Disclosed is a 2-phenyl-benzimidazolesulfonic acid according to the formula

The present invention relates to a 2-phenyl-benzimidazolesulfonic acids, to the use thereof as a UV filter, to cosmetic preparations which comprise these compounds, and to a preparation process for the compounds.
A suntan of the skin to whatever degree is regarded in today""s society as attractive and as an expression of vigor and health. As well as this desired effect of the sun on the skin, however, a number of undesired secondary effects arise, such as sunburn or premature skin aging and the development of wrinkles. A number of performance UV filters have been developed which, applied to the skin in the form of creams, lotions or gels, can effectively delay the development of sunburn even when the incidence of solar rays is relatively high.
The UV filter present in the pharmaceutical or cosmetic formulation forms a film or a layer on the surface of the skin and does not penetrate into deeper skin layers with other substances present in the formulation. Known UV filters or sun protection agents thus act only by absorbing certain regions of sunlight; meaning that this radiation cannot penetrate into deeper layers of the skin.
As is known, the most hazardous part of solar radiation is formed by the ultraviolet rays having a wavelength of less than 400 nm. The lower limit of the ultraviolet rays which reach the surface of the earth is limited by the absorption in the ozone layer to about 280 nm or above. The sun protection filters which are currently customary in cosmetics absorb in a wavelength range from 280 to 400 nm. This range includes UV-B rays having a wavelength between 280 and 320 nm, which play a decisive role in the formation of a solar erythema, and UV-A rays, having a wavelength between 320 and 400 nm, which tan the skin but also age it, and favor the triggering of an erythematous reaction or can exacerbate this reaction in certain people or even trigger phototoxic or photoallergic and irritative reactions.
The object of skin care cosmetics is to obtain the impression of a youthful skin. In principle, there are various ways of achieving this object. For example, existing skin damage, such as irregular pigmentation or the development of wrinkles can be smoothed out by covering powders or creams. Another approach is to protect the skin against environmental influences which lead to permanent damage and thus aging of the skin.
The idea is therefore to intervene in a preventative manner and thus to delay the aging process. One example of this is the UV filters already mentioned which, as a result of absorption of certain wavelength regions, prevent or at least reduce skin damage. Depending on the position of their absorption maxima, UV absorbers for cosmetic and dermatological preparations are divided into UV-A and UV-B absorbers. UV-A absorbers usually also absorb in the UV-B region and are thus alternatively referred to as broad-band absorbers or broad-band filters. However, particularly in avoiding skin damage as a result of the formation of solar erythemas, the UV-B filters are of particular importance, since formulations based on broad-band filters alone offer inadequate protection or prevent entirely the desired tanning of the skin. For this reason, there is a continuous need for substances having an absorption maximum in the UV-B region which can be incorporated easily into cosmetic formulations.
Of decisive importance for the formulation is the solubility of the filter substances in the oil and water phases since it is necessary, particularly for establishing a high protection factor, to incorporate filters into all phases of a formulation. The oil-soluble UV-B filters include isooctyl methoxycinnamate, isoamyl methoxycinnamate and methylbenzylidenecamphor. Examples of water-soluble UV filters are, in particular, the salts of 2-phenylbenzimidazole-5-sulfonic acid, the use of which as UV ray filter has already been described in German Reichspatent No. 676 103.
However, a disadvantage of these water-soluble UV-B filters is that formulation is only possible in an alkaline medium since the sulfonic acid precipitates out at a pH below 7.
There is thus also a need for water-soluble UV-B filters which are highly suitable for the formulation of cosmetic formulations.
It has now surprisingly been found that certain 2-phenylbenzimidazolesulfonic acids and salts thereof can be readily incorporated into cosmetic formulations, while avoiding the above-mentioned problems.
The present invention accordingly firstly provides 2-phenylbenzimidazolesulfonic acids of the formula I
in which n is 0, 1 or 2 and m is 2 or 3. R1, R2, R3, R4 and R5 are each a radical from the group H, C1-8-alkyl, C1-8-alkoxy, hydroxyl, sulfate, nitro, F, Cl, Br or I radicals, and R6 is a C1-8-alkyl or C1-8-alkoxy radical.
For the purposes of the present invention, 2-phenyl-benzimidazolesulfonic acids are here in principle also understood as meaning the salts of these acids. The salts are preferably the alkali metal salts, and in particular the sodium or potassium salts, or the ammonium salts, in particular the triethanolammonium salts of the corresponding sulfonic acids.
In a preferred 2-phenylbenzimidazolesulfonic acid according to formula I, m=2 and n=0 or n=1, preferably at least 4 radicals from the group R1, R2, R3, R4 and R5 are H, and particularly preferably even all radicals R1-R5 are H. According to the invention, particular preference is accordingly given to 2-phenylbenzimidiazole-4,6-disulfonic acid which, as shown in formula Ia, is usually in betaine form.
The 2-phenylbenzimidazolesulfonic acid according to the invention can be obtained by any desired preparation process suitable for this purpose. Processes which have proven particularly suitable and economical are those in which an ortho-phenylenediamine or a derivative thereof is reacted with an arylcarboxylic acid or an arylcarboxylic acid derivative.
The present invention thus secondly provides a process for the preparation of the abovedescribed 2-phenylbenzimidazolesulfonic acids, in which an o-phenylenediamine according to formula II
is reacted with a second compound according to formula III
where R1, R2, R3, R4 and R5, in each case independently of one another, are a radical from the group of H, C1-8-alkyl, C1-8-alkoxy, hydroxyl, nitro, F, Cl, Br or I radicals, and X is chosen from the radicals xe2x80x94COOH, xe2x80x94COCl, xe2x80x94COBr, xe2x80x94CN or xe2x80x94COOR, where R is a C1-20-alkyl radical.
In a preferred embodiment of the process, sulfuric acid, in particular 96% sulfuric acid, is used as solvent. Here, even the sulfuric acid on its own effects sulfonation of the benzimidazole at a suitable temperature. Thus, international application WO 93/15061 has already described a process in which monosulfonated products are obtained by reaction in sulfuric acid.
However, in the process for the preparation of polysulfonated benzimidazoles, it is preferred if an activated sulfuric acid is used, activation preferably being carried out by chlorosulfonic acid or sulfur trioxide. Sulfuric acid alone typically is not strong enough to act as a reagent for this process because it is believed that water forms during the reaction and dilutes the sulfuric acid. Activation of the acid improved the reactivity of the acid in the process.
The use of chlorosulfonic acid for the preparation of bisbenzimidazoloylsulfonic acids has already been described in European patent application EP-A-669 323. However, there are no indications that it is also possible to use chlorosulfonic acid to prepare the compounds according to the invention in the specification.
If the activation is carried out using sulfur trioxide, use is preferably made of the xe2x80x9cfumingxe2x80x9d sulfuric acid called oleum, which is a solution of sulfur trioxide in concentrated sulfuric acid. The use of sulfur trioxide (oleum) for the activation of the sulfuric acid has various advantages compared with the use of chlorosulfonic acid:
gas (HCl) is not evolved during the reaction, meaning that pressure regulation is not necessary,
accordingly, the collection and disposal of the aggressive gas (HCl) is not required,
while extremely corrosion-resistant apparatuses are required for the chloride-containing sulfuric acid which is formed if chlorosulfonic acid is used, the process with oleum can be carried out in less complex equipment,
after hydrolysis of the oleum, sulfuric acid is present which can be recycled, with relative ease while the recycling of the chloride-containing sulfuric acid resulting from the use of chlorosulfonic acid is only possible with difficulty.
As a result of these advantages, it is preferred according to the present invention to activate the sulfuric acid using sulfur trioxide (oleum).
If the process according to the invention is carried out with activated sulfuric acid, then it is preferred that X in the second compound of formula III is a radical xe2x80x94COOH, i.e., that formula III is an arylcarboxylic acid. In another likewise preferred embodiment of the process, X in formula III is a radical xe2x80x94COOR, where R is a C1-20-alkyl radical, preferably a C1-8-alkyl radical and particularly preferably a methyl or ethyl radical.
Here, it is particularly preferred that the reaction is carried out at temperatures between 20xc2x0 C. and 200xc2x0 C., preferably between 160xc2x0 C. and 190xc2x0 C. The reaction temperature is usually maintained for 2 to 8 hours. At reaction times of less than 2 hours, monosulfonation products are still observed, which can only be separated off from the product with difficulty.
Implementation of the process according to the invention is in itself straightforward for one skilled in the art. A preferred embodiment for carrying out the reaction is given below. This may serve as an example, but does not limit the possible embodiments for carrying out the reaction:
The sulfuric acid, preferably in the form of a 50-100% solution, and in particular as a concentrated approximately 96% solution, is introduced. The orthophenylenediamine, or derivative thereof, is introduced. Activation with oleum (e.g. a 65% solution of sulfur trioxide in sulfuric acid) is then carried out at a temperature preferably below 150xc2x0 C. The amount of sulfur trioxide is chosen such that all of the water liberated during the reaction can be collected. For example, for the preparation of a benzimidazoledisulfonic acid, at least 4 mol of sulfur trioxide are used per mole of o-phenylenediamine.
