JP5846993B2 - 5-aminolevulinic acid-containing solid fertilizer and method for producing the same - Google Patents

Description

  The present invention relates to a solid fertilizer containing 5-aminolevulinic acid and a method for producing the same.

5-aminolevulinic acid, a derivative or a salt thereof, the improvement of photosynthetic activity, CO ₂ absorption capacity improved respiratory inhibition, chlorophyll content increased action, better shows the growth promoting effect, so that root promoting, lodging prevented, Yield improvement, cold resistance improvement, freshness maintenance, green improvement, green maintenance, healthy seedling growth, organ growth promotion, increase in the number of divisions, shortening the time required for growth, reduction of chemical damage and excellent survival improvement effect in cuttings, etc. It is known (Patent Document 1).

  Since 5-aminolevulinic acid is a water-soluble substance, as a fertilizing method for plants, it was supplied to plants in a state dissolved in liquid.

JP 04-338305 A

However, the method of fertilizing the solution on the plant is a very time-consuming method such as dilution to an optimal concentration, spraying to the plant body, and irrigation to the root.
In addition, when given as a solution, the duration of the growth promoting effect of 5-aminolevulinic acid is known to be about 2 weeks, and many regular doses are necessary to obtain a sufficient growth promoting effect. Met.
Accordingly, an object of the present invention is to provide means for producing an excellent plant growth promoting effect of 5-aminolevulinic acid with a small number of applications.

  From this point, the present inventor studied the means for applying 5-aminolevulinic acid and focused on forming 5-aminolevulinic acid in solid form together with the solid fertilizer raw material.

However, solid fertilizers are easy to fertilize even in the open ground, have not only a plant growth promoting effect, but also require long-term storage stability. That is, it is desired that the storage stability is excellent not only in the storage stability from the production to the distribution process but also in the actual application scene. In addition, it is desired that the solid fertilizer can be stably manufactured without deteriorating the moldability in the manufacturing process.
Therefore, the present inventor has developed a solid fertilizer containing 5-aminolevulinic acid, which can be produced without impairing moldability, has a plant growth promoting effect, and has excellent storage stability. As a result of various studies, solid fertilizers containing 5-aminolevulinic acid can be produced without sacrificing moldability by blending bone meal and citric acid, and solid fertilizers with excellent long-term storage stability can be obtained. As a result, the present invention has been completed.

That is, the present invention includes the following inventions.
[1] The following components (A), (B) and (C):
(A) The following general formula (I)
R ² R ¹ NCH ₂ COCH ₂ CH ₂ COR ³ (I)
(Wherein R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, an aryl group or an aralkyl group; R ³ represents a hydroxy group, an alkoxy group, an acyloxy group, an alkoxycarbonyloxy group) Group, an aryloxy group, an aralkyloxy group or an amino group.) 5-aminolevulinic acid, a derivative thereof or a salt thereof,
(B) bone meal,
(C) Solid fertilizer characterized by containing citric acid.
[2] The solid fertilizer according to [1], wherein the water content is 10% by mass or less in the total amount of the solid fertilizer.
[3] The solid fertilizer according to [1] or [2], containing 0.0001 to 1% by mass of component (A), 10 to 80% by mass of component (B), and 6 to 20% by mass of component (C). .
[4] Next steps (a) and (b):
(A) In the solid fertilizer raw material mixture containing the component (B) and the component (C), the following general formula (I)
R ² R ¹ NCH ₂ COCH ₂ CH ₂ COR ³ (I)
(Wherein R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an acyl group, an alkoxycarbonyl group, an aryl group or an aralkyl group; R ³ represents a hydroxy group, an alkoxy group, an acyloxy group, an alkoxycarbonyloxy group) A group, an aryloxy group, an aralkyloxy group or an amino group)), a step of spray-adding a solution containing 5-aminolevulinic acid, a derivative thereof or a salt thereof (A)
(B) The manufacturing method of the solid fertilizer in any one of [1]-[3] characterized by including the process to shape | mold.

  ADVANTAGE OF THE INVENTION According to this invention, the 5-aminolevulinic acid containing solid fertilizer which can be manufactured without deteriorating moldability and was excellent in long-term storage stability can be provided.

