Copper complex bactericide/fungicide and method of making same.
Abstract
There is disclosed an improved copper complex bactericide/fungicide and a method of making and using the same. The improved bactericide/fungicide is prepared by forming an aqueous solution of a partially neutralized, water-soluble polycarboxylic acid having a molecular weight of between approximately 1,000 and 300,000 and a pH of between approximately 3 and 9. To this aqueous solution is added a copper-containing compound which when combined with said aqueous solution releases copper (II) ions which will form a water-soluble complex with said partially neutralized polycarboxylic acid. The water-soluble copper complex is applied to plants to prevent or inhibit bacterial and fungal disease growth thereon. <IMAGE>

Term
Term ended
Expired 2 April 2008, 18.5 years ago.
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39 claims: 12 independent, 27 dependent
- 1A process for the preparation of a substantially non-phytotoxic bactericidal / fungicidal composition comprising the operations consisting of:1.- Processo para a preparação de iw composição bactericida/fungicida substancialmente não fitotóxica, caracterizado pelo facto de compreender as operações que consistem em: forming an aqueous solution of a partially neutralized water soluble polycarboxylic acid having a molecular weight of from about 1,000 to 300,000 and a pH of from about 3 to 9;and combining with said aqueous mixture a copper-containing compound which, when combined with said aqueous solution, releases copper (TI) which forms a water-soluble complex with said partially neutralized polycarboxylic acid. se formar uma solução aquosa de um ácido policarboxílico solúvel em água, parcialmente neutralizado, tendo uma massa, molecular compreendida entre aproximadamente 1 000 e 300 000 e um pH compreendido entre aproximadamente 3 e 9;e se combinar com a referida mistura aquosa um composto que contém cobre que, quando se combina com a mencionada solução aquosa, liberta ioes de cobre (TI) que formam um complexo solúvel em água com o citado ácido policarboxílico parcialmente neutralizado.
- 1616 A process for the preparation of a substantially non-phytotoxic bactericidal / fungicidal composition comprising the operations of:16. - Processo para a preparação de uma composição bactericida/fungicida substancialmente não fitotóxica, caracterizado pelo facto de compreender as operaçoes que consistem: in forming an aqueous solution of partially neutralized polyacrylic acid having a molecular weight of from about 2,000 to 50,000 and a pH of from about 3,5 to 5, said polyacrylic acid being added in an amount from about 0 to about 75Z and 20Z by weight;and in combination with said aqueous mixture of a copper-containing compound chosen from the group consisting of Cu (OH) 2, CuSO 4, C 10 -C 10, C 20 O, C 10 NO 4, CuC 4, copper oxychloride, tribasic copper sulfate. and basic copper carbonate, said copper compound being added in an amount sufficient to complex said partially neutralized polyacrylic acid. na formação de uma solução aquosa de ácido poliacrílico parcialmente neutralizado que tem uma massa mole5 cular compreendida entre aproximadamente 2 000 e 50 000 e um pH compreendido entre aproximadamente 3,5 e 5, sendo o citado ácido poliacrílico adicionado em uma quantidade compreendida entre aproximadamente 0,75Z e 20Z em peso;e na combinação com a referida mistura aquosa de um composto que contém cobre escolhido do grupo que consiste em Cu(0H)2» CuSO^, CuíCIO^^, CU2O, CuíNO^^, CuC^, oxicloreto de cobre, sulfato de cobre tribãsico e carbonato de cobre básico, sendo o mencionado composto de cobre adicionado em uma quantidade suficiente para complexar o citado ácido poliacrílico parcialmente neutralizado.
- 1818 - Substantial non-phytotoxic bactericidal / fungicidal composition, characterized in that it consists essentially of:18. - Composição bactericida/fungicida substancial, mente não fitotóxica, caracterizada pelo facto de consistir essencialmente em: an aqueous solution of a copper complex and a partially neutralized water-soluble polycarboxylic acid having a molecular weight of approximately 1,000 to 300,000 and a pH of approximately 3 to 9, said copper being derived from a substantially water-insoluble copper-containing compound selected from the group consisting of copper hydroxide, cuprous oxide, tribasic copper sulfate, basic copper carbonate and oxy. copper chloride. uma solução aquosa de um complexo de cobre e um ácido policarboxílico solúvel em água, parcialmente neutralizado, que tem uma massa molecular compreendida entre aproxima damente 1 000 e 300 000 e um pH compreendido entre aproximada mente 3 e 9, sendo o referido cobre derivado de um composto que contém cobre substancialmente insolúvel em água escolhido do grupo que consiste em hidróxido de cobre, óxido cuproso, sulfato de cobre tribãsico, carbonato de cobre básico e oxi. cloreto de cobre.
- 2020 A method for controlling plant / bacterial disease in plants comprising the operation of applying to said plants an amount of a bactericidal / fungicidal composition consisting essentially of:20. - Método para controlar doenças provocadas por bactérias/fungos em plantas, caracterizado pelo facto de compreender a operação que consiste em aplicar âs citadas plantas uma quantidade de uma composição bactericida/fungicida que consis te essencialmente em: a copper complex and a partially neutralized water soluble polycarboxylic acid having a molecular weight of from about 1,000 to 300,000, said partially neutralized polycarboxylic acid having a pH of from about 3 to 9 when said polycarboxylic acid is under the aqueous solution form prior to complexation with said copper. um complexo de cobre e um ácido policarboxílico solúvel em água parcialmente neutralizado que tem uma massa molecular compreendida entre aproximadamente 1 000 e 300 000, tendo o referido ácido policarboxílico parcialmente neutralizado um pH compreendido entre aproximadamente 3 e 9 quando o mencionado ácido policarboxílico se encontra sob a forma de solução aquosa antes da complexaçao com o citado cobre.
- 2323 - Method according to. Claim 20, characterized in that said pH is between about 3.5 and 5. 23. - Método de acordo com a. reivindicação 20, caracterizado pelo facto de o citado pH estar compreendido entre aproximadamente 3,5 e 5.
- 3232 A method for controlling plant / bacterial disease in plants comprising the operation of applying to said plants a bactericidal / fungicidal composition consisting essentially of a copper complex and a partially water-soluble polycarboxylic acid. which has a molecular weight of approximately 1 000 to 300 000, said partially neutralized polycarboxylic acid having a pH of from about 3 to 9, when said polycarboxylic acid is in aqueous solution prior to complexation with said copper. 32. - Método para controlar doenças provocadas por bactérias/fungos em plantas, caracterizado-pelo facto de compreender a operação que consiste em aplicar às referidas plan tas uma composição bactericida/fungicida que consiste essencialmente em um complexo de cobre e um ácido policarboxílico solúvel em ãgua parcialmente neutralizado que tem uma massa molecular compreendida aproximadamente entre 1 000 e 300 000, tendo o mencionado ácido policarboxílico parcialmente neutralizado um pH compreendido entre aproximadamente 3 e 9, quando o citado ácido policarboxílico se encontra em solução aquosa antes da complexação com o referido cobre.
- 3333 A method for controlling plant / bacterial disease in plants comprising the operation of applying to said plants a bactericidal / fungicidal composition consisting essentially of a copper complex and a partially neutralized water-soluble polycarboxylic acid which has a molecular weight of approximately 1 000 to 33. - Método para controlar doenças provocadas por bactérias/fungos em plantas, caracterizado pelo facto de compreender a operaçao que consiste em aplicar ãs mencionadas plantas unia composição bactericida/fungicida que consiste essencialmente num complexo de cobre e um ácido policarboxíli co solúvel em água parcialmente neutralizado que tem uma massa molecular compreendida entre aproximadamente 1 000 e 300 000, said partially neutralized polycarboxylic acid having a pH in aqueous solution of about 3 to 9 when said polycarboxylic acid is in aqueous solution prior to complexation with said copper, said copper being derived from a copper compound. substantially water-insoluble from the group consisting of copper hydroxide, cupric oxide, tribasic copper sulfate, tribasic copper carbonate and copper oxychloride. 300 000, tendo o citado ácido policarboxílico parcialmente neu tralizado um pH em solução aquosa compreendido entre aproxima damente 3 e 9 quando o referido ácido policarboxílico se encontra em solução aquosa antes da complexaçao com o mencionado cobre, sendo o citado cobre derivado de um composto de cobre substancialmente insolúvel em água escolhido do grupo que consiste em hidróxido de cobre, óxido cúprico, sulfato de cobre tribásico, carbonato de cobre tribásico e oxicloreto de cobre.
- 34A method for controlling bacterial / fungal diseases in cultures, characterized in that it comprises the operation of applying to said cultures, after said cultures have been harvested, a bactericidal / fungicidal amount of a composition consisting essentially of in:34.- Método para controlar doenças provocadas por bactérias/fungos em culturas, caracetrizado pelo facto de compreender a operação que consiste em aplicar ãs referidas culturas, depois de as mencionadas culturas terem sido colhidas, uma quantidade bactericida/fungicida de uma composição que consiste essencialmente em: an aqueous solution of a copper complex and a partially neutralized water-soluble polycarboxylic acid having a molecular weight of approximately 1,000 to 300,000, said partially neutralized polycarboxylic acid having a pH value in aqueous solution of approximately 3 to 9 prior to complexation with said copper. uma solução aquosa de um complexo de cobre e um ácido policarboxílico solúvel em água parcialmente neutralizado que tem uma massa molecular compreendida entre aproximadamente 1 000 e 300 000, tendo o citado ácido policarboxílico parcialmente neutralizado um valor do pH em solução aquosa compreendido aproximadamente entre 3 e 9 antes da complexaçao com o referido cobre.
