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WO1996023635A1 - Agents diffusibles de preservation du bois - Google Patents

Agents diffusibles de preservation du bois Download PDF

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Publication number
WO1996023635A1
WO1996023635A1 PCT/AU1996/000039 AU9600039W WO9623635A1 WO 1996023635 A1 WO1996023635 A1 WO 1996023635A1 AU 9600039 W AU9600039 W AU 9600039W WO 9623635 A1 WO9623635 A1 WO 9623635A1
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WIPO (PCT)
Prior art keywords
composition according
acid
composition
metal
chelate
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Application number
PCT/AU1996/000039
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English (en)
Inventor
Heikki Mamers
Kevin James Mccarthy
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Commonwealth Scientific And Industrial Research Organisation
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Priority to AU44758/96A priority Critical patent/AU700524B2/en
Publication of WO1996023635A1 publication Critical patent/WO1996023635A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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
    • 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
    • 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
    • B27K3/22—Compounds of zinc or 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
    • B27K3/34—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

  • the present invention relates to wood preservative compositions. More particularly, it relates to wood preservative compositions and formulations containing biocidal compounds suitable for providing protection to timber and similar wood-based materials.
  • a commonly used biocidal, water-soluble metal salt is cupric sulphate
  • CuSO 4l which is a component of the so called “Bordeaux mixture” for the treatment of surface fungal infections of agricultural crops. It is also part of the copper-chrome-arsenic formulation known as CCA and extensively used for the preservation of timber.
  • CCA copper-chrome-arsenic formulation
  • cupric sulphate predominantly exists as positively charged cupric ions (Cu ++ ) and negatively charged sulphate ions
  • the wood substance consists primarily of cellulose and lignin.
  • Cellulose is a high molecular weight polymer based on anhydroglucose monomer units, each of which contains three free hydroxyl groups. The average degree of polymerisation is about 4,000-5,000 anhydroglucose units for both softwood and hardwood cellulose.
  • Lignin a complex high molecular weight aromatic polymer of indeterminate structure, is known to be rich in phenolic, carboxylic and aldehydic groups.
  • the diffusibility barrier could be overcome by completely saturating all of the reactive sites within the wood substance by metal ions but, in practice, this would be a prohibitively expensive option.
  • water-soluble metal salts such as cupric sulphate can only provide biological protection to the open structured sapwood part of timber, where the treating solution is introduced by physical transport rather than by diffusion. It is found that ionic metal salts provide minimal protection to the denser heartwood components of timber, which are impermeable to the flow of treating solutions.
  • wood preservatives based on the copper tetra-ammine complex have a number of disadvantages that militate against their use. Firstly, it is found that excess ammonia must be present to stabilise the complex; when the ammonia evaporates the complex decomposes and the enhanced diffusibility is lost. Secondly, the necessary presence of excess ammonia poses a hazard in both manufacture and use of the complex and for many end uses the strong ammoniacal odour of the wood preservative is unacceptable.
  • the present invention provides a composition having biocidal and/or preservative properties, the composition including at least one metal chelate having a neutral or negative charge.
  • the metal chelate is one which is water soluble and non-volatile.
  • the metal chelate may be one in which the metal ion is co-ordinately bonded to an appropriate ligand such that the resultant metal ion complex has a neutral or negative charge.
  • Metal chelates or chelation complexes are known per se as compounds having a cyclic structure and formed by coordinate bonding of a compound containing donor atoms ("chelation agent” or "ligand") with a single metal ion. Depending on the choice of ligand, the resulting chelate may carry a positive or negative charge or be electrically neutral.
  • metal chelates are always in a state of equilibrium between the solvated metal ion, the ligand and the chelation complex as represented by:
  • Suitable metal ions for the preparation of biocidal chelates for the purposes of the present invention are those of the groups of metallic elements generally known as the transition elements and the rare earths.
  • the transition elements copper and zinc are preferred, either singly or in combination, or in admixture with one or more of the other transition metals.
