KR102439158B1 - Composition for coating fertilizer comprising polyurethane/acrylic hybrid polymer and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a fertilizer coating composition comprising a polyurethane/acrylic hybrid polymer and a preparation method thereof, and more particularly, to a fertilizer coating composition comprising a polyurethane/acrylic hybrid polymer in which a polyurethane polymer seed is prepared by polymerizing polyol and isocyanate and the advantages and disadvantages of an acrylic resin obtained by crosslinking the polyurethane polymer seed and an acrylic monomer and a polyurethane resin are mutually utilized and supplemented and to a preparation method thereof. The fertilizer coating composition comprising a polyurethane/acrylic hybrid polymer and the preparation method thereof of the present invention can solve various problems caused by insufficient physical properties of water-based polymers to provide a composition used for preparing a coated fertilizer in which fertilizer components are slowly eluted so as to suit the nutrient absorption characteristics of each crop.

Description

Fertilizer coating composition containing polyurethane / acrylic hybrid polymer and manufacturing method thereof

The present invention relates to a composition for fertilizer coating comprising a polyurethane/acrylic hybrid polymer and a method for manufacturing the same, and more particularly, to a polyurethane polymer seed by polymerizing a polyol and an isocyanate, and the polyurethane polymer seed and an acrylic monomer It relates to a composition for fertilizer coating comprising a polyurethane/acrylic hybrid polymer that uses and complements each other and the advantages and disadvantages of crosslinked acrylic resin and polyurethane resin, and a method for manufacturing the same.

Fertilizers used for crop growth can be broadly divided into short-acting and slow-acting fertilizers. Among them, short-acting fertilizers have a disadvantage of causing environmental pollution and waste of resources by spilling into the atmosphere, groundwater, and ditches before crops absorb all of the fertilizer nutrients due to their too fast solubility when fertilized in the soil. In order to solve the problem of such short-acting fertilizers, coating-type slow-acting fertilizers are being developed in which a polymer such as a polymer resin is coated on the surface of the fertilizer so that the fertilizer nutrients are slowly eluted through the coating film. The slow-acting cover fertilizer is evaluated as the best technology among the existing chemical fertilizer manufacturing technology because it can accurately supply the amount and type of nutrients required by the crop according to the growth stage of the crop.

Polymers used to manufacture coated slow-acting fertilizers are largely divided into solvent-based polymers using organic solvents and water-dispersion-type aqueous polymers using water, depending on the type of polymer solvent medium.

With respect to solvent-based polymers, Korean Patent Registration No. 10-1179469 suggests a method of manufacturing a coating fertilizer using tetrachlorethylene, an organic solvent, to dissolve olefinic polymers such as LDPE and EVA. It has disadvantages such as harm to human body due to the use of solvent, expensive equipment construction, rapid replacement delay in case of emergency in the process, and fire hazard in the workplace due to the use of volatile and flammable organic solvents.

Water-dispersible emulsion aqueous polymers are prepared by dispersing nano-sized polymers in water using a surfactant in water. Unlike solvent-based polymers, water is used, so there is no need to install a separate device for recovering organic solvents. , it is environmentally friendly as there are no substances harmful to human health such as VOC.

Korean Patent No. 10-0445536, which relates to an acrylic polymer, which is widely used in Korea among water-dispersible emulsion aqueous polymers, suggests a method for manufacturing a coating fertilizer using a reverse core-shell water-dispersion type acrylic polymer, but the polymer manufacturing process and fertilizer coating process It is complicated and expensive to manufacture, and due to the low water resistance of acrylic resin, it must be thickly coated to have a coverage ratio of at least 7%, generally 10% or more, to maintain long-term fertilizer nutrient dissolution performance for more than 100 days. There is a problem in that the solidification phenomenon of the coating fertilizer occurs under a high load.

As such, water-based polymers have relatively poor physical properties compared to oil-based polymers, and thus, various studies are needed to overcome them.

Korean Patent Publication No. 10-2204360 Korean Patent Publication No. 10-0445536

Accordingly, the present inventors have researched and tried to solve the problems that a thick coating is required due to the insufficient physical properties of the aqueous polymer and the solidification phenomenon of the coating fertilizer occurs. The present invention was completed by discovering that a composition for fertilizer coating that solved the problem could be prepared through an acrylic hybrid polymer.

Accordingly, an object of the present invention is to provide a composition for fertilizer coating comprising a polyurethane/acrylic hybrid polymer and a method for manufacturing the same.

The present invention is

It provides a composition for coating fertilizer comprising a polyurethane/acrylic hybrid polymer polymerized with a polyurethane polymer, an acrylic monomer and a crosslinking agent.

