Composition providing protective sun filter

A composition providing a sun protection filter

Field of technology

The present invention relates to novel and useful agents providing sunscreens for ultraviolet radiation, and to compositions exhibiting enhanced sunscreen, and methods of protecting human skin from the potentially harmful effects of sunlight.

Prior art

Although sunbathing has for many years been considered an accompanying sign of an individual's good health and his ability to devote enough of his free time to popular outdoor activities, such as swimming, tennis, golf, skiing, etc., excessive exposure of human skin to sunlight has proven harmful .

It is well documented that human skin is sensitive to sunlight and artificial light containing radiation of wavelengths between 290 nanometers (nm) and 400 nm. Ultraviolet radiation in the wavelength range 290 nm to 320 nm (UV-B region) has been shown to be harmful to the skin relatively early on and often to cause reddening of the skin or erythema, edema, blisters or other skin damage. Prolonged or chronic exposure of the skin to radiation in this wavelength range is associated with severe skin damage, such as radiation sceratosis and cancer. In recent years, attention has also focused on. ultraviolet radiation of wavelengths longer than 320 nm (UV-A region) and on φ φ * · «side effects of this radiation on human skin. Radiation at 320 nm and 400 nm also contributes to premature aging skin. In addition, recent studies have suggested that chronic exposure of the skin to sunlight limits the skin's immune response. It is also clear that while tanning will offer some protection against sunburn, it is relatively ineffective against other types of sun damage caused by sunlight.

The growing general belief that outdoor activities must go hand in hand with the use of adequate sunscreen has led to unexpected growth in the area of ​​sunscreen products. The desired product providing the desired sun visor should have the following features: it should provide protection in both the UV-A and UV-B ranges of ultraviolet radiation; it should retain its covering capabilities, ie. it must be water and sweat resistant; they should be easy to apply, and usable, ie easy to apply, invisible, non-sticky and non-greasy; and should be hypoallergenic, ie they should not be irritating and should minimize the risk of an allergic reaction. Recent interest in this area has focused in particular on the problems associated with skin irritation and sensitivity that may occur in some individuals using sunscreen products with high SPF values ​​containing organic sunscreens.

The effectiveness of a solar product is determined by its factor, or the sun protection factor (SPF). The sun protection factor represents the ratio of the length of exposure (dose) required for the occurrence of a minimal erythema reaction in protected skin to the length required for the occurrence of the same reaction in untreated skin. Absolute doses with an individual from ** tt · • · «* tttt *« · · 4 • tt tttt • «· *« tt · · · · · • · · tttt * · • · · tt tttt tttt ·· «· • · Tt ·· · • · ·· individuals vary and depend to a large extent on the individual's genetic predispositions and ethnic origin. If a person who normally needs ten minutes of sun exposure to start to experience the adverse effects of sun exposure (ie minimal redness), used a product with a protective filter SPF 15, then this time, during which the individual shows no minimal signs of redness, should be extended 15 times, ie to 150 minutes. Recent public interest in the problems associated with solar exposure has led to an increase in demand for sunscreen products with high SPF values, i.e. SPF values ​​of 8 and higher.

On the other hand, their ease of application and their cosmetic acceptability are important for the formulation of sunscreen compositions. These properties are assessed on the basis of subjective evaluations, for example on the basis of the visual and tactile feeling of the user. Consumer opinion studies show that the formulation providing the sun protection filter should spread easily and should be invisible and non-sticky to the skin after application. It has been shown that sunscreen compositions containing organic sunscreen agents can irritate the skin in some cases. Therefore, inorganic sunscreen agents such as titanium dioxide and zinc oxide have been used.

Japanese Patent Application 1981-161,881, for example, discloses cosmetic compositions containing 0.1 to 40% of very finely divided titanium dioxide with an average particle size of 10 to 30 nanometers (nm) which makes it hydrophobic. It turns out that when hydrophobically treated titanium dioxide with a particle size of 10 to 30 nm is mixed into

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0 «00. 00 · * ·« 0 «· cosmetic bases, transmits visible light, but reflects and scatters harmful ultraviolet rays. It has been shown that titanium dioxide-based compositions, when used in sunscreen compositions as sunscreen agents, can cause the loss of one or more desired properties of the compositions, e.g., invisibility.

U.S. Patent 5,028,417, issued July 2, 1991, discloses compositions providing a sunscreen comprising microscopically finely divided titanium dioxide. The patent states that it is desirable for the particle size to be less than 10 nanometers. The patent also states that other agents providing a sunscreen can be used in conjunction with titanium dioxide.

U.S. Patent No. 5,340,567, issued August 23, 1994, discloses a composition providing a sunscreen filter comprising a synergistic combination of titanium dioxide having a particle size of less than about 35 nm and zinc oxide having a particle size of less than about 50 nm, wherein the titanium dioxide and oxide zinc are present in given proportions.

German Patent 3,642,794 (1987) describes a cosmetic composition which is intended to prevent burning and which contains 1 to 25% of zinc oxide with a particle size of 70 to 300 micrometers. This patent also suggests that the composition may also contain titanium dioxide with a particle size of 30 to 70 micrometers. This composition is unsatisfactory due to the unaesthetic whitening it causes at high SPI values.

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U.S. Patent No. 5,188,831, issued February 23, 1993, discloses sunscreen compositions providing a sunscreen in which the formation of a sunscreen is achieved by incorporating a mixture of ultra-finely divided oil-dispersible titanium dioxide and water-dispersible titanium dioxide. However, by incorporating 0.5% w / w. titanium dioxide reached a maximum SPI of 10.

WO 90/06103, published June 14, 1990, discloses titanium dioxide solar filters in which phospholipid-coated titanium dioxide microparticles are made by powder milling or by preparing a phospholipid-containing oil phase dispersion in a high shear mixer. by stress. The phospholipid-coated titanium dioxide is then incorporated into the compositions providing a sunscreen filter. These compositions are, as stated in the application, highly effective. The data reported SPF values ​​of up to 11 for a 3.75% titanium dioxide concentration and 25 for a 7.5% concentration. The use of a high shear mixer or powder mill is a very complex and energy intensive process.

EP 535972 A1, published April 7, 1993, describes a process for the preparation of sun protection filters in which a dispersion of zinc oxide and / or titanium dioxide particles in oil is prepared by grinding.

EP 61999-9, published October 19, 1994, discloses an aqueous dispersion of a metal oxide with a particle size of less than 200 nm, mixed with an illuminator, an oil phase, and an organic hydrophobic sunscreen filter forming an O / W emulsion. The resulting sunscreen composition has a higher SPF value than would be expected if

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ΦΦ v * φΦ ·· provided only an additive effect. However, titanium dioxide alone at a concentration of 4% provided only an SPE of approximately 7 to 11.

EP 628303, published 19.10. 1994, describes a method of preparing a composition providing a sunscreen filter. This application describes the mixing of metal oxide particles of a sunscreen filter with a particle size of less than 200 nm, dispersed in oil with one or more emulsifiers and / or organic sunscreens with one or more emulsifiers and / or organic sunscreens. The resulting composition providing a sunscreen had a high SPF value only when the metal oxide was mixed with an organic sunscreen. In fact, if no organic sun protection filter is used, then only an SPE value of 7 is achieved.

WO 93/11742 discloses sunscreen compositions providing a sunscreen filter which comprise titanium dioxide and iron oxide with a particle size of less than 200 nm and preferably coated with a phospholipid.

An article published in DCI in September 1992 by Tioxide Specialties Ltd. describes various ways of incorporating oily or aqueous dispersions of titanium dioxide in emulsions. However, the article does not provide any data regarding the achieved SPF values.

An article published in Cosmetics and Toiletries, Vol.

107, October 1992, describes various formulation methods with physical, solar blocking agents. The discussion focuses on the use of titanium dioxide in the dispersion or on the use of an emulsifier, which is also an effective dispersant.

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0 · ·· * · titanium dioxide reagent. This article states that SPF values ​​higher than · 20 can be achieved. However, no example is given here and the article does not even mention specific components of the sunscreen or their compositions.

The brochure, published by Tioxide Company on March 15, 1994, describes inorganic solar filters having a high SPF value, which were achieved without the addition of any organic solar filter. Measurement of the SPF values ​​of the sunscreen compositions showed that the SPF measurements did indeed correspond to the values ​​reported in the publication, but the measured titanium dioxide concentrations were twice as high as the published values.

