Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
• • 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
  • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/59—Mixtures
  • A61K2800/596—Mixtures of surface active compounds

Definitions

• An aqueous shampoo composition of improved foaming and lathering power includes a major proportion of aqueous solvent medium and minor proportions of higher fatty alcohol sulfate and of a l-hydroxy-lower alkyl, 2- higher alkyl imidazoline, at a slightly basic pH.
• This invention relates to a shampoo of improved foaming and lathering characteristics, which is also of satisfactory high viscosity and condition the hair well. It comprises an aqueous solution of a salt of higher fatty alcohol sulfuric acid and a substituted imidazoline in an aqueous medium, at a slightly basic pH.
• shampoos for use on the human hair based only on higher alcohol sulfates are often not satisfactory.
• foam builders or stabilizers, thickeners, and conditioning agents such as lipophilic materials which may be deposited to some extent on the hair to replace the removed oils.
• substituted imidazolines such as l-beta-hydroxylower alkyl, 2-higher alkyl imidazolines, are known surface active materials, the salts of which are of higher water 'solubilities than the free amines.
• the substituted imidazolines of this type are unsatisfactory as the sole or principal detersi ve constituents of shampoos intended for use on human hair. They often behave much like cationic compounds and therefore, are generally considered to be incompatible with anionic surface active agents.
• an aqueous shampoo can be made comprising a higher alcohol sulfate detergent salt and a substituted imidazoline, such as 1- beta-hydroxy-lower alkyl, Z-higher alkyl imidazoline.
• a substituted imidazoline such as 1- beta-hydroxy-lower alkyl, Z-higher alkyl imidazoline.
• Such shampoo in addition to possessing excellent detersive powers, is of improved foaming and lathering characteristics, even when compared to the best commercially available foaming agents, the higher acyl di-lower alkanolamides and the higher alkyl di-lower alkyl amine oxides.
• the shampoos made are also af desirable increased viscosity and satisfactorily condition the hair, minimizing dryness and electrostatc effects, giving good wet combing characteristics and improving the lustre of the hair.
• an aqueous shampoo composition of improved foaming and lathering power comprises a major proportion of aqueous solvent medium, a minor proportion of a higher alcohol sulfate and a minor proportion, less than half the higher alcohol sulfate content, of a l-hydroxylower alkyl, Z-higher alkyl imidazoline, at a pH of from about 7.5 to 9.5.
• the higher alcohol sulfate detergent is a fatty alcohol sulfate, e.g., triethanolamine lauryl sulfate
• the substituted imidazoline is l-betahydroxyethyl
• Z-higher alkyl imidazoline in which the higher alkyl portion is fatty, preferably a mixture of long, straight-chain hydrophobe groups derived from coconut oil
• the pH is from 7.6 to 8.4
• the composition includes from 15 to 25% of the alcohol sulfate, from 1 to 10% of the substituted imidazoline and 65 to 84% of the aqueous solvent medium, which is essentially water.
• the higher alcohol sulfate detergent constituent of the invention includes various compounds of this type which are sufficiently water soluble, very effective in cleaning human hair and compatible with the present imidazolines.
• the higher alkyl portion is preferably lauryl or myristyl or mixtures of higher alkyls, preferably straight chained 'or fatty alkyls which average about 12 to 14 carbon atoms per group.
• various mixtures of such alkyls substantially all of which are within the carbon content range of 8 to 18, are useful, those which are either pure lauryl or myristyl or which are mixtures of alkyls corresponding to the higher fatty alcohols derivable from natural oils, such as coconut oil, are preferred.
• the alkyl mixture derived from coconut oil is designated as cocyl herein and contains about 8% C 7% C 48% C 18% C14, 9% C and 10% C Generally, such alkyls will have an even number of carbon atoms and will be terminally joined to the sulfate portion of the molecule but groups of odd number of carbon atoms may also be used. Also, a proportion of the higher alkyl content may be non-terminally sulfated but usually this is only a minor proportion, preferably less than 10%.
