US3636213A - Solubilization of heavy metal salts of 1-hydroxy-2-pyridinethione - Google Patents

Solubilization of heavy metal salts of 1-hydroxy-2-pyridinethione Download PDF

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Publication number
US3636213A
US3636213A US706604A US3636213DA US3636213A US 3636213 A US3636213 A US 3636213A US 706604 A US706604 A US 706604A US 3636213D A US3636213D A US 3636213DA US 3636213 A US3636213 A US 3636213A
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Prior art keywords
pyridinethione
heavy metal
salts
amine
salt
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Expired - Lifetime
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US706604A
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Terry Gerstein
William Perlberg
Milton Schwarz
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Revlon Inc
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Revlon Inc
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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • 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
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • 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
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/006—Antidandruff preparations

Definitions

  • the present invention relates to methods of solubilizing heavy metal salts of 1-hydroxy-2-pyridinethione, to such solubilized salts, and to compositions containing the solubilized salts. More in particular, the present invention relates to solubilizing heavy metal salts of l-hydroxy-2- pyridinethione by admixture of the salts with an amine, suitably a primary amine, or with a polyalkylene imine, to such solubilized salts, and to compositions containing the solubilized salts.
  • an amine suitably a primary amine, or with a polyalkylene imine
  • Heavy metal salts of 1-hydroxy-2-pyridinethione are described in detail in US. Pat. 2,809,971.
  • the heavy metal salts are conveniently prepared by reaction of a soluble heavy metal compound with a soluble salt of pyridinethione, such as an alkali metal salt or ammonium salt. On combination of these reactants, the heavy metal salt precipitates and is recovered.
  • a soluble heavy metal compound such as an alkali metal salt or ammonium salt.
  • the heavy metal salt precipitates and is recovered.
  • heavy metal salts in the present specification are meant salts like those disclosed in said US. Pat. 2,809,971, i.e.
  • heavy metal group is, inter alia, copper, iron, manganese, tin, mercuery, cobalt, chromium, lead, gold, cadmium, nickel, silver, zinc, titanium, arsenic, antimony, zirconium, or bismuth.
  • the term heavy metal as employed in the present specification includes elements of metallic character such as arsenic, characterized in the patent as semi-metals.
  • the heavy metal salts of pyridinethione are useful as fungicides and bactericides, and certain of them are particularly adaptable to topical application to the skin.
  • the zinc salt specifically is quite effective as an agent against seborrhea, and has found wide acceptance in the cosmetic art for use in soaps, shampoos, hairdressings, and the like.
  • the heavy metal salts of pyridinethione such as the zinc salt
  • the zinc salt for example, is substantially insoluble in water (10-20 p.p.m.), ethanol (310 p.p.m.), benzene (35 p.p.m.), petroleum oils, and most common organic solvents.
  • the material is slightly more soluble in chloroform (3400 ppm), dimethyl formamide (8100 ppm), and dimethyl sulfoxide (5.13 percent). Accordingly, it has been found difiicult to formulate suitable cosmetic and other compositions containing these heavy metal salts in dissolved form.
  • the insoluble heavy metal salts of pyridinethione can be solubilized in common organic solvents and/or water by combination with an amine, suitably a primary amine, or with a polyalkylene imine.
  • Solutions of the heavy metal salts in an amine or imine can be used per se for certain specialized cosmetic applications, such as hair straightening. However, most commonly, the resultant alkaline solutions are partially neutralized to form compositions of a pH acceptable for more general application to the skin and hair.
  • the zinc salt is soluble in Water at pH 7 to an extent of about 10-20 parts per million. This is raised to a value of 35-50 parts per millon at a pH of 8. According to the present invention, however, the solubility of the zinc salt in compositions having a pH of about 8 can be as high as at least 200 parts per million or higher.
  • the biological activity of salts such as zinc pyridinethione has been reported to increase in alkaline solutions as a result of its greater solubility. Because of the increased biological efficacy of the salts solubilized according to the present invention, minimum concentrations of the salt can be used in compositions containing the same to produce maximum beneficial elfects. Nevertheless, the increased solubility and increased biological activity of the solubilized heavy metal salts have not been observed to involve increased toxicity of the solubilized materials.
