阅读说明：本技术 水面漂浮型农药组合物用展着剂和包含其的农药组合物 (Spreading agent for water-surface floating type pesticide composition and pesticide composition containing same ) 是由 鬼头信臣 于 2021-05-17 设计创作，主要内容包括：本发明涉及水面漂浮型农药组合物用展着剂和包含其的农药组合物。本发明的目的在于,提供：对与农药活性成分组合使用而制备的粒状的农药组合物进行水面施用时得到优异的展着性、提供在水面整体崩解的水面漂浮型农药组合物的水面漂浮型农药组合物用展着剂。本发明的水面漂浮型农药组合物用展着剂含有HO-R～(1)-O-G～(1)-H所示的化合物(式中,R～(1)是碳原子数6～14的亚烷基,G～(1)是-(R～(5)O)-(s)-所示的2价的基团,R～(5)是碳原子数为2或3的亚烷基,s为1～10的整数,s为2以上的情况下,-(R～(5)O)-(s)-中的R～(5)任选全部相同或不同。)。(The present invention relates to a spreading agent for a water-surface floating type pesticidal composition and a pesticidal composition comprising the same. An object of the present invention is to provide: a spreading agent for a water-surface floating pesticide composition, which can give a granular pesticide composition prepared by using a pesticide active ingredient in combination with the pesticide active ingredient and which has excellent spreading properties when applied to water and can disintegrate the whole composition on the water surface. The spreading agent for the water-surface floating type pesticide composition of the invention contains HO-R 1 ‑O‑G 1 A compound represented by the formula (wherein R is 1 Is an alkylene group having 6 to 14 carbon atoms, G 1 Is- (R) 5 O) s -a group having a valence of 2 as indicated,R 5 is an alkylene group having 2 or 3 carbon atoms, s is an integer of 1 to 10, and s is 2 or more, - (R) 5 O) s R in (A-C) 5 Optionally all the same or different. ).)

1. A spreading agent for a water-floating agricultural chemical composition, characterized by containing a compound represented by the following general formula (1),

HO-R¹-O-G¹-H(1)

in the formula, R¹Is an alkylene group having 6 to 14 carbon atoms, G¹Is- (R)⁵O)_s-a group having a valence of 2, R⁵Is an alkylene group having 2 or 3 carbon atoms, s is an integer of 1 to 10, and s is 2 or more, - (R)⁵O)_sR in (A-C)⁵Optionally all the same or different.

2. The spreader for water-surface floating type agricultural chemical composition according to claim 1, wherein in the compound of the general formula (1), R is¹Is an alkylene group having 8 to 12 carbon atoms.

3. The spreading agent for water-surface floating type pesticidal composition according to claim 1 or 2, wherein in the compound of the general formula (1), R is¹Is an alkylene group having 8 or 9 carbon atoms, and s is an integer of 2 to 8.

4. The spreading agent for a water-surface floating type pesticidal composition according to any one of claims 1 to 3, further comprising a compound represented by the following general formula (2),

H-G²-O-R²-O-G³-H(2)

in the formula, R²Is an alkylene group having 6 to 14 carbon atoms, G²Is- (OR)⁷)_t-a group having a valence of 2, R⁷Is an alkylene group having 2 OR 3 carbon atoms, t is an integer of 1 to 10, and when t is 2 OR more, - (OR)⁷)_tR in (A-C)⁷Optionally all of the same or different, G³Is- (R)⁹O)_u-a group having a valence of 2, R⁹Is an alkylene group having 2 or 3 carbon atoms, u is an integer of 1 to 10, and u is 2 or more, - (R)⁹O)_uR in (A-C)⁹Optionally all the same or different.

5. The spreading agent for a water-surface floating type pesticide composition according to claim 4, wherein the content ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2) is 40 to 99% by mass and the content ratio of the compound represented by the general formula (2) is 1 to 60% by mass, based on 100% by mass of the total content of the compounds.

6. A water-surface floating type agricultural chemical composition, comprising: an agricultural chemical active ingredient, and the spreading agent for a water-surface floating agricultural chemical composition according to any one of claims 1 to 5.