• the salt-forming portions of the higher alkyl sulfates may be any of the various suitable bases generally employed to make such detergents that are used in shampoos.
• sodium, potassium. magnesium and ammonium ions have been so utilized, the most highlv preferred compounds, which exhibit a surprisingly effective foamand lather-enhancing activity, in addition to increasing viscosity and improving conditioning properties.
• the lower alkanolamines are the monoand dialkanol-amines.
• the trialkanolamines are considered far superior, having exceptionally good improving eifects on the shampoos with respect to the properties previously mentioned.
• the lower alkanolamines in which the alkyl is of l to 4 carbon atoms, are useful in the practice of this invention and the most preferred are those of 2 to 3 carbon atoms, e.g., ethyl, propyl and isopropyl.
• Exemplary of the best higher fatty alcohol sulfates for the practice of this invention are triethanolamine lauryl sulfate; triisopropanolamine lauryl sulfate; triethanolamine myristyl sulfate; triethanolamine higher fatty cocyl (cocyl being a mixture of higher alkyls obtainable from coconut oil) sulfate; tri-isopropanolamine cocyl sulfate; and triethanolamine mixed lauryl-myristyl sulfate.
• alcohol sulfate detergents that may be used, preferably in mixture with those previously mentioned, are the corresponding dialkanolamine and monoalkanolamine salts, e.g., diethanolamine lauryl sulfate; monoethanolamine myristyl sulfate; monoisopropanolamine cocyl sulfate; and di-tbutanolamine cocyl sulfate.
• dialkanolamine and monoalkanolamine salts e.g., diethanolamine lauryl sulfate; monoethanolamine myristyl sulfate; monoisopropanolamine cocyl sulfate; and di-tbutanolamine cocyl sulfate.
• alcohol sulfate salts such as the ammonium, sodium, potassium and magnesium salts, also usually as minor proportions of the shampoo alcohol sulfate content.
• these compounds are such as magnesium lauryl sulfate, ammonium lauryl sulfate, sodium cocyl sulfate and potassium cocyl sulfate.
• the substituted imidazolines which coact with the alcohol sulfates to produce improved shampoo compositions are those in which substitution is by a hydroxy-lower alkyl group and a higher alkyl, which substituents are on a nitrogen and a carbon of the imidazoline.
• the particular substituted imidazolines which have been found to produce greatly improved foaming, lathering, thickening and conditioning properties are those wherein substitutions are at adjoining ring atoms, particularly the 1- and 2- atoms.
• l-hydroxy-lower alkyl, Z-higher alkyl imidazolines produce the effects mentioned.
• the substituted imidazolines form salts, they will be discussed herein as if this is not the case, especially because the present compounds are employed primarily in basic solutions and salt formation usually occurs principally by reaction with acidic compounds, such as hydrochloric acid.
• acidic compounds such as hydrochloric acid.
• many of the imidazoline salts, such as those formed with higher fatty acids, alkyl aryl sulfonic acids or similar surface active or detergent acids are often water insoluble and would not be useful to make improved shampoo compositions such as those of the present invention.
• the free base form of the substituted imidazoline may also normally be considered to be insoluble in water, it has been found that it is sufficiently soluble in aqueous detergent solutions, such as the alcohol sulfates previously mentioned, to be useful in shampoos and to improve their properties in the ways mentioned. Solubilities of these compounds in such solutions are increased by having the free hydroxyl group on the lower alkyl in the 1-position and having the carbon atom content of the alkyl substituent in the 2-position sufiiciently low to produce satisfactory solubility.
• the hydroxyalkyl substituent on the l-nitrogen of the ring is a hydroxy-lower alkyl, usually of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms and most preferably of 2 to 3 carbon atoms, e.g., hydroxyethyl.
• the hydroxyl group it is preferred for the hydroxyl group to be terminally located on the alkyl substituent, as far away from the nitrogen as possible, in some cases intermediate positions will also be active.
