WO1998005206A1 - Compositions de sel d'ammonium quaternaire et procedes de traitement de substrats - Google Patents

Compositions de sel d'ammonium quaternaire et procedes de traitement de substrats Download PDF

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Publication number
WO1998005206A1
WO1998005206A1 PCT/US1997/013310 US9713310W WO9805206A1 WO 1998005206 A1 WO1998005206 A1 WO 1998005206A1 US 9713310 W US9713310 W US 9713310W WO 9805206 A1 WO9805206 A1 WO 9805206A1
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Prior art keywords
biocidal
composition
substrate
compositions
carbon atoms
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PCT/US1997/013310
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English (en)
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Eugene A. Pasek
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Hickson International Plc
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Priority to AU37417/97A priority Critical patent/AU3741797A/en
Publication of WO1998005206A1 publication Critical patent/WO1998005206A1/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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/36—Aliphatic compounds

Definitions

  • This invention is directed to compositions containing biocidal quaternary ammonium salts and to a method for treating substrates to protect them from fungal or microbial attack by contacting or impregnating the substrates with these compositions.
  • the invention is directed to an antifungal treatment compositions for fibrous materials or wood and to methods for providing these materials with antifungal properties by treating with the quaternary ammonium salts of the present invention.
  • synthetic materials such as plastics or synthetic fibers
  • plastics, or synthetic or naturally occurring fibers can also provide a substrate for the growth of microorganisms.
  • plastics, or synthetic or naturally occurring fibers are used in a health care setting or other setting requiring control or avoidance of the presence of microorganisms (in particular of pathogenic microorganisms which can result in the spread of disease) it is desirable to provide these materials with resistance to such microbial growth, e.g. by incorporating or coating the fiber or plastic with a biocide.
  • the biological activity of alkylamines, where some or all of the alkyl groups are long chain aliphatic groups (C g and larger), is well known.
  • Quaternary ammonium salts which are positively charged nitrogen atoms covalently bound to four substituents and ionically bound to a counter-ion, have been found to be especially biocidally active.
  • Quaternary ammonium salts are usually characterized by their broad spectrum biocidal activity against both gram-positive and gram-negative microorganisms. Their uses range from algaecides for water treatment to bacteriostats in consumer products such as shampoos and disinfectants.
  • Quaternary ammonium salts are typically secondary or tertiary amines which have undergone methylation with methyl chloride, such that the quaternary ammonium chloride salt is obtained.
  • DDAC didecyldimethylammonium chloride
  • quaternary ammonium salts are cationic. reactions with anionic substances can occur. For example, hydroxyl groups of materials such as cotton or cellulose can react with the ammonium action, which replaces the hydrogen ion to form strong bonds with these materials. However, in many cases the reaction of the quaternary ammonium action with hydroxyl groups is undesirable.
  • the interaction of typical quaternary ammonium salts with cellulose causes poor penetration of the biocide when used in the pressure treatment of wood (Walker, Leigh E.. "Alkylammonium Compounds as Wood Preservatives," Forest Product Society Meeting, Savannah, Georgia, September 26 - 28. 1994).
  • Another class of compounds known as biocides in the pressure treatment of wood are the dialkyldithiocarbamates.
  • sodium dimethyldithiocarbamate is approved for this use.
  • dithiocarbamate compounds are also very water soluble, and lead to similar leaching problems when used as biocides.
  • tetrafluoroborate and hexafluorophosphate compounds are also very water soluble, and would be expected to exhibit similar leaching behavior if used as biocides.
  • biocidal composition prepared from two biocides approved for the pressure treatment of wood, in a form that is relatively insoluble, thereby increasing the retention of the biocide in the substrate, achieving a more even distribution profile of biocide throughout the substrate, and a less acidic treatment solution
  • the present invention is directed to biocidal compositions formed combining a first biocidal compound, which is a quaternary ammonium salt, with a second biocidal compound, which is a salt of an anion selected from the group consisting of tetrafluoroborates. dialkyldithiocarbamates. monoalkyldithiocarbamates, and hexafluorophosphates. together with a suitable carrier More specifically, the present invention is directed to compositions formed by combining a first biocidal compound which is a quaternary ammonium salt having formula
  • R' R 2 R 3 R 4 N T X wherein R 1 and R 2 are straight, branched, or cyclic alkyl groups having 8 to 18 carbon atoms and R 3 and R 4 are straight alkyl groups having 1 to 7 carbon atoms, branched alkyl groups having 3 to 18 carbon atoms, or aralkyl groups having 7-18 carbon atoms, and X " is an anion, such as a halogen anion, with a second biocidal compound, which is a salt, such as an alkali metal salt or an ammonium salt, of a compound selected from the group consisting of dialkyldithiocarbamate, monoalkyldithiocarbamate, tetrafluoroborate, and hexafluorophosphate While not wishing to be bound by any theory, the inventors believe that the first biocidal compound and the second biocidal compound form a salt or complex that is relatively insoluble in water, and is somewhat soluble in organic solvents.
