Surface-modified effect pigment and nail varnish composition

Abstract

The invention relates to a surface-modified effect pigment comprising particular additives and to the production thereof. The present invention further provides a nail varnish composition comprising a) at least one effect pigment that has been surface-modified with a starting material (additive), where the effect pigment comprises a substrate in platelet form and optionally at least one coating applied to the substrate, b) at least one hydrocarbon resin as binder, and c) at least one solvent or solvent mixture, where the starting material (additive) for surface modification of the effect pigment is at least one compound taken from the group consisting of phosphoric ester-containing, phosphonic ester-containing, phosphonic acid-containing, fatty acid-containing and/or silane-containing compounds or mixtures thereof.

Claims

1. A nail varnish composition comprising: a) at least one effect pigment surface-modified with a starting material (additive), wherein the effect pigment comprises a PVD aluminum pigment in platelet form and optionally comprises at least one coating applied to the PVD aluminum pigment, the PVD aluminum pigment having an average thickness h.sub.50 ranging from 13 nm to 60 nm, and wherein the starting material (additive) used for surface modification of the PVD aluminum pigment or the coating comprises phosphoric acid cetyl ester in an amount ranging from 10% by weight to 50% by weight based on the total weight of the optionally coated PVD aluminum pigment; b) at least one hydrocarbon resin as binder; and c) at least one non-aqueous solvent.

2. The nail varnish composition as claimed in claim 1, wherein the hydrocarbon resin comprises 80% to 100% by weight of the total weight of binder comprised in the nail varnish composition.

3. The nail varnish compositions as claimed in claim 1, wherein the hydrocarbon resin comprises at least two different hydrocarbon resins having an average molecular weight MW of 1200 to 1600 and an average molecular weight MW of 4500 to 5500 in a weight ratio of 1:1 to 1:10.

4. The nail varnish compositions as claimed in claim 1, wherein the content of hydrocarbon resin is within a range from 25% by weight to 64% by weight, based on the total weight of the nail varnish composition.

5. The nail varnish composition as claimed in claim 1, comprising the non-aqueous solvent mixture, the non-aqueous solvent mixture comprising isopropanol, ethyl acetate and butyl acetate.

6. The nail varnish composition as claimed in claim 5, wherein the non-aqueous solvent mixture of isopropanol, ethyl acetate and butyl acetate comprises 70% to 100% by weight of the total weight of solvent comprised in the nail varnish composition.

7. The nail varnish composition as claimed in claim 5, wherein the proportion of isopropanol is below 20% by weight, based on the total weight of solvent comprised in the nail varnish composition.

8. The nail varnish composition as claimed in claim 1, additionally comprising at least one of a plasticizer, antioxidant, antisettling agent, preservative, oil, wax, free-radical scavenger, wetting additive, dispersing aid, wetting agent, antifoam, perfume, neutralizing agent, thickener, UV blocker, humectant, vitamin, protein, and combinations thereof.

9. The nail varnish composition as claimed in claim 1, wherein the nail varnish composition after application to a glass plate by means of a bar applicator in a wet film thickness of 100 μm and subsequent drying at room temperature has at least 150 gloss units, measured at 20° geometry, and at least 1200 haze units (Hlog).

10. A nail varnish composition comprising a) at least one effect pigment surface-modified with a starting material (additive), wherein the effect pigment comprises a PVD aluminum pigment and optionally comprises at least one coating applied to the PVD aluminum pigment, b) at least one hydrocarbon resin as binder and c) at least one non-aqueous solvent or non-aqueous solvent mixture, wherein one or more of the coating and the starting material (additive) used for surface modification of the effect pigment comprises phosphoric acid cetyl ester.

11. The nail varnish composition as claimed in claim 10, wherein the hydrocarbon resin comprises 80% to 100% by weight of the total weight of binder comprised in the nail varnish composition.

12. The nail varnish compositions as claimed in claim 10, wherein the hydrocarbon resin comprises at least two different hydrocarbon resins having an average molecular weight MW of 1200 to 1600 and an average molecular weight MW of 4500 to 5500 in a weight ratio of 1:1 to 1:10.

13. The nail varnish compositions as claimed in claim 10, wherein the content of hydrocarbon resin is within a range from 25% by weight to 64% by weight, based on the total weight of the nail varnish composition.

14. The nail varnish composition as claimed in claim 10, comprising the non-aqueous solvent mixture, the non-aqueous solvent mixture comprising isopropanol, ethyl acetate and butyl acetate.

15. The nail varnish composition as claimed in claim 14, wherein the non-aqueous solvent mixture of isopropanol, ethyl acetate and butyl acetate comprises 70% to 100% by weight of the total weight of solvent comprised in the nail varnish composition.

16. The nail varnish composition as claimed in claim 14, wherein the proportion of isopropanol is below 20% by weight, based on the total weight of solvent comprised in the nail varnish composition.

17. The nail varnish composition as claimed in claim 10, additionally comprising at least one of a plasticizer, antioxidant, antisettling agent, preservative, oil, wax, free-radical scavenger, wetting additive, dispersing aid, wetting agent, antifoam, perfume, neutralizing agent, thickener, UV blocker, humectant, vitamin, protein, and combinations thereof.

18. The nail varnish composition as claimed in claim 10, wherein the nail varnish composition after application to a glass plate by means of a bar applicator in a wet film thickness of 100 μm and subsequent drying at room temperature has at least 150 gloss units, measured at 20° geometry, and at least 1200 haze units (Hlog).

Description

EXAMPLES

(1) 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.

(2) I Production of the Surface-Modified Effect Pigments of the Invention that are to be Used with Preference in a Nail Varnish Composition and Production of the Surface-Modified Effect Pigments as Claimed in Claim 1

Examples 1 to 7

(3) In a 1 L jacketed reactor, 300 g of the aluminum effect pigment METALURE A 41010 AE (dispersion in ethyl acetate, solids content 10%, D.sub.50 (Horiba LA-930)=9.5 μm to 10.5 μm, from ECKART GmbH) in a solvent according to table 2 below were dispersed at 200 rpm/min and heated to 40° C. Subsequently, the phosphoric acid cetyl ester additive (CAS number: 3539-43-3, Hostaphat CC 100, from Clariant) according to table 2 below, dissolved in 30 g of the solvent used for dispersion, was added to the aluminum effect pigment dispersion. After stirring at 90° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. Surface-modified aluminum effect pigments were obtained in the form of 5-25% dispersions, which, after incorporation into the clearcoat according to IIa (pigmentation level: 0.4% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, gave a nail varnish having mirror-like gloss.

