US3697642A - Method of protecting the skin from ultraviolet radiation with titanic acid and esters of titanic acid - Google Patents
Method of protecting the skin from ultraviolet radiation with titanic acid and esters of titanic acid Download PDFInfo
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- US3697642A US3697642A US803951A US3697642DA US3697642A US 3697642 A US3697642 A US 3697642A US 803951 A US803951 A US 803951A US 3697642D A US3697642D A US 3697642DA US 3697642 A US3697642 A US 3697642A
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- skin
- titanic acid
- sun
- gel
- titanium
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- 238000000034 method Methods 0.000 title claims abstract description 22
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 title description 17
- 230000005855 radiation Effects 0.000 title description 9
- 150000002148 esters Chemical class 0.000 title description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 25
- 125000000217 alkyl group Chemical group 0.000 abstract description 10
- 239000013522 chelant Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000003446 ligand Substances 0.000 abstract description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract description 6
- 206010042496 Sunburn Diseases 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 5
- 230000009931 harmful effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 239000000499 gel Substances 0.000 description 16
- 239000010936 titanium Substances 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 13
- 239000000516 sunscreening agent Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000475 sunscreen effect Effects 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000002537 cosmetic Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- -1 keto alcohols Chemical class 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 229960005082 etohexadiol Drugs 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229930194542 Keto Natural products 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100001223 noncarcinogenic Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000037307 sensitive skin Effects 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/58—Metal complex; Coordination compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Definitions
- ABSTRACT An effective ultra-violet absorber composition and process for controlling sunburn by applying to the skin a composition which comprises a hydrated, substantially transparent gel represented by the formula:
- R, and R are independently selected from the group consisting of hydrogen, short chain alkyl, and ligands capable of chelate formation, and
- n is any integer in a dermatologically acceptable carrier, the gelbeing employed in an amount effective to protect the skin and other surfaces from the harmful effects of the burning rays of the sun.
- tanning may have some beneficial effects in that it protects the skin from further burning where there is continued exposure to the sun, nevertheless tanning in and of itself is associated with a general deterioration of the skin; and although the majority of people are not severely affected by tanning, many are extremely sensitive even to the tanning rays of the sun to the extent that exposure to these wave lengths creates serious health hazards. Included within the latter group are those persons who suffer from various dermatological problems, blood dyscriasis, skin cancer, and sensitive skin problems.
- compositions containing the novel compounds hereof which may be applied to the human skin to protect it against sunburn.
- transparent and/or translucent compounds which contain direct oxygen linkages to titanium possess outstanding sun-screening abilities to absorb the burning rays of sunlight, and particularly those wave lengths in the ultra-violet region of from about 200 N to about 400 N.
- Those compounds which contain direct oxygen linkages to titanium and are employed in the compositions and processes of this invention are substantially transparent gels having the following general formula:
- R, and R are preferably hydrogen, alkyl, and
- n represents any integer.
- the alkyl is preferably of the short chain variety having between three and eight carbon atoms such as propyl, isopropyl, butyl, isobutyl, branched eight carbon atom chains, as well as polymers and mixtures thereof.
- the ligands capable of chelate formation include the amino alcohol, keto alcohols, and glycols which upon esterification form relatively stable five or six membered ring structures with titanium. Preferred members of this latter group are triethanolamine, octylene glycol and acetyl acetone.
- the compounds are prepared as transparent gels as hereinafter described, and thereafter usually dispersed in a dermatologically acceptable carrier.
- one method forming the titanate occurs when alkyl ortho titanate esters are hydrolyzed. Hydrolysis proceeds rapidly with the intermediate formation of unstable coordination complexes between the ester and water thereby splitting out a molecule of alcohol according to the following reaction:
- Another and more preferred method of preparing the orthotitanic acid absorber of this invention involves hydrolyzing titanium tetrachloride at 0C by reacting the titanium tetrachloride with ice to form gelatinous orthotitanic acid having a pH of less than about 5.0.