  • the quaternary ammonium salts of the first biocidal compound of the compositions of the present invention contain two large alkyl, cycloalkyl. or aralkyl groups (i.e., having 8 to 18 carbon atoms) and two small alkyl or cycloalkyl groups (i.e., having 1 to 7 carbon atoms), for a total of four substituents.
  • the second biocidal compound contains a dialkyldithiocarbamate.
  • a composition formed by combining a didecyldimethylammonium halide with an alkali metal salt of dimethyldithiocarbamate is particularly suitable with respect to its ability to resist leaching, as well as its biocidal activity, e.g., its ability to prevent or decrease fungal decay.
  • the present invention is also directed to treated substrate compositions containing a substrate, to which it is desired to impart microbicidal or fungicidal properties, and one or more of the biocidal compositions described above.
  • the substrate may be a cellulosic material, such as wood or plant based fiber, such as cotton or jute, or may be a synthetic material or fiber, such as carpet fibers, or may be a fabric made from these fibers
  • the substrate may be an object made from plastic or other material and having surfaces or areas to which it is desired to impart biocidal properties
  • the substrate may be any surface or material which is conventionally treated with biocide compositions, in particular with quaternary ammonium salt biocide compositions
  • compositions of the present invention may also contain a carrier, solvent, adjuvant or auxiliary suitable for application to a surface, for mixing with a liquid, or for impregnation into a solid.
  • a carrier, solvent, adjuvant or auxiliary suitable for application to a surface for mixing with a liquid, or for impregnation into a solid.
  • an advantage of the composition of the present invention is that it is relatively insoluble in water, particularly as compared to didecyldimethylammonium chloride alone. This allows the formulation of compositions that can be administered in ways that will increase their penetration into the substrate without immediately bonding to. or undergoing ion exchange with, the substrate material.
  • compositions of the present invention could be formulated as emulsions containing, e.g., a polyquatemary ammonium compound (e.g., a polyquatemary compound based upon polyamines and polyamine ethers, polyvinyl pyrrolidones, polyquatemary ammonium polymers, or cationic polymers based on acrylates), thickening or dispersing agents (e.g., homopolymers or copolymers of (meth)acrylic acids and esters, vinyl homopolymers and copolymers, and polymers based on glvcol monomers and on ether monomers), and nonionic surfactants (such as polyalkoxylates of alkylphenols.
  • a polyquatemary ammonium compound e.g., a polyquatemary compound based upon polyamines and polyamine ethers, polyvinyl pyrrolidones, polyquatemary ammonium polymers, or cationic polymers based on
  • compositions of the present invention may be used to coat or impregnate a variety of substrate articles, such as textiles or fabrics, fibers, plastics, consumer articles, etc., or may be combined with conventional ingredients to form further compositions, such as paint compositions (e.g., oil based paint, latex based paint), coating compositions, plastic compositions, fibers (e.g., for carpeting or textiles), consumer products compositions (e.g., shampoos, household cleaners), or other compositions where biocidal or biostatic activity is desirable.
  • paint compositions e.g., oil based paint, latex based paint
  • coating compositions e.g., plastic compositions, fibers (e.g., for carpeting or textiles)
  • consumer products compositions e.g., shampoos, household cleaners
  • biocidal or biostatic activity is desirable.
  • the present invention is directed to compositions for the treatment and/or preservation of wood or other cellulosic products, more particularly, to compositions for the preservation of wood, fiber, fabric, cardboard, paper products, or other cellulosic products from fungal or other biocidal attack.
  • the present invention is also directed to methods for treating substrates to impart biocidal properties thereto by applying to or impregnating into the substrate an effective amount of the composition of the invention, discussed above.
  • the amount of composition applied will depend upon the formulation thereof, and is that amount which will deliver an amount of quaternary ammonium salt and dithiocarbamate effective to prevent or reduce fungal or other microbial attack. This amount may be equal to or less than that conventionally used for either the quaternary ammonium compound on the second biocidal compound individually, since the compositions of the present invention exhibit decreased leaching behavior, as discussed below.
  • a significant and unexpected advantage of treating substrates, such as wood, using the compositions of the present invention as compared to other compositions containing individual quaternary ammonium halide salts or other individual biocides is that the biocides of the present invention are less likely to be leached from the substrate by contact of the substrate with water or other liquid after treatment.
  • Water leaching can be measured, for example, in a manner similar to that described by the American Wood Preservers' Association (AWPA, 1989): "Standard Method of Determining the Leachability of Wood Preservatives" (El 1-87). Without being bound by any theory, the present inventors believe that the decreased leachability exhibited by the compositions of the present invention is due to the low water solubility of the biocides when used in the composition of the present invention.