U.S. Pat. No. 5,498,406 discloses compositions providing a sunscreen filter in the form of an oil-in-water emulsion which contains both organic and inorganic sunscreen filters and alcohols having 25 to 45 carbon atoms as emulsion stabilizers. This composition focuses mainly on the effectiveness of organic sun protection filters. Although the author mentions the use of stearic acid as part of an oil-in-water composition, he argues against the use of stearic acid in stabilizing titanium dioxide in the absence of alcohols with 22 to 45 carbon atoms.

The sun protection filter, which contains both an organic and an inorganic sun protection filter, acquired the trade name SUNDOWN later in the 1980s. In addition, Velsan contained D8P3 and isostearic acid. However, it was not an effective sunscreen filter, despite the addition of both organic and inorganic components of the sunscreen filter.

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The essence of the invention

It is therefore an object of the invention to provide improved agents and compositions providing a sunscreen.

Another object of the invention is to provide sunscreen compositions which contain sunscreen agents and which retain an adequate ability to protect human skin while overcoming the shortcomings of previously available materials.

Another object of the invention is to provide methods of protecting human skin from the harmful effects of sunlight.

These other objects and features of the invention will become more apparent to those skilled in the art upon reading the following detailed description.

The above objects and other features and advantages of the invention have been achieved by sunscreen compositions containing inorganic agents providing a sunscreen which have been used as active ingredients. More particularly, the invention relates to sunscreen compositions comprising titanium dioxide and optionally zinc oxide, the particle size of which is in the preferred range, said agents being present in preferred amounts and proportions as sunscreen agents.

These specific compositions make it possible to use much lower amounts of active ingredients providing a sunscreen than previously available, while at the same time maintaining the desired high SPF values ​​for these compositions without the unsightly whitening of the skin which occurs during # • · · ♦ · ·

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use of known tanning compositions at a concentration higher than 5%. In the sunscreen compositions according to the invention, considerably high concentrations of titanium dioxide can be used without undesired bleaching, for example concentrations of up to 15% can be used while maintaining an acceptable appearance, or even higher concentrations.

In addition, our invention does not relate to the use of hydrophilic titanium dioxide preparations required by the patent cited in the "Prior Art" section, nor does it require energy-intensive processes such as powder milling, nor does it require organic sunscreen agents to achieve high efficiency.

The compositions of the invention are oil-in-water emulsions which contain at least the following components:

(a) An inorganic agent providing a sunscreen filter, for example titanium dioxide or zinc oxide or a mixture thereof;

(b) an anionic emulsifier selected from the group consisting of saturated fatty acid salts and / or salts. straight chain fatty acids, alkyl sulfates, alkyl sulfosuccinates and alkyl phosphates; a.

(c) an oil component comprising an oil carrier and at least one emollient.

The composition of the invention provides sunscreen formulations having an SPF of at least 10 and a titanium dioxide concentration of about 4%. The compositions of the invention show extreme efficacy when using sunscreen components, especially titanium dioxide. Thus, the compositions of the invention may be formulated to contain relatively

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• lower amounts of titanium dioxide than known compositions having a given SPF value.

The compositions of the invention are readily prepared by simple mixing to provide an excellent dispersion of the inorganic sunscreen agent throughout the composition, thereby providing uniform skin coverage. The compositions of the invention are substantially invisible upon application.

The sunscreen compositions of the invention provide a highly effective UV shield, i.e. a given level of protection is achieved using a substantially lower concentration of titanium dioxide than was previously possible using commercially available titanium dioxide powders. These compositions do not require the use of unusual processing methods which were previously necessary to disperse titanium dioxide in the oil, for example the preparation of split grinding bases, mixing or mixing. high shear grinding or application of the latter method to the final products. Typical titanium dioxide-based SPF 15 protective sunscreen compositions require titanium dioxide concentrations that cause undesirable whitening of the skin. The compositions of the invention minimize this shortcoming.

The compositions of the invention are oil-in-water emulsions which cosmetically outperform conventional inorganic sunscreens, including water-in-oil titanium dioxide formulations, at corresponding SPF values, due to the low titanium dioxide values ​​required by the system of the invention. . The compositions according to the invention can be used for everyday sun protection or for products intended for the face, as well as for

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44 «4 4 4 4 · · · · 4 · · 44 · 44 4 4 4 4« 4 44 44 444 44 44 recreational tanning. Due to the high efficiency of this system, the formulations according to the invention are cheaper than other protective tanning systems.

There are several components that contribute to the unexpectedly high effectiveness of the compositions in blocking unwanted UV radiation. These elements may include the following materials:

The compositions of the invention should include one or more anionic emulsifiers. In particular, salts of certain fatty acids are useful in these formulations of the invention, preferably salts of saturated fatty acids and / or salts of straight chain fatty acids. Alkali metal salts, alkaline earth metal salts and amine salts are more preferred for the compositions of the invention. For example, stearic acid and its salts are useful as emulsifiers in the compositions of the invention, while isostearate salts tend to produce a composition that is not very effective when used as a sunscreen. Similarly, oleate salts are not useful because they are unsaturated and do not provide effective sunscreen compositions.

The following anionic emulsifiers are particularly suitable for the composition according to the invention: sodium stearate, sodium lauryl sulfate, DEA cetyl phosphate, sodium dioctyl sulfosuccinate and the like. It is more preferred that the emulsifier is sodium stearate. Although it is not yet clear why some fatty acid salts result in the composition of the invention, it is theoretically believed that straight chain fatty acid salts (fatty acids having a relatively high melting point, higher than 70 ° C) are due to their structure. conveniently. For example, salts of branched or »· ·· · ι ** ··

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The compositions of the invention should include. anionic emulsifiers present in amounts of about 0.01 to 10%, more preferably 0.1 to about 7%, and most preferably about 0.5 to 5%. Other emulsifiers may also be present in the compositions of the invention, for example nonionic emulsifiers known to those skilled in the art, such as sorbitan esters and ethoxylated sorbitan esters, ethoxylated fatty acids, fatty alcohols and ethoxylated fatty alcohols, fatty glyceride esters and ethoxylated fatty glycerides. in order to obtain the products of the invention, the composition of the invention should contain at least one anionic emulsifier. Emulsifiers based on fatty acid salts can be added to the composition in the form of a salt, or this salt can be formed in situ.

An oil carrier should further be present in the composition of the invention. The carrier may be selected from the group consisting of fatty alcohol esters of benzoic acid, alkoxylated fatty alcohols and polyether interrupted fatty acid esters. Said fatty alcohol and benzoic acid esters are commercially available under the tradename Finsolv, for example Finsolv TN, from Finetex. Alkoxylated fatty alcohols are available from a variety of sources, such as Eumulgin L and Eumulgin B2 from Henkel, Sandoxylates from Clariant, Marlox · FK86 from Huls America, Procetyl AWS from Croda Chemicals, and others.

These oil carriers should preferably be selected from the group of polyethylene interrupted fatty acid esters.

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More preferably, the oil carrier should be a fatty alkyl (optionally polypropyleneoxy) polyethylene oxycarboxylate ester having 8 to 22 carbon atoms in the alkyl chain, an ester having an alkyl group having one to twenty-two carbon atoms, optionally straight or branched chain, or may contain a phenyl group. Most preferably, the carrier oil should be isopropyl PPG-2 isodeceth-7 carboxylate, for example Velsan D8P3 or other commercially available materials from Clariant sold under the tradename Velsan. Other similar structures include Hetester PHA from Bernel.

Preferably, the oil carrier should be present in the composition in an amount of about 0.1% to 10%. More preferably, it should be present in an amount of about 1% to 5%, and most preferably in an amount of about 2% to 3%.

The oil phase should preferably contain at least two materials, a carrier oil and a plasticizer known to those skilled in the art, commonly used in sunscreen products, for example mineral oil, ester oils, vegetable oils, silicones, synthetic plasticizers such as fatty acid esters and the like. The ratio of this emollient to the oil carrier in said formulation should be about 1: 1 to 3: 1, most preferably about 2: 1. The oil carrier and emollient should comprise about 2% to 20% by weight of the composition.

Another element that should be present in the composition of the invention is an inorganic compound that filters solar radiation, for example titanium dioxide, zinc oxide or combinations thereof. Preferably an oxide should be used

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00 0000 0 0 0 0 0 0 «0 00« 00 00 titanium dioxide, having a particle size of less than about 300 nm. Should. be present in combination in an amount of about 2% to 25%. More preferably, it should be present in an amount of about 3% to 10%. The inorganic sunscreen compound should be dispersible in the oil and may optionally be coated.

