SA96170270B1 - Sunscreen formulations - Google Patents

Abstract

Abstract: This invention relates to novel sunscreen compositions containing inorganic sunscreen agents, anionic emulsifiers and an oil component that enables the use of large amounts of inorganic sunscreen agents in formulations without To have intense whitening effects and to achieve high sun protection.

Description

. SUNSCREEN COMPOSITIONS | Full Description Z 0 0 This order is a continuation of the order with serial number 08/498,774; Depositor: dated “gig A 1996 AD; currently assigning aie. 0 Scope of the Invention This invention contains novel and useful ultraviolet radiation sunscreen agents with formulations that demonstrate enhanced protection and methods for protecting human skin from the potentially harmful effects of sunlight. 0 BACKGROUND OF THE INVENTION Although a suntan tan was considered long ago Als indicates health | © The good - being able to spend a lot of free time enjoying outdoor activities such as swimming; tennis; skiing golf and the like; However, it has been clearly shown that excessive exposure of human skin to sunlight is harmful. It has been shown in scientific publications that human skin is sensitive to sunlight and artificial light that contains saturation with wavelengths ranging from about 900 nanometers (nm) to 501 nanometers. He knew that ultraviolet rays of wavelength vo ranged from about 0? Nanometer to 17? Nanometers (Uv-B region) quickly produces harmful effects on the skin Lay including reddening or erythema cerythema edema edema blistering Or any other skin eruptions in more severe cases.Long or chronic exposure to rays with wavelengths in this range is accompanied by serious skin conditions such as actinic keratoses ody

¥ and carcinomas and at present; Attention also focused on ultraviolet rays whose wavelength exceeds 771 nanometers (Ultraviolet A or UVA region) and its harmful effects on human skin. It was found that the rays whose wavelength ranges from 771 to Sasi 50800 Contributes to premature aging of the skin Lad In addition: Recent studies have indicated that chronic exposure to sunlight reduces the skin's immune response There is also evidence that sunburn offers some protection against Goad burning | But it is completely ineffective against other types of solar damage. © The increasing public awareness of the need for adequate sun protection while enjoying outdoor activities has led to the development of sunscreen products. products 0 is an unprecedented development The desired sunscreen product should have the following properties: to protect from ultraviolet radiation in both ranges (UV-B and UV-A | to maintain coverage; i.e. to be resistant Waterproof and sweat-proof To be put on and use sh ladle Easy to put on Not to be seen It is not stains and does not have an effect Sha does not irritate the skin because of its ingredients; Specifically; Its effective sunscreen ingredients are among the 0,0 ve recent research interests in this area. The problems of irritation and sensitivity are 7(6” Hunt) that may be experienced by some individuals who use sunscreen products with high SPF values. SPR contains organic sunscreen agents. It expresses the effectiveness of a sunscreen product with a sun protection factor (SPF) sun protection factor Y- and defines the sun protection factor Y- Sunlight is defined as the ratio of the time of sun exposure (dose) required to cause the Ji erythema reaction in protected skin to the time required to produce the same reaction in unprotected skin. The absolute dose varies from person to AY and is highly dependent On genetic predisposition: on the Bld of an individual's ethnic origin, if a person normally needs ten minutes of sun exposure to show the slightest erythema reaction, he should be likely to be reminded.

$ oo erythema reaction 151 minutes without an erythema reaction occurring in sunlight for a period not exceeding . Public awareness of today's 1© equals SPF when using a sunscreen product that has problems with sun exposure has led to the need for sunscreen products.

A is not less than SPF af, that is, when the SPF has high values of l "°. On the other hand, the ease of use and the appearance of the cosmetic are important in the formation of sunscreen formulations. These characteristics depend on subjective estimates ml m" user impression of look and feel. Consumer research studies have indicated that the sunscreen formula should be easy to rub in. leave the skin non-sticky and; above all, it should not be Seeing it on the skin after applying it.In some cases, it was found that sunscreen formulations that contain organic sunscreen factors irritate the skin.Accordingly, inorganic sunscreen agents such as carbon dioxide were used. A. zinc oxide and titanium dioxide Description of Japanese Patent Application No. 111,841 issued (JB) for example 0 fractionated in the form of titanium oxide Cosmetics containing titanium oxide (2) AA) year ranging from particle size to 7468 has a particle size of 11 _ ultrafine with a ratio ranging from 10 to water 16 m0 m 0 m 78:0. Processed to be hydrophobic and having a particle size ranging from titanium oxide to cosmetic base materials; It transmits a gill ge nanometer mixture of 70-01 Cad, but reflects and scatters harmful ultraviolet rays. It has found visible light Soa 0 which has the previous range of particle size titanium dioxide When titanium dioxide - © is used as a sunscreen in sunscreen formulations it may lead to Dale as a loss of one The most important desirable properties of these structures and they cannot be seen. American Invention No. 8,078:517; issued in-? July Bel yy prescribed titanium dioxide Sunscreen formulations containing titanium dioxide 49 (2) of Jd titanium dioxide The particle size of the titanium dioxide Jaa ve is required to be accurate: Z Z L

