Source: https://patents.google.com/patent/US8747908B2/en
Timestamp: 2018-05-24 18:19:24
Document Index: 571173942

Matched Legal Cases: ['application no. 60', 'Application No. 60', 'Application No. 60', 'art 5', 'art 5', 'art 1']

US8747908B2 - Micronized wood preservative formulations - Google Patents
US8747908B2
US8747908B2 US10970446 US97044604A US8747908B2 US 8747908 B2 US8747908 B2 US 8747908B2 US 10970446 US10970446 US 10970446 US 97044604 A US97044604 A US 97044604A US 8747908 B2 US8747908 B2 US 8747908B2
US10970446
US20050118280A1 (en )
The present invention provides wood preservative compositions comprising micronized particles. In one embodiment, the composition comprises dispersions of micronized metal or metal compounds. In another embodiment, the wood preservative composition comprises an inorganic component comprising a metal or metal compound and organic biocide. When the composition comprises an inorganic component and an organic biocide, the inorganic component or the organic biocide or both are present as micronized particles. When compositions of the present invention are used for preservation of wood, the micronized particles can be observed as uniformly distributed within the wood and there is minimal leaching of the metal and biocide from the wood.
This application claims priority to U.S. Provisional application no. 60/568,485 filed on May 6, 2004, the disclosure of which is incorporated herein by reference. This application is also a continuation-in-part of U.S. Non-provisional application Ser. No. 10/821,326 filed on Apr. 9, 2004, which in turn claims priority to U.S. Provisional Application No. 60/461,547, filed Apr. 9, 2003, and U.S. Provisional Application No. 60/518,994, filed Nov. 11, 2003, the disclosures of which are incorporated herein by reference.
Wood preserving compositions are well known for preserving wood and other cellulose-based materials, such as paper, particleboard, textiles, rope, etc., against organisms responsible for the destruction of wood, including fungi and insects. Many conventional wood preserving compositions contain copper amine complexes. Copper amine complexes have been used in the past because the amine solubilizes the copper in aqueous solutions. The copper in such copper amine complexes is obtained from a variety of copper bearing materials, such as copper scrap, cuprous oxide, copper carbonate, copper hydroxide, a variety of cuprous and cupric salts, and copper bearing ores. The amine in such copper amine complexes is normally obtained from an aqueous solution of ammonia and ammonium salts, such as ammonium carbonate, and ammonium sulfate, ethanolamines, etc. For example, U.S. Pat. No. 4,622,248 describes forming copper amine complexes by dissolving copper (II) oxide [CuO] (also known as cupric oxide) in ammonia in the presence of ammonium bicarbonate.
The disadvantage of using ammonia as a copper solubilizing agent lies in the strong odor of ammonia. Additionally, copper ammonia preservatives can affect the appearance of the treated wood giving surface residues an undesirable color. In recent years, many amine-containing compounds, such as the ethanolamines and aliphatic polyamines, have been used to replace ammonia to formulate water-soluble copper solutions. These compounds were chosen because of their strong complexing ability with copper and because they are essentially odorless. U.S. Pat. No. 4,622,248 discloses a method of preparing copper amine complexes by dissolving a mixture of copper (II) carbonate [CuCO3] and copper (II) hydroxide [Cu(OH)2] in ethanolamine and water. The complexing amine (i.e., the ligand) and copper (II) ion combine stoichiometrically and thus the weight ratio of reagents will be different for each complexing amine. However, copper amine based preservatives have higher copper loss due to leaching as compared to traditional copper based preservatives such as chromated copper arsenate (CCA).
In another embodiment, the compositions comprise metal or metal compounds and organic biocides. The metal is in an insoluble (micronized) form. The metal compounds may be in a soluble form or in a water insoluble (micronized) form. The organic biocides may be soluble or water insoluble (micronized). In the compositions of this embodiment, at least one component (either a metal/metal compound or a biocide) is micronized.
FIG. 6 depicts a scanning Electron Micrograph of a Southern Pine wood treated with a micronized copper carbonate dispersion showing two views at magnification of 1600×.
Unless stated otherwise, such as in the examples, all amounts and numbers used in this specification are intended to be interpreted as modified by the term “about”. Likewise, all elements or compounds identified in this specification, unless stated otherwise, are intended to be non-limiting and representative of other elements or compounds generally considered by those skilled in the art as being within the same family of elements or compounds. The term “micronized” as used herein means a particle size in the range of 0.001 to 25 microns. Furthermore, it should be understood that “micronized” does not refer only to particles which have been produced by the finely dividing, such as by mechanical grinding, of materials which are in bulk or other form. Micronized particles can also be formed by other mechanical, chemical or physical methods, such as, for example, formation in solution, with or without a seeding agent, grinding or impinging jet. The term “preservative” as used herein means a composition that renders the material to which it is applied more resistant to insect, fungal or microbial attack than the same material without having the composition applied. The term “particle size” refers to the largest axis of the particle, and in the case of a generally spherical particle, the largest axis is the diameter.