- 3535 Method for controlling diseases caused by bacteria / fungi in seeds, comprising the operation of applying to said seeds, before they are sown, a bactericidal / fungicidal amount of a composition consisting essentially of:35. - Método para controlar doenças provocadas por bactirias/fungos em sementes, caracterizado pelo facto de compreender a operaçao que consiste em aplicar ãs mencionadas sementes, antes de as mesmas serem semeadas, uma quantidade bactericida/fungicida de uma composição que consiste essencialmente em: an aqueous solution of a copper complex and a partially neutralized water soluble polycarboxylic acid having a molecular weight of from about 1,000 to 300,000, said partially neutralized polycarboxylic acid having a pH value in aqueous solution of about 3 and wherein said polycarboxylic acid is in aqueous solution prior to complexing with said copper. uma solução aquosa de um complexo de cobre e um ácido policarboxílico solúvel em água parcialmente neutraliza do que tem uma massa molecular compreendida entre aproximadamente 1 000 e 300 000, tendo o citado ácido policarboxílico parcialmente neutralizado um valor do pH em solução aquosa compreendido entre aproximadamente 3 e 9 quando o referido áci do policarboxílico se encontra em solução aquosa antes da com plexação com o mencionado cobre.
- 3636 A method for controlling bacterial / fungal diseases in ornamental plants, comprising the operation of applying to the foliage of the said ornamental plants a bactericidal / fungicidal amount of a composition consisting essentially of:36. - Método para controlar doenças provocadas por bactérias/fungos em plantas ornamentais, caracterizado pelo facto de compreender a operação que consiste em aplicar à folhagem das citadas plantas ornamentais uma quantidade bactericida/ fungicida de uma composição que consiste essencialmente em: an aqueous solution of a copper complex and a partially neutralized water soluble polycarboxylic acid having a molecular weight of from about 1,000 to 300,000, said partially neutralized tolicarboxylic acid having a pH value in aqueous solution of from about 3 and 9 when said polycarboxylic acid is in aqueous solution prior to complexation with said copper. uma solução aquosa de um complexo de cobre e um ácido policarboxílico solúvel em água parcialmente neutrali zado que tem uma massa molecular compreendida entre aproximadamente 1 000 e 300 000, tendo o referido ácido tolicarbo xílico parcialmente neutralizado um valor do pH em solução aquosa compreendido entre aproximadamente 3 e 9 quando o mencionado ácido policarboxílico se encontra em solução aquo sa antes da complexaçao com o citado cobre.
- 3737 A method for controlling bacterial / fungal diseases comprising the operation of applying to a substrate to be treated a bactericidal / fungicidal amount of a composition consisting essentially of:37. - Método para controlar doenças provocadas por bactérias/fungos, caracterizado pelo facto de compreender a operação que consiste em aplicar a um substrato a ser tratado uma quantidade bactericida/fungicida de uma composição que consiste essencialmente em: an aqueous solution of a copper complex and a partially neutralized water-soluble polycarboxylic acid having a molecular weight of approximately 1,000 to 300,000, said partially neutralized polycarboxylic acid having a pH value in aqueous solution of approximately 3 and 9 when said polycarboxylic acid is in aqueous solution prior to complexation with said copper. uma solução aquosa de um complexo de cobre e um ácido policarboxílico solúvel em água parcialmente neutralizado que tem uma massa molecular compreendida entre aproxima damente 1 000 e 300 000, tendo o referido ácido policarboxílico parcialmente neutralizado um valor do pH em solução aquo sa compreendido entre aproximadamente 3 e 9 quando o mencionado ácido policarboxílico se encontra em solução aquosa antes da complexaçao com o citado cobre.
- 3838 - Substantial non-phytotoxic bactericidal / fungicidal composition, characterized in that it consists essentially of:38. - Composição bactericida/fungicida substancial, mente não fitotóxica, caracterizada pelo facto de consistir essenciaLmente em: an aqueous solution of a copper complex and a partially neutralized water-soluble polycarboxylic acid having a molecular weight comprised of approximately 1 000 and 300 000, said polycarbonic acid having a carbon dioxide content. partially neutralized xyl an aqueous pH value of from about 3 to 9 when said polycarboxylic acid is in aqueous solution prior to complexation with said copper, said copper being derived from a compound selected from the group consisting of Cu (OH)2CuSO 4 Cu (ClO 4)2, Cu2O, Cu (NOg)2, CuCl2copper oxychloride, tribasic copper sulfate and basic copper carbonate;and an effective amount of a sticky compound that provides sufficient toughness to said copper complex to reduce rain removal from the plant surface. uma solução aquosa de um complexo de cobre e um ácido policarboxílico solúvel em água parcialmente neutrali zado que cem uma massa molecular compreendida encre aproximadamence 1 000 e 300 000, tendo o referido ácido policarbc? xílico parcialmente neutralizado um valor do pH em solução aquosa compreendido entre aproximadamente 3 e 9 quando o mencionado ácido policarboxílico se encontra em solução aquo sa antes da complexação com o citado cobre, sendo o referido cobre derivado de um composto escolhido do grupo que con siste em Cu(0H)2, CuSO^, Cu(ClO^)2, Cu2O, Cu(NOg)2, CuCl2, oxicloreto de cobre, sulfato de cobre tribãsico e carbonato de cobre básico;e uma quantidade eficaz de um composto pegajoso que proporciona uma tenacidade suficiente ao referido complexo de cobre para reduzir a remoção da superfície da planta por acção da chuva.
Independent claims12
314 paragraphs in 12 sections, as filed
REFERENCE TO RELATED PATENT APPLICATIONS This patent application is a partial continuation of U.S. Patent Application Serial No. 591,288, filed January 24, 1989.
FIELD OF INVENTION
The present invention generally relates to bactericidal and fungicidal compositions and more specifically to a bactericidal / fungicidal composition which is based on a copper complex and a partially neutralized polycarboxylic acid.
GENERAL BACKGROUND OF THE INVENTION
Bactericidal / fungicidal compositions which are agents used to protect agricultural crops against damage caused by pathogenic bacteria / fungi are known in the art. The use of these products is necessary due to the large losses caused by these microorganisms. To be economical, the cost of controlling plant diseases by applying bactericidal / fungicidal products must be offset by increased yield and crop quality.
Agricultural bactericidal / fungicidal compositions are available in different types of formulations including wettable powders, emulsifiable concentrates, water-based flowable products and dry flowable products (also known as water-dispersible granules).
Dry-flow products are generally free-flowing, dust-free granular products. As for. Dry-flowing formulations have recently gained popularity among users because they offer advantages such as substantial, improved shelf life: dust-free release, ease of dumping, higher percentage of active ingredient and more convenient packaging than other types of storage. formulations.
In agriculture, copper-based bactericidal / fungicidal compositions are used extensively. Various dry-flow copper-based bactericidal / fungicidal compositions are known in the art, including the following:
Kocide DF, available from Griffin Corporation of Valdosta, Georgina, United States of America; Blueshield
<img file="PT101248B_D0001.tif" />
DF and Nu-Cop WDG, available from Micro Wire Company of Lakeland, Florida, United States of America; and Sandoz COC DF and Sandoz Ci ^ O DF, available from Sandoz, Ltd., Switzerland.
Cupric hydroxide is itself unstable. However, it is known in the art that cupric hydroxide can be stabilized by a phosphate process. U.S. Patent No. Re. No. 24,324 (the information of which is incorporated herein by reference) relates to a process for the preparation of stable cupric hydroxide. U.S. Patent No. 3,428,731 (the indications of which are also incorporated herein by reference) relates to phosphate stabilized cupric hydroxide dispersions. Said patent discloses that aqueous dispersions of finely divided cupric hydroxide can be prepared by the phosphate process by carefully regulating the dispersion pH and the calcified hardness of the aqueous vehicle. The invention also discloses that approximately 1 to 3% by weight of a dispersing agent is added to the aqueous vehicle prior to the cupric hydroxide of the phosphate process. Suitable dispersing agents indicated include sodium bond sulfonate, sodium salt of a polymeric carboxylic acid, sulfonated naphthalene, technical protein colloid, tallow dimethyl benzylammonium alkyl chloride,
<img file="PT101248B_D0002.tif" />
polymerized 1-CH1-aryl-sulfonic acid sodium, diethanolamide of a special fraction of coconut fatty acids, condensed naphtho-1-mono-sulfonic acid sodium salt and iso-oct-1-phenyl-polyethoxy-ethane1.
Prior art copper-based bactericidal / fungicidal products require the use of relatively large amounts of copper to effectively control disease. This relatively high level of copper negatively contributes to product effectiveness, leads to soil residue problems and increases phytotoxicity potential. Furthermore, the processes used to manufacture these prior art products are not always cost effective.