The effect of promoting the growth of Japanese mustard spinach by 5-aminolevulinic acid-containing solid fertilizer is shown. The Tukey-HSD test was conducted. * Indicates that there is a significant difference at the 5% level and ** at the 1% level relative to the basic fertilizer. The effect of promoting the growth of Komatsuna by the inorganic fertilizer containing 5-aminolevulinic acid is shown. The relationship between a citric acid content and the 5-aminolevulinic acid residual rate in the solid fertilizer after a preservation | save is shown. The relationship between a moisture content and the 5-aminolevulinic acid residual rate in the solid fertilizer after a preservation | save is shown.

  The solid fertilizer of the present invention contains (A) 5-aminolevulinic acid represented by the general formula (I), a derivative thereof or a salt thereof, (B) bone meal, and (C) citric acid.

In general formula (I), the alkyl group represented by R ¹ and R ² is preferably a linear or branched alkyl group having 1 to 24 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, particularly A C1-C6 alkyl group is preferable. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group. As the acyl group, a linear or branched alkanoyl group, alkenylcarbonyl group or aroyl group having 1 to 12 carbon atoms is preferable, and an alkanoyl group having 1 to 6 carbon atoms is particularly preferable. Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group and the like. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 13 carbon atoms is preferable, and an alkoxycarbonyl group having 2 to 7 carbon atoms is particularly preferable. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and an isopropoxycarbonyl group. As an aryl group, a C6-C16 aryl group is preferable, for example, a phenyl group, a naphthyl group, etc. are mentioned. The aralkyl group is preferably a group consisting of an aryl group having 6 to 16 carbon atoms and the alkyl group having 1 to 6 carbon atoms, and examples thereof include a benzyl group.

The alkoxy group represented by R ³ is preferably a linear or branched alkoxy group having 1 to 24 carbon atoms, more preferably an alkoxy group having 1 to 16 carbon atoms, particularly preferably an alkoxy group having 1 to 12 carbon atoms. . Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group and the like. As the acyloxy group, a linear or branched alkanoyloxy group having 1 to 12 carbon atoms is preferable, and an alkanoyloxy group having 1 to 6 carbon atoms is particularly preferable. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, and a butyryloxy group. As the alkoxycarbonyloxy group, an alkoxycarbonyloxy group having 2 to 13 carbon atoms is preferable, and an alkoxycarbonyloxy group having 2 to 7 carbon atoms is particularly preferable. Examples of the alkoxycarbonyloxy group include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, and the like. The aryloxy group is preferably an aryloxy group having 6 to 16 carbon atoms, and examples thereof include a phenoxy group and a naphthyloxy group. As the aralkyloxy group, those having the aralkyl group are preferable, and examples thereof include a benzyloxy group.

In general formula (I), R ¹ and R ² are preferably hydrogen atoms. R ³ is preferably a hydroxy group, an alkoxy group or an aralkyloxy group, more preferably a hydroxy group or an alkoxy group having 1 to 12 carbon atoms, particularly a methoxy group or a hexyloxy group.

  Examples of 5-aminolevulinic acid derivatives include 5-aminolevulinic acid methyl ester, 5-aminolevulinic acid ethyl ester, 5-aminolevulinic acid propyl ester, 5-aminolevulinic acid butyl ester, 5-aminolevulinic acid pentyl ester, 5-aminolevulinic acid hexyl ester, etc. In particular, 5-aminolevulinic acid methyl ester or 5-aminolevulinic acid hexyl ester is preferable.

  Examples of salts of 5-aminolevulinic acid and its derivatives include hydrochloride, phosphate, nitrate, sulfate, sulfonate, acetate, propionate, butyrate, valerate, citrate, and fumarate. And acid addition salts such as maleate and malate, and metal salts such as sodium salt, potassium salt and calcium salt. 5-Aminolevulinic acid and a salt thereof can be used alone or in combination of two or more thereof.

  5-Aminolevulinic acid, a derivative thereof or a salt thereof can be produced by any method of chemical synthesis, production by a microorganism, and production by an enzyme. The product can be used as it is without separation and purification as long as it does not contain substances harmful to plants. Moreover, when a harmful substance is contained, it can be used after removing the harmful substance to a level not harmful.

  The content of the component (A) in the solid fertilizer of the present invention is preferably 0.0001 to 1% by mass, more preferably 0.001 to 1% by mass, from the viewpoint of plant growth promoting action and storage stability. 0.002-0.8 mass% is more preferable, and 0.003-0.6 mass% is more preferable.

