WO2019117650A1 - Engrais à libération contrôlée - Google Patents

Engrais à libération contrôlée Download PDF

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Publication number
WO2019117650A1
WO2019117650A1 PCT/KR2018/015866 KR2018015866W WO2019117650A1 WO 2019117650 A1 WO2019117650 A1 WO 2019117650A1 KR 2018015866 W KR2018015866 W KR 2018015866W WO 2019117650 A1 WO2019117650 A1 WO 2019117650A1
Authority
WO
WIPO (PCT)
Prior art keywords
fertilizer
vinyl acetate
weight
fine particles
inorganic fine
Prior art date
Application number
PCT/KR2018/015866
Other languages
English (en)
Korean (ko)
Inventor
김찬중
이준석
장일
이상려
김지연
최재훈
Original Assignee
주식회사 엘지화학
주식회사 팜한농
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
Priority claimed from KR1020180160288A external-priority patent/KR102510340B1/ko
Application filed by 주식회사 엘지화학, 주식회사 팜한농 filed Critical 주식회사 엘지화학
Priority to JP2020519767A priority Critical patent/JP7146331B2/ja
Priority to US16/646,681 priority patent/US11427514B2/en
Priority to CN201880054387.5A priority patent/CN111094214A/zh
Priority to AU2018385840A priority patent/AU2018385840B2/en
Publication of WO2019117650A1 publication Critical patent/WO2019117650A1/fr
Priority to PH12020550880A priority patent/PH12020550880A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity

Definitions

  • the present invention relates to a dissolution-controlled fertilizer, and more particularly, to a dissolution-control-type fertilizer having a high stability against moisture, a solid structure, and an easily controlling dissolution period of a fertilizer and realizing excellent photodissociation efficiency.
  • Controlled release fertilizers such as nitrogen, phosphorus and potassium
  • Conventional fertilizers that are sprayed in water or sprayed in powder form usually do not last for more than 20 days once sprayed. This is due to the fact that the crops are not able to sustain the fertilizer composition because they are washed away in the rain or deeply penetrated into the soil.
  • the controlled release type fertilizer lowers the release rate of the fertilizer component with the polymer capsules so that it is released over a long period of time.
  • the polymer capsules are made of olefin resin, urethane resin, latex, acrylic resin, etc. After the water vapor penetrates through the capsules, the fertilizer components are melted, and the capsules are permeated and released by the osmotic principle. The penetration rate of water and fertilizer components varies depending on the ingredients and the thickness of the capsules. This can be used to control the rate at which the fertilizer component is released. The period of release of the fertilizer component from the capsule can be adjusted from a minimum of 30 days to a maximum of 2 years. However, after release of the fertilizer, 2019/117650 1 » (: 1 ⁇ 1 ⁇ 2018/015866
  • biodegradable polymer As a capsule material. Since the biodegradable polymer is rapidly permeated by water and decomposed by microorganisms within 1 month to 6 months, It was not suitable for use in controlled-release fertilizers that had to be released over two years.
  • the present invention provides a controlled-release fertilizer having a high stability against water and a solid structure, capable of easily controlling the dissolution period of 10 of the fertilizer, and capable of realizing excellent photodegradation efficiency.
  • polyolefin and ethylene vinyl acetate binder resin containing the copolymer and (co) including a repeating unit selected at least one from the 15 group consisting of ethylene repeating units and vinyl acetate repeating units of the polymer, the surface of the agglomerates of the inorganic fine particles Or a photocatalytic composite comprising a photocatalyst composite and a photocatalytic composite, the photocatalytic composite comprising a photocatalytic composite and a photocatalytic composite, the photocatalytic composite comprising:
  • the (co) polymer is meant to include both a polymer and a copolymer.
  • the polyolefin and ethylene vinyl acetate binder resin including co-polymer; of and ethylene repeating units and vinyl including repeating units of at least one member selected from the group consisting of acetate repeating units (co) polymer, the inorganic fine particles the photocatalyst composite material bonded to the surface or interior of the aggregates; a dissolution-controlled fertilizer comprising the fertilizer contained in the space 30 surrounded by the photodegradable capsules and the capsules containing photodegradable can be provided.
  • a release-controlled fertilizer having a photocatalytic capsule containing the above-described photocatalytic composite together with a binder resin containing a polyolefin and an ethylene vinyl acetate copolymer has a high stability against moisture and a rigid structure and can easily control the duration of a fertilizer And it is possible to realize excellent photodecomposition efficiency.
  • the above-mentioned dissolution-controlled fertilizer is also characterized in that the photocatalytic composite is uniformly dispersed in the above-mentioned binder resin.
  • the (co) polymer containing at least one repeating unit selected from the group consisting of the ethylene repeating unit and the vinyl acetate repeating unit is bound to the surface or inside of the agglomerate of the inorganic fine particles, Or the inorganic fine particles can be uniformly dispersed in the leaching control type fertilizer, so that the agglomerate of the inorganic fine particles can have a large particle size.
  • the agglomerates of the inorganic fine particles are uniformly dispersed in the binder resin while having a small particle size, so that photodegradation reaction is locally caused when the photodegradable capsules are exposed to light, thereby preventing degradation of photodecomposition efficiency So that the photodegradable capsules do not remain in the soil.
  • the lanyard-controlled fertilizer can realize excellent photodegradation efficiency. More specifically, when light of a wavelength of 300 11111 to 800 is irradiated at a strength of 400 for 224 hours, the weight of the photodegradable capsule
  • the decomposition ratio of the binder resin to be derived may be 40% or more, or 50% or more.
  • the inorganic fine particles may serve as a photocatalyst.
  • the lance-controlled fertilizer of the embodiment is characterized in that the photocatalytic composite is uniformly dispersed in the binder resin in order to solve the problem that the photodegradable capsule remains in the soil.
  • the photocatalytic complex acts as a catalyst only during the light receiving period, the photocatalytic capsule is slowly decomposed while the photocatalytic capsule is not decomposed while the fertilizer is released in the soil where the light is blocked.
  • the photodegradable capsule may be decomposed by light.
  • the inorganic fine particle may comprise primary particles having a cross-sectional diameter of 5 to 50 nm.