Copper (II) ion complexes with partially neutralized polyacrylic acid and partially neutralized polymethacrylic acid in aqueous media are known. See, for example, F.Wall and S. Gill, Interaction of Cupric Ions with Polyacrylic Acid, J. Phys. Chem., Vol. 58, page 1128 (1954); A. Kotliar and H. Morawetz, Chelation of Copper (II) with polyacrylic and Polymethacry. Acid, J. American Chem. Soc., Vol. 77, page 3692 (1955). Until now, copper complexes with partially neutralized polycarboxylic acids have not been known to possess bactericidal or fungicidal properties. In particular, these
<img file="PT101248B_D0003.tif" />
complexes were not previously known to be made up. bactericidal or fungicidal compositions effective in agricultural use; Nor were they indicated to be substantially non-phytotoxic. Moreover, such complexes have not previously been known to be effective bactericidal or fungicidal compositions against copper tolerant bacteria.
Therefore, there was a need for a bactericidal / fungicidal copper-based formulation that provided biological activity particularly against copper tolerant bacteria, with virtually no phytotoxicity.
SUMMARY OF THE INVENTION
The present invention meets the needs described above by providing an improved bactericidal / fungicidal composition and an improved process for preparing and using it. The improved bactericidal / fungicidal compositions of the present invention are prepared by forming an aqueous solution of a partially neutralized water soluble polycarboxylic acid having a molecular weight of from about 1000 to 300,000 and a pH of from about 3 to 9. To this aqueous solution is added a copper-containing compound which, when combined with
With said aqueous solution releases copper (II) ions which form a water-soluble complex with said partially neutralized carboxylic acid.
The bactericidal / fungicidal composition according to the present invention is used to control bacterial / fungal diseases in plants by applying to the plants a bactericidal / fungicidal composition consisting essentially of. in a copper complex and a partially neutralized water soluble polycarboxylic acid having a molecular weight of from about 1000 to 300,000 and a pH of from about 3 to 9.
Accordingly, an object of the present invention is to provide an improved bactericidal / fungicidal composition and an improved process for preparing and using it.
Another object according to the present invention is to provide a bactericidal / fungicidal composition which is substantially non-phytotoxic to the plants to which it is applied.
A further object of the present invention is to provide a bactericidal / fungicidal composition which may be prepared from a variety of different types.
<img file="PT101248B_D0004.tif" />
sources of copper.
Yet another object of the present invention is to provide a bactericidal / fungicidal composition that can be used to control copper tolerant bacteria.
A still further object of the present invention is to provide a bactericidal / fungicidal composition that can be used in plants and crops that are attacked by conventional copper-based bactericidal / fungicidal agents when used in optimal proportions for disease control.
Yet another object of the present invention is to provide a bactericidal / fungicidal composition that is substantially water soluble, so that it can be removed relatively simply from the crops or plants to which it is applied and can thus be applied to crops almost at the end of the period. growth cycle and / or after harvest.
Another object of the present invention is to provide a bactericidal / fungicidal agent that leaves no stained residues on the crops or plants to which it is applied.
<img file="PT101248B_D0005.tif" />
Another object of the present invention is to provide a bactericidal / fungicidal agent which is useful in foil applications for disease control.
Still another object of the present invention is to provide a bactericidal / fungicidal composition which requires a smaller amount of copper usage to obtain the same level of protection as that provided by copper hydroxide bactericidal / fungicidal compositions.
Another object of the present invention is to provide a bactericidal / fungicidal composition that can be used to pre-treat seeds prior to seeding.
Another object of the present invention is to provide a bactericidal / fungicidal composition that controls the growth of bacteria and / or fungus on substrates of various materials.
These and other specific objects, features and advantages of the present invention will be apparent from the following detailed description of the described embodiments and the accompanying drawings and claims.
<img file="PT101248B_D0006.tif" />
BRIEF DESCRIPTION OF DRAWINGS
Figure 1 graphically depicts copper concentration versus pH of neutralized polyacrylic acid at 1 wt% (solids) concentration for three different copper ion sources.
Figure 2 graphically depicts the copper concentration versus pH of neutralized polycarboxylic acids at a concentration of 1 wt% (solids) for three different polycarboxylic acids.
Figure 3 graphically represents the change in copper concentration versus neutralized polycarboxylic acid (solids) concentration for three different polycarboxylic acids.
Figure 4 is a graphical representation of the change in copper concentration as a function of pH of neutralized polycarboxylic acid solutions for three different polyboxylic acids.
Figure 5 is a graphical representation of the variation in copper concentration versus pH of neutralized polyacrylic acid for three different neutral agents.
<img file="PT101248B_D0007.tif" />
Figure 6 is a graphical representation of the variation in Alternaria solani colony diameter (mm) versus copper concentration (ppm) for three different copper sources.
DETAILED DESCRIPTION OF EMBODIMENTS OF THIS
INVENTION
The present invention relates to an improved agricultural bactericidal / fungicidal formulation and a process for the preparation of a copper-based bactericidal / fungicidal composition. The novel product according to the present invention offers better biological activity over typical copper based products, while significantly requiring less copper in its formulation. 0 Lower copper content reduces the contribution of the bactericidal / fungicidal formulation to soil copper accumulation. Bactericidal / fungicidal compositions according to the present invention are also substantially non-phytotoxic to the plants to which they are applied; particularly in comparison. with other water-soluble copper formulations.
A bactericidal / fungicidal formulation according to the present invention may be prepared by the following process steps. An aqueous solution of an acid
<img file="PT101248B_D0008.tif" />
of the polycarboxylic acid by combining with water a water soluble polycarboxylic acid. As used herein, the term polycarboxylic acid means both homopolymers and copolymers of carboxylic acids. The aqueous solution of polycarboxylic acid is then partially neutralized with a basic material. To the aqueous solution of the water-soluble partially neutralized polycarboxylic acid, a copper-containing compound is added which, when added to the aqueous solution, liberates copper (II) ions (or cupric ions) that react with the partially neutralized polycarboxylic acid to It forms a complex. The resulting copper complex is substantially completely soluble in water.
As referred to herein, the weights of copper and polycarboxylic acid used as components are expressed as percent by weight in aqueous solution (unless specifically stated otherwise). Bactericidal / fungicidal compositions according to the present invention may also be prepared as dry compositions by drying the composition after complexing into the aqueous solution. Obviously, when water is removed from the aqueous solution of the copper complex, the weight percentages of copper and polycarboxylic acid change. However, these changes can easily be calculated by those skilled in the art on the basis of the
<img file="PT101248B_D0009.tif" />
weight percentages of the components present in the aqueous solution.
Polycarboxylic acids which are useful in the process according to the present invention include water soluble polycarboxylic acids which have molecular masses of from about 1000 to 300,000, preferably from about 2000 to 50,000. The exact structure of the polycarboxylic acid is not critical to the present invention.
Examples of polycarboxylic acids which are useful in accordance with the present invention include polyacrylic acid, polymethacrylic acid, acrylic acid and acrylamide copolymers, acrylic acid and methacrylamide copolymers, acrylic acid copolymers and acrylate esters, acrylic acid copolymers and methacrylic acid, acrylic acid and methacrylate esters copolymers, acrylic acid and maleic anhydride copolymers, carboxymethylcellulose, maleic acid and butadiene copolymers, maleic acid and maleic anhydride polymers, maleic acid and acrylic acid copolymers, and methyl vinyl ether and maleic anhydride copolymers.
Polycarboxylic acids which in themselves are not water soluble may also be useful according to the present invention by transforming the water insoluble polycarboxylic acid into a water soluble salt of the polycarboxylic acid.
<img file="PT101248B_D0010.tif" />
co. The techniques by which these salts are prepared are well known to those skilled in the art. Generally speaking, however, such salts are prepared by reacting polycarboxylic acid with basic materials such as sodium hydroxide; Potassium hydroxide; NaHCO3; Na2 CO0; NH4 OH, R<sub>4</sub>N<sup>+</sup>Wherein R is CH 2 or C 2 H 5; primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine, t-butylamine; secondary amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine; and tertiary amines, such as trimethylamine, triethylamine and tri-n-propylamine.
There is no particular upper limit to the concentration of polycarboxylic acid present in aqueous solutions. Polycarboxylic acid may be added to water to form a solution thereof in amounts sufficient to react with and form a complex containing it. However, as the concentration of polycarboxylic acid increases, the viscosity of the solution also increases. This is particularly true for high molecular weight polycarboxylic acids. In general, it is not desirable for the viscosity of the aqueous solution to be too high to effectively mix with the copper-containing compound.
Practically speaking, polycarboxylic acid concentrations useful in the process according to the present invention
<img file="PT101248B_D0011.tif" />
from about 0.2 wt% to 80 wt%, preferably from about 0.75 wt% to 20 wt%.
When polycarboxylic acid combines with water to form a solution, the solution generally has an acidic pH. It is a critical aspect of the present invention that polycarboxylic acid be partially neutralized with a basic material such that the pH of the solution is from about 3 to 9, preferably from about 3.5 to 5. Generally, it has been observed that the amount of copper that can be complexed with a partially neutralized polycarboxylic acid depends, at least in part, on the pH of the partially neutralized polycarboxylic acid aqueous solution.
The concentration of copper in the complex reaches a maximum of the above pH values. Outside the pH range of 3 to 9, the amount of copper that complexes with partially neutralized polycarboxylic acid is hardly useful.
