JP7156871B2 - Extender for water-floating pesticide formulation and pesticide formulation - Google Patents

Description

TECHNICAL FIELD The present invention relates to an extender for a water-floating agricultural chemical formulation and an agricultural chemical formulation.

In recent years, against the backdrop of the decrease in full-time farmers, the aging of farmers, and the increasing number of large-scale fields due to land readjustment, there is a demand for labor-saving in application of agricultural chemical formulations.
For example, when applying to agricultural land where water exists such as paddy fields, water floating type agricultural chemical formulations are used as throw-in type agricultural chemical formulations that can be sprayed by simply throwing them from the ridge without entering the paddy fields. In this water-floating pesticide formulation, it is necessary to devise a design in which a water-floating pesticide formulation containing a high concentration of the active ingredient spreads and diffuses on the surface of the water so that a single application can exhibit a wide range of control effects. It has been demanded.

Therefore, an ester compound having a polyoxyalkylene chain (Patent Document 1) and the like have been proposed as agents for assisting the spread of water-floating pesticide formulations (extending agents for water-floating pesticide formulations).

Japanese Patent No. 6279804

However, the spreading agent for a water-floating pesticide formulation described in Patent Document 1 does not have sufficient spreadability, and improvement is desired from the viewpoint of further labor saving in pesticide application.
Accordingly, an object of the present invention is to provide a spreader for a water-floating pesticide formulation that is superior in spreadability as compared with the prior art.

The present inventors arrived at the present invention as a result of sincere investigations to solve these problems.
That is, the present invention provides a water-floating pesticide formulation extender containing a nonionic surfactant (X) represented by the general formula (1),
The number average number of methyl groups per molecule in R ¹ in all (X) contained in the water-floating pesticide formulation extender is 2.0 or more,
An extender for a water-floating agricultural chemical formulation, wherein the number average nA per molecule of _n in all (X) contained in the water-floating agricultural chemical formulation is 2 to 15; It is an agricultural chemical formulation containing an application extender and an agricultural chemical active ingredient.
R ¹ O—(AO) _n B (1)
[In general formula (1), R ¹ represents an alkyl group having 8 to 11 carbon atoms; each n AO represents an alkyleneoxy group having 2 to 4 carbon atoms; n is an integer of 0 to 200; Yes; B represents —R ² or —COR ² ; R ² represents an alkyl group having 1 to 2 carbon atoms. ]

The spreader for a water-floating agricultural chemical formulation of the present invention has the effect of imparting excellent spreadability when used in combination with an agricultural chemical formulation.

The extender for a water-floating agricultural chemical formulation of the present invention is an extender for a water-floating agricultural chemical formulation containing a nonionic surfactant (X) represented by the general formula (1), The number average number of methyl groups per molecule in R ¹ in all (X) contained in the extender for a type agricultural chemical formulation is 2.0 or more, and the extender for a water-floating agricultural chemical formulation contains The number average n _A per molecule of n in all (X) is 2-15.
R ¹ O—(AO) _n B (1)

In general formula (1), R ¹ represents an alkyl group having 8 to 11 carbon atoms.

Examples of the alkyl group having 8 to 11 carbon atoms include an alkyl group having one methyl group (r1), an alkyl group having two methyl groups (r2), an alkyl group having three methyl groups (r3), and four methyl groups. and alkyl groups (r5) having 5 or more methyl groups.

Examples of the alkyl group (r1) having one methyl group include octan-1-yl group, nonan-1-yl group, decan-1-yl group and undecan-1-yl group.

Examples of the alkyl group (r2) having two methyl groups include octan-2-yl group, 2-ethylhexan-1-yl group, 6-methylheptan-1-yl group, nonan-2-yl group, 7-methyloctan-1-yl group, 8-methylnonan-1-yl group, 9-methyldecane-1-yl group and the like.

Examples of the alkyl group (r3) having three methyl groups include 3-methylheptan-3-yl group, 3,5-dimethylhexan-1-yl group, 2-methylnonan-3-yl group and 2-methyldecane. -2-yl group and the like.

Examples of the alkyl group (r4) having four methyl groups include a 3,5,5-trimethylhexan-1-yl group, a 2,6-dimethylheptan-4-yl group, and 2,3,5-trimethylhexane. -1-yl group, 3,5,5-trimethylheptan-1-yl group and 3,5,5-trimethyloctan-1-yl group.

