Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/60—Sulfonium or phosphonium compounds
• • 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
  • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
• • 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
  • A61Q17/005—Antimicrobial preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00

Definitions

• This invention relates to a new class of sulfur-containing cationic antibacterial surfactant compounds. More particularly, this invention relates to sulfoxonium compounds corresponding to the following structural formula:
• R is an aliphatic radical containing from about to about 20 carbon atoms which can be saturated or unsaturated, branched or straight chain.
• R and R are each selected from the group consist ing of lower alkyl, benzyl, halogenated benzyl and alkylbenzyl, wherein the alkyl substituent contains from i to about 4 carbon atoms, and wherein X is an anion which ermits adequate solubility of the suifoxonium salt.
• Suitable examples of such anions are halide, sulfate, methosufate, p-toluene sulfonate, and nitrate radicals.
• the compounds of the present invention are characterized by a unique combination of properties including adequate solubility in water, high bacteriostatic effectiveness, substantially odorless, having low volatility, high stability, and as mentioned, exceptional mildness.
• Most prior art compounds which are structurally related to the sulfoxonium compounds of this invention do not present these combined properties.
• the crude sulfonium salts often contain small amounts of odorous thioethers which are objectionable.
• the sulfoxonium salts described herein which are prepared by alkylation of odorless sulfoxides do not present such problems.
• novel cationic compounds described herein are compatible with other detergent surfactant compounds such as anionic, cationic and nonionic surfactant compounds. This is contrary to numerous references in the prior art which uniformly warn against mixing anionics with cationics.
• An object, therefore, of this invention is to provide a new and useful class of cationic surfactant compounds.
• a further object is to provide a new class of sulfur containing cationic surfactants whose members characteristically combine high bacteriostatic effectiveness and exceptional mildness on the skin and which are also compatible with other types of surfactants.
• An additional object is to provide a new class of high molecular weight sulfoxonium antibacterial surfactants which are produced as the S-alkylation products of dialkyl sulfoxides.
• Yet a further object is to produce a new and improved bacteriostatic composition comprising an organic water soluble detergent surfactant and a cationic sulfoxonium compound produced according to this invention.
• Another object is to provide detergent compositions containing sulfoxonium compounds of the present invention.
• the compounds of this invention have the following general formula: [RRRS(O)]+X- Where R is a high molecular wei ht, saturated or unsaturated, branched or straight chain aliphatic radical having from about 10 to about 20 carbon atoms.
• R is a high molecular wei ht, saturated or unsaturated, branched or straight chain aliphatic radical having from about 10 to about 20 carbon atoms.
• suitable long chain saturated alkyl radicals used alone or in admixture there can be mentioned, as examples, decyl, dodecyl, tetradecyl, hexadecyl, and eicosanyl.
• alkenyl radicals also used alone or in admixture are decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and eicosenyl.
• R and R" can each be lower alkyl such as, for example, methyl, ethyl, propyl, butyl, amyl and hexyl benzyl, halogenated benzyl, and alkylbenzyl in which the alkyl substituent contains from 1 to about 4 carbon atoms.
• the nature of the anionic substituent, X, is discussed later on in this specification.
• novel compounds described herein are prepared, for example, by condensing an R,R dialkyl sulfoxide, with a suitably active R"X alkylating agent.
• the end result of the reaction is that the alkyl radical of the alkylat ing agent attaches to the sulfur atom of the sulfoxide and the anionic group X of the alkylating agent becomes the anionic constituent in the sulfoxonium product.
• These new suifoxonium compounds bear a general similarity to quaternary ammonium compounds. As will be pointed out, however, the properties of the quaternary ammonium compounds diifer materially from the compounds of this invention.
• the sulfoxide starting material can be obtained by oxidizing a dialkyl sulfide or thioether according to the following equation:
• oxidizing agent various agents can be employed such as hydrogen peroxide, nitric acid and nitrogen oxides such as nitrogen tctroxide.
