JP6800945B2 - Method for producing paddy rice seed coating composition and paddy rice seed coating composition - Google Patents

Description

The present invention relates to a suitable paddy rice seed coating composition and coated paddy rice seed paddy in direct sowing cultivation of paddy rice.

In recent years, from the viewpoint of reducing the production cost of paddy rice cultivation, saving labor, and aging paddy rice producers, the direct sowing method of directly sowing paddy rice seeds (hereinafter, also simply referred to as seed paddy) in a flooded field has attracted attention. Has been done.

Conventionally, in the direct sowing cultivation method, a mixture containing reduced iron powder, gypsum, and water is applied to the surface of the seed paddy in order to suppress the buoyancy caused by the rice husk and ensure that the seed paddy is settled and settled in the soil under flooding to germinate. It is carried out by sowing covered paddy rice seeds with a large specific gravity.

The coating work for producing such coated paddy rice seeds is generally carried out by loading the seeds and a mixture of reduced iron powder and gypsum into a granulator and spraying water. There is a problem that the heat of oxidation accompanying the oxidation of the iron powder adhering to the surface of the seed paddy inadvertently transfers heat to the seed paddy and causes thermal deterioration of the seed paddy, resulting in a decrease in the germination rate of the seed paddy.

Japanese Unexamined Patent Publication No. 2013-146266 JP 2015-77100 Republished 2017-08223

However, in all of the above-mentioned conventional seed paddy coating techniques, since the coating treatment is performed in an aqueous system using a water-soluble resin, the seed paddy is stored in a high humidity environment or when the seed paddy is not sufficiently dried after being coated. In this case, there is a problem that mold is generated on the surface of the coated seed paddy and the coated seed paddy itself is easily deteriorated.

In view of the above-mentioned problems of the conventional iron oxide coating technique, the present invention relates to a case where the paddy rice seeds coated with the aqueous composition are not sufficiently dried after the coating treatment or are stored in a high humidity environment. Even so, it is an object of the present invention to provide a paddy rice seed coat coating composition and a paddy rice seed paddy which can suppress the generation of mold and prevent the deterioration of the seed paddy and do not reduce the germination rate after sowing.

That is, the present invention provides the following methods for producing the paddy rice seed paddy coating composition [1] to [2] and the paddy rice seed paddy coating composition [3] .
[1] with an oxidizing limonite containing iron oxide and silicon oxide (a), propyl paraben, anthocyanidins, rice seeds containing coating antifungal compound having a phenolic hydroxyl group which is selected from any of hinokitiol and (b), the a composition, wherein the oxide limonite (a), the ferric oxide against the iron oxide the molar ratio 0.2 to 0.8, the silicon oxide against before Symbol iron oxide has a molar ratio from 0.13 to 0.65 The paddy rice seed coating composition , wherein the antifungal compound (b) is contained in an amount of 0.008% by mass to 0.46% by mass with respect to the oxidized limonite (a), respectively.
[2] The paddy rice seed coating composition according to claim 1, which contains a polyester resin and a polyurethane resin.
[3] 0.008% by mass to 0.46% by mass with respect to the dispersant (f) , the foam suppressant (g) , the fertilizer component (d) , the thickener (e), and the oxide limonite (a) described later. a step of preparing propylparaben, anthocyanidins, antifungal compounds having a phenolic hydroxyl group which is selected from any of hinokitiol and (b), the water and ethanol (h) was added dispersion and mixed by攪拌by, include iron oxide and silicon oxide, wherein the molar ratio of the silicon oxide to the molar ratio of 0.2 to 0.8 and the iron oxide ferric oxide for the iron oxide is 0.13 to 0.65 the oxide limonite and (a), the It includes a step of preparing a prepaste by adding it to a dispersion liquid and stirring and kneading it, and a step of adding a resin (c) to the prepaste and stirring and kneading it to prepare a coating composition of paddy rice seeds. A method for producing a paddy rice seed coating composition.

The paddy rice seed coating composition of the present invention essentially solves the generation of mold on the seed paddy and the decrease in the activity of the seed paddy by the coating treatment with the conventional water-based composition. That is, by using a coating composition in which limonite oxide obtained by oxidizing limonite and a specific antifungal compound having a large interaction with the components thereof are used, the antifungal property can be enhanced and the coated seed paddy can be used. Paddy rice-coated seed paddy can be obtained in which the decrease in activity due to the generation of mold during storage is suppressed and the yield of seed paddy whose activity is maintained is improved.

It is a photograph of paddy rice-coated seed paddy coated with a coating composition.

The present inventor has made extensive studies as follows in order to solve the above problems. The coating layer formed on the surface of paddy rice seeds is treated with an aqueous system, the coating composition used has a high affinity for water, and the surface of the seeds is in a state of easily absorbing moisture. Therefore, when the coating treatment is insufficiently dried or when the product is stored in a high humidity environment, mold is likely to occur.

Therefore, the present inventor investigated whether the antifungal property can be enhanced by the interaction between the iron oxide component used in the coating composition and the structure of the antifungal compound.

As a result, it was found that the iron oxide component and the antifungal compound having a phenolic hydroxyl group exhibit excellent antifungal properties by interaction. Specifically, the antifungal compound having a phenolic hydroxyl group in the structure, or the antifungal compound having a hydroxyl group similar to the phenolic hydroxyl group and the oxidized limonite obtained by oxidizing natural limonite are combined to prevent mold. We found that the sexuality was enhanced, and came up with the present invention.

