WO2011122238A1 - 被覆粒状体及び該被覆粒状体の製造方法 - Google Patents
被覆粒状体及び該被覆粒状体の製造方法 Download PDFInfo
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- WO2011122238A1 WO2011122238A1 PCT/JP2011/055019 JP2011055019W WO2011122238A1 WO 2011122238 A1 WO2011122238 A1 WO 2011122238A1 JP 2011055019 W JP2011055019 W JP 2011055019W WO 2011122238 A1 WO2011122238 A1 WO 2011122238A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
Definitions
- the present invention relates to a coated granule in which the surface of a water-soluble particulate material is coated with a thermosetting resin and a method for producing the same.
- the elution control type fertilizer and pesticide is a coated granule in which elution of internal components is controlled by coating the surface of the granular fertilizer or granular pesticide with an organic or inorganic water-permeable coating material.
- coated granules using organic coating materials such as resins have a better elution control function, and such types occupy the mainstream of coated fertilizers and coated pesticides.
- thermosetting resins such as urethane resins have high coating strength, high water resistance, ease of control of elution characteristics, and do not use solvents. It is widely used because it can be applied.
- the present applicant also disclosed in Patent Document 1 a granular fertilizer, the surface of which is an isocyanate group-terminated prepolymer obtained from (A) an aromatic polyisocyanate and castor oil or castor oil derivative polyol, and (B) castor oil or castor oil derivative.
- a coated granular fertilizer formed by coating a polyol and (C) an amine-based polyol with a film made of a polyurethane resin obtained by curing is disclosed.
- coated granular materials such as water-soluble coated fertilizers and coated granular pesticides exhibit elution patterns such as long-term elution type, short-term elution type, and sigmoid type depending on the elution control period and elution characteristics. Therefore, it is required to finely adjust the elution pattern according to the application.
- a granular fertilizer coated with a granular fertilizer or a hydrophobic compound is coated with a polyurethane film formed by reacting hardened castor oil and a polyisocyanate component
- a granular coated fertilizer in which the equivalent ratio of the isocyanate group derived from the polyisocyanate component to the hydroxyl group derived from the cured castor oil in the reaction of the cured castor oil and the polyisocyanate component is 0.33 to 0.9
- Patent Document 3 a coated granule in which early elution in an early eluting type coated granular plant active substance is controlled by forming a urethane resin that coats the granular material using a polyol containing an alkylene oxide adduct of polycaprolactone. Plant actives are disclosed.
- thermosetting resin in the granular coating fertilizer coated with the thermosetting resin hardened
- Patent Document 5 in the method for producing a coated granular fertilizer coated with a thermosetting resin, (1) a step of turning the granular fertilizer into a rolling state, and (2) a layer thickness of the granular fertilizer in the rolling state. A step of adding a liquid uncured thermosetting resin in an amount of 1 to 10 ⁇ m, and (3) a step of maintaining the rolling state of the granular fertilizer and coating each fertilizer particle surface with the uncured thermosetting resin. (4) The step of maintaining the rolling state of the granular fertilizer and thermosetting the uncured thermosetting resin, (5) The step of repeating the steps (1) to (4) one or more times Are disclosed in order of (1) to (5) in order to produce a granular fertilizer free of coating defects.
- the layer thickness needs to be 10 ⁇ m or less in order to damage the resin surface. It is described that there is. Furthermore, since the granular fertilizer formed by the above method repeats the addition of a small amount of coating material, the coating layer has a large thickness.
- JP-A-10-265288 Japanese Patent Laid-Open No. 2005-041708 JP 2007-277429 A JP-A-9-208355 JP-A-9-202683
- elution control type fertilizers and pesticides are required to finely adjust the elution control period, and in particular, suppress elution after application (hereinafter sometimes referred to as “initial elution”).
- initial elution elution after application
- a substance that exhibits 80% by mass or more of elution in an arbitrary period after application for example, 10 days to 200 days.
- thermosetting resin in order to suppress defects generated in the coating film, a method of laminating 10 or more thin coating films with a thermosetting resin is widely used.
- the above method performs thermosetting for each layer of the coating film, there is a problem that the manufacturing time is long and the productivity is poor, and a short-term elution pattern is used for laminating the coating film. There was also a problem that it was difficult to achieve.
- an object of the present invention is to obtain a coated granule capable of simultaneously achieving a short-term elution type elution pattern and suppression of initial elution and maintaining good quality.
- the present invention relates to a granular water-soluble substance and a resin liquid formed on the granular water-soluble substance and having a molar ratio A represented by isocyanate groups / hydroxyl groups of isocyanate groups and hydroxyl groups of 0.5 to 0.99.
- the present invention also includes a step of bringing a particulate water-soluble substance into a fluidized state or a rolling state, a step of coating a particulate water-soluble substance in a fluidized state or a rolling state with a coating material, and an uncured coating layer comprising the coating material.
- the coated granule comprising: a step of forming on the surface of the particulate water-soluble substance; a step of forming a protective layer on the surface of the uncured coating layer; and a step of thermally curing the formed uncured coating layer and the protective layer.
- the coated granule of the present invention is a resin having a molar ratio A represented by isocyanate groups / hydroxyl groups of isocyanate groups and hydroxyl groups of at least 0.5 to 0.99 on at least the surface of the particulate water-soluble substance.
- the water permeates the coating and enters the coated granule to dissolve the elution component of the particulate water-soluble substance.
- the dissolved elution component permeates the coating and elutes out of the coating.
- the coating suppresses the permeation of water and the elution component, and eventually the coating is destroyed and the elution component moves out of the coating. Elute.
- the coating layer is formed as a uniform film on the surface of the particulate water-soluble substance, and the elution timing of the components is controlled by the coating layer covering the particulate water-soluble substance.
