EP0917425A1 - Solubilisation de biocides dans des solvants anhydres de type "onium" - Google Patents

Solubilisation de biocides dans des solvants anhydres de type "onium"

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Publication number
EP0917425A1
EP0917425A1 EP96941236A EP96941236A EP0917425A1 EP 0917425 A1 EP0917425 A1 EP 0917425A1 EP 96941236 A EP96941236 A EP 96941236A EP 96941236 A EP96941236 A EP 96941236A EP 0917425 A1 EP0917425 A1 EP 0917425A1
Authority
EP
European Patent Office
Prior art keywords
solution
biocide
compound
onium
compounds
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.)
Withdrawn
Application number
EP96941236A
Other languages
German (de)
English (en)
Inventor
Nigel Paul Maynard
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Individual
Original Assignee
Individual
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Filing date
Publication date
Priority claimed from NZ280716A external-priority patent/NZ280716A/xx
Application filed by Individual filed Critical Individual
Publication of EP0917425A1 publication Critical patent/EP0917425A1/fr
Withdrawn legal-status Critical Current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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/14—Derivatives of phosphoric acid

Definitions

  • the present invention relates to solubilising techniques for chemical moieties including not only the procedures themselves but the thus solubilised moieties and preparations thereof.
  • chemical moieties includes within its ambit any metal organic complex or organic entity.
  • the present invention relate to solubilising techniques allowing the achievement of solutions of a chemical moiety or moieties which may then be dispersed in common solvents (including water) to produce micro-emulsions, macro-emulsions or suspensions, such original solutions being non-aqueous and aprotic.
  • the solubilised moiety may be part of a process other than the formulation of a finished product, for example, where the 'onium' solubilised produce may be used in another manufacturing process as a step in another synthesis or in the application of the moiety to other non fluid substrates. This is especially so for biocidal applications.
  • metal organic complex or organic moiety encompasses within its scope any metal organic complex to be solubilised for a purpose and any organic moiety (whether containing one or more hetero atoms) to be solubilised also having some purpose (or mixtures of both) and such may include but are not restricted to metal organic complexes include those of (alone or in admixture) aluminium, bismuth, boron, cadmium, calcium, cobalt, copper, iron, lead, magnesium, manganese, molybdenum, nickel, thorium, titanium, tungsten, uranium, vanadium and zinc.
  • organic moieties include (alone or in admixture) benzimidazoles, IPBC, Chlorthalonil, substitute triazoles, synthetic pyrethroids, anmelmintics such as Mebendazole, Albendazole, Fenbendazole, Flubendazole, Oxfendazole and Thiabendazole, growth promotant/coccidiostats such as the ionophore antibiotics typified by Lasalocid, Monensin and Tylosin, antibiotics such as Diclazuril, Cationomycin, Virginiamycin, Maduramycin, Narasin, Salinomycin, Halofiiginone, Phenothiazines and Pyrimidines.
  • Other metal and organic moieties abound (for example, selenium, or, for example, a whole range of different ecto-or endo-parsitic compositions of an organic form or of a metal organic complex form
  • polar aprotic solvent or “highly polar aprotic solvent” includes but is not limited to glycol diethers (eg. tetraethylene glycol dimethyl ether), n-alkyl pyrrolidones (eg. n-octyl pyrrolidone), lactones (eg. butyrolactone), ketones (eg. acetophenone or cyclohexanone), lactams (eg. caprolactam), morpholines (eg. n-methyl morpholine or the N oxide thereof), substituted ureas (eg. tetramethyl urea), ring compounds containing oxygen and/or nitrogen groups (eg.
  • glycol diethers eg. tetraethylene glycol dimethyl ether
  • n-alkyl pyrrolidones eg. n-octyl pyrrolidone
  • lactones eg. butyrolactone
  • ketones
  • dioxane dioxane, dioxane, tetrahydrofuran, pyridine, alkyl carbonates or cychc carbonates, imidazolines).
  • the group can be extended to include sulphoxides, amides, organic phosphates and where suited esters.
  • onium compound in respect of anhydrous compounds refers to an anhydrous compound selected from quaternary ammonium, phosphonium, arsonium or similar compounds, ternary sulphonium compounds and may include amine or phosphine oxides and sulphoxides which can be viewed as quaternary compounds.
  • the preferred "onium” compound or compounds is or are selected from quaternary ammonium compounds or amine or phosphine oxides.
