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
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
• • 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
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
  • A01N59/20—Copper
• • 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
  • B27K3/16—Inorganic impregnating agents
  • B27K3/20—Compounds of alkali metals or ammonium
• • 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
  • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds

Definitions

• This invention relates to a composition and method for preserving wood and other cellulose based materials such as paper, particle board, textiles, rope, etc.... against destructive organisms responsible for rot and decay, namely fungus and insects. More particularly, this invention re ⁇ lates to an organometal preservative composition, having in- secticidal and fungicidal properties, in the form of an aqueous solution of a compound of metal ammonium complexes of certain specified dicarboxylic acids or mono, di or tri- carboxylic hydroxy acids.
• Copper sulfate was recommended for use in wood preservation as early. as 1767 and patented for that purpose in England in 1937 by Margary. Since its ini ⁇ tial use in the early 1800's copper sulfate has played a ma ⁇ jor role in the wood preserving industry.
• the use of copper sulfate as a wood preservative has two major dis- advantages. First, copper sulfate does not become perma ⁇ nently fixed in the wood and is therefore prone to leach ⁇ ing. Secondly, copper alone is not an effective preserva ⁇ tive against all forms of wood destroying organisms.
• U.S. patent 4,061,500 describes a wood preserva ⁇ tive effective against blue stain, containing a fatty acid of 6-11 carbon atoms, boric acid and an alkali compound- in stoichiometric excess of the fatty acids.
• the incorporation of copper salts with straight chain fatty acids and fatty alcohols is described in U.S. patent 4,001,400.
• cop ⁇ per, zinc, nickel, cadmium and cobalt are combined with an ammoniacal fatty acid salt to provide a water-borne preser ⁇ vative system which is claimed to be effective against fungi mould and blue stain.
• the branched chain fatty acid con ⁇ tains 6-12 carbon atoms per molecule.
• a process for preparing a homogeneous liquid compo- sition comprising a cuprammonium complex of one or more monocarboxylic acids containing 1-4 carbon atoms per mole ⁇ cule is described in U.S. patent 4,175,090. These parti ⁇ cular compositions are used as fungicides for treating wood, painting surfaces, fabrics and also to inhibit algal growth.
• U.S. patent 4,220,661 describes a preservative com- position useful for preventing the growth of mould, bacteria and fungi comprising an aqueous solution of a complex salt of an ion selected from NH+. and a Group I or Group II metal ion and one or more carboxylic acids selected from saturated and unsaturated aliphatic monocarboxylic acids containing from 2-8 carbon atoms.
• U.S. patent 4,193,993 discloses a process for pre ⁇ paring an aqueous fungicidal preservative solution com ⁇ prising a compound of a preservative metal, a branched-chain carboxylic acid having 6-20 carbon atoms or a dipentene- monocarboxylic acid or a dipentene-di-carboxylic acid and ammonia and/or an ammonium compound.
• U.S. patent 4,380,561 describes a preservative system comprising branched-chain aliphatic carboxylic acids containing 6-20 carbon atoms or their alkali or ammonium salts. This compo ⁇ sition is particularly suitable for the short term protec ⁇ tion of wood against sapstain and mould fungi, but not from attack by insects.
• a further object of this invention is to provide a wood preservative composition having fungicidal and insec- ticidal properties, which is particularly effective against insects such as termites.
• a still further object of this invention is to pro ⁇ vide a method for the treatment of wood and other cellulose based materials which comprises contacting these materials with the aqueous solution of this invention.
• At least one of the components must be an effec- tive biocide against the organisms responsible for the degradation of wood including bacteria, fungus and insects.
• the preservative components must be capable of readily penetrating the wood. 3) The components must become permanently fixed in the wood.
• the raw materials be read ⁇ ily available and that their cost is not prohibitive for commercial application. It is desirable that the preserva- tive be an aqueous based system since water is readily available and is an inexpensive diluent. The resulting treated wood products should also be readily paintable and should not pose a potential fire hazard as do some of the oil borne systems.