• straight chain alkyl groups are also most useful, in some cases branched chain hydroxyalkyl groups may comprise a part or all of the substituent on the l-nitrogen.
• the alkyl substituent at the 2-position is a higher alkyl of 7 to 17 carbon atoms, which is preferably a normal alkyl and which is terminally joined to the 2-carbon. In some cases branching and non-terminal joinders may be useful. For best water solubility, the carbon content and chain length of the higher alkyl substituent may be comparatively low. Thus, it is preferred to employ such higher alkyl groups containing from 7 to 13 carbon atoms, if pure materials are used, with the 11 carbon atom alkyl being the best.
• mixtures may be employed, including those obtained from fatty acids derived from natural oils, such as coconut oil. These acids generally have most of the acyl groups of from 8 to 18 or 10 to 16 carbon atoms, with the constituents in larger proportions being those of 12 to 14 carbon atoms. It will be noted that the fatty acids used to make the substituted imidazolines, as by reaction with an N-substituted ethylene diamine, are of one carbon atom more than the alkyl substituents on the imidazoline. See p. 142 of the text Surface Active Agents and Detergents, vol. II (1958), by Schwartz, Perry and Berch.
• the best materials are those which are inorganic and which comprise salts of strong acids and bases, such as those of sulfuric acid, hydrochloric acid, hydrobromic acid or equivalent or similar acids and sodium hydroxide, potassium hydroxide, ammonium hydroxide, or similar bases.
• the chlorides are preferred, especially the alkali metal chlorides, e.g., sodium chloride, potassium chloride.
• the presence of small proportions of such materials increases the viscosities of alcohol sulfatesubstituted imidazoline shampoos or allow a reduction in the content of substituted imidazoline, with the obtaining of a similar viscosity despite omission of some of the active ingredient.
• the solvent medium employed may be water, preferably deionized water or water low in hardness ions, e.g., containing less than 50 parts per million of such ions, calculated as calcium carbonate.
• active and adjuvant materials e.g., perfumes, viscosity modifiers, coloring agents
• organic solvents such as alcohols, preferably the lower monohydric alcohols of 2 to 4 carbon atoms, e.g., ethanol, may be employed and it will sometimes be desirable also to use dihydric and trihydric alcohols of 2 to 6 carbon atoms, e.g., ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol.
• Other known solvents which are useful in shampoo compositions may be included, providing that they have no unacceptable adverse etfects on the final products of this invention.
• Most shampoos contain minor proportions of adjuvants to modify their properties and to improve acceptance by the consumer.
• the present shampoos are of desirable cleaning, foaming, lathering and conditioning properties and therefore do not require additives to produce these characteristics, they may still be benefited by the use of certain compatible adjuvants for other purposes and, in some cases, the product may even be improved by suplemental effects of adjuvants to modify the properties of the lather and further to condition the hair.
• coloring agents including water soluble dyes and water dispersible pigments, ultraviolet-absorbing chemicals; fluorescent dyes; perfumes, preservatives; hydrolyzed animal protein conditioning agents; pH-adjusting materials, e.g., sodium hydroxide, sodium bicarbonate, buffers; lather and foam modifiers, e.g., dimethyl lauryl amine oxide; hair conditioners, e.g., lauric myristic diethanolamide, free oils, monoglycerides; detergents, e.g., nonionic detergents such as the block copolymers of ethylene and propylene oxides (Pluronics); bactericides; fungicides; bleaches; and sequestering agents, e.g., sodium salts of ethylene diamine tetraacetic acid and alkali metal salts of nitrilotriacetic acid.
• coloring agents including water soluble dyes and water dispersible pigments, ultraviolet-absorbing chemicals; fluorescent dyes; perfumes, preservatives; hydroly
• the pH of the invented aqueous shampos will usually be slightly alkaline. It has been found that acidic pHs favor an interaction between the alcohol sulfate detergent constituent and the substituted imidazolines. Thus, pHs will be at least 7 but, to prevent irritation of the scalp, will be held to less than 11. Generally, the pH will be from 7.5 to 9.5, preferably from 7.6 to 8.4 and most preferably will be about 8. The pHs of water dispersions of the various substituted imidazolines are usually over 11, making them generally unacceptable as shampoo constituents unless the pH is lowered.
