetting aids, antifoam agents, perfume, neutralizing agents, thickeners, UV blockers, humectants, vitamins, proteins and mixtures thereof.

[0132] In contrast to the leafing additives, these additional additives are only added to the nail polish composition during the formulation of this composition and not separately in advance to the embossed effect pigment.

[0133] In further embodiments, the nail polish composition according to the invention preferably contains no anti-settling agents. Surprisingly, any settled surface-modified effect pigments can generally be redispersed simply by shaking, even without the addition of anti-settling agents.

[0134] The nail polish composition according to the invention preferably has a viscosity of 10 sec to 16 sec, measured with a DIN flow cup (DIN 4 mm) according to DIN 53211.

[0135] In preferred embodiments, the nail polish composition according to the invention contains embossed aluminum PVD effect pigments with a periodic pattern with diffractive elements, which are preferably lines with a line density of 11,000 to 16,000 lines / cm. These embossed aluminum PVD effect pigments are preferably coated with monocetylphosphoric acid ester, dicetylphosphoric acid ester, and mixtures thereof as a leafing additive. Aromatic hydrocarbon resins based on styrene monomers are used as the binder, and a mixture of isopropanol, ethyl acetate, and butyl acetate is used as the solvent, with this solvent mixture accounting for 70 to 100 wt. % of the total solvent in the nail polish composition.

[0136] In a further preferred embodiment, the nail polish composition according to the invention contains aluminum PVD effect pigments with an average thickness h 50 in a range from 14 to 40 nm, preferably in a range from 15 to 35 nm, as well as at least two different aromatic hydrocarbon resins and a mixture of isopropanol, ethyl acetate, and butyl acetate as solvent, this solvent mixture accounting for 70 to 100 wt. % of the total solvent in the nail polish composition. Here, too, phosphoric acid cetyl esters are preferably used as a leafing additive. Procedure:

[0137] The invention further relates to a process for producing the nail varnish composition according to the invention, comprising the steps i) surface modification of the embossed effect pigment by an additive in a dispersion in a solvent, ii) dissolving the hydrocarbon resin in a solvent or solvent mixture iii) mixing and homogenizing the dispersion according to i) with the binder solution according to ii).

[0138] The dissolution of the hydrocarbon resin in a solvent after step ii) is preferably carried out in one (number: 1) solvent or a mixture of at least two, preferably three, solvents. A mixture of isopropanol, ethyl acetate, and butyl acetate is particularly preferably used as the solvent mixture.

[0139] Butyl acetate is preferred as the single solvent.

[0140] In further preferred embodiments, the solvent of step i) will also consist of isopropanol, ethyl acetate and butyl acetate or a mixture thereof in order not to introduce further, potentially interfering solvents into the nail polish.

[0141] Preferably, step i) is carried out according to the following procedure discussed above.

[0142] A process according to the invention for the surface modification of the embossed effect pigments comprises the following steps: i. Suspending the embossed effect pigment comprising a platelet-shaped metallic substrate with an embossed structure in at least one solvent; ii. Adding the leafing additive, optionally at elevated temperature, to the suspension from step i. and stirring the resulting suspension; iii. Separating and optionally drying the surface-modified embossed effect pigment obtained according to step ii. from the solvent.

[0143] Furthermore, when selecting the metallic embossed effect pigments, it is preferred to choose those which are present in their original dispersion in a solvent from the preferred group of isopropanol, ethyl acetate and butyl acetate or mixtures thereof, since the solvent of the metallic effect pigment dispersion also enters the nail varnish according to the invention in small amounts unless complex rewetting steps are used.

[0144] Particularly when using single-layer embossed metallic effect pigments, especially single-layer embossed aluminum effect pigments, these effect pigments produced by PVD processes are always present in a dispersion, since they tend to agglomerate as powders.

[0145] The invention also relates to a method for coating a natural or artificial fingernail comprising the steps: a) coating the natural or artificial fingernail with a nail varnish composition according to the invention and subsequent drying of the nail varnish, b) optionally subsequent coating of the nail varnish with a clear varnish.

[0146] Applying the clear coat significantly increases the abrasion resistance of the nail polish. Due to the pronounced leafing effect of the effect pigments in the nail polish, it naturally has rather low abrasion resistance.