- the coating layer is formed, if the molar ratio A of the resin liquid in the coating layer is in the range of 0.5 to 0.99, preferably 0.5 to 0.90, the thermosetting resin A that forms the coating layer The crosslink density of the resin can be reduced, the water permeability can be improved, and the elution pattern can be a short-term elution type.
- the molar ratio A is less than 0.5, crosslinking of the thermosetting resin A may be insufficient, and it may be difficult to coat the particulate water-soluble substance. It may be difficult to achieve the mold elution pattern.
- the coated granule of the present invention it is possible to suppress defects generated in the production process by covering the surface of the coating layer with a protective layer.
- the isocyanate group contained in the protective layer resin liquid reacts with the unreacted hydroxyl group of the coating layer in contact with the protective layer, so that the isocyanate group contained in the protective layer resin liquid is insufficient.
- the crosslink density of the protective layer is lowered, it is necessary to make the molar ratio B of the resin liquid in the protective layer larger than the molar ratio A of the resin liquid in the coating layer.
- the molar ratio B of the resin liquid in the protective layer is 0.75 to 2.0, preferably in the range of 0.8 to 1.5, the crosslinking density of the thermosetting resin B forming the protective layer The initial elution of components can be suppressed.
- the molar ratio B is less than 0.75, suppression of initial elution may be insufficient, and when it exceeds 2.0, crosslinking between an isocyanate group and a hydroxyl group may be insufficient. is there.
- the difference between the molar ratio A and the molar ratio B is preferably 0.1 or more.
- the difference between the molar ratio A and the molar ratio B is less than 0.1, the function as a protective layer for protecting the coating layer of the thermosetting resin B is insufficient, and the initial elution of the components of the particulate water-soluble substance The elution rate may be difficult to control.
- the difference between the molar ratio A and the molar ratio B is more preferably 0.15 or more.
- the protective layer coverage expressed by the mass of the protective layer / the mass of the coated granule ⁇ 100 is preferably 0.2 to 2% by mass. If the coating rate of the protective layer is less than 0.2% by mass, it becomes difficult to protect the coating layer because the film thickness becomes thin, and if it exceeds 2% by mass, the dissolution pattern of the coated granular material may be impaired.
- the coverage of the protective layer is preferably 0.4% by mass or more.
- the total isocyanate group and total hydroxyl group of the isocyanate group and the total hydroxyl group of the resin liquid forming the thermosetting resin A and the resin liquid forming the thermosetting resin B are total isocyanate groups / total hydroxyl groups.
- the represented molar ratio is preferably 0.6 to 1.2. When the molar ratio is less than 0.6 or exceeds 1.2, the resulting coating is not sufficiently crosslinked, and the elution rate of the components of the particulate water-soluble substance may be difficult to control.
- the particulate water-soluble substance is not limited as long as it is water-soluble.
- a water-soluble fertilizer or a water-soluble agricultural chemical is used depending on the application of the coated granule.
- the particle size of the particulate water-soluble substance is preferably 1 to 10 mm.
- the coating layer may be a single layer as long as a hydrophobic thermosetting resin is formed on the surface of the particulate water-soluble substance, but when the film thickness is increased, two or more layers are laminated.
- the thickness of each layer may be different as long as the elution performance is not impaired, and the components of the membrane may be different.
- the coating layer preferably has a water-absorbing resin.
- the water-absorbent resin expands by absorbing water that has passed through the coating, and helps to destroy the coating layer and the protective layer. By using the water-absorbent resin, the elution timing of the components can be further controlled. Is possible.
- the water-absorbing resin is more preferably contained in a layer of the coating layer that is not in contact with the protective layer, and particularly preferably contained in a layer adjacent to the particulate water-soluble substance.
- the water-absorbent resin may be contained on the surface of the particulate water-soluble substance.
- the coating layer has a water-absorbing resin
- the coating layer has a coating ratio of 0.5 to 5 mass expressed by the mass of the coating layer and the mass per layer of the coating layer, the mass per layer of the coating layer / the mass of the coated granule ⁇ 100. % And is preferably 0.5 to 3% by mass. If it is less than 0.5% by mass, it is difficult to achieve the target elution performance. If it exceeds 5% by mass, the film thickness becomes so thick that it is difficult to form a uniform coating layer. The elution pattern of the active substance may not be obtained.
- thermosetting resin A a urethane resin obtained from an aromatic polyisocyanate, a polyol compound, and an amine compound or an amine polyol is used. That is, the coating material A for forming the coating layer has a resin liquid composed of an aromatic polyisocyanate, a polyol compound, and an amine compound, and forms urethane bonds by the reaction of the resin liquid.
- the viscosity of the coating material A is preferably low in order to uniformly cover the surface of the granular material with the coating material A.
- it is preferably 0.1 to 200 mPa ⁇ s at the coating temperature.
- Aromatic polyisocyanates include, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate, polyphenyl polymethylene polyisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate, etc., or modified products thereof.
- TDI tolylene diisocyanate
- MDI diphenylmethane diisocyanate
- MDI diphenylmethane diisocyanate
- naphthalene diisocyanate polyphenyl polymethylene polyisocyanate
- phenylene diisocyanate phenylene diisocyanate
- xylylene diisocyanate tetramethylxylene diisocyanate
- tetramethylxylene diisocyanate etc.
- the aromatic polyisocyanate may be used as an isocyanate group-terminated prepolymer prepared from the aromatic polyisocyanate.
- the isocyanate group-terminated prepolymer may be prepared by a known method.
- the isocyanate group / active hydrogen group equivalent ratio of polyisocyanate and polyol is 1.1 to 50.0, preferably 1.2 to 25. 0.0 is obtained by carrying out the reaction at 30 to 130 ° C., preferably at 40 to 90 ° C. for 1 to 5 hours.