- the gel is then filtered and neutralized with an alkaline solution such as dilute ammonium hydroxide thereby forming a colloidal white transparent suspension.
- the suspension is thereafter reacidified with an organic acid, such as, citric acid to form a crystalline hydrated titanium dioxide precipitate which is further acidified to form a solution containing Ti(OH having a pH in the range of 5.0 to 9.0.
- the sun-screen agent prepared according to this procedure showed substantially complete absorption of all ultraviolet wave lengths shorter than about 375 nanometers as well as a gradual decreasing gradient of absorption of the higher ultraviolet wave lengths into the lower visible spectrum.
- titanium chelates which form a part of this invention may be satisfactorily utilized as effective sunscreen agents. Since titanium has a balance of four and a coordination number of six, it is possible to form chelated esters by coordinate bonding between titanium and electron-donating atoms, such as, nitrogen and oxygen. Accordingly, upon formation of alkyl esters of titanic acid from ligands such as amino alcohols, keto alcohols, or glycols, the hydroxyl groups of two of the ligand moles replace two alkoxy groups of the ester thereby forming a relatively stable fiveor six-membered ring via electron donation from the polar group to titanium.
- ligands such as amino alcohols, keto alcohols, or glycols
- These titanium chelates can be seen as having the following generalized formula:
- At is the polar group, i.e. oxygen or nitrogen
- y may be a two or three membered carbon chain thereby resulting in an unstrained fiveor six-membered ring.
- R may be hydrogen, alkyl, or another ligand group.
- Some of the commercially available chelates are triethanolamine titanate, titanium acetyl acetonate, tetra-octylene glycol titanate and titanium lactate. The titanium chelates are relatively stable and generally slow to hydrolyze, although they are soluble in various alcohols and alcohol-water solution, or miscible with water.
- the general procedure for preparing the titanium chelate sun-screen agents of this invention involves firstly, formation of the chelate as illustrated by the preferred embodiment and secondly, incorporation of the chelate into a suitable carrier.
- the preferred chelate embodiment of the present invention involves cosmetic compositions having triethanolamine titanate as the ultra-violet absorbing agent.
- the chelated form of triethanolamine titanate may be prepared be reacting 1 mole of tetraisopropyl titanate with two moles of triethanolamine at about 75C to give a water soluble, substantially transparent gel wherein the che late may be presented by the following formula:
- the compounds of this invention When the compounds of this invention are to be applied to the human skin, they may be incorporated in various carriers such as hydroalcoholic lotions, solvent oily solutions, water, water-in-oil and oil-in-water emulsions, creams and other cosmetic preparations. Dual purpose formulations are also contemplated, for example, a combination sun tan and insect repellant lotion. It should also be understood thatthe invention is not to be limited to these particular formulations but may be incorporated in a variety of topical preparations.
- the cosmetic formulations desirably contain between I and 50 percent of the sun-screen compound, although it should be understood that the concentrations are not critical but depend entirely upon the sun-screen protection desired. Furthermore, since each compound possesses differing ultra-violet wave length absorption abilities, each formulation should be chosen according to the desired effect.
- EXAMPLE 1 This example illustrates one method of forming the basic orthotitanic acid gel.
- a 500 ml. beaker was placed in an ice bath and cooled at 0C.
- 200 g. of purified titanium tetrachloride, TiCL were placed in the beaker and cooled to 0C. Thereafter, g. of ice were added and mixed with the titanium tetrachloride until a light yellow gel having a pH of about 3.5 was formed.
- the gel was identified as orthotitanic acid.
- the gel was then treated with a sufficient amount of ammonium hydroxide to a pH of about 7.0.
- the neutralized gel was then washed with distilled water and filtered.
