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WO1997000613A1 - Composition biocide - Google Patents

Composition biocide Download PDF

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Publication number
WO1997000613A1
WO1997000613A1 PCT/GB1996/001480 GB9601480W WO9700613A1 WO 1997000613 A1 WO1997000613 A1 WO 1997000613A1 GB 9601480 W GB9601480 W GB 9601480W WO 9700613 A1 WO9700613 A1 WO 9700613A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
component
metal complex
water
acid
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/GB1996/001480
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English (en)
Inventor
John David Payne
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.)
Syngenta Ltd
Original Assignee
Zeneca Ltd
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 Zeneca Ltd filed Critical Zeneca Ltd
Priority to AU61326/96A priority Critical patent/AU6132696A/en
Publication of WO1997000613A1 publication Critical patent/WO1997000613A1/fr
Anticipated expiration legal-status Critical
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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles

Definitions

  • the present invention relates to a biocidal composition
  • a biocidal composition comprising a metal complex of a cyclic thiohydroxamic acid and an organic water-solubilising agent and to the use of such compositions especially in personal care formulations, latices and paints.
  • EP 249,328 discloses novel cyclic thiohydroxamic acids including metal complexes thereof and EP 498,636 discloses that these complexes are particularly suitable for use as a preservative in personal care formulations.
  • the aqueous solubility of these metal complexes is very low and this necessitates expensive milling and formulation processes in order to provide suitable aqueous dispersions of these metal complexes.
  • OWSA exhibit higher aqueous solubility and higher anti-microbial activity than those disclosed in EP 500,352.
  • composition comprising a) a metal complex of a cyclic thiohydroxamic acid of Formula 1
  • R is hydrogen, hydrocarbyl, substituted hydrocarbyl or two groups R, together with the carbon atom or carbon atoms to which they are attached form a 5- or 6-membered ring system; and b) an organic water-solubilising agent (OWSA)
  • R When R is hydrocarbyl it can be aromatic or aliphatic and it may be substituted by any atom or group which does not seriously impair the microbiological properties of the metal complex.
  • R When R is aromatic it is preferably phenyl and when R is aliphatic, it is preferably alkyl, more preferably C ⁇ -alkyl and especially C ⁇ -alkyl.
  • the alkyl group may be linear or branched, but is preferably linear.
  • the substituent is preferably hydroxy, amino, C-,_ 6 -alkoxy or halogen.
  • the substituent is preferably fluorine, bromine and especially chlorine.
  • R is unsubstituted.
  • the metal of the metal complex of formula 1 is from groups 3a to 5a, 1 b to 7b or 8 of the Periodic Table according to Mandeleef, as set out, for example, on the inside rear cover of "Handbook of Chemistry and Physics" 49th Edition (1968-9) published by The Chemical Rubber Company, Cleveland, Ohio, USA.
  • the metal is from group 1 b, 2b or 8 of the Periodic Table and is more preferably Fe, Cu, Ag and especially Zn.
  • the metal complex can be a 1:1, 2:1 or 3:1 complex containing one, two or three units, respectively, of thiohydroxamic acid for each metal atom. It is particularly a 2:1 complex of Zn.
  • the preparation of these compounds are described in EP 249,328 and EP
  • Particularly useful metal complexes of formula 1 are those obtainable from 3-hydroxy-4-methylthiazol-2(3H)-thione; 3-hydroxy-4-phenylthiazol-2(3H)-thione; 3-hydroxy-4,5,6,7-tetrahydrobenzothiazol-2(3H)-thione;
  • the 2:1 Zn complex of 3-hydroxy-4-methylthiazol-2(3H)-thione is especially preferred.
  • the OWSA which is component b) of the composition is not a strong metal sequestrant and preferably does not significantly reduce the microbiological properties of the metal complex.
  • the microbiological properties of the composition are no worse than those of the metal complex alone.
  • the OWSA is also preferably devoid of phosphorus and is particularly a compound of general formula Y-X-Z wherein Y is a group which interacts with the metal complex, X is an organic divalent spacer group and Z is a water solubilising group.
  • Y is preferably a thiol and especially a hydroxy or amino group.
  • the amino group is preferably a primary or secondary amino group.
  • Z is preferably a sulphonic or a carboxylic acid group or a hydroxy group. It is particularly preferred that Z is hydroxy or carboxy.