• the coordinate link between the sulfur and the oxygen is a semipolar double bond, unlike that of carbonyl, (3:0, grouping. Accordingly, an arrow is used to identify this feature in place of a double bond.
• R and R are each as described earlier in this specification.
• the foregoing is not intended as a limitation imposed upon the method of preparing the new sulfoxonium compounds.
• a sulfoxide such as R'RS(O) is alkylated by RX, with R being a long chain saturated or unsaturated straight or branched chain aliphatic radical containing from about to carbon atoms, provided, of course, that RX possesses sufficient activity as an alkylating agent.
• the preferred embodiments of the present invention include compounds of the foregoing general formula in which R is a high molecular weight, long chain aliphatic radical, saturated or unsaturated, branched or straight chain containing from 10 to 20 carbon atoms.
• R is a high molecular weight, long chain aliphatic radical, saturated or unsaturated, branched or straight chain containing from 10 to 20 carbon atoms.
• R contains from 12 to 18 carbon atoms in the alkyl chain corresponding to chain lengths occurring, for example, in natural fatty materials.
• chain lengths containing below 10 carbon atoms are obtained, it has been discovered that the surface active properties of the compound tend to diminish, and when the chain length exceeds about 20 carbon atoms, a solubility problem is presented due to the increasing insolubility of the compounds.
• R and R" can be either lower alkyl radicals, e.g. those containing from 1 to 6 carbon atoms, benzyl, halogenated benzyl and alkyl benzyl radicals containing from 1 to about 4 carbon atoms in the alkyl substituent. Preferred compounds are obtained when R and R" are each selected from methyl, ethyl, propyl, butyl, benzyl, chlorinated benzyl and methylbenzyl radicals.
• anionic portion is thought to be immaterial so far as the bacteriostatic properties of the new compounds are concerned. Accordingly, virtually any organic or inorganic anion which permits adequate solubility of the sulfoxonium salt may be found suitable,
• anionic groupings which have shown value in the new compounds are halides, (e.g. chloride, bromide, iodide, fluoride), sulfates, methosulfate, p-toluene sulfonates, and nitrates.
• decyl dimethyl sulfoxonium iodide dodecyl dimethyl sulfoxonium iodide tetradecyl dimethyl sulfoxonium iodide hexadecyl dimethyl sulfoxonium iodide octadecyl dimethyl sulfoxonium iodide dodecenyl dimethyl sulfoxonium iodide decyl methyl benzyl sulfoxonium chloride dodecyl methyl benzyl sulfoxonium bromide dodecyl methyl benzyl sulfoxonium methosulf'ate dodecyl methyl o-chlorobenzyl sulfoxonium methosulfate dodecyl methyl p-methylbenzyl sulfoxonium methosulfate dodecyl methyl p-butyl benzyl sulfox
• the corresponding octadecyl compound can be prepared in essentially the same manner using equivalent quantities of reactants and the resulting octadecyl dimethyl sulfoxonium methosulfate possesses surface activy and bacteriostatic properties.
• Related compounds having similar properties and containing ten carbon atoms or a carbon chain length intermediate the C 43 range can also be prepared by following this example.
• this material was used in the form of an aqueous suspension which could be assayed by direct titration with standard alkylbenzene sulfonate solution.
• a dry sample of the product indicated 94% purity on titration, and has surface active and bacten'ostatic properties.
• Dodecyl methyl benzyl sulfoxonium merhosulfate Dodecylmethyl benzyl sulfoxonium methosulfate was prepared by bringing together 17.9 grams (0.058 mole) of dodecyl benzyl sulfoxide (M.P. 79-81 C.) and 14.6 grams (0.116 mole) of dimethyl sulfate and following the procedure outlined previously in Example I. Isolation of the dodecyl methyl benzyl sulfoxonium methosulfate yielded a product assaying 100% pure by titration. The product had surface active and bacteriostatic properties.