The polyurethane polymer may be prepared using a polyol, an isocyanate, an ionizer, a chain extender, a capping agent, a catalyst, and a neutralizing agent.

The polyol may be at least one selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polybutadiene polyol, acrylic polyol, and bio-polyol.

The isocyanate is from the group consisting of isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, methyldiphenyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, cyclohexane diisocyanate and xylene diisocyanate. It may be any one or more selected.

The ionizing agent may be dimethylolpropionic acid.

The chain extender is ethylenediamine, diaminobutane, diaminopropane, hydrazine, isophoronediamine, hexamethylenediamine, ethylene glycol, butanediol, diethylenetriamine, isosorbide, diaminodicyclohexylmethane and methyl. It may be any one or more selected from the group consisting of pentamethylenediamine.

The capping agent may be at least one selected from the group consisting of dihydroxybenzene, diallylbisphenol, naphthoresorcinol, dihydroxynaphthalene, proroglucinol, and resorcinol.

The polyurethane polymer may include 5 to 100 parts by weight of an isocyanate, 1 to 50 parts by weight of an ionizer, 0.1 to 50 parts by weight of a chain extender, and 0.1 to 50 parts by weight of a capping agent based on 100 parts by weight of the polyol.

The acrylic monomer is styrene, normal butyl acrylate, methyl methacrylate, acrylonitrile, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, acrylic acid, isobutyl methacrylate, vinyl It may be at least one selected from the group consisting of acetate and 2-hydroxyethyl methacrylate.

The acrylic monomer may be included in an amount of 10 to 300 parts by weight based on 100 parts by weight of the polyurethane polymer.

The crosslinking agent is allyl methacrylate, ethylene glycol dimethacrylate, tripropylene glycol diacrylate, divinylbenzene, triaryl cyanate, vinyl trimethoxysilane, vinyl triethoxysilane, trimethylolpropane trimethacrylic It may be any one or more selected from the group consisting of rate, 3-aminopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane.

The crosslinking agent may be included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the polyurethane polymer.

The polyurethane/acrylic hybrid polymer may have a weight average molecular weight of 80,000 to 200,000 g/mol, a pH of 7 to 12, a particle size of 80 to 250 nm, and a viscosity of 5 to 50 cps.

In addition, the present invention,

preparing a first reactant by polymerizing a polyol and an isocyanate;

preparing a secondary reactant by adding an ionizer and a catalyst to the first reactant;

preparing a tertiary reactant by adding a chain extender to the secondary reactant;

preparing a polyurethane polymer seed by adding a capping agent and a neutralizing agent to the tertiary reactant; and

It provides a method for preparing a fertilizer coating composition comprising the step of preparing a polyurethane/acrylic hybrid polymer by putting a mixture in which an acrylic monomer, an initiator, an emulsifier and a crosslinking agent are mixed in the polyurethane polymer seed and reacting.

The composition for fertilizer coating comprising a polyurethane/acrylic hybrid polymer according to the present invention and a method for manufacturing the same, solve various problems caused by insufficient physical properties of an aqueous polymer, and the fertilizer component slowly elutes according to the nutrient absorption characteristics of each crop There is an effect that can provide a composition used for manufacturing a coating fertilizer.

1 is a photograph of rice grown using a coating fertilizer coated with a composition according to the present invention.

Hereinafter, the present invention will be described in detail. Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and the inventor should properly understand the concept of the term in order to best describe his invention. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, the configuration described in the embodiment described in this specification is only the most preferred embodiment of the present invention and does not represent all of the technical idea of the present invention, so various equivalents and It should be understood that there may be variations.

The present invention features a fertilizer coating composition comprising a polyurethane/acrylic hybrid polymer polymerized with a polyurethane polymer, an acrylic monomer, and a crosslinking agent.

The polyurethane polymer may be prepared using polyols, isocyanates, ionizers, chain extenders, capping agents, catalysts and neutralizing agents.

Polyol refers to a liquid polymer material with two or more alcohol groups attached to the hydrocarbon chain. It forms the soft segment of polyurethane. As the molecular weight increases, it becomes softer and has elastic properties. In general, in the polyurethane industry, polyol refers to a compound that has a hydroxyl group (-OH) and reacts with isocyanate to produce polyurethane, and usually has a weight average molecular weight of about 200 to 8,000 g/mol.

The polyol may be at least one selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polybutadiene polyol, acrylic polyol and bio polyol, preferably polyether polyol and polyol It may be at least one selected from among ester polyols.

