Bordeaux liquid composition and method for producing the same

Abstract

Provided is a stock solution composition for Bordeaux liquid that has a neutral pH range, is less likely to cause discoloration or deterioration over time, is stable even when stored for a long period, and exhibits medicinal effects such as a sufficient bactericidal effect. 【Solution means】The Bordeaux liquid composition is a water suspension containing, in a quantitative ratio in 100 parts by mass of a solid component or a dry component, 50 to 95 parts by mass of gypsum, 2 to 30 parts by mass of posnjakite, and 2 to 30 parts by mass of calcium basic copper sulfate trihydrate, and containing no brochantite or containing at most 0.8 parts by mass thereof.

Description

Technical Field

[0001] The present invention relates to a bactericide and a pest control agent containing basic copper calcium sulfate trihydrate as an active ingredient, which is used as a pesticide for agricultural crops, does not discolor or deteriorate stably even after long-term storage, and is a stock solution for preparing a Bordeaux liquid dilution for dilution and spraying treatment during use. The present invention also relates to a diluted Bordeaux liquid composition for diluting the Bordeaux liquid composition and spraying it on agricultural crops during use, and a method for producing the Bordeaux liquid composition.

Background Art

[0002] The Bordeaux liquid composition is a bactericide and a pest control agent having high bactericidal properties against a wide range of pathogenic bacteria on agricultural crops such as fruit trees such as grapes, citrus fruits, peaches, and apples, and vegetables such as cabbages, cucumbers, and tomatoes, a preventive effect due to pathogen resistance, a relatively long residual effect, and high safety. It is a traditional pesticide with a history of about 120 years and is still used today. Since the Bordeaux liquid composition is a stock solution and its concentration is too high, it is appropriately diluted during use according to the target agricultural crops and used for spraying treatment on the desired agricultural crops.

[0003] Conventionally, for the Bordeaux liquid composition, agricultural workers have prepared a mixed suspension solution of an aqueous copper sulfate solution and a lime milk obtained by suspending slaked lime or quicklime in water on-site during use, and diluted it according to the crops, target pathogenic bacteria, and pests before use. At this time, after making slaked lime or quicklime into lime milk, while stirring at low temperature, an aqueous copper sulfate solution was added and appropriately diluted to prepare a Bordeaux liquid composition containing basic copper calcium sulfates during use, and it was quickly diluted and sprayed. For example, Non-Patent Document 1 describes the preparation of Bordeaux liquid compositions such as the 3-3 formula to 6-6 formula to 2-10 formula to 4-12 formula expressed by the number of grams of copper sulfate and slaked lime or quicklime in 100 ml of Bordeaux liquid, and they are still prepared at that ratio today.

[0004] When preparing a Bordeaux liquid composition, the digestion of quicklime and the dissolution of slaked lime are accompanied by rapid heat generation and are dangerous, and moreover, it is troublesome such as requiring cooling. Moreover, as time passes during mixing, the crystals of basic calcium copper sulfate grow too large, causing clogging during spraying, making it difficult to adhere to crops, and reducing the hanging property, so that the expression of high bactericidal properties and pathogen resistance is not inhibited. Therefore, temperature adjustment, stirring efficiency, mixing time, and mixing ratio are important factors for preparing high-quality basic calcium copper sulfates that are homogeneous and have a small particle size. As a result, a high degree of skill and a considerable amount of labor were required to prepare a high-quality Bordeaux liquid composition.

[0005] Therefore, recently, a Bordeaux liquid composition that pre-contains basic calcium copper sulfate as an active ingredient of an antibacterial agent and a pest control agent has been manufactured and sold, and it has come to be 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 in which a stock solution of a Bordeaux liquid obtained by mixing copper sulfate and quicklime or slaked lime is pulverized by 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 having 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, and each fine particle contains five different copper compounds, namely, antlerite Cu3 +2 (SO4)(OH)4, brochantite Cu4 +2 SO4(OH)6, chalcantite Cu +2 SO4·5H2O, natrocalcite NaCu2 +2Those having a regular crystalline microstructure composition containing (SO4)2OH·H2O and hydrated copper sulfate hydroxide Cu3(SO4)2(OH)2·4H2O / 2CuSO4·Cu(OH)2, and the size of the fine particles is 5 to 50 μm, copper fine particles are disclosed, and a process for preparing copper fine particles having antibacterial and / or biocidal activity, comprising: a) dissolving soluble copper sulfate in distilled water at a ratio of 1:10 w / w to prepare a solution; 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 and the precipitate, which is copper hydroxide gel, after 24 hours; d) emulsifying the gel-like precipitate obtained in step c) into a copper sulfate solution prepared by dissolving it in distilled water at a ratio of 1:5 w / v; 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 an outlet temperature of 80°C to 100°C. A process is disclosed that includes these steps.

[0007] In any of these Bordeaux liquid compositions, the pH tended to be alkaline because there was more of an alkaline component such as quicklime, slaked lime, or sodium hydroxide than copper sulfate.

[0008] Among these Bordeaux liquid compositions, those with a pH in the alkaline range containing basic copper sulfate calcium salts were preferably used. Such Bordeaux liquid compositions, by being alkaline and containing basic copper sulfate calcium salts, exhibit the effects of preventing phytotoxicity, improving adhesion or rain resistance compared to water-soluble copper sulfate because basic copper sulfate calcium salts contain calcium, and by being alkaline, they have strong bactericidal properties and can tilt the soil towards the alkaline side, thus having the effect of soil improvement.

[0009] With global warming, varietal improvement, and diversification, the types of pathogens and pests to be prevented have increased, and it has become necessary to mix multiple types of pesticides. Since the alkaline Bordeaux liquid composition may inhibit the efficacy of other pesticides and is difficult to mix, a Bordeaux liquid composition near neutrality has been desired.

[0010] However, when attempting to neutralize the Bordeaux liquid composition obtained by mixing while reducing the ratio of the raw material mass of slaked lime or quicklime in milk of lime to the raw material mass of copper sulfate in the copper sulfate aqueous solution to about 2:10, not only did it change color from light blue to dark gray within a few days, deviating from the regulations, but it also led to a decline in quality and could not be distributed on the market.

[0011] The inventors of the present invention have found that a new Bordeaux liquid composition prepared so as to contain different active ingredients as fungicides and pest control agents with a different pH in the neutral range compared to the conventional alkaline Bordeaux liquid composition with a higher ratio of the raw material mass of quicklime or slaked lime in milk of lime to the raw material mass of copper sulfate in the copper sulfate aqueous solution can exhibit equivalent efficacy without causing discoloration or deterioration, and have completed the present invention.

Prior Art Documents

Non-Patent Documents

[0012]

Non-Patent Document 1

Patent Documents

[0013]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0014] The present invention has been made to solve the above problems, and provides a Bordeaux liquid composition having a neutral pH range, being less likely to cause discoloration or deterioration over time, being stable even after long-term storage, and exhibiting medicinal effects such as a sufficient bactericidal effect, and a method for producing the same simply and safely.

Means for Solving the Problems

[0015] The Bordeaux liquid composition of the present invention made to achieve the above object is, in terms of mass ratio in 100 parts by mass of the solid component or dry component, Quality 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 calcium basic copper sulfate trihydrate, and is a water suspension that does not contain brochantite or contains 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, for example, such that 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, the gypsum, the posnjakite, and the calcium basic copper sulfate trihydrate in the aqueous suspension in an amount of 20 to 40% by mass, preferably 25 to 35% by mass, more preferably 30.00 to 30.52% by mass.

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

[0022] This Bordeaux liquid composition may have the solid component or the dry component as the filtrate and / or the dried product (for example, natural dried product, air-dried product, vacuum-dried product, or vacuum-dried product) of the aqueous suspension.

[0023] Specifically, this Bordeaux liquid composition is measured visually, for example, at normal temperature and normal pressure and under natural light, after storage at 25°C for 2 years, or after a corresponding accelerated test (for example, 2 weeks at 54°C), or after 7 days at 25°C, or after a corresponding accelerated test as 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 after storage at 54°C for 2 weeks, and compared with the product immediately after preparation. It is within the range of adjacent color tones according to the "Review Guidelines on the Quality of Pesticides (Types, Names, Compositions, Manufacturing Methods, Physical and Chemical Properties, and Analytical Methods of Pesticides) (Notice of the Director of the Agricultural Product Safety Management Section, Consumer and Safety Bureau, Ministry of Agriculture, Forestry and Fisheries, No. 6006, dated February 22, 2023) https: / / www.maff.go.jp / j / nouyaku / n_touroku / attach / pdf / index-53.pdf". The adjacent color tones are based on blue-green (2.5BG), and it is assumed that it can be visually confirmed whether it falls within the range of adjacent green (2.5G) and blue (2.5PB).

[0024] This Bordeaux liquid composition is about the gypsum, the posnjakite, the basic calcium copper sulfate trihydrate, and the brochantite. Among the solid components or 100 parts by mass of the dry components, The quality quantity ratio is , a calculated value from intensity ratio in X-ray powder crystal diffraction the solid component or the dry component is what is meant.

[0025] It is preferable that the pH of this Bordeaux liquid composition is 5.0 to 8.9, more preferably 5.8 to 8.6, and even more preferably 6.5 to 8.0 when diluted 500 times with water.

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

[0027] The method for producing the Bordeaux liquid composition of the present invention made to achieve the above object is to add an aqueous solution of a copper sulfate salt to an aqueous suspension of quicklime and / or slaked lime so 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, preferably 9.5 to 10.5:1.5 to 2.5, and more preferably 10:2. By doing so, in terms of quantity ratio in 100 parts by mass of the solid component or dry component, it contains 50 to 70 parts by mass of gypsum, preferably 55.3 to 60.7 parts by mass, 10 to 30 parts by mass of posnjakite, preferably 15.6 to 26.4 parts by mass, and 10 to 30 parts by mass of basic calcium copper sulfate trihydrate, preferably 18.2 to 25.2 parts by mass, and produces an aqueous suspension that does not contain brochantite or contains at most 0.1 part by mass. Quality is characterized by This production method is, for example, such 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. Specifically, this production method is such that the copper sulfate salt is copper sulfate (II) pentahydrate or anhydrous copper sulfate (II). In this production method, for example, the solid component or the dry component is that when it is the filtrate and / or dried product of the water suspension.

[0028] The method for producing this Bordeaux liquid composition is such that an aqueous solution of the copper sulfate salt is added to the water suspension of the quicklime and / or slaked lime at a rate of 3.33 volume parts or less per 100 volume parts of the aqueous solution of the copper sulfate salt (for example, added over 30 minutes).

[0029] The method for producing this Bordeaux liquid composition is such that the aqueous solution of the copper sulfate salt is preferably added to the water suspension of the quicklime and / or slaked lime at room temperature to 40°C.

[0030] The method for producing this Bordeaux liquid composition is such that the aqueous solution of the copper sulfate salt is preferably added to the water suspension of the quicklime and / or slaked lime while stirring.

Advantages of the Invention

[0031] The Bordeaux liquid composition of the present invention and a diluted solution of the Bordeaux liquid composition diluted as necessary have a pH in the neutral range, unlike the conventional Bordeaux liquid composition which is alkaline because the ratio of the raw material mass of slaked lime or quicklime in milk of lime to the raw material mass of copper sulfate in the copper sulfate aqueous solution is smaller. Therefore, not only can it be maintained in the neutral range even after dilution, but it can also be mixed with other pesticides.

[0032] This Bordeaux liquid composition and the diluted solution of the Bordeaux liquid composition are fungicides and pest control agents containing posnjakite and basic copper sulfate calcium trihydrate as active ingredients, and contain active ingredients completely different from those of the conventional alkaline Bordeaux liquid composition. As a result, it does not cause discoloration or deterioration even after long-term storage and is stable.

[0033] This Bordeaux liquid composition and the diluted solution of the Bordeaux liquid composition have excellent drug effects such as high bactericidal properties against a wide range of pathogenic bacteria on crops, preventive effects due to pathogen resistance, and relatively long residual effects, as well as high safety, equivalent to those of the conventional alkaline Bordeaux liquid composition and its diluted solution.

[0034] The diluted solution of this Bordeaux liquid composition can be prepared to exhibit the desired medicinal effect at the desired concentration simply and safely immediately before operations such as spraying on each crop, and the working efficiency is good.

[0035] According to the production method of this Bordeaux liquid composition, the active ingredients of posnjakite and calcium basic copper sulfate trihydrate can be suspended while maintaining an appropriate particle size that does not become too large, so the yield and production yield are good, and mass production can be easily achieved.

Brief Description of the Drawings

[0036]

Figure 1

Embodiments for Carrying Out the Invention

[0037] Hereinafter, embodiments for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these embodiments.

[0038] The Bordeaux liquid composition of the present invention is in a quantitative 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 represented by CaSO4·2H2O and / or CaSO4·0.5H2O, 2 to 30 parts by mass, preferably 15.6 to 26.4 parts by mass of posnjakite represented by Cu4(SO4)(OH)6·H2O, which is a hydrated basic copper sulfate mineral as an active ingredient of the antibacterial agent and insect repellent, 2 to 30 parts by mass, preferably 18.2 to 25.2 parts by mass of calcium basic copper sulfate trihydrate represented by CaCu4(SO4)2(OH)6·3H2O as another active ingredient of the antibacterial agent and insect repellent. The Bordeaux mixture composition is an aqueous suspension (slurry) containing the fungicide and pest control agent. Such a Bordeaux mixture composition has a neutral pH range, an appropriate particle size, and exhibits excellent efficacy such as a preventive effect due to high bactericidal activity and pathogen resistance, and a long residual effect, as well as high safety. Since the active ingredients of these fungicides and pest control agents are insoluble or poorly soluble in water, the Bordeaux mixture composition is preferably in the form of a slurry.

[0039] This Bordeaux mixture composition is preferably an aqueous suspension containing no Brochantite, a basic copper sulfate mineral represented by Cu4(SO4)(OH)6, or at most 0.8 parts by mass, preferably 0.5 parts by mass, and more preferably 0.1 parts by mass, per 100 parts by mass of solid or dry components. If Brochantite is contained in an amount exceeding this range, the color will change from light blue to dark gray over time during long-term storage, and the composition will deteriorate. Although the mechanism of discoloration and deterioration is not entirely clear, it is presumed that the Brochantite decomposes posnjakite and basic calcium copper sulfate trihydrate into copper oxide, causing the color to turn black and the discoloration to occur.

[0040] Moreover, this Bordeaux mixture composition is preferably an aqueous suspension that does not contain calcium hydroxide represented by Ca(OH)2, or contains only 0.5 parts by mass at most, per 100 parts by mass of dry components. 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 have a neutral pH of 5.0 to 8.9, preferably 5.8 to 8.6, and more preferably 6.5 to 8.0, making them suitable for mixing with other pesticides.

[0041] Furthermore, the Bordeaux mixture composition preferably contains Ca6Cu3(SO4)3(OH) 12 It is an aqueous suspension that does not contain any von Besinscheite, represented by von Besinscheite = 2H2O, or contains only a maximum of 0.5 parts by mass of von Besinscheite per 100 parts by mass of solid or dry components.

[0042] To obtain a Bordeaux liquid composition with such a composition, an aqueous solution of a copper sulfate salt, such as copper(II) sulfate pentahydrate represented by CuSO4·5H2O or anhydrous copper(II) sulfate, is added to a water suspension of quicklime and / or slaked lime. When preparing posnjakite and basic copper sulfate calcium trihydrate, which are the active ingredients of antibacterial and insect repellent agents, as the reactants, the copper sulfate salt and quicklime and / or slaked lime are mixed at a mass ratio of 8.5 - 11.5:1.5 - 2.5, preferably 9.5 - 11.5:1.5 - 2.5, more preferably 9.9 - 10.1:1.9 - 2.1, and even more preferably at a mixing ratio of 10:2 (equivalent to the 10 - 2 formula). The mixing is achieved by stirring at a specific temperature condition and a specific slow mixing rate with a desired stirring efficiency. If the mass ratio of quicklime and / or slaked lime exceeds this range, fonbeijingite will be generated and its production amount will increase. Moreover, the remaining amount of calcium hydroxide will increase, making it easier to show alkalinity, and it will cause discoloration over time during long-term storage.

[0043] The mass ratio of the composition in the solid component or dry component of this Bordeaux liquid composition is calculated from the intensity ratio in X-ray powder crystal diffraction. Rietveld analysis is to fit the explanatory pattern by powder X-ray analysis with crystal parameters related to the crystal structure and peak shape, such as lattice constant, atomic polarization coordinates, atomic occupancy, atomic displacement parameters, and calibration parameters, such as background, zero point shift, sample displacement parameter, sample transmission parameter, surface roughness parameter, profile symmetry parameter, etc., using the least squares method with the diffraction pattern calculated from these parameters to quantitatively estimate the powder components. For such Rietveld analysis, analysis software such as Highscore of Spectris Co., Ltd. is used.

[0044] This Bordeaux liquid composition has a mass of copper atoms present in the water suspension of 35 to 70,000 ppm, more preferably 39.5 to 49,500 ppm. The mass of copper atoms present is, for example, the result of analyzing the elemental amount by inductively coupled plasma mass spectrometry (ICP-MS). If it exceeds this range, the drug effects such as the desired antibacterial and insect repellent properties will not become stronger. On the other hand, if it is below this range, sufficient drug effects such as the desired antibacterial and insect repellent properties cannot be obtained.

[0045] Conventional Bordeaux liquid compositions such as those of formulas 3-3 to 6-6 to 2-10 to 4-12, etc. are prepared by adding an aqueous solution of a copper sulfate salt to a water suspension of quicklime and / or slaked lime to produce calcium copper sulfate, etc. When preparing, the quicklime and / or slaked lime are used in an amount equal to or more than the same mass part (i.e., more than equimolar) with respect to the copper sulfate salt as the raw material, so the pH tends to be in the alkaline range. Moreover, these conventional Bordeaux liquid compositions, for example, when the mass ratio of copper sulfate to quicklime and / or slaked lime is of formula 6-6, in the solid component or dry component, there is 22.5% by mass of gypsum, 36.9% by mass of calcium hydroxide, 37.6% by mass of fonbeijinzhaiite as an antibacterial and insect repellent component, and 0.0% by mass of brochantite. Therefore, because they have excellent stability over time even when stored for a long time, it is in good contrast with the present invention which exhibits stability over time by using posnjakite or basic calcium copper sulfate trihydrate as the active ingredient of the antibacterial and insect repellent agents.

[0046] Also, Bordeaux liquid compositions prepared using copper sulfate and copper chloride or sodium chloride in the conventional manner and having basic copper chloride as the active ingredient of the antibacterial and insect repellent agents, and other conventional Bordeaux liquid compositions prepared using copper sulfate and sodium hydroxide and having the active ingredient of the antibacterial and insect repellent agents, neither contain posnjakite, basic calcium copper sulfate trihydrate, nor fonbeijinshite as the active ingredient of the antibacterial and insect repellent agents. From this, it is in good contrast with the present invention which exhibits stability over time by using posnjakite or basic calcium copper sulfate trihydrate as the active ingredient of the antibacterial and insect repellent agents.

[0047] The solid or dry component of the Bordeaux liquid composition is obtained by filtration, for example, filtration through a filter paper with a retention particle size of 0.5 μm, followed by drying (air drying, vacuum drying, or freeze drying) and pulverization as necessary, or by drying (air drying, vacuum drying, or freeze drying) a small collected fraction and pulverizing it as necessary. Since the components do not deteriorate or change in such a drying method, the obtained solid or dry component reflects the composition of the active ingredient as an antibacterial agent and insect repellent in the Bordeaux liquid composition.

[0048] The Bordeaux liquid composition exhibits a sufficient bactericidal effect and pest control effect when the gypsum, the posnjakite, and the calcium basic copper sulfate trihydrate are contained, for example, in the water suspension, in an amount of 20 to 40% by mass, preferably 25 to 35% by mass, more preferably 30.00 to 30.52% by mass.

[0049] The Bordeaux liquid composition may contain additives as necessary, such as surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants; dispersion stabilizers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, 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 para-hydroxybenzoic acid esters; spreading agents such as paraffin, polyoxyethylene resin acid esters, and silicone; and dispersants such as sodium polycarboxylate, sodium condensed naphthalene sulfonate, and amine phosphonate salts.

[0050] This Bordeaux liquid composition forms a uniform suspension simply by shaking or stirring during use when the gypsum, the posnjakite, and the calcium basic copper sulfate trihydrate each have an average particle size of 3 to 5 μm, more preferably 3.5 to 4.5 μm. Moreover, when it is diluted to prepare a diluted Bordeaux liquid composition and then immediately sprayed, it does not cause clogging of the nozzle.

[0051] This Bordeaux liquid composition meets the standard of having a Suspensibility of 60% or more in terms of suspension property according to CIPAC MT 184.

[0052] This Bordeaux liquid composition, for example, refers to the case where, referring to the CIPAC (Collaborative International Pesticides Analytical Council Limited) MT46.3 accelerated storage test, an accelerated test is conducted by storing it at 40°C for 7 days (equivalent to 91 days at 25°C). As described in "5. Physical and Chemical Properties of Pesticides" in "Basic Considerations for the Third Review" in "Guidelines for Review of the Quality of Pesticides (Types, Names, Compositions, Manufacturing Methods, Physical and Chemical Properties, and Analytical Methods) (Notice from the Chief of the Agricultural Product Safety Management Section, Consumer and Safety Bureau, Ministry of Agriculture, Forestry and Fisheries, No. 6006, dated February 22, 2023) https: / / www.maff.go.jp / j / nouyaku / n_touroku / attach / pdf / index-53.pdf", in accordance with "(2) Appearance (Color Tone and Shape)" in "Physical and Chemical Properties of Pesticides", in "(E) Range of Color Tone", in "B) Hue", "Adjacent formulas, etc. shall mean that the hue symbols overlap in the display by three attributes." For example, it refers to those adjacent in the order of - red - yellowish red (brown) - yellow - yellowish green - green - blue - green - blue - purple - red - purple - red. In the case of the Bordeaux liquid composition, usually or at the beginning of preparation, the hue name: blue - green (2.5BG) [in the display symbol by three attributes, light blue - green 2.5G7 / 6 ~ blue - green 2.5BG4.5 / 8 ~ dark blue - green 2.5BG3 / 5]. After storage, it may be within the range of adjacent color tones where the hue name is blue - green, or the color tone adjacent to the green side is green (2.5g) [in the display symbol by three attributes, light green 2.5G7 / 6 ~ green 2.5G5 / 9 ~ dark green 2.5G3 / 5], or the color tone adjacent to the blue side is blue (2.5PB) [in the display symbol by three attributes, light blue 2.5PB6.5 / 7 ~ blue 2.5PB4 / 10 ~ dark blue 2.5PB2.5 / 5]. A color tone change exceeding that width is evaluated as discoloration. Specifically, when the Bordeaux liquid composition immediately after trial production is blue - green, for example, when stored at 40°C for 7 days (equivalent to 91 days at 25°C), it becomes blue - green, green, or blue, so it does not discolor even after long - term storage. Note that the results of this accelerated test are predictions of stability based on Arrhenius' equation, etc.According to this guideline, storage at a temperature of 40°C for one month is considered equivalent to storage at room temperature for one year, and for the case of the test stored at 40°C for six months, the expiration date is set to up to five years and six months. In addition, instead of storing at 40°C for 7 days, it may be stored at 25°C for 91 days, at 30°C for 24 days (equivalent to storage at room temperature for 91 years), or at 54°C for 2 days (equivalent to storage at room temperature for 91 years) to examine the color tone.

[0053] The Bordeaux liquid composition is a fungicide and pest control agent that exhibits a broad and strong bactericidal effect and insect repellent effect against filamentous fungi, bacterial diseases, and pests such as slugs. Specifically, it is effective against diseases such as blue mold (yam), late blight (sweet potato, tomato, potato, cherry tomato), gray star disease (yellow peach), scab (apricot, plum, citrus, kiwi, mango), brown spot disease (yellow peach), brown spot (walnut), wilt disease (fig), trunk rot (citrus, sweet potato), canker disease (loquat), scab (pear), black spot disease (persimmon), black rot (grape), black spot bacterial disease (walnut), black leaf blight (carrot), rust (grape), resin bacterial disease (yellow peach), purple spot disease (asparagus), spring rot (garlic), red burn disease (tea), pore bacterial disease (peach), sooty mold disease (citrus), anthracnose (avocado, strawberry, olive, walnut, watermelon, tea), wilt disease (watermelon), soft rot (vegetables), white spot disease (ginger), white leaf blight (garlic), leaf blight (asparagus, konjac, lily), leaf spot disease (carrot), spot bacterial disease (akebi), late rot (grape), putrefaction (konjac), powdery mildew (grape), snails (citrus), slugs (citrus), African giant snails (passion fruit, papaya), etc. It is a fungicide and pest control agent that exhibits a bactericidal effect against a wide range of pathogens and pests.

[0054] The mechanism of action of the bactericidal effect and insect repellent effect of the Bordeaux liquid composition and its dilutions is due to copper ions gradually dissolved from poorly soluble posnjakite or calcium basic copper sulfate trihydrate. These copper ions cause the Bordeaux liquid composition and its dilutions to exhibit a bactericidal effect through thiol inhibition that oxidizes sulfhydryl enzymes. In addition, since slugs and the like avoid copper ions, the Bordeaux liquid composition and its dilutions exhibit these pest control effects.

[0055] Even if it contains poorly soluble posnjakite or calcium basic copper sulfate trihydrate as an active ingredient like the Bordeaux liquid composition of the present invention, or even if it contains poorly soluble fonbezhindzhite or brochantite as an active ingredient like the conventional Bordeaux liquid compositions of formulas 3-3 to 6-6 to 2-10 to 4-12, since they have an appropriate particle size and easily adhere to and hang on crops, the medicinal effects are expressed by the common mechanism that copper ions elute gradually, so the medicinal effects are all equivalent. In fact, the antibacterial activity in vitro of the Bordeaux liquid composition of the present invention and the conventional Bordeaux liquid composition is almost the same.

[0056] When used for prevention and control according to the target crops and target pathogens, at the time of use, this Bordeaux liquid composition is diluted 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 with water to prepare a diluted Bordeaux liquid composition, which is then sprayed and used.

[0057] The Bordeaux liquid 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 a copper sulfate salt, especially copper(II) sulfate pentahydrate, is added slowly, and if necessary, with stirring, so 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, 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. By doing so, in terms of the quantitative ratio in 100 parts by mass of the solid component or dry component, 50 to 95 parts by mass of gypsum, preferably 55.3 to 60.7 parts by mass, 2 to 30 parts by mass of posnjakite, preferably 15.6 to 26.4 parts by mass, and 2 to 30 parts by mass of calcium basic copper sulfate trihydrate, preferably 18.2 to 25.2 parts by mass, are contained, and a water suspension containing no brochantite or containing at most 0.1 part by mass is produced. By having this step, the Bordeaux liquid composition can be produced.

[0059] A water suspension of quicklime and / or slaked lime, also called milk of lime, has calcium hydroxide: Ca(OH)₂ adjusted to about 5.0 to 52.6 g / 100 g, preferably 8.0 to 50.0 g / 100 g, more preferably 10.0 to 43.2 g / 100 g. On the other hand, an aqueous solution of copper sulfate salt, especially copper(II) sulfate pentahydrate, has the anhydrous form of copper(II): Cu(II)SO₄ adjusted to about 15.5 to 20.8 g / 100 g, preferably 17.3 to 19.1 g / 100 g, more preferably 18.0 to 18.4 g / 100 g.

[0060] The rate of adding the aqueous solution of copper sulfate salt to the water suspension of quicklime and / or slaked lime is at least over 30 minutes. Specifically, 100 parts by volume of the aqueous solution of copper sulfate salt is added at a rate of 3.33 parts by volume per minute or less. If it is faster than this range, fongbeijinite and brochantite will be produced and the production amount will increase. Moreover, it will cause discoloration over time during long-term storage. On the other hand, it is preferable that the production amount of fongbeijinite is within the above range. When the amount of brochantite increases and exceeds 0.1 part by mass in 100 parts by mass of the solid component or dry component, it will cause discoloration over time during long-term storage, deviate from the standards based on the Pesticide Control Law, and cannot be manufactured and sold as a product.

[0061] Although the reason why the quality and discoloration suppression effect deteriorate depending on the addition rate is not necessarily clear, it is presumed to be as follows. The 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, in the aqueous solution of copper sulfate salt such as copper sulfate (II), the solubility of copper sulfate (II) is 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 salt is added to the aqueous suspension of quicklime and / or slaked lime, basic copper calcium sulfate trihydrate is formed through reaction intermediates. At that time, the formation of brochantite becomes at most 0.1 part by mass in 100 parts by mass of the solid component or dry component of the Bordeaux liquid composition, and it is presumed that the change of basic copper calcium sulfate to copper oxide is inhibited, so that the deterioration of quality due to alteration is suppressed or the discoloration is suppressed even after long-term storage.

[0062] When adding the aqueous solution of copper sulfate salt to the aqueous suspension of quicklime and / or slaked lime, it is added at a temperature from room temperature to 40 °C such as 1 to 30 °C, preferably from normal temperature to 40 °C such as 15 to 25 °C, more preferably from 35 °C to 40 °C. Since the progress of the reaction accelerates if the temperature is too high and the composition ratio of the final product is different, resulting in discoloration, temperature adjustment is important.

[0063] The aqueous suspension prepared by adding quicklime to water generates heat. Therefore, when adding an aqueous solution of a copper sulfate salt to the aqueous suspension of quicklime and / or slaked lime, it is necessary to cool it to a temperature ranging from room temperature, such as 1 to 30 °C, up to 40 °C. However, if the cooling is insufficient, the progress of the reaction will be accelerated, the composition ratio of the final product will be different, and as a result, discoloration will occur. The aqueous solution of a copper sulfate salt, for example, copper sulfate (II), may be dissolved in cold water, normal temperature water, or warm water under heating. However, when adding the aqueous solution of the copper sulfate salt to the aqueous suspension of quicklime and / or slaked lime, it is necessary to cool it to a temperature ranging from room temperature, such as 1 to 30 °C, up to 40 °C. However, if the cooling is insufficient, the progress of the reaction will also be accelerated, the composition ratio of the final product will be different, and as a result, discoloration will occur.

[0064] When adding an aqueous solution of a copper sulfate salt to the aqueous suspension of quicklime and / or slaked lime, it is preferable to stir. The stirring operation is not particularly limited, but stirrers such as a stirrer, a stand mixer, a bag mixer, a Nauta mixer, a Henschel mixer, a kneader, a pony mixer, a clutch, etc. can be used. Examples of the stirring blades provided in the stirrer include a ribbon, a screw, an anchor, a gate, a fan turbine, a paddle, an inclined paddle, a DS impeller, a Kai cross, and a propeller-shaped blade. If the stirring is insufficient, the reaction will not proceed, the composition ratio of the final product will be different, and as a result, discoloration will occur. Therefore, it is preferable to ensure sufficient stirring.

[0065] Depending on the type of crop, the type of target pathogen or pest, the season, the number of past uses, and the timing of use, the Bordeaux liquid 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 liquid composition, and it is promptly sprayed onto the desired crop. Since the pH range of this diluted Bordeaux liquid composition is neutral, if necessary, it may be used as a diluted Bordeaux liquid composition mixed with other pesticides. The Bordeaux liquid composition and its diluted Bordeaux liquid composition contain gypsum, posnjakite, and basic copper sulfate calcium trihydrate with an appropriate particle size, and have high bactericidal properties against a wide range of pathogens on crops, a preventive effect due to pathogen resistance, excellent drug efficacy such as relatively long residual efficacy and hanging properties, and high safety, and can prevent and control pathogens and pests for a predetermined period.

Example

[0066] Hereinafter, the examples to which the present invention is applied and the comparative examples to which the present invention is not applied will be described while making a comparison.

[0067] (Example 1) 6.19 g of fine slaked lime was separated and placed in a 1-liter beaker. While stirring the diluted and dispersed product with 8.40 g of water, an aqueous copper sulfate solution in which 24.33 g of copper sulfate pentahydrate (CuSO4·5H2O) was dissolved in 61.08 g of water was added at an input rate of 180 minutes and a temperature of 40°C to prepare approximately 100 g of a liquid equivalent to the 10-2 formula Bordeaux liquid with a calcium equivalent mass of 2 relative to the anhydrous copper sulfate equivalent mass of 10.

[0068] (Component analysis and analysis) 5 ml of the Bordeaux liquid composition of Example 1 was dried at 25°C under a pressure of 1 torr. The obtained dried component was pulverized in a mortar, and X-ray crystal diffraction measurement was performed using an X-ray crystal diffraction measurement device (trade name: PANalytical EMPYREAN system, manufactured by Spectris Co., Ltd.). The X-ray crystal diffraction spectrum is shown in Figure 1. In addition, the X-ray crystal diffraction spectrum was subjected to Rietveld analysis using Rietveld analysis software (trade name: Highscore, manufactured by Spectris Co., Ltd.) to estimate and identify the contained composition. The results are shown in Table 1.

[0069] (Stability evaluation test) 2 ml of the Bordeaux liquid composition of Example 1 was stored at 25°C for 7 days, and then measured visually under normal temperature, normal pressure, and natural light. The difference in color tone from immediately after preparation was measured by visually confirming whether it fell within the range of adjacent green (2.5G) and blue (2.5PB) based on blue-green (2.5BG) in accordance with the "Review Guidelines on the Quality of Pesticides (Formulations)". As a result, it was evaluated in two levels: ○ when it was within the range of the width of adjacent color tones, and × when it exceeded the width of adjacent color tones. The results are shown in Table 1.

[0070] (Comparative Example 1) 18.7 g of fine slaked lime was separated and placed in a 1-liter beaker. While stirring the diluted and dispersed product with 20.4 g of water, an aqueous copper sulfate solution prepared by dissolving 14.8 g of copper sulfate (CuSO4·5H2O) in 44.4 g of water was gradually added at a temperature of 35 to 40°C to prepare approximately 100 g of a liquid equivalent to the 6-6 type Bordeaux liquid with a calcium equivalent mass of 6 relative to the anhydrous copper sulfate equivalent mass of 6.

[0071] (Component analysis and analysis) X-ray diffraction measurement was performed on the Bordeaux liquid composition of Comparative Example 1 in the same manner as in (Component analysis and analysis) of Example 1. The X-ray diffraction spectrum is shown in Figure 1, and the results of estimating and identifying the contained composition by Rietveld analysis of the X-ray diffraction spectrum are shown in Table 1.

[0072] (Stability test) 2 ml of the Bordeaux liquid composition of Comparative Example 1 was tested in the same manner as in the (Stability test) of Example 1. The results are shown in Table 1.

[0073]

Table 1

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

[0075] (Example 2, Comparative Example 2) (Preparation method) A Bordeaux liquid composition (corresponding to the 10-2 type Bordeaux liquid) of Example 2 was prepared in the same manner as in Example 1, except that the charging rate of the copper sulfate aqueous solution in Example 1 was 60 to 120 minutes. A Bordeaux liquid composition of Comparative Example 2 was prepared in the same manner as in Example 1, except that the charging rate of the copper sulfate aqueous solution in Example 1 was 10 to 20 minutes.

[0076] (Stability test, and its component analysis and analysis) After storing each Bordeaux liquid composition of Example 2 and Comparative Example 2 at 25°C for 0 weeks, 1 week, or 2 weeks, a stability test and X-ray crystal diffraction measurement were performed in the same manner as in (component analysis and analysis) of Example 1. Table 2 shows the results of estimating and identifying the contained composition by Rietveld analysis for the X-ray crystal diffraction spectrum.

[0077]

Table 2

[0078] As is clear from Table 2, the Bordeaux liquid composition of Example 2 to which the present invention is applied has a composition in each range of 50 to 70 parts by mass of gypsum, 10 to 30 parts by mass of posnjakite, and 10 to 30 parts by mass of calcium basic copper sulfate trihydrate, and is a composition having a pH of 6 to 8 when diluted 500 times with water. Based on these compositions, no discoloration or deterioration occurs in the stability evaluation test. However, the Bordeaux liquid composition of Comparative Example 2 outside the scope of the present invention, which is outside those ranges, shows a great difference from Example 2 because it lacks discoloration, deterioration, and stability depending on the difference in the ratio of the composition having a pH of 12 when diluted 100 times. In addition, as in Comparative Example 2-2, when the temperature of the water suspension of quicklime and / or slaked lime or the aqueous solution of copper sulfate salt is too low, even if the content of brochantite is small, the content of calcium basic copper sulfate trihydrate becomes too high, and it is presumed that it lacks discoloration, deterioration, and stability.

[0079] (Comparative Example 3) 37.1 g of fine slaked lime was separated and placed in a 1-liter beaker. While stirring the diluted and dispersed product with 50.4 g of water, an aqueous copper sulfate solution in which 112.3 g of copper sulfate (CuSO4·5H2O) was dissolved was gradually added at a temperature of 35 to 40°C to prepare approximately 100 g of a liquid equivalent to the 7-2 formula Bordeaux liquid having a calcium equivalent mass of 2 with respect to the anhydrous copper sulfate equivalent mass of 7.

[0080] (Component analysis and analysis) The Bordeaux liquid composition of Comparative Example 3 was subjected to a stability test and X-ray crystal diffraction measurement in the same manner as in (Component analysis and analysis) of Example 1. Table 3 shows the results of estimating and identifying the contained composition by Rietveld analysis for the X-ray crystal diffraction spectrum.

[0081]

Table 3

[0082] As is clear from Table 3, since the Bordeaux liquid equivalent of Comparative Example 3 has a completely different composition from both the Bordeaux liquid equivalent of Example 1 of the present invention and the Bordeaux liquid equivalent of Comparative Example 1, it was shown that the quantitative ratio of quicklime and / or slaked lime to the copper sulfate salt is a major factor in the difference in composition.

[0083] (Efficacy test) When the Bordeaux liquid composition of Example 1 and the Bordeaux liquid composition of Comparative Example 1 were diluted 500-fold with water and various sterilization tests were conducted in vitro, it was shown that the sterilization effects were equivalent.

Industrial applicability

[0084] According to the Bordeaux liquid composition of the present invention and its production method, a diluted solution of the Bordeaux liquid composition used as a pesticide that is a fungicide or a pest control agent can be simply and quickly prepared at the time of use, sprayed on crops, and used for sterilization of pathogenic bacteria and pest control.

Claims

1. In a mass ratio in 100 parts by mass of the solid component or the dry component, 50 to 95 parts by mass of gypsum, 2 to 30 parts by mass of posnjakite, 2 to 30 parts by mass of basic calcium copper sulfate trihydrate, and A Bordeaux liquid composition characterized by being a water suspension that does not contain brochantite or contains at most 0.8 parts by mass.

2. The Bordeaux liquid composition according to claim 1, wherein in 100 parts by mass of the solid component or the dry component, calcium hydroxide and fonbejsite are each independently not contained or contained at most 0.5 parts by mass.

3. The Bordeaux liquid composition according to claim 1, wherein the gypsum, the posnjakite, and the basic calcium copper sulfate trihydrate are contained in the water suspension at 20 to 40% by mass.

4. The Bordeaux liquid composition according to claim 1, which is for use diluted with water having a volume ratio exceeding 1 time and not exceeding 2000 times.

5. After storage at 25°C for 2 years or after a corresponding accelerated test, at normal temperature and pressure under natural light, within the range of adjacent color tones according to the "Review Guidelines on the Quality of Pesticides (Formulations)" as compared with the product immediately after prototype production. The Bordeaux liquid composition according to claim 1, characterized by this.

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

7. The Bordeaux liquid composition according to claim 1, wherein the pH is 5.0 to 8.9 when diluted 500 times.

8. The Bordeaux liquid 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. An aqueous suspension of quicklime and / or slaked lime is added with an aqueous solution of a copper sulfate salt such 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, thereby producing an aqueous suspension containing, in terms of mass ratio in 100 parts by mass of the solid component or dry component, 50 to 70 parts by mass of gypsum, 10 to 30 parts by mass of posnjakite, and 10 to 30 parts by mass of basic calcium copper sulfate trihydrate, and containing no brochantite or containing at most 0.1 part by mass of brochantite. A method for producing a Bordeaux liquid composition is characterized by this.

10. The method for producing a Bordeaux liquid 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 a Bordeaux liquid 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 a Bordeaux liquid composition according to claim 9, characterized in that the solid component or dry component is that when the filtrate and / or dried product of the aqueous suspension is taken.

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

14. The method for producing a Bordeaux liquid composition according to claim 9, characterized in that an aqueous solution of the copper sulfate salt is added to the aqueous suspension of the quicklime and / or slaked lime at room temperature to 40 °C.

15. The method for producing a Bordeaux liquid composition according to claim 9, characterized in that an aqueous solution of the copper sulfate salt is added to the aqueous suspension of the quicklime and / or slaked lime while stirring.

Images