A preferred metal is copper. Accordingly, in one embodiment, copper, copper compounds and/or copper complexes are used. The copper or copper compounds such as cuprous oxide (a source of copper (I) ions), cupric oxide (a source of copper (II) ions), copper hydroxide, copper carbonate, basic copper carbonate, copper oxychloride, copper 8-hydroxyquinolate, copper dimethyldithiocarbamate, copper omadine, copper borate, copper residues (copper metal byproducts) or any suitable copper source can be used as micronized particles having a particle size between 0.001 microns to 25 microns. These particles exhibit a relatively low solubility in water. Other metals, metal compounds or metal complexes as well as transition metals or transition metal compounds (including the lanthanide and actinide series elements) such as zinc, cadmium, silver, nickel, arsenic, bismuth, lead, chromium etc. can be used in place of copper, copper compounds or copper complexes.
The present invention includes any copper based compounds or copper complexes including chromated copper arsenates and other complexes. The present invention is not limited to ionically bound metals, and compounds in which the bonds to the metal are partially or totally covalent may be used.
The micronized particles can be obtained by wetting/dispersing and grinding copper compounds using a commercially available grinding mill or any other chemical, physical or mechanical means. Alternatively, the micronized copper compounds may also be purchased from commercial sources, which generally need to be ground further to be useful for wood preservation. For example, micronized copper hydroxide can be obtained from Phibro-Tech, Inc., Sumter, S.C. and ground further for use in the present invention. Micronized cupric oxide can also be obtained from Nanophase Technologies Corporation, Romeoville, Ill.
The present invention includes the situation in which a water-soluble inorganic biocide is used in conjunction with a micronized organic biocide. A range of water-soluble inorganic biocides can be used. Included in this range are water-soluble compounds which could otherwise be used as micronized inorganic biocides in other embodiments of the present invention. Examples of such are water-soluble compounds in the list of copper compounds above. Other examples are compounds such as sodium fluoride, sodium borate, and boric acid. In general, the inorganic biocide has a solubility which is greater than 10 grams per liter.
Water insoluble organic biocides are also well known. Some non-limiting examples of water insoluble organic biocides are provided below.
Fungicides, insecticides and bactericides that can be used with the system are well known to those skilled in the art and include azoles, quaternary ammonium compounds, boron compounds, fluoride compounds disclosed herein and combinations thereof.
Quaternary ammonium compounds that can be mixed with micronized metal formulations have the following structures:
Where R1, R2, R3, and R4 are independently selected from alkyl or aryl groups and X-selected from chloride, bromide, iodide, carbonate, bicarbonate, borate, carboxylate, hydroxide, sulfate, acetate, laurate, or any other anionic group. Preferred quaternary ammonium compounds include alkyldimethylbenzylammonium chloride, alkyldimethylbenzylammonium carbonate/bicarbonate, dimethyldidecylammonium chloride, dimethyldidecylammonium carbonate/bicarbonate, etc.
Examples of fungicides which can be mixed with micronized metal formulations are provided in Table 1:
Examples of insecticides which can be mixed micronized metal formulations are shown in Table 2:
Other biocides known by those skilled in the art that can optionally be used with the system would include insecticides, mold inhibitors, algaecides, bactericides and the like which may also be added to this system to further enhance the performance of this disclosure.
Wood treated with the micronized preservatives of the present invention exhibits reduced leaching. Accordingly, if wood is treated with micronized copper, copper compounds, copper complexes or combinations thereof such that copper or copper ions are present at a concentration of greater than 0.001 pcf, the leaching of copper from the wood is less that 50% of leaching observed with non-micronized formulations. In another embodiment, at concentrations of copper or copper ions in treated wood greater than 0.001 pcf, the leaching of copper is less than 20% of leaching observed with non-micronized formulations. In yet another embodiment, at concentrations of copper or copper ions in treated wood between 0.001 and 0.05 pcf, the leaching of copper is less than 20% of leaching observed from wood containing greater than 0.001 pcf of non-micronized copper. Preferably, the leaching of copper is less 10%, and more preferably less than 5%, of leaching observed with non-micronized copper formulations when the concentration of copper or copper ions is between 0.001 to 0.5 pcf.
Also important is the penetration of the dispersion formulation into the wood's or other cellulose-based material's cellular structure. If the copper source used in formulating the dispersion formulation disclosed herein has a particle size in excess of 30 microns, the particles may be filtered by the surface of the wood and thus may not be uniformly distributed within the cell and cell wall. As shown in FIG. 2, the primary entry and movement of fluids through wood tissue occurs primarily through the tracheids and border pits. Tracheids have a diameter of about thirty microns. Fluids are transferred between wood cells by means of border pits.