Polyether polyols and polyester polyols have excellent mechanical properties and heat resistance, and thus have the advantage of improving the physical properties of coating fertilizers.

The polyether polyol may be polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and polytetramethylene ether glycol, preferably polytetramethylene ether glycol.

The isocyanate is from the group consisting of isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, methyldiphenyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, cyclohexane diisocyanate and xylene diisocyanate. It may be any one or more selected, preferably isophorone diisocyanate.

The isocyanate, based on 100 parts by weight of the polyol, 5 to 100 parts by weight, preferably 20 to 70 parts by weight, more preferably 40 to 60 parts by weight may be included.

The ionizing agent serves to prepare a water-dispersible polyurethane by increasing the hydrophilicity of the hydrophobic polyurethane.

The ionizing agent may be dimethylol propionic acid, and may be added in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 15 parts by weight based on 100 parts by weight of the polyol.

When the amount of the ionizing agent added is less than 1 part by weight based on 100 parts by weight of the polyol, it is difficult to disperse in water and thus stability is poor. It has the disadvantage of poor performance.

The chain extender is used to obtain a high molecular weight polymer by linking the chains and chains between the reactants during the urethane reaction process. By using a chain extender, a high molecular weight polymer is formed, so that the dissolution performance of the coating fertilizer is maintained for a long time, and the dissolution period of the fertilizer nutrients is extended even if the coating thickness is not thickened.

The chain extender is ethylenediamine, diaminobutane, diaminopropane, hydrazine, isophoronediamine, hexamethylenediamine, ethylene glycol, butanediol, diethylenetriamine, isosorbide, diaminodicyclohexylmethane and It may be any one or more selected from the group consisting of methylpentamethylenediamine, preferably ethylenediamine.

The chain extender may be included in an amount of 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, and more preferably 5 to 10 parts by weight based on 100 parts by weight of the polyol.

When the molecular weight of the capping agent becomes too large by applying a chain extender, the high viscosity of the urethane resin and moisture drying problems occur during future coating fertilizer production. According to the viscosity of the capping agent, it also plays a role of adjusting the viscosity.

The capping agent may be at least one selected from the group consisting of dihydroxybenzene, diallylbisphenol, naphthoresorcinol, dihydroxynaphthalene, proroglucinol and resorcinol, preferably dihydroxybenzene can be

The capping agent may be included in an amount of 0.1 to 50 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 15 parts by weight based on 100 parts by weight of the polyol.

The catalyst may be an amine-based or tin-based catalyst, specifically dibutyltin dilaurate, triethylamine, dioctyltin diacetate, dibutyltin oxide, tin octanoate and bismuth carboxylate, etc., preferably For example, it may be dibutyltin dilaurate.

The catalyst may be used in an amount of 0.001 to 0.1 parts by weight, preferably 0.01 to 0.05 parts by weight, based on 100 parts by weight of the polyurethane polymer.

Neutralizers are used for dispersion stability and storage stability of polymer reactants.

The neutralizing agent may be at least one selected from the group consisting of aqueous ammonia, ethylamine, butylamine, dimethylamine, dimethylethylamine, tributylamine, triethylamine, dimethylethanolamine, diethylethanolamine and diisopropanolamine. and preferably triethylamine.

The neutralizing agent, based on 100 parts by weight of the polyurethane polymer, 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight may be used.

The acrylic monomer is styrene, normal butyl acrylate, methyl methacrylate, acrylonitrile, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, acrylic acid, isobutyl methacrylate, vinyl acetate and 2-hydroxy It may be any one or more selected from the group consisting of ethyl methacrylate, preferably styrene, normal butyl acrylate, methyl methacrylate and acrylonitrile.

The acrylic monomer may be included in an amount of 10 to 300 parts by weight, 20 to 150 parts by weight, and more preferably 30 to 50 parts by weight based on 100 parts by weight of the polyurethane polymer.

The crosslinking agent is to obtain an interpenetrating polymer network (IPN) by continuously crosslinking and polymerizing two types of polymers with different components. The dissolution rate can be determined.

The crosslinking agent is allyl methacrylate, ethylene glycol dimethacrylate, tripropylene glycol diacrylate, divinylbenzene, triaryl cyanate, vinyl trimethoxysilane, vinyl triethoxysilane, trimethylolpropane trimethacrylate , 3-aminopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane may be any one or more selected from the group consisting of, preferably allyl methacrylate.

The crosslinking agent, based on 100 parts by weight of the polyurethane polymer, 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, more preferably 1.5 to 3 parts by weight may be included.

