WO2003013491A1 - Compositions microbicides synergiques - Google Patents

Compositions microbicides synergiques Download PDF

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Publication number
WO2003013491A1
WO2003013491A1 PCT/US2002/023497 US0223497W WO03013491A1 WO 2003013491 A1 WO2003013491 A1 WO 2003013491A1 US 0223497 W US0223497 W US 0223497W WO 03013491 A1 WO03013491 A1 WO 03013491A1
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WO
WIPO (PCT)
Prior art keywords
isothiazolone
component
methyl
amino acid
acid derivative
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
PCT/US2002/023497
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English (en)
Inventor
Shauna Michelle Concannon
Michael John Day
Yves Duccini
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.)
Innospec Ltd
Rohm and Haas Co
Original Assignee
Associated Octel Co Ltd
Rohm and Haas Co
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
Priority claimed from GB0118516A external-priority patent/GB0118516D0/en
Priority claimed from GB0118515A external-priority patent/GB0118515D0/en
Priority claimed from GB0131120A external-priority patent/GB0131120D0/en
Application filed by Associated Octel Co Ltd, Rohm and Haas Co filed Critical Associated Octel Co Ltd
Publication of WO2003013491A1 publication Critical patent/WO2003013491A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
    • A61K31/425—Thiazoles
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/075—Ethers or acetals
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/185—Acids; Anhydrides, halides or salts thereof, e.g. sulfur acids, imidic, hydrazonic or hydroximic acids
    • A61K31/19—Carboxylic acids, e.g. valproic acid
    • A61K31/195—Carboxylic acids, e.g. valproic acid having an amino group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/21—Esters, e.g. nitroglycerine, selenocyanates
    • A61K31/215—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids
    • A61K31/235—Esters, e.g. nitroglycerine, selenocyanates of carboxylic acids having an aromatic ring attached to a carboxyl group
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
    • A61K31/415—1,2-Diazoles

Definitions

  • This invention relates to synergistic microbicidal combinations of amino acid derivatives having at least one chiral center, particularly ethylenediaminedisuccinic acid (EDDS) or salts thereof, with one or more selected commercial microbicides.
  • EDDS ethylenediaminedisuccinic acid
  • the present invention also involves the use of biodegradable chelants to enhance the activity of various antimicrobial compositions.
  • the resultant combinations provide control of the growth of microorganisms treated by the two compounds together that is greater than the sum of the control provided by each compound when used alone.
  • antimicrobial compounds are prevalent in many applications to prevent the growth of microbe contaminants, typically bacterial and fungal microorganisms. Although different antimicrobial compounds demonstrate a wide spectrum of activity against various unwanted species, it is not common for an antimicrobial agent to be entirely efficient at controlling all possible types of microbial contamination. To overcome this problem, combinations of active ingredients have been used against various microorganisms. When using some forms of treatment, "less-susceptible" strains of certain microorganisms have developed in response to conventional antimicrobial control methods, making it even more difficult to control these strains, that is, higher dose rates of antimicrobial agents are needed for a complete kill, and in some extreme cases it becomes impossible for 100% control of such organisms even using significantly higher dosage levels than usual.
  • Certain chelating agents are known for use as potentiators of conventional antimicrobial agents by way of allowing lower effective use levels of the antimicrobial agent.
  • the mechanism of action of the potentiating agent is believed to involve chelation of calcium or magnesium ions in the cell walls of the microorganism, resulting in easier permeation of the antimicrobial agent into the microorganism itself.
  • Some chelating agents are currently used in personal care formulations as potentiators of other antimicrobial agents as well for their preservative activity.
  • Typical chelating agents used are EDTA (sodium salt of ethylenediaminetetraacetic acid), HEEDTA (hydroxyethylethylenediaminetetra- acetic acid) and DTPA (diethylenetriaminepentaacetic acid); however, there is a need to avoid use of compounds such as EDTA that are resistant to biodegradation because of their persistence upon release into the environment.
