US3412033A - Germicidal detergent compositions - Google Patents
Germicidal detergent compositions Download PDFInfo
- Publication number
- US3412033A US3412033A US500173A US50017365A US3412033A US 3412033 A US3412033 A US 3412033A US 500173 A US500173 A US 500173A US 50017365 A US50017365 A US 50017365A US 3412033 A US3412033 A US 3412033A
- Authority
- US
- United States
- Prior art keywords
- pyridinethione
- hydroxy
- germicide
- skin
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 44
- 239000003599 detergent Substances 0.000 title claims description 38
- 230000002070 germicidal effect Effects 0.000 title claims description 29
- 239000000344 soap Substances 0.000 claims description 27
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 150000004665 fatty acids Chemical class 0.000 claims description 9
- YBBJKCMMCRQZMA-UHFFFAOYSA-N pyrithione Chemical compound ON1C=CC=CC1=S YBBJKCMMCRQZMA-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 21
- -1 pyridinethione compound Chemical class 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- 125000000129 anionic group Chemical group 0.000 description 11
- 230000003385 bacteriostatic effect Effects 0.000 description 10
- 125000002091 cationic group Chemical group 0.000 description 9
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical class SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 210000004247 hand Anatomy 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000443 aerosol Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000006916 nutrient agar Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 229940096992 potassium oleate Drugs 0.000 description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UMEWSJNRBXKWKZ-UHFFFAOYSA-M sodium;1,4-dioxo-1,4-dipentoxybutane-2-sulfonate Chemical compound [Na+].CCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCC UMEWSJNRBXKWKZ-UHFFFAOYSA-M 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical class CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- FFYRIXSGFSWFAQ-UHFFFAOYSA-N 1-dodecylpyridin-1-ium Chemical compound CCCCCCCCCCCC[N+]1=CC=CC=C1 FFYRIXSGFSWFAQ-UHFFFAOYSA-N 0.000 description 1
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- MARYDOMJDFATPK-UHFFFAOYSA-N 3-hydroxy-1h-pyridine-2-thione Chemical compound OC1=CC=CN=C1S MARYDOMJDFATPK-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000740206 Mus musculus Sal-like protein 1 Proteins 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 206010042618 Surgical procedure repeated Diseases 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 208000037386 Typhoid Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- HAXFWIACAGNFHA-UHFFFAOYSA-N aldrithiol Chemical compound C=1C=CC=NC=1SSC1=CC=CC=N1 HAXFWIACAGNFHA-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 201000008297 typhoid fever Diseases 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- 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
- 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
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4933—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having sulfur as an exocyclic substituent, e.g. pyridinethione
-
- 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
- A61Q19/10—Washing or bathing preparations
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
Definitions
- the present invention relates to germicidal detergent compositions, and more particularly to hydrophilic skin cleansing compositions comprising a skin substantive germicide.
- the compositions contemplated by this invention depend upon the presence of l-hydroxy-Z-pyridine thione, salts and esters thereof, and related compounds such as 2,2-dithio-pyridine-1-, l-dioxide as the substantive germicide.
- detergent is intended to denote soap and nonsoap surface active agents.
- Many compounds are known that have germicidal or bacteriostatic properties against specific microorganisms or groups thereof, but such property is generally destroyed or seriously impaired when the compound is incorporated into detergent compositions.
- It is another object of the present invention to provide a hydrophilic skin cleansing composition comprising a skin-substantive germicide.
- 1-hydroxy-2pyridinethione compounds when incorporated in detergent compositions retain their bacteriostatic properties and are skin substantive.
- the use of detergent compositions embodying 1-hydroxy-2-pyridinethione compounds retards the growth of body germs and bacteria for much longer periods than the use of detergent bases.
- Acids Lux Ivory (percent) (percent) Oleic and linoleic 45 46 S arlc 1D 14 Palmitic 30 30 Lower Fatty (myristic, lauric, etc.) 15 10 Potassium oleate is a liquid soap formed from 11 parts H20, 1 par KOH, 4 parts glycerin and 4 parts red 011 (oleic acid).
- 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 fgJ'ltrawet K is a sodium salt of sulfonated Gm petroleum hydrocar ons.
- Aerosol OS is a sodium alkyl sulfonate.
- Aerosol AY is diamyl sodium sulfosuccinate.
- Tween 80 is a polyoxethylene sorbitan monooleate.