  • common solvent includes water and/or common organic solvents some of which are referred hereinafter specifically by reference to carbendazim and oxine copper. Others include those referred to in the various scenarios hereinafter described (particularly with reference to scenario 1).
  • low solubility refers to any solubility of a kind below where the use ofthe present invention provides an advantage by way of delivery, stability or otherwise over the use of such "common solvents”.
  • the invention consists in a solution (solid or liquid) of at least one biocide which is a "metal organic complex or an organic moiety" which, at least in the absence of extreme conditions of pH (high or low), is of low solubility or insoluble in "common solvents", said solution having being prepared by dissolution of the biocide(s) with heating in
  • said "metal organic complex or an organic moiety" was prepared prior to the presence of the anhydrous "onium” compound or compounds.
  • said "metal organic complex or an organic moiety" was prepared subsequent to the presence of the anhydrous "onium” compound or compounds.
  • said "metal organic complex or an organic moiety" was prepared at least in part during the presence of the anhydrous "onium” compound or compounds.
  • aprotic solvent as in (ii)
  • no aprotic solvent is present during such dissolution.
  • At least one biocide is an organic moiety of low solubility in common solvents in the absence of extremes of pH.
  • At least one said biocide is a benzimidazole.
  • At least one said biocide is Carbendazim.
  • At least one said biocide is a metal chelate.
  • said metal chelate is a chelated biocidal metal and the chelating agent is selected from 8-hydroxyquinoline or analogues thereof, hydroxy aromatic acids or analogues thereof, nicotinic or picolinic acid or analogues thereof, or mixtures thereof.
  • said metal chelate is a chelate with 8-hydroxyquinolinolate ligands or is a mixed chelate of which at least one ligand is an 8-hydroxyquinolinolate.
  • said onium compound is selected from the group consisting of quaternary ammonium, quaternary sulphonium and quaternary phosphonium compounds and amine, phosphine oxide and sulphoxide equivalents of the parent compound.
  • said onium compound is anhydrous and free from protic solvents.
  • the at least one said biocide includes an atom of at least one of the group consisting of atoms of aluminium, bismuth, boron, cadmium, calcium, cobalt, copper, iron, lead, magnesium, manganese, molybdenum, nickel, thorium, titanium, tungsten, uranium, vanadium and zinc.
  • biocide includes an atom selected from atoms of copper, zinc and aluminium.
  • said atom is that of copper.
  • the resulting solution has been diluted by a polar aprotic solvent to reduce viscosity.
  • said onium compound(s) is or are biocidal.
  • a coloured metal chelate is included, eg; is bismuth 8-hydroxyquinolinolate .
  • said polar aprotic solvent(s) is selected from the group consisting of glycol diethers, n-alkyl pyrroUdones, lactones, ketones, lactams, mo ⁇ holines, substituted ureas, ring compounds containing oxygen and/or nitrogen groups, alkyl carbonates, cyclic carbonates, imidazolines, suplhoxides, amides, orgamc phosphates and, where suited, esters.
  • the solution induces more than one biocide.
  • each biocide has been dissolved with heating in the or an anhydrous "onium" compound or compounds (whether separately dissolved and subsequently blended or dissolved together).
  • one or more biocide(s) is a synthetic pyrethroid, an organochlorine, an organophosphate, a triazole, a phenol, an isothiazolinone, an imidazole, a thiocyanate, a carbamate, a benzimidazole, a thalonitrile, a n-nitroso-hydroxyamine metal sale, a sulphone and/or a thiazole.
  • one biocide is a metal chelate and the other biocide or biocides are added, if desired or necessary, after the dissolution with heating of the metal chelate in the anhydrous onium compound.
  • the solution is liquid at ambient temperatures.
  • hydrotrope/lipotrope balance [HLB] has been altered subsequent to the biocide(s) dissolution, eg; the solution has had added at least one surfactant.
  • composition is in the form of a micro suspension or micro emulsion.
  • the present invention consists in a method of preparing a biocidal solution (solid or liquid) which comprises the steps of (i) for a single biocidal compound, or (ii) for a mixture of biocidal compounds, or (iii) for separate biocidal compounds, dissolving each biocidal compound in an anhydrous onium compound (or compounds) [optionally including a highly polar aprotic solvent] with heating,
  • the invention consists in a method of solubilizing a biocide ("low solubility biocide") which is a metal organic complex or an organic moiety which, at least in the absence of extreme conditions of pH (high or low), is of low solubility or insoluble in "common solvents", said method comprising i) dissolving with heating the low solubility biocide (with or without any other biocidal compound) in an anhydrous "onium” compound or compounds, and ii) optionally, reducing the viscosity by dilution with an aprotic solvent, and iii) optionally, before or after optional step (ii) [if any step (ii)] blending the solution of step (i) or derived from step (i) with another biocide or a solution of another biocide.
