JPH03112882A - Spreader and composition for mixed fertilizer granule - Google Patents

Abstract

PURPOSE:To obtain a spreader for a mixed fertilizer granule excellent in spreading properties in water by using a sulfone group-containing vinyl polymer as a component. CONSTITUTION:A spreader composed of a sulfone group-containing vinyl polymer which is a water-dispersible or water-soluble polymer. Sulfonated polystyrenes and/or salts thereof, polymers of a sulfone group-containing vinyl monomer and copolymers of the sulfone group-containing monomer with other copolymerizable monomers are cited as the sulfone group-containing polymer. The polymer is preferably the salts of the sulfonated polystyrenes and the content of the styrenes in the copolymers of the styrenes is normally >=30mol%. The molecular weight of the polystyrenes is normally 500-1000000. The average molecular weight of the sulfone group-containing vinyl polymer is normally 1000-2000000 and viscosity thereof is normally 10-100000cPs expressed as the viscosity of a 30wt.% aqueous solution thereof.

Description

[Detailed description of the invention] [Conventional technology] Traditionally, fertilizers have been applied individually to each component.

However, due to diversification of consumer needs in recent years, compound fertilizers that can apply various fertilizers at once are being developed. A mixture of these fertilizers is granulated with an oil-based binder to form a product, which is diluted with water before application. As agents for improving dispersibility in water, alkylbenzenesulfonic acid sodium salts, alkylnaphthalenesulfonic acid sodium salts, and the like have been used.

[Problems to be Solved by the Invention] However, conventional dispersants do not have sufficient dispersibility in water.

[Means for Solving the Problems] As a result of intensive studies to solve this problem, the inventors have arrived at the present invention.

That is, the present invention provides an extender for compound fertilizers characterized by comprising a sulfone group-containing vinyl polymer;
6. A compounded fertilizer granule composition characterized by comprising the spreading agent according to any one of Item 6, a granulation binder, and a fertilizer.

In the present invention, the sulfone group-containing vinyl polymer is a water-dispersible or water-soluble polymer, such as a sulfonated product of polystyrene and/or its salt, a polymer of a sulfone group-containing vinyl monomer, a sulfone group-containing monomer, etc. Examples include copolymers with copolymerizable monomers. Preferred are salts of sulfonated polystyrenes.

Specifically, the following sulfone group-containing vinyl polymers may be mentioned.

(A) Sulfonated polystyrenes Polystyrenes include styrene, α-methylstyrene, α
- Including homopolymers of styrenes such as ethylstyrene and copolymers of styrenes and monomers copolymerized therewith.

Monomers that copolymerize with styrenes include (meth)acrylic acid alkyl esters [methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. ,
lauryl (meth)acrylate, stearyl (meth)acrylate, etc., vinyl ester monomers [vinyl acetate, vinyl propionate, vinyl phthalate, etc.], aromatic hydrocarbon vinyl monomers [vinylnaphthalene, vinyltoluene, p-methyl styrene, etc.], unsaturated (di)carboxylic acids or their anhydrides [(meth)acrylic acid, maleic anhydride, itaconic anhydride, etc.], (chlorinated) olefins [α-olefin, isoprene, inbutylene, diisobutylene , butadiene, chloroprene, etc.],
Examples of the nitrile base include vinyl monomers [(meth)acrylonitrile, etc.] listed below as examples of other copolymerizable monomers in (B), and two or more thereof.

The styrene content of the styrene copolymer is usually 30 mol% or more, preferably 50 mol% or more. The molecular weight of polystyrenes is usually 500 to 1.000,000.
, preferably 2,000 to 500,000, more preferably 3,000 to 100,000.

The sulfonated product can be produced by a conventional sulfonation method. In addition, the applicant has filed a patent application for patent application Hei 1-
81111i! It can also be produced by the methods described in Japanese Patent Application No. 1-114593, Japanese Patent Application No. 1-117832, and Japanese Patent Application No. 1-161027.

