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WO2022131217A1 - Method for manufacturing coated granular fertilizer, and coated granular fertilizer - Google Patents

Method for manufacturing coated granular fertilizer, and coated granular fertilizer Download PDF

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Publication number
WO2022131217A1
WO2022131217A1 PCT/JP2021/045850 JP2021045850W WO2022131217A1 WO 2022131217 A1 WO2022131217 A1 WO 2022131217A1 JP 2021045850 W JP2021045850 W JP 2021045850W WO 2022131217 A1 WO2022131217 A1 WO 2022131217A1
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WO
WIPO (PCT)
Prior art keywords
granular fertilizer
polyol
component
polyisocyanate
rolling state
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/045850
Other languages
French (fr)
Japanese (ja)
Inventor
満弘 笹川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority to KR1020237018868A priority Critical patent/KR20230115299A/en
Priority to JP2022569989A priority patent/JPWO2022131217A1/ja
Publication of WO2022131217A1 publication Critical patent/WO2022131217A1/en
Priority to CONC2023/0007286A priority patent/CO2023007286A2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/40Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G5/00Fertilisers characterised by their form
    • C05G5/10Solid or semi-solid fertilisers, e.g. powders
    • C05G5/12Granules or flakes
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES 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
    • C05G5/00Fertilisers characterised by their form
    • C05G5/30Layered or coated, e.g. dust-preventing coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/36Hydroxylated esters of higher fatty acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes

Definitions

  • the present invention relates to a method for producing a coated granular fertilizer and a coated granular fertilizer.
  • a method for producing a resin-coated granular fertilizer a method of adding uncured urethane containing a catalyst to the granular fertilizer in a rolling state is known in order to coat the surface of the granular fertilizer with urethane resin.
  • Patent Document 1 a method of adding uncured urethane containing a catalyst to the granular fertilizer in a rolling state is known in order to coat the surface of the granular fertilizer with urethane resin.
  • the granular fertilizers stick to each other or adhere to the rolling apparatus of the granular fertilizers, so that the homogeneity of the coating of the resin-coated granular fertilizers and the efficiency of production are not always satisfactory. It wasn't.
  • An object of the present invention is to provide a method for producing a coated granular fertilizer having excellent homogeneity of resin coating.
  • the present inventor has studied to find an excellent method for producing a resin-coated granular fertilizer.
  • the method for producing a coated granular fertilizer by using diazabicyclononen as a catalyst in forming a film, particles are used.
  • a coated granular fertilizer can be obtained in which the aggregation of the fertilizer and the adhesion of particles to the rolling element are suppressed, and the present invention has been completed. That is, the present invention is as follows. [1] A method for producing a coated granular fertilizer comprising a granular fertilizer and a urethane resin coating for coating the granular fertilizer.
  • a method for producing a coated granular fertilizer which comprises a step of forming the urethane resin film on the surface of the granular fertilizer by adding the mixture.
  • a process of forming a resin film on the surface of granular fertilizer by adding components in layers [7] The production method according to any one of [1] to [6], wherein the polyisocyanate component contains an aromatic polyisocyanate. [8] The production method according to any one of [1] to [7], wherein the polyol component contains castor oil-modified diol. [9] The polyol component contains two or more compounds selected from the group consisting of castor oil-modified diols, alkylene diols having 2 to 8 carbon atoms, and compounds having 3 or more hydroxyl groups [1] to [7]. The manufacturing method according to any one of the above.
  • the generation of agglomeration between particles during resin coating on granular fertilizer and adhesion of particles to a rolling element is suppressed, and a resin coating can be uniformly formed on each particle. It is possible to provide a coated granular fertilizer in which variation in the elution pattern is suppressed.
  • the production method of the present invention a polyisocyanate component, a polyol component, and diazabicyclononen are added to the surface of a granular fertilizer in a rolling state.
  • the granular fertilizer used in the present invention may be a granular material containing a fertilizer component. Further, the granular fertilizer used in the present invention may be, for example, a granular material in which the fertilizer component is granulated by itself, or a granular material containing a fertilizer component and a carrier holding the fertilizer component.
  • the fertilizer component is not particularly limited and can be appropriately selected depending on the use and purpose of use of the coated granular fertilizer.
  • fertilizer components include urea, ammonium nitrate, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, sodium nitrate, calcium nitrate, potassium nitrate, lime nitrogen, formaldehyde processed urea (UF), and acetaldehyde processed urea (CDU).
  • Nitrogen fertilizer components such as isobutylaldehyde-processed urea (IBDU) and guanylurea (GU); lime perphosphate, lime perphosphate, fused phosphorus, phosphorus rot, calcined phosphorus, heavy roasted phosphorus, bitter phosphorus.
  • Phosphoric acid fertilizer components such as acid, ammonium polyphosphate, potassium metaphosphate, calcium metaphosphate, bittersweet phosphoric acid, phosphoric acid sulphate, potassium phosphonitrous, and salt phosphorus; and potassium chloride, potassium sulfate, potassium sulfate, potassium sulfate. Examples thereof include potassium fertilizer components such as bitter soil, potassium bicarbonate, and potassium phosphate. As these fertilizer components, one type may be used alone, or two or more types of fertilizer components may be used in combination.
  • the carrier that retains the fertilizer component can be appropriately selected according to the type of fertilizer component, the use of the coated granular fertilizer, the purpose of use, and the like.
  • Carriers include, for example, kaolin minerals such as kaolinite, mineral substances such as montmorillonite, smectite, talc, wax stone, silica, zeolite, acidic white clay; vegetable substances such as cellulose, rice husks, starch, soybean flour; lactose, sugar, dextrin, etc. It may contain water-soluble substances such as salt and sodium tripolyphosphate.
  • the carrier may contain one of these components alone, or may contain a plurality of of these components.
  • the granular fertilizer may contain one kind of carrier, or may contain two or more kinds of carriers.
  • the granular fertilizer may further contain a fertilizer component and other components other than the carrier.
  • the granular fertilizer used in the present invention is produced, for example, by a method of granulating a fertilizer component alone, a method of mixing a fertilizer component and a carrier (with other components if necessary), and the like. be able to.
  • the granulation method may be a normal granulation method for granules. Examples of such a granulation method include an extrusion granulation method, a fluidized bed type granulation method, a rolling granulation method, a compression granulation method, a bread granulation method, a coated granulation method and an adsorption granulation method.
  • the particle size of the granular fertilizer used in the present invention is not particularly limited, and can be appropriately selected depending on the type of fertilizer component and carrier, the use and purpose of the coated granular fertilizer, and the like.
  • the average particle size of the granular fertilizer may be 0.1 to 15 mm, 1 to 10 mm, or 1 to 5 mm.
  • granular fertilizer having an arbitrary particle size can be obtained by obtaining granular fertilizer by the above-mentioned production method and then classifying using a sieve having an appropriate opening diameter.
  • the average particle size of the granular fertilizer is defined by an arithmetic mean value (also referred to as an arithmetic mean value) of the diameter corresponding to the projected area circle, and is defined by a microscopy method (for example, an electron microscope or an optical microscope). Measured at.
  • the measuring method may vary depending on the size of the particle size of the granular fertilizer to be measured and the like.
  • the shape of the granular fertilizer used in the present invention is not particularly limited, and can be appropriately selected depending on the type of fertilizer component and carrier, the use and purpose of the resin-coated granular fertilizer, and the like.
  • the shape of the granular fertilizer may be, for example, a spherical shape, a polyhedral shape, a columnar shape, an irregular shape, or the like, and a shape close to a spherical shape is preferable.
  • the diazabicyclononene used in the present invention is also called 1,5-diazabicyclo (4.3.0) nonene-5 or DBN, and is represented by the structural formula (I) below.
  • diazabicyclononen examples include DBN (manufactured by San-Apro Co., Ltd.).
  • diazabicyclononen may be a catalytic amount, preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, based on the total amount of the polyisocyanate component and the polyol component. Used at a rate of%. More preferably, it is used in a proportion of 0.02 to 0.07% by weight.
  • the urethane resin means a resin that is three-dimensionally crosslinked by reacting a polyisocyanate component and a polyol component.
  • the mixture of the polyisocyanate component and the polyol component (sometimes referred to as "uncured urethane") is such that the polyisocyanate component and the polyol component do not react at all or are not three-dimensionally crosslinked. It means a part that has been partially reacted in advance.
  • the form of the mixture may be any of a solvent-free type, a solution type, an aqueous emulsion type and the like, but a solvent-free type and a liquid type in the step of adding to the granular fertilizer can be preferably used.
  • polyisocyanate means a compound having two or more isocyanate groups.
  • examples of such polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates, and derivatives thereof.
  • the polyisocyanate preferably contains an aromatic polyisocyanate from the viewpoint of sustained release performance (also referred to as slow release).
  • the aromatic polyisocyanate means a compound having an aromatic ring and two or more isocyanate groups.
  • the aromatic polyisocyanate may be a compound having one aromatic ring in the molecule, or may be a compound having a plurality of aromatic rings.
  • the isocyanate group of the aromatic polyisocyanate is preferably directly bonded to the aromatic ring.
  • the aromatic ring may be a benzene ring.
  • aromatic polyisocyanates include 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), trizine diisocyanate (TODI), naphthalene-1,5-diisocyanate (NDI). ), Tetramethylene xylylene diisocyanate (TMXDI), and polymethylene polyphenyl polyisocyanate (polymeric MDI), and derivatives thereof (for example, modified products such as isocyanurate form, biuret form, uretdione form, etc.).
  • MDI 4,4'-diphenylmethane diisocyanate
  • TDI tolylene diisocyanate
  • XDI xylylene diisocyanate
  • TODI trizine diisocyanate
  • NDI naphthalene-1,5-diisocyanate
  • TXDI Te
  • the aromatic polyisocyanate may be an aromatic polyisocyanate having two or more benzene rings having an isocyanate group from the viewpoint of sustained release performance.
  • the number of isocyanate groups directly bonded to each benzene ring may be one, or may be two or more.
  • aromatic polyisocyanates include MDI, TDI, TODI, and oligomers derived from them (for example, polypeptide MDI and the like).
  • the aliphatic polyisocyanate means a compound having a fatty chain and two or more isocyanate groups.
  • specific examples of such an aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), dimerate diisocyanate (DDI), and norbornene diisocyanate (NBDI).
  • the alicyclic polyisocyanate means a saturated or unsaturated carbocycle having no aromaticity and a compound having two or more isocyanate groups.
  • examples of such alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated XDI and the like.
  • lysine triisocyanate lysine diisocyanate and the like can also be used as polyisocyanate.
  • Derivatives of polyisocyanate include, for example, modified products such as isocyanurate form, biuret form, and uretdione form.
  • the ratio of the aromatic polyisocyanate to the polyisocyanate component may be 30% by weight or more, and may be 50% by weight or more from the viewpoint of sustained release performance. , Or 100% by weight.
  • the polyol component means a compound having 2 or more hydroxyl groups per molecule.
  • examples of such polyol components include alkylene diols having 2 to 8 carbon atoms, polyether polyols, polyester polyols, vegetable oils having two or more hydroxyl groups, and modified products thereof.
  • the polyether polyol means a compound having two or more ether bonds and two or more hydroxyl groups in the molecule.
  • the polyether polyol can be obtained, for example, by using a polyhydric alcohol, an amino alcohol, or an amine as an initiator and adding ethylene oxide or propylene oxide in a double manner.
  • the polyether polyol examples include polytetramethylene ether glucol obtained by polymerizing tetrahydrofuran.
  • the polyester polyol means a compound having two or more ester bonds and two or more hydroxyl groups in the molecule.
  • the polyester polyol can be obtained, for example, by reacting a polyhydric alcohol with a polyether polyol and a carboxylic acid-containing compound. It can also be obtained, for example, by ring-opening polymerization of a cyclic ester compound using a polyhydric alcohol as an initiator.
  • Examples of vegetable oils having two or more hydroxyl groups include castor oil, soybean oil, and cottonseed oil.
  • Examples of the modified product of the vegetable oil having 2 or more hydroxyl groups include castor oil-modified diol and castor oil-modified polyol having 3 or more hydroxyl groups.
  • the polyol component contains castor oil-modified diol from the viewpoint of sustained release performance. Further, from the viewpoint of sustained release performance, the polyol component is two or more (that is, two or three) selected from the group consisting of castor oil-modified diols, alkylene diols having 2 to 8 carbon atoms, and compounds having 3 or more hydroxyl groups. It is more preferable to contain the compound of (1).
  • the castor oil-modified diol means a compound that can be derived from castor oil by a chemical reaction and has two hydroxyl groups.
  • the castor oil-modified diol may be derived from castor oil, or may be a compound that can be derived from castor oil and may be a compound produced from a raw material other than castor oil.
  • Castor oil is a fatty oil containing a glyceride of ricinoleic acid as a main component, and the castor oil-modified diol may be, for example, ricinoleic acid-modified diol.
  • a commercially available product can be used as the castor oil-modified diol.
  • examples of such commercially available products include URIC H-62 (hydroxyl value: 245 to 275, manufactured by Ito Oil Co., Ltd.), URIC Y-202 (hydroxyl value: 110 to 120, manufactured by Ito Oil Co., Ltd.), and URIC Y-403.
  • the "hydroxyl value” means the number of mg of potassium hydroxide corresponding to the hydroxyl group in 1 g of the sample, as described in the Japanese Industrial Standards (JIS) Polyurethane Polyether Test Method (K 1557). Actually, it is a value calculated by esterifying a test sample with a pyridine solution of phthalic anhydride and titrating the excess reagent with a sodium hydroxide solution.
  • the content of castor oil-modified diol in the polyol component may be 6% by weight or more, and 8% by weight or more, based on the total amount of the polyol component, from the viewpoint of sustained release performance. It may be 10% by weight or more, 30% by weight or more, 50% by weight or more, or 65% by weight or more. Further, the content of the castor oil-modified diol may be 93% by weight or less, 90% by weight or less, or 85% by weight or less based on the total amount of the polyol component from the viewpoint of sustained release performance. It's okay.
  • alkylene diol having 2 to 8 carbon atoms may be contained as a polyol component.
  • the carbon number of the alkylenediol is preferably 3 or more, more preferably 4 or more, preferably 7 or less, or more preferably 6 or less.
  • the content of the alkylene diol in the polyol component may be 4% by weight or more, and 6% by weight or more, based on the total amount of the polyol component, from the viewpoint of sustained release performance. It may be 8% by weight or more, or 10% by weight or more. Further, the content of the alkylene diol may be 25% by weight or less, 21% by weight or less, or 20% by weight or less based on the total amount of the polyol component from the viewpoint of sustained release performance. , 18% by weight or less, or 15% by weight or less.
  • a compound having 3 or more hydroxyl groups may be contained as a polyol component from the viewpoint of sustained release performance.
  • the compound having 3 or more hydroxyl groups means a compound having 3 or more hydroxyl groups per molecule.
  • a compound having 3 or more hydroxyl groups may have 3 to 8 hydroxyl groups or 3 to 6 hydroxyl groups per molecule.
  • Examples of the compound having 3 or more hydroxyl groups include a polyether polyol having 3 or more hydroxyl groups, a castor oil, a castor oil modified polyol having 3 or more hydroxyl groups (for example, a castor oil modified triol), and a poly (meth) having 3 or more hydroxyl groups.
  • Examples thereof include acrylic acid polyols, condensed polyester polyols having 3 or more hydroxyl groups, and lactone-based polyester polyols having 3 or more hydroxyl groups.
  • the compound having 3 or more hydroxyl groups one type may be used alone, or two or more types may be used in combination.
  • a compound contained in a commercially available product may be used.
  • a castor oil-modified polyol having 3 or more hydroxyl groups and a polyether polyol having 3 or more hydroxyl groups are preferable from the viewpoint of sustained release performance.
  • the content of the compound having 3 or more hydroxyl groups in the polyol component is 2% by weight or more based on the total amount of the polyol component from the viewpoint of sustained release performance. It may be 3% by weight or more, or 8% by weight or more.
  • the content of the compound having three or more hydroxyl groups may be 87% by weight or less, 80% by weight or less, and 76% by weight or less based on the total amount of the polyol component from the viewpoint of sustained release performance. It may be 60% by weight or less, 40% by weight or less, or 20% by weight or less.
  • the polyol component may be a mixture of castor oil-modified diol, an alkylene diol having 2 to 8 carbon atoms, and a compound having 3 or more hydroxyl groups.
  • the amount of castor oil-modified diol with respect to the total amount of the polyol component may be 7% by weight or more, preferably 10% by weight or more, or 30% by weight or more from the viewpoint of sustained release performance. It may be 50% by weight or more, or 65% by weight or more.
  • the amount of castor oil-modified diol may be 93% by weight or less, or preferably 80% by weight or less, from the viewpoint of sustained release performance.
  • the amount of the alkylene diol having 2 to 8 carbon atoms with respect to the total amount of the polyol component may be 4% by weight or more, 6% by weight or more, and 8 by weight, from the viewpoint of sustained release performance. It is preferably 7% by weight or more, or 10% by weight or more.
  • the amount of the alkylene diol having 2 to 8 carbon atoms may be 25% by weight or less, 21% by weight or less, 20% by weight or less, and 18% by weight from the viewpoint of sustained release performance. It may be less than or equal to, or preferably 15% by weight or less.
  • the amount of the compound having 3 or more hydroxyl groups per molecule with respect to the total amount of the polyol component may be 2% by weight or more, and may be 8% by weight or more from the viewpoint of sustained release performance. preferable. From the viewpoint of sustained release performance, the amount of the polyol having more than 2 hydroxyl groups per molecule may be 87% by weight or less, preferably 78% by weight or less, and may be 60% by weight or less. , 40% by weight or less, or 20% by weight or less.
  • the urethane resin is a heavy addition of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a castor oil modified diol, an alkylene diol having 2 to 8 carbon atoms, and a polyether polyol. It may be a thing.
  • the content of the aromatic polyisocyanate, the castor oil modified diol, the alkylene diol having 2 to 8 carbon atoms and the polyether polyol is 30 to 60 weight by weight with respect to the total amount of the polyisocyanate component and the polyol component, respectively. %, 30-60% by weight, 3-10% by weight, or 2-20% by weight.
  • the urethane resin is a heavy addition of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a castor oil-modified diol, an alkylene diol having 2 to 8 carbon atoms, and a castor oil-modified polyol. It may be a thing.
  • the contents of the aromatic polyisocyanate, the castor oil-modified diol, the alkylene diol having 2 to 8 carbon atoms and the castor oil-modified polyol are 30 to 60, respectively, with respect to the total amount of the polyisocyanate component and the polyol component. It may be% by weight, 5 to 60% by weight, 3 to 10% by weight, or 5 to 50% by weight.
  • the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a polyether polyol and castor oil.
  • the contents of the aromatic polyisocyanate, the polyether polyol and the castor oil are 30 to 60% by weight, 5 to 60% by weight, or 5 to 5 to 60% by weight, respectively, with respect to the total amount of the polyisocyanate component and the polyol component. It may be 30% by weight.
  • the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a polyether polyol.
  • the content of the aromatic polyisocyanate and the polyether polyol may be 30 to 60% by weight or 30 to 60% by weight, respectively, with respect to the total amount of the polyisocyanate component and the polyol component.
  • the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a polyether diol and a polyether polyol.
  • the content of the aromatic polyisocyanate, the polyether diol and the polyether polyol is 30 to 60% by weight, 5 to 30% by weight, or 5 with respect to the total amount of the polyisocyanate component and the polyol component, respectively. It may be up to 60% by weight.
  • the urethane resin may be a heavy adduct of a polyisocyanate component containing an aliphatic polyisocyanate and a polyol component containing a polyether diol and a polyether polyol.
  • the content of the aliphatic polyisocyanate, the polyether diol and the polyether polyol is 30 to 60% by weight, 5 to 30% by weight, or 5 with respect to the total amount of the polyisocyanate component and the polyol component, respectively. It may be up to 60% by weight.
  • the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing castor oil-modified diliol.
  • the content of the aromatic polyisocyanate and the castor oil-modified diliol may be 20 to 70% by weight or 20 to 70% by weight, respectively, based on the total amount of the polyisocyanate component and the polyol component.
  • the urethane resin comprises 30 to 60 parts by weight of aromatic polyisocyanate, 30 to 60 parts by weight of castor oil modified diol, and 3 to 10 parts by weight of alkylene diol having 2 to 8 carbon atoms. It may be a heavy adduct of 2 to 20 parts by weight of a polyether polyol.
  • the urethane resin comprises 30 to 60 parts by weight of aromatic polyisocyanate, 5 to 60 parts by weight of castor oil-modified diol, and 3 to 10 parts by weight of alkylene diol having 2 to 8 carbon atoms. It may be a heavy adduct of 5 to 50 parts by weight of castor oil-modified polyol.
  • the urethane resin is a heavy adduct of 30 to 60 parts by weight of aromatic polyisocyanate, 5 to 60 parts by weight of a polyether polyol and 5 to 30 parts by weight of castor oil. It's okay.
  • the urethane resin may be a heavy adduct of 30 to 60 parts by weight of an aromatic polyisocyanate and 30 to 60 parts by weight of a polyether polyol.
  • the urethane resin is a heavy adduct of 30 to 60 parts by weight of aromatic polyisocyanate, 5 to 30 parts by weight of a polyether diol and 5 to 60 parts by weight of a polyether polyol. It may be there.
  • the urethane resin is a heavy adduct of 30 to 60 parts by weight of an aliphatic polyisocyanate, 5 to 30 parts by weight of a polyether diol, and 5 to 60 parts by weight of a polyether polyol. It may be there.
  • the ratio M2 / M1 of the number of moles of hydroxyl groups M2 of the polyol component to the number of moles of isocyanate groups M1 of the polyisocyanate component is preferably 0.7 or more, more preferably 0.9 or more. It is preferably 1.7 or less, and more preferably 1.5 or less. When the ratio M2 / M1 is in the above range, excellent sustained release performance tends to be obtained.
  • the coated granular fertilizer of the present invention may have a resin film other than the urethane resin film.
  • the content of the urethane resin in the entire resin film may be 80% by weight or more, 90% by weight or more, or 100% by weight based on the total amount of the resin film.
  • the content of the urethane resin in the coated granular fertilizer is preferably 1 part by mass or more, and more preferably 2 parts by mass or more with respect to 100 parts by mass of the granular fertilizer.
  • the content of the urethane resin is preferably 20 parts by mass or less, or more preferably 16 parts by mass or less, based on 100 parts by mass of the granular fertilizer.
  • a polyisocyanate component, a polyol component, and diazabicyclononen are used. Examples of the steps using these components include those shown below, and the method for producing a resin-coated granular fertilizer of the present invention may include these steps.
  • a step of forming a urethane resin film on the surface of the granular fertilizer by adding a polyisocyanate component and a polyol component in a layered manner by maintaining the rolling state of the granular fertilizer (A-3) (hereinafter, step A-1).
  • ⁇ A-3 may be collectively referred to as “process A”).
  • B-2 a step (B-3) (hereinafter referred to as a step) of forming a urethane resin film on the surface of the granular fertilizer by repeatedly adding a polyisocyanate component and a polyol component by maintaining the rolling state of the granular fertilizer.
  • B-1 to B to 3 may be collectively referred to as "process B").
  • C-2 a step (C-3) (hereinafter referred to as a step) of forming a urethane resin film on the surface of the granular fertilizer by repeatedly adding a polyisocyanate component and a polyol component by maintaining the rolling state of the granular fertilizer.
  • C-1 to C-3 may be collectively referred to as "process C”).
  • steps D-1 to D-2 may be collectively referred to as "step D" to form a urethane resin film on the surface of the granular fertilizer. May be.
  • the order of addition is the polyisocyanate component, the polyol component, and the diazabicyclononen, the polyol component, the polyisocyanate component, and the diazabicyclononen.
  • Polyol component, diazabicyclononen, and polyisocyanate component polyisocyanate component, diazabicyclononen, and polyol component, diazabicyclononen, polyisocyanate component, and polyol component, or diah. It may be any of the order of the zabicyclononen, the polyol component, and the polyisocyanate component.
  • the temperature at which the step A is carried out is appropriately set according to the types of the polyisocyanate component and the polyol component used, the size of the granular fertilizer, and the like, but in a rotary tank in which the granular fertilizer is in a rolling state.
  • the temperature at which step B is carried out is appropriately set according to the types of the polyisocyanate component and the polyol component used, the size of the granular fertilizer, and the like, but in a rotary tank in which the granular fertilizer is in a rolling state.
  • the temperature is usually in the range of 40 to 100 ° C, preferably in the range of 55 to 75 ° C.
  • the heavy addition of the polyisocyanate component and the polyol component proceeds to cure the urethane, and the resin-coated granules do not adhere to each other.
  • the heavy addition of the polyisocyanate component and the polyol component proceeds to cure the urethane, and the resin-coated granules do not adhere to each other.
  • the rolling state of the granular fertilizer is maintained until, but the time for maintaining the rolling state is usually about 2 to 40 minutes, and from the viewpoint of production efficiency, it is about 2 to 30 minutes.
  • the temperature at which step D is carried out is appropriately set according to the types of the polyisocyanate component and the polyol component used, the size of the granular fertilizer, and the like, but in a rotary tank in which the granular fertilizer is in a rolling state.
  • the temperature is usually in the range of 40 to 100 ° C, preferably in the range of 55 to 75 ° C. Further, after the addition of the polyisocyanate component, the polyol component and diazabicyclononen, the polyisocyanate component, the polyol component and the heavy addition proceed to the extent that the urethane is cured and the resin-coated granules do not adhere to each other.
  • the rolling state of the granular fertilizer is maintained, but the time for maintaining the rolling state is usually about 2 to 40 minutes, and from the viewpoint of production efficiency, it is about 2 to 30 minutes.
  • the coated granular fertilizer of the present invention can be produced by a production method including any of the above steps A to D, but step A is preferable from the viewpoint of homogeneity of the resin film.
  • any one of the above steps A to D may be performed only once. Further, any of the steps A to D may be repeated once or more on the resin-coated granules obtained by any of the steps A to D (hereinafter, may be referred to as "step E").
  • the steps A to D to be added repeatedly may be the same as or different from the one-time or a plurality of steps A to D performed earlier.
  • Step E may be continuously carried out while maintaining the rolling state of the granular fertilizer in the previous step.
  • the polyisocyanate component and the polyol component used in the step E may be the same as or different from the polyisocyanate component and the polyol component used in the previous step, but are usually of the same type from the viewpoint of production efficiency. Ingredients and polyol components are used.
  • the total amount of the polyol component and the polyisocyanate component used in the method for producing a resin-coated granular fertilizer of the present invention is appropriately determined depending on the size and shape of the granular fertilizer used and the degree of elution control required for the resin-coated granular fertilizer to be produced. Although it is set, it is the total amount of the polyol component and the polyisocyanate used in steps A to D and, if necessary, step E, and is usually 2 to 30 weights per 100 parts by weight of granular fertilizer. About parts, preferably about 4 to 18 parts by weight.
  • the device As a method for putting the granular fertilizer into a rolling state, there is no particular limitation on the device, and known and conventional ones can be used. Examples of such an apparatus include a concrete mixer and a drum mixer. Among the above-mentioned devices, the device equipped with the heating equipment is preferably used because it is possible to improve the accuracy and adjust the processing time in the manufacturing method of the present invention.
  • the coated granular fertilizer of the present invention may further contain a resin film other than the resin film containing urethane resin and diazabicyclononen, which are heavy adducts of the polyisocyanate component and the polyol component.
  • a resin film include a film containing urethane resin, which is a heavy adduct of an arbitrary polyisocyanate component and an arbitrary polyol component, and not containing diazabicyclononen.
  • the resin film may further contain components other than the urethane resin and diazabicyclononen.
  • it may contain a solvent such as an organic solvent and water, and these may be the solvents used in the production of the urethane resin.
  • the resin film may further contain a pigment, a dye, an antibacterial agent, a preservative, a plasticizer, a decomposition accelerator, the above-mentioned carrier and the like, depending on the purpose.
  • the coated granular fertilizer of the present invention may further contain components other than the granular fertilizer and the resin film (for example, antifloating material, anti-caking material, pesticide active ingredient, waxes, etc.).
  • components other than the granular fertilizer and the resin film for example, antifloating material, anti-caking material, pesticide active ingredient, waxes, etc.
  • the coated granular fertilizer of the present invention may further contain a hydrophobic liquid compound having a boiling point of 100 ° C. or higher (hereinafter, also referred to as "the present hydrophobic liquid compound").
  • the present hydrophobic liquid compound means a compound having fluidity at 20 ° C. and having a water solubility at 20 ° C. of 10 ppm or less.
  • the present hydrophobic liquid compound may be contained in the granular fertilizer and may be present as a film covering the granular fertilizer. When the present hydrophobic liquid compound is present as a film, the film may be formed directly on the surface of the granular fertilizer, or may be formed on the resin film covering the granular fertilizer.
  • This hydrophobic compound is blended, for example, when producing a resin-coated granular fertilizer using an apparatus that puts the granular fertilizer in a rolling state.
  • the hydrophobic compound include aliphatic hydrocarbons such as liquid paraffin, aromatic hydrocarbons such as phenylxysilylethane and alkylbenzene (specifically, Solvesso150, manufactured by Exxon Mobile Chemical).
  • the content of the hydrophobic liquid compound in the resin-coated granular fertilizer may be 0.1 to 5 parts by mass with respect to 100 parts by mass of the granular fertilizer.
  • the resin film may be formed so as to cover the entire surface of the granular fertilizer, or may be formed so as to cover a part of the surface of the granular fertilizer.
  • the thickness of the resin coating can be appropriately selected according to the use and purpose of use of the resin-coated granular fertilizer.
  • the thickness of the resin film may be, for example, 8 ⁇ m or more, preferably 10 ⁇ m or more.
  • the thickness of the resin film may be, for example, 400 ⁇ m or less, preferably 200 ⁇ m or less.
  • the thickness of the resin coating is 8 ⁇ m or more and 4200 ⁇ m or less, 8 ⁇ m or more and 200 ⁇ m or less, 10 ⁇ m or more and 400 ⁇ m or less, or 10 ⁇ m or more and 200 ⁇ m or less. ..
  • the thickness of the resin coating indicates a value measured by a scanning electron microscope (SEM) observation of a cross section of the resin-coated granular fertilizer.
  • the thickness of the resin film can also be expressed as, for example, the average value of the measured values of the thicknesses at 10 points.
  • the particle size of the coated granular fertilizer can be appropriately selected according to the intended use and purpose of use of the coated granular fertilizer.
  • the average particle size of the coated particle size fertilizer may be 0.1 to 15 mm, or may be 1 to 5 mm.
  • the average particle size of the coated granular fertilizer is defined as an arithmetic mean value of the diameter corresponding to the projected area circle, and is measured by a microscope method or the like.
  • a polyol mixture I 2677.08 g of the obtained polyol mixture and 2.50 g of diazabicyclononen (trade name: DBN) were mixed at room temperature to obtain a polyol mixture I.
  • the granular urea in a rolling state is heated to about 66 ° C. by applying hot air from a hot air generator, and then liquid paraffin (manufactured by Matsumura Petroleum Research Institute, trade name: Moresco White P-350P, 37.78 ° C.).
  • aromatic diisocyanate manufactured by Sumika Bayer Urethane, trade name: SBU isocyanate J243
  • the above operation (stirring and mixing of polyol mixture I and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, until the total addition amount of the mixture of polyol mixture I and aromatic diisocyanate reaches 5,002.5 g, And maintenance of the rolling state) was repeated to obtain the coated granular fertilizer of the present invention.
  • the above manufacturing process no remarkable agglomeration of the granules and adhesion of the granules to the inner wall of the concrete mixer were observed, and the rolling state of the granules in the concrete mixer was good.
  • the coated granular fertilizer obtained by the above manufacturing process was visually observed, the coated state was uniform.
  • the above operation (stirring mixing of polyol mixture I and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, until the total addition amount of the mixture of polyol mixture I and aromatic diisocyanate reaches 4,877.47 g, And maintenance of the rolling state) was repeated to obtain the coated granular fertilizer of the present invention.
  • the coated granular fertilizer obtained by the above manufacturing process was visually observed, the coated state was uniform.
  • Production example 3 A polyol mixture A2677.08 g and diazabicyclononen (San Apro Co., Ltd., trade name: DBN) 3.50 g were mixed at room temperature to obtain a polyol mixture II. 50,000 g of granular urea (large-grain urea, particle size of about 3 mm, spherical shape, about 60 grains per 1 g) was charged into a concrete mixer and put into a rolling state. The granular urea in a rolling state is heated to about 66 ° C. by applying hot air from a hot air generator, and then liquid paraffin (manufactured by Matsumura Petroleum Research Institute, trade name: Moresco White P-350P, 37.78 ° C.).
  • aromatic diisocyanate manufactured by Sumika Bayer Urethane, trade name: SBU isocyanate J243
  • the above operation (stirring and mixing of polyol mixture II and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, until the total addition amount of the mixture of polyol mixture II and aromatic diisocyanate reaches 5,003.5 g, And maintenance of the rolling state) was repeated to obtain the coated granular fertilizer of the present invention.
  • the coated granular fertilizer obtained by the above manufacturing process was visually observed, the coated state was uniform.
  • Comparative manufacturing example 1 50,000 g of granular urea (large-grain urea, particle size of about 3 mm, spherical shape, about 60 grains per 1 g) was charged into a concrete mixer and put into a rolling state.
  • the granular urea in a rolling state is heated to about 66 ° C. by applying hot air from a hot air generator, and then liquid paraffin (manufactured by Matsumura Petroleum Research Institute, trade name: Moresco White P-350P, 37.78 ° C.). Viscosity: 76 mm 2 / S) 500 g was added, and the rolling state was continued for 3 minutes. Next, 267.71 g of the polyol mixture heated to 50 ° C.
  • Comparative manufacturing example 2 A polyol mixture A 2677.08 g and an ethyleneamine derivative (Tosoh Corporation, trade name: TOYOCAT-DB30) 2.50 g were mixed at room temperature to obtain a polyol mixture III. The same operation as in Production Example 1 was carried out except that the polyol mixture III was used instead of the polyol mixture I, and a coated granular fertilizer for comparison was obtained. In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.
  • Comparative manufacturing example 3 Mixture A 2677.08 g and 2.50 g of 1,8-diazabicyclo (5.4.0) Undecen-7 (San Apro Co., Ltd., trade name: DBU®) at room temperature to obtain a polyol mixture IV. Obtained. The same operation as in Production Example 1 was carried out except that the polyol mixture IV was used instead of the polyol mixture I, and a coated granular fertilizer for comparison was obtained. In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.
  • Comparative manufacturing example 4 Mixture A 2677.08 g and 3.50 g of 1,8-diazabicyclo (5.4.0) Undecen-7 (San Apro Co., Ltd., trade name: DBU®) at room temperature to obtain a polyol mixture V. Obtained. The same operation as in Production Example 3 was carried out except that the polyol mixture V was used instead of the polyol mixture II, and a coated granular fertilizer for comparison was obtained. In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.
  • Comparative manufacturing example 5 2.50 g of the polyol mixture A 2677.08 g and the phenol salt of 1,8-diazabicyclo (5,4,0) undecene-7 (San Apro Co., Ltd., trade name: U-CAT (registered trademark) SA-1) at room temperature. The mixture was obtained with a polyol mixture VI. The same operation as in Production Example 1 was carried out except that the polyol mixture VI was used instead of the polyol mixture I, and a coated granular fertilizer for comparison was obtained. In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.
  • Comparative manufacturing example 6 A polyol mixture A 2677.08 g and 2,4,6-tris (dimethylaminomethyl) phenol (chemical drug Axo Co., Ltd., trade name: TAP) 25.0 g were mixed at room temperature to obtain a polyol mixture VII. 50,000 g of granular urea (large-grain urea, particle size of about 3 mm, spherical shape, about 60 grains per 1 g) was charged into a concrete mixer and put into a rolling state. The granular urea in a rolling state is heated to about 66 ° C.
  • the mixture was added to the granular urea in the rolling state, and the rolling state was maintained while applying hot air from the hot air generator for 10 minutes or more. Until the total amount of the mixture of polyol mixture VII and aromatic diisocyanate added reaches 5025.0 g, the above operations (stirring and mixing of polyol mixture VII and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, and (Maintenance of rolling state) was repeated to obtain a coated granular fertilizer for comparison. In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.
  • the method for producing a coated granular fertilizer of the present invention it is possible to provide a coated granular fertilizer in which the occurrence of aggregation between particles and adhesion of particles to a rolling device is suppressed.