  • the spacer group X may be aromatic or aliphatic but is preferably aliphatic.
  • X is aliphatic it may be linear or branched, saturated or unsaturated, substituted or unsubstituted.
  • X is linear and it is also preferred that X is saturated.
  • the substituent is preferably a water-solubilising group, more preferably one or more further groups Z and especially a carboxylic acid and/or a hydroxy group.
  • the OWSA preferably has a MW below 300 and especially below 250. It is also preferred that the MW is greater than 70.
  • a preferred class of OWSA is an aminocarboxylic acid, especially an aminocarboxylic acid of formula 2:
  • R 1 and R 2 are each, independently, hydrogen or C ⁇ -alkyl; R 3 is hydrogen or optionally substituted C ⁇ -alkyl; or R 1 and R 3 together with the nitrogen and carbon atom to which they are attached form a ring.
  • R 1 , R 2 or R 3 is alkyl, it may be linear or branched. Preferably, R 1 and R 2 are both hydrogen.
  • R 3 When R 3 is substituted alkyl the substituent may be any atom or group which does not seriously impair the microbiological properties of the metal complex.
  • suitable substituents are guanidinyl, carbonamide, carboxy, mercapto (including the disulphide oxidation product), imidazolyl, amino, C 1 - 4 -alkylthio, phenyl, substituted phenyl (such as 4-hydroxyphenyl) and indolyl.
  • R 1 and R 3 together with the carbon and nitrogen atoms to which they are attached form a ring, the ring is preferably 5-membered.
  • an OWSA of formula 2 are alanine, arginine, asparagine, aspartic acid, cysteine, cystine, glutamic acid, glutamine, glycine, histidine, iso-glutamine, iso ⁇ leucine, leucine, lysine, methionine, nor-leucine, nor-valine, ornithine, penicillamine, phenylalanine, proline, sarcosine, serine, threonine, tryptophan, tyrosine and valine.
  • other amino carboxylic acids are ⁇ -alanine and betaine.
  • a preferred amino carboxylic acid of formula 2 is histidine.
  • OWSA is an iminocarboxylic acid of Formula 3
  • R 4 and R 5 are each, independently, C ⁇ -alkylene carboxylic acid.
  • the alkylene group may be linear or branched but is preferably linear.
  • R 4 and R 5 are each, independently, C-i- 4 -alkylene carboxylic acid and it is especially preferred that R 4 and R 5 are the same.
  • iminocarboxylic acids of formula 3 are iminodiacetic and iminodipropionic acids.
  • a further preferred class of OWSA are alkanolamines which may be primary, secondary or tertiary. Preferred alkanolamines are primary or secondary. It is also preferred that the number of carbon atoms in each alkylene chain of the alkanolamine is not greater than 6 and especially from 2 to 4. The alkylene chain may be linear or branched but is preferably linear. Examples of suitable alkanolamines are monoethanolamine, diethanolamine, triethanolamine, 2-aminobutanol and aminomethylpropanol.
  • a still further preferred class of OWSA is a hydroxycarboxylic acid (hereinafter "HCA") especially a hydroxy-(C- ⁇ - 6 -alkylene) carboxylic acid.
  • the alkylene group may be linear or branched and may be substituted. Preferred substituents are those that further increase the water solubility of the OWSA and are particularly hydroxy and/or carboxylic acid groups.
  • a preferred HCA contains one or more additional C ⁇ - 6 -a'kylene carboxylic acid group attached to the alkylene group of the HCA.
  • the HCA has a MW below 250 and especially below 200.
  • HCA glycolic and citric acids.
  • a still further preferred class of OWSA is a polyol which is substantially devoid of dispersing properties.
  • Preferred polyols have a MW below 250 and especially below 200. They may contain more than two hydroxy groups as in sugars but are preferably derived from propylene oxide and especially ethylene oxide.
  • Particularly preferred polyols are glycols and their mono ethers such as di(C 1 - )-alkylene glycols.
  • suitable polyols are glucose, sucrose, mannitol and especially ethylene glycol, propylene glycol, butylene glycol, propylene diglycol and ethylene diglycol.
  • Another still further class of OWSA are aryl and C ⁇ -alkyl ethers of C ⁇ -alkanols, particularly C ⁇ -alkyl ethers of C ⁇ -alkanols and especially C ⁇ -alkyl ethers of ethanol.
  • suitable ethers are ethoxyethanol and especially phenoxyethanol.
  • the amount of component (b) in the composition according to the present invention may be just sufficient to give an improvement in the aqueous solubility of the metal complex which is component (a) or it may be present in a much greater amount.
  • the amount of component (b) is at least 0.3, more preferably at least 0.5 molar with respect to the metal complex.