• the alkylation reaction generally is conducted on an equimolar basis. To insure completion, an excess of the alkylating agent can be used, especially if it is one of relatively lower reactivity.
• the temperature during the alkylation usually is between 80 and 120 C. and at atmospheric pressure. With the less reactive alkyl halides use of pressure vessels and of temperatures between 100- 150 are preferred.
• the sulf-oxonium compounds described herein have been discovered to be valuable bacteriostatic agents.
• the antibacterial activity of these compounds was determined by conducting Standard Tube Dilution Tests. Such tests are conducted in vitro and consist essentially of preparing test tubes of a standardized broth medium containing serial dilutions (diminishing concentrations) of a compound being tested, inoculating each tube with a preselected microorganism and after an incubation period, determining the growth of bacteria in each tube.
• the broth medium employed in these assay tests was an FDA phenol coefficient test nutrient broth. Stock solutions of the test product were then prepared in sterile distilled water. Serial dilutions were prepared of the test stock solution and then placed into the contact tubes containing the nutrient broth.
• the contact tubes were then inoculated with bacterial organisms prepared in the following manner.
• a Washed 24 hour broth culture of gram-positive Staphylococcus aureus ATCC 6538 was standardized to a predetermined optical density, by dilution with sterile FDA nutrient broth, to contain about 500,000,000 organisms per milliliter.
• Onetenth milliliter quantities of the standardized inoculum were added per each previously prepared contact tube.
• Gram-negative Escherichia coli ATCC 26 cultures were prepared as inoculum in a similar manner.
• the inoculated tubes were shaken thoroughly, allowed to stand 10 minutes for air bubbles to disperse, then read for a zero-hour turbidity value using a Coleman Junior Model 6A spectrophotometer set at a wave length of 610 millirnicrons.
• alkyl benzene sulfonate sodium dodecylbenzene sulfonate
• ABS organic anionic surfactant compound
• the alkyl benzene sulfonate employed was the sodium salt of the sulfonic acid derived from the condensation product of benzene and propylenes having from 9 to about 15 carbon atoms and averaging 12 carbon atoms.
• Alkyl benzene sulfonate is probably one of the most widely used synthetic detergent surfactants and one which is regarded as having relatively good bacteriostatic efiectiveness. Compounds which evidence substantially greater antibacterial effec tiveness than alkyl benzene sulfonate are considered in the art to be good bacteriostats and as such are always in great demand for manifold useful purposes.
• breakpoint values are averages of the three contact tubes prepared at each serial dilution.
• the members of the new class of compounds possess marked bacteriostatic effectiveness as each was found to be superior to alkyl benzene sulfonate.
• the compounds of this invention are especially potent against gram-positive type of organisms such as Staphylococcus aureus ATCC 6538. This bacteria is one most commonly found on human skin and, in the art, it is regarded as being representative of the entire field of gram-positive types of microorganisms.
• the new compounds described herein are seen to be less effective than against the grampositivc microorganism, but in any event, they are substantially superior to alkyl benzene sulfonate.
• the compounds of this invention In view of the general structural similarity between the compounds of this invention and quaternary ammonium cationic surfactants, they might be expected to share common physical properties. Therefore, since the quaternary ammonium cationics have a rather harsh and irritating effect upon human skin, it should be anticipated that the instant sulfoxonium compounds would behave similarly. Unexpectedly, however, the compounds prepared according to this invention have been discovered to be extremely mild on human skin. This exceptional behavior is an extremely desirable and useful property since it affords compounds offering a unique blend of properties, i.e. bacteriostatic effectiveness and excellent mildness characteristics.
• guinea pig immersion test In these tests, groups of three guinea pigs which had their abdomens shaved were immersed up to the thorax in a 2% aqueous solution of the test material. The bath was maintained at a constant temperature of about 37 C., and the immersion periods were for 4%. hours at the same period of time on each of three consecutive days. The readings were made about 72 hours after the conclusion ofv the third exposure.
