EP1583420A4 - Biocides pyrithione renforces par des ions metalliques de zinc et par des amines organiques - Google Patents

Biocides pyrithione renforces par des ions metalliques de zinc et par des amines organiques

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Publication number
EP1583420A4
EP1583420A4 EP02808337A EP02808337A EP1583420A4 EP 1583420 A4 EP1583420 A4 EP 1583420A4 EP 02808337 A EP02808337 A EP 02808337A EP 02808337 A EP02808337 A EP 02808337A EP 1583420 A4 EP1583420 A4 EP 1583420A4
Authority
EP
European Patent Office
Prior art keywords
zinc
pyrithione
antimicrobial composition
combinations
organic amine
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.)
Ceased
Application number
EP02808337A
Other languages
German (de)
English (en)
Other versions
EP1583420A1 (fr
Inventor
Michelle L Rioux
Diana T Ciccognani
Thomas J Palys
Patricia A Turley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arch Chemicals Inc
Original Assignee
Arch Chemicals Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Arch Chemicals Inc filed Critical Arch Chemicals Inc
Publication of EP1583420A1 publication Critical patent/EP1583420A1/fr
Publication of EP1583420A4 publication Critical patent/EP1583420A4/fr
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof

Definitions

  • the present invention is directed to pyrithione biocides, and more particularly to a stable, soluble biocidal composition displaying an enhanced biocidal effect, comprising an antimicrobially effective combination of pyrithione, pyrithione salt, or pyrithione adduct, a zinc source such a zinc alloy, zinc oxide, zinc hydroxide, or zinc salt, and 1,2- 1,3 alkanolamines and 1,2- 1 ,3-alkyldiamines.
  • the biocidal composition is provided in the form of a biocidal composition concentrate that is suitably incorporated directly into a functional fluid (such as a metalworking fluid) or incorporated into a functional fluid "masterbatch".
  • Polyvalent metal salts of pyrithione are known to be effective biocidal agents, and are widely used as fungicides and bacteriocides in paints and metalworking fluids. Pyrithiones are also used as fungicides and bacteriocides in personal care products such as anti-dandruff shampoos.
  • the polyvalent metal salts of pyrithione are only sparingly soluble in water and include ferric pyrithione, ferrous pyrithione, aluminum pyrithione, bismuth pyrithione, strontium pyrithione, copper pyrithione, zinc pyrithione, cadmium pyrithione, and zirconium pyrithione.
  • the most widely used divalent pyrithione salts are zinc pyrithione and copper pyrithione.
  • Zinc and copper pyrithione are useful as antimicrobial agents active against gram- positive and negative bacteria, fungi, and yeasts.
  • Zinc pyrithione is used as an antidandruff component in shampoos, while technical suspensions of zinc pyrithione andor copper pyrithione are used as preservatives in paints and polymers. Powders of these same salts are also used as cobiocides in antifouling paints. Synthesis of polyvalent pyritliione salts are described in U.S. Patent No. 2,809,971 to Berstein et al. Other patents disclosing similar compounds and processes for making them include U.S. Patent Nos. 2,786,847; 3,589,999; 3,590,035; 3,773,770.
  • pyrithione biocides have proven useful for a wide range of applications as outlined above, the utility of these compounds is limited to the control of select species and strains of fungi and bacteria. Further, while higher concentrations of pyrithione or its salts have been observed to control the growth of a wider range of organisms, the useful amount of pyrithione or its salts that can be added to a commercial product is limited by efficacy and economic considerations, and, to a lesser extent, environmental and toxicological concerns.
  • Inorganic salts of zinc such as zinc chloride, zinc sulfate, and zinc oxide, have been employed as a bacteriostatic and/or f ⁇ ingistatic compounds in a large variety of products including paints, coatings, and antiseptics.
  • zinc salts are less toxic than pyrithione or its salts, these compounds do not possess the high biocidal efficacy that is desired in many commercial applications.
  • U.S. Patents Nos. 5,854,266 and 5,883,154 disclose an aqueous antimicrobial composition protected against discoloration attributable to the presence of ferric ion or cupric ion therein, wherein the composition comprises pyrithione and a discoloration-inhibiting amount (between 0.001% to 10%) of a zinc compound selected from the group consisting of zinc salts of organic acids, zinc salts of inorganic acids, zinc hydroxide, zinc oxide, and combinations thereof.
  • a zinc compound selected from the group consisting of zinc salts of organic acids, zinc salts of inorganic acids, zinc hydroxide, zinc oxide, and combinations thereof.
  • this patent does not describe any advantageous antimicrobial effects between pyrithione and zinc.
  • U.S. Patent No. 4,161,526 discloses a white to cream yellow pyrithione salt or dipyrithione for application to skin or hair containing 0.01% to 1% of the zinc salt of an organic or inorganic acid, zinc hydroxide, zinc oxide, or combinations thereof.
  • this patent does not describe any advantageous effect between pyrithione and the zinc salt nor would it form a soluble composition of pyrithione and zinc.
  • Biofilms While bacteria and fungi have presented microbial contamination problems for many years, biofilms have recently been appreciated as a significant new source of microbial contamination.
  • Biofilms are generally characterized as aggregates of cells adhered to one another or to surfaces by an extracellular layer of slime. Biofilms are commonly found as contaminants in metalworking fluids because these fluids contain good carbon sources for growth of the organisms that are found in biofilms.
  • metalworking fluids contain good carbon sources for growth of the organisms that are found in biofilms.
  • high concentrations of biofilms in metalworking fluid result in rapid deterioration of the fluid, and can cause equipment problems and failure.
