Nail Varnish Composition Containing Embossed Effect Pigments and Surface-Modified Embossed Effect Pigments

Abstract

The invention relates to a nail varnish composition comprising: a) an embossed effect pigment comprising a metallic substrate in platelet form with embossed structure having a periodic pattern with diffractive elements, said substrate having been produced by PVD methods, and optionally at least 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 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.

The invention further relates to a process for producing the nail varnish composition.

Claims

1. A nail varnish composition comprising: a) an embossed effect pigment comprising a metallic substrate in platelet form with embossed structure having a periodic pattern with diffractive elements, the substrate having been produced by PVD methods, wherein the substrate has an elemental metal content of 80% to 100% by weight, based on the substrate, and wherein the effect pigment has been treated with a leafing additive for surface modification, b) a binder including at least one hydrocarbon resin, and c) at least one solvent or solvent mixture.

2. The nail varnish composition as claimed in claim 1, wherein the leafing additive includes at least one of a phosphoric ester of the general formula:
(RO).sub.xP(O)(OR.sup.1).sub.(3-x)(I) a phosphonic ester and/or a phosphonic acid of the general formula
RP(O)(OR.sup.2)(OR.sup.3)(II) a fatty acid of the general formula
RCOOH(III) or an organofunctional silane of the general formula
RSi(OR.sup.4).sub.3(Iv) where x=1 to 3 and the R, R, R, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 radicals are defined as follows: R is a linear or branched alkyl radical having a carbon chain ranging from C.sub.8 to C.sub.20; R is a linear or branched alkyl radical having a carbon chain ranging from C.sub.12 to C.sub.26; R is a linear or branched alkyl radical having a carbon chain ranging from C.sub.8 to C.sub.24; R.sup.1 is H or a linear and/or branched alkyl radical having a carbon chain ranging from C.sub.1 to C.sub.6, wherein when x=1 R.sup.1s may be identical or different; R.sup.2 is H or a linear and/or branched alkyl radical having a carbon chain ranging from C.sub.1 to C.sub.6, R.sup.3 is H or a linear and/or branched alkyl radical having a carbon chain ranging from C.sub.1 to C.sub.6, where R.sup.2 and R.sup.3 may be identical or different, and R.sup.4 is a linear and/or branched alkyl radical having a carbon chain ranging from C.sub.1 to C.sub.4.

3. The nail varnish composition as claimed in claim 2, wherein the additive is a phosphoric ester of formula (I) with R being a linear or branched alkyl radical having a carbon chain ranging from C.sub.12 to C.sub.18 and R.sup.1 being H.

4. The nail varnish composition as claimed in claim 2, wherein the leafing additive used for surface modification of the effect pigment includes laurylphosphonic acid methyl ester, laurylphosphonic acid ethyl ester, laurylphosphonic acid (R=12), monocetylphosphoric ester, dicetylphosphoric ester (R=16), or mixtures thereof.

5. The nail varnish composition as claimed in claim 1, wherein the metallic substrate in platelet form with an embossed structure has 5,000 to 20,000 diffractive elements/cm.

6. The nail varnish composition as claimed in claim 1, wherein the metallic substrate in platelet form with embossed structure includes aluminum, copper, chromium, iron, or alloys thereof.

7. The nail varnish composition as claimed in claim 6, wherein the metallic substrate in platelet form with embossed structure includes aluminum.

8. The nail varnish composition as claimed in claim 1, wherein the at least one hydrocarbon resin includes a coumarone-indene resin, a polystyrene-containing resin, a resin derived from a formaldehyde resin by polycondensation, or mixtures thereof.

9. The nail varnish composition as claimed in claim 8, wherein the at least one hydrocarbon resin includes a polystyrene-containing resin obtained predominantly to entirely by polymerization of different styrene monomers.

10. The nail varnish composition as claimed in claim 1, wherein the at least one hydrocarbon resin accounts for 80% to 100% by weight of the overall binder.

11. The nail varnish compositions as claimed in claim 1, wherein the content of the at least one hydrocarbon resin is within a range from 25% by weight to 63% by weight, based on the overall nail varnish composition.

12. The nail varnish compositions as claimed in claim 1, wherein the at least one hydrocarbon resin includes at least two different hydrocarbon resins, a first resin of the at least two different hydrocarbon resins having a first average molecular weight M.sub.W ranging from 1000 to 2000 g/mol, a second resin of the at least two different hydrocarbon resins having a second average molecular weight M.sub.W ranging from 4000 to 5900 g/mol, and the first resin and the second resin being included in a weight ratio of 1:1 to 1:10.