(4) TABLE-US-00002 TABLE 2 Amount of Amount of Example Solvent solvent [g] additive [g] NVC [%].sup.1) 1 butyl acetate 85/100 0 3 10 2 butyl acetate 85/100 50 3 9 3 butyl acetate 85/100 100 3 11 4 butyl acetate 85/100 200 3 7 5 butyl acetate 85/100 300 3 23 6 butyl acetate 85/100 300 6 21 7 ethyl acetate 200 5.4 6 .sup.1)Nonvolatile content of the surface-modified effect pigment.

Examples 8 to 12

(5) In a 1 L jacketed reactor, 300 g of the aluminum effect pigment METALURE A 41506 EN (dispersion in ethanol, solids content 15%, D.sub.50 (Horiba LA-930)=5.5 μm to 6.5 μm, from ECKART GmbH) were dispersed in 300 g of solvent according to table 3 below at 200 rpm/min and heated to 40° C. Subsequently, the additive according to table 3 below in 30 g of the appropriate solvent was added to the aluminum effect pigment dispersion. After stirring at 90° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. Surface-modified aluminum effect pigments were obtained in each case in the form of a 10-20% dispersion, which, after incorporation into the clearcoat according to IIa (pigmentation level: 0.4% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, gave a nail varnish having mirror-like gloss.

(6) TABLE-US-00003 TABLE 3 Amount NVC Example Solvent Additive [g] [%] 8 butyl acetate 85/100 Hostaphat CC 100.sup.2) 3 18 9 butyl acetate 85/100 Hostaphat CC 100 6 15 10 methoxypropanol Hostaphat CC 100 9 18 11 methoxypropanol laurylphosphonic 6 14 acid.sup.3) 12 butyl acetate 85/100 laurylphosphonic acid 6 15 .sup.2)Phosphoric acid cetyl ester, CAS number: 3539-43-3, from Clariant. .sup.3)From Rhodia.

Example 13

(7) In a 1 L jacketed reactor, 300 g of the aluminum effect pigment METALURE A 41010 AE (dispersion in ethyl acetate, solids content 10%, D.sub.50 (Horiba LA-930)=9.5 μm to 10.5 μm, from ECKART GmbH) were dispersed in 50 g of butyl acetate 85/100 at 200 rpm/min and heated to 80° C. Subsequently, 3 g of the phosphoric acid cetyl ester additive (CAS number: 3539-43-3, Hostaphat CC 100, from Clariant) in 30 g of butyl acetate 85/100 were added to the aluminum effect pigment dispersion. After stirring at 40° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. A surface-modified aluminum effect pigment was obtained in the form of a 15% dispersion, which, after incorporation into the clearcoat according to IIa (pigmentation level: 0.4% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, gave a nail varnish with mirror-like gloss.

Example 14

(8) In a 1 L jacketed reactor, 300 g of the aluminum effect pigment METALURE A 41010 AE (dispersion in ethyl acetate, solids content 10%, D.sub.50 (Horiba LA-930)=9.5 μm to 10.5 μm, from ECKART GmbH) were dispersed in 50 g of butyl acetate 85/100 at 200 rpm/min and heated to 60° C. Subsequently, 3 g of the phosphoric acid cetyl ester additive (CAS number: 3539-43-3, Hostaphat CC 100, from Clariant) in 30 g of butyl acetate 85/100 were added to the aluminum effect pigment dispersion. After stirring at 40° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. A surface-modified aluminum effect pigment was obtained in the form of a 10% dispersion, which, after incorporation into the clearcoat according to IIa (pigmentation level: 0.4% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, gave a nail varnish with mirror-like gloss.

Examples 15 to 18

(9) In a 1 L jacketed reactor, 300 g of effect pigment according to table 4 below were dispersed in 300 g of solvent according to table 4 below at 200 rpm/min and heated to 90° C. Subsequently, the phosphoric acid cetyl ester additive (CAS number: 3539-43-3, Hostaphat CC 100, from Clariant) in 30 g of the appropriate solvent was added to the effect pigment dispersion. After stirring at 40° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. Surface-modified effect pigments were obtained in each case as a dispersion which, after incorporation into the clearcoat according to IIa (pigmentation level: 0.4% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, gave a nail varnish, the visual appearance of which was attributable to the effect pigment used in each case.

(10) TABLE-US-00004 TABLE 4 Additive NVC Example Effect pigment [g] Solvent [%] 15 SILVERSHINE S 3 monopropylene glycol 35 1500.sup.4) monomethyl ether.sup.8) 17 SYNCRYSTAL 3 monopropylene glycol 72 Silk Blue.sup.5) monomethyl ether 17 METALURE A 3 butyl acetate 85/100 12 31017 AE.sup.6) 18 METALURE A 6 butyl acetate 85/100 12 31017 AE.sup.6) .sup.4)Aluminum effect pigment paste, solids content 23% to 27%, D.sub.50 (CILAS 1064) = 12 μm to 18 μm, from ECKART GmbH. .sup.5)Titanium dioxide-coated pearlescent pigment with blue interference color, D.sub.50 (Malvern Mastersizer 2000) = 13 μm, from ECKART GmbH. .sup.67)Aluminum effect pigment, dispersion in ethyl acetate, solids content 10%, D.sub.50 (Horiba LA-930) = 17 μm, from ECKART GmbH.

Examples 19 to 24

(11) In a 1 L jacketed reactor, 300 g of the aluminum effect pigment METALURE L 55350 AE (dispersion in ethyl acetate, solids content 10%, D.sub.50 (Horiba LA-930)=11 μm to 12 μm, from ECKART GmbH) were dispersed in 300 g of solvent according to table 5 below at 200 rpm/min and heated to 40° C. Subsequently, the additive used in each case in 30 g of butyl acetate 85/100 was added to the aluminum effect pigment dispersion. After stirring at 100° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. Surface-modified aluminum effect pigments were obtained in each case in the form of a 11-20% dispersion, which, after incorporation into the clearcoat according to IIa (pigmentation level: 0.4% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, gave a nail varnish with mirror-like gloss.