  • biofilms can also enhance the rates of corrosion of metal surfaces and degradation of paints, surface coatings and the construction materials underlying these coatings.
  • Biofilms are often responsible for both internal and cutaneous infections.
  • the increased resistance of biofilms to antimicrobial treatments often make biofilm-related infections more difficult to treat.
  • Medical devices, such as cardiac implants and catheters, and medical instruments, such as dialysis machines and dental waterlines also become contaminated by biofilms and can spread infection.
  • biofilm cells are much more resistant to disinfection than free-living cells, due in large part to the extracellular slime layer which acts as a protective coating.
  • strategies to control microbial contamination heretofore were typically developed in the laboratory against free-living organisms, and little or no attention was given towards determining the effectiveness of antimicrobial agents against biofilm.
  • the resistant biofilms are generally not affected by previously employed antimicrobials. If not removed or destroyed, biofilms can cause a multitude of problems in functioning fluid applications, such as corrosion, clogging, slime build up on surfaces, foul odors, fluid instability, machine down-time, and the like.
  • U.S. Patent 4,654,213 discloses an antimicrobial composition in which a water- soluble salt of zinc enhances the activity of the MgSO 4 adduct of 2,2'-dithiopyridine-l,l '- dioxide (MDS).
  • MDS 2,2'-dithiopyridine-l,l '- dioxide
  • U.S. Patent 4,370,325 discloses a composition containing 2,2'-dithiopyridine-l,l '- dioxide or one of its metal salt adducts, including MgSO 4 (MDS) and Zn salts, for treating eye and ear irritation and inflammation.
  • MDS metal salt adducts
  • Zn salts for treating eye and ear irritation and inflammation.
  • U.S. Patent 4,235,873 discloses a deodorant composition containing 2,2'- dithiopyridine-l, -dioxide or one of its metal salt adducts, including MgSO 4 (MDS) and Zn salts.
  • MgSO 4 MgSO 4
  • British Patent GB 2230 190 A discloses a preservative composition containing an isothiazolone and the ZnCl 2 adduct of 2,2'-dithiopyridine-l,l '-dioxide.
  • this patent does not describe any advantageous effect between pyrithione and the zinc salt.
  • Japanese patent application 6-134227 discloses an antibacterial filter incorporating ZnO or ZnO and zinc pyrithione. However, this patent does not describe any advantageous effect between pyrithione and the zinc salt.
  • Japanese patent application 7-118103 discloses an antimicrobial composition for coating stainless steel washing machine drums to prevent fouling of inner surfaces wherein ZnO is used as a carrier in a ZPT thermoplastic resin coating.
  • this patent does not describe any advantageous effect between pyrithione and the zinc salt.
  • a technical journal article discloses that the presence of 0.2% metallic copper or 0.2% metallic zinc was found to decrease the biocidal activity of sodium pyrithione in 12 different metalworking fluids (E.O. Bennet et al. (1982) Int. Biodeterioration Bull. 18[1]:7- 12).
  • Another technical journal article (M.M. Khattar & W.G. Salt, Journal of
  • Antimicrobial Chemotherapy (1993) 175-177) discloses the enhancement on the activity of pyrithione against Klebsiella pnenmoniae bacteria. More specifically, Figure 2(a) of the Khattar & Salt article describes a favorable enhancement in the activity of 0.1% pyrithione against that bacteria that is attributable to the use of 0.01% of zinc chloride in combination with the pyrithione.
  • Copending patent application Serial No. 09/599,371, filed on June 22, 2000 discloses a biocidal composition comprising a combination of pyrithione, pyrithione salt, or pyrithione adduct, and a zinc or copper source, such as copper and/or zinc metal, oxide, hydroxide, or salt thereof.
  • a zinc or copper source such as copper and/or zinc metal, oxide, hydroxide, or salt thereof.
  • the antimicrobial compositions disclosed in this patent application will readily form insoluble precipitates as the concentrations of pyrithione and the zinc source are increased in the compositions, such as would be required to construct a concentrated biocidal composition (or "composition concentrate").
  • compositions of pyrithione and zinc with concentrations greater than 0.0005% pyrithione and O.OOOOP/o ⁇ zinc will tend to form insoluble precipitates.
  • These insoluble precipitates reduce the effectiveness of the composition as an antimicrobial agent, present problems for the long-term storage of a commercial product, and prohibit use where soluble biocides are required.
  • the inability heretofore to construct a soluble, concentrated, biocidal composition of pyrithione and a zinc source necessitates the costly and inefficient administration of these components individually to applications, rather than in combination.
  • U.S. Patent No. 3,636,213 discloses solubilization of heavy metal salts of pyrithione (e.g., zinc pyrithione, copper pyrithione, and the like) using primary amines or polyalkyleneimines. However, this patent does not disclose any enhanced anti-microbial or anti-bio film effect of the resulting solubilized pyrithione salts as compared to pyrithiones alone.
  • pyrithione e.g., zinc pyrithione, copper pyrithione, and the like
  • U.S. Patent No. 3,940,482 discloses solubilization of heavy metal salts of pyrithione using long-chain polyamines for use in personal care products, such as soaps, shampoos, hairdressings, and the like. However, like the above patent, this patent does not disclose any improved or enhanced anti-microbial or anti-biofilm effect of the resulting solubilized pyrithione salts as compared to pyrithiones alone.