The addition of the second reactant (arylcarboxylic acid or arylcarboxylic acid derivative) is preferably only carried out for safety reasons after cooling to a temperature below 100xc2x0 C. since the temperature of the reaction mixture may increase further as the result of the addition. The arylcarboxylic acid is expediently used in the ratio 1:1 to the phenylenediamine to obtain products according to the invention.
The reaction mixture is slowly heated to temperatures between 150 and 250xc2x0 C., preferably between 160 and 200xc2x0 C. and maintained at this temperature for 2 to 8 hours, optionally with stirring. The reaction mixture is then cooled, preferably to temperatures below 10xc2x0 C., and hydrolyzed in water.
After the mixture has been stirred briefly, preferably 20 minutes to 2 hours, the solid constituents are separated off, preferably washed with warm water and dried.
To purify the dried crude product, it is preferably dissolved in sodium hydroxide solution, and the resulting solution is purified, preferably with activated carbon. The end-product is precipitated out of the colorless solution using an acid, preferably a mineral acid; for example sulphuric acid.
Because of its absorption maxima in the UV-B region, the 2-phenylbenzimidazolesulfonic acid according to the invention is suitable as a UV-B filter substance. Accordingly, the present invention further provides for the use of a 2-phenylbenzimidazolesulfonic acid as a UV filter, in particular as a UV-B filter.
Because of this use option, the substances according to the invention are highly suitable for use in cosmetic formulations. The invention thus further relates to cosmetic formulations having UV protection properties which comprise at least one compound of formula I according to the invention.
The protective action of these formulations against UV radiation can be improved if the formulation comprises one or more additional UV filter substances in addition to the UV filter according to the invention.
In principle, it appears that all UV filters are suitable for combination with the filter substance herein. Particular preference is given to combination with those UV filters whose physiological safety has already been demonstrated. There are many tried and tested substances known from the specialist literature both for UVA and also UVB filters, such as:
benzylidenecamphor derivatives, such as 3-(4xe2x80x2-methylbenzylidene)-dl-camphor (e.g. Eusolex(copyright) 6300), 3-benzylidenecamphor (e.g. Mexoryl(copyright) SD), polymers of N-{(2 and 4)-[(2-oxoborn-3-ylidene)-methyl]benzyl}acrylamide (e.g. Mexoryl(copyright) SW), N,N,N,-trimethyl-4-(2-oxoborn-3-ylidenemethyl)-anilinium methylsulfate (e.g. Mexoryl (copyright) SK) or xcex1-(2-oxoborn-3-ylidene)toluene-4-sulfonic acid (e.g. Mexoryl(copyright) SL),
benzoylmethanes or dibenzoylmethanes, such as 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione (e.g. Eusolex(copyright) 9020) or 4-isopropyldibenzoylmethane,
benzophenones, such as 2-hydroxy-4-methoxy-benzophenone (e.g. Eusolex(copyright) 4360) or 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (e.g. Uvinul(copyright) MS-40),
methoxycinnamic esters, such as octyl methoxycinnamate (e.g. Eusolex(copyright) 2292), isopentyl 4-methoxycinnamate, e.g. as a mixture of the isomers (e.g. Neo Heliopan(copyright) E 1000),
salicylate derivatives, such as 2-ethylhexyl salicylate (e.g. Eusolex(copyright) OS), 4-isopropylbenzyl salicylate (e.g. Megasol(copyright)) or 3,3,5-trimethyl-cyclohexyl salicylate (e.g. Eusolex(copyright) HMS),
4-aminobenzoic acid and derivatives, such as 4-aminobenzoic acid, 2-ethylhexyl 4-(dimethyl-amino)benzoate (e.g. Eusolex(copyright) 6007), ethoxylated ethyl 4-aminobenzoate (e.g. Uvinul(copyright) P25),
benzimidazole derivatives, such as 2-phenylbenzimidazole-5-sulfonic acid, and its potassium, sodium, lithium, ammonium and triethanolamine salts (e.g. Eusolex(copyright) 232), 2,2xe2x80x2-(1,4-phenylene)bis(1H-benzimidazole-4,6-disulfonic acid, monosodium salt) (CAS No. 180 898-37-7) and 2,2xe2x80x2-(1,4-phenylene)bis(1H-benzimidazole-5-sulfonic acid) and its potassium, sodium and triethanolamine salts
and further substances, such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (e.g. Eusolex(copyright) OCR), 3,3-(1,4-phenylenedimethylene)bis(7,7-dimethyl-2-oxobicyclo-[2.2.1]hept-1-ylmethanesulfonic acid, and its salts (e.g. Mexoryl(copyright) SX), 2,4,6-trianilino-(p-carbo-2xe2x80x2-ethylhexyl-1xe2x80x2-oxy)-1,3,5-triazine (e.g. Uvinul(copyright) T 150), 2-(2H-benzo-triazole-2-yl)-4-methyl-6-(2-methyl-3-(1,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)-propyl)phenol (e.g. Silatriazole(copyright)), 4,4xe2x80x2-[(6-[4-((1,1,-dimethylethyl)aminocarbonyl)phenylamino]-1,3,5-triazine-2,4-diyl)diimino]bis(benzoic acid 2-ethylhexyl ester) (e.g. Uvasorb(copyright) HEB), xcex1-trimethylsilyl)-xcfx89-[trimethylsilyl)oxy]poly[oxy-(dimethyl [and approximately 6% methyl[2-8 p-[2,2-bis (ethoxycarbonyl]vinyl]phenoxy]-1-methylene-ethyl] and about 1.5% methyl[3-8 p-2,2-bis(ethoxy-carbonyl) vinyl)phenoxy)propenyl) and 0.1 to 0.4% (methylhydrogen)silylene]] (n≃60) (CAS No. 207 574-74-1), 2,2xe2x80x2-methylenebis(6-(2H-benzotriazole-2-yl) -4-(1,1,3,3-tetramethylbutyl)phenol) (CAS No. 103 597-45-1) and 2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (CAS No. 103 597-45-[lacuna], 187 393-00-6).
The compounds given in the list are only to be regarded as examples. It is of course also possible to use other UV filters. These organic UV filters are, and the 2-phenylbenzimidazolesulfonic acids according to the invention, are typically each incorporated into cosmetic formulations in an amount of from 0.5 to 20% by weight of the formulation, preferably in an amount of 1-15% by weight and particularly preferably in an amount of from 2 to 8% by weight per individual substance. Overall, the organic filters usually comprise up to 40% by weight, preferably 5 to 25% by weight, of the formulation, which includes the filter substance of the invention and any additional organic filter substances.
Inorganic UV filters such as those from the group of titanium dioxides, such as, for example, coated titanium dioxide (e.g. Eusolex(copyright) T-2000, Eusolex(copyright) T-AQUA), zinc oxides (e.g. Sachtotec(copyright)), iron oxides and also cerium oxides can also be combined. These inorganic UV filters are usually incorporated into cosmetic formulations in an amount of from 0.5 to 20 per cent by weight of the overall formulation, preferably 2-10%.
If various inorganic or organic UV filters are used, then these can be used in virtually any ratios relative to one another. The ratios of the individual substances to one another are usually in the range 1:10-10:1, preferably in the range 1:5-5:1 and particularly preferably in the range 1:2-2:1. If UV-A filters are used in addition to UV-B filters, then it is advantageous for most applications if the proportion of UV-B filters predominates and the ratio of UV-A filters:UV-B filters is preferably in the range 1:1 to 1:3.
Preferred filter compounds for combination with the 2-phenylbenzimidazolesulfonic acids according to the invention, preferred compounds having UV-filtering properties for the cosmetic preparations are 3-(4xe2x80x2-methylbenzylidine) -dl-camphor, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)propane-1,3-dione, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzo-phenone, octyl methoxycinnamate, 3,3,5-trimethyl-cyclohexyl salicylate, 2-ethylhexyl 4-(dimethyl-amino) benzoate, 2-ethylhexyl 2-cyano-3,3-diphenyl-acrylate, coated titanium dioxide and in particular 2-phenylbenzimidazole-5-sulfonic acid and 2,2xe2x80x2-(1,4-phenylene) bis(1H-benzimidazole-5-sulfonic acid) and its potassium, sodium, lithium, ammoniium and triethanolamine salts.
The protecting action against oxidative stress or against the effect of free radicals can be further improved if the formulation comprises one or more antioxidants.
There are many tried and tested substances known from the specialist literature which can be used as an antioxidant in the formulation such as amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (e.g. anserine), carotinoids, carotenes (e.g. xcex1-carotene, xcex2-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, xcex3-linoleyl, cholesteryl and glycerylesters thereof), and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), and sulfoximine compounds (e.g. buthionine-sulfoximine, homocysteine-sulfoximine, buthionine-sulfone, penta-, hexa- and heptathionine-sulfoximine) in very low tolerated doses (e.g. pmol to xcexcmol/kg), and also (metal) chelating agents, (e.g. xcex1-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), xcex1-hydroxy acids (e.g. citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof, vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E acetate), vitamin A and derivatives (e.g. vitamin A palmitate), and coniferyl benzoate of benzoin resin, rutin and salts of the sulfuric ester of rutin and derivatives thereof, xcex1-glycosyl rutin, ferulic acid, furfurylidineglucitol, carosine, butylhydroxy-toluene, butylhydroxyanisol, nordihydroguaretic acid, trihydroxybutyrophenone, quercetin, uric acid and derivatives thereof, mannose and derivatives thereof, zinc and derivatives thereof (e.g. ZnO, ZnSO4), selenium and derivatives thereof (e.g. selenomethionine), and stilbenes and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide).
Mixtures of antioxidants are likewise suitable for use in the cosmetic formulations according to the invention. Known and commercial mixtures are, for example, mixtures comprising, as active ingredients, lecithin, L-(+)-ascorbyl palmitate and citric acid (e.g. Oxynex(copyright) AP), natural tocopherols, L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citric acid (e.g. Oxynex(copyright) K LIQUID), tocopherol extracts from natural sources, L-(+)-ascorbyl palmitate, L-(+)-ascorbic acid and citric acid (e.g. Oxynex(copyright) L LIQUID), DL-xcex1-tocopherol, L-(+)-ascorbyl palmitate, citric acid and lecithin (e.g. Oxynex(copyright) LM) or butylhydroxytoluene (BHT), L-(+)-ascorbyl palmitate and citric acid (e.g. Oxynex(copyright) 2004).
The formulations according to the invention can also comprise vitamins as ingredients. Preferably, the vitamins used are vitamins and vitamin derivatives chosen from vitamin A, vitamin A propionate, vitamin A palmitate, vitamin A acetate, retinol, vitamin B, thiamine chloride hydrochloride (vitamin B1), riboflavin (vitamin B2) nicotinamide, vitamin C (ascorbic acid), vitamin D, ergocalciferol (vitamin D2), vitamin E, DL-xcex1-tocopherol, tocopherol E acetate, tocopherol hydrogensuccinate, vitamin K1, esculin (vitamin P active ingredient), thiamine (vitamin B1) nicotinic acid (niacin), pyridoxine, pyridoxal, pyridoaxmine, (vitamin B6), panthothenic acid, biotin, folic acid and cobalamine (vitamin B12) are present in the cosmetic formulations according to the invention, particularly preferably vitamin A palmitate, vitamin C, DL-xcex1-tocopherol, tocopherol E acetate, nicotinic acid, panthothenic acid and biotin.
