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WO2011071876A1 - Dispersion aqueuse stabilisée d'analogues du folpet, son procédé de préparation et composition en contenant - Google Patents

Dispersion aqueuse stabilisée d'analogues du folpet, son procédé de préparation et composition en contenant Download PDF

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Publication number
WO2011071876A1
WO2011071876A1 PCT/US2010/059227 US2010059227W WO2011071876A1 WO 2011071876 A1 WO2011071876 A1 WO 2011071876A1 US 2010059227 W US2010059227 W US 2010059227W WO 2011071876 A1 WO2011071876 A1 WO 2011071876A1
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Prior art keywords
aqueous dispersion
biocide
water
hydrolysis
iodo
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English (en)
Inventor
Raman Premachandran
Daniel H. Brown
Blanca Gomez
Karen Winkowski
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ISP Investments LLC
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ISP Investments LLC
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Priority to US13/513,084 priority Critical patent/US20130045241A1/en
Publication of WO2011071876A1 publication Critical patent/WO2011071876A1/fr
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    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing >N—S—C≡(Hal)3 groups

Definitions

  • This invention relates to biocides, more particularly, to aqueous dispersions of hydrolysis-sensitive biocides, such as Folpet or analogues thereof.
  • Folpet a chloroalkylthio compound with broad spectrum protectant fungicide (N- (trichloromethylthio) phthalimide, has been in use for the last several decades. Folpet is predominantly used in agronomic practice along with other industrial applications today.
  • Folpet has low water solubility or is practically insoluble in water and only slightly soluble in organic solvents. Further, the rates of aqueous hydrolysis increase in alkaline conditions and are more rapid for Folpet analogues. The higher hydrolytic rates for Folpet analogues are related to the higher standard free energy of the phthalimide ring structure. The half-life of the majority of these compounds in aqueous system is from a few minutes to hours at alkaline to neutral pH ranges which are a favorable delivery medium for numerous industrially applicable formulations or compositions.
  • U.S. Patent Publication No. 2002/0055566 discloses aqueous systems comprising at least one hydrolysis-sensitive active compound in combination with binders which consist of alkyd resins based on vegetable oils and or acrylate dispersions.
  • the aqueous systems or ready-to-use formulation with fungicidal activity is particularly aimed at tolylfluanid and its storage stability is demonstrated in water-based wood preservatives.
  • the disclosed formulations are limited to compositions having pH ⁇ 7.
  • a stable, solvent-free, aqueous dispersion composition of hydrolysis-sensitive biocide such as trihalogenomethylthio phthalimide biocides, for example, Folpet and Folpet analogues.
  • the hydrolysis sensitive biocide is present in a mixture of finely divided particles with an iodo-derived hydrophobic biocide such as iodopropynyl butylcarbamate (IPBC) and an inert carrier.
  • IPBC iodopropynyl butylcarbamate
  • the aqueous dispersion may also include and one or more additives.
  • aqueous dispersions have a mixture of a hydrolysis-sensitive biocide, an iodo-derived hydrophobic biocide and an inert carrier dispersed in water.
  • the iodo-derived hydrophobic biocide forms a complex with the inert carrier and the hydrolysis-sensitive biocide that is dispersible in water.
  • the hydrophobic coating includes an inert carrier and the hydrolysis-sensitive biocide may be trihalogenomethylthio phthalimide or an analogue thereof and the iodo-derived hydrophobic biocide may be iodopropynyl butylcarbamate.
  • the inert carrier may be selected from ground natural minerals, ground synthetic minerals, metal oxides, and combinations thereof.
  • the inert carrier includes at least one of a clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomacious earth, perlite, zeolite, highly-disperse silica, alumina, titanium dioxide and silicates.
  • the inert carrier includes a metal oxide and a silica.
  • the aqueous dispersion may also include a water-repelling layer coating the complex.
  • the pH of said aqueous dispersion is between about 7.0 to about 1 1.0. In another embodiment, the pH is at least about 8.0.
  • the wt. % ratio of trihalogenomethylthio phthalimide analogue:IPBC is from about 0.1 :9.9 to about 9.9:0.1 in the composition.
  • a process for preparing a stable, solvent-free, aqueous dispersion composition of hydrolysis-sensitive biocide includes (a) preparing a dry blend of particles comprising a mixture of a hydrolysis-sensitive biocide, an iodo-derived hydrophobic biocide, and an inert carrier to form a complex, (b) mixing the complex with water containing at least one of a dispersant, grind aid, and a thickener, and (c) mechanically processing the mixture from step (b) to yield a desired mean particle size.
  • the process may also include the step of coating the complex with a water-repelling agent.