(12) TABLE-US-00005 TABLE 5 Amount NVC Example Additive Solvent [g] [%] 19 laurylphosphonic acid butyl acetate 85/100 3 18 20 laurylphosphonic acid butyl acetate 85/100 6 18 21 laurylphosphonic acid monopropylene 6 18.5 glycol monomethyl ether 22 Hostaphat CS 120.sup.6) butyl acetate 85/100 6 15 23 Hostaphat CS 120 butyl acetate 85/100 15 15 24 Hostaphat CC 100 butyl acetate 85/100 3 11.7 .sup.6)Phosphoric acid stearyl ester, CAS number: 39471-52-8, from Clariant.

Examples 25 to 31, Comparative Example 1

(13) In a 1 L jacketed reactor, 200 g of Silverdream Moonlight 501 L (solids content 50%, D.sub.50 (CILAS 1064)=15 μm to 20 μm, from ECKART GmbH) were dispersed in 525 g of butyl acetate 85/100 at 200 rpm/min and heated to 40° C. Subsequently, the additive used according to table 6 in 30 g of butyl acetate 85/100 was added to the aluminum effect pigment dispersion. After stirring at 90° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. Surface-modified aluminum effect pigments were obtained in the form of a 45-60% dispersion, which, after incorporation into the clearcoat according to IIa (pigmentation level: 0.4% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, in the case of use of the surface-modified aluminum effect pigments from examples 26 to 32 gave a nail varnish having mirror-like gloss, or in the case of use of the surface-modified aluminum effect pigment from comparative example 1 gave a nail varnish without mirror-like gloss, with a matt aluminum gray hue.

(14) TABLE-US-00006 TABLE 6 Example/ comparative example Additive Amount [g] NVC [%] Example 25 Hostaphat CC 100 2.5 50 Example 26 Hostaphat CC 100 5 53 Example 27 Hostaphat CC 100 7.5 53 Example 28 Hostaphat CC 100 20 61 Example 29 Hostaphat CS 120 5 55 Example 30 Hostaphat CS 120 10 53 Example 31 Amphisol.sup.7) 10 46 Comparative example 1 Hostaphat CS 120 20 58 .sup.7)1-Hexadecanol phosphate, 2,2′-iminobis[ethanol] 1:1, CAS 69331-39-1, from DSM.

Comparative Examples 2 to 8

(15) In a 1 L jacketed reactor, 300 g of the aluminum effect pigment METALURE L 55350 AE (dispersion in ethyl acetate, solids content 10%, D.sub.50 (Horiba LA-930)=11 μm to 12 μm, from ECKART GmbH) were dispersed in 300 g of butyl acetate 85/100 at 200 rpm/min and heated to 100° C. Subsequently, the additive used according to table 7 in 30 g of butyl acetate 85/100 was added to the aluminum effect pigment dispersion. After stirring at 40° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. Surface-modified aluminum effect pigments were each obtained in the form of a 10-20% dispersion, which, after incorporation into the clearcoat according to IIa (pigmentation level: 0.4% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, gave a nail varnish without mirror-like gloss, but rather a nail varnish with a matt aluminum gray hue.

(16) TABLE-US-00007 TABLE 7 Comparative example Additive Amount [g] NVC [%] 2 SilCare Silicone 41M80.sup.8) 3 18 3 SilCare Silicone 41M80 15 15 4 Hostaphat KW 340 D.sup.9) 3 13 5 Hostaphat KW 340 D 15 13 6 Hostaphat KL 340 D.sup.10) 3 16 7 Hostaphat KL 340 D 15 14 .sup.8)INCI: C24-28 Alkyl Dimethicone, CAS number: 192230-29-8, from Aako BV or from Clariant. .sup.9)Mono-, di- and tri(alkyl tetraglycol ether) o-phosphoric ester, CAS number: 119415-05-3, from Clariant. .sup.10)Mono-, di- and tri(alkyl tetraglycol ether) o-phosphoric ester, CAS number: 121158-63-2; 121158-61-0; 121158-62-1, from Clariant.

Comparative Examples 9 to 11

(17) In a 1 L jacketed reactor, 300 g of Silverdream Moonlight 501 L (solids content 50%. D.sub.50 (CILAS 1064)=15 μm to 20 μm, from ECKART GmbH) were dispersed in 470 g of butyl acetate 85/100 at 200 rpm/min and heated to 90° C. Subsequently, the additive used in table 8 in 30 g of butyl acetate 85/100 was added to the aluminum effect pigment dispersion. After stirring at 40° C. for 6 hours, the mixture was cooled down and filtered through a Bichner funnel. Surface-modified aluminum effect pigments were obtained in the form of a 55-65% dispersion, which, after incorporation into the clearcoat according to IIa (pigmentation level: 1.5% by weight, based on total weight of the clearcoat), application to a synthetic fingernail and subsequent drying, gave a nail varnish without mirror-like gloss and/or without leafing effect.

(18) TABLE-US-00008 TABLE 8 Comparative example Additive Amount [g] NVC [%] 8 Hostaphat CK 100.sup.11) 7.5 59 9 Hostaphat CK 100 15 61 10 Hostaphat CK 100 30 59 11 Hostaphat CC 100 75 57 .sup.11)Potassium hexadecylhydrogenphosphate, CAS 19035-79-1, Hostaphat CK 100; from Clariant.

Comparative Example 12

(19) PVD aluminum pigment dispersion in ethyl acetate METALURE A-41010 AE, from ECKART GmbH, NVC: 10%, D.sub.50=9.50 μm to 10.50 μm.

Comparative Example 13

(20) PVD aluminum pigment dispersion in ethyl acetate METALURE L-55350 AE, from ECKART GmbH, NVC: 10%, D.sub.50=11.00 μm to 12.00 μm.

