Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3236733 A
Publication typeGrant
Publication dateFeb 22, 1966
Filing dateApr 1, 1965
Priority dateSep 5, 1963
Publication numberUS 3236733 A, US 3236733A, US-A-3236733, US3236733 A, US3236733A
InventorsKenneth S Karsten, Wilbur S Taylor, John J Parran
Original AssigneeVanderbilt Co R T, Procter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Method of combatting dandruff with pyridinethiones metal salts detergent compositions
US 3236733 A
Images(6)
Previous page
Next page
Description  (OCR text may contain errors)

United States Patent 3 236 733 METHOD or coMBAiTriNG DANDRUFF WITH PYRIDINETHKONES METAL SALTS DETERGENT COMPOSITIONS Kenneth S. Karsten, Westport, and Wilbur S. Taylor,

Norwalk, Conn, and John J. Parran, Springfield T ownship, Hamilton County, Ohio; said Karsten and said Taylor assignors to R. T. Vanderbilt Company, Inc.,

New York, N.Y., a corporation of New York, and said Parran assignor to The Procter & Gamble Company,

Cincinnati, Ohio, a corporation of Ohio No Drawing. Original application Sept. 5, 1963, Ser. No.

306,684. Divided and this application Apr. 1, 1965,

Ser. No. 444,858

12 Claims. (Cl. 16737) The present invention is a divisional application of application Serial No. 306,684, filed September 5, 1963. Application Serial No. 306,684 is a continuation-impart of application Serial No. 85,005, filed January 26, 1961, and now abandoned. Application Serial No. 85,005 is a continuation-impart of copendin-g application Serial No. 741,- 994, filed June 16, 1958, and now abandoned.

The present invention relates to a novel shampoo composition possessing remarkable anti-dandrufi' effectiveness. The invention also relates to germicidal detergent compo'si. tions. The compositions contemplated by this invention depend upon the presence of 1-hydroXy-2-pyridinethione, salts and esters thereof, and related compounds such as 2,2'-dithiopyridine-1,1-dioxide.

Dandruff is a common affliction most usually associated with the human scalp area. It is recognized that skin normally 'sloughs off the skin surfaces of the human body. On most areas of the body, the skin which is sloughed off is normally washed away at frequent intervals so that the slough-ing-off process is not noticeable. On the scalp, which is not normally washed as often as other parts of the body, the sloughed-off skin tends to accumulate. This skin together with the natural oils exuded by the scalp form a suitable environment for the growth of bacteria, and in fact certain bacteria are known to be associated with a dandruff condition.

The presence of bacteria in a dandruff condition suggests than an obvious cure is to treat the afflicted area with an agent which is capable of killing the bacteria. Heretofore, this obvious cure has not been successful although some oi the most powerful .bacteriostats have been used. Accordingly, it is believed that factors other than bacteriostatic activity are needed in order to provide an effective dandruff cure. Thus, sulfur is recognized as having a beneficial effect which is far greater than other materials which are tar more potent germicides. The particular properties of sulfur which render it helpful in combatting dandruff are not known.

It has become increasingly desirable to improve the bacteniostatic effect of detergent compositions. The term detergent is intended to denote soap and non-soap surface active agents. Many compounds are known that have germicidal or bacteriostatic properties against specific micro-organisms or groups thereof, but such property is generally destroyed or seriously impaired when the compound is incorporated into detergent compositions.

The retention of germicidal properties by a compound after inclusion in a detergent composition is only one of the necessary or desirable properties the compound must have to be considered as a desirable additive to the detergent composition designed for application to the human body. It is extremely important that the compound exhibit substantivity, i.e., the property of remaining on the skin and retaining germicidal activity over a period of time after washing and rinsing of the skin.

Other properties that are not concerned with the germicidal properties directly are, however, important as far as commercial use of the detergent composition by the general public is concerned. These include the following properties of a detergent bar, powder, liquid, etc. after inclusion of the specific compound:

(1) Initial whiteness (2) Color stability under sunlight exposure (3) Color stability under aging (4) Absence of discoloration by copper in stamping dies (5) Non-irritating to skin (6) No unpleasant odor Accordingly, it is an object of this invention to provide a shampoo composition including a material which is an effective anti-dandruff agent.

It is another object of this invention to provide a shampoo composition containing an active amount of l-hydroxy-Z-pyridinethione, salts :and esters thereof or related compounds.

It is ,a further object of this invention to provide a detergent composition which exhibits substantive germicidal properties and has a prolonged effect in maintaining skin germs and bacteria :at a reduced level.

It has been discovered that l-hydroXy-2-pyridinethione, salts and esters thereof, and related compounds have a totally unexpected effectiveness when used to treat the human scalp and other areas which are subject to dandruff condition. This anti-dandruff effect is all the more remarkable because it is not predictable on the basis of bacteriostatic activity. There are factors, unknown at present, which require that an effective anti-dandrufi? agent be more than simply an effective bacteriostat.

Clinical tests were performed which show the remarkable anti-dandrutf properties of the compositions of this invention. Four shampoo compositions were selected for the clinical tests. Two of the shampoo compositions contained 2.0% by weight, of the zinc salt of 1-hydroxy-2- pyridinethione. These two compositions embodied different detergent bases. The third shampoo composition is a control which has the same detergent base as one of the above two compositions. The fourth shampoo composition is a commercial paste shampoo containing a known bacteriostat (2,2-.thiobis (4,6-dichlorophenol)) and colloidal sulfur. The above four shampoo compositions are set forth in Table I below, with the shampoo compositions identified as #1, #2, #3 and #4, respectively.

TABLE I Shampoo compositions Code Letter #1 #3 Sulfated coconut fatty alcoholSodium salt Sodium stearate Sodium alkyl glyceryl ether sulfonate L Sodium acyl sarcosinate 2 Sodium sulfate Sodium chloride Trisodium phosphate Diethanolamide of coconut fatty acids Acetylated lanolin Phenyl mercuric acct e 3 Perfume 1-Hydroxy-2-pyridinethionc, no Water (Make up balance).

pH 2,2-thiobis(4,6-dichl0rophenol) Colloidal sulfur 1 Alkyl radicals derived from fatty alcohol, 25.3% from coconut and 3% from tallow.