  • the additives for preparing the desired composition can be a wetting agent, suspending agent, water repelling agent, preservative, algaecide, antimicrobial or silicon fluid alone or in combination thereof.
  • the inert carrier is selected from the group comprising ground natural minerals, ground synthetic minerals and/or metal oxides.
  • aqueous dispersion composition prepared according to the said process containing the stable, hydrolysis-sensitive Folpet/ analogues is employed in the field of paint, building materials, stucco, concrete, caulks, sealants, joint compounds, adhesives, leather, wood, inks, pigment dispersions, metal working fluids, drilling mud and/or clay slurries.
  • hydrolysis-sensitive means the ability of a compound or substance to undergo a chemical reaction that breaks down the compound or substance, typically into two parts, by the additional FI 2 O, which may lead to an unwanted degradation product.
  • solvent-free as used herein is referring to a composition of matter, designates that no external solvent constituent has been added in the present aqueous dispersion composition during the process of making the composition. However, the composition may include about 5% or less residual solvent, more preferably 1% or less residual solvent.
  • aqueous medium may be about 8 and results in a stable aqueous dispersion composition of the biocide.
  • the biocide(s) as a result of the dispersion process may include a hydrophobic coating thereon that enhances the longevity of the biocides in the aqueous medium, i.e., hydrolysis or the rate of hydrolysis of the hydrolysis-sensitive biocide is reduced.
  • the preferred hydrolysis-sensitive biocides would include but are not limited to compounds having a functional group of -N-S-CX 3 or -N-S-CCI 2 X and wherein X is any halogen, for example CI or F, or CH 2 X 2, wherein X is a halogen.
  • the specific hydrolysis-sensitive trihalogenomethylthio compounds can be selected from Captan, Captafol, Dichlofluanid, Tolyfluanid, Folpet and/or Fluorofolpet.
  • aqueous stabilization of the hydrolysis-sensitive trihalogenomethylthio phthalimide analogues is also carried out by employing other iodo derived compounds apart from IPBC which would include iodoalkynyl compounds or compounds wherein one or more iodine atoms are attached to double or triple bond systems, or compounds in which one or more iodine atoms are attached to singly bonded carbon atoms.
  • Non-limiting iodine- containing active compounds include: 3-iodo-2-propynylpropyl carbamate, 3-iodo-2- propynylbutyl carbamate (IPBC), 3-iodo-2-propynyl-m-chlorophenyl carbamate, 3-iodo-2- propynylphenyl carbamate, 3-iodo-2-propynyl 2,4,5 -trichloro-phenyl ether, 3-iodo-2- propynyl 4-chlorophenyl formal (IPCF), di(3-iodo-2-propynyl)hexyl dicarbamate, 3-iodo- 2-propynyloxyethanol ethylcarbamate, 3-iodo-2-propynyloxyethanol phenyl carbamate, 3- iodo-2-propynylthioxothioethyl carbamate, 3-iodo-2
  • finely divided particles of at least one of trihalogenomethylthio phthalimides and IPBC are obtained through known mechanical processing methods such as, but not limited to, pulverizing, crushing, grinding and/or milling methods in order to achieve the resultant mixture of particles.
  • the particles may have a particle size of less than about 0.5 ⁇ to about 10.0 ⁇ and preferably about 0.5 ⁇ to about 3.0 ⁇ .
  • the particle size reduction is carried out in mills, such as, for example, ball mills, agitator ball mills, circulating mills (agitator ball mills with pin grinding system), disk mills, annular chamber mills, double cone mills, triple roll mills and batch mills.
  • the grinding chambers are preferably fitted with cooling systems.
  • Grinding or milling media useful for the preparation of the finely ground mixture includes, but is not limited to, steel shots, carbon steel shots, stannous steel shots, chrome steel shots, tungsten carbide, silicon nitride, silicon, carbide, ceramic, zirconium based media including zirconia, zirconium silicate, zirconium oxide, stabilized zirconia such as yttrium stabilized zirconia, calcium stabilized zircona, magnesium stabilized zirconia, cerium stabilized zirconia, stabilized magnesium oxide, stabilized aluminum oxide and the like.
  • the finely divided particles of the mixture of trihalogenomethylthio phthalimide and IPBC may be further mixed with an inert carrier, more particularly a hydrophobic inert carrier.
  • the IPBC adsorbs onto the other particles, including the trihalogenomethylthio phthalimide to form a water insoluble complex. It is believed that the complex improves the hydro lytic stability of the trihalogenomethylthio phthalimide and a combination biocide efficacy. Examples of suitable inert carriers are discussed below.