13. The nail varnish compositions as claimed in claim 12, wherein the first average molecular weight M.sub.W ranges from 1200 to 1600 g/mol and the second average molecular weight M.sub.W ranges from 4500 to 5500 g/mol.

14. The nail varnish composition as claimed in claim 1, comprising a solvent mixture including isopropanol, ethyl acetate and butyl acetate, wherein the solvent mixture of isopropanol, ethyl acetate and butyl acetate accounts for 70% to 100% by weight of the overall solvent.

15. (canceled)

16. The process as claimed in claim 22, wherein step i) is effected by a process comprising the following steps: i. suspending the embossed effect pigment comprising the 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 obtained in step i. and stirring the suspension including the leafing additive, iii. separating and optionally drying the surface-modified embossed effect pigment obtained in step ii. from the solvent.

17. A process for coating a natural or synthetic fingernail, comprising the steps of: a) coating the natural or synthetic fingernail with a nail varnish composition as claimed in claim 1 and then drying the nail varnish composition, b) optionally subsequently coating the dried nail varnish composition with a clearcoat.

18. The process as claimed in claim 17, wherein the dried nail varnish composition is coated with a solvent-based clearcoat based on a binder including polyvinyl butyral, polyvinylpyrrolidone or mixtures thereof.

19. The nail varnish compositions as claimed in claim 2, wherein R.sup.1, R.sup.2, and R.sup.3 are each H or a linear and/or branched alkyl radical having a carbon chain ranging from C.sub.1 to C.sub.3, and R.sup.4 is a linear and/or branched alkyl radical having a carbon chain ranging C.sub.1 to C.sub.2.

20. The nail varnish composition as claimed in claim 8, wherein the at least one hydrocarbon resin includes a polystyrene-containing resin obtained predominantly to entirely by polymerization of different, largely optically transparent, styrene monomers.

21. The nail varnish composition as claimed in claim 1, the substrate including at least one coating applied thereon.

22. A process for producing a nail varnish composition comprising i) surface-modifying an embossed effect pigment by means of a leafing additive in a dispersion in a solvent, the effect pigment comprising a metallic substrate in platelet form with embossed structure having a periodic pattern with diffractive elements, the substrate having been produced by PVD methods, wherein the substrate has an elemental metal content of 80% to 100% by weight, based on the substrate; and ii) mixing and homogenizing the dispersion according to i) with a binder solution comprising a solvent and at least one hydrocarbon binder.

23. A process according to claim 22, including dissolving the at least one hydrocarbon resin in a solvent or solvent mixture to form said binder solution.

Description

EXAMPLES

[0291] The examples which follow serve for further description of the invention and are not supposed to be restrictive in any way. All percentages are percentages by weight. The terms NVC (nonvolatile content), proportion of solids and solids content are usable interchangeably.

[0292] I Production of the Surface-Modified Effect Pigments of the Invention

Example 1

[0293] In a 1 L jacketed reactor, 198 g of the PVD aluminum effect pigment dispersion of commercially available Metalure Prismatic H-50550 AE (dispersion in ethyl acetate, solids content 5.05% by weight, D.sub.50 (Horiba LA-950)=about 50 m, from ECKART America) was dispersed in a solvent according to table 1 below at 200 rpm/min and heated to 80 C. Subsequently, the phosphoric acid cetyl ester additive (CAS number: 3539-43-3, Hostaphat CC 100, from Clariant) according to table 1 below, dissolved in 20 g of the solvent (AE) used for dispersion, was added to the aluminum effect pigment dispersion. After stirring at 80 C. for 6 hours, the mixture was cooled down and filtered through a Buechner funnel. Surface-modified PVD aluminum effect pigments were obtained as 5-25% dispersions. These have been supplemented with ethyl acetate to give a pigment dispersion having an NVC of 5%.

Examples 2 to 10

[0294] The procedure was as in example 1, except that the PVD aluminum effect pigment used in some cases was commercially available Silverdream Prismatic H-50720 (dispersion in ethyl acetate, solids content 7.05% by weight, D.sub.50 (Horiba LA-950)=about 20 m, from ECKART America) and the additive used was in some cases laurylphosphonic acid (abbreviation: LPS), and the solvent used was butyl acetate (BA) rather than ethyl acetate (AE). The details relating to the substances used, the amounts thereof and the absorption temperature can be found in table 1 below.

