JP2020007263A - Agricultural water-surface spreader - Google Patents

Abstract

To provide an agricultural water-surface spreader excellent in a water-surface spreading property.SOLUTION: The agricultural water-surface spreader comprises a compound represented by the specified general formula (I) and a compound represented by the specified general formula (II), where the molar ratio between the compound represented by the general formula (I) and the compound represented by the general formula (II) is between 30:70 and 70:30. (In the general formula (I), Ris a C6-10 linear or branched alkyl group; AO are C2-4 oxyalkylene groups and may be identical to or different from each other; n is a number from 1 to 3 representing an average number of moles of AO added; the type of addition of AO may be any of homo, random, block and alternating; and Mare Na, K, NH, or H, and may be identical to or different from each other. In the general formula (II), Rare C6-10 linear or branched alkyl groups and may be identical to or different from each other; AO are C2-4 oxyalkylene groups and may be identical to or different from each other; n is a number from 1 to 3 representing an average number of moles of AO added; the type of addition of AO may be any of homo, random, block and alternating; and Mis Na, K, NH, or H.)SELECTED DRAWING: None

Description

  The present invention relates to a water surface spreader for agricultural chemicals containing a phosphate salt.

  From the viewpoint of the effect of the pesticide and the safety on the human body, it is desired that the pesticide sown in the paddy field is uniformly distributed without being localized in the paddy field. For this reason, it has been practiced to spray pesticides on rice fields together with a water surface spreader. A pesticide water surface spreader is an agent that spreads a pesticide over a wide area from the point of introduction on the water surface. Therefore, the water surface spreading agent for pesticides is required to have a long water surface spreading distance, and the water surface spreading speed must be high in order to disperse the pesticides before they settle. In order to prevent this, it is also required to expand without agglomeration on the water surface.

An ether type surfactant having a polyoxyalkylene alkyl ether moiety has been used as a water surface spreader for agricultural chemicals. Patent Document 1 examines an alkyl chain and an alkylene oxide group for a C _{4 to} C ₁₀ alkyl alcohol C _{2 to} C ₄ alkylene oxide adduct which is an ether type surfactant having a polyoxyalkylene alkyl ether moiety. I have. It also discloses a phosphate salt of an alkylene oxide adduct of an alkyl alcohol. Phosphate ester-type surfactants have the advantage of being excellent in spreadability of dispersing pesticides far away. Patent Literature 2 discloses a mixture of a monoester salt and a diester salt of a phosphate ester salt of an alkylene oxide adduct of an alkyl alcohol as an ether type surfactant having a polyoxyalkylene alkyl ether moiety.

JP 2000-351701 A JP-A-2002-128605

  However, in Patent Document 2, although the spreading distance has been confirmed, no consideration has been given to agglomeration that may occur when the water surface spreading agent is thrown onto the water surface. In addition, the performance may not be stable due to the mixing ratio of the mixture of the monoester salt and the diester salt of the phosphate ester salt, and it is necessary to examine how the mixing ratio affects the effect of the water surface spreader for agricultural chemicals. Was needed. Furthermore, it was necessary to examine each component of the phosphate salt.

  Therefore, the present invention relates to a water surface spreader for agricultural chemicals comprising a monoester salt and / or a diester salt of a phosphate ester salt having a polyoxyalkylene alkyl ether moiety, which is excellent in water surface spreadability. The purpose is to provide.

The inventors of the present invention provide a mixture ratio of a mixture of a monoester salt and a diester salt in a phosphate ester salt, an average number of moles of an alkyl group and an oxyalkylene group in a polyoxyalkylene alkyl ether portion, and selection of a cation portion. However, the present inventors have studied the effects on the water surface spreadability and completed the present invention.
The present invention relates to, for example, the following.
[1] A water surface spreader for agricultural chemicals comprising a compound represented by the following general formula (I) and a compound represented by the following general formula (II),
A water spreader for agricultural chemicals, wherein the molar ratio of the compound represented by the following general formula (I) to the compound represented by the following general formula (II) is from 30:70 to 70:30.

(In the general formula (I), R ¹ is a linear or branched alkyl group having 6 to 10 carbon atoms, and AO is an oxyalkylene group having 2 to 4 carbon atoms, And n is a number from 1 to 3 indicating the average number of moles of AO added, the form of addition of AO may be any of homo, random, block and alternating, and M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ , which may be the same as or different from each other, In the general formula (II), R ¹ is a straight-chain or branched-chain having 6 to 10 carbon atoms. AO is an alkyl group, which may be the same or different, AO is an oxyalkylene group having 2 to 4 carbon atoms, which may be the same or different, and n is , A number of 1 to 3 indicating the average number of moles of AO, Random, may be either block or alternating, ^{M +} is ^{Na +,} K +, an _NH ^{4 +} or ^{H +.)}
[2] A water surface spreader for agricultural chemicals comprising a compound represented by the following general formula (III) and a compound represented by the following general formula (IV),
A water spreader for agricultural chemicals, wherein the molar ratio of the compound represented by the following general formula (III) to the compound represented by the following general formula (IV) is more than 70: less than 30 to 100: 0.