It is presumed that this phenomenon is due to the action of hydrogen bonding force between the particle surface of silicon oxide contained in limonite oxide and the phenolic hydroxyl group of the antifungal compound. Furthermore, it is presumed that the phenolic hydroxyl group of the antifungal compound also interacts with the particle surface of ferric oxide (β-oxyferride hydroxide).

Hereinafter, the paddy rice seed coating composition and the coated paddy rice seed paddy of the present invention will be described in detail. The present invention is not limited to the embodiments shown below. In the present invention, paddy rice seed paddy is coated with a paddy rice seed paddy coating composition containing limonite oxide (a) containing silicon oxide as a component and an antifungal compound (b) having a phenolic hydroxyl group.

[Oxidized limonite (a)]
In the present embodiment, the limonite oxide (a) used as the material of the coating composition is obtained by oxidizing limonite (limonite) for a long time in a natural environment and converting ferrous oxide into ferric oxide. Can be mentioned. This brown iron ore (limonite) contains ferrous oxide (FeO) and ferric oxide β-oxyferride hydroxide (FeOOH), and ferrous oxide is converted to ferric oxide (β-) by oxidation treatment. It changes to iron oxyhydroxide) and the content of ferric oxide increases. In addition, limonite oxide also contains a large amount of silicon oxide.

The above-mentioned oxidation change from ferrous oxide to ferric oxide is indicated by 2θ of the (111) plane of ferrous oxide and the (110) plane of ferric oxide by reflection intensity analysis in X-ray diffraction. The peak intensity ratio can be traced, and the content of silicon oxide can be measured by elemental analysis using fluorescent X-ray (XRF). The above-mentioned silicon oxide content may be 0.1 or more in a molar ratio of silicon oxide / iron oxide. It is preferably 0.2 or more, and more preferably 0.4 or more. Further, the above-mentioned ferrous oxide / iron oxide ratio may be 0.2 or more, preferably the ferric oxide / iron oxide ratio is 0.3 or more, and more preferably 0.5 or more.

As the limonite oxide, one that has undergone an oxidation treatment period such as outdoor exposure after mining, and then pulverized by a crusher such as a spike mill and classified by a sieve may be used.

In the present embodiment, limonite oxide (a) contains ferrous oxide, ferric oxide and silicon oxide, but for iron oxide, Fe ₂ O ₃ (iron (III) oxide), α-Fe ₂ O ₃ (α-iron oxide (III)), β-Fe ₂ O ₃ (β-iron oxide (III)), γ-Fe ₂ O ₃ (γ-iron oxide (III)), ε-Fe ₂ O ₃ It may contain iron oxide such as (ε-iron oxide (III)) and iron hydroxide such as δ-FeOOH (δ-iron oxyhydroxide) and Fe (OH) ₃ iron hydroxide (III).

The average particle size of limonite oxide (a) is preferably in the range of 30 to 100 μm, more preferably 30 to 80 μm, and even more preferably 30 to 75 μm. When the average particle size is 30 μm or more, the volume of the coating layer required for the large bulk specific gravity is small, and the work efficiency is improved. When the average particle size is 100 μm or less, the coating layer is less likely to collapse in water and peel off from the surface of paddy rice seeds. The average particle size is the volume cumulative particle size D50 measured by a laser diffraction / scattering type particle size distribution measuring device.

The content of limonite oxide (a) in the coating layer coated on the coated paddy rice seed of the present invention is preferably 0.1 to 0.5, more preferably 0.2 to 0.4 in terms of the weight ratio of limonite oxide / paddy rice seed. When the weight ratio of limonite oxide (a) is 0.1 or more, the apparent specific gravity increases and it becomes difficult to be washed away after sowing, and when it is 0.5 or less, the coating layer can be easily maintained. The content of limonite oxide (a) in the coating layer is preferably 30 to 50% by mass, more preferably 35 to 50% by mass, and even more preferably 40 to 50% by mass. If it is 30% by mass or more, the floating of the seed paddy can be effectively prevented, and if it is 50% by mass or less, the strength of the coating layer can be maintained.

The above limonite is produced in Japan at the Kashiwabara mine (Shinano-cho, Kamiminochi-gun, Nagano) and the Daiichi Aso mine (Aso-shi, Kumamoto). Limonite mined by open pit mining from the ore deposit is oxidized to obtain limonite oxide, and the limonite oxide is crushed by a crusher such as a spike mill and classified by a sieve.

[Antifungal compound having a phenolic hydroxyl group (b)]
In the present embodiment, the type of the antifungal compound having a phenolic hydroxyl group used as a material of the coating composition is not particularly limited, but the phenolic hydroxyl group and the antifungal compound having a hydroxyl group having similar characteristics are contained in limonite oxide. Is preferable from the viewpoint of interaction with silicon oxide and ferrous dioxide.

Examples of the antifungal compound (b) having a phenolic hydroxyl group include paraoxybenzoic acid esters such as ethyl paraoxybenzoate, propyl paraoxybenzoate (propylparaben), butyl paraoxybenzoate, isopropyl paraoxybenzoate, and isobutyl paraoxybenzoate. (Paraben), catechin, anthocyanidin, flavon, isoflavone, flavonol and other flavonoids, coumarin, curcumin, lignan and other polyphenols, orthophenylphenol, hinokithiol, hiba oil and the like. These can also be mixed and used. As the antifungal compound, it is more preferable to use an antifungal compound obtained from a natural product from the viewpoint of environmental load. Examples of antifungal compounds include imidazoles such as thiabendazole and fludioxonyl, but those having these structures are not preferable because of their low effectiveness.