The nature of the basic material that is used to neutralize polycarboxylic acid is not critical to the process according to the present invention. Suitable neutralizing agents include sodium hydroxide; water
Potassium oxide; NaHCOg; Na ^ CO ^; NH4 OH, R<sub>4</sub>N<sup>+</sup>Wherein R is CH 2 or C 2 H 4; primary amines such as methylamine, ethylamine, n-propylamine, iso-
<img file="PT101248B_D0012.tif" />
propylamine, t-butylamine; secondary amines such as dimethylamine, diethylamine, di-n-propylamine and diisopropylamine; and tertiary amines such as trimethylamine, triethylamine and tri-n-propylamine.
The resulting partially neutralized polycarboxylic acid is a combination of a polycarboxylic acid copolymer and a polycarboxylic acid salt, such as sodium polyacrylate. Suitable partially neutralized polycarboxylic acids are commercially available. These products include Goodrite K-752, available from BF Goodrich Co. of Cleveland, Ohio, United States. Goodrite K-752 is a polyacrylic acid partially transformed into sodium salt in water having the formula (C<sub>3</sub>H<sub>4</sub>0<sub>2</sub>)<sub>χ</sub>(Ç<sub>3</sub>H<sub>3</sub>No<sub>2</sub> )<sub>y</sub> ; and DP6-2696 and DISPEX No. 40 are both aqueous polymeric carboxylic acid salts sold by Allied Colloids, Inc. of Suffolk, Virginia, United States of America.
Copper-containing compounds useful in accordance with the present invention are compounds which, when combined with a partially neutralized aqueous solution of polycarboxylic acid, provide copper (II) ions which
<img file="PT101248B_D0013.tif" />
complex with partially neutralized polycarboxylic acid. Copper-containing compounds useful in accordance with the present invention include Cu (OH)<sub>2></sub> CuS0<sub>4</sub>CuíClO ^^, C u £O 0, Cu (NO0)<sub>3</sub>) 2 'CuCl2, copper oxychloride, basic copper carbonate and tribasic copper sulfate. Copper oxychloride has the chemical formula 3 Cu (OH) CuCl;
basic copper carbonate has the chemical formula Cu (OH) .CuCO3; and tribasic copper sulphate has the chemical formula 3Cu (OH) 2-CuS0<sub>4</sub>.
Copper containing compounds may be either water soluble, such as CuS0<sub>4</sub>Cu (C10)<sub>4</sub>) 2> Cu (NO<sub>3</sub>)<sub>2</sub> and CuC ^, or substantially water-insoluble, such as CuOH ^, Cu<sub>2</sub>O, tribasic copper sulfate, basic copper carbonate and copper oxide chloride. Water-insoluble copper-containing compounds to date were not known to form complexes.
Copper hydroxide compounds which are useful in the process according to the present invention include both technical (phosphate stabilized cupric hydroxide) using the process described in U.S. Patent Nos. 24,324 and 3,428,731, the memories of which are described in FIG. These are both herein incorporated by reference) and copper hydrate, a purer form of copper hydroxide. Other stabilized forms of copper hydroxide may also be used.
<img file="PT101248B_D0014.tif" />
Copper-containing compounds useful in accordance with the present invention are commercially available. These commercially available products include Kocide'- 'cupric hydroxide, an agricultural fungicide phosphate stabilized cupric hydroxide formulation containing 88% copper hydroxide and 12% inert available from Griffin Corporation of Valdosta, Georgia, United States.
States of America. Processes for the preparation of phosphate stabilized cupric hydroxide are also disclosed in U.S. Patent Nos. 3,428,731 and Re. 24,324.
The amount of the copper-containing compound that is added to the partially neutralized aqueous solution of polycarboxylic acid is an amount that is useful in the final product as a bactericide / fungicide. Generally speaking, in the manufacture of the bactericidal / fungicidal composition according to the present invention, it is desirable to complex the largest possible amount of copper with partially neutralized polycarboxylic acid. Factors affecting the amount of copper that can be complexed with partially neutralized polycarboxylic acid are the pH of the partially neutralized polycarboxylic acid aqueous solution, the molecular weight of the partially neutralized polycarboxylic acid and the concentration of the partially neutralized polycarboxylic acid.
<img file="PT101248B_D0015.tif" />
Generally, it has been observed that when there is an excess of the water-insoluble copper-containing compound that reacts to complex polycarboxylic acid, the excess of the copper-containing compound does not dissolve in the aqueous solution. This may or may not be an undesirable situation. If the water-insoluble copper-containing solid compound is not desired in the composition according to the present invention, it may be separated from the liquid by conventional means such as filtration. An excess of water-soluble copper-containing compound results in the presence of uncomplexed copper ions in the solution. These uncomplexed copper ions in solution can make the solution phytotoxic. Therefore, when the copper source to complex with partially neutralized polycarboxylic acid comes from a water-soluble copper-containing compound, the amount of this copper-containing compound that is used should be sufficient to react with the carboxylic acid. but not an amount that produces an excessive amount of uncomplexed copper ions that may render the solution phytotoxic.
The copper amounts of the copper-containing compound which are useful in accordance with the present invention are from about 0.1 wt% to 5 wt% (metal copper equivalent); preferably between about 0.1 wt% and 3.2 wt% (equivalent of
<img file="PT101248B_D0016.tif" />
metallic copper).
The aqueous copper complex solution may be used to treat plants in their liquid form as produced by the process described above or may optionally be dried to provide substantially dry solids which may be redispersed in water to form aqueous solutions for application by water. pulverization. The aqueous solution of the copper complex may be dried in conventional drying equipment, such as a kiln dryer or spray dryer, or by freeze drying techniques. For spray drying, a single fluid injector spray dryer, hydraulic injector or rotary disc atomizer may be used. Such a spray dryer should typically have an inlet temperature of approximately 176.7 ° C to 248.9 ° C (approximately 350 ° F to 480 ° F) and an outlet temperature of approximately 65.60 ° C to 126.7 ° C (approximately 150 ° F and 260 ° F). Spray drying equipment and dispersion and solution spray drying techniques are well known in the art. Similarly, freeze drying equipment and techniques for freeze drying of dispersions and solutions are known in practice. Using techniques known to those skilled in the art, the bactericidal / fungi composition can be prepared.
<img file="PT101248B_D0017.tif" />
pesticide according to the present invention in various forms such as flakes, powders, granules, tablets and solutions.
Bactericidal / fungicidal compositions according to the present invention may be applied directly to plant leaves to control bacterial / fungal diseases. The bactericidal / fungicidal composition is applied in its liquid form as prepared by proces. They are described above or by mixing the dry form with water to re-form an aqueous solution and spray the resulting solution onto the plants to be treated using conventional agricultural sprayers and spraying techniques known to those skilled in the art. The bactericidal / fungicidal composition according to the present invention in liquid form is preferably diluted with water and applied to plant leaves by spraying or (aerial or on the ground) or by chemigation with an application rate of approximately from 0.112 to 6, 72 Kg / Hectare (0.1 and 61 lbs per acre) of metallic copper equivalent in a water volume of approximately 9.35 to 7450 liters per hectare (1 and 800 gallons per acre).
Bactericidal / fungicidal compositions according to the present invention are useful in treating bacterial and fungal diseases in various plants including citrus fruits such as grapefruit, lemon, lime, orange,
<img file="PT101248B_D0018.tif" />
and mandarin orange; field crops such as alfalfa, oats, groundnuts, potatoes, sugar beets, wheat and barley;
small fruits such as blackberry, cranberry, blackcurrant, blackcurrant, raspberry and strawberry; arable crops such as almond, apple, apricot, avocado, banada, cocoa, cherry, coffee, hazelnut, mango, nectarine, olive, peach, pear, pecan, plum, prune and walnut; vegetables such as beans, Brussels sprouts, broccoli, sprouts, cantaloupe, carrots, cauliflower, celery, cauliflower, cucumber, aubergine, manna, melon, onion, pea, bell pepper, pumpkin, pumpkin-girl, tomato and watermelon; climbing plants such as grapes, hops and kiwi; miscellaneous, such as ginseng, charcoal and sycamore; and ornamental plants such as aralia, azalea, begonia, bulbs (Easter-lilies), tulip, gladiolus), carnations, chrysanthemums, cotoneaster, eponym, hawthorn, paquissandra, congossa, philodendron, piracanth, pink and yucca (Adams-Need1e).
Bactericidal / fungicidal agent according to the present invention is useful in the treatment of plants with bacterial or fungal diseases such as melanose, crust, red spot, brown spot greasy stain, phytophthora attack, citrus cancer, xanthomonas leaf spotting and by ceróspora, black leaf spot (alternaria), alternaria rust, botrytis rust, powdery mildew,
<img file="PT101248B_D0019.tif" />
leaf spot caused by xanthomonas, anthracnose, leaf spot caused by pseudomonas, leaf spot caused by septory, leaf spot caused by entomosporium, leaf rust caused by volutella, stem rust caused by phomopsis, leaf spot caused by bacteria, fire-colored rust, black spot, leaf wrinkling, coryneum (stem hole) rust, inflorescence rust, fer. roar caused by pseudomonas, bark and center rot (Phytophthora cactorum), zoned leaf spot (Cris_ tulariella pyramida 1is), chestnut rust, bacterial rust (with halo and common), brown spot, black rot ( xantomonas), downy mildew, early rust caused by cercospora, late septory rust, angular leaf spot, phomopsis, large purple spot, small spot caused by bacteria, gray leaf mold, septoria leaf spot, dead bud (Pseudomonas syringae), Erwinia herbicola, Pseudomonas fluorescens, stem rust, spherical moss, leptosphaerulina leaf spot, large helminthosporium spot, leaf spot , sugarcane stain, fruit rot, flower chestnut rot, bacterial rust (pseudomonas), European cancer, crown or paste rot, sigatoca, black spots, black pods, coffee berry disease (Co11ectrotrichum coffeanum), tree rust
<img file="PT101248B_D0020.tif" />
leaf (Hemileia vastatrix), iron stain (Cercospora Cojf feicola), red disease (Corticum salmonicolor), western hazel rust and peacock spot.