- Brij 35 is a polyoxyethylene lauryl ether.
- Pluronic F-GS is a condensate of ethylene oxide with a hydrocarbon base formed by condensing propylene oxide with propylene glycol.
- Sterox AI is a polyoxyethyleue 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 se was tested -by taking plugs of the blended solid com-positions (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), Staphsubstantivity, i.e., the property of remaining on the skin ylacoccus aureus (found on the human skin) and Sal- 3 4 monella typhosa (cause of typhoidfever). These three Substantivity was measured by soaking untanned calfbacteria are conventionally used in in vitro testing for acskin buttons in an 8% aqueous solution of the test soap, tivity and substantivity.
- the initial whiteness is reported both after mixing of the pyridinethione compound 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.
- samples 29 and 33 (zinc salt of I hydroxy 2 pyridinethione) gave excellent results in the color tests and, in fact, slightly better than the control bars containing no bacteriostatic agent.
- Samples 48 and 50 (2,2' dithiopyridine 1,1 dioxide) were also fairly good except for the surface sheen on the initial bar, a feature which might be overcome by changing the barforming 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 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 IV.
- Bacterio'static activity and TABLE II'LfiQPLIT-USE HAND WASHING TEST From the results reported in Table III, it will be noted that the bacteriostatic activity and substantivity of the substantivity were then determined by the same methods described and reported in Table II.
- Table V shows the pyridinethione compounds can be demonstrated in an post-aging results of these tests.
- 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, so-
- 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.
- pyridinethione compounds have excellent germicidal and substantive properties, which are maintained after prolonged aging, but these compounds also give excellent results in the various color tests which are so important in oifering 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.
- This invention is concerned with l-hydroxy-Z-pyridinethione (and derivatives) which has the following structural formula in tautomeric form, the sulfur being attached to No. 2 position of the pyridine ring:
- 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.
- a hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and a germicide selected from the group consisting of l-hydroxy-Z-pyridinethione, 2,2-dithiopyridine-l,l-dioxide, and inorganic metal salts of l-hydroxy-Z-pyridinethione in which the cation is selected from the group consisting of sodium, zinc, titanium, iron, manganese, zirconium, tin, cadmium, and barium, in an amount of from about .0l% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
- a hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of an inorganic salt of l-hydroxy-Z- pyridinethione in which the cation is selected from the group consisting of sodium, zinc, titanium, iron, manganese, zirconium, tin, cadmium and barium, in an amount of from about .0l% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
- a hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the zinc salt of l-hydroxy-Z-pyridinethione in an amount of from about 01%; to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
- a hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the cadmium salt of l-hydroxy-Z-pyridinethione in an amount of from about .0l% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
- a hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the tin salt of 1-hydroxy-2-pyridinethione in an amount of from about .0l% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
- a hydrophlic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic,
- nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents and a germicide consisting of the zirconium salt of l-hydroxy-Z-pyridinethione in an amount of from about .01% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said compositon.
- a hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the titanium salt of I-hydroxy-Z-pyridinethione in an amount of from about 301% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
Description
United States Patent This application is a continuation-in-part of copending application Ser. No. 306,684, filed Sept. 5, 1963, and now abandoned; application Ser. No. 306,684 is a continuation-in-part of copending application Ser. No. 85,005,
filed Jan. 26, 1961, and now abandoned; and application Ser. No. 85,005 is a continuation-in-part of copending application Ser. No. 741,994, filed June 16, 1958, and now abandoned.
The present invention relates to germicidal detergent compositions, and more particularly to hydrophilic skin cleansing compositions comprising a skin substantive germicide. The compositions contemplated by this invention depend upon the presence of l-hydroxy-Z-pyridine thione, salts and esters thereof, and related compounds such as 2,2-dithio-pyridine-1-, l-dioxide as the substantive germicide.
It has become increasingly desirable to improve the bacteriostatic etfect of detergent compositions. The term detergent is intended to denote soap and nonsoap surface active agents. Many compounds are known that have germicidal or bacteriostatic properties against specific microorganisms 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 3,412,033 Patented Nov. 19, 1968 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) Nonirritating to skin.
(6) No unpleasant odor.
It is an 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 is another object of the present invention to provide a hydrophilic skin cleansing composition comprising a skin-substantive germicide.