If the content of the crosslinking agent is less than 0.5 parts by weight, the chain extension effect may be insufficient and mechanical properties may be reduced, and if it exceeds 10 parts by weight, excessive increase in hardness and decrease in elongation may result.

The polyurethane/acrylic hybrid polymer may have a weight average molecular weight of 80,000 to 200,000 g/mol, preferably 100,000 to 150,000 g/mol, and a pH of 7 to 12, preferably 8 to 11, more preferably It may be 9.5 ~ 10.5, the particle size may be 80 ~ 250nm, preferably 90 ~ 230nm, more preferably 100 ~ 200nm, the viscosity is 5 ~ 50cps, preferably 10 ~ 45cps, more preferably 15 It can be ~ 40 cps.

In addition, the present invention comprises the steps of preparing a first reactant by polymerizing a polyol and an isocyanate;

preparing a secondary reactant by adding an ionizer and a catalyst to the first reactant;

preparing a tertiary reactant by adding a chain extender to the secondary reactant;

preparing a polyurethane polymer seed by adding a capping agent and a neutralizing agent to the tertiary reactant; and

Another feature of a method for preparing a composition for fertilizer coating comprising the step of preparing a polyurethane/acrylic hybrid polymer by adding a mixture of an acrylic monomer, an initiator, an emulsifier and a crosslinking agent to the polyurethane polymer seed and reacting.

Specifically, the method for preparing the composition for coating fertilizer is as follows.

First, a primary reactant is prepared by polymerizing a polyol and an isocyanate.

The polyol may be at least one selected from the group consisting of polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polybutadiene polyol, acrylic polyol and bio polyol, preferably polyether polyol and polyol It may be at least one selected from among ester polyols.

Polyether polyols and polyester polyols have excellent mechanical properties and heat resistance, and thus have the advantage of improving the physical properties of coating fertilizers.

The polyether polyol may be polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and polytetramethylene ether glycol, preferably polytetramethylene ether glycol.

The isocyanate is from the group consisting of isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, methyldiphenyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, cyclohexane diisocyanate and xylene diisocyanate. It may be any one or more selected, preferably isophorone diisocyanate.

The polymerization may be carried out at 60 ~ 90 ℃, preferably 65 ~ 75 ℃, the isocyanate, based on 100 parts by weight of the polyol, 5 to 100 parts by weight, preferably 20 to 70 parts by weight, more preferably It can be made by adding 40 to 60 jungnang part.

The solvent used in the polymerization may be deionized water.

The content of the deionized water may be 100 to 300 parts by weight based on 100 parts by weight of the polyurethane polymer. When it exceeds the above range, the content of non-volatile substances in the reaction product is lowered, and thus, when the composition for fertilizer coating is used, there is a disadvantage in that the cost of transporting and storing the coating fertilizer is increased.

Next, an ionizer and a catalyst are added to the first reactant to prepare a second reactant.

The ionizing agent may be dimethylol propionic acid, and may be added in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 15 parts by weight based on 100 parts by weight of the polyol.

When the amount of the ionizing agent added is less than 1 part by weight based on 100 parts by weight of the polyol, smooth water dispersion is difficult and the stability is poor. There is a disadvantage that the dissolution performance is lowered.

The catalyst may be an amine-based or tin-based catalyst, specifically dibutyltin dilaurate, triethylamine, dioctyltin diacetate, dibutyltin oxide, tin octanoate and bismuth carboxylate, etc., preferably For example, it may be dibutyltin dilaurate.

The catalyst may be used in an amount of 0.001 to 0.1 parts by weight, preferably 0.01 to 0.05 parts by weight, based on 100 parts by weight of the polyurethane polymer.

Next, a tertiary reactant is prepared by adding a chain extender to the secondary reactant.

The chain extender is ethylenediamine, diaminobutane, diaminopropane, hydrazine, isophoronediamine, hexamethylenediamine, ethylene glycol, butanediol, diethylenetriamine, isosorbide, diaminodicyclohexylmethane and methyl. It may be any one or more selected from the group consisting of pentamethylenediamine, and may preferably be ethylenediamine.

The chain extender may be included in an amount of 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, and more preferably 5 to 10 parts by weight based on 100 parts by weight of the polyol.

Next, a capping agent and a neutralizing agent are added to the tertiary reactant to prepare a polyurethane polymer seed.

The capping agent may be at least one selected from the group consisting of dihydroxybenzene, diallylbisphenol, naphthoresorcinol, dihydroxynaphthalene, proroglucinol and resorcinol, preferably dihydroxy It may be benzene.

The capping agent may be included in an amount of 0.1 to 50 parts by weight, preferably 5 to 30 parts by weight, and more preferably 10 to 15 parts by weight based on 100 parts by weight of the polyol.