The content of the antifungal compound (b) in the coating composition of the present embodiment is preferably 0.005 to 3.000% by mass, more preferably 0.010 to 1.000% by mass, and further preferably 0.050 to 0.500% by mass. Is. When the content of the antifungal compound is 0.005% by mass or more, the antifungal effect is likely to be exhibited, and when it is 3.000% by mass or less, it can be effectively mixed with the composition.

It is presumed that the antifungal compound in the coating composition can obtain antifungal properties by polarization the phenolic hydroxyl group by the interaction between the phenolic hydroxyl group and silicon oxide or ferric oxide in the coating composition. It is estimated that it depends on the content of silicon oxide or ferric oxide.

[Resin (c)]
The type of resin used for the coating layer in the present invention is not particularly limited, but it is preferably used as an emulsion from the viewpoint of coating strength. An aqueous resin emulsion in which the dispersion medium is water or a biodegradable resin emulsion is more preferable from the viewpoint of reducing deterioration of seed paddy and burdening the environment. Examples of the resin used for the aqueous emulsion include polyester resin, polyurethane resin, vinyl resin, acrylic resin, diene resin, at least two copolymer resins of vinyl monomer, acrylic monomer and diene monomer, polylactic acid, alginic acid, cellulose and the like. Can be mentioned. These can also be mixed and used.

Examples of the polyester resin include polybutylene succinate copolymers such as polycaprolactone, polybutylene succinate and polybutylene succinate core zipate, polyethylene succinate copolymers such as polyethylene succinate and polyethylene succinate core zipate, and polylactic acid. Examples thereof include polyglycolic acid copolymers such as polyglycolic acid, lactic acid-glycolic acid copolymer, glycolic acid-caprolactone copolymer, and glycolic acid-trimethylene carbonate copolymer, polydioxanone, and poly-3-hydroxybutyrate. More preferable aqueous resin emulsions are polylactic acid, polyglycolic acid, lactic acid-glycolic acid copolymer, and polyglycolic acid copolymer.

Examples of the polyurethane resin include polyether urethane resin which is a heavy adduct of polyethylene glycol, polypropylene glycol and the like and polyisocyanate, polyesterdiol urethane resin which is a heavy adduct of polyesterdiol and polyisocyanate, and weight of polycarbonatediol and polyisocyanate. Examples thereof include a polycarbonate-based urethane resin as an adduct.

Examples of the copolymer resin include an aqueous emulsion of a vinyl acetate polymer, an aqueous emulsion of an acrylic acid ester copolymer, an aqueous emulsion of an ethylene / vinyl acetate / acrylic acid copolymer, and an aqueous emulsion of an ethylene / vinyl acetate copolymer.

The content of the resin solid content in the coating composition of the present embodiment is preferably 2 to 50% by mass because it is easy to handle, more preferably 3 to 40% by mass, and further preferably 5 to 30% by mass. %. When the content of the resin solid content is 2% by mass or more, a coating layer having excellent coating strength can be obtained, and when it is 50% by mass or less, the workability when forming the coating layer becomes good.

[Fertilizer component (d)]
In the present embodiment, a fertilizer component may be added as a material of the coating composition, if necessary. Examples of the fertilizer component (d) include KH ₂ PO ₄ (potassium dihydrogen phosphate), K ₂ HPO ₄ (dipotassium hydrogen phosphate), K ₃ PO ₄ (tripotassium phosphate), and K ₄ P ₂ O ₇ Potassium phosphate salts such as (tetrapotassium pyrophosphate), K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), (KPO ₃ ) _n (potassium metaphosphate, n = 10000), and MoO ₃ (molybdenum oxide (VI)). ), Adenosine, guanosine, thymidine, citidine, uridine, xanthosine, and inosin, and their 2'-deoxy compounds, and nucleotides include adenyl acid (adenosine-5'-phosphate), guanylate (guanosine-). 5'-Phosphoric Acid), Timidylic Acid (Timidin-5'-Phosphoric Acid), Uridilic Acid (Ulysine-5'-Phosphoric Acid), Xanthylic Acid (Xanthosine-5'-Phosphoric Acid), and Inosinic Acid (Inosin-5) '-Phosphoric acid), as well as nucleosides such as these 2'-deoxys, nucleotides, uric acid and inosin. The nucleoside and the nucleotide may be a free form, or may be a salt such as a sodium salt or a potassium salt. Of these, it is preferably selected from food additives (KPO ₃ ) _n (potassium metaphosphate, n = 10000), MoO ₃ (molybdenum oxide (VI)), inosine, and inosinic acid (inosin-5'-phosphoric acid). One or more. These fertilizer components may be used alone or in combination of two or more.

The content of the fertilizer component of the present embodiment is preferably 0.01 to 10.00% by mass, more preferably 0.03 to 5.00% by mass, and further preferably 0.05 to 3.00% by mass. When the content of the fertilizer component is 0.01% by mass or more, the fertilizer component can sufficiently obtain the growth promoting effect. When the content of fertilizer component is 10.00% by mass or less, it is good in terms of productivity and cost.

[Thickener (e)]
In the present embodiment, the thickener (e) may be added as a material of the coating composition. Since the thickener (e) is contained in the coating composition, it is possible to prevent the oxidized limonite (a) from separating in the composition, and it is possible to obtain a composition in which the composition components are in a uniform state. .. As a result, a coating layer having a uniform composition is obtained.

