2. Description of the Prior Art Sunscreen compositions have been described extensively in the prior art. See, for example, U. S.

Patents 4, 810,489; 5, 026, 540; 5, 041, 281; 5, 207, 998; 5, 219, 559; 5, 306, 485; 5,445,815; 5,508,024; 5,599,529; and 5,603,863. Such compositions usually are formulated by admixing the several components in predetermined amounts. However, disadvantageously, such admixing often requires an elaborate sequence of addition of each of the components in expensive mixing equipment in order to assure a homogeneously dispersed composition.

Accordingly, it is an object of this invention to provide a sunscreen concentrate in the form of a stable, homogeneous dispersion from which a sunscreen composition can be formed readily by simple dilution with a carrier.

Another object of the invention is to provide a sunscreen concentrate comprising a stable, homogeneous dispersion of ultrafine titanium dioxide or zinc oxide, in an organic sunscreen agent, with polyvinylpyrrolidone alkylated with an alpha-olefin as a dispersing aid.

Still another object herein is to provide a waterproofing sunscreen concentrate having both an inorganic sunblock agent and a UV-absorbing organic sunscreen agent therein, in a hydrophilic or hydrophobic copolymer of polyvinylpyrrolidone and an alpha-olefin, wherein the particle size of the concentrate is about 0.01-0.2 , preferably about 0.05-0.1 , and a Brookfield viscosity of about 4, 000 to 1, 000, 000 cps, preferably about 5, 000 to 400, 000 cps.

These and other objects and features of the invention will be made apparent from the following more detailed description of the invention.

SUMMARY OF THE INVENTION What is described herein is a waterproofing sunscreen concentrate in the form of a stable, uniform dispersion comprising, by weight: (a) about 30-65% of ultrafine titanium dioxide or zinc oxide, or mixtures thereof, (b) about 30-70% of an organic sunscreen agent, and (c) about 0.25-25% of a dispersing aid which is polyvinylpyrrolidone alkylated with a C4-C36 alpha-olefin.

Suitably, the particle size of. the concentrate is about 0.01-0.2 , preferably about 0.05-0.1 p; and the Brookfield viscosity is about 4, 000 to 1, 000, 000 cps, preferably 5, 000 to 400, 000 cps.

Commercial sunscreen compositions may be prepared easily by mixing the sunscreen concentrate of the invention with water and other conventional. ingredients of such compositions.

DETAILED DESCRIPTION OF THE INVENTION The waterproofing sunscreen concentrate of the invention includes a sunblock component (a) which is ultrafine titaniumn dioxide or zinc oxide, present in an amount of about 30-65% by weight of the concentrate.

Ultrafine titanium dioxide is preferred.

The sunscreen concentrate of the invention also includes an UV-absorbing sunscreen agent which is the active component (b). Suitable organic sunscreen agents include cinoxate (2-ethoxyethyl-p-methoxycinnamate); diethanolamine-p-methoxycinnamate; digalloyl trioleate ethyl 4-bis (hydroxypropyl) aminobenzoate; ethylhexyl-p- methoxy-cinnamate; 2-ethylhexyl salicylate; glyceryl aminobenzoate; homosalate (3, 3, 5-trimethylcyclohexyl salicylate); triethanolamine salicylate; 2-phenyl- benzimidazole-5-sulfonic acid; sulisobenzone (2-hydroxy-4- methoxybenzophenone-5-sulfonic acid); Padimate A (amyl p- dimethylaminobenzoate); Padimate O (octyl dimethyl para aminobenzoate); and menthyl anthranilate, and mixtures thereof.

The sunscreen agents also may include a sunscreen material particulary suitable for ultraviolet-A (320-400 nm) protection. This compound suitably is selected from oxybenzone, dioxybenzone; 2-ethylhexyl-2-cyano-3, 3 diphenylacrylate; methyl benzilidine camphor; 4-t-butyl- 4'-methoxydibenzoyl-methane and mixtures thereof.

The total amount of organic sunscreen agent suitably is present in an amount ranging from about 30% to 70%, preferably about 35-550, by weight of the total concentrate.