7. The water surface floating type pesticidal composition according to claim 6, which further comprises an extender.

8. The water-surface-floating pesticide composition according to claim 7, wherein the content ratio of the pesticide active ingredient, the water-surface-floating pesticide composition spreading agent and the extender is 0.1 to 80% by mass, 0.1 to 10% by mass and 10 to 97% by mass, based on 100% by mass of the total content of the components.

Technical Field

The present invention relates to: a granular agricultural chemical composition which is contained together with an agricultural chemical active ingredient (an agricultural chemical active ingredient) and applied to the water surface of agricultural land, and a spreading agent for a water-floating agricultural chemical composition which spreads the agricultural chemical active ingredient sufficiently on the water surface.

Background

For example, in order to obtain a sufficient effect of an agricultural chemical sprayed on a paddy field, that is, in order to disperse the sprayed agricultural chemical over the entire paddy field without localized presence, an agricultural chemical (agricultural chemical composition) having a granular form using an agricultural chemical active ingredient in combination with a spreading agent is widely used. The spreading agent is required to have long spreading distance and fast spreading speed after contacting with water.

Patent document 1 discloses a pesticide preparation for paddy field input, which is obtained by packaging solid pesticides floating on water on a spreading water-soluble paper, respectively, and in which active ingredients are dispersed or dissolved in water, the solid pesticides floating on water comprising: an active ingredient of a pesticide; contains 1 or more than 2 water surface floating grains selected from roasted vermiculite, foamed perlite, foamed white sand (Japanese: シラス) and cork; and 1 or more than 2 water surface spreaders selected from the group consisting of acetylene alcohols and acetylene glycols and surfactants to which alkylene oxides are added.

Patent document 2 discloses a spreading agent for a water-surface floating type agricultural chemical composition, which comprises: selected from (RCOO)_mX(OH)_n(R is an aliphatic hydrocarbon group having 6 to 9 carbon atoms, X is a residue obtained by removing all hydroxyl groups from a 1 to 4-valent aliphatic hydroxyl compound having 2 to 8 carbon atoms, m is an integer of 1 to 3, n is 0 or an integer of 1 to 3, and an integer satisfying 1. ltoreq. m + n. ltoreq.4) and at least one or more of phosphate ester salts and sulfate ester salts thereof.

Patent document 3 discloses a spreading agent for a water-surface floating type agricultural chemical composition, which is characterized by comprising: selected from C6-C14 chain diols and HO-A¹-O-R-O-A²-OH (R: a residue obtained by removing all hydroxyl groups from a C6-14 chain diol, A)¹、A²: one or more chain diol derivatives represented by (poly) alkylene glycol having (poly) oxyalkylene group(s) comprising 1 to 7 oxyalkylene unit(s) in total and having 2 to 4 carbon atoms, wherein all hydroxyl groups are removed).

Patent document 4 discloses a water-surface-floating pesticide granular composition containing: a pesticide active ingredient; HO- (A)¹-O)_m-X¹-(O-A²)_n-OH(X¹2-valent saturated with 6-14 carbon atomsAnd a hydrocarbon group, A¹And A²Each represents an alkylene group having 2 to 4 carbon atoms, and m and n each represent an integer. m and n are any one of integers of 1 to 7 in total, and when m is an integer of 2 or more, each A¹The same or different, each A is an integer of 2 or more²The same or different) are selected from the group consisting of chain diol derivatives; condensed phosphoric acid or a salt thereof; and, a flotation aid and an extender.

Patent document 5 discloses a spreading agent for a water-floating agricultural chemical composition, which is characterized by comprising: r¹COO-(AO)_n-R²(R¹: a C6-9 linear alkyl group or a C6-9 branched alkyl group, AO: oxyalkylene group having 2 carbon atoms, n: an integer of 3 to 4, R²: a C1-2 linear alkyl group. ) Ester compounds are shown.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 6-336403

Patent document 2: japanese patent laid-open publication No. 2003-238307

Patent document 3: japanese patent laid-open No. 2007-39344

Patent document 4: japanese patent laid-open publication No. 2009-114102

Patent document 5: japanese patent laid-open publication No. 2018-100261

Disclosure of Invention

Problems to be solved by the invention

An object of the present invention is to provide: a spreading agent for a water-floating agricultural chemical composition, which contains an agricultural chemical active ingredient together with the agricultural chemical active ingredient, for example, is suitable for providing a granular agricultural chemical composition and is used as an additive capable of sufficiently spreading the agricultural chemical active ingredient on the water surface of agricultural land. Another object of the present invention is to provide: a water-floating agricultural chemical composition which is applied to the water surface of agricultural land and has excellent spreadability of an agricultural active ingredient on the water surface after application.