  The component (B) bone meal used in the solid fertilizer of the present invention is a pulverized product of animal bones, and examples of animal bones include mammals such as cows, pigs, chickens, horses, sheep, goats and fish, and birds. Or a fish bone is mentioned. Moreover, what heat-processed before the grinding | pulverization, ie, the thing which grind | pulverized after heat-processing the animal bone, is preferable. As the bone meal, steamed bone meal obtained by steaming raw animal bones, removing a part of oil and protein, drying and pulverizing is preferable, and one containing nitrogen and phosphoric acid is preferable.

  The particle diameter of the component (B) bone powder used in the solid fertilizer of the present invention is preferably 50 mm or less, more preferably 0.1 to 50 mm, further preferably 0.2 to 30 mm, from the viewpoint of moldability of the solid fertilizer. 2 to 20 mm is particularly preferable. Here, by setting the particle diameter of the bone powder to 0.1 to 50 mm, the moldability of the solid fertilizer containing 5-aminolevulinic acid can be improved, the molded product can be stably produced, and the product quality is improved. Can be made. On the other hand, in the case of bone powder having a particle size of less than 0.1 mm, it is possible to produce a 5-aminolevulinic acid-containing solid fertilizer, but there is a possibility that the raw material adheres to the production apparatus, and countermeasures are required. There is. Here, the particle diameter can be measured by ordinary sieving. In the granulation process, the component (B) bone powder having a certain particle size or more is pulverized to produce the solid fertilizer of the present invention. Therefore, the particle size of the component (B) bone powder constituting the solid fertilizer of the present invention is: It becomes smaller than the particle size at the time of manufacture.

  The content of the component (B) in the solid fertilizer of the present invention is preferably 10 to 80% by mass, more preferably 10 to 70% by mass from the viewpoints of moldability, storage stability and plant growth promoting action. 60 mass% is further more preferable, and 10-50 mass% is further more preferable. In addition, the content ratio (A / B) of the component (A) and the component (B) in the solid fertilizer of the present invention is preferably 0.00001 to 0.1 from the viewpoint of moldability and storage stability. 0.0001 to 0.1 is more preferable, and 0.0001 to 0.05 is even more preferable.

  (C) Citric acid used in the solid fertilizer of the present invention is a component that greatly contributes to the storage stability of the solid fertilizer. As the citric acid, either an anhydride or a monohydrate can be used, and the content in the present invention is in terms of anhydride.

The content of the component (C) in the solid fertilizer of the present invention is preferably 6 to 20% by mass, more preferably 6 to 15% by mass, and further preferably 6 to 10% by mass from the viewpoint of storage stability and moldability. preferable. If the citric acid content is low, sufficient storage stability cannot be obtained, and if it is too high, moldability deteriorates.
In addition, the mass ratio (A / C) of the component (A) and the component (C) in the solid fertilizer of the present invention is preferably 0.0001 to 0.15 from the viewpoint of storage stability and moldability. 0.0001 to 0.1 is more preferable.

  The water content in the solid fertilizer of the present invention is preferably 10% by mass or less, more preferably 1 to 8% by mass, further preferably 1 to 7% by mass, and further preferably 1 to 3% by mass from the viewpoint of storage stability. preferable.

  The solid fertilizer of the present invention includes, in addition to the above components, humus such as peat moss and black peat, solid organic matter such as raw rice bran, soybean oil cake, rapeseed oil cake, fish cake, dried cells, feather meal; Regulators, sugars, amino acids, organic acids, alcohols, vitamins, minerals, etc. can be blended.

  Examples of plant growth regulators include, for example, brassinolides such as epibrassinolide, choline agents such as choline chloride and choline nitrate, indole butyric acid, indole acetic acid, ethiclozate agent, 1-naphthylacetamide agent, isoprothiolane agent, nicotinic acid Amide agent, Hydroxyisoxazole agent, Calcium peroxide agent, Benzylaminopurine agent, Metasulfocamb agent, Oxyethylene docosanol agent, Ethephon agent, Crokinhonac agent, Gibberellin, Streptomycin agent, Daminogit agent, Benzylaminopurine agent, 4 -A CPA agent, an animidol agent, an inapentide agent, a uniconazole agent, a chlorme coat agent, a dike black agent, a mefluidide agent, a calcium carbonate agent, a piperonyl butoxide agent, etc. can be mentioned.