  • U.S. Patent No. 4,835,149 discloses a method of solubilizing insoluble metal salts of pyrithione (such as zinc pyrithione, copper pyrithione, and the like) in the presence of certain amine compounds and certain aminocarboxylic acids. However, like the above patents, this patent does not disclose any improved or enhanced anti-microbial or anti- biofilm effect of the resulting solubilized pyrithione salts as compared to pyrithiones alone.
  • U.S. Patent No. 5,114,984 discloses a process for imparting anti-bacterial and anti- fungal properties to a polyurethane foam by dissolving a pyrithione salt in an alkanolamine which is miscible in a polyol. However, like the above patents, this patent does not disclose any improved or enhanced anti-microbial or anti-bio film effect of the resulting solubilized pyrithione salts as compared to pyrithiones alone.
  • a stable, soluble, concentrated biocidal composition of pyrithione, pyrithione salt, or pyrithione adduct, and a zinc source which permits the concurrent deliverance of high concentrations of pyrithione and zinc ions to an application, and which also offers an enhanced biocidal efficacy to pyrithione and its derivatives against free-living microorganisms and biofilms.
  • Such a composition concentrate would be broadly useful, highly efficacious, cost-effective, and possess an enhanced biocidal effect both as an "in can" preservative and when diluted to form a "masterbatch" for use in a functional fluid, or when diluted directly into a functional fluid.
  • the present invention is believed to be an answer to that need.
  • the present invention is directed to a stable, soluble, antimicrobial composition concentrate comprising pyrithione, pyrithione salt or a pyrithione complex in an amount of from about 0.05% to about 20 weight percent, a zinc source in an amount of from about 0.01% to about 5%, and an organic amine component in an amount of from about 30% to about 80%, said percents being based upon the total weight of the composition concentrate.
  • the organic amine component comprises a first organic amine selected from the group consisting of 1,2-alkanolamines, and 1,3-alkanolamines, and combinations thereof, alone or in combination with a second organic amine selected from the group consisting of monomeric and polymeric forms of 1,2-alkyldiamines, monomeric and polymeric forms of 1,3-alkyldiamines, and combinations thereof.
  • the first organic amine must be present in the antimicrobial composition concentrate in an amount sufficient to insure that the amine component is soluble in the antimicrobial composition concentrate.
  • the antimicrobial composition concentrate advantageously can also contain a formaldehyde source in order to provide available formaldehyde in the antimicrobial composition concentrate.
  • the antimicrobial composition concentrate of the present invention is suitably diluted to form a functional fluid "masterbatch", or it can be diluted directly into a functional fluid itself, as desired.
  • the present invention relates to a stable, soluble, antimicrobial composition made by diluting the above antimicrobial composition concentrate, and comprising: from about 0.05% to about 5 wt% pyrithione or a pyrithione complex; from about 0.005% to about 1 wt% of a zinc source selected from the group consisting of zinc salts, zinc oxides, zinc hydroxides, zinc borates, zinc sulfates, zinc chlorides, zinc alloys, zinc complexes, and combinations thereof; and from about 0.5% to about 40 wt% of an amine component comprising a first organic amine selected from the group consisting of 1,2-alkanolamines, and 1,3- alkanolamines, and combinations thereof, alone or in combination with a second organic amine selected from the groups consisting of monomeric and polymeric forms of 1,2- alkyldiamines, and monomeric and polymeric forms of 1,3-alkyldiamines, and combinations thereof, with the proviso that the first organic amine selected from
  • the present invention relates to a method for providing a stable, soluble antimicrobial concentrate comprising from about 0.5% to about 20% of pyrithione, and a zinc source in an amount for from about 0.01% to about 5%.
  • the method comprises incorporating into said concentrate a stabilizing effective amount of at least one organic amine component selected from the group consisting of a first organic amine selected from the group consisting of 1,2-alkanolamines, and 1,3-alkanolamines, and combinations thereof, alone or in combination with a second organic amine selected from the group consisting of monomeric and polymeric forms of 1,2-alkyldiamines, and monomeric and polymeric forms of 1,3-alkyldiamines, and combinations thereof, with the proviso that the first organic amine is present in said antimicrobial composition in an amount sufficient to insure that said amine component is soluble in said antimicrobial composition.
  • the stabilizing effective amount of said organic amine is from 30% to about 80% based upon the total weight of said organic amine component
  • the present invention relates to a method of inhibiting the growth of free-living microorganisms or biofilm in a metalworking fluid, comprising the steps of: (A) incorporating the above antimicrobial composition concentrate into a metalworking fluid "masterbatch" concentrate comprising: (a) from about 0.05 to about 5% pyrithione or a pyrithione complex;
  • This soluble, stable antimicrobial composition concentrate comprises pyrithione or a pyrithione complex in combination with a zinc source, for example, a zinc salt, and certain 1,2- alkanolamines, and 1,3-alkanolamines, and combinations thereof, alone or in combination with a second organic amine selected from the group consisting of monomeric and polymeric forms of 1,2-alkyldiamines, and monomeric and polymeric forms of 1,3- alkyldiamines, and combinations thereof.
  • Particularly preferred organic amines are monoethanolamine, l-amino-2-propanol, 3-amino-l-propanol, and combinations thereof.
  • the zinc source employed in the present invention is selected from the group consisting of zinc salts, zinc oxides, zinc borates, zinc hydroxides, zinc sulfates, zinc chlorides, zinc alloys, zinc complexes, and combinations thereof.
  • composition concentrate of the present invention is suitably diluted to provide a so-called "masterbatch" for a functional fluid, such as a metalworking fluid concentrate or other coating composition, such as a paint.
  • a functional fluid such as a metalworking fluid concentrate or other coating composition, such as a paint.