  • EDTA sodium salt of ethylenediaminetetraacetic acid
  • HEEDTA hydroxyethylethylenediaminetetra- acetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • Patent application WO 97/02010 discloses the use of a chelant as bactericidal agent either alone or in combination with conventional bactericides, including the use of EDDS together with chlorophenols or quaternary ammonium compounds to control Pseudomonas aeruginosa.
  • Patent applications WO 97/44006 and WO 99/18791 disclose the use of optically active ethylenediaminedisuccinic acid (S,S-EDDS) as antibacterial or antifungal agents.
  • the problem addressed by the present invention is to overcome deficiencies of previous antimicrobial combinations by providing an antimicrobial formulation that is more effective than the individual antimicrobials used alone and that can be used at lower overall levels while providing efficacy similar to the original individual antimicrobial levels while also providing the antimicrobial formulation in a readily biodegradable form.
  • the present invention provides a microbicidal composition
  • a microbicidal composition comprising a synergistic mixture, the first component of which is one or more microbicide selected from the group consisting of 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, benzisothiazolone, 2-bromo- 2-nitro-l,3-propanediol, imidazolidinyl urea, l,3-dimethylol-5,5-dimethyl- hydantoin, phenoxyethanol and methyl para-hydroxybenzoate; and the second component of which is an amino acid derivative having at least one chiral center and is in free acid or salt form; wherein the ratio of the first component to the second component is from 1/0.01 to 1/10,000.
  • the present invention further provides a method of inhibiting the growth of microorganisms in a locus comprising introducing to, at or on, the locus a microorganism inhibiting amount of the aforementioned synergistic mixture; and wherein the amount of synergistic mixture is from 0.1 to 10,000 parts per million active ingredient.
  • the present invention provides a microbicidal composition
  • a microbicidal composition comprising a synergistic mixture, the first component of which is a microbicide selected from one or more antibacterial and antifungal compounds, and the second component of which is S,S-ethylenediaminedisuccinic acid or salts thereof; wherein the ratio of the first component to the second component is from 1/0.01 to 1/10,000.
  • amino acid derivatives having at least one chiral center particularly ethylenediaminedisuccinic acid and salts thereof, may be combined with selected commercial microbicides to provide enhanced microbicidal efficacy at a combined active ingredient level lower than that of the combined individual amino acid derivative and commercial microbicide effective use levels; these combination compositions are especially useful to protect personal care compositions against microbial contamination.
  • microbicide or “antimicrobial” refers to a compound capable of inhibiting the growth of or controlling the growth of microorganisms at a locus; microbicides include antibacterial compounds (bactericides), antifungal compounds (fungicides) and algaecides.
  • microorganism includes, for example, fungi (such as yeast and mold), bacteria and algae.
  • locus refers to an industrial system or product subject to contamination by microorganisms.
  • mixtures of amino acid derivatives having at least one chiral center with a microbicide selected from one or more antibacterial. and antifungal compounds (such as commercial microbicides selected from the group consisting of 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, benzisothiazolone, 2-bromo-2-nitro-l,3-propanediol, imidazolidinyl urea, l,3-dimethylol-5,5-dimethylhydantoin, phenoxyethanol and methyl para-hydroxybenzoate) result in synergistic microbicidal activities against a wide range of microorganisms; preferably the amino acid derivative is optically active.
  • Synergy occurs when the disruptive interaction on the organisms treated by the two compounds together is greater than the sum of such interactions of both compounds when used alone. Such synergy does not arise from the expected activity of the components when added together.
  • optically active chelants such as amino acid derivatives, in particular act in a synergistic manner with other selected antimicrobial compounds. This is surprising, in that many optically active chelants are biodegradable and should be degraded by microorganisms, thus negating their effectiveness in potentiating the activity of other antimicrobial compounds.
  • Suitable amino acid derivatives include those having at least one chiral center, preferably at least two chiral centers.
  • the amino acid derivative is a naturally occurring amino acid, such as derivatives of glycine, alanine, cystine, valine, leucine, norleucine, phenylalanine, tyrosine, serine, threonine, methionine, thyroxine, tryptophan, proline and hydroxyproline.