  • a biocide which is a metal organic complex or an organic moiety which, at least in the absence of extreme conditions of pH (high or low), is of low solubility or insoluble in “common solvents
  • heating is to a temperature or temperatures of from 50 °C to 170°C.
  • said "metal organic complex or an organic moiety” was prepared prior to the presence of the anhydrous "onium” compound or compounds. In some cases said “metal organic complex or an organic moiety” was prepared subsequent to the presence of the anhydrous "onium” compound or compounds.
  • said "metal organic complex or an organic moiety" was prepared at least in part during the presence of the anhydrous "onium” compound or compounds.
  • aprotic solvent as in (ii)
  • no aprotic solvent is present during such dissolution.
  • said at least one biocide is an organic moiety of low solubility in common solvents in the absence of extremes of pH.
  • At least one said biocide is a benzimidazole.
  • At least one said biocide is Carbendazim.
  • the at least one said biocide is a metal chelate.
  • said metal chelate is a chelated biocidal metal and the chelating agent is selected from 8-hydroxyquinoline or analogues thereof, hydroxy aromatic acids or analogues thereof, nicotinic or picolinic acid or analogues thereof, or mixtures thereof.
  • said metal chelate is a chelate with 8-hydroxyquinolinolate ligands or is a mixed chelate of which at least one ligand is an 8-hydroxyquinolinolate.
  • said onium compound is selected from the group consisting of quaternary ammonium, quaternary sulphonium and quaternary phosphonium compounds and amine, phosphine oxide and sulphoxide equivalents of the parent compound.
  • said onium compound is anhydrous and free from protic solvents.
  • the at least one said biocide includes an atom of at least one ofthe group consisting of atoms of aluminium, bismuth, boron, cadmium, calcium, cobalt, copper, iron, lead, magnesium, manganese, molybdenum, nickel, thorium, titanium, tungsten, uranium, vanadium and zinc.
  • biocide includes an atom selected from atoms of copper, zinc and aluminium.
  • said atom is that of copper.
  • the resulting solution has been diluted by a polar aprotic solvent to reduce viscosity.
  • said onium compound(s) is or are biocidal.
  • a coloured metal chelate is included, eg; bismuth 8- hydroxyquinolinolate.
  • said polar aprotic solvent(s) is selected from the group consisting of glycol diethers, n-alkyl pyrrolidones, lactones, ketones, lactams, morpholines, substituted ureas, ring compounds containing oxygen and/or nitrogen groups, alkyl carbonates, cyclic carbonates, imidazolines, suplhoxides, amides, organic phosphates and, where suited, esters.
  • the composition includes more than one biocide.
  • the solution includes more than one biocide, each biocide having been dissolved with heating in the or an anhydrous "onium” compound or compounds (whether separately dissolved and subsequently blended or dissolved together).
  • one or more biocide(s) is a synthetic pyrethroid, an organochlorine, an organophosphate, a triazole, a phenol, an isothiazolinone, an imidazole, a thiocyanate, a carbamate, a benzimidazole, a thalonitrile, a n-nitroso-hydroxyamine metal sale, a sulphone and/or a thiazole.
  • one biocide is a metal chelate and the other biocide or biocides are added, if desired or necessary, after the dissolution with heating of tiie metal chelate in the anhydrous onium compound.
  • the resulting solution is liquid at ambient temperatures.
  • hydrotrope/lipotrope balance [HLB] is altered subsequent to d e biocide(s) dissolution, ie; the resulting solution is altered to include at least one surfactant.
  • the solution is modified so that there is also an aqueous phase.
  • micro suspension or micro emulsion results.
  • the composition has the metal chelate dissolved without the need to resort to use of phenols, strong acids or metal soaps, in an anhydrous aprotic compound chosen from quaternary compounds of nitrogen and phosphorus, tertiary compounds, sulphur and amine, phosphine oxide or sulphoxide equivalent.
  • the metal chelate is the 8-hydroxyquinoline chelate of copper and the dissolution has required heating.
  • the invention consists in a method of fixing a biocidal metal species or organic species in an environment subject to aqueous leeching, said method comprising applying into said environment the biocidal species whilst solubilised in an onium compound (with or without dilution widi an aprotic diluent).