[0147] Before step a), the natural or artificial nail can also be coated with a clear varnish to create the smoothest possible surface. This procedure is recommended if the nails are very rough.

[0148] The subsequent coating with clear varnish in step b) can be carried out with the same or a different clear varnish as the nail varnish according to the invention. However, this clear varnish must not contain any effect pigments, as these would overshadow the desired effect of the nail varnish according to the invention.

[0149] However, the clear coat in step b) may contain conventional color pigments or dyes. Particularly in combination with metallic PVD aluminum pigments or with thin, wet-milled aluminum effect pigments with an h 50 value of 20 to less than 100 nm, visually very attractive effects can be achieved. Preferably, the nail polish compositions according to the invention pigmented with the effect pigments exhibit a mirror finish after step a).

[0150] In a further embodiment, the nail polish composition according to the invention can be overcoated with a low-viscosity UV-curing clear coat in order to increase the abrasion resistance of the nail polish composition according to the invention.

[0151] Solvent-based clearcoats can also preferably be used. Without being bound by theory, the clearcoat is preferably based on polar binders that interact only slightly with the hydrocarbon resins of the clearcoat according to the invention. In particularly preferred embodiments, these clearcoats are based on binders such as polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), or mixtures thereof.

[0152] Furthermore, the clearcoat preferably contains solvents that do not dissolve or partially dissolve the non-polar hydrocarbon resins of the coating according to the invention. For example, isopropanol is preferably used for this purpose. Otherwise, the leafing effect pigments may also be partially dissolved and their orientation may be disrupted, thereby impairing the mirror gloss effect.

[0153] Surprisingly, these preferred clear coats have very good adhesion resistance to the nail polish according to the invention. Embossed surface-modified effect pigments according to the invention:

[0154] A further object of the present invention is to provide an embossed effect pigment for use in a nail polish composition which has an improved rainbow effect as well as improved chroma and brilliance.

[0155] The invention also relates to an embossed effect pigment comprising a platelet-shaped metallic substrate with an embossed structure, which is produced by PVD processes and by coating with a leafing additive made of phosphoric acid esters of the general formula: (RO) x -P(O)(OR 1< ) (3-x) (I) where x = 1 or 2, R = linear and / or branched alkyl radical with a carbon chain from a range of C 12 to C 20 and R 1< = H.

[0156] This embossed effect pigment is preferably a single-layer effect pigment with a metallic aluminum substrate. The embossed structure is also preferably composed of lines with a line density of 5,000 to 20,000 lines / cm. The lines are preferably wavy ("sinusoidal") lines, as this structure is particularly easy to produce.

[0157] According to the invention, this preferred embossed effect pigment is treated with a leafing additive for surface modification, which consists of monocetylphosphoric acid ester, dicetylphosphoric acid ester and mixtures thereof.

[0158] In a further preferred embodiment, the embossed surface-modified effect pigment is produced in a process which comprises the following steps: i. Suspending the embossed effect pigment comprising a platelet-shaped metallic substrate with an embossed structure in at least one solvent; ii. Adding the leafing additive, optionally at elevated temperature, to the suspension from step i. and stirring the resulting suspension; iii. Separating and optionally drying the surface-modified embossed effect pigment obtained according to step ii. from the solvent.

[0159] The leafing additive will be used in a range of 15 wt% to 50 wt% based on the total amount of substrate.

[0160] An excess of additive is necessary to achieve a stable leafing effect.

[0161] In a further aspect of the invention, the embossed surface-modified effect pigments described above can also be used in other nail varnishes.

[0162] In a further aspect of the invention, the embossed, surface-modified effect pigments described above can be used in other cosmetic applications. These include, for example, body powder, face powder, pressed or loose powder, powder cream, eye makeup such as eye shadow, mascara, eyeliner, liquid eyeliner, eyebrow pencil, lip balm, lipstick, lip gloss, lip liner, hair styling compositions such as hairspray, hair mousse, hair gel, hair wax, hair mascara, permanent or semi-permanent hair dyes, temporary hair dyes, or skin care compositions such as lotions, gels, and emulsions.