Means for solving the problems

The inventors of the present invention conducted extensive studies and found that: when a granular product prepared by using a combination of an agricultural chemical active ingredient and a specific diol compound is sprayed on water, the agricultural chemical active ingredient spreads sufficiently.

The present invention is as follows.

The spreading agent for a water-floating agricultural chemical composition of the present invention is characterized by containing a compound represented by the following general formula (1).

HO-R¹-O-G¹-H (1)

(in the formula, R¹Is an alkylene group having 6 to 14 carbon atoms, G¹Is- (R)⁵O)_s-a group having a valence of 2, R⁵Is an alkylene group having 2 or 3 carbon atoms, s is an integer of 1 to 10, and s is 2 or more, - (R)⁵O)_sR in (A-C)⁵Optionally all the same or different. )

The spreading agent for a water-surface floating type agricultural chemical composition of the present invention may further contain a compound represented by the following general formula (2).

H-G²-O-R²-O-G³-H (2)

(in the formula, R²Is an alkylene group having 6 to 14 carbon atoms, G²Is- (OR)⁷)_t-a group having a valence of 2, R⁷Is an alkylene group having 2 OR 3 carbon atoms, t is an integer of 1 to 10, and when t is 2 OR more, - (OR)⁷)_tR in (A-C)⁷Optionally all of the same or different, G³Is- (R)⁹O)_u-a group having a valence of 2, R⁹Is an alkylene group having 2 or 3 carbon atoms, u is an integer of 1 to 10, and u is 2 or more, - (R)⁹O)_uR in (A-C)⁹Optionally all the same or different. )

The water-surface floating type agricultural chemical composition of the present invention is characterized by containing: an agricultural chemical active ingredient, and the above-mentioned spreading agent for a water-surface floating agricultural chemical composition of the present invention.

The water-surface floating type pesticidal composition of the present invention may further contain an extender.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, if a granulated product (water-surface-floating agricultural chemical composition) prepared by using a spreading agent for a water-surface-floating agricultural chemical composition and an agricultural chemical active ingredient in combination is sprayed on water, an effect of spreading the agricultural chemical active ingredient sufficiently can be obtained. Therefore, the water-surface floating type pesticidal composition of the present invention is useful for application to agricultural land having a water surface. In addition, the spreading agent for a water-surface-floating pesticide composition of the present invention is excellent in the granulation property of the pesticide active ingredient, and therefore, the granular water-floating pesticide composition can be easily applied to water surfaces.

Drawings

FIG. 1 is a schematic view of a container used for evaluating the spreadability of a pesticide composition in [ example ].

FIG. 2 is a schematic diagram illustrating the evaluation of the spreadability of the pesticide composition in [ example ].

Fig. 3 is a schematic view illustrating how the agricultural chemical composition is put on the water surface in evaluating the spreadability of the agricultural chemical composition in [ example ].

Detailed Description

The spreading agent for a water-surface floating type agricultural chemical composition of the present invention contains a compound represented by the following general formula (1) (hereinafter, referred to as "diol compound (a)").

HO-R¹-O-G¹-H (1)

(in the formula, R¹Is an alkylene group having 6 to 14 carbon atoms, G¹Is- (R)⁵O)_s-a group having a valence of 2, R⁵Is an alkylene group having 2 or 3 carbon atoms, s is an integer of 1 to 10, and s is 2 or more, - (R)⁵O)_sR in (A-C)⁵Optionally all the same or different. )

In the above general formula (1), the alkylene group R¹The structure of (b) is not particularly limited, and may be linear or branched. R¹The alkylene group in (1) has 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms, and more preferably 8 to 9 carbon atoms. Alkylene radical R from the viewpoint of surface spreadability¹A branched alkylene group having 8 to 12 carbon atoms is preferred. Preferred R¹Specific examples of (3) are as follows.