Certain strains of bacteria have become resistant to conventional copper-based bactericidal treatments. However, bactericidal / fungicidal agents according to the present invention are especially well suited for controlling copper tolerant bacteria such as Xanthomonas campestris and Pseudomonas syringae.
Since the bactericidal / fungicidal agent of the present invention is water soluble, it can be applied to various plants and crops and then relatively simply removed by washing or spraying with water. Accordingly, the bactericidal / fungicidal agent according to the present invention may be applied to cultures later in their growth cycle than would be possible with conventional bactericidal / fungicidal agents. In addition, bactericidal / fungicidal agents according to the present invention may also be used to treat postharvest crops such as oranges, citrus fruits, cucumbers and apples to provide a protective barrier that can be easily removed by washing.
-24/
<td></td><td></td>
<td>The agents</td><td>bactericides / fungicides according to</td>
present invention when applied to plants and then dried on them where they leave a colored residue on the plants, as with conventional copper-based bactericidal / fungicidal agents. Accordingly, the bactericidal / fungicidal agents of the present invention may be used to treat crops in nurseries and ornamental greenhouse plants.
The reduced phytotoxicity of the bactericidal / fungicidal agents according to the present invention allows them to be used to treat copper sensitive plants and crops such as peaches, pears, apples and lettuces that would otherwise be harmed by the bactericidal agents. conventional copper-based fungicides when they are used at optimal doses for disease control.
Bactericidal / fungicidal agents according to the present invention may also be used to treat seeds before they are sown. Bactericidal / fungicidal agents may be applied to seeds using conventional seed treatment equipment known in the art by spraying the bactericidal / fungicidal agents onto the seeds and allowing them to dry, thereby providing a coating on the seed. In addition, the treated seed can be handled and sown in the manner
<img file="PT101248B_D0021.tif" />
for seed which has been treated with known conventional copper-based bactericidal / fungicidal agents. The bactericidal / fungicidal agents of the present invention are particularly useful in controlling seed-borne inoculum and preventing germinating seedling infection. While the bactericidal / fungicidal agents of the present invention may be useful in seed treatment, they are generally particularly useful in the treatment of seed from crops such as rice, wheat, cotton, soybeans, beans, corn and peanuts.
Enhanced retention of bactericidal / fungicidal agents according to the present invention on plant surfaces after exposure to rain may be accomplished by adding certain functional agents to the concentrated composition or spray solution. These compounds which are useful in accordance with the present invention include (but are not limited to) polyvinyl pyrrolidone (PVP), polyoxyethylene, polyvinyl alcohol and polyacrylamide. These compounds are known in the art as sticky compounds. The sticky compounds are added in an amount that provides the desired degree of rain resistance without unduly affecting the bactericidal / fungal properties of the copper complex solution. Generally, amounts of the adhesive compound that are added to the copper complex solution and which are useful herein
<img file="PT101248B_D0022.tif" />
invention are between 0.1% and 10% by weight.
The amount of copper that can be complexed with a partially neutralized polycarboxylic acid has been found to be related to the molecular weight of the carboxylic acid. Generally, the larger the molecular weight of polycarboxylic acid, the more copper can be complexed with it. As stated above, however, as the molecular weight of polycarboxylic acid increases, it simultaneously increases viscosity.
Accordingly, in choosing polycarboxylic acid for use in accordance with the present invention, the competitive factors of copper content and viscosity must be balanced with each other.
It is specifically contemplated that the bactericidal / fungicidal agent of the present invention may also be used to treat different substrates of plants and crops.
For example, the bactericidal / fungicidal agents of the present invention may be used to protect against bacterial and / or fungal growth on or on various non-living substrates such as textiles, plastics, metals, glass, wood, paper , foams, concrete, stone and the like. Bactericidal / fungicidal agents according to the present invention may be applied to the surface
<img file="PT101248B_D0023.tif" />
substrate by processes known in the art, such as spraying, painting, dipping and the like. In addition, for appropriate materials, the bactericidal / fungicidal agents according to the present invention may be impregnated. on the substrate. Bactericidal / fungicidal agents according to the present invention may be used to prevent the growth of bacteria and fungi in hospital or medical environments, such as suits, white clothing, carpets, floors, tiles or linoleum and plastic counter surfaces. For these applications, the copper complex according to the present invention is applied at a rate sufficient to prevent or inhibit the growth of bacteria and / or debris on the treated surface. The application rate of the copper complex varies depending on the type of material to which it is applied and the conditions to which the substrate is subjected. Generally, the bactericidal / fungicidal agent according to the present invention is applied to substrates at a rate that provides from about 1 to 1000 mg of copper (metal equivalent) per square centimeter of substrate surface.
The following examples illustrate the present invention and are not intended to limit its scope as set forth in the appended claims.
<img file="PT101248B_D0024.tif" />
EXAMPLES
Example 1
An aqueous solution is prepared by combining 959 grams of water and 40 grams of Goodrite K-752 (a 63% solution in water of 2100 molecular weight polyacrylic acid), which is neutralized to pH 7 with a 50% NaOH solution. The solution is mixed at room temperature to ensure complete dissolution of the partially neutralized Goodrite K-752 in water. To this solution is added 1.42 grams of Cu (OH)<sub>2</sub> (56.4% metallic copper).
The mixture is stirred for twelve to twenty four hours to ensure complete dissolution of Cu (OH)<sub>2</sub>. The resulting clear blue solution is analyzed for copper content. Analysis shows that the aqueous solution contains 800 ppm copper.
Example 2
An aqueous solution of Goodrite K-752 at pH 4.5 is prepared by dissolving 113.4 grams of Goodrite K-752 in 433.8 grams of water and neutralizing with 21.4 grams of 50% NaOH. Partially neutralized Goodrite K-752 is added to 789 grams of water and stirred until the solution is homogeneous.
<img file="PT101248B_D0025.tif" />
To this solution is added 32.3 grams of copper hydrate (62% metallic copper).
The mixture is stirred for twelve to twenty four hours to ensure complete dissolution of the copper hydrate. The resulting clear blue solution contains 2% by weight of equivalent metallic copper.
Example 3
An aqueous solution is prepared by combining 940 grams of deionized water and 60 grams of Goodrite K-752 (63% solution in water of a 2100 mole mass polyacrylic acid), which is neutralized with sodium hydroxide only. . 50% at about pH 7. The solution is mixed at room temperature to ensure complete dissolution of Goodrite K-752 in water. To the partially neutralized aqueous solution of Goodrite K-752 is added 10 grams of CuOH. The aqueous dispersion is then mixed over a period of twenty-four to forty-eight hours to provide sufficient time for complete reaction of copper hydroxide with partially neutralized polyacrylic acid. Since copper hydroxide is substantially insoluble in water, excess undissolved copper hydroxide remains in solid form in the dispersion. The dispersion is then filtered to separate the liquid phase from solid copper hydroxide.
<img file="PT101248B_D0026.tif" />
using a 0.20 micrometer filter.
The filtrate is then analyzed for its copper content. Analysis shows that the aqueous solution contains 1270 ppm Cu (metal equivalent).
Example 4
An aqueous solution is prepared by combining 989 grams of water with 10 grams of Goodrite K-752 (a 63% water solution of a 2100 molecular weight polyacrylic acid) which is neutralized with 50% sodium hydroxide to a pH of approximately 7. The solution is mixed at room temperature to ensure complete dissolution of Goodrite K-752 in water. To the partially neutralized aqueous solution of Goodrite K-752 is added 1.0 gram of CuSO4. The mixture is stirred for a period of thirty minutes to ensure complete dissolution of copper sulfate. The solution is then analyzed for its copper content. Analysis shows that the aqueous solution contains 800 ppm Cu (metal equivalent). The solution is tested for biological activity and found to have essentially no phytotoxicity similar to conventional aqueous dispersions at an equal level of copper content. Equal levels of ionic copper from copper sulphate result in severe plant damage and necrosis.
-31Example 5
An aqueous solution is prepared by combining 1000 grams of water with 20 grams of Goodrite K-752 (a polyacrylic acid having a molecular weight of approximately 2100).
The solution is mixed at room temperature to ensure complete dissolution of Goodrite K-752 in water. To this solution, sufficient copper hydroxide is added to partially neutralize Goodrite K-752 to a pH of approximately 7. The neutralized aqueous solution of Goodrite K-752 is added with 2 grams of CuC3. . The mixture is stirred for a period of thirty minutes to ensure complete dissolution of the cupric chloride. The solution is then analyzed for copper content. Analysis shows that the aqueous solution contains 1000 ppm Cu (metal equivalent).