It has been discovered that 1-hydroxy-2pyridinethione compounds when incorporated in detergent compositions retain their bacteriostatic properties and are skin substantive. The use of detergent compositions embodying 1-hydroxy-2-pyridinethione compounds retards the growth of body germs and bacteria for much longer periods than the use of detergent bases.
The specific procedures 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 I.
TABLE I Code Letter B C D E Luv 100 Ivory. 100 Dial". 100
Percent Detergent Compositions F G H I J K L M N O P Q Carney. 100 Cashmere Bouquet" Potassium Oleate "Ultrawet K (Anionic). Aerosol'OS" (Anionic) Aerosol'AY (Anionic). Carboxymethyl Cellulose "Tween 80 (Nonionic) Bn'j 35'." (Nom'onic) Pluronic F438 (Nonionic) Sterox AJi' (Nonionic)-- Parafiinj Intracol 0A" (Cationic) Antaron FC-34 (Amphoteric)- Mixed Phosphates- Key to Table I 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:
Acids Lux Ivory (percent) (percent) Oleic and linoleic 45 46 S arlc 1D 14 Palmitic 30 30 Lower Fatty (myristic, lauric, etc.) 15 10 Potassium oleate is a liquid soap formed from 11 parts H20, 1 par KOH, 4 parts glycerin and 4 parts red 011 (oleic acid).
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 fgJ'ltrawet K is a sodium salt of sulfonated Gm petroleum hydrocar ons.
Aerosol OS is a sodium alkyl sulfonate.
Aerosol AY is diamyl sodium sulfosuccinate.
Tween 80 is a polyoxethylene sorbitan monooleate.
Brij 35 is a polyoxyethylene lauryl ether.
Pluronic F-GS is a condensate of ethylene oxide with a hydrocarbon base formed by condensing propylene oxide with propylene glycol.
Sterox AI is a polyoxyethyleue 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 se was tested -by taking plugs of the blended solid com-positions (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), Staphsubstantivity, i.e., the property of remaining on the skin ylacoccus aureus (found on the human skin) and Sal- 3 4 monella typhosa (cause of typhoidfever). These three Substantivity was measured by soaking untanned calfbacteria are conventionally used in in vitro testing for acskin buttons in an 8% aqueous solution of the test soap, tivity and substantivity. The plates were incubated for 24 then repeatedly rinsing the buttons in distilled water, and hours at about 37 C. and then the diameter of the Zone subsequently placing the buttons on nutrient agar plates of no bacterial growth around each plug was measured 5 inoculated with the same bacteria as noted above. Therein millimeters (diameter of plug or peni-cup excluded) after, the procedure is the same as following for bacterioand recorded. static activity per se. The results are reported in Table II.
TABLE IL-BACTERIOSTAIIC ACTIVITY AND SUBSTANTIVITY Inhib. Zone-Diameter (mm.)
Number Additive Percent Soap Soap Plug Cal s S A T S A T 1 None (Control) B 0 0 O 0 0 2 do C 0 0 0 0 0 0 H 0 0 0 0 0 O I 20 14 20 0 0 0 J 30 26 24 0 6 0 K 0 0 0 0 0 0 L O 0 0 0 0 0 M 9 3 11 0 0 0 0. C 26 18 24 9 3 6 1 C 30 20 24 4 8 0. 5 B 33 22 28 9 5 6 1 B 35 22 28 9 8 8 0. 5 B 29 23 6 4 3 1 B 28 19 23 10 10 6 1 O 40 20 40 16 14 18 1 B 40 28 35 15 12 22 1 B 48 18 12 3 8 1 C 50 30 30 12 16 10 1 G 48 32 30 16 14 12 0. 5 G 46 31 30 9 13 10 0. 