The weight ratio of titanium dioxide to carrier oil and plasticizer should be about 0.3: 1 to 1: 1. Most preferred is a ratio of between about 0.5: 1 and 2: 3. For example, the composition of the invention may contain 15% titanium dioxide, 8.33% Velsan D8P3 carrier oil, 12.5% ​​Miglyol 812, and the remainder of the composition is identical to the composition in Example 1 below, resulting in a sunscreen filter with SPF 43. The whitening value of this composition is acceptable and represents only a slight whitening of the skin.

In cases where fatty acid salts are used, care should be taken to maintain the pH of the compositions of the invention greater than about 5, more preferably greater than about 5.5. Maintaining the pH at this level will ensure that these anionic emulsifiers remain in the form of a salt, which is important for maintaining the stability and effectiveness of the composition. If the other anionic emulsifiers mentioned are used, then the stability and effectiveness of the composition at pH values ​​lower than said pH value will not be affected in any way.

Furthermore, elements which are commonly used in a modern emulsion system for filtering solar radiation, for example polymeric thickeners and stabilizers, can be incorporated into the composition according to the invention without particular limitation and selection, φ φ »» • φφ φφ · φ • · · · • · ··· «• 9 9 · *; One or more other emollient oils, microbial preservatives, water-resistant agents, antioxidants, odors, humectants, and wetting agents. of course an aqueous vehicle.

The base formulation of the compositions of the invention may also be used as a carrier composition for active topical agents having dermatological effects, including depigmenting agents, anti-aging agents, fungicides, antimicrobial agents, insecticidal repellents and the like. Depigmenting agents may include, for example, magnesium ascorbyl phosphate or hydroquinone. Anti-aging agents may include, for example, retinoid compounds and alpha-hydroxy acids. Fungicidal agents that may be included in the composition of the invention are, for example, azole compounds including, for example, ketoconazole and the like. Antimicrobial agents may include triclosan. Insecticidal repellents may also be included in the compositions of the invention. Other products known to those skilled in the art can be delivered to the skin using the compositions of the invention. The compositions of the invention should then. double effect, as they would contain both sunscreen agents and other additives designed to protect and / or treat the skin.

The compositions of the invention may be incorporated into a variety of cosmetic and / or body care products, for example, hand and body lotions, oils, ointments and creams, lip care balms, facial cosmetics, and the like.

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The sunscreen filtering compositions of the invention can be prepared using at least one of two methods: a two-pot method, in which the oil and aqueous phases are prepared separately, and a one-pot method, in which all components are added in a selected predetermined order. Both of these processes will produce a fine, uniform, white to ivory emulsion.

Using the two-pot process, the aqueous phase is prepared by metering deionized water into a beaker and stirring. Aqueous phase elements, including emulsifiers and humectants, chelating agents, thickeners, water resistance agents, neutralizing agents, and antioxidants, should be added to this water, and the resulting solution should be heated. The anionic emulsifier can be introduced into the aqueous phase or into the oil phase, the choice depending on the nature of the emulsifier. The oil phase, which should contain the anionic emulsifier, the carrier oil, the plasticizer and the inorganic agent providing the sun filter, is prepared separately in a second vessel. The two phases obtained are then mixed at a relatively high temperature.

More specifically, using a two-pot process, the aqueous phase is prepared by metering deionized water into a beaker and stirring. Subsequently, Carbopol 940 (from BF Goodrich of Cincinnati, Ohio) should be added and the composition should be mixed until properly hydrated. Subsequently, propylene glycol should be added and the EDTA composition should be mixed until a homogeneous solution is obtained. The solution should then be heated to 70-80 ° C and at this time. the temperature should be maintained until the phases are mixed.

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Clariant Corporation, Charlotte, North Carolina), stearic acid, cetyl alcohol and Miglyol 812 (from Huls Company of Piscataway, New Jersey). The beaker should be placed in a water bath on an electric hotplate and the components of the oil phase should be heated on this hotplate to approximately 80 ° C or to the temperature at which it melts. Titanium dioxide should be gradually added to such heating of the phase and the composition should be stirred at high speed until it becomes homogeneous. The mixture should be maintained at a temperature of about 80 ° C until the phases are mixed.

Subsequently, the oil and aqueous phases are mixed by maintaining the temperature at about 80 ° C for another five minutes. Sodium hydroxide (as a 10% solution) should then be added and the composition stirred vigorously for another five minutes. Subsequently, the stirring speed should slow down and start cooling. Once the batch temperature reached 40-45 ° C, Dowicil 200 (33% Quaternia 15 solution from Dow Chemical Company, Dearborn, MI) and optionally fragrance were added. The pH of the composition should be checked and the value adjusted to greater than 5.0 by the addition of 10% sodium hydroxide if necessary. If necessary, deionized water can be added to make up the batch to final weight. Stirring and cooling can be stopped as soon as the batch temperature reaches 28 to 32 ° C.

In a one-pot process, the aqueous and oil phases can be prepared in a single vessel, provided that the individual components are added in the appropriate order. For example, the aqueous phase should be formed in the vessel first by adding water and possibly certain emulsifiers that are compatible • 00 0 0 0 0 · · *

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00 000 »00 0000 0 • 00» 0 «0 000» · 0 · · 00 00 0 »with aqueous phase. The vessel should be heated to approximately 85 ° C to 95 ° C. Once the temperature has reached this value, oil phase components may be added to the vessel, optionally including an anionic emulsifier if compatible with the oil phase and oil carrier, as well as other oil phase emulsifiers, antioxidants and plasticizers, the addition of which may be desirable. The temperature should be maintained at this value for about .15 minutes and the inorganic agent providing the sun filter should be added slowly and the composition should be stirred for at least another 30 minutes. After cooling, the pH should be checked and adjusted if necessary. Finally, Dowicil, a preservative and optionally a fragrance should be added to the composition thus prepared.

More specifically, deionized water can be added to the beaker, followed slowly by Carbopol 940. EDTA is then added and the composition is stirred at high speed for another 15 to 20 minutes or until Carbopol is properly hydrated. Heating of the mixture to 92-95 ° C should begin, and the required amount of propylene glycol should be added during heating to this temperature. Once the temperature reaches 92-95 ° C, BHT, Velsan D8P3, stearic acid, cetyl alcohol and Miglyol 812 are added. The temperature of the mixture should be maintained at about 92 to 95 ° C for about 15 minutes. Subsequently, titanium dioxide should be added and the composition should be stirred for another 30 minutes. After this time, sodium hydroxide (as a 10% solution) should be added and the composition should be stirred for an additional 30 minutes at 88-92 ° C. The composition should then be cooled and a solution of Dowicil 200 and optionally an odor added to the composition at 40 ° C. The pH should be adjusted to a value higher than by adding sodium hydroxide

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5.0. Finally, sufficient water should be added to replenish the batch to the required weight.

The following examples, which are intended to illustrate the compositions of the invention, do not limit the scope of the invention, which is clearly defined by the appended claims.

Examples of embodiments of the invention

Example 1

743.07 ml of deionized water was added to the beaker. Subsequently, 2.5 g of Carbopol 940 (from BF Goodrich of Cincinnati, Ohio) was slowly added to the beaker. Then 1.0 g of sodium EDTA was added and the composition was stirred rapidly for 15 to 20 minutes or until Carbopol was properly moistened. The mixture was heated to 92-95 ° C and 30 g of propylene glycol was added. Once the temperature reached 92-95 ° C, 0.5 g of BHT, 25 g of Velsan D8P3 (from Clariant Corporation, Charlotte, NC), 50 g of stearic acid, 10 g of cetyl alcohol, and 37.5 g of Miglyol 812 (from Huls Company of Piscataway, New Jersey). Subsequently, 45 g of MT-100T titanium dioxide (very fine (micrometers) titanium dioxide coated with aluminum stearate from Tri-K Industries, Emerson, NJ) was added to the vessel and the composition was stirred at 88-92 ° C for 30 minutes. Cooling was started and once the composition reached 40 ° C, 3 g of Dowicil 200 (33% solution) was added to the tank.

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Quaternia 15) and 2.5 g of fragrance. The pH was adjusted to 8-8.5 by adding 49.93 g of 10% sodium hydroxide solution (target pH is 8.25). Finally, the batch was supplemented with a sufficient amount of deionized water to reach the final weight.