2 Acyl radicals derived from coconut fatty acids. 3 3 5% solution in oleic acid in #1 and #2. 4 Maxlmum particle diameter10 microns.

The clinical test was conducted by first selecting 260 volunteers to shampoo their hair with their regular shampoo exactly one week before reporting to determine their initial dandruff grading. The grading was done by skilled graders who parted the hair over the complete scalp area sectionally to expose the entire scalp for visual examination. Grades from 10 to were assigned to each subject examined, according to the following scale:

10 Excellent, no scaling Good, slight scaling 2 Fair, some scaling 2 Moderate, moderate scaling 3 Poor, heavy scaling Very poor, heavy incrustations, erythema Only those receiving an initial grade of 6 or lower were retained for actual testing of the instant shampoo. They were given one of the four shampoos, told to shampoo at least twice a week for the first two weeks and to use no shampoo during the third week, after which they were graded. Then they were told to use their same designated shampoo at their pleasure for the fourth and fifth weeks and to use no shampoo during the sixth week, after which they were again graded for dandruff and also asked to rate their own dandruff condition on the trained graders scale. Neither the grader nor the subjects knew the identity of or distinction between the shampoos. The results of the tests by mean grades are summarized in Table II 2 Averaged scores rounded oft to one decimal place.

Careful analysis of this data shows accumulative change in average dandruff scores for each of the shampoos containing the zinc salt of 1-hydroxy-2-pyridinethione is significantly better than the other two shampoo compositions for both the 3-week and 6-week periods. Moreover, the subjects were able to observe the anti-dandruff effectiveness of the new shampoos relative to the control shampoos. It is thus clear that a detergent composition containing the zinc salt of 1-hydroxy-2-pyridinethione has a remarkable anti-dandruff efficacy which is not shown by the control which has the same detergent base. More importantly, shampoo composition #4 which contains a known baeteriostat has shown no improvement. Thus, the mere inclusion of a bacteriostat in a detergent composition does not assure that such composition will be effective in combatting dandruff. Certain other functions apparen ly m st be provid d o imp rt an i-dandruff propv respectively, contain 10 to 20 carbon atoms.

erties. These properties are inherent in the pyridinethione compositions of this invention.

The anti-dandruff shampoo compositions of this invention contain from about /4% to about 5% of the active material (1-hydroxy-2-pyridinethione compounds), preferably 1 /2% to 3%, in an aqueous detergent base. The compositions contain from about 5% to about 60% of a detergent. The detergent can be anionic, amphoteric, or cationic, although anionic organic detergent compounds are preferred, since they appear to provide the greatest anti-dandruff effectiveness when the shampoo compositions of this invention are used.

Anionic detergents include both the soap and non-soap detergents. Examples of suitable soaps are the sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids c o e. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow. Examples of anionic non-soap detergents are alkyl glyceryl ether sulfonates, alkyl sulfates, alkyl monoglyceride sulfates or sulfonates, alkyl polyethoxy ether sulfates, acyl sarcosinates, acyl esters of isethionates, acyl N-methyl taurides, alkyl benzene sulfanates, and alkyl phenol polyethoxy sulfonates. In these compounds the alkyl and acyl groups, They are used in the form of water-soluble salts, the sodium, potassium, ammonium and alkanolammonium salts, for example. Specific examples are sodium lauryl sulfate, potassium N-methyl lauroyl tauride; and triethanolamine dodecyl benzene sulfonate.

Suitable examples of cationic detergents are dilauryldimethyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethylbenzyl ammonium chloride, cetyl trimethyl ammonium bromide, N-cetyl pyridinium bromide and benzethonium chloride, which are classed as quaternary ammonium salts.

Suitable examples of amphoteric detergents are alkyl beta-imino dipropionates, and alkyl beta-amino propionates, wherein the alkyl group contains 10 to 20 carbon atoms, and basic quaternary ammonium compounds derived from 2-alkyl-substituted imidazoline.

Shampoo formulations can, of course, contain any of the usual shampoo additives such as color, perfume, thickeners, solvents, opacifiers, suds builders, conditioning agents, preservatives, buffers, and anti-static agents.

In view of the fact that shampoo formulation needs a small particle size in a dispersed medium, it has been found desirable to take a wet filter cake of about 50% of the zinc salt of l-hydroxy-2-pyridinethione, add 2% of Darvan 1 (sodium polyalkyl aryl sulfonate) and 0.3% of CMC-70 (medium viscosity sodium carboxymethyl cellulose) and then grind it in a pebble mill for about fifteen hours. The Darvan adds a charge to the individual particles which prevents subsequent coalescing and the CMC slows the settling, or after settling, aids the quick redispersion of the solution by mere stirring.

It has been discovered that l-hydroxy-2-pyridinethione compounds when incorporated in detergent compositions retain their bacteriostatic properties and are skin substantive. The use of detergent compositions embodying l-hydroxy-2-pyridinethione compounds retard the growth of body germs and bacteria for much longer periods than the detergent bases.

The specific precedures used to test the properties hereinbefore enumerated are described here in some detail, as there are no established procedures yet widely adopted in the art. The particular pyridinethione compound was blended at various concentrations with detergents which are anionic, cationic, nonionic, amphoteric and mixtures thereof, specific compositions thereof being set forth in Table III. A

TABLE in Code Letter Percent Detergent Compositions Cashmere Bouquet Potassium Oleate Ultrawet K (Anionic) Aerosol OS (Anionic)- Aerosol AY (Anionic) Carboxymethyl cellulose- Tween 80 (nonionic) Brij 35 (nonionic) Pluronie F-68 (nonionic) Sterox AJ (nonionic) Paraffin Intracol 0A (Cationic) Antaron FC-34 (amphoteric) 40 Mixed phosphates 60 60 60 60 Key to Table III:

The first five soaps listed are well known proprietary soaps without germicidal agents composed of a mixture of alkali metal salts of fatty acids, the general composition of Lux and Ivory being as follows:

Potassium oleate is a liquid soap formed from 11 parts H 0, 1 part KOH, 4 parts glycerin and 4 parts red oil (oleic acid).