1 G 46 32 31 7 8 6 07 G 46 26 32 5 8 4 1 H 32 14 22 5 4 4 1 I 32 30 22 19 12 10 1 .l' 50 30 10 12 8 1 K 44 30 26 11 7 7 1 L 26 26 11 12 6 1 M 25 9 18 9 4 9 l B 40 13 24 14 4 12 07 B 30 18 22 6 6 4 07 C 31 21 21 6 7 5 0. 5 C 40 20 32 8 5 9 1 C 18 30 10 8 11 1 C 44 24 26 18 13 10 07 D 30 20 26 4 6 4 07 E 30 18 22 5 6 4 07 F 28 18 24 5 6 4 1. 0 G 48 46 16 16 12 0. 5 G 42 30 41 6 8 6 0. 1 G 34 28 34 4 6 4 07 G 32 27 30 4 3 3 1 H 38 16 24 14 7 7 1 I 30 28 20 10 11 8 1 J 40 30 40 8 8 6 1 K 42 18 22 10 9 5 1 L 32 26 28 8 6 4 1 M 20 8 16 2 2 1 1 B 50 18 25 15 9 16 0. 5 C 43 23 25 14 6 9 1 1 C 51 21 34 13 5 14 1. 0 G 46 34 40 16 16 12 0. 5 G 44 30 33 7 12 8 0. 1 G 42 28 30 5 7 5 07 G 38 27 30 6 7 3 1 C 42 22 28 18 10 10 1 H 24 14 18 1 0 Tr. 1 I 16 12 16 4 0 2 1 .1 28 18 20 2 1 2 1 K 27 14 36 4 1 8 1 L 34 10 19 4 2 5 1 M 22 17 15 5 2 1 1 B 30 14 20 14 3 12 l-H-2-P, manganous 1 C 40 28 28 9 10 8 1-H2P, zirconyl 1 C 45 34 31 15 15 10 1-H-2-P, lauryl pyridinium. 1 C 36 28 29 7 6 3 1-H-2-P, stannic.- 1 C 45 32 30 13 15 14 1-H-2-P, cadmium 1 O 22 21 19 11 9 9 1-H-2-P, manganous 0.75 C 46 30 28 14 15 12 0. 5 C 44 28 24 8 9 7 0. 1 C 34 25 22 T1. 0 0 0. C 43 28 32 12 12 9 0. 5 C 40 28 31 11 12 5 O. 1 C 30 23 22 Tr 0 0 0. 75 C 38 25 27 10 7 Tr. 0. 5 C 43 26 26 5 7 1 O. 1 C 32 26 21 Tr, Tr 0 0. 75 C 46 29 32 11 11 4 0. 5 C 40 29 31 15 14 11 0. 1 O 29 21 20 0 0 0 0. 75 C 25 21 16 10 10 10 0. 5 C 25 21 18 7 9 9 0. 1 C 24 20 15 2 6 2 1. 0 C 46 26 26 19 14 11 1. 0 C 42 22 26 13 14 11 1. 9 C 46 25 24 14 15 13. 5 1. 0 C 44 24 24 12 14 8 1. 0 C 41 23 24 7 10 5 1. 0 C 46 25 23 20 14 10 1. 0 C 26 19 18 Tr. 3 0 1. 0 C 46 26 26 19 15. 5 14 Key to Table II: S-Bac-illus s-ubtz'lis; ASzaphylocuccus aureus; T-Salmonella typhosa; 1H-2P1-hydroxy-2- ridinetiione- 1-H2P d1 11' "-dithiopyridine-1,l-dloxidc; Ziram-Zine dimethyldithiocarbamate; ThiramTetramethylthlurarn ausinna z an V It is clear from the results reported in Table H that the pyridinethione compounds exhibit both bacteriostatic activity and substantivity. Samples number 33 and 50 were further tested in a modification of the split-use hand washing test described by Quinn et al., Applied Microbiology 2, 2024 (1954). In the modified test, first the right hand was uncovered and the left hand covered with a neoprene glove. Then both hands were soaped for 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 wrists for 75 seconds, followed by rinsing the hands for 20 seconds while immersed in the wash water and then draining for 20 seconds. Thereafter, the left hand was uncovered, the right hand was covered with a neoprene glove, and the actual hand washing technique. Various other desirable properties of the same soap-pyridinethione compound mixtures of Table II are reported in Table IV.
The initial whiteness is reported both after mixing of the pyridinethione compound 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 IV are of the same numbered samples of Table II, but all the samples of Table II were not tested here.
TABLE IV.COLOR CHANGES DUE TO AGING 1 See Table II.
2 This slight surface sheen, caused evidently by contact with the brass bar-forming die was removed before the oven and sunlight aging tests washing procedure repeated using unmedicated soap, i.e., control soap. Thus, the left hand serves as an unmedicated soap-washed control for the test soap-washed right hand.