Examples of the alkyl group (r5) having 5 or more methyl groups include a 2,2-dimethyl-5-methylhexan-4-yl group.

Among these R ¹ , the alkyl groups (r2) to (r5) having two or more methyl groups are preferable from the viewpoint of expandability, and the alkyl groups having three or more methyl groups are more preferable. Groups (r3) to (r5), particularly preferred are alkyl groups (r4) having 4 methyl groups, most preferred is the 3,5,5-trimethylhexan-1-yl group.

As described above, the number average number of methyl groups possessed by R ¹ in all (X) contained in the water-floating agricultural chemical formulation extender is 2.0 or more.
If the number average number of methyl groups is less than 2.0, the spreadability is deteriorated.
In addition, the number average number of methyl groups can be determined, for example, by ¹ H-NMR measurement and gas chromatographic measurement of alcohol in which a hydroxyl group is bonded to R ¹ of the raw material used in synthesizing (X) (the synthesis method will be described later). It can be calculated by measuring the tee.

In general formula (1), n AOs each independently represent an alkyleneoxy group having 2 to 4 carbon atoms.
Examples of the alkyleneoxy group having 2 to 4 carbon atoms include ethyleneoxy group, 1,2-propyleneoxy group, 1,3-propyleneoxy group, 1,2-butyleneoxy group and 1,4-butyleneoxy group. be done.

In the general formula (1), n is an integer of 0 to 200, and the number average _n per molecule of n in all (X) contained in the water-floating pesticide formulation extender is 2 to 15.
When the _nA is less than 2 or more than 15, the spreadability is deteriorated. In particular, when the water-floating pesticide formulation contains less than 1% of the nonionic surfactant (X) represented by the general formula (1), it is remarkably deteriorated.

In general formula (1), B represents —R ² or —COR ² , and R ² represents an alkyl group having 1 to 2 carbon atoms. Among R ² , a methyl group is preferable from the viewpoint of expandability.

In general formula (1), (AO) _n is preferably [(C ₃ H ₆ O) _p /(C ₂ H ₄ O) _q ]. [(C ₃ H ₆ O) _p /(C ₂ H ₄ O) _q ] indicates that the order of bonding of p propyleneoxy groups and q ethyleneoxy groups is arbitrary. In addition, p is an integer of 0-100, and q is an integer of 0-100.
Here, the number average p _A per molecule of p in all (X) contained in the water-floating agricultural chemical formulation spreader is preferably 0 to 5 from the viewpoint of spreadability, It is more preferably 0-3.
In addition, the number average q _A per molecule of q in all (X) contained in the water-floating pesticide formulation spreader is preferably 1 to 10 from the viewpoint of spreadability, and 2 ~8 is more preferred.
Moreover, the relationship between p _A and q _A is preferably p _A ≤ q _A from the viewpoint of expandability.

From the viewpoint of spreadability, the spreader for a water-floating pesticide formulation of the present invention preferably contains a molecule in which n is 2 to 15 in general formula (1).
Further, from the viewpoint of further improving the spreadability, the spreader for a water-floating pesticide formulation of the present invention has the general formula (1) in which (AO) _n is [(C ₃ H ₆ O) _p /(C ₂ H ₄ O) _q ], p is 0 to 5, and q is 1 to 10. In general formula (1), (AO) _n is It is further preferred to contain a molecule where [(C ₃ H ₆ O) _p /(C ₂ H ₄ O) _q ] and p is 0-3 and q is 2-8. .

The addition form of the propyleneoxy group and the ethyleneoxy group of [(C ₃ H ₆ O) _p /(C ₂ H ₄ O) _q ] is [(C ₃ H ₆ O) _p -(C ₂ H ₄ O) _q ] [i.e., an addition form in which p (C ₃ H ₆ O) are attached to “R ¹ O” followed by q (C ₂ H ₄ O)] or [ (C ₂ H ₄ O) _q —(C ₃ H ₆ O) _p ] [that is, “R ¹ O” is bound to q (C ₂ H ₄ O) _q , followed by p (C ₃ H ₆ O)] is preferred, and [(C ₃ H ₆ O) _p -(C ₂ H ₄ O) _q ] is more preferred.