  • Cross-sectional diameter of the primary particles of said inorganic fine particles are conventionally known method, for example, verification by the TEM image and, BET Measurement and so on.
  • the degree of crystallization can be the photocatalytic efficiency is lowered away. Further, the cross-sectional diameter of the primary particles is too large, the photocatalytic particles contained in the inorganic fine particle The specific surface area is lowered and the photocatalytic efficiency may be lowered.
  • the agglomerates of the inorganic fine particles contained in the dissolution-controlled fertilizer of the above embodiment may have a particle size not so large.
  • the cross-sectional diameter and the diameter of the agglomerate of the inorganic fine particles can be confirmed by a commonly known method, for example, SEM or TEM microtome.
  • the cross-sectional diameter or overall size of the aggregates of the inorganic fine particles 25 is too large, there is a localized photolytic reaction in the photodegradable capsule can be up or decrease the efficiency of photolysis reaction, due to the inefficient photolysis reaction entire photodegradable capsule It may not be decomposed and residues may remain.
  • inorganic fine particles include titanium dioxide ( TiO2), zinc oxide (ZnO), and mixtures thereof.
  • the binder resin may be a main material forming the outer structure of the photodegradable capsule, and as described above, the binder resin may include a polyolefin and an ethylene vinyl acetate copolymer.
  • polystyrene resin examples include, but are not limited to, high density or low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, butene-ethylene copolymer, butene- Mixtures thereof, or copolymers of two or more thereof.
  • the ethylene vinyl acetate copolymer contained in the binder resin is not particularly limited.
  • an ethylene vinyl acetate copolymer containing 1 to 45% by weight of vinyl acetate repeating units may be used.
  • the ethylene vinyl acetate copolymer has a melt index of 0.5 / 10 11 to 5.0 / 10 11 or 1.0 / 10 11 to 3.0 ⁇ measured at 190 and 2.161 ⁇ load, / 10 1 can be 11 days.
  • the binder resin may include a polyolefin: ethylene vinyl acetate copolymer in a weight ratio of 1: 1 to 6: 1 have.
  • the dissolution rate of the fertilizer can be more easily controlled as the binder resin contains the polyolefin resin equal to or more than the ethylene vinyl acetate copolymer.
  • the photocatalytic composite may have a structure in which a (co) polymer containing at least one repeating unit selected from the group consisting of ethylene repeating units and vinyl acetate repeating units is bonded to the surface or inside of aggregates of inorganic fine particles.
  • the agglomerate of the inorganic fine particles can act as a photocatalyst, and when the dissolution-controlled fertilizer is exposed to the surface of the soil or the like, the photolytic reaction can be started in the photodegradable capsule.
  • the (co) polymer containing at least one repeating unit selected from the group consisting of the ethylene repeating unit and the vinyl acetate repeating unit is preferably a 2019/117650 1 » (: 1 ⁇ 1 ⁇ 2018/015866
  • the inorganic fine particles are prevented from excessively growing in size and have higher compatibility with the binder resin so that the photocatalytic composite is uniformly dispersed in the binder resin, .
  • ethylene repeating units and vinyl acetate repeating units one or more kinds selected from the group consisting of repeating units of the (co) polymer can contain both an ethylene vinyl acetate repeating units, or repeating units thereof.
  • Examples of the above ethylene repeating units and vinyl acetate (co) including a repeating unit selected at least one from the group consisting of repeating units of the polymer is 10 and the number of the ethylene vinyl acetate copolymers, and vinyl acetate repeating units from 1% to by weight 45 may be used an ethylene-vinyl acetate copolymer containing by weight%.
  • the ethylene-vinyl acetate copolymer shows ⁇ 1) on by 1901 1238: and 2.16 ⁇ 3 ⁇ 4 load a melt index of 0.5 for a / 10 to 5.0 for a / 10 1 or / 101 11 - / 10 per 3.0 1.0 measured at ⁇ Can be.
  • the photocatalyst composite may be prepared through the step of dispersing (co) polymer containing a repeating unit at least one selected from the group consisting of the inorganic fine particles and the ethylene repeating units and vinyl acetate repeating units in the organic solvent.
  • the weight ratio of the inorganic fine particles (co) polymer is not limited to a great extent, and the weight ratio can be controlled by controlling the amount of the organic fine particles dispersed in the organic solvent according to the characteristics of the dissolution control type fertilizer. It can be contained in 100 parts by weight of the aggregate compared to the ethylene repeating units and 25 vinyl (co) polymer, from 1 to 500 parts by weight of a repeating unit including at least one selected from the group consisting of acetate repeating units, or from 20 to 200 parts by weight. On the other hand, 0.1 to 8 parts by weight of 30 aggregates of the inorganic fine particles may be included relative to 100 parts by weight of the binder resin. 2019/117650 1 » (: 1 ⁇ 1 ⁇ 2018/015866
  • the photolysis reaction efficiency may be lowered, and the entire photodegradable capsule may not be decomposed due to insufficient photolysis reaction, .
  • the agglomerate of the inorganic fine particles may grow to a large extent, thereby causing a local photodegradation reaction in the photodegradable capsule, The efficiency of the photolysis reaction is lowered, so that the entire photodegradable capsule is not decomposed and the residue may remain.