  • the hydrolytic stability is further improved by coating the complex with a water repellant layer.
  • the inert carrier may be selected from the group consisting of finely ground natural minerals, ground synthetic minerals and/or metal oxides and preferably selected from the group consisting of clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, perlite or "expanded perlite", zeolite including microphorous aluminosilicate, highly-disperse silica, alumina, mica, wollastonite, silicate or aluminosilicate.
  • Clay minerals of kandite group for example kaolinite, dickite, nacrite and halloysite, have been found to be particularly advantageous.
  • Kaolinite includes kaolin type clays, ball clays, fire clays and China clays. Such clays occur in nature in the form of kaolinite plus other minerals, eg. one or more of illite, mica, quartz and feldspar.
  • the kaolinite clay mineral may be used in its natural, hydroxylated or hydrous state.
  • the aluminosilicate comprises of smectite clay, it may comprise for example one or more of bentonite, hectorite and saponite.
  • the silicates may be oxidized silicon compounds such as Si0 3 , Si0 4 , Si 2 0 6 and Si 2 0 7 .
  • the inert carriers is a silicate clay, for example, an aluminosilicate clay.
  • aluminosilicate clay is a kaolin clay composed of the mineral kaolinite, an aluminosilicate and is a hydrated silica of alumina with a composition of about 46% silica, about 40% alumina and about 14% water.
  • suitable kaolin clay particles are KaMinTM 80 clay, KaMinTM 90 clay, Polygloss® 80 clay and Polygloss® 90 clay.
  • Other suitable examples of natural refined kaolin clay are DixieClay® fillers, Par® clay fillers and Bilt-Plates® 156 clay fillers from R.T. Vanderbilt Company, Inc.
  • the inert carrier is a metal or metal compound selected from one or more of the groups IIIB, IVB, VB, VIB VIIB or VIIIB of the Periodic Table.
  • the metal or metal compounds may be employed in the form of salts, colloidal metal oxides, aluminates, silicates, titanates, zincate, zirconates, zircoaluminate, aluminium titanate, aluminium silicate, stannates or argentates of aluminum, silicon, titanium, zirconium or copper, cobalt, cadmium, nickel, tin, silver, zinc, lead, bismuth, chromium, manganese, iron or arsenic alone or in combination thereof.
  • the inert carrier is or includes titanium dioxide, which may be present in a concentration of 0.01% to 10%, or from 1.0% to 5.0%.
  • the complex may be coated with a water- repelling agent.
  • the water-repelling agent provide a coating that makes it more difficult for water to interact with the hydrolysis-sensitive biocide.
  • the water- repelling agent may be a film forming polymer.
  • the water-repelling film forming polymer may be or include, but is not limited to, poly(acrylic), poly(methacrylics), poly(vinyl ether), poly(vinyl ester), polystyrene, polyurethane, polyoxide, polycarbonate, cellulose ester, cellulose ether, polyester, vinyl pyrrolidone copolymers like alkyl grafted PVP (Ganex®/Agrimer® AL 30, 22, 25, WP 660 polymers) Agrimer® VA PVP -vinyl acetate copolymers, alkylated polyvinylpyrrolidone-hexadecane copolymer, polydiemethyl silane, beeswax and alkyl vinyl ether-maleic acid half-ester polymers, polyvinyl alkyl ether, polyacrylate-polyoctylacrylamide copolymer (Dermacryl®79 and Dermacryl® LT), a copolymer of a vinyl alkyl
  • Condensation polymers include, for example, polyesters, polyamides, polyurethanes, polyureas, polyethers, polycarbonates, polyacid anhydrides, and polymers comprising combinations of the above- mentioned types.
  • Addition polymers are polymers formed from polymerization of vinyl- type monomers including, for example, allyl compounds, vinyl ethers, vinyl heterocylic compounds, styrenes, olefins and halogenated olefins, unsaturated acids and esters derived from them, unsaturated nitrites, vinyl alcohols, acrylamides and methacrylamides, vinyl ketones, multifunctional monomers, or copolymers formed from various combinations of these monomers. Long chain film forming amines may also be used for this purpose.
  • suitable polymers for coating the particles include natural rubber, prevulcanized natural rubber, butyl rubber, isobutene-isoprene copolymers, polyisoprene, polybutadiene, acrylonitrile-butadiene copolymers, stryrene-butadiene copolymers, chloroprene rubber, polyvinylacetate, vinyl acetate copolymerized with one or more vinyl esters of an alkanoic acid, acrylates and/or olefinic hydrocarbons, acrylics (i.e., homopolymers or copolymers of alkyl acrylates, alkyl methacrylates, acrylic acid and/or methacrylic acid), polyurethanes, polyvinylidene chloride, polyvinyl chloride, vinyl chloride- vinylidene chloride copolymers, polyvinylidene fluoride, blends of ployvinylidene fluoride and acrylics, ethylene-vinylacetate
  • polymers can be prepared by emulsion polymerization, solution polymerization, suspension polymerization, dispersion polymerization, ionic polymerization (cationic, anionic), Atomic Transfer Radical Polymerization, and other polymerization methods known in the art of polymerization.