Component (c) of the sunscreen concentrate of the invention is a dispersing aid to provide the concentrate as a stable uniform dispersion. The dispersing aid herein is polyvinylpyrrolidone (PVP) alkylated with a C4-C36 alpha-olefin; suitably present in an amount of about 0.25 to 25% by weight of the concentrate.

Component (c) may be a hydrophilic or hydrophobic polymer. A hydrophilic copolymer is made by grafting a C4 alpha-olefin upon the PVP; it is sold by International Specialty Products Inc. (ISP), as Ganex P-904LC and P-904. The hydrophilic copolymer suitably is present in the concentrate in an amount of about 0.25-4%, preferably about 0.5-2%, by weight of the concentrate. Hydrophobic copolymers are made by grafting a C16 to C36 alpha-olefin upon PVP. These hydrophobic copolymers also are available from ISP as Ganexs V-216, a liquid, or Ganex V-220 and WP 660, which are available in the form of waxy solids or flakes. Ganexs V-216 suitably is present in the concentrate in an amount of about 0.25-25%, and optimally 5-20W/while Ganexs V-220. suitably is present in an amount of about 5-250, preferably 10-20%. A preferred hydrophobic copolymer is Ganexs V-216. A C20 alpha-olefin containing copolymer preferably is present in an amount of about 5-25%.

The sunscreen concentrate of the invention may be formed by simply mixing components (a), (b) and (c), using conventional, inexpensive agitation equipment. The sunscreen concentrate thus formed is a stable, homogeneous dispersion of an inorganic sunblock, an organic sunscreen agent, and a Ganex dispersion aid, having a particle size of about 0.01-0.2,0.01-0.2, preferably 0.05-0.1 g, and a Brookfield viscosity of 4, 000 to 1, 000, 000 cps, preferably about 5, 000 to 400, 000 cps.

Thereafter, upon simple dilution of the sunscreen concentrate with an appropriate carrier, and other adjuvants, if desired, an end-use broad spectrum waterproofing sunscreen composition can be readily prepared which can provide a uniform distribution of active sunblock and sunscreen agents upon the skin of the user at selected SPF values.

The invention will now be illustrated by the following working examples.

EXAMPLE 1 An organic sunscreen solution was prepared by dissolving 100 g of Ganex V-216 in 200 g of Escalol 557 with the aid of a homogenizer. Then 500 g of 2 mm zirconium silicate beads were introduced into a Sand Mill vessel and enough of the solution was added to cover the beads. Then 200 g of Kemiras W-Titan M-262 ultrafine titanium dioxide was slowly added to the zirconium beads.

The mill was run for 4 hours, and the zirconium beads were filtered off. A white dispersion was obtained having a Brookfield viscosity of 6040 cps (Helipath, spindle TB @ 10 rpm).

EXAMPLE 2-16 Following the procedure of Example 1, the following dispersion systems were prepared.

EXAMPLE 2 A white dispersion of <BR> Ganex V-216--75 g<BR> Escalol 557--225 g UF Ti02, Kemira W Titan M262--200 g with a Brookfield viscosity of 7800 cps (spindle TB @ 10 rpm).

EXAMPLE 3 A white dispersion of <BR> Ganex V-216--50 g<BR> Escalol 557--250 g UF Ti02, Kemira UV Titan M262--200 g with a Brookfield viscosity of 16, 200 cps (spindle TB @ 10 rpm).

EXAMPLE 4 A white dispersion of Ganex V-216--25 g Escalol 557--275 g UF Ti02, Kemira UV Titan M262--200 g with a Brookfield viscosity of 22, 600 cps (spindle TB @ 10 rpm).

EXAMPLE 5 A white dispersion of Ganex V-216--10 g Escalol 557--290 g UF TiO2/Kemira W Titan M262--200 g with a Brookfield viscosity of 21, 900 cps (spindle TB @ 10 rpm).

EXAMPLE 6 A white dispersion of Ganex V-216--5 g Escalol 557--295 g UF Tio2, Kemira UV Titan M262--200 g with a Brookfield viscosity of 25, 200 cps (spindle TB @ 10 rpm).