Oh 0 nm. The patent also mentioned that other sunscreen agents can be used: with titanium dioxide and described US Patent No. ONY 6 issued in YY August 564 AD; A sunscreen formulation comprising a synergistic combination of O2 titanium dioxide having a particle size of less than about 0 nm and zinc oxide: Eden having a particle size of less than 0 00 nm There is titanium dioxide and Cady zine oxide (ya Jal) specified. German Patent No. 7,147,794 issued in CS a) AY described. A cosmetic used to prevent sunburn containing zinc oxide 0 2 at a ratio of 1-1705 with a particle size ranging from 00-700 microns. Also on titanium dioxide 0 has a particle size ranging from 70-710 microns. This combination is undesirable due to its unaesthetic whitening properties at high SPF levels and US Patent No. 0,188,871 describes; issued in ?? February © 10 1557 A.D. Sunscreen formulations where the sunscreen effect is obtained from a synergistic mixture of titanium dioxide ultra-fine cal 0 in oil and JAS titanium dioxide dispersible in oil water. Other than Ca the resulting SPF level was only 01 and the concentration of XS titanium dioxide 05 w/w: 2 and the description of the International Patent Application No. (A [IVY] published in VE June 0; Sunscreen formulations consisting of titanium dioxide 0, where fine particles of titanium dioxide are coated with phospholipid, either by using a powder mill or by making a dispersion in An oil phase containing phospholipids using a high shear mixer Yo then incorporates titanium dioxide coated with phospholipids 0 O 7 F

:: phospholipid | in sunscreen formulations. And it claimed to achieve high efficacy: as the available data showed that the SPF values were not more than 11 for titanium dioxide with a concentration equal to 77.70 and not more than yo for titanium dioxide with a concentration equal to 7 The use of a Me shear mixer or a crushing mill is a complex and energy-intensive process. 1 European Patent No. OY0,AVY published in 7 Jad 44 0 ) describes a method for preparing sunscreen formulations where a dispersion of particles | zine oxide and/or titanium dioxide oil by crushing. European Patent No. A2 114,999 (published October 19 Ve 54) described a “Lila tide of particulate metallic oxide having a particle size of less than 100 nm mixed with an emulsifying agent and an oily phase.” As well as a non-call organic factor: hydrophobic 5 (3) from the sun's rays to form an oil emulsion in o/w emulsion sla. The SPF value of the resulting sunscreen formulation was higher than what was expected when using the formulation It contains only additional substances, however, when titanium dioxide © No was used alone at a concentration equal to 74, a combination product with an SPF ranging from only 7 to about AY was described: European Patent No. 1778:7807 published On October 19, 1984, a process for the preparation of a sunscreen formulation (35). It comprises the mixing of sunscreen particles of metallic oxide having a size of less than 700 nm dispersed in 0 oil with one or more emulsifying agents and /or one or more organic sunscreen factors ye I have claimed that the resulting sunscreen formulations have a significantly higher than expected SPF value A high SPF value can only be obtained when mixing metallic oxide i With an organic sunscreen, a blend. Indeed; Laie does not use an organic sunscreen with an SPF value of only around 17. 7 Ah, remember it

The international patent application No. 117457/97 described sunscreen formulations comprising titanium dioxide and iron oxide with a particle size of less than 100 nanometers and preferably coated with a phospholipid: Article published by Tioxide Specialaties Ltd. © 2010 in Journal 00 of September 1999 Several methods of incorporating aqueous or oil-based dispersions of titanium dioxide into emulsions. is that; The article did not give any data on the resulting SPF values. He described an article published in the Journal of Cosmetics and Toiletries | Volume 017 of October; 94Y (2) Several ways to form 0 with a physical sunscreen agent. The article focused on the use of titanium dioxide in a dispersant or the use of an emulsifying agent which is an effective dispersing agent for titanium dioxide as well. I mentioned that much higher SPF values than Xe could be achieved however, the article did not cite any examples, nor specific sunscreen ingredients or formulations. © 0 14440 Mar Organic sunscreen formulations with high SPF values obtained without the addition of any organic sunscreen agents The SPF values when measured in the sunscreen formulations were as actually described. odd When the titanium dioxide concentration was measured, it was at least double what was claimed. Another of the present invention in providing sunscreen formulations that contain sunscreen agents that overcome the disadvantages of materials available to date and provide LAS protection that is safe for human skin. Lo cay

An additional objective of this invention is to provide methods for protecting human skin from the harmful effects of sunlight. These objectives, features, etc. of the present invention will be readily apparent to a person skilled in the art from the detailed description provided hereinafter. l 0 General Description Invention . The previous objectives and the other fats and advantages of the present invention are achieved by sunscreen formulations containing inorganic sunscreen factors as the active ingredients. More specifically, the present invention relates to sunscreen formulations containing titanium dioxide and zinc oxide having preferred properties of 0 particle size; They are preferably coated and present in preferred amounts and proportions as effective sunscreen agents. These special formulations allow the use of amounts of sun protection ingredients that are much lower than those achieved by Gila while achieving the high SPF values desired for the formulations and without the unsightly whitening that occurs when previous sun protection formulations are used at concentrations greater than about 70 and in sun protection formulations according to 0 ve of this invention; Much higher concentrations of titanium dioxide can be used .. : without exposure to the bleaching effect; Such as a concentration of up to 700 and possibly higher with an acceptable bleaching incidence. oo and moreover. This invention does not depend on the use of hydrophilic preparations of titanium dioxide as requested in the aforementioned patent “Yo” and does not depend on energy-intensive processes “Jie” crushing; No active organic sunscreen agents are required to achieve high efficacy. The compositions of the present invention are oil-in-water emulsions containing at least the following components: - (i) an inorganic sunscreen agent; Jf titanium dioxide Yo or zinc oxide or a mixture thereof; oqy