The thickener (e) includes cellulosic compounds such as hydroxyethyl cellulose, hydroxypropyl cellulose and cellulosic nanofibers, glycols such as polyethylene glycol distearate, sodium polyacrylate, and guar gum, xanthan gum and gum ace. And their mixtures can be exemplified. Among these, hydroxypropyl cellulose, guar gum, xanthan gum, which are known as food additives, and mixtures thereof and cellulose nanofibers can be preferably used as the thickener (e).

The content of the thickener (e) of the present embodiment is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and further preferably 0 to 1% by mass. When the content of the thickener (e) is 5% by mass or less, the composition containing the thickener (e) has good handleability.

[Dispersant (f)]
In the present embodiment, a general dispersant (f) can be added as a material for the coating composition. By mixing the dispersant with the coating composition and then coating the paddy rice seeds, the wetting and dispersibility of the powder surface can be improved.

As the dispersant (f), a surfactant can be used. As the surfactant, various known surfactants can be selected and used according to the surface condition of the limonite oxide (a) to be used. Specifically, as anionic surfactants, polycarboxylic acids such as Demol (registered trademark) EP, Homogenol (registered trademark) L-18, Poise (registered trademark) 520, and 530 (all manufactured by Kao Corporation). There are type surfactants and naphthalene sulfone formalin condensate type surfactants such as Demol (registered trademark) N (manufactured by Kao Corporation). As nonionic surfactants, Surfinol (registered trademark) TG, Acetylene glycol-type activators such as 104E (manufactured by Nissin Chemical Industry Co., Ltd.), Emargen (registered trademark) 102KG, 103, 104P, 105, 106, 108, 109P, 120, Polyoxyethylene lauryl ethers such as 123P, 130K, 147 and 150 (manufactured by Kao Corporation) and polyoxyethylene such as Emargen (registered trademark) 210P and 220 (manufactured by Kao Corporation). Cetyl ether, polyoxyethylene stearyl ether such as Emulgen (registered trademark) 306P, 320P, 350 (above, manufactured by Kao Corporation), Emargen (registered trademark) 404, 408, 409V, 420, 420, the same. Polyoxyethylene oleyl ether such as 430 (manufactured by Kao Corporation), Pegnor (registered trademark) O-6A (manufactured by Toho Kagaku Kogyo Co., Ltd.), Thirabazole (registered trademark) L-01, W-01 (Taiyo) Fatty acid esters such as Chemical Co., Ltd., polyoxyethylene alkyl ether-type surfactants such as Neugen (registered trademark) ET (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Nonal 210, 212 (trade name, Toho Chemical Co., Ltd.) Polyoxyethylene alkylphenyl ether type surfactants such as (manufactured by Kogyo Co., Ltd.) can be mentioned. These surfactants may be used alone or in combination of two or more.

The content of the dispersant (f) of the present embodiment is preferably 0.01 to 20.00% by mass, more preferably 0.10 to 0.000% by mass, and further preferably 1.00 to 0.000% by mass. When the content of the dispersant (f) is 0.01% by mass or more, the effect of improving the dispersibility of the limonite oxide (a) can be sufficiently obtained. When the content of the dispersant (f) is 20.00% by mass or less, the influence on the disintegration property of the coating layer is small.

[Defoamer (g)]
In the present embodiment, a defoaming agent (g) can be added as a material of the coating composition. When the antifoaming agent (g) is contained in the coating composition, the workability at the time of forming the coating layer is improved.

As the foam suppressant (g), Nopco (registered trademark) 8034, Nopco (registered trademark) 8034-L, SN deformer 477, SN deformer 5013, SN deformer 247, SN deformer 382 (trade name, manufactured by San Nopco Co., Ltd.) , Anti-Home 08 (trade name), Emargen (registered trademark) 903 (above, manufactured by Kao Corporation), Hourbreak G-109, SO-101, L-01, LJ-01, H-01 (above) , Taiyo Kagaku Co., Ltd.) and other commercially available products can be used.

The content of the defoaming agent (g) of the present embodiment is preferably 0.01 to 2.00% by mass, more preferably 0.03 to 1.50% by mass, and further preferably 0.10 to 1.00% by mass. When the content of the defoaming agent (g) is 0.01% by mass or more, a good defoaming effect can be obtained. Further, when the content of the defoaming agent (g) is 2.00% by mass or less, the influence on the disintegration property of the coating layer is small.

[Organic solvent (h)]
In the present embodiment, the organic solvent (h) can be added as a material of the coating composition. As the organic solvent (h), it is preferable to use one that acts as a dispersion medium and is miscible with water. Specifically, as the organic solvent (h), from the viewpoint of shortening the time for drying the dispersion medium when forming the coating layer and sterilizing the composition, such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol. It is preferable to use alcohols. Among these, it is more preferable to use ethanol from the viewpoint of reducing the environmental load.

The content of the organic solvent of the present embodiment is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass, based on the total amount of the dispersion medium contained in the coating composition. It is as follows. By reducing the content of the organic solvent to 50% by mass or less, the composition has excellent workability and hygiene with a low environmental load.

In particular, in the coating composition to which the organic solvent (h) is added, the organic solvent (h) can function as a developing layer of the antifungal compound (b). For example, when two or more kinds of coating compositions having phenolic hydroxyl groups are added, the moving distance changes according to the unique polarity according to the interaction with silicon oxide or ferric oxide in the coating composition. It is presumed to make it.