The neutralizing agent is any one selected from the group consisting of aqueous ammonia, ethylamine, butylamine, dimethylamine, dimethylethylamine, tributylamine, triethylamine, dimethylethanolamine, diethylethanolamine and diisopropanolamine or more, preferably triethylamine.

The neutralizing agent, based on 100 parts by weight of the polyurethane polymer, 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight may be used.

The neutralizing agent, after cooling the temperature of the tertiary reactant to 30 ~ 50 ℃, the tertiary reactant has a pH of 7 to 12, preferably a pH of 8 to 11, more preferably a pH of 9.5 to 10.5 can be added until

Next, a mixture of an acrylic monomer, an initiator, an emulsifier and a crosslinking agent is added to the polyurethane polymer seed and reacted to prepare a polyurethane/acrylic hybrid polymer.

The acrylic monomer is styrene, normal butyl acrylate, methyl methacrylate, acrylonitrile, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, acrylic acid, isobutyl methacrylate, vinyl acetate And it may be any one or more selected from the group consisting of 2-hydroxyethyl methacrylate, preferably styrene, normal butyl acrylate, methyl methacrylate and acrylonitrile.

The acrylic monomer may be included in an amount of 10 to 300 parts by weight, 20 to 150 parts by weight, and more preferably 30 to 50 parts by weight based on 100 parts by weight of the polyurethane polymer.

The initiator may be at least one selected from the group consisting of ammonium persulfate, potassium persulfate, benzoyl peroxide, sodium persulfate, Vazo 68 WSO (V68), ammonium persulfate, t-butyl hydroperoxide and perbenzoic acid. have.

The initiator, based on 100 parts by weight of the polyurethane polymer, 0.05 to 1 parts by weight, preferably 0.1 to 0.5 parts by weight, more preferably 0.15 to 0.3 parts by weight may be included.

The initiator may be used at a reaction temperature of 50 to 85 °C.

The emulsifier is used to maintain the stability of the emulsion, and is divided into an anionic emulsifier having a hydrophilic group and a nonionic emulsifier having a hydrophobic group.

The emulsifier is an anionic emulsifier consisting of sodium dodecyl sulfate, potassium dodecyl sulfate, sodium dodecylbenzene sulfate, dioctyl sodium sulfosuccinate, sodium stearate and potassium stearate, and polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl At least one may be selected from nonionic emulsifiers composed of ethers, polyoxyethylene fatty acid esters and polyoxyethylene polypropylene copolymers.

The emulsifier, based on 100 parts by weight of the polyurethane polymer, 0.05 to 1 parts by weight, preferably 0.1 to 0.5 parts by weight, more preferably 0.15 to 0.3 parts by weight may be included.

The crosslinking agent is allyl methacrylate, ethylene glycol dimethacrylate, tripropylene glycol diacrylate, divinylbenzene, triaryl cyanate, vinyl trimethoxysilane, vinyl triethoxysilane, trimethylolpropane trimethacrylic It may be any one or more selected from the group consisting of rate, 3-aminopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane.

The crosslinking agent, based on 100 parts by weight of the polyurethane polymer, 0.1 to 5 parts by weight, preferably 0.3 to 2 parts by weight, more preferably 0.5 to 1 parts by weight may be included.

If the content of the crosslinking agent is less than 0.5 parts by weight, the chain extension effect may be insufficient and mechanical properties may be reduced, and if it exceeds 10 parts by weight, excessive increase in hardness and decrease in elongation may result.

The polyurethane/acrylic hybrid polymer may have a weight average molecular weight of 80,000 to 200,000, preferably 100,000 to 150,000, and a pH of 7 to 12, preferably 8 to 11, more preferably 9.5 to 10.5. , the particle size may be 80 to 250 nm, preferably 90 to 230 nm, more preferably 100 to 200 nm, and the viscosity may be 5 to 50 cps, preferably 10 to 45 cps, more preferably 15 to 40 cps.