Ultrawet K is a sodium salt of sulfonated Cm petroleum hydrocarbons.

Aerosol OS is a sodium alkyl naphthalene sulfonate. Aerosol AY" is diarnyl sodium sulfosuccinate. Tween 80 is a polyoxyethylene sorbitan monooleate. Brij 35 is a polyoxyethylene lauryl ether.

Pluronic F-68 is a condensate of ethylene oxide with a hydrocarbon base formed by condensing propylene oxide with propylene glycol.

Sterox AJ is a polyoxyethylene ether.

Intracol 0A is a long chain fatty acid amide containing several amine groups.

Antaron FC-34 is a complex fatty amide compound.

Bacteriostatic activity per so was tested by taking plugs of the blended solid compositions (liquid compositions were placed in peni-cups) and placing them on separate nutrient agar plates inoculated with Bacillus subtilis (found in soil and decomposing organic material), Staphylococcus aureus (found on the human skin) and Salmonella typhosa (cause of typhoid fever). These three bacteria are conventionally used in in vitro testing for activity and substantivity. The plates were incubated for 24 hours at about 37 C. and then the diameter of the zone of no bacterial growth around each plug was measured in millimeters (diameter of plug or peni-cup excluded) and recorded.

Substantivity was measured by soaking untanned calfskin buttons in an 8% aqueous solution of the test soap, then repeatedly rinsing the buttons in distilled water, and subsequently placing the buttons on nutrient agar plates inoculated with the same bacteria as noted above. Thereafter, the procedure is the same as following for bacterioitatic activity per se. The results are reported in Table TABLE IV Bacteriostatic activity and substantivity Inhib. Zone-Diameter (mm.)

Per-

Additive cent Soap Soap Plug Calfskin SAT A None (ControL.

TABLE IVCntinued 4 4 100 111585 00 4 m T 1 m m k 11 05 5 590 77 0 964 0 43 t 0 w 1 m 1 1 5 31A I O-B 0729 7 o m s mmrn n mm m mm m mmwm m n 1 111 am1t1 r11 1 bum 2t m e 222066 4212 624 0 404 00 65540 00 8606 50 19 49.210176121068566444 38 6 Z r 1 640t 6 1 76 0 6 8 140 7 U7 4 21 5 356699 1106254 59 6 b D A 2lsaw2 wmzwmnwmmwww2l%3m2 1%233%2w. mmmmllm%3%32m%2%%22222222222222% 21 2 .1 1 a 1 0 n 622040500105 00 8 428002200316428246 7420056526443008326095 462641 6 p a "w GHIJKLMBBCOOODEFGGGGHIJKLMBOCGGGGcHIJKLMnccoocooococcocoocoooccoo0 00 C 7 77 777 7 7 5 0 1111111 Qll LQOW 11111110 1L0 0 1111111111 IIQQQQQQQQQQQQQQQLLLLL LL L M0 P m m n u u Tm. n. n i n 1 r e .1 9 n 1n d d .1 .HO n .n m n gse .nb m 6 0 V. 0 m V. "e m m1 m V P 1 p M ma .1 iia l 1 YD u .5 m H n g t t m u nmn w u 1 m mw n C n .a a m mama w miwwm m n A w zlsem l bbaldmdo t 1 t y 1 1 i 1 y y y y y y P rrrrr u r u urrr rr m 222222 0 0 0 22222 22 2 9nd d d. a: a es at fi hts I: 111111 1 11111 11 1 u 0 N 2 0 n 9 draining for seconds. Thereafter, the left hand was uncovered, the right hand was covered with a neoprene activity and substantivity. Samples number 33 and 5 hand Applied Microglove, and the washing procedure repeated using unmedi cated, i.e., control soap. Thus the left hand serves as an unmedicated soap-washed control for the test soap-washed were further tested in a modification of the split-use washing test described by Quinn et al biology 2, 2024 (1954). In the modified test, first the right hand.

ed and the left hand covered The hands of each subject were washed three times each Then both hands were soaped day and bacterial counts made on the wash water used for 20 seconds by briskly rubbing the moistened medicated test bar with a small amount of wash water held in the cupped hands, the lather being worked up as far as the in the second washing on the third and fifth days of the test. The control or unmedicated soap is used for the washings at which bacterial counts are made so that none wrist for seconds, followed by rinsing the hands for of the test compound is present in the wash water to 20 seconds while immersed in the Wash water and then 75 influence the results. Aliquots of the wash water in which 9 each hand is washed were added to nutrient agar pour plates within one minute after completion of washing. The plates were incubated for 48 hours at 37 C., the bacterial colonies counted and the results calculated for the entire wash water. The results are summarized in 10 weeks, a very severe test, while the C (Ivory) soaps were tested after the normal two weeks aging at 125 F. as described for Table VI. Bacteriostatic activity and substantivity were then determined by the same methods described and reported in Table IV. Table VII shows 5 Table V. the post-aging results of these tests.

TABLE V Split-use hand washing test Three Day Results Five Day Results No. Subject Bacteria Count Bacteria Count (Millions) Percent (Millions) Percent Decrease Decrease On Right On Right Left Right Left Right V 2. 75 0. 48 82. 5 2. 12 0. 186 91. 2 W 2. 0. 84 61. 8 2. 15 0. 88. 4 X 2. 11 0. 47 77. 7 3. 33 0. 17 94. 9 Y 2. 94 1.93 34. 4 4. 32 0. 37 91. 4 Z 3.86 0.423 89.0

1 See Table IV.

From the results reported in Table V, it will be noted that the bacteriostatic activity and substantivity of the pyridinethione compounds can be demonstrated in an actual hand washing technique. Various other desirable properties of the same soap-pyridinethione compound mixtures of Table IV are reported in Table VI.

The initial whiteness is reported both after mixing of the pyr-idinethione compounds with the soap and after the soap bar had been formed in the conventional brass die.