Comparative Example 14

(21) PVD aluminum pigment dispersion in ethyl acetate METALURE A-31017 AE, from ECKART GmbH, NVC: 10%, D.sub.50=9.50 to 10.50 μm.

Comparative Example 15

(22) Aluminum pigment paste SILVERSHINE S2100, from ECKART GmbH, NVC: 48.0% to 52.0%, D.sub.50=17.0 μm to 23.0 μm.

Comparative Example 16

(23) Mixture of 13% by weight of METALURE A-41010 AE, from ECKART GmbH and 0.2% by weight of Hostaphat CS 120, from Clariant.

(24) II Production of the Nail Varnish Compositions of the Invention

(25) IIa Production of the Clearcoat:

(26) In a suitable stirred vessel, a 70% by weight binder solution F100 was produced. For this purpose, 70 g of the binder Kristalex F100 Hydrocarbon Resin (from Eastman) were added to an initial charge of 30 g of butyl acetate 98/100 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.

(27) In a second suitable stirred vessel, a 60% by weight binder solution 5140 was produced. For this purpose, 60 g of the binder Kristalex 5140 Hydrocarbon Resin (from Eastman) were added to an initial charge of 40 g of butyl acetate 98/100 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.

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

(29) For production of the clearcoat, the 70% by weight binder solution F100 and the 60% by weight binder solution 5140 were combined according to the table below while stirring at 900 rpm/min with the IKA RW 20 Digital laboratory stirrer (from IKA) at room temperature and stirred for a further 5 to 10 minutes. Subsequently, the solvents according to the respective table below were added successively while stirring at 600 rpm/min.

(30) IIb Production of the Nail Varnish Compositions of the Invention

(31) For production of the inventive nail varnish compositions of examples 32 to 35, 96 g of the clearcoat were added to an initial charge of 4 g of the respective surface-modified effect pigment according to tables 9, 10 and 11 below with stirring at 600 rpm/min.

(32) TABLE-US-00009 TABLE 9 The inventive nail varnish compositions of examples 32 to 35 had a binder solids content of 30% by weight, based on the total weight of the clearcoat. Weight Example Product name (g) Weight ratio Example Clearcoat Kristalex F100 Hydrocarbon 22.3 Kristalex F100 Hydrocarbon 32 Resin, 70% by weight in butyl Resin:Kristalex 5140 acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 26.0 1:1 Resin, 60% by weight in butyl acetate Isopropanol 5.0 Ethyl acetate 18.7 Butyl acetate 98/100 28.0 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon 14.8 Kristalex F100 Hydrocarbon 33 Resin, 70% by weight in butyl Resin:Kristalex 5140 acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 34.6 1:2 Resin, 60% by weight in butyl acetate Isopropanol 4.5 Ethyl acetate 19.0 Butyl acetate 98/100 27.5 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon 8.9 Kristalex F100 Hydrocarbon 34 Resin, 70% by weight in butyl Resin:Kristalex 5140 acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 41.6 1:4 Resin, 60% by weight in butyl acetate Isopropanol 4.5 Ethyl acetate 19.0 Butyl acetate 98/100 26.0 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon 4.8 Kristalex F100 Hydrocarbon 35 Resin, 70% by weight in butyl Resin:Kristalex 5140 acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 46.3 1:8 Resin, 60% by weight in butyl acetate Isopropanol 4.5 Ethyl acetate 17.9 Butyl acetate 98/100 26.5 Effect pigment according to 4.0 example 5, NVC: 23

(33) TABLE-US-00010 TABLE 10 The inventive nail varnish compositions of examples 36 to 39 had a binder solids content of 40% by weight, based on the total weight of the clearcoat. Weight Example Product name (g) Weight ratio Example Clearcoat Kristalex F100 Hydrocarbon 27.9 Kristalex F100 Hydrocarbon 36 Resin, 70% by weight in butyl Resin:Kristalex 5140 acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 32.5 1:1 Resin, 60% by weight in butyl acetate Isopropanol 3.0 Ethyl acetate 11.6 Butyl acetate 98/100 25.0 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon 19.8 Kristalex F100 Hydrocarbon 37 Resin, 70% by weight in butyl Resin:Kristalex 5140 acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 46.3 1:2 Resin, 60% by weight in butyl acetate Isopropanol 3.1 Ethyl acetate 12.3 Butyl acetate 98/100 18.5 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon 11.8 Kristalex F100 Hydrocarbon 38 Resin, 70% by weight in butyl Resin:Kristalex 5140 acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 55.4 1:4 Resin, 60% by weight in butyl acetate Isopropanol 2.9 Ethyl acetate 11.9 Butyl acetate 98/100 20.0 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon 6.7 Kristalex F100 Hydrocarbon 39 Resin, 70% by weight in butyl Resin:Kristalex 5140 acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 61.5 1:8 Resin, 60% by weight in butyl acetate Isopropanol 2.9 Ethyl acetate 11.5 Butyl acetate 98/100 17.4 Effect pigment according to 4.0 example 5, NVC: 23%

(34) TABLE-US-00011 TABLE 11 The inventive nail varnish compositions of examples 40 to 43 had a binder solids content of 60% by weight, based on the total weight of the clearcoat. Weight Example Product name (g) Weight ratio Example Clearcoat Kristalex F100 Hydrocarbon Resin, 42.9 Kristalex F100 Hydrocarbon Resin:Kristalex 40 70% by weight in butyl acetate 5140 Hydrocarbon Resin Kristalex 5140 Hydrocarbon Resin, 50.0 1:1 60% by weight in butyl acetate Isopropanol 0.6 Ethyl acetate 2.6 Butyl acetate 98/100 3.9 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon Resin, 28.6 Kristalex F100 Hydrocarbon Resin:Kristalex 41 70% by weight in butyl acetate 5140 Hydrocarbon Resin Kristalex 5140 Hydrocarbon Resin, 66.7 1:2 60% by weight in butyl acetate Isopropanol 0.4 Ethyl acetate 1.7 Butyl acetate 98/100 2.6 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon Resin, 17.1 Kristalex F100 Hydrocarbon Resin:Kristalex 42 70% by weight in butyl acetate 5140 Hydrocarbon Resin Kristalex 5140 Hydrocarbon Resin, 80.0 1:4 60% by weight in butyl acetate Isopropanol 0.2 Ethyl acetate 1.0 Butyl acetate 98/100 1.7 Effect pigment according to 4.0 example 5, NVC: 23% Example Clearcoat Kristalex F100 Hydrocarbon Resin, 9.6 Kristalex F100 Hydrocarbon Resin:Kristalex 43 70% by weight in butyl acetate 5140 Hydrocarbon Resin Kristalex 5140 Hydrocarbon Resin, 88.8 1:8 60% by weight in butyl acetate Isopropanol 0.1 Ethyl acetate 0.6 Butyl acetate 98/100 0.9 Effect pigment according to 4.0 example 5, NVC: 23%