  • the coating on the finely divided particles may also provide enhanced storage- protection.
  • the coating may be applied by various methods, including any conventional coating method. Suitable non-limiting coating methods include brushing, dip-coating, flowing and spraying. Spraying methods may include conventional techniques such as compressed air spraying, electronic spraying, and other manual or automatic methods known to one of skill in the art. Once applied to a mixture, the coating compositions can be cured at ambient or elevated temperatures.
  • the aqueous medium can be any type of water including, but not limited to, distilled water, de-ionized water, double distilled water, triple distilled water, tap water, de-mineralized water, reverse-osmosis water and combination thereof.
  • the aqueous dispersions because of the inclusion of a biocide, provide potent activity against various microorganisms, hence the following non-limiting genera of microorganisms are preferably specified herein as the interest of the present invention: Alternaria, such as Alternaria alternata Alternaria tenuis, Aspergillus, such as Aspergillus niger and Aspergillus terreus, Aureobasidium, such as Aureobasidium pullulans, Chaetomium, such as Chaetomium globosum, Cladosporium, such as Cladosporium herbarum, Coniophora, such as Coniophora souna, Gliocladium, such as Gliocladium virens, Lentinus, such as Lentinus tigrinus, Paecilomyces, such as Paecilomyces varioti, Penicillium, such as Penicillium brevicaule, Penici
  • additives include, but are not limited to, antifoams, plasticizers, surfactants, suspending agents, wetting agents, fillers, coloring agents, dispersing agents, thickening agents, thixotropic agents, antifreezing agents, pH adjusting agents, silicon fluid, corrosion inhibitors, ultraviolet light stabilizers, antioxidants, algaecide, preservative, antimicrobial agents and the like.
  • the aqueous dispersions may include a thickening agent.
  • the thickening agent preferably is one that can provide dispersal of the ingredients of the composition in a uniform manner. Further, the thickening agent may be one that enhances the viscosity of the dispersions without modifying its original properties, which may also increase the stability thereof.
  • the thickening agent may be a hydrocolloid gums such as xanthan gum, guar gum, gellan gum, locust bean gum, gum arabicand alginates, which impart thixotropic properties to the dispersion.
  • cellulose thickening agents are employed.
  • the cellulose thickening agents may be or include, but are not limited to, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, ethyl hydroxyethyl cellulose, methyl ethyl hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxyethylmethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, microcrystalline cellulose, and combinations thereof.
  • hydrophilically modified ethoxylated urethane (HEUR) and/or hydrophobically modified ethoxylated urethane alkali swellable emulsions (HEURASE) are optional thickening agents.
  • thickening agents include water-soluble gums as described in the Encyclopedia of Polymer Science and Engineering, vol.7, pp. 589-613 (John Wiley & Sons, Inc. N.Y., N.Y. 1987), the disclosure of which is incorporated by reference.
  • Suitable commercial thickening agents include, but are not limited to, xanthan gums such as (Kelzan® xanthan gum or Vanzan D xanthan gum), Rhodopol®23 thickener (from Rhone Poulenc) or Veegum® thickener (from R.T.
  • Vanderbilt organic phyllosilicates such as Attaclay® thickener (from Engelhardt), HASE Thickener (RHEOLATE 425), ALCOGUMTM VEP-II (from Alco Chemical Corporation), RHEO VISTM and VISCALEXTM (from Ciba Ceigy), UCAR®, ETHOCELTM or METHOCELTM (from The Dow Chemical Company) and PARAGUMTM 241 (from Para-Chem Southern, Inc.), or BERMACOLTM (from Akzo Nobel) or AQUALONTM (from Hercules) or ACUSOL® (from Rohm and Haas).