• the present invention provides an aque ⁇ ous preservative composition for treating cellulose based products such as wood to prevent deterioration of such prod ⁇ ucts caused by known decay causing organisms and insects
• a composition of a preservative metal selected from the group consisting of copper, cobalt, cadmium, nickel, and zinc in a preservative amount
• an organic acid also in a preservative amount, selected from the group consisting of aliphatic di ⁇ carboxylic acids containing 2-10 carbon atoms per molecule, aliphatic mono, di, or tricarboxylic hy ⁇ droxy acids containing 2-6 carbon atoms per molecule, a mixture of these acids and/or their salts
• ammonia and/or an ammonium compound such as am ⁇ monium carbonate, ammonium hydroxide, ammonium bi ⁇ carbonate, ammonium sulfate or mixtures thereof in an amount sufficient to solubilize the
• the preservative metals suitable for use in this sys ⁇ tem include copper, cobalt, cadmium, nickel or zinc. Copper is the metal most preferred and may be incorporated into the system as a salt such as copper oxide, copper carbonate, copper sulfate, copper hydroxide or as copper metal, pro ⁇ vided a suitable oxidizing agent such as air, hydrogen peroxide or nitric acid is present. When cobalt, cadmium, nickel or zinc are used they may be incorporated into the system as a metal compound or metal salt such as a metal oxide, metal hydroxide, metal carbonate, etc.... or as the metal itself provided a suitable oxidizing agent is pres ⁇ ent.
• the ratio or organic acid to preservative metal com ⁇ pound used in this process will generally depend on simple stoichiometrics, i.e. one equivalent of metal per equivalent of acid. It is preferable to have an amount sufficient to react stoichiometrically with the dicarboxylic acid or with the mono, di or tricarboxylic hydroxy acid. However, the ratio of metal to organic acid may be varied to less than or greater than the stoichiometric proportion depending upon the preservative effect desired.
• aliphatic dicarboxylic acids suitable for use in this preservative system are oxalic acid, malonic acid, succinic acid-, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
• Ali ⁇ phatic dicarboxylic acids containing 2-10 carbon atoms per molecule are preferred, based on solubility considerations. Still more preferred acids are those containing 2-4 carbon atoms per molecule.
• Branched chain dicarboxylic acids are not considered suitable for use in carrying out the instant process as it is theorized that such compounds do not have sufficient mobility to allow good penetration into the wood. It has been found that only straight chain dicar ⁇ boxylic acids combined with metal preservatives exhibit both fungicidal and insecticidal properties.
• Suitable aliphatic mono, di, or tricar- boxylic hydroxy acids are glycolic acid, lactic acid, alpha hydroxybutyric acid, glyceric acid, malic acid, tartaric acid, mesotartaric acid, and citric acid. It is preferable to have an aliphatic mono, di, or tricarboxylic hydroxy acid containing from 2-6 carbon atoms per molecule. Combinations of two or more organic acids and/or the salts of such acids may be used in carrying out this in ⁇ vention and it is acceptable to use any known commercially available product. Isomers of these acids or mixtures of iso ers are also usable within the scope of this invention.
• ammonia and/or ammonia and carbon di ⁇ oxide in this system is necessary for the purpose of solu- bilizing the metal compounds and/or neutralizing the organic acid.
• the ammonia may be incorporated into the system as ammonia or as an ammonium salt such as ammonium hydroxide, ammonium carbonate, ammonium bicarbonate and/or some com- bination of such a salt and ammonia. It is desirable that the ammonium hydroxide (30% NH,) be at least 1.75 times the weight of the copper expressed as the metal and that the ammonium compounds such as ammonium carbonate and/or am ⁇ monium bicarbonate if required be at least 0.50 times the weight of the copper expressed as the metal.
• ratios may vary, but there must be sufficient ammonia present to fully complex the metal and to completely neutralize the or ⁇ ganic acidticianso that the organic acid will be adequately solu- bilized. If sufficient ammonia is not present the preserva- tive will undergo precipitation during storage or during the treatment process.
• the preservative may be prepared by first mixing the organic acid with water and allowing the dissolution to oc ⁇ cur to the extent possible based on the inherent solubility of the acid. The metal or metal compound is then added to this solution and permitted to react. Reaction may take a few minutes or several hours depending upon the reactivity of the organic acid. The ammonia and/or ammonium compounds are then added to dissolve the product resulting from the reaction between the metal and the organic acid.
• the preservative metal compound may be first mixed with an aqueous solution of the ammonia and/ or ammonia compound.
• the organic acid may then be added to the solution at any time prior to treatment.
• the ammonia and/or the ammonia compounds may be ini ⁇ tially added to the organic acid. Thereafter this solution is mixed with the preservative metal.
• preservative metal or metal compounds
• organic acid and the ammonia and/or ammonia compounds
• a still further alternative method of prepara- tion would permit the substitution of carbon dioxide for the ammonium carbonate and/or ammonium bicarbonate in any of the above described preparation procedures. However, some mini ⁇ mum amount of ammonia would still be required to insure suf- ficient solubility.
• the preservative solution may be formulated over a broad temperature range, although the preferred temperature is between about 60° to 80°F (about 15° to 30°C).
• the limiting factors for selecting a suitable temperature are the freezing point of the preservative and the loss of ammonia at high temperature due to evaporation. Such am ⁇ monia loss may be controlled by maintaining the system under suitable pressure.
