JPH03161407A - Stabilized agricultural chemical composition - Google Patents

Abstract

PURPOSE:To provide an agricultural chemical composition stable to water contained during storage or preparation by adding a specific isocyanate com pound to a hydrolyzable agricultural chemical or adding the isocyanate com pound and an emulsier not reacting with the isocyanate compound. CONSTITUTION:A hydrolyzable agricultural chemical composition having im proved stability to water, readily employed and having excellent storability comprises an agricultural chemical component comprising a hydrolyzable agricul tural chemical (e.g. 2-chlorobisphenyl phosphate) and one or more compounds selected from an isocyanate, a polyisocyanate and an urethane prepolymer. The composition may be further compounded with an emulsifier comprising one or two surfactants selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant and not reacting with the isocyanate compound to provide an agricultural composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Publication ffJ Field] The present invention relates to a new hydrolyzable agricultural chemical composition that is stable in water.

[Prior Art] In general, many hydrolyzable pesticides are physically and chemically unstable.

For this reason, emulsions obtained by blending these pesticides with solvents and emulsifiers tend to change over time due to reaction with existing (F) or mixed moisture during storage or formulation, resulting in decomposition of the active ingredients and decomposition of the emulsifier. There are problems in that deterioration such as defects, turbidity, precipitation, and deterioration of the container occur, resulting in a significant decrease in marketability.

Therefore, studies have been made on various stabilizers to prevent deterioration due to moisture.

For example, Tokuko Sho 35-10550 bow, Tokko Shou 48
- Epoxy stabilizers such as No. 43860.

[Problem to be solved by the invention]

The problem to be solved by this proposal is to improve the stability of agrochemical compositions containing the above-mentioned hydrolyzable pesticides as an effective ingredient in water, and to create hydrolyzable agrochemical compositions that are easier to use and have a longer shelf life. It's about getting the.

(Means for solving the problem) The present expert has been working diligently on ways to improve stability against moisture that is mixed into the formulation during storage or into the formulation. As a result of repeated iJF research, by adding isocyanate-based compounds to Δ11, this isocyanate reacts with moisture present or mixed in the formulation or during storage, resulting in storage stability of hydrolyzable pesticides. ↑He discovered that life could be improved in a name and completed the mission of Masaaki Moto.

In other words, Masaaki Moto says that the hydrolyzable drug is 0 active ingredients.
``A stabilized agricultural chemical composition comprising JJ5 and one or more compounds selected from isocyanates 1 to 1, polyisocyanates, and urethane prepolymers, and the agricultural mulberry silk composition. Further, an emulsifier comprising one or more surfactants selected from anionic surfactants, cationic surfactants, nonionic surfactants/i4 agents, and amphoteric surfactants, and The present invention provides a stabilized agricultural chemical crude product to which an emulsifier that does not react with isocyanate compounds is added.

When blending the latter emulsifier, depending on the type of emulsifier, the added isocyanate compound may react with the OH group, and thus react with the terminal OHM of the emulsifier, resulting in poor emulsifying properties. It is necessary to use a surface active agent that does not react with isocyanate compounds or a surfactant whose terminal reactive group is blocked.

The isocyanate compound used in the present invention is a monoisocyanate, diisocyanate, or polyisocyanate shown below, or a urethane prepolymer obtained by reacting a diisocyanate or a polyisocyanate with a heptanool, diol, or polyol, either singly or as a mixture of two or more. used.

Examples of diisocyanates, diisocyanates and polyisocyanates include methyl isocyanate, ethyl isocyanate, probyl isocyanate, butyl isocyanate, phenolic diisocyanate, pendyl isocyanate, naphthyl isocyanate, tolylene diisocyanate, Diphenylmethane diisocyanate, naphthalene diisocyanate, tolylene diisocyanate, hexylymethylene diisocyanate 1~, isophorone diisocyanate, xylylene diisocyanate 1.
, hydrogenated diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, torino-deninolemethane triisocyanate, undecane triisocyanate, hexyl-nomethylene triisocyanate, lysine ester triisocyanate, polymethylene polyphenyl isocyanate-1, etc. It will be done.

Examples of monools, diols and polyols include phenol, polyoxyethylene phenol ether, ethylene glycol, propylene glycol, hekylene diol, trimethylolpropane, glycerin, pentaerythrol, sorbitol, and Polyhydric alcohols such as claus, and these polyhydric alcohols contain ethylene oxide, propylene oxylide, etc.
polyether polyols to which alkylene oxylide has been added, ethylene adipate, diethylene adipate,
Examples include polyester polyols such as butylene adipate, polycarbonate polyols, acrylic polyols, and polybutadiene polyols.