[0163] The surface-modified effect pigments according to the invention are combined with raw materials, auxiliaries, and active ingredients suitable for the respective application. The total concentration of surface-modified effect pigments according to the invention in the cosmetic formulation can be between 0.001 wt. % for rinse-off products and 40.0 wt. % for leave-on products, each based on the total weight of the formulation. Aspects:

[0164] According to one aspect 1), the present invention relates to an embossed effect pigment comprising a platelet-shaped metallic substrate with an embossed structure, which is produced by PVD processes and by coating with a leafing additive made of phosphoric acid esters of the general formula: (RO) x -P(O)(OR 1< ) (3-x) where x = 1 or 2, R = linear and / or branched alkyl radical with a carbon chain from a range of C 12 to C 20 and R 1< = H.

[0165] According to one aspect 2), the present invention relates to an embossed effect pigment according to aspect 1, wherein the metallic substrate consists of aluminum and the embossed structure is lines having a line density of 5,000 to 20,000 lines / cm.

[0166] According to one aspect 3), the present invention relates to an embossed effect pigment according to one of aspects 1 or 2, wherein monocetylphosphoric acid esters, dicetylphosphoric acid esters and mixtures thereof are used as leafing additive for the surface modification of the metallic embossed substrate.

[0167] According to one aspect 4), the present invention relates to an embossed effect pigment according to one of aspects 1 to 3, wherein the leafing additives are applied by a process comprising the following steps: i. Suspending the embossed effect pigment comprising a platelet-shaped metallic substrate with an embossed structure in at least one solvent, ii. Adding the leafing additive at optionally elevated temperature to the suspension from step i. and stirring the resulting suspension, iii. Separating and optionally drying the surface-modified embossed effect pigment obtained according to step ii. from the solvent, and wherein the leafing additive is used in a range of 15 wt% to 50 wt% based on the total amount of substrate.

[0168] According to a further aspect 5), the present invention relates to the use of the surface-modified, embossed effect pigments according to aspects 1 to 4 in further cosmetic applications which are taken from the group consisting of body powder, face powder, pressed or loose powder, powder cream, eye make-up such as eye shadow, mascara, eyeliner, liquid eyeliner, eyebrow pencil, lip balm, 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 or skin care compositions such as lotions, gels, emulsions. Examples:

[0169] The following examples serve to further describe the invention and are not intended to be limiting in any way. All percentages are by weight. The terms NFA (nonvolatile content), solids content, and solids content are used interchangeably. I Preparation of the surface-modified effect pigments according to the invention Example 1:

[0170] In a 1L double-walled reactor, 198 g of the PVD aluminum effect pigment dispersion, commercially available Metalure Prismatic H-50550 AE (dispersion in ethyl acetate, solids content 5.05 wt. %, D 50 (Horiba LA-950) = approx. 50 µm, ECKART America) were dispersed in a solvent according to Table 1 below at 200 rpm and heated to 80°C. Subsequently, the additive phosphoric acid cetyl ester (CAS number: 3539-43-3, Hostaphat CC 100, Clariant) according to Table 1 below, dissolved in 20 g of the solvent used for dispersion (AE), was added to the aluminum effect pigment dispersion. After stirring for 6 hours at 80°C, the mixture was cooled and filtered through a Buchner funnel. Surface-modified PVD aluminum effect pigments were obtained as 5–25% dispersions. These were supplemented with ethyl acetate to form a pigment dispersion with an NFA of 5%. Examples 2 to 10:

[0171] The procedure was as in Example 1, except that commercially available Silverdream Prismatic H-50720 (dispersion in ethyl acetate, solids content 7.05 wt. %, D 50 (Horiba LA-950) = approx. 20 µm, ECKART America) was used as the PVD aluminum effect pigment, laurylphosphonic acid (LPS) was used as the additive, and butyl acetate (BA) was used as the solvent instead of ethyl acetate (AE). Details on the substances used, their amounts, and the adsorption temperature can be found in Table 1 below.

[0172] The solvents used in the final addition of the suction filtered product to the pigment dispersion as well as the resulting non-volatile fractions (NFA) of the dispersions can be found in columns 4 and 3 of Table 2 and Table 3, respectively.

[0173] Comparative Example 1: Here, the uncoated commercially available PVD aluminum effect pigment dispersion Metalure Prismatic H- 50550 AE with engraved wavy line grating (line density: 12,500 lines / cm) was used.