  • biocidal species is applied as a solution or composition of the present invention.
  • the invention conists in a biocidally treated matrix or animal, said matrix or animal being an environment treated by a solution or composition ofthe present invention or by a metiiod of the present invention.
  • the present invention also includes the animal pour on application of a solution or composition of the present invention.
  • the present invention also consists in the biocidal product of the method of the present invention.
  • the method may include dilution of the resulting solution to reduce viscosity, by inclusion of polar aprotic solvents such as glycol diethers eg. tetraethylene glycol dimethyl etiier; n-alkyl pyrrolidones eg. n-octyl pyrrolidone; lactones eg. butyrolactone; ketones eg. acetophenone or cyclohexanone; lactams eg. caprolactam; mo ⁇ holines eg. n- methyl mo ⁇ holine or the N oxide thereof; substituted ureas eg. tetramethyl urea; ring compounds containing oxygen and/or nitrogen groups eg.
  • polar aprotic solvents such as glycol diethers eg. tetraethylene glycol dimethyl etiier; n-alkyl pyrrolidones eg. n-octyl
  • dioxane dioxane, dioxane, tetrahydrofuran, pyridine, alkyl carbonates or cyclic carbonates, imidazolines.
  • the group can be extended to include sulphoxides, amides, organic phosphates and where suited esters.
  • the method preferably includes addition of additional surfactants when compatibility with specific solvents is required.
  • the method preferably includes addition of surfactants where the formation of specific macro or micro emulsions are desired, including betaines, phosphate esters, and nonionics such as amine or alcohol ethoxylates or propoxylates, and glycol esters.
  • surfactants where the formation of specific macro or micro emulsions are desired, including betaines, phosphate esters, and nonionics such as amine or alcohol ethoxylates or propoxylates, and glycol esters.
  • the method preferably includes addition of co-biocides including insecticides or co-fungicides when broader spectrum of biocidal performance is required.
  • co-biocides including insecticides or co-fungicides when broader spectrum of biocidal performance is required.
  • insecticides eg. synthetic pyrethroids such as Permithrin, Deltamethrin, Cypermethrin, etc; organochlorine insecticides such as Lindane; organophosphates such as Chlo ⁇ yriphos; or fungicides eg.
  • triazoles such as Hexaconazole [(RS)-2-(2,4- dichlorophyenyl)- 1-( IH- 1,2,4-triazol- l-yl)hexan-2ol], although Azanconazole, Tebuconazole, Cyprocanazole, Flusilazole and Propiconazole, may be used depending on the biological problem to be controlled; phenols such as pentachlorophenol; isothiazolinones such as 4,5-dichloro-2-(n-octyl0-4-isothiazolinone; imidazoles; thiocyanates such as methylene bis thiocyanate; carbamates such as 3-iodo-2-propyl- butyl-carbamate; benzimidazoles such as Carbendazim; thalonitriles such as Chlorothalonil; n-nifroso-hydroxyamine metal salts such as bis-(n- cyclohexyldi
  • the present invention consists in a method of fixing a biocidal metal species or organic species in an environment subject to aqueous leeching, said method comprising applying into said environment the biocidal species whilst, as in the case of a metal biocidal species, solubilised as a metal organic complex in an onium compound (with or without dilution with an aprotic diluent) [and irrespective of whether or not it is applied as a solution or as a slurry or emulsion].
  • said slurry or emulsion is at least a partial aqueous system.
  • the arrangement is substantially as hereinafter described.
  • the environment can be a pour on zone of an animal or a zone of skin for transdermal penetration of an animal or human.
  • the environment can be on and/or in wood.
  • the present invention consists in a biocidally treated matrix or animal, said matrix or animal being an environment treated by a method in accordance with the present invention.
  • the present invention allows solubilisation of biocides which are otherwise insoluble, or have low solubility in common solvents, without recourse to extreme conditions of pH (high or low).
  • examples include (as a metal organic complex) Oxine Copper (as hereinafter defined) and (as an organic moiety) Carbendazim. These are typically soluble to the extent following;
  • any suitable solubilisation regime also allows addition by mixing or blending of co-biocides.
  • the co-biocides are not critical with respect to solubility ie. they may be soluble in known solvents. They are however preferably also solubilised by addition to the formulations of this technology and maybe used in combination of two or more. Scenario 1. To create a 'solution' of biocide, where the solution can be solid or liquid.