- EXAMPLE 2 The gelatinous compound of Example 1 was dissolved in distilled water at a ratio of 50 parts orthotitanic acid to 50 parts distilled water. The product was then tested for ultra-violet absorption ability. From the following tabulated results, it is evident that substantially all of the burning wavelengths, as well as a major portion of the shorter tanning rays were absorbed:
- This example illustrates a further procedure by which a buffered orthotitanic acid sun-screen was obtained.
- T hirty-five g. of the gel product from Example 1 were dissolved in 20 g. of distilled water.
- the pH of the solution was brought to about 6.0 through the addition of 11 g. of a 50 percent ammonium hydroxide solution and 100 ml. of distilled water to obtain a pH of about eight whereupon a colloidal white suspension formed.
- the hydro-gel was decanted, washed with distilled water and filtered.
- the gel was then reacidified by mixing one part gel with twenty parts alcohol and a sufficient amount of a 20 percent citric acid solution to form a crystalline precipitate of hydrous orthotitanic acid having a pH of 67.
- the precipitate was filtered from the solution and incorporated into a cosmetic vanishing cream base.
- the sun-screen formulation had the following composition:
- the above composition was then tested for ultraviolet absorption abilities by applying it to the skin of a human subject and exposing the subject to sunlight 1 hour between 2:00 and 3:00 P.M.
- the physical exposure exposure was conducted next to a lake while using a white background.
- EXAMPLE 4 This example illustrates the preparation of the preferred chelated form and the sun-screening abilities thereof.
- the PH of the solution was 7.0.
- EXAMPLE 5 The gelatinous triethanolamine titanate product of Example 4 was incorporated in the following cream composition and tested for its ultra-violet absorption hours after exposure showed the compound to be percent effective in preventing sunburn.
- a method for protecting human skin against actinic radiation in the ultraviolet region of 200N to 400N which comprises applying to the skin a composition comprising:
- R, and R are independently selected from the group consisting of hydrogen, alkyl groups having from three to eight carbon atoms, triethanolamine, octylene glycol and acetyl acetone,
- n is the number one
- a dermatologically acceptable carrier said compound being present in the carrier in an effective sun-screening amount to protect the human skin from the burning wave lengths of actinic radiation.
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- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
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- Epidemiology (AREA)
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Abstract
An effective ultra-violet absorber composition and process for controlling sunburn by applying to the skin a composition which comprises a hydrated, substantially transparent gel represented by the formula: WHEREIN: A. R1 and R2 are independently selected from the group consisting of hydrogen, short chain alkyl, and ligands capable of chelate formation, and B. N IS ANY INTEGER IN A DERMATOLOGICALLY ACCEPTABLE CARRIER, THE GEL BEING EMPLOYED IN AN AMOUNT EFFECTIVE TO PROTECT THE SKIN AND OTHER SURFACES FROM THE HARMFUL EFFECTS OF THE BURNING RAYS OF THE SUN.
Description
United States Patent Madigan [54] METHOD OF PROTECTING THE SKIN FROM ULTRAVIOLET RADIATION WITH TITANIC ACID AND ESTERS OF TITANIC ACID [72] Inventor: Edward J. Madigan, Denver, C010.
[73] Assignee: Cosmetics & Pharmaceuticals, Inc.,
Denver, C010.
[22] Filed: March 3, 1969 [21] Appl. No.: 803,951
[52] US. Cl. ..424/59, 260/4293, 260/429.9,
[51] Int. Cl. ..A61l 23/00 [58] Field of Search ..424/59; 260/4293, 429.5
[56] References Cited UNITED STATES PATENTS 760,319 5/1904 Dreher ..260/429.5
2,684,972 7/1954 Haslam ..260/429.3 X
2,824,1 l5 2/1958 Beacham et al. ...260/429.3 X
2,935,522 5/1960 Samour .......260/429.5
[451 Oct. 10,1972
Primary Examiner-Albert T. Meyers Assistant Examiner-Dale R. Ore Attorney-John E. Reilly [57] ABSTRACT An effective ultra-violet absorber composition and process for controlling sunburn by applying to the skin a composition which comprises a hydrated, substantially transparent gel represented by the formula:
wherein:
a. R, and R are independently selected from the group consisting of hydrogen, short chain alkyl, and ligands capable of chelate formation, and
b. n is any integer in a dermatologically acceptable carrier, the gelbeing employed in an amount effective to protect the skin and other surfaces from the harmful effects of the burning rays of the sun.