Sulfonates are typically hydroxides, carbonates, or ammonia, such as alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium,
It is neutralized with a neutralizing agent such as amines, such as alkylamines such as triethylamine, dimethylamine, laurylamine, and stearylamine, and alkanolamines such as monoethanolamine and jetanolamine.

Preferred are sodium salts, potassium salts, and ammonium salts.

(B) Polymer of sulfonic group-containing vinyl monomer Polymers of sulfonic group-containing monomer include aromatic hydrocarbon vinyl sulfonic acid, sulfonic acid group-containing (meth)acrylamide, (meth)acrylate with sulfonic acid group, aliphatic Examples include (co)polymers of one or more monomers such as hydrocarbon vinyl sulfonic acid and salts thereof, or copolymers with other copolymerizable monomers. Among these, aromatic hydrocarbon vinyl sulfonic acid (salt) is preferred. Specific examples of the sulfone group-containing monomer include the following monomers.

(B-1) Aromatic hydrocarbon vinyl sulfonic acid p- and 0-styrene sulfonic acid, styrene disulfonic acid, α-
Methylstyrenesulfonic acid, vinylphenylmethanesulfonic acid, etc. and their salts (B-2) Sulfonic acid group-containing (meth)acrylamide 2-(meth)acrylamide-2-methylpropanesulfonic acid, 3-(meth)acrylamidepropane- 1-sulfonic acid, 2-(meth)acrylamidoethyl-1-sulfonic acid, 3-(meth)acrylamido-2-hydroxypropanesulfonic acid, p-(meth)acrylamidomethylbenzenesulfonic acid, etc. and salts thereof (B- 3) Sulfonic acid group-containing (meth)acrylate 3-(meth)acryloyloxypropane-1-sulfonic acid, 4-(meth)acryloyloxybutane-1-sulfonic acid, 4-(meth)acryloyloxybutane- 2-sulfonic acid, 2-(meth)acryloyloxyethyl-1=sulfonic acid, 3-Cmeth)acryloyloxy-2-hydroxypropanesulfonic acid, sulfopropyl (meth)acrylate, 2-hydroxy-3-(meth) Acryloxypropylsulfonic acid, 2-(meth)acryloylamino-2,2-dimethylethanesulfonic acid, etc. 3-(meth)
Acryloyloxyethanesulfonic acid, 3-(meth)acryloyloxy-2-hydroxypropanesulfonic acid, etc. and salts thereof (B-4) Aliphatic hydrocarbon vinyl sulfonate vinylsulfonic acid, (meth)allylsulfonic acid, etc. These salts Salts of sulfonic acid group-containing monomers include alkali metal salts such as sodium, potassium, and lithium, calcium,
Examples include alkaline earth metal salts such as magnesium, ammonium salts, amine salts such as ethanolamine, jetanolamine, monomethylamine, trimethylamine, and triethylamine, and preferred are sodium salts, potassium salts, and ammonium salts. - Other copolymerizable monomers copolymerized with the sulfone group-containing vinyl monomer include the following monomers.

Other copolymerizable monomers in the present invention include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, amide group-containing monomers, hydrophilic monomers such as hydroxyl group-containing monomers, unsaturated monocarboxylic acid alkyl esters, unsaturated dicarboxylic acids, etc. Examples include hydrophobic monomers such as alkyl esters, conjugated dienes, chain olefins and cyclic olefins, vinyl ester monomers, and nitrile group-containing monomers, and one or more of these can be used in combination.

Examples of unsaturated monocarboxylic acids include acrylic acid and methacrylic acid, and examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.

Further, as the salts of the above acids, for example, alkali metal salts (such as sodium), ammonium salts, organic amine salts (triethanolamine salts), and mixtures thereof can also be used.

Examples of the amide group-containing monomer include (meth)acrylamide or Fl,N-di(hydroxy)alkyl(meth)acrylamide.