  • Representative derivatives include, for example, ornithine, arginine, lysine, histidine, aspartic acid and glutamic acid.
  • the amino acid derivative is an optically active isomer of aspartic acid, glutamic acid or phenylalanine, particularly the L-form isomer.
  • the amino acid derivative may comprise at least two nitrogen atoms linked by a hydrocarbyl or substituted hydrocarbyl group, such as ethylenediaminedisuccinic acid (EDDS); or the amino acid may comprise one nitrogen atom and at least two carboxylic acid groups, such as N-(2-propionic acid)-iminodiacetic acid (also known as MGDA or methylglycine diacetic acid), 3-hydroxy-2,2'-iminodisuccinic acid (HIDS) or iminodisuccinic acid (IDS) and salts thereof.
  • EDDS ethylenediaminedisuccinic acid
  • the amino acid may comprise one nitrogen atom and at least two carboxylic acid groups, such as N-(2-propionic acid)-iminodiacetic acid (also known as MGDA or methylglycine diacetic
  • Amino acid derivatives useful in compositions of the present invention include those comprising at least one succinate group, such as EDDS, IDS and HIDS and salts thereof, preferably the sodium salts.
  • the amino acid derivative is selected from one or more of the group consisting of ethylenediaminedisuccinic acid, 3-hydroxy-2,2'-iminodisuccinic acid, iminodisuccinic acid and N-(2-propionic acid)-iminodiacetic acid and salts thereof; more preferably, the amino acid is an optically active form of ethylenediaminedisuccinic acid, such as the R,R-, R,S- or S,S- form; most preferably, the amino acid is the S,S-form of ethylenediaminedisuccinic acid (S,S-EDDS); however, the term "EDDS" includes racemic or optical isomers thereof, active salts and active derivatives thereof.
  • iminodiacetic acid derivatives are represented by formula (I) where X may be hydrogen, another acetate group, an alkyl group, or a substituted acid group such as propionic acid; and R may be a hydrogen, hydroxyl or alkyl group:
  • aminodisuccinic acid derivatives are represented by formula (II) where Y may be hydrogen, another succinate group, a substituted acid group, an alkyl group or an alkylene linking group attached to another iminodisuccinate group; and R may be a hydrogen, hydroxyl or alkyl group:
  • the second components of the combinations of the present invention are well-known and generally commercially available microbicides, and include 5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-n-octyl-3- isothiazolone, benzisothiazolone, 2-bromo-2-nitro-l,3-propanediol, imidazolidinyl urea, l,3-dimethylol-5,5-dimethylhydantoin, phenoxyethanol and methyl para-hydroxybenzoate.
  • the ratio of the commercial biocide component to the amino acid derivative is typically from 1/0.01 to 1/10,000, and preferably from 1/0.02 to 1/8,000.
  • microbicides may be used in the synergistic mixtures of the present invention "as is" or may first be formulated together with a suitable solvent, a solid carrier or as a dispersion.
  • suitable solvents include, for example, water; glycols, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; glycol ethers; alcohols, such as methanol, ethanol, propanol, phenethyl alcohol and phenoxypropanol; ketones, such as acetone and methyl ethyl ketone; esters, such as ethyl acetate, butyl acetate, triacetyl citrate and glycerol triacetate; carbonates, such as propylene carbonate and dimethyl carbonate; and mixtures thereof.
  • the solvent is selected from water, glycols, glycol ethers, esters and mixtures thereof.
  • Suitable solid carriers include, for example, cyclodextrin, silicas, diatomaceous earth, waxes, cellulosic materials and charcoal. It is preferred that the microbicide is formulated in water.
  • end-use formulations containing the synergistic mixtures of the present invention are in the form of aqueous solutions and have pH values from 2 to 14, preferably from 4 to 7.
  • any formulated composition of the amino acid derivative may be used with any formulated composition of the commercial microbicide component in the synergistic mixtures of the present invention.
  • the solvent used for the amino acid derivative may be the same as or different from the solvent used to formulate the commercial microbicide. It is preferred that the two solvents are miscible.
  • the amino acid derivative and the commercial microbicide may be combined directly and then a solvent added to the mixture.