(In the general formula (III), R ² is a linear or branched alkyl group having 8 to 10 carbon atoms, and AO is an oxyalkylene group having 2 to 4 carbon atoms, M is a number of 2 to 4 indicating the average number of moles of AO added, the addition form of AO may be any of homo, random, block and alternating, and M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ , which may be the same as or different from each other, In the general formula (IV), R ² represents a straight or branched chain having 8 to 10 carbon atoms. An alkyl group, which may be the same or different, AO is an oxyalkylene group having 2 to 4 carbon atoms, which may be the same or different, and m is , AO is an average number of addition moles of 2 to 4, and the addition form of AO is Mode, random, may be any of block and alternating, ^{M +} is ^{Na +,} K +, an _NH ^{4 +} or ^{H +.)}
[3] The water spreader for agricultural chemicals according to [1], wherein n in the general formulas (I) and (II) is a number of 2 to 3.
[4] The water spreader for agricultural chemicals according to [2], wherein m in the general formulas (III) and (IV) is a number of 3 to 4.
[5] An agricultural chemical composition comprising the agricultural chemical water surface spreader according to any one of [1] to [4] and an agricultural active ingredient.

  The water surface spreader for agrochemicals of the present invention has excellent water surface spreadability.

It is a figure which shows an example of the state of evaluation of the expansion state of an Example which is (circle). It is a figure which shows an example of the state of evaluation of an expansion state of an Example with (circle). It is a figure showing an example of a state where evaluation of an expansion state of an example is x.

<Water surface extender for pesticides>
1. A first aspect of the present invention A first aspect of the present invention is a water surface spreader for agricultural chemicals comprising a compound represented by the following general formula (I) and a compound represented by the following general formula (II). ,
A water surface spreader for agricultural chemicals, wherein the molar ratio of the compound represented by the following general formula (I) to the compound represented by the following general formula (II) is from 30:70 to 70:30.

(In the general formula (I), R ¹ is a linear or branched alkyl group having 6 to 10 carbon atoms, and AO is an oxyalkylene group having 2 to 4 carbon atoms, And n is a number from 1 to 3 indicating the average number of moles of AO added, the form of addition of AO may be any of homo, random, block and alternating, and M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ , which may be the same as or different from each other, In the general formula (II), R ¹ is a straight-chain or branched-chain having 6 to 10 carbon atoms. AO is an alkyl group, which may be the same or different, AO is an oxyalkylene group having 2 to 4 carbon atoms, which may be the same or different, and n is , A number of 1 to 3 indicating the average number of moles of AO, Random, may be either block or alternating, ^{M +} is _{^{Na +, K +, NH 4}} +, or ^{H +.)}

  The compound represented by the above general formula (I) (hereinafter also referred to as "monoester" in the present specification) and the compound represented by the above general formula (II) (hereinafter also referred to as a "diester" in the present specification) ) Is a molar ratio of the compound represented by the general formula (I): the compound represented by the general formula (II) = 30: 70 to 70:30, and 40:60 to 60: 40, and more preferably 50:50 to 60:40, from the viewpoint of the extension distance. This ratio is a mixing ratio when a monoester and a diester are mixed and produced, but is determined by potentiometric titration when a monoester and a diester are produced as a mixture. Details will be described in Examples.

R ¹ is a linear or branched alkyl group having 6 to 10 carbon atoms. Examples of the linear or branched alkyl group having 6 to 10 carbon atoms include n-hexyl, 1-ethylpentyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, and 2, Examples include a 4,4-trimethylpentyl group, a 2,6-dimethylheptyl group, and an n-decyl group. Among these, an n-hexyl group, a 2-ethylhexyl group, and an n-decyl group are preferred, and an n-decyl group is more preferred. In formula (II), a plurality of R ^{1 s} may be the same or different, but are preferably the same.

AO is an oxyalkylene group having 2 to 4 carbon atoms. A is a linear or branched alkylene group having 2 to 4 carbon atoms, and includes an ethylene group, an n-propylene group, a propylene group (—CH ₂ —CH (CH ₃ ) —), an n-butylene group, 1-methyl propylene group _{(-CH 2 -CH 2 -CH (CH} 3) -), 2- methylpropylene group _{(-CH 2 -CH (CH 3)} -CH 2 -), dimethylethylene group (-CH ₂ - _{C (CH 3) 2 -)} , ethyl ethylene group _{(-CH 2 -CH (CH 2 CH} 3) -), and the like. Further, in A, it is preferable that the number of carbon atoms in the portion constituting the main chain of (AO) _n is 2 or less. That is, A preferably has at least one selected from the group consisting of an ethylene group, a propylene group, and an ethylethylene group. N indicating the average number of added moles of AO is 1 to 3, preferably 2 to 3, and more preferably 3. The AOs may be the same or different from each other, and the addition form may be any of homo, random, block and alternate, but is preferably the same and homo form. Examples of AO include an oxyethylene group, an oxypropylene (—O—CH ₂ —CH (CH ₃ ) —) group, and a combination of an oxyethylene group and an oxypropylene group (—O—CH ₂ —CH (CH ₃ ) —). Is preferable, and an oxyethylene group is more preferable.

M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ , with Na ⁺ being preferred. In formula (I), a plurality of M ⁺ may be the same or different, but are preferably the same.
Between the compound represented by the general formula (I) and the compound represented by the general formula (II), R ¹ , AO, the addition form of AO, n and M ⁺ are each independently selected, , it is preferable that the R ¹ are identical in the compound represented by the general formula R ¹ and the general formula in the compound represented by (I) (II), a compound represented by the general formula (I) And AO, n and the addition form thereof in the compound represented by the general formula (II) are preferably the same as AO, n and the addition form thereof in the compound represented by the general formula (II). ⁺ And M ⁺ in the compound represented by the general formula (II) are preferably the same.
The pesticide water surface spreader may contain other components, but is preferably composed of only the compound represented by the general formula (I) and the compound represented by the general formula (II).