• Each pig after exposure to the bath is assigned a relative skin grade value based on a rangeof 1 to 10. Within this range increasing mildness is represented by higher numerical values. Accordingly, a value of 1 indicates bleeding and skin fissures while a value of represents the ultimate in mildness.
• the new sulfoxonium compounds offer a still further unexpected property; namely, that the members of this new series of sulfoxonium compounds retain their antibacterial properties when combined with cleaning compositions such as fatty acid soaps and organic synthetic surfactant detergent formulations. Very frequently antibacterials lose their effectiveness in the presence of such materials with which they are combined.
• the method consists of direct inoculation of the treated fabric with suitable test organisms and the subsequent enumeration of growing colonies which develop when the fabric is implanted and incubated in a nutrient medium.
• Onesquare-inch fabric swatches are treated with a bacteriostatic compound in any desired manner.
• the fabrics may be treated by a conventional textile finishing padding process.
• the fabric was treated with the antimicrobial agent via a laundering cycle using a detergent formulation containing the bacteriostatic compound being tested.
• the dried swatches are next planted with the inoculated surface up onto a solidified sterile agar medium in previously prepared Petri dishes.
• An overlay of nutrient is then made by pouring 0.2 ml. to 0.3 ml. of cooled (42-45 C.) molten agar medium over the fabric. This embeds the cloth under a thin film of agar nutrient. It is of paramount importance that a thin film be used and that it be applied very carefully to avoid flushing off those organisms loosely fixed to the fabric.
• the plates are incubated at 37 C. for about 48 hours. Colony counts are then made by means of a low-power (23x) dissecting microscope, using a wire grid with spacings of 3 mm. to facilitate counting of the colonies. The entire cloth swatch is counted when less than several hundred colonies develop. However, when the colony density is heavy, five 9 mm. areas are counted, a factor of 71 is applied to the average value to obtain the colony count per square inch of cloth. In most experiments, six replicate swatches are inoculated with each organism.
• Staphylococcus aureas ATCC 6538 was used as a representative of the gram-positive class of organisms and Escherichia coli ATCC 26 was used as a representative of the class of gram-negative organisms. Both of these are commonly found among the microorganisms on human skin.
• EXAMPLE 8 The foregoing procedure was followed in which the detergent composition used during the laundering cycle of the fabric swatches was a standardized detergent washing formulation in which the active organic anionic detergent surfactant compound was sodium tallow alkyl glyceryl ether sulfonate.
• the tallow alkyl glyceryl ether sulfonate was prepared according to the method described in Whyte Patent 2,989,547, issued June 20, 1961.
• the composition of the detergent composition was about 17.5% tallow alkyl glyceryl ether sulfonate, 50.0% sodium tripolyphosphate, 6% sodium silicate 14.2% sodium sulfate, the balance being Water. All percentages are by weight.
• Fabric swatches were first washed in 20 milliliters of a .25% washing solution of the above composition. They were then dried, placed into the prescribed drying chamber, and inoculated with 0.1 ml. solution of a diluted Staphylococcus aareas ATCC 6538. After drying, the swatches were implanted on a solidified sterile agar medium in a previously prepared Petri plate in the following manner. The dried swatches were placed on the solid agar medium and an overlay of nutrient having a thickness of approximately 0.1 mm. was made by pouring 0.2 to 0.3 ml. of cooled (4245 C.) molten sterile agar medium over the fabric.
• the cloth thus became embedded between a thin film of nutrient base agar and the solidified sterile agar medium in the Petri plate.
• the plates were incubated at 37 C. for 48 hours after which the colony counts were made by means of a low (23x) dissecting microscope, using a wire grid with spacings of 3 mm. (stainless steel wire 0.008 in. in diameter) to facilitate counting the colonies.
• Six replicate swatches were inoculated with each organism and an average colony growth determined. To obtain a control figure in the present test, the above described standardized washing preparation was used, and a colony count of 3500 was obtained.