• the treating solution may be applied to wood by dip- ping, soaking, spraying, brushing, or any other, well known means. Vacuum and/or pressure techniques may also be used to impregnate the wood in accord with this invention in ⁇ cluding both the "Empty Cell” process and the "Full Cell” process which are well known to those skilled in the art.
• the "Full Cell”, or Bethell, process is employed in the creosoting of railway sleepers and marine timbers and is the normal method of treatment of any class of timber with water-borne preservatives, and may be used with the treating solution of the invention.
• the pressure period is by far the most important factor af ⁇ fecting the amount and depth of impregnation. In practice it is the magnitude and duration of the pressure that gov- erns the absorption of the treating solution by the timber. In the early stages of the pressure period the absorption by the timber is fairly uniform but then it gradually slows down until the absorption is too slow to be readily ob ⁇ served. When this point is reached the timber is said to have been treated to refusal.
• the rate of absorption varies greatly with different species, and timbers such as beech or Corsican pine will be completely impregnated in a few min ⁇ utes while others like Douglas fir, larch or oak heartwood are not completely penetrated even when under pressure for several days.
• the "Empty Cell” treatment using an initial ai ' r pressure, is also known as the Rueping Process and is the standard method for the creosoting of transmission poles. It is also used for wood paving blocks, fencing, and build- ing timbers, and may be used with the treatment solution of the invention.
• the treating schedules aim at obtaining com ⁇ plete penetration of any sapwood present.
• the Rueping treatment was introduced about 1912 and differs from the full cell method in that the timber is initially subjected to compressed air instead of a vacuum. The cylinder is then filled with the treating solution while maintaining this pressure, and pressure is then increased with a hydraulic pump until the desired amount of treating solution is in ⁇ jected into the timber.
• the pressure is then released and the air compressed in the interior of the timber is allowed to escape and in so doing expels the excess liquid, leaving the cell walls coated with treating solution.
• This method of treatment allows a deep impregnation of the timber with ⁇ out a heavy absorption.
• the compression of the air origi- nally in the wood serves to recover a small amount of the injected treating solution when the pressure is released.
• a long final vacuum is also used to assist in this.
• EXAMPLE 1 A preservative solution was prepared by dissolving 87 grams of citric acid in 500 grams of water. To this solu- tion 100 grams of basic copper carbonate were added and al ⁇ lowed to react until the evolution of C0 2 was complete. Upon completion of this reaction, 446 grams of 30% ammonium hydroxide were added to solubilize the product. The re ⁇ sulting solution was diluted to a concentration of 1.5% and used to treat southern yellow pine stakes (1/8" x 1/2" x
• EXAMPLE 2 A preservative solution was prepared by dissolving 114 grams of oxalic acid in 500 grams of water. Upon dis ⁇ solution of the oxalic acid, 100 grams of basic copper car- bonate were added to the solution. The solution was then heated to 120 to insure complete reaction of the copper carbonate with the oxalic acid. Upon completion of the re ⁇ action, 446 grams of 30% ammonium hydroxide were added to solubilize the product.
• the product was then diluted to a 2% working solution and used to treat southern yellow pine stakes (1/8" x 1/2" x 10") using the Full Cell process wherein the wood was initially placed under a vacuum of 30" Hg for 30 minutes followed by the addition of the treat ⁇ ing solution. The system was then pressurized for 30 min- utes at a pressure of 110 lbs. per square inch. The re ⁇ sulting stakes were air dried and found to be resistant to fun-gal and insect attack.
• EXAMPLE 3 A preservative solution was prepared by dissolving 45 grams of tartaric acid in 150 grams of water. To this solu ⁇ tion 38 grams of Cu(0H) 2 were added, followed by the ad ⁇ dition of 37 grams of ammonium carbonate and 75 grams of 30% ammonium hydroxide. The solution was then diluted to a 1-1/2% concentration and used to treat southern yellow pine stakes by the Full Cell process. The treated wood was found to be resistant to fungal and insect attack.
• EXAMPLE 4 To a mixture of 150 grams of water and 150 grams of 30% ammonium hydroxide were added 30 grams of basic copper carbonate. The solution was agitated until the copper car ⁇ bonate dissolved, at which time 44 grams of adipic acid were added and agitated until dissolved. The resulting solution was diluted to a concentration of 2.0% and used to treat southern yellow pine stakes by the Full Cell process. The resulting stakes were air dried and found to be resistant to decay and insect attack.