The Sun Protection Factor (SPF) of this composition was measured in vitro using the system described by Cole and VanFossen [Cole, C., VanFossen R., (1990) In-vitro model for UVB and UVA protection. in: Sunscreens: Development, Evaluation and Regulators Aspects, N. Shaath and N. Lowe Eds., Marcel Dekker Pub. New York, NY]. Briefly, this system involves measuring the passage of solar simulated UV radiation through a composition (2.0 mg / cm 3)²) applied to the substrate, which in this case was Transpose ™. The system consists of an optical sensor that is sensitive only to sunlight causing sunburn and a sensitivity scale similar to that of reddening of human skin. SPF is the value of the optical signal passing through the substrate which is not provided with a sun protection filter divided by the value of the optical signal passing through the substrate coated with the sun protection filter. This system is calibrated using a variety of sunscreen filters having known SPF values ​​(from 4 to 36), which were determined in-vivo using the FDA monographic method (Federal Register, Aug. 25, 1978, Sunscreen drug products for over -the-counter human drugs, pp. 38206-38269). The resulting SPF index value of the composition prepared in Example I was 16.9. The composition prepared was satisfactory in terms of aesthetics and stable.

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Examples 2 to 13

The following series of examples examined the use of several titanium dioxide of different origins and / or coatings, which were used at the same concentration of 4.5%. All compositions were prepared as described in the example and the same ingredients were used in the same amount. The results obtained are summarized in Table I below.

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TABLE I

<td colspan="3">Influence of TiO₂ coating on the SPF (4.5% TiO₂)</td>

<td>Source T1O2</td><td>Surface finish</td><td>SPF</td>

<td>(2) MT-100T (Tri-K Industries, Inc.)</td><td>Al, Stearic acid</td><td> 16,9</td>

<td>(3) MT-500B (Tri-K Industries, Inc.)</td><td>none</td><td> 13, 6 9,9</td>

<td>(4) SMT-100SAS (Tri-K Industries, Inc.)</td><td>methylhydrogenpolysiloxane</td><td> 5,0</td>

<td>(5) UV Titanium M262 (Presperse, lne.)</td><td>alumina, dimethicone</td><td>18, Oi 12.0-</td>

<td>(6) UV Titanium M212 (Presperse, lne.)</td><td>alumina, glycerin</td><td> 8,5-</td>

<td>&lt;7} P25 (Degussa)</td><td> none- </td><td>. 9, L -</td>

<td>(8) STT65C-S (Kobo)</td><td>none</td><td> 12,1'</td>

<td>(9) DM140 KSI (Kobo)</td><td>STT65C-S with silicone coating</td><td> 11, 5</td>

<td>(10) STT-30D-S (Kobo)</td><td>Al, Si, silicone</td><td> 3,8</td>

<td>(11) STT-30S-L (Kobo)</td><td>Al, stearic acid 1</td><td> 7,3</td>

<td>(12) TiO2 (hydrophobic) Creative Polymers)</td><td>methicone, dimethicone</td><td> 12,0</td>

<td>(13) TiO2 (hydrophilic) Creative Polymers)</td><td>dimethicone copolyol</td><td> ' 7,7</td>

φφ φφφ · φ φ φφφφ * φ φφφ φ φ φφφ φ φ ·· · 'φ φ φφφ φ φφ φφφφ φ • φφφ · Φ φ φφφ φφ φφ φφ φφφ φφ φφφ ²³

Examples 14 to 17

In this series of examples, different concentrations of titanium dioxide were used and again the SPF values ​​were measured. The procedure described in Example 1 and various concentrations of titanium dioxide were again used to prepare the formulations. The difference was made up by adding deionized water.

Titanium dioxide concentration MT-100T SPF

<td> (14)</td><td> 4,5 %</td><td> 17,1</td>

<td> (15)</td><td> 6, 0 %</td><td> 25,3</td>

<td> (16)</td><td> 7,5%</td><td> 20,4</td>

<td> (17)</td><td> 15,0 %</td><td> 43,1</td>

Examples 18 to 38

The following examples are intended to show which anionic emulsifiers which lead to high SPF protection indices. The compositions were identical to the compositions of Example 1 except that they contained various anionic emulsifiers, which are listed in Table II. From the data given in Table II, it is clear that dioctyl sodium sulphosuccinate, DEA cetyl phosphate (Amphisol) for «φφφ

ΦΦΦΦ 1

Φ · i φ * φφ φ

φφφ under the right conditions, sodium lauryl sulfate and sodium stearate are effective in achieving an SPF higher than 10.

TABLE II

<td colspan="2">Influence of anionic emulators on SPF</td>

<td></td><td>SPF</td>

<td>(18) Sodium stearate (NaOH neutr.) - stearic acid and sodium hydroxide</td><td> 11,6</td>

<td>(19) Sodium stearate in the aqueous phase</td><td> 15,7</td>

<td>(20) 5.0% isostearic acid, no Brij, 721, no stearic acid with Miglyol 812 and Velsan D8P3</td><td> 4,5</td>

<td>(21) 5.0% isostearic acid (added to H 2 O + NaOH) 3.0% Brij 721</td><td> 8,6</td>

<td>(22) 5.0% oleic acid, no acid stearic, pH adjusted</td><td> 6,1; 5,2</td>

<td>(23) 5.0% lauric acid, no acid stearic</td><td> 6,4</td>

<td>(24) 2.0% Amphisol with 3.0% Brij 721 and stearic acid, was not without pH adjustment</td><td> 12,3</td>

<td>(25) 2.0% Amphisol with Brij 721 and without stearic acid</td><td> 8,1</td>

<td>(26) 2,0% Ampl5,0hisol with Brij 721 and beeswax without stearic acid and without pH adjustment</td><td> 15,1</td>

<td>(27) 0.5% sodium lauryl sulfonate with stearic acid, 3.0% Brij 721, no PH setting</td><td> 15,0</td>

<td>(28) Avanel S150 (2.5%), · Miglyol 812 (3.75%), stearic acid (5.0%), without pH adjustment</td><td> 5,1 (2,3)</td>

<td>(29) Avanel S150 (2.0%), stearic acid (0%), Velsan D8P3 (2.5%), Miglyol 812 (3.75%), Brij 721 (3%)</td><td> 3,2 (2,0)</td>

«· • * ι ·« · ·

Table II (continued)

<td>(30) Avanel S150 (5,74%), Velsan D8P3 (0%), Miglyol 812 (0%)</td><td> 7,0 (2,6)</td>

<td>(31) 2.7% Brij 721, 0.3% Brij 72 and 0.5% Rewoderm S1333, no stearic acid, pH = 7</td><td> 4,1</td>

<td>(32) 2.7% Tween 60, 0.3% Sleep 60 and 0.5% Rewoderm S1333, no stearic acid, pH = 7</td><td> 4,2</td>

<td>(33) 3.0% Glucam E-20 distearate and 0.5% Rewoderm S1333, no stearic acid, pH = 7</td><td> 3,8</td>

<td>(34) 3,0% Glucam SSE-20, 0,5% Rewoderm S1333, no stearic acid, pH = 7 </td><td> 3,5</td>

<td>(35) 1.0% lecithin, no stearic acid, 3.0% Brij 721, no pH adjustment</td><td> 3,0</td>

<td>(36) Aerosol OT-75 with stearic acid, Brij 721, without pH adjustment</td><td> 11,2</td>

<td>(37) Aerosol OT-75 with stearic acid, Brij 721, 0.5% sodium stearate, without pH adjustment</td><td> 16,2</td>

<td>(38) Hamposyl C-30, no stearic acid</td><td> 5,9</td>

The above trade names refer to the following compounds:

Brij 721: nonionic surfactant polyoxyethylene 21 stearyl ether

Miglyol 812: capric and caprylic acid triglyceride Velsan D8P3: PPG-2 isodeceth-7 carboxylate Rewoderm S-1333: ricinolamido MEA sodium sulfosuccinate Amphisol: DAA cetyl phosphate

Aerosol OT-75: dioctyl sodium sulfosuccinate

Hamposyl is sodium cocoyl sarcosinate, an anionic emulsifier

<img file="CZ9703969A3_D0006.tif" />

» 0 ·

0 «• ·« 0 0 ·· • · · · * β * 00 *

Examples 39 to 46

The following Examples 39 to 46 show that nonionic emulsifiers do not provide high SPF per se. The tested compositions are identical to the composition of Example 1 except for the changes indicated in Table III below.