The compounding ratio of these isocyanate compounds varies depending on the type of hydrolyzable agricultural chemical and the content thereof, but in general, it is contained in the emulsion in an amount of 0.01 to 20%, preferably 0.1 to 5%.
It is.

Examples of emulsifiers used in the present invention include the following.

(1) Anionic surfactant Any surfactant commonly used for emulsification can be used. For example, alkyl lylphate, polyoxyethylene alkyl ether mononorphate, polyoxyethylene alkyl allyl ether lylphate, polyoxyethylene poly(A)-xypropylene block polymer polyolephate, alkanesnorphonate, dialkyl sulfosuccinate, etc. nate, alkylaryl sulfonate, fatty acid salt,
These include rotary extraction, polyoxyethylene alkyl ether phosphate, alkyl phosphate, and the like.

(2) Cadion interface active agents, such as primary amine salts, secondary amine salts, tertiary amine salts, modified amine salts, tetraalkyl tertiary ammonium salts, modified trialkyl quaternary ammonium salts, and modified trialkyl quaternary ammonium salts. 21 cum salt,
Trialkyl benzyl quaternary ammonium salt, modified trialgyl benzyl quaternary ammonium salt, alkylpyridinium salt, modified alkylpyridinium salt, alkyl quinolinium salt, alkyl phosphonium salt,
Alkyl sulfurium salts and the like are used.

(3) Non-ionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene rosin ester, polyoxypropylene alkyl ether, polyoxyethylene sorbitan resin fl/
j m Esdel, polyoxyethylene styrylphenyl ether, etc. are used. These are used in a form in which the terminal primary or secondary 0}-1 group of these polyethylene chains is chemically chained by a known method and reacted with an isocyanate group, if necessary.

(4) Double-sided surfactant such as resin, a! Requinoleaminokanolebonate, alkyl dimedyl betaine, alkyl didroxyethyl betaine, etc. are used.

Note that (1) to (4) above may be used in combination as appropriate. Typically, mixtures of anionic surfactants and nonionic surfactants are preferably used. The blending amount of these surfactants is usually 1 to 25% by weight.

Next, when the reactivity of a surfactant and an isocyanate compound is determined, the i'J chain method of the reactive group will be explained.

First, we will explain the case of the terminal O-group of a nonionic surfactant as an example.The methods for sealing this are known: ■ etherification method, ■ esterification method, ■ urethanization method, and ■ tertiary O-group. This can be carried out by a method appropriately selected from the laws and the like.

Among these, the etherification method (2) can be usually carried out by reacting a nonionic surfactant with an alkyl halide such as methylene chloride or medyl iodide. In addition, in the esterification method of
1ij; It can be carried out by reacting any tricarboxylic acids or anhydrides of these carboxylic acids.

The urethanization method (2) uses polyisocyanates such as medyl isocyanate, edyl isocyanate, probyl isocyanate, phenyl isocyanate, etc., tolylene diisocyanate, xylylene diisocyanate, and triphenylmethane isocyanate as a nonionic surfactant. This can be done by reacting the following. The tertiary oxygen conversion method (2) can be carried out, for example, by adding isobublene oxylide to a nonionic surfactant.

There are few anionic surfactants other than nonionic surfactants, cationic surfactants, and amphoteric surfactants that have reactive groups, but O
In the case of salts with H groups, the above-mentioned blocking method may be used, or Na, K. It can also be carried out by using metal salts such as Ca salts, ammonium salts, etc.

In addition, the hydrolyzable agricultural chemicals that are the subject of the present invention include 2-
Dichlorobiphenyl sulfate, O-methyl-O-
Para-nitrophenylbenzene A-sulfoate,
Examples include <2-isopropyl-4-methylpyrimidyl-6>-diethylbuophosphate, 0,0-dimethyl O-4-nitrolylphosphodioate, and the like.

(Example) The present invention will be specifically described below with reference to Examples and Comparative Examples. In addition, the test method in the following examples and comparative examples was performed by the method shown below.

Storage Stability Test Method: The residual rate (%) of the effective fraction in the emulsion compositions stored at 40'C for 1 month and 3 months at the time of preparation was determined.

Emulsification test: Take a part of the emulsion composition used for the storage stability test and heat it at 20°C.
After diluting and mixing with 3 degree hard water to iooo times, the IL formation stability after 2114 hours was visually determined at 11 yen.

Further, in the examples, the "part" indicating the usage amount of each precept in ffJ means "double star part".