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Abstract

Provided are a method for manufacturing a coated granular fertilizer that has high homogeneity in a resin coating, and this coated granular fertilizer. The method for manufacturing a coated granular fertilizer that is composed of a granular fertilizer and a urethane resin coating film coating the granular fertilizer, said method comprising a step for adding a polyisocyanate component, a polyol component and diazabicyclononene to the granular fertilizer in a rotated state, and a step for performing polyaddition of the polyisocyanate component and the polyol component while maintaining the granular fertilizer in the rotated state to thereby form the urethane resin coating film on the surface of the granular fertilizer; and the coated granular fertilizer that has high homogeneity in the resin coating.

Description

被覆粒状肥料の製造方法及び被覆粒状肥料Manufacturing method of coated granular fertilizer and coated granular fertilizer

 本特許出願は、日本国特許出願2020-206637号(2020年12月14日出願)に基づくパリ条約上の優先権および利益を主張するものであり、ここに引用することによって、上記出願に記載された内容の全体が本明細書中に組み込まれるものとする。 This patent application claims priority and interests under the Paris Convention under Japanese Patent Application No. 2020-206637 (filed December 14, 2020) and is described in the above application by reference here. The entire contents of the above shall be incorporated herein by reference.

 本発明は、被覆粒状肥料の製造方法及び被覆粒状肥料に関する。 The present invention relates to a method for producing a coated granular fertilizer and a coated granular fertilizer.

 従来、農業就労者の高年齢化、就労者数の減少、兼業農家の増加から、より省力型の肥料として、植物の成長にあわせ所定の時期に肥料成分を溶出させる機能を有する種々の肥効調整型被覆肥料が提案されている。古くは粒状肥料を樹脂やワックス、あるいは硫黄などで被覆、カプセル化して肥料成分の溶出速度を制御するものが知られている。また、樹脂被覆粒状肥料の製造方法としては、粒状肥料の表面をウレタン樹脂で被覆するために、転動状態に付された粒状肥料に触媒を含む未硬化ウレタンを添加する方法が知られている(例えば、特許文献1参照)。しかし、これらの方法においては、粒状肥料同士の固着、或いは、粒状肥料の転動装置への付着などが生じるため、樹脂被覆粒状肥料の被覆の均質性や製造の効率性は、必ずしも満足できるものではなかった。このような問題を解決する手段として、被覆粒状肥料の製造方法において、樹脂を被覆する前に粒状尿素の表面へ流動パラフィンなどを添加することによって、粒子間の凝集及び転動装置への粒子の付着等の発生を抑制する方法が提案されている(特許文献2参照)。しかしながら、この方法においても粒子間の凝集及び転動装置への粒子の付着等の発生の抑制には、なお改善の余地がある。 Conventionally, due to the aging of agricultural workers, the decrease in the number of workers, and the increase in the number of part-time farmers, various fertilizer effects that have the function of elution of fertilizer components at a predetermined time according to the growth of plants as a more labor-saving fertilizer. Adjustable coated fertilizers have been proposed. In the olden days, it has been known that granular fertilizer is coated with resin, wax, sulfur, etc. and encapsulated to control the elution rate of fertilizer components. Further, as a method for producing a resin-coated granular fertilizer, a method of adding uncured urethane containing a catalyst to the granular fertilizer in a rolling state is known in order to coat the surface of the granular fertilizer with urethane resin. (See, for example, Patent Document 1). However, in these methods, the granular fertilizers stick to each other or adhere to the rolling apparatus of the granular fertilizers, so that the homogeneity of the coating of the resin-coated granular fertilizers and the efficiency of production are not always satisfactory. It wasn't. As a means for solving such a problem, in a method for producing a coated granular fertilizer, by adding liquid paraffin or the like to the surface of granular urea before coating the resin, the particles are aggregated between the particles and the particles are transferred to the rolling element. A method for suppressing the occurrence of adhesion and the like has been proposed (see Patent Document 2). However, even in this method, there is still room for improvement in suppressing the occurrence of aggregation of particles and adhesion of particles to the rolling element.

特開平9-202683号公報Japanese Unexamined Patent Publication No. 9-202683 特開2011-16685号公報Japanese Unexamined Patent Publication No. 2011-16685

 本発明は、樹脂被覆の均質性に優れた被覆粒状肥料の製造方法を提供することを課題とする。 An object of the present invention is to provide a method for producing a coated granular fertilizer having excellent homogeneity of resin coating.

 本発明者は、樹脂被覆粒状肥料の優れた製造方法を見出すべく検討を行った結果、被覆粒状肥料の製造方法において、被膜の形成の際に触媒としてジアザビシクロノネンを使用することによって、粒子間の凝集及び転動装置への粒子の付着等の発生が抑制された、被覆粒状肥料が得られることを見出し、本発明を完成するに至った。
 すなわち本発明とは、次の通りである。
[1]粒状肥料と、当該粒状肥料を被覆するウレタン樹脂被膜とを備える被覆粒状肥料の製造方法であって、
 転動状態にある前記粒状肥料にポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンを添加する工程;および、該粒状肥料の転動状態を維持しながら該ポリイソシアネート成分と該ポリオール成分とを重付加させて、前記粒状肥料の表面に前記ウレタン樹脂被膜を形成する工程、を含む、被覆粒状肥料の製造方法。
[2]ジアザビシクロノネンの添加量が、ポリイソシアネート成分及びポリオール成分の合計量に対して0.01~2重量%である、[1]に記載の製造方法。
[3]以下の工程を含む[1]又は[2]に記載の製造方法:
(a)ポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンとを混合し、混合物を得る工程、
(b)転動状態にある粒状肥料に前記工程(a)で得た混合物を添加する工程、および
(c)該粒状肥料の転動状態を維持し、ポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面に樹脂被膜を形成する工程。
[4]以下の工程を含む[1]又は[2]に記載の製造方法:
(a)ポリイソシアネート成分とポリオール成分とを混合し、混合物を得る工程、
(b)転動状態にある粒状肥料に前記工程(a)で得た混合物とジアザビシクロノネンとを別々に添加する工程、および
(c)該粒状肥料の転動状態を維持し、ポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面に樹脂被膜を形成する工程。
[5]以下の工程を含む[1]又は[2]に記載の製造方法:
(a)ポリオール成分とジアザビシクロノネンとを混合し、混合物を得る工程、
(b)転動状態にある粒状肥料にポリイソシアネート成分と前記工程(a)で得た混合物とを別々に添加する工程、および
(c)該粒状肥料の転動状態を維持し、ポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面に樹脂被覆を形成する工程。
[6]以下の工程を含む[1]又は[2]に記載の製造方法:
(a)転動状態にある粒状肥料にポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンを別々に添加する工程、および
(b)該粒状肥料の転動状態を維持し、ポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面に樹脂被膜を形成する工程。
[7]前記ポリイソシアネート成分が、芳香族ポリイソシアネートを含む、[1]~[6]のいずれか1つに記載の製造方法。
[8]前記ポリオール成分が、ヒマシ油変性ジオールを含む、[1]~[7]のいずれか1つに記載の製造方法。
[9]前記ポリオール成分が、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール、及び水酸基を3以上有する化合物からなる群から選ばれる2つ以上の化合物を含む、[1]~[7]のいずれか1つに記載の製造方法。
[10]前記ポリオール成分が、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール、及び水酸基を3以上有する化合物、を含む、[1]~[8]のいずれか1つに記載の製造方法。
[11]粒状肥料と、当該粒状肥料を被覆する樹脂被膜とを備え、
 前記樹脂被膜が、ポリイソシアネート成分とポリオール成分との重付加物であるウレタン樹脂とジアザビシクロノネンとを含む、被覆粒状肥料(以下、「本発明の被覆粒状肥料」と称する)。
The present inventor has studied to find an excellent method for producing a resin-coated granular fertilizer. As a result, in the method for producing a coated granular fertilizer, by using diazabicyclononen as a catalyst in forming a film, particles are used. We have found that a coated granular fertilizer can be obtained in which the aggregation of the fertilizer and the adhesion of particles to the rolling element are suppressed, and the present invention has been completed.
That is, the present invention is as follows.
[1] A method for producing a coated granular fertilizer comprising a granular fertilizer and a urethane resin coating for coating the granular fertilizer.
A step of adding a polyisocyanate component, a polyol component, and diazabicyclononen to the granular fertilizer in a rolling state; and a weighting of the polyisocyanate component and the polyol component while maintaining the rolling state of the granular fertilizer. A method for producing a coated granular fertilizer, which comprises a step of forming the urethane resin film on the surface of the granular fertilizer by adding the mixture.
[2] The production method according to [1], wherein the amount of diazabicyclononen added is 0.01 to 2% by weight based on the total amount of the polyisocyanate component and the polyol component.
[3] The production method according to [1] or [2], which comprises the following steps:
(A) A step of mixing a polyisocyanate component, a polyol component, and diazabicyclononen to obtain a mixture.
(B) The step of adding the mixture obtained in the above step (a) to the granular fertilizer in the rolling state, and (c) maintaining the rolling state of the granular fertilizer, and adding the polyisocyanate component and the polyol component repeatedly. The process of forming a resin film on the surface of granular fertilizer.
[4] The production method according to [1] or [2], which comprises the following steps:
(A) A step of mixing a polyisocyanate component and a polyol component to obtain a mixture.
(B) A step of separately adding the mixture obtained in the above step (a) and diazabicyclononen to the granular fertilizer in a rolling state, and (c) maintaining the rolling state of the granular fertilizer and polyisocyanate. A process of forming a resin film on the surface of granular fertilizer by adding components and polyol components in layers.
[5] The production method according to [1] or [2], which comprises the following steps:
(A) A step of mixing a polyol component and diazabicyclononen to obtain a mixture.
(B) A step of separately adding the polyisocyanate component and the mixture obtained in the above step (a) to the granular fertilizer in the rolling state, and (c) maintaining the rolling state of the granular fertilizer and the polyisocyanate component. And a polyol component are heavily added to form a resin coating on the surface of granular fertilizer.
[6] The production method according to [1] or [2], which comprises the following steps:
(A) A step of separately adding a polyisocyanate component, a polyol component, and diazabicyclononen to a granular fertilizer in a rolling state, and (b) maintaining the rolling state of the granular fertilizer, a polyisocyanate component and a polyol. A process of forming a resin film on the surface of granular fertilizer by adding components in layers.
[7] The production method according to any one of [1] to [6], wherein the polyisocyanate component contains an aromatic polyisocyanate.
[8] The production method according to any one of [1] to [7], wherein the polyol component contains castor oil-modified diol.
[9] The polyol component contains two or more compounds selected from the group consisting of castor oil-modified diols, alkylene diols having 2 to 8 carbon atoms, and compounds having 3 or more hydroxyl groups [1] to [7]. The manufacturing method according to any one of the above.
[10] The production method according to any one of [1] to [8], wherein the polyol component contains a castor oil-modified diol, an alkylene diol having 2 to 8 carbon atoms, and a compound having 3 or more hydroxyl groups. ..
[11] A granular fertilizer and a resin film for covering the granular fertilizer are provided.
A coated granular fertilizer (hereinafter referred to as "coated granular fertilizer of the present invention") in which the resin film contains urethane resin and diazabicyclononen, which are heavy adducts of a polyisocyanate component and a polyol component.

 本発明によれば、粒状肥料への樹脂被覆時の粒子間の凝集及び転動装置への粒子の付着等の発生が抑制され、各々の粒子により均質に樹脂被膜を設けることができるので、粒子ごとの溶出パターンのばらつきが抑制された被覆粒状肥料を提供することができる。 According to the present invention, the generation of agglomeration between particles during resin coating on granular fertilizer and adhesion of particles to a rolling element is suppressed, and a resin coating can be uniformly formed on each particle. It is possible to provide a coated granular fertilizer in which variation in the elution pattern is suppressed.

 本発明の被覆粒状肥料の製造方法(以後、「本発明の製造方法」と記す。)は、転動状態にある粒状肥料の表面にポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンを添加する工程;および、粒状肥料の転動状態を維持しながらポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面にウレタン樹脂被膜を形成する工程、を含む。 In the method for producing a coated granular fertilizer of the present invention (hereinafter referred to as "the production method of the present invention"), a polyisocyanate component, a polyol component, and diazabicyclononen are added to the surface of a granular fertilizer in a rolling state. A step; and a step of forming a urethane resin film on the surface of the granular fertilizer by repeatedly adding a polyisocyanate component and a polyol component while maintaining the rolling state of the granular fertilizer.

 本発明で使用される粒状肥料は、肥料成分を含む粒状物であってよい。また、本発明で使用される粒状肥料は、例えば、肥料成分が単独で造粒された粒状物であってよく、あるいは肥料成分及び肥料成分を保持する担体を含む粒状物であってよい。 The granular fertilizer used in the present invention may be a granular material containing a fertilizer component. Further, the granular fertilizer used in the present invention may be, for example, a granular material in which the fertilizer component is granulated by itself, or a granular material containing a fertilizer component and a carrier holding the fertilizer component.

 本発明において、肥料成分は特に限定されず、被覆粒状肥料の用途及び使用目的等に応じて適宜選択できる。肥料成分としては、例えば、尿素、硝酸アンモニウム、硝酸苦土アンモニウム、塩化アンモニウム、硫酸アンモニウム、リン酸アンモニウム、硝酸ソーダ、硝酸カルシウム、硝酸カリウム、石灰窒素、ホルムアルデヒド加工尿素(UF)、アセトアルデヒド加工尿素(CDU)、イソブチルアルデヒド加工尿素(IBDU)、グアニル尿素(GU)等の窒素質肥料成分;過リン酸石灰、重過リン酸石灰、熔成リン、腐植酸リン、焼成リン、重焼リン、苦土過リン酸、ポリリン酸アンモニウム、メタリン酸カリウム、メタリン酸カルシウム、苦土リン酸、硫リン安、リン硝安カリウム、塩リン安等のリン酸質肥料成分;および、塩化カリウム、硫酸カリウム、硫酸カリソーダ、硫酸カリ苦土、重炭酸カリウム、リン酸カリウム等のカリウム質肥料成分などが挙げられる。これらの肥料成分は、1種を単独で用いてよく、あるいは2種以上の肥料成分を組み合わせて用いてもよい。 In the present invention, the fertilizer component is not particularly limited and can be appropriately selected depending on the use and purpose of use of the coated granular fertilizer. Examples of fertilizer components include urea, ammonium nitrate, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium phosphate, sodium nitrate, calcium nitrate, potassium nitrate, lime nitrogen, formaldehyde processed urea (UF), and acetaldehyde processed urea (CDU). Nitrogen fertilizer components such as isobutylaldehyde-processed urea (IBDU) and guanylurea (GU); lime perphosphate, lime perphosphate, fused phosphorus, phosphorus rot, calcined phosphorus, heavy roasted phosphorus, bitter phosphorus. Phosphoric acid fertilizer components such as acid, ammonium polyphosphate, potassium metaphosphate, calcium metaphosphate, bittersweet phosphoric acid, phosphoric acid sulphate, potassium phosphonitrous, and salt phosphorus; and potassium chloride, potassium sulfate, potassium sulfate, potassium sulfate. Examples thereof include potassium fertilizer components such as bitter soil, potassium bicarbonate, and potassium phosphate. As these fertilizer components, one type may be used alone, or two or more types of fertilizer components may be used in combination.

 本発明において、肥料成分を保持する担体は、肥料成分の種類、被覆粒状肥料の用途及び使用目的等に応じて適宜選択できる。担体は、例えば、カオリナイト等のカオリン鉱物、モンモリロナイト、スメクタイト、タルク、蝋石、シリカ、ゼオライト、酸性白土などの鉱物質;セルロース、籾殻、澱粉、大豆粉等の植物質;乳糖、蔗糖、デキストリン、食塩、トリポリリン酸ナトリウム等の水溶性物質などを含むものであってよい。担体は、これらの成分のうち1種を単独で含むものであってよく、あるいは複数種を含むものであってよい。また、粒状肥料は、1種の担体を含むものであってよく、あるいは2種以上の担体を含むものであってよい。 In the present invention, the carrier that retains the fertilizer component can be appropriately selected according to the type of fertilizer component, the use of the coated granular fertilizer, the purpose of use, and the like. Carriers include, for example, kaolin minerals such as kaolinite, mineral substances such as montmorillonite, smectite, talc, wax stone, silica, zeolite, acidic white clay; vegetable substances such as cellulose, rice husks, starch, soybean flour; lactose, sugar, dextrin, etc. It may contain water-soluble substances such as salt and sodium tripolyphosphate. The carrier may contain one of these components alone, or may contain a plurality of of these components. Further, the granular fertilizer may contain one kind of carrier, or may contain two or more kinds of carriers.