  • the masterbatch suitably contains, for example, from 0.05% to 5% by weight of pyrithione, and the other components of the composition concentrate are proportionately diluted in preparing the masterbatch.
  • the antimicrobial combination of the present invention exhibits both "in-can” preservation and an enhanced biocidal effect, relative to pyrithione alone, and relative to pyrithione and zinc alone, against a wide range microorganisms in both the free-living and biofilm state.
  • This antimicrobial performance is greater than might be expected based upon the additive effect of the individual components of this composition.
  • the enhanced biocidal effectiveness associated with the composition of the present invention permits the use of smaller amounts of the pyrithione component of the present composition, as compared to the conventionally employed amounts of pyrithione-based biocides.
  • the term "enhanced biocidal effect” refers to an interaction between the pyrithione or pyrithione salt component, the water-soluble zinc component, and the organic amine component that results in the biocidal effect of the composition being greater than any of the components taken individually. Thus, the antimicrobial results of the composition exceed the expected biocidal effect of the combination based upon the performance of the individual components.
  • the present invention also permits manufacture of a concentrated, stable and soluble biocidal composition of pyrithione or pyrithione salt component, and a zinc component.
  • a concentrated, stable and soluble biocidal composition of pyrithione or pyrithione salt component, and a zinc component allows the simultaneous delivery of high concentrations of solubilized pyrithione and zinc components, and the resultant enhanced biocidal effects, efficiently to an application.
  • the invention permits the use of pyrithione in applications containing iron.
  • the presence of iron in applications commonly results in reduced efficacy of pyrithiones, and an accompanying blue discoloration of the application due to the formation of iron pyrithione.
  • the present invention displays a higher efficacy and a reduced propensity for discoloration when utilized in the presence of iron.
  • biofilm refers to any aggregate of cells anchored to one another, or to surfaces, by extracellular slime.
  • biofilms While most unicellular organisms produce a protective coating of slime, cells aggregated into biofilms are physically different from free-living cells and produce much more extracellular slime than free-living cells.
  • the slime structures which make up part of the biofilm are quite complex both biologically and architecturally. They are composed of discreet microbial aggregates (microcolonies) separated by water channels which can form large tower-shaped or mushroom-shaped structures. As biofilms develop, free-living cell detach from the biofilm and migrate through the environment in search of new areas to colonize and form new biofilm.
  • biofilms can cause many problems, including fluid deterioration/degradation, foul odors, corrosion, clogging of filters, transfer lines, nozzles, and crevices, fouling of machine surfaces, machine down-time, shorter tool life, fouling and damage of the workpiece, and the like.
  • biofilms can also enhance the rate of degradation of other fluids such as paints or other surface coatings.
  • Medical equipment such as cardiac implants, catheters, dialysis machines, dental waterlines, and the like, may also become contaminated by biofilms and spread infection.
  • Pyrithione in its acid form, or a pyritliione complex may be used in the composition of the present invention.
  • pyrithione complex refers to combinations of one or more pyrithione molecules and one or more metal atoms, such as pyrithione salts and adducts of pyrithione (e.g., 2,2 '-dithiopyridine- 1,1 '-dioxide in combination with a metal ion such as magnesium).
  • organic amine salt of pyrithione as well as the magnesium disulfide salt.
  • the two most preferred salts of pyrithione useful in the present invention are the sodium salt (i.e., sodium pyrithione) and zinc pyrithione.
  • Sodium pyrithione is a well-known commercial product that is commonly made by reacting 2-chloropyridine-N-oxide with NaSH and NaOH, as illustrated in the disclosure of U.S. Patent No. 3, 159,640.
  • Zinc pyrithione may be made by reacting l-hydroxy-2-pyridinethione (i.e., pyrithione acid) or a soluble salt thereof with a zinc salt (e.g., zinc sulfate) to form a zinc pyrithione precipitate, as illustrated in U.S. Patent No. 2,809,971.
  • the pyrithione or pyrithione complex is suitably employed in an amount in the range of from about 0.05 to about 20 wt.%, preferably from about 0.5 to about 15 wt.%, more preferably from about 1 to about 10 wt.%.
  • a "masterbatch" is suitably prepared with the pyrithione or pyrithione complex present in an amount in the range of from about 0.05% to about 5 wt.%, more preferably from about 0.01% to about 2.5 wt.%, all based on the total weight of the composition.
  • Zinc sources useful in the composition of the present invention include, for example, zinc alloys, zinc salts, zinc oxides, zinc hydroxides, zinc sulfates, zinc chlorides, zinc borates, and combinations thereof.
  • Examples of zinc salts that may be used in the composition of the present invention include zinc acetate, zinc oxide, zinc borate, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate, zinc citrate, zinc fluoride, zinc iodide, zinc lactate, zinc oleate, zinc oxalate, zinc phosphate, zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc tannate, zinc tartrate, zinc valerate, and the like. Combinations of zinc salts may also be used in the composition of the invention.
  • the zinc source is generally present in a range of from about 0.01 wt% to about 5 wt%, preferably from about 0.05 wt% to about 3 wt.%, based upon the weight of the concentrate.
  • This enables the final "working" functional fluid to contain an amount of the zinc source within the range of from 0.005 to 1 wt.%, advantageously from 0.01 to 0.1 wt.%, all based on the total weight of the working fluid.