TABLE III

<td colspan="2">Influence of nonionic emulsifier on SPF</td>

<td></td><td>SPF</td>

<td>(39) 6.0% cetyl alcohol, no stearic acid, 3.0% Brij 721 and no pH adjustment</td><td> 2,7</td>

<td>(40) 5.0% glyceryl monostearate, 2.0% tween 60, 1.0% Arlacel 60, no stearic acid, pH = 7.</td><td> 2,9</td>

<td>(41) 5.0% glyceryl monostearate, 3.0% Brij 721, no stearic acid</td><td>τ-1 it</td>

<td>(42) 2.7% Brij 721, 0.3% Brij 72, no stearic acid, pH = 7</td><td> 2,5</td>

<td>(43) 2, -7% Tween 60, 0.3% Span 60, no stearic acid</td><td> 3, 6</td>

<td>(44) 3.0% Glucam E-20 distearate, no stearic acid</td><td> 2,9</td>

<td>(45) 3.0% Glucam SSE-20, no stearic acid</td><td> 3,3</td>

<td>(46) 5.0% Glucam P-20, no stearic acid</td><td> 2,5</td>

Tween 60 means polyoxyethylene (20) sorbitan monostearate

Arlacel 60 is sorban monostearate

Arlacel 165 is glycerol monostearate and polyoxyethylene stearate

Sleep 60 is sorbitan monostearate • tt ···· • · ** · ♦ • »*

tt • · · «. · * • tt ··· · * ··· • tt · ··· · · • * · '· «· · tttt ·· ·· tt * · ·· ··

Glucam E-20 distearate is methylglyceth 20 distearate Glucam SSE-20 is ethoxylated (20) methylglucoside sequistearate.

Examples 47 to 90

The following Examples 47 to 90 illustrate the importance of using carrier oils in the products of the invention in conjunction with emollient oils known to those skilled in the art and commercially available. These compositions are similar to the composition of Example 1 and differ only in the oil component, as shown in Table IV below.

TABLE IV

Influence of individual oils and oil mixtures

SPF¹'² (-47) Finsolv TN (48) Finsolv TN (3.75%) (6.25%) (2.5%) / Miglyol 812

7,0

15,8

<td> (49)</td><td>Finsolv</td><td>TN</td><td>(3.75%) / Velsan D8P3</td><td> 16,4 1</td><td> (4,1),</td>

<td> (2,5</td><td> %)</td><td></td><td></td><td> 18,4</td><td> (4,4)</td>

<td>(50) oil</td><td colspan="2">Finsolv TN NF (3.125%)</td><td>(3.125%) / Mineral</td><td> 9,1</td><td> (3,2)</td>

<td> (51)</td><td>Finsolv</td><td>TN</td><td>(3.125%) / Cetiol 868</td><td> 8,2</td><td> (2,9)</td>

(3,125%)

<td> (52)</td><td>Miglyol 812</td><td> (6,25%)</td><td> 8, 9</td><td> (3,2)</td>

<td> (53)</td><td>Velsan D8P3</td><td> (6,25%)</td><td> 10,0</td><td> (3,3)</td>

<td> (54)</td><td>Procetyl AWS</td><td> (6,25%)</td><td> 9, 9</td><td> (3,4)</td>

(55) Procetyl AWS (3.75%) / Velsan D8P3 (3.25%)

16,8 (4,2) aa ♦ te aa ate ♦ ··· ·· a · aa · * * · · • a aa * * · ··· · · ·· • aa a «te · · · te · ·· · te a ♦ aa · · · · · aa aa te · ·· ♦ ·· ··

<td></td><td>TABLE IV (continued)</td><td></td><td></td>

<td>(56) Procetyl AWS (2,5%)</td><td>(3.75%) / Miglyol 812</td><td> 10,6</td><td> (3,3)</td>

<td>(57) Procetyl AWS oil NF (3.125%)</td><td>(3.125%) / Mineral</td><td> 10,7</td><td> (3,2)</td>

<td>(58) Procetyl AWS</td><td>(3.125%) / Citmol 316</td><td> 11, 6</td><td> (3,5)</td>

(3,125%)

<td>(59) Isopropyl myristate (6.25%)</td><td colspan="2"> 8,7 (2,8), 5 (2,4)</td>

<td>(60) Isopropyl myristate (3,75%) / Velsan D8P3 (2,5%)</td><td> 13,0</td><td> (3,4)</td>

<td>(61) Cetiol 868 (7.25%)</td><td> 8,7</td><td> (3,0)</td>

<td>(62) Cetiol 868 (3.75%) / Velsam D8P3 (2.5%)</td><td> 14,2</td><td> (3,7)</td>

<td>(63) NF mineral oil (6.25%)</td><td> 6,7</td><td> (2,8)</td>

<td>(64) Mineral oil NF (3.75%) / Velsan D8P3 (2.5%)</td><td> 15,2</td><td> (3,8)</td>

<td>(65) Mineral oil NF (3.125%) / Citmol 316 (3.125%)</td><td> 4,3</td><td> (2,4)</td>

<td>(66) Mineral oil NF (3.125%) / Minno 21 (3.125%)</td><td> 4,6</td><td> (2,1)</td>

<td>(67) Drakeol-7 (2.5%) / Miglyol 812 (3.75%)</td><td> 6,9</td><td> (2,9)</td>

<td>(68) Clearol (5.0%)</td><td> 11,0</td><td> (3,4)</td>

<td>(69) Clearol (2.5%) / Miglyol 812 (3.75%)</td><td colspan="2"> 6,6 (2,9);5, (2,6); 7,0 (3, 7,7 (2,5)</td>

<td>(70) Arlamol E (6.25%)</td><td> 5, 3</td><td> (2,2)</td>

<td>(71) Arlamol E (3.75%) / Velsan D8P3</td><td> 14,3</td><td> (3,4)</td>

(2,5%)

44

4 4 4

4 44

4 4 4 4

4 4

44 «4

4 4

4 444

4 4 4 4

4 4 4 * 4 4 ·· 4444

4

44 4

4

4 • «

44

TABLE XV (continued)

<td>(72) Dimethicone (6.25%)</td><td> 7,3 (3,0).</td>

<td>(73) Dimethicone (3.75%) / Velsan D8P3 (2.74%)</td><td> 14,1 (3,7)</td>

<td>(74) Dimethicone (2.5%) / Miglyol 812 (3.75%)</td><td> 3,5 (2,0)</td>

<td>(75) Miglyol 812 (3.0%) / Velsan D8P3 (2.5%)</td><td> 15,1 (3,5)</td>

<td>(75A) Eumulgin L (2.5%) / Miglyol 812 (3.75%)</td><td> 11,8 (2,8)</td>

<td>(76) Eumulgin L (6.25%) / Miglyol 812 (3.75%)</td><td> 11,2 (3,6)</td>

<td>(77) Crodamol ML (2.5%) / Miglyol 812 (3.75%)</td><td> 10,4 (3,0)</td>

<td>(78) Hetester PHA (2.5%) / Miglyol 812 (3.75%)</td><td> 13,1 (3,4)</td>

<td>(79) Procetyl 10 (2.5%) / Miglyol 812 (3.75%)</td><td> 9,5 (3,0)</td>

<td>(80) Marlox FK86 (2.5%) / Miglyol 812 (3.75%)</td><td> 11,0 (3,0)</td>

<td>(81) Ucon 50 HB-660 (2.5%) / Miglyol 812 (3.75%)</td><td> 9,4 (2,8)</td>

<td>(82) Eumulgin B-2 (2.5%) / Miglyol 812 (3.75%)</td><td> 12,5 (3,2)</td>

<td>(83) Eumulgin B-2 (6.25%)</td><td> 9,3 (3,0)</td>

<td>(84) Sandoxylate 424 (2.5%) / Miglyol 812 (3.75%)</td><td> 13,0 (3,4)</td>

<td>(85) Sandoxylate 418 (2.5%) / Miglyol 812</td><td> 12,8 (3,1)</td>

(3,75%)

Μ 44 · 4 4444 4 «· 4 &lt;φ φ · 4 4444

4444 4 4444 4 444 »4 » 4 4 · 44 4444 4

4&gt; 44 44 4 444 • V 44 »· 444 44 ··

TABLE IV (continued)

<td>(86) Sandoxylate 412 (3.75%)</td><td>(2.5%) / Miglyol</td><td> 812</td><td> 16,0</td><td> (3,3)</td>

<td>(87) Sandoxylate 408 (3.75%)</td><td>(2.5%) / Miglyol</td><td> 812</td><td> 15,1</td><td> (3,3)</td>

<td>(88) UCON 50 HB-660 (3.75%)</td><td>(2.5%) / Miglyol</td><td> 812</td><td> 9,4</td><td> (2,8)</td>

<td>(89) Velsan P83 (2, (3.75%)</td><td>5%) / Miglyol 812</td><td></td><td> 11,0</td><td> (3,0)</td>

<td>(90) Miglyol 812 (3</td><td>, 0%) / Velsan D8P3</td><td></td><td> 15,1</td><td> (3,5)</td>

(2,5%) ¹Values ​​in parentheses indicate protection indices in the UVA region of the spectrum ²multiple data indicate a set of independent tests

The trade names listed in Table IV refer to the following commercially available compounds:

Eumulgin L: PPG-1-PEG-9 lauryl glycol ether

PHA ester: PG isoceteth-3-acetate

Sandoxylates: PPG-2 isodeceth (4 to 12)

Eumulgin B2: ceteareth-20

Procetyl AWS: PPG-2 ceteth-20

Cetiol 868: octyl stearate

Citmol 316: triisocetyl citrate

Minno 21: Neopentyl glycol dioctanoate (a) neopentyl glycol Drakeol-7: mineral oil Clearol: mineral oil.