 本発明において、粒状肥料は、肥料成分及び担体以外の他の成分を更に含んでいてよい。 In the present invention, the granular fertilizer may further contain a fertilizer component and other components other than the carrier.

 本発明で使用される粒状肥料は、例えば、肥料成分を単独で造粒する方法、肥料成分と担体と(必要に応じて更に他の成分と)を混合して造粒する方法等により製造することができる。造粒方法は、通常の粒状物の造粒方法であってよい。かかる造粒方法としては、例えば、押出造粒法、流動層式造粒法、転動造粒法、圧縮造粒法、パン造粒法、被覆造粒法及び吸着造粒法が挙げられる。 The granular fertilizer used in the present invention is produced, for example, by a method of granulating a fertilizer component alone, a method of mixing a fertilizer component and a carrier (with other components if necessary), and the like. be able to. The granulation method may be a normal granulation method for granules. Examples of such a granulation method include an extrusion granulation method, a fluidized bed type granulation method, a rolling granulation method, a compression granulation method, a bread granulation method, a coated granulation method and an adsorption granulation method.

 本発明で使用される粒状肥料の粒径は特に限定されず、肥料成分及び担体の種類、被覆粒状肥料の用途及び使用目的等に応じて適宜選択できる。例えば、粒状肥料の平均粒径は、0.1~15mmであってよく、1~10mmであってよく、または1~5mmであってよい。本実施形態では、例えば、上述した製造方法により粒状肥料を得た後、適切な開口径の篩を用いて分級することによって任意の粒径を有する粒状肥料を得ることができる。なお、本明細書中、粒状肥料の平均粒径は、投影面積円相当径の算術平均値(または相加平均値とも称する)で定義され、顕微鏡法(例えば、電子顕微鏡、または光学顕微鏡)などで測定される。測定法は、測定対象の粒状肥料の粒径の大きさ等によって変わり得る。 The particle size of the granular fertilizer used in the present invention is not particularly limited, and can be appropriately selected depending on the type of fertilizer component and carrier, the use and purpose of the coated granular fertilizer, and the like. For example, the average particle size of the granular fertilizer may be 0.1 to 15 mm, 1 to 10 mm, or 1 to 5 mm. In the present embodiment, for example, granular fertilizer having an arbitrary particle size can be obtained by obtaining granular fertilizer by the above-mentioned production method and then classifying using a sieve having an appropriate opening diameter. In the present specification, the average particle size of the granular fertilizer is defined by an arithmetic mean value (also referred to as an arithmetic mean value) of the diameter corresponding to the projected area circle, and is defined by a microscopy method (for example, an electron microscope or an optical microscope). Measured at. The measuring method may vary depending on the size of the particle size of the granular fertilizer to be measured and the like.

 本発明で使用される粒状肥料の形状は特に限定されず、肥料成分及び担体の種類、樹脂被覆粒状肥料の用途及び使用目的等に応じて適宜選択できる。粒状肥料の形状は、例えば、球状、多面体状、円柱状、および不定形状等であってよく、球状に近いものが好ましい。 The shape of the granular fertilizer used in the present invention is not particularly limited, and can be appropriately selected depending on the type of fertilizer component and carrier, the use and purpose of the resin-coated granular fertilizer, and the like. The shape of the granular fertilizer may be, for example, a spherical shape, a polyhedral shape, a columnar shape, an irregular shape, or the like, and a shape close to a spherical shape is preferable.

 本発明に用いられるジアザビシクロノネンとは、1,5-ジアザビシクロ(4.3.0)ノネン-5やDBNとも呼ばれ、以下の式(I)の構造式で表される。

Figure JPOXMLDOC01-appb-C000001
The diazabicyclononene used in the present invention is also called 1,5-diazabicyclo (4.3.0) nonene-5 or DBN, and is represented by the structural formula (I) below.
Figure JPOXMLDOC01-appb-C000001

 本発明において用いられるジアザビシクロノネンとしては、例えば、DBN(サンアプロ株式会社製)が挙げられる。本製造方法において、ジアザビシクロノネンは、ポリイソシアネート成分及びポリオール成分の合計量に対して、触媒量であり得て、好ましくは0.01~2重量%、より好ましくは0.01~1重量%の割合で使用される。更に好ましくは0.02~0.07重量%の割合で使用される。 Examples of the diazabicyclononen used in the present invention include DBN (manufactured by San-Apro Co., Ltd.). In the present production method, diazabicyclononen may be a catalytic amount, preferably 0.01 to 2% by weight, more preferably 0.01 to 1% by weight, based on the total amount of the polyisocyanate component and the polyol component. Used at a rate of%. More preferably, it is used in a proportion of 0.02 to 0.07% by weight.

 本発明において、ウレタン樹脂とはポリイソシアネート成分とポリオール成分とを反応させることにより3次元架橋させた樹脂を意味する。本発明において、ポリイソシアネート成分とポリオール成分との混合物(「未硬化ウレタン」と称する場合もある)とは、ポリイソシアネート成分とポリオール成分とが全く反応していないか、あるいは3次元架橋しない程度に予め一部を反応させたものを意味する。かかる混合物の形態としては無溶剤型、溶液型、水系エマルジョン型等の何れでも良いが、無溶剤型であり、かつ、粒状肥料に添加する工程において液状であるものが好ましく使用できる。 In the present invention, the urethane resin means a resin that is three-dimensionally crosslinked by reacting a polyisocyanate component and a polyol component. In the present invention, the mixture of the polyisocyanate component and the polyol component (sometimes referred to as "uncured urethane") is such that the polyisocyanate component and the polyol component do not react at all or are not three-dimensionally crosslinked. It means a part that has been partially reacted in advance. The form of the mixture may be any of a solvent-free type, a solution type, an aqueous emulsion type and the like, but a solvent-free type and a liquid type in the step of adding to the granular fertilizer can be preferably used.

 本発明において、ポリイソシアネートとは、2以上のイソシアネート基を有する化合物を意味する。かかるポリイソシアネートとしては、芳香族ポリイソシアネート、脂肪族ポリイソシアネートおよび脂環族ポリイソシアネート、およびそれらの誘導体が挙げられる。
 本発明においては、徐放性能(緩効性とも称する)の観点から、ポリイソシアネートは芳香族ポリイソシアネートを含むことが好ましい。
In the present invention, polyisocyanate means a compound having two or more isocyanate groups. Examples of such polyisocyanates include aromatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates, and derivatives thereof.
In the present invention, the polyisocyanate preferably contains an aromatic polyisocyanate from the viewpoint of sustained release performance (also referred to as slow release).

 本発明において、芳香族ポリイソシアネートとは、芳香環及び2以上のイソシアネート基を有する化合物を意味する。芳香族ポリイソシアネートは、分子内に芳香環を1つ有する化合物であってよく、あるいは複数の芳香環を有する化合物であってよい。芳香族ポリイソシアネートが有するイソシアネート基は、芳香環に直接結合していることが好ましい。芳香環はベンゼン環であってよい。 In the present invention, the aromatic polyisocyanate means a compound having an aromatic ring and two or more isocyanate groups. The aromatic polyisocyanate may be a compound having one aromatic ring in the molecule, or may be a compound having a plurality of aromatic rings. The isocyanate group of the aromatic polyisocyanate is preferably directly bonded to the aromatic ring. The aromatic ring may be a benzene ring.

 芳香族ポリイソシアネートの具体例としては、4,4’-ジフェニルメタンジイソシアネート(MDI)、トリレンジイソシアネート(TDI)、キシリレンジイソシアネート(XDI)、トリジンジイソシアネート(TODI)、ナフタレン-1,5-ジイソシアネート(NDI)、テトラメチレンキシリレンジイソシアネート(TMXDI)、およびポリメチレンポリフェニルポリイソシアネート(ポリメリックMDI)、およびこれらの誘導体(例えば、イソシアヌレート体、ビウレット体、ウレトジオン体等の変性物)が挙げられる。芳香族ポリイソシアネートは、これらの1種を単独で用いてよく、あるいは2種以上を組み合わせて用いてもよい。 Specific examples of aromatic polyisocyanates include 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), trizine diisocyanate (TODI), naphthalene-1,5-diisocyanate (NDI). ), Tetramethylene xylylene diisocyanate (TMXDI), and polymethylene polyphenyl polyisocyanate (polymeric MDI), and derivatives thereof (for example, modified products such as isocyanurate form, biuret form, uretdione form, etc.). As the aromatic polyisocyanate, one of these may be used alone, or two or more thereof may be used in combination.

 芳香族ポリイソシアネートは、徐放性能の観点から、イソシアネート基を有するベンゼン環を2以上有する芳香族ポリイソシアネートであってよい。このような芳香族ポリイソシアネートにおいて、各ベンゼン環に直接結合しているイソシアネート基の数は1つであってよく、あるいは2つ以上であってもよい。このような芳香族ポリイソシアネートとしては、例えば、MDI、TDI、TODI、およびこれらから誘導されるオリゴマー体(例えば、ポリメリックMDI等)が挙げられる。 The aromatic polyisocyanate may be an aromatic polyisocyanate having two or more benzene rings having an isocyanate group from the viewpoint of sustained release performance. In such an aromatic polyisocyanate, the number of isocyanate groups directly bonded to each benzene ring may be one, or may be two or more. Examples of such aromatic polyisocyanates include MDI, TDI, TODI, and oligomers derived from them (for example, polypeptide MDI and the like).

 本発明において、脂肪族ポリイソシアネートとは、脂肪鎖及び2以上のイソシアネート基を有する化合物を意味する。かかる脂肪族ポリイソシアネートの具体例としては、例えば、ヘキサメチレンジイソシアネート(HDI)、ダイマー酸ジイソシアネート(DDI)、およびノルボルネン・ジイソシアネート(NBDI)が挙げられる。 In the present invention, the aliphatic polyisocyanate means a compound having a fatty chain and two or more isocyanate groups. Specific examples of such an aliphatic polyisocyanate include hexamethylene diisocyanate (HDI), dimerate diisocyanate (DDI), and norbornene diisocyanate (NBDI).

 本発明において、脂環族ポリイソシアネートとは、芳香族性を有しない飽和または不飽和の炭素環、及び2以上のイソシアネート基を有する化合物を意味する。かかる脂環族ポリイソシアネートとしては、例えば、イソホロンジイソシアネート(IPDI)、ジシクロヘキシルメタンジイソシアネート(水添MDI)、および水添XDIなどが挙げられる。 In the present invention, the alicyclic polyisocyanate means a saturated or unsaturated carbocycle having no aromaticity and a compound having two or more isocyanate groups. Examples of such alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated XDI and the like.

 本発明においては、リジントリイソシアネートやリジンジイソシアネート等もポリイソシアネートとして用いることができる。ポリイソシアネートの誘導体としては、例えば、イソシアヌレート体、ビウレット体、およびウレトジオン体等の変性物が挙げられる。 In the present invention, lysine triisocyanate, lysine diisocyanate and the like can also be used as polyisocyanate. Derivatives of polyisocyanate include, for example, modified products such as isocyanurate form, biuret form, and uretdione form.

 ポリイソシアネート成分が芳香族ポリイソシアネートを含む場合、ポリイソシアネート成分に占める芳香族ポリイソシアネートの割合は、徐放性能の観点からは、30重量%以上であってよく、50重量%以上であってよく、あるいは100重量%であってよい。 When the polyisocyanate component contains an aromatic polyisocyanate, the ratio of the aromatic polyisocyanate to the polyisocyanate component may be 30% by weight or more, and may be 50% by weight or more from the viewpoint of sustained release performance. , Or 100% by weight.

 本発明において、ポリオール成分とは、1分子当たりの水酸基数が2以上の化合物を意味する。かかるポリオ-ル成分としては、例えば、炭素数2~8のアルキレンジオール、ポリエーテルポリオール、ポリエステルポリオール、水酸基を2以上有する植物油、及びそれらの変性物が挙げられる。
 本発明において、ポリエーテルポリオールは、分子内に2以上のエーテル結合及び2以上の水酸基を有する化合物を意味する。ポリエーテルポリオールは、例えば、多価アルコール、アミノアルコール、アミンを開始剤として用い、エチレンオキサイドやプロピレンオキサイドを重付加して得られる。ポリエーテルポリオールの具体例としては、テトラヒドロフランを重合して得られるポリテトラメチレンエーテルグルコールが挙げられる。
 本発明において、ポリエステルポリオールは、分子内に2以上のエステル結合及び2以上の水酸基を有する化合物を意味する。ポリエステルポリオールは、例えば、多価アルコ-ルとポリエーテルポリオールとカルボン酸含有化合物とを反応させることにより得られる。また、例えば、多価アルコールを開始剤とし、環状エステル化合物を開環重合させることによっても得られる。
In the present invention, the polyol component means a compound having 2 or more hydroxyl groups per molecule. Examples of such polyol components include alkylene diols having 2 to 8 carbon atoms, polyether polyols, polyester polyols, vegetable oils having two or more hydroxyl groups, and modified products thereof.
In the present invention, the polyether polyol means a compound having two or more ether bonds and two or more hydroxyl groups in the molecule. The polyether polyol can be obtained, for example, by using a polyhydric alcohol, an amino alcohol, or an amine as an initiator and adding ethylene oxide or propylene oxide in a double manner. Specific examples of the polyether polyol include polytetramethylene ether glucol obtained by polymerizing tetrahydrofuran.
In the present invention, the polyester polyol means a compound having two or more ester bonds and two or more hydroxyl groups in the molecule. The polyester polyol can be obtained, for example, by reacting a polyhydric alcohol with a polyether polyol and a carboxylic acid-containing compound. It can also be obtained, for example, by ring-opening polymerization of a cyclic ester compound using a polyhydric alcohol as an initiator.

 水酸基を2以上有する植物油としては、例えば、ヒマシ油、大豆油、および綿実油が挙げられる。水酸基を2以上有する植物油の変性物としては、例えば、ヒマシ油変性ジオール、および水酸基を3以上有するヒマシ油変性ポリオールが挙げられる。
 本発明においては、徐放性能の観点から、ポリオール成分が、ヒマシ油変性ジオールを含むことが好ましい。また、徐放性能の観点から、ポリオール成分が、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール、及び水酸基を3以上有する化合物からなる群から選ばれる2つ以上(すなわち、2つまたは3つ)の化合物を含むことがより好ましい。
Examples of vegetable oils having two or more hydroxyl groups include castor oil, soybean oil, and cottonseed oil. Examples of the modified product of the vegetable oil having 2 or more hydroxyl groups include castor oil-modified diol and castor oil-modified polyol having 3 or more hydroxyl groups.
In the present invention, it is preferable that the polyol component contains castor oil-modified diol from the viewpoint of sustained release performance. Further, from the viewpoint of sustained release performance, the polyol component is two or more (that is, two or three) selected from the group consisting of castor oil-modified diols, alkylene diols having 2 to 8 carbon atoms, and compounds having 3 or more hydroxyl groups. It is more preferable to contain the compound of (1).

 本発明において、ヒマシ油変性ジオールとは、ヒマシ油から化学反応により誘導され得る化合物であって、水酸基を2つ有する化合物を意味する。ヒマシ油変性ジオールは、ヒマシ油から誘導されたものであってよく、あるいはヒマシ油から誘導され得る化合物であってヒマシ油以外の原料から製造された化合物であってよい。ヒマシ油は、リシノレイン酸のグリセリドを主成分とする脂肪油であり、ヒマシ油変性ジオールは、例えばリシノレイン酸変性ジオールであってよい。 In the present invention, the castor oil-modified diol means a compound that can be derived from castor oil by a chemical reaction and has two hydroxyl groups. The castor oil-modified diol may be derived from castor oil, or may be a compound that can be derived from castor oil and may be a compound produced from a raw material other than castor oil. Castor oil is a fatty oil containing a glyceride of ricinoleic acid as a main component, and the castor oil-modified diol may be, for example, ricinoleic acid-modified diol.

 本発明においては、ヒマシ油変性ジオールとして、市販品を用いることができる。かかる市販品としては、例えば、URIC H-62(水酸基価:245~275、伊藤製油株式会社製)、URIC Y-202(水酸基価:110~120、伊藤製油株式会社製)、URIC Y-403(水酸基価:150~170、伊藤製油株式会社製)、URIC Y-332(水酸基価:113~133、伊藤製油株式会社製)、URIC AC-005(水酸基価:194~214、伊藤製油株式会社製)、URIC AC-006(水酸基価:168~187、伊藤製油株式会社製)、URIC PH-5001(水酸基価:45、伊藤製油株式会社製)、URIC PH-5002(水酸基価:43、伊藤製油株式会社製)、HS 2G-120(水酸基価:122、豊国製油株式会社製)、HS 2G-160R(水酸基価:121、豊国製油株式会社製)、HS 2G-270B(水酸基価:261、豊国製油株式会社製)、HS 2B-5500(水酸基価:178、豊国製油株式会社製)、およびHS KA-001(水酸基価:224、豊国製油株式会社製)が挙げられるが、これらに限定されない。
 ここで、「水酸基価」とは、日本工業規格(JIS)のポリウレタン用ポリエーテル試験方法(K 1557)に記載の通り、試料1g中の水酸基に相当する水酸化カリウムのmg数を意味する。実際には、被験試料を無水フタル酸のピリジン溶液でエステル化し、その過剰の試薬を水酸化ナトリウム溶液で滴定することにより算出される値である。
In the present invention, a commercially available product can be used as the castor oil-modified diol. Examples of such commercially available products include URIC H-62 (hydroxyl value: 245 to 275, manufactured by Ito Oil Co., Ltd.), URIC Y-202 (hydroxyl value: 110 to 120, manufactured by Ito Oil Co., Ltd.), and URIC Y-403. (Filament value: 150-170, manufactured by Ito Oil Co., Ltd.), URIC Y-332 (hydroxyl value: 113-133, manufactured by Ito Oil Co., Ltd.), URIC AC-005 (hydroxyl value: 194-214, manufactured by Ito Oil Co., Ltd.) , URIC AC-006 (hydroxyl value: 168-187, manufactured by Ito Oil Co., Ltd.), URIC PH-5001 (hydroxyl value: 45, manufactured by Ito Oil Co., Ltd.), URIC PH-5002 (hydroxyl value: 43, manufactured by Ito). (Manufactured by Oil Refinery Co., Ltd.), HS 2G-120 (hydroxyl value: 122, manufactured by Toyokuni Oil Co., Ltd.), HS 2G-160R (hydroxyl value: 121, manufactured by Toyokuni Oil Co., Ltd.), HS 2G-270B (hydroxyl value: 261), (Toyogoku Oil Co., Ltd.), HS 2B-5500 (hydroxyl value: 178, manufactured by Toyokuni Oil Co., Ltd.), and HS KA-001 (hydroxyl value: 224, manufactured by Toyokuni Oil Co., Ltd.), but are not limited thereto. ..
Here, the "hydroxyl value" means the number of mg of potassium hydroxide corresponding to the hydroxyl group in 1 g of the sample, as described in the Japanese Industrial Standards (JIS) Polyurethane Polyether Test Method (K 1557). Actually, it is a value calculated by esterifying a test sample with a pyridine solution of phthalic anhydride and titrating the excess reagent with a sodium hydroxide solution.