  • Another significant and unexpected advantage of the present invention is the excellent penetration of the biocides into the substrate, in particular wood or other cellulosic material capable of absorbing the biocides. resulting in a more desirable distribution of the biocides throughout the thickness of the substrate.
  • the present inventors believe that this is due to the relative insolubility of the biocides when applied as the composition of the present invention, allowing for a deeper absorption of the biocides before the occurrence of any binding or ion exchange of the quaternary ammonium biocide with sites inside the substrate, such as cellulosic hydroxy compounds.
  • compositions of the present invention can be prepared, for example, by combining the quaternary alkylammonium chloride of the first biocidal compound with a sodium or ammonium salt of a biocidal anion of the second biocidal compound, such as a sodium dialkyldithiocarbamate, ammonium tetrafluoroborate. or ammonium hexafluorophosphate.
  • a sodium dialkyldithiocarbamate such as a sodium dialkyldithiocarbamate, ammonium tetrafluoroborate. or ammonium hexafluorophosphate.
  • Preparation techniques for both quaternary alkylammonium chlorides and alkali or ammonium dialkyldithiocarbamates, tetrafluoroborates, or hexafluorophosphates are well known to those of skill in the art.
  • compositions of the present invention have biocidal activity, including, but not limited to, antifungal activity and antimicrobial activity.
  • a biocidally effective amount of the compositions of the present invention is an amount sufficient to inhibit or prevent the growth of fungi or other microbes, for at least some period of time, preferably on the order of months or years.
  • Antifungal or fungicidal activity denote activity (e.g., growth inhibition or prevention) against fungi, including molds, in particular against the Basidiomycetes fungi which attack wood or other cellulosic material, and may include fungi associated with or causing brown rot (wherein cellulose is attacked preferentially and lignin is left basically unchanged), soft rot.
  • compositions of the present invention can be shown, for example, by exposing treated wood to various wood destroying fungi, and comparing the results to those obtained when untreated wood is similarly exposed, as discussed below.
  • Antimicrobial or microbiocidal activity denote activity against microbes or microorganisms different from fungi, such as bacteria, slime molds, protozoa, etc. This activity can be shown, for example by assaying the effect of the compositions of the present invention against microorganisms, as discussed below.
  • alkyl refers to a saturated straight chain hydrocarbon of 1 to 24 carbon atoms, or a branched hydrocarbon of 3 to 24 carbon atoms, including, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl. 3-methylpentyl, 2.2-dimethylbutyl, 2,3-dimethylbutyl, and decyl.
  • cycloalkyl refers to a cyclic hydrocarbon of 3 to 24 carbon atoms, including, e.g., cyclopentyl and cyclohexyl.
  • aryl as used herein, and unless otherwise specified, means aromatic hydrocarbyl, and refers to phenyl, naphthyl, or anthranyl. each of which may be unsubstituted or have up to three substituents. wherein each substituent is independently halo or alkyl.
  • aralkyl refers to an alkyl group, as defined above, that has an aryl substituent. as defined above.
  • Heteroaralkyl substituents. in which an alkyl group has a heteroaryl substituent. can be used in place of or in addition to aralkyl substituents.
  • water soluble refers to a solubility in water of at least about 3% by weight.
  • Water insoluble refers to a solubility in water of less than about 3% by weight.
  • compositions of the present invention provide the biocides in a form that is relatively insoluble in water, as compared to the individual biocides alone, and which is somewhat soluble in organic solvents.
  • the compositions of the present invention usually having a solubility of about 5% by weight or more in a polar organic solvent, such as acetonitrile, methylene chloride, and the like.
  • Suitable alkyl substituents for the dialkyldithiocarbamates include those alkyl groups defined above, in particular alkyl substituents having 1 to 8 carbon atoms.
  • biocidal compositions of the present invention are formed by mixing a first biocidal compound which is a quaternary ammonium salt biocide which has the following formula
  • R' R 2 R 3 R N T X " wherein R 1 and R ⁇ are alkyl, cycloalkyl. or aralkyl groups having 8 to 18 carbon atoms.
  • R J and R are alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups having 3 to 18 carbon atoms, or aralkyl groups having 7 to 18 carbon atoms, and
  • X " is an anion. such as a halogen anion, with a second biocidal compound containing an alkali metal or ammonium action and an anion selected from the group consisting of dialkyldithiocarbamates, monoalkyldithiocarbamates, BF ⁇ and PF 6 " .
  • the quaternary ammonium salts preferably have two large alkyl groups (having 8 to 18 carbon atoms) and two small alkyl groups (having 1 to 7 carbon atoms), for a total of four groups.