• EXAMPLE 5 A solution was prepared by adding 61 grams of copper metal to 150 grams of water containing 100 grams of 30% am ⁇ monium hydroxide and 70 grams of ammonium bicarbonate. The mixture was agitated and aerated until all of the copper metal dissolved. A second solution, was prepared by adding 31 grams of malonic acid to 100 grams of water. The second solution was mixed with the first and the resulting product diluted with water to 2.5%. This solution was used to treat southern yellow pine stakes by the Full Cell process. The stakes were then air dried and found to be resistant to de- cay and insect attack.
• EXAMPLE 6 To 500 grams of water containing 450 grams of 30% am ⁇ monium hydroxide were added to 132 grams of basic copper carbonate. Upon dissolution of the copper carbonate, 59 grams of citric acid were added to the solution. The prod ⁇ uct was agitated until a clear solution was obtained. This solution was then diluted with water to a concentration of 1.5% and used to treat Douglas fir stakes by the Full Cell process. The stakes were oven dried and found to be resis- tant to decay and insect attack.
• EXAMPLE 7 A solution was prepared by dissolving 75 grams of ox ⁇ alic acid in 250 grams of water. To this solution were ad ⁇ ded 75 grams of zinc carbonate. This mixture was allowed to react until the evolution of CO- was complete. Upon com ⁇ pletion of the reaction, 200 grams of 30% ammonium hydroxide were added to solubilize the product. This solution was then diluted to 2.0% and used to treat southern yellow pine stakes by the Empty Cell process. The resulting stakes were air dried and found to be resistant to fungal and in ⁇ sect attack.
• EXAMPLE 8 A preservative solution was prepared by dissolving 54 grams of sodium oxalate in 150 grams of water. A second so ⁇ lution was prepared by adding 100 grams of copper sulfate pentahydrate to 150 grams of water containing 42 grams of 30% ammonium hydroxide and 29 grams of ammonium bicar ⁇ bonate. Both solutions were mixed and the resulting product diluted with water to a 1.5% concentration. This solution was used to treat southern yellow pine test stakes by the Full Cell process. The resulting stakes were then air dried and found to be resistant to decay and insect attack.
• Southern yellow pine sapwood stakes (1-1/2" x 1/8" x 10") were Impregnated with several preservative solutions using the Full Cell process. Test stakes were preserved with copper naphthenate, copper citrate and copper oxalate at three different retention (concentration) levels measured
• the rating system used to evaluate decay and insect attack is as follows: 10 - sound, 9 - slight attack, 7 - moderate attack, 4 - severe attack, 0 - failure.
• the copper citrate and copper oxalate performed well af ⁇ ter 36 months exposure, as did the copper naphthenate, which is a well known oil-borne preservative.
• the untreated con ⁇ trols exhibited moderate to severe attack after 12 months exposure and complete failure due to termite attack after 24 months exposure.
• aqueous solutions prepared according to the present invention may also be used to treat living plants and seeds to prevent fungal and/or insect attack.
• the treatment solution would most likely be ap ⁇ plied by spraying, but these solutions may be applied by any method commonly used to apply known insecticides to plants or agricultural crops.

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• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Dentistry (AREA)
• Wood Science & Technology (AREA)
• Plant Pathology (AREA)
• Environmental Sciences (AREA)
• Engineering & Computer Science (AREA)
• Agronomy & Crop Science (AREA)
• Zoology (AREA)
• Pest Control & Pesticides (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Toxicology (AREA)
• Chemical And Physical Treatments For Wood And The Like (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)

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• 1985
  • 1985-03-26 ZA ZA852282A patent/ZA852282B/xx unknown
  • 1985-04-02 WO PCT/US1985/000536 patent/WO1985004668A1/en active Application Filing
  • 1985-04-02 GB GB08529662A patent/GB2166956A/en not_active Withdrawn
  • 1985-04-02 DE DE19853590150 patent/DE3590150T1/de not_active Withdrawn
  • 1985-04-02 BR BR8506433A patent/BR8506433A/pt unknown
  • 1985-04-02 MX MX204820A patent/MX161835A/es unknown
  • 1985-04-02 EP EP85901852A patent/EP0175771A1/en not_active Withdrawn
  • 1985-04-02 JP JP60501526A patent/JPS61501763A/ja active Pending
  • 1985-04-02 AU AU41182/85A patent/AU4118285A/en not_active Abandoned
  • 1985-04-03 BE BE0/214782A patent/BE902109A/fr not_active IP Right Cessation
  • 1985-04-03 FR FR8505058A patent/FR2562463A1/fr active Pending
  • 1985-11-25 NO NO854702A patent/NO854702L/no unknown
  • 1985-12-03 FI FI854786A patent/FI854786A/fi not_active Application Discontinuation
  • 1985-12-04 SE SE8505739A patent/SE8505739L/xx not_active Application Discontinuation

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