Arlamol E: PPG-15 stearyl ether Crodamol ML: myristyl lactate Procetyl. 10: PPG-10 cetyl ether Marlox FK86: PPG-8 deceth-6

AA AA

AAAA • AAA

AAAA A

AAA

AA A *

AA AAAA

AAA «AAA ·

A · A ·· A

A AAA

AA ·· • A · • · · «· * 'A A- · • · A' ·

AA ··

Ucon 50 HB-660: PPG-12 buteth-16

Avanel S150: sodium C12-15 pareth-15 sulfonate Velsan P8-3: Isopropyl C12-15 pareth-9 carboxylate

Examples 91 to 94

In the following Examples 91 to 94, different types of Velsan material were used. Otherwise, these compositions are identical to the composition of Example 1.

TABLE V

<td colspan="2">Influence of Velsan type * on SPF (with 3.75% Miglyol 812)</td>

<td></td><td>SPF^1,2</td>

<td>(91) Velsan D8P3</td><td> 15,3 (3,3) 21,0 (4,2)</td>

<td>(92) Velsan D8P16 (pasta)</td><td> 12,6 (3,0)</td>

<td>(93) Velsan D8P16 (liquid)</td><td> 14,0 (3,4)</td>

<td>(94) Velsan P8-3 (liquid)</td><td> 14,0 (3,3)</td>

* Velsan concentration was 2.5% ¹Values ​​in parentheses indicate protection indices in the UVA region of the spectrum ²multiple data indicate a set of independent tests

The trade names listed in Table V refer to the following commercially available compounds:

• Φ φφ φφ · ΦΦΦ ·· ·· φφφ φφφ^{* 1} · · · · • i φφφ · · φφφ · · ·· φ · φφ. ΦΦ · φ · · ·· · · · φφφ'φ φφ · φφφ ·· φ * φφ φφφ * · ··

Velsan D8P16: cetyl PPG-2 isodeceth-7 carboxylate Velsan P8-3: isopropyl C12-15 pareth-9 carboxylate

Example 95

A composition useful as a sunscreen was prepared, the components of which were identical to those of the composition of Example 1, but 3% octylmethoxy-3-phenyl-2-propenate was added in the oil phase and the water concentration was reduced by 3%. The resulting composition had an SPF value of 23.3. Thus, it will be appreciated that the compositions of the invention may include organic sunscreen agents as well as inorganic agents.

Example 96 '

A composition usable as a sunscreen was prepared, the components of which coincided with the components of the composition of the example

1, except that 5% zinc oxide and 3% Brije 721 were added. The resulting composition had an SPF value of 20.4 in terms of UVB. The pK value of this composition was set to 7. This composition had a significantly higher UVB protection.

Example 97

A composition useful as a sunscreen that reduces the signs of premature skin aging was prepared as follows. The formulation in this Example 97 contains the following ingredients:

00 00 0000 00 00 0 0 0 &gt;00 0· 0 · • 0 000 0 00·· 0 000 0 00 000 · ·· ··♦ · ·

0 0 00 0 000

Basic formulas with retinol

<td>WATER PHASE</td><td>wt./wt</td>

<td>Deionized water</td><td> 74,50</td>

<td>Carbopol 940.</td><td> 0,25</td>

<td>Propylene glycol</td><td> 3,00</td>

<td>Citric acid</td><td> 0,10</td>

<td>Sodium stearate</td><td> 0,50</td>

<td>Dowicil 200</td><td> 0,10</td>

<td>OIL PHASE</td><td></td>

<td>BHT</td><td> 0,05</td>

<td>Velsan D8P3</td><td> 2,50</td>

<td>Stearic acid</td><td> 5,00</td>

<td>Cetyl alcohol</td><td> 1,00</td>

<td>Miglyol 812</td><td> 3,75</td>

<td>Retinol (10% in soybean oil)</td><td> 1,65</td>

<td>Tocopherol acetate</td><td> 0,10</td>

<td>Titanium dioxide</td><td> 3,00</td>

Brij 721

The formulation in this example was prepared as follows. The aqueous phase was prepared by weighing the water into a suitable vessel. Carbopol 940 was then gradually added to the water weighed in this manner with constant stirring, thus allowing Carbopol 940 to hydrate accordingly. Then propyl glycol and then sodium stearate and acid were added

9 «9» ·· 9999 · * ·· • 9 9 9 9 * · 9 · - 9 • i 9 99 «9 · 9 * 9 9 9 99

99 999 9 99 9*9 9 9

9*99 99 9 999

99 «9 9 * 9 ·· 9» lemon. After adding these components, the mixture was stirred for another 30 minutes. The mixture was then heated to 90 ° C. All components of the oil phase, with the exception of retinol, were mixed separately, mixed well and heated to 90 ° C. Retinol was then added to the oil phase under yellow light, and this phase was then added to the aqueous phase and the system was cooled with stirring. Dowicil 200 was added when the product reached 40 ° C. The whole mixture was then homogenized for three minutes on a rotor-stator homogenizer. The pH was adjusted to 6.42 by the addition of sodium hydroxide. The resulting product was then filled into aluminum tubes and purged with argon gas. The product thus prepared could then be stored.

Example 98 - Control Example

The following composition 98A contained both an inorganic and an organic sunscreen agent. Compositions 98B were prepared using the same formulation except that organic additives providing a sunscreen were omitted. The compositions in this example have the following composition:

<td></td><td>98A</td><td>98B</td>

<td>Component</td><td>% w / w</td><td>% w / w</td>

<td>non - ionized water</td><td> 57,89</td><td> '60,15</td>

<td>Cárbopol.940</td><td> 0, 40</td><td> 0, 40</td>

<td>Propylene glycol</td><td> 3,00</td><td> 3,00 </td>

<td>Disodium EDTA</td><td> 0,10</td><td> 0,10</td>

• 0 * 0 ·· 0 · 00 Μ ·

0 0 · 0 «0 Μ · ·

00«· · 0000 · 000 • 00 0 · · 0 0« « « 0 0 « 000· 0 0 0 000

00 «0 000 00 00 35

<td>Carboset XL-19-X2</td><td> 7,50</td><td> 7, 50</td>

<td>Ammonia solution (7.5%)</td><td> 2,60</td><td> 2, 60</td>

<td>Aerosol OT (75%)</td><td> 0,01</td><td> —</td>

<td>Vitamin E acetate</td><td> 0,10</td><td> 0,10</td>

<td>Isopropyl isostearate</td><td> 2,50</td><td> 2,50</td>

<td>Butylated hydroxytoluene</td><td> 0,05</td><td> 0,05</td>

<td>Finsolv TN</td><td> 5,00</td><td> 5,00</td>

<td>Velsan D8P3</td><td> 2,50</td><td> 2,50</td>

<td>Dimethicone</td><td> 0,50</td><td> 0, 50</td>

<td>Isostearic acid</td><td> 2,00</td><td> 2,00</td>

<td>Cetyl alcohol</td><td> 1,00</td><td> 1,00</td>

<td>Amphisol</td><td> 2,00</td><td> 2, 00</td>

<td>Oxybenzone</td><td> 2,75</td><td> --</td>

<td>Parsol MCX</td><td> 6,50</td><td> —</td>

<td>Hombifine S-35 (TiO₂)</td><td> 1,00</td><td> 3, 96</td>

<td>Octyl salicylate</td><td> 1,00</td><td> --</td>

<td>Lexamul GDL</td><td> 1,00</td><td> 1, 00</td>

<td>Dowicil 200 (33% solution)</td><td> 0,30</td><td> 0,30</td>

<td>Scent</td><td> 0,30</td><td> 0,30</td>

<td>Mineral oil</td><td> —</td><td> 2,52</td>

<td>Isopropyl myristate</td><td> --</td><td> 2,52</td>

<td>SPF</td><td> 20,2</td><td> 2,4</td>

As the previous SPF values ​​show, formulation 98B, which does not contain any organic reagents providing ·· 4444 ♦ · 44

4 · · · • 4 · 44 » 4 • 4 4 4 4 4 4 *44« 44

44 4·

44

4*44

444 4 4 44

4 4 4 4 4 4

4 4 4

4 * 4 44 44 sun protection filter, had an extremely low value of the protection index SPF and was relatively ineffective. Thus, the mere removal of the organic sunscreen agents from Formulation 98A does not result in comparable SPF values.