: : (b) a tanionic emulsifier and (c) a carrier oil The compositions of this invention provide sunscreen formulations having SPF values of not less than 0.01 and are easily made with simple mixing and provide excellent dispersion For the inorganic protective agent “0 sunshine during formulation”; Thus, the skin is also covered. These structures are not visible JS 0 substantial when applied to the skin. Detailed description of the invention The sunscreen formulations according to this invention produce highly effective UV protection capabilities; That is, a finish providing a specified level of protection using titanium dioxide at a significantly lower concentration than previously obtained using commercially available powdered titanium dioxides. These formulations do not require the extraordinary processing methods that were previously necessary to disperse titanium dioxide in oil, such as preparation by batch grinding principles, high shear mixing, high shear grinding, or the application of these grinding procedures to the product formulation. Ultimate: Typical titanium dioxide sunscreen formulas with an SPF of V0 require levels of titanium dioxide to impart a significant whitening effect on the skin; This invention minimizes this defect, and the composition according to this invention is an oil-in-water emulsion that is cosmetically superior to conventional inorganic sunscreen preparations, including formulations containing only titanium dioxide. Bide in an oil-in-water emulsion; at equivalent ratings of SPF due to the low levels of titanium dioxide required in the system of the invention The compositions of this invention can be used for sun protection in everyday wear or in products applied to the face daily plus 0qy

1 .. to the recreations. And because of the effectiveness of the system, the cost of the innovative formulations is significantly lower than the cost of other sun protection systems. These elements include the following materials: l The compositions of this invention should include a selection of one or more emulsifying agents. In particular, certain salts of anionic emulsifiers are useful in the compositions of this invention. More specifically, the following anionic sodium stearate fatty acids emulsifying agents are useful in the compositions of this invention: DEA sodium stearate phosphate sodium lauryl sulfate csodium laurate and the like That., dioctyl sulfosuccinate ccetyl phosphate stearate 0 sodium stearate and most preferred; that the emulsifying agent is sodium stearate and it is believed that the salts of straight-chain fatty acids are relatively high (the melting points do not decrease Estraight-chain fatty acid salts having melting points of about 0 are not preferred because of their structure. For example, branched “a Ve” (about 0) acids are not acceptable for use in the compositions of this invention. 1 agents should be present Anionic emulsifiers in the compositions of this invention range from about 0.01 to about go and the most preferred from about 70.5 to about 717 and the best from 70.1 to about 0 emulsifying agents other than Jie and additional emulsifying agents may be present in the formulations This invention; Co and ionic sorbitan esters known by those familiar with this technique; Such as sorbitan esters of lemons, fatty acids, cethoxylated sorbitan esters, Y. cethoxylated fatty alcohols, fatty alcohols, fatty alcohols, and fatty glyceride esters. fatty glycerides and the like. is that; At least one anionic ethoxylted fatty glycericle esters emulsifying agent must be present to produce the products of the present invention. Emulsifying agents of the salt of the fatty acid may be added to the composition in the form of the salt; Or the salt may form in the same reaction zone. ve and e

Vy | A carrier oil should also be present in the formulations of this invention. amy chooses these carrier oils from the group of -polyether interrupted fatty acid esters | the best; That the carrier oil is a carboxylate ester 0 ether carboxylate ester interspersed with polyethylene (and optionally polypropylene) z 0 alkyl fatty nine fatty alkyl coptionally polypropylenoxyl polyethlenoxy 0-0 so that the ester does not contain an alkyl group It has 1-1? carbon atom and it may be straight or optionally branched. the most favourable; That the carrier oil be isopropyl propylene glycol-2-isodeceth-7 carboxylate ye | | Or any other commercially available material sold by Sandoz Company under the trade name of Velsan. about 75. and the most favourable; that | present in amounts from about 7+ to about JY vo preferably; that the oil phase contains at least two substances; They are carrier oil 0 poly ether and a traditional emollient known by those familiar with this technique as useful in sunscreen products; such as mineral oil; And ester oils or other 0 materials familiar to the millennium. With these AENs like mineral oils, mineral oils, vegetable oils, silicones are 0:21; Synthetic emollients le fatty acid esters Y. and the like. The ratio of this emollient to the concentration of the carrier in the formulation should range from about 1:1 to about 7, and the most spats should be about 7:. The oily and emollient carrier should consist of about #7 to about 771 composition by weight. As for the third element that should be present in the formulations of this invention, it is an inorganic sunscreen compound. Such as titanium dioxide or zinc oxide, or a combination of them. preferably; The use of titanium dioxide:

1" | 0 titanium dioxide having a particle size of no more than 7000 nm in diameter. It should be present in the composition in an amount ranging from about #7 to about ©77. Better yet, it should be present in an amount ranging from about #7 to about 715 and maximum Sait should be present in an amount ranging from: about ?/ to about 0 TY The inorganic sunscreen compound should be dispersible in oil; And to exist with or without a surface coating. The ratio of titanium dioxide to the weight of the oily carrier and emollient mixture should range from about 0:0 to about 1:1, which is more favourable; The :z ratio ranges from about 0:08 to THY for example; The composition contains 5 titanium dioxide at a ratio of 719, Velsan D8P3, at a ratio of 0:78:77, and a ratio of 7.0 to Miglyol, and the remainder of the composition is identical to the remainder of the example composition. 1 below and this formula produces a sunscreen formula with SPF equal to NY and the degree of whiteness of this formula is acceptable and it only slightly whitens the skin. The pH of the compositions of this invention should be kept at a level higher than about ©; the best; higher than about 10.0 and keeping the pH at this 10 _ level will ensure that the anionic emulsion remains in salt form; This is important to maintain product stability. Z In addition to lA, the ordinary elements of a modern sunscreen emulsion system are used; As a polymeric thickener or polymeric stabilizer One or more additional rain oil Preservatives 010:01 microbial cantioxidants Fragrances cfragrance Humectants Humectant Of course Sle dala without Choose © > or ad selected. The compositions of this invention may be in liquid form or in acrosol form (aerosol). It can be combined into beauty products (Ale) and various personal products (Ale) J gue Jie hands and body ¢hand and body lotions oils pal —all-coils ointments s emollients clip balm products facial cosmetics facial cosmetics Yo and the like. ogy

Gy sunscreen compositions may be prepared for this invention by using one of

At least the following two methods: Cus dwo-vessel method The two oil phases Ally are prepared separately; And the one-vessel method, where it is added

All ingredients in a selective and special order. Either of these operations will produce Ca Gat ae

© Regular, white to light ivory. Udy, : for the ole fl process greening an aqueous phase by measuring deionized water | } into a beaker mug and mix. Then the elements of the aqueous phase are added; including cyl ally emulsifying agents chelating agents chelators thickeners; Water-proofing agents, neutralizing agents, and antioxidants 0 | Then the solution is heated. The anionic emulsifying agent may be placed in the aqueous phase or in the lac 5 30 phase due to the nature of the emulsifying agent. The oil phase is prepared in the AT vessel separately; It includes an anionic emulsifying agent; Carrier oil and inorganic protective agent: sunscreen. Then the two phases are kept at a relatively high temperature and mixed. More precisely; In the oles process the aqueous phase is prepared by measuring the deionized water z ae ions in a beaker and then mixing. Then Carbopol 9460 940 ‎Carbopol is added and the composition is mixed until it is suitably hydrated. Then, propylene glycol and diamine tetraacetic acid EDTA should be added to the mixture and mixed until a homogeneous solution is produced. The solution is then heated to a temperature of 1 to 1 ℃. The solution should be kept at a temperature SAY spe for phase adjustment. Yes, then the oil phase is prepared by adding the following ingredients to a mug: butylated hydroxytoluene “BHT,” Veslan D8P3 V, stearic acid, Cetyl alcohol, and Miglyol 812 AVY, then The mug is placed in a water bath on an electrically heated plate. Then the components are settled to about 88 m or until they melt. Then it is added Titanium dioxide slowly and stir the composition at high speed until it becomes homogenous. Then vo the mixture is kept at about 80 °C until the phase is set. : 0 ody |

': The composition Lad may be separated into phases by adding the oil phase 0:1 to the aqueous phase and mixing with the temperature being kept at about 88°C for minutes. Then sodium hydroxide (in the form of a solution of concentration )/01 is added and the composition is mixed for minutes at high speed. The mixing speed is reduced. Tagg cooling. When the temperature of the paste reaches 40-60 ca, Dowicil 200 001 "0 solution is added and optionally fragrance is added. The pH should be checked and adjusted at A0=A with 0 sodium hydroxide solution (at a concentration of 107); if required (target pH is 8,7 ).Deionized water may be added if needed to bring the dough weight up to the final weight.When the dough temperature reaches the range of 77-748°C the mixing stops 0 In the vessel process the aqueous and oily phases can be prepared in the same cole) provided that the components are added in a suitable order. the vessel to a temperature of about 85 to about 46 C. Once it reaches 0

#1 Temperature To this cs final add the phase components Lay cil in that factor

anionic emulsification optionally; if it corresponds to the oil phase and carrier oil; in addition to any emulsifying agents; Additional oil-phase oxidants and emollients as desired. And should

keep the temperature at this level of about 11 minutes; The inorganic organic sunscreen factor coda is added and the formulation is blended for a minimum period of time

| Then add Dauessel cA, YO min. Then the pH is checked and set at about Ye ve, which is a preservative in addition to an optional perfume. Dowicil

More precisely: Deionized water may be added to a beaker to which carbopol 940 95400 is slowly added. Then add EDTA and mix the composition at Alle speed for Yo-Yo minutes or until Carbopol is suitably hydrolyzed. Then the mixture begins to heat up

: During this propylene glycol the required amount of propylene glycol J q0-4Y Yo is added

Just

time. And when the temperature reaches 46-47 C; Add BHT felzan de A bih - ? <Velsan D8P3 Stearic Acid Cetyl Alcohol Miglyol 812 17 | The temperature of the mixture should be kept at around 240-4 for approximately 10 minutes. Then titanium dioxide is added and the composition is mixed for Ye minutes. M: Sodium hydroxide is added (in the form of a solution of concentration + (1) and the composition is mixed for 0 minutes at a temperature ranging from YAN 2, then the composition is cooled to “a 560 die” and Duacyl’s solution is added Dowicil 200 0000 in addition to the optional fragrance.Then the pH was adjusted to about 8.5-8/ using sodium hydroxide (the target pH is AYO) and finally, water was added in an amount sufficient for a gel: 0 Dough weight reaches target weight. : z The following examples illustrate the compositions of this invention but do not specify the scope of the invention described herein Example 1 4.07 mL of deionized water was added to a beaker Then ,7* was added 0 0 1 g | Carbopol 9580 940 carbopol (available from BF Goodrich)