3 Claims, N0 Drawings METHOD OF PROTECTING THE SKIN FROM ULTRAVIOLET RADIATION WITH TITANIC ACID AND ESTERS OF TITANIC ACID ,This invention relates to new and useful ultraviolet absorber compounds, to compositions containing such compounds, to a method of preparing a sun-screen composition, and to methods for protecting the human skin and other surfaces against the burning effects of sunlight. More particularly the invention relates to substantially transparent gelatinous compounds adapted for incorporation into cosmetic formulations, said compounds being capable of absorbing the burning wavelengths of actinic radiation.
Extensive studies have been made of ultraviolet radiation and its effects on the human skin. It has been established that the radiation from about 290 to 315 N (l Nanometer being equivalent to Angstrom Units) contains a major portion of detrimental burning wave lengths, while the radiation from about 315 to 400 N promote the more desirable aesthetic feature known as tanning. The effect of the lower wavelengths on human skin is to produce, in most instances, severe burning, blistering and deterioration of the skin. As a result, various sun-screen compositions have been developed to screen out or block these burning wavelengths. While tanning may have some beneficial effects in that it protects the skin from further burning where there is continued exposure to the sun, nevertheless tanning in and of itself is associated with a general deterioration of the skin; and although the majority of people are not severely affected by tanning, many are extremely sensitive even to the tanning rays of the sun to the extent that exposure to these wave lengths creates serious health hazards. Included within the latter group are those persons who suffer from various dermatological problems, blood dyscriasis, skin cancer, and sensitive skin problems. Consequently, for those who must have protection against the burning rays as well as a portion of the shorting tanning rays of the sun, there has been a need for a broad spectrum, non-toxic, non-carcinogenic, sun-screen composition that will afford adequate protection to the skin, is sufficiently stable to remain effective for several hours, and can be readily applied to the skin.
it is therefore a primary object of the present invention to provide relatively transparent gelatinous compounds which possess excellent absorption abilities for filtering out the burning wave lengths in the ultraviolet spectrum.
is is another object of the present invention to provide compositions containing the novel compounds hereof which may be applied to the human skin to protect it against sunburn.
It is still another object of the present invention to provide a method of preparing an ultra-violet absorber compound for subsequent incorporation into various dermatologically acceptable carriers.
In accordance with the present invention, it has now been discovered that transparent and/or translucent compounds which contain direct oxygen linkages to titanium possess outstanding sun-screening abilities to absorb the burning rays of sunlight, and particularly those wave lengths in the ultra-violet region of from about 200 N to about 400 N. Those compounds which contain direct oxygen linkages to titanium and are employed in the compositions and processes of this invention are substantially transparent gels having the following general formula:
wherein R, and R are preferably hydrogen, alkyl, and
ligands capable of chelate formation, and n represents any integer. Thus, when the formula represents: (1) a condensation product of orthotitanic acid, then n may be any integer greater than 1: and (2) the chelated form, then n is l. The alkyl is preferably of the short chain variety having between three and eight carbon atoms such as propyl, isopropyl, butyl, isobutyl, branched eight carbon atom chains, as well as polymers and mixtures thereof. The ligands capable of chelate formation include the amino alcohol, keto alcohols, and glycols which upon esterification form relatively stable five or six membered ring structures with titanium. Preferred members of this latter group are triethanolamine, octylene glycol and acetyl acetone. The compounds are prepared as transparent gels as hereinafter described, and thereafter usually dispersed in a dermatologically acceptable carrier.