The compound represented by the general formula (I) can be produced in the case of M ⁺ = H ⁺ by reacting a polyoxyalkylene alkyl ether with polyphosphoric acid, and in other cases, the compound is further neutralized thereafter. Can be manufactured. The compound represented by the above general formula (II) is obtained by reacting a polyoxyalkylene alkyl ether with diphosphorus pentoxide, hydrolyzing with an alkali, and then neutral when M ⁺ = H ^+. When M ⁺ = H ⁺ , the product can be produced by washing and purifying with water and washing with acidic water. Details are described in Examples.

  The pesticide water surface spreader is used by being dropped on a paddy field together with the pesticide active ingredient. The pesticide water surface spreader of the present invention has excellent water surface spreading distance, water surface expansion speed and ability to disperse the water surface without agglomeration, so that the pesticide is quickly dropped before sedimentation without coagulation of the pesticide. Since the pesticide can be spread to a place distant from the point, the pesticide is uniformly dispersed without being locally solidified in the paddy field, which is preferable from the viewpoint of the effect of the pesticide and safety on the human body.

2. Second Embodiment of the Present Invention A second embodiment of the present invention is a water surface spreader for agricultural chemicals comprising a compound represented by the following general formula (III) and a compound represented by the following general formula (IV): ,
A water surface spreader for agricultural chemicals wherein the molar ratio of the compound represented by the following general formula (III) to the compound represented by the following general formula (IV) is more than 70: less than 30 to 100: 0.

(In the general formula (III), R ² is a linear or branched alkyl group having 8 to 10 carbon atoms, and AO is an oxyalkylene group having 2 to 4 carbon atoms, M is a number of 2 to 4 indicating the average number of moles of AO added, the addition form of AO may be any of homo, random, block and alternating, and M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ , which may be the same as or different from each other, In the general formula (IV), R ² represents a straight or branched chain having 8 to 10 carbon atoms. An alkyl group, which may be the same or different, AO is an oxyalkylene group having 2 to 4 carbon atoms, which may be the same or different, and m is , AO is an average number of addition moles of 2 to 4, and the addition form of AO is Mode, random, may be any of block and alternating, ^{M +} is ^{Na +,} K +, an _NH ^{4 +} or ^{H +.)}

  A compound represented by the above general formula (III) (hereinafter also referred to as "monoester" in the present specification) and a compound represented by the above general formula (IV) (hereinafter also referred to as a "diester" in the present specification) Is a compound represented by the general formula (III): the compound represented by the general formula (IV) = more than 70: less than 30 to 100: 0, and 75:25 to It is preferably contained at 100: 0, more preferably at 75:25 to 99: 1. This ratio is a mixing ratio when a monoester and a diester are mixed and produced, but is determined by potentiometric titration when a monoester and a diester are produced as a mixture. Details will be described in Examples.

R ² is a linear or branched alkyl group having 8 to 10 carbon atoms. Examples of the linear or branched alkyl group having 8 to 10 carbon atoms include a 2-ethylhexyl group, an n-octyl group, an n-nonyl group, a 2,4,4-trimethylpentyl group, a 2,6-dimethylheptyl group, and n-decyl group. Among these, a 2-ethylhexyl group and an n-decyl group are preferable, and an n-decyl group is more preferable. A plurality of R ² in the general formula (IV) may be the same or different, but are preferably the same.

AO is an oxyalkylene group having 2 to 4 carbon atoms. A is a linear or branched alkylene group having 2 to 4 carbon atoms, and includes an ethylene group, an n-propylene group, a propylene group (—CH ₂ —CH (CH ₃ ) —), an n-butylene group, 1-methyl propylene group _{(-CH 2 -CH 2 -CH (CH} 3) -), 2- methylpropylene group _{(-CH 2 -CH (CH 3)} -CH 2 -), dimethylethylene group (-CH ₂ - _{C (CH 3) 2 -)} , ethyl ethylene group _{(-CH 2 -CH (CH 2 CH} 3) -), and the like. Further, in A, it is preferable that the number of carbon atoms in the portion constituting the main chain of (AO) _m is 2 or less. That is, A preferably has at least one selected from the group consisting of an ethylene group, a propylene group, and an ethylethylene group. M indicating the average number of added moles of AO is 2 to 4, preferably 3 to 4, and more preferably 3. In the general formula (III), AOs may be the same as or different from each other, and the addition form may be any of homo, random, block and alternating, but is preferably the same and homo form. . AO is preferably an oxyethylene group, an oxypropylene group, or a combination of an oxyethylene group and an oxypropylene group, and more preferably an oxyethylene group.