  • the amount of component (b) is stoichiometric relative to component (a).
  • the molar concentration of component (b) relative to component (a) is preferably less than 5, more preferably less than 3 and especially less than 2 times the molar concentration of (a).
  • component (b) increases the aqueous solubility of the metal complex.
  • component (a) and (b) dissolved in water there is provided an aqueous solution of components (a) and (b) dissolved in water.
  • the amount of the metal complex in the aqueous solution is as high as possible and is sufficient to be commercially useful.
  • the aqueous solution contains 2% by weight of the metal complex.
  • the aqueous solution of the metal complex can be made by adding component (a) and component (b) to water or it may be formed during the preparation of component (a).
  • component (b) may be added to the unmetallised thiohydroxamic acid prior to the addition of a metal salt and the formation of the metal complex. It is preferred, however, that the aqueous solution is made using the pre-formed metal complex.
  • the aqueous solution according to the invention may be made by suspending the metal complex in water, optionally in the presence of a water miscible organic liquid as cosolvent. Generally, no co-solvent is required.
  • the mixture of metal complex, OWSA and water is heated, preferably above 50 and especially above 65°C. Generally, it is not necessary to heat to 100°C and it is preferred that it is not heated above 80°C.
  • the metal complex in the presence of the OWSA under alkaline conditions, preferably above pH9 and especially above pH11.
  • the pH is raised by adding a water-soluble inorganic base such as a carbonate and especially a hydroxide of an alkali metal.
  • the alkali metal is lithium, potassium or especially sodium.
  • the pH of the solution is preferably adjusted towards neutral pH values whereupon the metal complex remains in solution.
  • the OWSA is a ligand which reacts with the metal of the metal complex.
  • a compound which is a metal complex of a cyclic thiohydroxamic acid of formula 1 containing a ligand derivable from the OWSA preferably, the compound is a 2:1 metal complex with zinc and it contains preferably one ligand derivable from the OWSA for each metal atom in the metal complex.
  • the composition according to the present invention has biocidal properties and can therefore be used as a preservative to inhibit microbiological degradation of any medium which is susceptible of microbial damage.
  • the composition may therefore, be used as an industrial biocide to inhibit the growth of micro-organisms in cooling waters, metal-working fluids, paper-mill liquors, paints, latices, recreational waters such as swimming pools, adhesives, leather, wood and formulations such as aqueous dyestuff solutions and dispersions, printing inks, agricultural flowables and personal care formulations.
  • the low toxicity of the metal complexes of formula 1 makes the composition according to the present invention particularly suitable for the preservation of personal care formulations, especially such formulations comprising oil-in-water and water-in-oil emulsions.
  • personal care formulations are hand lotions, foundation creams, emollient creams, facial washing creams, shaving creams, after shave lotions, sunscreen lotions and creams, sunscreen hair protectors, after-sun lotions, antiperspirants, deodorants, hair gels, hair colourants, hair mousse, mascara, eye shadow, eye liners, lipstick, lip gloss, facial blushes, rouges, foundations, fragrances, shampoos, shampoo gels, conditioning rinses, toothpaste, mouthwashes, foam bath liquids, miscible and soluble bath oils, soaps and liquid soap formulations.
  • the amount of the composition according to the invention which is incorporated into the medium to be protected may be just sufficient to confer an antimicrobial effect or it may be significantly higher.
  • the amount of the composition should be such that greater than 5ppm, more preferably greater than 10ppm and especially greater than 20ppm of the metal complex of formula 1 is present in the medium.
  • the amount of composition in the medium should be such that the amount of metal complex of formula 1 is less than 1000 ppm, more preferably less than 500 ppm and especially less than 100 ppm.
  • the metal complex of formula 1 may be the only biologically active material in the medium to be protected or it may be present together with one or more other biologically active compounds especially where it is desirable to widen the spectrum of activity or to increase the rate of kill.