The compound according to the invention can be incorporated into cosmetic formulations in the customary manner. Suitable formulations are those for external use, such as cream, lotion, gel or as a solution which can be sprayed onto the skin. In this respect, it is preferred if the preparation comprises at least one oil phase and at least one water phase, and that the 2-phenylbenzimidazolesulfonic acid according to the invention is present in at least one aqueous phase.
The cosmetic or pharmaceutical formulations according to the invention can take a number of terms, such as: solutions, suspensions, emulsions, PIT emulsions, pastes, ointments, gels, creams, lotions, powders, soaps, surfactant-containing cleansing preparations, oils, aerosols and sprays. Examples of other application forms are sticks, shampoos and shower preparations. Any customary carriers, auxiliaries and optionally further active ingredients may be added to the formulation.
Preferred auxiliaries originate from the group of preservatives, antioxidants, stabilizers, solubility promoters, vitamins, colorants, odour improvers.
Ointments, pastes, creams and gels may comprise the customary carriers, e.g. animal and vegetable fats, waxes, paraffins, starch, tragacanth, cellulose derivatives, polyethylene glycols, silicones, bentonites, silica, talc and zinc oxide or mixtures of these substances.
Powders and sprays may comprise the customary carriers, e.g. lactose, talc, silica, aluminium hydroxide, calcium silicate and polyamide powder or mixtures of these substances. Sprays can additionally comprise customary propellants, e.g. chlorofluorocarbons, propane/butane or dimethyl ether.
Solutions and emulsions can comprise the customary carriers, such as solvents, solubility promoters and emulsifiers, e.g. water, ethanol, isopropanol, ethyl carbonate, ethyl acetate, benzyl alcohol, benzyl benzoate, propylene glycol, 1,3-butylglycol, oils, in particular cotton seed oil, peanut oil, wheatgerm oil, olive oil, castor oil and sesame oil, glycerol fatty acid ester, polyethylene glycols and fatty acid esters of sorbitan or mixtures of these substances.
Suspensions can comprise the customary carriers such as liquid diluents, e.g. water, ethanol or propylene glycol, suspending agents, e.g. ethoxylated isostearyl alcohols, polyoxyethylene sorbitol esters and polyoxyethylene sorbitan esters, microcrystalline cellulose, aluminium metahydroxide, bentonite, agar and tragacanth or mixtures of these substances.
Soaps can comprise the customary carriers, such as alkali metal salts of fatty acids, salts of fatty acid mono esters, fatty acid protein hydrolysates, isethionates, lanolin, fatty alcohol, vegetable oils, plant extracts, glycerol, sugars or mixtures of these substances.
Surfactant-containing cleansing products can comprise the customary carrier substances, such as salts of fatty alcohol sulfates, fatty alcohol ether sulfates, sulfosuccinic monoesters, fatty acid protein hydrolysates, isethionates, imidazolinium derivatives, methyl taurates, sarcosinates, fatty acid amide ether sulfates, alkylamidobetaines, fatty alcohols, fatty acid glycerides, fatty acid diethanolamides, vegetable and synthetic oils, lanolin derivatives, ethoxylated glycerol fatty acid esters or mixtures of these substances.
Face and body oils can comprise the customary carrier substances such as synthetic oils, such as fatty acid esters, fatty alcohols, silicone oils, natural oils, such as vegetable oils and oily plant extracts, paraffin oils, lanolin oils or mixtures of these substances.
Cosmetic application forms also typical forms such as lipsticks, lip care sticks, mascara, eyeliner, eye shadow, blusher, powder makeup, emulsion make-up and wax make-up, and such protection products such as sunscreen, pre-sun and after-sun preparations.
All compounds or components which can be used in the cosmetic formulations are either known and available commercially or can be synthesized by known processes.
The cosmetic formulation according to the invention is particularly suitable for protecting human skin against the harmful influences of the UV constituents in sunlight. It can also offer protection to the skin against aging processes of the skin and against oxidative stress, i.e. against damage caused by free radicals, as are produced, for example, by solar irradiation, heat or other influences. In this connection, it is in various forms customarily used for this application. For example, the formulation may be in the form of a lotion or emulsion, such as in the form of a cream or milk (O/W, W/O, O/W/O, W/O/W), in the form of oily-alcoholic, oily-aqueous or aqueous-alcoholic gels or solutions, in the form of solid sticks or may be formulated as an aerosol.
The formulation may comprise cosmetic auxiliaries which are customarily used in this type of preparation, such as thickeners, softeners, moisturizers, surface-active agents, emulsifiers, preservatives, antifoams, perfumes, waxes, lanolin, propellants, dyes and/or pigments which color the composition itself or the skin, and other ingredients customarily used in cosmetics.
It is possible to use an oil, wax or other fatty substance, a lower monoalcohol or a lower polyol or mixtures thereof as a dispersant or solubilizer. Preferred monoalcohols or polyols include ethanol, isopropanol, propylene glycol, glycerol and sorbitol.
A preferred embodiment of the invention is an emulsion in the form of a protective cream or milk and which, apart from the 2-phenylbenzimidazolesulfonic acid(s) according to the invention and preferably further UV filters, comprise, for example, fatty alcohols, fatty acids, fatty acid esters, in particular triglycerides of fatty acids, lanolin, natural and synthetic oils or waxes and emulsifiers in the presence of water.
Further preferred embodiments include oily lotions based on natural or synthetic oils and waxes, lanolin, fatty acid esters, in particular triglycerides of fatty acids, or oily-alcoholic lotions based on a lower alcohol, such as ethanol, or a glycerol, such as propylene glycol, and/or a polyol, such as glycerol, and oils, waxes and fatty acid esters, such as triglycerides of fatty acids.
The cosmetic preparation according to the invention can also be in the form of an alcoholic gel which comprises one or more lower alcohols or polyols, such as ethanol, propylene glycol or glycerol, and a thickener, such as siliceous earth. The oily-alcoholic gels also comprise natural or synthetic oil or wax.
The solid sticks consist of natural or synthetic waxes and oils, fatty alcohols, fatty acids, fatty acid esters, lanolin and other fatty substances.
If a preparation is formulated as an aerosol, the customary propellants, such as alkanes, fluoroalkanes and chlorofluoroalkanes are usually used.
The cosmetic formulation can also be used to protect the hair against photochemical damage in order to prevent changes of color shades, decoloration or damage of a mechanical nature. In this case, a suitable formulation is in the form of a shampoo, lotion, gel or emulsion for rinsing out, the formulation in question being applied before or after shampooing, before or after coloring or bleaching or before or after permanent waving. It is also possible to choose a formulation in the form of a lotion or gel for styling or treating the hair, in the form of a lotion or gel for brushing or blow-waving, in the form of a hair lacquer, permanent waving composition, colorant or bleach for the hair. Apart from the 2-phenyl-benzimidazolesulfonic acid(s) according to the invention and further UV filters, the cosmetic formulation may comprise various adjuvants used in this type of composition, such as surface-active agents, thickeners, polymers, softeners, preservatives, foam stabilizers, electrolytes, organic solvents, silicone derivatives, oils, waxes, antigrease agents, dyes and/or pigments which color the composition itself or the hair, or other ingredients customarily used for hair care.
The cosmetic preparations according to the invention can be prepared using techniques which are well known to the person skilled in the art.
To protect the skin and/or natural or sensitized hair against solar rays, a cosmetic preparation comprising the compound of the invention is applied to the skin or the hair. Sensitized hair is understood here as meaning hair which has been subjected to a chemical treatment, such as a permanent waving treatment, a coloring process or bleaching process.
In addition, the compound of the invention also has a stabilizing effect on the formulation. When used in corresponding products, the formulations are thus also stable for longer and do not change their appearance. In particular, even in the case of longer-lasting application or relatively long storage, the effectiveness of the ingredients, e.g. vitamins, is retained. This is particularly advantageous in the case of compositions for protecting the skin against the effect of UV rays since these cosmetics are exposed to particularly high stresses by UV radiation.
The invention further provides for the stabilization of particular UV filters. A known high-performance class of light protection filter substances is formed by the dibenzoylmethane derivatives. However, a disadvantage is that these substances are very readily decomposed by UV light and thus their protecting properties are lost. An example of a light protection filter from this compound class which is available commercially is 4-(tert-butyl)-4xe2x80x2-methoxydibenzoylmethane, which has the structure given in formula IV.
Surprisingly, it has now been found that the compound of the invention has a very good stabilizing action for the dibenzoylmethanes, in particular 4-(tert-butyl)-4-Methoxydibenzoylmethane. By incorporating mixtures of these compounds into cosmetics, it is now possible to prepare light protection compositions using dibenzoyl-methanes which show no or only a low decrease in the protective action against UV rays, even in the case of a relatively long period of solar action, for example during sunbathing for a number of hours.
The entire disclosure of all applications, patents and publications, cited above and below, and of corresponding German Application No. 100 30 663.2, filed Jun. 23, 2000 is hereby incorporated by reference.