  • amines useful for solubilizing heavy metal pyridinethione salts a wide variety of materials, principally primary amines, can be used.
  • Suitable amines include such diverse materials as the alkyl and aryl monoand polyamines including 1,3-propane diamine, dodecyl amine and other fatty amines, aniline, N-methyl aniline, and benzylamine; amino alcohols such as 2-amino-2-methyl-1,3-propanediol, and ethanolamine; and primary amines additionally containing aliphatic hetero atoms of nitrogen, oxygen, or sulfur such as imino-bis-propylamine, methylimino-bispropylamine, N-(3-aminopropyl)-diethanolamine, bis-(2- aminoethyl) sulfide, diglycol amine, di-ethoxyand triethoxy-propylamine, and S-methoxy-n-propylamine.
  • the heavy metal pyridinethioine salts are soluble in these typical materials to an extent of at least about 10 percent.
  • zinc pyridinethione is soluble to more than 10 percent in dodecyl amine, and to about 42 percent in diglycol amine.
  • the last mentioned amine is a preferred amine for solubilizing zinc pyridinethione.
  • the heavy metal salts are somewhat less soluble, but still usefully so, in amines such as ethoxylatedor propoxylated-polyethylene imine (about one part of alkoxy groups to 9 parts by weight of imine); some heterocyclic secondary amines such as pyrrolidine, piperidine, morpholine and 4-(3-aminopropyl) morpholine; and isocyclic amines such as cyclohexyl amine.
  • amines such as ethoxylatedor propoxylated-polyethylene imine (about one part of alkoxy groups to 9 parts by weight of imine); some heterocyclic secondary amines such as pyrrolidine, piperidine, morpholine and 4-(3-aminopropyl) morpholine; and isocyclic amines such as cyclohexyl amine.
  • amines such as ethoxylatedor propoxylated-polyethylene imine (about one part of alkoxy groups to
  • the salt and amine may be warmed, for example by gentle heating on a steam bath.
  • the resulting solutions can be diluted with organic solvent materials such as ethanol or with small amounts of Water.
  • organic solvent materials such as ethanol or with small amounts of Water.
  • the addition of a large amount of water to combinations of an amine of the above type with a heavy metal pyridinethione salt usually results in undue lowering of the pH and precipitation of a portion of the salt.
  • Solutions of pyridinethione salts in an amine such as diglycol amine have a pH value of about 11. Such highly alkaline solutions per se have limited utility, for example as hair straightening agents having anti-seborrheic properties. However, the most useful cosmetic and dermatologic compositions have a lower pH, commonly between about 7.5 and 9.5.
  • the alkaline amine solutions of heavy metal salts of pyridinethiones disclosed above can be neutralized to these lower pH values while still retaining relatively large amounts of the salt in soluble form in the resulting solution.
  • any acid can be used for the neutralizing function, the use of certain acids is preferred in compounding compositions for topical application to the skin.
  • physiologically acceptable acids are employed. Although mineral acids or simple carboxylic acids can be used, it is usually desired that the acid employed have properties other than acidity which are useful in compounding the composition, i.e. that the acid is a functional cosmetic acid.
  • Numerous functional cosmetic acids have been employed according to the present invention to neutralize amine solutions of heavy metal salts of pyridinethione in the formulation of cosmetic compositions.
  • the acids also function as thickening agents, surface-active agents, or the like.
  • compositions suitable for topical application to the hair and scalp show typical cosmetic compositions suitable for topical application to the hair and scalp.
  • the compositions have been formulated with a variety of functional cosmetic acids, as noted in detail in the examples.
  • EXAMPLE 1 A one-percent solution of zinc pyridinethione in diglycol amine was prepared. One part of the resulting solution was diluted with nine parts of ethyl alcohol to give a 0.1 percent solution of the salt. Seven parts of the resulting solution were then combined with 5-15 parts of glycerine and 15-35 parts of propylene glycol functioning as hair grooming agents. The composition was brought to a pH of 9 with an aqueous or ethanolic solution of an acid, and brought to 100 parts by weight with additional water or alcohol. Perfume was added as desired.
  • the resulting clear composition contains the so-lubilized zinc pyridinethione in a concentration of 700 parts per million, or 0.07 percent.
  • the following physiologically acceptable and/ or functional cosmetic acids can be employed: sebacic acid; oleic acid; isostearic acid; lauroyl amino diacetic acid; phosphated oleyl alcohol; an ethoxylated lauryl alcohol ester of phosphoric acid; oleyl sarcosine; various hydrolyzed copolymers of methyl vinyl ether and maleic anhydride of differing molecular weight and marketed under the tradename Gantrez; carboxylated copolymers of polyvinyl acetate; an oleic acid polypeptide; stearyland undecenylderivatives of imidazoline of the following structure:
  • the compositions had a slight tendency to form crystals on standing for extended periods of time. This crystal formation can be completely inhibited by reducing the concentration of the pyridinethione salt in the compositions, for example to half the value given or about 350 parts per million.
  • foaming action is provided by the foaming additive and by soaps formed between the diglycol amine and the acid component, which may comprise C C saturated or unsaturated fatty acids.
  • Polyethylene and polypropylene imines are complex materials whose formulas are generally shown as -(CH CH NH),, and (CH CH CH NH) respectively.
  • the polymers are branched, rather than completely linear, and contain primary and tertiary nitrogens in addition to the secondary nitrogens shown in the formulas.
  • the ratio of primary to secondary to tertiary nitrogens in these polyalkylene imines is approximately 122:1.
  • the polymers are prepared by the polymerization of ethylene or propylene imine in the presence of a proton donor such as an acid or a quaternizing or alkylating agent.
  • Zinc pyridinethione can be dissolved in polyethylene imine of an approximate molecular weight of 600 to an extent of about 33 percent. With increasing molecular weight, solubility decreases but is still about 10 percent in an imine having a molecular weight of 100,000 (the highest available commercially). Such solutions do not precipitate the original salt upon infinite dilution with water. However, the addition of undue amounts of acid to the solution will cause precipitation of the salt.
  • aqueous solutions of zinc pyridinethione in polyethylene or polypropylene imine are conveniently neutralized with concentrated hydrochloric acid or citric acid to a pH of about 8.5. Decreasing the acidity below this level causes the formation of a haze, and precipitation generally occurs at pH 8.3. Because of the water compatibility of the materials, polyalkylene iminesolubilized salts are widely useful, as in the typical formulations shown below.
  • EXAMPLE 3 The following clear solution is useful as a disinfectant or antiseptic.
  • the composition is bactericidal for Staph. aureus, Staph. albus, E. coli, Pityrasporum ovali, and Candida albfcans, as has been determined by applying the solution to a tube containing a culture of one of these bacteria and then plating out in agar to determine the extent of regrowth.
  • the formulation is a suitable clear medicated hair rinse.
  • EXAMPLE 4 0.5 part by weight of zinc pyridinethione is combined with 1 part by Weight of polyethylene imine and water is added to give parts.
  • This clear aqueous solution has a pH of about 11 and can be used as an anti-dandruff agent in hair straightening solutions, or in highly alkaline hair coloring solutions.
  • hydrochloric acid On combination with hydrochloric acid to bring the pH to a value of 8.5-9.0, a composition suitable as a hair rinse is obtained.
  • Polyalkylene glycol e.g. polypropylene glycol
  • ethoxylated glycols mixed polypropylenepolyethylene glycols
  • Fatty esters e.g. isopropyl myristate
  • Vegetable oils e.g. castor oil
  • Zinc pyridinethione 0.12.0
  • Polyethylene imine 1 0.24.0
  • Water 0-16 Denatured ethanol (95%) 45-95 Hydrochloric acid to pH 8.5 q.s. Perfume oil q.s.
  • polypropylene imine 0.8-16 parts (replacing ethanol).
  • additional grooming agents such as glycerine.
  • propylene glycol, or cellulose other derivatives, or of hair fixative polymers such as polyvinyl pyrrolidone may also be included.
  • An aqueous alcoholic clear hair setting lotion typically has the following composition:
  • the resin in the formula may be any one of several known to the art for hai rsetting uses such as polyvinyl pyrrolidone (PVP), PVP-vinyl acetate copolymers, methacrylate resins, or amino-methacrylate resins.
  • the plasticizers are also known in the art and may suitably include silicones, fatty esters, fatty alcohols, fatty amines, lanolin derivatives, aromatic esters, and proteinaceous materials.
  • compositions shown in Examples 16 are clear, and such clear compositions are only attainable using the solubilized pyridinethione heavy metal salts of the invention.
  • solubilized salts in water, can be used to prepare oiland-water emulsions useful for cosmetic or dermatologic purposes.
  • the salts are present in dissolved solubilized form-and not suspended-principally in the aqueous phase.
  • the method of solubilizing a fungicidally and bactericidally effective amount of a heavy metal salt of 1- hydroxy-2-pyridinethione in a member selected from the group consisting of dodecyl amine and diglycol amine which method comprises mixing the salt and the amine and then bringing the mixture to a pH between about 7.5 and about 9.5 by the addition thereto of a physiologically acceptable acid.