The nonionic surfactant (X) can be produced by a known method, for example, by the following method.
An alkali catalyst (potassium hydroxide, etc.) or an acid catalyst (boron trifluoride, etc.) is added to the above alcohol having a hydroxyl group bonded to R ¹ , and ethylene oxide and propylene oxide are subjected to an addition reaction in a nitrogen atmosphere to form an alkylene of the alcohol. An oxide adduct is obtained.
Thereafter, etherification by Williamson reaction, acetylation by acetic anhydride, or esterification by Ficher esterification reaction can be carried out to obtain the desired nonionic surfactant (X).
Examples of the alcohol having a hydroxyl group bonded to R ¹ include “Exar 9S”, “Exar 10” and “Exar 11” manufactured by ExxonMobil, and “Oxocol 900” and “Nonanol” manufactured by KH Neochem Co., Ltd. and commercially available as "decanol" and the like.

The extender for a water-floating pesticide formulation of the present invention contains, in addition to the nonionic surfactant (X), a nonionic surfactant other than (X), an anionic surfactant, and the like. Also good. Further, the extender for a water-floating agricultural chemical formulation of the present invention may contain components (disintegrating dispersant, binder, etc.) used in the water-floating agricultural chemical formulation described below.
Nonionic surfactants other than the above (X) include alcohols having 8 to 18 carbon atoms (3,5,5-trimethylhexanol, 2-ethylhexanol, dodecanol, octadecanol, etc.). 1 to 40 mol adducts of 1 to 4 alkylene oxides, 1 to 40 mol adducts of 1 to 40 mol alkylene oxides of 2 to 4 carbon atoms to alkylphenols (octylphenol, nonylphenol, etc.) and 2 carbon atoms to fatty acids (oleic acid, stearic acid, etc.) 1 to 40 mol adducts of alkylene oxides of ∼4 and the like.
Examples of the anionic surfactant include sulfonates (sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, etc.), sulfates (sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, etc.) and alkyl fatty acid salts ( lauric acid monoethanolamine salt, lauric acid diethanolamine salt, etc.) and the like.

The weight ratio of the nonionic surfactant (X) contained in the extender for a water-floating agricultural chemical formulation of the present invention is based on the weight of the extender for a water-floating agricultural chemicals formulation from the viewpoint of spreadability. , 50 to 100% by weight.

The water-floating pesticide formulation contains the extender for the water-floating pesticide formulation of the present invention and the active ingredient of the pesticide (active ingredient) as essential ingredients. etc. may be included.

The active ingredient of agricultural chemicals may be liquid or solid as long as it can be applied to the surface of water, and examples thereof include insecticides, fungicides, herbicides and plant regulators.

Insecticides include isoxathion, diazinon, disulfoton, propafos, trichlorfone, formothion, dimethoate, monocrotophos, acephate, carbofuran, carbosulphan, thiocyclam, cartap, bensultap, benfuracarb, furatiocarb, buprofezin, fenocarb, metolcarb, propoxure, imidacloprid, nittenpyram, acetamiprid, cycloprotoline, etofenprox, silafluofen and the like.

Bactericides include probenazole, isoprothiolane, iprobenfos, tricyclazole, pyroquilone, carpropamide, olibright, azoxystrobin, flutolanil, mepronil, thifluzamide, furametpyr and tecloftalam.

Herbicides include pyrazolyl, benzofenap, pyrazoxifene, piributicarb, bromoptide, butamiphos, mefenacet, anilophos, butachlor, thiobencarb, chlornitrophene, daimuron, bifenox, naproanilide, oxadiazone, oxadiargyl, bentazone, molinate, piperophos, dimepiperate, esprocarb, and dithiopyr. , caffenstrol, pretilachlor, simetryn, bensulfuron-methyl, quinclolac, pentoxazone, thenylchlor, etobenzanide, dimethamethrin and indanophan.

Plant regulators include inabenfide, paclobutrazole, uniconazole, tripentenol, and the like.

The above-mentioned flotation aid may be one that allows the pesticide formulation to float on the surface of water, such as hollow glass (foamed shirasu, foamed perlite, etc.), foamed pumice, calcined vermiculite, cork, wood flour, expanded styrol, synthetic resin powder, and plastics. Hollow bodies and the like can be mentioned.