  • the biocide is inherently insoluble in standard solvents, which include those typically used for solubilisation including water, aliphatic and aromatic hydrocarbons, chlorinated solvents, ethers, esters, lactams, ketones, alcohols, carbonates, nitrohydrocarbons, amides, and other solvents and variations of these known to those versed in the art of biocide formulation.
  • solvents include those typically used for solubilisation including water, aliphatic and aromatic hydrocarbons, chlorinated solvents, ethers, esters, lactams, ketones, alcohols, carbonates, nitrohydrocarbons, amides, and other solvents and variations of these known to those versed in the art of biocide formulation.
  • Copper 8- Hydroxyquinolinolate (Oxine Copper) and Carbendazim are only soluble to any extent in acids. This technology enables these compounds to be solubilised easily at neutral pH.
  • the onium compound may be selected from quaternary Ammonium, Phosphonium, Arsonium or similar compounds, ternary Sulphonium compounds and may include amine or phosphine oxides which can be viewed as quaternary compounds.
  • the preferred onium compound is selected from quaternary ammonium compounds, amine or phosphine oxides.
  • the temperature of dissolution will depend on the biocide selected. For example, copper 8-hydroxyquinolinolate requires heating for approximately one hour 140° Celsius, whereas Carbendazim requires only fifteen minutes at 100° Celsius.
  • Steps 2, 3 and 4 may be combined.
  • Scenario 2 To create a 'solution' combination of biocides, where the solution can be solid or liquid.
  • Step 4 Diluted as required with a Step 4 highly polar aprotic solvent Specifications of scenario 1 apply. Steps 3 and 4 may be exchanged.
  • Steps 2, 3 and 4 may be combined.
  • Steps 2, 3 and 4 may be combined.
  • Organo-metallic complexes are formed in a number of ways between multivalent metal ions and organic ligands. They are highly valued in industry, agriculture and medicine for uses including biocides, catalysts, feed supplements and pigments. Many metal complexes are water soluble and may readily be formulated for end use by appropriate techniques. A large number, however, are not readily soluble in water and may only be made so by use of severe chemical conditions.
  • insoluble metal complexes are those formed between multivalent metal ions and 8-hydroxyquinoline, or the mixed chelates of 8-hydroxyquinoline and aryl hydroxy acids (for example salicylic acid). Although soluble in very acid conditions, these complexes precipitate from aqueous solutions as the pH rises to 3 or 4. In order to solubilise the complexes they must be reacted with strong acids (organic or inorganic) to form further complexes which themselves are soluble, and then the acid concentration must be maintained at a sufficient strength to prevent precipitation, or they must be maintained at very low pH conditions such that the complex is solubilised. Extremes of this may however separate the metals from the complex.
  • the above complexes can be solubilised by dissolution at elevated temperature in anhydrous tetra - substituted nitrogen and phosphorous compounds and trisubstituted sulphur compounds, for example, quaternary ammonium, phosphonium and tertiary sulphonium compounds.
  • This process which although relatively simple is clearly novel since those working in many fields of use of the complexes have continued to utilise traditional formulating techniques.
  • the pH is at the other extreme ie. a high pH, corrosion is still a problem and any person dealing with the formulation must also contend with noxious fumes from the ammonia or amines.
  • the latter compounds are a significant cost because they are lost from the formulation by volatilisation after treatment of the substrate and therefore provide little long term value. They are also a threat to the environment since they are classified as toxic gases.
  • NZ Patent No. 1975250 to Kenogard teaches a variation on the organic acid solubilised metal complex in that a second chelating ligand is introduced to the 8- hydroxyquinoline complex, namely the hydroxy substituted aromatic acids.
  • the metal complex be solubilised in aliphatic or aromatic solvents. This may apply where the complex is to be used as a biocide applied, for example, in an aliphatic solvent system or where the complex may be used in some catalytic process.
  • UK Patent GB 2152816 describes a method wherein the above metal complexes are reacted witii both strong organic acids and an alkyl phenol to give a product which produces relatively stable solutions with these solvents. Again, strong acids and additional expensive adjuvants are essential for the success of the technique.
  • NZ Patent No. 246976 and NZ Patent No. 243460 both to Hickson International document efforts made to overcome some ofthe inherent problems of using quaternary ammonium compounds in conjunction with preservative metals. These remove to some extent the difficulties inherent in the Domtar and Kenogard patents in that relatively neutral solutions can be formed by using water soluble complexing agents for the metal (simple organic hydroxy acids and phosphonic acids are included as examples), which remained soluble in the aqueous solvent system used ie. in the presence of water. Although improvements have been realised, the cost of adjuvants has not been negated and there is therefore room for further improvement.