  • the metallic rare earth elements cerium, lanthanum and yttrium are preferred but the whole group of sixteen naturally occurring metallic rare earth elements are suitable, either individually or in combinations of two or more thereof. Mixtures of transition elements and the rare earths may also be employed for the purposes of the invention.
  • the metal ion is present in an amount of 0.1 to 35% m/m of the composition of the invention.
  • the selection of ligands suitable for use in the practice of the invention is governed, inter alia, by the position of the abovementioned equilibrium between the metal ions complexed to the wood substance and the metal ions bound up in the chelate complex.
  • the position of this equilibrium is a function of the K-. value of the chelate and the relative abundance and complexing ability of the ligands in the timber structure.
  • the ability to select ligands to produce chelates of different K. values is an important and preferred feature of the invention. Chelates with a low K 1 value favour a limited extent of diffusion of metal ion into the timber substrate but a high degree of retention of the metal ion in the timber within the diffusion zone.
  • chelates with a high K, value favour extensive penetration of the chelate into the timber but a lower retention of the metal ion by the wood substance. It is thus possible by suitable choice of ligand to achieve any desired balance between the extent of diffusion and the degree of retention of the metal ion.
  • the metal chelate complex when in solution, should have a neutral or negative charge to ensure that the complex is not rapidly bonded to the negatively charged groups in the cellulose and lignin of the wood and thus insolubilised, prematurely restricting the diffusibility of the metal complex within the wood substance.
  • Suitable ligands include, but are not limited to, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, natural and synthetic amino acids, aliphatic and aromatic amines and complex inorganic acids and salts thereof.
  • Suitable ligands are salicylic acid, maleic acid, oxalic acid, malic acid, tartaric acid, phthalic acid, citric acid, glycine, alanine, valine, glutamic acid, iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), propylene diamine, triethylene tetramine, methylpyridine, polyphosphoric acid, and soluble salts thereof.
  • suitable ligands are salicylic acid, maleic acid, oxalic acid, malic acid, tartaric acid, phthalic acid, citric acid, glycine, alanine, valine, glutamic acid, iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), propylene diamine, triethylene tetramine, methylpyridine, polyphosphoric acid, and soluble salts thereof.
  • EDTA ethylene
  • the metal chelates of the invention may be simply prepared by known methods such as by reacting appropriate proportions of an aqueous solution of the chelating agent with a suitable salt of the chosen metal until a clear solution of the chelate is obtained.
  • suitable metal salts include but are not limited to carbonates, basic carbonates, hydroxides, basic oxides and oxides of metals having appropriate biocidal activity.
  • the reaction conditions required to form the metal chelates may vary from dissolution at ambient temperature to several hours' vigorous stirring under reflux and must be determined by experiment. In some cases it may be necessary to adjust the pH of the solution to obtain a clear solution of the chelate.
  • the clear solution may then be evaporated to dryness to yield the solid chelate which may then be ground to an appropriate size for incorporation into wood preservative formulations.
  • the chelate solution may be used directly in the formulation of wood preservative compositions without the need to isolate the solid chelate. This approach is essential in the case of metal chelates which are stable in aqueous solution but decompose upon drying as, for example, is the case with chelates prepared from ligands such as propylene diamine or triethylene tetramine.
  • compositions of the invention may include biocidal metal chelates individually or in combinations as treatment agents for the preservation of timber and similar cellulosic materials.
  • mixtures of chelates which incorporate different metals may be used to enhance the efficacy of the composition, for example to counter destructive organisms which may have acquired a tolerance towards a particular metallic element.
  • the metal chelates may also be used to supplement the activity of other, known biocidal elements or compounds.
  • the metal chelates may be introduced into the timber substrate by any of the methods known to those experienced in the art of timber treatment and protection.
  • the composition of the invention may be in the form of a aqueous solution or emulsion for application to timber by spraying, dipping or pressure impregnation.
  • the composition of the invention may also be in the form of a powder, tablet, rod, paste or other formulation appropriate for application as a wood preservative in particular circumstances.
  • the composition of the invention may be in the form water-soluble rods or tablets for insertion into holes drilled in the wooden structure to be protected.