In the above general formula (1), G is the structure¹Alkylene of (A) to (B)⁵Is an alkylene group having 2 or 3 carbon atoms, that is, an ethylene group or a linear or branched propylene group. Thus, G¹Containing oxyethylene (-C)₂H₄O-) or oxypropylene (-C)₃H₆O-)。

In the diol compound (A), s, which is the total number of oxyethylene groups or oxypropylene groups, is 1 to 10, preferably 2 to 8, and more preferably 3 to 8. When s is 2 or more, - (R)⁵O)_SR in (A-C)⁵When both oxyethylene groups and oxypropylene groups are contained, these groups may be bonded to each other regularly or irregularly.

The diol compound (a) contained in the spreading agent for a water-surface floating type agricultural chemical composition of the present invention may be 1 kind or 2 or more kinds.

The method for producing the diol compound (a) is not particularly limited. A preferred production method is a method including the following steps (hereinafter referred to as "reaction steps"): reacting a C6-14 chain diol with at least one selected from the group consisting of ethylene oxide and propylene oxide in the presence of a catalyst. The following describes the production method.

Examples of the chain diol include straight chain alkanediols such as hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, tridecanediol, and tetradecanediol; branched alkanediols such as 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 3-pentanediol and 2-methyl-1, 8-octanediol. The number of the chain diols used in the reaction step may be only 1, or may be 2 or more.

In the reaction step, a catalyst is used. The catalyst is not particularly limited, and a basic compound is preferred in terms of efficiently obtaining a desired product. The alkaline compound can be inorganic compound and organic compoundThe inorganic compound may be any of compounds, and examples thereof include potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, and lithium carbonate. Examples of the organic compound include CH₃ONa、C₂H₅ONa、CH₃OLi、C₂H₅OLi、CH₃OK、C₂H₅OK, etc. The amount of the catalyst to be used is preferably 0.1 to 10 millimolar equivalents based on 1 mole of the chain diol.

The above reaction step is carried out as follows: in a pressure reactor such as an autoclave, the temperature of the reaction system is preferably 100 to 170 ℃, more preferably 130 to 150 ℃, and the raw materials are stirred and pushed. To form a diol compound having a desired structure, ethylene oxide or propylene oxide may be added while changing the order, ratio, etc.

The above production method may further include a purification step, if necessary, after the reaction step. The purification step may include conventionally known operations such as chromatographic separation and concentration, which are performed in the synthesis of general organic compounds.

The spreading agent for a water-surface floating type agricultural chemical composition of the present invention may further contain a compound represented by the following general formula (2) (hereinafter, referred to as "diol compound (B)") in order to improve the spreading property.

H-G²-O-R²-O-G³-H (2)

(in the formula, R²Is an alkylene group having 6 to 14 carbon atoms, G²Is- (OR)⁷)_t-a group having a valence of 2, R⁷Is an alkylene group having 2 OR 3 carbon atoms, t is an integer of 1 to 10, and when t is 2 OR more, - (OR)⁷)_tR in (A-C)⁷Optionally all of the same or different, G³Is- (R)⁹O)_u-a group having a valence of 2, R⁹Is an alkylene group having 2 or 3 carbon atoms, u is an integer of 1 to 10, and u is 2 or more, - (R)⁹O)_uR in (A-C)⁹Optionally all the same or different. )

In the above general formula (2), the alkylene group R²The structure of (b) is not particularly limited, and may be linear or branched. R²The alkylene group in (1) has 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms. Alkylene radical R from the viewpoint of surface spreadability²A branched alkylene group having 8 to 12 carbon atoms is preferred. Preferred R²Specific examples of (3) are as follows.

In the above general formula (2), G is the structure²Alkylene of (A) to (B)⁷Is an alkylene group having 2 or 3 carbon atoms, that is, an ethylene group or a linear or branched propylene group. Thus, G²Containing oxyethylene groups (-OC)₂H₄-) or oxypropylene (-OC)₃H₆-)。

In the diol compound (B), t, which is the total number of oxyethylene groups or oxypropylene groups, is 1 to 10, preferably 2 to 6, and more preferably 3 to 5. When t is 2 OR more, - (OR)⁷)_tR in (A-C)⁷When both oxyethylene groups and oxypropylene groups are contained, these groups may be bonded regularly or irregularly.

