JPH0229641B2 - SUICHUHOKAISEINORYOKONARYUJONOYAKUSOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention provides a granular agricultural chemical composition with good disintegration in water,
In particular, the present invention relates to a granular agricultural chemical composition that has good disintegration properties even in hard water. The dosage forms of agricultural chemicals used today include powders, emulsions, wettable powders, granules, and flowables. Among these, granules are easy to handle and Unlike powders, emulsions, etc., there is no risk of scattering fine powder or mist droplets during spraying, so it is highly regarded for its safety, and is therefore expected to develop in the field of herbicides and insecticides in the future. However, existing granules have drawbacks such as causing eutrophication of rivers, lakes and marshes, and their disintegration properties in water are affected by the hardness of the water and are particularly markedly reduced in hard water. In other words, granular pesticides have an inorganic mineral carrier such as bentonite, calcium carbonate, clay, talc, or kaolin as the main ingredient, and a viscosity such as starch, polyvinyl alcohol, gelatin, sodium carboxymethyl cellulose, or sodium alginate. Binder and inorganic phosphates such as sodium tripolyphosphate and sodium pyrophosphate, polyethylene glycol nonyl phenyl ether (HLB12-14), sodium salt of dialkyl sulfosuccinate, sodium lignin sulfonate or sodium alkylbenzene sulfonate, etc. It is granulated by adding a disintegrant selected from surfactants, but even if the disintegrants, such as phosphates, are cheap, they can enrich water if it flows into rivers or lakes. It has the disadvantage of being nutrient-rich and, as a result, prone to various pollution problems. Also, surfactants have little effect on extremely hard water. In view of the above-mentioned drawbacks of the known disintegrants, a polymer composed of an unsaturated monocarboxylic acid and an unsaturated dicarboxylic acid as described in Japanese Patent Publication No. 48-1501 has been proposed as an improvement. There is. Although this latter improves disintegration in hard water compared to conventional disintegrants, it is still far from the level required today. The object of the present invention is to improve the shortcomings of known disintegrants for granular pesticides, to provide a composition for granular pesticides containing a novel disintegrant that has good disintegration properties in hard water and does not cause eutrophication of water quality. The goal is to provide the following. As a result of numerous studies aimed at improving the drawbacks of the above-mentioned known disintegrants, the present inventors have now developed a sulfonated product of a binary or tertiary copolymer resin of a monoolefin and/or vinyl compound and an ethylenically unsaturated dicarboxylic acid. It has been discovered that the water-soluble salt has extremely excellent performance as a disintegrant for granular agricultural chemicals containing inorganic minerals as a carrier, and is not easily affected by the hardness of the water used. The present invention is based on this knowledge,
The gist of this method is to use a water-soluble salt of a sulfonated product of a binary or tertiary copolymer resin of a monoolefin and/or a vinyl compound and an ethylenically unsaturated dicarboxylic acid as a disintegrant for granular agricultural chemicals. In the above invention, "monoolefin" means an ethylene series hydrocarbon represented by the general formula C _o H _2o , and specifically includes, for example, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1
-Pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2
-butene, 1-hexene, 2,3-dimethyl-2
-Butene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. Furthermore, “vinyl compound” refers to a vinyl group (CH ₂ =
CH-) or alcohols, ethers, aldehydes, ketones derived therefrom,
Refers to compounds such as carboxylic acids or esters, specifically, for example, styrene, methyl vinyl ether,
Examples include ethyl vinyl ether and acrylic ester. Furthermore, "ethylenic unsaturated dicarboxylic acid" refers to a dicarboxylic acid having a -C=C- bond in the molecule, and specifically includes fumaric acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, etc. ,
Industrially, maleic acid or its dehydrate (maleic anhydride) is the most important. The disintegrant according to the present invention is produced by sulfonating the copolymer of the monoolefin and/or vinyl compound and ethylenically unsaturated dicarboxylic acid, and then converting the sulfonic acid groups of the polymer into a salt form with an appropriate basic substance. Although obtained by conversion, the monoolefin and vinyl compound may each be single or plural. And when a plurality of monoolefins or vinyl compounds are reacted, one of them can be a monoolefin and the other a vinyl compound. One of the most preferred copolymer resins for purposes of the present invention is a styrene-maleic anhydride copolymer, which is a binary reaction product of a single vinyl compound and maleic anhydride; The copolymer resin is a binary copolymer of isobutylene and maleic anhydride. Furthermore, the styrene/isobutylene/maleic anhydride copolymer, which is an example of a still more preferred copolymer resin, is a ternary copolymer of one type of vinyl compound, one type of monoolefin, and one type of ethylenically unsaturated dicarboxylic acid. be. The above copolymerization reaction can be carried out by a known copolymerization reaction. For example, styrene/maleic anhydride copolymer is prepared by combining styrene and maleic anhydride in a P-cymene solvent in the presence of a radical catalyst such as benzoyl peroxide. Obtained by reaction at a temperature of 150-180°C. Furthermore, the subsequent sulfonation can be carried out by known sulfonation means,
For example, by reacting the styrene/maleic anhydride copolymer obtained above with a sulfating agent such as sulfuric anhydride, sulfuric acid, or chlorosulfonic acid in a halogenated solvent such as dichloroethane or methylene chloride, the desired sulfonated resin can be easily obtained. can be obtained. This sulfonated resin is finally treated with sodium hydroxide,
By neutralization with an inorganic or organic base such as potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, monoethanolamine, ethylenediamine or triethanolamine, it is converted to a water-soluble salt useful as a composition of the invention. . The composition of the present invention contains the above-mentioned disintegrant as an essential component in addition to the agricultural chemical raw material (powder or liquid) that is a necessary component as a granular agricultural chemical, the mineral powder and binder as the carrier. The amount of disintegrant is preferably selected at a ratio of about 0.2 to 3.0% (by weight) based on the total amount of the composition. However, this amount is only a tentative guideline, and the properties should be determined experimentally as appropriate, depending on the expected slow disintegration rate of the target granule, the presence or absence of other types of disintegrants, and other factors. Of course. Granulation of the agricultural chemical, which is the final form of the composition of the present invention, can be carried out by wet granulation methods such as rolling granulation in an inclined rotating pan, extrusion using an extruder, or slug tableting, as well as general formulation methods. This can be carried out by a dry granulation method using crushing or other known means. In general, dry granulation is preferable in order to prevent deterioration of the base ingredient, but in this case, a small amount of lubricant such as stearic acid or magnesium stearate is added to the composition to avoid the composition from adhering to the die or punch. is preferable. The embodiments of the invention will be described below with reference to Examples, but the examples are, of course, for illustrative purposes and are not meant to limit the spirit of the invention. Example After adding water to the granular agricultural chemical compositions shown in the following formulations () and () and kneading them, they were granulated using an extrusion type granulator, and the water disintegration of the obtained granules was tested according to the following test method. Therefore, it was evaluated. The results are shown in Table-2. Formula () NIP raw material 9 (wt%) Bentonite 30 Calcium carbonate 59 Sodium carboxymethyl cellulose
1 Disintegrant (see Table 1 below) 1 Prescription () NAC bulk 5 (wt%) Bentonite 50 Clay 43 Polyvinyl alcohol 1 Disintegrant 1