As the disintegrating dispersant, any agent can be used as long as it disintegrates the agricultural chemical formulation on the surface of water or in water and suspends and disperses the active ingredient of the agricultural chemical in water. , phenolsulfonate, condensate of phenolsulfonate and formalin, styrenesulfonate and its polymer, polyacrylate, salt of copolymer of acrylic acid and maleic acid, alkylbenzenesulfonate , dialkyl sulfosuccinates and polyoxyalkylene alkyl ether sulfates.

Any binder may be used as long as it imparts hardness to the granular pesticide formulation obtained by granulation, and includes starch and its derivatives, polyvinylpyrrolidone, polyacrylate, carboxymethylcellulose salt, polyvinyl alcohol, lignin sulfone. acid salts, gum arabic, montmorillonite, and the like.
The binder also includes a compound that functions as a disintegrating dispersant (polyacrylate, carboxymethylcellulose salt, ligninsulfonate, etc.).

The bulking agent may absorb a liquid active ingredient for agricultural chemicals or dilute a solid active ingredient for agricultural chemicals. .

The water-floating pesticide formulation contains an extender for water-floating pesticide formulation, and from the viewpoint of spreadability, the weight ratio of the nonionic surfactant (X) is 0.00% based on the weight of the water-floating pesticide formulation. It is preferably contained in an amount of 01 to 10% by weight, more preferably 0.1 to 8% by weight.
The weight ratio of the agricultural chemical active ingredient contained in the water-floating agricultural chemical formulation is preferably 0.1 to 80% by weight, more preferably 1 to 80% by weight based on the weight of the water-floating agricultural chemical formulation, from the viewpoint of control effect. 50% by weight.
The weight ratio of the floating aid contained in the water-floating agricultural chemical formulation is preferably 1 to 80% by weight, more preferably 10 to 50%, based on the weight of the water-floating agricultural chemical formulation, from the viewpoint of spreadability. % by weight.
The total weight ratio of the disintegrating dispersant and binder contained in the water-floating pesticide formulation is 0.01 to 30% by weight based on the weight of the water-floating pesticide formulation, from the viewpoint of disintegration and formulation strength. is preferred, and more preferably 0.05 to 20% by weight.
The weight ratio of the extender contained in the water-floating agricultural chemical formulation is preferably 1 to 80% by weight, more preferably 2 to 50% by weight, based on the weight of the water-floating agricultural chemical formulation, from the viewpoint of handling. is.

A water-floating pesticide formulation can be prepared by a known method. for example,
1) After kneading the extender for a water-floating pesticide formulation of the present invention, the active ingredient of the pesticide, the flotation aid, the disintegrating dispersant, the binder, the extender and water in a mixer, the mixture is granulated using a granulator. and drying method,
2) After kneading the water surface-floating pesticide formulation extender, floating aid, disintegrating dispersant, binder, extender and water of the present invention in a mixer, granulating with a granulator, Examples include a method of impregnating and adsorbing the active ingredient of the agricultural chemical to the granules, followed by drying.
As the mixer, a Nauta mixer, a ribbon mixer, a rotary blender, a V-shaped mixer, or the like can be applied.
As the granulator, an extrusion granulator, a mixing granulator, a tumbling granulator, and the like can be applied.

The above-mentioned water-floating pesticide formulation can be sprayed by manual spraying, mechanical spraying, transfer spraying, frame spraying, and the like, like general agricultural granules.
In addition, the water-floating pesticide formulation can be packed in water-soluble paper and thrown from a ridge. Water-soluble papers used for throwing application are films or sheets that are soluble or dispersible in water and include polyvinyl alcohol or its derivatives, pullulan, carboxymethylcellulose salts and cellulose.

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited thereto. Examples 3 to 6 and 10 are Reference Examples 1 to 5, respectively.

