Embossed Effect Pigment and Method of Manufacture of Embossed Effect Pigment

Abstract

An embossed effect pigment includes a metallic substrate in platelet form with embossed structure having a periodic pattern with diffractive elements, said 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. A method of manufacture of an embossed effect pigment includes suspending a metallic substrate in in at least one solvent, adding a leafing additive to the suspension including the metallic substrate in the at least one solvent and stirring the suspension including the leafing additive, and separating the embossed effect pigment from the at least one solvent.

Claims

1-18. (canceled)

19. 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, wherein the leafing additive has the formula:
(R—O).sub.x—P(O)(OR.sup.1).sub.(3-x) wherein x=1 or 2, R is a linear or branched alkyl radical having a carbon chain ranging from C.sub.8 to C.sub.20 and R.sup.1 is H.

20. The embossed effect pigment according to claim 19, wherein the metallic substrate in platelet form includes aluminum with an embossed structure having 5,000 to 20,000 diffractive elements/cm.

21. The embossed effect pigment according to claim 19, wherein R is a linear or branched alkyl radical having a carbon chain ranging from C.sub.12 to C.sub.18.

22. The embossed effect pigment according to claim 19, wherein the leafing additive includes laurylphosphonic acid (R=12), monocetylphosphoric ester, dicetylphosphoric ester (R=16), or mixtures thereof.

23. The embossed effect pigment according to claim 19, wherein the substrate contains at least 80 wt-% aluminum.

24. The embossed effect pigment according to claim 19, wherein R is a linear or branched alkyl radical having a carbon chain ranging from C.sub.12 to C.sub.20.

25. The embossed effect pigment according to claim 19, wherein the metallic substrate is a single layered substrate made from aluminum.

26. 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, wherein the leafing additive has the formula:
(R—O).sub.x—P(O)(OR.sup.1).sub.(3-x) wherein x=1 or 2, R is a linear or branched alkyl radical having a carbon chain ranging from C.sub.8 to C.sub.20 and R.sup.1 is H, the embossed effect pigment having been produced by a process comprising: suspending the metallic substrate in at least one solvent, adding the leafing additive to the suspension comprising the metallic substrate and the at least one solvent and stirring the suspension including the leafing additive, separating the embossed effect pigment from the at least one solvent, wherein the amount of the leafing additive on the embossed effect pigment is in a range of 15 to 50 wt. %, based on the metallic substrate.

27. The embossed effect pigment according to claim 26, wherein adding the leafing additive to the suspension of the metallic substrate in the at least one solvent is conducted at a temperature within a range from 40° C. to 100° C.

28. The embossed effect pigment according to claim 26, wherein the process further comprises drying the embossed effect pigment treated with the leafing additive that has been separated from the at least one solvent.

29. A method of manufacture of an embossed effect pigment, the 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, wherein the leafing additive has the formula:
(R—O).sub.x—P(O)(OR.sup.1).sub.(3-x) wherein x=1 or 2, R is a linear or branched alkyl radical having a carbon chain ranging from C.sub.8 to C.sub.20 and R.sup.1 is H, the method comprising: suspending the metallic substrate in in at least one solvent, adding the leafing additive to the suspension comprising the metallic substrate in the at least one solvent and stirring the suspension including the leafing additive, separating the embossed effect pigment from the at least one solvent, wherein the amount of the leafing additive on the embossed effect pigment is in a range of 15 to 50 wt. %, based on the weight of the metallic substrate.

30. The method according to claim 29, wherein the at least one solvent comprises one or more of ethylacetate and butylacetate.

31. The method according to claim 29, wherein the at least one solvent is butylacetate.

32. The method according to claim 29, wherein adding the leafing additive to the suspension of the metallic substrate in the at least one solvent is conducted at a temperature within a range from 40° C. to 100° C.

33. The method according to claim 29, further comprising drying the embossed effect pigment treated with the leafing additive that has been separated from the at least one solvent.

Description

EXAMPLES

[0237] 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.

[0238] I Production of the Surface-Modified Effect Pigments of the Invention

Example 1

[0239] 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 μm, 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

[0240] 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 μm, 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.

[0241] 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.

[0242] Comparative example 1: 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.

[0243] Comparative example 2: 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 Amount of Amount PVD solvent for of additive pigment dispersion of [in % by dispersion/ the PVD wt., Solvent for Coating Engraved PVD amount of pigment based on dissolving temperature Example pigment used Al [g] Additive 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/10g 269.3 Hostaphat CC 20% BA 80 Prismatic H- 100 50550 AE 8 Metalure 198 g/10g 269.3 Hostaphat CC 30% BA 80 Prismatic H- 100 50550 AE 9 Metalure 198 g/10g 269.3 LPS 20% BA 80 Prismatic H- 50550 AE 10 Metalure 198 g/10g 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

[0244] II Production of the Nail Varnish Compositions of the Invention

[0245] IIa Production of the Nail Varnish Clearcoat of the Invention:

[0246] 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.

[0247] 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.

[0248] The nonvolatile content (binder solids content) of the above-described binder solutions was determined according to DIN EN ISO 3251:2008.

[0249] 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.

[0250] IIb Production of the Pigmented Nail Varnish Compositions of the Invention

[0251] 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.

[0252] 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.

[0253] 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.

[0254] 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).

[0255] 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 of PVD Weight of Addition Addition Addition of pigment pigment PVD of of iso- used dispersion pigment AE* BA** propanol Sample according to % SV*** dispersion % % 85/15% % BM1% BM2% Σ % 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 PVD Weight of Addition Addition pigment PVD Addition of of used NVC pigment of BA isoprop. Base Sample according to % SV dispersion % AE % 85/15% % 18840% Σ % 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 Base content BA % Kristalex Kristalex Isopropanol % AE % 18840% Sample % total F100% 5140% total total total Σ % 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.

[0256] III Characterization of the Optical Properties of Nail Varnish Compositions

[0257] IIIa Determination of Chroma (25° Geometry)

[0258] 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 μm 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).

[0259] 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.

[0260] IIIb: Rainbow Effect and Brilliance:

[0261] 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.

[0262] 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 181340) (Nail varnish of the invention) Rainbow effect Brilliance Chroma 25° Rainbow effect Brilliance Chroma 25° Pigments 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

[0263] IV Results:

[0264] 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 μm (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.

[0265] It was also found that, for the embossed PVD pigment having a d.sub.50 of about 20 μm, 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.

[0266] 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.