  • the amino acid derivative and the commercial microbicide component of the present invention may be added to a locus sequentially, simultaneously, or may be combined before being added to the locus. It is preferred that the amino acid derivative and the commercial microbicide component be added to a locus simultaneously or combined prior to being added to the locus.
  • the microbicides When the microbicides are combined prior to being added to a locus, such combination may optionally contain adjuvants, such as, for example, solvent, thickeners, anti-freeze agents, colorants, dispersants, surfactants, stabilizers, scale inhibitors and anti- corrosion additives.
  • compositions of the present invention may also contain other antimicrobial compounds, provided that their presence does not interfere with the synergistic efficiency of the composition.
  • Suitable optional antimicrobial compounds include, for example, 4,5-trimethylene-2-methyl-3- isothiazolone, benzyl alcohol, benzalkonium chlorides, cetylpyridinium chlorides, 2,2-dibromo-3-nitrilopropionamide, glutaraldehyde, formaldehyde releasers, salicylic acid, chlorexydine, l,2-dibromo-2,4-dicyanobutane, 5-bromo-5-nitro-l,3- dioxane and 3-iodo-2-propynylbutylcarbamate.
  • microbicidal compositions of the present invention can be used to inhibit the growth of microorganisms by introducing a microbicidally effective amount of the compositions onto, into, or at a locus subject to microbial attack.
  • Suitable loci include, for example: cooling towers; air washers; boilers; mineral slurries; wastewater treatment; ornamental fountains; reverse osmosis filtration; ultrafiltration; ballast water; evaporative condensers; heat exchangers; pulp and paper processing fluids; plastics; emulsions; dispersions; paints; latexes; coatings, such as varnishes; construction products, such as mastics, caulks, and sealants; construction adhesives, such as ceramic adhesives, carpet backing adhesives, and laminating adhesives; industrial or consumer adhesives; photographic chemicals; printing fluids; household products, such as bathroom and kitchen cleaners; cosmetics; toiletries; shampoos; soaps; detergents; industrial cleaners; floor polishes; laundry rinse water; metal
  • the microbicidal compositions of the present invention are used to inhibit the growth of microorganisms at a locus selected from one or more of emulsions, dispersions, paints, latexes, household products, cosmetics, toiletries, shampoos, soaps, detergents and industrial cleaners.
  • the microbicidal compositions are useful in personal care applications, such as hair care (for example, shampoo and dyes) and skin care (for example, sunscreens, cosmetics, soaps, lotions and creams) formulations.
  • the formulated compositions may also comprise one or more ingredients selected from UV radiation-absorbing agents, surfactants, rheology modifiers or thickeners, fragrances, moisturizers, humectants, emollients, conditioning agents, emulsifiers, antistatic aids, pigments, dyes, tints, colorants, antioxidants, reducing agents and oxidizing agents.
  • the specific amount of the synergistic combinations necessary to inhibit or control the growth of microorganisms in a locus depends upon the particular compounds in the combination and particular locus to be protected. Typically, the amount of the synergistic combinations of the present invention to control the growth of microorganisms in a locus is sufficient if it provides from 0.1 to 10,000 ppm total active ingredient of the synergistic mixture in the locus. It is preferred that the synergistic mixture (active ingredients) be present in an amount of 1 to 5000 ppm, more preferably from 100 to 3000 ppm and most preferably from 1000 to 2000 ppm, in the locus.
  • the ratio of 5-chloro-2-methyl-3-isothiazolone/2-methyl-3- isothiazolone mixture to amino acid derivative is from 1/1 to 1/10,000 and more preferably from 1/10 to 1/8,000.
  • 2-methyl-3-isothiazolone where the composition is substantially free of halogenated 3-isothiazolone; that is, zero up to 3%, preferably zero up to 1% and more preferably zero up to 0.5%, of halogenated 3-isothiazolone may be present, based on combined weight of halogenated 3-isothiazolone and 2-methyl-3-isothiazolone; in this case where 2-methyl-3- isothiazolone is used in the synergistic mixtures of the present invention, it is preferred that the ratio of 2-methyl-3-isothiazolone to amino acid derivative is from 1/0.01 to 1/500 and more preferably from 1/0.02 to 1/200.