  • the organic amine component comprises one or more 1,2 and 1,3 alkanolamines encompassed by the formula:
  • amine component in the present invention is any soluble combination of one or more alkanolamines encompassed by Formula 1 with one or more alkanolamines encompassed by the formula: NR r R 2 R 3 (Formula 2) wherein
  • amine component in the present invention is any soluble combination of one or more amines encompassed by Formula 1 and one or more amines selected from the group consisting of monomers and polymers of alkyl diamines of the formula: R 1 R 2 N-[(CH 2 ) n -CH 2 -NH-] m -H (Formula 3) where: n is 1 or 2, and m is about 1 to
  • R and R are hydrogens or lower alkyl groups having a total number of carbons less than or equal to 4.
  • 2-Amino-2-methyl-l -propanol also called AMP
  • 2-Amino-2-ethyl-l,3-propanediol also called AEPD
  • 2-Amino-2-ethyl-l,3-propanediol also called AEPD
  • 2-Aminoethoxy)ethanol also called diglycol amine
  • N-Methyldiethanolamine N,N-Dimethylethanolamine N,N-Diethylethanolamine N,N-Dibutylaminoethanol N,N Dimethylamino-2-propanol
  • the amount of organic amine suitably employed in the composition concentrates of the present invention suitably ranges from about 30 to about 80 wt%, preferably from about 40 to about 70 wt%, based upon the total weight of the concentrate. Upon dilution in the "masterbatch" or the "working" functional fluid, the organic amine amount is suitably from about 0.5 to 40 wt%, based upon the weight of the fluid.
  • a solvent or combination of solvents may be included in the antimicrobial composition of the invention. Suitable solvents include aqueous media such as water, or water in combination with one or more water-miscible organic solvent(s). Useful organic solvents include alcohols, such as methanol, ethanol, ethers, esters, glycols, and the like.
  • composition of the invention may also include formaldehyde as an additional biocide.
  • formaldehyde may be added directly, or in the form of a formaldehyde-releasing agent or donor such as, but not limited to, cis l-(3-chloroallyl)- 3,5,7-triaza-l-azoniaadamantane chloride, hexahydro-l,3,5-tris (2-hydroxyethyl)-s- triazine, 4,4-dimethyloxazolidine, 5-hydroxymethoxymethyl-l-l aza-3,7-dioxabicyclo- octane, dimethyloldimethyldantoin, N,N"-methylene bis [N'-[hydroxymethyl)-2,5-dioxo- 4-imidazolidinyl]urea], N-(hydroxymethyl)-N-(l ,3-dihydroxymethyl-2,5-dioxo-4- imidazolidinyl)-
  • formaldehyde-releasing agent is TRIADINE 10 (a combination of hexahydro-l,3,5-tris (2- hydroxyethyl)-s-triazine and omadine salts sold by Arch Chemicals, Inc. Norwalk, CT).
  • the formaldehyde is suitably employed in an amount in the range of from about 0.1 to about 30 wt.%, preferably from about 0.5% to about 15 wt%, based on the total weight of the composition.
  • formaldehyde-releasing agents generally only a fraction of the material is released to form formaldehyde.
  • hexahydro-l,3,5-tris (2-hydroxyethyl)-s-triazine undergoes formaldehyde release.
  • the appropriate conversion factor must be taken into account in order to provide the above ranges of formaldehyde in the composition of the invention, h an illustrative example, 500 ppm of hexahydro-l,3,5-tris (2-hydroxyethyl)-s-triazine results in about 160 ppm of formaldehyde being released.
  • 1500 ppm of hexahydro-l,3,5-tris (2-hydroxyethyl)-s-triazine results in about 480 ppm of formaldehyde being released.
  • the composition of the invention can be made by first mixing together one or more selected zinc sources and one or more organic 1 ,2- or 1 ,3- alkanolamines and optionally monomers and polymers of 1,2- or 1,3- alkyldiamines in an appropriate solvent or carrier, and then adding the pyrithione or pyrithione complex.
  • the composition of the invention may be made by adding the individual components separately to a solvent or functional blend or fluid being treated to impart antimicrobial protection.
  • the biocidal composition of the invention is useful as an algaecide, bactericide, and/or fungicide, and is particularly useful in inhibiting the growth of microorganisms such as gram positive bacteria, gram negative bacteria, fungi (e.g. yeast, mold, mildew), algae and protozoa.
  • microorganisms such as gram positive bacteria, gram negative bacteria, fungi (e.g. yeast, mold, mildew), algae and protozoa.
  • composition is particularly effective against Pseudomonas aeruginosa, Aspergillus niger, Fusarium, Cephalosporium, Pseudomonas fluorescens, Pseudomonas r bescens, Pseudomonas stutzeri, Pseudomonas olevorans, Alcaligenes faecalis, Escherichia coli, Citrobacter freundii, and the like.
  • the biocidal composition of the invention is a useful additive in industrial fluids (e.g., metalworking fluids), paints, coatings, adhesives, wet-state preservatives, hard surface cleaners, fabric care compositions, wood products, plastic products, medical products, fibers, or any other application where microorganism growth, and particularly biofilm growth, must be stopped or slowed.
  • industrial fluids e.g., metalworking fluids
  • One significant use application for the antimicrobial compositions of the present invention is in functional fluids, such as metalworking fluids, cutting fluids and the like.
  • Metalworking fluids are typically supplied as a "masterbatch" concentrate containing the antimicrobial composition and the other components of the formulation.
  • a sufficient amount of the antimicrobial composition is provided such that the diluted "working" fluid will contain a biocidally effective amount thereof.
  • antimicrobials are typically incorporated into the concentrate of metalworking fluid in an amount of from about 10 to 100 times the concentrations required in diluted "working" fluid.