That is, the organic solvent is used as the stationary phase, the antifungal compound is used as the mobile phase, and two or more antifungal compounds having different moving distances as the organic solvent volatilizes during drying of the dispersion medium when forming the coating layer are formed on the surface of the seed paddy. It is presumed that the amount of distribution differs between inside and outside in the thickness direction of the coating layer formed over the entire area.

[Manufacturing method of coating composition]
In order to produce the paddy rice seed coating composition of the present invention, limonite oxide (a), an antifungal compound (b) having a phenolic hydroxyl group, a resin (c), and the other additives (e) to (h) described above are used. ) Can be uniformly dispersed, and the mixing method and the order of adding the materials are not limited.

For example, a method of preparing a paste by stirring and mixing all the materials at once, or a method of stirring and mixing materials other than the resin (c) to prepare a mill base in advance, and adding the resin (c) to the mill base. Further, a method of stirring and mixing can be used.

The combination of materials for producing the mill base is not particularly limited, and it is sufficient that all the materials are contained in the final paste and dispersed uniformly. In the present invention, the method of preparing the mill base in advance is preferable because the dispersibility of the resin (c) is improved and the production efficiency is improved.

[Manufacturing method of covered paddy rice seeds]
The method for producing paddy rice-coated paddy having a coating layer composed of the coating composition of the present invention includes the paddy rice seed paddy, the above-mentioned limonite oxide (a), an antifungal compound (b) having a phenolic hydroxyl group, and a resin (c). After mixing the substances to form a coating layer on the surface of the seed paddy, the dispersion medium of the resin is dried. That is, after the coating layer of the paddy rice seed covering composition is formed on the surface of the paddy rice seed paddy, the coating layer is dried to form a dry coating layer, and the paddy rice seed covering paddy coated with the dry coating layer is obtained.

When the coating layer is formed on the surface of the seed paddy by the coating composition, it is sufficient that the coating composition can be applied to the dry paddy of paddy rice seed paddy that has not been soaked and then dried, and the coating method and the drying method are not limited. For example, after loading the dry paddy of paddy rice seeds that has not been soaked into a device such as a rolling granulator, the coating composition is added while rotating, and the coating composition is added to the dry paddy of paddy rice seeds that have not been soaked. After applying the material, a resin coating layer having excellent mechanical properties can be formed by air-drying the material on a container such as a stainless steel bat, a vinyl sheet, a straw mat, newspaper, etc. for several hours to 24 hours at room temperature.

When the coating composition is applied and dried as described above, the viscosity of the coating composition is preferably 5000 to 30000 mPa · s, more preferably 6000 to 28000 mPa · s, still more preferably 6000 to 25000 mPa · s. is there. If the viscosity is 5000 to 30000 mPa · s, it is suitable for handling as a paste.

The purpose of drying after the coating is to increase the hardness of the coating layer that adheres to the seed paddy by evaporating the dispersion medium or the like contained in the coating composition.

The hardness of the coating layer is preferably 50 to 200 N. When the hardness of the coating layer is 50 N or more, it is difficult for powder to fall off, and when it is 200 N or less, the germination rate is good. The hardness of the coating layer is a value measured for each seed pad on which the coating layer is formed, and a hardness meter HH-411 or the like manufactured by Mitutoyo Co., Ltd. can be used as the measuring instrument.

The coating ratio of the coated paddy rice seed paddy (the ratio of the mass of the coating layer of the coated paddy rice seed paddy to the mass of the dry paddy (mass of the coating layer / mass of the dry paddy)) is preferably 0.1 to 0.7, preferably 0.3 to 0.6. Is more preferable. When the coating ratio of the coated paddy rice seeds is 0.1 or more, the coated paddy rice seeds become sufficiently heavy and the coated paddy rice seeds can be prevented from floating in the water of the paddy field, and when it is 0.7 or less, after the coated paddy rice seeds are sown in the field. It is preferable because the individual difference in germination timing becomes smaller.

The coated paddy rice seeds of the present invention obtained by the above production method are soaked before sowing because they are dried as shown in FIG. 1 after the coating composition is applied to the dry paddy of the paddy rice seeds that have not been soaked. It can be treated and sown, or it can be sown without soaking.

Hereinafter, Examples and Comparative Examples according to the present invention will be specifically described in the following order.
(1) Main base materials used in Examples and Comparative Examples:
(2) Preparation example of coating composition according to Examples and Comparative Examples:
(3) Verification experiment of germination and antifungal properties of Examples and Comparative Examples:
In the following, the coating compositions 1 to 50 obtained in Preparation Examples 1 to 50 correspond to Examples 1 to 50, which are seed paddies coated with the coating compositions 1 to 50, and Adjustment Example 51. The coating compositions 51 to 60 obtained in each of ~ 58 correspond to Comparative Examples 1 to 10 which are seeds coated with the same coating compositions 51 to 60. Therefore, the types and additions of materials in various tables are the same according to their respective correspondences. Moreover, the present invention is not limited to the following examples.

(1) Main base materials used in Examples and Comparative Examples:
The main base materials used in the examples and comparative examples of the present invention are limonite oxide (a), antifungal compound (b), and resin emulsion (c). Hereinafter, these main base materials will be described.