The hands of each subject were washed three times each day and bacterial counts made on the wash water used 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 of the test compound is present in the wash water to infiuence the results. Aliquots of the wash water in which 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 Table III:
It will be noted that samples 29 and 33 (zinc salt of I hydroxy 2 pyridinethione) gave excellent results in the color tests and, in fact, slightly better than the control bars containing no bacteriostatic agent. Samples 48 and 50 (2,2' dithiopyridine 1,1 dioxide) were also fairly good except for the surface sheen on the initial bar, a feature which might be overcome by changing the barforming 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 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 IV. Bacterio'static activity and TABLE II'LfiQPLIT-USE HAND WASHING TEST From the results reported in Table III, it will be noted that the bacteriostatic activity and substantivity of the substantivity were then determined by the same methods described and reported in Table II. Table V shows the pyridinethione compounds can be demonstrated in an post-aging results of these tests.
TABLE V.-BACTERIOSTATIC ACTIVITY AND SUBSTAN- TIVITY AFTER HEAT AGING Inhibition ZoneDiameter (mm) Weeks Number 1 Aged Soap Plug Calfskin Button 5 A '1 S A T 2 0 0 O 0 0 0 6 0 0 0 0 0 0 2 36 18 24 16 10 2 36 18 36 12 8 16 6 44 1o 16 1o 2 Tr. 20 6 33 12 20 13 7 13 2 42 13 22 10 7 14 2 44 12 11 7 ll 1 See Table II.
2 Tr.Growth touching button in one place.
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, so-
dium, 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 or 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 excellent germicidal and substantive properties, which are maintained after prolonged aging, but these compounds also give excellent results in the various color tests which are so important in oifering 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 5% 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 10% 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-Z-pyridinethione (and derivatives) which has the following structural formula in tautomeric form, the sulfur being attached to No. 2 position of the pyridine ring:
N l 1%srr 5 3 Q-pyridinethiol-l-oxide, or 2-mercaptopyridine l-oxide 1-hydroxy-Z-pyridinethione specifically disclosed, it will be apparent to one skilled in the art that inorganic salts other than those tested are suitable. Further, other amine salts, quaternary ammonium salts and other esters are also suitable. The disulfide (2,2- dithiodipyridine l,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 l-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 hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and a germicide selected from the group consisting of l-hydroxy-Z-pyridinethione, 2,2-dithiopyridine-l,l-dioxide, and inorganic metal salts of l-hydroxy-Z-pyridinethione in which the cation is selected from the group consisting of sodium, zinc, titanium, iron, manganese, zirconium, tin, cadmium, and barium, in an amount of from about .0l% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
2. A hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of an inorganic salt of l-hydroxy-Z- pyridinethione in which the cation is selected from the group consisting of sodium, zinc, titanium, iron, manganese, zirconium, tin, cadmium and barium, in an amount of from about .0l% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
3. A hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the zinc salt of l-hydroxy-Z-pyridinethione in an amount of from about 01%; to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
4. A hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the cadmium salt of l-hydroxy-Z-pyridinethione in an amount of from about .0l% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
5. A hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the tin salt of 1-hydroxy-2-pyridinethione in an amount of from about .0l% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
6. A hydrophlic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic,
nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the zirconium salt of l-hydroxy-Z-pyridinethione in an amount of from about .01% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said compositon.
7. A hydrophilic skin cleansing composition consisting essentially of at least one synthetic organic detergent selected from the group consisting of nonsoap anionic, nonionic, cationic and amphoteric detergents and fatty acid soaps and nonsoap surface active agents, and a germicide consisting of the titanium salt of I-hydroxy-Z-pyridinethione in an amount of from about 301% to about 10% by weight, said germicide being both skin-substantive and germicidally active in said composition.
References Cited UNITED STATES PATENTS 2,742,393 4/1956 Bernstein et a1. 167-33 2,742,476 4/1956 Bernstein et al 260294.8 2,809,971 10/ 1957 Bernstein et al 260270 2,846,398 8/1958 Beaver et a1 252-106 10 LEON D. ROSDOL, Primary Examiner.
S. E. DARDEN, Assistant Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,412,033 November 19, 1968 Kenneth S. Karsten et al.
It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 8, lines 38, 50, 59 and 68, and column 9, lines 2 and 10, strike out "and nonsoap surface active agents", each OCCUTTBHCG Signed and sealed this 22nd day of July 1969.