It is generally accepted that titanium chemistry is a complex subject and for this reason, the invention should not be limited to the theory herein presented. However, it is known that orthotitanic acid, i.e., Ti(0l-l)., hydrolyzes readily upon exposure to water to produce higher molecular weight condensation products and/or polymeric titanates thereof.
For example, one method forming the titanate occurs when alkyl ortho titanate esters are hydrolyzed. Hydrolysis proceeds rapidly with the intermediate formation of unstable coordination complexes between the ester and water thereby splitting out a molecule of alcohol according to the following reaction:
However, since the monohydroxy ester is unstable it immediately undergoes further reaction and condensation to form a dimeric condensed titanium ester, i.e., hexalkoxy titanate. Upon further hydrolysis and under controlled temperature conditions, it is possible to obtain a hydrous polymeric ortho titanate gel of the type represented by the following formula:
HO Ti (OI-I 0-], H
wherein 1: represents any integer.
Of course the rate of hydrolysis is dependent also upon the size and complexity of the alkyl group; the hydrolysis rate decreasing with increasing alkyl group size. Accordingly, because of the instability of the lower alkyl titanates they well undergo hydrolysis. Thus, the foregoing illustrates one method of forming an ultraviolet absorber of this invention.
Another and more preferred method of preparing the orthotitanic acid absorber of this invention involves hydrolyzing titanium tetrachloride at 0C by reacting the titanium tetrachloride with ice to form gelatinous orthotitanic acid having a pH of less than about 5.0. The gel is then filtered and neutralized with an alkaline solution such as dilute ammonium hydroxide thereby forming a colloidal white transparent suspension. The suspension is thereafter reacidified with an organic acid, such as, citric acid to form a crystalline hydrated titanium dioxide precipitate which is further acidified to form a solution containing Ti(OH having a pH in the range of 5.0 to 9.0. The sun-screen agent prepared according to this procedure showed substantially complete absorption of all ultraviolet wave lengths shorter than about 375 nanometers as well as a gradual decreasing gradient of absorption of the higher ultraviolet wave lengths into the lower visible spectrum.
The titanium chelates which form a part of this invention may be satisfactorily utilized as effective sunscreen agents. Since titanium has a balance of four and a coordination number of six, it is possible to form chelated esters by coordinate bonding between titanium and electron-donating atoms, such as, nitrogen and oxygen. Accordingly, upon formation of alkyl esters of titanic acid from ligands such as amino alcohols, keto alcohols, or glycols, the hydroxyl groups of two of the ligand moles replace two alkoxy groups of the ester thereby forming a relatively stable fiveor six-membered ring via electron donation from the polar group to titanium. These titanium chelates can be seen as having the following generalized formula:
wherein at is the polar group, i.e. oxygen or nitrogen, and y may be a two or three membered carbon chain thereby resulting in an unstrained fiveor six-membered ring. R may be hydrogen, alkyl, or another ligand group. Some of the commercially available chelates are triethanolamine titanate, titanium acetyl acetonate, tetra-octylene glycol titanate and titanium lactate. The titanium chelates are relatively stable and generally slow to hydrolyze, although they are soluble in various alcohols and alcohol-water solution, or miscible with water.
The general procedure for preparing the titanium chelate sun-screen agents of this invention involves firstly, formation of the chelate as illustrated by the preferred embodiment and secondly, incorporation of the chelate into a suitable carrier. Specifically, the preferred chelate embodiment of the present invention involves cosmetic compositions having triethanolamine titanate as the ultra-violet absorbing agent. The chelated form of triethanolamine titanate may be prepared be reacting 1 mole of tetraisopropyl titanate with two moles of triethanolamine at about 75C to give a water soluble, substantially transparent gel wherein the che late may be presented by the following formula:
(HO amon zlfic H2011:
aID
When the compounds of this invention are to be applied to the human skin, they may be incorporated in various carriers such as hydroalcoholic lotions, solvent oily solutions, water, water-in-oil and oil-in-water emulsions, creams and other cosmetic preparations. Dual purpose formulations are also contemplated, for example, a combination sun tan and insect repellant lotion. It should also be understood thatthe invention is not to be limited to these particular formulations but may be incorporated in a variety of topical preparations. In general, the cosmetic formulations desirably contain between I and 50 percent of the sun-screen compound, although it should be understood that the concentrations are not critical but depend entirely upon the sun-screen protection desired. Furthermore, since each compound possesses differing ultra-violet wave length absorption abilities, each formulation should be chosen according to the desired effect.