Goodrich in Cincinnati, Ohio (Ohio) slowly to beaker. Then add 1 g Disodium EDTA and mix the composition on high speed for >1-7 minutes or until hydrated carbopol appropriately The mixture was heated to 5-47°C and 0 g of propylene glycol was added When the temperature reached 48-97°C 0,+ g of YO (BHT) g of Felzan was added D A P? Velsan D8P3 (available from Sandoz Corporation. 06” (Sandoz Corporation) 10 g stearic acid 10 g YV,0 4 cetyl alcohol 4 g Magliol Miglyol 812 AVY (available from Huls Company of Piscataway, New Jersey) Then 0 pounds of titanium dioxide MT-100 was added. 100T vo which is titanium dioxide flour coated with aluminum stearate

: 0 z aluminum stearate to the container. Then, £9.4Y gm of sodium hydroxide solution was added.. sodium hydroxide at a concentration of 701 and the composition was mixed for a period of ye minutes at a temperature ranging from 3.04 AA—Y. Cooling began and when the composition temperature reached 0°C Add 7 gm of Dowicil + Dowicil 200 Yo (a solution of Quaternium 10 15 777): : 6 in addition to 7.5 gm of perfume. The pH was adjusted at A.0-A using 44.97 gram of sodium hydroxide solution. Its concentration is 701 (target pH 0 is 8.7 ): Finally enough deionized water was added to make The dough weight reaches the target weight. The SPF (sun protection factor) of this formulation was measured in test tubes using the system described by Cole and VanFossen, C. Cole and R. VanFossen. (R VonFossen) in the book “Sunscreens: Development, Evaluation and Regulatory Aspects” Sunscreens: Development, Evaluation and Regulatory Aspects, published by N. Schatth: N.Shaath and N. Lowe Published by JS le Marcel Dekker NewYork © Ne - New York State NY. 1490 In short, this system consists of measuring access Simulated solar ultraviolet radiation through a composition applied to the skin at a rate of 1.7 mg / cm twice.The system consists of an optical sensor that is affected by scorching rays only and has a sensitivity spectrum (J Alas sensitivity spectrum) for the erythema sensitivity spectrum in humans - erythema sensitivity spectrum |«p|»«i. SPF is defined as the ratio of the optical signal © passing from excised mouse skin without sunscreen on it divided by the optical signal passing from excised JB skin with no sunscreen on it Sunscreen. Regularity was titrated against a series of sunscreen formulations with known SPF af (range 4-76) determined in test tubes using the FDA monograph method (in the Federal Register; ve products). Sunscreen drugs given to humans without a prescription Lk oqy

Sunscreen drug products for over-the-counter human drugs p (1+) (YA Y14-YAY) issued on “Yo August” AVA (2) and the SPF value resulting from the example combination was 1 Previous 4 The composition was satisfactory and stable from an aesthetic point of view Examples from VEY: ° In the following series of examples, the use of titanium dioxide compounds of different sources and/or types of coatings at the same concentration of £.0 / was discussed. A. All Gay compositions for the method shown in Example 1a contained the same components with the same concentrations except for the variable component.The results are shown in Table 1. Table 1 Effect of TiO coating on SPF 3S 5 710 0,£( ) ¥) Source TiO; Surface Treatment .. SPF 1 (7) Al MT-100T Stearic Acid Y1,4 Stearic Acid (Tri-K Industries, Inc.) 1 (Tri-K Industries, Inc.) al (4) T-00*T MT-500T © None , 1 (Tri-K Industries, Inc.) 4,4 (©) SMT-100 SMT-Polysiloxane Hydrogen Instance OR 10055 (Methyl hydrogen polysiloxane (Tri-K Industries, Inc.) } (7) U. V Than M7717 UV Than M262 Alumina Dimethicone YA, (Presperse, Inc.) (Y) UV Titanium Titan M212 701 of alumina alumina glycerin A Glycerin (Presperse, Inc.)

(A) P25 Yo N/A for 5.11 (Degussa Corporation): (?) STT Te C-S 51276505 N/A 17.1 (Kobo) (01) DM VE KSI DMI40KST Surface STT 16C-S 11.0° (Kobo Corporation) ) STT65C-S surface (Kobo) Silicon (MV) STT-0*DS “Si” Al STT-30D-S Silicon YA Silicon (Kobo Corporation)

(Kobo)

(VY) s. t. STT-30S-L has V,¥ Stearic Acid

: (Kobo) : (Kobo) TiO, (VY) (not all for water) cMethicone Dimethicone Wooo A Creative Polymers Dimethicone: 7 - ( ? titanium dioxide

The resulting SPF dad was measured. The compositions were prepared according to the method shown in Example 1, and their concentrations differed according to the amount of titanium dioxide only. Make up for the difference with water