(Limonite Oxidation (a))
The mined limonite can be oxidized for a long time in a natural environment to obtain rimonite oxide containing ferrous oxide and ferric oxide (β-hydroxyferrous hydroxide) in different ratios. Further, although limonite contains silicon oxide, it hardly changes by the above-mentioned oxidation treatment.

The ratio of ferric oxide / iron oxide contained in the above limonite oxide was measured by X-ray diffraction, and the content of silicon oxide / iron oxide was measured by fluorescent X-ray.

Limonite oxide was divided into 11 types A to K according to the molar ratio of ferric oxide / iron oxide and the molar ratio of silicon oxide / iron oxide. The specific ferric oxide / iron oxide molar ratio and the silicon oxide / iron oxide molar ratio of each limonite oxide are shown in Tables 3 to 17 described later.

(Resin emulsion (c) and antifungal compound (b))
The types of the resin emulsion (c) used in the examples of the present invention are shown in Table 1, and the types of the antifungal compound (b) are shown in Table 2.

(2) Preparation example of coating composition according to Examples and Comparative Examples:
(Preparation Examples 1 to 4)
In a 100 mL polyethylene container, 0.23 g of tirabazole W-01 (manufactured by Taiyo Kagaku Co., Ltd.) as a dispersant (f), 0.23 g of Awabreak L-01 (manufactured by Taiyo Kagaku Co., Ltd.) as a foam suppressant (g), and a thickener (e). Gum Ace SG-30 (manufactured by Taiyo Kagaku Co., Ltd.) 0.11 g, potassium metaphosphate (manufactured by Taiyo Kagaku Kogyo Co., Ltd., (KPO ₃ ) n, n ≒ 10000) 0.23 g as fertilizer component (d), protection having phenolic hydroxyl group As the mold compound (b), the antifungal compound A (propylparaben (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)) shown in Table 2 was weighed as shown in Table 3.

After adding 9.4 g of water and 1.1 g of ethanol as the organic solvent (h), the mixture was stirred and mixed using a rotation / revolution type stirring device.

To the mill base prepared by adding 25.5 g of oxidized limonite A (listed in Table 3) as the oxidized limonite (a) and stirring and mixing using a rotation / revolution type stirrer, the resin (c) is shown in Table 1. Add 5.5 g of resin A (water-based resin emulsion Randy PL-3000 (manufactured by Miyoshi Oil & Fat Co., solid content concentration 40%)) and 0.73 g of resin B (NeoRezR-600 (manufactured by Kusumoto Kasei Co., Ltd., solid content concentration 33%)). Coating compositions 1 to 4 were obtained by stirring and mixing using a rotation / revolution type stirring device.

(Preparation Examples 5 to 8)
Use 0.69 g of resin C (NeoRezR-4000 (manufactured by Kusumoto Kasei Co., Ltd., solid content concentration 35%)) instead of 0.73 g of resin B, and use antifungal compound B (anthocyanidin (Fuji Film Wako Pure Chemical Industries, Ltd.) instead of antifungal compound A. The coating compositions 5 to 8 were obtained in the same manner as in Preparation Examples 1 to 4 except that the amounts described in Table 4 were used.

(Preparation Examples 9 to 12)
Coating compositions 9 to 12 were obtained in the same manner as in Preparation Examples 1 to 4, except that the antifungal compound C (hinokitiol (manufactured by Tokyo Chemical Industry Co., Ltd.)) was used instead of the antifungal compound A in the amounts shown in Table 5. It was.

(Preparation Examples 13 to 16)
Coating compositions 13 to 16 were obtained in the same manner as in Preparation Examples 1 to 4, except that 25.5 g of limonite oxide B shown in Table 6 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 17 to 20)
Coating compositions 17 to 20 were obtained in the same manner as in Preparation Examples 1 to 4, except that 25.5 g of limonite oxide C shown in Table 7 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 21-23)
Coating compositions 21 to 23 were obtained in the same manner as in Preparation Examples 1 to 3 except that 25.5 g of limonite oxide D shown in Table 8 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 24-26)
Coating compositions 24-26 were obtained in the same manner as in Preparation Examples 1 to 3 except that 25.5 g of limonite oxide E shown in Table 9 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 27 to 29)
Coating compositions 27 to 29 were obtained in the same manner as in Preparation Examples 1 to 3 except that 25.5 g of limonite oxide F shown in Table 10 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 30 to 32)
Coating compositions 30 to 32 were obtained in the same manner as in Preparation Examples 1 to 3 except that 25.5 g of limonite oxide shown in Table 11 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 33 to 35)
Coating compositions 33 to 35 were obtained in the same manner as in Preparation Examples 1 to 3 except that 25.5 g of limonite oxide H shown in Table 12 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 36 to 38)
Coating compositions 36 to 38 were obtained in the same manner as in Preparation Examples 1 to 3 except that 25.5 g of limonite I oxide shown in Table 13 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 39 to 41)
Coating compositions 39 to 41 were obtained in the same manner as in Preparation Examples 1 to 3 except that 25.5 g of limonite oxide J shown in Table 14 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 42 to 44)
Coating compositions 42 to 44 were obtained in the same manner as in Preparation Examples 1 to 3 except that 25.5 g of limonite oxide shown in Table 15 was used instead of 25.5 g of limonite oxide A (listed in Table 3).