  • the quaternary ammonium salt of the first biocidal compound may be didecyldimethyl ammonium chloride and the second biocidal compound mixed therewith to form the composition of the present invention is desirably sodium dimethyldithiocarbamate.
  • the preparation of the compositions of the present invention can be accomplished by mixing the first and second biocidal compounds together using known mixing methods, e.g., in water or other polar solvent.
  • the compositions are formed by mixing the water soluble first biocidal compound, e.g.. didecyldimethylammonium chloride, with the water soluble second biocidal compound, e.g., sodium dimethyldithiocarbamate, ammonium tetrafluoroborate, etc., in water.
  • Any convenient molar ratio of the first and second biocidal compounds may be used, especially a molar ratio of first biocidal compound to second biocidal compound of 2:1, more especially of l :l .
  • Example 2 Didecyldimethylammonium chloride (181.0 grams of an 80 percent by weight solution, 0.400 moles) in 800 mL of water was mixed with 144.0 grams (0.202 moles) of an aqueous solution of sodium dimethyldithiocarbamate (40 wt. %). A cream colored solid precipitated immediately. The slurry was stirred for two hours, vacuum filtered, and washed with 150 mL of water. The resulting solids were air dried to constant weight to give a solid yellow product (132.9 grams, 74.4%). The calculated analysis in weight percent for this composition is: C 67.20; H 12.12; N 6.27: S 14.35. Found (wt. %): C 66.91 ; H 12.26; N 6.28; and S 14.51.
  • Example 3 In a two liter beaker, didecyldimethylammonium chloride (181.1 grams of an 80 percent by weight solution. 0.400 moles) and sodium diethyldithiocarbamate (90.12 grams of a 40 percent by weight solution. 0.400 moies) were mixed together. The mixture was stirred for one hour. The resulting dark brown oil was separated from the aqueous phase and dried over Drierite to yield 214.7 grams of a dark brown oil. The calculated analysis in weight percent for this composition is: C 68.29; H 12.31 ; N 5.90; S 13.50. Found (wt. %): C 60.89; H 12.56; N 4.91 ; S 10.77.
  • Didecyldimethylammonium chloride (181.0 grams of 80 weight percent solution. 0.4 moles) in 800 mL water was mixed with sodium di-n-butyldithiocarbamate (196.0 grams of a 46.4 percent by weight solution, 0.400 moles). The resulting dark brown oil was separated from the aqueous phase, washed with 200 mL water, and dried over Drierite. The calculated analysis in weight percent for this composition is: C 70.39; H 12.19; N 5.30; and S 12.12. Elemental analyses found (wt. %): C 63.83; H 12.32; N 4.38; and S 8.94.
  • Example 6 An aqueous solution of benzalkonium chloride (a quaternary ammonium chloride consisting of a benzyl group, two methyl groups, and a long chain alkyl group ranging from C g to C
  • benzalkonium chloride a quaternary ammonium chloride consisting of a benzyl group, two methyl groups, and a long chain alkyl group ranging from C g to C
  • Example 7 Benzalkonium chloride (129.57 grams of a 50% aqueous solution) was diluted with
  • the biocides of the present invention can be used in compositions that provide antifungal or antimicrobial properties to a substrate incorporated or treated therewith, e.g., in compositions for antifungal treatment of wood and other lignocellulosic or cellulosic materials, or in compositions for use in sanitizing other substrates, such as floors, carpets, countertops or other surfaces, etc Due to their decreased water solubility relative to other, individual, biocides, the compositions of the present invention are less likely to leach out of or wash off of the substrate under conditions of use, especially under conditions where the substrate is exposed to the elements, e.g., in outdoor uses, or is exposed to contact with aqueous solutions, e.g..
  • compositions of the present invention can be formulated into a solution (in organic solvents), a suspension, or an emulsion, and impregnated into a substrate under pressure and pH conditions known in the art for impregnating wood with didecyldimethylammonium chloride (DDAC). These conditions can be varied in accordance with methods known in the art for use with DDAC in order to obtain a desired retention of the biocide of the present invention.
  • DDAC didecyldimethylammonium chloride
  • Retention is defined, for purposes of this invention, as the amount of biocide absorbed per unit volume of substrate or wood, prior to any leaching testing. For instance, the initial air pressure or vacuum method, the empty cell method, the modified full cell method, the full cell method, or the refusal method, as described in AWPA Standard (1994) Cl-94, can be used.