(35) The visual appearance of the inventive nail varnish compositions of examples 32 to 43 was determined after application to a synthetic fingernail and subsequent drying by the surface-modified effect pigment from example 5 used in each case. The surface-modified effect pigment used in each case, in the clearcoat produced according to IIa, showed marked leafing characteristics and in some cases marked specular gloss. With regard to application characteristics, it was found that the nail varnish compositions of the invention with a binder solids content of 60% by weight, based on the total weight of the clearcoat, owing to their high viscosity, have poorer applicability than the nail varnish applications of the invention with a binder solids content of 30% by weight or 40% by weight, based in each case on the total weight of the clearcoat.

(36) For the inventive nail varnish compositions of examples 44 to 48, the clearcoat was produced as described below under IIa. For production of the inventive nail varnish compositions of examples 44 to 48, 96 g of the clearcoat were added to an initial charge of 4 g of the respective surface-modified effect pigment according to table 12 below with stirring at 600 rpm/min.

(37) TABLE-US-00012 TABLE 12 Pigmentation, Weight samples Product name (g) Weight ratio Example 44 Clearcoat Kristalex F100 Hydrocarbon 22.3 Kristalex F100 Hydrocarbon Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 26.0 1:1 Resin, 60% by weight in butyl acetate Isopropanol 4.7 Ethyl acetate 19.0 Butyl acetate 98/100 28.0 Effect pigment according to 4.0 example 5, NVC: 23% Example 45 Clearcoat Kristalex F100 Hydrocarbon 22.3 Kristalex F100 Hydrocarbon Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 26.0 1:1 Resin, 60% by weight in butyl acetate Isopropanol 4.7 Ethyl acetate 19.0 Butyl acetate 98/100 28.0 Effect pigment according to 4.8 example 5, NVC: 23% Example 46 Clearcoat Kristalex F100 Hydrocarbon 22.3 Kristalex F100 Hydrocarbon Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 26.0 1:1 Resin, 60% by weight in butyl acetate Isopropanol 4.7 Ethyl acetate 19.0 Butyl acetate 98/100 28.0 Effect pigment according to 2.0 example 5, NVC: 23% Example 47 Clearcoat Kristalex F100 Hydrocarbon 22.3 Kristalex F100 Hydrocarbon Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 26.0 1:1 Resin, 60% by weight in butyl acetate Isopropanol 4.7 Ethyl acetate 19.0 Butyl acetate 98/100 28.0 Effect pigment according to 7.0 example 5, NVC: 23% Example 48 Clearcoat Kristalex F100 Hydrocarbon 22.3 Kristalex F100 Hydrocarbon Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 26.0 1:1 Resin, 60% by weight in butyl acetate Isopropanol 4.7 Ethyl acetate 19.0 Butyl acetate 98/100 28.0 Effect pigment according to 9.0 example 5, NVC: 23%

(38) For the inventive nail varnish compositions of examples 49 to 64, the clearcoat according to table 13 was produced as described above under IIa.

(39) TABLE-US-00013 TABLE 13 Clearcoat for examples 49 to 64 and comparative examples 24 to 30 Product name Weight (g) Weight ratio Clearcoat for Kristalex F100 Hydrocarbon 19.8 Kristalex F100 Hydrocarbon examples 49 to 64 Resin, 70% by weight in butyl Resin:Kristalex 5140 and comparative acetate Hydrocarbon Resin examples 26 to 33 Kristalex 5140 Hydrocarbon 46.3 1:2 Resin, 60% by weight in butyl acetate Isopropanol 3.1 Ethyl acetate 12.3 Butyl acetate 98/100 18.5

(40) For production of the inventive nail varnish compositions of examples 49 to 64, the clearcoat from table 13 was added according to table 14 below to an initial charge of the respective surface-modified effect pigment according to table 14, with stirring at 600 rpm/min. The inventive nail varnish compositions of examples 50 to 66 had a binder solids content of 40% by weight, based on the total weight of the clearcoat.

(41) TABLE-US-00014 TABLE 14 Weights of effect pigment dispersion and clearcoat for examples 49 to 64. Weight Example Nail varnish composition (g) 49 Effect pigment according to example 1, NVC: 10% 13.20 Clearcoat from table 13 86.80 50 Effect pigment according to example 15, NVC: 35% 3.80 Clearcoat from table 13 96.20 51 Effect pigment according to example 14, NVC: 10% 14.60 Clearcoat from table 13 85.40 52 Effect pigment according to example 11, NVC: 14% 9.65 Clearcoat from table 13 90.35 53 Effect pigment according to example 12, NVC: 15% 9.65 Clearcoat from table 13 90.35 54 Effect pigment according to example 10; NVC: 18% 7.65 Clearcoat from table 13 92.35 55 Effect pigment according to example 21, 7.36 NVC: 18.5% Clearcoat from table 13 92.64 56 Effect pigment according to example 45, 11.64 NVC: 11.7% Clearcoat from table 13 88.36 57 Effect pigment according to example 17, NVC: 12% 11.44 Clearcoat from table 13 88.56 58 Effect pigment according to example 18, NVC: 12% 11.44 Clearcoat from table 13 88.56 59 Effect pigment according to example 5, NVC: 23% 6.00 Clearcoat from table 13 94.00 60 Effect pigment according to example 26, NVC: 53% 2.60 Clearcoat from table 13 97.40 61 Effect pigment according to example 28, NVC: 61% 2.23 Clearcoat from table 13 97.70 62 Effect pigment according to example 29, NVC: 55% 2.47 Clearcoat from table 13 97.53 63 Effect pigment according to example 25, NVC: 50% 2.72 Clearcoat from table 13 97.28 64 Effect pigment according to example 27, NVC: 53% 2.57 Clearcoat from table 13 97.43

Comparative Examples

(42) For the nail varnish compositions of comparative examples 17 to 20, the clearcoat was produced as described above under IIa. For production of the nail varnish compositions of comparative examples 18 to 20, 96 g of the clearcoat were added to an initial charge of 4 g of the respective surface-modified effect pigment according to table 15 below with stirring at 600 rpm/min.