(Preparation Examples 45 to 47)
Preparation Examples 1 to 1 except that 4.88 g of the resin D (Lonefix Eco700 (manufactured by Showa Denko, solid content concentration 50%)) shown in Tables 1 and 16 was used instead of 5.5 g of the resin A and 0.73 g of the resin B. Coating compositions 45 to 47 were obtained in the same manner as in 3.

(Preparation Examples 48 to 50)
Instead of 25.5 g of limonite oxide A (listed in Table 3), 25.5 g of limonite oxide shown in Table 17 was used, and instead of 5.5 g of resin A and 0.73 g of resin B, the resins shown in Tables 1 and 17 were used. Coating compositions 48 to 50 were obtained in the same manner as in Preparation Examples 1 to 3 except that D4.85 g was used.

(Preparation Example 51)
In a 100 mL polyethylene container, 0.23 g of tirabazole W-01 (manufactured by Taiyo Kagaku Co., Ltd.) as a dispersant (f), 0.23 g of Awabreak L-01 (manufactured by Taiyo Kagaku Co., Ltd.) as a foam suppressant (g), and a thickener (e). Gum Ace SG-30 (manufactured by Taiyo Kagaku Co., Ltd.) was weighed 0.11 g, and potassium metaphosphate (manufactured by Taiyo Kagaku Kogyo Co., Ltd., (KPO ₃ ) n, n≈10000) 0.23 g was weighed as a fertilizer component (d).

After adding 9.4 g of water and 1.1 g of ethanol as the organic solvent (h), the mixture was stirred and mixed using a rotation / revolution type stirring device.

To the mill base prepared by adding 25.5 g of the oxidized limonite A shown in Table 18 and stirring and mixing using a rotation / revolution type stirring device, 5.5 g of resin A and 0.73 g of resin B are added thereto to the rotation / revolution type stirring device. The coating composition 51 to which the antifungal compound was not added was obtained by stirring and mixing with the above.

(Preparation Example 52)
The coating composition 52 to which the antifungal compound was not added was prepared in the same manner as in Preparation Example 51 except that 4.88 g of the resin D shown in Tables 1 and 18 was used instead of 5.5 g of the resin A and 0.73 g of the resin B. Obtained.

(Preparation Example 53)
As a 100 mL dispersant (f), 0.23 g of tirabazole W-01 (manufactured by Taiyo Kagaku Co., Ltd.) in a polyethylene container, 0.23 g of awabreak L-01 (manufactured by Taiyo Kagaku Co., Ltd.) as a foam suppressant (g), and a thickener (e). Gum Ace SG-30 (manufactured by Taiyo Kagaku Co., Ltd.) 0.11 g, fertilizer component (d) as potassium metaphosphate (manufactured by Taiyo Kagaku Kogyo Co., Ltd., (KPO ₃ ) n, n ≒ 10000) 0.23 g, as shown in Table 2. The mold compound D (thiabendazole (manufactured by Tokyo Chemical Industry Co., Ltd.)) was weighed in the amount shown in Table 18.

After adding 9.4 g of water and 1.1 g of ethanol as the organic solvent (h), the mixture was stirred and mixed using a rotation / revolution type stirring device.

To a mill base prepared by adding 25.5 g of Limonite Oxide A (listed in Table 18) and stirring and mixing using a rotation / revolution type agitator, 5.5 g of resin A and 0.73 g of resin B are added thereto and rotation / revolution type stirring is performed. The coating composition 53 was obtained by stirring and mixing using an apparatus.

(Preparation Example 54)
A coating composition 54 was obtained in the same manner as in Preparation Example 53 except that 4.88 g of the resin D shown in Tables 1 and 18 was used instead of 5.5 g of the resin A and 0.73 of the resin B.

(Preparation Example 55)
The coating composition 55 to which the antifungal compound was not added was prepared in the same manner as in Preparation Example 51 except that 25.5 g of limonite oxide C shown in Table 19 was used instead of 25.5 g of limonite oxide A (listed in Table 18). Obtained.

(Preparation Example 56)
Coating composition 56 to which no antifungal compound was added in the same manner as in Preparation Example 52 except that 25.5 g of limonite oxide C (listed in Table 19) was used instead of 25.5 g of limonite oxide A (listed in Table 18). Got

(Preparation Example 57)
A coating composition 57 was obtained in the same manner as in Preparation Example 53 except that 25.5 g of limonite oxide C (listed in Table 19) was used instead of 25.5 g of limonite oxide A (listed in Table 18).

(Preparation Example 58)
A coating composition 58 was obtained in the same manner as in Preparation Example 54 except that 25.5 g of limonite oxide C (listed in Table 19) was used instead of 25.5 g of limonite oxide A (listed in Table 18).

(Preparation Example 59)
A coating composition 59 was obtained in the same manner as in Preparation Example 3 except that 25.5 g of iron (III) oxide (manufactured by Kanto Chemical Co., Inc.) shown in Table 20 was used instead of limonite oxide A (listed in Table 3). ..

(Preparation Example 60)
A coating composition 60 was obtained in the same manner as in Preparation Example 3 except that 12.5 g of silicon oxide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) shown in Table 20 was used instead of limonite oxide A (listed in Table 3). ..

(3) Verification experiment of germination and antifungal properties of Examples and Comparative Examples:
(Examples 1 to 50)
20 g of paddy rice seeds were loaded into a rolling granulator equipped with an 18 cm granulation pan. The granulated pan was rotated, and 1.5 g of the coating compositions 1 to 50 obtained in Preparation Examples 1 to 50 was scraped off from the container with a spatula and added thereto to coat the seed paddy with the coating composition.