Particle size of the metal, metal compounds or organic biocide used in the dispersion formulation disclosed herein typically does not exceed 30 microns or the metal and or organic biocide used in conjunction with the metal tends to be filtered by the surface of the wood thus not attaining a desired penetration and fluid flow through the wood tissue. In one embodiment particle size of the micronized particles used in the dispersion formulation disclosed herein can be between 0.001-10 microns. In another embodiment, the particle size is between 0.005 to 1.0 micron. In another embodiment, the particle size is between 0.05 to 10.0 microns. If a more uniform penetration is desired, particle size of the metal/metal compounds or the organic biocide used in the dispersion formulation disclosed herein can be between 0.05-1.0 microns.
Thus, the present invention also provides a method for the preparation of wood containing the micronized particle preservative biocidal compositions of the present invention. The method comprises forming micronized particles of metal compound, biocide, or both, on or within the wood to be protected.
Furthermore, wood which contains a preservative composition of the present invention generally has the advantage of being less corrosive of nails and other metal implements than wood which contains other commonly used preservative compositions which contain amine compounds. Nails which contain iron, copper, nickel, (and other metals which would be used in nails and would have some susceptibility to alkaline corrosion) and/or other metals which are susceptible to alkaline corrosion will generally show some degree of corrosion after exposure to wood which contains non-micronized amine-containing preservative formulations. The same type nails when exposed to wood containing a micronized metal preservative can generally be expected to show less or no corrosion after an equivalent exposure period.
Moreover, in comparison to wood which has been treated with commonly available preservatives, wood which has been treated with micronized preservatives of the present invention is particularly resistant to mold growth. Without desiring to be bound by theory, it is thought that the amines and other nitrogenous compounds in currently used preservative compositions serve as an energy source for molds. Because the disclosed preservative compositions containing micronized copper are free of amines, wood which has been treated with them can be found to have less mold than wood which has been treated with other compositions and similarly exposed.
Wood which comprises micronized biocidal formulations generally exhibits reduced biocide leaching relative to wood which contains non-micronized biocidal compositions. Without desiring to be bound by theory, it is thought that the ability of a given component to be solvated in an aqueous environment is one of the most important considerations with respect to leaching. All other variables being equal, easily solvated compounds and ions exhibit greater leaching than chemical species which may not have the same ability to be solvated in a given aqueous environment. Thus, the presence of a biocide in micronized form prevents much of the biocide from being in direct contact with the aqueous environment, reducing its ability to be solvated. In environments which are conducive to leaching, the result is reduced leaching.
Wood treated with the compositions of the present invention has been observed to have a uniform distribution of micronized particles. This can be observed simply in the coloration (when a colored composition is used) or it can also be observed via the use of microscopy. For example, when scanning electron microscopy is combined with energy dispersive X-ray analysis (SEM-EDXA), the presence of, as well as the distribution of the micronized particles can be observed. SEM-EDXA is also useful for determination of the elements present in the micronized particles and therefore, the composition of the particles can be determined. Alternatively or additionally, specific staining methods can be carried out on SEM sections to determine the identity of the composition of the particles.
A preservative treating formulation was prepared by adding 0.15 kg of copper carbonate dispersion from Example 2 to 0.025 kg of a quaternary ammonium compound, dimethyl didecyl ammonium carbonate/bicarbonate and 4.825 kg of water. This fluid was allowed to mix until a homogenous fluid was prepared. This fluid was used to treat southern pine test stakes measuring 0.156×1.5×10.0 inches (4×38×254 mm) by the full-cell process. The resulting stakes showed a uniform distribution of copper throughout the wood cells. The treated test stakes were installed in the field to evaluate the field performance of the preservative following the procedure described in AWPA Standard E7-01 “Standard Method of Evaluating Wood Preservatives by Field Tests with Stakes”. The test results indicated that the treated stakes were resistant to decay and insect attack. The fluid was also used to treat southern pine wood cube blocks measuring ¾″×¾″×¾″ (19 mm×19 mm×19 mm). The treated cubes were exposed to several test fungi to evaluate the bio-efficacy of the preservative formulation following the procedure described in AWPA Standard E10-01 “Standard Method of Testing Wood Preservatives by Laboratory Soil-Block Cultures”. Upon the completion of the soil-block test, the cubes were found to have less than 2.0% weight loss, indicating essentially no fungal attack to the treated cubes. In comparison, untreated wood cubes had approximately 50% weight loss after being exposed to the test fungi. The soil block test results indicated wood treated the above preservative formulation was resistant to fungal attack.