Production example 1
144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol and 0.5 parts of potassium hydroxide were placed in a 2-liter autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping bomb, vacuum and nitrogen introduction line. After 5 parts by weight was added and stirring was started, nitrogen was sealed, the temperature was raised to 100° C., and dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130° C., and 58 parts by weight (1 mol part) of propylene oxide was successively added dropwise over 5 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred for 1 hour until pressure equilibrium was reached at the same temperature (first stage). . Then, 176 parts by weight (4 mol parts) of ethylene oxide was added dropwise over 3 hours, and the mixture was stirred for 1 hour until pressure equilibrium was reached at the same temperature (second step). After cooling to 60° C., 10 parts of an adsorption treatment agent [Kyoward 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and treated by stirring at 60° C. for 1 hour. A 5,5-trimethylhexanol PO 1 mol-EO 4 mol adduct (PX-1) was obtained.

Production example 2
3,5,5-trimethylhexanol PO1 mol-EO8 A molar adduct (PX-2) was obtained.

Production example 3
In Production Example 1, 58 parts by weight (1 mol part) of propylene oxide was changed to 290 parts by weight (5 mol parts), and 176 parts by weight (4 mol parts) of ethylene oxide was changed to 440 parts by weight (10 mol parts). A 3,5,5-trimethylhexanol PO 5 mol-EO 10 mol adduct (PX-3) was obtained in the same manner as in Production Example 1.

Production example 4
144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol and 0.5 parts of potassium hydroxide were placed in a 2-liter autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping bomb, vacuum and nitrogen introduction line. After 5 parts by weight was added and stirring was started, nitrogen was sealed, the temperature was raised to 100° C., and dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130° C., and 264 parts by weight (6 mol parts) of ethylene oxide was successively added dropwise over 5 hours at a pressure of 0.3 MPaG or less, followed by stirring for 1 hour until pressure equilibrium was reached at the same temperature. After cooling to 60° C., 10 parts of an adsorption treatment agent [Kyoward 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and treated by stirring at 60° C. for 1 hour. A 5,5-trimethylhexanol EO 6 mol adduct (PX-4) was obtained.

Production example 5
144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol and 0.5 parts of potassium hydroxide were placed in a 2-liter autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping bomb, vacuum and nitrogen introduction line. After 5 parts by weight was added and stirring was started, nitrogen was sealed, the temperature was raised to 100° C., and dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130° C., and 264 parts by weight (6 mol parts) of ethylene oxide was successively added dropwise over 3 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred for 1 hour until pressure equilibrium was reached at the same temperature (first stage). . Then, 116 parts by weight (2 mol parts) of propylene oxide was added dropwise over 5 hours, and the mixture was stirred for 1 hour until pressure equilibrium was reached at the same temperature (second step). After cooling to 60° C., 10 parts of an adsorption treatment agent [Kyoward 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and treated by stirring at 60° C. for 1 hour. A 5,5-trimethylhexanol EO 6 mol-PO 2 mol adduct (PX-5) was obtained.

Production example 6
144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol and 0.5 parts of potassium hydroxide were placed in a 2-liter autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping bomb, vacuum and nitrogen introduction line. After 5 parts by weight was added and stirring was started, nitrogen was sealed, the temperature was raised to 100° C., and dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130° C., and 264 parts by weight (6 mol parts) of ethylene oxide and 116 parts by weight (2 mol parts) of propylene oxide were simultaneously added dropwise over 5 hours at a pressure of 0.3 MPaG or less, and the pressure was balanced at the same temperature. Stirred for 1 hour until . After cooling to 60° C., 10 parts of an adsorption treatment agent [Kyoward 600: manufactured by Kyowa Chemical Industry Co., Ltd.] is added and treated by stirring at 60° C. for 1 hour. A 2 mol PO/6 mol EO adduct (PX-6) of 5,5-trimethylhexanol was obtained.

Production example 7
Compound (PX-7) was obtained in the same manner as in Production Example 1, except that 144 parts of 3,5,5-trimethylhexanol was changed to 144 parts of Exar 9S (manufactured by ExxonMobil).
As a result of analysis by ¹ H-NMR and gas chromatography, Exar 9S was an alcohol in which a hydroxyl group was bonded to the above R ¹ . The number of carbon atoms in R ¹ was 9.0, and the number average number of methyl groups in R ¹ per molecule was 3.0.