EXAMPLE 7 The procedure of Example 1 was followed using 6.28 g of Ganex V-216 in 119 g of Escalol 557, 314 g of 2 mm zirconium silicate beads, titanium dioxide and 94.5 g of Finex 25 ultrafine zinc oxide. A white dispersion with a Brookfield viscosity of 28, 000 cps (. spindle TC @ 10 rpm) was obtained.

EXAMPLE 8 A white dispersion of Ganex V-216--5 g Escalol 557--295 g UF T'02, Tayca SMT-100 SAS--200 g with a Brookfield viscosity of 83, 000 cps (spindle TC @ 10 rpm).

EXAMPLE 9 A white dispersion of Ganex V-216--6 g Escalol 557--354 g UF Ti02, Kemira W-X161--240 g with a Brookfield viscosity of 256, 000 cps (spindle TE @ 10 rpm).

EXAMPLE 10 A light beige dispersion of Ganex V-216--6 g Escalol 557--380 g UF Ti02, Tayca MT-100T--240 g with a Brookfield viscosity of 302, 000 cps (spindle TE @ 10 rpm).

EXAMPLE 11 A white dispersion of Ganex P-904--5 g Escalol 557--295 g UF Ti02, Kemira UV-Titan M-262--200 g with a Brookfield viscosity of 104, 000 cps (spindle TE @ 10 rpm).

EXAMPLE 12 A light beige dispersion of Ganex P-904--5 g Escalol 557--295 g UF Ti02, Tayca MT-100T--200 g with a Brookfield viscosity of 334, 000 cps (spindle TE@ 10 rpm).

EXAMPLE 13 A paste of Ganex V-220--100 g Escalol 557--250 g UF Ti02, Kemira UV-Titan M-262--200 g The dispersion was a paste.

EXAMPLE 14 A white dispersion of Ganex P-904--12 g Escalol 557--348 g UF ZnO, Z-Cote HP-1--240 g with a Brookfield viscosity of 12, 000 cps (spindle TB @ 10 rpm).

EXAMPLE 15 A white dispersion of Ganex V-516--12 g Escalol 557--348 g UF Ti02, Kemira UV-Titan M-262--240 g with a Brookfield viscosity of 84,400 cps (spindle TD @ 10 rpm).

EXAMPLE 16 A white dispersion of Ganex WP-660--18 g Escalol 557--402 g UF Ti02, Tayca MT-100T--180 g with a Brookfield viscosity of 142,000 cps (spindle TE @ 10 rpm).