  • the composition of the invention may further include an effective amount of a boron compound and/or a fluorine compound.
  • the boron compound may be in the form of a soluble salt.
  • the fluorine compound may be in the form of a soluble salt.
  • the boron compound may be present in an amount of 0.1 to 30% m/m of the composition of the invention.
  • the fluorine compound may be present in an amount of 0.1 to 40% m/m of the composition of the invention.
  • composition of the invention may also include a polyhydric polyol, for example, ethylene glycol, propylene glycol or glycerol.
  • a polyhydric polyol for example, ethylene glycol, propylene glycol or glycerol.
  • Boron and fluorine in the form of soluble salts such as borates, fluoroborates and fluorides, are becoming increasingly important as environmentally acceptable timber preservatives.
  • water-soluble rods containing relatively high concentrations of borates and fluorides are rapidly becoming the preferred method for the ground line remedial preservation of wooden utility poles.
  • the chelates of the present invention may be used to introduce diffusible biocidal metals into such rod formulations and that, surprisingly, the metal component remains diffusible throughout the lifetime of the preservative treatment and does not form insoluble borates and fluorides by reaction with the other constituents of the rod formulation.
  • the present invention provides a method of treating wood or a wood-containing product, the method including applying to the wood a composition in accordance with the invention.
  • the present invention provides novel metal chelates.
  • This example demonstrates the preparation and diffusion/ fungitoxic testing of a neutrally charged metal chelate prepared by reacting basic copper carbonate with two equivalents of the bidentate ligand glycine to form copper di-glycinate chelate.
  • the glycine acts as a bidentate ligand, forming a double ring to enclose the copper atom in an electrically neutral complex having a copper content of about 30% m/m and a reported log K-, value of 8.6:
  • the solubility of the complex is about 10 g/L at 21 °C, the pH of the saturated solution being about 9.
  • the chelate was prepared by dissolving 54.3 parts of glycine in about 1600 parts of boiling water. Basic copper carbonate (40 parts) was then introduced and the reaction mixture stirred and boiled under reflux for about three hours, during which period the basic copper carbonate dissolved and combined with the glycine to form a dark blue solution of copper di-glycinate chelate. The solution was evaporated to dryness under atmospheric conditions at about 65°C to give a dark blue residue of substantially anhydrous copper di-glycinate crystals, which were then further ground to a powder passing through a 40 mesh sieve.
  • the diffusibility and fungitoxicity of the copper di-glycinate chelate was tested by the slab diffusion method described by Da Costa and Greaves ("Laboratory Test Procedures", Proceedings of Tropical Wood Preservation Seminar, Port Moresby, 1975).
  • the prospective preservative is contacted with a strip of open celled sponge in the bottom of a Petri dish.
  • a water saturated timber slab measuring 50x50x6 mm, with the edges sealed by dipping in petroleum jelly and paraffin wax, is placed on top of the sponge.
  • Diffusion of toxicant through the slab is assessed by placing a strip of inoculated agar on top of the slab, at right angles to the grain direction of the slab. Inhibition of fungal growth on the strip of inoculated medium will occur if the toxicant diffuses through the slab and attains a sufficiently high concentration in the strip of inoculated medium.
  • the upper surface of the slabs was inoculated with an agar strip infected with a mixed inoculum. The same procedure was also carried out for the untreated controls. The slabs were then incubated at 28°C and 85% RH and scored for fungal activity after 7, 14, 21 and 28 days. Scoring was on the following basis:
  • Table 1 shows that the copper di-glycinate chelate had an averaged score of zero after 28 days, making it a "Very Effective” preservative and demonstrating that the neutrally charged copper chelate was both diffusible and fungitoxic. Th untreated control slabs supported vigorous fungal growth throughout the 28 da test period.
  • This example illustrates the preparation and diffusion/fungitoxic testing of a negatively charged metal chelate.
  • the chelate was prepared by reacting basic zinc carbonate with two equivalents of iminodiacetic acid in the presence o ammonium hydroxide to form the zinc diammonium di-iminodiacetic acid chelate.