  • Attaclay® thickener from Engelhardt
  • HASE Thickener RHEOLATE 425
  • ALCOGUMTM VEP-II from Alco Chemical Corporation
  • RHEO VISTM and VISCALEXTM from Ciba Ceigy
  • UCAR® ETHOCELTM or METHOCELTM
  • PARAGUMTM 241 from Para
  • HEUR hydrophobically modified ethoxylated urethane
  • Various other HEUR thickener would include Borchi Gel 0434, Borchi Gel 0435 and Borchi Gel 0011, Borchi Gel 0620, Borchi Gel 0621, Borchi Gel 0622, Borchi Gel 0625, Borchi Gel 0626, Borchi Gel PW 25, Borchi Gel LW44, Borchi Gel 0024, Borchi Gel WN50S, Borchi Gel L75N, Borchi Gel L76 available from Borchers; Acrysol SCT-275, Acrysol RM8, Acrysol RM 825, Acrysol RM 895 Acrysol TT615 from Rohm and Haas; Tafigel PUR 40, Tafigel PUR 41, Tafigel PUR 50, Tafigel PUR 60 Tafigel PUR 61 available from Munzig; UCAR DR-73 available
  • the amount of thickening agent employed in the present aqueous dispersion composition will vary according to the nature and effectiveness of the thickening agent and the viscosity desired of the aqueous dispersions, but it may generally range between about 0.1% to about 10.0% based on the total weight of the composition, more particularly from about 0.1% to about 5.0%.
  • the viscosity of the dispersions in absence of a thickening agent will be in the range of 10 to 100 centipoise (cp).
  • the quantity of thickener will generally be sufficient to impart to the dispersion a viscosity greater than 100 cp, for example from about 150 cp to about 5,000 cp.
  • a "wetting agent” is a substance, which, at low concentrations, alter the interfacial tension and thus will stabilize the dispersion system or interacts between the surface of a particle and the surrounding liquid to improve dispersion.
  • the organic surface- active material is preferably anionic, nonionic or ampholytic in nature.
  • Wetting agents are amphipathic in structure having both polar and non-polar regions in the same molecule. Examples of surface active agents used in the formulation arts are given in Corrigan, O. I.; Healy, A. M. "Surfactants in Pharmaceutical Products and Systems” in Encyclopedia of Pharmaceutical Technology 2 nd ed. Taylor and Francis, 2006, pp 3583-3596.
  • Useful anionic surface active agents include sulfonic acid types, such as salts of alkanesulfonic acid, alphaolefinsulfonic acid, alkylbenzenesulfonic acid, alkylnaphthalenesulfonic acids, acylmethyltaurines, and dialkylsulfosuccinic acids, alkylsulfuric ester, sulfated oils, sulfated olefins, polyoxyethylene alkyl ether sulfuric ester salts, carboxylic acid types, e.g., fatty acid salts and alkylsarcosine salts and phosphoric acid ester types, such as alkylphosphoric ester salts, polyoxyethylene alkyl ether phosphoric ester salts, and glycerophosphoric ester salts.
  • sulfonic acid types such as salts of alkanesulfonic acid, alphaolefinsulfonic acid, alkylbenzenesulfonic
  • water-soluble nonionic surfactants are condensation products of ethylene oxide with various reactive hydrogen-containing compounds reactive therewith having long hydrophobic chains (e.g. aliphatic chains of about 12 to 20 carbon atoms), which condensation products (“ethoxamers”) contain hydrophilic polyoxyethylene moieties, such as condensation products of poly(ethylene oxide) with fatty acids, fatty alcohols, fatty amides, polyhydric alcohols (e.g. sorbitan monosterate), polypropyleneoxide (e.g.
  • Pluronic materials poloxamers, polyoxyethylene sorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides and/or dialkyl sulfoxides.
  • Suitable amphoteric surfactants include without limitation derivatives of Cs-2o aliphatic secondary and tertiary amines having an anionic group such as carboxylate, sulfate, sulfonate, phosphate or phosphonate.
  • the aqueous dispersions contain an acetylene glycol surface active agent and/or an acetylene alcohol surface active agent to reduce the surface tension.
  • the acetylene glycol may be 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne- 3,6-diol, and 3,5-dimethyl-l-hexyn-3-ol.
  • acetylene glycol surface active agents include, but are not limited to Surfynol series 61, 104, 82, 440, 465, 485, TG and CT-111 CT-121, CT-131, CT21 1 agents available from Air Products and Chemicals, Inc., and Olfine series STG and E1010 These surface active agents are preferably used in amounts of 0.01 to 10% by weight, particularly 0.1 to 2% by weight, based on the total aqueous dispersion composition.
  • Suitable dispersing agent may be employed for the preparation of the aqueous dispersions, for example, cationic, amphoteric or nonionic compounds alone or in combinations thereof; however they are not limited to the dispersants that are described herein. Suitable examples are for instance described in C. R. Martens, Emulsion and Water-Soluble Paints and Coatings, Reinhold Publishing Corporation, 1965.