- compatibility with other components is improved, and the reactivity during use is promoted, and the viscosity is adjusted to be easy to work with. There are effects such as being able to.
- polyol component examples include castor oil and derivatives thereof (for example, castor oil, alkylene oxide adduct of castor oil, polyhydric alcohol modified product of castor oil fatty acid, etc.), alkylene oxide adduct of low molecular weight polyfunctional alcohol (for example, diols, triols).
- alkylamines or amine-based polyols are used as the amine compound.
- alkylamine include trimethylamine, triethylamine, dimethylethylamine, dimethylisopropylamine and the like.
- the amine compound is preferably an amine polyol.
- examples of such amine polyols include low molecular amine polyols such as di-, tri-, ethanolamine, N-methyl-N, N'-diethanolamine.
- amine-based polyols obtained by adding an alkylene oxide such as propylene oxide (PO) or ethylene oxide (EO) to an amino compound such as ethylenediamine, 1,3-propanediamine, or 1,6-hexanediamine.
- PO propylene oxide
- EO ethylene oxide
- the ratio of addition is not particularly limited, but is 1 to 200, preferably 1 to 50, alkylene oxide per nitrogen atom, but about 2 to 2.4 is used for adjusting physical properties related to the hydrophilicity of the film. Is particularly preferred.
- N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine, N, N, N ′, N′-tetrakis [2-hydroxyethyl] ethylenediamine, N, N, N ', N'-tetrakis [2-hydroxypropyl] -1,3-propanediamine, N, N, N', N'-tetrakis [2-hydroxyethyl] -1,6-hexanediamine and the like can be mentioned.
- amine-based polyol when used as the polyol component, good compatibility with the resin composition can be obtained, and a uniform film can be easily formed, which can be preferably used.
- An amine-based polyol is preferable because it accelerates the reaction and also acts as a cross-linking agent and a chain extender, and provides good curability and tough film properties.
- the amount of the amine polyol used may be adjusted so that the crosslinking reaction proceeds after the coating material A is uniformly coated, and the curing rate is usually set in the range of 0.1 to 50% by mass of the urethane resin mass. Can be adjusted.
- the water-absorbing resin is a resin that swells to 5 times or more of the dry volume by absorbing a large amount of water, and the resin itself exhibits water absorption or has a water-absorbing substance.
- a gel that has low solubility upon water absorption and becomes a gel.
- acrylate polymer for example, Sumikagel S, L, R type manufactured by Sumitomo Chemical Co., Ltd., Aquakeep 10SH, 10SHP, 10SH-NF (20) manufactured by Sumitomo Seika Co., Ltd.
- SA60NTYPE2 Aquamate AQ-200, AQ-200B-02 manufactured by Sekisui Plastics Co., Ltd., Sunfresh ST-250MPS, ST-500MPSA manufactured by Sanyo Chemical Industries, Ltd.
- isobutylene polymers for example, KI Gel-201K, KI Gel-201K-F2, KI Gel Solution System, KI Gel Compound manufactured by Kuraray Co., Ltd., acrylic acid / vinyl alcohol copolymer, polyethylene oxide modified resin, starch graft polymer, starch (for example, , Potato starch, corn starch, sweet potato starch, soluble starch), carboxymethyl cellulose (CMC), include CMC metal salt and bentonite.
- an organic solvent for example, an organic solvent, organic
- the particle size of the water absorbent resin is preferably 1 to 100 ⁇ m, and more preferably 2 to 50 ⁇ m. If it is less than 1 ⁇ m, the change in elution time and elution rate due to the addition of the water-absorbent resin is small, and it is not effective to adjust the elution characteristics with this. On the other hand, if the thickness exceeds 100 ⁇ m, a coating layer with good uniformity cannot be formed, and defects may easily occur in the coating film.
- the amount of water-absorbing resin added varies depending on the particle size, but is usually 0.1 to 30% by mass, preferably 0.5 to 20% by mass, more preferably 1% of the total mass of urethane resin and water-absorbing resin. ⁇ 10% by mass. If it is less than 0.1% by mass, the change in elution time and elution rate due to the addition of the water-absorbing resin is small compared to the additive-free resin, and it is not effective to adjust the elution characteristics with this. Moreover, when it exceeds 30 mass%, hydrophilicity will become large and adjustment of the elution start time may become difficult.
- the water-absorbing resin is mixed and dispersed in advance with the polyol component to prepare a dispersion, and immediately after mixing the dispersion with the polyisocyanate component, it is added to the particulate water-soluble substance, or separately in the coating apparatus. It is preferably added by adding to the substance.
- an organic or inorganic additive can be added to the coating composition as long as the properties of the coating layer are not substantially impaired.
- the additive include alkyd resin, urethane resin, fatty acid ester, rosin and derivatives thereof, ester gum, surfactant, petroleum resin, talc, diatomaceous earth, silica, urea, sulfur powder and the like. These may be added in an amount of 0.1 to 50 parts by mass with respect to 100 parts by mass of the urethane resin of the present invention, and workability or elution characteristics may be adjusted depending on the type and addition amount thereof.
- the coating material A is a compound in which an aromatic polyisocyanate, a polyol component, and an amine compound are reacted to form a urethane bond, and a catalyst is further added to promote the formation of the urethane bond.
- organometallic catalysts such as dibutyltin laurate and lead octenoate can be used.
- the coating material A may contain vegetable oil.
- the vegetable oil is a non-reactive component when the polyol component and the polyisocyanate component react, and when the vegetable oil is added, the original three-dimensional structure of the urethane resin becomes sparse because the vegetable oil acts as a kind of void. Can easily penetrate water into the voids, change the water resistance of the urethane resin, reduce adhesiveness during curing, and reduce the film thickness of the coating layer.