Various embodiments of the invention will be further illustrated by the representative examples as set forth below wherein parts are given by weight unless otherwise indicated.
EXAMPLE 1 This example illustrates one method of forming the basic orthotitanic acid gel.
A 500 ml. beaker was placed in an ice bath and cooled at 0C. 200 g. of purified titanium tetrachloride, TiCL, were placed in the beaker and cooled to 0C. Thereafter, g. of ice were added and mixed with the titanium tetrachloride until a light yellow gel having a pH of about 3.5 was formed. The gel was identified as orthotitanic acid. The gel was then treated with a sufficient amount of ammonium hydroxide to a pH of about 7.0. The neutralized gel was then washed with distilled water and filtered.
EXAMPLE 2 The gelatinous compound of Example 1 was dissolved in distilled water at a ratio of 50 parts orthotitanic acid to 50 parts distilled water. The product was then tested for ultra-violet absorption ability. From the following tabulated results, it is evident that substantially all of the burning wavelengths, as well as a major portion of the shorter tanning rays were absorbed:
This example illustrates a further procedure by which a buffered orthotitanic acid sun-screen was obtained.
T hirty-five g. of the gel product from Example 1 were dissolved in 20 g. of distilled water. The pH of the solution was brought to about 6.0 through the addition of 11 g. of a 50 percent ammonium hydroxide solution and 100 ml. of distilled water to obtain a pH of about eight whereupon a colloidal white suspension formed. The hydro-gel was decanted, washed with distilled water and filtered. The gel was then reacidified by mixing one part gel with twenty parts alcohol and a sufficient amount of a 20 percent citric acid solution to form a crystalline precipitate of hydrous orthotitanic acid having a pH of 67. The precipitate was filtered from the solution and incorporated into a cosmetic vanishing cream base. The sun-screen formulation had the following composition:
The above composition was then tested for ultraviolet absorption abilities by applying it to the skin of a human subject and exposing the subject to sunlight 1 hour between 2:00 and 3:00 P.M. The physical exposure exposure was conducted next to a lake while using a white background. The results 24 hours after exposure indicated that the sun-screen was 100 percent in preventing sunburn.
EXAMPLE 4 This example illustrates the preparation of the preferred chelated form and the sun-screening abilities thereof.
One hundred ml. of tetraispropyl titanate were mixed with 50 ml. of triethanolamine at 75C to form a chelated triethanolamine titanate product. To this product was added, slowly, l00 ml. of distilled water at 75C. The mixture was stirred until a thin, relatively transparent gel formed. The product was than tested for ultra-violet absorption ability by dissolving the mixture in distilled water at a ratio of 50 parts of the gel to 50 parts water. From the following tabulated results, it is apparent that substantially all of the burning wavelengths, as well as a portion of the tanning rays were absorbed:
The PH of the solution was 7.0.
EXAMPLE 5 The gelatinous triethanolamine titanate product of Example 4 was incorporated in the following cream composition and tested for its ultra-violet absorption hours after exposure showed the compound to be percent effective in preventing sunburn.
It will be appreciated that various modifications and changes may be made to the various compounds, compositions, and processes of the invention by those skilled in the art, in addition to those set forth above, without departing from the spirit thereof. For instance, zirconium may be substituted for titanium in the examples given to provide an effective ultra-violet absorber. Therefore, the invention is to be limited only by the scope of the appended claims.