[0295] The solvents used in the final supplementation of the product separated by suction filtration to give the pigment dispersion and the nonvolatile contents (NVCs) of the dispersions established can respectively be found in columns 4 and 3 of table 2 and table 3.

Comparative Example 1

[0296] Here, the uncoated commercially available PVD aluminum effect pigment dispersion Metallic Prismatic H-50550 AE with engraved wavy line lattice (line density: 12 500 lines/cm) was used.

Comparative Example 2

[0297] Here, the uncoated commercially available PVD aluminum effect pigment dispersion Silverdream Prismatic H-50720 with engraved wavy line lattice (line density: 12 500 lines/cm) was used.

TABLE-US-00001 TABLE 1 Experimental parameters for coating of the engraved PVD aluminum pigments with additive Amount of PVD Amount of Amount pigment solvent for of additive dispersion/ dispersion of [in % by Solvent for Coating Engraved PVD amount of the PVD wt., based dissolving temperature Example pigment used Al pigment [g] Additive on aluminum] additive [ C.] 1 Metalure 198 g/10 g 269.3 Hostaphat CC 20% AE* 60 Prismatic H- 100 50550 AE 2 Metalure 198 g/10 g 269.3 Hostaphat CC 30% AE 60 Prismatic H- 100 50550 AE 3 Silverdream 141.8/10 g 325.5 Hostaphat CC 20% BA 80 Prismatic H-50720 100 4 Silverdream 141.8/10 g 325.5 Hostaphat CC 30% BA** 80 Prismatic H-50720 100 5 Silverdream 141.8/10 g 325.5 LPS 20% BA 80 Prismatic H-50720 6 Silverdream 141.8/10 g 325.5 LPS 30% BA 80 Prismatic H-50720 7 Metalure 198 g/10 g 269.3 Hostaphat CC 20% BA 80 Prismatic H- 100 50550 AE 8 Metalure 198 g/10 g 269.3 Hostaphat CC 30% BA 80 Prismatic H- 100 50550 AE 9 Metalure 198 g/10 g 269.3 LPS 20% BA 80 Prismatic H- 50550 AE 10 Metalure 198 g/10 g 269.3 LPS 30% BA 80 Prismatic H- 50550 AE *AE: ethyl acetate; **BA: butyl acetate 85/15: mixture of 85% butyl acetate and 15% n-butanol

[0298] II Production of the Nail Varnish Compositions of the Invention

[0299] IIa Production of the Nail Varnish Clearcoat of the Invention:

[0300] In a suitable stirred vessel, a 70% by weight binder solution BM1 was produced. For this purpose, 70 g of the binder Kristalex F100 Hydrocarbon Resin (M.sub.w=about 1300 g/mol, from Eastman) was added to an initial charge of 30 g of butyl acetate 85/15 while stirring and cooling (12 C.) with the Dispermat CNf2 dissolver (from Getzmann GmbH), and then the mixture was stirred at 3000 to 4000 rpm/min for a further 30 minutes.

[0301] In a second suitable stirred vessel, a 60% by weight binder solution BM2 was produced. For this purpose, 60 g of the binder Kristalex 5140 Hydrocarbon Resin (M.sub.w=about 4900 g/mol, from Eastman) was added to an initial charge of 40 g of butyl acetate 85/15 while stirring and cooling (12 C.) with the Dispermat CNf2 dissolver (from Getzmann GmbH), and then the mixture was stirred at 3000 to 4000 rpm/min for a further 30 minutes. The nonvolatile content (binder solids content) of the above-described binder solutions was determined according to DIN EN ISO 3251:2008.

[0302] Comparative nail clearcoat: The unpigmented Nail Polish Base 18840 nail clearcoat from International Lacquers was used as a comparative lacquer. This nail lacquer contains nitrocellulose as binder, and the solvents ethyl acetate, n-butyl acetate and propan-2-ol.

[0303] IIb Production of the Pigmented Nail Varnish Compositions of the Invention

[0304] For production of the nail varnish compositions of the invention according to example 11, the entirety of an initial charge of 5.49 g of BM1 and 12.84 g of BM2 was well dispersed by stirring. Then 2.08 g of the surface-modified PVD pigment from example 1 and subsequently 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 varnish was well dispersed.