M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ , or H ⁺ , with Na ⁺ being preferred. In the general formula (III), a plurality of M ⁺ may be the same or different, but are preferably the same.
R ² , AO, the addition form of AO, m, and M ⁺ are independently selected between the compound represented by the general formula (III) and the compound represented by the general formula (IV). Is preferably the same as R ² in the compound represented by the general formula (III) and R ² in the compound represented by the general formula (IV), and represented by the general formula (III) It is preferable that AO, m and the addition form thereof in the compound are the same as AO, m and the addition form thereof in the compound represented by the general formula (IV), and the compound represented by the above general formula (III) it is preferred that the M ⁺ are the same in the compound represented by M ⁺ and the general formula (IV).
The water surface spreader for agrochemicals may contain other components, but is composed of only the compound represented by the general formula (III) and the compound represented by the general formula (IV), or It preferably comprises only the compound represented by (III).

The compound represented by the above general formula (III) can be produced in the case of M ⁺ = H ⁺ by reacting a polyoxyalkylene alkyl ether with polyphosphoric acid. In other cases, the compound is further neutralized thereafter. Can be manufactured. The compound represented by the above general formula (IV) is obtained by reacting a polyoxyalkylene alkyl ether with diphosphorus pentoxide, hydrolyzing with an alkali, and then neutralizing other than M ⁺ = H ^+. When M ⁺ = H ⁺ , the product can be produced by washing and purifying with water and washing with acidic water. Details are described in Examples.

  The pesticide water surface spreader is used by being dropped on a paddy field together with the pesticide active ingredient. The pesticide water surface spreader of the present invention has excellent water surface spreading distance, water surface expansion speed and ability to disperse the water surface without agglomeration, so that the pesticide is quickly dropped before sedimentation without coagulation of the pesticide. Since the pesticide can be spread to a place distant from the point, the pesticide is uniformly dispersed without being locally solidified in the paddy field, which is preferable from the viewpoint of the effect of the pesticide and safety on the human body.

<Agrochemical composition>
The pesticide composition contains the pesticide water surface spreader of the first aspect of the present invention or the pesticide water surface spreader of the second aspect and an agrochemical active ingredient. Such an agricultural chemical composition is also referred to as a water-floating agricultural chemical composition.
The active ingredient of the pesticide is not particularly limited as long as it is used as a pesticide. For example, reference is made to the pesticides described in the “Agrochemical Handbook” (2016 edition, Japan Plant Protection Association).

The pesticidal composition may contain a floating aid, a bulking agent, a dispersant, another surfactant, a solvent, and the like as long as the effects of the present invention are not impaired.
Examples of the floating aid include known inorganic floating aids and organic floating aids. Examples of the inorganic floating aid include hollow shirasu, foamed shirasu, foamed pumice, foamed pearlite, fired vermulite, and hollow glass. Can be Examples of the organic floating auxiliary include waxy substances, paraffin wax, cork, wood powder, foamed synthetic resin, synthetic resin hollow body, synthetic resin powder, and the like. As the bulking agent, a finely divided mineral substance carrier having good dispersibility can be used. Mineral substance fine powder carriers include inorganic salts such as potassium chloride, calcium carbonate, magnesium carbonate, ammonium sulfate, sodium sulfate, potassium phosphate, and sodium phosphate, diatomaceous earth, clay, bentonite, pyrophyllite clay and kaori. Knight-based clay and the like can be mentioned. Other extenders that can be used include resins, sugars, starch, wood flour, rice bran, bran, peach and the like. Examples of the dispersant include sodium polyacrylate, sodium carboxymethylcellulose, and white carbon.
Other surfactants include nonionic surfactants, anionic surfactants, and the like. The solvent includes water.
These may be used alone or as a mixture of two or more.
Note that, in the present specification, these optional components, such as a floating auxiliary, a bulking agent, and a composition containing a dispersant, which contain no pesticidal active ingredient, are also referred to as a pesticide water spreader. Say.

As a method for producing the pesticide composition, a known method can be adopted. For example, in the first embodiment of the present invention, water is added to a mixture of the compound represented by the general formula (I), the compound represented by the general formula (II), the pesticidal active ingredient and an optional ingredient. In addition, it can be manufactured by kneading and sizing to an appropriate size, followed by drying at a temperature of less than 100 ° C. In the second aspect of the present invention, water is added to a mixture of the compound represented by the general formula (III), the compound represented by the general formula (IV), the pesticidal active ingredient and an optional ingredient. It can be manufactured by kneading, sizing to an appropriate size, and drying at a temperature of less than 100 ° C.
Examples of the dosage form of the agricultural chemical composition include tablets, granules, and dosage forms in which the agricultural chemical composition is wrapped in a water-soluble film.
The shape of the granule is not particularly limited, and examples thereof include a granule and a string.
The composition ratio of each component in the pesticide composition is not particularly limited, but is represented by the sum of the compounds represented by the above general formulas (I) and (II), or represented by the above general formulas (III) and (IV) The total amount of the compounds is preferably 0.1 to 20% by weight, more preferably 0.2 to 10% by weight, and the agrochemical active ingredient is preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight. Including. When the above-mentioned optional components are contained, the floating auxiliary is preferably 1 to 80% by weight, more preferably 10 to 50% by weight, and the extender is preferably 1 to 80% by weight, more preferably 5 to 60% by weight. The dispersant preferably contains 0.1 to 10% by weight, more preferably 1 to 7% by weight.
The composition ratio of each component in the pesticide-expandable water surface preparation is not particularly limited, but may be the sum of the compounds represented by the general formulas (I) and (II) or the general formulas (III) and (IV). The total amount of the represented compounds is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. When the above optional components are included, the floating auxiliary is preferably 35 to 55% by weight. %, The extender preferably contains 30 to 55% by weight, and the dispersant preferably contains 1 to 10% by weight.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the examples, the monoester refers to the phosphoric acid monoester salt of the general formulas (I) and (III), and the diester refers to the phosphoric diester salt of the general formulas (II) and (IV); Also in the comparative examples, they are referred to correspondingly.