2-phenyl-benzimidazolesulfonic acids as UV-B filters

Abstract: in which

Abstract: n is 0, 1 or 2 and

Abstract: m is 2 or 3,

Abstract: R1, R2, R3, R4 and R5, are each a radical such as H, C1-8-alkyl, C1-8-alkoxy, hydroxyl, sulfate, nitro, F, Cl, Br or I radicals, and

Abstract: This compound can be effectively used as a UV filter, and as part of a cosmetic formulation which comprise these compounds. A process for preparation of the compound is disclosed as well.

Merck Patent Gesellschaft Mit Beschraenkter Haftung


A dead bolt lock system which may use one or more security locks in conjunction with a dead bolt to provide various levels of security access to a door. Generally, the lock system tests the condition of the security lock or locks before allowing retraction of the dead bolt. An inside escape lever is provided as a life safety feature to allow egress from the secured area regardless of the conditions of the security locks. A trigger hold back device maintains the dead bolt in a retracted position until the door has been opened and closed again. Lock covers include associated locked-on-by-combination and relock features. A night latch or lock down feature is provided to prevent access, including authorized access through the outside of the lock system. A force blocking assembly is provided to prevent force applied to the dead bolt from harming internal components of the system. A torque override clutch prevents excessive torque applied to the outside door handle from harming internal lock system components.

The present invention is directed generally to dead bolt locks and, more particularly, to dead bolt locks used on doors for accessing secure areas.
The use of dead bolts for security purposes is widespread. One example of a high security dead bolt lock is shown in U.S. Pat. No. 5,257,519 to Miller, the disclosure of which is incorporated herein by reference. Another example of these types of dead bolt mechanisms is shown in U.S. Pat. No. 4,601,504 to Wolfe, the disclosure of this patent also incorporated by reference herein. These dead bolt locks are combined with a safe lock for security purposes. The lock bolt of the safe lock provides the motive force to extend and retract the dead bolt of the dead bolt lock during operation. When using a combination type lock, a correct combination will permit retraction of the lock bolt. One drawback of such devices is that safe lock bolts and actuating mechanisms may not be well suited for long term use in this manner. In other words, they may not be designed to exert the necessary pushing or pulling force during extension and retraction of the dead bolt.
A dead bolt hold back feature has also been provided which retains the dead bolt in a retracted state. The dead bolt automatically extends as the door closes and a trigger member contacts the door strike. The extended dead bolt may be retracted from the inside of the secured area by rotation of a dead bolt knob. The aforementioned patents also disclose a life safety feature which retains the dead bolt in a retracted position so that a person inside a secured area can close the door without having the dead bolt extend. This feature enables quick exit from the secured area, however, it is not usually desirable to leave the door unlocked in this manner. On the other hand, when the life safety feature is not enabled, the above-mentioned dead bolt knobs do not provide a particularly easy manner of escape for individuals with various disabilities.
Often times, dead bolt locks on doors are combined with a second electric lock. The second lock often takes the form of an electronic access control linked to an electric door strike or lock associated with the door knob. Unlocking information provided to the access control actuates the door strike and, upon the additional retraction of any dead bolt, allows the door to be opened. It will be appreciated that this combination of a dead bolt lock and a doorknob lock makes it difficult to exit the secured area. A person leaving the secured area must use two hands to turn the doorknob and the dead bolt retraction knob simultaneously to open the door. Again, disabled individuals may have problems when trying to exit through such a door, particularly in the event of an emergency.
In view of these and other problems in this area of the lock industry, a need has developed to provide an improved dead bolt lock system.
In one general aspect, therefore, the present invention provides a dead bolt lock system for use on a door, for example, for accessing a secure area. The dead bolt lock system includes at least one security lock or access control having a movable lock member and requiring the input of correct unlocking information to change the lock from a locked to an unlocked condition. When the security lock is in an unlocked condition, a dead bolt element may be withdrawn and the door opened, for example, simply by turning a door handle on the outside of the door. In the first general aspect of this invention, a test member is provided in the dead bolt lock system, and is operatively connected to the security lock to test whether the security lock is in the locked or unlocked condition. If the security lock is unlocked, the test member can move into a space previously occupied by the movable lock member. The test member is also operatively connected to the dead bolt element such that movement of the test member in the described manner allows retraction of the dead bolt element. If the security lock is in a locked condition, then the test member is prevented from moving through the space occupied by the lock member and either the test member or other structure operatively associated with the test member prevents retraction of the dead bolt element. Preferably, this testing occurs each time the user attempts to turn the door handle.
The dead bolt lock system may be operatively coupled to more than one security lock. As an illustrative example, one security lock may be used as a primary or high security lock and one or more additional security locks may be used as secondary high or lower security locks. In each case, a locked or unlocked condition of the security lock is tested by the dead bolt lock system and, if each security lock operating in the system is found to be in an unlocked condition, the dead bolt system may be operated by the door handle to withdraw the dead bolt and open the door. The security locks may specifically include lock bolts, such as linearly extendable bolts or swing bolts, and may comprise mechanical, electrical or electro-mechanical locks. For example, in the case of locks having linearly extendable bolts, the lock bolt will block the test member when extended and will not block the test member when retracted. In the case of swing bolts, the swing bolt will block the test member when in a locked condition, but may be forced into a retracted position by the test member when in an unlocked condition. Other types of security locks and lock bolts are also within the scope of this invention. A torque override clutch is preferably connected to the door handle to prevent transmission of excessive force to the internal components of the dead bolt lock system when the system is locked and the door handle is being rotated with excessive torque.
Stated generally, the dead bolt lock can provide different levels of security and monitoring capability. By providing at least one primary lock and one secondary lock, the dead bolt lock system can have at least two levels of control or security. The primary lock in combination with the secondary lock may be used for nighttime control and the secondary lock may be used alone for daytime control. That is, the primary lock or high security lock can remain unlocked during the day and entry into the secured area can be controlled by the operation of one or more high or lower security lock devices. Another type of security lock device which may be optionally incorporated into the system is referred to herein as an access control device. This device includes an electrically actuated movable lock member which normally blocks movement of a test member similarly associated with retraction of the dead bolt element. If the movable lock member is actuated through the input of proper unlocking information, then the test member will be able to move through the space previously occupied by the movable lock member. Due to the movement of the test member in this manner, the dead bolt element will retract, for example, as the operator turns the door handle. Preferably, the access control device comprises a solenoid having an electrically actuated movable member, such as a reciprocating piston element. This device may be controlled, for example, simply by one or more push button switches or by higher security controls like card readers, retinal scanners, voice identifiers or fingerprint identifiers.
An escape lever is also provided on the interior side of the lock system and may be operated by either pushing or pulling on the lever. This actuating movement is preferably a pushing movement toward the door or a pulling movement away from the door, but may also be a sideward or up and down pushing or pulling movement. This overrides all locking mechanisms associated with the system, except for a relock feature to be discussed below, to allow quick escape from the secure area. The lever is configured to be easily operated by persons having various disabilities.
Preferably, the inventive dead bolt lock also includes one or more blocking elements positioned to receive a force applied to an end face of the dead bolt, usually during an unauthorized entry attempt. This prevents damage to the dead bolt lock system components. The blocking element may be automatically disengaged when the dead bolt is retracted during normal operation.
The preferred dead bolt lock system also includes a unique dead bolt hold back feature employing a pivoting member disposed between a spring biased trigger member and the dead bolt element. For purposes of carrying out this feature, the dead bolt element is normally spring biased in an extended position. The pivoting member cooperates with the dead bolt element to maintain the dead bolt element in a retracted position when the door is open. The trigger automatically actuates to allow the dead bolt element to extend upon contact with a door strike or the like.
As another feature of this invention, a night latch or lock down feature is provided and prevents operation of the dead bolt lock system regardless of whether the security locks are inputted with correct unlocking information. Even when the night latch feature is enabled, however, the escape lever may be operated to allow a person to leave the secure area.
As another optional feature, the dead bolt lock system may also include a lock override mechanism. This mechanism allows each of the security locks, access controls and lock down feature to be overridden from the outside of the door through the use of an appropriate key. This key may be inserted and rotated to withdraw the dead bolt without the necessity of inputting the correct unlocking information into the security locks and/or access control.
The dead bolt lock system also includes one or more interior housing covers referred to in the industry generally as locked-on-by-combination covers, but operating in a unique manner in the present invention. The covers are removable only when the dead bolt is retracted through normal operation and the outside door handle is in a rotated position. This helps prevent unauthorized access to the interior of the lock system.
Also in connection with the housing covers, relock mechanisms may be provided to ensure that the dead bolt lock system cannot be operated after removal of the housing covers. Specifically, if the housing covers are removed, the relock mechanism automatically shifts into a position that prevents operation of the dead bolt retracting structure. This provides an additional level of security against unauthorized access through the dead bolt lock system of this invention.
Electrical sensing devices, such as microswitches, can be provided to sense, monitor, audit or even control various lock operations. The most basic of these may be to indicate on a control panel, for example, whether the dead lock bolt is in a retracted or extended position. Similarly, indicator switches can be provided to detect whether the other lock bolts combined with the dead bolt are in retracted or extended positions. It is also contemplated that the indicator switches can be wired in series, for example, to provide one overall indication of a locked or unlocked condition.
The various features, assemblies and systems described above can be used in combination with each other or separately depending on the particular application of the dead bolt lock system. In addition, various mechanical or electrical component designs and configurations could be used within the spirit and scope of the inventive concepts.
The inventive dead bolt lock provides significant advantages over prior dead bolt locks. First, a dead bolt lock system of this invention can accept any conventional safe lock, e.g., a combination lock, mechanical lock or electro-mechanical lock, manufactured to a standard specification or, in other words, with a standard footprint. More specifically, one or more housings of the dead bolt lock system accept locks having a standard footprint, as is often required by government specifications. Moreover, the dead bolt lock system functions with a variety of security lock devices, including those using standard lock bolts which extend and retract linearly from the lock casing or locks using swing type bolts which pivot from the lock casing, for example, with a spring bias. In any case, however, the lock member or bolt does not apply or receive significant pushing or pulling force during operation of the dead bolt lock system. Because housing or support structure may be situated adjacent the lock member or bolt, and because of the torque override clutch, the system prevents significant side loads on the lock members or bolts. Security lock bolts generally are subjected to only side loads, either from the lock bolt testers as described above or from an unauthorized entry attempt. As another advantage of the invention, the security locks and access controls may be eliminated and the system will still function as a dead bolt passage set. In this type of use, for example, the lock down feature may still be a functional part of the system.