Example 6
An aqueous solution is prepared by combining 960 grams of water with 40 grams of Goodrite K-752 (a 63% water solution of a 2100 molecular weight polyacrylic acid) which is neutralized with 50% sodium hydroxide until a pH of approximately 7 is obtained.
The solution is mixed at room temperature to ensure
-32th complete dissolution of Goodrite K-752 in water. The solution
<img file="PT101248B_D0027.tif" />
Partially neutralized aqueous solution of Goodrite K-752 is added 10 grams of copper oxychloride. The aqueous dispersion is mixed over a period of twenty-four to forty-eight hours to provide the time required for copper to be complexed with the polymer. Since copper oxychloride is substantially insoluble in water, excess copper oxychloride remains essentially in solid form within the dispersion. The dispersion is then filtered to separate the liquid phase from solid copper hydroxide using a 0.20 micrometer filter. The filtrate is then analyzed for copper content.
Analysis shows that the aqueous solution contains 325 ppm Cu (metal equivalent).
Example 7
A series of six samples is prepared containing
800 copper ppm (4 χ the lethal dose DL<sub>go</sub> calculated from 200 ppm for control of Col letotrichum lagenarium in cucumber plants) from copper sulfate. Copper is complexed into partially neutralized aqueous solutions of polycarboxylic acid (Goodr K-752) to pH 7 with sodium hydroxide. The different samples contained the following polymer concentrations: 4%, 2%, 1%, 0.75%, 0.5% and 0.25%. Samples containing 4%, 2% and 1% polymer
<img file="PT101248B_D0028.tif" />
have yielded transparent blue solutions, although the color becomes greener as the polymer content decreases. In the case of a polymer content of less than 0.75%, a green-blue precipitate forms which gives a higher colorless aqueous phase. Excess copper is assumed to have caused the polymer to become insoluble, possibly by crosslinking. Samples containing between 4% and 0.75% polymer do not have substantially phytotoxicity relative to greenhouse cucumbers, while samples containing 1% and 0.75% polymer have the minimum phytotoxicity ratio. These samples also have efficacy as bactericidal / fungicidal agents against Co11etotrichum lagenarium in cucumber plants. Cucumber plants treated with the same rate of free ionic copper from copper sulfate were severely damaged and even necrotic. Plants treated with copper sulfate could not be evaluated for efficacy due to the severe damage they suffered.
Example 8
Copper complexes of polycarboxylic acids according to Examples 1 and 4 described above are prepared using CuSO 4 and Cu (OH) separately.<sub>2</sub> as sources of copper. Samples are prepared from each copper source with concentrations of 800, 400, 200 and 100 ppm copper (metal equivalents). A phytotoxicity test is performed
<img file="PT101248B_D0029.tif" />
cumulative quality in tomato plants and pepper plants. Each sample is applied to the plants four times at weekly intervals. No phytotoxicity of any species is observed.
Example 9
Copper complexes of polycarboxylic acids are prepared according to the procedure described in Example 1, with the difference that the molecular weight of the polyacrylic acid as well as the pH of the partially neutralized polyacrylic acid varies for different samples. Several polyacrylic acid samples with different molecular masses are obtained from BF Goodrich. These samples are as follows: Goodrite K-752 (molecular mass 2100); Goodrite K-732 (molecular mass 5100); Goodrite K-XP82) (molecular mass 2800); and Goodrite K-XP83 (molecular weight 5800). Aqueous solutions of the polymer are prepared; Each solution contains 1.6% polymer solids. The samples are neutralized with sodium hydroxide until the pH values given below are obtained. Copper complexes are prepared from each neutralized sample using excess amounts of Cu (OH)<sub>2</sub>Samples are filtered through a 0.22 micrometer syringe filter and analyzed for copper content. The results obtained are shown in Table 1.
<img file="PT101248B_D0030.tif" />
Following.
TABLE 1 <sub>f</sub> Solution pH
Polyacrylic Acid (PAA) Cu Filtered Complex NaPAA pH (ppm)
<td>Goodri te</td><td>K-752</td><td> 5,0</td><td> 6,9</td><td> 2940</td>
<td>Goodrite</td><td>K-752</td><td> 5,7</td><td> 7,6</td><td> 1320</td>
<td>Goodrite</td><td>K-752</td><td> 6,7</td><td> 9,2</td><td> 503</td>
<td>Goodrite</td><td>K-752</td><td> 7,0</td><td> 9,5</td><td> 500</td>
<td>Goodrite</td><td>K-752</td><td> 7,6</td><td> 9,9</td><td> 770</td>
<td>Goodrite</td><td>K-732</td><td> 5,0</td><td> 7,0</td><td> 3086</td>
<td>Goodrite</td><td>K-732</td><td> 5,5</td><td> 8,0</td><td> 2840</td>
<td>Goodrite</td><td>K-732</td><td> 6,0</td><td> 8,6</td><td> 1095</td>
<td>Goodrite</td><td>K-732</td><td> 6,6</td><td> 9,5</td><td> 444</td>
<td>Goodrite</td><td>K-732</td><td> 7,1</td><td> 9,8</td><td> 795</td>
<td>Goodrite</td><td>K-732.</td><td> 7,6</td><td> 10,0</td><td> 200</td>
<td>Goodrite</td><td>K-XP82</td><td> 7,1</td><td> 9,7</td><td> 119</td>
<td>Goodrite</td><td>K-XP83</td><td> 7,1</td><td> 9,7</td><td> 217</td>
As can be concluded from the values in Table 1, although there is considerable variation in results, pH clearly has a much more significant effect on the amount of copper that can be complexed than the molecular mass in this range between 2100 and 5800. .
<img file="PT101248B_D0031.tif" />
Additional samples were prepared as described above using three different polymers and copper hydrate as the copper source. The three polymers that have been used are: Goodrite K-752 (2100 molecular weight polyacrylic acid); Colloid WJ61 (60,000 molecular weight polyacrylic acid) available from Rhône-Pou1enc and Colloid 204 (10,000 molecular weight polyacrylic acid) also available from Rhône-Poulenc. The results of this comparison are shown in Figure 2, where the concentration of copper (metal equivalent) as a function of neutralized polymer pH at 1 wt% polyacrylic acid solids concentration for the three different polymers is plotted.
Also, as can be seen from Figure 2, the dominant factor over the amount of complexed copper is the pH of the neutralized polymer, but the larger molecular complex polymer (Colloid WJ61) significantly more copper than the other polymers. in the pH range from 3.5 to 6.
Using the same copper complex solutions described above, the amount of copper complexed is determined for solutions where the pH of partially neutralized polycarboxylic acid is optimal for complexing copper and the amount of polymer varied between 1% and 10% by weight
<img file="PT101248B_D0032.tif" />
of polyacrylic acid solids. The results of this assay are shown in Figure 3, where the amount of copper is plotted against polymer concentrations for each of the three different polymers.
Example 10
Copper complexes of polycarboxylic acid according to Example 3 are prepared, except that the pH of the partially neutralized polyacrylic acid in the different samples is varied. Complexes are formed by preparing aqueous solutions containing 1% by weight of polymer solids of a polyacrylic acid (Goodrite K-752), which are partially neutralized using sodium hydroxide to give pH values of from about 3 to about 8. 5 Excess copper amounts from three different copper sources are then added to the partially neutralized polymer solutions. One source is technical cupric hydroxide (phosphate stabilized using the process described in U.S. Patent Nos. 24,324 and 3,428,731); another source is copper hydrate (a purer form of hydroxide); The third source is basic cupric carbonate. The liquid parts are separated from the samples of the copper-containing solid compounds and the liquid parts are analyzed.
<img file="PT101248B_D0033.tif" />
re1 actively to its copper content. The results of the tests are plotted in Figure 1, where the concentration of copper (metal equivalent in ppm) as a function of pH of neutralized polymer solutions for each of the various samples is plotted.
From the graph it can be concluded that when technical cupric hydroxide is used as a copper source, the maximum amount of copper that can be complexed occurs at a pH of approximately 4.5. However, when copper hydrate is used as a copper source, the maximum copper complexation is at approximately the same pH value but approximately 35% more copper can be complexed using the same amount of polyacrylic acid. Impurities present in the technical cupric hydroxide, most likely the residual salts, apparently affect the ability of the copper complex polymer.
Example 11
Copper complexes of polyacrylic acid are prepared from various copper sources by adding copper containing compounds to the partially neutralized 4% aqueous Goodrite K-752 solutions to pH 7 using sodium hydroxide. Samples are prepared according to the procedures described in Examples 3 and 4, depending on whether the copper is water soluble or water insoluble.
<img file="PT101248B_D0034.tif" />
Copper sources used to prepare the complexes are cupric chloride, copper oxychloride, cuprous oxide and basic copper carbonate. All copper sources formed complexes with partially neutralized polyacrylic acid.
Example 12
A copper polyacrylic acid complex is prepared by adding 1.5% copper (metal equivalent) of cupric hydroxide to a 12% by weight aqueous solution of partially neutralized Goodrite K-752 polymer solids to pH to 4.8 using sodium hydroxide.
The mixture is stirred for approximately twelve hours to give a clear dark blue solution without undissolved cupric hydroxide. The solution is then lyophilized at -50 ° C using a Labconco lyophilizer under vacuum. The resulting product is a blue honeycomb friable solid which easily dissolves again in water to give a bluish-green solution. The dry product contains 8.57% copper and 5% water. 0 X-ray powder diffraction spectrum shows no peaks. This indicates that the dry copper complex does not have a crystalline structure.