Hereinafter, examples and experimental examples will be described in detail to explain the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1: Preparation of a first composition comprising a polyurethane/acrylic hybrid polymer

Nitrogen was injected into a 1000ml 4-neck round flask connected with a stirrer, reflux condenser, thermometer, and temperature controller, and 90 g of polytetramethylene ether glycol and 55 g of isoprondiisocyanate were put into the reactor, and then gradually increased the temperature and stirred at 80 °C while stirring. polymerized. Immediately, 10 g of the ionizing agent, dimethylolpropionic acid, was dissolved in 16 g of dimethylacetamide and slowly added to the reactor. After adding 50 mg of dibutyltin dilaurate as a reaction catalyst, the reaction was allowed to proceed at 80° C. for 80 minutes while the isocyanate group (-NCO) was terminated. Nated prepolymers were prepared. Next, 5 g of ethylenediamine as a chain extender was added, and the reaction was continued for 60 minutes, and then 12 g of dihydroxybenzene as a capping agent was added to cap the urethane prepolymer. Thereafter, the reaction temperature was lowered to 50° C. and cooled, and after adding 5 g of triethylamine as a neutralizing agent and stirring for 30 minutes, deionized water was dropped at a constant rate and neutralized for 1 hour to synthesize a water-dispersed polyurethane polymer seed. . In the water-dispersed polyurethane polymer seed, 140 g of acrylic monomer, styrene, 90 g, normal butyl acrylate, 82 g of methyl methacrylate, 50 g of acrylonitrile, 0.3 g of ammonium sulfate as an initiator, 1 g of sodium dodecyl sulfate as an emulsifier, and allyl methacrylic as a crosslinking agent A mixture of 3 g of rate (AMA) was injected at a rate of 1 ml/min. At this time, the reaction was carried out at a temperature of 80° C. for 3 hours to prepare a water-dispersed polyurethane/acrylic hybrid polymer using the final polyurethane seed polymerization method.

The hybrid polymer thus prepared had a weight average molecular weight of 121,710 g/mol, pH 9.8, a particle size of 185 nm, and a viscosity of 38 cps.

Example 2: Preparation of a second composition comprising a polyurethane/acrylic hybrid polymer

In Example 1, except that 60 g of styrene, 40 g of normal butyl acrylate, 30 g of methyl methacrylate, and 20 g of acrylonitrile were added in the amount of acrylic monomer added, the rest were prepared in the same manner.

The hybrid polymer thus prepared had a weight average molecular weight of 138,490 g/mol , pH 9.8, a particle size of 110 nm, and a viscosity of 35 cps.

Example 3: Preparation of a third composition comprising a polyurethane/acrylic hybrid polymer

In Example 1, except that 30 g of styrene, 20 g of normal butyl acrylate, 15 g of methyl methacrylate, and 10 g of acrylonitrile were added in the amount of the acrylic monomer, the rest were prepared in the same manner.

The hybrid polymer thus prepared had a weight average molecular weight of 143,830 g/mol, a pH of 10.0, a particle size of 155 nm, and a viscosity of 15 cps.

Comparative Example 1: Preparation of water-dispersible polyurethane polymer

Nitrogen was injected into a 1000ml 4-neck round flask connected with a stirrer, reflux condenser, thermometer, and temperature controller, and 90 g of polytetramethylene ether glycol and 55 g of isoprondiisocyanate were put into the reactor, and then gradually increased the temperature and stirred at 80 °C while stirring. polymerized. Immediately, 10 g of dimethylolpropionic acid, an ionizing agent, was dissolved in 16 g of dimethylacetamide and slowly added to the reactor. After adding 50 mg of dibutyltin dilaurate as a reaction catalyst, the reaction was allowed to proceed at 80° C. for 80 minutes while the isocyanate group (-NCO) was terminated. Nated prepolymers were prepared. Next, 5 g of ethylenediamine as a chain extender was added, and the reaction was continued for 60 minutes, and then 12 g of dihydroxybenzene as a capping agent was added to cap the urethane prepolymer. Thereafter, the reaction temperature was lowered to 50° C. and cooled, and after adding 5 g of triethylamine as a neutralizer and stirring for 30 minutes, deionized water was dropped at a constant rate and neutralized for 1 hour to synthesize a water-dispersed polyurethane polymer seed. .

The polyurethane polymer thus prepared had a weight average molecular weight of 87,460 g/mol, a pH of 9.2, a particle size of 105 nm, and a viscosity of 15 cps.

Comparative Example 2: Preparation of water-dispersed acrylic polymer

Nitrogen was injected into a 1000ml 4-neck round flask connected to a stirrer, reflux condenser, thermometer, temperature controller, and stirrer, acrylic monomer 140g, n-butyl acrylate 90g, methyl methacrylate 82g, acrylonitrile 50g, initiator A final acrylic polymer was prepared by mixing 0.3 g of ammonium sulfate, 1 g of sodium dodecyl sulfate as an emulsifier, and 3 g of allyl methacrylate (AMA) as a crosslinking agent, reacting at 80° C. for 3 hours, and then neutralizing with ammonia water.