Dead bolt system having multiple security features


An add-on card is provided for use within a computer system that has an expansion slot connected to a bus. The bus has a first supply line for supplying a first predetermined voltage and a second supply line for supplying a second predetermined voltage which is higher than the first predetermined voltage. The add-on card is adapted to operate properly regardless of whether the respective predetermined voltages are supplied on (1) the first supply line only, (2) the second supply line only, or (3) both supply lines. In a PCI bus implementation, where 3.3V and 5V are the predetermined voltage levels, the add-on card operates properly regardless of whether: only a 5V level is provided, only a 3.3V level is provided, or both 3.3V and 5V levels are provided.

1. Field of the Invention
The present invention relates to computer systems. More particularly, the present invention relates to voltage supply circuits for add-on cards in PCs and other computer systems.
2. Brief Description of the Related Art
Personal Computers (PCs) and other types of computer systems commonly include expansion slots for receiving add-on cards. The expansion slots are typically provided on the host computer's motherboard, and provide access to signal lines of the computer's main bus. Any of a variety of different types of cards can be added to the computer system using the expansion slots, including host adapter boards, network cards, and hardware accelerators.
The add-on cards receive power from the host computer's power supply using power supply lines of the main bus. In computers that use a Peripheral Component Interconnect (PCI) type bus, these power supply lines have traditionally provided a voltage level of 5V. Recently, however, there has been a trend in the industry towards using 3.3V components that consume less power. As a result, manufacturers of PC systems sometimes provide a PCI bus that includes an additional, 3.3V power supply line. When this extra voltage supply level is provided, both 3.3V and 5V type cards can be used within the system.
Unfortunately, because not all PCs are provided with a 3.3V power level, add-on cards are commonly designed to use only the 5V supply, and to step down to 3.3V internally. This step-down method causes the cards to consume more system power than is necessary. In addition, the provision of such cards impedes the ability of PC manufacturers to eventually eliminate the 5V supply, as is desirable for reducing manufacturing costs. The elimination of the 5V supply also has the effect of reducing the cost of power supplies since only a single voltage level is provided.

Add-on card with automatic bus power line selection circuit


A miniature antenna includes a radiating arm that defines a grid dimension curve. In one embodiment, the radiating arm includes a planar portion and at least one extruded portion. The planar portion of the radiating arm defines the grid dimension curve. The extruded portion of the radiating arm extends from the planar portion of the radiating arm to define a three-dimensional structure. In one embodiment, the miniature antenna includes a first radiating arm that defines a first grid dimension curve within a first plane and a second radiating arm that defines a second grid dimension curve within a second plane. In one embodiment, the miniature antenna includes a radiating arm that forms a non-planar structure.

Miniature antenna structures are known in this field. For example, a miniature antenna structure utilizing a geometry referred to as a space-filling curve is described in the co-owned International PCT Application WO 01/54225, entitled "Space-Filling Miniature Antennas," which is hereby incorporated into the present application by reference. FIG. 1 shows one example of a space-filling curve 10. A space-filling curve 10 is formed from a line that includes at least ten segments, with each segment forming an angle with an adjacent segment. In addition, when used in an antenna, each segment in the space-filling curve 10 should be shorter than one-tenth of the free-space operating wavelength of the antenna.
It should be understood that a miniature antenna as used within this application refers to an antenna structure with physical dimensions that are small relative to the operational wavelength of the antenna. The actual physical dimensions of the miniature antenna will, therefore, vary depending upon the particular application. For instance, one exemplary application for a miniature antenna is a long wavelength HF communication antenna. Such antennas are often located onboard ships for which a small dimensioned antenna structure may be desirable. A typical long wavelength HF antenna onboard a ship that operates in the 2-30 MHz range may, for example, be ten (10) to fifty (50) meters in height, and can be significantly reduced in size using a miniature antenna structure, as described herein. In comparison, if a miniature antenna structure, as describe herein, is used as the antenna in a cellular telephone, then the overall physical dimensions of the miniature antenna will be significantly smaller.

Miniature antenna having a volumetric structure


The invention provides personal wash compositions with soap like rinsability. The composition contains a lathering surfactant system and a specifically defined polymer/oil blend.