  • the dispersants may be selected from tetra-potassium pyrophosphate or "TKPP" compounds such as StrodexTM, StrodexTM PK-90, StrodexTM PK-0VOC, StrodexTM MOK-70 available from Dexter Chemical L.L.C.
  • a dispersant may be a particulate material supplied with trade name of Winnofil.® SPT Premium, Winnofil® S, Winnofil® SPM, and Winnofil® SPT available from Solvay Advanced Functional Minerals.
  • a variety of preparations of customized montmorillonite clay dispersants (Bentone® clay) and castor wax under various trade names such as Crayvallac® SF, Crayvallac® MT, and Crayvallac®, AntiSettle CVP are available from Cray Valley Limited.
  • the dispersing agents can also be selected from standard organic polymeric dispersants known in the art for preparing aqueous dispersion compositions.
  • the dispersants may be polyelectrolytes such as polyacrylates and copolymers having polyacrylate compounds, for example various salts of polyacrylic acid compounds, sodium hexametaphosphates, polyphosphoric acid, condensed form of sodium phosphate, alkanolamines, and other reagents commonly used for this function.
  • Exceptional dispersing agents would include poly(methylvinyl ether-co-maleic acid) partially neutralized with sodium hydroxide (EasySperse, EaseySperse P20 by ISP, Wayne NJ) and non-ionic copolymers including but are not limited to EO/PO block copolymers or poloxamers such as Pluronics (for e.g. L101&P103) from BASF, polymers of acrylic and methacrylic acid, C11-C15 secondary ethoxylated alcohols and diols, PEG-PLGA-PEG copolymers and polyether polyols. Additional examples of suitable dispersants would include sodium silicate, sodium carbonate, lignosulphonic acid salts (e.g.
  • sulfonated naphthalene/formaldehyde condensate e.g. Morwet
  • a block copolymer with pigment affinic group e.g. Disperbyck 190
  • 1,4 bis(2-ethylhexyl)sodiumsulfosuccinate e.g. Triton GR PG 70
  • Polyether-polycarbonate sodium salt e.g. Ethacryl P
  • maleic acid- olefin co-polymer e.g. Vultamol 4501
  • ammonium polyacrylate e.g.
  • Dispex GA 40 C6-C15 secondary alcohol and alkyl aryl sulfonate (e.g. Zetasperse 2300) and alkyl naphthalene sulfonate (e.g. Agnique), henolsulphonic or naphthalenesulphonic acid salts, 2-amino-2-methyl-l-propanol, tri and tetra sodium salts of pyrophosphate and polyphosphate and water-soluble sodium or ammonium salts of polyacrylates, polycarboxylates and polymethacrylates.
  • alkyl aryl sulfonate e.g. Zetasperse 2300
  • alkyl naphthalene sulfonate e.g. Agnique
  • henolsulphonic or naphthalenesulphonic acid salts 2-amino-2-methyl-l-propanol
  • Another object of the present invention is to provide a process for preparing a stable, solvent-free, aqueous dispersion composition of hydrolysis-sensitive biocide comprising the steps of: i. preparing a dry blend of finely divided particles of mixture of IPBC, least one trihalogenomethylthio phthalimide analogue, and inert carrier;
  • aqueous medium comprising dispersed particles of mixture of wetting agent, partial amount of suspending and dispersing agent by means of milling/grinding with a suitable media to yield a desired mean particle size
  • the pH of the aqueous dispersion composition prepared according to the above procedure will be at least 7.0, and may be in the range of about 7.0 to about 1 1.0. In one embodiment, the pH may be between about 7.5 to about 8.5. In another embodiment, the pH may be at least 8.0 and may be between 8.0 to 10.5.
  • a silicone oil or fluid may be employed during preparation of the dispersion.
  • the IPBC and Folpet/analogues are ground together in presence of suitable inert carrier and silicone fluid followed by dispersing the resultant mixture in aqueous media to provide the aqueous dispersion composition having pH of about 8.1 to form a stable aqueous dispersion.
  • silicone oils include, but are not limited to, dialkyl polysiloxane (e.g., hexamethyl disiloxane, tetramethyl disiloxane, octamethyl trisiloxane, hexamethyl trisiloxane, heptamethyl trisiloxane, decamethyl tetrasiloxane, trifluoropropyl heptamethyl trisiloxane, diethyl tetramethyl disiloxane), cyclic dialkyl polysiloxane (e.g., hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, tetramethyl cyclotetrasiloxane, tetra(trifluoropropyl)tetramethyl cyclotetrasiloxane), and methylphenyl silicone oil.