[0174] Comparative Example 2: Here, the uncoated commercially available PVD aluminum effect pigment dispersion Silverdream Prismatic H-50720 with engraved wavy line grating (line density: 12,500 lines / cm) was used. Table 1: Test parameters for coating the engraved PVD aluminum pigments with additive Example Engraved PVD pigment used Amount of PVD pigment dispersion / Amount of Al Amount of solvent for dispersing the PVD pigment [g] Additive Quantity of additive [in wt.%, based on aluminum] Solvent for dissolving additive Coating temperature [°C] 1 Metalure Prismatic H-50550 AE 198g / 10g 269,3 Hostaphat CC 100 20% AE* 60 2 Metalure Prismatic H-50550 AE 198g / 10g 269,3 Hostaphat CC 100 30% AE 60 3 Silverdream Prismatic H-50720 141,8 / 10 g 325,5 Hostaphat CC 100 20% BA 80 4 Silverdream Prismatic H-50720 141,8 / 10 g 325,5 Hostaphat CC 100 30% BA** 80 5 Silverdream Prismatic H-50720 141,8 / 10 g 325,5 LPS 20% BA 80 6 Silverdream Prismatic H-50720 141,8 / 10 g 325,5 LPS 30% BA 80 7 Metalure Prismatic H-50550 AE 198g / 10g 269,3 Hostaphat CC 100 20% BA 80 8 Metalure Prismatic H-50550 AE 198g / 10g 269,3 Hostaphat CC 100 30% BA 80 9 Metalure Prismatic H-50550 AE 198g / 10g 269,3 LPS 20% BA 80 10 Metalure Prismatic H-50550 AE 198g / 10g 269,3 LPS 30% BA 80 *AE: Ethyl acetate; **BA: Butyl acetate 85 / 15: Mixture of 85% butyl acetate and 15% n-butanol II Preparation of the nail varnish compositions according to the invention IIa Preparation of the nail varnish according to the invention:

[0175] In a suitable stirred vessel, a 70 wt.% binder solution BM1prepared. For this purpose, 30 g of butyl acetate 85 / 15 were initially introduced, and 70 g of the binder Kristalex F100 Hydrocarbon Resin (M w = approx. 1,300 g / mol, Eastman) were added with stirring and cooling (12 °C) using a Dispermat CNf2 dissolver (Getzmann GmbH). The mixture was then stirred for 30 minutes at 3,000 to 4,000 rpm.

[0176] In a second suitable mixing vessel, a 60 wt.% binder solution BM2 For this purpose, 40 g of butyl acetate 85 / 15 were initially introduced, 60 g of the binder Kristalex 5140 Hydrocarbon Resin (M w = approx. 4,900 g / mol, Eastman) were added with stirring and cooling (12 °C) using a Dispermat CNf2 dissolver (Getzmann GmbH), and then stirred for 30 minutes at 3,000 to 4,000 rpm. The non-volatile content (binder solids content) of the binder solutions described above was determined according to DIN EN ISO 3251:2008.

[0177] Comparison nail polish: The unpigmented nail polish Nail Polish Base 18840 from International Lacquers was used as a comparison polish. This nail polish contains nitrocellulose as a binder and the solvents ethyl acetate, n-butyl acetate, and propan-2-ol. IIb Preparation of the pigmented nail varnish compositions according to the invention

[0178] To prepare the nail varnish compositions according to the invention according to Example 11, 5.49 g of BM1 and 12.84 g of BM2 and everything was thoroughly dispersed by stirring. Then, 2.08 g of the surface-modified PVD pigment from Example 1, followed by 2.04 g of isopropyl alcohol, 3.27 g of N-butyl acetate 85 / 15, and 0.87 g of ethyl acetate were added, and the nail polish was thoroughly dispersed.

[0179] The nail varnish compositions according to Examples 11 to 20 were prepared analogously to Example 11, the amounts of the individual components being selected so that the proportions listed in Table 2 below were each obtained in % by weight, based on the total nail varnish composition.

[0180] As comparative examples 3 to 12, defined amounts of the respective surface-modified embossed PVD aluminum effect pigment (according to examples 1 to 10) and non-surface-modified embossed PVD aluminum effect pigments (comparative examples 1 and 2) were also presented according to Table 3 below and incorporated into the comparative nail varnish.