The present invention relates to liquid personal wash composition comprising surfactant (e.g., synthetic surfactant with or without soap) and mixtures of hydrophobic polymer with emollient oils. Specifically, the polymers used in the mixtures must have minimum tackiness value (e.g., greater than about 100 g), defined also by MW and viscosity; and mixture must also have minimum viscosity ( greater than 3000 cps defined at 30xc2x0 C.) and defined particle size. No more than maximum levels of cationic may be used.
The rinsing sensation a product has on the skin can be perceived by many consumers. In many parts of the world, notably China, Japan and other parts of Asia, a soap-like rinsing property (e.g., soap-like xe2x80x9cdraggyxe2x80x9d feeling) is perceived as being thoroughly cleansing and is highly preferred.
Most mild cleansers, especially 2-in-1 moisturizing liquids such as Dove(copyright) or Olay(copyright), however, do not provide consumer desirable soap-like rinsing characteristics.
Unexpectedly, it has been found that selection of the depositing moisturizing agents can be used to provide moisturizing liquids with soap-like rinsing attributes (e.g., as defined by xe2x80x9cdraggyxe2x80x9d feel after certain number of counts). Specifically, by depositing large (e.g., 20-5000 micrometers), viscous (e.g., higher than 3000 cps at 30xc2x0 C. at 1.0 Sxe2x88x921) drops of a blend of hydrophobic polymer and emollient oils, the desired skin-feel is obtained. Preferred hydrophobic polymers include high MW (i.e., MW greater than 900, preferably greater than 1000) C2-C10 polyalkenes (e.g., polybutenes) and preferred oils which are mixable with the hydrophobic polymers include mineral oil, petrolatum, or triglycerides.
The use of hydrophobic polymers (e.g., polybutene) in shampoo and PW liquid compositions is not new as seen, for example, from U.S. Pat. No. 5,441,730 to Gough et al. and U.S. Pat. No. 5,580,550 to Gough et al.
WO 99/09948 and WO 99/09950 (both assigned to Procter and Gamble) both disclose compositions in which polybutenes of MW 600 to about 1000 are used to enhance rinsability. Among the long, long recitation of optional ingredients which may be used is included hydrocarbons such as mineral oils and petrolatum (see WO 99/09950 at page 27, line 16).
There is absolutely no teaching or suggestion in these references of the criticalities of the invention, e.g., using polymers which must have MW greater than 900, preferably greater than 1000; using these necessarily in combination with oils of defined viscosity to obtain defined benefits; using critical size polymer/oil mixtures; and ensuring no more than certain level (less than 0.5%, preferably less than 0.3%) cationic is used (contrast with, for example, page 19, lines 12xe2x80x9413 of WO 99/09950 where cationic can be used up to levels as high as 3%).
U.S. Pat. No. 5,854,293 to Glenn, Jr. discloses liquid PW compositions containing large drop lipophilic moisturizing agent which agent may be a blend of petrolatum and polybutenes (column 3, lines 43-47).
Again, there is no recognition that polymers must be of certain size and certain molecular weight (e.g., higher than 900), that no more than certain amount of cationic may be used (contrast with column 5, lines 44-45) or that very specific criticalities will yield compositions which rinse well and provide xe2x80x9cdraggyxe2x80x9d feel.
Finally, U.S. Pat. No. 5,869,070 to Dixon et al. disclose personal cleansing composition containing skin moisturizing agent which is selected from the group consisting of petrolatum, hydrogenated polybutene and mixtures thereof, where ratio of petrolatum to polybetaine is 3:1 to 5:1. The composition also comprises 0.5 to 1.0 part polyquaternium 10 and 1 to 2.5 parts sodium polyacrylate. There is no recognition that specific criticalities, e.g., less than 0.5% cationic, are required to achieve xe2x80x9cdraggyxe2x80x9d feel as defined.
Unexpectedly, applicants have found that use of specific polymers (i.e., minimum tackiness defined by minimum viscosity) in combination with specific oils provide not only moisturizing benefits, but also can provide good rinsability and soap-like xe2x80x9cdraggyxe2x80x9d feel desirable by many consumers. Moreover, to the extent there is a balance between sticky feel of the polymers and greasy feel of oils, the invention provides for a method to achieve desired soap-like rinsability (e.g., rinsability with soap-like feel) by manipulating the polymer/oil ratio of the blend. Soap-like rinsability is dependent not only on polymer molecular weight and polymer/oil ratio, but also on low level (or absence) of cationic polymer.
More specifically, the invention comprises a personal cleansing composition having soap-like rinsability comprising:
(1) 70% to 99% of a lathering surfactant system containing 5 to 35% by wt. of a surfactant composition having a slippery, slightly draggy or draggy wet skin feel during rinsing after a six rubbing cycle as measured by in-shower rinsability evaluation method;
(2) 1 to 30% by wt. of a polymer/oil blend comprising:
(a) 20 to 90% of a polymer having MW greater than about 900, preferably greater than about 1000 and viscosity greater than 10,000 centistoke at 30xc2x0 C. at 1.0 Sxe2x88x921 and a tackiness of greater than about 100 grams as measured by tackiness test;
(b) 10% to 80% of a hydrophobic oil,
wherein tackiness of polymer/oil blend is 30-400 g measured by tackiness test,
wherein viscosity of polymer/oil blend is higher than 3000 centistoke at 30xc2x0 C. at 1.0 Sxe2x88x921; and
wherein average particle size of blend is 20 to 5000 micrometers;
(3) 0.1 to 10% by wt. of organic, inorganic or polymeric stabilizer in amount sufficient to provide physical stability of oil droplets at 40xc2x0 C. for over 4 weeks;
wherein composition has less than 0.4 wt. % cationic polymer,
wherein composition has draggy or very draggy wet skin feel in less than 8 rubbing cycles as determined by in-shower evaluation method.
The present invention relates to personal cleansing compositions comprising polymer/oil blends which are used to provide soap-like rinsability as measured by in-shower evaluation test. The invention further relates to a method of providing soap-like rinsability by carefully balancing ratio of polymer/oil and ensuring no more than maximum amount cationic polymer is used.
Specifically, the compositions of the invention comprise:
(1) 70-99% lathering surfactant system containing 5 to 35% by wt. surfactant composition with slippery, slightly draggy or draggy wet skin feel after 6 rubbing cycles (as measured by defined test),
(2) 1 to 30% of specifically defined polymer/oil blends wherein polymers are selected for specific tackiness (as further defined by MW and viscosity); and polymer oil blends have specific tackiness, viscosity and average particle size; and
(4) stabilizer;
wherein the composition has less than 0.4 wt. % cationic polymer and wherein selection yields compositions which are soap-like in feel (draggy or very draggy wet skin feel in less than 8 rubbing cycles).
Each of the various components of the composition is described in more detail below.
Surfactant System
The composition of the invention comprises 70 to 99% of a xe2x80x9clatheringxe2x80x9d surfactant system containing 5 to 35% by wt. surfactant composition having a slippery, slightly draggy or draggy wet skin feel (as defined by in-shower rinsability evaluation method).
The surfactants in the composition may be anionic, nonionic, amphoteric/zwitterionic, cationic or mixtures thereof as long as the compositions retain minimal lathering profile. That is, the surfactant or mixture combined should have an equilibrium surface tension between 15 and 50 dynes/cm, preferably 20-40 dynes/cm as measured at CMC at 25xc2x0 C. Some surfactant mixes can have tension lower than those of individual components. Also the overall surfactant system, in the absence of polymer/oil blend, has slippery, slightly draggy or draggy wet skin rinsing feel (in contrast to very draggy feeling produced by soap-based cleansers).
The anionic surfactant may be, for example, an aliphatic sulfonate, such as a primary alkane (e.g., C8-C22) sulfonate, primary alkane (e.g., C8-C22) disulfonate, C8-C22 alkene sulfonate, C8-C22 hydroxyalkane sulfonate or alkyl glyceryl ether sulfonate (AGES); or an aromatic sulfonate such as alkyl benzene sulfonate.
The anionic may also be an alkyl sulfate (e.g., C12-C18 alkyl sulfate) or alkyl ether sulfate (including alkyl glyceryl ether sulfates). Among the alkyl ether sulfates are those having the formula:
RO(CH2CH2O)nSO3M
wherein R is an alkyl or alkenyl having 8 to 18 carbons, preferably 12 to 18 carbons, n has an average value of greater than 1.0, preferably between 2 and 3; and M is a solubilizing cation such as sodium, potassium, ammonium or substituted ammonium. Ammonium and sodium lauryl ether sulfates are preferred.
These differ from ether sulfates of the invention in that they are not branched.
The anionic may also be alkyl sulfosuccinates (including mono- and dialkyl, e.g., C6-C22 sulfosuccinates); alkyl and acyl taurates, alkyl and acyl sarcosinates, sulfoacetates, C8-C22 alkyl phosphates and phosphates, alkyl phosphate esters and alkoxyl alkyl phosphate esters, acyl lactates, C8-C22 monoalkyl succinates and maleates, sulphoacetates, and acyl isethionates.
Sulfosuccinates may be monoalkyl sulfosuccinates having the formula:
R4O2CCH2CH(SO3M)CO2M;
amido-MEA sulfosuccinates of the formula
R4CONHCH2CH2O2CCH2CH(SO3M)CO2M
wherein R4 ranges from C8-C22 alkyl and M is a solubilizing cation;
amido-MIPA sulfosuccinates of formula
RCONH(CH2)CH(CH3)(SO3M)CO2M
where M is as defined above.
Also included are the alkoxylated citrate sulfosuccinates; and alkoxylated sulfosuccinates such as the following:
wherein n=1 to 20; and M is as defined above.
Sarcosinates are generally indicated by the formula RCON(CH3)CH2CO2M, wherein R ranges from C8 to C20 alkyl and M is a solubilizing cation.
Taurates are generally identified by formula
R2CONR3CH2CH2SO3M
wherein R2 ranges from C8-C20 alkyl, R3 ranges from C1-C4 alkyl and M is a solubilizing cation.
Another class of anionics are carboxylates such as follows:
Rxe2x80x94(CH2CH2O)nCO2M
wherein R is C8 to C20 alkyl; n is 0 to 20; and M is as defined above.
Another carboxylate which can be used is amido alkyl polypeptide carboxylates such as, for example, Monteine LCQ(copyright) by Seppic.
Another surfactant which may be used are the C8-C18 acyl isethionates. These esters are prepared by reaction between alkali metal isethionate with mixed aliphatic fatty acids having from 6 to 18 carbon atoms and an iodine value of less than 20. At least 75% of the mixed fatty acids have from 12 to 18 carbon atoms and up to 25% have from 6 to 10 carbon atoms.
Acyl isethionates, when present, will generally range from about 0.5-15% by weight of the total composition. Preferably, this component is present from about 1 to about 10%.
The acyl isethionate may be an alkoxylated isethionate such as is described in llardi et al., U.S. Pat. No. 5,393,466, hereby incorporated by reference into the subject application. This compound has the general formula:
In general the xe2x80x9cadditionalxe2x80x9d anionic component will comprise from about 1 to 20% by weight of the composition, preferably 2 to 15%, most preferably 5 to 12% by weight of the composition. It may also include a C8 to C14 unbranched fatty acid hydrocarbon (e.g., lauric acid, palmitic acid, capric, etc.) in levels of 10-50%, preferably 10-30% of total surfactant. Of course, soap may comprise less than 5% or may be absent altogether.
Zwitterionic and Amphoteric Surfactants
Zwitterionic surfactants are exemplified by those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight or branched chain, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. A general formula for these compounds is:
wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of from about 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxide moieties and from 0 to about 1 glyceryl moiety; Y is selected from the group consisting of for example nitrogen, atoms; R3 is an alkyl or monohydroxyalkyl group containing about 1 to about 3 carbon atoms; X is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen or phosphorus atom; R4 is an alkylene or hydroxyalkylene of from about 1 to about 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Amphoteric detergents which may be used in this invention include at least one acid group. This may be a carboxylic or a sulphonic acid group. They include quaternary nitrogen and therefore are quaternary amido acids. They should generally include an alkyl or alkenyl group of 7 to 18 carbon atoms. They will usually comply with an overall structural formula:
where R1 is alkyl or alkenyl of 7 to 18 carbon atoms;
R2 and R3 are each independently alkyl, hydroxyalkyl or carboxyalkyl of 1 to 3 carbon atoms;
n is 2 to 4;
m is 0 to 1;
X is alkylene of 1 to 3 carbon atoms optionally substituted with hydroxyl, and
Y is xe2x80x94CO2xe2x80x94 or xe2x80x94SO3xe2x80x94
Suitable amphoteric detergents within the above general formula include simple betaines of formula:
and amido betaines of formula:
where m is 2 or 3.
In both formulae R1, R2 and R3 are as defined previously. R1 may in particular be a mixture of C12 and C14 alkyl groups derived from coconut so that at least half, preferably at least three quarters of the groups R1 have 10 to 14 carbon atoms. R2 and R3 are preferably methyl.
A further possibility is that the amphoteric detergent is a sulphobetaine of formula
where m is 2 or 3, or variants of these in which xe2x80x94(CH2)3SOxe2x88x923 is replaced by
In these formulae R1, R2 and R3 are as discussed previously.
Amphoacetates and diamphoacetates are also intended to be covered in possible zwitterionic and/or amphoteric compounds which may be used.
The surfactant system may also optionally comprise a nonionic surfactant.
The nonionic which may be used includes in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C6-C22) phenols-ethylene oxide condensates, the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
The nonionic may also be a sugar amide, such as a polysaccharide amide. Specifically, the surfactant may be one of the lactobionamides described in U.S. Pat. No. 5,389,279 to Au et al. which is hereby incorporated by reference or it may be one of the sugar amides described in U.S. Pat. No. 5,009,814 to Kelkenberg, hereby incorporated into the subject application by reference.
Other surfactants which may be used are described in U.S. Pat. No. 3,723,325 to Parran Jr. and alkyl polysaccharide nonionic surfactants as disclosed in U.S. Pat. No. 4,565,647 to Llenado, both of which are also incorporated into the subject application by reference.
Preferred alkyl polysaccharides are alkylpolyglycosides of the formula
xe2x80x83R2O(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 0 to 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from 1.3 to about 10, preferably from 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
Nonionic generally comprises 0 to 10% by wt. of the composition.