• trialkanolamine higher alkyl sulfate has the desirable effect of moderating the pH of the substituted imidazoline and the alcohol'sulfate additionally aids in solubilizing the imidazoline. Furthermore, the desirable hair conditioning, foaming, lathering and thickening properties of the described compositions are evidenced I at the mentioned pHs.
• pH adjustment may be effected by using the desired proportions of trialkanolamine alkyl sulfate and substituted imidazoline, as will be described hereafter, or acids, bases or buffering agents may be utilized, for such purpose.
• the higher alcohol sulfate which is preferably a trilower alkanolamine alcohol sulfate, to be present in an effective cleansing proportion, generally constitutes a minor proportion, from 8 to 40% of the final shampoo composition, preferably from 10 to 30% and most preferably from to thereof.
• shampoos will generally be too concentrated and the desired effects of the compositions may not be obtained to the greatest extent.
• detergency is diminished and solubilizing effects on the substituted imidazolines not sufficient to have those compounds exert their beneficial effects to the de- I sired extent.
• the substituted imidazolines of the said l-hydroxylower alkyl, Z-higher alkyl imidazoline type usually constitute 10% of the shampoo, preferably from 1 to 8% and most preferably from 2 to 5% thereof. In such proportions they can be satisfactorily solubilized and will have their desired thickening, foaming, lathering and conditioning effects on the alcohol sulfate shampoos. Normally, the contents of the mentioned substituted imidazolines will be less than half of the proportions of the higher alcohol sulfate constituents present. Of course, proportions of the imidazolines used will be adjusted, de-
• the electrolyte salt present to aid in increasing the shampoo viscosity, will usually be in a proportion less than that of the l-beta-hydroxy-lower alkyl, Z-higher alkyl imidazoline present and will generally 'be from 0.4 to 10%, preferably from 0.9 to 8% and most preferably from about 1 to 6% of the shampoo. In such proportions the electrolyte effects a significant thickening action on the shampoo, while not adversely affecting clarity or solubility of the alcohol sulfate and the substituted imidazoline. Neither is it insolubilized by the presence of such materials, the organic solvent and adjuvants.
• the solvent system will normally comprise a major proportion of the shampoo, except in some borderline cases wherein paste, cream or solid shampoos are made.
• the solvent medium will be the major component, generally comprising from 51 to 90% of the shampoo and preferably from 65 to 84% thereof.
• the solvent medium will be at least water and the balance Will be 1 to 10% a lower monohydric alcohol of 2 to 3 carbon atoms, but may also include glycerol, glycols and equivalent solvent materials.
• the proportions of the various solvents and components will be chosen for best compatibility and desired solvent effects with the other shampoo constituents.
• the various adjuvants previously mentioned may be present in the shampoos in proportions from 0 to 10% each but normally the amounts will be sufficiently low so that the total proportion of adjuvants is 10% or less of the shampoo, preferably 5% or less thereof.
• Each individual constituent will preferably comprise less than 5% of the shampoo and most often will be less than 2% thereof.
• the present shampoo compositions may be made in any suitable form, as clear liquids, solutions, lotions, pastes, gels or solids, but the liquids, especially the clear liquids, are preferred.
• the shampoos may be made by suitably blending the various constituents by any generally accepted technique for making such compositions.
• the alcohol sulfate will be dissolved in a portion of the Water
• the substituted imidazoline will be dispersed in another portion of water, sometimes with some additional solvent present
• the various adjuvants, especially those which are considered to be lipophilic will be dis persed in a different portion of the solvent medium, preferably with a solubilizing proportion of a suitable solvent included.