In the above general formula (2), G is the structure³Alkylene of (A) to (B)⁹Is an alkylene group having 2 or 3 carbon atoms, that is, an ethylene group or a linear or branched propylene group. Thus, G³Containing oxyethylene (-C)₂H₄O-) or oxypropylene (-C)₃H₆O-)。

In the diol compound (B), u, which is the total number of oxyethylene groups or oxypropylene groups, is 1 to 10, preferably 2 to 6, and more preferably 3 to 5. When u is 2 or more, - (R)⁹O)_uR in (A-C)⁹When both oxyethylene groups and oxypropylene groups are contained, these groups may be bonded regularly or irregularly.

The method for producing the diol compound (B) is not particularly limited. A preferred production method is a production method including the steps of: reacting a C6-14 chain diol with at least one selected from the group consisting of ethylene oxide and propylene oxide in the presence of a catalyst comprising a basic compound. In this case, the amount of the catalyst to be used is preferably 10 to 100 milliequivalents, and more preferably 15 to 50 milliequivalents, based on 1 mole of the chain diol.

When the above diol compound (B) is contained in the above-mentioned spreading agent for a water-floating agricultural chemical composition of the present invention, the content ratio of the diol compound (a) and the diol compound (B) is preferably 40 to 99% by mass and 1 to 60% by mass, more preferably 60 to 98% by mass and 2 to 40% by mass, and further preferably 80 to 98% by mass and 2 to 20% by mass, respectively, when the total of these is 100% by mass.

The spreading agent for a water-surface floating type agricultural chemical composition of the present invention may further contain other components such as a binder, a disintegration accelerator, a dispersant, an emulsifier, a liquid medium (water, glycol, paraffin oil, etc.), a stabilizer, and the like, as required.

The spreading agent for a water-surface-floating agricultural chemical composition of the present invention is applied to the water surface of agricultural land and is suitable as a raw material for producing a granular water-surface-floating agricultural chemical composition having excellent spreadability of an agricultural active ingredient on the water surface after application.

The water-surface floating type agricultural chemical composition of the present invention is characterized by containing: an agricultural chemical active ingredient, and the above-mentioned spreading agent of the present invention.

The pesticidal active ingredient is not particularly limited as long as the activity is not impaired in the coexistence with water. Examples thereof include herbicides, insecticides, acaricides, nematicides, antiviral agents, plant growth regulators, bactericides, inducers, and insect repellents. These pesticidal active ingredients may be both water-soluble and water-insoluble. The pesticide active ingredient contained in the water-surface floating type pesticide composition of the present invention may be only 1 kind, or 2 or more kinds.

The content ratio of the above-mentioned pesticidal active ingredient and the spreading agent is not particularly limited.

The water-surface floating type agricultural chemical composition of the present invention may further contain other components such as an extender, a binder, a disintegration accelerator, a dispersant, an emulsifier, a liquid medium (water, glycol, paraffin oil, etc.), a stabilizer, and the like.

The water-surface floating type agricultural chemical composition of the present invention preferably contains an extender as another component. As extenders, it is possible to use: powders or particles such as clay, silica, talc, clay, diatomaceous earth, silica, bentonite, calcium carbonate, barium sulfate, titanium dioxide, starch, lactose, potassium chloride, urea, hollow glass, white carbon, wood powder, cork powder, expandable white sand, microspheres, and carboxymethyl cellulose.

When the water-surface floating type agricultural chemical composition of the present invention contains an extender, the content ratios of the agricultural chemical active ingredient, the above-mentioned spreading agent of the present invention (the total amount of the above-mentioned diol compound (a), or the total amount of the diol compound (a) and the diol compound (B)) and the extender are preferably 0.1 to 80 mass%, 0.1 to 10 mass%, and 10 to 97 mass%, more preferably 0.2 to 70 mass%, 0.5 to 8 mass%, and 20 to 95 mass%, respectively, when the total amount of these components is 100 mass%.