[0305] The nail varnish compositions according to examples 11 to 20 were produced analogously to example 11, choosing the amounts of the individual components so as to achieve the quantity ratios listed in table 2 below, each in wt.-% by weight, based on the overall nail varnish composition.

[0306] 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) according to table 3 below were likewise initially provided and incorporated into the comparative nail varnish.

[0307] As further comparative examples, the effect pigments that have not been surface-modified with additives from comparative examples 1 and 2 were each incorporated with the nail varnish of the invention (comparative examples 14 and 15) and with the comparative nail clearcoat (comparative examples 16 and 17).

[0308] The exact quantities (in % by weight) can be found in tables 2 and 3 below. (There is no comparative example 13.)

TABLE-US-00002 TABLE 2 Quantity ratios in % by weight of the added components of the nail varnishes of the invention PVD NVC pigment of PVD Weight of Addition used pigment PVD Addition of Addition of according dispersion pigment of BA** iso- Sample to % SV*** dispersion % AE* % 85/15% propanol % BM1% BM2% % Comparative Comparative 5 AE 11.52 12.88 3.39 21.64 50.59 100.0 example 14 example 1 Comparative Comparative 7 AE 8.23 3.31 12.88 3.39 21.64 50.59 100.0 example 15 example 2 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 8.98 10.99 4.49 3.39 21.64 50.59 100.0 85/15 Example 14 Example 4 7 BA 8.23 10.99 5.20 3.39 21.64 50.59 100.0 85/15 Example 15 Example 5 7.35 BA 7.84 10.99 5.67 3.39 21.64 50.59 100.0 85/15 Example 16 Example 6 7.31 BA 7.88 10.99 5.55 3.39 21.64 50.59 100.0 85/15 Example 17 Example 7 6.68 BA 8.62 10.99 4.84 3.39 21.64 50.59 100.0 85/15 Example 18 Example 8 4.27 BA 13.49 10.99 0 3.39 21.64 50.59 100.0 85/15 Example 19 Example 9 6.64 BA 8.67 10.99 4.84 3.39 21.64 50.59 100.0 85/15 Example 20 Example 10 6.25 BA 9.21 10.99 4.25 3.39 21.64 50.59 100.0 85/15 *AE: ethyl acetate; **BA: butyl acetate; ***SV: solvent of the pigment dispersion of the coated PVD pigment

TABLE-US-00003 TABLE 3 Quantity ratios in % by weight of the added components for the comparative examples of the nail varnishes Weight of PVD PVD Addition Addition pigment pigment Addition of of used dispersion of BA isoprop. Base Sample according to NVC % SV % AE % 85/15% % 18840% % Comparative Comparative 5 AE 9.75 1.67 88.58 100.0 example 16 example 1 Comparative Comparative 7 AE 6.96 4.46 88.58 100.0 example 17 example 2 Comparative Example 1 7.13 AE 6.84 4.58 88.58 100.0 example 3 Comparative Example 2 7.94 AE 6.14 5.28 88.58 100.0 example 4 Comparative Example 3 6.41 BA 7.61 3.81 88.58 100.0 example 5 85/15 Comparative Example 4 7 BA 6.96 4.46 88.58 100.0 example 6 85/15 Comparative Example 5 7.35 BA 6.63 4.79 88.58 100.0 example 7 85/15 Comparative Example 6 7.31 BA 6.67 4.75 88.58 100.0 example 8 85/15 Comparative Example 7 6.68 BA 7.30 4.12 88.58 100.00 example 9 85/15 Comparative Example 8 4.27 BA 11.42 0.00 88.58 100.0 example 10 85/15 Comparative Example 9 6.64 BA 7.34 4.08 88.58 100.0 example 11 85/15 Comparative Example 10 6.25 BA 7.80 3.62 88.58 100.0 example 12 85/15