[0181] As further comparative examples, the effect pigments of Comparative Examples 1 and 2 which were not surface-modified with additives were each incorporated with the nail varnish according to the invention (Comparative Examples 14 and 15) and the comparative nail clear varnish (Comparative Examples 16 and 17).

[0182] The exact amounts (in wt.%) can be found in Tables 2 and 3 below. (Comparative Example 13 is not available). Table 2: Quantities in wt.% of the added components of the nail polishes according to the invention sample PVD pigment used according to NFA PVD pigment dispersion % LSM*** Weight of PVD pigment dispersion% Addition AE* % Addition BA** 85 / 15% Addition of isopropanol % BM1% BM2% Σ% Comparative example 14 Comparison example 1 5 AE 11,52 12,88 3,39 21,64 50,59 100,0 Comparative example 15 Comparison example 2 7 AE 8,23 3,31 12,88 3,39 21,64 50,59 100,0 Example 11 Example 1 7,13 AE 8,08 3,43 12,88 3,39 21,64 50,59 100,0 Example 12 Example 2 7,94 AE 7,25 4,25 12,88 3,39 21,64 50,59 100,0 Example 13 Example 3 6,41 BA 85 / 15 8,98 10,99 4,49 3,39 21,64 50,59 100,0 Example 14 Example 4 7 BA 85 / 15 8,23 10,99 5,20 3,39 21,64 50,59 100,0 Example 15 Example 5 7,35 BA 85 / 15 7,84 10,99 5,67 3,39 21,64 50,59 100,0 Example 16 Example 6 7,31 BA 85 / 15 7,88 10,99 5,55 3,39 21,64 50,59 100,0 Example 17 Example 7 6,68 BA 85 / 15 8,62 10,99 4,84 3,39 21,64 50,59 100,0 Example 18 Example 8 4,27 BA 85 / 15 13,49 10,99 0 3,39 21,64 50,59 100,0 Example 19 Example 9 6,64 BA 85 / 15 8,67 10,99 4,84 3,39 21,64 50,59 100,0 Example 20 Example 10 6,25 BA 85 / 15 9,21 10,99 4,25 3,39 21,64 50,59 100,0 *AE: Ethyl acetate; **BA: Butyl acetate; *** LSM: Solvent of the pigment dispersion of the coated PVD pigment Table 3: Quantities in wt% of the added components for the comparative examples of nail polishes sample PVD pigment used according to NFA % LSM Weight of PVD pigment dispersion% Addition AE % Addition BA 85 / 15% Addition of isopropanol % Base 18840% Σ% Comparison example 16 Comparison example 1 5 AE 9,75 1,67 - - 88,58 100,0 Comparative example 17 Comparison example 2 7 AE 6,96 4,46 - - 88,58 100,0 Comparison example 3 Example 1 7,13 AE 6,84 4,58 - - 88,58 100,0 Comparison example 4 Example 2 7,94 AE 6,14 5,28 - - 88,58 100,0 Comparison example 5 Example 3 6,41 BA 85 / 15 7,61 - 3,81 - 88,58 100,0 Comparison example 6 Example 4 7 BA 85 / 15 6,96 - 4,46 - 88,58 100,0 Comparison example 7 Example 5 7,35 BA 85 / 15 6,63 - 4,79 - 88,58 100,0 Comparative example 8 Example 6 