 ポリオール成分がヒマシ油変性ジオールを含む場合、ポリオール成分におけるヒマシ油変性ジオールの含有量は、徐放性能の観点から、ポリオール成分の全量基準で、6重量%以上であってよく、8重量%以上であってよく、10重量%以上であってよく、30重量%以上であってよく、50重量%以上であってよく、あるいは65重量%以上であってもよい。また、ヒマシ油変性ジオールの含有量は、徐放性能の観点から、ポリオール成分の全量基準で、93重量%以下であってよく、90重量%以下であってよく、あるいは85重量%以下であってよい。 When the polyol component contains castor oil-modified diol, the content of castor oil-modified diol in the polyol component may be 6% by weight or more, and 8% by weight or more, based on the total amount of the polyol component, from the viewpoint of sustained release performance. It may be 10% by weight or more, 30% by weight or more, 50% by weight or more, or 65% by weight or more. Further, the content of the castor oil-modified diol may be 93% by weight or less, 90% by weight or less, or 85% by weight or less based on the total amount of the polyol component from the viewpoint of sustained release performance. It's okay.

 本発明においては、徐放性能の観点から、ポリオール成分として、炭素数2~8のアルキレンジオール(以下、単に「アルキレンジオール」とも称する。)を含んでいてもよい。アルキレンジオールの炭素数は、好ましくは3以上、より好ましくは4以上であり、好ましくは7以下、あるいはより好ましくは6以下である。 In the present invention, from the viewpoint of sustained release performance, an alkylene diol having 2 to 8 carbon atoms (hereinafter, also simply referred to as “alkylene diol”) may be contained as a polyol component. The carbon number of the alkylenediol is preferably 3 or more, more preferably 4 or more, preferably 7 or less, or more preferably 6 or less.

 アルキレンジオールは、直鎖状又は分岐鎖状であってよい。直鎖状のアルキレンジオールとしては、例えば、エチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、および1,8-オクタンジオール等が挙げられる。分岐鎖状のアルキレンジオールとしては、例えば、2-メチル-1,3-プロパンジオール、2-メチル-1,4-ブタンジオール、および2,3-ジメチル-1,4-ブタンジオール等が挙げられる。 The alkylene diol may be linear or branched chain. Examples of the linear alkylene diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol. Can be mentioned. Examples of the branched alkylene diol include 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, and 2,3-dimethyl-1,4-butanediol. ..

 ポリオール成分にアルキレンジオールが含まれる場合、ポリオール成分におけるアルキレンジオールの含有量は、徐放性能の観点から、ポリオール成分の全量基準で、4重量%以上であってよく、6重量%以上であってよく、8重量%以上であってよく、あるいは10重量%以上であってよい。また、アルキレンジオールの含有量は、徐放性能の観点から、ポリオール成分の全量基準で、25重量%以下であってよく、あるいは21重量%以下であってよく、20重量%以下であってよく、18重量%以下であってよく、あるいは15重量%以下であってよい。 When the polyol component contains an alkylene diol, the content of the alkylene diol in the polyol component may be 4% by weight or more, and 6% by weight or more, based on the total amount of the polyol component, from the viewpoint of sustained release performance. It may be 8% by weight or more, or 10% by weight or more. Further, the content of the alkylene diol may be 25% by weight or less, 21% by weight or less, or 20% by weight or less based on the total amount of the polyol component from the viewpoint of sustained release performance. , 18% by weight or less, or 15% by weight or less.

 本発明においては、徐放性能の観点から、ポリオール成分として、水酸基を3以上有する化合物を含んでいてもよい。本発明において、水酸基を3以上有する化合物とは、一分子当たり有する水酸基の数が3以上である化合物を意味する。水酸基を3以上有する化合物は1分子当たり有する水酸基の数は、3~8であってよく、あるいは3~6であってよい。 In the present invention, a compound having 3 or more hydroxyl groups may be contained as a polyol component from the viewpoint of sustained release performance. In the present invention, the compound having 3 or more hydroxyl groups means a compound having 3 or more hydroxyl groups per molecule. A compound having 3 or more hydroxyl groups may have 3 to 8 hydroxyl groups or 3 to 6 hydroxyl groups per molecule.

 水酸基を3以上有する化合物としては、例えば、水酸基を3以上有するポリエーテルポリオール、ヒマシ油、水酸基を3以上有するヒマシ油変性ポリオール(例えば、ヒマシ油変性トリオール)、水酸基を3以上有するポリ(メタ)アクリル酸ポリオール、水酸基を3以上有する縮合系ポリエステルポリオール、および水酸基を3以上有するラクトン系ポリエステルポリオール等が挙げられる。水酸基を3以上有する化合物としては、1種を単独で用いてよく、あるいは2種以上を組み合わせて用いてもよい。なお、水酸基を3以上有する化合物としては、市販品に含まれるものを用いても良い。水酸基を3以上有する化合物としては、徐放性能の観点から、水酸基を3以上有するヒマシ油変性ポリオール、及び水酸基を3以上有するポリエーテルポリオールが好ましい。 Examples of the compound having 3 or more hydroxyl groups include a polyether polyol having 3 or more hydroxyl groups, a castor oil, a castor oil modified polyol having 3 or more hydroxyl groups (for example, a castor oil modified triol), and a poly (meth) having 3 or more hydroxyl groups. Examples thereof include acrylic acid polyols, condensed polyester polyols having 3 or more hydroxyl groups, and lactone-based polyester polyols having 3 or more hydroxyl groups. As the compound having 3 or more hydroxyl groups, one type may be used alone, or two or more types may be used in combination. As the compound having 3 or more hydroxyl groups, a compound contained in a commercially available product may be used. As the compound having 3 or more hydroxyl groups, a castor oil-modified polyol having 3 or more hydroxyl groups and a polyether polyol having 3 or more hydroxyl groups are preferable from the viewpoint of sustained release performance.

 ポリオール成分に水酸基を3以上有する化合物が含まれる場合、ポリオール成分における水酸基を3以上有する化合物の含有量は、徐放性能の観点からは、ポリオール成分の全量基準で、2重量%以上であってよく、3重量%以上であってよく、あるいは8重量%以上であってよい。水酸基を3つ以上有する化合物の含有量は、徐放性能の観点からは、ポリオール成分の全量基準で、87重量%以下であってよく、80重量%以下であってよく、76重量%以下であってよく、60重量%以下であってよく、40重量%以下であってよく、あるいは20重量%以下であってよい。 When the polyol component contains a compound having 3 or more hydroxyl groups, the content of the compound having 3 or more hydroxyl groups in the polyol component is 2% by weight or more based on the total amount of the polyol component from the viewpoint of sustained release performance. It may be 3% by weight or more, or 8% by weight or more. The content of the compound having three or more hydroxyl groups may be 87% by weight or less, 80% by weight or less, and 76% by weight or less based on the total amount of the polyol component from the viewpoint of sustained release performance. It may be 60% by weight or less, 40% by weight or less, or 20% by weight or less.

 一態様において、ポリオール成分は、ヒマシ油変性ジオールと、炭素数2~8のアルキレンジオールと、水酸基を3以上有する化合物との混合物であってよい。
 この態様において、ポリオール成分の全量に対するヒマシ油変性ジオールの量は、徐放性能の観点からは、7重量%以上であってよく、10重量%以上であることが好ましく、あるいは、30重量%以上であってよく、50重量%以上であってよく、または65重量%以上であってよい。ヒマシ油変性ジオールの量は、徐放性能の観点からは、93重量%以下であってよく、あるいは80重量%以下であることが好ましい。
 また、この態様において、ポリオール成分の全量に対する炭素数2~8のアルキレンジオールの量は、徐放性能の観点からは、4重量%以上であってよく、6重量%以上であってよく、8重量%以上であることが好ましく、あるいは10重量%以上であってよい。炭素数2~8のアルキレンジオールの量は、徐放性能の観点からは、25重量%以下であってよく、21重量%以下であってよく、20重量%以下であってよく、18重量%以下であってよく、あるいは15重量%以下であることが好ましい。さらに、この態様において、ポリオール成分の全量に対する1分子当たりの水酸基を3以上有する化合物の量は、徐放性能の観点からは、2重量%以上であってよく、8重量%以上であることが好ましい。1分子当たりの水酸基数が2より大きいポリオールの量は、徐放性能の観点からは、87重量%以下であってよく、78重量%以下であることが好ましく、60重量%以下であってよく、40重量%以下であってよく、あるいは20重量%以下であってよい。
In one embodiment, the polyol component may be a mixture of castor oil-modified diol, an alkylene diol having 2 to 8 carbon atoms, and a compound having 3 or more hydroxyl groups.
In this embodiment, the amount of castor oil-modified diol with respect to the total amount of the polyol component may be 7% by weight or more, preferably 10% by weight or more, or 30% by weight or more from the viewpoint of sustained release performance. It may be 50% by weight or more, or 65% by weight or more. The amount of castor oil-modified diol may be 93% by weight or less, or preferably 80% by weight or less, from the viewpoint of sustained release performance.
Further, in this embodiment, the amount of the alkylene diol having 2 to 8 carbon atoms with respect to the total amount of the polyol component may be 4% by weight or more, 6% by weight or more, and 8 by weight, from the viewpoint of sustained release performance. It is preferably 7% by weight or more, or 10% by weight or more. The amount of the alkylene diol having 2 to 8 carbon atoms may be 25% by weight or less, 21% by weight or less, 20% by weight or less, and 18% by weight from the viewpoint of sustained release performance. It may be less than or equal to, or preferably 15% by weight or less. Further, in this embodiment, the amount of the compound having 3 or more hydroxyl groups per molecule with respect to the total amount of the polyol component may be 2% by weight or more, and may be 8% by weight or more from the viewpoint of sustained release performance. preferable. From the viewpoint of sustained release performance, the amount of the polyol having more than 2 hydroxyl groups per molecule may be 87% by weight or less, preferably 78% by weight or less, and may be 60% by weight or less. , 40% by weight or less, or 20% by weight or less.

 また、他の一態様において、ウレタン樹脂は、芳香族ポリイソシアネートを含むポリイソシアネート成分と、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール、及びポリエーテルポリオールを含むポリオール成分と、の重付加物であってよい。上記態様において、芳香族ポリイソシアネート、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール及びポリエーテルポリオールの含有量は、ポリイソシアネート成分とポリオール成分の合計量に対して、それぞれ、30~60重量%、30~60重量%、3~10重量%、あるいは2~20重量%であってよい。 In another aspect, the urethane resin is a heavy addition of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a castor oil modified diol, an alkylene diol having 2 to 8 carbon atoms, and a polyether polyol. It may be a thing. In the above embodiment, the content of the aromatic polyisocyanate, the castor oil modified diol, the alkylene diol having 2 to 8 carbon atoms and the polyether polyol is 30 to 60 weight by weight with respect to the total amount of the polyisocyanate component and the polyol component, respectively. %, 30-60% by weight, 3-10% by weight, or 2-20% by weight.

 また、他の一態様において、ウレタン樹脂は、芳香族ポリイソシアネートを含むポリイソシアネート成分と、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール及びヒマシ油変性ポリオールを含むポリオール成分と、の重付加物であってよい。上記態様において、芳香族ポリイソシアネート、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール及びヒマシ油変性ポリオールの含有量は、ポリイソシアネート成分とポリオール成分の合計量に対して、それぞれ、30~60重量%、5~60重量%、3~10重量%、あるいは5~50重量%であってよい。 In another aspect, the urethane resin is a heavy addition of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a castor oil-modified diol, an alkylene diol having 2 to 8 carbon atoms, and a castor oil-modified polyol. It may be a thing. In the above embodiment, the contents of the aromatic polyisocyanate, the castor oil-modified diol, the alkylene diol having 2 to 8 carbon atoms and the castor oil-modified polyol are 30 to 60, respectively, with respect to the total amount of the polyisocyanate component and the polyol component. It may be% by weight, 5 to 60% by weight, 3 to 10% by weight, or 5 to 50% by weight.

 また、他の一態様において、ウレタン樹脂は、芳香族ポリイソシアネートを含むポリイソシアネート成分と、ポリエーテルポリオール及びヒマシ油を含むポリオール成分と、の重付加物であってよい。上記態様において、芳香族ポリイソシアネート、ポリエーテルポリオール及びヒマシ油の含有量は、ポリイソシアネート成分とポリオール成分の合計量に対して、それぞれ、30~60重量%、5~60重量%、あるいは5~30重量%であってよい。 Further, in another embodiment, the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a polyether polyol and castor oil. In the above embodiment, the contents of the aromatic polyisocyanate, the polyether polyol and the castor oil are 30 to 60% by weight, 5 to 60% by weight, or 5 to 5 to 60% by weight, respectively, with respect to the total amount of the polyisocyanate component and the polyol component. It may be 30% by weight.

 また、他の一態様において、ウレタン樹脂は、芳香族ポリイソシアネートを含むポリイソシアネート成分と、ポリエーテルポリオールを含むポリオール成分と、の重付加物であってよい。上記態様において、芳香族ポリイソシアネート及びポリエーテルポリオールの含有量は、ポリイソシアネート成分とポリオール成分の合計量に対して、それぞれ、30~60重量%、あるいは30~60重量%であってよい。 Further, in another embodiment, the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a polyether polyol. In the above embodiment, the content of the aromatic polyisocyanate and the polyether polyol may be 30 to 60% by weight or 30 to 60% by weight, respectively, with respect to the total amount of the polyisocyanate component and the polyol component.

 また、他の一態様において、ウレタン樹脂は、芳香族ポリイソシアネートを含むポリイソシアネート成分と、ポリエーテルジオール及びポリエーテルポリオールを含むポリオール成分と、の重付加物であってよい。上記態様において、芳香族ポリイソシアネート、ポリエーテルジオール及びポリエーテルポリオールの含有量は、ポリイソシアネート成分とポリオール成分の合計量に対して、それぞれ、30~60重量%、5~30重量%、あるいは5~60重量%であってよい。 Further, in another embodiment, the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a polyether diol and a polyether polyol. In the above embodiment, the content of the aromatic polyisocyanate, the polyether diol and the polyether polyol is 30 to 60% by weight, 5 to 30% by weight, or 5 with respect to the total amount of the polyisocyanate component and the polyol component, respectively. It may be up to 60% by weight.

 また、他の一態様において、ウレタン樹脂は、脂肪族ポリイソシアネートを含むポリイソシアネート成分と、ポリエーテルジオール及びポリエーテルポリオールを含むポリオール成分と、の重付加物であってよい。上記態様において、脂肪族ポリイソシアネート、ポリエーテルジオール及びポリエーテルポリオールの含有量は、ポリイソシアネート成分とポリオール成分の合計量に対して、それぞれ、30~60重量%、5~30重量%、あるいは5~60重量%であってよい。 Further, in another embodiment, the urethane resin may be a heavy adduct of a polyisocyanate component containing an aliphatic polyisocyanate and a polyol component containing a polyether diol and a polyether polyol. In the above embodiment, the content of the aliphatic polyisocyanate, the polyether diol and the polyether polyol is 30 to 60% by weight, 5 to 30% by weight, or 5 with respect to the total amount of the polyisocyanate component and the polyol component, respectively. It may be up to 60% by weight.

 また、他の一態様において、ウレタン樹脂は、芳香族ポリイソシアネートを含むポリイソシアネート成分と、ヒマシ油変性ポリオールを含むポリオール成分と、の重付加物であってよい。上記態様において、芳香族ポリイソシアネート及びヒマシ油変性ポリオールの含有量は、ポリイソシアネート成分とポリオール成分の合計量に対して、それぞれ、20~70重量%、あるいは20~70重量%であってよい。 Further, in another embodiment, the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing a castor oil-modified polyol. In the above embodiment, the content of the aromatic polyisocyanate and the castor oil-modified polyol may be 20 to 70% by weight or 20 to 70% by weight, respectively, with respect to the total amount of the polyisocyanate component and the polyol component.

 また、他の一態様において、ウレタン樹脂は、芳香族ポリイソシアネートを含むポリイソシアネート成分と、ヒマシ油変性ジリオールを含むポリオール成分と、の重付加物であってよい。上記態様において、芳香族ポリイソシアネート及びヒマシ油変性ジリオールの含有量は、ポリイソシアネート成分とポリオール成分の合計量に対して、それぞれ、20~70重量%、あるいは20~70重量%であってよい。 Further, in another embodiment, the urethane resin may be a heavy adduct of a polyisocyanate component containing an aromatic polyisocyanate and a polyol component containing castor oil-modified diliol. In the above embodiment, the content of the aromatic polyisocyanate and the castor oil-modified diliol may be 20 to 70% by weight or 20 to 70% by weight, respectively, based on the total amount of the polyisocyanate component and the polyol component.