• the imidazoline and alcohol sulfate portions will be blended together, with agitation, and possibly, With some heating to solubilize the constituents better. Generally, however, the temperature will not be raised over 60 C. After cooling of such mixture or solution, the solvent-water medium containing adjuvants will be added to it. Heating will be avoided, if possible. In some circumstances, some of the adjuvants may accompany either the alcohol sulfate or imidazoline constituent, rather than being initially blended with the other additives.
• the shampoos may be employed as shampoos normally are, usually being applied in two treatments to the hair, the initial application being to remove gross amounts of oils, sebum, dirt, hardness ions, lacquers and hair treatment chemicals and other materials, and the second application being to remove balances of such materials and to deposit conditioning agent from the shampoo on the hair.
• To make a lather from 1 to 50% by weight of shampoo may be employed with water, preferably Warm water, and usually from 5 to 30% and most preferably from about 8 to 25% of the shampoo will be used. This results in a thick cleansing and conditioning lather which helps to float away the various undesirable materials from the hair and yet, leaves it sat isfactorily conditioned and not unduly dry or electrostatic.
• the advantages of the present shampoos were alluded to above, especially with respect to the superiorities of the substituted imidazolines over comparable additives mentioned earlier. They are of improved viscosity, foaming, lathering and haid conditioning powers, comparable to the best agents for such purposes previously discovered. They are often superior to the higher fatty acid di-lower alkanolamides and higher fatty alkyl dimethyl amine oxides.
• the substituted imidazolines and the alcohol sulfates both exert their cleansing effects and the alcohol sulfates help to solubilize the substituted imidazolines. Despite the insolubility of the imidazolines in water, they are active in the present shampoos and do not adversely interact with the higher alkyl sulfates.
• compositions are compatible with various adjuvants for other purposes.
• the washed hair is easy to control, (manageable) and is not dry, brittle, frizzy or susceptible to flyaway due to the presence of electrostatic charges.
• the cleaning, lathing and conditioning properties are obtainable despite the presence of comparatively large amounts of greases, oils, sebum or other deposits on the hair being washed.
• the above composition is prepared by dissolving the triethanolamine lauryl sulfate in half of the combined solution of water and alcohol and the substituted imidazoline is dispersed in the remaining half of such solution, after which the two are admixed at room temperature.
• a clear shampoo is obtained, with a pH of 7.8, without the addition of any pH modifier or buffer.
• the shampoo produced is of sparkling appearance and shows no insoluble residue or dispersed particles. It is stable for over one year and the constituents do not settle out in that time.
• the shampoo When employed to shampoo the hair of human sub jects with normal, dry or oily hair and skin, whether brunette or blonde, the shampoo gives excellent cleaning, removing lacquers and residues from hair sprays, sebum, oil, soap film, dirt and other deposits on the hair and leaving it shining clean. Yet, the hair is not unduly dry and exhibits very little static or fiyaway properties. It is readily manageable, combs easily, even when wet, and possesses an attractive lustre after drying.
• alkyl sulfate of this invention At 20% concentration, corresponding more to the higher lathering concentrations, it is clearly superior, showing a 25% improvement in foam volume and about a 40% increase in the time in which the foam remains stable.
• Such results are consistent with in vivo test results on dirty hair being shampooed. Similar results are also obtainable when the load of synthetic sebum is increased or decreased, within the range of from 0.5 to 5% of the sum of wash water and shampoo, instead of the 3% load employed in the present tests. Similarly, the presence of good wet combing, dry hair lustre and low static properties of the shampoo, as shown by in vivo tests, is verified by controlled in vitro tests on human hair.
• the shampoos are thickened even more than observed with the above formulas and the desirable conditioning properties, etc., are similarly obtained.
• the thickening efiect noted with the above formulas, without additional electrolyte salt, is about the same as that observed with good thickening agents, such as lauric myristic diethanolamide.
• ad'juvants such as thickeners, e.g., sodium carboxymethyl cellulose; perfumes; dyes; dispersible pigments; other detergents; additional solvents; stabilizers; sequestrants; and pearlescent materials are also present, similar improvements in foaming, lathering and conditioning powers, plus viscosity increases are obtainable.