  • Typical concentrations of pyrithione in metalworking concentrates range from about 0.05 to 1.0% pyrithione. At these concentrations of pyrithione, small amounts of zinc will result in the formation of a precipitate, which is unacceptable for use in a metalworking fluid concentrate.
  • the present biocidal composition permits the addition of combinations of pyrithione and zinc at concentrations that are sufficient for use in a metalworking fluid concentrate, yet do not form precipitates when formulated as concentrated biocidal compositions or in the metalworking fluid concentrates.
  • the enhanced biocidal effects imparted by the present biocidal composition can be efficiently provided care compositions, hard surface cleaners and disinfectants, textile and fabric care compositions, as well as in plastics and medical products applications.
  • the antimicrobial combination is suitably incorporated into a functional fluid containing a component that is effective in treating a substrate, such as wood and wood composites, masonry and stone, leather, hard surfaces, textiles, fabrics, plastics, medical products, and combinations thereof.
  • compositions of the present invention are useful, in any of the variety of applications described herein, as disinfectants and preservatives, in a liquid or spreadable solid form, alone or in combination with an inert carrier such as water, liquid hydrocarbons, ethanol, isopropanol, or the like. They can be employed using conventional procedures to control bacteria and fungi in various substrates, and can be applied to bacterial or fungal organisms or their substrates in an antimicrobial amount by conventional procedures such as spraying, dipping, drenching impregnation, and the like.
  • the present invention permits the use of reduced amounts of the pyrithione primary biocide, in conjunction with a zinc salt co-biocide that is less expensive than the primary biocide, thereby providing an antimicrobial composition that is inexpensive to produce and that possesses the above-mentioned characteristic of enhanced antimicrobial effectiveness against a variety of microorganisms.
  • the amine component of the composition of the invention provides significant solubility to the composition, as well as enhanced stability against the formation of precipitates, and allows the composition to remain commercially active for extended periods.
  • the present invention permits delivery of the enhanced biocidal composition of the pyrithione biocide, the zinc salt and the 1,2- and 1,3-alkanolamines alone or in combination with monomers and polymers of alkyldiamines in applications as a concentrated, soluble, and stable composition.
  • the soluble oil was made from the following ingredients:
  • the Semi-Synthetic fluid was made from the following ingredients:
  • the Synthetic Concentrate fluid was made from the following ingredients:
  • NaPT NaPTalone
  • 21 PPM ZnCl 2 alone 21 PPM ZnCl 2 alone
  • 600 PPM of an amine alone either monethanolamine, l-amino-2-propanol, or 3-amino-l-propanol
  • flasks were set up for testing mixtures of 100 PPM NaPT and 21 PPM ZnCl 2 , and mixtures of 21 PPM ZnCl 2 and 600 PPM of one of the above three amine compounds.
  • three treatment flasks were set up and treated with final concentrations of 1000 PPM of mixtures A, B, or C composed of NaPT, ZnCl 2 , and one of the amines.
  • Mixture A consisted of 10% NaPT, 1.8% ZnCl 2 and 60.5% monoethanolamine.
  • Mixture B consisted of 10% NaPT, 1.8% ZnCl 2 and 60.5% 1-amino- 2- ⁇ ropanol.
  • Mixture C consisted of 10% NaPT, 1.8% ZnCl 2 and 60.5% 3-amino-l- propanol. All concentrations displayed above for controls are the final concentrations of the compounds in the test flasks. Final concentrations of the mixing components in the treatment test flasks were 100 PPM NaPT, 18 PPM ZnCl 2 and 605 PPM amine.
  • the pH of each flask was determined.
  • the addition of the amines to soluble oil flasks raised the pH of the fluid to about 9.9.
  • the pH was adjusted to the pH of the untreated control by the addition of HCl. This was done to eliminate or minimize any biocidal effects against the test organism due to pH.
  • h semi-synthetic or synthetic fluids, amines raised the pH no more than 0.3 over the untreated controls.
  • the pH of the soluble oil, semi-synthetic and synthetic flasks were 8.5 to 8.7, 8.2 to 8.5, and 8.1 to 8.5, respectively.
  • bacteria were added to final concentration of 10 7 bacteria/ml.
  • the bacterial innoculum consisted of an equal number of cells from Pseudomonas aeruginosa 9027, Escherichia coli 8739, Pseudomonas fluorescens 12201,
  • Vlasks were incubated at room temperature (23 °C ⁇ 2°C) on a shaker at 130 rpms. Fluid samples were obtained from flasks after one and four days of incubation. Samples were serially diluted (1:10) in sterile, de-ionized water and spread plated for bacterial and fungal viable counts. Plates were incubated at 28°C. for two to three days and then scored for colony forming units. Experimental results are displayed in Table 1.
  • All three mixtures A, B, and C showed at least 100-fold fewer bacteria in soluble oils within four days compared to untreated and reduced counts to zero in the semi-synthetic fluid within one day. Relative to untreated controls, bacterial counts were not affected much by the control treatments in soluble oil and semi-synthetic fluids. Mixtures A and C reduced bacteria counts in the synthetic fluid by about at least 500-fold and 10-fold respectively. In the synthetic fluid, controls containing zinc alone were very effective against bacteria. None of the mixtures had much effect on fungi in the synthetic fluid.
  • Two five gallon glass aquarium tanks were disinfected with bleach and set up to simulate recirculating metalworking fluid systems.
  • One aquarium pump was attached to each tank as a means to recirculate fluid through the tank.