 また、他の一態様において、ウレタン樹脂は、30~60重量部の芳香族ポリイソシアネートと、30~60重量部のヒマシ油変性ジオール、3~10重量部の炭素数2~8のアルキレンジオール及び2~20重量部のポリエーテルポリオールと、の重付加物であってよい。 In another aspect, the urethane resin comprises 30 to 60 parts by weight of aromatic polyisocyanate, 30 to 60 parts by weight of castor oil modified diol, and 3 to 10 parts by weight of alkylene diol having 2 to 8 carbon atoms. It may be a heavy adduct of 2 to 20 parts by weight of a polyether polyol.

 また、他の一態様において、ウレタン樹脂は、30~60重量部の芳香族ポリイソシアネートと、5~60重量部のヒマシ油変性ジオール、3~10重量部の炭素数2~8のアルキレンジオール及び5~50重量部のヒマシ油変性ポリオールと、の重付加物であってよい。 In another aspect, the urethane resin comprises 30 to 60 parts by weight of aromatic polyisocyanate, 5 to 60 parts by weight of castor oil-modified diol, and 3 to 10 parts by weight of alkylene diol having 2 to 8 carbon atoms. It may be a heavy adduct of 5 to 50 parts by weight of castor oil-modified polyol.

 また、他の一態様において、ウレタン樹脂は、30~60重量部の芳香族ポリイソシアネートと、5~60重量部のポリエーテルポリオール及び5~30重量部のヒマシ油と、の重付加物であってよい。 In another aspect, the urethane resin is a heavy adduct of 30 to 60 parts by weight of aromatic polyisocyanate, 5 to 60 parts by weight of a polyether polyol and 5 to 30 parts by weight of castor oil. It's okay.

 また、他の一態様において、ウレタン樹脂は、30~60重量部の芳香族ポリイソシアネートと、30~60重量部のポリエーテルポリオールと、の重付加物であってよい。 Further, in another aspect, the urethane resin may be a heavy adduct of 30 to 60 parts by weight of an aromatic polyisocyanate and 30 to 60 parts by weight of a polyether polyol.

 また、他の一態様において、ウレタン樹脂は、30~60重量部の芳香族ポリイソシアネートと、5~30重量部のポリエーテルジオール及び5~60重量部のポリエーテルポリオールと、の重付加物であってよい。 In another embodiment, the urethane resin is a heavy adduct of 30 to 60 parts by weight of aromatic polyisocyanate, 5 to 30 parts by weight of a polyether diol and 5 to 60 parts by weight of a polyether polyol. It may be there.

 また、他の一態様において、ウレタン樹脂は、30~60重量部の脂肪族ポリイソシアネートと、5~30重量部のポリエーテルジオール及び5~60重量部のポリエーテルポリオールと、の重付加物であってよい。 In another embodiment, the urethane resin is a heavy adduct of 30 to 60 parts by weight of an aliphatic polyisocyanate, 5 to 30 parts by weight of a polyether diol, and 5 to 60 parts by weight of a polyether polyol. It may be there.

 ポリイソシアネート成分が有するイソシアネート基のモル数M1に対する、ポリオール成分が有する水酸基のモル数M2の比M2/M1は、0.7以上であることが好ましく、0.9以上であることがより好ましく、1.7以下であることが好ましく、1.5以下であることがより好ましい。比M2/M1が上記範囲である場合、優れた徐放性能が得られる傾向がある。 The ratio M2 / M1 of the number of moles of hydroxyl groups M2 of the polyol component to the number of moles of isocyanate groups M1 of the polyisocyanate component is preferably 0.7 or more, more preferably 0.9 or more. It is preferably 1.7 or less, and more preferably 1.5 or less. When the ratio M2 / M1 is in the above range, excellent sustained release performance tends to be obtained.

 本発明の被覆粒状肥料は、ウレタン樹脂被膜以外の樹脂被膜を有していてもよい。その場合、樹脂被膜全体におけるウレタン樹脂の含有量は、樹脂被膜の全量基準で80重量%以上であってよく、90重量%以上であってよく、100重量%であってよい。 The coated granular fertilizer of the present invention may have a resin film other than the urethane resin film. In that case, the content of the urethane resin in the entire resin film may be 80% by weight or more, 90% by weight or more, or 100% by weight based on the total amount of the resin film.

 被覆粒状肥料におけるウレタン樹脂の含有量は、粒状肥料100質量部に対して、1質量部以上であることが好ましく、2質量部以上であることがより好ましい。また、ウレタン樹脂の含有量は、粒状肥料100質量部に対して、20質量部以下であることが好ましく、あるいは16質量部以下であることがより好ましい。 The content of the urethane resin in the coated granular fertilizer is preferably 1 part by mass or more, and more preferably 2 parts by mass or more with respect to 100 parts by mass of the granular fertilizer. The content of the urethane resin is preferably 20 parts by mass or less, or more preferably 16 parts by mass or less, based on 100 parts by mass of the granular fertilizer.

 本発明の樹脂被覆粒状肥料の製造方法においては、ポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンを使用する。それらの成分を使用する工程としては、例えば、以下に示すものが挙げられ、本発明の樹脂被覆粒状肥料の製造方法は、これら工程を含み得る。
 ポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンを混合し、混合物を得る工程(A-1)、転動状態にある粒状肥料に工程A-1で得た混合物を添加する工程(A-2)、粒状肥料の転動状態を維持することによりポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面にウレタン樹脂被膜を形成する工程(A-3)(以下、工程A-1~A-3をまとめて「工程A」と記す場合がある。)であってもよい。
 ポリイソシアネート成分とポリオール成分とを混合し、混合物を得る工程(B-1)、転動状態にある粒状肥料に工程B-1で得た混合物とジアザビシクロノネンとを別々に添加する工程(B-2)、粒状肥料の転動状態を維持することによりポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面にウレタン樹脂被膜を形成する工程(B-3)(以下、工程B-1~B~3をまとめて「工程B」と記す場合がある。)であってよい。
 ポリオール成分とジアザビシクロノネンとを混合し、混合物を得る工程(C-1)、転動状態にある粒状肥料に工程C-1で得た混合物とポリイソシアネート成分とを別々に添加する工程(C-2)、粒状肥料の転動状態を維持することによりポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面にウレタン樹脂被膜を形成する工程(C-3)(以下、工程C-1~C-3をまとめて「工程C」と記す場合がある。)であってもよい。
 転動状態にある粒状肥料に、ポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンを別々に添加する工程(D-1)、粒状肥料の転動状態を維持することによりポリイソシアネート成分とポリオール成分とを重付加させて粒状肥料の表面にウレタン樹脂被膜を形成する工程(D-2)(以下、工程D-1~D-2をまとめて「工程D」と記す場合がある。)であってもよい。ポリイソシアネート成分、ポリオール成分、ジアザビシクロノネンを別々に添加する場合、その添加順序は、ポリイソシアネート成分、ポリオール成分、およびジアザビシクロノネンの順、ポリオール成分、ポリイソシアネート成分、およびジアザビシクロノネンの順、ポリオール成分、ジアザビシクロノネン、およびポリイソシアネート成分の順、ポリイソシアネート成分、ジアザビシクロノネン、およびポリオール成分の順、ジアザビシクロノネン、ポリイソシアネート成分、およびポリオール成分の順、あるいはジアザビシクロノネン、ポリオール成分、およびポリイソシアネート成分の順のいずれであってもよい。
 工程Aを実施する際の温度は、使用するポリイソシアネート成分及びポリオール成分の種類や粒状肥料の大きさ等に応じて適宜設定されるものであるが、粒状肥料を転動状態とする回転槽内の温度として、通常40~100℃の範囲であり、好ましくは55~75℃の範囲である。また、ポリイソシアネート成分とポリオール成分及びジアザビシクロノネンの混合物の添加後、ポリイソシアネート成分とポリオール成分との重付加が進行してウレタンが硬化し、樹脂被覆粒状物同士の付着が生じなくなる程度まで粒状肥料の転動状態は維持されるが、転動状態を維持する時間は通常1~30分間程度、製造効率の観点から、好ましくは1~20分間程度である。
 工程Bを実施する際の温度は、使用するポリイソシアネート成分及びポリオール成分の種類や粒状肥料の大きさ等に応じて適宜設定されるものであるが、粒状肥料を転動状態とする回転槽内の温度として、通常40~100℃の範囲であり、好ましくは55~75℃の範囲である。また、ポリイソシアネート成分とポリオール成分の混合物とジアザビシクロノネンの添加後、ポリイソシアネート成分とポリオール成分との重付加が進行してウレタンが硬化し、樹脂被覆粒状物同士の付着が生じなくなる程度まで粒状肥料の転動状態は維持されるが、転動状態を維持する時間は通常2~40分間程度、製造効率の観点から、好ましくは2~30分間程度である。
 工程Cを実施する際の温度は、使用するポリイソシアネート成分及びポリオール成分の種類や粒状肥料の大きさ等に応じて適宜設定されるものであるが、粒状肥料を転動状態とする回転槽内の温度として、通常40~100℃の範囲であり、好ましくは55~75℃の範囲である。また、ポリオール成分とジアザビシクロノネンの混合物と、ポリイソシアネート成分の添加後、ポリイソシアネート成分とポリオール成分との重付加が進行してウレタンが硬化し、樹脂被覆粒状物同士の付着が生じなくなる程度まで粒状肥料の転動状態は維持されるが、転動状態を維持する時間は通常は2~40分間程度、製造効率の点からは2~30分間程度である。
 工程Dを実施する際の温度は、使用するポリイソシアネート成分及びポリオール成分の種類や粒状肥料の大きさ等に応じて適宜設定されるものであるが、粒状肥料を転動状態とする回転槽内の温度として、通常40~100℃の範囲であり、好ましくは55~75℃の範囲である。また、ポリイソシアネート成分、ポリオール成分及びジアザビシクロノネンの添加後、ポリイソシアネート成分とポリオール成分と重付加の重付加が進行してウレタンが硬化し、樹脂被覆粒状物同士の付着が生じなくなる程度まで粒状肥料の転動状態は維持されるが、転動状態を維持する時間は通常は2~40分間程度、製造効率の点からは2~30分間程度である。
In the method for producing a resin-coated granular fertilizer of the present invention, a polyisocyanate component, a polyol component, and diazabicyclononen are used. Examples of the steps using these components include those shown below, and the method for producing a resin-coated granular fertilizer of the present invention may include these steps.
A step of mixing a polyisocyanate component, a polyol component, and diazabicyclononen to obtain a mixture (A-1), and a step of adding the mixture obtained in step A-1 to a granular fertilizer in a rolling state (A-2). ), A step of forming a urethane resin film on the surface of the granular fertilizer by adding a polyisocyanate component and a polyol component in a layered manner by maintaining the rolling state of the granular fertilizer (A-3) (hereinafter, step A-1). ~ A-3 may be collectively referred to as “process A”).
A step of mixing the polyisocyanate component and the polyol component to obtain a mixture (B-1), and a step of separately adding the mixture obtained in step B-1 and diazabicyclononen to the granular fertilizer in a rolling state (B-1). B-2), a step (B-3) (hereinafter referred to as a step) of forming a urethane resin film on the surface of the granular fertilizer by repeatedly adding a polyisocyanate component and a polyol component by maintaining the rolling state of the granular fertilizer. B-1 to B to 3 may be collectively referred to as "process B").
A step of mixing the polyol component and diazabicyclononen to obtain a mixture (C-1), and a step of separately adding the mixture obtained in step C-1 and the polyisocyanate component to the granular fertilizer in a rolling state (C-1). C-2), a step (C-3) (hereinafter referred to as a step) of forming a urethane resin film on the surface of the granular fertilizer by repeatedly adding a polyisocyanate component and a polyol component by maintaining the rolling state of the granular fertilizer. C-1 to C-3 may be collectively referred to as "process C").
The step of separately adding the polyisocyanate component, the polyol component, and diazabicyclononen to the granular fertilizer in the rolling state (D-1), and the polyisocyanate component and the polyol component by maintaining the rolling state of the granular fertilizer. (D-2) (hereinafter, steps D-1 to D-2 may be collectively referred to as "step D") to form a urethane resin film on the surface of the granular fertilizer. May be. When the polyisocyanate component, the polyol component, and the diazabicyclononen are added separately, the order of addition is the polyisocyanate component, the polyol component, and the diazabicyclononen, the polyol component, the polyisocyanate component, and the diazabicyclononen. , Polyol component, diazabicyclononen, and polyisocyanate component, polyisocyanate component, diazabicyclononen, and polyol component, diazabicyclononen, polyisocyanate component, and polyol component, or diah. It may be any of the order of the zabicyclononen, the polyol component, and the polyisocyanate component.
The temperature at which the step A is carried out is appropriately set according to the types of the polyisocyanate component and the polyol component used, the size of the granular fertilizer, and the like, but in a rotary tank in which the granular fertilizer is in a rolling state. The temperature is usually in the range of 40 to 100 ° C, preferably in the range of 55 to 75 ° C. Further, after the addition of the mixture of the polyisocyanate component, the polyol component and the diazabicyclononene, the heavy addition of the polyisocyanate component and the polyol component progresses to cure the urethane, and the resin-coated granules do not adhere to each other. Although the rolling state of the granular fertilizer is maintained, the time for maintaining the rolling state is usually about 1 to 30 minutes, preferably about 1 to 20 minutes from the viewpoint of production efficiency.
The temperature at which step B is carried out is appropriately set according to the types of the polyisocyanate component and the polyol component used, the size of the granular fertilizer, and the like, but in a rotary tank in which the granular fertilizer is in a rolling state. The temperature is usually in the range of 40 to 100 ° C, preferably in the range of 55 to 75 ° C. Further, after the addition of the mixture of the polyisocyanate component and the polyol component and diazabicyclononen, the heavy addition of the polyisocyanate component and the polyol component proceeds to cure the urethane, and the resin-coated granules do not adhere to each other. Although the rolling state of the granular fertilizer is maintained, the time for maintaining the rolling state is usually about 2 to 40 minutes, preferably about 2 to 30 minutes from the viewpoint of production efficiency.
The temperature at which step C is carried out is appropriately set according to the types of the polyisocyanate component and the polyol component used, the size of the granular fertilizer, and the like, but in a rotary tank in which the granular fertilizer is in a rolling state. The temperature is usually in the range of 40 to 100 ° C, preferably in the range of 55 to 75 ° C. Further, after the addition of the mixture of the polyol component and the diazabicyclononen and the polyisocyanate component, the heavy addition of the polyisocyanate component and the polyol component proceeds to cure the urethane, and the resin-coated granules do not adhere to each other. The rolling state of the granular fertilizer is maintained until, but the time for maintaining the rolling state is usually about 2 to 40 minutes, and from the viewpoint of production efficiency, it is about 2 to 30 minutes.
The temperature at which step D is carried out is appropriately set according to the types of the polyisocyanate component and the polyol component used, the size of the granular fertilizer, and the like, but in a rotary tank in which the granular fertilizer is in a rolling state. The temperature is usually in the range of 40 to 100 ° C, preferably in the range of 55 to 75 ° C. Further, after the addition of the polyisocyanate component, the polyol component and diazabicyclononen, the polyisocyanate component, the polyol component and the heavy addition proceed to the extent that the urethane is cured and the resin-coated granules do not adhere to each other. The rolling state of the granular fertilizer is maintained, but the time for maintaining the rolling state is usually about 2 to 40 minutes, and from the viewpoint of production efficiency, it is about 2 to 30 minutes.

 本発明の被覆粒状肥料は、前記工程A~Dのいずれを含む製造方法によって製造することができるが、樹脂被膜の均質性の観点からは、工程Aが好ましい。 The coated granular fertilizer of the present invention can be produced by a production method including any of the above steps A to D, but step A is preferable from the viewpoint of homogeneity of the resin film.

 本発明の樹脂被覆粒状肥料の製造方法においては、前記工程A~Dのいずれかを1回だけ行ってもよい。また、前記工程A~Dのいずれかにより得られる樹脂被覆粒状物に、前記工程A~Dのいずれかを更に1回以上繰り返してもよい(以下、「工程E」と記す場合がある)。ここで、繰り返して追加する工程A~Dは、先に行った1回または複数回の工程A~Dとは互いに、同じであってもよく、または相異なってもよい。工程Eを行う回数を調整することにより、樹脂被膜の厚みを調整することができる。
 工程Eは、その前の工程における粒状肥料の転動状態を維持したまま、続けて実施してもよい。工程Eにおいて用いられるポリイソシアネート成分及びポリオール成分は、その前の工程で用いられたポリイソシアネート成分及びポリオール成分と同種でも相異なっていてもよいが、製造効率の点から、通常は同種のポリイソシアネート成分及びポリオール成分が用いられる。
In the method for producing a resin-coated granular fertilizer of the present invention, any one of the above steps A to D may be performed only once. Further, any of the steps A to D may be repeated once or more on the resin-coated granules obtained by any of the steps A to D (hereinafter, may be referred to as "step E"). Here, the steps A to D to be added repeatedly may be the same as or different from the one-time or a plurality of steps A to D performed earlier. By adjusting the number of times the step E is performed, the thickness of the resin film can be adjusted.
Step E may be continuously carried out while maintaining the rolling state of the granular fertilizer in the previous step. The polyisocyanate component and the polyol component used in the step E may be the same as or different from the polyisocyanate component and the polyol component used in the previous step, but are usually of the same type from the viewpoint of production efficiency. Ingredients and polyol components are used.

