JPS58131903A - Granular agricultural chemical composition having improved disintegrating property in water - Google Patents

Abstract

PURPOSE:The titled composition having improved disintegrating properties in water especially in hard water, having no fear of making water quality rich in nutrient, comprising a water-soluble salt of a sulfonated monoolefin.ethylenic unsaturated dicarboxylic acid copolumer resin, etc. as an essential disintegrating agent component. CONSTITUTION:The titled composition comprising 0.2-0.3wt% based on the composition of water-soluble salt of a sulfonated monoolefin (ethylenic hydrocarbon of C12H2n) and/or vinyl compound.ethylenic unsaturated dicarboxylic acid copolymer resin such as sulfonated styrene.maleic anhydride copolymer resin, sulfonated.isobutylene.maleic anhydride copolymer resin, sulfonated.styrene.isobutylene.maleic anhydride terpolymer resin, etc. as a disintegrating agent for a granular agricultural chemical. The water-soluble salt is blended with a base material for agricultural chemical (granular or liquid), a carrier of an inorganic mineral substance, a binder and water, kneaded, extruded, granulated by a granulator, and used as a granular agricultural chemical.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a granular agricultural chemical composition that has good disintegration properties in water, and particularly 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 and #A swamps, and that their disintegration properties in water depend on the hardness of the water, and are particularly markedly reduced in hard water. In other words, granular pesticides contain bentonite,
The main component is an inorganic mineral carrier such as cal/rum carbonate, clay, talc, or kaolin, and a binder such as starch, polyvinyl alcohol, gelatin, sodium carpoquin methylcellulose, or sodium alginate.
and inorganic phosphoric acids such as sodium tripolyphosphate and sodium pyrophosphate! [Ya;t? ! J ethylene glycol nonylphenyl ether (I(LB12/-14),
It is granulated by adding a disintegrant selected from surfactants such as sodium salt of dialkyl sulfosuccinate, sodium lignin sulfonate, or sodium alkylbenzene sulfonate. Even though acid salts are inexpensive, they have the disadvantage that if they flow into rivers or lakes, they tend to eutrophic the water, resulting in various pollution problems. Additionally, 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 already described in Japanese Patent Publication No. 48-1501 has been proposed as an improvement. There is. The latter improves disintegration in hard water compared to conventional disintegrants, but is still fast enough to meet today's demands.

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 to improve the drawbacks of the above-mentioned known disintegrants, the present inventors have now developed a sulfonated monoolefin and/or vinyl compound, an ethylenically unsaturated dicarboxylic acid copolymer, an ethylenically unsaturated dicarboxylic acid copolymer, and the like. It has been discovered that a water-soluble salt of an acid copolymer resin has extremely excellent performance as a disintegrant for granular agricultural chemicals containing inorganic minerals as a carrier, in that it is hardly affected by the hardness of the water used. The present invention is based on this knowledge, and its gist lies in the use of a water-soluble salt of a sulfonated monoolefin and/or a vinyl compound/ethylenic unsaturated dicarboxylic acid copolymer as a disintegrant for granular agricultural chemicals.

In the above invention number, the term 'monoolefin' means an ethylene series hydrocarbon represented by the general formula Cl2H2n, and specifically, examples include ethylene, propylene, 1-butene, 2-butene, isobutylene, l -Pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, l-hexene, 2.3
-Dimethyl-2-butene, l-heptene, l-octene, 1-nonene, 1-decene, etc.

Mata “vinyl compound” is vinyl M (CM2=CH
-) or alcohols derived therefrom, ethers 1. It refers to compounds such as aldehydes, ketones, carboxylic acids, or esters, and specific examples include styrene, methyl vinyl ether, ethyl vinyl ether, and acrylic ester.

In addition, "ethylenically unsaturated dicarboxylic acid 1" refers to a dicarboxylic acid having a -C=C- bond in the molecule, specifically fumaric acid, maleic acid, citraconic acid, mesaconic acid,
Although itaconic acid and the like are included, maleic acid or its dehydrate (seleic anhydride) is the most important industrially.

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. In addition, when a plurality of monoolefins or vinyl compounds are reacted, one of them can be a monoolefin and the other can be a vinyl compound. One of the most preferred copolymer resins for purposes of the present invention is a styrene/maleic anhydride copolymer, which is also a binary copolymer of imbutylene and maleic anhydride. Furthermore, styrene/imbutylene/maleic anhydride copolymer, which is an example of a still more preferable copolymer resin, is
It is a ternary copolymer of one type of vinyl compound, one type of monoolefin, and one type of ethylenically unsaturated dicarboxylic acid.