<img file="PT101248B_D0035.tif" />
Example 13
Copper complexes of polyacrylic acids (obtained from Polysciences) having various molecular masses are prepared by adding excess amounts of copper from cupric hydroxide and a 1% by weight aqueous solution of the partially neutralized polymer at a pH of 5 (neutralized using sodium hydroxide). The liquid phase is separated from the solid cupric hydroxide by filtration and the active liquid phase is actively analyzed for its copper content. 0 Table 2 below shows the maximum amount of copper complexed by these samples.
TABLE 2
<td>Molecular mass</td><td>Cu concentration (ppm)</td>
<td> 2.000</td><td> 2330</td>
<td> 5.000</td><td> 2730</td>
<td> 50.000</td><td> 3500</td>
<td> 90.000</td><td> 3530</td>
<td> 150.000</td><td> 3200</td>
Example 14
Copper complexes of polycarboxylic acids are prepared from three different polymers. The three aci
<img file="PT101248B_D0036.tif" />
The polycarboxylic acids are as follows: Alcosperse 475-2, a 70/30 acrylic acid and maleic acid copolymer having a molecular weight of 20,000 available from Alco Chemical Corp; Gantrez AN-119, a 50/50 copolymer of methyl vinyl ether and maleic anhydride, having a molecular weight of 20,000, available from GAF Corporation; and Goodrite K-752. Complexes are formed by preparing aqueous solutions containing 1% by weight of polymer solids of a polyacrylic acid (Goodrite K-752) which are partially neutralized using sodium hydroxide until pH values of approximately 2.5 to approximately 9. Excess cupric hydroxide is then added to the polymer solutions. The liquid phase is separated from the undissolved solid cupric hydroxide by filtration, and the liquid phase is analyzed for its copper content. The test results are shown in Figure 4, where the concentration of copper in the complexed product is plotted against the pH of the neutralized polymer solutions. Analysis shows that all three polymers formed complexes with copper. These copper complexes are biologically active against Alternaria solani and Xanthomonas campestris pv. I dug up the ....
Example 15
Copper complexes of polyacrylic acids are prepared.
<img file="PT101248B_D0037.tif" />
according to the Examples depending on whether the source is or insoluble in water.
The liquid phases of the complexes described above and found to be soluble in copper water are then tested for efficacy against Xanthomonas campestri s pv. I dug a. Separate casitone yeast extract (CYE) samples are treated in culture media with copper complexes to obtain concentrations of metallic copper equal to 1, 2, 4, 6, 8, 10, 20, 40. , 60, 80 and 100 ppm respectively of copper. All comparisons are made with copper sulfate at the same rates as this form of copper is known to be biologically active on agar media. Bacterial cultures grown on CYE media are minced on the agar and incubated for five days at 27 ° C. Control is based on the presence or absence of bacterial decolonies. All copper complex samples and copper sulfate samples control bacteria at 6 ppm and higher. These assays show that copper complex samples made in accordance with the present invention are as active as copper sulfate samples. The results of the tests are gathered in the
Table 3 below.
-43QUADR03
Polycarboxylic Acid Polyacrylic Acid Polyacrylic Acid Polyacrylic Acid Polyacrylic Acid Polyacrylic Acid Polyacrylic Acid Polyacrylic Acid Polyacrylic Acid Polyacrylic Acid Polyacrylic Acid Polymethyl Acrylic Copolymer Acrylic Acid Copolymer and Methacrylamide Acid Copolymer Acid Acrylic Acid Copolymer Acrylic Acid Copolymer acrylic and methacrylic acid copolymer of acrylic acid and methacrylate esters acrylic acid and maleic acid copolymer carboxymethylcellulose maleic acid and butadiene copolymer maleic acid and maleic anhydride copolymer maleic acid and acrylic acid copolymer methyl viyl ether copolymer is maleic anhydride nothing
Example 16
--------- Complexes of
<td>Copper Fountain</td><td>DL 95 on CYE Agar, ppm Cu</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric sulfate</td><td> 6</td>
<td>Cu (C10)<sub>4</sub>)<sub>2</sub></td><td> 6</td>
<td>Ass<sub>2</sub>0</td><td> 6</td>
<td>Cu (NO<sub>3</sub>)<sub>2</sub></td><td> 6</td>
<td>CuC1<sub>2</sub></td><td> 6</td>
<td>copper oxychloride</td><td> 6</td>
<td>tribasic sulfate from</td><td>covers 6</td>
<td>basic carbonate</td><td>covers 6</td>
<td>copper hydrate</td><td> 6</td>
<td>copper hydrate</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>cupric hydroxide</td><td> 6</td>
<td>copper sulfate</td><td> 6</td>
copper of polyacrylic acids according to the Examples set forth in Table 4 below. The liquid phases of the copper complexes are then tested for their effectiveness against Alternaria solani. The copper complexes
<img file="PT101248B_D0038.tif" />
are assayed in CYE-containing culture media inoculated with the desired fungi. Separate culture media samples are treated with the copper complexes to obtain copper metal concentrations of 1, 10, 20, 40, 60, 80 and 100 ppm copper, respectively. All comparisons are made with copper sulphate at the same rates, as this form of copper is known to be biologically active in agar media. Actively developing Alternar ia so1ani cultures are sampled with a 7mm cork-driller around the outer circumference of the colony and placed in the center of culture Petri capsules containing the copper mixed media. These samples are incubated at 28 ° C for ten days. The radial diameters of the cultures are measured to determine the effect of copper on fungal development. The DLgg of copper complex samples is 100 ppm copper, while DL<sub>g0</sub> of copper sulfate equals 80 ppm copper. These assays demonstrate that copper complex samples made in accordance with the present invention are substantially as active as copper sulphate samples. The results of the efficacy trials of the various carboxylic acids and different sources of copper are shown in Table 4 and Figure 6.
TABLE 4
<td>Cone, PAA solids</td><td>PAA Molecular Mass</td><td>pH of partially neutralized PAA</td><td>Copper fountain</td><td>Preparation Example</td><td>Copper concentration in complex solution</td><td>OLqn θ ™ with CYE,</td>
<td> 2,50</td><td> 2.100</td><td> 7,0</td><td>cupric hydroxide</td><td> 3</td><td>1270 ppm</td><td> 100</td>
<td> 1.67*</td><td> 2.100</td><td> 7,0</td><td>cupric hydroxide</td><td> 1</td><td>800 ppm</td><td> 100</td>
<td> 0.42</td><td> 2.100</td><td> 7.0</td><td>cupric sulfate</td><td> 4</td><td>800 ppm</td><td> 100</td>
<td> 6.67</td><td> 2.100</td><td> 5,3</td><td>copper hydrate</td><td> 1</td><td> 1,01</td><td> 100</td>
<td> 6,67</td><td> 2.100</td><td> 5,0</td><td>copper hydrate</td><td> 1</td><td> 1.01</td><td> 100</td>
<td> 0.64</td><td> 2.100</td><td> 4,8</td><td>cupric hydroxide</td><td> 1</td><td>1000 ppm</td><td> 100</td>
<td> 1.74</td><td> 2.100</td><td> 4,8</td><td>cupric hydroxide</td><td> 1</td><td>2000 ppm</td><td> 100</td>
<td> 1.30</td><td> 2.100</td><td> 4,8</td><td>cupric hydroxide</td><td> 1</td><td>2000 ppm</td><td> 100</td>
<td> 12,00*·</td><td> 2.100</td><td> 4,8</td><td>cupric hydroxide</td><td> 12</td><td> 1.51</td><td> 100</td>
<td> 1.20</td><td> 2.100</td><td> 7,0</td><td>cupric chloride</td><td> 5</td><td>1030 ppm</td><td> 100</td>
<td> 1.67</td><td> 2.100</td><td> 7,0</td><td>copper oxychloride</td><td> 6</td><td>325 ppm</td><td> 100</td>
<td> 7.14</td><td> 2.100</td><td> 4,5</td><td>copper hydrate</td><td> 2</td><td> 2,01</td><td> 100</td>
<td> 20,00</td><td> 2.100</td><td> 4,5</td><td>copper hydrate</td><td> 1</td><td> 3,51</td><td> 100</td>
<td> 1,00</td><td> 5.000</td><td> 5,2</td><td>cupric hydroxide</td><td> 3</td><td>2730 ppm</td><td> 100</td>
<td> 1,60</td><td> 5.800</td><td> 7,1</td><td>cupric hydroxide</td><td> 3</td><td>220 ppm</td><td> 100</td>
<td> 5,00</td><td> 10.000</td><td> 4,1</td><td>copper hydrate</td><td> 3</td><td> 1,21</td><td> 100</td>
<td> 1,00</td><td> 50.000</td><td> 5,0</td><td>cupric hydroxide</td><td> 3</td><td>3500 ppm</td><td> 100</td>
<td> 2,85</td><td> 60.000</td><td> 4.1</td><td>copper hydrate</td><td> 1</td><td> 1.01</td><td> 100</td>
<td> 1,00</td><td> 90.000</td><td> 5,0</td><td>cupric hydroxide</td><td> 3</td><td>3530 ppm</td><td> 100</td>
<td> 1,00</td><td> 150.000</td><td> 5,0</td><td>cupric hydroxide</td><td> 3</td><td>3200 ppm</td><td> 100</td>
<td> 1,00</td><td> 240.000</td><td> 5,0</td><td>cupric hydroxide</td><td> 3</td><td>3150 ppm</td><td> 100</td>
<td>Null</td><td></td><td></td><td>cupric sulfate</td><td></td><td></td><td> 80</td>
The complexes used in the assay ra 6.