  • NZ Patent 215943 to Kop-Coat, Inc. discloses wood preservative compositions comprising a synergistic combination of DDMAC (didecyldimethyl ammonium chloride) of formula
  • IPBC 3-iodo-2-propynyl butyl carbamate
  • DDMAC as an aqueous solution is used to emulsify an organic solvent solution of IPBC.
  • the present invention provides the prospect of the same synergism or synergism from the other biocidal moieties being used in combination biocidally but without the need for a separate organic solvent dissolution of one active moiety prior to the presence ofthe other active moiety (where it is an "onium" compound) and indeed well prior to any deliberate inclusion of an aqueous phase.
  • One objective ofthe present invention to solubilise otherwise very insoluble metal complexes of, as an example of 8-hydroxyquinoline, hydroxy aromatic acids and their mixed complexes and other otherwise aqueous insoluble metal complexes, to give relatively neutral compositions without the need for acids, additional complexing agents, ammonia or amines or additional adjuvants. Also, for example, where the composition may be used in wood preservation, where one active ingredient does in fact solubilise the second otherwise insoluble active ingredient considerably minimising the added cost of adjuvants.
  • biocidal composition may be required to preserve lignocellulosic composites.
  • These products are typically manufactured using formaldehyde based adhesive systems where polymerisation of the resin is catalysed by acids. Acid solubilised biocides can cause premature polymerisation and therefore difficulties in production and plant cleanup.
  • metal complexes of this invention are reported to have far greater efficacy from being applied to the substrate at a higher pH than the aforementioned acid solubilised metal complexes.
  • compositions wherein complexes of metals are demonstrated to dissolve in aprotic solutions of ammonium, phosphonium and sulphonium compounds.
  • compounds such at metal 8- hydroxyquinolinolates for example, copper 8-hydroxyquinolinolate (Oxine Copper) have very low solubility in water, under normal conditions around 0.22 parts per million.
  • the literature also states the compound is insoluble in ethanol and common organic solvents. It has been found that by agitating the copper complex in aprotic and anhydrous quaternary compounds at elevated temperature that significant solubility can be gained, for example, as high as 20% (200000 ppm). This is a significant enhancement over previous techniques.
  • aprotic solvents such as the glycol diethers, n-alkyl substituted pyrrolidones, lactones and numerous other aprotic solvents available and known to those versed in the art.
  • the concentrated solutions of metal complexes may find utility in a number of areas, for example, catalysis, it is convenient to note that when used as a biocide the solutions may be diluted directly with water to produce macro-emulsions or micro-emulsions depending on which quaternary compound is used, and that the physical properties of the emulsions can be manipulated by addition of further solvents and/or surfactants if so desired. These techniques are also known to those versed in the art of emulsion production.
  • a further advantage of this technology is that by selection of the quaternary compound and/or solvent, there is the ability to form transparent solutions or emulsions in organic solvent systems which might typically be used in wood preservation, for example, in aliphatic white spirts.
  • the metal selected for solubilisation may be any or a mixture of complexes of aluminium, bismuth, boron, cadmium, calcium, cobalt, copper, iron, lead, magnesium, manganese, molybdenum, nickel, thorium, titanium, tungsten, uranium, vanadium or zinc.
  • Other cationic species such as beryllium, strontium and the rare earth metals also form complexes and are hereby included by implication.
  • the preferred species for biological performance are copper, zinc, aluminium, nickel or mixtures thereof. Of these species copper, zinc and aluminium are more preferred, with copper being the most preferred.
  • Bismuth may be advantageously used to provide a level of colour to the substrate since, by way of an example of a metal organic complex, the bismuth 8- hydroxyquinolinolate is red in colour. Trace metal deficiences (eg. selenium) are also a possibility.
  • the metal(s) selected may be inco ⁇ orated directly into the formulation by dissolution of the metal 8-hydroxyquinolinolate, for example, (or other chelates) or by production in situ by reaction of 8-hydroxyquinoline (or other ligands) with a relatively weakly associated metal compound such as the carbonate, hydroxide, oxide or acetate although for economic reasons the hydroxide or oxide are preferred.
  • a relatively weakly associated metal compound such as the carbonate, hydroxide, oxide or acetate although for economic reasons the hydroxide or oxide are preferred.
  • the organic compounds of this invention may be selected from those with preferably low solubihty in known common solvents as hereinbefore defined but may also include compounds which although otherwise soluble may be benefit from being used in the primary solubilising process of this invention.