Hydroxyethyl (meth) as a hydroxyl group-containing monomer
Examples include acrylate and hydroxy lower alkyl (meth)acrylate such as hydroxypropyl (meth)acrylate.

Other polyethylene glycol (meth)acrylates such as triethylene glycol (meth)acrylate;
Unsaturated alcohols such as (meth)allylic alcohol are also used as hydrophilic monomers.

Specific examples of unsaturated monocarboxylic acid alkyl esters and unsaturated dicarboxylic acid alkyl esters include the aforementioned alkyl esters of unsaturated (mono- or alkyl) carboxylic acids (the number of carbon atoms in the alkyl group is usually 1 to 20). Specific examples of alkyl groups include methyl, ethyl, propyl, n-, sec-.

tert-butyl, pentyl, hexyl, dodecyl,
Examples include eicosyl and 2-ethylhexyl groups. More specifically, methyl (meth)acrylate, (
Examples include ethyl meth)acrylate, butyl (meth)acrylate, ethylhexyl (meth)acrylate, and stearyl methacrylate.

Examples of the conjugated diene include butadiene, and examples of the chain olefin include ethylene, propylene, and isoprene.

Examples of cyclic olefins include styrene and alkyl group-substituted styrene (α-methylstyrene, p-methylstyrene,
(vinylnaphthalene, vinyltoluene, etc.).

Vinyl ester monomers include vinyl acetate, vinyl fluohionate and vinyl phthalate.

Examples of the nitrile group-containing monomer include (meth)acrylonitrile.

Preferred among these are hydrophilic monomers.

Among the above sulfonate salts, the salts include sodium salt,
Examples include alkali metal salts such as potassium salts and lithium salts, alkaline earth metal salts such as calcium salts and magnesium salts, and amine salts such as ethanolamine salts and triethanolamine salts. Preferred are sodium, potassium, lithium, calcium, and magnesium salts, and particularly preferred are (1) sodium and (2) salts.
It is a salt used in combination with potassium and/or lithium. In the case of combined salts, the molar ratio of (+) and (2) is usually 99:l-1
:99.

In the case of combined salts, a copolymer having two or more types of salts in the molecule is preferred, but a mixture of two or more types of salts may be used.

There are no particular restrictions on the production of the polymer of the sulfone group-containing vinyl monomer, but it can be produced by an ordinary solution polymerization method. For example, it can be manufactured by the method described in Japanese Patent Application No. Hei 1-IEi1027.

The average molecular weight of the sulfone group-containing vinyl polymer in the present invention is usually 1.000 to 2,000,000, preferably,
5.000 to 500.000. Average molecular weight is 1,
000 grooves do not have sufficient underwater expansibility, and 2,000,
If it exceeds 000, the underwater dispersibility deteriorates. The viscosity is usually 10 to 100,00 when expressed as a 30% by weight aqueous solution viscosity.
0 cps, preferably about 20-1.000 cps.

The content of sulfonic group-containing monomers is usually from 5% to 100%, preferably from 30% to 100%, based on the weight of the entire polymer.
: The content of other copolymerizable monomers is usually 0% to 95%, preferably 0% to 50%.

The compound fertilizer expander of the present invention may contain binders (starch, CMC1 sodium alginate, etc.), disintegration accelerators (alkali metal phosphates, etc.), decomposition inhibitors, antifoaming agents, etc., as necessary. It is possible.

In addition to the above components, a surfactant such as polyoxyethylene alkylaryl ether may be added as a wetting agent if necessary.

Furthermore, anionic surfactants and nonionic surfactants can also be contained. As these surfactants, those described in Japanese Patent Publication No. 57-39878 can be used.

Examples of the anionic surfactant include sodium alkylbenzene sulfonate, sodium lignin sulfonate, and polyoxyethylene alkyl sulfate salt. Preferred are sodium dodecylbenzenesulfonate and sodium ligninsulfonate.