Example 1 40 parts of pyridanoene, 25 parts of ethylene A
- 10 parts of an emulsifier consisting of 50 parts of acetate ester (Hill addition) and 50 parts of calcium dodecylbenzenesulfonate;
Deixsol MGIOO (urethane prebolymer from Daiichi Kogyo Seiyaku (l1 company km)) 10 parts and xylene 40
An emulsion composition was prepared by mixing and stirring the following parts.

Comparative Example 1 10 parts of an emulsifier consisting of 40 parts of pyridafenethione, 50 parts of ffi! ester of polyoxyethylene distyryl phenol ether (ethylene oxy}oid 25-7 addition), and 50 parts of dodecylbenzenesulfonic acid calcium salt;
and 50 parts of xylene were mixed to prepare an emulsion composition.

Example 2 50 parts of diazinon, 10 parts of an emulsifier consisting of 50 parts of acetate ester of S1 polyoxyethylene disdylyl phenol ether (added with 20 moles of ethylene oxylide) and 50 parts of sodium dodecylbenvinsulfonate, Dixsol MDIOO (part 1) An emulsion composition was prepared by mixing 5 parts of urethane prepolymer (manufactured by Ichi Kogyo Seiyaku ■) and 35 parts of xylene.

Comparative Example 2 50 parts of diazinon, polyoxyethylene distyryl phenol ether (addition of 20 moles of ethylene oxylide)
10 parts of an emulsifier consisting of 50 parts of IM ester and 50 parts of dodecylbenvinsulfonic acid sodium salt;
A crude emulsion was prepared by mixing and stirring 0 parts.

Example 3 50 parts of chlorpyrifos, 10 parts of an emulsifier consisting of 50 parts of acetate ester of polyoxyethylene styryl phenyl ether (20 moles of ethylene oxide (J added)) and 50 parts of sodium dodecylbenvinsulfonate, 70 parts of Monotac
An emulsion composition was prepared by mixing and stirring 10 parts of urethane prepolymer manufactured by Daiichi Koyo Pharmaceutical Co., Ltd. and 30 parts of xylene.

Comparative Example 3 50 parts of chlorpyrifos, 50 parts of acetate ester of polyA xyethylene styryl phenyl ether (addition of 20 moles of ethylene oxide: 1: lead), and sodium dodecylbenvinsulfonate! An emulsion composition was prepared by mixing 10 parts of an emulsifier consisting of 50 parts of A and 40 parts of xylene.

Example 4 40 parts of Fendi A, M of polyoxyethylene dilylphenyl ether (addition of 20 moles of ethylene oxylide)
An emulsion composition was prepared by mixing 10 parts of an emulsifier consisting of 50 parts of L ester and 50 parts of sodium dodecylbenzine sulfonate, 3 parts of tolylene diisocyanate, and 47 parts of xylene.

Comparative Example 4 40 parts of Fuenbuon, polyoxyethylene styrene ■
10 parts of an emulsifier consisting of 50 parts of Ml ester of nyl ether (addition of 20 moles of eblene oxinoid) and 50 parts of dodecylbenzenesulfonic acid sodium salt, and 50 parts of xylene.
An emulsion phase composition was prepared by mixing and stirring the following parts.

Table 1 shows the storage stability test results of the above examples and comparative examples.
Shown below.

As is clear from Table 1, the effective fractions in the emulsion compositions of Examples 1 to 4 are more stable, whereas the effective fractions in the emulsion compositions of Comparative Examples 1 to 4 are unstable. I understand that there is something.

Next, the results of the emulsion stability test are shown in Table 2.

○: Good Recognize.

[Effect of enrichment]

With this invention, hydrolyzability, which has been a problem in the past! f
The stability against moisture of the agrochemical composition containing fi2 as an effective fraction has been significantly improved, and its storage stability and emulsion stability have been improved. As a result, the agrochemical composition is easier to use than conventional products, and The present invention has the effect of being easier to preserve and having superior effects, greatly increasing its commercial value.

Special applicant: Chugai Pharmaceutical Co., Ltd. Daiichi Kogyo Seiyaku Co., Ltd.

Claims (1)

[Claims] 1. Stabilization characterized by comprising a pesticide containing a hydrolyzable pesticide as an active ingredient and one or more compounds selected from isocyanates, polyisocyanates, and urethane prepolymers. pesticide composition. 2. An emulsifier consisting of one or more surfactants selected from anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants,
2. The stabilized agrochemical composition according to claim 1, further comprising an emulsifier that does not react with isocyanate compounds. 3. The stabilized agricultural chemical composition according to claim 2, wherein the emulsifier that does not react with the isocyanate compound is an emulsifier in which a group that reacts with the isocyanate compound is blocked.