  • the ratio of benzisothiazolone to amino acid derivative is from 1/10 to 1/1,000 and more preferably from 1/20 to 1/500.
  • 2-bromo-2-nitro-l,3-propanediol is used in the synergistic mixtures of the present invention, it is preferred that the ratio of 2-bromo-2-nitro-l,3-propanediol to amino acid derivative is from 1/0.01 to 1/1,000 and more preferably from 1/0.05 to 1/500.
  • the ratio of 1,3-dimethylol- 5,5-dimethylhydantoin to amino acid derivative is from 1/0.01 to 1/1 and more preferably from 1/0.02 to 1/0.5.
  • the ratio of phenoxyethanol to the amino acid derivative is from 1/0.01 to 1/0.5 and more preferably from 1/0.02 to 1/0.2.
  • the ratio of methyl parahydroxybenzoate to amino acid derivative is from 1/0.01 to 1/1,000 and more preferably from 0.1 to 1/500.
  • 2-n-octyl-3-isothiazolone is used in the synergistic mixtures of the present invention, it is preferred that the ratio of 2-n-octyl-3-isothiazolone to amino acid derivative is from 1/10 to 1/1,000 and more preferably from 1/20 to 1/500.
  • the ratio of imidazolidinyl urea to the amino acid derivative is from 1/0.01 to 1/1 and more preferably from 1/0.02 to 1/0.5.
  • QA concentration of compound A (first component) in ppm, acting alone, which produced an end point (MIC of Compound A).
  • Qa concentration of compound A in ppm, in the mixture, which produced an end point.
  • QB concentration of compound B (second component) in ppm, acting alone, which produced an end point (MIC of Compound B).
  • Qb concentration of compound B in ppm, in the mixture, which produced an end point.
  • antagonism is indicated.
  • additivity is indicated, and when less than one, synergism is demonstrated.
  • SI value the greater the synergy shown by that particular mixture, for example, SI values less than about 0.8 are representative of moderate synergy and SI values less than about 0.5 are representative of strong synergy.
  • the minimum inhibitory concentration (MIC) of a microbicide is the lowest concentration tested under a specific set of conditions that prevents the growth of added microorganisms.
  • NB medium Broth (NB medium) was also used for testing both bacteria and fungi. A wide range of combinations of microbicides was tested by conducting MIC assays in the presence of various concentrations of EDDS. For evaluations involving
  • M9GY or PDB media high resolution MIC assays were determined by adding varying amounts of microbicide to one column of a microtitre plate and doing subsequent ten-fold dilutions using an automated liquid handling system to obtain a series of endpoints ranging from about 1 ppm to >10,000 ppm active ingredient.
  • MIC assays were determined using a tube-dilution method based on the method of the European
  • the bacteria were used at a concentration of about 10 5 to 10 6 bacteria per mL and the yeast and mold at about 10 5 fungi per mL. These microorganisms are representative of natural contaminants in many consumer and industrial applications.
  • the plates were visually evaluated for microbial growth (turbidity) to determine the MIC after various incubation times at 25°C (yeast and mold) or 30°C (bacteria) for systems evaluated in M9GY or PDB media; for systems evaluated in NB media, the samples were incubated for 72 hours at 37°C.