  • the overall reaction may be represented as:
  • the structure of the negatively charged 2:1 binary zinc chelate may be represented as: coo-
  • the chelate was prepared by dissolving 199.7 parts of iminodiacetic acid in 1000 parts of water at about 60°C. Basic zinc carbonate (84.5 parts) was then dispersed in the iminodiacetic acid solution and sufficient ammonium hydroxide added to raise the pH of the mixture to about 9. The clear solution was evaporated to dryness at about 65°C and the residual chelate ground to pass through a 40 mesh sieve.
  • the zinc diammonium di-iminodiacetic acid chelate had a zinc content of about 18.0% m/m and a solubility of about 286 g/L at 21 °C.
  • the log K, value for this chelate has been reported as 7.0.
  • the negatively charged zinc diammonium di-iminodiacetic acid chelate scored 0.33, making it an "Effective" preservative.
  • This example relates to the preparation and diffusion/fungitoxic testing of chelates prepared from the rare earths lanthanum, yttrium and cerium.
  • the chelates prepared were lanthanum tri-maleic acid, yttrium tri-iminodiacetic acid and cerium/di-sodium ethyienediaminetetraacetic acid (EDTA).
  • EDTA cerium/di-sodium ethyienediaminetetraacetic acid
  • the ligand was dissolved in the indicated quantity of water and the oxides (lanthanum, yttrium) or carbonate (cerium) dispersed in the resultant ligand solution.
  • the reaction mixture was then stirred under reflux for about two to three hours until a clear solution was obtained.
  • the chelates were recovered from the solutions by evaporation under atmospheric conditions at about 65°C.
  • This example illustrates the preparation and diffusion/fungitoxic testing of an inorganic chelate derived from the reaction of basic copper carbonate with sodium tripolyphosphate (STPP).
  • STPP sodium tripolyphosphate
  • the copper-STPP chelate had a solubility of about 510 g/L at 21°C, a copper content of about 5.3% m/m and a pH of about 8 in saturated solution. Its log K, value has been reported to be 7.3.
  • the diffusion/fungitoxic characteristics of the copper-STPP chelate were evaluated by the method of Example 1. Kenyan Oak heartwood was used as the diffusion substrate. The results are summarised in Table 4. 16 TABLE 4
  • Table 4 shows that the copper-STPP chelate eliminated all fungal activity on the Georgian Oak heartwood slabs after 28 days, indicating the negatively charged inorganic chelate to be a "Very Effective" preservative.
  • the untreated control slabs supported vigorous fungal growth throughout the 28 day test period.
  • This example illustrates the preparation and testing of a water soluble wood preservative rod which includes a copper chelate, a boron compound and a fluorine compound and in which all three fungitoxic elements boron, fluorine and copper remain diffusible through a timber substrate.
  • the mixture was then heated for 15 minutes at 115°C to polymerise the propylene glycol borate ester and form a malleable paste.
  • the paste was cast into PTFE-lined moulds 15mm in diameter by 50mm long. After cooling of the moulds to ambient temperature, the product was recovered therefrom in the form of tough, glassy rods which on an elemental basis contained about 12.9% m/m boron, 14.9% m/m fluorine and 6.2% m/m copper, for a total of about 34.0% m/m active elements.
  • BFC Boron, Fluorine, Copper
  • Fluorine - Zirconium oxychloride - wood containing sodium fluoride turns yellow but untreated wood becomes dark red.
  • Copper- Chrome azurol S - gives a deep blue in the presence of copper.
  • This example demonstrates that the amount of copper retained within the wood structure as insoluble copper-wood complexes can be regulated by the selection of copper chelates having different stability constants (Ki values). It also shows how appropriate selection of the ligand to prepare a metal chelate may be used to vary the proportion of the metallic element which becomes bonded to the timber substrate under treatment.