  Examples of the saccharide include glucose, sucrose, xylitol, sorbitol, galactose, xylose, mannose, arabinose, majurose, sucrose, ribose, rhamnose, fructose, maltose, lactose, maltotriose and the like.

  Examples of amino acids include asparagine, glutamine, histidine, tyrosine, glycine, arginine, alanine, tryptophan, methionine, valine, proline, leucine, lysine, and isoleucine.

  Examples of the organic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, phthalic acid, benzoic acid, lactic acid, citric acid, tartaric acid, malonic acid, malic acid, succinic acid, glycolic acid, glutamic acid, asparagine Examples thereof include acid, maleic acid, caproic acid, caprylic acid, myristic acid, stearic acid, palmitic acid, pyruvic acid, α-ketoglutaric acid, levulinic acid and the like, and citric acid is particularly preferable.

  Examples of the alcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, glycerol and the like.

Examples of vitamins include nicotinamide, vitamin B ₆ , vitamin B ₁₂ , vitamin B ₅ , vitamin C, vitamin B ₁₃ , vitamin B ₁ , vitamin B ₃ , vitamin B ₂ , vitamin K ₃ , vitamin A, vitamin D ₂ , Vitamin D ₃ , vitamin K ₁ , α-tocopherol, β-tocopherol, γ-tocopherol, σ-tocopherol, p-hydroxybenzoic acid, biotin, folic acid, nicotinic acid, pantothenic acid, α-liponic acid, etc. it can.

  Examples of the mineral include nitrogen, phosphorus, potassium, calcium, boron, manganese, magnesium, zinc, copper, iron, molybdenum, and magnesium.

  As the type of nitrogen source, nitrates and ammonium salts are preferable, and potassium nitrate, ammonium sulfate, and ammonium nitrate are more preferable. Although there is no restriction | limiting in particular in these density | concentrations, It is preferable that 1% or more is contained as a nitrogen content in solid fertilizer.

As a kind of phosphorus source, phosphoric acid and phosphorous acid are preferable, and phosphoric acid is more preferable. Not particularly limited to these concentrations, it preferably contains 1% or more as P ₂ O ₅ in solid fertilizers.

  Among these optional components, the solid fertilizer of the present invention preferably contains the solid organic material and a nitrogen source and / or a phosphorus source from the viewpoint of a plant growth promoting effect. The solid organic material is preferably contained in the solid fertilizer of the present invention in an amount of 30 to 80% by mass, particularly 50 to 70% by mass. The nitrogen source and the phosphorus source are preferably contained in a total of 2 to 20% by mass, particularly 5 to 15% by mass. The solid fertilizer of the present invention can be mixed (bulk blended) with solid fertilizers of other compositions and fertilized as an optimal fertilizer composition for plants.

  Examples of the method for producing the solid fertilizer of the present invention include a method in which the component (A) is spray-added to a mixture of fertilizer raw materials containing the component (B) and the component (C) and granulated with a granulator. Not only this but a component (A) may be spray-added to the mixture of the fertilizer raw material containing the component (B) and the component (C) granulated previously. Further, various salt crystals of 5-aminolevulinic acid may be mixed with the component (B) and the component (C).

  More specifically, the component (A) -containing solution is spray-added to a part of the mixture of the solid fertilizer raw material containing the component (B) and the component (C), and then mixed and molded into a granule with a granulator Can be manufactured.

  The solid fertilizer of the present invention is dried after granulation. Usually, natural drying is sufficient, but it may be forced to dry using outside air or warm air.

  The granulator used for granulation of the solid fertilizer of the present invention may be either a continuous type or a batch type as long as the effect of mixing and granulation can be sufficiently obtained. Examples thereof include a pellet granulator, a tablet granulator, a rotary mixing drum, a bread granulator, an extrusion molding machine, and the like.

  The shape of the solid fertilizer of the present invention is preferably in the form of a granule from the viewpoint of usability, and more preferably, for example, a granule having a particle size of 3 to 10 mm.

  The solid fertilizer of the present invention is used by being premixed in the soil in which the plant is planted, embedded in the surface of the soil, or administered to the soil surface around the plant.

  The treatment time of the solid fertilizer of the present invention is not particularly limited, but when mixed and used, it is preferable to mix in advance in the soil before planting, and when used as additional fertilizer, the plant grows. As long as it is in the period.

  The fertilizer application amount of the solid fertilizer of the present invention may be 1 to 1000 kg / 10a as the amount of solid fertilizer.