Both lyophilized are shown in Fig. The copper complex solution and material contain 8.57% Cu prepared in Example 12.
Example 17
Copper complexes of polyacrylic acids are prepared according to the list of copper complexes for their effectiveness against a strain of
Xanthomonas campestris pv. vescatoria, which is known to be
<img file="PT101248B_D0039.tif" />
<img file="PT101248B_D0040.tif" />
resistant to conventional copper-based bactericidal / fungicidal agents. The material prepared according to Example 12 is dissolved in agar for testing. Copper complexes are tested on CYE agar, inoculated with the bacteria to be tested. Several samples of the culture media are treated with copper complexes to obtain medium samples containing copper metal concentrations of 50, 100, 200 and 300 ppm copper respectively.
All comparisons are made with copper sulphate at the same rates, as this form of copper is known to be biologically active on agar media. Bacterial cultures grown in CYE medium to which 25 ppm of copper are added are minced on the agar and incubated for five days at 27 ° C. Control is based on the presence or absence of bacterial colonies. Complex copper samples control the copper tolerant bacteria at a concentration of 300 ppm and copper sulfate controls the bacteria at a concentration of 100 ppm. The results of the efficacy trials are shown in Table 5 below.
-47FRAME 5
<img file="PT101248B_D0041.tif" />
<td>Cone. PAA solids</td><td>PAA Molecular Mass</td><td>pH of partially neutralized PAA</td><td>Copper fountain</td><td>Preparation Example</td><td>Copper concentration in complex solution</td><td colspan="2">0Lq<sub>0</sub> on CYE containing agar. ppm of</td>
<td> 1.67</td><td> 2.100</td><td> 7.0</td><td>cupric hydroxide</td><td> 1</td><td>800 ppm</td><td></td><td> 300</td>
<td> 0.42</td><td> 2.100</td><td> 7,0</td><td>cupric sulfate</td><td> 4</td><td>800 ppm</td><td></td><td> 300</td>
<td> 6,67</td><td> 2.100</td><td> 5.3</td><td>copper hydrate</td><td> 1</td><td>1.0X</td><td></td><td> 300</td>
<td> 6.67</td><td> 2.100</td><td> 5,0</td><td>copper hydrate</td><td> 1</td><td> 1.01</td><td></td><td> 300</td>
<td> 12.00*</td><td> 2.100</td><td> 4,8</td><td>cupric hydroxide</td><td> 12</td><td>1.5X</td><td></td><td> 300</td>
<td> 0,30</td><td> 2.100</td><td> 4.8</td><td>copper hydrate</td><td> 1</td><td>2000 ppm</td><td></td><td> 300</td>
<td> 1,06</td><td> 2.100</td><td> 4.8</td><td>copper hydrate</td><td> 1</td><td>2000 ppm</td><td></td><td> 300</td>
<td> 1.60</td><td> 2.100</td><td> 4.8</td><td>copper hydrate</td><td> 1</td><td>2000 ppm</td><td></td><td> 300</td>
<td> 3.75</td><td> 2.100</td><td> 4.5</td><td>copper hydrate</td><td> 1</td><td>I.OX</td><td></td><td> 300</td>
<td> 6,25</td><td> 2.100</td><td> 4,5</td><td>copper hydrate</td><td> 1</td><td>1.0X</td><td></td><td> 300</td>
<td> 3,00</td><td> 2.100</td><td> 4,5</td><td>copper hydrate</td><td> 1</td><td> 1.02</td><td></td><td> 300</td>
<td> 7.14</td><td> 2.100</td><td> 4.5</td><td>copper hydrate</td><td> 2</td><td>2.0X</td><td></td><td> 300</td>
<td> 20.00</td><td> 2.100</td><td> 4,5</td><td>copper hydrate</td><td> 1</td><td>3.5X</td><td></td><td> 300</td>
<td> 5,00</td><td> 10.000</td><td> 4,1</td><td>copper hydrate</td><td> 3</td><td>1.2X</td><td></td><td> 300</td>
<td> 2.50</td><td> 60.000</td><td> 3.8</td><td>copper hydrate</td><td> 3</td><td>1.0X</td><td></td><td> 300</td>
<td>Nothing</td><td> -</td><td> -</td><td>cupric sulfate</td><td> -</td><td> -</td><td></td><td> 100</td>
Both the copper complex solution and 8.57% Cu-containing lyophilized material prepared in Example 12 are tested.
Example 18
The copper complex solution prepared according to Example 2 is applied to wheat seeds in the proportions of 0.15, 0.31 and 0.62 g / kg 7, 14 and 28 grams Cu / cwt. seed spray by spraying the composition onto the seeds using a laborial seed treatment device. Treated seeds are air dried in trays before sowing. Fifty seeds are sown in
<img file="PT101248B_D0042.tif" />
soil contained in trays to evaluate germination and growth after emergence. All treatments are compared with a conventional copper-based bactericidal / fungicidal agent (Kocide Seed Dressing) at 0.62 g / kg 28 grams Cu / cwt. Germination rate and growth are similar for all treatments (see Table 6 below). No phytotoxicity is noted in re. to the emerging plauticles.
TABLE 6
<td colspan="2">Seed treatment g / kg</td><td>g / cwt of seed</td><td>Germination%</td>
<td>Kocide Seed</td><td>Dressing 0.62</td><td> 28</td><td> 47</td>
<td>Example 2</td><td> 0,155</td><td> 7</td><td> 48</td>
<td>Example 2</td><td> 0,31</td><td> 14</td><td> 48</td>
<td>Example 2</td><td> 0,62</td><td> 0</td><td> 45</td>
Untreated
Example 19
The copper complex solution prepared according to Example 2 is applied to oranges in the proportions of 100, 500 and 1000 ppm by dipping the fruits in the respective solutions and allowing the solution to dry on the surface of the fruits.
Before dipping the fruits, they are inoculated with Alternaria citri, Phytophthora citrophthora, penicillium.
<img file="PT101248B_D0043.tif" />
di gatatum and Co 11 etotrichum gloeosporioides. The fruits are stored at 5<sup>O</sup> At 80% relative humidity for fourteen days, after which the number of fruits attacked is counted. At the end of this trial period, 100% of the untreated fruits were attacked by the disease and 35%, 10% and 8% of the fruits treated with 100, 500 and 1000 ppm Cu were respectively attacked.
No alarm or discoloration of the fruits is observed.
Example 20
The copper complex solution prepared according to Example 2 is applied to 1000 ppm Cu geranium plants five times at one week intervals. At the end of the test period, the residues are evaluated and compared with conventional copper-based bactericidal / fungicidal agents applied at the same copper rate. Compared to conventional treatments, the residues are not clearly visible to the naked eye. After evaluating the residues, the plants are watered from the top. After the plants have dried, the residues are evaluated again. Treatment with conventional fungicides leaves a very visible residue, while plants treated with the copper complex have no trace of residues present. No phytotoxicity is observed.
<img file="PT101248B_D0044.tif" />
Example 21
The copper complex solution prepared according to Example 2 is applied to cotton burlap fabric. Separate tissue samples are treated by dipping the tissue into a solution containing 1000 ppm copper complex and a copper sulfate solution respectively. Another tissue sample is not treated. Tissue samples are then buried in unsterile field land for a time period of two months. At the end of this test period, the untreated tissue is partially decomposed and the copper complex and copper sulfate treated samples are substantially intact and not decomposed.
Example 22
A copper complex solution is prepared according to Example 3, except that the polyacrylic acid is neutralized with three different basic compounds at a pH of 3 to 6. The three basic compounds used are sodium hydroxide, hydr. potassium oxide and ammonium hydroxide.
The samples contain 1% by weight of Goodrite K-752 polymer solids. The different samples are analyzed for their copper content. The test results
<img file="PT101248B_D0045.tif" />
are graphically depicted in Figure 5, where copper concentration is plotted against pH of neutralized polyacrylic acid for the three different neutralizing compounds.
It will be understood, of course, that the foregoing description relates only to certain embodiments of the present invention and that numerous modifications or alterations may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Contents12
6 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6
73 members in 29 offices
Priority claims4
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| 86321792 | United States of America | A | |
| 863217 | – | – | – |
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Numbers
- Publication, DOCDB
- 101248
- Publication, EPODOC
- PT101248
- Application
- 101248
- Application, DOCDB
- 10124893
- Application, EPODOC
- PT19930101248
Titles2
- Portuguese
- COMPOSICOES BACTERIANAS/FUNGICIDAS CONTENDO COMPLEXOS DE COBRE E PROCESSO PARA A SUA PREPARACAO
- English
- Compositions BACTERIAL / FUNGICIDES CONTAINING COMPLEX COPPER AND PROCESS FOR PREPARATION
Classification
- CPC, 2
- A01N37/04
- A01N59/20
- IPC, 8
- A01C1 06
- A01N25 24
- A01N25 10
- A01N37 04
- A01N59 20
- A01P3 00
- A61L2 16
- C08F8 42