<Synthesis of polyoxyethylene alkyl ether>
[Synthesis Example 1]
102 parts by mass of n-hexanol and 2 parts by mass of potassium hydroxide were charged into an autoclave, and after the temperature was raised to 150 ° C., 44 parts by mass of ethylene oxide was injected under the condition of 0.5 MPa or less, and reacted for 5 hours to react oxyethylene. Polyoxyethylene hexyl ether having an average number of moles of addition of 1 was obtained.

[Synthesis Example 2]
Polyoxyethylene hexyl ether having an average number of moles of added oxyethylene of 2 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide was changed to 88 parts by mass.

[Synthesis Example 3]
Polyoxyethylene hexyl ether having an average addition mole number of oxyethylene of 3 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide was changed to 132 parts by mass.

[Synthesis Example 4]
Polyoxyethylene hexyl ether having an average number of moles of added oxyethylene of 4 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide was changed to 176 parts by mass.

[Synthesis Example 5]
130 parts by mass of 2-ethylhexanol and 2 parts by mass of potassium hydroxide were charged into an autoclave, heated to 150 ° C., and then 44 parts by mass of ethylene oxide were injected under a condition of 0.5 MPa or less, reacted for 5 hours, and reacted with oxyethylene. To obtain polyoxyethylene 2-ethylhexyl ether having an average addition mole number of 1.

[Synthesis Example 6]
Polyoxyethylene 2-ethylhexyl ether having an average number of moles of oxyethylene added of 2 was obtained in the same manner as in Synthesis Example 5 except that the amount of ethylene oxide was changed to 88 parts by mass.

[Synthesis Example 7]
Polyoxyethylene 2-ethylhexyl ether having an average addition mole number of oxyethylene of 3 was obtained in the same manner as in Synthesis Example 5 except that the amount of ethylene oxide was changed to 132 parts by mass.

[Synthesis Example 8]
Polyoxyethylene 2-ethylhexyl ether having an average number of moles of added oxyethylene of 4 was obtained in the same manner as in Synthesis Example 5 except that the amount of ethylene oxide was changed to 176 parts by mass.

[Synthesis Example 9]
158 parts by mass of n-decanol and 2 parts by mass of potassium hydroxide were charged into an autoclave, and the temperature was raised to 150 ° C. Polyoxyethylene decyl ether having an average addition mole number of 1 was obtained.

[Synthesis Example 10]
Polyoxyethylene decyl ether having an average number of moles of oxyethylene added of 2 was obtained in the same manner as in Synthesis Example 9 except that the amount of ethylene oxide was changed to 88 parts by mass.

[Synthesis Example 11]
Polyoxyethylene decyl ether having an average number of moles of added oxyethylene of 3 was obtained in the same manner as in Synthesis Example 9 except that the amount of ethylene oxide was changed to 132 parts by mass.

[Synthesis Example 12]
Polyoxyethylene decyl ether having an average number of moles of added oxyethylene of 4 was obtained in the same manner as in Synthesis Example 9 except that the amount of ethylene oxide was changed to 176 parts by mass.

[Synthesis Example 13]
Polyoxyethylene decyl ether having an average number of moles of added oxyethylene of 5 was obtained in the same manner as in Synthesis Example 9 except that the amount of ethylene oxide was changed to 220 parts by mass.

[Synthesis Example 14]
186 parts by mass of n-dodecanol and 2 parts by mass of potassium hydroxide were charged into an autoclave, heated to 150 ° C., and then 88 parts by mass of ethylene oxide was injected under a condition of 0.5 MPa or less, reacted for 5 hours, and reacted for 5 hours. Polyoxyethylene dodecyl ether having an average number of moles of addition of 2 was obtained.

[Synthesis Example 15]
After charging 74 parts by mass of n-butanol and 2 parts by mass of potassium hydroxide to an autoclave and heating to 150 ° C., 88 parts by mass of ethylene oxide was injected under the condition of 0.5 MPa or less, reacted for 5 hours, and reacted for 5 hours. Polyoxyethylene butyl ether having an average addition mole number of 2 was obtained.

<Synthesis of phosphate ester>
[Synthesis Example A: Synthesis of Molar Ratio of Monoester and Diester = 100: 0]
Each of the polyoxyethylene alkyl ethers obtained in Synthesis Examples 1 to 15 was reacted with polyphosphoric acid. Thereafter, water was added to hydrolyze the unreacted polyphosphoric acid, and then the mixture was heated, blown with nitrogen, dehydrated, and filtered. The molar ratio between the monoester and the diester in the filtrate was measured by a potentiometric titration method described later, and after confirming that the molar ratio was a predetermined molar ratio, the product was neutralized with sodium hydroxide to obtain the desired product.
For the compound having an average addition mole number of ethylene oxide of 0, the desired product was obtained in the same manner except that n-hexanol, 2-ethylhexanol or n-decanol was used instead of polyoxyethylene alkyl ether.