The acrylic polymer thus prepared had a weight average molecular weight of 95,210 g/mol, a pH of 11.2, a particle size of 190 nm, and a viscosity of 35 cps.

Comparative Example 3: Preparation of fertilizer coating composition comprising non-crosslinked polyurethane/acrylic hybrid polymer

In comparison with Example 1, except that allyl methacrylate (AMA), a crosslinking agent, was not added, the rest were prepared in the same manner.

The non-crosslinked hybrid polymer thus prepared had a weight average molecular weight of 104,560 g/mol, a pH of 10.2, a particle size of 180 nm, and a viscosity of 20 cps.

Preparation Example 1: Preparation of Covered Fertilizer

Weigh 1.5 kg of granular fertilizer, put it into a fluidized bed coater, levitate the granular fertilizer in the air at a flow rate of about 300 m ³ /hr, and apply the polymers of Examples 1 to 3 and Comparative Examples 1 to 3 using a metering pump. It was supplied to the two-fluid nozzle at a rate of 10 g/min, and was sprayed and coated on the surface of the granular fertilizer. The coating temperature in the fluidized bed coater was kept constant at 60° C., and when the coating process was completed, the temperature was cooled to room temperature to obtain a final finished product. At this time, the standard coverage was 5%.

Experimental Example 1: Dissolution rate experiment

To evaluate the sustainability of nutrients in the coating fertilizer, put 2.5 g of the coating fertilizer into a 250 ml glass flask, fill it with distilled water, seal it, and leave it in a thermostat at 30 ° C. (RI Dector) was measured using high-performance liquid chromatography (HPLC) attached. Since a single component of nitrogen was measured, a separate HPLC column was not installed, and the elution amount of the unknown sample was measured by calibrating a standard sample of known concentration, and Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1 below. The dissolution rate of the coating fertilizer coated with the polymer is shown.

division Dissolution rate (%) note 1 day 10 days 30 days 50 days 70 days 90 days 110 days 130 days Example 1 9 19 37 62 91 100 Example 2 6 11 21 43 69 92 100 Example 3 2 6 15 32 49 72 89 100 Comparative Example 1 - - - - - - - - Coating fertilizer manufacturing failure due to slow drying characteristics Comparative Example 2 43 67 100 Comparative Example 3 18 38 79 100

As can be seen from the results of Table 1, it can be seen that Examples 1 to 3 according to the present invention are much superior to Comparative Examples 1 to 3.

Experimental Example 2: Solidification rate experiment and glass transition temperature (Tg) experiment

To measure the solidification rate of the coating fertilizer, put 90 g of the coating fertilizer in a sample bag of 9.5 cm × 9.5 cm, seal it completely with a heat-heating sealing machine, and place a 20 kg specimen in a dryer at 60 ° C to reduce the load pressure applied to the coating fertilizer by 0.21 kgf. /cm2 was made. The load at this time is the pressure at the bottom when about 20 layers of cover fertilizer are loaded. The solidification rate of the coating fertilizer was quantified using a solidification tester (manufactured by Imeda, Japan).

For the glass transition temperature (Tg) experiment, TGA/DSC equipment (product of Perkin-Elmer), which is a thermal analysis equipment, was used, and the Tg of each polymer was analyzed at a heat flow of 2.5°C/min. The results are shown.

division Solidification result (kgf) Tg note Example 1 0 103 Example 2 0 110 Example 3 0 132 Comparative Example 1 - 151 Coating fertilizer manufacturing failure due to slow drying characteristics Comparative Example 2 4.7 26 Comparative Example 3 0.1 96

As can be seen from the results of Table 2, in the case of the polymers according to Examples 1 to 3 of the present invention, the glass transition temperature (Tg) value is 100° C. or higher, and it can be confirmed that the solidification phenomenon of the coating fertilizer does not occur.

Experimental Example 3: Rice Growth Experiment Using Cover Fertilizer

Granular urea fertilizer (46-0-0), granular ammonium diphosphate fertilizer (18-46-0), and granular NK fertilizer in a fluidized bed coater using the water-dispersed polyurethane/acrylic hybrid polymer prepared according to Example 2 (5-0-47) The surface was coated to prepare a coated slow-acting compound fertilizer, and the Wagner pot was filled with paddy soil. Then, 3 seedlings of Nampyeong rice, a mid-late-ripening variety, were planted, and fertilizers were applied to each treatment group. Conventional fertilization, which is a general fast-acting fertilizer treatment unit, was fertilized once with the base manure and 2 times with the top manure, and the prototype district, which is an all-coating fertilizer treatment unit, was fertilized with the base fertilization once, and no top manure was applied separately. In the case of fertilization amount and fertilization method, conventional fertilization was treated according to the standard fertilization method recommended by the Rural Development Administration, and in the prototype district, 100%, 70%, and 50% of the conventional fertilization amount were fertilized, respectively. The crude fertilization method was carried out, and the growth results are shown in Table 3 below.