The sunlight color stability was tested by breaking a soap bar in two and exposing one portion in an east window for two weeks, rotating it one-quarter turn daily.

The heat aging color stability was tested by placing a sample bar in a closed glass jar within an oven at 125 F. for two weeks which is presumed to be approximately equivalent to one year shelf storage.

The tests reported in Table VI are of the same numbered samples of Table IV but all the samples of Table IV were not tested here.

TAB-LE VI Color changes due to aging TABLE VII Bacteriostatic activity and sn'bstantivity after heat aging 1 See Table IV. R TrGrowth touching button in one place.

No. Initial Blend Initial Bar Heat Aged Sunlight Aged 1. White. White Slightly oil-white. Slightly oil-white. 2 dn do rlo D0, 15 Off-white- Off-white Brown Brown. 16. White White. Off-White- Cream.

' Off-white Light brown Light brown.

White. White White. dn rlo D Blue-black sheen on .do- D0.

surface only. Blue-black Butt Bufi.

sheen on surface only. 2

1 See Table IV.

2 This slight surface sheen, caused evidently by contact with the brass bar-forming die, was removed before the oven and sunlight aging tests.

It will be noted that samples 29 and 33 (zinc salt of 1-hydroxy-2-pyridinethione) gave excellent results in the color tests and, in fact, slightly better than the control bars containing no bacter-iostatic agent. Samples 48 and 50 (2,2'-dithiopyridine-1,l-dioxide) were also fairly good except for the surface sheen on the initial bar, a feature which might be overcome by changing the bar-forming conditions or dies.

The soaps showing the more desirable results in the color tests were subjected to bacteriostatic and substantivity tests after heat aging in an attempt to determine the extent of loss of bacteriostatic effect, if any, during heat aging. The B (LUX) soaps were aged for six After the aging tests, these samples retained their bacteriostatic activity and substantivity.

Detergent compositions N, O, P and Q were dry granular formulations of heavy-duty laundry type to which were added for separate test 1% by weight of zinc, sodium, disulfide and cetyl ammonium derivatives of the 1-hydroxy-2-pyridinethione. It was found that fabrics washed with these formulations had drastic reductions in bacteria count relative to fabrics washed in the same formulation without the active agent and further that this reduction was partly maintained after rinsing. Fabrics laundered in this manner would be particularly useful for wear or use that contacts the skin, or where large numbers of bacteria are encountered such as hospital and diaper laundries.

No skin irritation has been noted with any of the pyridinethione compounds tested.

The pyridinethione compounds do not impart odors to a detergent composition. This is a property highly desirable to both the manufacturer and the user of the detergent.

Not only do the pyridinethione compounds have exelement germicidal and substantive properites, which are maintained after prolonged aging, but these compounds also give excellent results in the various color tests which are so important in offering soap to the consumer market. As will be noted, many of the compounds stay white through the heat aging and sunlight aging tests and the others have only slight discoloration.

The specific examples reported in the tables have included 0.07 to by weight of the pyridinethione compounds in the detergent composition (based on solids) in order that specific comparisons could be made with the various compounds and also with various controls and prior art compounds. However, it will be obvious that a wider range of pyridinethione compounds can be used and we have found from 0.01 to to be generally a satisfactory range although this should not be a limiting feature of our invention.

It is obvious from these results that the l-hydroxy-Z- pyridinethione and its derivatives have properties which indicate their use as an ingredient of a germicidal or medicinal soap or detergent.

This invention is concerned with l-hydroxy-2-pyridinethi-one (and derivatives) which has the following structural formula in tautomeric form, the sulfur being attached to No. 2 position of the pyridine ring:

2-rnercaptopyridine l-oxide The salts and esters disclosed herein represent substitution of the corresponding cation for the hydrogen of one of the tautomeric forms. Depending, of course, on the valence of the cation involved, there may be more than one of the 1-hydroxy-2-pyridinethione rings in the com-pound. Although a number of compounds have been specifically disclose-d, it will be apparent to one skilled in the art that inorganic salts other than those tested are suitable. Further, other amine salts, quaternary arnmonium salts, and other esters are also suitable. The disulfide (2,2-dithiodipyridine-1,1-dioxide) represents the attachment of two 1-hydroxy-2-pyridinethione rings by the elimination of the two hydrogens from the sulfur atoms to give a sulfur-to-sulfur linkage. Other substituted or derived compounds of 1-hydroxy-2-pyridinethione which retain the bacteriostatic and substantive properties are considered to be within the scope of this invention.

The active pyridinethione compounds may be incorporated into liquid, bar or powder detergent compositions as desired to satisfy the particular product requirement. The detergent compositions herein are hydrophilic but the composition as a whole may include hydrophobic components, e.g., paraffin. Detergent compositions may, of course, include conventional additives such as perfume, color, emollients, binders, inert fillers, etc.

What is claimed is:

1. A method for combatting dandruff comprising the step of applying to the hair and scalp of humans a detergent composition comprising an amount of zinc pyridinethione sufficient to provide effective anti-dandruff control.

2. A method for combatting dandruff comprising the step of applying to the hair and scalp of humans a detergent composition comprising an amount of cadmium pyridinethione sufficient to provide effective antidandruff control.

3. A method for combatting dandruff comprising the step of applying to the hair and scalp of humans a detergent composition comprising an amount of tin pyridinethione sufficient to provide effective anti-dandruff control.

4. A method for combatting dandruff comprising the step of applying to the hair and scalp of humans a detergent composition comprising an amount of zirconium pyridinethione sufficient to provide effective anti-dandruff control.

5. A method for combatting dandruff comprising the step of treating the hair and scalp with a composition comprising an anionic detergent base and an amount of zinc pyridinethione sufficient to provide effective antidandruff control.

6. A method for combatting dandruff comprising the step of treating the hair and scalp with a composition comprising an anionic detergent base and an amount of cadmium pyridinethione sufficient to provide effective anti-dandruff control.