  The plants to which the solid fertilizer of the present invention is applied are all plants that are effective when administered with a 5-aminolevulinic acid-containing solution. Leafy vegetables are preferred, and komatsuna is more preferred, but is not limited thereto.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, these are raise | lifted for the purpose of illustration only, This invention is not limited to these Examples.

[Example 1] Production of 5-aminolevulinic acid-containing solid fertilizer Fertilizer composed of ammonium sulfate, potassium chloride, steamed bone meal (particle size: 0.1 to 50 mm), rapeseed oil cake, raw rice bran, dried cells, and citric acid After adding 5-aminolevulinic acid hydrochloride (ALA.HCl) aqueous solution as a 5-aminolevulinic acid to the raw material so as to be 0.3% by mass and 0.03% by mass and granulating with a pellet granulator, The temperature was sufficiently lowered to prepare 5-aminolevulinic acid-containing solid fertilizers A to C, respectively. The fertilizer raw material was blended so that the content of nitrogen (TN), phosphoric acid (P ₂ O ₅ ), and potassium (K ₂ O) was 5-5-5% as the fertilizer composition. At this time, the same solid fertilizer D not containing 5-aminolevulinic acid hydrochloride was also granulated. The compositions of the prepared solid fertilizers A to D are shown in Table 1.

  The test for ALA storage stability was carried out by the following method. Moreover, about the solid fertilizer AC shown in Table 1, the plant growth promotion effect was evaluated with the following method.

(1) Storage stability test: The content of 5-aminolevulinic acid contained in the solid fertilizer after being stored in a sealed container at 40 ° C. and 75% external humidity for 14 days was measured. From the 5-aminolevulinic acid content in the solid fertilizer before and after the test, the 5-aminolevulinic acid residual rate was calculated according to the following formula.

Residual rate (%) = (Amount of 5-aminolevulinic acid contained in solid fertilizer after test (g) / Amount of 5-aminolevulinic acid contained in solid fertilizer before test (g)) × 100

(2) Plant growth promotion effect test;
[Example 2] Growth promotion effect of Japanese mustard spinach with 5-aminolevulinic acid-containing organic chemical fertilizer Using the solid fertilizer containing 5-aminolevulinic acid obtained in Example 1, the growth promotion effect of Japanese mustard spinach was tested. A polymultipot with a diameter of 15 cm was mixed with 0.8 kg of culture soil and 10 g of test fertilizer, and 4 seeds of Komatsuna were sown. At this time, the amount of fertilizer applied was 28 kg per 10a per element amount of nitrogen. The fertilizer used for the test is a mixture of ALA-free solid fertilizer D and ALA-containing solid fertilizers A to C at a ratio of 9: 1, whereby the 5-aminolevulinic acid content is 0.03% and 0.0. 003% and 0.0003% solid fertilizers EG were made and used for testing. The composition of the solid fertilizers E to G is as shown in Table 2. 30 days after sowing, one strain per pot was thinned out at the time of true leaf development. The crop was harvested 58 days after fertilization and the fresh weight was measured to evaluate the growth of Komatsuna (n = 100). The results are shown in FIG.

  As shown in FIG. 1, it was found that the growth of Komatsuna was significantly promoted by fertilizing the solid fertilizer containing 5-aminolevulinic acid.

[Comparative Example 1]
Effect of promoting growth of Japanese mustard spinach by solid fertilizer not containing solid organic matter In Example 1, by using a solid inorganic fertilizer raw material instead of solid organic matter and spraying an aqueous solution of 5-aminolevulinic acid on this inorganic fertilizer raw material, the concentration of 5-aminolevulinic acid 0.3-0.003% and 0.003% 5-aminolevulinic acid-containing inorganic fertilizers were prepared (a composition having a 5-aminolevulinic acid concentration of 0.3% is defined as composition 5). The composition of the chemical fertilizer was 13-8-10% in terms of the contents of nitrogen (TN), phosphoric acid (P ₂ O ₅ ), and potassium (K ₂ O), respectively.

  Using this 5-aminolevulinic acid-containing chemical fertilizer, the content of 5-aminolevulinic acid contained in the chemical fertilizer after 14 days storage in a sealed container at 40 ° C. and an external humidity of 75% was measured. The 5-aminolevulinic acid residual rate after storage was 30%.

