KR102754376B1 - The environmentally friendly fungicide in which the colloidal sulfur and copper components are included - Google Patents

Abstract

The present invention relates to an environmentally friendly sterilizing agent comprising a composition of nanometer-sized colloidal sulfur produced by a cation ion exchange method of sodium thiosulfate using a cation exchange resin, and at least one copper component selected from among copper salts, lime Bordeaux mixture, copper hydroxide, copper chloride, and Burgundy solution.
That is, the present invention is characterized by an environmentally friendly sterilizer containing sulfur (S) and copper (Cu) components in water, wherein a sodium thiosulfate solution is prepared in which anhydrous sodium thiosulfate or pentahydrate sodium thiosulfate exists as sulfur (S) in an amount of 0.05 to 7.5 parts by weight, and the prepared sodium thiosulfate solution is contacted with a cation exchange resin that binds a sulfonic acid group (-SO ₃ H) and a carboxyl group (-COOH) as exchange groups to a basic polymer matrix of a network structure, thereby creating a composition composed of colloidal sulfur in water, and the environmentally friendly sterilizer containing colloidal sulfur and copper components, wherein the composition in water composed of colloidal sulfur also contains 0.5 to 10 parts by weight of copper.

Description

{The environmentally friendly fungicide in which the colloidal sulfur and copper components are included}

The present invention relates to an environmentally friendly antibacterial agent containing colloidal sulfur and copper components, and more particularly, to an environmentally friendly antibacterial agent containing at least one copper component selected from among copper salts, lime Bordeaux mixture, copper hydroxide, copper chloride, and Burgundy solution, in a composition of nanometer-sized colloidal sulfur produced by a cation ion exchange method of sodium thiosulfate using a cation exchange resin.

Disinfectants are a general term for substances used to kill microorganisms, and can be broadly classified into fungicides that inhibit or kill the growth of fungi, bactericides that can kill bacteria when exposed to them, antiseptics that prevent decay due to microbial growth or unwanted chemical changes, and disinfectants that kill microorganisms except bacterial spores on the surface of objects.

When looking at fungicides in the plant field, their purpose is to protect crops by preventing the occurrence of plant pathogens such as molds and bacteria that cause diseases in plants or by treating diseases. Fungicides for this purpose include protective fungicides, direct fungicides, and other fungicides.

Protective fungicides are chemicals used to prevent pathogen spores from germinating and invading plants. They are used for preventive purposes by treating crops before the disease occurs. Protective fungicides have a long duration of effect and good adhesiveness and fixation.

Direct disinfectants are agents that prevent germination and invasion of pathogens and have toxic effects on invading pathogens. They are used for the purpose of treatment and provide sufficient control.

Other fungicides are classified into seed disinfectants to prevent pathogens infecting seeds or seedlings, soil disinfectants used to kill pathogens in the soil, and fruit preservatives to prevent fruit from rotting during storage. They are further classified into blast and anthracnose agents according to the type of pest.

Looking at other types of chemical disinfectants, they can be broadly classified into phenol (carboxylic acid), halogen, alcohol, and heavy metal. In the case of phenol (carboxylic acid) disinfectants, Lister was the first chemical disinfectant used in the operating room, _{and it has the function of promoting sterilization through phenol (carboxylic acid, C6H5OH )} protein denaturation and soap. Among halogen disinfectants, iodide is used as a disinfectant for skin disinfection and water purification by combining with iodine and regular tyrosine, and acts on water, air, household items and all types of microorganisms to provide a sterilizing function, and oxidizes tyrosine of enzymes or structural proteins to provide a sterilizing effect, and in the case of chlorine, it reacts with organic substances by an oxidizing agent for water purification using chlorine gas Cl ₂ , chlorochloric acid [Ca(OCl) ₂ ] and sodium hypochlorite (NaClO) to disinfect tap water, sewage water and swimming pool water. In the case of alcohol disinfectants, although they have no effect on bactericidal properties, cell spores or viruses, they are used as disinfectants due to their bacteria washing and sterilizing effects and sterilizing by denaturing bacteria's proteins, and are also used as algaecides and fungicides using metal components such as mercury, silver and copper.

In general, there are three different ways in which disinfectants affect or kill germs and bacteria. Disinfectants are chemicals, so they must be handled with care. The type of disinfectant you choose depends on the intended use. For this reason, you must know how to use the disinfectant.

Alcohol-based disinfectants and phenol-based disinfectants use cross-linking, coagulation, and clustering. Alcohol-based disinfectants are very effective in inhibiting spore germination because they affect bacteria and their enzymes. Alcohol coagulates cell proteins, making them ineffective, so alcohol-based disinfectants should be diluted in water to achieve maximum effectiveness, while phenol kills bacteria by blocking the cell walls of bacteria and their cells.

Chlorine-based disinfectants kill germs and bacteria by oxidation. These types of disinfectants target and destroy some of the important metabolic enzymes of germs and bacteria, and chlorine-based disinfectants show rapid bacterial killing effects.

Peroxide disinfectants are powerful oxidizing agents that are lethal to many species of bacteria, and hydroxyl radicals attack bacteria and their essential cellular components and cell membranes, causing their breakdown.

The use of disinfectants may vary depending on the location where disinfection is being done, but the most important thing to remember is to use disinfectants correctly according to their instructions. Disinfectants can be toxic, so they must be handled with care. Understanding the mechanism of action of disinfectants can help ensure the safety of your home.

Disinfectants containing sulfur (S) are permitted substances for pest control under the Enforcement Decree of the Act on Promotion of Eco-Friendly Agriculture and Fisheries and Management and Support of Organic Foods, etc. under the Ministry of Agriculture, Food and Rural Affairs. It is a non-metallic element with no taste or odor. In nature, it exists as pure sulfur, or in the form of sulfide or sulfate. It is an essential element for life, and sulfur is contained in two types of amino acids. It is the main component of fertilizers, and in addition to its uses in gunpowder, matches, insecticides, and disinfectants, it is also widely used in the pharmaceutical field for treating dermatitis, hair loss, and as an emollient for constipation and hemorrhoids.

Fungicides containing copper are also recognized as substances that can be used for pest control in accordance with the Enforcement Decree of the Act on Promotion of Eco-Friendly Agriculture and Fisheries and Management and Support of Organic Foods, etc. under the Ministry of Agriculture, Food and Rural Affairs. They are substances used to prevent fungal diseases existing in plants as well as viral infections in homes and industrial sites. Commonly used copper-containing fungicides are copper salts, lime Bordeaux mixture (an eco-friendly fungicide made by mixing copper sulfate and quicklime), copper hydroxide, copper oxychloride, and Burgundy solution. Copper fungicides treat various fungal and bacterial diseases of plants such as black spot, rust, and powdery mildew, and farmers who grow fruits, vegetables, and field crops use copper-based fungicides to prevent various plant diseases. Copper fungicides can be used on all types of plants when used as per the given directions, the copper ions present in copper fungicides are components that destroy proteins and enzymes in pathogen cells before the pathogen can infect the plant, increasing number of fungal species, increasing demand for strong fungal resistance in plants, increasing demand for food across the world, increasing demand from developing countries, and increasing pests and diseases in plants are some of the factors driving the growth of the market.

As mentioned above, sulfur (S) and copper (Cu) are recognized as allowable substances for use in pest control under the Enforcement Decree of the Act on Promotion of Eco-Friendly Agriculture and Fisheries and Management and Support of Organic Foods, etc. under the Ministry of Agriculture, Food and Rural Affairs. As environmental conservation has become a major concern for human survival in the 21st century, there is a growing awareness that the agricultural sector should also seek ways to develop sustainable environmental agriculture that preserves the natural environment, produces and supplies high-quality, safe agricultural products, and expand the development of environmentally friendly disinfectants that can prevent soil and air pollution and maintain and develop agriculture as a way of putting this into practice.

Eco-friendly agriculture refers to all forms of low-input sustainable agriculture that minimizes the use of chemical substances such as fertilizers and pesticides, while cultivating the vitality of the soil and continuously conserving the agricultural environment by utilizing cutting-edge agricultural technologies such as comprehensive crop nutrient management, comprehensive pest control, and utilization of natural enemies.

However, as the side effects of pesticides, such as environmental pollution, poisoning accidents, and food safety due to pesticide use, and the side effects of excessive use of fertilizers, such as water pollution due to direct salt exposure and nutrient runoff from farmland, become a problem, the importance of environmentally friendly agriculture that stably produces high-quality and safe agricultural products while preserving human and livestock health, the agricultural environment, and the ecosystem cannot be overemphasized.

In addition, disinfectants containing sulfur (S) and copper (Cu) are recognized as environmentally friendly disinfectant ingredients, but the scope of application of the disinfectant is narrow, the disinfectant effect is unstable, and the disinfectant's control effect is minimal due to independent research and development of the composition of each ingredient.

Disinfectants containing sulfur (S) and copper (Cu) play a major role in preventing infections caused by contact with microorganisms in all areas of human life, including the plant field, and in preventing or preserving spoilage of food that is easily spoiled by microorganisms as a medium. However, since the sterilizing effect is minimal and the scope of application is narrow due to the single technology composed of sulfur (S) and copper (Cu) developed so far, it is necessary to seek a method that has low environmental toxicity and excellent sterilizing power.

Accordingly, the technical composition of a sterilizing agent containing colloidal sulfur with a large surface area in the nanometer size obtained by the cation ion exchange method of sodium thiosulfate using a cation exchange resin and an active ingredient such as copper salt, lime Bordeaux mixture, copper hydroxide, copper acid chloride, or Burgundy solution can provide a sterilizing agent with low toxicity to the human body and doubled sterilizing power due to the composition of sulfur particles with a large surface area in the nanometer size.

The environmentally friendly disinfectant technologies available so far are as follows:

Korean Patent Registration No. 10-2474511 discloses a method for producing detoxified sulfur from which the toxicity of sulfur has been removed, a method for producing detoxified sulfur, a fertilizer, a disinfectant, and an insecticide using the same, and a saponin sulfur fertilizer, an eco-friendly disinfectant, and a wild herb insecticide produced using the same.

Korean Patent Registration No. 10-1922807 discloses a copper nano composition for controlling plant diseases and a method for producing the same, comprising: 100 parts by weight of a copper nanocolloid aqueous solution (A) containing nonionic copper nanoparticles having an average particle diameter (D50) of 2 nm to 10 nm; 1 to 5 parts by weight of a nonionic surfactant (B); and 1 to 5 parts by weight of a stabilizer (C), wherein the nonionic copper nanoparticles are contained in a concentration of 1,800 ppm to 3,000 ppm.

Korean Patent Registration No. 10-0755465 proposes a composition for controlling powdery mildew and anthracnose using riboflavin, methionine, copper sulfate, and natural organic sulfur without causing toxicity to humans and livestock and without polluting the soil and water environment.

Korean Patent Registration No. 10-1446208 proposes a method for producing Bordeaux mixture of sulfur, characterized in that it is produced by adding water, quicklime, and sodium hydroxide to liquid sulfur.

Korean Patent Registration No. 10-0826635 proposes a sterilizing compound fertilizer composition that can provide nutrients to crops while minimizing the use of expensive silver and achieving the best sterilizing power.

In the present invention, the technical idea of a disinfectant containing a colloidal sulfur composition having a large surface area in the nanometer size obtained by the cation ion exchange method of sodium thiosulfate using a cation exchange resin and an active ingredient such as a copper salt, lime Bordeaux mixture, copper hydroxide, copper chloride, or Burgundy solution, is mainly based on the core technical idea of providing a disinfectant capable of doubling the disinfecting power due to the composition of sulfur particles having a specific surface area in the nanometer size while providing low toxicity to the human body and the environment, and the technical composition and technical idea of a disinfectant that can be applied to various fields including agriculture in an environmentally friendly manner while minimizing toxicity to the human body and the environment by being composed of colloidal sulfur and copper components have not been suggested yet, and is a new technology that cannot achieve the purpose that the present invention aims to provide even when prior arts are combined and applied.

KR No. 10-2474511 KR No. 10-1922807 KR No. 10-0755465 KR No. 10-0826635

The technical idea of the present invention disclosed as a means to achieve the above object is to provide an environmentally friendly sterilizing agent containing colloidal sulfur and copper salt, which has low toxicity to the human body and doubles sterilizing power, by mixing a composition of colloidal sulfur produced by an ion exchange method of sodium thiosulfate using a cation exchange resin composed of a sulfonic group or a carboxyl group and a copper component composition such as a copper salt, lime Bordeaux mixture, copper hydroxide, copper chloride, or Burgundy solution, thereby containing an active copper component.

The present invention relates to an environmentally friendly sterilizer containing sulfur (S) and copper (Cu) components in water, wherein a sodium thiosulfate solution is prepared in which anhydrous or pentahydrate sodium thiosulfate exists as sulfur (S) in an amount of 0.05 to 7.5 parts by weight, and the prepared sodium thiosulfate solution is contacted with a cation exchange resin that binds a sulfonic acid group (-SO ₃ H) and a carboxyl group (-COOH) as exchange groups to a basic polymer matrix having a network structure, thereby producing a composition composed of colloidal sulfur in water, and the environmentally friendly sterilizer containing colloidal sulfur and copper components is characterized by including 0.5 to 10 parts by weight of copper in the composition composed of colloidal sulfur in water.

The above copper component is characterized in that at least one component is selected from among copper sulfate, copper chloride, copper nitrate, copper acetate, lime Bordeaux mixture, copper hydroxide, copper acid chloride, and Burgundy solution.

The present invention relates to a composition of colloidal sulfur manufactured into nanometer-sized particles by the cation ion exchange method of sodium thiosulfate using a cation exchange resin, and a composition of a sterilizing agent including a copper component such as a copper salt, lime Bordeaux mixture, copper hydroxide, copper acid chloride, or Burgundy solution, which, unlike hazardous sterilizing agents such as pesticides, does not pose a high risk of harming health because it is not highly hazardous to the human body, is easy to handle, and has doubled sterilizing power, so it is expected to have a great effect in providing an environmentally friendly sterilizing agent that can be applied to various fields of daily life including agriculture.

Hereinafter, the technical idea of the present invention will be described in detail as follows.

The present invention relates to an environmentally friendly fungicide containing sulfur (S) and copper components (copper salts), among the components recognized as allowable substances usable for pest control in the Enforcement Decree of the Act on Promotion of Eco-Friendly Agriculture and Fisheries and Management and Support of Organic Foods, etc. under the jurisdiction of the Ministry of Agriculture, Food and Rural Affairs, wherein a composition of sulfur (S) is obtained by the cation ion exchange method of sodium thiosulfate, a composition of large water-dispersible colloidal sulfur having a specific surface area of nanometers, and at least one copper component selected from copper salts, lime Bordeaux mixture, copper hydroxide, copper chloride, and Burgundy solution is mixed with the colloidal sulfur to form an environmentally friendly fungicide containing colloidal sulfur and copper salts.

The environmentally friendly sterilizing agent comprising the colloidal sulfur (S) and copper components is characterized by comprising 0.05 to 7.5 parts by weight of colloidal sulfur (S) in water and 0.5 to 10 parts by weight of copper in the form of copper salts, so that it can be applied to various fields of daily life including agriculture.

The colloidal sulfur (S) according to the present invention can be provided by the cation ion exchange method of sodium thiosulfate, and the reaction formula therefor is as follows.

When anhydrous sodium thiosulfate (Sodium thiosulfateanhydrous) or pentahydrate sodium thiosulfate (Sodium thiosulfateㆍpentahydrate) is dissolved in water in an amount such that colloidal sulfur (S) can be formed in water at a concentration of 0.05 to 7.5 parts by weight, and the solution is brought into contact with a cation exchange resin having sulfonic acid groups (-SO ₃ H) and carboxyl groups (-COOH) as exchange groups bonded to the basic polymer matrix of a network structure, pure, high-concentration colloidal sulfur (S) of nanometer size is produced in water at a concentration of 0.05 to 7.5 parts by weight, and at this time, colloidal non-metallic sulfur (S) generated by the following chemical reaction scheme 1 is created.

R-SO ₃ H + Na ₂ S ₂ O ₃ → R-SO ₃ Na + S ₂ O ₃ + 2H ⁺ ----------<Chemical Reaction Formula 1>

→ S (sulfur in nanometer size) + SO ₂ + H ₂ O

The copper salt is selected from at least one of copper sulfate, copper chloride, copper nitrate, and copper acetate, and it is desirable to provide an environmentally friendly sterilizing agent that is directly supplied to water composed of colloidal sulfur (S) of nanometer size at a concentration of 0.05 to 7.5 parts by weight and dissolved to form sulfur (S) and copper components together.

Before describing the embodiments of the invention to implement the technical idea of the present invention as examples, it should be noted that terms or words used in the specification or claims of this application should not be interpreted as being limited to their usual or dictionary meanings, and the scope of protection of the present application should be interpreted as having meanings and concepts that are consistent with the technical idea of the present invention, and the examples described in this specification are only the most preferred embodiments of the present invention and do not represent all of the technical idea of the present invention. Therefore, it should be understood that there may be various equivalents and modified examples that can replace them at the time of this application.

In order to implement the technical configuration of the present invention, sodium thiosulfate (Samchun Pure Chemical Industries, Ltd.) pentahydrate containing 0.05 parts by weight of colloidal sulfur (S) was supplied to a 1-liter beaker, about 1 liter of distilled water was supplied, stirred to completely dissolve sodium thiosulfate, about 100 g of a strongly acidic cation exchange resin (Samyang Corporation, TRILITE® SPC320H) composed of sulfone groups was supplied, stirred for 10 minutes, and then filtered through a 100-mesh sieve to prepare an aqueous solution containing colloidal sulfur (S), and copper sulfate (Samchun Pure Chemical Industries, Ltd.) pentahydrate containing 0.5 parts by weight of copper (Cu) was directly supplied thereto and dissolved to produce an environmentally friendly sterilizer containing 0.05 parts by weight of colloidal sulfur and 0.5 parts by weight of copper (Cu).

Sodium thiosulfate pentahydrate (Samjeon Pure Chemical Industries, Ltd.) containing 2.5 parts by weight of colloidal sulfur (S) was supplied to a 1-liter beaker, then about 1 liter of distilled water was supplied, stirred to completely dissolve sodium thiosulfate, and about 200 g of a strongly acidic cation exchange resin (Samyang Corporation, TRILITE® SPC320H) consisting of sulfone groups was supplied, stirred for 10 minutes, and then filtered through a 100-mesh sieve to prepare an aqueous solution containing colloidal sulfur (S). To this, lime Bordeaux mixture (Kyungnong Co., Ltd.) containing 2.0 parts by weight of copper (Cu) was directly supplied, and stirred to produce an environmentally friendly sterilizer containing 2.5 parts by weight of colloidal sulfur and 2.0 parts by weight of copper.

Sodium thiosulfate pentahydrate (Samchun Pure Chemical Industries, Ltd.) containing 5.0 parts by weight of colloidal sulfur (S) was supplied to a 1-liter beaker, then about 1 liter of distilled water was supplied, stirred to completely dissolve sodium thiosulfate, and about 300 g of a strongly acidic cation exchange resin (Samyang Corporation, TRILITE® SPC320H) consisting of sulfone groups was supplied, stirred for 10 minutes, and then filtered through a 100-mesh sieve to prepare an aqueous solution containing colloidal sulfur (S). To this, copper hydroxide [Samchun Pure Chemical Industries, Ltd.] containing 5.0 parts by weight of copper (Cu) was supplied and stirred to produce an environmentally friendly sterilizer containing 5.0 parts by weight of colloidal sulfur and 5.0 parts by weight of copper.

Sodium thiosulfate pentahydrate (Samchun Pure Chemical Industries, Ltd.) containing 5.0 parts by weight of colloidal sulfur (S) was supplied to a 1-liter beaker, then about 1 liter of distilled water was supplied, stirred to completely dissolve sodium thiosulfate, and about 300 g of a strongly acidic cation exchange resin (Samyang Corporation, TRILITE® SPC320H) consisting of sulfone groups was supplied, stirred for 10 minutes, and then filtered through a 100-mesh sieve to prepare an aqueous solution containing colloidal sulfur (S). To this, a Burgundy solution containing 10 parts by weight of copper (Cu) was supplied and stirred to produce an environmentally friendly sterilizer containing 5.0 parts by weight of colloidal sulfur and 5.0 parts by weight of copper.

For the environmentally friendly fungicides containing sulfur and copper for Examples 1 to 4, the toxicity test for carp and the phytotoxicity and control effects on tomatoes were confirmed.

The tomatoes used at this time were sown in a plastic pot with a diameter of 4.5 cm, filled about 70% with horticultural soil, and grown in a greenhouse at 25℃ for 1 to 4 weeks. Tomato seedlings in the 3- to 4-leaf stage were used in the experiment.

The pathogen, Phytophthora infestans, was inoculated onto oatmeal agar and cultured in an incubator at 20°C. The zoosporangia formed on the medium were harvested by adding sterile distilled water, and the spore concentration was examined using a hemocytometer under an optical microscope to create a spore suspension of 3 × 10 ⁴ sporangia/㎖. The suspension was then sprayed onto tomato seedlings after low-temperature treatment to release the zoosporia. Each sample was sprayed onto tomato leaves, air-dried for 24 hours, and then inoculated with each plant pathogen.

For the fish toxicity test on carp, the environmentally friendly disinfectant containing sulfur and copper of Example 1 was diluted 1/10, and the environmentally friendly disinfectants containing sulfur and copper of Examples 2 to 4 were diluted 1/1,000 to prepare samples for the fish toxicity test. Five carps were each put into the fish toxicity sample solutions prepared in Examples 1 to 4, and the mortality rates of the carp were confirmed after 24 hours, 48 hours, 72 hours, and 96 hours. The fish toxicity results according to Examples 1 to 4 are shown in Table 1.

In order to confirm the control effect against tomato late blight, Example 1 was diluted to 1/5, and Examples 2 to 4 were diluted to 1/100, and foliar spraying was performed on the leaves of Seogwang tomatoes in the 3rd to 4th leaf stage. The damage to the tomatoes was confirmed by visual and sensory method, and the results are shown in Table 2.

division Carp water
(number of animals) Cumulative fatalities (Marines) Fatality rate(%) 24 hours 48 hours 72 hours 96 hours 48 hours 96 hours Example 1 5 0 0 0 0 0 0 Example 2 5 0 0 0 0 0 0 Example 3 5 0 0 0 0 0 0 Example 4 5 0 0 0 0 0 0 Voice control group 5 0 0 0 0 0 0

division Invention degree (%) Note*
(DMRT) The pest control
(%) Weak ⅠRepeat ⅡRepeat ⅢRepeat average Example 1 4.7 4.4 5.3 4.7 a 86.9 doesn't exist Example 2 1.8 2.5 3.3 2.5 a 93.0 doesn't exist Example 3 1.0 1.1 0.6 0.9 a 97.6 doesn't exist Example 4 0.7 0.6 0.9 0.7 a 98.0 doesn't exist Untreated area 82.3 43.8 64.8 63.6 c - doesn't exist *Shin Dajung Duncan Test

As shown in Table 1, the composition of an environmentally friendly sterilizing agent containing colloidal sulfur and copper according to the present invention was diluted to a concentration applicable to the sterilization field, and a fish toxicity test was performed for 96 hours. As a result, the mortality rate was confirmed to be 0%. Therefore, it was expected that the composition of a sterilizing agent containing colloidal sulfur and copper would be a sterilizing agent that can minimize toxicity to the human body while providing sterilizing power.

As shown in Table 2, it was confirmed that the composition of the fungicide containing colloidal sulfur and copper according to the present invention did not cause any phytotoxicity to tomato crops. In addition, as a result of confirming the control efficacy of the fungicide composition, it was confirmed that the higher the content of colloidal sulfur and copper, the higher the control efficacy. It is expected that the technical idea of the fungicide containing colloidal sulfur and copper according to the present invention can be widely used in an environmentally friendly manner in various fields including agriculture.

Although the present invention has been described above with reference to the above embodiments, it is of course possible to make various modifications within the technical scope of the present invention.

Claims (2)

In an environmentally friendly disinfectant containing sulfur (S) and copper (Cu) in water,
An environmentally friendly sterilizer containing colloidal sulfur and copper, characterized in that a sodium thiosulfate solution is prepared in which anhydrous or pentahydrate sodium thiosulfate exists in water as sulfur (S) in an amount of 0.05 to 7.5 parts by weight, and a composition comprising colloidal sulfur is produced in water by an ion exchange method using a contact method of a cation exchange resin in which the prepared sodium thiosulfate solution is bonded to a basic polymer matrix of a network structure with a sulfonic acid group ( _-SO 3 H) and a carboxyl group (-COOH) as exchange groups, and the composition in water comprising colloidal sulfur also contains 0.5 to 10 parts by weight of copper.
In the first paragraph,
An environmentally friendly disinfectant containing colloidal sulfur and copper, characterized in that the copper component is selected from at least one of copper sulfate, copper chloride, copper nitrate, copper acetate, lime Bordeaux mixture, copper hydroxide, copper acid chloride, and Burgundy solution.