7. A method for combatting dandruff comprising the step of treating the hair and scalp with a composition comprising an anionic detergent base and an amount of tin pyridinethione sufficient to provide effective antidandruff control.

8. A method for combatting dandruff comprising the step of treating the hair and scalp with a composition comprising an anionic detergent base and an amount of zirconium pyridinethione sufficient to provide effective anti-dandruff control.

9. A method for combatting dandruff comprising the step of treating the hair and scalp with a shampoo composition comprising a detergent base and from about .25% to about 5% of zinc pyridinethione.

10. A method for combatting dandruff comprising the step of treating the hair and scalp with a shampoo composition comprising a detergent base and from about .25% to about 5% of cadmium pyridinethione.

11. A method for combatting dandruff comprising the step of treating the hair and scalp with a shampoo composition comprising a detergent base and from about .25 to about 5% of tin pyridinethione.

12. A method for combatting dandruff comprising the step of treating the hair and scalp with a shampoo composition comprising a detergent base and from about .25% to about 5% of zirconium pyridinethione.

References Cited by the Examiner UNITED STATES PATENTS 2,742,393 4/1956 Bernstein 260294.8 X 2,742,476 4/ 1956 Bernstein 260-2948 2,809,971 10/ 1957 Bernstein 260294.8 X 2,846,398 8/1958 Beaver et al. 252107 OTHER REFERENCES Elder et al.: Drug and Cosmetic Industry, vol. 77, No. 5, pp. 622-623, 714-717, 719 and 721 (November 1955).

Schimmel Briefs, No. 271, October 1957.