Example 99 - control example

In this example, Formulation 99A contained isostearic acid as a branched chain anionic emulsifier. Formulation 99B contained stearic acid, a straight chain anionic emulsifier, in accordance with the products of the invention. The formulations in this example had the following composition:

<td></td><td>99A</td><td>99B</td>

<td>Component</td><td>% w / w</td><td>% w / w</td>

<td>Deionized water</td><td> 80,95</td><td> 80,95</td>

<td>Carbopol 940</td><td> 0,40</td><td> 0,40</td>

<td>Propylene glycol</td><td> 3,00</td><td> 3,00</td>

<td>Disodium EDTA</td><td> 0,10</td><td> 0,10</td>

<td>Vitamin E acetate</td><td> 0,10</td><td> 0,10</td>

<td>Butylated hydroxytoluene</td><td> 0,05</td><td> 0,05</td>

<td>Velsan D8P3</td><td> 2,50</td><td> 2,50</td>

Isostearic acid

5,00 • 4 ·« »4 4·«« »· «·

444 4 · 4 »44* • · 4 44 4 4 44« 4 4 44 *4 444 · 44 «44 4 4

4444 44 · 444

44*4 «« 444 ·* 44

<td>Stearic acid</td><td> “ —</td><td> 5,00</td>

<td>Cetyl alcohol</td><td> 1,00</td><td> 1,00</td>

<td>Micro TiO2 SA-20</td><td> 4,00</td><td> 4,00</td>

<td>Dowicil 200 (33% solution)</td><td> 0,30</td><td> 0,30</td>

<td>Scent</td><td> 0,30</td><td> 0,30</td>

<td>D&amp;C Red # 33 (0.1% solution)</td><td> 0, 90</td><td> 0, 90</td>

<td>Sodium hydroxide (50% solution)</td><td> 1,40</td><td> 1,40</td>

<td>SPF</td><td> 7,1</td><td> 21,2</td>

It will be appreciated that Formulation 99B, which contains stearic acid, a straight chain anionic emulsifier of the invention, has a substantially higher SPF value than Formulation 99A, which contains isostearic acid, a branched chain anionic emulsifier.

Example 1QQ

A composition providing a sunscreen that could be suitably used as a dual-action carrier formulation was prepared and contained the following materials:

99

9 9 » 9 «9

999 9 9

9 9

99 • 9 9*

9 9

9 999

9 9 9 · 9 9

9» «9 9999

999

<td>CTFA folder designation</td><td>% w / w</td>

<td>Deionized water</td><td> 78,15</td>

<td>Glycerin 99%</td><td> 3,00</td>

<td>Carbopol 940</td><td> 0,25</td>

<td>Disodium edetate.</td><td> 0,10</td>

<td>Acetamide CEA</td><td> 2,50</td>

<td>Velsan D8P3</td><td> 2,50</td>

<td>Stearic acid</td><td> 4,00</td>

<td>Acid triglyceride caprylic and caprine</td><td> 3,75 .</td>

<td>Titanium dioxide</td><td> 4,50</td>

<td>Cetaryl alcohol, cetaryl sulphate sodium and sodium sulfate</td><td> 1,00</td>

<td>Bisabolol</td><td> 0,20</td>

<td>Butylated hydroxytoluene</td><td> 0,05</td>

<td>Sodium hydroxide</td><td>adjusts the pH to 7.5</td>

The formulation in Example 100 can be prepared as follows. The aqueous phase was prepared by weighing the water into a suitable vessel. Carbomer was slowly introduced into the water thus weighed with constant stirring, which allowed the Carbomer to hydrate accordingly. EDTA was then added and the aqueous phase was stirred for another 30 minutes. After these thirty minutes, the mixture was heated to 90 ° C. Glycerol a • 0 was then added to this phase

0* · 00 ··· • 0 0 · 0 ·

0000 0 0000 · 0 0* * ·· *0* 0 00 0000 0 • 0 0 0 00 0 00» ” ** ** ··

AREA. Then BHT, Velsan D8P3, stearic acid, cetaryl alcohol and caprylic and capric acid triglyceride and Bisabolol were added. The phase temperatures were maintained at 90 ° C for another 15 minutes. Titanium dioxide was then added slowly and the composition was stirred for another 30 minutes. The pH was adjusted to 7-7.5 by adding sodium hydroxide as a solution. The resulting solution was stirred for an additional 30 minutes at 88-92 ° C to form an emulsion. The composition was then cooled to 35 ° C and the pH was readjusted. To make up for the evaporation losses, additional water was added and the batch was homogenized for 5 minutes.

In the manner described in Example 100, other formulations could be prepared which were compositions according to the invention which contained, in addition to the sunscreen, one or more active ingredients. The carrier base of the present invention provides a sprayable, cosmetically attractive composition by which both sunscreen agents and other topically active materials are applied.

The following formulations can be prepared as described in Example 100, however, it will be appreciated that this method may be adapted to the particular materials. Adjustments may include, but are not limited to, adjusting the pH of the final product, changing the order of addition of the raw materials, and / or changing the operating temperature.

« · *· ···

Example 100A - Composition containing dihydroxyacetate (self-tanning composition)

CTFA designation of the component% wt./wt.

Deionized water 74.15

Glycerin 99% 3.00

Carbopoi 940 0.25

Disodium edetate 0.10

Acetamide AMEA 2.50

Velsan D8P3 2.50

Stearic acid 4.00

3.75 caprylic and capric acid triglyceride

Dihydroxyacetate 4.00

Titanium dioxide MT 100T 4.50

Cetaryl alcohol, sodium cetaryl sulphate 1.00 and sodium sulphate

Bisabolol 0.20

Butylated hydroxytoluene 0.05

Sodium hydroxide adjusts the pH to 7.5 φφφφ

<img file="CZ9703969A3_D0007.tif" />

• · φ

<img file="CZ9703969A3_D0008.tif" />

Φ Φ φφφ

Example 100Β - Composition containing a skin whitening agent, magnesium ascorbyl phosphate:

CTFA designation of the component% w / w.

Deionized water 75.15

Glycerin 99% 3.00

Carbopol 940 0.25

Disodium edetate 0.10

Magnesium ascorbyl phosphate 3.00

Acetamide AMEA 2.50

Velsan D8P3 2.50

Stearic acid 4.00

3.75 caprylic and capric acid triglyceride

Titanium dioxide 4.50

Cetaryl alcohol, sodium cetaryl sulphate 1.00 and sodium sulphate

Bisabolol 0.20

Butylated hydroxytoluene 0.05

Sodium hydroxide adjusts the pH to 7.5

99 99 999.9 9· ·· • · 9 499 49·· • 9999 9 * 9 4 9 9 9 «·

4 4 · * 4 9 9 999« 9 • ·4· · · 4 4 9 9 •4 · 94 4 4 · 44 4

Example 100C - Composition comprising a skin whitening agent, hydroquinone:

CTFA designation of the component% wt./wt.

Deionized water 76.15

Glycerin 99% 3.00 '

Carbopol 940 0.25

Disodium edetate 0.10

Hydroquinone 2.00

Acetamide AMEA 2.50

Velsan D8P3 2.50

Stearic acid 4.00

3.75 caprylic and capric acid triglycerides

Titanium dioxide 4.50

Cetaryl alcohol, sodium cetaryl sulphate 1.00 and sodium sulphate

Bisabolol 0.20

Butylated hydroxytoluene 0.05

Sodium hydroxide adjusts the pH to 7.5

4 4 4 4 9 4 4 4 4 * 99 * 4 9 Β · 9 4 94 4 · 4 · * Β »·· 9 · 4 9 4« «4 44 44 4 ·&gt; 4 4 4«

Example 100D - Composition containing oil soluble retinoic acid

CTFA designation of the component% wt./wt.