[Synthesis Example B: Synthesis of Molar Ratio of Monoester and Diester = 50: 50]
Each of the polyoxyethylene alkyl ethers obtained in Synthesis Examples 1 to 15 was reacted with diphosphorus pentoxide, and the molar ratio between the monoester and the diester was measured by a potentiometric titration method described later. After confirming that there was, the product was neutralized with sodium hydroxide to obtain the desired product.

[Synthesis Example C: Synthesis of Molar Ratio of Monoester and Diester = 0: 100]
Water and sodium hydroxide were added to the reaction of each of the polyoxyethylene alkyl ethers obtained in Synthesis Examples 1 to 15 with diphosphorus pentoxide to hydrolyze the monoester, followed by liquid chromatography described below. After confirming that no monoester peak was present, the product was purified by washing with water to obtain the desired product.

[Synthesis Example D: Synthesis of Molar Ratio of Monoester and Diester = 90: 10, 75:25, 60:40, 40:60 and 25:75 (Molar Ratio)]
The desired products were obtained by mixing the mixtures obtained in Synthesis Examples A, B, and C at a molar ratio of monoester to diester of 100: 0, 50:50, and 0: 100 so as to have a predetermined molar ratio. Was.

[Examples 1 to 37, Comparative Examples 1 to 43]
Using the monoesters, diesters, and mixtures of monoesters and diesters obtained in Synthesis Examples A to D, water-spread formulations for agricultural chemicals were prepared according to the following preparation examples.
<<< Preparation of water surface expansion formulation for pesticides >>
Based on the following formulation, hollow shirasu, compost, bentonite, and sodium polyacrylate were weighed and mixed in a plastic container to prepare a mixed powder. Monoester and diester were added to the mixed powder, ion-exchanged water was added to the mixture in a mortar, and the mixture was further kneaded to obtain a viscous material. This viscous material was extruded with a net having a diameter of 0.8 mm and dried in a thermostat at 70 ° C. for 1 day to obtain a granular water-spread formulation for agrochemicals.

<Method of measuring molar ratio of monoester and diester>
(1) Potentiometric Titration Potentiometric titration was performed by dissolving 0.5 g of a sample in 100 ml of water and titrating with a 1 / 2N aqueous sodium hydroxide solution.
It was determined as follows from the obtained first equivalent point and second equivalent point.
Monoester ratio = (second equivalent point−first equivalent point) / first equivalent point × 100 (%)
Diester ratio = 100-Monoester ratio (%)
(2) Liquid chromatography 0.2 g of a sample was dissolved in 10 ml of the following eluent, and the measurement was performed under the following conditions.
Column: Inertsil ODS-3 (46 x 250 mm) (manufactured by GL Sciences Inc.)
Eluent: 10 mM potassium dihydrogen phosphate acetonitrile / water = 50/50 mixture flow rate: 1 ml / min Temperature: 40 ° C.
Detector: Differential refractometer

<Evaluation method>
Tap water was collected in a plastic container (length 10 cm, width 250 cm) to a depth of 2 cm.
0.2 g of the water surface-expandable formulation for agricultural chemicals prepared as described above was charged into this container, and the following evaluation was performed.
1. Spreading distance The distance from the pouring position was measured with respect to the position of the leading end that was spread 120 seconds after the water surface spreading formulation for agrochemicals was put on the water surface. The measurement was performed three times, and the average value was evaluated based on the following criteria.
◎: 200 cm or more ○: 150 cm or more and less than 200 cm △: 100 cm or more and less than 150 cm ×: less than 100 cm

2. Spreading speed The spreading distance after 10 seconds from the introduction of the pesticidal water surface spreading formulation to the water surface was measured in the same manner as 1 and the spreading speed was calculated by the following formula.
The measurement was performed three times, and the average value was evaluated according to the following criteria.
Calculation formula: Extension speed (cm / sec) = Extension distance (cm) / 10 (sec) after 10 seconds
◎: 8 cm / sec or more ○: 6 cm / sec or more and less than 8 cm / sec Δ: 4 cm / sec or more and less than 6 cm / sec ×: less than 4 cm / sec

3. Spreading state The water-surface-expandable pesticide formulation was placed on the surface of the water, and the spread state immediately after the introduction was visually observed and evaluated according to the following criteria.
：: As shown in FIG. 1, the particles of the water-surface-expandable pesticide spread while being dispersed one by one without agglomeration.
Δ: As shown in FIG. 2, the water-based spread formulation for agrochemicals spreads with some of the particles aggregated.
×: As shown in FIG. 3, most of the particles of the water-surface-expandable agricultural chemical formulation agglomerated and did not spread, and only some non-aggregated particles spread.

Tables 2 and 3 show the results of Examples and Comparative Examples. In Tables 2 and 3, R ¹ , R ² , n and m correspond to the contents shown in the structures of the above general formulas (I) to (IV). In Tables 2 and 3, R ¹ and R ^{2 each} have 4 carbon atoms in an n-butyl group, 6 carbon atoms in an n-hexyl group, 8 carbon atoms in a 2-ethylhexyl group, and 10 carbon atoms in n-decyl. The group having 12 carbon atoms represents an n-dodecyl group. AO is an oxyethylene group.