• bacteriostatic compound of this invention was employed in conjunction with the detergent preparation.
• 1 milligram of dodecyl methyl benzyl sulfoxonium methosulfate was used as the 'bacteriostatic compound to be tested. This amounted to 2% by Weight of the detergent composition. After inoculation and incubation, a colony count of about 1300 was determined, down from about the 3500 figure obtained when no bacteriostatic agent was employed.
• the colony count for the detergent preparation alone was about 3800.
• the count factor dropped to about 1900, an improvement in growth control of the gram-negative organism of about 50%.
• comparable results were obtained. It is generally agreed in the art that the gram-negative bacteria are more dimcult to control than the gram-positive organisms.
• the gram-negative organisms were indeed more resistant than the gram-positive, yet compatibility is still present between the anionic active and the novel cationic bacteriostatic sulfoxonium compound, dodecyl methyl benzyl sulfoxonium methosulfate.
• Example 9 The procedure of Example 8 was repeated using as in the first instance the same gram-positive organism, Staphylococcus aureus ATCC 6540. Again, three separate growth control determinations were made; once with a standardized detergent composition, again with the same composition used in Example 8 (except as noted below) in combination with 2% of a compound of this invention, and a third time with the same preparation in combination with 1% of the same new compound.
• the active anionic detergent surfactant in the detergent composition of this example was 17.5% sodium tallow alkyl sulfate in place of the 17.5 sodium tallow alkyl glyceryl sulfonate used in the standardized detergent composition of Example 8. Otherwise the laundering preparation was exactly as in Example 8.
• the colony count was about 3500.
• the colony count was reduced to about 1380, and at 1% concentrations the colony count was only about 1610.
• EXAMPLE 10 The organic anionic detergent active in the standardized detergent composition in this experiment was 17.5 sodium coconut alkyl sulfate. Against gram-positive Staphylococcus aurcus ATCC 6538, the detergent composition produced a colony count of 3500. The addition of 2% dodecyl methyl benzyl sulfoxonium methosulfate reducedthe count almost in half, to 1890. Surprisingly, somewhat greater improvement was obtained with only 1% of the agent since the colony count was 1720.
• EXAMPLE 1 1 Dirnethyl dodecyl amine oxide was employed at 17.5% concentration as a nonionic active in the standardized detergent formulation used in Example 8. The representative compound of this invention remained as dodecyl methyl benzyl sulfoxonium methosulfate.
• the standardized detergent composition resulted in a colony growth of 3500 against gram-positive Staphylococcus aureus, ATCC 6538.
• Addition of 2% dodecyl methyl benzyl sulfoxonium methosulfate reduced the colony growth to 750 and addition of 1% provided a colony count of 770.
• EXAMPLE 12 A detergent composition was prepared in which the active was Armeen 16D at 17.5% of the standardized composition in Example 8.
• Armeen 16D is a cationic surface active agent which is a primary aliphatic amine havings as its formula RNH where R is a normal aliphatic radical derived from naturally occurring fatty acids. Due to a natural raw material source, Armeen 16D contains a mixture of long-chain components.
• the primary amine content of Armeen 16D breaks down to be tetradecyl 13%, hexadecyl 76%, and octadecyl 11.5
• the sulfoxonium compound in this example was dodecyl methyl benzyl sulfoxonium methosulfate and behavior against gram-positive and gram-negative microorganisms was again evaluated.
• the detergent composition alone resulted in a colony Count of 2520 using Staphylococcus aureus ATCC 6538, as compared with a count of 155 obtained when the detergent composition was combined with 2% by weight of dodecyl methyl benzyl sulfoxonium methosulfate.
• a count of 1320 was obtained with the detergent formulation combinedwith 1% of dodecyl methyl benzyl sulfoxonium methosulfate.