DISPERSION COMPOSITIONS OF EXAMPLES 1-16 TABLE Ingredients % By Wt. Brookfield Viscosity Example 1 GanexV-216 20 Escalol557 40 Kemira M262 40 6040 cps Example 2 Ganex V-216 15 Escalol 557 45 KemiraM262 40 7800 cps Example 3 Ganex V-216 10 Escalol 557 50 Kemira M262 40 16,200 cps Example 4 Ganex V-216 5 Escalol 557 55 Kemira M262 40 22,600 cps Example 5 Ganex V-216 2 Escalol 557 58 Kemira M262 40 21,900 cps Example 6 Ganex V-216 1 Escalol 557 59 Kemira M262 40 25,200 cps Example 7 Ganex V-216 2 Escalol 557 38 Kemira M262 (TiO2) 30 Finex 25 (ZnO) 30 28,000 cps Example 8 Ganex V-216 1 Escalol 557 59 Tayca SMT-100SAS 40 83,000 cps Example 9 Ganex V-216 1 Escalol 557 59 Kemira X-161 40 256, 000 cps Example 10 Ganex V-216 1 Escalol 557 60.7 Tayca MT 100T 38. 3 302, 000 cps Example 11 Ganex P-904 1 Escalol 557 59 Kemira M262 40 104,000 cps Example 12 Ganex P-904 1 Escalol 557 59 Tayca MT 100T 40 334,000 cps Example 13 Ganex V-220 18.1 Escalol 557 45.5 Kemira M262 36. 4 Paste Example 14 Ganex P-904 2 Escalol 557 58 Z-Cote HP-1 (ZnO) 40 12, 000 cps Example 15 Ganex V-516 2 Escalol 557 58 Kemira M262 40 84,400 cps Example 16 X Ganex WP-660 3 Escalol 557 67 Tayca MT 100T 30 142, 000 cps PREPARATION OF SUNSCREEN CONCENTRATE OF INVENTION EXAMPLE 17 A stable, uniform dispersion of the sunscreen concentrate of the invention was prepared by mixing ultrafine titanium dioxide (Kemira UV Titan M262, Tayca MT-100T or Tayca SMT-100 SAS), (240 g, 40 wt. %), GanexO P-904 (6 g, 1 wt. %) and Escalol0 557 (357 g, 59 wt. %) as follows: The Ganexs P-904 and the Escalol 557 components then were heated to 50°C with vigorous stirring provided by a Cowles blade affixed to a Premier Dispersator. When the mixture reached 50°C, the ultrafine titanium dioxide powder was slowly introduced into the vortex of the mixture while maintaining its temperature at 50°C. The resultant admixture began to thicken; then agitation was set at 3, 000-5, 000 rpm, and the batch was stirred continuously for another 15 minutes, then the contents were cooled to room temperature. The resultant dispersion was milled twice through a 3-roll mill. The viscosity of the concentrate as determined in a Brookfield viscometer (Spindle TC, 10 rpm) was 149, 000 cps.

PREPARATION OF WATER RESISTANT SUNSCREEN COMPOSITIONS EXAMPLE 18 Ingredient W By Weight Phase A 12A 12B** Deionized Water 69.80 69.80 V Gum Ultra 1.00 1.00 (Magnesium Aluminum Silicate; Titanium Dioxide; Cristobalite; proprietary substance) Glycerine, USP 1.00 1.00 CMC (7H3SF) 0.50 0.50 Phase B ProLipid'"131 3.00 3.00 (Stearic Acid (and) Behenyl Alcohol (and) Glyceryl Stearate (and) Maleated Soybean Oil (and) Lecithin (and) Cl2l6 Alcohols (and) Palmitic Acid Ceraphyl 791@ 13.50 13.50 (Isocetyl Stearoyl Stearate) Ceraphyl 847@ 1.00 1.00 (Octyldodecyl Stearoyl Stearate) * Concentrate of Invention 10.00 10.00 Phase C Germall Pluss 0.20 0.20 (diazolidinyl urea (and) iodopropynyl butylcarbamate) 100.00 100.00 * Escalol T {Kemira UV Titan M262@ 40% + Ganex V-220 @ 20% + Escalol 557 @ 20*il ** Tayca MT100T in Escalol T Procedure: Phase A 1. Add the water into an suitable sized vessel depending on the batch size. Begin the mixing while powdering in the V-Gum Ultra. This is done without any heat.

Continue mixing until there are no visible signs (beading) of the Gum.

2. At this point you can premix the CMC and glycerin.

(It should be noted that the glycerin and CMC should not be made ahead of time, as this mixture thickens up very quickly). While adding in the premix you can begin heating this phase until it reaches a temperature of 75°C.

Phase B 1. Add all of the oil phase ingredients into an appropriate sized vessel with the exception of the titanium dioxide dispersion (Escalol T) which gets added in later. Place the beaker into a water bath and heat until completely melted.

2. Into this add in the titanium dioxide dispersion (Escalol T) and mix until completely dispersed into the oil phase.

3. When the water phase has reached a temmperature of 75°C, add in phase B, and continue mixing for about 30 minutes. After 30 minutes homogenize the emulsion for about 5 minutes using the homogenization mode of an Arde Barinco dual mode mixer.

4. Once the emulsion is homogenized you can continue <BR> mixing until the batch reaches a temperature of 35°C-40°C at which time phase C is added in. Continue mixing until the batch reaches a temperature of 25°C.