TABLE-US-00004 TABLE 4 Final quantity ratios of the individual components of the nail varnish compositions of the invention and of the comparative examples in % by weight, based on the overall nail varnish composition Al Isopropanol Base content BA % Kristalex Kristalex % AE % 18840% Sample % total F100% 5140% total total total % Comparative 0.58 39.61 15.15 30.36 3.39 12.12 100.0 example 14 Comparative 0.58 39.61 15.15 30.36 3.39 12.15 100.0 example 15 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 Comparative 0.49 0.00** ** 10.93** 88.58* 100.0 example 16 Comparative 0.49 0.00 10.94 88.58 100.0 example 17 Comparative 0.49 0.00 10.93 88.58 100.0 example 3 Comparative 0.49 0.00 10.93 88.58 100.0 example 4 Comparative 0.49 10.93 0.00 88.58 100.0 example 5 Comparative 0.49 10.94 0.00 88.58 100.0 example 6 Comparative 0.49 10.94 0.00 88.58 100.0 example 7 Comparative 0.49 10.93 0.00 88.58 100.0 example 8 Comparative 0.49 10.93 0.00 88.58 100.0 example 9 Comparative 0.49 10.93 0.00 88.58 100.0 example 10 Comparative 0.49 10.93 0.00 88.58 100.0 example 11 Comparative 0.49 10.93 0.00 88.58 100.0 example 12 *The exact content of binder in the commercially available comparative nail varnish 18840 was not determined. **The exact contents of the solvents in the commercially available comparative nail varnish 18840 were not analyzed. In this table, for comparative examples 3 to 12, only the added proportions by weight of ethyl acetate and butyl acetate were listed. Isopropanol was not added.

[0309] III Characterization of the Optical Properties of Nail Varnish Compositions

[0310] IIIa Determination of Chroma (25 Geometry)

[0311] To determine the visual appearance of the nail varnish compositions of the invention and of the nail varnish compositions from the comparative examples, the respective nail varnish composition was applied to contrast charts in a wet film thickness of 100 m by means of a spiral applicator (K Control Coater model 623, from Erichsen) and then dried at room temperature. As an indirect measure of leafing characteristics, the chroma (25 geometry) of the nail varnish compositions thus applied was analyzed by the BYK Mac instrument (from BYK Gardner).

[0312] The values were determined at at least 5 different sites in the nail varnish application. Table 5 below lists the averages formed therefrom for chroma (25 geometry). Since this colorimetric parameter is supposed to rise with rising leafing effect of the pigments, it can be regarded as an indirect measure of the leafing characteristics of the embossed PVD pigments.

[0313] IIIb: Rainbow Effect and Brilliance:

[0314] The quality of the rainbow effect was assessed visually from a scale from 0 (no rainbow effect) to 10 (excellent rainbow effect) on the applicator drawdowns. Using the colorimeters available on the market, measurement of the optical effects of embossed effect pigments that are based on diffraction processes is barely viable, and therefore a visual assessment was preferred here.

[0315] Additionally likewise assessed by the same grade system was brilliance, for which values measured with conventional colorimeters can likewise be not very meaningful.

TABLE-US-00005 TABLE 5 Results for the visual appearance of all examples and comparative examples from applicator drawdowns: Comparative examples Examples (Nail Polish Base 18840) (Nail varnish of the invention) Pigments Rainbow effect Brilliance Chroma 25 Rainbow effect Brilliance Chroma 25 used visual visual colorimetry visual visual colorimetry Comparative 1 2 11.7 0 0 1.1 Example 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 Comparative 2 1 9.3 0 0 1.1 Example 2 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

[0316] IV Results

[0317] All inventive examples 1 to 10 have a higher rainbow effect compared to the corresponding comparative examples in the commercially available nail varnish system. The differences are particularly major in the case of the embossed PVD pigment with a d.sub.50 of about 20 m (examples 7 to 10). In these examples, distinct differences are likewise apparent in the brilliance and in the chroma in the two paint systems. In the case of the coarser embossed PVD pigment, a trend to higher chroma values is likewise apparent, although no improvements were apparent in brilliance.

[0318] It was also found that, for the embossed PVD pigment having a d.sub.50 of about 20 m, examples coated with Hostaphat CC100 (cetylphosphoric ester) tended to give the best results compared to examples coated with laurylphosphonic acid (cf. examples 7 and 8 with examples 8 and 10). For the coarser embossed PVD pigments, however, this trend is not clear.

[0319] In all cases, the embossed PVD pigments used without additive pretreatment are poor with regard to rainbow effect and brilliance both in the comparative nail varnish system and in the inventive nail varnish system (comparative examples 1 and 2). It is apparent that the leafing effect of the embossed PVD pigments induced by the additive treatment is essential to the occurrence of an appealing rainbow effect.