Examples of nonionic surfactants include polyoxyethylene alkylaryl ether and polyoxyethylene alkyl ether.

The spreading agent (A) for compounded fertilizer granules of the present invention is used as a spreading agent for a granular compounded fertilizer composition containing a fertilizer (B) and a granulating binder (C).

Fertilizers (B) include nitrogen fertilizers (sodium nitrate, ammonium sulfate, ammonium nitrate, ammonium chloride, urea, etc.), phosphorus fertilizers (superphosphate lime, heavy superphosphate lime,
ammonium phosphate, etc.), potassium fertilizers (potassium chloride,
potassium nitrate, etc.), lime fertilizers (quicklime, slaked lime, etc.)
, chemical fertilizers such as magnesium fertilizers (such as magnesium sulfate), silicate fertilizers (such as ammonium silicate), manganese fertilizers (such as manganese sulfate), and organic fertilizers such as rapeseed meal.

As the binder for granulation (C), anything can be used as long as it has a certain degree of caking property (for example, alcohol waste liquid after alcohol fermentation and alcohol distillation, mineral powder (waxite, talc, kaolin, calcium carbonate, bench, etc.). night,
silica powder 9 silica powder, acid clay, silica powder 1 gypsum,
pumice powder, etc.). Also, sometimes the fertilizer itself acts as a binder.

The amounts of each component are as follows based on the weight of the combined fertilizer granule composition. The expander (A) for compounded fertilizer granules is usually 0.
It is 1 to 10%, preferably 0.5 to 5%.

If the amount is less than 0.1%, no effect can be expected, and if the amount exceeds 10%, the benefits of increasing the amount may be outweighed by the deterioration of the formulation condition.
Problems such as economic disadvantage arise.

The blended fertilizer (B) is usually 50 to 98%, preferably 80 to 98%.
It is 85%.

The content of the granulating binder (C) is usually 0 to 50%, preferably 5 to 30%.

The method for producing the compounded fertilizer granule composition of the present invention involves blending the extender, compounded fertilizer, and granulation binder of the present invention in the above-mentioned proportions, pulverizing if necessary, mixing uniformly, and then adding an appropriate amount of water. After mixing and kneading, the mixture is granulated and dried to obtain the desired product.

For granulation, extrusion type granulation machine, pressure type granulation machine, fluidized bed granulation machine,
This can be carried out using a granulator such as a spray dryer, or a crushing granulation method or the like may be employed.

The particle size of the resulting blended fertilizer granules is usually 0.1 to 10 mm.

The compounded fertilizer granule composition of the present invention prepared using the above-mentioned spreader for compounded fertilizer granules is poured into water and dispersed to prepare a spray solution for use. The amount of compounded fertilizer granules added to water is arbitrary, but is preferably about 20 to 50% by weight. The spray liquid is applied to fields etc. in a form according to each fertilizer component.

[Examples] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.

The abbreviations in the table are as follows.

al: Styrenesulfonic acid a2: 2-acrylamido-2-methylpropanesulfonic acid bl= Acrylic acid b2: Maleic acid () Numbers in parentheses are % by weight.

The numbers in the salt column indicate molar ratios.

Table 1 Example 6 Sulfonated polystyrene (molecular weight: 2G, 000
, degree of sulfonation 100%) Example 7 Sulfonated product of copolymer of styrene and maleic acid (molar ratio of styrene and maleic acid 7:3) (molecular weight: 280
0, degree of sulfonation 100%) Dispersants of comparative examples are shown below.