In Tables 2 and 3, all the evaluation items of the expansion distance, the expansion speed, and the expansion state were ○ or more.
When Examples 2 and 3 are compared with Comparative Examples 1 and 2, when the number of carbon atoms of R ¹ is 6 and the average number of added moles of oxyethylene groups is 2 or 3, the molar ratio of monoester to diester is obtained. However, when the proportion of the monoester is larger than 70:30, the spreading distance and the spreading speed are deteriorated.

  Comparing Examples 19 to 27 with Comparative Examples 25 to 32, when the molar ratio between the monoester and the diester is less than 30:70, the proportion of the monoester is smaller, but the extension distance and the extension speed are good. However, the state of expansion is poor, leading to the localization of pesticides.

Comparing Examples 1 to 27 with Comparative Examples 4 to 24, when the molar ratio between the monoester and the diester is in the range of 30:70 to 70:30, the carbon number of R ¹ is 6 to 10, and the oxyethylene group has When the average number of moles is 1 to 3, all evaluations of the extension distance, the extension speed, and the extension state are good. On the other hand, if the average number of added moles of the oxyethylene group is less than 1, the extension distance becomes poor, and if the average number of added moles of the oxyethylene group exceeds 3, the extension distance and the expansion speed become poor. Or, the state of expansion becomes worse. If the number of carbon atoms of R ¹ is less than 6, all the evaluations of the extension distance, the extension speed, and the state of extension are poor, and if the number of carbon atoms of R ¹ exceeds 10, the extension distance and the extension speed are low. Is bad.

Comparing Examples 28 to 37 with Comparative Examples 1 to 3 and 34 to 43, when the molar ratio between the monoester and the diester is more than 70: less than 30 to 100: 0, the carbon number of R ² is 8 When the average number of added moles of the oxyethylene group is 2 to 4, the evaluation of the expansion distance, the expansion speed and the expansion state is all good. On the other hand, if the average number of added moles of the oxyethylene group is less than 2, the extension distance and the extension speed become poor. Gets worse. When the carbon number of R ² is less than 8, the extension distance and the extension speed are poor, and when the carbon number of R ² exceeds 10, the extension distance and the extension speed are poor.

In the general formulas (I) and (II), R ¹ is a 2-ethylhexyl group, AO is an oxyethylene group, n is 2, and a molar ratio of monoester to diester = 50: 50. According to No. 1, a water surface-expandable pesticide formulation was prepared, and the effect of the difference in M ⁺ was confirmed as shown in Table 4.

^The example of M _{+ =} ^NH 4 _+, N- ethyl -N- hydroxyethyl ammonium cations and N- methyl -N- hydroxyethyl ammonium cation, in Synthesis Example B, instead, each ammonium hydroxide sodium hydroxide , N-ethyl-N-hydroxyethylamine, and N-methyl-N-hydroxyethylamine.
From the results in Table 4, it can be seen that when Na ⁺ and NH ₄ ⁺ are used as M ⁺ , the spreading distance is larger than when N-ethyl-N-hydroxyethylammonium cation and N-methyl-N-hydroxyethylammonium cation are used. Excellent.

The inventors of the present invention provide a mixture ratio of a mixture of a monoester salt and a diester salt in a phosphate ester salt, an average number of moles of an alkyl group and an oxyalkylene group in a polyoxyalkylene alkyl ether portion, and selection of a cation portion. However, the present inventors have studied the effects on the water surface spreadability and completed the present invention.
The present invention relates to, for example, the following.
[1] A water surface spreader for agricultural chemicals comprising a compound represented by the following general formula (I) and a compound represented by the following general formula (II),
A water spreader for agricultural chemicals, wherein the molar ratio of the compound represented by the following general formula (I) to the compound represented by the following general formula (II) is from 30:70 to 70:30.

(In the general formula (I), R ¹ is a linear or branched alkyl group having 6 to 10 carbon atoms, and AO is an oxyalkylene group having 2 to 4 carbon atoms, And n is a number from 1 to 3 indicating the average number of moles of AO added, the form of addition of AO may be any of homo, random, block and alternating, and M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ , which may be the same as or different from each other, In the general formula (II), R ¹ is a straight-chain or branched-chain having 6 to 10 carbon atoms. AO is an alkyl group, which may be the same or different, AO is an oxyalkylene group having 2 to 4 carbon atoms, which may be the same or different, and n is , A number of 1 to 3 indicating the average number of moles of AO, Random, may be either block or alternating, ^{M +} is ^{Na +,} K +, an _NH ^{4 +} or ^{H +.)}
[2 ] The water spreader for agricultural chemicals according to [1], wherein n in the general formulas (I) and (II) is a number of 2 to 3.
[ 3 ] An agricultural chemical composition comprising the agricultural chemical water surface spreader according to [1] or [2] and an agricultural active ingredient.