What is claimed is:
1. A method for protecting human skin against actinic radiation in the ultraviolet region of 200N to 400N which comprises applying to the skin a composition comprising:
I. a transparent gelatinous compound of the formula:
a. R, and R are independently selected from the group consisting of hydrogen, alkyl groups having from three to eight carbon atoms, triethanolamine, octylene glycol and acetyl acetone,
b. n is the number one, and
II. a dermatologically acceptable carrier; said compound being present in the carrier in an effective sun-screening amount to protect the human skin from the burning wave lengths of actinic radiation.
2. The method of claim 1 wherein both R and R, are
hydrogen.
3. The method of claim 1 wherein R is isopropyl,
and R, is triethanolamine.
Il ll I0 II
Claims (2)
- 2. The method of claim 1 wherein both R1 and R2 are hydrogen.
- 3. The method of claim 1 wherein R1 is isopropyl, and R2 is triethanolamine.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US80395169A | 1969-03-03 | 1969-03-03 |
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US3697642A true US3697642A (en) | 1972-10-10 |
Family
ID=25187836
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Application Number | Title | Priority Date | Filing Date |
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US803951A Expired - Lifetime US3697642A (en) | 1969-03-03 | 1969-03-03 | Method of protecting the skin from ultraviolet radiation with titanic acid and esters of titanic acid |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4275118A (en) * | 1979-01-15 | 1981-06-23 | Dow Corning Corporation | Pigment-free coatings with improved resistance to weathering |
EP0154928A2 (en) * | 1984-03-12 | 1985-09-18 | Kao Corporation | Long wavelength ultraviolet ray absorber |
US5032390A (en) * | 1985-12-18 | 1991-07-16 | Kao Corporation | Anti-suntan cosmetic composition |
US5250289A (en) * | 1987-07-24 | 1993-10-05 | The Boots Company Plc | Sunscreen compositions |
US5453267A (en) * | 1989-02-28 | 1995-09-26 | Boots Company Plc | Sunscreen compositions |
EP0884320A2 (en) * | 1997-06-13 | 1998-12-16 | Industrial Research Limited | Titanium amino alcohol complex, method for manufacturing the same, titanium dioxide solution of the complex, titanium oxide film, titanium oxide powder, and method for manufacturing the titanium oxide film |
-
1969
- 1969-03-03 US US803951A patent/US3697642A/en not_active Expired - Lifetime
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4275118A (en) * | 1979-01-15 | 1981-06-23 | Dow Corning Corporation | Pigment-free coatings with improved resistance to weathering |
EP0154928A2 (en) * | 1984-03-12 | 1985-09-18 | Kao Corporation | Long wavelength ultraviolet ray absorber |
EP0154928A3 (en) * | 1984-03-12 | 1987-05-13 | Kao Corporation | Long wavelength ultraviolet ray absorber |
US5032390A (en) * | 1985-12-18 | 1991-07-16 | Kao Corporation | Anti-suntan cosmetic composition |
US5250289A (en) * | 1987-07-24 | 1993-10-05 | The Boots Company Plc | Sunscreen compositions |
US5453267A (en) * | 1989-02-28 | 1995-09-26 | Boots Company Plc | Sunscreen compositions |
EP0884320A2 (en) * | 1997-06-13 | 1998-12-16 | Industrial Research Limited | Titanium amino alcohol complex, method for manufacturing the same, titanium dioxide solution of the complex, titanium oxide film, titanium oxide powder, and method for manufacturing the titanium oxide film |
EP0884320A3 (en) * | 1997-06-13 | 2000-11-02 | Industrial Research Limited | Titanium amino alcohol complex, method for manufacturing the same, titanium dioxide solution of the complex, titanium oxide film, titanium oxide powder, and method for manufacturing the titanium oxide film |
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