  • dialkyl polysiloxane e.g., hexa
  • the dimethyl polysiloxane is typically obtained commercially as silicone oil which is added to the blend of other constituents and ground together to form the final dispersion composition and wherein dimethyl polysiloxane from Dow Corning sold under the trademark 200 FLUID or from General Electric sold under the trademark SF96 polydimethylsiloxane fluid.
  • Preservatives of conventional types may be added to the present aqueous dispersion composition of the present invention to extend the shelf life of the composition.
  • the preservative may serve as bactericide and a fungicide. Addition of preservatives is often appreciated, because various organic thickening agents are sensitive to microbial attack and can be stabilized by presence of suitable preservatives.
  • Preservative compounds such as formaldehyde donor compounds, phenolic compounds, isothiazolinones, parabens, benzoates, aldehydes, hydroxybenzoic acid esters, bicyclic oxazolidones can be employed.
  • Suitable preservative compounds for the present composition include, but are not limited to, 2-methyl-4-isothiazolin-3-one (MIT), 1,2- Benzisothiazolin-3-one (BIT), 5-Chloro-2-methyl-4-isothiazolin-3-one (CMIT), methyl p- hydroxybenzoate, glutaraldehyde, 2-bromo-2-nitropropane-l,3-diol (bronopol, benzyl alcohol, diazolidinyl urea, imidazolidinyl urea, methyl paraben, ethyl paraben, phenoxy ethanol, propyl paraben, sodium methyl paraben, sodium ethyl paraben, sodium dehydroacetate, polyhexamethylenebiguanide hydrochloride, formaldehyde or hexahydrotriazine derivatives, and formaldehyde donors (Nuosept 95, Nuosept 91, Nuosept 101).
  • an algaecide can be incorporated into the aqueous dispersion to prevent any possibility of formation of algae and wherein the suitable algaecide compounds are selected from non-limiting examples of algaecides such as terbutylazine, copper sulfate, dichlorophen, endothal, fentin acetate, quinoclamine, quinonamid, irgarol, diuron, terbutryn, oxfluorfen, simmazine, and/or DCOIT.
  • algaecides such as terbutylazine, copper sulfate, dichlorophen, endothal, fentin acetate, quinoclamine, quinonamid, irgarol, diuron, terbutryn, oxfluorfen, simmazine, and/or DCOIT.
  • the dispersion according to the invention optionally comprises one or more other biocidal active ingredients in order to enhance the composition activity and wherein said biocide would include one or more of insecticides, acaricides, algicides, molluscicides, biocides, bactericides, herbicides, plant growth regulators, fungicides and the like. Addition of these biocide compounds to the present dispersion system yields increased activity and spectrum.
  • aqueous dispersion compositions disclosed herein are suitable for protecting industrial materials and wherein the industrial materials in the present context are nonliving materials which have been prepared for use in industry.
  • Aqueous dispersions of the present invention can be employed in the following non-limiting fields such as paint, building materials, stucco, concrete, caulks, sealants, joint compounds, adhesives, paper, card, textiles, coating materials and plastic articles, cooling lubricants, cooling water circulations, leather, wood, inks, pigment dispersions, metal working fluids, aqueous hydraulic fluids, drilling mud, and/or clay slurries those may be attacked or decomposed by microorganisms.
  • IPBC, Folpet, titanium dioxide and silica were mixed together and ground dry for 15 minutes.
  • CoatOSilTM 1211 coating additive (an 1.0-2.0 organomodified silicone)
  • HPMC Hydroxypropyl methyl cellulose
  • HPMC Hydroxypropyl methyl cellulose
  • CoatOSilTM 1211 coating additive (an

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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

La présente invention concerne une dispersion aqueuse contenant un mélange d'un biocide sensible à l'hydrolyse, d'un biocide hydrophobe dérivé de l'iode et d'un support inerte dispersé dans l'eau. Ledit biocide hydrophobe dérivé de l'iode forme un complexe avec le support inerte et le biocide sensible à l'hydrolyse pouvant être dispersé dans l'eau. Ce revêtement hydrophobe comprend un support inerte et le biocide sensible à l'hydrolyse peut être du trihalogénométhylthio phtalidimide ou un analogue de celui-ci, tandis que le biocide hydrophobe dérivé de l'iode peut être du butylcarbamate d'iodopropynyle. Ladite dispersion aqueuse peut également comporter une couche hydrofuge venant revêtir le complexe.