  • a vacuum impregnation method can be used wherein the wood or other cellulosic material to be treated, which may be weighted, is placed in a pressure vessel, which is then evacuated. The material is allowed to remain in the evacuated vessel for a period of time, usually around 1 hour. A treating solution, suspension, or emulsion containing a composition of the present invention is then allowed to enter the pressure vessel (still under vacuum) until the vessel is about 2/3 to 3/4 full. The substrate is totally immersed in the solution, and is then subjected to a pressure of around 100 to 200 psi for a period of time, usually about an hour. The pressure and treatment time may be varied depending on the type of substrate, the thickness or shape of the pieces, etc. After the treatment time has elapsed, the substrate is removed from the vessel, allowed to drain, and weighed, so that the solution retention can be calculated. The substrate can then be dried and used as is known in the art for treated substrate, such as for treated wood or lumber.
  • solutions, suspensions, or emulsions containing the compositions of the present invention can be sprayed or otherwise coated onto the surfaces of the substrate. and any solvent present allowed to evaporate, according to methods known in the art for applying biocidal compositions to objects or materials.
  • a particular substrate of interest is wood.
  • the present inventors have found that the biocides for use in preservatives for wood (or other substrates) desirably have low water solubility, particularly when the wood is intended for exterior use, in order to prevent or minimize leaching of the preservative by rain or other water or aqueous solutions, which can both decrease the resistance of the wood to decay and contaminate the resulting leachate water with biocide.
  • low water solubility is very desirable in biocidal preservative compounds to be impregnated in, or coated on, wood or other substrates.
  • the present inventors have found that the composition of the present invention provides a biocide that exhibits this low water solubility, a result that is surprising in view of the water solubility of DDAC.
  • compositions of the present invention were impregnating the wood with a composition prepared by dissolving the biocide composition of the present invention in an organic solvent, such as methylene chloride.
  • an organic solvent such as methylene chloride.
  • compositions of the present invention could be formulated into, and applied as. an aqueous emulsion using commercially available emulsifiers.
  • AWPA American Wood Preservers' Association
  • El 1 -87 Water leaching tests were performed on wood treated with a biocidal compositions prepared according to Examples 1. 2. and 5. The tests performed were similar to the test described by the American Wood Preservers' Association (AWPA) in "Standard Method of Determining the Leachability of Wood Preservatives" (El 1 -87).
  • the AWPA method involves the use of six 3/4 inch blocks of treated wood, which are impregnated with water prior to the leaching process. The blocks are submerged in 300 L of water, which is agitated by magnetic stirring. The water is exchanged for fresh water at various time intervals (6, 24, 48. etc. hours) and the leached chemical is quantified by the appropriate analytical procedure.
  • the leaching study used four 3/4" blocks, treated to a 0.20 pcf (8.0 kg m ) retention, and 230 mL of leaching water per time interval. The study was done in duplicate.
  • the results obtained are described in Table 1 below as percentages of total biocide loaded that were leached at the various time intervals, as well as the total amount leached.
  • the leachate was analyzed by inductively coupled plasma (ICP) spectroscopy.
  • the dimethyldithiocarbamate concentration was determined by measuring sulfur content: the hexafluorophosphate concentration was determined by measuring phosphorus content, and the tetrafluoroborate concentration was determined by measuring boron content.
  • concentration of the didecyldimethylammonium ion was not directly measured.
  • DDAC didecyldimethylammonium chloride
  • quaternary ammonium salts of the present invention leached during every leaching time interval are approximately consistent or constant. This is not true with other, individual biocides, such as DDAC, which typically exhibits a large release of chemical followed by smaller amounts over time.
  • the leaching data strongly suggest that the solubility or solubility product of the biocide composition is an important parameter for leaching. Review of the leaching data shows that the biocide composition of Example 2 produces a leachate solution containing about 2.0 ppm sulfur, the biocide composition of Example 5 produces a solution containing about 4.5 ppm phosphorus, and the biocide composition of Example 1 produces a solution containing approximately 6.0 ppm of boron for each time interval. Using these quantities and assuming the didecyldimethylammonium species is also leached at the same level, the solubility products (K sp ) can be obtained, and are given below in Table 2.
  • K sp [quaternary ammonium species] [second biocidal compound anion]
  • solubility product enable the biocide compositions of the present invention to have good permanence (i.e., low leachability) in exterior applications.
  • the salts provide excellent resistance to fungal and bacterial degradation, as shown here.
  • the treating solution consisted of a methylene chloride solution of the biocidal compositions of Examples 1 and 2 and an ethanol solution of the biocidal composition of Example 5.
  • Sixteen southern yellow pine (SYP) 3/4 inch blocks were treated to each retention by vacuum impregnation.. Approximately one dozen of these blocks were used, in order to provide meaningful fungal decay data. Prior to efficacy testing, the treated blocks were water leached according to AWPA El 1-87. Untreated SYP blocks were used as controls. Blocks treated with aqueous solutions of didecyldimethylammonium chloride at the above retentions were employed for comparative purposes.
  • the method used for testing efficacy was a modified AWPA soil block test.