As a method for producing the pesticide composition, a known method can be adopted. For example, in the first embodiment of the present invention, water is added to a mixture of the compound represented by the general formula (I), the compound represented by the general formula (II), the pesticidal active ingredient and an optional ingredient. in addition to kneading, after an appropriate size, it can be produced by drying at a temperature below 100 ° C..
The dosage form of pesticides composition, tablets, granules, and agrochemical compositions soluble film wrapped dosage form and the like.
The shape of the granule is not particularly limited, and examples thereof include a granule and a string.
The composition ratio of each component of the pesticidal composition is not particularly limited, the total of the compound represented by the general formula (I) and (II), preferably 0.1 to 20 wt%, more preferably 0.2 to 10% by weight, and preferably 0.1 to 80% by weight, more preferably 1 to 50% by weight, of the pesticidal active ingredient. When the above-mentioned optional components are contained, the floating auxiliary is preferably 1 to 80% by weight, more preferably 10 to 50% by weight, and the extender is preferably 1 to 80% by weight, more preferably 5 to 60% by weight. The dispersant preferably contains 0.1 to 10% by weight, more preferably 1 to 7% by weight.
The composition ratio of each component of the agrichemical water extender formulation, especially but not limited to, the total of the compound represented by general formula (I) and (II), preferably 0.1 to 10 wt%, More preferably, it contains 0.5 to 5% by weight, and when it contains the above optional components, the floating aid is preferably 35 to 55% by weight, the bulking agent is preferably 30 to 55% by weight, and the dispersant is Preferably, it contains 1 to 10% by weight.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
In the examples, the monoester refers to the phosphoric acid monoester salt of the general formula (I) , and the diester refers to the phosphoric diester salt of the general formula (II). Referred to as

[Examples 1 to 27 , Comparative Examples 1 to 33 ]
Using the monoesters, diesters, and mixtures of monoesters and diesters obtained in Synthesis Examples A to D, water-spread formulations for agricultural chemicals were prepared according to the following preparation examples.
<<< Preparation of water surface expansion formulation for pesticides >>
Based on the following formulation, hollow shirasu, compost, bentonite, and sodium polyacrylate were weighed and mixed in a plastic container to prepare a mixed powder. Monoester and diester were added to the mixed powder, ion-exchanged water was added to the mixture in a mortar, and the mixture was further kneaded to obtain a viscous material. This viscous material was extruded with a net having a diameter of 0.8 mm and dried in a thermostat at 70 ° C. for 1 day to obtain a granular water-spread formulation for agrochemicals.

Table 2 shows the results of Examples and Comparative Examples. In Table 2 , R ¹ and n correspond to the contents shown in the structures of the general formulas (I) and (II) . In Table 2 , R ¹ and R ^{2 each} have 4 carbon atoms as an n-butyl group, 6 carbon atoms as an n-hexyl group, 8 carbon atoms as a 2-ethylhexyl group, 10 carbon atoms as an n-decyl group, Formula 12 represents an n-dodecyl group. AO is an oxyethylene group.

Oite Table 2, extender distance, all evaluation items extender speed and extender condition as Example what was ○ over.
When Examples 2 and 3 are compared with Comparative Examples 1 and 2, when the number of carbon atoms of R ¹ is 6 and the average number of added moles of oxyethylene groups is 2 or 3, the molar ratio of monoester to diester is obtained. However, when the proportion of the monoester is larger than 70:30, the spreading distance and the spreading speed are deteriorated.

Claims (5)

A water surface spreader for agricultural chemicals comprising a compound represented by the following general formula (I) and a compound represented by the following general formula (II),
A water spreader for agricultural chemicals, wherein the molar ratio of the compound represented by the following general formula (I) to the compound represented by the following general formula (II) is from 30:70 to 70:30.

(In the general formula (I), R ¹ is a linear or branched alkyl group having 6 to 10 carbon atoms, and AO is an oxyalkylene group having 2 to 4 carbon atoms, And n is a number from 1 to 3 indicating the average number of moles of AO added, the form of addition of AO may be any of homo, random, block and alternating, and M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ , which may be the same as or different from each other, In the general formula (II), R ¹ is a straight-chain or branched-chain having 6 to 10 carbon atoms. AO is an alkyl group, which may be the same or different, AO is an oxyalkylene group having 2 to 4 carbon atoms, which may be the same or different, and n is , A number of 1 to 3 indicating the average number of moles of AO, Random, may be either block or alternating, ^{M +} is ^{Na +,} K +, an _NH ^{4 +} or ^{H +.)} A water spreader for agricultural chemicals comprising a compound represented by the following general formula (III) and a compound represented by the following general formula (IV),
A water spreader for agricultural chemicals, wherein the molar ratio of the compound represented by the following general formula (III) to the compound represented by the following general formula (IV) is more than 70: less than 30 to 100: 0.
(In the general formula (III), R ² is a linear or branched alkyl group having 8 to 10 carbon atoms, and AO is an oxyalkylene group having 2 to 4 carbon atoms, M is a number of 2 to 4 indicating the average number of moles of AO added, the addition form of AO may be any of homo, random, block and alternating, and M ⁺ is Na ⁺ , K ⁺ , NH ₄ ⁺ or H ⁺ , which may be the same as or different from each other, In the general formula (IV), R ² represents a straight or branched chain having 8 to 10 carbon atoms. An alkyl group, which may be the same or different, AO is an oxyalkylene group having 2 to 4 carbon atoms, which may be the same or different, and m is , AO is an average number of addition moles of 2 to 4, and the addition form of AO is Mode, random, may be any of block and alternating, ^{M +} is ^{Na +,} K +, an _NH ^{4 +} or ^{H +.)} The water spreader for agricultural chemicals according to claim 1, wherein n in the general formulas (I) and (II) is a number of 2 to 3. The water spreader for agricultural chemicals according to claim 2, wherein m in the general formulas (III) and (IV) is a number of 3 to 4. An agricultural chemical composition comprising the agricultural chemical surface extender according to any one of claims 1 to 4 and an agricultural active ingredient.