  • Copper chelates based on the ligands listed in Table 6 were prepared by the method of Example 1. Each chelate solution was diluted to contain the equivalent of 5 g/L elemental copper content prior to being impregnated into batches of twelve 20x20x10 mm air-dry blocks of P. radiata sapwood of basic density about 480 kg/m 3 , using successive pressure and vacuum cycles to saturate the wood structure with the solutions. Six of the saturated blocks from each batch were air dried immediately and analysed for their copper content. The remaining blocks were leached for seven days in a shaker bath held at
  • This example illustrates the preparation and diffusion/fungitoxic testing of water-based preservative rods containing copper, boron and fluorine as active elements, in which the copper chelate was prepared in situ during the formulation of the product. It also demonstrates that metal chelates may be used in conjunction with known fungitoxic elements such as boron and fluorine without antagonistic reactions occurring, such as the formation of insoluble metallic borates or fluorides which would otherwise occur if the metals were introduced as their cations.
  • Table 7(a) shows the components required for one thousand parts of such a preservative rod formulation containing about 4.0% m/m copper, 12.4% m/m boron and 11.0% m/m fluorine, for a total of about 27.4% m/m active elements.
  • the hot paste was cast into PTFE-lined cylindrical moulds as described in Example 5 to give a product in the form of tough, glassy rods.
  • the rods were ground to pass through a 40 mesh sieve and the ground material wetted with water to form a paste which was tested for diffusibility and fungitoxicity by the slab diffusion method of Example 1 , using Kenyan Oak heartwood as the diffusion substrate.
  • Table 7(b) The results are summarised in Table 7(b).

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Inorganic Chemistry (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)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention se rapporte à une composition présentant des propriétés biocides et/ou préservatrices, et contenant au moins un chélate métallique de charge neutre ou négative.
PCT/AU1996/000039 1995-01-30 1996-01-30 Agents diffusibles de preservation du bois WO1996023635A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU44758/96A AU700524B2 (en) 1995-01-30 1996-01-30 Diffusible wood preservatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPN0827A AUPN082795A0 (en) 1995-01-30 1995-01-30 Diffusible wood preservatives
AUPN0827 1995-01-30

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6110263A (en) * 1996-03-05 2000-08-29 Dr. Wolman Gmbh Timber preserving agent for maintenance purposes
WO2002009522A1 (fr) * 2000-07-31 2002-02-07 Sicit Chemitec S.P.A. Agents fongicides et bactericides a base de cuivre et utilisation de ces derniers
US6352583B1 (en) 1997-03-05 2002-03-05 Dr. Wolman Gmbh Wood preservative for subsequent application
WO2003035342A1 (fr) * 2001-10-25 2003-05-01 Teredo Marine Protection Aps Procede de prevention contre les attaques de bernacles
US7214407B2 (en) 2001-10-25 2007-05-08 Teredo Marine Protection Aps Method for the prevention of barnacle attacks
WO2010029127A3 (fr) * 2008-09-10 2011-01-06 Teredo Marine Protection Aps Agents biocides contre les xylophages marins
KR101039746B1 (ko) * 2008-08-26 2011-06-08 한국원자력연구원 희토류 화합물 또는 희토킬레이트 화합물을 유효성분으로 함유하는 항진균 조성물, 농약제제 및 농업용 액비
US20140004265A1 (en) * 2008-12-19 2014-01-02 E I Du Pont De Nemours And Company Copper complexes and their use as wood preservatives
WO2017112848A1 (fr) * 2015-12-23 2017-06-29 American Chemet Corporation Procédés pour améliorer la préservation de matériaux cellulosiques et matériaux cellulosiques préparés par celui-ci

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SU480553A1 (ru) * 1973-12-04 1975-08-15 Сенежская Лаборатория Консервирования Древесины Центрального Научноисследовательского Института Механической Обработки Древесины Огнебиозащитный состав дл древесины