Production example 8
In Production Example 1, 144 parts of 3,5,5-trimethylhexanol was changed to 158 parts of decanol [manufactured by KH Neochem Co., Ltd.], and 176 parts by weight (4 mol parts) of ethylene oxide was added to 264 parts by weight (6 mol parts). Compound (PX-8) was obtained in the same manner as in Production Example 1 except that
As a result of analysis by ¹ H-NMR and gas chromatography, decanol was found to be an alcohol in which a hydroxyl group was bonded to the above R ¹ . In addition, the number of carbon atoms in R ¹ was 10.0, and the number average number of methyl groups in R ¹ per molecule was 3.5.

Production example 9
In Production Example 1, 144 parts of 3,5,5-trimethylhexanol was changed to 172 parts of Exar 11 (manufactured by ExxonMobil), and 176 parts by weight (4 mol parts) of ethylene oxide was changed to 352 parts by weight (8 mol parts). Compound (PX-9) was obtained in the same manner as in Production Example 1 except that
As a result of analysis by ¹ H-NMR and gas chromatography, Exar 11 was an alcohol in which a hydroxyl group was bonded to the above R ¹ . In addition, the number of carbon atoms in R ¹ was 11.0, and the number average number of methyl groups in R ¹ per molecule was 3.7.

Production example 10
In Production Example 1, except that 144 parts of 3,5,5-trimethylhexanol was changed to 130 parts of 2-ethylhexanol, and 176 parts by weight (4 mol parts) of ethylene oxide were changed to 88 parts by weight (2 mol parts). A compound (PX-10) was obtained in the same manner as in Production Example 1.

Production Example 11
378 parts by weight (1 mol part) of (PX-1) and 60 parts by weight of sodium hydroxide (1.5 parts by weight) were added to a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, vacuum and nitrogen introduction line. (mol part) was added, and after purging with nitrogen, the inside was sealed and cooled to 20°C. After adding dropwise 71 parts by weight (1.4 mol parts) of methyl chloride over 10 hours while adjusting the temperature to 20° C., the mixture was aged at 20° C. for 10 hours. Then, 500 parts of water was added, and the mixture was stirred at 20° C. for 1 hour.

Production example 12
Manufactured in the same manner as in Production Example 11 except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX-2) 554 parts by weight (1 mol part) in Production Example 11, a nonionic interface An active agent (X-2) was obtained.

Production example 13
In Production Example 11, except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX-3) 874 parts by weight (1 mol part). An active agent (X-3) was obtained.

Production example 14
In Production Example 11, except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX-4) 408 parts by weight (1 mol part). An active agent (X-4) was obtained.

Production example 15
In Production Example 11, except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX-5) 524 parts by weight (1 mol part). An active agent (X-5) was obtained.

Production example 16
In Production Example 11, except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX-6) 524 parts by weight (1 mol part). An active agent (X-6) was obtained.

Production Example 17
In Production Example 11, (PX-1) 378 parts by weight (1 mol part) was changed to (PX-7) 378 parts by weight (1 mol part). An active agent (X-7) was obtained.

Production example 18
In Production Example 11, (PX-1) 378 parts by weight (1 mol part) was changed to (PX-8) 480 parts by weight (1 mol part). Activator (X-8) was obtained.

Production Example 19
In Production Example 11, (PX-1) 378 parts by weight (1 mol part) was changed to (PX-9) 582 parts by weight (1 mol part). An active agent (X-9) was obtained.

Production example 20
Manufactured in the same manner as in Production Example 11 except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX-10) 276 parts by weight (1 mol part) in Production Example 11, Activator (X-10) was obtained.

Production example 21
In Production Example 12, a nonionic surfactant ( X-11) was obtained.

Production example 22
554 parts by weight (1 mol part) of (PX-2) was added to a reaction vessel equipped with a stirrer, a heating/cooling device and a dropping funnel, and 112 parts by weight (1.1 mol part) of acetic anhydride was added to the dropping funnel. did. After purging with nitrogen, the mixture was sealed, the temperature was raised to 100° C., acetic anhydride was added dropwise over 2 hours, aged for 8 hours, the pressure was reduced for 1 hour, and 60 parts (1 mol part) of acetic acid and 10 parts of unreacted acetic anhydride ( 0.1 mol part) was distilled off to obtain a nonionic surfactant (X-12).