JULIAN S. LEVITT, Primary Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2742393 *May 19, 1953Apr 17, 1956Olin MathiesonDerivatives of 2-mercaptopyridine-1-oxide
US2742476 *Oct 26, 1953Apr 17, 1956Olin MathiesonDerivatives of 2-mercaptopyridine 1-oxide
US2809971 *Nov 22, 1955Oct 15, 1957Olin MathiesonHeavy-metal derivatives of 1-hydroxy-2-pyridinethiones and method of preparing same
US2846398 *Dec 27, 1955Aug 5, 1958Monsanto ChemicalsAntiseptic detergent composition
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3281366 *Nov 4, 1965Oct 25, 1966Procter & GambleSynergistic antibacterial compositions
US3489686 *Dec 11, 1967Jan 13, 1970Procter & GambleDetergent compositions containing particle deposition enhancing agents
US3527864 *Nov 18, 1966Sep 8, 1970Procter & GambleCompositions for topical application to animal tissue and method of enhancing penetration thereof
US3671634 *Feb 16, 1970Jun 20, 1972Vanderbilt Co R TStable aqueous anti-dandruff shampoo containing captan
US3890434 *Mar 28, 1974Jun 17, 1975Olin CorpHair and antiseptic formulations containing adducts of bis-(2-pyridyl-1-oxide) disulfide
US3928605 *Jun 27, 1974Dec 23, 1975Procter & GamblePhenylantimony bis(2-pyridinethiol-1-oxide in antibacterial and antifungal compositions
US3950532 *May 10, 1972Apr 13, 1976L'orealAntidandruff
US3961054 *Dec 27, 1974Jun 1, 1976Ciba-Geigy CorporationShampoo
US4033895 *Dec 24, 1975Jul 5, 1977Revlon, Inc.Non-irritating shampoo compositions containing stearyl amine oxide
US4080465 *Jan 27, 1976Mar 21, 1978Societe Anonyme Dite: L'orealTopical application of cis or trans 3,4-thiolannediol to reduce or substantially eliminate the greasy appearance of the skin
US4089945 *Jan 6, 1977May 16, 1978The Procter & Gamble CompanyAntidandruff shampoos containing metallic cation complex to reduce in-use sulfide odor
US4161526 *Jul 20, 1978Jul 17, 1979Sterling Drug Inc.Zinc salt prevention or removal of discoloration in pyrithione, pyrithione salt and dipyrithione compositions
US4185106 *Aug 15, 1975Jan 22, 1980Hoechst AktiengesellschaftPyridones as antidandruff agents
US4307089 *Jul 30, 1980Dec 22, 1981Rewo Chemische Werke GmbhCompositions of pyrithione metal salts and undecylenic acid alkylolamide derivatives
US4552754 *Apr 6, 1983Nov 12, 1985Lion CorporationQuaternary ammonium salts, 1-hydroxy-2-pyridone salts, polyol components
US4557928 *Nov 2, 1983Dec 10, 1985Amway CorporationZinc pyrithione with cationic polymer
US4665064 *Oct 31, 1984May 12, 1987National Research Development CorporationIn blood; zinc chelate
US4711775 *Dec 4, 1984Dec 8, 1987Hoechst AktiengesellschaftAntidandruff hair lotions and shampoos
US4745071 *Oct 2, 1986May 17, 1988Sequoia-Turner CorporationMethod for the volumetric differentiation of blood cells types
US4832950 *May 10, 1988May 23, 1989Kao CorporationPolyvalent metal salts of 2-mercaptopyridine-n-oxide
US4894455 *Feb 18, 1987Jan 16, 1990National Research Development CorporationFood supplements for zinc deficiency
US5008202 *Nov 29, 1988Apr 16, 1991Sequoia Turner CorporationAqueous solution of inorganic salts, stabilizer, organic buffer, ethylenediaminetetraacetic acid as antimicrobial agent
US5104645 *Feb 2, 1990Apr 14, 1992The Proctor & Gamble Company1-hydroxy-2-pyridinethione metal salt inplatelet form of specific size; a synergizer; effective
US5104865 *Sep 1, 1989Apr 14, 1992National Research Development CorporationIron complexes of hydroxypyridones useful for treating iron overload
US5155119 *Mar 5, 1992Oct 13, 1992The Dow Chemical Company3-(2-pyridinylthio)-N-oxide, 2-halo-2-propenenitrile compounds useful as antimicrobials
US5227156 *Apr 14, 1992Jul 13, 1993Amway CorporationUse of zinc compounds to stabilize a thiazolinone preservative in an anti-dandruff shampoo
US5776960 *Oct 16, 1996Jul 7, 1998Buckman Laboratories International, Inc.Synergistic antimicrobial compositions containing an ionene polymer and a pyrithione salt and methods of using the same
US5854266 *Mar 10, 1997Dec 29, 1998Olin CorporationSynergistic antimicrobial composition pyrithione and alcohol
US6008236 *Apr 30, 1998Dec 28, 1999Buckman Laboratories International, Inc.Microbiocide mixture for controlling the growth of microorganisms and prevent spoilage caused by microorganisms
US6054450 *Dec 28, 1998Apr 25, 2000Pacific CorporationSolution of zinc pyrithione in n-acylethylenediaminetriacetate.
US6645476Jul 14, 2000Nov 11, 2003Clariant GmbhPreparable by free-radical copolymerization of macromonomers containing an end-group capable of polymerization, a hydrophilic moiety based on polyalkylene oxides, and a hydrophobic moiety with olefincally unsaturated comonomers
US6849584Nov 1, 2002Feb 1, 2005The Procter & Gamble CompanyComposition containing a cationic polymer and water insoluble solid material
US6908912Dec 20, 2002Jun 21, 2005Arch Chemicals, Inc.For controlling free-living microorganisms/biofilm growth
US7026308Jun 22, 2000Apr 11, 2006The Procter & Gamble CompanyTopical anti-microbial compositions
US7455851Jun 22, 2000Nov 25, 2008Arch Chemicals, Inc.Antimicrobial; mixture of a pyrithione or a salt or adduct thereof and a zinc source such as zinc salts, zinc oxides, or zinc hydroxides with alkanolamine solvent; free of thiazolinone; use against biofilms, free-living microorganisms
US7528125Mar 20, 2007May 5, 2009Jonathan L. SesslerWater-soluble zinc ionophores, zinc chelators, and/or zinc complexes and use for treating cancer
US7531497Sep 15, 2005May 12, 2009The Procter & Gamble CompanyPersonal care composition containing a cleansing phase and a benefit phase
US7585827Aug 20, 2007Sep 8, 2009The Procter & Gamble Companyconditioning copolymer containing noncrosslinked cationic monomer units selected from diallyldimethyl ammonium chloride and 1-Propanaminium, N,N,N-trimethyl-3-[(2-methyl-1-oxo-2-propenyl)amino]-, chloride, and one or more nonionic monomers such as acrylates, vinylamine; an anionic detersive surfactant
US7598213Oct 31, 2007Oct 6, 2009The Procter & Gamble Companycleansing compounds comprising a detersive surfactant selected from anionic, amphoteric and zwitterionic surfactants, a water soluble cationic homopolymer promotes the formation of lyotropic liquid crystals that exhibit birefringence and water; hair conditioners
US7674785Dec 8, 2005Mar 9, 2010The Procter & Gamble Companypolyvalent metal salts of pyrithione; salt of zinc, copper, silver, nickel, cadmium, mercury, and/or bismuth; di- or polyamines, diethylene triamine penta-acetic acid, tetraethylene triamine, ethylene diamine, and/or diethylene triamine strong chelator