7,31 BA 85 / 15 6,67 - 4,75 - 88,58 100,0 Comparison example 9 Example 7 6,68 BA 85 / 15 7,30 - 4,12 - 88,58 100,00 Comparison example 10 Example 8 4,27 BA 85 / 15 11,42 - 0,00 - 88,58 100,0 Comparative example 11 Example 9 6,64 BA 85 / 15 7,34 - 4,08 - 88,58 100,0 Comparison example 12 Example 10 6,25 BA 85 / 15 7,80 - 3,62 - 88,58 100,0 Table 4: Final proportions of the individual components of the nail polish compositions according to the invention and the comparative examples in wt.%, based on the total nail polish composition sample Al content % BA % Total Kristalex F100% Kristalex 5140% Isopropanol % Total AE % Total Base 18840 % Total Σ% Comparative example 14 0,58 39,61 15,15 30,36 3,39 12,12 -- 100,0 Comparative example 15 0,58 39,61 15,15 30,36 3,39 12,15 -- 100,0 Example 11 0,58 39,61 15,15 30,36 3,39 12,12 -- 100,0 Example 12 0,58 39,61 15,15 30,36 3,39 12,13 -- 100,0 Example 13 0,58 39,52 15,15 30,36 3,39 10,99 -- 100,0 Example 14 0,58 39,57 15,15 30,36 3,39 10,99 -- 100,0 Example 15 0,58 39,57 15,15 30,36 3,39 10,99 -- 100,0 Example 16 0,58 39,57 15,15 30,36 3,39 10,99 -- 100,0 Example 17 0,58 39,57 15,15 30,36 3,39 10,99 -- 100,0 Example 18 0,58 39,57 15,15 30,36 3,39 10,99 -- 100,0 Example 19 0,58 39,57 15,15 30,36 3,39 10,99 -- 100,0 Example 20 0,58 39,57 15,15 30,36 3,39 10,99 -- 100,0 Comparison example 16 0,49 0,00** -- -- -- ** 10,93** 88,58* 100,0 Comparative example 17 0,49 0,00 -- -- -- 10,94 88,58 100,0 Comparison example 3 0,49 0,00 -- -- -- 10,93 88,58 100,0 Comparison example 4 0,49 0,00 -- -- -- 10,93 88,58 100,0 Comparison example 5 0,49 10,93 -- -- -- 0,00 88,58 100,0 Comparison example 6 0,49 10,94 -- -- -- 0,00 88,58 100,0 Comparison example 7 0,49 10,94 -- -- -- 0,00 88,58 100,0 Comparative example 8 0,49 10,93 -- -- -- 0,00 88,58 100,0 Comparison example 9 0,49 10,93 -- -- -- 0,00 88,58 100,0 Comparison example 10 0,49 10,93 -- -- -- 0,00 88,58 100,0 Comparative example 11 0,49 10,93 -- -- -- 0,00 88,58 100,0 Comparison example 12 0,49 10,93 -- -- 0,00 88,58 100,0 * The exact binder content in the commercially available comparative nail polish 18840 was not determined. ** The exact solvent contents of the commercially available comparative nail polish 18840 were not analyzed. In this table, only the added weight fractions of ethyl acetate and butyl acetate are listed for comparative examples 3 to 12. Isopropanol was not added. III Characterization of the optical properties of nail polish compositions IIIa Determination of chroma (25° geometry)