US4193993A (en) * 1977-05-12 1980-03-18 Cuprinol Limited Compositions containing preservative metals and their use for the preservation of wood and like materials and as fungicides
EP0039538A1 (fr) * 1980-03-22 1981-11-11 BP Chemicals Limited Carboxylates de métalamines et leur utilisation comme préservatifs
US4335109A (en) * 1979-11-21 1982-06-15 Koppers Company, Inc. Water repellent aqueous wood treating solutions
US4656060A (en) * 1982-09-28 1987-04-07 John Krzyzewski Arsenical creosote wood preservatives
US4883689A (en) * 1987-02-20 1989-11-28 Rhone Poulenc, Inc. Method of preserving wood with lanthanide derivatives
EP0423674A2 (fr) * 1989-10-20 1991-04-24 Dr. Wolman GmbH Agent préservateur du bois contenant des composés polymériques d'azote

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SU480553A1 (ru) * 1973-12-04 1975-08-15 Сенежская Лаборатория Консервирования Древесины Центрального Научноисследовательского Института Механической Обработки Древесины Огнебиозащитный состав дл древесины
US4193993A (en) * 1977-05-12 1980-03-18 Cuprinol Limited Compositions containing preservative metals and their use for the preservation of wood and like materials and as fungicides
US4335109A (en) * 1979-11-21 1982-06-15 Koppers Company, Inc. Water repellent aqueous wood treating solutions
EP0039538A1 (fr) * 1980-03-22 1981-11-11 BP Chemicals Limited Carboxylates de métalamines et leur utilisation comme préservatifs
US4656060A (en) * 1982-09-28 1987-04-07 John Krzyzewski Arsenical creosote wood preservatives
US4883689A (en) * 1987-02-20 1989-11-28 Rhone Poulenc, Inc. Method of preserving wood with lanthanide derivatives
EP0423674A2 (fr) * 1989-10-20 1991-04-24 Dr. Wolman GmbH Agent préservateur du bois contenant des composés polymériques d'azote

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6110263A (en) * 1996-03-05 2000-08-29 Dr. Wolman Gmbh Timber preserving agent for maintenance purposes
US6352583B1 (en) 1997-03-05 2002-03-05 Dr. Wolman Gmbh Wood preservative for subsequent application
WO2002009522A1 (fr) * 2000-07-31 2002-02-07 Sicit Chemitec S.P.A. Agents fongicides et bactericides a base de cuivre et utilisation de ces derniers
WO2003035342A1 (fr) * 2001-10-25 2003-05-01 Teredo Marine Protection Aps Procede de prevention contre les attaques de bernacles
US7214407B2 (en) 2001-10-25 2007-05-08 Teredo Marine Protection Aps Method for the prevention of barnacle attacks
KR101039746B1 (ko) * 2008-08-26 2011-06-08 한국원자력연구원 희토류 화합물 또는 희토킬레이트 화합물을 유효성분으로 함유하는 항진균 조성물, 농약제제 및 농업용 액비
WO2010029127A3 (fr) * 2008-09-10 2011-01-06 Teredo Marine Protection Aps Agents biocides contre les xylophages marins
US20140004265A1 (en) * 2008-12-19 2014-01-02 E I Du Pont De Nemours And Company Copper complexes and their use as wood preservatives
WO2017112848A1 (fr) * 2015-12-23 2017-06-29 American Chemet Corporation Procédés pour améliorer la préservation de matériaux cellulosiques et matériaux cellulosiques préparés par celui-ci
US10449691B2 (en) 2015-12-23 2019-10-22 American Chemet Corporation Methods for enhancing the preservation of cellulosic materials and cellulosic materials prepared thereby
US20200047370A1 (en) * 2015-12-23 2020-02-13 American Chemet Corporation Methods for enhancing the preservation of cellulosic materials and cellulosic materials prepared thereby
US10786926B2 (en) 2015-12-23 2020-09-29 American Chemet Corporation Methods for enhancing the preservation of cellulosic materials and cellulosic materials prepared thereby
US11453142B2 (en) 2015-12-23 2022-09-27 American Chemet Corporation Methods for enhancing the preservation of cellulosic materials and cellulosic materials prepared thereby
US11919191B2 (en) 2015-12-23 2024-03-05 American Chemet Corporation Methods for enhancing the preservation of cellulosic materials and cellulosic materials prepared thereby

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