  • Such low solubility compounds may include metal complexes such as Copper 8- hydroxyquinolinolate or other equivalent metal complexes; benzimidazoles such as Carbendazim, Albendazole, Mebendazole etc; triazoles including the benzotriazoles; indazoles; phthalonitriles such as Chloro thalonil; thiazoles such as Thiabendazole or Benzthiazuron.
  • the selection of organic compound may include biocides selected from fungicides, insecticides, herbicides, anthelmintics, growth promotants, algacides, bactericides and others known to those versed in bio-control.
  • the present invention will allow pour-on formulations for the treatment of ecto-or endo-parasites where the or one of the biocidal compounds is such an organic moiety or a metal organic complex. Similarly with a range of transdermal medications.
  • the ratio of metal 8-hydroxyquinolinolate may be reduced, additional metal ions added and the remainder of the complex built by addition of a second (or third) complexing agent such as, for example, salicylic acid.
  • a second (or third) complexing agent such as, for example, salicylic acid.
  • the ratios are adjustable such that they may range from 100% primary chelate to 100% secondary chelate.
  • the mol ratio of primary to secondary complexing agent or ligand is 1 : 1 as this is known to form a true compound with strong bio-activity, otherwise the composition becomes a mixture of complexes.
  • analogues of 8-hydroxyquinoline and salicylic acid are included, for example, 5-chloro-8-hydroxyquinoline, 5-chloro-salicylic acid or 2-hydroxy-naphthoic acid, but including other compounds and analogues such as nicotinic acid and picolinic acid and analogues, however for economic reasons unsubstituted 8-hydroxyquinoline and salicylic acid are preferred.
  • the following structures illustrate some of the broad families of ligands or complexing agents which can be used, A preferred principal complexing ligand;
  • R' and R" are sirnilar or different and selected from H, C l, F, I or Br.
  • R', R", R"' are similar or t and selected from H, Cl, F, I
  • Rl and R2 are COOH or Oh but wherein when one is COOH the other must be OH and where R', R", R'" are similar or different and selected from H, Cl, F, I or Br or where R' and R" may combine to form an aromatic ring
  • R' is H, Me, Ph,Cl, F, I or Br.
  • R', R", R"' are H or OH but within only one need be OH.
  • R' is OH
  • the solubilising compound may be chosen from ammonium, phosphonium, arsonium. sulphonium or mixtures of these compounds.
  • the compounds may have a variety of substituents including alkyl, aryl, alkaryl and variations of these. A large number and variety are produced commercially, the list too large to group in this document. Those versed in the art of quaternary chemistry will recognise the diversity of options. If producing a biocidal combination the choice might automatically revert to the dimethyl benzalkonium chlorides or the dialkyl dimethyl ammonium compounds since these have pronounced efficacy against fungi and bacteria in their own right and therefore in combination with biocidal metal complexes would produce effective products.
  • Tne anion associated with the quaternary compound is not critical to the invention.
  • Anions normally encountered include bromide, chloride, chlorate, fluoride, iodide, sulphate, nitrate and others. For reasons of cost one would preferably use chloride since this is normally commercially available, but special circumstances might dictate use of another.
  • R', R", R"' is an alkyl or substituted alkyl
  • R'- - R'" group but when A is S, R' is absent and R"
  • I R"' can not form an unsaturated ring
  • R'" R"" is an alkyl group, aralkyl group or oxygen, or R" and R"" form part of a saturated ring structure which may include one or more moieties such as N, O, S in the ring and may have substitution groups on the ring or R' is absent and R" and R"" form part of an unsaturated ring which may carry substitution groups
  • any solvents used for dilution or reduction in viscosity should necessarily be aprotic ie. have no accessible or labile hydrogen functionality as for example occurs with water, alcohol etc. This is because these materials cause reprecipitation of the metal complex.
  • n-methyl morpholine or the n oxide substituted ureas eg. tetramethyl urea; ring compounds containing oxygen and/or nitrogen groups eg. dioxane, dioxane, tetrahydrofuran, pyridine, alkyl carbonates, imidazolines.
  • the group can be extended to include sulphoxides, amides, organic phosphates and where suited esters. The range is extensive and too large to fully document, the preferred properties are high solvency with very low protic functionality.
  • HLB hydrotrope/lipotrope balance
  • the HLB may be altered by addition of surfactant materials. This technique is well known to those versed in the art.