  • other biologically active compounds which may be used with the composition according to the present invention are quaternary ammonium compounds such as N,N-diethyl-N-dodecyl-N-benzylammonium chloride; N,N-dimethyl-N-octadecyl-N-(dimethylbenzyl)ammonium chloride; N,N-dimethyl-N,N-didecylammonium chloride; N,N-dimethyl-N,N-didodecylammonium chloride; N,N,N-trimethyl-N-tetradecylammonium chloride; N-benzyl-N,N-dimethyl-N (C 12 -C 18 -alkyl)ammonium chloride; N
  • Example 1 3-hydroxy-4-methylthiazol-2(3H)-thione as its 2:1 complex with zinc (1 part) and l-histidine (1.5 parts ex Aldrich) were stirred in water (45 parts). Concentrated aqueous sodium hydroxide solution was added to give a pH of about 10.5 and the reactants heated to 65°C with stirring. As the metal complex dissolved, the pH dropped and further sodium hydroxide solution was added to maintain the pH at about 9.5. When all the metal complex had dissolved, the resultant yellow solution was screened, cooled to 20°C and the pH adjusted to about 8 by addition of hydrochloric acid. A 2% (w/w) aqueous solution of the metal complex was obtained.
  • Example 2 Example 1 was repeated except that 0.5 parts of the metal complex was used and the histidine was replaced by ethylene giycol (0.27 parts). A 1% (w/w) aqueous solution of the metal complex was obtained.
  • Example 3 and 4 3-hydroxy-4-methylthiazol-2(3H)-thione as its 2:1 complex with zinc (0.2 parts) was stirred in water (20 parts) with an OWSA (0.5 parts).
  • the pH was raised to pH 11 by addition of concentrated aqueous sodium hydroxide solution and heated with stirring at 75°C for 4 hours.
  • the solution was filtered hot and cooled to give 1% (w/w) aqueous solution of the metal complex.
  • the OWSA and colour of the resulting aqueous solution are given in Table 1 below.
  • Example 2 was repeated except that the ethylene glycol was replaced by diethylene triamine penta-acetic acid (0.5 parts, 0.0014M). A 1% (w/w) pale yellow aqueous solution was obtained.
  • Example 2 was repeated except that the ethylene glycol was replaced by tetra sodium pyrophosphate (2.2 parts, 0.0084 M). Again, a 1% pale yellow aqueous solution was obtained.
  • An oil-in-water emollient cream was prepared from the following components.
  • capric/caprylic triglyceride (Miglycol 812) 2 parts stearyl alcohol-15 PO (Arlamol S3)
  • Formulations A and B were prepared separately by stirring the components and heating at 75°C prior to mixing formulation A with formulation B and allowing to cool. An aliquot of the resulting cream (50 parts) was placed in a 60ml sterile glass bottle and an aqueous solution of an OWSA and 3-hydroxy-4-methylthiazol-2(3H)-thione as its 2:1 zinc complex added as indicated in Table 2 below.
  • Each aliquot was inoculated with a 1 ml sample of a culture of Staphylococcus aureus, NCTC 10788, grown ovemight at 30°C in nutrient agar and diluted in sterile Ringer's solution in a haemocytometer to give 1 X 10 8 (E8) cells/ml. After thorough mixing, the aliquots were incubated at 30°C and 1 part samples removed after 1 ,2 and 7 day periods and the number of viable bacteria determined by streaking onto nutrient agar.
  • Al is active ingredient - is no growth + is little growth ++ is some growth +++ is confluent growth
  • a shampoo was prepared according to the following recipe 16.5 parts Sodium Laureth Sulphate 2 parts Empilan 2502
  • the pH was adjusted to pH 7 by addition of citric acid.
  • E is exponential e.g. 2E7 is 2x10 7
  • An acrylic paint was prepared by mixing a methyl methacrylate/2- ethylhexylacrylate copolymer in water (34 parts, Revacryl IA ex Harlow Chemical Company) with a millbase containing titanium dioxide, calcium carbonate and carboxymethyl cellulose in ethylene glycol and water (57 parts ex Marcel Guest) and making up to 100 parts with water.
  • the paint had a pH value of about 9.
  • yeast extract was added prior to dilution with water. The final paint was pasteurised for 20 minutes at 72.2°C and finally cooled.
  • Aeromonas hydrophila (Paint Research Association No. 8)
  • Cell suspensions were prepared for each organism in one quarter strength Ringers Solution and adjusted to give 10 8 cells/ml.
  • a mixed bacterial suspension was prepared by combining the individual suspensions and 1ml of the mixed bacterial 0 suspensions was added as inoculum to the 50 parts paint.
  • the inoculated paint samples were incubated at 30°C and tested for growth after 1 , 2, 3, 4 and 7 days by streaking out on nutrient agar and incubation for 2 days at 30°C. Bacterial growth was assessed visually.