- Vegetable oils include coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, rapeseed oil, canola oil, safflower oil (safflower oil), sesame oil, soybean oil, sunflower oil, linseed oil, tall oil, And mixtures thereof.
- vegetable oils for example, rapeseed oil, canola oil, soybean oil, etc.
- rapeseed oil and canola oil are particularly preferred.
- part or all of the vegetable oil can be used in place of the triglycerides of fatty acids contained in these vegetable oils.
- fatty acids examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, ricinoleic acid and the like.
- the amount of vegetable oil added varies depending on the particle size, but is usually preferably in the range of 0.1 to 50% by weight, more preferably 0.1 to 30% by weight, and still more preferably 0.1 to 50% by weight of the total weight of the urethane resin and vegetable oil. It may be ⁇ 15% by weight. If the amount is less than 0.1% by mass, the effect of adding vegetable oil is not sufficient. If the amount exceeds 50% by mass, the coating material A is not sufficiently cross-linked and a tough film cannot be formed. Sometimes vegetable oil adheres to the coating device, making it difficult to form a uniform film.
- the vegetable oil may be added alone, but is preferably added as a uniform liquid by mixing with the polyisocyanate component or polyol component in advance.
- the protective layer may be a single layer or a plurality of layers as long as a hydrophobic thermosetting resin is formed on the surface of the coating layer, and in the case of lamination, the components of the film may be different.
- thermosetting resin B a urethane resin obtained from an aromatic polyisocyanate, a polyol compound, an amine compound or an amine-based polyol is used. That is, the coating material B for forming the protective layer has a resin liquid composed of an aromatic polyisocyanate, a polyol compound, and an amine compound, and forms a urethane bond by the reaction of the resin liquid. .
- the coating material B may add an organic or inorganic additive, an organometallic catalyst, or vegetable oil to the coating material composition.
- the adhesiveness of the protective layer decreases, so damage due to adhesion between the protective layers, or damage caused by peeling or abrasion due to adhesion and contact with a device that maintains a fluid state or rolling state. This is preferable because the thickness of the protective layer can be reduced.
- the surface of the protective layer may be treated with an inorganic powder for the purpose of preventing mutual sticking between the coated granular materials.
- the inorganic powder include talc, sulfur, calcium carbonate, silica, zeolite, diatomaceous earth, clay, and metal oxide. These may be used alone or in combination, and talc is easy to handle. It is preferable to use it.
- the inorganic powder is preferably used in an amount of 0.1 to 15% by mass, more preferably 1 to 10% by mass, based on the total mass of the coating layer and the protective layer. If it is less than 0.1% by mass, the effect of preventing sticking is weak, and even if it exceeds 15% by mass, it does not adhere to the surface of the coated granular material.
- the inorganic powder is preferably sprayed on the coated granular material that is in a rolling or fluidized state after the protective layer is cured, and further, the inorganic powder undergoes a urethanization reaction and the protective layer is cured. It is preferable to spray in a state having a previous adhesive force. In this case, since the inorganic powder stays on the surface and does not enter the coating material, elution is also stabilized.
- the method of manufacturing the coated granular material of the present invention includes a step of turning a granular water-soluble substance into a fluidized state or a rolling state, and a coating material on the granular water-soluble substance in a fluidized state or a rolling state.
- thermosetting resin begins to gel, and gradually becomes sticky as the tackiness increases, and further the thermosetting reaction proceeds. The spinnability decreases, and eventually the adhesiveness is lost and the cured state is reached.
- the surface of a granular water-soluble substance is coated with a resin liquid, the granular water-soluble substances are adhered to each other as the tackiness increases, and a mass consisting of a large number of particles is formed. As a result, a cured thermosetting resin is formed on the surface of the particulate water-soluble substance.
- uncured refers to a state in which the resin liquid has adhesiveness in the course of the thermosetting reaction.
- the uncured coating layer is a layer having a sticky surface, and acts as a coating layer when a thermosetting reaction proceeds to become a cured state.
- the uncured coating layer is a layer in which the next layer is laminated in an uncured state in which the resin liquid is sticky.
- the uncured coating layer is formed by thermal curing, the surface of the uncured coating layer is protected. The layers are covered and the protective layer is formed, thereby preventing damage caused by the uncured coating layers sticking to each other and peeling off.
- it is necessary to maintain a fluidized state or a rolling state for a predetermined time for thermosetting and the coating surface is likely to be damaged from the device as the thermosetting progresses. It is possible to prevent damage to the surface of the coating layer.
- the uncured coating layer existing in the inner layer rather than the protective layer becomes a cured state by heat applied in the step of thermally curing the protective layer. Since the protective layer and the uncured coating layer are thermally cured at the same time, the curing time can be shortened and the productivity can be improved.
- the coating material A may be added to the granular water-soluble substance in a fluidized state or a rolling state, and the coating material B may be added after forming the coating layer.
- the coating material B may be added after forming the coating layer.
- it may be mixed in the coating apparatus, or a part or all of the resin liquid components may be mixed in advance and added to the particulate water-soluble substance.
- the granular water-soluble substance When the granular water-soluble substance is brought into a fluidized state or a rolling state, the granular water-soluble substance is preheated for a certain period of time with hot air or the like in advance. At this time, the preheating time and the preheating temperature may be appropriately adjusted so that the water content of the granular water-soluble substance does not significantly affect the coating material, and the temperature of the granular material becomes the coating temperature.
- An apparatus such as a fluidized bed or a spouted bed can be used for fluidizing the particulate water-soluble substance, and an apparatus such as a rotating pan or a rotating drum can be used for rolling.
- an apparatus such as a rotating pan or a rotating drum can be used for rolling.
- the method of adding the coating material A and the coating material B is not particularly limited as long as it can be dispersed and added efficiently.