US7838536Mar 24, 2009Nov 23, 2010Jonathan L. Sesslerdelivers zinc to cancer cells or zinc chelation within the cancer cells using the unbound ligand; bioavailability; with texaphyrin metal complex;
US8119168Mar 18, 2003Feb 21, 2012The Procter & Gamble CompanyTopical antidandruff agents comprising mixtures of group IIB compounds such as zinc pyrithione, zinc oxide or calamine
US8206732Oct 21, 2008Jun 26, 2012Arch Chemicals, Inc.Pyrithione biocides enhanced by silver, copper, or zinc ions
US8268764Dec 8, 2009Sep 18, 2012The Procter & Gamble CompanyPorous, dissolvable solid substrate and surface resident starch perfume complexes
US8273333Apr 16, 2009Sep 25, 2012The Procter & Gamble CompanyNon-lathering personal care composition in the form of an article
US8349301Sep 16, 2005Jan 8, 2013The Procter & Gamble CompanyMixture of surfactants, fatty amphiphiles and aqueous carrier
US8349302Jun 27, 2006Jan 8, 2013The Procter & Gamble CompanyShampoo containing a gel network and a non-guar galactomannan polymer derivative
US8349341Dec 8, 2010Jan 8, 2013The Procter & Gamble CompanyPorous, dissolvable solid substrate and a surface resident coating of cationic surfactant conditioner
US8349786Dec 8, 2009Jan 8, 2013The Procter & Gamble CompanyPorous, dissolvable solid substrates and surface resident cyclodextrin perfume complexes
US8349787Dec 8, 2010Jan 8, 2013The Procter & Gamble CompanyPorous, dissolvable solid substrate and a cationic surfactant conditioner material
US8361448Jun 27, 2006Jan 29, 2013The Procter & Gamble CompanyMixture of surfactants, crystalline fatty alcohol, and aqueous carrier; dispersed gel network
US8361449Mar 3, 2008Jan 29, 2013The Procter & Gamble CompanyShampoo containing a gel network
US8361450Nov 21, 2006Jan 29, 2013The Procter & Gamble CompanyShampoo containing a gel network and a non-guar galactomannan polymer derivative
US8361516Jul 31, 2007Jan 29, 2013SedermaComposition comprising sarsasapogenin
US8367048Nov 21, 2006Feb 5, 2013The Procter & Gamble CompanyShampoo containing a gel network
US8404648Feb 16, 2006Mar 26, 2013SedermaPolypeptides KXK and their use
US8415287Dec 8, 2009Apr 9, 2013The Procter & Gamble CompanyPorous, dissolvable solid substrate and surface resident inorganic particulate perfume complexes
US8425622May 23, 2012Apr 23, 2013The Procter & Gamble CompanySoluble solid hair coloring article
US8439981May 23, 2012May 14, 2013The Procter & Gamble CompanySoluble solid hair coloring article
US8444716May 23, 2012May 21, 2013The Procter & Gamble CompanySoluble solid hair coloring article
US8461090Dec 8, 2009Jun 11, 2013The Procter & Gamble CompanyPersonal care composition in the form of an article having a porous, dissolvable solid structure
US8461091Dec 8, 2009Jun 11, 2013The Procter & Gamble CompanyPersonal care composition in the form of an article having a porous, dissolvable solid structure
US8466099Dec 8, 2009Jun 18, 2013The Procter & Gamble CompanyProcess of making an article for dissolution upon use to deliver surfactants
US8470305Dec 7, 2007Jun 25, 2013The Procter & Gamble CompanyMixture of deteresive surfactant, solid, crystalline fatty acid gel network and aqueous carrier
US8476211Jul 30, 2012Jul 2, 2013The Procter & Gamble CompanyPorous, dissolvable solid substrates and surface resident starch perfume complexes
US8491877Mar 17, 2004Jul 23, 2013The Procter & Gamble Companycontaining a surfactant having an anionic group; treatment of microbial and fungal infections on the skin or scalp, especially dandruff; may also contain a pyrithione or polyvalent metal salt of pyrithione, particularly zinc pyrithione.
US8507531Oct 15, 2010Aug 13, 2013Jonathan L. SesslerWater-soluble zinc ionophores, zinc chelators, and/or zinc complexes and use for treating cancer
US8507649May 4, 2007Aug 13, 2013SedermaCosmetic compositions comprising at least one peptide with at least one immobilized aromatic cycle
US8628706Aug 29, 2012Jan 14, 2014The Procter & Gamble CompanyNon-lathering personal care composition in the form of an article
US8653014Oct 5, 2012Feb 18, 2014The Procter & Gamble CompanyShampoo composition containing a gel network
US8673274Dec 12, 2007Mar 18, 2014The Procter & Gamble CompanyComposition comprising pyrithione or a polyvalent metal salt of a pyrithione and furametpyr
US8685908Feb 28, 2012Apr 1, 2014The Procter & Gamble CompanyBar soap comprising pyrithione sources
US8697656Jan 15, 2010Apr 15, 2014SedermaCompounds, in particular peptides, compositions comprising them and cosmetic and dermo-pharmaceutical uses
US8741357Jan 13, 2006Jun 3, 2014Sederma SasCosmetic or dermopharmaceutical composition comprising an euglena extract
US8765170Jan 29, 2009Jul 1, 2014The Procter & Gamble CompanyPersonal care composition in the form of an article
CN1646124BMar 18, 2003May 26, 2010宝洁公司;阿尔什化学公司Use of materials having zinc ionophoric behavior
EP0023676A1 *Jul 24, 1980Feb 11, 1981REWO Chemische Werke GmbHCombination of active ingredients for cosmetics
EP0158481A2 *Mar 27, 1985Oct 16, 1985THE PROCTER & GAMBLE COMPANYHair care compositions
EP2082723A1Jun 23, 2000Jul 29, 2009The Procter and Gamble CompanyTopical anti-microbial compositions
EP2510982A1May 4, 2007Oct 17, 2012SedermaCosmetic compositions comprising at least one peptide with at least one immobilized aromatic cycle
EP2666457A2Apr 16, 2009Nov 27, 2013The Procter and Gamble CompanyProcess for forming a non-lathering personal care article in the form of a dissolvable solid foam
EP2666458A2Apr 16, 2009Nov 27, 2013The Procter and Gamble CompanyPre-mix for a non-lathering personal care article, the article having the form of a solid foam
EP2687287A2May 12, 2010Jan 22, 2014The Procter and Gamble CompanyDelivery particles
EP2687590A2May 12, 2010Jan 22, 2014The Procter and Gamble CompanyDelivery particles
WO2001000021A1 *Jun 23, 2000Jan 4, 2001Arch Chem IncPyrithione biocides enhanced by silver, copper, or zinc ions
WO2003088965A1 *Mar 18, 2003Oct 30, 2003Arch ChemicalUse of materials having zinc ionophoric behavior
WO2004082648A1Mar 18, 2004Sep 30, 2004Procter & GambleComposition comprising particulate zinc materials having a defined crystallite size
WO2010067327A1Dec 10, 2009Jun 17, 2010SedermaCosmetic composition containing acetylated oligoglucuronans
WO2010077653A2Dec 8, 2009Jul 8, 2010The Procter & Gamble CompanyPersonal care composition in the form of an article having a hydrophobic surface-resident coating