(SEAL) Attest:
WILLIAM E. SCHUYLER, JR.
Edward M. Fletcher, Jr.
Commissioner of Patents Attesting Officer
Claims (1)
1. A HYDROPHILIC SKIN CLEANSING COMPOSITION CONSISTING ESSENTIALLY OF AT LEAST ONE SYNTHETIC ORGANIC DETERGENT SELECTED FROM THE GROUP CONSISTING OF NONSOAP ANIONIC, NONIONIC, CATIONIC AND AMPHOTERIC DETERGENTS AND FATTY ACID SOAPS AND A GERMICIDE SELECTED FROM THE GROUP CONSISTING OF 1-HYDROXY-2-PYRIDINETHIONE, 2,2''-DITHIOPYRIDINE -1,1-DIOXIDE, AND INORGANIC METAL SALTS OF 1-HYDROXY-2-PYRIDINETHIONE IN WHICH THE CATION IS SELECTED FROM THE GROUP CONSISTING OF SODIUM, ZINC, TITANIUM, IRON, MANGANESE, ZIRCONIUM, TIN, CADMIUM, AND BARIUM, IN AN AMOUNT OF FROM ABOUT .01% TO ABOUT 10% BY WEIGHT, SAID GERMICIDE BEING BOTH SKIN-SUBSTANTIVE AND GERMICIDALLY ACTIVE IN SAID COMPOSITION.
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US30668463A | 1963-09-05 | 1963-09-05 | |
US444858A US3236733A (en) | 1963-09-05 | 1965-04-01 | Method of combatting dandruff with pyridinethiones metal salts detergent compositions |
US500173A US3412033A (en) | 1963-09-05 | 1965-10-21 | Germicidal detergent compositions |
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Cited By (19)
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US3852441A (en) * | 1970-12-14 | 1974-12-03 | Procter & Gamble | Synergistic mixtures of diphenylbismuth acetate and the zinc salt of 1-hydroxy-2-pyridine thione effect as antibacterial and antifungal agents |
US3890434A (en) * | 1971-10-18 | 1975-06-17 | Olin Corp | Hair and antiseptic formulations containing adducts of bis-(2-pyridyl-1-oxide) disulfide |
US3949071A (en) * | 1972-09-18 | 1976-04-06 | Ferraton Aktieselskab | Method and composition for treating burns and scalds |
US4161526A (en) * | 1978-07-20 | 1979-07-17 | Sterling Drug Inc. | Zinc salt prevention or removal of discoloration in pyrithione, pyrithione salt and dipyrithione compositions |
US4379753A (en) * | 1980-02-07 | 1983-04-12 | The Procter & Gamble Company | Hair care compositions |
US4496559A (en) * | 1981-09-02 | 1985-01-29 | Olin Corporation | 2-Selenopyridine-N-oxide derivatives and their use as fungicides and bactericides |
EP0158481A2 (en) * | 1984-03-28 | 1985-10-16 | THE PROCTER & GAMBLE COMPANY | Hair care compositions |
US5103500A (en) * | 1990-04-09 | 1992-04-14 | Nager Frank B | Odor suppressing disposable garment shield |
US5284649A (en) * | 1992-09-29 | 1994-02-08 | The Procter & Gamble Company | Deodorant gel sticks containing 1-hydroxy pyridinethione active |
WO1996029049A1 (en) * | 1995-03-20 | 1996-09-26 | Unilever Plc | Liquid cleansing formulations |
US20110197907A1 (en) * | 2010-02-16 | 2011-08-18 | James Robert Schwartz | Method For Providing Maximum Malodor And Irritation Control |
WO2012118783A1 (en) * | 2011-02-28 | 2012-09-07 | The Procter & Gamble Company | Bar compositions comprising platelet zinc pyrlthione |
WO2012118798A1 (en) * | 2011-02-28 | 2012-09-07 | The Gillette Company | Razor comprising a molded shaving aid composition comprising a pyrithione source |
WO2012116466A1 (en) * | 2011-02-28 | 2012-09-07 | The Procter & Gamble Company | Bar soap comprising pyrithione sources |
US8685908B2 (en) | 2011-02-28 | 2014-04-01 | The Procter & Gamble Company | Bar soap comprising pyrithione sources |
US8795695B2 (en) | 2011-08-15 | 2014-08-05 | The Procter & Gamble Company | Personal care methods |
US9333157B2 (en) | 2013-03-14 | 2016-05-10 | The Procter & Gamble Company | Bar soap compositions containing zinc pyrithione and a metal-pyridine oxide complex |