- spraying, dropping, and the like can be mentioned.
- the method of spraying with a two-fluid nozzle using compressed air is good. Since it is possible to form a thick film, it is preferably used.
- the uncured coating layer is formed by adding a coating material to the surface of the granular water-soluble substance and then maintaining the rolling or fluidized state at a specific temperature and coating the surface of the granular water-soluble substance with the coating material A.
- the formation time, formation temperature, and the like of the uncured coating layer may be appropriately determined depending on the type and amount of the coating material A.
- a coating material B for forming an uncured coating layer or a protective layer is further added to the upper layer of the uncured coating layer to coat the surface of the uncured coating layer.
- the coating material B is added in a state where the surface of the uncured coating layer to be coated has adhesiveness. If the surface of the uncured coating layer is sticky, the coatings adhere to each other, but the adhered coating and coating are not completely integrated. The covering material B penetrates into the two, making it possible to separate them. When the surface of the uncured coating layer becomes sticky, the granular water-soluble substance may start to form a lump, and from the time when the formation of lump starts to be observed, from the time when it no longer shows stickiness. It is preferable that the coating material B is added before.
- the heating time, the heating temperature, and the like are appropriately selected according to the types of the uncured coating layer and the protective layer.
- thermosetting under a heating temperature atmosphere of usually room temperature (about 25 ° C.) to 150 ° C., preferably about 40 to 100 ° C.
- room temperature about 25 ° C.
- urea a granular material containing components that are easily decomposed or altered by heat
- it is necessary to coat at a relatively low temperature and when urea is used, it is preferable to coat at a temperature of 90 ° C. or less.
- the heating time varies depending on the heating temperature, the types and amounts of the coating material A and the coating material B, but it is sufficient that the heating is performed at least until the protective layer does not exhibit adhesiveness.
- the protective layer may be further heated to promote the urethane reaction.
- the heating time is too long, not only will the productivity decrease, but the protective layer will gradually cover. Since it may be worn by contact with the apparatus and damage the coating surface, it is necessary to prevent the coating surface from being damaged. For example, it is good also as 10 times or less of the time when a protective layer does not show adhesiveness.
- coated granular material of the present invention can be produced even in a mass production facility, and can be applied to, for example, a granular water-soluble substance of 100 kg or more.
- the manufacturing method of the present invention can naturally be applied to equipment other than mass production equipment.
- the coated granule of the present invention is suitably used as a coated granular fertilizer coated with granular fertilizer because the elution pattern of the eluted components can be adjusted.
- the coated granular fertilizer may be a water-soluble granular fertilizer, and examples thereof include urea, ammonium sulfate, ammonium sulfate, ammonium nitrate, potassium chloride, potassium sulfate, potassium nitrate, sodium nitrate, potassium phosphate, ammonia phosphate, lime phosphate. And at least one fertilizer or compound fertilizer selected from the group consisting of, and granular organic fertilizer.
- the coated granular material of the present invention is suitably used as a coated granular agricultural chemical coated with a granular agricultural chemical.
- the coated granular pesticide may be a water-soluble granular pesticide, and examples thereof include various insecticides, insect repellents, fungicides, herbicides, insecticides, plant growth regulators, and the like.
- Resin liquids A to G were prepared as follows.
- a coated granule was produced using the prepared resin solution by the following procedure. Table 1 shows the production conditions of each example and comparative example. The coverage was calculated by subtracting the obtained coated granular fertilizer and ((mass of coating layer + mass of protective layer) / mass of coated granular fertilizer ⁇ 100).
- Example 1 100 kg of granular urea (particle diameter: 2.5 to 4.0 mm) was charged in a drum type rolling coating apparatus having a diameter of 1.4 m, and the granular urea temperature was maintained at 70 ° C. by a hot air generator while rolling at 7 rpm.
- the resin liquid B is sprayed as a coating material A (total 1,603 g, corresponding to 1.5 mass%) from the two-fluid nozzle into the apparatus over 30 seconds as the first uncured coating layer ( Applied).
- a coating material A total 1,603 g, corresponding to 1.5 mass
- the lump was loosened.
- 3.5 minutes after the spraying of the first layer of the coating material the same component and the same amount (1.5% by mass) of the coating material A as the first layer are applied as the second uncured coating layer. Spraying from the two-fluid nozzle into the apparatus took 30 seconds.
- the resin liquid A is used as a protective layer B as a protective layer B (total of 534 g, corresponding to 0.5% by mass) from the two-fluid nozzle to the apparatus over 10 seconds. Sprayed. Seven minutes after the spraying of the coating material B, the protective layer almost lost the adhesiveness, and the coated granular ureas were not adhered to each other.
- the coating film on the granular urea was cured by rolling for 30 minutes after the spraying of the coating material B. This was cooled to room temperature (about 25 ° C.) to obtain the desired coated granular fertilizer. At this time, the coverage was 3.5% by mass.
- Example 2 100 kg of granular urea (particle diameter: 2.5 to 4.0 mm) was charged in a drum type rolling coating apparatus having a diameter of 1.4 m, and the granular urea temperature was maintained at 70 ° C. by a hot air generator while rolling at 7 rpm.
- 63 g of a water-absorbent resin cross-linked acrylate polymer having an average particle diameter of 25 ⁇ m; ST-500MPSA manufactured by Sanyo Chemical Industries
- a resin liquid D as a first uncured coating layer were coated with a coating material A (total 1,317 g, corresponding to 1.2% by mass), and sprayed in the apparatus over 30 seconds.
- the same component and the same amount (1.2% by mass) of the coating material A as the first layer were sprayed in the apparatus over 30 seconds as the second uncured coating layer.
- the resin liquid D is used as the coating material A (corresponding to a total of 1,647 g, 1.5% by mass) as the third uncured coating layer. Sprayed in for 30 seconds.