  • the soil used was taken from a field stake test plot in Conley, Georgia, and was used as is, and not sterilized.
  • the soil was placed in plastic containers (8 x 16 x 30 inches) or tubs, to a depth of approximately four inches. The moisture content was adjusted and maintained at 40 percent.
  • Untreated wafers of southern yellow pine (0.25 x 1.5 x 1.5 inches) were used as fungi feeder strips.
  • the 3/4 inch SYP treated blocks were placed on the feeder strips and the container covered and placed in a constant temperature chamber, which was maintained at 80°F (27°C). Seven tubs were used for this five month, fungal efficacy testing.
  • Table 3 gives the percent of the sample blocks having no decay, questionable decay, initial or early stages of decay, and decay in the form of either brown, white, or soft rot.
  • the data provided by the modified soil block efficacy testing on water leached blocks can be related to the retention level, as summarized below in Table 4.
  • This Table assumes that questionable decay is essentially no decay.
  • the results indicate that the salts of the present invention perform as well as. or better than, the didecyldimethylammonium chloride (DDAC) alone.
  • DDAC didecyldimethylammonium chloride
  • the biocidal composition of Example 2 showed the best performance in this five month modified soil block test, followed by the biocidal composition of Example 1, the biocidal composition of Example 5. then the DDAC treated control and. lastly, the untreated control (as can he seen from Table 3, the untreated controls have no (zero percent) samples in the "no decay” or "questionable” decay categories).
  • Table 4 clearly shows that the biocidal composition of Example 2 is superior to the other tested biocidal compositions of the present invention, and is far superior to DDAC. It also indicates that the biocidal compositions of Examples 1 and 5 show improved antifungal activity over the DDAC control.
  • the water leaching data can be used to calculate the remaining biocides in each of the test blocks.
  • the weights or pounds per cubic foot (pcf) of each biocide. as well as the number of moles of biocide or didecyldimethylammonium ion remaining in each test set of blocks can be determined.
  • the calculated pcf and number of moles of didecyldimethylammonium ion for each biocide is given in Table 5 for the 0.2 pcf target retention used for fungal testing and the water leaching test (AWPA El 1 -87).
  • DDAC Didecyldimethylammonium chloride
  • CCA chromated copper arsenate
  • the loading amounts are in lb/ft , and the rating is normalized based upon a 0.440 lb/ft J loadine of DDAC.
  • compositions of the present invention allow for the delivery of the quaternary ammonium species deep into the substrate matrix, due to its insolubility in combination with the additional biocide.
  • This insolubility also helps to keep the quaternary ammonium moiety from washing out of the matrix, thereby providing stable, long-term protection of the substrate throughout.
  • the improved retention of the lipophilic, water insoluble biocides of the present invention results in a better distribution profile of the biocide throughout an impregnated substrate, as well as longer lasting protection in impregnated and coated substrates, particularly when the substrate is to be used in exterior applications, or is to be exposed to contact with aqueous solutions.
  • biocidal compositions of the present invention have also been shown to possess antimicrobial activity against a wide variety of organisms, both fungi and bacteria, including Staphylococc s aureus. Bacillus megaterium, Aspergillus niger. Pseudomonas aeruginosa, Pseudomonas putida, Trichoderma viride. Phanerochaete chrysosporium, Aureobasidium pullulans, Penicillium marneffei, Rhizopus oryzae. Beauveria bassiana, and Cunninghamella echinulata var. elegans.
  • a microemulsion composition containing 20 % of the biocidal composition of Example 2 was prepared as set forth below.
  • the ethylene glycol monopropyl ether and Agsolex-8 were first weighed and mixed. and then the nonyl phenol 12 mole ETO was slowly added with constant stirring. The resulting mixture was then heated to 40-45 °C. The biocidal composition of Example 2 was then added slowly to the mixture with stirring until complete dissolution occurred. The mixture was then cooled to room temperature. The resulting 20 % mixture can then be further diluted by addition of water, and will be stable on dilution at different temperature ranges.
  • This composition was tested to determine the minimum inhibitory concentration (MIC, the lowest concentration of test substance that completely inhibits growth) against a variety of microorganisms using the agar plate dilution method with an incubation period of 24 to 72 hours.
  • MIC minimum inhibitory concentration
  • one gram of the 20 % solution discussed above was dissolved in 100 mL of sterile reagent grade water to prepare a 10000 ppm primary stock solution, which was then serially diluted to prepare secondary stock solutions having concentrations of 1000, 100, and 10.0 ppm.
  • Agar media and media broths were autoclaved at 121 °C for 20 minutes prior to use. and stored under aseptic conditions.
  • Appropriate amounts of the secondary stock solutions (2 mL) were mixed with melted agar or broth (18 mL). and the mixtures were poured into Petri dishes and allowed to solidify.