  • the release-controlled fertilizer may further comprise a filler to be dispersed in the binder resin but are not the kind of the filler largely limited, and for example the filler is talc, bentonite, yellow earth, diatomaceous earth, silica-alumina Silicate, kaolite, starch, carbon, or a mixture of two or more thereof.
  • the content of the filler is not limited, but the lumber-controlling type fertilizer may contain 25 to 75 % by weight of the filler in relation to the total weight of the photodegradable capsule in consideration of the mechanical properties and structural stability of the photodegradable capsule
  • the fertilizer may be any of a variety of known fertilizers, such as urea or compound fertilizer.
  • the fertilizer may be a granular core fertilizer having a granular form in order to be easily contained in the photodegradable capsule.
  • the specific kind of the above-mentioned fertilizer is not limited, and conventionally known fertilizers can be used. Preferred examples are urea, aldehyde condensation element
  • 25 isobutylaldehyde condensation element, formaldehyde condensation element guanyl ureasulfate, and nitrogen containing organic compounds such as oxamide, ammonium nitrate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium sulfate ammonium chloride, and ammonium nitrate such as sodium nitrate And potassium salts such as potassium nitrate, potassium nitrate, potassium nitrate, potassium phosphate, potassium sulfate, and potassium chloride, calcium phosphate, calcium sulfate, calcium nitrate,
  • magnesium nitrate magnesium chloride
  • magnesium phosphate and Iron salts such as ferric chloride, ferric nitrate, ferric phosphate, ferric phosphate, ferrous sulfate, ferric sulfate, ferrous chloride and ferric chloride, and their double salts or a mixture of two or more thereof.
  • the content of the fertilizer in the leaching control type fertilizer is not limited to a great extent.
  • 100 parts by weight of the photodegradable capsule may contain 200 to 3000 parts by weight of the fertilizer.
  • the photocatalytic composite may have a specific degree of dispersion in the photodegradable capsule. More specifically, the photocatalytic composite can be produced by dispersing (co) polymer containing the inorganic fine particles and one or more repeating units selected from the group consisting of ethylene repeating units and vinyl acetate repeating units in an organic solvent ,
  • a high-shear mixer or a bead mill may be used to disperse the inorganic fine particles and the (co) polymer in an organic solvent to transfer strong energy to the (co) polymer May be bonded to the surface or inside of the aggregate of the inorganic fine particles.
  • the photocatalytic composite thus produced can be dispersed very uniformly in the binder resin, and the decomposition efficiency of the photocatalyst can be remarkably increased.
  • the lanyard-controlled fertilizer may further comprise a component included in a known line-controlled fertilizer.
  • such components include, but are not limited to, amphipathic polymers.
  • the leaching control type fertilizer can be provided through various manufacturing methods.
  • the dispersion of inorganic fine particles is dispersed in an organic solvent to which an ethylene vinyl acetate copolymer is added to prepare a dispersion of the photocatalytic composite.
  • Preparing a coating composition by mixing a polyolefin, an ethylene vinyl acetate copolymer, a dispersion of the photocatalytic composite, and optionally a filler; And coating the surface of the granular fertilizer core with the coating composition.
  • organic solvent are not limited, 2019/117650 1 » (: 1 ⁇ 1 ⁇ 2018/015866
  • a dispersion can be prepared by using a strong energy such as a 5-ultrasonic wave ( 11 ratio 1 011 ) or a bead mill For example, ultrasonic waves ( 3011 ratio 31 ; 1 is 1 ), etc.
  • the dissolution-controlled fertilizer prevents the photodegradable capsule or the hydrophilic polymer from remaining in the soil, thereby preventing soil contamination.
  • Fig. 1 is a table photograph of each of the agglomerates of inorganic fine particles and the agglomerates of fine particles contained in the coated fertilizer of Comparative Example 2 in Example 1 and the photocatalytic composite contained in the dissolution-controlled fertilizer.
  • Figure 2 schematically depicts the photodegradation mechanism of a dissolution-controlled fertilizer
  • Ultrasonic waves were applied to prepare 5 dispersions of the photocatalytic composite coated with ethylene vinyl acetate copolymer.
  • the coating solution was applied to the nitrogen fertilizer particles using a fluidized bed dryer to prepare dissolution-controlled coated fertilizers (Examples 1 to 5 ).
  • 1613 ⁇ 4 load shows ⁇ 1) 1238): about 1.8 I / 10 1 11, I) (density): 0.94 ⁇ / 011 3) about 20% by weight vinyl acetate content, a melting point 85 ° 0], And talc were mixed with tetrachlorethylene at a mixing ratio of 100: 1 at a mixing ratio of 100: 1 by using the ingredients as shown in Table 1, and a coating liquid was prepared so that the solid concentration was 5% by weight.
  • the coating film was irradiated with light having a wavelength of 800 1 L at an intensity of 40 (1 ⁇ 2 / 111 2 ).
  • the degradation rate of the binder resin which is also reduced by the weight change of the coating film upon irradiation with light for 224 hours under the above conditions, was determined by the following general formula 1, and the results are shown in Table 1 below.
  • the z-average dispersion particle size of the TiO 2 of the dispersion containing the photocatalytic composite of Example 1 and the Ti3 ⁇ 4 of Comparative Example 2 was measured using Dynamic Light Scatterin g (M arvern Ze tasizer Nano ZS 90 ). The results are shown in Table 3 below.