- the same component and the same amount (1.5% by mass) of the coating material A as the third layer were sprayed into the apparatus over 30 seconds.
- a coating material B (total of 659 g, corresponding to 0.6% by mass) of resin liquid A as a protective layer was sprayed into the apparatus over 10 seconds. Seven minutes after the spraying of the coating material B, the protective layer almost lost adhesiveness, and the coated granular ureas did not stick to each other. In order to further accelerate the curing of the thermosetting resin of the coating film, the coating film on the granular urea was cured by rolling for 30 minutes after spraying the coating material B. This was cooled to room temperature (about 25 ° C.) to obtain the desired coated granular fertilizer. The coverage was 6.0% by mass.
- Example 3 When forming the third and fourth uncured coating layers, the resin liquid F is used as a coating material (corresponding to a total of 1,647 g and 1.5% by mass), and the resin liquid G is coated as a protective layer.
- a coated granular fertilizer was obtained in the same manner as in Example 2 except that the material (corresponding to 659 g in total, corresponding to 0.6% by mass) was used. The coverage was 6.0% by mass.
- the resin liquid A is used as a coating material (corresponding to a total of 1,603 g and 1.5% by mass), and the resin liquid A is coated as a protective layer.
- a coated granular fertilizer was obtained by the same method as in Example 1 except that the material (corresponding to 534 g in total, corresponding to 0.5 mass%) was used. The coverage was 3.5% by mass.
- the resin liquid C is used as a coating material (corresponding to a total of 1,603 g and 1.5% by mass), and the resin liquid C is coated as a protective layer.
- a coated granular fertilizer was obtained by the same method as in Example 1 except that the material (corresponding to 534 g in total, corresponding to 0.5 mass%) was used. The coverage was 3.5% by mass.
- the resin liquid B is used as a coating material (corresponding to a total of 1,603 g and 1.5% by mass), and the resin liquid B is coated as a protective layer.
- a coated granular fertilizer was obtained by the same method as in Example 1 except that the material (corresponding to 534 g in total, corresponding to 0.5 mass%) was used. The coverage was 3.5% by mass.
- Example 1 and Comparative Example 3 From the comparison between Example 1 and Comparative Example 3, it is found that the initial elution can be largely suppressed by making the molar ratio of the isocyanate group and the hydroxyl group of the coating layer the same and making the molar ratio of the protective layer larger than that of the coating layer. It was. Moreover, when Example 1 and Comparative Example 2 are compared, the elution rate in Example 1 tends to be higher as the number of days elapses, whereas the initial elution is suppressed in Example 1. there were. Furthermore, when Example 1 and Comparative Example 1 are compared, the initial elution is equivalent, but Comparative Example 1 has an elution rate of less than 80% by mass even after 56 days. It was not achieved.
- Example 1 and Comparative Example 1 provided with a protective layer having a molar ratio of 1.0 showed a high yield rate of 80% by mass or more. From this, it was found that defects can be suppressed by making the molar ratio of the protective layer suitable.