  • stainless steel washer coupons 1.2 cm 2 surface area
  • polycarbonate disc coupons 3.8 cm 2 surface area
  • Two steel and polycarbonate coupons were placed on each holder. 12.5 liters of dilute (1:20) semi-synthetic metalworking fluid was added to each tank.
  • Tank 1 served as an untreated control.
  • Mixture D (16% NaPT, 2% ZnCl 2 , 20% monoethanolamine, 20% 3-amino-l-propanol
  • tank 2 was added to tank 2 to a final concentration of 1250 PPM which yielded final active concentrations of 200 PPM NaPT, 25 PPM ZnCl 2 , 250 PPM monoethanolamine, and 250 PPM 3-amino-l-propanol in the 12.5 liters of diluted metalworking fluid.
  • the pH of tank 1 and tank 2 was 7.8 and 8.3, respectively. pH of tank 1 was adjusted to 8.3 with HCl.
  • bacteria were added to a final concentration of 10 6 bacteria/ml.
  • the bacterial innoculum consisted of an equal number of cells from Pseudomonas aeruginosa 9027, Escherichia coli 8739, Pseudomonas fluorescens 12201, Pseudomonas rubescens 12202, and Pseudomonas putida.
  • Fungal spores were added to each flask to final concentration of 10 4 spores/ml.
  • Fungal additions consisted of an equal number of spores from Fusa ⁇ um sp. and Cephalosporium sp. metalworking fluid field isolates. Bacterial and fungal additions were repeated three times per week. Tanks were
  • Samples of the bulk metalworking fluid and biofilm were obtained after 19 days.
  • the tank treated with mixture D showed at least 200-fold fewer bacteria in the bulk fluid than the untreated tank. There was little difference between treated and untreated tanks for the numbers of fungi in the bulk fluid. There was at least 1000-fold to 3000-fold fewer bacteria and at least 25-fold to 250-fold few fungi present in the biofilms of the tank treated with mixture D than the untreated tank. Although 10 5 bacteria ml were present per ml of slime material from the air-fluid interface of the untreated tank, no bacteria or fungi could be detected from the slime material in the tank treated with mixture D.
  • the bacterial innoculum consisted of an equal number of cells from Pseudomonas aeruginosa, Escherichia coli, Pseudomonas fluorescens, Pseudomonas rubescens, and Pseudomonas putida. Fungal additions were composed of equal numbers of spores from Fusarium sp and Cephalosporium sp. Tubes
  • Mixture A 10% Sodium pyrithione, 1.8% ZnCl 2 , 60.5% monoethanolamine;
  • Triazine 78.5% Hexahydro-l,3,5-tris(2-hydroxyethyl)-s-triazine.
  • Triazine used is a 78.5% aqueous solution of hexahydro-l,3,5-tris(2-hydroxyethyl)-s-triazine. It is known that hexahydro- l,3,5-tris(2- hydroxyethyl)-s-triazine is in equilibrium with free formaldehyde and typically releases about 31% formaldehyde when used as a formaldehyde releasing agent in metalworking fluids at in use concentrations. The relationship between triazine, hexahydro-l,3,5-tris(2- hydroxyethyl)-s-triazine, and formaldehyde in Examples 52, 53, and 54 is shown in Table 4:
  • PPM triazine
  • 500 PPM of Mixture A can reduce the amount of hexahydro-l,3,5-tris(2-hydroxyethyl)-s-triazine required to reduce fungi levels by 4-fold.
  • Mixture A is used at concentrations of about 1000 PPM, no hexahydro- 1, 3, 5-tris(2-hydroxyethyl)-s-triazine is required to eliminate the microbial contamination.
  • EXAMPLE 53 Efficacy of a Mixture of Sodium pyrithione, ZnCl 2 , monoethanolamine and a Formaldehyde Releasing Biocide at Preventing Microbial Contamination in a Metalworking Fluid.
  • 1,3 ,5-tris(2-hydroxyethyl)-s-triazine, or Mixture A (10% sodium pyrithione, 1.8% ZnCl 2 and 60.5% monoethanolamine) were added in the appropriate amounts to create mixtures of the biocides and controls for each of the biocides.
  • Bacteria and fungi were added to each flask to total final concentrations of 10 7 bacteria/ml and 10 5 fungal spores/ml, respectively.
  • the bacterial innoculum consisted of an equal number of cells from
  • Mixture A 10% Sodium pyrithione, 1.8% ZnCl 2 , 60.5% monoethanolamine;
  • Triazine 78.5% Hexahydro-l,3,5-tris(2-hydroxyethyl)-s-triazine.
  • mixtures of Mixture A and hexahydro-l,3,5-tris(2- hydroxyethyl)-s-triazine provide a longer duration of protection from microbial contamination than mixtures of NaPT and hexahydro- l,3,5-tris(2-hydroxyethyl)-s-triazine.
  • Mixture A and hexahydro-l,3,5-tris(2-hydroxyethyl)-s-triazine mixtures also permit the use of less sodium pyrithione or less hexahydro-l,3,5-tris(2-hydroxyethyl)-s- triazine than mixtures of sodium pyrithione and hexahydro-l,3,5-tris(2-hydroxyethyl)-s- triazine while retaining the same duration of efficacy.
  • EXAMPLE 54 Effects of Iron Ions on the Discoloration and Biocidal Efficacy a Mixture of Sodium pyrithione, ZnCl 2 , and an Amine in Metalworking Fluid.
  • iron ions The presence of iron ions is known to cause blue discoloration of metalworking fluids containing sodium pyrithione. Furthermore, iron ions also reduce the biocidal efficacy of sodium pyrithione. An experiment was conducted to examine whether a mixture of sodium pyrithione, ZnCl 2 , and monoethanolamine would similarly show lower efficacy against microorganisms and produce blue discoloration in the presence of iron.