0 deionized. -

and tee EP Se concentration of titanium dioxide SPF sun protection factor al. MT-100T Titanium dioxide : WY 74,0 (0 5) (M1): 71.6 his (Ov) 8 l ' Y vd Examples 11-18 The following examples are meant to illustrate which of the anionic emulsifying agents give a high SPF value. shown in Table oF below.From the data in Table oF it can be seen that dioctylsucfosuccinate and DEA cetyl phosphate (Amphisol) under the right conditions; lauryl sulfate Sodium lauryl sulfate and sodium stearate are all effective in producing SPF 2 values of 1.01 . Table CY } Effect of anionic emulsifiers on SPF SPF 1 A) Sodium Stearate (equivalent to a solution of 3 - 1 Stearic Acid with Sodium Hydroxide). : (14) Sodium stearate in an aqueous phase Vo,¥ (Y4) 70 Isostearic Acid 15% (¢Brij 721 771 £0, without Stearic Acid, in the presence of Miglyol 812 AVY and Felzan D A P 7 Velsan D8P3 ( \ ¥) 1.0 isostearic acid (added to A + H,0 (NaOH) in the presence of 7 Brij 721 771 (YY) 58 oleic acid Oleic Acid without Stearic Acid 1 with pH adjustment ¥, °

0 | A 7 Y 9 (10 of Lauric acid yd without Stearic acid, 1 Acid 3 7 of Amphisol with 1 of Brij 721 YY) and acid YY | Stearic Acid Without pH Adjustment 0 7Y (¥ °) from Amphisol with Brij 721 YY without Stearic Acid (77) AN 77 from Amphisol Amphisol with Brij 721 YY) and Beeswax 15.1 Beeswax without Stearic Acid and without Aa ja pH (YV) Co 5 control from Sodium lauryl sulfate with Vo, (aaa stearic acid and 7 from Brij 721 YY) and without 1 (Y A) of lecithin without stearic acid in the presence of Ye AY: from the tower Brij 721 YYY Without pH Adjustment: (YA) 0 º Aerosol Oh. T-78 Aerosol OT-75 with Stearic Acid YV,Y - Stearic Acid and Brij 721 771 without pH control da (Y) Aerosol Oh. Aerosol OT-75 Yo—i with ALY Stearic Acid ly li ull 12 and Brij 721 YY) without pH adjustment and 0.9 of: Sodium Stearate (VY) Hambucil added C-107 cHamposyl C30 without aaa stearic 4 2 ol acid ssssssssssssssssssscsssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssssss with stearic acid without stearic acid. Polyoxyethylene, YY, stearyl ether: “polyoxyethylene 21 stearyl ether: Miglyol: Miglyol 812 AVY. Capric/caprylic triglyceride °.

71 | Qalzan D A Peh Y 0803 SADFC-7: Isopropyl Propylene Glycol Carboxylate- “-isodeceth-<no” isopropyl propylene glycol-2-isodeceth-7 carboxylate Amphisol : DEA phosphate. cetyl phosphate DEA b Aerosol O.T-H L 01-5 'Aerosol Dioctyl -sodium sulfosuccinate ° 1 tHampocyl cocoylsarcosinate sodium anionic emulsifying agent Examples 7-77 Examples 7-1_the following show that unless sodium stearate is an emulsifying agent (Gal), non-ionic emulsifiers do not lead to Alle values and the structures shown below are inclined. Example Composition 1 Refer to the changes indicated in the body table below table The effect of a non-ionic emulsion on SPF SPF - (YY) £1 of cetyl alcohol without (aes) Stearic 1 Y,Y Stearic Acid in the presence of LY from Borg 771 1 and without pH adjustment (YY): 70 cglycetyl monostearate and 7 tween v.4 Tween 60 0 7) Arlacel 01 without stearic acid with pH adjusted at Y (0© ¢ from glycetyl monostearate and 7 from Brij 721 YY ce): Without Stearic Acid (° ¥) A from Tower 1 YA v/v from Brij 72 YY Tower Without Stearic Acid pH set at 17 (YT) 7 7, from Tower 10.,7/771 from Tower Brij 72 YY 10,0 from Rewoderm (£) Eps Rewoderm 81333 1177 without Stearic Acid with no pH adjustment

YY 5,1 without “Span 60 1 from Span 7+, ¥/Tween 60 01newt from 77,7 (YY): 17 with pH adjustment at stearic acid L 7.040 5 Span 60 01 Span 0, Y [Tween 60 01 Newt 77,7 (YA) With Stearic Acid Without Stearic Acid Rewoderm 51333 177 Rewoderm S

Y Adjust pH at 9.3 and without ¢ Glucam E-20 Diastearate from Glucam E-10 Distearate 77 (79) 0 stearic acid and 1.9 Mo Glucam 15-20 Diastearate From Glucam E-10 Distearate 77 (450) stearic acid and without stearic acid Rewoderm 51333 1777 ul From Rewoderm: 1 with pH adjustment at and without R ¢ Glucam SSE-20 00 0 t - wd ol p) from glucam (stearic acid) stearic acid Y,o and 70.6 from Rioderm Glucam 5512-20 Y= from glucam SS 77 (£7) with control stearic acid Without stearic acid Rewoderm 51333 117 S: L Y pH at