The above copolymerization reaction can be carried out by a known copolymerization reaction. For example, a 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 benzyl peroxide. 150-1
It is obtained by reacting at a temperature of 80°C. Further, the subsequent sulfonation can be carried out by known sulfonation means, for example, the styrene/maleic anhydride copolymer obtained above is mixed in a halogenated solvent such as dichloroethane or methylene chloride, for example, sulfuric anhydride, sulfuric acid, chloride, etc. By reacting with a sulfating agent such as sulfonic acid, the desired sulfonated resin can be easily obtained. The sulfonated resin is finally neutralized with an inorganic or organic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, monoethanolamine, ethylenediamine or triethanolamine to form a composition according to the invention. converted into commercially useful water-soluble salts.

The composition of the present invention contains the above-mentioned disintegrating agent as an essential component in addition to the agricultural chemical raw material (powder or liquid) which is a necessary component for a granular agricultural chemical, the mineral powder and binder mentioned above as a carrier. The amount of disintegrant is about 0.2-3 based on the total amount of the composition.
, 0% (weight l). However,
This amount is only a rough guideline, and it goes without saying that the properties will be determined experimentally depending on the slow disintegration rate expected of the target granule, the presence or absence of other types of disintegrants, and other factors. It is.

Granulation of the agricultural chemical, which is the final form of the composition of the present invention, can be carried out by a wet granulation method such as a transfer granulation method in an inclined rotating pan, an extrusion method using an extruder, or a slug tableting and crushing method, as well as general formulation methods. It can be carried out by a dry granulation method according to the above method, or by 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 may be added to the composition to prevent the composition from adhering to the die or punch. is preferred. Hereinafter, embodiments of the invention will be described with reference to Examples, but the examples are of course for illustration only and are not intended to limit the spirit of the invention.

After adding and kneading, the mixture was granulated using an extrusion type granulator, and the disintegrability of the resulting granules in water was evaluated according to the following test method. The results are shown in Table-2.

Prescription (I) NIP drug substance 9 (wt%) Bentonite 30 Calcium carbonate 59 Sodium carboxymethylcellulose 1 Disintegrant (see Table-1 below) l Prescription ■ NAC drug substance 5 (wt%) Bentonite 50 Clay 43 Polyvinyl alcohol 1 Disintegrant 1 Table-1 This invention disintegrant ** Control disintegrant disintegration test method> Standard hard water 0 in a petri dish with a diameter of 25 cm and a depth of 4 crn
．． Put 5 g into a glass tube. The static value of this glass tube is used as an index of the degree of collapse.

Comprehensive evaluation> O: Excellent disintegration in water O: Good △: l/ Slightly poor ×: ll Extremely poor (blank below) Table 2 As shown in the above table, the compositions of the present invention (experiment numbers 1 to 6) Even in the case of extremely hard water with a hardness of 2 (7'), it shows a disintegration index similar to that for water of lower hardness, whereas the disintegration index of the control compositions (experiments no. 7 to 12) is clearly compared to the former. In particular, the results of experiments I61θ to 12 in which polyoxydiethylene nonylphenyl ether, sodium alkylbenzene sulfonate, and sodium lignin sulfonate were used as disintegrants were extremely poor.From these results, it is clear that the sulfone according to the present invention It is clear that water-soluble salts of monoolefins and/or vinyl compounds/ethylenically unsaturated dicarboxylic acid copolymers are highly effective as hard water-resistant disintegrants in improving the physical properties of granular agricultural chemicals.

Procedural Amendment (Imported) February 5, 1980 Haruki Shimada, Commissioner of the Japan Patent Office Tonoki 2, Title of the invention: Granular agricultural chemical composition with good disintegration in water 3, Relationship with the person making the amendment: Patent applicant 4, agent

Claims (1)

[Scope of Claims] +1+ A granular agricultural chemical composition having good disintegratability in water and containing a sulfonated monoolefin and/or a water-soluble salt of a vinyl compound/ethylenic unsaturated dicarboxylic acid copolymer resin as an essential disintegrant component. (2) The sulfonated copolymer resin is a sulfonated styrene/maleic anhydride copolymer resin, a sulfonated imbutylene/maleic anhydride copolymer resin, or a sulfonated styrene/maleic anhydride copolymer resin.
The composition according to claim 11, which is an inbutylene/maleic anhydride copolymer resin. (3) A water-soluble salt of a sulfonated monoolefin and/or a vinyl compound/ethylenic unsaturated dicarboxylic acid copolymer resin The composition according to claim 1 or 2, wherein the composition contains 0.2 to 0.3% of the composition. Claim number +1
The composition according to item (+), item (21) or item (3).