  • Bacterial additions were composed of an equal number of cells for Pseudomonas aeruginosa 9027, Escherichia coli 8739, Pseudomonas fluorescens 12201, Pseudomonsa rubescens 12202, and Pseudomonas putida.
  • the fungal challenge consisted of equal numbers of spores of Fusarium sp. and Cephalosporium sp. Flasks were incubated on a shaker at room temperature (23 °C ⁇ 2°C )and at 120 rpms. Initial color of the metalworking fluids was determined by visual inspection.
  • AMP 95 diethanolamine, AEPD 85, 2(2-aminoethoxy)ethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, tnethanolamine, ethylenediamine, triethylamine, triisopropanolamine, and diisopropanolamine showed precipitates after 24 and 72 hours.
  • Part B of Table 7 demonstrates that certain amine mixtures provide suitable solubility when employed in combination.

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Abstract

La présente invention concerne un concentré de composition antimicrobienne, soluble et stable comprenant un pyrithione ou un complexe pyrithione dans une quantité comprise entre environ 0,5 % et environ 30 % en poids, une source zinc dans une quantité comprise entre environ 0,1 % et environ 10 % et, un élément amine organique dans une quantité comprise entre environ 30 % et environ 80 % en poids, ces pourcentages étant basés sur le poids total du concentré de composition. Cette invention concerne aussi des procédés permettant de commander la croissance de micro-organismes vivant librement ou de biofilms utilisant cette composition antimicrobienne et, des produits fabriqués avec la composition antimicrobienne de l'invention.
EP02808337A 2002-12-19 2002-12-19 Biocides pyrithione renforces par des ions metalliques de zinc et par des amines organiques Ceased EP1583420A4 (fr)

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JP5057538B2 (ja) * 2005-05-02 2012-10-24 国立大学法人徳島大学 セメント組成物、コンクリート組成物
US7893047B2 (en) * 2006-03-03 2011-02-22 Arch Chemicals, Inc. Biocide composition comprising pyrithione and pyrrole derivatives
JP5116295B2 (ja) * 2006-11-30 2013-01-09 日本曹達株式会社 塗料用抗菌・防カビ組成物および水性抗菌・防カビ性塗料
CN101631457B (zh) * 2007-01-12 2013-09-25 安格斯化学公司 用于水基体系的氨基醇和杀生物剂组合物
EP2042489A1 (fr) * 2007-09-26 2009-04-01 Straetmans high TAC GmbH Elimination et prévention du changement de couleur de matières contenant du pyrithione
EP2244570A2 (fr) * 2007-12-20 2010-11-03 Dow Global Technologies Inc. Contrôle amélioré de la corrosion et microbien dans des compositions hydrocarbonées
EP2282634B1 (fr) * 2008-05-15 2016-11-23 ANGUS Chemical Company Compositions à base d'aminoalcool et de biocides pour systèmes en milieu aqueux
WO2009140062A1 (fr) 2008-05-15 2009-11-19 Angus Chemical Company Lutte améliorée contre la corrosion et contre les microbes dans des compositions hydrocarbonées
US20090298805A1 (en) * 2008-06-03 2009-12-03 Polson George A Topical pyrithione compositions and methods for treatment of nail fungus
EP2424924B1 (fr) * 2009-04-29 2014-04-23 Angus Chemical Company Aminoalcools tertiaires utilisés comme additifs à faible teneur en composés organiques volatils (cov) pour les peintures et les enduits
PL2587920T3 (pl) * 2010-07-01 2017-01-31 Janssen Pharmaceutica, N.V. Kombinacje związków pyrionu i polietylenoiminy do zwalczania drobnoustrojów
JP5529834B2 (ja) * 2010-12-22 2014-06-25 ダウ グローバル テクノロジーズ エルエルシー グリホサート化合物とｚｐｔとの相乗的組み合わせ
WO2014030155A2 (fr) * 2012-08-20 2014-02-27 Kamedis Ltd Compositions topiques pour le traitement du psoriasis et de la séborrhée
MY174003A (en) * 2013-09-06 2020-03-03 Jubilant Life Sciences Ltd Anti-dandruff compositions and hair care formulations containing zinc pyrithione and quaternary ammonium salt
CN109836613B (zh) * 2019-01-22 2021-03-02 重庆太岳新材料科技有限公司 有机酸锌烷醇胺复合物及其热稳定剂用途
JP6708764B1 (ja) * 2019-01-28 2020-06-10 久保田　徹 機能水
KR102367150B1 (ko) * 2021-02-26 2022-02-25 엔트리움 주식회사 항균 항바이러스 코팅제 및 이의 제조방법
KR102535593B1 (ko) * 2022-08-31 2023-05-26 아성정밀화학 주식회사 석고보드형 비유독 수용성 방균제 및 그 제조방법

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WO2001000021A1 (fr) * 1999-06-25 2001-01-04 Arch Chemicals, Inc. Biocides de pyrithione renforces a l'aide d'ions argent, cuivre, ou zinc

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WO2001000021A1 (fr) * 1999-06-25 2001-01-04 Arch Chemicals, Inc. Biocides de pyrithione renforces a l'aide d'ions argent, cuivre, ou zinc

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EP1583420A1 (fr) 2005-10-12
WO2004057964A1 (fr) 2004-07-15
CN1713815A (zh) 2005-12-28
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BR0215972A (pt) 2005-09-13

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