Deionized water 78.14

Glycerin 99% 3.00

Carbopol 940 0.25

Disodium edetate 0.10

Acetamide AMEA 2.50

Velsan D8P3 2.50

Stearic acid 4.00

3.75 caprylic and capric acid triglyceride

Titanium dioxide MT 100T 4.50

Cetaryl alcohol, sodium cetaryl sulphate 1.00 and sodium sulphate

Retinoic acid 0.01

Bisabolol 0.20

Butylated hydroxytoluene 0.05

Sodium hydroxide adjusts the pH to 7.5

Example 100E - Composition containing oil-soluble retinaldehyde:

• · · 4« · · 4 · * · · 44 • · · 4 9 · · ► · 4 · · · • 4 4 4 4« 4 444

4· 4* 4 4 **♦ 9 9 9 9

CTFA designation of the component% wt./wt.

Deionized water 78.07

Glycerin 99% 3.00

Carbopol 940 0.25

Disodium edetate 0.10

Acetamide AMEA 2.50

Velsan D8P3 2.50

Stearic acid 4.00

3.75 caprylic and capric acid triglyceride

Titanium dioxide MT 100T 4.50

Cetaryl alcohol, sodium cetaryl sulphate 1.00 and sodium sulphate

Retinaldehyde 0.08

Bisabolol 0.20

Butylated hydroxytoluene 0.05

Sodium hydroxide adjusts the pH to 7.5

Example 100F: Oil-soluble retinol-containing composition:

&gt; 00 «* 0··· 0 0 · 0 0

0000 0 0 0 0 0

0 0 0 0 0 0

0 0 0 0 0

I · 0 00 0 · 0

CTFA folder designation

Deionized water

Glycerin 99%

Carbopol 940

Disodium edetate

Acetamide AMEA

Velsan D8P3

Stearic acid

Caprylic and capric acid triglyceride

Titanium dioxide MT 100T

Cetaryl alcohol, sodium cetaryl sulphate and sodium sulphate

Retinol

Bisabolol

Butylated hydroxytoluene% w / w.

78,07

3,00

0,25

0,10

2,50

2.50

4,00

3,75

4.50

1,00

0,08

0,20

0, 05

Sodium hydroxide adjusts pH to 7.5 • * · * 9 '

9 9 9 9 » 9 »

9

Example 100G: Composition containing oil-soluble retinyl palmitate:

CTFA folder designation

Deionized water

Glycerin 99%

Carbopol 940

Disodium edetate

Acetamide AMEA

Velsan D8P3

Stearic acid

Caprylic and capric acid triglyceride

Titanium dioxide MT 100T

Cetaryl alcohol, sodium cetaryl sulphate and sodium sulphate

Retinyl palmitate

Bisabolol

Butylated hydroxytoluene% w / w.

77,35 ' . 3,00

0,25

0,10

2,50

2.50

4,00

3,75

4.50

1,00

0,80

0,20

0,05

Sodium hydroxide adjusts the pH to 7.5

<td></td><td> «· 0* 00 000 0 0» *0 0 0 0 0 0 * 0 01 0 0 0. 0 000 0 0 0 00 0 0 00 • 00 000 0 *0 ··♦ · » 0000 00 0 000</td>

<td> 47</td><td> ·« «« ·· «·· ·· ··</td>

<td>Example 100H - A composition comprising</td><td>fungicidal agent:</td>

<td>CTFA folder designation</td><td>% w / w</td>

<td>Deionized water</td><td> 76,15</td>

<td>Glycerin 99%</td><td> 3,00</td>

<td>Carbopol 940</td><td> 0,25</td>

<td>Disodium edetate</td><td> 0,10</td>

<td>Acetamide AMEA</td><td> 2,50</td>

<td>Velsan D8P3</td><td> 2,50</td>

<td>Stearic acid</td><td> 4,00</td>

<td>Acid triglyceride</td><td> 3,75</td>

<td>caprylic and caprine</td><td></td>

<td>Titanium dioxide MT 100T</td><td> 4,50</td>

<td>Cetaryl alcohol, cetaryl sulphate</td><td> 1,0.0</td>

<td>sodium and sodium sulfate</td><td></td>

<td> »3</td><td></td>

<td>Ketokonaz.ol</td><td> 2,00</td>

<td>. Bisabolol</td><td> 0,20</td>

<td>Butylated hydroxytoluene</td><td> 0,05</td>

Sodium hydroxide adjusts pH to 7.5 »» * · • AA • A · «· • A · * • AA«

ΑΑ ΑΑ • Α · * »»

AA A Α

A Al A Α

AAA Α

A *** »A.

AA Α «Α» Α

Example 100J - Composition containing an antimicrobial agent:

CTFA folder designation

Deionized water

Glycerin 99%

Carbopol 940

Disodium edetate

Acetamide AMEA

Velsan D8P3

Stearic acid

&gt; Caprylic and capric acid triglyceride .Titanium dioxide MT 100T

Cetaryl alcohol, sodium cetaryl sulphate and sodium sulphate

Trickosan

Bisabolol

Butylated hydroxytoluene% w / w.

77, 65

3,00

0,25

0,10

2,50

2.50

4,00

3,75

4.50

1,00

0, 50

0,20

0,05

Sodium hydroxide adjusts pH to 7.5 φφ φφφφ φ 'φ · φ φφφφ φ φ φ

Φ ·

Φ «Φ ··

ΦΦ φφ • Φ Φ φ

Φ · ΦΦ

ΦΦ ·· · φ Φ φ

ΦΦ φφ

ΦΦ φφ

Example 1Q0K - A composition comprising "insect repellent odor:

• · φφφ · · φ • φ φ * φφ «φ

CTFA folder designation

Deionized water

Glycerin 99%

Carbopoi 940

Disodium edetate

Acetamide AMEA

Velsan D8P3

Stearic acid

Caprylic and capric acid triglyceride

Titanium dioxide MT 100T

Cetaryl alcohol, sodium cetaryl sulphate and sodium sulphate

Insect repellent odor

Bisabolol

Butylated hydroxytoluene

Sodium hydroxide% w / w

72,15

3,00

0,25

0,10

2,50

2.50

4,00

3,75

4.50

1,00

6,00

0.20. 0.05 adjusts the pH to 7.5

44

4 4 4

4! · ·» • 44 « 4

4-4 4

W4 • 4 · * * · • · · 44 «· · · · 4 4» 4 · 4 · 4

4« 44 ·· ··· «4 ··»·

4' 4 * • 4 444

Example 100L - Composition containing iron oxides:

CTFA folder designation

Deionized water

Glycerin 99%

Veegum

Carbopol 940

Disodium edetate

Acetamide AMEA

Velsan D8P3

Stearic acid

Caprylic and capric acid triglyceride

Titanium dioxide MT 100T

Cetaryl alcohol, sodium cetaryl sulphate and sodium sulphate

Keltrol

Bisabolol

Butylated hydroxytoluene% w / w.

76,49

3, 00

0, 60

0,25

0,10

2,50

2.50

4,00

3,75

4.50

1,00·

0,40 ' 0,20

0,05

Sodium hydroxide adjusts the pH to 7.5

<img file="CZ9703969A3_D0009.tif" />

Example 100M - Composition containing alpha-hydroxy acid

CTFA folder designation

Deionized water

Carbopol 940

Disodium edetate

Sodium sterate

Propylene glycol

Butylated hydroxytoluene

Velsan D8P3

Brij 721

Cetaryl alcohol, sodium cetaryl sulphate and sodium sulphate

Caprylic and capric acid triglyceride

Stearic acid

Titanium dioxide MT 100T

Glycolic acid (70% solution)

Sodium hydroxide (20% solution)

Dowicil 200% w / w,

55,95

0,25

0,10

5,00

3,00

0,05

2.50

3,00

1,00

3,75

5,00

4.50

7,14

8,66

0.10 ·· tt · tttt · «» · ♦. · * '·' ····, '»tt» ·· · &lt;«♦« · • tttt «tttt tt · · tttt · * tt« · ·· tttt ·· ···

<img file="CZ9703969A3_D0010.tif" />

The pH of this product should be adjusted to approximately 5.15.