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Cette composition comprend un complexe métallique d'un acide thiohydroxamique cyclique, tel qu'un complexe de zinc 2:1 de 3-hydroxythiazol-2(3H)-thione, ainsi qu'un agent organique de dissolution dans l'eau pouvant notamment être un composé possédant la formule Y-X-Z dans laquelle Y représente un groupe qui interagit avec le complexe métallique, X est un groupe séparateur divalent organique et Z est un groupe de dissolution dans l'eau. L'agent de dissolution dans l'eau que l'on préfère est un acide aminocarboxylique tel que l'histidine.
PCT/GB1996/001480 1995-06-22 1996-06-20 Composition biocide Ceased WO1997000613A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU61326/96A AU6132696A (en) 1995-06-22 1996-06-20 Composition biocidal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9512703.1A GB9512703D0 (en) 1995-06-22 1995-06-22 Composition and use
GB9512703.1 1995-06-22

Publications (1)

Publication Number Publication Date
WO1997000613A1 true WO1997000613A1 (fr) 1997-01-09

Family

ID=10776481

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/001480 Ceased WO1997000613A1 (fr) 1995-06-22 1996-06-20 Composition biocide

Country Status (3)

Country Link
AU (1) AU6132696A (fr)
GB (1) GB9512703D0 (fr)
WO (1) WO1997000613A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8785679B2 (en) 2012-12-10 2014-07-22 Empire Technology Development Llc Hydrophilic biocidal coatings

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57209210A (en) * 1981-06-18 1982-12-22 Shiseido Co Ltd Solubilization of bis (2-pyridylthio-1-oxide) zinc
EP0259249A2 (fr) * 1986-07-23 1988-03-09 Ciba-Geigy Ag Préparations microbicides
WO1992001380A1 (fr) * 1990-07-18 1992-02-06 Imperial Chemical Industries Plc Composition biocide
EP0500352A1 (fr) * 1991-02-21 1992-08-26 Zeneca Limited Compositions biocides contenant des composées oxy-phosphore pour atteindre une solubilité améliorée.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57209210A (en) * 1981-06-18 1982-12-22 Shiseido Co Ltd Solubilization of bis (2-pyridylthio-1-oxide) zinc
EP0259249A2 (fr) * 1986-07-23 1988-03-09 Ciba-Geigy Ag Préparations microbicides
WO1992001380A1 (fr) * 1990-07-18 1992-02-06 Imperial Chemical Industries Plc Composition biocide
EP0500352A1 (fr) * 1991-02-21 1992-08-26 Zeneca Limited Compositions biocides contenant des composées oxy-phosphore pour atteindre une solubilité améliorée.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8306, Derwent World Patents Index; Class B03, AN 83-13036K, XP002018032 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8785679B2 (en) 2012-12-10 2014-07-22 Empire Technology Development Llc Hydrophilic biocidal coatings

Also Published As

Publication number Publication date
AU6132696A (en) 1997-01-22
GB9512703D0 (en) 1995-08-23

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