Cationic synthetic surfactant should not serve as the sole surfactant in this product, but can be used as a co-surfactant at a lower level of from about 0.5% to about 6% by weight. The more preferred types of cationic surfactant are selected from the group consisting of: alkyl trimonium chloride and methosulfate, and dialkyldimonnium chloride and methyl sulphate, and alkyl alkonium chloride and methyl sulphate and mixtures thereof. These surfactants contain C12 to C24 carbon atoms per alkyl chain. The most preferred cationic is selected from the group consisting of stearylalkonium chloride, stearyltrimonium chloride. Di-stearyl-dimonium chloride, and mixtures thereof.
Polymer/Oil Blend
The polymer/oil blend of the invention comprises 1 to 30%, preferably 3 to 20% by wt. of composition which comprises 10 to 90%, preferably 20 to 80% polymer and about 20 to 90%, preferably 30 to 80% hydrophobic oil.
The polymer may be any oil mixable hydrophobic linear or branched polymer having molecular weight greater than 900, preferably greater than 1000 daltons, a viscosity greater than 10,000 centistokes at 30xc2x0 C. and 1 Sxe2x88x921 and a tackiness of greater than 100 grams as measured by tackiness test. Preferred polymers may be hydrogenated or non-hydrogenated polymer of alkylene or isoalkylene such as polybutene, polyisobutene, polybutadiene or polyisoprene, polyalphaolefin, polyester, and polyacrylate and its copolymers. Most preferred polymers are commercially available polymers such as Indopol H1500(copyright), Indopol H1900(copyright), and Panalane H300E(copyright) from Amoco, Aquapel 32S(copyright), Aquapel 15L(copyright), and Puresyn ME2500(copyright) from Mobil.
The oil may be any emollient oils mixable with the said hydrophobic polymers and provide properties noted below after blended with the hydrophobic polymer. The preferred emollient oils may be petrolatum, mineral oil, triglyceride oils such as sunflower seed oil, soybean oil or caster oil, and esters such as isopropyl palmitate.
Specifically, the oil is mixed with oil-mixable polymer at ratio of 9 to 1 to 1 to 8 to provide a blend which together has viscosity higher than 3000 centistoke at 30xc2x0 C. at 1Sxe2x88x921.
The blend is also characterized in that the tackiness value of the blend is in the range of 30 to 400 grams, preferably 50 to 300 grams, as measured by the TA texture analyzer; and that average particle size as existed in the liquid cleanser is in range of 20 to 5000 micrometers, preferably 50 to 1000 micrometers.
According to the subject invention, it has been surprisingly found that the wet skin feel is dependent on both the molecular weight of the oil-mixable polymer (e.g., polyalkalene) and the ratio of polymer to oil.
Polymeric Stabilizer
A third required component of the invention is organic, inorganic or polymeric stabilizer. Specifically, the compositions comprise 0.1 to 10% by wt. of an organic, inorganic or polymeric stabilizer which provides physical stability of the large oil droplets, (droplets of polymer/oil blend) in the surfactant composition at 40xc2x0 C. for over four weeks.
Generally the organic polymeric stabilizer of the invention include, but are not limited to any of several long chain acyl derivatives or mixtures thereof. Included are the glycol mono- di- and triesters having about 14 to about 22 carbon atoms. Preferred glycol esters include the ethylene glycol mono- and distearates, glyceryl stearates, palm oil glyceride, tripalmitin, tristearin and mixtures thereof. Another example of suspending agent useful in the present invention include the alkanolamides having from about 14 to about 22 carton atoms. Preferred alkanolamides are stearic monoethanolamide, stearic diethanolamide stearic monoisopropanolamide, stearic monoethanolamide stearate and mixtures thereof. Still another example of a suspending agent useful in the present invention include the long chain fatty acid esters such as stearyl stearate, stearyl palmitate, palmityl palmitate, trihydroxystearylglycerol and tristearylglycerol. Still another example of a suitable suspending agent useful in the present invention include the long chain amine oxides having from about 14 to about 22 carbon atoms. Preferred amine oxides are hexadecyldimethylamine oxide and octadecyldimethylamide oxide.
Example of a suitable polymeric suspending agent (or thickening agent) useful in the present invention include the carbohydrate gums such as cellulose gum, microcrystalline cellulose, cellulose gel, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethylcellulose, hydroxymethyl carboxymethyl cellulose, hydroxymethyl carboxypropyl cellulose, methyl cellulose, ethyl cellulose, guar gum, gum karaya, gum tragacanth, gum arabic, gum acacia, gum agar, xanthan gum and mixtures thereof. Preferred carbohydrate gums are the cellulose gums and xanthan gum. Of all the above described types of suspending agents, preferred compounds include the long chain glycol ester and the carbohydrate gums. Other stabilizers which may be used are set forth in U.S. Pat. No. 5,854,293 to Glenn, Jr. at column 4, line 36 to column 6, line 65. This reference is hereby incorporated by reference into the subject application.
The suspending agent or mixtures of agent may be present from about 0.1 to 10% of the composition.
Cationic Polymer
Although the composition may contain cationic polymer, one criticality of the invention is that it should contain less than 0.4%, preferably less than 0.3% to obtain the drag feel and rinsability desired by the invention.
Suitable cationic polymers include Guar hydroxypropyltrimonium chloride, Quaternium-19, -23, -40, -57, poly(dimethyidiallylammonium chloride), poly (dimethyl butenyl ammonium chloride)-, w-bis(triethanolammonium chloride), poly (dipropyldiallylammonium chloride), poly(methyl-beta propaniodiallylammonium chloride), poly(diallylpiperidinium chloride), poly(vinyl pyridinium chloride), quaternised poly(vinyl alcohol),quaternized poly(dimethylaminoethylmethacrylate) and mixtures thereof.
Finally, it is another criticality of the invention that the final composition provides a draggy or very draggy wet skin feel after fewer than 8 rubbing cycles as determined by in-shower evaluation method.
Optionals
Compositions invention may suspend oil/emollient particles. The following oil/emollients may optionally be suspended in the compositions.
Various classes of oils are set forth below.
Vegetable oils: Arachis oil, castor oil, cocoa butter, coconut oil, corn oil, cotton seed oil, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, sesame seed oil and soybean oil.
Esters: Butyl myristate, cetyl palmitate, decyloleate, glyceryl laurate, glyceryl ricinoleate, glyceryl stearate, glyceryl isostearate, hexyl laurate, isobutyl palmitate, isocetyl stearate, isopropyl isostearate, isopropyl laurate, isopropyl linoleate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, propylene glycol monolaurate, propylene glycol ricinoleate, propylene glycol stearate, and propylene glycol isostearate.
Animal Fats: acetylated lanolin alcohols, lanolin, lard, mink oil and tallow.
Other examples of oil/emollients include mineral oil, petrolatum, silicone oil such as dimethyl polysiloxane, lauryl and myristyl lactate.
The emollient/oil is generally used in an amount from about 1 to 30%, preferably 5 to 20% by wt. of the composition. Generally, it should comprise no more than 30% of the composition.
In addition, the compositions of the invention may include optional ingredients as follows:
Organic solvents, such as ethanol; auxiliary thickeners, sequestering agents, such as tetrasodium ethylenediaminetetraacetate (EDTA), EHDP or mixtures in an amount of 0.01 to 1%, preferably 0.01 to 0.05%; and coloring agents, opacifiers and pearlizers such as zinc stearate, magnesium stearate, TiO2, EGMS (ethylene glycol monostearate) or Lytron 621 (Styrene/Acrylate copolymer); all of which are useful in enhancing the appearance or cosmetic properties of the product.
The compositions may further comprise antimicrobials such as 2-hydroxy-4,2xe2x80x24xe2x80x2 trichlorodiphenylether (DP300); preservatives such as dimethyloldimethylhydantoin (Glydant XL1000), parabens, sorbic acid etc.
The compositions may also comprise coconut acyl mono- or diethanol amides as suds boosters, and strongly ionizing salts such as sodium chloride and sodium sulfate may also be used to advantage.
Antioxidants such as, for example, butylated hydroxytoluene (BHT) may be used advantageously in amounts of about 0.01% or higher if appropriate.
Another optional ingredient which may be added are the deflocculating polymers such as are taught in U.S. Pat. No. 5,147,576 to Montague, hereby incorporated by reference.
Other ingredients which may be included are exfoliants such as polyoxyethylene beads, walnut sheets and apricot seeds
Particle Size of Oil/Polymer Blend and its Process
Particle size of the oil/polymer blend has a significant effect on cleanser rinsability. In general the larger the droplet size the more efficient the oil/polymer blend to increase cleanser""s rinsability. To work as an efficient rinsing aid, the droplet size should be larger than 20 microns, preferably larger than 50 microns. The upper limit of the oil droplets can be as large as 5000 microns, preferably 1000 microns depending on the cleanser""s suspension properties and also the tackiness of the oil/polymer blends. For oil/polymer blend with tackiness higher than 200 grams, the upper limit of the particle size is preferably less than 1000 microns to prevent undesirable sticky patch wet-skin feel. For good rinsability and good in-use sensory properties, the weight average particle size of oil/polymer blend should be in the range of 20 to 5000 microns, preferably 50 to 1000 microns, most preferably 100 to 400 microns.
Liquid cleansers containing oil/polymer droplets with size in the range of 20 to 5000 microns can be accomplished either in a batch wise process or in a continuous process depending on how the oil/polymer blend and the surfactant solution are mixed. A batch process such as an overhead mixer or a floatation machine, or a continuous process such as a two fluid co-extrusion nozzle, an in-line injector, an in-line mixer or an in-line screen can be used to make the oil/polymer blend with the desired particle size. The size of the oil/polymer blend can be manipulated by changing the mixing speed, mixing temperature, mixing time, viscosity of the surfactant solution or oil/polymer blend, and the mixing device. In general, by reducing the mixing time, decreasing the mixing speed, lowing the viscosity of the surfactant solution, increasing the viscosity of the oil/polymer blend, or using a mixing device that produces less shear force during mixing, one can produce larger size.
The most preferred process to make large droplet of oil/polymer blend is continuous injection/low shear mixing process described as following. Oil and polymer are mixed either at ambient or elevated temperature to form a uniform mixture. The oil/polymer blend is then injected into or co-extruded with a well structured surfactant solution (e.g., a surfactant solution capable of suspend large oil/polymer particles) to form elongated oil/polymer particles with length from several centimeters to several decimeters. The elongated oil/polymer particles are then broken to particles of 20 to 5000 microns by passing through in-line screen, in-line static mixer or combination of both. Particle size can be controlled easily by the opening size of the screen and/or the diameter and length of the static mixer.
Other than directly mixing oil/polymer blend with surfactant solution, the oil/polymer blend can also be added into the surfactant solution as particles with the oil/polymer blend encapsulated inside a shell or a matrix of polymer coating. This route might provide better way to control the particle size of the oil/polymer blend. However, it is less preferred due to the cost of additional process to make the capsules.
The invention will now be described in greater detail by way of the following non-limiting examples. The examples are for illustrative purposes only and not intended to limit the invention in any way.
Except in the operating and comparative examples, or where otherwise explicitly indicated, all number in this description indicating amounts or ratios of materials or conditions or reaction, physical properties of materials and/or use are to be understood as modified by the word xe2x80x9caboutxe2x80x9d.
Where used in the specification, the term xe2x80x9ccomprisingxe2x80x9d is intended to include the presence of stated features, integers, steps, components, but not to preclude the presence or addition of one or more features, integers, steps, components or groups thereof.
All percentages in the specification and examples are intended to be by weight unless stated otherwise.
Methodology
Tackiness Measurement
A Texture Analyzer (TA-XT2 from Textile Technologies Corp.) equipped with TA-57R probe was used for tackiness measurement. 0.1 to 0.15 cc of materials was injected onto a glass plate. The TA was set so that the probe passes through the liquid and presses it against the glass plate. Once the probe attains a 0.5 grams trigger force, the Texture Expert software begins taking measurements of the force as a function of time. The probe continues to compress the sample at the set applied force. The TA will retract once the set time delay has elapsed. The TA measures the force as it retracts from the surface. The maximum force required to pull the probe away from a material is recorded as the tackiness value of the material and is used to compare the relative tackiness of different material. A tackier material has a higher tackiness value. Three measurements were taken consecutively and the average was calculated and shown in Table 2 for some polymers and oil/polymer blends. The TA settings used in the measurement is shown in the Table 1.
For good rinsability, polymers should have a tackiness higher than 100 grams and the mixture of polymer and oil is preferably has a tackiness value higher than 20 grams, more preferably higher than 30 grams.
In-Shower Rinsability Evaluation Method
Method described below was used to evaluate rinsability of personal cleanser in the shower. A soap-based personal washing liquid such as Lux from Taiwan has a very drag wet skin feel after 3 to 4 rubbing cycle during rinsing. A synthetic-based liquid such as Taiwan Dove body wash has a slightly drag wet skin feel after 8 to 10 rinsing cycles. A cationic polymer-containing shower liquid such as U.S. Dove has a very slippery wet-skin feel after 10 to 12 rubbing cycles.
1. First wet the body under running water.
2. Stay away from the running water, apply and lather about 5 cc of liquid all over the body.
3. Stand in front of the shower and start to rinse while rubbing the chest up and down with both hands at a speed of about 1.5 to 1.8 seconds per cycle.
4. Count the times of rubbing cycle to perceive a drag feel, and determine the drag feel 2 to 3 more cycles after perceiving the initial drag. Degree of drag is rated as following