  • Staphylococcus aureus (S. aureus - ATCC #9144, NCIMB #9518) Pseudomonas aeruginosa (P. eruginosa - ATCC #9027 and #13388, NCIMB #8626)
  • Pseudomonas putida P. putida - ATCC #12633
  • Burkholderia cepacia B. cepacia - ATCC #25416
  • Escherichia coli E. coli - ATCC #10536
  • Candida albicans C. albicans - ATCC #10231 and #2051, NCPF#3179
  • Aspergillus niger A. niger - ATCC #16404 and #6271, IMI #149007
  • First Component (A) 5-chloro-2-methyl-3-isothiazolone (CMI)/
  • First Component (A) 2-bromo-2-nitro-l,3-propanediol (BNPD)
  • Second Component (B) EDDS
  • First Component (A) ImidazoUdinyl urea (IU)
  • Second Component (B) EDDS
  • First Component (A) l,3-Dimethylol-5,5-dimethylhydantoin (DMDMH)
  • Second Component (B) EDDS
  • Second Component (B) EDDS
  • First Component (A) 2-Methyl-3-isothiazolone (MI)
  • Second Component (B) EDDS
  • A. niger (ATCC #16404) 0 2400 1.00 —
  • First Component (A) 2-n-Octyl-3-isothiazolone (OI)
  • Second Component (B) EDDS
  • E. coli (ATCC #10536) 0 >26200 1.00 M9GY@2days 22.4 2240 ⁇ 0.49 1/100
  • P. aeruginosa (ATCC #9027) 0 >60545 1.00 M9GY@2days 33.5 3350 ⁇ 0.17 1/100
  • First Component (A) Benzisothiazolone (BIT)
  • Second Component (B) EDDS
  • E. coli (ATCC #10536) 0 >26200 1.00 M9GY@lday 4.4 440 ⁇ 0.79 1/100
  • First Component (A) Methyl Paraben (MP)
  • Second Component (B) EDDS
  • A. niger (ATCC #6271) 0 261 1.00 M9GY@7days 1.06 106 0.41 1/100
  • E.coli (ATCC #10536) 0 >26200 1.00 M9GY@2days 67 6700 ⁇ 0.38 1/100
  • putida (Pp-ls) was isolated from an alkyl ether sulphate surfactant solution; the MIC of this strain was found to be 4.4 ppm active ingredient of a 3/1 mixture of CMI/MI, approximately 10-20 times greater than the MIC of the corresponding laboratory strain.
  • First Component (A) 5-chloro-2-methyl-3-isothiazolone (CMI)/
  • P. aeruginosa (Pa-Is) 0 49163 1.00 M9GY @ 5 days 25 2500 0.55 1/100 50 0 1.00
  • First Component (A) 2 -Methyl- 3 -isothiazolone (MI)
  • Second Component (B) EDDS

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Abstract

La présente invention concerne des compositions antimicrobiennes basées sur une association synergique d'un dérivé d'acide aminé présentant un centre chiral et des agents microbicides commerciaux sélectionnés. Des combinaisons préférées sont notamment de l'acide éthylènediaminedisuccinique et ses sels avec du 5-chloro-2- méthyl-3-isothiazolone, 2-méthyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, benzisothiazolone, 2-bromo-2-nitro-1,3-propanediol, imidazolidinyl urée, 1,3-diméth- ylol-5,5-diméthylhydantoïne, phénoxyéthanol or méthyle parahydroxybenzoate, pour procurer une efficacité antimicrobienne améliorée à un niveau d'ingrédients actifs associés inférieur à celui des niveaux d'utilisation efficace de la combinaison du dérivé d'acide aminé seul et des compositions microbicides dans le commerce.
PCT/US2002/023497 2001-07-30 2002-07-24 Compositions microbicides synergiques Ceased WO2003013491A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB0118516A GB0118516D0 (en) 2001-07-30 2001-07-30 Composition
GB0118515.6 2001-07-30
GB0118516.4 2001-07-30
GB0118515A GB0118515D0 (en) 2001-07-30 2001-07-30 Compostion
GB0131120A GB0131120D0 (en) 2001-12-20 2001-12-20 Synergistic blends of biocides and biodegradable chelant
GB0131120.8 2001-12-20

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1665933A3 (fr) * 2004-11-16 2006-08-16 Rohm and Haas Company Composition microbicide
ES2264605A1 (es) * 2004-07-02 2007-01-01 Labiana Development, S.L. "procedimiento para la obtencion de 2-alquilisotiazolonas y de sus formulaciones en forma estable solas o asociadas a otras moleculas con actividad biocida".