  • Surfactants may be selected from a large range, recognising the potential incompatibility that can occur with quaternary compounds, including, betaines, phosphate esters, and nonionics such as amine or alcohol ethoxylates or propoxylates, glycol esters, or combinations thereof. Numerous other surfactants are also able to be substituted for those here listed.
  • the metal or organic biocidal complex solution may have utility as a biocide it may be convenient to include additional complementary or supplementary biocides.
  • additional complementary or supplementary biocides can be chosen from insecticides eg. synthetic pyrethroids such as Perntithrin, Deltamethrin, Cypermethrin, etc; organochlorine insecticides such as Lindane; organophosphates such as Chlorpyriphos; or fungicides eg.
  • triazoles such as Hexaconazole [(RS(-2-(2,4-dichlorophenyl)-l-(lH-l,2,4-triazol-l-yl)hexan-2ol], although Azaconazole, Tebuconazole, Cyproconazole, Flusilazole and Propiconazole, may be used depending on the biological problem to be controlled; phenols such as pentachlorophenol; isothiazolinones such as 4,5-dichloro-2-(n-octyl0-4-isothiazolinone; imidazoles; thiocyanates such as methylene bis thiocyanate; carbamates such as 3-iodo-2-propyl- butyl-carbamate; benzimidazoles such as Carbendazim; thalonitriles such as Chlorothalonil; n-nitroso-hydroxyamine metal salts such as bis-(n- cyclohexyldi
  • the invention can contain other additives which might be employed with, for example, timber preservatives such as water repellents, colour additives, corrosion inhibitors, fire retardants and viscosity modifiers.
  • timber preservatives such as water repellents, colour additives, corrosion inhibitors, fire retardants and viscosity modifiers.
  • the oxine copper is heated with stirring in the 50% aqueous quaternary compound to 105 Celsius, continuing until all water has distilled off. The temperature is increased to approximately 150 Celsius until a red-brown solution with a green tinge is formed containing a concentration of Oxine Copper estimated at 16%.
  • example 4 To 10 parts of example 4 were added 0.5 part of a proprietary phosphate ester surfactant. Dilution of this to 0.5% in water resulted in a colloidal micro suspension.
  • example 5 To a portion of example 5 was added 0.5% of Hexaconazole technical. The triazole dissolved to give a clear solution.
  • Example 7 To a sample from Example 7 was added 5% Permethrin technical. The Permethrin dissolved to give a clear solution. Dilution to 2% in water resulted in a transparent emulsion.

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  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention porte sur une solution obtenue par chauffage d'au moins un biocide dans un ou des composés anhydres d''onium' (par exemple de l'ammonium quaternaire) ou dans une solution à solvant aprotique polaire de ces composés. Le procédé s'applique à des complexes organométalliques (par exemple des chélates de cuivre et de 8-hydroxyquinoline) ou à des biocides organiques qui sauf en cas de conditions extrêmes de pH sont peu solubles dans les solvants usuels. Une fois constituée, une telle solution peut être traitée de différentes manières, par exemple pour créer une microémulsion ou une microsuspension dans une phase aqueuse.
EP96941236A 1995-12-20 1996-12-17 Solubilisation de biocides dans des solvants anhydres de type "onium" Withdrawn EP0917425A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
NZ28071695 1995-12-20
NZ280716A NZ280716A (en) 1995-12-20 1995-12-20 Method for dissolution of insoluble biocides using an onium compound
NZ28606996 1996-02-26
NZ28606996 1996-02-26
NZ29930296 1996-09-05
NZ29930296 1996-09-05
PCT/NZ1996/000143 WO1997022246A1 (fr) 1995-12-20 1996-12-17 Solubilisation de biocides dans des solvants anhydres de type 'onium'

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EP0917425A1 true EP0917425A1 (fr) 1999-05-26

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CN100496246C (zh) 2004-06-07 2009-06-10 辛根塔参与股份公司 减轻线虫损害的方法
CA2659908C (fr) * 2005-06-15 2014-07-29 Rohm And Haas Company Composition antimicrobienne utile comme agent de conservation du bois comprenant un sel d'alkyldimethylammonium de cuivre et du 2-n-octyl-4-isolthiazolin-3-one
KR102061609B1 (ko) * 2018-06-18 2020-01-09 대한민국 농산물에 잔류하는 옥신코퍼 및 그 분석방법

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AU732685B2 (en) 2001-04-26
WO1997022246A1 (fr) 1997-06-26
AU1043497A (en) 1997-07-14

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