  • each inoculum culture was removed and serially diluted to verify the inoculum concentration, and then further diluted, if necessary, to obtain a concentration of 10 4 to 10 6 organisms per milliliter.
  • Each Petri dish was streaked with 10 4 to 10 6 cfu/mL of the desired organism.
  • a sterile water control (reagent grade) and solvent control (formulation without active ingredients) were prepared for each test species following the same procedures, except that no test substances were added. Duplicate exposures were prepared for each concentration and control, however, only one replicate per solvent concentration was established. All transfers and inoculations were performed using aseptic techniques.
  • Staphylococcus aureus Bacillus megatenum. Pseudomonas putida. Trichoderma viride. Phanerochaete chrysosporium, Aureobasidium pullulans. and Penicillium marneffei were inhibited at concentrations of 100 ppm and lower. None of the organisms were inhibited by the solvent at 100 ppm, however the solvent was not tested against Pseudomonas putida. The test results show that didecyldimethylammonium dimethyldithiocarbamate is inhibitive against a wide range of microorganisms taken from widely diverse ecological niches.
  • compositions of the present invention can be used to inhibit, prevent, or control the growth of microorganisms on fibrous materials or surfaces.
  • the composition according to the present invention can be impregnated into air purification filters, clothing, carpeting, paper products, or other cellulosic or fibrous substrate material, particularly where the substrate material will be exposed to an environment conducive to the growth of microorganisms, or where a microbe-free environment is especially desirable, such as in a healthcare setting.
  • compositions according to the present invention can be impregnated into or coated onto solid surfaces, such as plastic articles for use in a healthcare setting.
  • compositions may be applied or impregnated in a form (such as an emulsion) that provides at least about 1 0 ppm of the biocidal composition, preferably at least about 1000 ppm. of the biocidal composition, to the substrate.
  • a form such as an emulsion
  • the composition according to Example 2 can be formulated as an emulsion, and then diluted with water until the formulation contains at least 100 ppm of the mixture of the first and second biocidal composition. This formulation can then be impregnated into or coated onto the substrate, and then allowed to dry.

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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 invention concerne des compositions et des procédés qui permettent de traiter et de préserver des substrats tels que des matières cellulosiques, des fibres de bois ou des fibres végétales. Cette invention concerne des compositions biocides insolubles dans l'eau, lesquelles comprennent une quantité suffisante d'un biocide qui est obtenu à l'aide d'un premier composé biocide consistant en un sel d'ammonium quaternaire et correspondant à la formule R?1R2R3R4N+X-. R1 et R2¿ représentent indépendamment des groupes alkyle droits, réticulés ou cycliques comportant de 8 à 18 atomes de carbone. R3 et R4 représentent indépendamment des groupes alkyle droits comportant de 1 à 7 atomes de carbone ou, encore, des groupes alkyle réticulés ou cycliques comportant de 3 à 7 atomes de carbone. X- représente quant à lui un anion. Ce premier composé biocide est mélangé à un second composé biocide choisi dans le groupe comprenant des sels d'alcali ou d'ammonium de dialkyldithiocarbamate, de monoalkyldithiocarbamate, de tetrafluoroborate et d'hexafluorophosphate. Cette composition possède une solubilité dans l'eau qui est inférieure à celle du premier composé biocide. Elle peut être appliquée sur des substrats et servir au traitement antifongique et anti-microbien de ces derniers. Ces compositions apportent de grandes améliorations en ce qui concerne l'aspect commercial, ainsi que l'utilisation de chlorure de didécyldiméthylammonium, et la résistance à la lixiviation. Les compositions et les procédés décrits dans cette invention conviennent tout particulièrement au traitement du bois utilisé en milieu extérieur.