[0183] To determine the visual appearance of the nail polish compositions according to the invention and the nail polish compositions of the comparative examples, the respective nail polish composition was applied to contrasting cardboard using a spiral doctor blade (K Control Coater Model 623, Erichsen) in a wet film thickness of 100 µm and then dried at room temperature. The chroma (25° geometry) of the nail polish compositions applied in this way was measured as an indirect measure of leafing behavior using a BYK Mac device (BYK Gardner).

[0184] The values ​​were determined at at least five different locations during nail polish application. The resulting mean values ​​for chroma (25° geometry) are listed in Table 5 below.

[0185] Since this colorimetric quantity should increase with increasing leafing effect of the pigments, it can be regarded as an indirect measure of the leafing behavior of the embossed PVD pigments. IIIb: Rainbow effect and brilliance:

[0186] The quality of the rainbow effect was assessed visually on a scale of 0 (no rainbow effect) to 10 (excellent rainbow effect) using the squeegee prints. Commercially available colorimeters are difficult to meaningfully measure the optical effects of embossed effect pigments, which are based on diffraction processes, so a visual assessment was preferred here.

[0187] Furthermore, the brilliance was also assessed using the same grading system, where values ​​measured with conventional colorimeters can also be of little significance. Table 5: Results of the visual appearance of all examples and comparison examples based on squeegee prints: Pigments used Comparison examples (Nail Polish Base 18840) Examples (Nail polish according to the invention) Rainbow effect visual Brilliance visual Chroma 25° color measurement Rainbow effect visual Brilliance visual Chroma 25° color measurement Comparison example 1 1 2 11,7 0 0 1,1 Example 1 1 2 12,2 3 2 11,8 Example 2 1 2 13,2 3 2 15,8 Example 3 1 2 9,8 3 3 17,7 Example 4 1 2 10,5 2 2 11,6 Example 5 1 2 9,1 2 2 10,1 Example 6 1 2 9,4 3 3 16,7 Comparison example 2 2 1 9,3 0 0 1,1 Example 7 2 1 8,4 8 8 44,7 Example 8 2 1 9,0 10 10 55,9 Example 9 2 1 9,5 6 6 32,8 Example 10 2 1 8,9 6 6 31,2 IV Results:

[0188] All inventive examples 1 to 10 exhibit a higher rainbow effect than the corresponding comparative examples in the commercially available nail polish system. The differences are particularly significant for the embossed PVD pigment with a d 50 value of approximately 20 µm (Examples 7 to 10). These examples also show clear differences in brilliance and chroma between the two lacquer systems. The coarser embossed PVD pigment also tends to exhibit higher chroma values, although no improvements in brilliance were evident. Furthermore, it can be seen that, for the embossed PVD pigment with a d 50 value of approximately 20 µm, examples coated with Hostaphat CC100 (cetylphosphoric acid ester) tended to perform better than examples coated with laurylphosphonic acid (compare Examples 7 and 8 with Examples 8 and 10). However, this trend is not clear for the coarser embossed PVD pigments.

[0189] In all cases, the embossed PVD pigments used without additive pretreatment in both the comparative nail polish system and the nail polish system according to the invention (Comparative Examples 1 and 2) exhibit poor rainbow effect and brilliance. Apparently, the leafing effect of the embossed PVD pigments induced by the additive treatment is essential for the creation of an appealing rainbow effect.

Claims

1. Embossed effect pigment comprising a metallic substrate in platelet form with embossed structure, having been produced by PVD methods and by coating with a leafing additive composed of phosphoric esters of the general formula:         (R-O)x-P(O)(OR1)(3-x) wherein x = 1 or 2, R = linear and / or branched alkyl radical having a carbon chain from a range from C12 to C20, and R1 = H.

2. Embossed effect pigment according to Claim 1, wherein the metallic substrate consists of aluminium and the embossed structure are lines having a line density of 5000 to 20 000 lines / cm.

3. Embossed effect pigment according to either of Claims 1 and 2, wherein the leafing additive used for surface modification of the metallic embossed substrate is monocetyl phosphate, dicetyl phosphate and mixtures thereof.

4. Embossed effect pigment according to any of Claims 1 to 3, wherein the leafing additives are applied by a process comprising the following steps: i. suspending the embossed effect pigment comprising a metallic substrate in platelet form with embossed structure in at least one solvent, ii. adding the leafing additive at optionally elevated temperature to the suspension from step i. and stirring of the suspension then obtained, iii. separating and optionally drying the surface-modified embossed effect pigment obtained in step ii. from the solvent, and wherein the leafing additive, based on the total amount of substrate, is used within a range from 15% by weight to 50% by weight.

5. Embossed effect pigment according to any of Claims 1 to 4, which is a single-layer effect pigment having a metallic substrate of aluminium.

6. Process for producing an embossed effect pigment according to any of Claims 1 to 3, wherein the leafing additives are applied by a process comprising the following steps: i. suspending the embossed effect pigment comprising a metallic substrate in platelet form with embossed structure in at least one solvent, ii. adding the leafing additive at optionally elevated temperature to the suspension from step i. and stirring the suspension then obtained, iii. separating and optionally drying the surface-modified embossed effect pigment obtained in step ii. from the solvent, and wherein the leafing additive, based on the total amount of substrate, is used within a range from 15% by weight to 50% by weight.

7. Process according to Claim 6, wherein the solvents are ethyl acetate and butyl acetate and mixtures thereof.

8. Process according to Claim 6 or 7, wherein the solvent is butyl acetate.

9. Use of the surface-modified embossed effect pigments according to Claims 1 to 5 in nail varnishes, wherein the embossed effect pigments have a periodic pattern with diffractive elements and optionally one coating applied to the substrate, wherein the substrate has an elemental metal content of 80% to 100% by weight, based on the substrate, and wherein the nail varnishes further comprise b) at least one hydrocarbon resin as binder, c) at least one solvent or solvent mixture and d) optionally further auxiliaries.