US7758851B2 (en) * 2001-08-09 2010-07-20 Laboratorios Miret, S.A. Preservative systems and their use in cosmetic preparations
US8138212B2 (en) 2009-07-30 2012-03-20 Rohm And Haas Company Synergistic microbicidal compositions
WO2016209789A1 (fr) * 2015-06-25 2016-12-29 Rohm And Haas Company Composition microbicide
WO2018212963A1 (fr) * 2017-05-19 2018-11-22 Troy Corporation Mélanges antimicrobiens de benzisothiazolinone-carboxylate métallique
FR3068211A1 (fr) * 2017-06-30 2019-01-04 L'oreal Melange antimicrobien contenant du 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one et un ester de l’acide 4-hydroxybenzoique, et composition cosmetique le contenant

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EP0787430A1 (fr) * 1995-12-23 1997-08-06 Riedel-De Haen Aktiengesellschaft Agent de conservation contenant des dérivés de isothiazolinone et des agents complexants

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EP0787430A1 (fr) * 1995-12-23 1997-08-06 Riedel-De Haen Aktiengesellschaft Agent de conservation contenant des dérivés de isothiazolinone et des agents complexants

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7758851B2 (en) * 2001-08-09 2010-07-20 Laboratorios Miret, S.A. Preservative systems and their use in cosmetic preparations
ES2264605A1 (es) * 2004-07-02 2007-01-01 Labiana Development, S.L. "procedimiento para la obtencion de 2-alquilisotiazolonas y de sus formulaciones en forma estable solas o asociadas a otras moleculas con actividad biocida".
ES2264605B1 (es) * 2004-07-02 2007-12-16 Labiana Development, S.L. "procedimiento para la obtencion de 2-alquilisotiazolonas y de sus formulaciones en forma estable solas o asociadas a otras moleculas con actividad biocida".
EP1665933A3 (fr) * 2004-11-16 2006-08-16 Rohm and Haas Company Composition microbicide
US7468384B2 (en) 2004-11-16 2008-12-23 Rohm And Haas Company Microbicidal composition
AU2010246414B2 (en) * 2004-11-16 2011-08-04 Rohm And Haas Company Microbicidal composition
CN103493825A (zh) * 2009-07-30 2014-01-08 罗门哈斯公司 协同杀微生物组合物
CN103478138B (zh) * 2009-07-30 2015-07-01 罗门哈斯公司 协同杀微生物组合物
CN103478138A (zh) * 2009-07-30 2014-01-01 罗门哈斯公司 协同杀微生物组合物
CN103493824A (zh) * 2009-07-30 2014-01-08 罗门哈斯公司 协同杀微生物组合物
US8138212B2 (en) 2009-07-30 2012-03-20 Rohm And Haas Company Synergistic microbicidal compositions
CN103548843A (zh) * 2009-07-30 2014-02-05 罗门哈斯公司 协同杀微生物组合物
CN103609568A (zh) * 2009-07-30 2014-03-05 罗门哈斯公司 协同杀微生物组合物
EP2289335A3 (fr) * 2009-07-30 2012-05-09 Rohm and Haas Company Compositions microbicides synergiques contenant la 2-methyl-4-isothiazolin-3-one (MIT) ou la 1,2-benzisothiazolin-3-one (BIT)
CN103609568B (zh) * 2009-07-30 2015-07-22 罗门哈斯公司 协同杀微生物组合物
CN103548843B (zh) * 2009-07-30 2015-09-30 罗门哈斯公司 协同杀微生物组合物
WO2016209789A1 (fr) * 2015-06-25 2016-12-29 Rohm And Haas Company Composition microbicide
CN107708418A (zh) * 2015-06-25 2018-02-16 罗门哈斯公司 杀微生物组合物
WO2018212963A1 (fr) * 2017-05-19 2018-11-22 Troy Corporation Mélanges antimicrobiens de benzisothiazolinone-carboxylate métallique
FR3068211A1 (fr) * 2017-06-30 2019-01-04 L'oreal Melange antimicrobien contenant du 4-(3-ethoxy-4-hydroxyphenyl)butan-2-one et un ester de l’acide 4-hydroxybenzoique, et composition cosmetique le contenant

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