(43) TABLE-US-00015 TABLE 15 Comparative Weight example Product name (g) Weight ratio Comparative Clearcoat Kristalex F100 Hydrocarbon 22.25 Kristalex F100 Hydrocarbon example 17 Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 26.0 1:1 Resin, 60% by weight in butyl acetate Isopropanol 14.31 Ethyl acetate — Butyl acetate 98/100 37.44 Effect pigment according to 4.0 example 5 Comparative Clearcoat Kristalex F100 Hydrocarbon 19.13 Kristalex F100 Hydrocarbon example 18 Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 19.13 1:1 Resin, 60% by weight in butyl acetate Isopropanol 22.33 Ethyl acetate 39.42 Butyl acetate 98/100 — Effect pigment according to 4.0 example 5 Comparative Clearcoat Kristalex F100 Hydrocarbon 14.87 Kristalex F100 Hydrocarbon example 19 Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 34.63 1:2 Resin, 60% by weight in butyl acetate Isopropanol 18.5 Ethyl acetate 32.0 Butyl acetate 98/100 — Effect pigment according to 4.0 example 5 Comparative Clearcoat Kristalex F100 Hydrocarbon 14.9 Kristalex F100 Hydrocarbon example 20 Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 34.69 1:2 Resin, 60% by weight in butyl acetate Isopropanol 4.6 Ethyl acetate 15.18 Butyl acetate 98/100 27.5 Acetone 3.12 Effect pigment according to 4.0 example 5

(44) The nail varnish compositions of comparative examples 17 to 20, after application to a synthetic fingernail and subsequent drying, showed a distinctly poorer visual appearance than the nail varnish compositions of the invention, which is probably attributable to the omission of one of the solvents (comparative example 17) and/or an excessively high relative proportion of the solvents isopropanol and/or ethyl acetate in relation to butyl acetate (comparative examples 18 and 19). Moreover, the addition of an additional solvent (acetone in comparative example 20) has an adverse effect. The nail varnish applications of the comparative examples were affected by white bloom and were cloudy, probably owing to excessively rapid drying. The exact compositions of the nail varnishes of the inventive examples and comparative examples can also be found in table 18.

(45) For the nail varnish compositions of comparative examples 21 to 24, the clearcoat was produced as described above under IIa. For production of the nail varnish compositions of comparative examples 21 to 24, 96 g of the clearcoat were added to an initial charge of 4 g of the respective surface-modified effect pigment according to table 16 below with stirring at 600 rpm/min.

(46) The nail varnish compositions of comparative examples 21 to 24 had a binder solids content of 20% by weight, based on the total weight of the clearcoat.

(47) TABLE-US-00016 TABLE 16 Comparative Weight example Product name (g) Weight ratio Comparative Clearcoat Kristalex F100 Hydrocarbon 14.3 Kristalex F100 Hydrocarbon example 21 Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 16.6 1:1 Resin, 60% by weight in butyl acetate Isopropanol 6.3 Ethyl acetate 25.1 Butyl acetate 98/100 37.9 Effect pigment according to 4.0 example 5, NVC: 23% Comparative Clearcoat Kristalex F100 Hydrocarbon 9.6 Kristalex F100 Hydrocarbon example 22 Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 22.2 1:2 Resin, 60% by weight in butyl acetate Isopropanol 6.2 Ethyl acetate 24.8 Butyl acetate 98/100 37.2 Effect pigment according to 4.0 example 5, NVC: 23% Comparative Clearcoat Kristalex F100 Hydrocarbon 5.7 Kristalex F100 Hydrocarbon example 23 Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 26.6 1:4 Resin, 60% by weight in butyl acetate Isopropanol 6.1 Ethyl acetate 24.4 Butyl acetate 98/100 37.0 Effect pigment according to 4.0 example 5, NVC: 23% Comparative Clearcoat Kristalex F100 Hydrocarbon 3.1 Kristalex F100 Hydrocarbon example 24 Resin, 70% by weight in Resin:Kristalex 5140 butyl acetate Hydrocarbon Resin Kristalex 5140 Hydrocarbon 29.6 1:8 Resin, 60% by weight in butyl acetate Isopropanol 6.1 Ethyl acetate 24.5 Butyl acetate 98/100 36.7 Effect pigment according to 4.0 example 5, NVC: 23%

(48) The nail varnish compositions of comparative examples 21 to 24, after application to a synthetic fingernail and subsequent drying, showed a much poorer visual appearance than the nail varnish applications of the invention applied, which is probably attributable to the excessively low binder solids content of about 20% by weight, based on the total weight of the clearcoat. The surface-modified effect pigment was probably wetted by the solvent present in the clearcoat, and for that reason the effect pigment was unable to adopt an orientation at the surface of the clearcoat on or after application.

(49) For production of the nail varnish compositions of comparative examples 25 to 30, the clearcoat from table 13 was added according to table 17 below to an initial charge of the respective surface-modified effect pigment according to table 17 with stirring at 600 rpm/min. The nail varnish compositions of comparative examples 25 to 30 had a binder solids content of 40% by weight, based on the total weight of the clearcoat.