Production example 23
554 parts by weight (1 mol part) of (PX-2) and 0.5 part of methanesulfonic acid are added to a reaction vessel equipped with a stirrer, a heating/cooling device and a dropping funnel, and 74 parts by weight of propionic acid ( 1 mol part) was added. After purging with nitrogen, the mixture was sealed, the temperature was raised to 100° C., and propionic acid was added dropwise over 2 hours. After reacting for 8 hours while dehydrating at the same temperature under reduced pressure, a nonionic surfactant (X-13) was obtained.

Comparative production example 1
In Production Example 1, 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol was changed to 130 parts by weight (1 mol part) of 1-octanol, and 58 parts by weight (1 mol part) of propylene oxide was added. ) was changed to 116 parts by weight (2 mol parts) to obtain a 1-octanol PO 2 mol-EO 4 mol adduct (PX'-1).

Comparative production example 2
In Production Example 1, 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol was changed to 158 parts by weight (1 mol part) of 1-decanol, and 58 parts by weight (1 mol part) of propylene oxide was added. ) was changed to 232 parts by weight (4 mol parts), and 176 parts by weight (4 mol parts) of ethylene oxide was changed to 264 parts by weight (6 mol parts). A 4 mol PO-6 mol EO adduct (PX'-2) was obtained.

Comparative production example 3
In Production Example 4, production was carried out in the same manner as in Production Example 1 except that 264 parts by weight (6 mol parts) of ethylene oxide was changed to 704 parts by weight (16 mol parts), and 16 mols of 3,5,5-trimethylhexanol EO was added. A product (PX'-3) was obtained.

Comparative production example 4
In Production Example 4, production was carried out in the same manner as in Production Example 1 except that 264 parts by weight (6 mol parts) of ethylene oxide was changed to 44 parts by weight (1 mol part), and 1 mol of 3,5,5-trimethylhexanol EO was added. A product (PX'-4) was obtained.

Comparative production example 5
In Production Example 1, 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol was changed to 200 parts by weight (1 mol part) of tridecanol [manufactured by KH Neochem Co., Ltd.], and 58 parts by weight of propylene oxide. In the same manner as in Production Example 1, except that parts by weight (1 mol part) were changed to 116 parts by weight (2 mol parts), and ethylene oxide 176 parts by weight (4 mol parts) was changed to 220 parts by weight (5 mol parts). to obtain a compound (PX'-5).
As a result of analysis by ¹ H-NMR and gas chromatography, tridecanol was an alcohol in which a hydroxyl group was bonded to an alkyl group having 13 carbon atoms. The number average number of methyl groups per molecule in the residue obtained by removing the OH group from tridecanol was 4.0.

Comparative production example 6
In Production Example 11, produced in the same manner as in Production Example 11 except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX′-1) 422 parts by weight (1 mol part). A nonionic surfactant (X'-1) was obtained.

Comparative Production Example 7
In Production Example 11, produced in the same manner as in Production Example 11 except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX′-2) 654 parts by weight (1 mol part). A nonionic surfactant (X'-2) was obtained.

Comparative Production Example 8
In Production Example 11, produced in the same manner as in Production Example 11 except that (PX-1) 378 parts by weight (1 mol part) was changed to (PX′-3) 848 parts by weight (1 mol part). A nonionic surfactant (X'-3) was obtained.

Comparative Production Example 9
In Production Example 11, (PX-1) 378 parts by weight (1 mol part) was changed to (PX′-4) 188 parts by weight (1 mol part). A nonionic surfactant (X'-4) was obtained.

Comparative Production Example 10
In Production Example 11, (PX-1) 378 parts by weight (1 mol part) was changed to (PX′-5) 536 parts by weight (1 mol part). A nonionic surfactant (X'-5) was obtained.

Comparative Production Example 11
144 parts by weight (1 mol part) of octanoic acid and 197 g of triethylene glycol monomethyl ether were placed in a reaction vessel equipped with a stirrer and a heating/cooling device, and 1.4 g of methanesulfonic acid was added as a catalyst. 82 g and 0.37 g of a 50% aqueous solution of hypophosphorous acid were added. The reaction temperature was maintained at 120 to 150° C. with stirring, and the esterification reaction was carried out while distilling off the produced water. The reaction was terminated when the distillate reached 18 ml. After cooling to about 50° C., 2.9 g of a 28% methanol solution of sodium methoxide was added for neutralization. After adding 154 g of water and stirring, stratification separation was performed at 60 to 80° C. to obtain an oil layer. The obtained oil layer was dehydrated at 80 to 100° C. under reduced pressure to obtain a nonionic surfactant (X'-6) for comparison.