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  • Life Sciences & Earth Sciences (AREA)
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  • Veterinary Medicine (AREA)
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US706604A 1967-02-20 1968-02-19 Solubilization of heavy metal salts of 1-hydroxy-2-pyridinethione Expired - Lifetime US3636213A (en)

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GB8055/67A GB1202716A (en) 1967-02-20 1967-02-20 Solubilized metal salts of pyridinethione

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928605A (en) * 1972-09-29 1975-12-23 Procter & Gamble Phenylantimony bis(2-pyridinethiol-1-oxide in antibacterial and antifungal compositions
US3940482A (en) * 1971-04-21 1976-02-24 Colgate-Palmolive Company Solubilization of the zinc salt of 1-hydroxy-2-pyridinethione
US4832950A (en) * 1984-08-29 1989-05-23 Kao Corporation Antimicrobial suspensions and antimicrobial hair treatment compositions
US4835149A (en) * 1986-11-13 1989-05-30 Basf Corporation Solubilization of salts of pyridine-2-thiol-1-oxide
US5114984A (en) * 1991-04-26 1992-05-19 Olin Corporation Process for producing an antimicrobially effective polyurethane
US5284649A (en) * 1992-09-29 1994-02-08 The Procter & Gamble Company Deodorant gel sticks containing 1-hydroxy pyridinethione active
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
US5955415A (en) * 1997-08-04 1999-09-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polyethyleneimines for enhanced peroxygen bleach stability
US6908912B2 (en) 1999-06-25 2005-06-21 Arch Chemicals, Inc. Pyrithione biocides enhanced by zinc metal ions and organic amines
JP2006510713A (ja) * 2002-12-19 2006-03-30 アーチ ケミカルズ，インコーポレイテッド 亜鉛金属イオン及び有機アミンにより増強されたピリチオン殺生物剤
US20090298805A1 (en) * 2008-06-03 2009-12-03 Polson George A Topical pyrithione compositions and methods for treatment of nail fungus
US9464261B2 (en) 2010-05-14 2016-10-11 The Sun Products Corporation Polymer-containing cleaning compositions and methods of production and use thereof
US9968537B2 (en) 2013-09-06 2018-05-15 Jubilant Life Sciences Limited Anti-dandruff compositions and hair care formulations containing zinc pyrithione and quaternary ammonium salt

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0093541A3 (en) * 1982-04-29 1984-09-12 Beecham Group Plc Antidandruff compositions
US4443222A (en) * 1983-08-30 1984-04-17 The United States Of America As Represented By The Secretary Of Agriculture Zinc pyrithione process to impart antimicrobial properties to textiles
WO1990006125A1 (en) * 1988-12-05 1990-06-14 Olin Corporation Use of pyrithione-containing polymers as antimicrobial agents in personal care products
DE69319921T2 (de) * 1992-12-01 1999-04-15 Minnesota Mining And Mfg. Co., Saint Paul, Minn. Dauerhafte antimikrobische mittel

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3940482A (en) * 1971-04-21 1976-02-24 Colgate-Palmolive Company Solubilization of the zinc salt of 1-hydroxy-2-pyridinethione
US3928605A (en) * 1972-09-29 1975-12-23 Procter & Gamble Phenylantimony bis(2-pyridinethiol-1-oxide in antibacterial and antifungal compositions
US4832950A (en) * 1984-08-29 1989-05-23 Kao Corporation Antimicrobial suspensions and antimicrobial hair treatment compositions
US4835149A (en) * 1986-11-13 1989-05-30 Basf Corporation Solubilization of salts of pyridine-2-thiol-1-oxide
US5114984A (en) * 1991-04-26 1992-05-19 Olin Corporation Process for producing an antimicrobially effective polyurethane
US5284649A (en) * 1992-09-29 1994-02-08 The Procter & Gamble Company Deodorant gel sticks containing 1-hydroxy pyridinethione active
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
US5955415A (en) * 1997-08-04 1999-09-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polyethyleneimines for enhanced peroxygen bleach stability
US6908912B2 (en) 1999-06-25 2005-06-21 Arch Chemicals, Inc. Pyrithione biocides enhanced by zinc metal ions and organic amines
US20050158263A1 (en) * 1999-06-25 2005-07-21 Arch Chemicals, Inc., A Corporation Of The State Of Virginia Pyrithione biocides enhanced by zinc metal ions and organic amines
US8796252B2 (en) 1999-06-25 2014-08-05 Arch Chemicals, Inc. Pyrithione biocides enhanced by zinc metal ions and organic amines
JP2006510713A (ja) * 2002-12-19 2006-03-30 アーチ ケミカルズ，インコーポレイテッド 亜鉛金属イオン及び有機アミンにより増強されたピリチオン殺生物剤
EP1583420A4 (en) * 2002-12-19 2006-04-26 Arch Chem Inc PYRITHION BIOZIDE REINFORCED WITH ZINC METALLIONS AND ORGANIC AMINES
US20090298805A1 (en) * 2008-06-03 2009-12-03 Polson George A Topical pyrithione compositions and methods for treatment of nail fungus
WO2009148794A1 (en) 2008-06-03 2009-12-10 Arch Chemicals, Inc. Compositions and methods for nail fungus treatment
EP2293670A4 (en) * 2008-06-03 2011-11-30 Arch Chem Inc COMPOSITIONS AND METHOD FOR THE TREATMENT OF NAIL BED MUSHROOMS
US9464261B2 (en) 2010-05-14 2016-10-11 The Sun Products Corporation Polymer-containing cleaning compositions and methods of production and use thereof
US9968537B2 (en) 2013-09-06 2018-05-15 Jubilant Life Sciences Limited Anti-dandruff compositions and hair care formulations containing zinc pyrithione and quaternary ammonium salt

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GB1202716A (en) 1970-08-19

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