(50) TABLE-US-00017 TABLE 17 Comparative Weight example Nail varnish composition (g) 25 Effect pigment according to comparative example 2.30 10, NVC: 59% Clearcoat from table 13 97.70 26 Effect pigment according to comparative example 2.40 1, NVC: 58% Clearcoat from table 13 97.60 27 Effect pigment according to comparative example 2.70 15, NVC: 48-52% Clearcoat from table 13 97.30 28 Effect pigment according to comparative example 13.00 12, NVC: 10% Clearcoat from table 13 87.00 29 Effect pigment according to comparative example 13.00 13, NVC: 10% Clearcoat from table 13 87.00 30 Effect pigment according to comparative example 13.00 14, NVC: 10% Clearcoat from table 13 87.00

(51) Table 18 summarizes the calculated compositions of the inventive examples and comparative examples that address the variation of the nail varnish parameters (always with the same effect pigment from example 5).

(52) TABLE-US-00018 TABLE 18 Total Pigment binder Total acc. to content Total Total butyl Kristallex Kristalex Ethyl Butyl Further example in % by effect Total ethyl acetate Sample F100 5140 Isopropanol acetate acetate solvent 5: Total weight pigment iso acetate content Example 32 22.3 26 5 18.7 28 4 104 30.0 0.88 6.96 26.02 67.02 Example 33 14.8 34.6 4.5 19 27.5 4 104.4 29.8 0.88 6.22 26.26 67.52 Example 34 8.9 41.6 4.5 19 26 4 104 30.0 0.88 6.26 26.43 67.31 Example 35 4.8 46.3 4.5 17.9 26.5 4 104 29.9 0.88 6.26 24.88 68.86 Example 36 27.9 32.5 3 11.6 25 4 104 37.5 0.88 4.68 18.11 77.21 Example 37 19.8 46.3 3.1 12.3 18.5 4 104 40.0 0.88 5.05 20.02 74.93 Example 38 11.8 55.4 2.9 11.9 20 4 106 39.2 0.87 4.56 18.72 76.72 Example 39 6.7 61.5 2.9 11.5 17.4 4 104 40.0 0.88 4.72 18.70 76.58 Example 40 42.9 50 0.6 2.6 3.9 4 104 57.7 0.88 1.39 6.04 92.57 Example 41 28.6 66.7 0.4 1.7 2.6 4 104 57.7 0.88 0.93 3.95 95.12 Example 42 17.1 80 0.2 1 1.7 4 104 57.7 0.88 0.46 2.32 97.22 Example 43 9.6 88.8 0.1 0.6 0.9 4 104 57.7 0.88 0.23 1.39 98.38 Example 44 22.3 26 4.7 19 28 4 104 30.0 0.88 6.54 26.44 67.02 Example 45 22.3 26 4.7 19 28 4.8 104.8 29.8 1.05 6.48 26.21 67.30 Example 46 22.3 26 4.7 19 28 2 102 30.6 0.45 6.68 27.02 66.30 Example 47 22.3 26 4.7 19 28 7 107 29.2 1.50 6.34 25.61 68.05 Example 48 22.3 26 4.7 19 28 9 109 28.6 1.90 6.21 25.09 68.70 Comparative 22.25 26 14.31 0 37.44 4 104 30.0 0.88 19.90 0.00 80.10 example 17 Comparative 19.13 19.13 22.33 39.42 0 4 104.01 23.9 0.88 28.55 50.40 21.06 example 18 Comparative 14.87 23.63 18.5 32 0 4 93 26.4 0.99 27.41 47.41 25.18 example 19 Comparative 14.9 34.69 4.6 15.18 27.5 3.12 4 103.99 30.0 0.88 6.40 21.13 68.12 example 20 (acetone) Comparative 14.3 16.6 6.3 25.1 37.9 4 104.2 19.2 0.88 7.56 30.13 62.31 example 21 Comparative 9.6 22.2 6.2 24.8 37.2 4 104 19.3 0.88 7.47 29.87 62.67 example 22 Comparative 5.7 26.6 6.1 24.4 37 4 103.8 19.2 0.89 7.36 29.42 63.22 example 23 Comparative 3.1 29.6 6.1 24.5 36.7 4 104 19.2 0.88 7.34 29.46 63.20 example 24

(53) III Characterization of the Surface-Modified Effect Pigments of the Invention for Use with Preference in a Nail Varnish Composition and of the Surface-Modified Effect Pigments

(54) IIIa Measurement of Particle Size

(55) The size distribution curve of the surface-modified effect pigments of the invention that are to be used with preference in a nail varnish composition, of the surface-modified effect pigments as claimed in claim 1 and of the pigments from the comparative examples, based in each case on nonmetallic substrates in platelet form, was determined with the Malvern Mastersizer 2000 instrument according to the manufacturer's instructions. For this purpose, about 0.1 g of the respective pigment in the form of an aqueous suspension without addition of dispersing aids, with constant stirring, was introduced by means of a Pasteur pipette into the sample preparation cell of the instrument and analyzed repeatedly. The individual measurement results were used to form the averages. The scattered light signals were evaluated by the Fraunhofer method.

(56) The size distribution curve of the surface-modified effect pigments of the invention that are to be used with preference in a nail varnish composition, of the surface-modified effect pigments as claimed in claim 1 and of the pigments from the comparative examples, based in each case on metallic substrates in platelet form, was measured with the Quantachrome Cilas 1064 instrument or the Horiba LA-930 instrument, in each case according to manufacturer's instructions. For this purpose, about 50 ml of the respective pigment were suspended in isopropanol, treated in an ultrasound bath for 300 seconds (instrument: Sonorex IK 52, from Bandelin) and then introduced by means of a Pasteur pipette into the sample preparation cell of the instrument and analyzed repeatedly. The individual measurement results were used to form the averages. The scattered light signals were evaluated by the Fraunhofer method.

(57) In the context of this invention, average particle size D.sub.50 is understood to mean the D.sub.50 of the cumulative frequency distribution of the volume-averaged size distribution function as obtained by laser diffraction methods. The D.sub.50 means that 50% of the pigments have a volume-averaged diameter less than or equal to the value specified, for example 20 μm. Correspondingly, the D.sub.10 and D.sub.90 values mean that, respectively, 10% and 90% of the pigments have a volume-averaged diameter equal to or less than the respective measurement.

(58) The span ΔD, defined as

(59) $\Delta D=\frac{D_{90}-D_{10}}{D_{50}},$
indicates the range of the particle size distribution.