Comparative Example 1 Alkylnaphthalenesulfonic acid Na salt Formalin condensate (molecular weight: 12,000) 2 Polyoxyethylene (10 mol) alkyl ether 3 Alkylbenzenesulfonic acid Na salt 4 Polycarboxylic acid Na salt (Molecular weight: 15,000) 5 Poly Oxyethylene (lO mol) nonylphenyl ether Examples 8 to I4 and Comparative Examples 6 to 10 The formulations shown in Tables 2 and 3 were mixed in a bench kneader and granulated in an extrusion molding machine (1,2 ■/■) I did. Next, dry in a hot air dryer (Cafe Roaster) (12
0 to 150°C), a blended fertilizer granule composition was obtained.

Examples 8 to 14 and Comparative Example 6! The chemical fertilizer (B) and binder (C) used in O are as follows.

Fertilizer Indigo Ammonium sulfate 2 Potassium sulfate 3 Urea 4 Ammonium phosphate 5 Rapeseed meal binder Physical properties of alcohol fermentation waste liquid Examples 8 to 14 and Comparative Example G-10 were evaluated by the following method.

(1) Spreadability Take 20g of the granules obtained above in a 100ml measuring cylinder with a stopper, add 80ml of 3 degree hard water (water containing 30 ppm as CaO) and 10 degree hard water (water containing toopppm as CaO) 30 times ( 2 seconds/time) falls. Observe the color of the liquid in the upper layer, and if it is dark, it is considered good. Then 0.
After transferring to a 5 mm wire mesh and drying (130° C., 2 hours), the amount remaining on the wire mesh was measured and the disintegration rate was calculated using the following formula. Those with a high rate of disintegration are considered good.

-B Suspension rate (%) X 1GG A: Weight of the sample accurately weighed at the beginning (g) B: Dry residue weight (g) The above evaluation results are shown in Table 5.

(2) Precisely weigh 10.0 g of the foaming sample into a beaker, add 10+al of 3 degree hard water at 20°C, and mix and disperse well. That's 25
Transfer to a 0m1 framed cylinder and add 20"C 3 degree hard water to make it 2501. After leaving it for 15 minutes,
The foam height (am) is measured immediately after vigorous shaking.

The lower the height of the bubbles, the better.

table Unit indicates weight% (The weight of the composition is 100) table Unit indicates weight% (The weight of the composition is 100).

The evaluation results are shown in Table 4.

Table 4 A: 3 degree hard water B: 10 degree hard water [Effects of the invention] The spreader for compound fertilizers of the present invention is a dispersant with excellent water spreadability, and has low foaming properties and has a spreadability comparable to that of water. It is also excellent in that it is not affected by hardness.

Claims (1)

[Scope of Claims] 1. A spreading agent for compounded fertilizer granules, characterized by comprising a sulfone group-containing vinyl polymer. 2. The extending agent according to claim 1, wherein the sulfone group-containing vinyl polymer is a sulfonated polystyrene and/or a salt thereof. 3. The extending agent according to claim 1, wherein the sulfone group-containing vinyl polymer is a copolymer of a sulfone group-containing monomer and another copolymerizable monomer. 4. Other copolymerizable monomers include unsaturated monocarboxylic acids, unsaturated monocarboxylic acid alkyl esters, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid alkyl esters, amide group-containing monomers, hydroxyl group-containing monomers, conjugated dienes, and chain olefins. , 1 selected from the group consisting of cyclic olefins, vinyl ester monomers, and nitrile group-containing monomers
The extender according to claim 3, which is one or more monomers. 5. The weight average molecular weight of the sulfone group-containing vinyl polymer is 1
The expanding agent according to any one of claims 1 to 4, which has a molecular weight of 1,000 to 2,000,000. 6. Claims 1 to 5 that the compounded fertilizer is a fertilizer selected from the group consisting of nitrogen fertilizer, phosphoric acid fertilizer, potassium fertilizer, lime fertilizer, magnesia fertilizer, silicate fertilizer, manganese fertilizer, and rapeseed meal.
The extender described in any of the above. 7. A blended fertilizer granule composition comprising the spreading agent according to any one of claims 1 to 6, a granulating binder, and a fertilizer.