WO2010082175A2Jan 15, 2010Jul 22, 2010SedermaNew compounds, in particular peptides, compositions comprising them and cosmetic and dermopharmaceutical uses
WO2010082176A2Jan 15, 2010Jul 22, 2010SedermaCosmetic composition containing kxk type peptides and uses
WO2010082177A2Jan 15, 2010Jul 22, 2010SedermaNew compounds, in particular peptides, compositions comprising them and cosmetic and dermopharmaceutical uses
WO2010136965A2May 25, 2010Dec 2, 2010SedermaCosmetic use of tyr-arg dipeptide to combat cutaneous sa
WO2010141683A2Jun 3, 2010Dec 9, 2010The Procter & Gamble CompanyMultiple product system for hair
WO2011103146A2Feb 16, 2011Aug 25, 2011The Procter & Gamble CompanyA post foaming gel composition comprising an anti-irritation agent
WO2011103173A2Feb 16, 2011Aug 25, 2011The Procter & Gamble CompanyNon-aerosol personal care compositions comprising an anti-irritation agent
WO2011123727A2Apr 1, 2011Oct 6, 2011The Procter & Gamble CompanyOrganosilicones
WO2011123732A1Apr 1, 2011Oct 6, 2011The Procter & Gamble CompanyComposition comprising modified organosilicones
WO2011123734A1Apr 1, 2011Oct 6, 2011The Procter & Gamble CompanyCare polymers
WO2011123736A1Apr 1, 2011Oct 6, 2011The Procter & Gamble CompanyCare polymers
WO2011123739A1Apr 1, 2011Oct 6, 2011The Procter & Gamble CompanyCompositions comprising organosilicones
WO2011156551A1Jun 9, 2011Dec 15, 2011The Procter & Gamble CompanyMethod for preparing a non-ionic surfactant stable personal care dispersion
WO2011156558A1Jun 9, 2011Dec 15, 2011The Procter & Gamble CompanyCocoamide monoethanolamine (cmea) composition
WO2011156566A2Jun 9, 2011Dec 15, 2011The Procter & Gamble CompanyChemically stabilized anti-dandruff compositions for use in personal care compositions
WO2011156584A1Jun 9, 2011Dec 15, 2011The Procter & Gamble CompanyMethods of preparing personal care compositions
WO2012051374A2Oct 13, 2011Apr 19, 2012The Procter & Gamble CompanyUse of monoamine oxidase inhibitors to improve epithelial biology
WO2012058216A2Oct 25, 2011May 3, 2012The Gillette CompanyComposition dispensing device comprising a non-foaming hydrating composition
WO2012058526A1Oct 28, 2011May 3, 2012The Procter & Gamble CompanyInhibition of microbial growth by aconitase inhibition
WO2012058557A2Oct 28, 2011May 3, 2012The Procter & Gamble CompanyPersonal care compositions comprising a pyrithione and an iron chelator
WO2012116466A1 *Feb 28, 2011Sep 7, 2012The Procter & Gamble CompanyBar soap comprising pyrithione sources
WO2012118798A1Feb 28, 2012Sep 7, 2012The Gillette CompanyRazor comprising a molded shaving aid composition comprising a pyrithione source
WO2012135651A1Mar 30, 2012Oct 4, 2012The Procter & Gamble CompanySystems, models and methods for identifying and evaluating skin-active agents effective for treating dandruff/seborrheic dermatitis
WO2012138696A2Apr 4, 2012Oct 11, 2012The Procter & Gamble CompanyShampoo compositions with increased deposition of polyacrylate microcapsules
WO2012162331A2May 23, 2012Nov 29, 2012The Procter & Gamble CompanyCompositions comprising an efficient perfume bloom
WO2012174091A2Jun 13, 2012Dec 20, 2012The Procter & Gamble CompanyPERSONAL CARE COMPOSITIONS COMPRISING A pH TUNEABLE GELLANT AND METHODS OF USING
WO2012174096A2Jun 13, 2012Dec 20, 2012The Procter & Gamble CompanyPersonal care compositions comprising a di-amido gellant and methods of using
WO2012177757A2Jun 20, 2012Dec 27, 2012The Procter & Gamble CompanyPersonal care compositions comprising shaped abrasive particles
WO2013025772A2Aug 15, 2012Feb 21, 2013The Gillette CompanyComposition dispensing device comprising a moisturizing composition
WO2013025857A1Aug 16, 2012Feb 21, 2013The Gillette CompanySkin engaging member comprising an anti-irritation agent
WO2013025886A1Aug 16, 2012Feb 21, 2013The Gillette CompanyShave preparations comprising an anti-irritation agent
WO2013025891A1Aug 16, 2012Feb 21, 2013The Gillette CompanyAn aerosol shave composition comprising a hydrophobical agent forming at least one microdroplet and an anti-irritation agent
WO2013025893A1Aug 16, 2012Feb 21, 2013The Gillette CompanyPersonal care compositions comprising an anti-irritation agent
WO2013052771A2Oct 5, 2012Apr 11, 2013The Procter & Gamble CompanyPersonal care compositions and methods of making same
WO2013052820A2Oct 5, 2012Apr 11, 2013The Procter & Gamble CompanyMethod of achieving improved hair feel
WO2013092698A2Dec 19, 2012Jun 27, 2013Akzo Nobel Chemicals International B.V.Bioactive compositions having hair anti aging activity
WO2013106367A2Jan 9, 2013Jul 18, 2013The Procter & Gamble CompanyHair care compositions
WO2013142654A2Mar 21, 2013Sep 26, 2013The Procter & Gamble CompanyCompositions for delivering perfume to the skin
WO2013158380A2Apr 5, 2013Oct 24, 2013The Procter & Gamble CompanyHair care composition comprising metathesized unsaturated polyol esters
WO2013158381A2Apr 5, 2013Oct 24, 2013The Procter & Gamble CompanyHair care composition comprising metathesized unsaturated polyol esters
WO2013163491A1Apr 26, 2013Oct 31, 2013The Procter & Gamble CompanyApplicator assembly for applying a composition
WO2013163492A1Apr 26, 2013Oct 31, 2013The Procter & Gamble CompanyApplicator assembly for applying a composition
WO2013170004A2May 9, 2013Nov 14, 2013The Procter & Gamble CompanyHair treatment comprising silicone grafted starch
WO2014004800A2Jun 27, 2013Jan 3, 2014The Procter & Gamble CompanyAerosol composition comprising a particulate tapioca starch
WO2014004847A2Jun 27, 2013Jan 3, 2014The Procter & Gamble CompanyAerosol composition comprising a particulate tapioca starch
WO2014028568A1Aug 14, 2013Feb 20, 2014The Procter & Gamble CompanySystems, models and methods for identifying and evaluating skin-active agents effective for treating an array of skin disorders
WO2014028569A1Aug 14, 2013Feb 20, 2014The Procter & Gamble CompanySystems, models and methods for identifying and evaluating skin-active agents effective for treating an array of skin disorders
WO2014028572A2Aug 14, 2013Feb 20, 2014The Procter & Gamble CompanySystems, models and methods for identifying and evaluating skin-active agents effective for treating an array of skin disorders
Classifications
U.S. Classification514/188, 510/131, 510/500, 514/852, 510/382, 510/492, 510/390, 510/123, 424/DIG.400, 510/319, 510/133, 510/138
International ClassificationC11D3/48, A61Q5/02, C07D213/89, C11D1/00, A61K8/49, A61Q5/00
Cooperative ClassificationY10S514/852, Y10S424/04, A61Q5/006, A61K8/4933, C11D3/48, A61Q5/02
European ClassificationC11D3/48, A61Q5/02, A61Q5/00F, A61K8/49C6