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  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)

Abstract

La présente invention concerne un engrais à libération contrôlée comprenant : une capsule photodégradable comprenant une résine liante comprenant une polyoléfine et un copolymère d'éthylène-acétate de vinyle ; et un composite photocatalytique dans lequel un (co)polymère comprenant au moins un motif récurrent choisi parmi un motif récurrent éthylénique et un motif récurrent d'acétate de vinyle est couplé à la surface ou à l'intérieur d'un agrégat de microparticules inorganiques ; et un engrais contenu dans un espace entouré par la capsule photodégradable.
PCT/KR2018/015866 2017-12-14 2018-12-13 Engrais à libération contrôlée WO2019117650A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2020519767A JP7146331B2 (ja) 2017-12-14 2018-12-13 溶出制御型肥料
US16/646,681 US11427514B2 (en) 2017-12-14 2018-12-13 Controlled-release fertilizers
CN201880054387.5A CN111094214A (zh) 2017-12-14 2018-12-13 控释肥料
AU2018385840A AU2018385840B2 (en) 2017-12-14 2018-12-13 Controlled-release fertilizers
PH12020550880A PH12020550880A1 (en) 2017-12-14 2020-06-11 Controlled-release fertilizers

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0172272 2017-12-14
KR20170172272 2017-12-14
KR1020180160288A KR102510340B1 (ko) 2017-12-14 2018-12-12 용출 제어형 비료
KR10-2018-0160288 2018-12-12

Publications (1)

Publication Number Publication Date
WO2019117650A1 true WO2019117650A1 (fr) 2019-06-20

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PCT/KR2018/015866 WO2019117650A1 (fr) 2017-12-14 2018-12-13 Engrais à libération contrôlée

Country Status (1)

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WO (1) WO2019117650A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1143391A (ja) * 1997-07-24 1999-02-16 Asahi Chem Ind Co Ltd 分解性被覆粒状肥料およびその製造方法
KR20000071159A (ko) * 1997-02-19 2000-11-25 야마모토 카즈모토 분해성 피복 필름으로 피복된 입상 비료 및 이의 제조 방법
KR101179469B1 (ko) * 2009-12-16 2012-09-07 동부팜한농 주식회사 용출제어형 입상배합 타입의 피복비료 및 그것의 제조방법
KR101331454B1 (ko) * 2013-08-07 2013-11-26 수산고분자 주식회사 완효성 입상 비료 및 이의 제조방법
KR20140039288A (ko) * 2011-06-13 2014-04-01 인비스타 테크놀러지스 에스.에이 알.엘. 폴리우레탄 및 폴리이소시아누레이트 중합체를 위한 전구체로서의, 시클로헥산 산화 부산물 스트림으로부터 유래된 지방족 폴리에스테르 폴리올

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000071159A (ko) * 1997-02-19 2000-11-25 야마모토 카즈모토 분해성 피복 필름으로 피복된 입상 비료 및 이의 제조 방법
JPH1143391A (ja) * 1997-07-24 1999-02-16 Asahi Chem Ind Co Ltd 分解性被覆粒状肥料およびその製造方法
KR101179469B1 (ko) * 2009-12-16 2012-09-07 동부팜한농 주식회사 용출제어형 입상배합 타입의 피복비료 및 그것의 제조방법
KR20140039288A (ko) * 2011-06-13 2014-04-01 인비스타 테크놀러지스 에스.에이 알.엘. 폴리우레탄 및 폴리이소시아누레이트 중합체를 위한 전구체로서의, 시클로헥산 산화 부산물 스트림으로부터 유래된 지방족 폴리에스테르 폴리올
KR101331454B1 (ko) * 2013-08-07 2013-11-26 수산고분자 주식회사 완효성 입상 비료 및 이의 제조방법

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