5. Check the pH nitially and post 24 hours. Measure initial viscosity and post 24 hours.

Physical Characteristics: 12A: Initial Viscosity (Brookfield Model RV TDV II, Spindle #4 @ 20 rpm) 7, 680 cps Post 72 hour viscosity (TC spindle @ 10 rpm) 15, 580 Initial pH 6.18; post 72 hours 6.24 Rub-in: Not too whitening on rub-out, however, the"waxy" feel of Ganex V-220 creates drag.

12B Initial Viscosity (Brookfield Model RV TDV II, Spindle #4 @ 20 rpm) 11,300 cps Post 72 hour viscosity (TC Spindle @ 20 rpm) 22, 900 cps Initial pH 6.0; post 72 hours 5.94 Rub-in: Not too whitening on rub-out, however, the"waxy" feel of Ganex V-220 creates drag.

EXAMPLE 19 Ingredient W By Weight Phase A 13A 13B** Deionized Water 69.80 69.80 V Gum Ultra 1.00 1.00 (Magnesium Aluminum Silicate; Titanium Dioxide; Cristobalite; proprietary substance) Glycerine, USP 1.00 1.00 CMC (7H3SF) 0.50 0.50 Phase B ProLipidw 131 3.00 3.00 (Stearic Acid (and) Behenyl Alcohol (and) Glyceryl Stearate (and) Maleated Soybean Oil (and) Lecithin (and) C12-16 Alcohols (and) Palmitic Acid Ceraphyl 791@ 13.50 13.50 (Isocetyl Stearoyl Stearate) Ceraphyl 8479 1.00 1.00 (Octyldodecyl Stearoyl Stearate) * Concentrate of Invention 10.00 10.00 Phase C Germall Pluss 0.20 0.20 (diazolidinyl urea (and) iodopropynyl butylcarbamate) _ 100.00 100.00 * Escalol T {Tayca MT100T @ 40% + Ganex V-216 @ 20% + Escalol 557 @ 20%} ** Uses Kemira UV Titan M262 in Escalol T Procedure: Phase A 1. Add the water into an suitable sized vessel depending on the batch size. Begin the mixing while powdering in the V-Gum Ultra. This is done without any heat.

Continue mixing until there are no visible signs (beading) of the Gum.

2. At this point you can premix the CMC and glycerin.

(It should be noted that the glycerin and CMC should not be made ahead of time, as this mixture thickens up very quickly). While adding in the premix you can begin heating this phase until it reaches a temperature of 75°C.

Phase B 1. Add all of the oil phase ingredients into an appropriate sized vessel with the exception of the titanium dioxide dispersion (Escalol T) which gets added in later. Place the beaker into a water bath and heat until completely melted.

2. Into this add in the titanium dioxide dispersion (Escalol T) and mix until completely dispersed into the oil phase.

3. When the water phase has reached a temmperature of 75°C, add in phase B, and continue mixing for about 30 minutes. After 30 minutes homogenize the emulsion for about 5 minutes using the homogenization mode of an Arde Barinco dual mode mixer.

4. Once the emulsion is homogenized you can continue mixing until the batch reaches a temperature of 35°C-40°C at which time phase C is added in. Continue mixing until the batch reaches a temperature of 25°C.

5. Check the pH nitially and post 24 hours. Measure initial viscosity and post 24 hours.

Physical Characteristics: 13A : Initial Viscosity (Brookfield Model RV TDV II, TC Spindle @ 10 rpm) 16, 300 cps Post 72 hour viscosity (TC spindle @ 10 rpm) 14, 750 Initial pH 5.82; post 72 hours 5.97 Rub-in: Not too whitening on rub-out. Very nice after feel and smooth glossy appearance.

13B: Initial Viscosity (Brookfield Model RV TDV II, TC Spindle @ 10 rpm) 14, 800 cps Post 72 hour viscosity (TC Spindle @ 10 rpm) 15, 000 cps Initial pH 5.97; post 72 hours 6.20 Rub-in: Not too whitening on rub-out. Very nice after feel and smooth glossy appearance.

While the invention has been described with particular reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art. Accordingly, it is intended to be bound only by the following claims, in which: