Liquid calcium fertilizer and diluted solution

Abstract

To provide a liquid calcium fertilizer which is hardly suspended when mixed with agricultural chemicals or other fertilizers. [Solution] A liquid calcium fertilizer comprising a calcium source and an organic acid, wherein the calcium source comprises calcium chloride, the organic acid comprises one or more acids selected from the group consisting of acetic acid, citric acid, and malic acid, the concentration of the calcium source being 7.0 to 18.5 mass % in terms of CaO, the concentration of the organic acid being 1.0 to 9.5 mass %, and the pH being 2.0 or less.

Description

[Technical Field]

[0001] The present invention relates to a liquid calcium fertilizer and a dilution containing the liquid calcium fertilizer and water. [Background technology]

[0002] Calcium fertilizers are used in plant cultivation for nutritional supplementation and soil improvement. For example, Patent Document 1 discloses a liquid calcium fertilizer that is a liquid composition obtained by mixing and reacting a water-soluble organic acid, calcium chloride, slaked lime and / or quicklime in water to dissolve the same, and that has a calcium concentration of 11% or more in terms of CaO, a calcium concentration derived from calcium chloride of 45 to 65% of the total calcium concentration, and a pH of 3 to 4.5. Furthermore, Patent Document 2 discloses a calcium fertilizer characterized by containing calcium formate and calcium propionate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 09-263477 [Patent Document 2] Japanese Patent Application Publication No. 05-139872 Summary of the Invention [Problem to be solved by the invention]

[0004] Calcium fertilizers are generally used after dilution with water. Furthermore, calcium fertilizers are rarely sprayed alone, but are generally mixed with pesticides and other fertilizers. However, it has been found that when conventional calcium fertilizers are mixed with pesticides, insoluble matter is generated, resulting in the formation of a suspension. When sprayed on leaves, suspensions containing a large amount of insoluble matter can be difficult to spray evenly on the leaves and can cause clogging of spraying equipment. Therefore, there has been a demand for calcium fertilizers that can be mixed with pesticides and other fertilizers without causing suspension. Under these circumstances, an object of the present invention is to provide a liquid calcium fertilizer that is less likely to become suspended when mixed with pesticides or other fertilizers, and a dilution solution containing the liquid calcium fertilizer and water. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the following invention meets the above object, thereby completing the present invention.

[0006] That is, the present invention relates to the following inventions. <1> A liquid calcium fertilizer comprising a calcium source and an organic acid, wherein the calcium source comprises calcium chloride, and the organic acid comprises one or more acids selected from the group consisting of acetic acid, citric acid, and malic acid, the concentration of the calcium source being 7.0 to 18.5 mass % in terms of CaO, the concentration of the organic acid being 1.0 to 9.5 mass %, and the pH being 2.0 or less. <2> the ratio of the mass of the organic acid to the mass of the calcium source calculated as CaO is 0.06 to 0.80; <1> 1. A liquid calcium fertilizer according to claim 1. <3> The calcium source is calcium chloride, and the organic acid is acetic acid. <1> or <2> 1. A liquid calcium fertilizer according to claim 1. <4> The above-mentioned vinegars include brewed vinegars. <1> from <3> 1. A liquid calcium fertilizer according to any one of the preceding claims. <5> The above-mentioned method further comprises the steps of: <1> from <4> 1. A liquid calcium fertilizer according to any one of the preceding claims. <6> The above-mentioned is either (a) or (b) below: <4> 1. A liquid calcium fertilizer according to claim 1. (a) A liquid calcium fertilizer comprising the calcium source, brewed vinegar, and water. (b) A liquid calcium fertilizer comprising the calcium source, brewed vinegar, manganese chloride, boric acid, and water. <7> The aforementioned <1> from <6> 1. A diluted solution containing the liquid calcium fertilizer according to any one of the above items and water, and having a pH of 3.0 to 7.0. <8> A method for producing a liquid calcium fertilizer, comprising: a first step of mixing water with an organic acid containing at least one acid selected from the group consisting of acetic acid, citric acid, and malic acid to obtain a first mixed solution; and a second step of mixing the first mixed solution with a calcium source containing calcium chloride to dissolve the calcium source, wherein the liquid calcium fertilizer has a calcium source concentration of 7.0 to 18.5 mass % calculated as CaO, a concentration of the organic acid of 1.0 to 9.5 mass %, and a pH of 2.0 or less. <9> In the first step, brewed vinegar having an acidity of 10% or more and water are mixed to obtain a first mixture. <8> A method for producing the liquid calcium fertilizer described in claim 1. [Effects of the Invention]

[0007] According to the present invention, there are provided a liquid calcium fertilizer that is less likely to become suspended when mixed with agricultural chemicals or other fertilizers, and a dilution containing the liquid calcium fertilizer and water. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a photograph of a diluted solution obtained by diluting and mixing the liquid calcium fertilizer of Example 1 with another fertilizer. [Figure 2] 1 is a photograph of a diluted solution obtained by diluting and mixing the liquid calcium fertilizer of Reference Example 1 with another fertilizer. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following describes in detail an embodiment of the present invention, but the following description of the constituent elements is one example (typical example) of an embodiment of the present invention, and the present invention is not limited to the following content unless the gist of the present invention is changed. Note that when the expression "to" is used in this specification, it is used as an expression including the numerical values ​​or physical property values ​​before and after it.

[0010] <Liquid calcium fertilizer> The present invention relates to a liquid calcium fertilizer (hereinafter, sometimes referred to as "the liquid calcium fertilizer of the present invention") comprising a calcium source and an organic acid, wherein the calcium source comprises calcium chloride, the organic acid comprises one or more acids selected from the group consisting of acetic acid, citric acid, and malic acid, the concentration of the calcium source is 7.0 to 18.5 mass % in terms of CaO, the concentration of the organic acid is 1.0 to 9.5 mass %, and the pH is 2.0 or less.

[0011] (calcium source) The liquid calcium fertilizer of the present invention includes a calcium source, and the calcium source includes calcium chloride. The calcium chloride may be anhydrous or a hydrate such as a dihydrate, tetrahydrate, or hexahydrate, but is preferably calcium chloride anhydrous and / or calcium chloride dihydrate.

[0012] In addition to calcium chloride, calcium salts such as organic acid calcium, calcium sulfate, and calcium nitrate are known as calcium sources. However, organic acid calcium has a low percentage of calcium atoms in its molecule, and calcium sulfate has low solubility in water, making it difficult to increase the calcium content in the fertilizer. Furthermore, calcium nitrate contains nitrogen atoms, which may result in excessive nitrogen addition and adversely affect plants. By including calcium chloride as a calcium source, the liquid calcium fertilizer of the present invention can easily increase the calcium content, is less likely to crystallize during storage, and maintains stable quality. The percentage of calcium chloride in the calcium source is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. It is particularly preferred that all calcium is derived from calcium chloride (i.e., the calcium source is calcium chloride).

[0013] In the liquid calcium fertilizer of the present invention, the concentration of the calcium source is 7.0 to 18.5 mass% in terms of CaO. As described below, the liquid calcium fertilizer of the present invention is used after dilution. However, if the calcium concentration is too low, the dilution rate must be increased to supply sufficient calcium to the plant, which is uneconomical. On the other hand, if the calcium concentration is too high, there are problems such as the calcium source remaining undissolved or being prone to crystallization. The concentration of the calcium source is preferably 10.0 to 18.0 mass%, more preferably 13.0 to 18.0 mass%, and even more preferably 15.0 to 17.5 mass% in terms of CaO.

[0014] (organic acid) The liquid calcium fertilizer of the present invention contains an organic acid, and the organic acid includes one or more selected from the group consisting of acetic acid, citric acid, and malic acid. The concentration of the organic acid is 1.0 to 9.5% by mass. If the organic acid concentration is less than 1.0% by mass, there is a problem that the mixture is easily suspended when mixed with pesticides or other fertilizers. If the organic acid concentration is more than 9.5% by mass, there is a problem that the calcium source is difficult to dissolve, resulting in the formation of insoluble matter. The concentration of the organic acid is preferably 1.5 to 9.0% by mass, more preferably 2.0 to 8.5% by mass, even more preferably 2.5 to 8.0% by mass, even more preferably 3.0 to 7.5% by mass, and particularly preferably 4.0 to 7.0% by mass. The organic acid may contain one type or two or more types. If two or more types of organic acids are contained, the total concentration of the two or more organic acids must be 1.0 to 9.5% by mass, and the total concentration of the two or more organic acids is preferably within the above-mentioned range.

[0015] (acetic acid) The organic acid preferably contains acetic acid. The acetic acid is not limited to acetic acid (synthetic product) used for industrial purposes, etc., but may be acetic acid derived from brewed vinegars such as grain vinegar, fruit vinegar, rice vinegar, brown rice vinegar, apple vinegar, and grape vinegar; or synthetic vinegar. Among these, the liquid calcium fertilizer of the present invention preferably contains brewed vinegar. The brewed vinegar is not limited to vinegar used for food applications, and may be vinegar used for purposes other than food applications. The brewed vinegar is preferably vinegar with a high acidity, and specifically, it is preferable to use vinegar with an acidity of 10% or more, or 15% or more. The term "brewed vinegar" refers to brewed vinegar as defined in the Japanese Agricultural Standards for Brewed Vinegar. The "acidity" can be measured according to the method described in the Japanese Agricultural Standards for Brewed Vinegar.

[0016] The organic acid preferably contains at least 70% by mass, more preferably at least 80% by mass, even more preferably at least 90% by mass of one or more selected from the group consisting of acetic acid, citric acid, and malic acid. Among these, it is preferred that at least 70% by mass of the organic acid is acetic acid, more preferably at least 80% by mass of the organic acid is acetic acid, even more preferably at least 90% by mass of the organic acid is acetic acid, and it is particularly preferred that the total amount of the organic acid is acetic acid.

[0017] Furthermore, in the liquid calcium fertilizer of the present invention, the ratio of the mass of the organic acid to the mass of the calcium source converted into CaO (mass of organic acid / mass of calcium source converted into CaO) is preferably 0.06 to 0.80, more preferably 0.06 to 0.60, even more preferably 0.08 to 0.50, and even more preferably 0.15 to 0.40. By keeping the ratio within these numerical ranges, the amount of Ca in the fertilizer after dilution can be increased, while making it less likely to suspend when mixed with pesticides or other fertilizers.

[0018] (Other ingredients) The liquid calcium fertilizer of the present invention is liquid and contains water as a solvent. The water can be tap water, ion-exchanged water, distilled water, groundwater, or the like.

[0019] The liquid calcium fertilizer of the present invention contains a calcium source, an organic acid, and water as its main components, and the content of the calcium source, the organic acid, and the water can be, for example, 97.0% by mass or more, 97.5% by mass or more, 98.0% by mass or more, 98.5% by mass or more, or 99.0% by mass or more.

[0020] The liquid calcium fertilizer of the present invention can further contain manganese chloride and boric acid in addition to the calcium source and organic acid. By including manganese chloride and boric acid, the effect of strengthening the cell walls of the applied plant can be enhanced.

[0021] When the liquid calcium fertilizer of the present invention contains manganese chloride, the content of manganese chloride can be, for example, 0.1 to 1.0 mass % or 0.2 to 0.7 mass %.

[0022] When the liquid calcium fertilizer of the present invention contains boric acid, the content of boric acid can be, for example, 0.1 to 2.0 mass % or 0.5 to 1.5 mass %.

[0023] (pH) The liquid calcium fertilizer of the present invention has a pH of 2.0 or less, preferably 1.5 or less, more preferably 1.2 or less, even more preferably 1.0 or less, and may be 0.70 or less or 0.50 or less. The lower limit of the pH can be, for example, -1.0 or more, 0.00 or more, or 0.10 or more. As will be described later, the liquid calcium fertilizer of the present invention is used by diluting with water. Setting the pH of the liquid calcium fertilizer of the present invention within the above range is preferable because it can be diluted about 250 to 1000 times and used to achieve a pH suitable for application to plants. By diluting the fertilizer for use in this manner, the volume during storage can be reduced, making it easier to handle.

[0024] Preferred embodiments of the liquid calcium fertilizer of the present invention include the following (a) and (b). (a) A liquid calcium fertilizer comprising a calcium source containing calcium chloride, brewed vinegar, and water. (b) A liquid calcium fertilizer comprising a calcium source containing calcium chloride, brewed vinegar, manganese chloride, boric acid, and water.

[0025] <Manufacturing method> The liquid calcium fertilizer of the present invention is preferably produced by a production method including a first step of mixing water with an organic acid containing at least one selected from the group consisting of acetic acid, citric acid, and malic acid to obtain a first mixed solution, and a second step of mixing the first mixed solution with a calcium source containing calcium chloride to dissolve the calcium source.When the liquid calcium fertilizer contains manganese chloride and boric acid in addition to the calcium source and organic acid, it is preferable to mix manganese chloride and boric acid into the first mixed solution.

[0026] In particular, when producing the liquid calcium fertilizer of the present invention using a brewed vinegar with a high acidity of 10% or more or 15% or more as the organic acid, adding the organic acid after mixing the water and calcium source, or mixing the organic acid, water, and calcium source all at once, can make it difficult to dissolve the calcium source, resulting in a failure to increase the calcium source concentration and a tendency for the calcium source to precipitate after production. By mixing the organic acid and water and then adding the calcium source, the calcium source concentration can be increased even when using a brewed vinegar with a high acidity, and salt precipitation is less likely to occur after production. Therefore, when using a brewed vinegar with a high acidity, it is preferable to produce the liquid calcium fertilizer using a production method including a first step of mixing the brewed vinegar with water to obtain a first mixture and a second step of mixing the calcium source with the first mixture to dissolve the calcium source. Furthermore, in the first step, an organic acid other than the brewed vinegar may be used in combination.

[0027] In the first step, the organic acid and water are mixed so that the resulting liquid calcium fertilizer has an organic acid concentration of 1.0 to 9.5% by mass and a pH of 2.0 or less. In the first step, the organic acid and water are mixed, depending on the amount of calcium source used in the second step, so that the organic acid concentration in the liquid after mixing with the calcium source is preferably 1.5 to 9.0% by mass, more preferably 2.0 to 8.5% by mass, even more preferably 2.5 to 8.0% by mass, even more preferably 3.0 to 7.5% by mass, and particularly preferably 4.0 to 7.0% by mass. Furthermore, in the second step, the first mixed liquid and the calcium source are mixed so that the resulting liquid calcium fertilizer has a calcium source concentration, calculated as CaO, of 7.0 to 18.5% by mass. The calcium source is mixed so that its content, calculated as CaO, is preferably 10.0 to 18.0 mass%, more preferably 13.0 to 18.0 mass%, and even more preferably 15.0 to 17.5 mass%. Mixing can be carried out, for example, at room temperature, which makes it difficult for the calcium source to precipitate at room temperature.

[0028] <Dilution> The liquid calcium fertilizer of the present invention is used by diluting with water, and is preferably diluted so that the pH is 3.0 to 7.0 when diluted with water. That is, the present invention relates to a diluted solution (hereinafter sometimes referred to as "the diluted solution of the present invention") that contains the liquid calcium fertilizer of the present invention and water and has a pH of 3.0 to 7.0. The pH of the diluted solution is preferably 3.5 to 6.6, more preferably 3.8 to 6.0, and even more preferably 4.0 to 5.5.

[0029] The dilution ratio, in mass ratio, of the liquid calcium fertilizer of the present invention to water is preferably 1:250 to 1:1000, more preferably 1:300 to 1:800, and even more preferably 1:350 to 1:600.

[0030] The diluted solution may also contain something other than the liquid calcium fertilizer of the present invention and water. The diluted solution of the present invention may be prepared by mixing the liquid calcium fertilizer of the present invention with a pesticide and / or a fertilizer other than a calcium fertilizer and water, and then applying the diluted solution to plants. The pesticide is not particularly limited, and known pesticides such as insecticides, fungicides, insecticides and fungicides, herbicides, rodenticides, and plant growth regulators can be used. For example, organophosphorus compounds, neonicotinoid compounds, and pyrethroid compounds can be used. Furthermore, fertilizers other than calcium fertilizers are also not particularly limited, and known fertilizers such as nitrogen fertilizers, phosphate fertilizers, and potassium fertilizers can be used.

[0031] <How to use> The liquid calcium fertilizer of the present invention can be diluted with water and applied to plants as a fertilizer to prevent calcium deficiency. The method of application of the liquid calcium of the present invention is not particularly limited, and can be sprayed, atomized, irrigated to soil or plants, or added to a culture solution for hydroponic cultivation. Alternatively, the liquid calcium fertilizer of the present invention may be applied to plants as a diluted solution containing a pesticide and / or a fertilizer other than calcium fertilizer. For example, the diluted solution can be sprayed on the leaf surfaces, fruit surfaces, stems, trunks, branches, etc. of plants such as leafy vegetables and fruit trees. [Example]

[0032] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not changed.

[0033] (Examples 1 to 14, Comparative Examples 1 to 10) Liquid calcium fertilizer (stock solution) was prepared using calcium chloride dihydrate, organic acids (brewed vinegar (acidity 15%), 80% acetic acid, citric acid, malic acid, gluconic acid, 88% lactic acid), and water according to the formulations shown in Tables 1 to 3. First, the organic acid and water were mixed, and calcium chloride dihydrate was added and dissolved to obtain liquid calcium fertilizer. The pH of the resulting liquid calcium fertilizer and that after dilution were measured at 25°C using a Toa DKK HM-41X.

[0034] (Reference example (control)) The commercially available liquid calcium fertilizer used was Agrimate (registered trademark) manufactured by Nisso Green Co., Ltd. This fertilizer contains half of its CaO derived from calcium chloride and the other half from organic acid calcium, and contains acetic acid, lactic acid, gluconic acid, and formic acid as organic acids.

[0035] (Dilution and Mixing Test) As Ca agents, liquid calcium fertilizers of Examples 1 to 14, Comparative Examples 1 to 3, 6 to 10, and Reference Example 1 were used, and as other fertilizers, Leafferar (registered trademark) manufactured by Nisso Green Co., Ltd. was used. 1 mL of the Ca agent, 1 mL of another fertilizer, and 498 mL of water were mixed to prepare a diluted solution (total volume 500 mL). The prepared diluted solution was visually observed to evaluate whether or not it was suspended. The results are shown in Tables 1 to 3.

[0036] [Table 1]

[0037] [Table 2]

[0038] [Table 3]

[0039] 1 shows a photograph of a diluted solution obtained by diluting and mixing the liquid calcium fertilizer of Example 1 with other fertilizers, and Fig. 2 shows a photograph of a diluted solution obtained by diluting and mixing the liquid calcium fertilizer of Reference Example 1 with other fertilizers. As shown in Figs. 1 and 2, the diluted solution obtained by diluting and mixing the liquid calcium fertilizer of Example 1 with other fertilizers was clear, but the diluted solution obtained by diluting and mixing the liquid calcium fertilizer of Reference Example 1 with other fertilizers was suspended, with insoluble matter settling.

[0040] Example 15 A liquid calcium fertilizer was prepared with a mixture of 45.00% calcium chloride dihydrate, 40.00% brewed vinegar (acidity 15%), 0.40% manganese chloride, 0.95% boric acid, and 13.65% water. First, organic acid and water were mixed, and then calcium chloride dihydrate, manganese chloride, and boric acid were added and dissolved to obtain the liquid calcium fertilizer. 1 mL of the obtained liquid calcium fertilizer, 1 mL of Leaf Ferrer (registered trademark) manufactured by Nisso Green Co., Ltd., and 498 mL of water were mixed to prepare a diluted solution (total volume 500 mL), and the presence or absence of suspension was evaluated visually. As a result, no suspension was observed.

Claims

1. a calcium source and an organic acid, the calcium source comprises calcium chloride; the organic acid includes one or more selected from the group consisting of acetic acid, citric acid, and malic acid; the concentration of the calcium source is 13.0 to 18.5 mass% in terms of CaO; The concentration of the organic acid is 1.0 to 9.5% by mass, A liquid calcium fertilizer with a pH of 2.0 or less.

2. 2. The liquid calcium fertilizer according to claim 1, wherein the ratio of the mass of the organic acid to the mass of the calcium source calculated as CaO is 0.06 to 0.

80.

3. the calcium source is calcium chloride; 2. The liquid calcium fertilizer according to claim 1, wherein the organic acid is acetic acid.

4. The liquid calcium fertilizer according to claim 1 , comprising brewed vinegar.

5. 2. The liquid calcium fertilizer according to claim 1, further comprising manganese chloride and boric acid.

6. The liquid calcium fertilizer according to claim 4, which is the following (a) or (b): (a) A liquid calcium fertilizer comprising the calcium source, brewed vinegar, and water. (b) A liquid calcium fertilizer comprising the calcium source, brewed vinegar, manganese chloride, boric acid, and water.

7. A diluted solution comprising the liquid calcium fertilizer according to any one of claims 1 to 6 and water, and having a pH of 3.0 to 7.

0.

8. a first step of mixing water with an organic acid including at least one selected from the group consisting of acetic acid, citric acid, and malic acid to obtain a first mixture; a second step of mixing a calcium source containing calcium chloride with the first mixed liquid to dissolve the calcium source, The liquid calcium fertilizer has a calcium source concentration of 13.0 to 18.5 mass % in terms of CaO, a concentration of the organic acid of 1.0 to 9.5 mass %, and a pH of 2.0 or less.

9. 9. The method for producing a liquid calcium fertilizer according to claim 8, wherein in the first step, brewed vinegar having an acidity of 10% or more and water are mixed to obtain a first mixed liquid.

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