<Examples 1 to 16 and Comparative Examples 1 to 8>
Nonionic surfactants (X-1) to (X-13) of the present invention listed in Table 1 or comparative nonionic surfactant (X'-1) as an extender for water-floating pesticide formulations ~ (X'-6), caffenstrol as a pesticide active ingredient, hollow glass [manufactured by Tokai Kogyo Co., Ltd., "CEL-STAR Z-27"] as a flotation aid, and bentonite [manufactured by Kunimine Industry Co., Ltd.] as a bulking agent , "Kunigel V1"] were mixed in the amounts shown in Table 2, and 40 parts of water was added to the mixture and sufficiently kneaded. The resulting kneaded product was subjected to molding in a basket-type granulator equipped with a screen having an opening of 1.0 mm, cut, and dried in a 50° C. air circulating dryer. The resulting dried product was sized to a length of about 3 mm, and the water-floating pesticide formulations (P-1) to (P-16) of the present invention and the water-floating pesticide formulation (P'-1) for comparison were prepared. ~ (P'-8) was obtained.

<Spreadability test>
A total of 38 cylindrical obstacles with a diameter of 2 cm and a height of 5 cm were placed at intervals of 3.3 cm in the horizontal direction and 10 cm in the vertical direction in a rectangular container made of stainless steel with a length of 200 cm, a width of 10 cm, and a depth of 4 cm. Water was poured into the container to a depth of 2 cm, 0.2 g of the water-floating pesticide formulation was added from the center of one end in the vertical direction of the container, and the vertical spread distance was measured after 2 minutes. The results are listed in Table 2.

As shown in Table 2, the water-floating pesticide formulations of Examples 1 to 13 using the nonionic surfactants (X-1) to (X-13) of the present invention are nonionic surfactants for comparison. The spreading distance was longer and the spreadability was excellent as compared with the water surface floating pesticide formulations of Comparative Examples 1 to 8 using the active agents (X'-1) to (X'-6).
Further, from a comparison between Examples 14 to 16 and Comparative Examples 7 to 8, when the nonionic surfactant (X) of the present invention was used as an extender for surface-floating agricultural chemical formulations, water-floating agricultural chemicals Spreadability was excellent even when the blending amount of the formulation spreader was small.

The spreader for a water-floating pesticide formulation of the present invention has excellent spreadability on the water surface where obstacles are present, and can spread the pesticide active ingredient over a wide area with a single application, thus saving labor in pest control work. To contribute.

Claims (3)

An extender for a water-floating pesticide formulation containing a nonionic surfactant (X) represented by the general formula (1),
The number average number of methyl groups per molecule in R ¹ in all (X) contained in the water-floating pesticide formulation extender is 3.0 or more,
An extender for a water surface-floating agricultural chemical formulation, wherein the number average nA per molecule of _n in all (X) contained in the water surface-floating agricultural chemical formulation is 2 to 15.
R ¹ O—(AO) _n B (1)
[In general formula (1), R ¹ represents an alkyl group having 8 to 11 carbon atoms; each n AO represents an alkyleneoxy group having 2 to 4 carbon atoms; n is an integer of 0 to 200; Yes; B represents —R ² or —COR ² ; R ² represents an alkyl group having 1 to 2 carbon atoms. In general formula (1), (AO) _n is [(C ₃ H ₆ O) _p -(C ₂ H ₄ O) _q ], p is an integer of 0 to 100, and q is 0 to 100. The extender for a water-floating agricultural chemical formulation is an integer, and the number average p _A per molecule of p in all (X) contained in the water-floating agricultural chemicals formulation is 1 to 3, and the water-floating agricultural chemicals formulation extender. The number average q _A per molecule of q in all (X) containing is 4 to 8. ] 2. The extender for water-floating agricultural chemical formulations according to claim 1 , wherein in general formula (1), R ¹ is a 3,5,5-trimethylhexan-1-yl group. 3. An agricultural chemical formulation comprising the water surface-floating agricultural chemical formulation extender according to claim 1 or 2 and an agricultural chemical active ingredient.