Furthermore, the growth promotion effect of Komatsuna was tested using the solid fertilizer after 30 days storage.
A cultivation test of Komatsuna was performed in the same manner as in Example 2 (n = 100). The results are shown in FIG.

  As shown in FIG. 2, it can be seen that the 5-aminolevulinic acid-containing inorganic fertilizer has poor ALA storage stability and does not have a plant growth promoting effect even when compared with a chemical fertilizer not containing 5-aminolevulinic acid. .

Example 3
The solid fertilizer H having the composition shown in Table 3 was prepared in the same manner as in Example 1 except that the steamed bone meal in the solid fertilizer A had a particle size of less than 0.1 mm. Table 4 shows the results of the production status (manufacturer stability) and moldability (product manufacturability) of solid fertilizer A and solid fertilizer H, and the quality of the prepared solid fertilizer.

About the bone meal used as a raw material, although there was adhesion of the raw material at the time of manufacture, etc., it was confirmed that solid fertilizer can be manufactured regardless of the particle diameter.
In particular, as shown in Table 4, by using bone meal having a particle diameter of 0.1 to 50 mm as a raw material, it is possible to prevent the raw material from adhering to the production apparatus, and to stably produce a solid fertilizer. Can do.

[Example 4] Effect of citric acid content on storage stability of 5-aminolevulinic acid-containing solid fertilizer The same as solid fertilizer A except that the citric acid content is 0, 1, 2, 5, 9.1% Solid fertilizers I to L were blended in composition (pellet granulation was not performed). About compounded solid fertilizer IL, the 4-aminolevulinic acid content in the solid fertilizer 14 days after was measured at 40 degreeC, and 5-aminolevulinic acid residual rate was computed. The results are shown in FIG.

  From FIG. 3, it can be seen that the solid fertilizer having a citric acid content of 9.1% or less has a significantly decreased storage rate of 5-aminolevulinic acid due to storage after 14 days at 40 ° C. and poor storage stability. On the other hand, a solid fertilizer having a citric acid content of 9.1% has a residual ratio of 5-aminolevulinic acid of 70% or more even after long-term storage, and is excellent in storage stability.

[Example 5] Effect of moisture content in solid fertilizer on storage stability of solid fertilizer containing 5-aminolevulinic acid Solid fertilizer M having the composition shown in Table 5 was moisture-absorbed (water content 23%), immediately after preparation Of three types of solid fertilizers (water content 6.0%) and those dried at 40 ° C. for 14 hours (water content 3.3%) in a sealed container at 40 ° C. and external humidity 75%. The 5-aminolevulinic acid content contained in the solid fertilizer after storage for days was measured. The residual ratio of 5-aminolevulinic acid in the solid fertilizer after storage is shown in FIG.

  It can be seen that the solid fertilizer having a water content of 23% has a significantly reduced storage stability of 5-aminolevulinic acid due to long-term storage, and poor storage stability. On the other hand, the solid fertilizer having a moisture content of 6.0% and 3.3% has a residual ratio of 5-aminolevulinic acid of 80% or more even after long-term storage, and is found to have excellent storage stability. .

Claims (4)

The following components (A), (B), (C) and (D):
(A) The following general formula (I)
R ² R ¹ NCH ₂ COCH ₂ CH ₂ COR ³ (I)
(In the formula, R ¹ and R ² represent a hydrogen atom; R ³ represents a hydroxy group or an alkoxy group.)
5-aminolevulinic acid represented by the following:
(B) bone meal,
(C) Citric acid (D) Solid fertilizer characterized by containing solid organic substances other than components (A), (B) and (C) .   The solid fertilizer according to claim 1, wherein the water content is 10% by mass or less in the total amount of the solid fertilizer.   The solid fertilizer according to claim 1 or 2, comprising 0.0001 to 1% by mass of component (A), 10 to 80% by mass of component (B), and 6 to 20% by mass of component (C). Next steps (a) and (b):
(A) In the solid fertilizer raw material mixture containing component (B), component (C) and component (D), the following general formula (I)
R ² R ¹ NCH ₂ COCH ₂ CH ₂ COR ³ (I)
(In the formula, R ¹ and R ² represent a hydrogen atom; R ³ represents a hydroxy group or an alkoxy group.)
A step of spray-adding a solution containing 5-aminolevulinic acid, an ester thereof or a salt thereof (A) represented by:
(B) The manufacturing method of the solid fertilizer in any one of Claims 1-3 including the process to shape | mold.