PCT/US1997/013310 1996-08-02 1997-07-22 Compositions de sel d'ammonium quaternaire et procedes de traitement de substrats WO1998005206A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU37417/97A AU3741797A (en) 1996-08-02 1997-07-22 Quaternary ammonium salt compositions, and methods for treating substrates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69187596A 1996-08-02 1996-08-02
US08/691,875 1996-08-02

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6897191B2 (en) 2003-04-30 2005-05-24 Specialty Construction Brands, Inc. Disinfecting, antimicrobial sealing compositions and methods of using the same
US7179348B2 (en) * 2000-04-24 2007-02-20 Weyerhaeuser Company Method for producing cellulose fiber having improved biostability and the resulting products
CN102066062A (zh) * 2008-12-11 2011-05-18 北京林业大学 一种木材防腐剂和木材防腐处理方法
CN102239836A (zh) * 2010-05-11 2011-11-16 中国林业科学研究院木材工业研究所 四氟硼季铵盐木材防腐防虫剂、其制备方法和应用
US8158208B2 (en) * 2004-05-17 2012-04-17 Osmose, Inc. Method of preserving wood by injecting particulate wood preservative slurry
US8871277B2 (en) 2003-06-17 2014-10-28 Osmose, Inc. Particulate wood preservative and method for producing the same
US9775350B2 (en) 2004-10-14 2017-10-03 Koppers Performance Chemicals Inc. Micronized wood preservative formulations in organic carriers
WO2022144867A1 (fr) * 2021-01-04 2022-07-07 Harcros Chemicals, Inc. Composés antimicrobiens à base d'acides glucoheptoniques et de leurs sels
WO2022189043A3 (fr) * 2021-06-22 2023-02-02 Giesecke+Devrient Currency Technology Gmbh Papier biocide, document de valeur biocide et procédé de fabrication correspondant

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1058618A (fr) * 1952-06-21 1954-03-17 Consortium De Prod Chim Et De Procédé pour rendre les textiles résistants aux attaques des champignons saprophytes
GB902627A (en) * 1957-12-16 1962-08-01 Aagrunol Chemische Fabrieken N Fungicidal compositions containing quaternary ammonium salts of dithiocarbamic acids
EP0277556A2 (fr) * 1987-01-31 1988-08-10 Dr. Wolman GmbH Sels de composés organiques azotés et d'acide fluoroborique et agents de protection du bois les contenant
EP0332578A1 (fr) * 1988-03-08 1989-09-13 Ciba-Geigy Ag Composés du phoshonium avec activité biocide
WO1989010956A1 (fr) * 1988-04-25 1989-11-16 National Starch And Chemical Corporation Composes de dithiocarbamate d'ammonium quaternaire
WO1994028715A1 (fr) * 1993-06-09 1994-12-22 Lonza Inc. Ammonium quaternaire et compositions impermeabilisantes/antiputrides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1058618A (fr) * 1952-06-21 1954-03-17 Consortium De Prod Chim Et De Procédé pour rendre les textiles résistants aux attaques des champignons saprophytes
GB902627A (en) * 1957-12-16 1962-08-01 Aagrunol Chemische Fabrieken N Fungicidal compositions containing quaternary ammonium salts of dithiocarbamic acids
EP0277556A2 (fr) * 1987-01-31 1988-08-10 Dr. Wolman GmbH Sels de composés organiques azotés et d'acide fluoroborique et agents de protection du bois les contenant
EP0332578A1 (fr) * 1988-03-08 1989-09-13 Ciba-Geigy Ag Composés du phoshonium avec activité biocide
WO1989010956A1 (fr) * 1988-04-25 1989-11-16 National Starch And Chemical Corporation Composes de dithiocarbamate d'ammonium quaternaire
WO1994028715A1 (fr) * 1993-06-09 1994-12-22 Lonza Inc. Ammonium quaternaire et compositions impermeabilisantes/antiputrides

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7179348B2 (en) * 2000-04-24 2007-02-20 Weyerhaeuser Company Method for producing cellulose fiber having improved biostability and the resulting products
US7244338B2 (en) * 2000-04-24 2007-07-17 Weyerhaeuser Company Method for producing cellulose fiber having improved biostability and the resulting products
US6897191B2 (en) 2003-04-30 2005-05-24 Specialty Construction Brands, Inc. Disinfecting, antimicrobial sealing compositions and methods of using the same
US8871277B2 (en) 2003-06-17 2014-10-28 Osmose, Inc. Particulate wood preservative and method for producing the same
US8158208B2 (en) * 2004-05-17 2012-04-17 Osmose, Inc. Method of preserving wood by injecting particulate wood preservative slurry
US20150056258A1 (en) * 2004-05-17 2015-02-26 Osmose, Inc. Particulate wood preservative and method for producing same
US9314030B2 (en) * 2004-05-17 2016-04-19 Koppers Performance Chemicals Inc. Particulate wood preservative and method for producing same
US9775350B2 (en) 2004-10-14 2017-10-03 Koppers Performance Chemicals Inc. Micronized wood preservative formulations in organic carriers
CN102066062A (zh) * 2008-12-11 2011-05-18 北京林业大学 一种木材防腐剂和木材防腐处理方法
CN102239836A (zh) * 2010-05-11 2011-11-16 中国林业科学研究院木材工业研究所 四氟硼季铵盐木材防腐防虫剂、其制备方法和应用
WO2022144867A1 (fr) * 2021-01-04 2022-07-07 Harcros Chemicals, Inc. Composés antimicrobiens à base d'acides glucoheptoniques et de leurs sels
WO2022189043A3 (fr) * 2021-06-22 2023-02-02 Giesecke+Devrient Currency Technology Gmbh Papier biocide, document de valeur biocide et procédé de fabrication correspondant

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