• EXAMPLE 2 The formula for the preferred experimental shampoo of Example 1 is modified by replacing 3% of the water thereof with an additional 3% of the preferred substituted imidazoline therein, making a total of 5% of such compound, and its properties are compared to those of a comparable composition containing 5% of lauric myristic diethanolamide, a preferred viscosity improving,
• the substituted imidazoline still has desirable thickening, foaming-improving and conditioning effects.
• other similarly soluble substituted imidazolines of the l-beta-hydroxy-lower alkyl, Z-higher alkyl imidazoline type are used, such as 1-alpha-hydroxyethyl, -2-undecyl imidazoline or l-gamma-hydroxy-n-propyl, 2-n-octyl imidazoline, viscosity, foam, lathering and conditioning improvements are obtained.
• compositions there is added about 2 to 4% of sodium chloride or potassium chloride, either in the absence of adjuvants or with other materials, such as other thiekeners, e.g., polyvinyl alcohol; bactericides, e.g., hexachlorophene, tetrachlorosalicylanilide; conditioning agents, e.g., proteinaceous hair treating compounds, monoglycerides, fatty oils, mineral oils; sequestrants, e.g., glucono-delta-lactone; and other biodegradable detergents, e.g., coconut oil fatty acids monoglyceride sulfates.
• other materials such as other thiekeners, e.g., polyvinyl alcohol; bactericides, e.g., hexachlorophene, tetrachlorosalicylanilide; conditioning agents, e.g., proteinaceous hair treating compounds, monoglycerides, fatty oils
• An aqueous shampoo composition of improved foaming and lathering power which comprises from about 51% to about 90% by weight of an aqueous solvent medium, from about 8% to about 40% by weight of a water soluble salt of a higher alcohol sulfate of from about 8 to about 18 carbon atoms and from about 0.5% to about 10% of 1 hydroxy-lower alkyl, 2-higher alkyl imidazoline, having 1 to 6 carbon atoms in the l-hydroxylower alkyl and 7 to 17 carbon atoms in the higher alkyl, at a pH of from about 7.5 to 9.5.
• An aqueous shampoo composition according to claim 4 wherein the alcohol sulfate is triethanolamine lauryl sulfate, the imidazoline is l-beta-hydroxyethyl, 2- higher alkyl imidazoline wherein higher alkyl is amixture of alkyls of 7 to 17 carbon atoms, corresponding to the mixture of reactant fatty acids derivable from coconut oil, from which the imidazoline is formed, the aqueous solvent medium is essentially water and the pH is from about 7.6 to 8.4.
• An aqueous shampoo composition according to claim 1 which also comprises, in a proportion less than 1 1 that of the l-hydroxy-lower alkyl, Z-higher alkyl imidazoline, 0.4 to 10% by weight of a strong electrolyte salt, which further increases the viscosity of the shampoo.
• An aqueous shampoo composition according to claim 5 which also contains from 0.4 to 10% of sodium chloride to further increase the viscosity of the shampoo.

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Cited By (6)

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• 1971
  • 1971-03-24 US US00127842A patent/US3723360A/en not_active Expired - Lifetime
• 1972
  • 1972-03-06 ZA ZA721480A patent/ZA721480B/xx unknown
  • 1972-03-15 AU AU40000/72A patent/AU460147B2/en not_active Expired
  • 1972-03-20 FR FR7209697A patent/FR2130472B1/fr not_active Expired
  • 1972-03-20 IT IT49116/72A patent/IT988055B/it active
  • 1972-03-21 BE BE780990A patent/BE780990A/xx unknown
  • 1972-03-21 GB GB1317072A patent/GB1343865A/en not_active Expired
  • 1972-03-22 DE DE19722213739 patent/DE2213739A1/de active Pending
  • 1972-03-23 SE SE7203742A patent/SE382750B/xx unknown
  • 1972-03-23 CA CA137,969A patent/CA986415A/en not_active Expired
  • 1972-03-23 DK DK139772AA patent/DK131365B/da unknown

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