 本発明の樹脂被覆粒状肥料の製造方法に用いられるポリオール成分とポリイソシアネート成分の合計量は、用いられる粒状肥料の大きさ、形状及び製造される樹脂被覆粒状肥料に求められる溶出制御の程度により適宜設定されるものであるが、工程A~工程D、及び、必要に応じて行われる工程Eで用いられるポリオール成分とポリイソシアネートの合計量で、粒状肥料100重量部に対して通常2~30重量部程度、好ましくは4~18重量部程度である。 The total amount of the polyol component and the polyisocyanate component used in the method for producing a resin-coated granular fertilizer of the present invention is appropriately determined depending on the size and shape of the granular fertilizer used and the degree of elution control required for the resin-coated granular fertilizer to be produced. Although it is set, it is the total amount of the polyol component and the polyisocyanate used in steps A to D and, if necessary, step E, and is usually 2 to 30 weights per 100 parts by weight of granular fertilizer. About parts, preferably about 4 to 18 parts by weight.

 粒状肥料を転動状態とする方法としては、特に装置に制限はなく公知、慣用のものを用いることができる。かかる装置としては、例えば、コンクリートミキサー、およびドラムミキサーなどが挙げられる。なお、上記装置のうち、加温設備を備えた装置は、本発明の製造方法における高精度化や加工時間の調整が可能であることから、好適に使用される。 As a method for putting the granular fertilizer into a rolling state, there is no particular limitation on the device, and known and conventional ones can be used. Examples of such an apparatus include a concrete mixer and a drum mixer. Among the above-mentioned devices, the device equipped with the heating equipment is preferably used because it is possible to improve the accuracy and adjust the processing time in the manufacturing method of the present invention.

 本発明の被覆粒状肥料は、ポリイソシアネート成分とポリオール成分との重付加物であるウレタン樹脂とジアザビシクロノネンとを含む樹脂被膜以外の樹脂被膜を更に含んでいてもよい。かかる樹脂被膜としては、例えば、任意のポリイソシアネート成分と任意のポリオール成分との重付加物であるウレタン樹脂を含み、ジアザビシクロノネンを含まない被膜が挙げられる。
 樹脂被膜は、ウレタン樹脂とジアザビシクロノネン以外の成分を更に含んでよい。例えば、有機溶媒、水等の溶剤を含んでいてよく、これらはウレタン樹脂の製造時に使用された溶剤であってよい。また、樹脂被膜は、顔料、染料、抗菌剤、防腐剤、可塑剤、分解促進剤及び前記した担体等を目的に応じて更に含んでいてよい。
The coated granular fertilizer of the present invention may further contain a resin film other than the resin film containing urethane resin and diazabicyclononen, which are heavy adducts of the polyisocyanate component and the polyol component. Examples of such a resin film include a film containing urethane resin, which is a heavy adduct of an arbitrary polyisocyanate component and an arbitrary polyol component, and not containing diazabicyclononen.
The resin film may further contain components other than the urethane resin and diazabicyclononen. For example, it may contain a solvent such as an organic solvent and water, and these may be the solvents used in the production of the urethane resin. Further, the resin film may further contain a pigment, a dye, an antibacterial agent, a preservative, a plasticizer, a decomposition accelerator, the above-mentioned carrier and the like, depending on the purpose.

 本発明の被覆粒状肥料は、粒状肥料及び樹脂被膜以外の他の成分(例えば、浮上防止材、固結防止材、農薬有効成分及びWAX類等)を更に含んでいてもよい。 The coated granular fertilizer of the present invention may further contain components other than the granular fertilizer and the resin film (for example, antifloating material, anti-caking material, pesticide active ingredient, waxes, etc.).

 本発明の被覆粒状肥料は、沸点が100℃以上の疎水性液状化合物(以下、「本疎水性液状化合物」とも称する。)を更に含んでいてよい。本発明において、本疎水性液状化合物とは、20℃において流動性を有し、20℃における水溶解度が10ppm以下である化合物を意味する。本疎水性液状化合物は、粒状肥料中に含有されていてよく、粒状肥料を被覆する被膜として存在していてもよい。本疎水性液状化合物が被膜として存在する場合、当該被膜は、粒状肥料の表面に直接形成されていてよく、粒状肥料を被覆する樹脂被膜上に形成されていてもよい。 The coated granular fertilizer of the present invention may further contain a hydrophobic liquid compound having a boiling point of 100 ° C. or higher (hereinafter, also referred to as "the present hydrophobic liquid compound"). In the present invention, the present hydrophobic liquid compound means a compound having fluidity at 20 ° C. and having a water solubility at 20 ° C. of 10 ppm or less. The present hydrophobic liquid compound may be contained in the granular fertilizer and may be present as a film covering the granular fertilizer. When the present hydrophobic liquid compound is present as a film, the film may be formed directly on the surface of the granular fertilizer, or may be formed on the resin film covering the granular fertilizer.

 本疎水性化合物は、例えば、粒状肥料を転動状態とする装置を用いて樹脂被覆粒状肥料を製造する際に配合される。本疎水性化合物としては、例えば、流動パラフィン等の脂肪族炭化水素、フェニルキシリルエタン、アルキルベンゼン(具体的には、Solvesso150、エクソンモービルケミカル製)等の芳香族炭化水素などが挙げられる。樹脂被覆粒状肥料における疎水性液状化合物の含有量は、粒状肥料100質量部に対して、0.1~5質量部であってよい。 This hydrophobic compound is blended, for example, when producing a resin-coated granular fertilizer using an apparatus that puts the granular fertilizer in a rolling state. Examples of the hydrophobic compound include aliphatic hydrocarbons such as liquid paraffin, aromatic hydrocarbons such as phenylxysilylethane and alkylbenzene (specifically, Solvesso150, manufactured by Exxon Mobile Chemical). The content of the hydrophobic liquid compound in the resin-coated granular fertilizer may be 0.1 to 5 parts by mass with respect to 100 parts by mass of the granular fertilizer.

 樹脂被膜は粒状肥料の表面に直接形成されていてよい。樹脂被膜以外の被膜(例えば、上述の疎水性液状化合物の被膜)が粒状肥料表面に形成されている場合には、当該被膜上に樹脂被膜が形成されていてもよい。 The resin film may be formed directly on the surface of the granular fertilizer. When a film other than the resin film (for example, a film of the above-mentioned hydrophobic liquid compound) is formed on the surface of the granular fertilizer, a resin film may be formed on the film.

 樹脂被膜は、粒状肥料の表面全体を覆うように形成されていてよく、あるいは粒状肥料の表面の一部を覆うように形成されていてもよい。 The resin film may be formed so as to cover the entire surface of the granular fertilizer, or may be formed so as to cover a part of the surface of the granular fertilizer.

 樹脂被膜の厚みは、樹脂被覆粒状肥料の用途及び使用目的等に応じて適宜選択できる。樹脂被膜の厚みは、例えば8μm以上であってよく、好ましくは10μm以上であってよい。また、樹脂被膜の厚みは、例えば400μm以下であってよく、好ましくは200μm以下であってよい。ある実施態様によれば、樹脂被膜の厚みは、8μm以上、且つ4200μm以下であり、8μm以上、且つ200μm以下であり、10μm以上、且つ400μm以下であり、あるいは、10μm以上、且つ200μm以下である。なお、本明細書中、樹脂被膜の厚みは、樹脂被覆粒状肥料の断面の走査型電子顕微鏡(SEM)観察によって測定される値を示す。樹脂被膜の厚みは、例えば、10箇所の厚みの測定値の平均値として表すこともできる。樹脂被膜の厚みを調整することで、例えば肥料成分の溶出量及び溶出曲線の形を調整することができる。 The thickness of the resin coating can be appropriately selected according to the use and purpose of use of the resin-coated granular fertilizer. The thickness of the resin film may be, for example, 8 μm or more, preferably 10 μm or more. The thickness of the resin film may be, for example, 400 μm or less, preferably 200 μm or less. According to one embodiment, the thickness of the resin coating is 8 μm or more and 4200 μm or less, 8 μm or more and 200 μm or less, 10 μm or more and 400 μm or less, or 10 μm or more and 200 μm or less. .. In the present specification, the thickness of the resin coating indicates a value measured by a scanning electron microscope (SEM) observation of a cross section of the resin-coated granular fertilizer. The thickness of the resin film can also be expressed as, for example, the average value of the measured values of the thicknesses at 10 points. By adjusting the thickness of the resin film, for example, the elution amount of the fertilizer component and the shape of the elution curve can be adjusted.

 被覆粒状肥料の粒径は、被覆粒状肥料の用途及び使用目的等に応じて適宜選択できる。例えば、被覆粒径肥料の平均粒径は、0.1~15mmであってよく、あるいは1~5mmであってよい。なお、本明細書中において、被覆粒状肥料の平均粒径は、投影面積円相当径の算術平均値と定義され、顕微鏡法などで測定される。 The particle size of the coated granular fertilizer can be appropriately selected according to the intended use and purpose of use of the coated granular fertilizer. For example, the average particle size of the coated particle size fertilizer may be 0.1 to 15 mm, or may be 1 to 5 mm. In the present specification, the average particle size of the coated granular fertilizer is defined as an arithmetic mean value of the diameter corresponding to the projected area circle, and is measured by a microscope method or the like.

 次に本発明を製造例等の実施例により、さらに詳細に説明するが、本発明はこれらの例のみに限定されるものではない。 Next, the present invention will be described in more detail with reference to examples such as manufacturing examples, but the present invention is not limited to these examples.

製造例1
 ヒマシ油変性ジオール(伊藤製油株式会社製、商品名:URIC H-62、1分子当たりの水酸基数:2、水酸基価:274) 、ヒマシ油変性ポリオール(伊藤製油株式会社製、商品名:URIC H-73X、1分子当たりの水酸基数:3、水酸基価:270)、1,4-ブタンジオール(BASF出光株式会社製、商品名:1,4-BDO) を67.8 :20.8:11.4の重量比にて任意の量で、室温で混合し、ポリオール混合物Aを得た。次いで、得られたポリオール混合物A2677.08g、及びジアザビシクロノネン(サンアプロ株式会社、商品名:DBN)2.50gを室温で混合し、ポリオール混合物Iを得た。
 粒状尿素(大粒尿素、粒径約3mm、球状、1g当たりの粒数約60個)50,000gをコンクリートミキサーに仕込み、転動状態とした。転動状態の該粒状尿素を熱風発生装置の熱風を当てることにより約66℃まで加熱した後、流動パラフィン(松村石油研究所製、商品名:モレスコホワイトP-350P、37.78℃における動粘度:76mm/S)500gを添加し、3分間転動状態を維持した。次いで、50℃に加温した前記ポリオール混合物I 267.96gと、50℃に加温した芳香族ジイソシアネート(住化バイエルウレタン製、商品名:SBUイソシアネートJ243)232.29gとを素早く撹拌混合して得た混合物を、転動状態の粒状尿素に添加し、7分間以上、熱風発生装置の熱風を当てながら転動状態を維持した。ポリオール混合物Iと芳香族ジイソシアネートの混合物の総添加量が5,002.5gになるまで、上記操作(ポリオール混合物Iと芳香族ジイソシアネートとの撹拌混合、転動状態の粒状尿素への混合物の添加、及び、転動状態の維持)を繰り返し、本発明の被覆粒状肥料を得た。
 上記製造工程において、粒状物同士の顕著な凝集及びコンクリートミキサー内壁への粒状物の付着は観察されず、コンクリートミキサー内での粒状物の転動状態は良好であった。また、上記製造工程により得られた被覆粒状肥料を目視観察したところ、被覆状態は均一であった。
Production Example 1
Himashi oil-modified diol (manufactured by Ito Oil Co., Ltd., trade name: URIC H-62, number of hydroxyl groups per molecule: 2, hydroxyl value: 274), Himashi oil-modified polyol (manufactured by Ito Oil Co., Ltd., trade name: URIC H) -73X, number of hydroxyl groups per molecule: 3, hydroxyl value: 270), 1,4-butanediol (manufactured by BASF Idemitsu Co., Ltd., trade name: 1,4-BDO) 67.8: 20.8: 11 The mixture was mixed in an arbitrary amount at a weight ratio of 4 at room temperature to obtain a polyol mixture A. Then, 2677.08 g of the obtained polyol mixture and 2.50 g of diazabicyclononen (trade name: DBN) were mixed at room temperature to obtain a polyol mixture I.
50,000 g of granular urea (large-grain urea, particle size of about 3 mm, spherical shape, about 60 grains per 1 g) was charged into a concrete mixer and put into a rolling state. The granular urea in a rolling state is heated to about 66 ° C. by applying hot air from a hot air generator, and then liquid paraffin (manufactured by Matsumura Petroleum Research Institute, trade name: Moresco White P-350P, 37.78 ° C.). Viscosity: 76 mm 2 / S) 500 g was added and the rolling state was maintained for 3 minutes. Next, 267.96 g of the polyol mixture I heated to 50 ° C. and 232.29 g of aromatic diisocyanate (manufactured by Sumika Bayer Urethane, trade name: SBU isocyanate J243) heated to 50 ° C. are quickly stirred and mixed. The obtained mixture was added to the granular urea in the rolling state, and the rolling state was maintained while applying hot air from the hot air generator for 7 minutes or more. The above operation (stirring and mixing of polyol mixture I and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, until the total addition amount of the mixture of polyol mixture I and aromatic diisocyanate reaches 5,002.5 g, And maintenance of the rolling state) was repeated to obtain the coated granular fertilizer of the present invention.
In the above manufacturing process, no remarkable agglomeration of the granules and adhesion of the granules to the inner wall of the concrete mixer were observed, and the rolling state of the granules in the concrete mixer was good. Moreover, when the coated granular fertilizer obtained by the above manufacturing process was visually observed, the coated state was uniform.

製造例2
 粒状尿素(大粒尿素、粒径約3mm、球状、1g当たりの粒数約60個)50,000gをコンクリートミキサーに仕込み、転動状態とした。転動状態の該粒状尿素を熱風発生装置の熱風を当てることにより約66℃まで加熱した後、流動パラフィン(松村石油研究所製、商品名:モレスコホワイトP-350P、37.78℃における動粘度:76mm/S)500gを添加し、3分間転動状態を継続した。次いで、50℃に加温した前記ポリオール混合物I200.97gと、50℃に加温した芳香族ジイソシアネート(住化バイエルウレタン製、商品名:SBUイソシアネートJ243)174.22gとを素早く撹拌混合して得た混合物を、転動状態の粒状尿素に添加し、6分間以上、熱風発生装置の熱風を当てながら転動状態を維持した。ポリオール混合物Iと芳香族ジイソシアネートの混合物の総添加量が4,877.47gになるまで、上記操作(ポリオール混合物Iと芳香族ジイソシアネートとの撹拌混合、転動状態の粒状尿素への混合物の添加、及び、転動状態の維持)を繰り返し、本発明の被覆粒状肥料を得た。
 上記製造工程を通じて、粒状物同士の顕著な凝集及びコンクリートミキサー内壁への粒状物の付着は観察されず、コンクリートミキサー内での粒状物の転動状態は良好であった。また、上記製造工程により得られた被覆粒状肥料を目視観察したところ、被覆状態は均一であった。
Manufacturing example 2
50,000 g of granular urea (large-grain urea, particle size of about 3 mm, spherical shape, about 60 grains per 1 g) was charged into a concrete mixer and put into a rolling state. The granular urea in a rolling state is heated to about 66 ° C. by applying hot air from a hot air generator, and then liquid paraffin (manufactured by Matsumura Petroleum Research Institute, trade name: Moresco White P-350P, 37.78 ° C.). Viscosity: 76 mm 2 / S) 500 g was added, and the rolling state was continued for 3 minutes. Next, the polyol mixture I heated to 50 ° C. I200.97 g and aromatic diisocyanate (manufactured by Sumika Bayer Urethane, trade name: SBU isocyanate J243) 174.22 g heated to 50 ° C. were quickly stirred and mixed to obtain the mixture. The mixture was added to the granular urea in the rolling state, and the rolling state was maintained while applying hot air from the hot air generator for 6 minutes or more. The above operation (stirring mixing of polyol mixture I and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, until the total addition amount of the mixture of polyol mixture I and aromatic diisocyanate reaches 4,877.47 g, And maintenance of the rolling state) was repeated to obtain the coated granular fertilizer of the present invention.
Through the above manufacturing process, no remarkable agglomeration of the granules and adhesion of the granules to the inner wall of the concrete mixer were observed, and the rolling state of the granules in the concrete mixer was good. Moreover, when the coated granular fertilizer obtained by the above manufacturing process was visually observed, the coated state was uniform.