Mild moisturizing liquids with soap-like rinse feel comprising polymer/oil blend

Unilever Home and Personal Care USA, division of Conopco, Inc.


Low density semifinished product for manufacturing buoyant products, comprising a plurality of layers of closed-cell expanded material, having a specific gravity lower than that of water, the said layers being flexible and elastic and being joined together by quilting spaced so as to define between them pockets of air, characterised in that the said quilting is preferably distributed in closed patterns.

The invention concerns a low density semifinished product for manufacturing buoyant products, comprising a plurality of layers of closed-cell expanded material, having a specific gravity lower than that of water, the said layers being flexible and elastic and being joined together by means of consecutive quilting spaced so as to define pockets of air between them to increase buoyancy.
Such a semifinished product, classified in the category of xe2x80x9cnon-woven fabricxe2x80x9d, is employed mainly for manufacturing items of clothing, such as jackets, overalls, items of clothing for specific uses, for fishing, sailing, or other activities, particularly for use in marine or aquatic environments in general, and for manufacturing objects aiding in natatorial activities, as well as bags, or holders in general for use in proximity to these environments and which require protection against the risk of sinking.
Conventional items of clothing that enable a person to remain afloat are most uncomfortable and do not allow the degree of agility of movement that would be preferable when carrying out working activities, or sporting activities, or other types of activities.
Furthermore, when manufacturing buoyant products in general, to obtain holders, covers, bags, or other items, a limitation has been found consisting of the fact that it is necessary to adopt special manufacturing processes which entail considerable costs. Also, the products obtained with these processes turn out to be rigid and difficult to handle.
Examples of products having buoyant characteristics are available from the documents U.S. Pat. No. 5,267,519, FR-A-2.724.569 and, in particular, from WO-A-9422712, the last one teaching a product based on a plurality of superimposed layers.
Such prior art may be subject to further improvements with a view to eliminating the said drawbacks.
From the foregoing emerges the need to solve the technical problem of inventing a semifinished product that is suitable for manufacturing, in an extremely simple manner, buoyant products or that assist buoyancy, such as items of clothing, that are soft and easy to handle; in the case of clothing, these have to offer an adequate degree of buoyancy without excessively limiting freedom of movement.
The invention solves the said technical problem by adopting a semifinished product of the type mentioned in the preamble characterised in that the quilting is preferably arranged in closed patterns.
This considerably improves the buoyancy in water of objects made with the semifinished product, in that it creates a series of pockets in which air isxe2x80x94so sayxe2x80x94trapped, providing a more stable and long-lasting aid to buoyancy.
The closed patterns may also be obtained with cross quilting; in this case, the items of clothing manufactured with such a semifinished product have an improved wearability and are more comfortable.
The cross quilting also confers a particular resistance to mechanical stresses to the semifinished product, especially during processing, in that it keeps the layers securely joined together.
As a result of this invention it is possible to manufacture buoyant products of pleasant appearance, substantially without imposing limitations on the creative impulse of fashion designers, in that the semifinished product may substantially be processed like a fabric and may be inserted in any type of item of clothing, or accessory, without compromising the look and/or the practicality of said item.