(60) With regard to the visual appearance of the surface-modified effect pigments of the invention that are to be used with preference in a nail varnish composition, or of the surface-modified effect pigments as claimed in claim 1, preference is given to a small value of ΔD, i.e. a small span.

(61) IIIb Determination of the Average Thickness of the Metallic or Nonmetallic Substrates in Platelet Form, Determination of the Average Total Thickness of the Surface-Modified Effect Pigment

(62) The average thicknesses h.sub.50 of the surface-modified effect pigments of the invention that are to be used with preference in a nail varnish composition, the surface-modified effect pigments as claimed in claim 1 and the pigments from the comparative examples were determined by the method described in WO 2004/087816 A2 (pages 24 and 25) by means of SEM.

(63) IIIc Determination of the Metal Oxide Content of the Synthetic Mica Platelets

(64) The metal oxide contents of the synthetic mica platelets were determined by means of x-ray fluorescence analysis (XRF). For this purpose, the synthetic mica platelets were incorporated into a lithium tetraborate glass tablet, fixed in solid sample measurement cups and analyzed therefrom. The instrument used was the Thermo Scientific Advantix ARL instrument.

(65) IV Optical Characterization of the Nail Varnish Compositions of the Invention

(66) IVa Determination of Gloss (20° Geometry) and Haze

(67) For objective determination of 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 glass plates in a wet film thickness of 110 μm by means of a bar applicator (Erichsen System Wasag Model 288 film applicator, from Erichsen) and then dried at room temperature. The gloss value (20° geometry) and the haze value (H log) of the nail varnish compositions thus applied were measured with the haze gloss instrument (from BYK Gardner).

(68) For the measurement of gloss, the 20° geometry for high-gloss surfaces was employed (Byk-Gardner, digital catalog “Qualitatskontrolle fir Lacke and Kunststoffe”, page 16). Both the gloss (20° geometry) and the haze (H log) were determined at least 5 different points in the nail varnish application. Table 18 below lists the averages formed therefrom for gloss (20° geometry) and haze (H log).

(69) V Results:

(70) Table 19 lists the gloss and haze values for selected examples and comparative examples. In addition, the pigmentation levels, the binder concentrations and the compositions of the solvents in the nail varnish compositions have been calculated.

(71) The gloss and haze values listed in table 19 should not be considered independently of one another. Thus, a nail varnish composition having a high haze value and simultaneously a low gloss value can nevertheless have a mirror-like effect.

(72) After application, the inventive nail varnish compositions of examples 48 to 64 showed marked leafing characteristics up to and including a mirror-like effect.

(73) The nail varnish applications of the highest visual quality with an excellent mirror effect were obtained through the use of PVD pigments coated with phosphoric acid cetyl ester (Hostaphat CC 100) (examples 49, 51, 54, 56, 57, 58 and 59).

(74) By contrast, the nail varnish compositions of comparative examples 27 to 30, where no additive was used, did not show any leafing effect and in some cases even showed significant formation of specks after application. The resultant gloss and haze values were accordingly poor.

(75) In comparative example 25, the potassium salt of cetylphosphoric ester was used, which is disadvantageous.

(76) In comparative example 26, the application contained specks. This is probably attributable to an excessively high proportion of the additive in the production of the coated metal pigment.

(77) TABLE-US-00019 TABLE 19 Results of optical studies and the most important composition parameters for selected examples and comparative examples Content of the preferred 3-solvent Pigment mixture*** Content of Example/ Type of content based on the hydrocarbon Gloss Comparative effect Additive/pigment [% by total solvent resin (20° Haze example pigment Additive ratio in % wt.] content [% by wt.] geometry) (Hlog) Example 49 PVD* CC 100 10 1.20 71.2 57.4 624.3 1353.9 Example 50 Pt-$** CC 100 4 1.28 95.8 63.6 137.5 1344.9 Example 51 PVD CC 100 10 1.33 95.8 63.6 358.4 1510.7 Example 52 PVD Laurylphosphonic 13.3 1.19 75.9 56.4 84.1 1289.1 acid Example 53 PVD Laurylphosphonic 13.3 1.28 78.7 59.7 130.7 1415.0 acid Example 54 PVD CC 100 20.0 1.15 90.8 59.7 221.2 1450.5 Example 55 PVD Laurylphosphonic 20.0 1.13 83.3 61.0 120.2 1383.1 acid Example 56 PVD CC 100 10.0 1.24 84.8 61.2 149.6 1390.4 Example 57 PVD CC 100 20.0 1.14 88.5 58.4 240.1 1568.0 Example 58 PVD CC 100 40.0 0.98 88.4 58.5 455.8 1496.1 Example 59 PVD CC 100 10.0 1.25 88.4 58.5 176.6 1499.3 Example 60 Pt-$ CC 100 5.0 1.31 95.1 62.1 101.0 1290.0 Example 61 Pt-$ CC 100 20.0 1.13 100.0 64.4 107.0 1317.7 Example 62 Pt-$ CS 100 5.0 1.29 100.0 64.6 125.1 1366.0 Example 63 Pt-$ CC 100 2.5 1.33 100.0 64.5 121.1 1347.6 Example 64 Pt-$ CC 100 7.5 1.27 100.0 64.3 99.9 1289.0 Comparative PVD — 0 1.30 100.0 36.2 101.8 121.6 example 28 Comparative PVD — 0 1.30 100.0 36.2 19.2 565.6 example 29 Comparative PVD — 0 1.30 100.0 36.2 100.4 134.5 example 30 Comparative Pt-$ — 0 1.35 96.1 40.5 104.4 175.5 example 27 Comparative Pt-$ Hostaphat 20 1.13 100.0 64.6 73.2 1154.9 example 25 CK 100 Comparative Pt-$ CS 120 20 1.16 100.0 64.5 125.2 1363.5 example 26 *All PVD pigments are abbreviated here merely to “PVD”; the further details can be found in the corresponding tables above. **“Pt-$” refers in this table to all wet-ground pigments having an average thickness below 100 nm. Further details can be found in the corresponding tables above. ***Mixture of ethyl acetate, butyl acetate and isopropanol.