PCT/US2010/059227 2009-12-07 2010-12-07 Dispersion aqueuse stabilisée d'analogues du folpet, son procédé de préparation et composition en contenant Ceased WO2011071876A1 (fr)

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US26712309P 2009-12-07 2009-12-07
US61/267,123 2009-12-07

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150148457A1 (en) * 2012-06-06 2015-05-28 Rohm And Haas Company Process for preparing multi-color dispersions and multi-color dispersions made thereof
WO2015187788A1 (fr) * 2014-06-03 2015-12-10 E. I. Du Pont De Nemours And Company Enrobages de parties reproductrices de plantes
WO2020190773A1 (fr) * 2019-03-15 2020-09-24 The Sherwin-Williams Company Compositions de revêtement aqueuses comprenant un emballage rhéologique à base de gomme xanthane
WO2021219242A1 (fr) * 2020-04-28 2021-11-04 Thor Gmbh Dispersions aqueuses stables d'ipbc

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2718147A1 (fr) * 2008-03-28 2009-10-01 Isp Investments Inc. Procede de production d'une dispersion aqueuse stable de particules finement divisees, concentrees d'un biocide
WO2011115912A1 (fr) * 2010-03-15 2011-09-22 Isp Investments Inc. Compositions de conservation synergiques
US10041246B2 (en) * 2013-07-04 2018-08-07 Industrias Kolmer, S.A. Sprayable, thermal and acoustic insulating surfacing
US10058542B1 (en) 2014-09-12 2018-08-28 Thioredoxin Systems Ab Composition comprising selenazol or thiazolone derivatives and silver and method of treatment therewith

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641804A (en) * 1992-09-15 1997-06-24 Novo Nordisk A/S Fungicidal compound comprising a cyclic polylactone
US5965213A (en) * 1996-04-04 1999-10-12 Basf Coatings Ag Aqueous dispersions of a transparent powder coating
US20080281017A1 (en) * 2003-12-18 2008-11-13 Wacker Polymer Systems Gmbh & Co. Use of Biocide-Containing, Water-Redispersible Polymer Powder Compositions in Mineral Construction Materials

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
UA44220C2 (uk) * 1991-11-07 2002-02-15 Агрево Юк Лімітед Сульфонаміди,що мають гербіцидну активність,спосіб їх одержання, гербіцидна композиція та спосіб боротьби з бур'янами
US5874476A (en) * 1997-07-14 1999-02-23 Rohm And Haas Company Dihaloformaldoxime carbamates as antimicrobial agents
JP2000336080A (ja) * 1999-05-28 2000-12-05 Nippon Bayer Agrochem Co Ltd イソチアゾールカルボキサミド類
US6884741B2 (en) * 2002-07-23 2005-04-26 H.B. Fuller Licensing & Financing, Inc. Antimicrobial sheeting article
DE102006004526A1 (de) * 2006-02-01 2007-08-02 Lanxess Deutschland Gmbh IPBC haltige Koazervate
US20070224135A1 (en) * 2006-03-24 2007-09-27 Xianbin Liu Stable aqueous suspension concentrate for delivery of UV-labile water-insoluble biocides
WO2010148158A1 (fr) * 2009-06-17 2010-12-23 Isp Investments Inc. Procédé de préparation de substances actives biocides stables, microencapsulées et à libération lente et composition apparentée

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5641804A (en) * 1992-09-15 1997-06-24 Novo Nordisk A/S Fungicidal compound comprising a cyclic polylactone
US5965213A (en) * 1996-04-04 1999-10-12 Basf Coatings Ag Aqueous dispersions of a transparent powder coating
US20080281017A1 (en) * 2003-12-18 2008-11-13 Wacker Polymer Systems Gmbh & Co. Use of Biocide-Containing, Water-Redispersible Polymer Powder Compositions in Mineral Construction Materials

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150148457A1 (en) * 2012-06-06 2015-05-28 Rohm And Haas Company Process for preparing multi-color dispersions and multi-color dispersions made thereof
US10767070B2 (en) * 2012-06-06 2020-09-08 Dow Global Technologies Llc Process for preparing multi-color dispersions and multi-color dispersions made thereof
WO2015187788A1 (fr) * 2014-06-03 2015-12-10 E. I. Du Pont De Nemours And Company Enrobages de parties reproductrices de plantes
WO2020190773A1 (fr) * 2019-03-15 2020-09-24 The Sherwin-Williams Company Compositions de revêtement aqueuses comprenant un emballage rhéologique à base de gomme xanthane
US11952511B2 (en) 2019-03-15 2024-04-09 Swimc Llc Aqueous coating compositions including xanthan gum-based rheology package
WO2021219242A1 (fr) * 2020-04-28 2021-11-04 Thor Gmbh Dispersions aqueuses stables d'ipbc
US20230157295A1 (en) * 2020-04-28 2023-05-25 Thor Gmbh Stable Aqueous IPBC Dispersions

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