• EXAMPLE 13 A zwitterionic surfactant compound, 3 (dodecylammoniuin) propane-l-sulfonate was incorporated as the active surfactant in the standardized detergent composition of Example 8, replacing the 17.5% tallow alkyl glyceryl sulfonate therein. With dodecyl methyl benzyl sulfoxonium methosulfate as the bacteriostatic compound, the series of experiments were duplicated as before, both against gram-positive and gram-negative organisms.
• the basic formulation alone gave a colony count of 2790 when the fabrics were inoculated with Staphylococcus aueras ATCC 6538.
• 2% docecyl methyl benzyl sulfoxonium methosulfate was added to the washing formulation, the colony count dropped to only 170.
• the colony count rose to about 1800, which is still substantially below the figure achieved with the initial standardized formulation in this example.
• the washing composition was 17.5% active, 45% sodium dodecyl (tetrapolypropylene) benzene sulfonate and 55% sodium tallow alkyl sulfate, 50% sodium tripolyphosphate, 6% sodium silicate, 13.4% sodium sulfate, 10% water and the remainder miscellaneous ingredients such as perfumes, etc.
• EXAMPLE 15 An excellent cleaning composition was obtained by taking another commercial laundering formulation and using it in conjunction with a compound of this invention.
• the formulation comprised essentially 17.5% sodium dodecyl (tetrapolypropylene) benzene sulfonate, 50% sodium tripolyphosphate, 6% sodium silicate, 13.4% sodium sulfate, 10% water and the balance miscellaneous ingredients.
• the composition just described yielded a colony count of about 3500.
• the count fell to 900, reflecting excellent control of the growth of the microorganism.
• the colony count was about 1353, a substantial improvement over the 3500 13 growth figure scored by the commercial washing formula used alone.
• EXAMPLE 16 A product comprising 14% sodium dodecyl (tetrapolypropylene) benzene sulfonate, 47.7% sodium tripolyphosphate, 19.1% sodium sulfate, 9.7% sodium silicate, 1.6%
• EXAMPLE 17 The tests were also extended to bar soap formulations to determine the usefulness in such cases. The results were excellent. No problems were encountered in using bar soap formulations along with the compounds of this invention. The exceptional mildness of these compounds is another advantage which they lend to such a formulation.
• a milled toilet soap comprising 83.5% of an 80% tallow: 20% coconut sodium soap, 13.0% volatiles, 2.0% unsaponifiables, and the remaining minor amounts of miscellaneous ingredients, was used as a bar soap formula.
• Examples 8 through 17 were repeated in almost identical fashion. The only variation was that a different member of the new series of sulfoxonium compounds was selected, namely, hexadecyl methyl benzyl sulfoxonium methosulfate. The Quinn procedure discussed immediately preceding Examples 8 through 17 was followed explicitly.
• the compounds of this invention including those prepared by Examples I through VII, can be employed in all types of detergent compositions, as for example, liquid, bar or granular compositions.
• Such detergents may contain varying amounts of these new compounds but generally there can be present from 1% to about 20% of the new compounds per total weight of the detergent composition.
• compositions of course, various colors, antioxidents, perfume, water softeners, and other materials can be used without affecting the desirable properties of the new class of sulfoxonium surfactant materials.
• a bacteriostatic composition consisting essentially of a detergent surface active agent selected from the group consisting of anionic, nonionic and cationic surfactants and from 1% to about 20% of a high molecular weight sulfoxonium compound corresponding to the structural formula:
• R is an alkyl radical containing from 10 to 20' 16 the sulfoxonium compound is dodecyl methyl benzyl sulfoxoniurn methosulfate.
• sulfoxonium compound is dodecyl methyl o-chlorobenzyl sulfoxonium methosulfate.
• sulfoxonium compound is dodecyl dimethyl sulfoxonium methosulfate.

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  • BE BE630489D patent/BE630489A/xx unknown
• 1964
  • 1964-11-16 US US411639A patent/US3352786A/en not_active Expired - Lifetime

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