Bordeaux mixture composition and method for producing same

Abstract

Provided is a stock solution composition for a Bordeaux mixture. The stock solution composition has a pH in a neutral range, is less likely to undergo discoloration or deterioration with time, remains stable even after long-term storage, and exhibits sufficient efficacy including a fungicidal effect.　A Bordeaux mixture composition according to the present invention is an aqueous suspension containing, relative to 100 parts by mass of solid components or dry components, 50 to 95 parts by mass of gypsum, 2 to 30 parts by mass of posnjakite, 2 to 30 parts by mass of basic copper calcium sulfate trihydrate, and no brochantite or at most 0.8 parts by mass of brochantite.

Description

Bordeaux mixture composition and method for producing the same

[0001] The present invention relates to a Bordeaux mixture composition containing basic copper calcium sulfate trihydrate as an active ingredient, which is a fungicide and pesticide used as an agricultural chemical for crops, which remains stable even after long-term storage without discoloration or deterioration, and which is a stock solution for making a Bordeaux mixture diluted solution for spraying treatment etc. when needed, as well as a Bordeaux mixture diluted solution for spraying etc. on crops when needed, and a method for producing the Bordeaux mixture composition.

[0002] Bordeaux mixture is a fungicide and pesticide that has a history of approximately 120 years and is still used today. It has high fungicidal and pathogen-resistant preventative effects against a wide range of pathogens affecting fruit trees such as grapes, citrus fruits, peaches, and apples, as well as crops such as cabbage, cucumbers, and tomatoes. It also has a relatively long residual effect and high safety. Because the undiluted Bordeaux mixture is highly concentrated, it is diluted appropriately at the time of use depending on the target crop before being used for spraying or other treatments on the desired crop.

[0003] Traditionally, Bordeaux mixture compositions were prepared on-site by agricultural workers as a mixed suspension solution of copper sulfate aqueous solution and lime milk (made by suspending slaked lime or quicklime in water), and then diluted according to the crop and target pathogens / pests. At this time, after making lime milk from slaked lime or quicklime, copper sulfate aqueous solution was added while stirring at cold temperatures and diluted as needed to prepare a Bordeaux mixture composition containing basic copper calcium sulfates, which was then quickly diluted and sprayed. For example, Non-Patent Literature 1 describes the preparation of Bordeaux mixture compositions such as formulas 3-3 to 6-6 to 2-10 to 4-12, which are expressed as the grams of copper sulfate and quicklime or slaked lime in 100 ml of Bordeaux mixture, and these ratios are still used today.

[0004] When preparing the Bordeaux liquid composition, the slaking of quicklime and the dissolution of slaked lime are accompanied by rapid heat generation, which is dangerous and troublesome as cooling is required. Moreover, as time passes during mixing, the crystals of basic copper sulfate calcium grow too large, causing clogging during spraying, making it difficult to adhere to crops, reducing the suspension property, and inhibiting the expression of high bactericidal properties and pathogen resistance. Therefore, temperature control, stirring efficiency, mixing time, and mixing ratio are important factors for preparing high-quality basic copper sulfate calcium with a uniform and small particle size. As a result, preparing a high-quality Bordeaux liquid composition requires a high level of skill and a considerable amount of effort.

[0005] Therefore, recently, Bordeaux liquid compositions containing basic copper sulfate calcium as an active ingredient of antibacterial agents and pest control agents have been manufactured and sold, and are now diluted and used at the time of use. As a Bordeaux liquid composition, for example, Patent Document 1 describes a method for preparing a Bordeaux liquid by pulverizing a stock solution of a Bordeaux liquid obtained by mixing copper sulfate and quicklime or slaked lime with a wet pulverizer. As such a Bordeaux liquid composition, the applicant of the present application has already manufactured and sold IC Bordeaux 66D, 48Q, and 412 (6-6 formula, 4-8 formula, and 4-12 formula, respectively) in Japan.

[0006] In addition, a Bordeaux liquid composition with a pH in the alkaline range containing basic copper sulfate, which is prepared using copper sulfate and sodium hydroxide without using slaked lime or quicklime, is also commercially available. For example, Patent Document 2 describes copper fine particles having antibacterial and / or biocidal activity, each fine particle being composed of five different copper compounds, namely, antlerite Cu ３ ＋２ (SO ４ )(OH) ４ , brochantite Cu ４ ＋２ SO ４ (OH) ６ , chalcanthite Cu ＋２ SO ４ ・5H ２ O, natrocalcite NaCu ２ ＋２ (SO ４ ) ２ OH・H２ O and hydrated copper sulfate hydroxide Cu ３ (SO ４ ) ２ (OH) ２ 4H ２ 0 / 2CuSO ４ Cu(OH) ２ Disclosed are copper nanoparticles having a regular crystalline microstructure composition including and having a size of 5 to 50 μm, and a process for preparing copper nanoparticles having antimicrobial and / or biocide activity, comprising: a) preparing a solution by dissolving solubilized copper sulfate in distilled water at a ratio of 1:10 w / w; b) adding a 10% w / v sodium hydroxide solution and distilled water to the solution obtained in step a) to obtain a solution with a pH of 4 to 6; c) separating the supernatant from the precipitate, which is a copper hydroxide gel, after 24 hours; d) emulsifying the gel-like precipitate obtained in step c) in a copper sulfate solution prepared by dissolving it in distilled water at a ratio of 1:5 w / v; and e) subjecting the emulsion obtained in step d) to a drying process using a spray dryer, preferably at an inlet temperature of 220°C to 280°C and preferably at an outlet temperature of 80°C to 100°C.

[0007] All of these Bordeaux mixture compositions had a higher pH than copper sulfate because they contained more alkaline components such as quicklime, slaked lime, or sodium hydroxide.

[0008] Among these Bordeaux mixture compositions, those containing basic copper calcium sulfates and having an alkaline pH were preferred. Such Bordeaux mixture compositions, being alkaline and containing basic copper calcium sulfates, exhibit effects such as preventing phytotoxicity, improving adhesion, and enhancing rain resistance compared to water-soluble copper sulfate due to the presence of calcium in the basic copper calcium sulfates. Furthermore, their alkalinity provides strong bactericidal properties, shifting the soil towards alkalinity and thus improving soil quality.

[0009] Due to global warming and the improvement and diversification of plant varieties, the number of pathogens and pests that need to be prevented has increased, making it necessary to mix multiple types of pesticides. Since alkaline Bordeaux mixture compositions may inhibit the efficacy of other pesticides and are difficult to mix, there is a growing demand for Bordeaux mixture compositions that are close to neutral.

[0010] However, when the ratio of raw material mass of slaked lime or quicklime in milk lime to raw material mass of copper sulfate in copper sulfate aqueous solution was reduced to about 2:10, and the resulting Bordeaux mixture was neutralized, it changed color from light blue to dark gray within a few days, deviating from the specifications and leading to a decline in quality, making it unsuitable for market distribution.

[0011] The present inventors have discovered that a new Bordeaux mixture composition, prepared to have a different pH in the neutral range and containing different active ingredients as a fungicide and pesticide, exhibits equivalent efficacy without causing discoloration or deterioration, compared to conventional alkaline Bordeaux mixture compositions in which the ratio of raw material mass of quicklime or slaked lime in lamellar lime to raw material mass of copper sulfate in aqueous copper sulfate solution is greater. This invention completes the present invention. The present applicant has filed a patent application in Japan as described in Patent Document 3, and that application has already been granted a patent. This application is identical in content to the Japanese patent application that has been granted a patent.

[0012] Osaka Prefecture Agricultural Pest Control Guidelines 2020: https: / / www.jppn.ne.jp / osaka / shishin / body / 2403 / pdf / 2403_17_09_borudo.pdf

[0013] JP-A-2-279611 Publication Special Publication No. 2021-532065 Publication Patent Application No. 2025-019670

[0014] The present invention was made to solve the aforementioned problems, and aims to provide a Bordeaux mixture composition that has a neutral pH, is less prone to discoloration or deterioration over time, is stable even after long-term storage, and exhibits sufficient medicinal effects such as bactericidal activity, as well as a simple and safe method for producing it.

[0015] The Bordeaux liquid composition of the present invention made to achieve the above object is a water suspension containing, in terms of mass ratio in 100 parts by mass of the solid component or dry component, 50 to 95 parts by mass, preferably 55.3 to 60.7 parts by mass of gypsum, 2 to 30 parts by mass, preferably 15.6 to 26.4 parts by mass of posnjakite, and 2 to 30 parts by mass, preferably 18.2 to 25.2 parts by mass of basic calcium copper sulfate trihydrate, and containing no brochantite or at most 0.8 parts by mass, preferably 0.5 parts by mass, more preferably 0.1 parts by mass.

[0016] This Bordeaux liquid composition preferably contains no calcium hydroxide and fonbezhinskite or at most 0.5 parts by mass of each, independently, in 100 parts by mass of the solid component or dry component.

[0017] This Bordeaux liquid composition is such that the solid component or dry component is, for example, a reaction product of a copper sulfate salt and quicklime and / or slaked lime.

[0018] This Bordeaux liquid composition is such that, for example, the copper sulfate salt and the quicklime and / or slaked lime are in a mass ratio of 8.5 to 11.5:1.5 to 2.5, preferably 9.5 to 10.5:1.5 to 2.5, more preferably 10:2.

[0019] This Bordeaux liquid composition preferably has the copper sulfate salt being copper(II) sulfate pentahydrate or anhydrous copper(II) sulfate.

[0020] This Bordeaux liquid composition contains, for example, 20 to 40% by mass, preferably 25 to 35% by mass, more preferably 30.00 to 30.52% by mass of the gypsum, the posnjakite, and the basic calcium copper sulfate trihydrate in the water suspension.

[0021] This Bordeaux liquid composition is for use, for example, diluted with water in a volume ratio of more than 1 time and 2000 times or less, preferably 2 to 10000 times, and then used.

[0022] The Bordeaux mixture composition may also consist of a solid component or a dry component which may be a filtrate and / or dry product of the aqueous suspension (for example, a naturally dried product, an air-dried product, a vacuum-dried product, or a vacuum-dried product).

[0023] Specifically, this Bordeaux mixture composition is prepared according to CIPAC MT46.3 (https: / / cipac.org / images / members-area / draft / CIPAC_method_4956_m_accelerated_storage_LN_prep.docx) after storage at 25°C for 2 years, or after a corresponding accelerated test (e.g., 2 weeks at 54°C), or after 7 days at 25°C, or as a corresponding accelerated test, 2.42 days (58 hours) at 30°C, or 1.07 days (26 hours) at 40°C, or 0.27 days (6 hours) at 54°C, or at 54°C. After storage for two weeks, the product is measured visually, for example, at room temperature, pressure, and under natural light, and compared to the product immediately after preparation. The result must be within the range of adjacent colors as specified in the "Guidance on Quality Assessment of Pesticides (Types, Names, Composition, Manufacturing Methods, Physical and Chemical Properties, and Analytical Methods of Pesticides) (Notification No. 4-Shoan-6006, dated February 22, 2023) https: / / www.maff.go.jp / j / nouyaku / n_touroku / attach / pdf / index-53.pdf". Adjacent colors refer to those that can be visually confirmed to fall within the range of adjacent green (2.5G) and blue (2.5PB), with blue-green (2.5BG) as the standard.

[0024] This Bordeaux mixture composition is such that the mass ratio of the gypsum, the posnakite, the basic copper calcium sulfate trihydrate, and the brochantite in 100 parts by mass of the solid or dry component is calculated from the intensity ratio of the solid or dry component obtained by X-ray powder crystal diffraction.

[0025] This Bordeaux mixture composition is preferably diluted 500 times with water to a pH of 5.0 to 8.9, more preferably 5.8 to 8.6, and even more preferably 6.5 to 8.0.

[0026] This Bordeaux mixture composition may contain at least one additive selected from surfactants, dispersion stabilizers, alkalizing agents, acidifying agents, chelating agents, preservatives, spreading agents, and dispersants.

[0027] To achieve the above objective, the present invention provides a method for producing a Bordeaux mixture composition, characterized by adding an aqueous solution of copper sulfate to an aqueous suspension of quicklime and / or slaked lime such that the mass ratio of the copper sulfate to the quicklime and / or slaked lime is 8.5 to 11.5:1.5 to 2.5, preferably 9.5 to 10.5:1.5 to 2.5, more preferably 10:2, thereby producing an aqueous suspension containing, by mass ratio of 50 to 70 parts by mass, preferably 55.3 to 60.7 parts by mass, gypsum, 10 to 30 parts by mass, preferably 15.6 to 26.4 parts by mass, and 10 to 30 parts by mass, preferably 18.2 to 25.2 parts by mass, basic copper calcium sulfate trihydrate, and containing no or at most 0.1 parts by mass of brochant copper ore. This manufacturing method involves, for example, using a mass ratio of 8.5 to 11.5:1.5 to 2.5 for the copper sulfate salt and the quicklime and / or slaked lime. Specifically, in this manufacturing method, the copper sulfate salt is copper(II) sulfate pentahydrate or anhydrous copper(II) sulfate. In this manufacturing method, for example, the solid component or dry component is the filtrate and / or dried product of the aqueous suspension.

[0028] In the method for producing this Bordeaux mixture composition, it is preferable to add the aqueous solution of copper sulfate to the aqueous suspension of quicklime and / or slaked lime at a rate of 100 parts by volume of the aqueous solution of copper sulfate at a rate of 3.33 parts by volume / minute or less (for example, over 30 minutes).

[0029] In the method for producing this Bordeaux mixture composition, it is preferable to add an aqueous solution of the copper sulfate to the aqueous suspension of quicklime and / or slaked lime at room temperature to 40°C.

[0030] In producing this Bordeaux mixture composition, it is preferable to add the aqueous solution of copper sulfate to the aqueous suspension of quicklime and / or slaked lime while stirring.

[0031] The Bordeaux mixture composition of the present invention, and any diluted Bordeaux mixture composition thereof, have a neutral pH because the ratio of slaked lime or quicklime raw materials in the lamellar lime to the mass of copper sulfate raw materials in the copper sulfate aqueous solution is smaller than that of conventional Bordeaux mixture compositions, which are alkaline due to a higher ratio. Therefore, it can be maintained in a neutral pH even after dilution, and can also be mixed with other pesticides.

[0032] This Bordeaux mixture composition and its diluted solution are fungicides and pesticides containing posnichiite and basic copper calcium sulfate trihydrate as active ingredients. They contain active ingredients that are completely different from those of conventional alkaline Bordeaux mixture compositions. As a result, they are stable and do not discolor or deteriorate even when stored for long periods.

[0033] This Bordeaux mixture composition and its diluted solution possess excellent efficacy and high safety, comparable to conventional alkaline Bordeaux mixture compositions and their diluted solutions, including high bactericidal activity against a wide range of pathogens affecting crops, preventive effects due to pathogen resistance, and relatively long residual effects.

[0034] This Bordeaux mixture composition can be easily and safely prepared at the desired concentration to exhibit the intended efficacy immediately before tasks such as spraying on individual crops, resulting in high work efficiency.

[0035] According to this method for producing Bordeaux mixture, the active ingredients, posnachite and basic copper calcium sulfate trihydrate, can be suspended while maintaining an appropriate particle size that is not excessively large. As a result, the yield and production yield are good, and large-scale production can be easily carried out.

[0036] This figure shows a combined chart of X-ray crystal diffraction of the dry components of Bordeaux mixture compositions to which the present invention is applied and Bordeaux mixture compositions to which the present invention is not applied.

[0037] The following describes in detail embodiments for carrying out the present invention, but the scope of the present invention is not limited to these embodiments.

[0038] The Bordeaux mixture composition of the present invention contains, in a quantity ratio of 100 parts by mass of solid or dry components, CaSO4. ４ ・2H ２ O and / or CaSO ４ 0.5H ２ 50 to 95 parts by mass of gypsum represented by O, preferably 55.3 to 60.7 parts by mass, and a hydrated basic copper sulfate mineral, Cu, as the active ingredient of the antibacterial agent / insecticide. ４ (SO ４ )(OH) ６ ・H ２ 2 to 30 parts by mass of posnyacite, preferably 15.6 to 26.4 parts by mass, and CaCu as another active ingredient for antibacterial and insecticidal agents. ４ (SO ４ ) ２ (OH) ６ 3H ２ This is an aqueous suspension (slurry) containing 2 to 30 parts by mass, preferably 18.2 to 25.2, of basic copper calcium sulfate trihydrate represented by O. Such a Bordeaux mixture composition has a neutral pH, an appropriate particle size, and exhibits excellent efficacy such as high bactericidal activity, preventive effect due to pathogen resistance, and long residual effect, as well as high safety. Because the active ingredients of these fungicides and pesticides are insoluble or sparingly soluble in water, the Bordeaux mixture composition is preferably in slurry form.

[0039] This Bordeaux mixture composition preferably consists of a basic copper sulfate mineral, Cu. ４ (SO ４ )(OH) ６ This refers to an aqueous suspension that contains no brochantite, or if present, a maximum of 0.8 parts by mass, preferably 0.5 parts by mass, and more preferably 0.1 parts by mass, of the solid or dry components per 100 parts by mass. If brochantite is present in amounts exceeding this range, it will change color from light blue to dark gray over time during long-term storage and deteriorate. The mechanism of discoloration and deterioration is not entirely clear, but it is presumed that the brochantite decomposes posnakite and basic copper calcium sulfate trihydrate into copper oxide, leading to a blackening and subsequent discoloration.

[0040] Furthermore, this Bordeaux mixture composition preferably contains Ca(OH) ２ This means that the aqueous suspension contains no calcium hydroxide, or at most 0.5 parts by mass, per 100 parts by mass of the dry component. As a result, this Bordeaux mixture composition, and a 500-fold aqueous dilution of the Bordeaux mixture composition obtained by appropriately diluting it at the time of use, will have a pH in the neutral range of 5.0 to 8.9, preferably pH 5.8 to 8.6, and more preferably pH 6.5 to 8.0, allowing it to be mixed with other pesticides.

[0041] Furthermore, this Bordeaux mixture composition preferably contains Ca ６ Cu ３ (SO ４ ) ３ (OH) １２ ・2H ２ This refers to an aqueous suspension in which the substance represented by O, vonbezin-Scheit, is not contained in 100 parts by mass of the solid or dry components, or if it is contained, it is contained in a maximum of 0.5 parts by mass.

[0042] To create a Bordeaux mixture composition of this type, a copper sulfate salt, such as CuSO4, is added to an aqueous suspension of quicklime and / or slaked lime. ４ ・5H ２ This is achieved by adding an aqueous solution of copper(II) sulfate pentahydrate or anhydrous copper(II) sulfate, represented by O, to prepare posnakite or basic copper calcium sulfate trihydrate, which are active ingredients in antibacterial and insecticidal agents, as reaction products, by mixing copper sulfate and quicklime and / or slaked lime in a mass ratio of 8.5 to 11.5:1.5 to 2.5, preferably 9.5 to 11.5:1.5 to 2.5, more preferably 9.9 to 10.1:1.9 to 2.1, and even more preferably 10:2 (equivalent to formula 10-2), while stirring with desired stirring efficiency under specific temperature conditions and a specific slow mixing speed. If the mass ratio of quicklime and / or slaked lime is greater than this range, vonbezingite will be produced in large quantities, and the amount of residual calcium hydroxide will increase, making it more likely to exhibit alkalinity, as well as causing discoloration over time during long-term storage.

[0043] The mass ratio of the solid or dry components in this Bordeaux mixture composition is calculated from the intensity ratio obtained by X-ray powder crystal diffraction. Rietveld analysis quantitatively estimates the powder components by fitting the explanatory pattern obtained from powder X-ray analysis with a diffraction pattern calculated from crystal parameters related to crystal structure and peak shape, such as lattice constant, atomic polarization coordinates, atomic occupancy, and atomic displacement parameters, and calibration parameters such as background, zero-point shift, sample displacement parameter, sample transmission parameter, surface roughness parameter, and profile symmetry parameter, using methods such as the least squares method. Analysis software such as Highscore from Spectris Corporation is used for such Rietveld analysis.

[0044] This Bordeaux mixture composition has a copper atom mass of 35 to 70,000 ppm, more preferably 39.5 to 49,500 ppm, in an aqueous suspension. The copper atom mass is determined, for example, by analyzing the elemental amount using inductively coupled plasma mass spectrometry (ICP-MS). If the amount exceeds this range, the desired antibacterial or insecticidal effects will not be further enhanced. On the other hand, if the amount falls below this range, sufficient antibacterial or insecticidal effects will not be obtained.

[0045] Conventional Bordeaux mixture compositions, such as formulas 3-3 to 6-6, and 2-10 to 4-12, are prepared by adding an aqueous solution of copper sulfate to an aqueous suspension of quicklime and / or slaked lime to produce copper calcium sulfate, etc. In this process, the amount of quicklime and / or slaked lime is equal to or greater than the amount of copper sulfate (i.e., more than equimolar) relative to the raw material copper sulfate, so the pH tends to be in the alkaline range. Moreover, in these conventional Bordeaux mixture compositions, for example, in formula 6-6 where the mass ratio of copper sulfate to quicklime and / or slaked lime is 22.5% by mass of gypsum, 36.9% by mass of calcium hydroxide, 37.6% by mass of vonbezingite as an antibacterial and insecticidal component, and 0.0% by mass of brochant copper ore in the solid or dry components, and as a result they have excellent long-term stability even when stored for a long period of time, which is in stark contrast to the present invention, which exhibits long-term stability by using posnakite or basic copper calcium sulfate trihydrate as the active ingredient of the antibacterial and insecticidal agent.

[0046] Furthermore, conventional Bordeaux mixture compositions prepared using copper sulfate and copper chloride or sodium chloride, with basic copper chloride as the active ingredient in antibacterial and insecticidal agents, and other conventional Bordeaux mixture compositions prepared using copper sulfate and sodium hydroxide, neither contain posnikaite, basic copper calcium sulfate trihydrate, nor vonbezinscheith as active ingredients in antibacterial and insecticidal agents. This is in stark contrast to the present invention, which exhibits long-term stability by using posnikaite or basic copper calcium sulfate trihydrate as the active ingredient in antibacterial and insecticidal agents.

[0047] The solid or dried components of the Bordeaux mixture composition are obtained by filtration, for example, filtration using filter paper with retaining particles of 0.5 μm, followed by drying (air drying, vacuum drying, or vacuum drying) and grinding as necessary, or by drying (air drying, vacuum drying, or vacuum drying) a small sample fraction and grinding as necessary. Since the components do not deteriorate or change with such drying methods, the obtained solid or dried components reflect the composition of the active ingredients in the Bordeaux mixture composition that act as antibacterial and insecticidal agents.

[0048] The Bordeaux mixture composition exhibits sufficient bactericidal and pest control effects by containing, for example, 20 to 40% by mass, preferably 25 to 35% by mass, and more preferably 30.00 to 30.52% by mass of the gypsum, posnichiite, and basic copper calcium sulfate trihydrate in the aqueous suspension.

[0049] The Bordeaux mixture composition may optionally contain additives, such as surfactants including anionic surfactants, cationic surfactants, and nonionic surfactants; dispersing stabilizers such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, and starch; alkaline agents such as sodium silicate and sodium phosphate; acidifying agents such as adipic acid, citric acid, and trisodium citrate; chelating agents such as EDTA, etidronic acid, and sodium citrate; preservatives such as benzoic acid and parahydroxybenzoic acid esters; spreading agents such as paraffin, polyoxyethylene resin acid esters, and silicones; and dispersants such as sodium polycarboxylate, sodium condensed naphthalene sulfonate, and phosphonic acid amine salts.

[0050] This Bordeaux mixture composition, in which the gypsum, posnichiite, and basic copper calcium sulfate trihydrate each have an average particle size of 3 to 5 μm, more preferably 3.5 to 4.5 μm, becomes a uniform suspension simply by shaking or stirring at the time of use. Moreover, when the diluted Bordeaux mixture is prepared and sprayed immediately, it does not cause nozzle clogging.

[0051] This Bordeaux mixture composition meets the CIPAC MT 184 standard for suspensibility, with a Suspensibility of 60% or higher.

[0052] This Bordeaux mixture composition, for example, was subjected to an accelerated storage test by storing it at 40°C for 7 days (equivalent to 91 days at 25°C), referencing the Collaborative International Pesticides Analytical Council Limited (CIPAC) MT46.3 accelerated storage test. The results were in accordance with Section 3 of the "Guidance on Quality Assessment of Pesticides (Formulations) (Types, Names, Composition, Manufacturing Methods, Physical and Chemical Properties and Analytical Methods of Pesticides) (Notification No. 4-Sho-An 6006, dated February 22, 2023, issued by the Director of the Agricultural Products Safety Management Division, Consumer and Food Safety Bureau, Ministry of Agriculture, Forestry and Fisheries) https: / / www.maff.go.jp / j / nouyaku / n_touroku / attach / pdf / index-53.pdf". As stated in "B) Hue" under "(E) Range of Color" in "5. Physical and Chemical Properties of Pesticides" of the "Basic Principles of Review," it is defined that "adjacent formulas, etc., are defined as those whose hue symbols overlap in the representation using the three attributes." For example, this refers to adjacent formulas in the permutation of -Red-Yellow-Red (Brown)-Yellow-Yellow-Green-Green-Blue-Blue-Blue-Violet-Violet-Red-Violet-. In the case of a Bordeaux mixture composition, the hue name is normally: blue-green (2.5BG) [indicated by the three-attribute symbol, light blue-green 2.5G7 / 6 to blue-green 2.5BG4.5 / 8 to dark blue-green 2.5BG3 / 5]. After storage, the hue name may remain blue-green, or it may be green (2.5g) [indicated by the three-attribute symbol, light green 2.5G7 / 6 to green 2.5G5 / 9 to dark green 2.5G3 / 5], or blue (2.5PB) [indicated by the three-attribute symbol, light blue 2.5PB6.5 / 7 to blue 2.5PB4 / 10 to dark blue 2.5PB2.5 / 5], within the range of adjacent hues. A change in hue exceeding this range is evaluated as discoloration. Specifically, if the Bordeaux mixture composition is blue-green immediately after preparation, it will turn blue-green, green, or blue after, for example, 7 days at 40°C (equivalent to 91 days at 25°C), indicating that it will not discolor even after long-term storage. The stability was predicted based on the results of this accelerated test, using the Arrhenius equation and other methods.According to these guidelines, storage at 40°C for one month is equivalent to storage at room temperature for one year, and the expiration date for a test stored at 40°C for six months should be set to five years and six months. Alternatively, instead of storing at 40°C for seven days, the color may be examined after storage at 25°C for 91 days, 30°C for 24 days (equivalent to storage at room temperature for 91 years), or 54°C for two days (equivalent to storage at room temperature for 91 years).

[0053] Bordeaux mixture is a fungicide and pesticide that exhibits broad and strong fungicidal and insecticidal effects against filamentous fungi, bacterial diseases, slugs, and other pests. Specifically, it is effective against blue mold (yam), late blight (taro, tomato, potato, cherry tomato), gray mold (yellow peach), canker (apricot, plum, citrus, kiwi, mango), brown spot (yellow peach), brown spot (walnut), stem blight (fig), trunk rot (citrus, sweet potato), canker (loquat), black spot (pear), black spot (citrus), black rot (grape), bacterial black spot (walnut), black leaf blight (carrot), rust (grape), bacterial resin disease (yellow peach), purple spot (asparagus), spring rot (garlic), red blight (brown), bacterial spot (peach), and so on. This fungicide and pest control agent exhibits fungicidal effects against a wide range of pathogens and pests, including leaf blight (citrus), anthracnose (avocado, strawberry, olive, walnut, watermelon, tea), corn blight (watermelon), soft rot (vegetables), white spot (ginger), white leaf spot (garlic), leaf blight (asparagus, konjac, lily), leaf spot (carrot), bacterial leaf spot (akebi), late blight (grape), rot (konjac), downy mildew (grape), snails (citrus), slugs (citrus), and African giant snails (passion fruit, papaya).

[0054] The mechanism of action for the bactericidal and insecticidal effects of Bordeaux mixture compositions and their diluted solutions is due to copper ions gradually dissolving from poorly soluble posnichiite and basic copper calcium sulfate trihydrate. These copper ions exert their bactericidal effect through thiol inhibition, which oxidizes sulfhydryl enzymes. Furthermore, since slugs and other insects avoid copper ions, Bordeaux mixture compositions and their diluted solutions exert their pest control effects.

[0055] Whether the Bordeaux mixture composition of the present invention uses sparingly soluble posnichiite or basic copper calcium sulfate trihydrate as an active ingredient, or whether it uses sparingly soluble vonbezingite or brochantite as an active ingredient, as in the conventional Bordeaux mixture compositions of formulas 3-3 to 6-6 to 2-10 to 4-12, the pharmacological effects are equivalent because they all exhibit the same mechanism of action: copper ions are gradually released due to the moderate particle size that allows them to easily adhere to and suspend crops. In fact, the in vitro antibacterial activity of the Bordeaux mixture composition of the present invention and the conventional Bordeaux mixture composition are almost equivalent.

[0056] When using this Bordeaux mixture composition for prevention and control of target crops and target pathogens, it is diluted with water 2 to 10,000 times, preferably 2 to 2,000 times, more preferably 100 to 2,000 times, and even more preferably 500 to 2,000 times, to prepare a diluted Bordeaux mixture composition, which is then used by spraying.

[0057] The Bordeaux mixture composition of the present invention is produced by the following method.

[0058] To an aqueous suspension of quicklime and / or slaked lime, an aqueous solution of copper sulfate, particularly copper(II) sulfate pentahydrate, is slowly added, stirring as necessary, so that the mass ratio of the copper sulfate to the quicklime and / or slaked lime is 8.5 to 11.5:1.5 to 2.5, preferably 9.5 to 10.5:1.5 to 2.5, more preferably 9.9 to 10.1:1.9 to 2.1, and even more preferably 10:2, thereby forming a solid. A Bordeaux mixture composition can be produced by a step of producing an aqueous suspension containing, in a monetary ratio of 50 to 95 parts by mass, preferably 55.3 to 60.7 parts by mass, gypsum, 2 to 30 parts by mass, preferably 15.6 to 26.4 parts by mass, and 2 to 30 parts by mass, preferably 18.2 to 25.2 parts by mass, basic copper calcium sulfate trihydrate, in 100 parts by mass of the components or dry components, and containing no or at most 0.1 parts by mass of brochant copper ore.

[0059] Aqueous suspension of quicklime and / or slaked lime, also known as milk lime, is composed of calcium hydroxide: Ca(OH) ２The amount is adjusted to approximately 5.0 to 52.6 g / 100 g, preferably 8.0 to 50.0 g / 100 g, and more preferably 10.0 to 43.2 g / 100 g. On the other hand, an aqueous solution of copper sulfate salt, particularly copper(II) sulfate pentahydrate, is copper(II) sulfate: Cu(II)SO ４ The non-hydrated substance is adjusted to approximately 15.5 to 20.8 g / 100 g, preferably 17.3 to 19.1 g / 100 g, and more preferably 18.0 to 18.4 g / 100 g.

[0060] The rate at which the aqueous solution of copper sulfate is added to the aqueous suspension of quicklime and / or slaked lime is at least 30 minutes, specifically, at a rate of 3.33 parts by volume / minute or less for every 100 parts by volume of the aqueous solution of copper sulfate. If the rate is faster than this, vonbezingite and brochantite will be formed in large quantities, and this will cause discoloration over time during long-term storage. On the other hand, it is preferable that the amount of vonbezingite formed is within the above range, and if the amount of brochantite increases and exceeds 0.1 parts by mass per 100 parts by mass of solid or dry components, this will cause discoloration over time during long-term storage, causing the product to fall outside the standards based on the Agricultural Chemicals Control Law and making it impossible to manufacture and sell as a product.

[0061] The reason why the quality and discoloration suppression effect deteriorate depending on the rate of addition is not entirely clear, but it is presumed to be due to the following reasons. An aqueous suspension of quicklime and / or slaked lime is an aqueous suspension of calcium hydroxide, but the solubility of calcium hydroxide is only about 0.185 g / 100 ml at 0°C, about 0.17 g / 100 ml at 25°C, and about 0.077 g / 100 ml at 100°C, and the solubility decreases as the temperature increases. On the other hand, an aqueous solution of copper sulfate, such as copper(II) sulfate, has a solubility of 14.3 g / 100 ml at 0°C, about 32 g / 100 ml at 20°C, and 75.4 g / ml at 100°C, and the solubility improves as the temperature increases. Therefore, when an aqueous solution of copper sulfate is added to an aqueous suspension of quicklime and / or slaked lime, it forms basic copper calcium sulfate trihydrate via a reaction intermediate. In this case, the formation of brochant copper ore is at most 0.1 parts by mass per 100 parts by mass of the solid or dry components of the Bordeaux mixture composition, which inhibits the conversion of basic copper calcium sulfate to copper oxide. Therefore, it is presumed that deterioration and quality degradation are suppressed, and discoloration is also suppressed even when stored for a long period of time.

[0062] When adding an aqueous solution of copper sulfate to an aqueous suspension of quicklime and / or slaked lime, the addition should be made at a temperature between room temperature (1-30°C) and 40°C, preferably between room temperature (15-25°C) and more preferably between 35°C and 40°C. Temperature control is important because if the temperature is too high, the reaction will accelerate, the composition ratio of the final product will differ, and as a result, discoloration will occur.

[0063] The aqueous suspension prepared by adding quicklime to water is exothermic, so when adding an aqueous solution of copper sulfate to the aqueous suspension of quicklime and / or slaked lime, it is necessary to cool the suspension to a temperature between room temperature (1-30°C) and 40°C. If the cooling is insufficient, the reaction will proceed more rapidly, resulting in a different composition ratio of the final product and consequently discoloration. Alternatively, an aqueous solution of copper sulfate, such as copper(II) sulfate, may be dissolved in cold water, room temperature water, or warm water under heating, but when adding the aqueous solution of copper sulfate to the aqueous suspension of quicklime and / or slaked lime, it is necessary to cool the suspension to a temperature between room temperature (1-30°C) and 40°C. If the cooling is insufficient, the reaction will similarly proceed more rapidly, resulting in a different composition ratio of the final product and consequently discoloration.

[0064] When adding an aqueous solution of copper sulfate to an aqueous suspension of quicklime and / or slaked lime, stirring is preferable. The stirring operation is not particularly limited, but stirrers such as stirrers, stand mixers, bag mixers, Nauta mixers, Henschel mixers, kneaders, pony mixers, and crutches can be used. Examples of stirring blades for stirrers include ribbons, screws, anchors, gates, fan turbines, paddles, inclined paddles, DS impellers, cross-shaped blades, and propeller-shaped blades. If stirring is insufficient, the reaction will not proceed, the composition ratio of the final product will differ, and as a result discoloration will occur, so it is preferable to stir thoroughly.

[0065] Depending on the type of crop, the type of target pathogen or pest, the season, and the number and timing of past applications, the Bordeaux mixture composition is diluted with water at a predetermined volume ratio of 2 to 10,000 times, preferably 2 to 2,000 times, to prepare a diluted Bordeaux mixture composition, which is then promptly sprayed onto the desired crop. Since this diluted Bordeaux mixture composition has a neutral pH, it may be used in the form of a diluted Bordeaux mixture composition mixed with other pesticides as needed. The Bordeaux mixture composition and its diluted Bordeaux mixture composition contain gypsum, posnichiite, and basic copper calcium sulfate trihydrate with appropriate particle sizes, and possess excellent efficacy and high safety, including high bactericidal activity and pathogen resistance against a wide range of pathogens affecting crops, as well as relatively long residual effect and suspension, allowing for the prevention and control of pathogens and pests for a predetermined period.

[0066] The following describes examples to which the present invention is applied and comparative examples to which the present invention is not applied, in comparison with each other.

[0067] (Example 1) 6.19 g of fine slaked lime was taken and placed in a 1 liter beaker, diluted with 8.40 g of water to disperse it, and while stirring, copper sulfate pentahydrate (CuSO4) was added to 61.08 g of water. ４ ・5H ２ O) An aqueous solution of copper sulfate containing 24.33 g was added at a rate of 180 minutes and a temperature of 40°C to prepare approximately 100 g of a solution equivalent to 10-2 Bordeaux mixture, where the calcium equivalent mass was 2 for every 10 units of anhydrous copper sulfate equivalent mass.

[0068] (Component Analysis) 5 ml of the Bordeaux mixture composition from Example 1 was dried at 25°C under a pressure of 1 torr. The resulting dried components were ground in a mortar and pestle, and X-ray crystal diffraction measurements were performed using an X-ray crystal diffraction analyzer (Panalytical EMPYREAN system: product name of Spectris Corporation). The X-ray crystal diffraction spectrum is shown in Figure 1. Furthermore, Rietveld analysis was performed on the X-ray crystal diffraction spectrum using Rietveld analysis software (Highscore: product name of Spectris Corporation) to estimate and identify the contained components. The results are shown in Table 1.

[0069] (Stability Evaluation Test) Two ml of the Bordeaux mixture composition from Example 1 was stored at 25°C for seven days. After storage, it was visually measured at room temperature, atmospheric pressure, and under natural light. The difference in color from immediately after preparation was measured in accordance with the "Guidance on Quality Assessment of Agricultural Chemicals (Formulations)," using blue-green (2.5BG) as the reference and visually confirming whether it fell within the range of adjacent green (2.5G) and blue (2.5PB). This was evaluated in two stages: ○ if it was within the range of adjacent colors, and × if it exceeded the range of adjacent colors. The results are shown in Table 1.

[0070] (Comparative Example 1) 18.7 g of fine slaked lime was taken, placed in a 1 liter beaker, diluted with 20.4 g of water, and dispersed. While stirring, copper sulfate (CuSO4) was added to 44.4 g of water. ４ ・5H ２O) A copper sulfate aqueous solution containing 14.8 g of dissolved copper sulfate was gradually added at a temperature of 35-40°C to prepare approximately 100 g of a 6-6 Bordeaux mixture equivalent to 6 parts anhydrous copper sulfate and 6 parts calcium.

[0071] (Component Analysis) The Bordeaux mixture composition of Comparative Example 1 was subjected to X-ray crystal diffraction measurement in the same manner as in Example 1. The X-ray crystal diffraction spectrum is shown in Figure 1, and the results of estimating and identifying the constituent components using Rietveld analysis of the X-ray crystal diffraction spectrum are shown in Table 1.

[0072] (Stability Test) Two ml of the Bordeaux mixture composition of Comparative Example 1 was tested in the same manner as the (stability test) of Example 1. The results are shown in Table 1.

[0073]

[0074] As is clear from Figure 1 and Table 1, the Bordeaux mixture composition of Example 1 to which the present invention is applied has the composition of gypsum, posnachite, and basic copper calcium sulfate trihydrate, and has a pH of 5.0 to 8.9 when diluted 500 times. The Bordeaux mixture composition of Comparative Example 1 to which the present invention is not applied (the dry components correspond to granular IC Bordeaux 66D manufactured by Inoue Lime Industry Co., Ltd.) has the composition of gypsum, calcium hydroxide, and von bengite, and has a pH of 12 when diluted 100 times. The compositions of the two are completely different. Based on their compositions, neither composition shows discoloration or deterioration in stability evaluation tests.

[0075] (Example 2, Comparative Example 2) (Preparation Method) The Bordeaux mixture composition of Example 2 (corresponding to formula 10-2 Bordeaux mixture) was prepared in the same manner as in Example 1, except that the rate of adding the copper sulfate aqueous solution was 60 to 120 minutes. The Bordeaux mixture composition of Comparative Example 2 was prepared in the same manner as in Example 1, except that the rate of adding the copper sulfate aqueous solution was 10 to 20 minutes.

[0076] (Stability Test and Component Analysis) After storing each Bordeaux mixture composition of Example 2 and Comparative Example 2 at 25°C for 0 weeks, 1 week, or 2 weeks, stability tests and X-ray crystal diffraction measurements were performed in the same manner as in Example 1 (Component Analysis). The results of estimating and identifying the contained composition from the X-ray crystal diffraction spectrum using Rietveld analysis are shown in Table 2.

[0077]

[0078] As is clear from Table 2, the Bordeaux mixture composition of Example 2, to which the present invention is applied, has a composition in the ranges of 50 to 70 parts by mass of gypsum, 10 to 30 parts by mass of posnakite, and 10 to 30 parts by mass of basic copper calcium sulfate trihydrate, and is a composition with a pH of 6 to 8 when diluted 500 times with water. Based on these compositions, it does not discolor or deteriorate in stability evaluation tests. However, the Bordeaux mixture composition of Comparative Example 2, which is outside the application range of the present invention and is outside these ranges, shows a significant difference from Example 2, as it lacks discoloration, deterioration, and stability due to the difference in the composition ratio, resulting in a pH of 12 when diluted 100 times. It should be noted that, as in Comparative Example 2-2, if the temperature of the aqueous suspension of quicklime and / or slaked lime or the aqueous solution of copper sulfate is too low, it is presumed that even if the content of brochantite is low, the content of basic copper calcium sulfate trihydrate becomes too high, resulting in discoloration, deterioration, and lack of stability.

[0079] (Comparative Example 3) 37.1 g of fine slaked lime was taken, placed in a 1 liter beaker, diluted with 50.4 g of water to disperse, and while stirring, copper sulfate (CuSO4) was added to 400.1 g of water. ４ ・5H ２ O) A copper sulfate aqueous solution containing 112.3 g of dissolved copper sulfate was gradually added at a temperature of 35-40°C to prepare approximately 100 g of a 7-2 formula Bordeaux mixture equivalent to 7 parts anhydrous copper sulfate and 2 parts calcium.

[0080] (Component Analysis) The Bordeaux mixture composition of Comparative Example 3 was subjected to stability testing and X-ray crystal diffraction measurement in the same manner as in Example 1. The results of estimating and identifying the constituent components from the X-ray crystal diffraction spectrum using Rietveld analysis are shown in Table 3.

[0081]

[0082] As is clear from Table 3, the Bordeaux mixture equivalent of formula 7-2 in Comparative Example 3 has a completely different composition from both the Bordeaux mixture equivalent of formula 10-2 in Example 1 of the present invention and the Bordeaux mixture equivalent of formula 6-6 in Comparative Example 1. This indicates that the ratio of quicklime and / or slaked lime to copper sulfate is a major factor in the difference in composition.

[0083] (Efficacy Test) The Bordeaux mixture composition of Example 1 and the Bordeaux mixture composition of Comparative Example 1 were diluted 500 times with water, and various bactericidal tests were performed in vitro. The results showed that their bactericidal effects were equivalent.

[0084] According to the Bordeaux mixture composition and its manufacturing method of the present invention, a diluted solution of the Bordeaux mixture composition, which is used as an agricultural chemical such as a fungicide or insecticide, can be easily and quickly prepared for use, sprayed on crops, and used to kill pathogens and control pests.

Claims

1. A Bordeaux mixture composition characterized by being an aqueous suspension containing, in a mass ratio of 50 to 95 parts by mass of gypsum, 2 to 30 parts by mass of posnachite, and 2 to 30 parts by mass of basic copper calcium sulfate trihydrate, in 100 parts by mass of solid or dry components, and containing no or at most 0.8 parts by mass of brochant copper ore.

2. The Bordeaux mixture composition according to claim 1, characterized in that, in 100 parts by mass of the solid component or dry component, calcium hydroxide and vonbezin Scheith are each independently present in no part or at most 0.5 parts by mass.

3. The Bordeaux mixture composition according to claim 1, characterized in that the gypsum, the posnichiite, and the basic copper calcium sulfate trihydrate are contained in the aqueous suspension in an amount of 20 to 40% by mass.

4. The Bordeaux mixture composition according to claim 1, characterized in that it is intended to be used after being diluted with water in a volume ratio of more than 1:2000:1 or less.

5. The Bordeaux mixture composition according to claim 1, characterized in that, after storage at 25°C for two years, or after a corresponding accelerated test, when compared with the product immediately after preparation under natural light at room temperature and pressure, the color is within the range of adjacent colors in accordance with the "Guidance on Quality Assessment of Agricultural Chemicals (Formulations)".

6. The Bordeaux mixture composition according to claim 1, characterized in that the mass ratio of the gypsum, the posnakite, the basic copper calcium sulfate trihydrate, and the brochantite in 100 parts by mass of the solid component or dry component is a value calculated from the intensity ratio of the solid component or dry component in X-ray powder crystal diffraction.

7. The Bordeaux mixture composition according to claim 1, characterized in that the pH is 5.0 to 8.9 when diluted 500 times.

8. The Bordeaux mixture composition according to claim 1, characterized by containing at least one additive selected from surfactants, dispersion stabilizers, alkalizing agents, acidifying agents, chelating agents, preservatives, spreading agents, and dispersants.

9. A method for producing a Bordeaux mixture composition, characterized by adding an aqueous solution of copper sulfate to an aqueous suspension of quicklime and / or slaked lime in a mass ratio of 8.5 to 11.5:1.5 to 2.5 between the copper sulfate and the quicklime and / or slaked lime, thereby producing an aqueous suspension containing, by mass ratio of 50 to 70 parts by mass of gypsum, 10 to 30 parts by mass of posnakite, and 10 to 30 parts by mass of basic copper sulfate calcium trihydrate, and containing no or at most 0.1 parts by mass of brochant copper ore, per 100 parts by mass of solid or dry components.

10. The method for producing the Bordeaux mixture composition according to claim 9, characterized in that the mass ratio of the copper sulfate salt to the quicklime and / or slaked lime is 8.5 to 11.5:1.5 to 2.

5.

11. The method for producing the Bordeaux mixture composition according to claim 9, characterized in that the copper sulfate salt is copper(II) sulfate pentahydrate or anhydrous copper(II) sulfate.

12. The method for producing the Bordeaux mixture composition according to claim 9, characterized in that the solid component or dry component is the filtrate and / or dry product of the aqueous suspension.

13. A method for producing a Bordeaux mixture composition according to claim 9, characterized in that 100 parts by volume of the aqueous solution of the copper sulfate salt is added to the aqueous suspension of quicklime and / or slaked lime at a rate of 3.33 parts by volume / min or less.

14. A method for producing a Bordeaux mixture composition according to claim 9, characterized by adding an aqueous solution of the copper sulfate to the aqueous suspension of quicklime and / or slaked lime at room temperature to 40°C.

15. A method for producing a Bordeaux mixture composition according to claim 9, characterized by adding an aqueous solution of copper sulfate to the aqueous suspension of quicklime and / or slaked lime while stirring.

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