【table】

[Table] * Disintegrant of the present invention ** Control disintegrant (disintegration test method) Add standard hard water to a depth of 1 cm in a shear dish with a diameter of 25 cmφ and a depth of 4 cm. Next, hold the double-cut glass tube upright in the center of the shear plate and add 0.5% of the test granules.
Put g into a glass tube. Gently pull up the glass tube and measure the shortest and longest parts of the spread part of the granules every 5, 15, and 30 minutes, and use the average value as an index of the degree of disintegration. <Comprehensive evaluation> ◎: Excellent disintegration in water ○: 〃 Good △: 〃 Slightly poor ×: 〃 Extremely poor

[Table] As shown in the table above, the compositions of the present invention (Experiment No. 1 to
6) Even in the case of extremely hard water with a hardness of 20°,
Shows a similar disintegration index to less hard water. In contrast, the control compositions (experiments no. 7-12)
The disintegration index of the former is clearly lower than that of the former, especially in Experiment No. using polyoxyethylene nonyl phenyl ether, sodium alkylbenzenesulfonate, and sodium ligninsulfonate as disintegrants.
A score of 10-12 is extremely poor. From these results,
It is clear that the water-soluble salt of the sulfonated monoolefin and/or vinyl compound/ethylenic unsaturated dicarboxylic acid copolymer according to the present invention is highly effective as a hard water-resistant disintegrant in improving the physical properties of granular agricultural chemicals.

Claims (1)

[Scope of Claims] 1. A water-disintegrating product containing, as an essential component, a water-soluble salt of a sulfonated product of a binary or tertiary copolymer resin of a monoolefin and/or a vinyl compound and an ethylenically unsaturated dicarboxylic acid. Good granular pesticide composition. 2. Claim 1, wherein the sulfonated copolymer resin is a sulfonated styrene/maleic anhydride copolymer resin, a sulfonated isobutylene/maleic anhydride copolymer resin, or a sulfonated styrene/isobutylene/maleic anhydride copolymer resin. Compositions as described. 3. The composition according to claim 1 or 2, wherein the water-soluble salt of the sulfonated copolymer resin is contained in the composition in an amount of 0.2 to 3% by weight. 4. The composition according to any one of claims 1 to 3, wherein the composition comprises a mineral carrier.