division Super long (cm) Chastity Yield (g/pot) customary practice
(quick-acting fertilizer) 67 23 prototype 100% 70 33 70% 68 30 50% 68 28

As can be seen from the results in Table 3, both plant growth and rice yields were excellent in the prototype plot fertilized with the polymer-coated fertilizer according to Example 2, compared to the conventional fertilization plant, which was a general fast-acting fertilizer treatment plant. Even though the fertilizer was applied at 50% of the application amount, the results were still excellent, and it was confirmed that a coating fertilizer in which the fertilizer nutrient elution was constant during the entire period of plant growth could be prepared through the fertilizer coating composition of the present invention.

Claims (14)

Polyurethane polymer, a monomer and a crosslinking agent comprising a polymerized polyurethane / acrylic hybrid polymer,
The polyurethane polymer is prepared using polyether polyol and isocyanate,
The polyether polyol is any one selected from the group consisting of polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol and polytetramethylene ether glycol,
The isocyanate is
Any one selected from the group consisting of isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, methyldiphenyl diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, cyclohexane diisocyanate and xylene diisocyanate more than,
The monomer includes 30 to 50 parts by weight of an acrylic monomer, styrene and acrylonitrile based on 100 parts by weight of the polyurethane polymer,
The weight ratio of the styrene / acrylonitrile is 2.8 to 3.0,
The acrylic monomer is, normal butyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, acrylic acid, isobutyl methacrylate and 2-hydroxyethyl methacrylic Any one or more selected from the group consisting of rate,
The crosslinking agent is allyl methacrylate, tripropylene glycol diacrylate, divinylbenzene, triaryl cyanate, vinyl trimethoxysilane, vinyl triethoxysilane, trimethylolpropane trimethacrylate, 3-aminopropyl tri Fertilizer coating composition, characterized in that at least one selected from the group consisting of ethoxysilane and 3-mercaptopropyltrimethoxysilane.
According to claim 1,
The polyurethane polymer,
Fertilizer coating composition, characterized in that it is prepared by additionally using an ionizer, a chain extender, a capping agent, a catalyst and a neutralizing agent.
delete delete 3. The method of claim 2,
The ionizing agent is a fertilizer coating composition, characterized in that dimethylol propionic acid.
3. The method of claim 2,
The chain extender,
ethylenediamine, diaminobutane, diaminopropane, hydrazine, isophoronediamine, hexamethylenediamine, ethylene glycol, butanediol, diethylenetriamine, isosorbide, diaminodicyclohexylmethane and methylpentamethylenediamine. Fertilizer coating composition, characterized in that any one or more selected from the group.
3. The method of claim 2,
The capping agent,
Fertilizer coating composition, characterized in that at least one selected from the group consisting of dihydroxybenzene, diallylbisphenol, naphthoresorcinol, dihydroxynaphthalene, proroglucinol and resorcinol.
3. The method of claim 2,
The polyurethane polymer,
Fertilizer coating composition comprising 5 to 100 parts by weight of isocyanate, 1 to 50 parts by weight of an ionizer, 0.1 to 50 parts by weight of a chain extender, and 0.1 to 50 parts by weight of a capping agent based on 100 parts by weight of a polyol.

delete delete delete According to claim 1,
The crosslinking agent,
Fertilizer coating composition, characterized in that 0.5 to 10 parts by weight are included with respect to 100 parts by weight of the polyurethane polymer.
According to claim 1,
The polyurethane / acrylic hybrid polymer,
A composition for fertilizer coating, characterized in that the weight average molecular weight is 80,000 ~ 200,000 g/mol, the pH is 7 ~ 12, the particle size is 80 ~ 250nm, and the viscosity is 5 ~ 50cps.
preparing a first reactant by polymerizing polyether polyol and isocyanate;
preparing a secondary reactant by adding an ionizer and a catalyst to the first reactant;
preparing a tertiary reactant by adding a chain extender to the secondary reactant;
preparing a polyurethane polymer seed by adding a capping agent and a neutralizing agent to the tertiary reactant; and
Putting a mixture of a monomer, an initiator, an emulsifier and a crosslinking agent in the polyurethane polymer seed and reacting it to prepare a polyurethane/acrylic hybrid polymer,
The method of claim 1, wherein the monomer comprises an acrylic monomer, styrene and acrylonitrile.

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