Southern Pine wood was treated with a micronized copper carbonate dispersion from Example 9. Scanning electron microscopy with EDXA was performed by standard methods. Results are shown in FIG. 6. A uniform distribution of the micronized particles is observed. This examples indicates that the presence of micronized particles can be identified in treated wood and that the distribution of these particles was found to be uniform.
1. Wood comprising an aqueous wood preservative composition, wherein the composition comprises:
(a) a biocidally effective amount of particles of a copper compound with a particle size of between 0.001 and 1.0 microns, dispersed in water; and
(b) a biocidally effective amount of one or more organic biocides;
wherein the copper compound is selected from the group consisting of copper hydroxide, cupric oxide, cuprous oxide, copper carbonate, basic copper carbonate, copper oxychloride, copper dimethyldithiocarbamate, copper omadine, and copper borate, and
wherein the particles of the copper compound are obtained by milling, distributed throughout a cross-section of the wood, and render the wood resistant to fungal decay.
2. The wood of claim 1, wherein the organic biocide is selected from a group consisting of fungicide, insecticide, algaecide, moldicide, and bactericide.
3. The wood of claim 1, wherein the organic biocide is an azole, a borate, or a fluoride.
4. The wood of claim 3, wherein the organic biocide is an azole.
5. The wood of claim 4, wherein the azole is tebuconazole.
6. The wood of claim 1, wherein the organic biocide is a solid.
7. The wood of claim 6, wherein the organic biocide has a particle size of between 0.001 and 25 microns.
8. The wood of claim 7, wherein the organic biocide is tebuconazole.
9. The wood of claim 1, wherein the wood comprises coniferous wood.
10. The wood of claim 9, wherein the coniferous wood comprises southern pine.
11. The wood of claim 1, wherein the particles of copper compound are uniformly distributed throughout a cross-section of the wood.
12. The wood of claim 11, wherein copper leaching from the wood is reduced as compared to copper leaching from a wood comprising copper monoethanolamine complex.
13. The wood of claim 1, wherein the wood is lumber.
14. Wood comprising an aqueous wood preservative composition, wherein the composition comprises:
wherein the copper compound is selected from the group consisting of copper hydroxide, cupric oxide, cuprous oxide, copper carbonate, basic copper carbonate, copper oxychloride, copper dimethyldithiocarbamate, copper omadine, and copper borate,
wherein the particles of the copper compound are distributed throughout a cross-section of the wood and render the wood resistant to fungal decay, and
wherein copper leaching from the wood is reduced as compared to copper leaching from a wood comprising copper monoethanolamine complex.
15. The wood of claim 14, wherein the organic biocide is selected from a group consisting of fungicide, insecticide, algaecide, moldicide, and bactericide.
16. The wood of claim 14, wherein the organic biocide is an azole, a borate, or a fluoride.
17. The wood of claim 16, wherein the organic biocide is an azole.
18. The wood of claim 17, wherein the azole is tebuconazole.
19. The wood of claim 14, wherein the organic biocide is a solid.
20. The wood of claim 19, wherein the organic biocide has a particle size of between 0.001 and 25 microns.
21. The wood of claim 20, wherein the organic biocide is tebuconazole.
22. The wood of claim 14, wherein the wood comprises coniferous wood.
23. The wood of claim 22, wherein the coniferous wood comprises southern pine.
24. The wood of claim 14, wherein the particles of copper compound are uniformly distributed throughout a cross-section of the wood.
25. The wood of claim 14, wherein the wood is lumber.
US10970446 2003-04-09 2004-10-21 Micronized wood preservative formulations Active 2026-01-16 US8747908B2 (en)
CA 2584210 CA2584210A1 (en) 2004-10-21 2005-10-18 Micronized wood preservative formulations
EP20050812212 EP1802458A4 (en) 2004-10-21 2005-10-18 Micronized wood preservative formulations
PCT/US2005/037303 WO2006047126A3 (en) 2004-10-21 2005-10-18 Micronized wood preservative formulations
US12153167 US20080210121A1 (en) 2003-04-09 2008-05-14 Micronized wood preservative formulations
US11526765 Continuation-In-Part US8637089B2 (en) 2003-04-09 2006-09-26 Micronized wood preservative formulations
US20050118280A1 true US20050118280A1 (en) 2005-06-02
US8747908B2 true US8747908B2 (en) 2014-06-10
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US10970446 Active 2026-01-16 US8747908B2 (en) 2003-04-09 2004-10-21 Micronized wood preservative formulations
US (1) US8747908B2 (en)
EP (1) EP1802458A4 (en)
CA (1) CA2584210A1 (en)
WO (1) WO2006047126A3 (en)
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WO2006047126A2 (en) 2006-05-04 application
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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LEACH, ROBERT M.;ZHANG, JUN;SIGNING DATES FROM 20050103 TO 20050105;REEL/FRAME:016222/0095