US9375389B2 (en) | 2013-04-18 | 2016-06-28 | The Procter & Gamble Company | Personal care compositions containing zinc pyrithione and a metal-phosphonate complex |
US9504638B2 (en) | 2012-05-11 | 2016-11-29 | The Procter & Gamble Company | Personal cleansing compositions comprising zinc pyrithione |
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US3852441A (en) * | 1970-12-14 | 1974-12-03 | Procter & Gamble | Synergistic mixtures of diphenylbismuth acetate and the zinc salt of 1-hydroxy-2-pyridine thione effect as antibacterial and antifungal agents |
US3890434A (en) * | 1971-10-18 | 1975-06-17 | Olin Corp | Hair and antiseptic formulations containing adducts of bis-(2-pyridyl-1-oxide) disulfide |
US3949071A (en) * | 1972-09-18 | 1976-04-06 | Ferraton Aktieselskab | Method and composition for treating burns and scalds |
US4161526A (en) * | 1978-07-20 | 1979-07-17 | Sterling Drug Inc. | Zinc salt prevention or removal of discoloration in pyrithione, pyrithione salt and dipyrithione compositions |
US4379753A (en) * | 1980-02-07 | 1983-04-12 | The Procter & Gamble Company | Hair care compositions |
US4496559A (en) * | 1981-09-02 | 1985-01-29 | Olin Corporation | 2-Selenopyridine-N-oxide derivatives and their use as fungicides and bactericides |
EP0158481A2 (en) * | 1984-03-28 | 1985-10-16 | THE PROCTER & GAMBLE COMPANY | Hair care compositions |
EP0158481A3 (en) * | 1984-03-28 | 1986-12-30 | THE PROCTER & GAMBLE COMPANY | Hair care compositions |
US5103500A (en) * | 1990-04-09 | 1992-04-14 | Nager Frank B | Odor suppressing disposable garment shield |
US5284649A (en) * | 1992-09-29 | 1994-02-08 | The Procter & Gamble Company | Deodorant gel sticks containing 1-hydroxy pyridinethione active |
WO1996029049A1 (en) * | 1995-03-20 | 1996-09-26 | Unilever Plc | Liquid cleansing formulations |
US20110197907A1 (en) * | 2010-02-16 | 2011-08-18 | James Robert Schwartz | Method For Providing Maximum Malodor And Irritation Control |
US8978666B2 (en) | 2010-02-16 | 2015-03-17 | The Procter & Gamble Company | Method for providing maximum malodor and irritation control |
WO2012118783A1 (en) * | 2011-02-28 | 2012-09-07 | The Procter & Gamble Company | Bar compositions comprising platelet zinc pyrlthione |
WO2012118798A1 (en) * | 2011-02-28 | 2012-09-07 | The Gillette Company | Razor comprising a molded shaving aid composition comprising a pyrithione source |
WO2012116466A1 (en) * | 2011-02-28 | 2012-09-07 | The Procter & Gamble Company | Bar soap comprising pyrithione sources |
US8685908B2 (en) | 2011-02-28 | 2014-04-01 | The Procter & Gamble Company | Bar soap comprising pyrithione sources |
US9119796B2 (en) | 2011-02-28 | 2015-09-01 | The Gillette Company | Razor comprising a molded shaving aid composition comprising a pyrithione source |
US8795695B2 (en) | 2011-08-15 | 2014-08-05 | The Procter & Gamble Company | Personal care methods |
US9504638B2 (en) | 2012-05-11 | 2016-11-29 | The Procter & Gamble Company | Personal cleansing compositions comprising zinc pyrithione |
US9333157B2 (en) | 2013-03-14 | 2016-05-10 | The Procter & Gamble Company | Bar soap compositions containing zinc pyrithione and a metal-pyridine oxide complex |
US9655831B2 (en) | 2013-03-14 | 2017-05-23 | The Procter & Gamble Company | Bar soap compositions containing zinc pyrithione and a metal-pyridine oxide complex |
US9375389B2 (en) | 2013-04-18 | 2016-06-28 | The Procter & Gamble Company | Personal care compositions containing zinc pyrithione and a metal-phosphonate complex |
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