- Example 2 and Example 3 in which the water-absorbing resin was sprayed to further increase the elution rate showed short-term elution type elution patterns.
- Example 2 and Example 3 since the molar ratio in the coating layer is smaller than that in Comparative Example 4, the suppression of initial elution is expected to be inferior, but by increasing the molar ratio in the protective layer, Although the molar ratio in the coating layer was small, the effect of suppressing the initial elution was larger than that in Comparative Example 4.
- the effect which can suppress an initial stage elution was improved by making the difference of the molar ratio of a coating layer and a protective layer large.
- the coated granule of the present invention forms a protective layer on the coating layer and makes the molar ratio of the protective layer suitable so that the initial dissolution can be achieved while showing a short-term dissolution pattern. It can be suppressed, and further good quality can be maintained. Furthermore, the preferred method for producing the coated granule has high productivity because the time for thermally curing the coating can be shortened.
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Abstract
Description
本発明の被覆粒状体は、少なくとも粒状水溶性物質表面上に、イソシアネート基と水酸基とのイソシアネート基/水酸基で表されるモル比Aが0.5~0.99である樹脂液からなる熱硬化性樹脂Aを有する被覆層と、該被覆層上に、イソシアネート基と水酸基とのイソシアネート基/水酸基で表されるモル比Bが0.75~2.0である樹脂液からなる熱硬化性樹脂Bを有する保護層とを有し、保護層のモル比Bが被覆層のモル比Aよりも大きいことを特徴とする。
粒状水溶性物質は水溶性であればよく、その種類は限定されない。好適には、被覆粒状体の用途に応じて、水溶性肥料や水溶性農薬などが用いられる。粒状水溶性物質の粒径は1~10mmであるのが好ましい。
被覆層は粒状水溶性物質の表面に疎水性の熱硬化性樹脂が形成されるものであれば単層でもよいが、膜厚が厚くなる場合は2層以上積層されることが好ましく、各層は溶出性能を損なわない程度であれば、膜厚は異なっていてもよく、また、膜の成分が異なっていても差し支えない。
保護層は前記被覆層表面に疎水性の熱硬化性樹脂が形成されれば単層でも複数を積層するものでもよく、積層する場合は膜の成分が異なっていてもよい。
本発明の被覆粒状体を製造する方法は、粒状水溶性物質を流動状態又は転動状態にする工程と、流動状態又は転動状態の粒状水溶性物質に被覆材Aを被覆する工程と、被覆材Aからなる未硬化被覆層を粒状水溶性物質表面に形成する工程と、未硬化被覆層の表面に被覆材Bを被覆して保護層膜を形成する工程と、形成した未硬化被覆層及び保護層を熱硬化させる工程と、を含む。
本発明の被覆粒状体は、溶出成分の溶出パターンが調節可能であることから、粒状肥料を被覆した被覆粒状肥料として好適に使用される。該被覆粒状肥料は、水溶性の粒状肥料であればよく、その例としては、尿素、塩安、硫安、硝安、塩化カリ、硫酸カリ、硝酸カリ、硝酸ソーダ、燐酸カリ、燐酸アンモニア、燐酸石灰、からなる群から選ばれる少なくとも1種の肥料又は複合肥料、および粒状の有機肥料等が挙げられる。
下記の通り、樹脂液A~Gを調製した。
以下の成分1、成分2をイソシアネート基/水酸基=1.0となるように調製した。
(成分1)MDI変成ひまし油(ひまし油を過剰量のMDIと混合してイソシアネート基の質量を全質量の19質量%としたイソシアネート基末端プレポリマー)
(成分2)aとbを水酸基のモル比=8:2で混合した混合液
a:ひまし油(水酸基価160mgKOH/g)
b:エチレンジアミンのプロピレンオキサイド付加物(プロピレンオキサイド/窒素原子の比;2.2、水酸基価;760mgKOH/g)
以下の成分1、成分2をイソシアネート基/水酸基=0.8となるように調製した。
(成分1)樹脂液Aの成分1と同様のMDI変成ひまし油
(成分2)樹脂液Bの成分2と同様の混合液
以下の成分1、成分2をイソシアネート基/水酸基=0.9となるように調製した。
(成分1)樹脂液Aの成分1と同様のMDI変成ひまし油
(成分2)樹脂液Bの成分2と同様の混合液
以下の成分1、成分2をイソシアネート基/水酸基=0.6となるように調製した。
(成分1)樹脂液Aの成分1と同様のMDI変成ひまし油
(成分2)樹脂液Bの成分2と同様の混合液
以下の成分1、成分2をイソシアネート基/水酸基=0.7となるように調製した。
(成分1)樹脂液Aの成分1と同様のMDI変成ひまし油
(成分2)樹脂液Bの成分2と同様の混合液
以下の成分1、成分2をイソシアネート基/水酸基=0.63となるように調製した。
(成分1)樹脂液Aの成分1と同様のMDI変成ひまし油
(成分2)樹脂液Bの成分2と同様の混合液
以下の成分1、成分2をイソシアネート基/水酸基=0.78となるように調製した。
(成分1)樹脂液Aの成分1と同様のMDI変成ひまし油
(成分2)樹脂液Bの成分2と同様の混合液
下記の手順により、調製した樹脂液を用いて被覆粒状体を製造した。各実施例、比較例の製造条件を表1に示す。
粒状尿素(粒径2.5~4.0mm)100kgを直径1.4mのドラム型転動被覆装置に仕込み、7rpmで転動させながら、熱風発生機により粒状尿素温度を70℃に保持した。次に、第1層目の未硬化被覆層として樹脂液Bを、被覆材A(合計1,603g、1.5質量%に相当する)として二流体ノズルから装置内に30秒かけて噴霧(塗布)した。被覆材Aを加えてから2.5分後に粒状尿素は粘着されはじめ、3分後に塊状物となり、3.5分後には粘着性が低下しはじめ、被覆粒状肥料同士は強い粘着性を有するものの塊状物がほぐれた状態となった。次に、第1層目の被覆材の噴霧から3.5分後に第2層目の未硬化被覆層として第1層目と同一成分、同一量(1.5質量%)の被覆材Aを二流体ノズルから装置内に30秒かけて噴霧した。さらに、第2層目の噴霧から3.5分後に、保護層として樹脂液Aを被覆材B(合計534g、0.5質量%に相当する)として二流体ノズルから装置内に10秒かけて噴霧した。被覆材Bの噴霧から7分後には保護層は粘着性をほとんど失い、被覆された粒状尿素同士が粘着することはなくなった。熱硬化性樹脂をさらに硬化促進させるため被覆材Bの噴霧後から30分間転動させ、粒状尿素上の被覆膜を硬化させた。これを常温(約25℃)まで冷却し、目的の被覆粒状肥料を得た。このとき被覆率は3.5質量%であった。