製造例3
 ポリオール混合物A2677.08g、及びジアザビシクロノネン(サンアプロ株式会社、商品名:DBN)3.50gを室温で混合し、ポリオール混合物IIを得た。
 粒状尿素(大粒尿素、粒径約3mm、球状、1g当たりの粒数約60個)50,000gをコンクリートミキサーに仕込み、転動状態とした。転動状態の該粒状尿素を熱風発生装置の熱風を当てることにより約66℃まで加熱した後、流動パラフィン(松村石油研究所製、商品名:モレスコホワイトP-350P、37.78℃における動粘度:76mm/S)500gを添加し、3分間転動状態を継続した。次いで、50℃に加温した前記ポリオール混合物II268.06gと、50℃に加温した芳香族ジイソシアネート(住化バイエルウレタン製、商品名:SBUイソシアネートJ243)232.29gとを素早く撹拌混合して得た混合物を、転動状態の粒状尿素に添加し、7分間以上、熱風発生装置の熱風を当てながら転動状態を維持した。ポリオール混合物II及び芳香族ジイソシアネートの混合物の総添加量が5,003.5gになるまで、上記操作(ポリオール混合物IIと芳香族ジイソシアネートとの撹拌混合、転動状態の粒状尿素への混合物の添加、及び、転動状態の維持)を繰り返し、本発明の被覆粒状肥料を得た。
 上記製造工程を通じて、粒状物同士の顕著な凝集及びコンクリートミキサー内壁への粒状物の付着は観察されず、コンクリートミキサー内での粒状物の転動状態は良好であった。また、上記製造工程により得られた被覆粒状肥料を目視観察したところ、被覆状態は均一であった。
Production example 3
A polyol mixture A2677.08 g and diazabicyclononen (San Apro Co., Ltd., trade name: DBN) 3.50 g were mixed at room temperature to obtain a polyol mixture II.
50,000 g of granular urea (large-grain urea, particle size of about 3 mm, spherical shape, about 60 grains per 1 g) was charged into a concrete mixer and put into a rolling state. The granular urea in a rolling state is heated to about 66 ° C. by applying hot air from a hot air generator, and then liquid paraffin (manufactured by Matsumura Petroleum Research Institute, trade name: Moresco White P-350P, 37.78 ° C.). Viscosity: 76 mm 2 / S) 500 g was added, and the rolling state was continued for 3 minutes. Next, 268.06 g of the polyol mixture heated to 50 ° C. and 232.29 g of aromatic diisocyanate (manufactured by Sumika Bayer Urethane, trade name: SBU isocyanate J243) heated to 50 ° C. are quickly stirred and mixed. The mixture was added to the granular urea in the rolling state, and the rolling state was maintained while applying hot air from the hot air generator for 7 minutes or more. The above operation (stirring and mixing of polyol mixture II and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, until the total addition amount of the mixture of polyol mixture II and aromatic diisocyanate reaches 5,003.5 g, And maintenance of the rolling state) was repeated to obtain the coated granular fertilizer of the present invention.
Through the above manufacturing process, no remarkable agglomeration of the granules and adhesion of the granules to the inner wall of the concrete mixer were observed, and the rolling state of the granules in the concrete mixer was good. Moreover, when the coated granular fertilizer obtained by the above manufacturing process was visually observed, the coated state was uniform.

比較製造例1
 粒状尿素(大粒尿素、粒径約3mm、球状、1g当たりの粒数約60個)50,000gをコンクリートミキサーに仕込み、転動状態とした。転動状態の該粒状尿素を熱風発生装置の熱風を当てることにより約66℃まで加熱した後、流動パラフィン(松村石油研究所製、商品名:モレスコホワイトP-350P、37.78℃における動粘度:76mm/S)500gを添加し、3分間転動状態を継続した。次いで、50℃に加温した前記ポリオール混合物A267.71gと、50℃に加温した芳香族ジイソシアネート(住化バイエルウレタン製、商品名:SBUイソシアネートJ243)232.29gとを素早く撹拌混合して得た混合物を、転動状態の粒状尿素に添加し、9分間以上、熱風発生装置の熱風を当てながら転動状態を維持した。ポリオール混合物Aと芳香族ジイソシアネートの混合物の総添加量が5,000.0gになるまで、上記操作(ポリオール混合物Aと芳香族ジイソシアネートとの撹拌混合、転動状態の粒状尿素への混合物の添加、及び、転動状態の維持)を繰り返し、比較用の被覆粒状肥料を得た。
 上記製造工程において、粒状物同士の凝集した塊状物が一部で見られ、コンクリートミキサー内での粒状物の転動状態は充分ではなかった。
Comparative manufacturing example 1
50,000 g of granular urea (large-grain urea, particle size of about 3 mm, spherical shape, about 60 grains per 1 g) was charged into a concrete mixer and put into a rolling state. The granular urea in a rolling state is heated to about 66 ° C. by applying hot air from a hot air generator, and then liquid paraffin (manufactured by Matsumura Petroleum Research Institute, trade name: Moresco White P-350P, 37.78 ° C.). Viscosity: 76 mm 2 / S) 500 g was added, and the rolling state was continued for 3 minutes. Next, 267.71 g of the polyol mixture heated to 50 ° C. and 232.29 g of aromatic diisocyanate (manufactured by Sumika Bayer Urethane, trade name: SBU isocyanate J243) heated to 50 ° C. are quickly stirred and mixed. The mixture was added to the granular urea in the rolling state, and the rolling state was maintained while applying hot air from the hot air generator for 9 minutes or more. The above operation (stirring and mixing of polyol mixture A and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, until the total addition amount of the mixture of polyol mixture A and aromatic diisocyanate reaches 5,000.0 g, And maintenance of the rolling state) was repeated to obtain a coated granular fertilizer for comparison.
In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.

比較製造例2
 ポリオール混合物A 2677.08g、及びエチレンアミン誘導品(東ソー株式会社、商品名:TOYOCAT-DB30)2.50gを室温で混合してポリオール混合物IIIを得た。
 ポリオール混合物Iの代わりに、ポリオール混合物IIIを用いた以外は、製造例1と同様の操作を行い、比較用の被覆粒状肥料を得た。
 上記製造工程において、粒状物同士の凝集した塊状物が一部で見られ、コンクリートミキサー内での粒状物の転動状態は充分ではなかった。
Comparative manufacturing example 2
A polyol mixture A 2677.08 g and an ethyleneamine derivative (Tosoh Corporation, trade name: TOYOCAT-DB30) 2.50 g were mixed at room temperature to obtain a polyol mixture III.
The same operation as in Production Example 1 was carried out except that the polyol mixture III was used instead of the polyol mixture I, and a coated granular fertilizer for comparison was obtained.
In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.

比較製造例3
 ポリオール混合物A 2677.08g、及び1,8-ジアザビシクロ(5.4.0)ウンデセン-7(サンアプロ株式会社、商品名:DBU(登録商標))2.50gを室温で混合してポリオール混合物IVを得た。
 ポリオール混合物Iの代わりに、ポリオール混合物IVを用いた以外は、製造例1と同様の操作を行い、比較用の被覆粒状肥料を得た。
 上記製造工程において、粒状物同士の凝集した塊状物が一部で見られ、コンクリートミキサー内での粒状物の転動状態は充分ではなかった。
Comparative manufacturing example 3
Mixture A 2677.08 g and 2.50 g of 1,8-diazabicyclo (5.4.0) Undecen-7 (San Apro Co., Ltd., trade name: DBU®) at room temperature to obtain a polyol mixture IV. Obtained.
The same operation as in Production Example 1 was carried out except that the polyol mixture IV was used instead of the polyol mixture I, and a coated granular fertilizer for comparison was obtained.
In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.

比較製造例4
 ポリオール混合物A 2677.08g、及び1,8-ジアザビシクロ(5.4.0)ウンデセン-7(サンアプロ株式会社、商品名:DBU(登録商標))3.50gを室温で混合してポリオール混合物Vを得た。
 ポリオール混合物IIの代わりに、ポリオール混合物Vを用いた以外は、製造例3と同様の操作を行い、比較用の被覆粒状肥料を得た。
 上記製造工程において、粒状物同士の凝集した塊状物が一部で見られ、コンクリートミキサー内での粒状物の転動状態は充分ではなかった。
Comparative manufacturing example 4
Mixture A 2677.08 g and 3.50 g of 1,8-diazabicyclo (5.4.0) Undecen-7 (San Apro Co., Ltd., trade name: DBU®) at room temperature to obtain a polyol mixture V. Obtained.
The same operation as in Production Example 3 was carried out except that the polyol mixture V was used instead of the polyol mixture II, and a coated granular fertilizer for comparison was obtained.
In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.

比較製造例5
 ポリオール混合物A 2677.08g、及び1,8-ジアザビシクロ(5,4,0)ウンデセン-7のフェノール塩(サンアプロ株式会社、商品名:U-CAT(登録商標) SA-1)2.50gを室温で混合してポリオール混合物VIを得た。
 ポリオール混合物Iの代わりに、ポリオール混合物VIを用いた以外は、製造例1と同様の操作を行い、比較用の被覆粒状肥料を得た。
 上記製造工程において、粒状物同士の凝集した塊状物が一部で見られ、コンクリートミキサー内での粒状物の転動状態は充分ではなかった。
Comparative manufacturing example 5
2.50 g of the polyol mixture A 2677.08 g and the phenol salt of 1,8-diazabicyclo (5,4,0) undecene-7 (San Apro Co., Ltd., trade name: U-CAT (registered trademark) SA-1) at room temperature. The mixture was obtained with a polyol mixture VI.
The same operation as in Production Example 1 was carried out except that the polyol mixture VI was used instead of the polyol mixture I, and a coated granular fertilizer for comparison was obtained.
In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.

比較製造例6
 ポリオール混合物A 2677.08g、及び2,4,6-トリス(ジメチルアミノメチル)フェノール(化薬アクゾ株式会社、商品名:TAP)25.0gを室温で混合し、ポリオール混合物VIIを得た。
 粒状尿素(大粒尿素、粒径約3mm、球状、1g当たりの粒数約60個)50,000gをコンクリートミキサーに仕込み、転動状態とした。転動状態の該粒状尿素を熱風発生装置の熱風を当てることにより約66℃まで加熱した後、流動パラフィン(松村石油研究所製、商品名:モレスコホワイトP-350P、37.78℃における動粘度:76mm/S)500gを添加し、3分間転動状態を継続した。次いで、50℃に加温した前記ポリオール混合物VII270.21gと、50℃に加温した芳香族ジイソシアネート(住化バイエルウレタン製、商品名:SBUイソシアネートJ243)232.29gとを素早く撹拌混合して得た混合物を、転動状態の粒状尿素に添加し、10分間以上、熱風発生装置の熱風を当てながら転動状態を維持した。ポリオール混合物VII及び芳香族ジイソシアネートの混合物の総添加量が5025.0gになるまで、上記操作(ポリオール混合物VIIと芳香族ジイソシアネートとの撹拌混合、転動状態の粒状尿素への混合物の添加、及び、転動状態の維持)を繰り返し、比較用の被覆粒状肥料を得た。
 上記製造工程において、粒状物同士の凝集した塊状物が一部で見られ、コンクリートミキサー内での粒状物の転動状態は充分ではなかった。
Comparative manufacturing example 6
A polyol mixture A 2677.08 g and 2,4,6-tris (dimethylaminomethyl) phenol (chemical drug Axo Co., Ltd., trade name: TAP) 25.0 g were mixed at room temperature to obtain a polyol mixture VII.
50,000 g of granular urea (large-grain urea, particle size of about 3 mm, spherical shape, about 60 grains per 1 g) was charged into a concrete mixer and put into a rolling state. The granular urea in a rolling state is heated to about 66 ° C. by applying hot air from a hot air generator, and then liquid paraffin (manufactured by Matsumura Petroleum Research Institute, trade name: Moresco White P-350P, 37.78 ° C.). Viscosity: 76 mm 2 / S) 500 g was added, and the rolling state was continued for 3 minutes. Next, the polyol mixture VII270.21 g heated to 50 ° C. and 232.29 g of aromatic diisocyanate (manufactured by Sumika Bayer Urethane, trade name: SBU isocyanate J243) heated to 50 ° C. were rapidly stirred and mixed. The mixture was added to the granular urea in the rolling state, and the rolling state was maintained while applying hot air from the hot air generator for 10 minutes or more. Until the total amount of the mixture of polyol mixture VII and aromatic diisocyanate added reaches 5025.0 g, the above operations (stirring and mixing of polyol mixture VII and aromatic diisocyanate, addition of the mixture to granular urea in a rolling state, and (Maintenance of rolling state) was repeated to obtain a coated granular fertilizer for comparison.
In the above manufacturing process, agglomerated lumps of granules were partially observed, and the rolling state of the granules in the concrete mixer was not sufficient.

 本発明の被覆粒状肥料の製造方法によれば、粒子間の凝集および転動装置への粒子の付着等の発生が抑制された、被覆粒状肥料を提供することができる。 According to the method for producing a coated granular fertilizer of the present invention, it is possible to provide a coated granular fertilizer in which the occurrence of aggregation between particles and adhesion of particles to a rolling device is suppressed.

Claims (11)

 粒状肥料と、当該粒状肥料を被覆するウレタン樹脂被膜とを備える被覆粒状肥料の製造方法であって、
 転動状態にある前記粒状肥料にポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンを添加する工程;および、該粒状肥料の転動状態を維持しながら該ポリイソシアネート成分と該ポリオール成分とを重付加させて、前記粒状肥料の表面に前記ウレタン樹脂被膜を形成する工程、を含む、被覆粒状肥料の製造方法。
A method for producing a coated granular fertilizer comprising a granular fertilizer and a urethane resin coating for coating the granular fertilizer.
A step of adding a polyisocyanate component, a polyol component, and diazabicyclononen to the granular fertilizer in a rolling state; and a weighting of the polyisocyanate component and the polyol component while maintaining the rolling state of the granular fertilizer. A method for producing a coated granular fertilizer, which comprises a step of forming the urethane resin film on the surface of the granular fertilizer by adding the mixture.
 ジアザビシクロノネンの添加量が、ポリイソシアネート成分及びポリオール成分の合計量に対して0.01~2重量%である、請求項1に記載の製造方法。 The production method according to claim 1, wherein the amount of diazabicyclononen added is 0.01 to 2% by weight based on the total amount of the polyisocyanate component and the polyol component.  以下の工程を含む請求項1又は2に記載の製造方法:
(a)ポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンとを混合し、混合物を得る工程、
(b)転動状態にある粒状肥料に前記工程(a)で得た混合物を添加する工程、および
(c)該粒状肥料の転動状態を維持し、ポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面に樹脂被膜を形成する工程。
The manufacturing method according to claim 1 or 2, which comprises the following steps:
(A) A step of mixing a polyisocyanate component, a polyol component, and diazabicyclononen to obtain a mixture.
(B) The step of adding the mixture obtained in the above step (a) to the granular fertilizer in the rolling state, and (c) maintaining the rolling state of the granular fertilizer, and adding the polyisocyanate component and the polyol component repeatedly. The process of forming a resin film on the surface of granular fertilizer.
 以下の工程を含む請求項1又は2に記載の製造方法:
(a)ポリイソシアネート成分とポリオール成分とを混合し、混合物を得る工程、
(b)転動状態にある粒状肥料に前記工程(a)で得た混合物とジアザビシクロノネンとを別々に添加する工程、および
(c)該粒状肥料の転動状態を維持し、ポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面に樹脂被膜を形成する工程。
The manufacturing method according to claim 1 or 2, which comprises the following steps:
(A) A step of mixing a polyisocyanate component and a polyol component to obtain a mixture.
(B) A step of separately adding the mixture obtained in the above step (a) and diazabicyclononen to the granular fertilizer in a rolling state, and (c) maintaining the rolling state of the granular fertilizer and polyisocyanate. A process of forming a resin film on the surface of granular fertilizer by adding components and polyol components in layers.
 以下の工程を含む請求項1又は2に記載の製造方法:
(a)ポリオール成分とジアザビシクロノネンとを混合し、混合物を得る工程、
(b)転動状態にある粒状肥料にポリイソシアネート成分と前記工程(a)で得た混合物とを別々に添加する工程、および
(c)該粒状肥料の転動状態を維持し、ポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面に樹脂被覆を形成する工程。
The manufacturing method according to claim 1 or 2, which comprises the following steps:
(A) A step of mixing a polyol component and diazabicyclononen to obtain a mixture.
(B) A step of separately adding the polyisocyanate component and the mixture obtained in the above step (a) to the granular fertilizer in the rolling state, and (c) maintaining the rolling state of the granular fertilizer and the polyisocyanate component. And a polyol component are heavily added to form a resin coating on the surface of granular fertilizer.
 以下の工程を含む請求項1又は2に記載の製造方法:
(a)転動状態にある粒状肥料にポリイソシアネート成分、ポリオール成分、及びジアザビシクロノネンを別々に添加する工程、および
(b)該粒状肥料の転動状態を維持し、ポリイソシアネート成分とポリオール成分とを重付加させて、粒状肥料の表面に樹脂被膜を形成する工程。
The manufacturing method according to claim 1 or 2, which comprises the following steps:
(A) A step of separately adding a polyisocyanate component, a polyol component, and diazabicyclononen to a granular fertilizer in a rolling state, and (b) maintaining the rolling state of the granular fertilizer, a polyisocyanate component and a polyol. A process of forming a resin film on the surface of granular fertilizer by adding components in layers.
 前記ポリイソシアネート成分が、芳香族ポリイソシアネートを含む、請求項1~6のいずれか1つに記載の製造方法。 The production method according to any one of claims 1 to 6, wherein the polyisocyanate component contains an aromatic polyisocyanate.  前記ポリオール成分が、ヒマシ油変性ジオールを含む、請求項1~7のいずれか1つに記載の製造方法。 The production method according to any one of claims 1 to 7, wherein the polyol component contains castor oil-modified diol.  前記ポリオール成分が、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール、及び水酸基を3以上有する化合物からなる群から選ばれる2つ以上の化合物を含む、請求項1~7のいずれか1つに記載の製造方法。 One of claims 1 to 7, wherein the polyol component contains two or more compounds selected from the group consisting of castor oil-modified diols, alkylene diols having 2 to 8 carbon atoms, and compounds having 3 or more hydroxyl groups. The manufacturing method described in.  前記ポリオール成分が、ヒマシ油変性ジオール、炭素数2~8のアルキレンジオール、及び水酸基を3以上有する化合物、を含む、請求項1~8のいずれか1つに記載の製造方法。 The production method according to any one of claims 1 to 8, wherein the polyol component contains a castor oil-modified diol, an alkylene diol having 2 to 8 carbon atoms, and a compound having 3 or more hydroxyl groups.  粒状肥料と、当該粒状肥料を被覆する樹脂被膜とを備え、
 前記樹脂被膜が、ポリイソシアネート成分とポリオール成分との重付加物であるウレタン樹脂とジアザビシクロノネンとを含む、被覆粒状肥料。
It is provided with a granular fertilizer and a resin film that covers the granular fertilizer.
A coated granular fertilizer in which the resin film contains urethane resin and diazabicyclononen, which are heavy adducts of a polyisocyanate component and a polyol component.
PCT/JP2021/045850 2020-12-14 2021-12-13 Method for manufacturing coated granular fertilizer, and coated granular fertilizer Ceased WO2022131217A1 (en)

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