A stearic without stearic acid “Glucam 7-20 Yo —dwm” from Glucam 8 ¢ 9: acid The above trademarks refer to the following compounds: : polyoxyethylene (20) (01) sorbitan monostearate 'Tween 60 01 LA .srbitan monostearate .sorbitan monotearate Support: sorbitan monostearate 60 00 Arlesl | .polyoxyethylene stearate . : sorbitan monostearate . Span 60 01 Span . Multifunctional anionic surfactant 'Rewoderm §-1333 / 717' Glucam E-20 01-J Glucam SSN-17 5838-20 S.O.S.A.: Monostearate 0:7. ethoxylated (20) methyl glucside sequitearate (01) sequitearate Ethoxyly afc

Examples 11-44: Show the following examples of; ;-99 The importance of using carrier oils in the products of this invention with emollient oils known to those familiar with this LE that are commercially available. The compositions shown below are the same as Example 1 except for the oil only; As shown below. Effect of single oils and oil mixtures on sun protection factor SPF SPF | (£0) 71.76 Finsoly TN Y, Finsoly TN (£7) 6 Finsolv TN 77.76 MY Miglyol 812 v) What From Finsolv TN 17 JAR o [Finsolv from Velsan D A P-?2 0 1 ) A 3 4 ( YALA Velsan D8P-3 )£2 ( 7Y, VO (EA) from Finsolv TN 77,170 [Finsolv TN Mineral Oil N.1 (*.Y) F Mineral Oil NF YO (£9)) , 71 Finsoly TN 17,176 From (Y,3) AY ATA pfs Cetiol 868 (24) 77,72 From Miglyol 817 812 (r.¥) As Miglyol (Y) °) 1,8 From felzan de A pih Ve Velsan D8P-3 )7 7.1,Y0 (0) from Procetyl AWS (v.€) 1.4 Procetyl AWS (OY) 77,75 from Procetyl AWS od 77,720 of d 1,(47) A felzan pi-? 08-3 Velsan | (0%) 77.75 Procetyl AWS 5 Miglyol 0 (¥.¥) Miglyol 812 AVY VARA (°°) Procetyl AWS LY, [Procetyl AWS of ¥ (vs Y) Ya Mineral Oil NF 0 7F

: Yt (Y,e) 5 from Cytmall 77,1709 [Procetyl AWS from Prosteel AWS 77,175 (07) 1 | Citmol 316 17 (Y,A) AY Isopropyl Myristate 7.7,Y0 (0V) (Y.£) “art 54” 10 derivate from 7,9 Isopropyl Myristate 77 Velsan D8P-3 Yan A, 75 (*.0) AY Octyl stearate Cetiol 868 ATA 7V, YO (04) (VY) 47 Yaw A Velsan De Cetiol 868 ATA from Cetiol 77.75 (14)

Velsan 08-3 : (YA) LY Mineral Oil NF Mineral Oil N.V. F 71,75 (11) (Y.A) 17 and 77,8 from Felzan de Mineral Oil NF from Mineral Oil N. F 77,75 (TY)

Velsan D8P-3 Bh-? A: (V.£) £¥ Ge 7,176 and Mineral Oil NF from Mineral Oil N.V. F 77,175 (TY) citmol 11 citmol: (YY) £3 and 77,179 of Mino Mineral Oil NF of Mineral Oil N. F 77,175 (TE) | minno 21 1 = (¥,9) 1.4 Miglyol 812 AVY from Miglyol 7Y,Y0/Drakeol-7 1-Leuica a from 7.Y,0 (10) (v £) VY, ~Klearol 7.0 (17( (Y.9) 1,1 Miglyol 812 AVY Miglyol 7Y,Y0/Klearol 7.Y,0 (TV) : (Y, 1) 8

NAR

(Y.°) vv (Y.Y) oY : Arlamol E (from Arlamol in (1A) (¥.¢) VEY Yd uA and ©*,77 from Valzan de Addamol B i from Arlamol 7,75 (19) Velsan D8P-3 Horizon vo (Yo) VY | Dimethicone of Dimethicone 7,75 (V+) (69) VEY pH A and 7,8 / Dimethicone of Dimethicone 5 (VY)

Velsan D8P-3 (0,1) 0 0 MY Maglioleol 7¥,Y0 5 Dimethicone SLB 77, (VY)

Miglyol 812. (v0) 01,1 Velsan p-?A from Velsan D 7,2 5 Migyol 812 AVY Magliole LY, (vv) (Y,A) VV, A Stearic Acid 3p -“ A nil de felzan Eumulgin 1 Eumulgin El 2Y,0 (IVY)

Stearic Acid Velsan DSP-3 0 (FDNY Ym uA) No Velsan Di Bumulgin L 77, Y0 (VE)

Miglylol 812 AYY N/A Velsan D8P-3 (Yoo) 01,6 pH-?A N/A Velsan D Crodamol ML L a} of Crodamol 5 (Ve)

Velsan D8P-3 } ) (v8) 0 Hetester PHA 43 7Y.0 (V1) (v4) 8 Procetyl 10 01 Procetyl 77.8 (VV) (Ye) 0 Marlox FK86 A Marlux FK 7Y.0 (VA) i (Y.A) 9.¢ Ucon 50 HB-660 1768 HP *0 Yucon 1LY.0 (V9): : (vy ) 18 Eumulgin 3-2 Eumulgin B-? 2 ("0) (vs 0) i,v Eumulgin B-2 Y= Eumulgin 98 (A 1) (Y,¥) eo) There is Velsan and there is no valsan Avanel 8 150 Yoo of the active S 7,0 (AY) b Miglyol of the active 7,2 (¥ ' ) vy Stearic Avanel 8 0 of the active SAH AR (AY ). ) 7¥ 3 Miglyol and there are 77,758 of Velsan's 7Y,0 Velsan and there is Acid 7H