The same operation was repeated, and finally 15 g of the coating composition was coated on the seed paddy and then dried on a 20 cm × 20 cm stainless steel vat for 24 hours to obtain 1 to 50 coated paddy rice seeds. The obtained coated paddy rice seeds 1 to 50 were subjected to an antifungal property test and a germination test as Examples 1 to 50 shown in Tables 3 to 17, respectively.

(Comparative Examples 1 to 10)
20 g of paddy rice seeds were loaded into a rolling granulator equipped with an 18 cm granulation pan. The granulated pan was rotated, and 1.5 g of the coating composition 51 to 60 obtained in Preparation Examples 51 to 60 was scraped off from the container with a spatula and added thereto to coat the seed paddy with the coating composition.

The same operation was repeated, and finally 15 g of the coating composition was coated on the seed paddy and then dried on a 20 cm × 20 cm stainless steel vat for 24 hours to obtain 51 to 60 coated paddy rice seed paddy.

The obtained coated paddy rice seeds 51 to 60 were subjected to an antifungal test and a germination test as Comparative Examples 1 to 10 shown in Tables 18 to 20, respectively.

(Germination test)
A stainless steel mesh with a mesh of 2 mm was installed at a position 8 mm below the surface of the water. 100 seeds of coated paddy rice seeds prepared in Examples and Comparative Examples were placed on this mesh and cultivated for 10 days in a constant temperature room at room temperature of 20 ° C while maintaining the water level, and the number of germinated seeds was measured. The germination rate was evaluated.

(Antifungal test)
100 grains of coated paddy rice seeds prepared in Examples and Comparative Examples were placed on a petri dish with a diameter of 200 mm and a depth of 50 mm, placed in a constant temperature and humidity device, and exposed at a temperature of 27 ° C and a humidity of 65% for 10 days, and mold was generated. The number of covered paddy rice seeds was measured and the antifungal property was evaluated.

The test results of Examples 1 to 50 and Comparative Examples 1 to 10 are shown in Table 21, Table 22 and Table 23 for each of the germination test and the antifungal property test.

As shown in Table 21, Table 22 and Table 23, the coated paddy rice seeds 1 to 50 of Examples 1 to 50 have extremely good antifungal properties as compared with the coated paddy rice seeds 51 to 60 of Comparative Examples 1 to 10. It has been shown.

In addition, the germination rate of the coated paddy rice seeds of Examples 1 to 50 was 100% despite being exposed under high humidity conditions.

On the other hand, the germination rate of Comparative Examples 1 to 10 is low, and deterioration of the covered paddy rice seeds is presumed. Furthermore, the antifungal results of Example 17, Example 36, Example 42, and Example 48 show that it depends on the amount of silicon oxide and ferric oxide in the coating composition. It was speculated that the synergistic effect was large.

In particular, Comparative Example 3, Comparative Example 4, Comparative Example 7, and Comparative Example 8 are examples of coating compositions containing an antifungal compound having no phenolic hydroxyl group, but are antifungal as compared with Examples. It was shown that the sexual effect was low. From this, it was speculated that the antifungal compound having a phenolic hydroxyl group specifically interacts with silicon oxide or ferric oxide in limonite oxide.

Further, it is presumed that the coated paddy rice seeds of the examples maintain the germination rate and suppress the deterioration of the seeds as compared with the comparative examples.

From the above results, it is clear that the coating layer obtained from the coated paddy rice composition of the present invention, which is a combination of limonite oxide and an antifungal compound having a phenolic hydroxyl group, has an excellent antifungal effect and an effect of suppressing a decrease in activity after sowing. ..

According to the present invention, paddy rice seeds coated with a coating composition combining limonite oxide and an antifungal compound having a phenolic hydroxyl group can suppress the generation of mold even when stored in a high humidity environment, and can be stored. It is possible to improve the yield.

Claims (3)

Oxide limonite, including the iron oxide and silicon oxide and (a),
A paddy rice seed coating composition containing an antifungal compound (b) having a phenolic hydroxyl group selected from any of propylparaben, anthocyanidins, and hinokitiol .
The oxide limonite (a), the ferric oxide against the iron oxide the molar ratio 0.2 to 0.8, is said silicon oxide molar ratio from 0.13 to 0.65 which pairs before Symbol iron oxide,
The paddy rice seed coating composition, wherein the antifungal compound (b) is contained in an amount of 0.008% by mass to 0.46% by mass with respect to the oxidized limonite (a). The paddy rice seed coating composition according to claim 1, which contains a polyester resin and a polyurethane resin. 0.008% by mass to 0.46% by mass of propylparaben with respect to the dispersant (f) , the foam suppressant (g) , the fertilizer component (d) , the thickener (e), and the oxidized limonite (a) described later . anthocyanidins, a step of preparing a dispersion by mixing with攪拌added antifungal compound (b), water and ethanol (h) having a phenolic hydroxyl group which is selected from any of the hinokitiol,
Include iron oxide and silicon oxide, wherein the molar ratio of the silicon oxide to the molar ratio of 0.2 to 0.8 and the iron oxide ferric oxide for the iron oxide is from 0.13 to 0.65 the oxide limonite and (a), the The process of preparing prepaste by adding to the dispersion and stirring and kneading, and
A method for producing a paddy rice seed coating composition, which comprises a step of adding a resin (c) to the prepaste and stirring and kneading to prepare a coating composition of paddy rice seed paddy.