粒状尿素(粒径2.5~4.0mm)100kgを直径1.4mのドラム型転動被覆装置に仕込み、7rpmで転動させながら、熱風発生機により粒状尿素温度を70℃に保持した。次に、第1層目の未硬化被覆層として吸水性樹脂(平均粒径25μmの架橋アクリル酸塩重合体;三洋化成工業製ST-500MPSA)63gと樹脂液Dとを、被覆材A(合計1,317g、1.2質量%に相当する)として装置内に30秒かけて噴霧した。被覆材噴霧から3分後に第2層目の未硬化被覆層として第1層目と同一成分、同一量(1.2質量%)の被覆材Aを装置内に30秒かけて噴霧した。次に、第2層目の噴霧から3.5分後に、第3層目の未硬化被覆層として樹脂液Dを被覆材A(合計1,647g、1.5質量%に相当する)として装置内に30秒かけて噴霧した。次に第4層目の未硬化被覆層として第3層目と同一成分、同一量(1.5質量%)の被覆材Aを装置内に30秒かけて噴霧した。さらに、保護層として樹脂液Aを被覆材B(合計659g、0.6質量%に相当する)を装置内に10秒かけて噴霧した。被覆材Bの噴霧から7分後には、保護層は粘着性をほとんど失い被覆された粒状尿素同士が粘着することはなくなった。被覆膜の熱硬化性樹脂をさらに硬化促進させるため被覆材Bの噴霧後から30分間転動させ、粒状尿素上の被覆膜を硬化させた。これを常温(約25℃)まで冷却し、目的の被覆粒状肥料を得た。被覆率は6.0質量%であった。
第3層目及び第4層目の未硬化被覆層を形成する際、樹脂液Fを被覆材(合計1,647g、1.5質量%に相当する)とし、保護層として樹脂液Gを被覆材(合計659g、0.6質量%に相当する)とした以外は、実施例2と同様の方法で被覆粒状肥料を得た。被覆率は6.0質量%であった。
第1層目及び第2層目の未硬化被覆層を形成する際、樹脂液Aを被覆材(合計1,603g、1.5質量%に相当する)とし、保護層として樹脂液Aを被覆材(合計534g、0.5質量%に相当する)とした以外は、実施例1と同様の方法で被覆粒状肥料を得た。被覆率は3.5質量%であった。
第1層目及び第2層目の未硬化被覆層を形成する際、樹脂液Cを被覆材(合計1,603g、1.5質量%に相当する)とし、保護層として樹脂液Cを被覆材(合計534g、0.5質量%に相当する)とした以外は、実施例1と同様の方法で被覆粒状肥料を得た。被覆率は3.5質量%であった。
第1層目及び第2層目の未硬化被覆層を形成する際、樹脂液Bを被覆材(合計1,603g、1.5質量%に相当する)とし、保護層として樹脂液Bを被覆材(合計534g、0.5質量%に相当する)とした以外は、実施例1と同様の方法で被覆粒状肥料を得た。被覆率は3.5質量%であった。
第1層目~第4層目の未硬化被覆層を形成する際、樹脂液Dを樹脂液Eとして装置内に噴霧し、第5層目を形成する際、樹脂液Eを被覆材(合計659g、0.6質量%に相当する)を噴霧し、第5層目を保護層とした以外は実施例2と同様の方法で被覆粒状肥料を得た。被覆率は6.0質量%であった。
縮分した被覆粒状肥料のうち10gを採取して、予め希釈したインキ(S-1(赤),シヤチハタ社製)希釈液(2.5g/250ml純水)を、被覆粒状肥料が完全に浸漬するまで加え25℃で1時間静置し、該被覆粒状肥料をろ過回収した。続いて該被覆粒状肥料に付着したインキを水洗後、インキで着色された被覆粒状肥料および溶出が完了した被覆樹脂を取り除き、着色されなかった被覆粒状肥料の質量から良品率((非着色被覆粒状肥料の質量)g/10g×100)を算出した。
得られた被覆粒状肥料を縮分して溶出試験を行い、その結果を表2に示した。溶出試験は縮分した被覆粒状尿素のうち10gを採取して200ccのイオン交換水に投入し、25℃の恒温槽内に保存して所定時間経過後に取り出し、水中に溶出した尿素を定量して求めた。尚、表2には、それぞれ3日、7日、14日、21日、28日、42日、56日経過した時の尿素の溶出率(質量%)を示した。
Claims (7)
- 粒状水溶性物質と、該粒状水溶性物質上に形成され、イソシアネート基と水酸基とのイソシアネート基/水酸基で表されるモル比Aが0.5~0.99である樹脂液からなる熱硬化性樹脂Aを有する被覆層と、該被覆層上に形成され、イソシアネート基と水酸基とのイソシアネート基/水酸基で表されるモル比Bが0.75~2.0である樹脂液からなる熱硬化性樹脂Bを有する保護層と、を備え、保護層のモル比Bが被覆層のモル比Aよりも大きい、被覆粒状体。
- 保護層の質量/被覆粒状体の質量×100で表される被覆率が0.2~2質量%であることを特徴とする、請求項1に記載の被覆粒状体。
- 熱硬化性樹脂A及び熱硬化性樹脂Bが、芳香族ポリイソシアネートと、ポリオール化合物と、アミン化合物又はアミン系ポリオールと、から得られるウレタン樹脂であることを特徴とする、請求項1又は請求項2に記載の被覆粒状体。
- 被覆層が吸水性樹脂を含むことを特徴とする、請求項1乃至請求項3のいずれか1項に記載の被覆粒状体。
- 粒状水溶性物質が水溶性肥料であることを特徴とする、請求項1乃至請求項4のいずれか1項に記載の被覆粒状体。
- 粒状水溶性物質が水溶性農薬であることを特徴とする、請求項1乃至請求項4のいずれか1項に記載の被覆粒状体。
- 粒状水溶性物質を流動状態又は転動状態にする工程と、流動状態又は転動状態の粒状水溶性物質に被覆材を被覆する工程と、被覆材からなる未硬化被覆層を粒状水溶性物質表面に形成する工程と、未硬化被覆層の表面に保護層を形成する工程と、形成した未硬化被覆層及び保護層を熱硬化させる工程と、を含む、請求項1乃至請求項6のいずれか1項に記載の被覆粒状体を製造する方法。
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MY164276A (en) * | 2011-11-21 | 2017-11-30 | Malaysian Palm Oil Board | A controlled-release fertilizer |
US9321699B2 (en) * | 2012-11-21 | 2016-04-26 | The Mosaic Company | Granular fertilizers having improved dust control |
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- 2011-03-04 WO PCT/JP2011/055019 patent/WO2011122238A1/ja active Application Filing
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Also Published As
Publication number | Publication date |
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EP2554528B1 (en) | 2019-08-07 |
EP2554528A4 (en) | 2017-08-23 |
AU2011233207A1 (en) | 2012-08-23 |
JP5810544B2 (ja) | 2015-11-11 |
US20130039965A1 (en) | 2013-02-14 |
KR101423577B1 (ko) | 2014-07-25 |
CA2788098A1 (en) | 2011-10-06 |
KR20120135279A (ko) | 2012-12-12 |
EP2554528A1 (en) | 2013-02-06 |
AU2011233207B2 (en) | 2013-09-12 |
JP2011225424A (ja) | 2011-11-10 |
CA2788098C (en) | 2014-10-21 |
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