A 1 A from Brij 721 VY (A£) 4 from Aqil S Avanel 8 150 150 n/a 38 Velsan (J nor (Y 1) Y,” : there is a mogul Miglyol (Ae) 7,0 Sandoxylate 4 57 424 (vs £) \Y, Sandoxylate (AY) 7,2 Sandoxylate £418 YA COS gail (v 1) (AY) 75.0 Sandoxylate 412 5407 Br (¥ (v, (MN) ©,) of (v, ¥) 1,11 Sandoxylate 408 £ +A ( M4) 7.8 Ucon +0 H2 (Y.A) 54 Ucon S0HB-660 V1 v= (+9) 77.8 VY, Velsan P8-3 Y—A )0 ,¥ ( a 7 (1): smiglyol 812 AVY 17,8 of DHC p2 (Yo) Yo, Velsan D8P-3 and stearic acid Examples from )—46 in examples From 911-44 the change of the type of velsan material, otherwise the compositions of these will be - the examples are similar to that for Example 1 0: The effect of the type of velsan material *velsan on the sun protection factor SPF: with a fixed concentration of the substance Magliol Miglyol 812 AVY equals 77.75 (11) D-felon A p--7 07 Veslan D8P-3 (¥,¥) (£,Y) 0 (AY) D-felon A P-7 Veslan D8P-16 1 (paste). : What is (Y.£) (14) a bi-felon? Veslan P8-3 696 aN * Was the concentration of felzan de A pH-? i 17,0 Velsan D8P-3 se

2 7 b 3 . Example: A composition was made to be used as a sunscreen and contained ingredients similar to those: for example 0; but 7 octylmethoxycinnamates were added in the oil phase and the water concentration was adjusted by JY Gaal, and the resulting composition had an SPF equal to And so on. It can be noted that the compositions of this invention may contain organic agents in addition to inorganic agents that protect from the rays of Conall 'Example 97. A composition was made to be used as a sunscreen and contained ingredients similar to those of Example 0 and added 70% of oxide Zinc zine oxide and 7 from Brij 721 771 and the resulting formulation SPF was 0 00 equal to LY o,f and the pH of the formulation was adjusted at 1. This formulation had a significantly enhanced protection value in the UV area UVA ody

Claims (1)

! Ya. safeguards ; 1-1 Sunscreen Composition comprising: Sale ( i ) Y inorganic Gl ¢ inorganic sunscreen agent v : (b) anionic emulsifying agent ' anionic emulsifier and ¢(c) U Sa oil component comprising at least one carrier oil and emollient; where said carrier oil is a polyether interrupted fatty acid ester yo "- the sunscreen composition according to protectin 1 where Y selects the inorganic protective agent 10 *- Gi sunscreen composition Gi sunscreen composition For protective agent ¥ where m is Y SA) inorganic sunscreen agent le r 3 for titanium dioxide 1 — sunscreen composition According to the element of protection? Where the particle size of the aforementioned titanium dioxide is less than about , and Ve in a tanometer. : 0-1 Gi sunscreen composition of protection factor 1 where ¥ said anionic emulsifier is a salt of a fatty acide 7 horizon 03. 5 1 | sodium laurate sodium lauryl sulfate ¢ DEA cetyl phosphate DEA sulfosuccinate: dioctyl sulfosuccinate (JS sf -1 -1 | sunscreen composition 85°) of claim 1 wherein Y 0 is the polyether interrupted fatty acid ester 0 7 said is a 3-ethyleneoxy (possibly polypropyloxy)alkyl ester (Rd) “Cp-Cy fatty alkyl (optionally polypropylenoxyl) polyethylenoxy©” so that the ester contains: an alkyl group that has 1-17 carbon atoms and may be Lana or Te Optionally ita v =A 1 : sunscreen composition 5 8 of SPF 1 where Y : said composition also includes nonionic emulsifers or mixtures of v From her. 1 4- A sunscreen composition according to the element of protection 1, where “Y” pH The aforementioned composition is not less than 0-2 1: A sunscreen composition SPF 45 composition where 7" stated pH ranges from about HLA to about Ae ——- -11 1 sunscreen composition: SPF 1 sunscreen composition 0 7 7 sun protection factor of at least 0.01 VY 1 20 method for making sunscreen composition includes: Y (1) add deionized water in the vessel; v (b) then heat the water; $ (c) then; add oil, carrier oil and shall anionic surfactant ° | to the vessel; 4 (2) Then » add inorganic sunscreen agent slowly to said container and heat and mix the said resulting composition; and A (e) then; adjust the pH of said composition above 0 SAVY: Protective A sunscreen composition comprising an inorganic sunscreen agent Y in a ratio of about 7 to about 1 YO anionic surfactant in a ratio of about § ) to About 70 and an oil component, 0il component, includes a carrier oil ° and an emollient emollient at a ratio ranging from about 750.9 to about 01, where the said carrier oil 1 is a fatty acid ester that is polysevered. No polyether interrupted fatty acid ester. : : 3 to the oil component from about 0:07 to about AN 7F