The water-surface floating type agricultural chemical composition of the present invention may be a mixture (hereinafter referred to as "1 st agricultural chemical composition") having no shape in which the respective components are mixed as they are, or a granular molded article (granulated product) obtained by using the 1 st agricultural chemical composition. In the case of granules, the granules may or may not contain a liquid medium.

When the water-surface floating type agricultural chemical composition of the present invention is applied to the water surface of agricultural land, it is preferably a granulated substance.

The water-surface floating type agricultural chemical composition of the present invention can be applied by manual application, mechanical application, or transfer application, as in the case of ordinary agricultural chemical granules, but it may be applied by so-called frame application in which the composition is applied from a ridge, a bank, or the like, or may be applied by packaging the composition on water-soluble paper and applying the composition from the ridge, the bank, or the like. The water-soluble paper used for application is a film or sheet having solubility or dispersibility in water, and examples thereof include: a film or sheet formed from polyvinyl alcohol or a derivative thereof, pullulan, a sodium salt of carboxymethyl cellulose, polyethylene oxide or a derivative thereof, and the like, and among these, a film or sheet formed from polyvinyl alcohol or a derivative thereof is preferable.

In the case of producing the granulated product, the 1 st agricultural chemical composition may be processed by, for example, an extrusion molding machine, a screw type molding machine, a roll type molding machine, a plate type molding machine, or the like. The above-mentioned spreading agent of the present invention is excellent in the formability of the granulated product and the shape stability, and therefore, the obtained granular water-surface-floating agricultural chemical composition is easy to handle.

Examples

The present invention will be specifically described below with reference to examples. In the following description, "part" is based on mass unless otherwise specified.

1. Raw material of spreading agent for water surface floating type pesticide composition

1-1. diol compound (A)

The compounds A-1 to A-25 and a-1 to a-4 obtained in the following synthetic examples 1 to 29 were used.

Synthesis example 1

160.3g (1 mol) of 2-butyl-2-ethyl-1, 3-propanediol was charged into an autoclave, 0.3g (6 mmol equivalent to the raw material) of potassium hydroxide powder as a catalyst was added, and the inside of the autoclave was sufficiently replaced with nitrogen. Then, while stirring them, 176g (4 moles) of ethylene oxide was introduced thereinto under pressure while maintaining the temperature of the reaction system at 130 to 150 ℃ to start the addition polymerization reaction. Then, the mixture was aged at the same temperature for 1 hour to terminate the addition polymerization reaction. Thereafter, the catalyst of the reaction system was neutralized with phosphoric acid, and then the reaction product was separated and recovered by liquid chromatography. The obtained reaction product was analyzed by LC-MS, and as a result, it was found to be a compound represented by the following formula. Hereinafter, this compound is represented as A-1 (see Table 1).

ESI-MS：m/z＝337(M+H)⁺

Synthesis example 2

Compound a-2 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that 4 moles of propylene oxide were used instead of 4 moles of ethylene oxide.

Synthesis example 3

Compound a-3 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that a mixture of 2 moles of ethylene oxide and 2 moles of propylene oxide was used instead of 4 moles of ethylene oxide alone.

Synthesis example 4

160.3g (1 mol) of 2-butyl-2-ethyl-1, 3-propanediol was charged into an autoclave, 0.3g (6 mmol equivalent to the raw material) of potassium hydroxide powder as a catalyst was added, and the inside of the autoclave was sufficiently replaced with nitrogen. Then, the temperature of the reaction system was maintained at 130 to 150 ℃ while stirring them, 2 moles of ethylene oxide were introduced thereinto, and after aging at the same temperature for 1 hour, 2 moles of propylene oxide were introduced thereinto at 130 to 150 ℃ and aging at the same temperature for 1 hour was carried out to complete the addition polymerization. After completion of the reaction, the same operation as in Synthesis example 1 was carried out to obtain Compound A-4 (see Table 1).

Synthesis example 5

Compound a-5 (see table 1) was obtained by performing the same operation as in synthesis example 4, except that the order of ethylene oxide (2 moles) and propylene oxide (2 moles) introduced was reversed.

Synthesis example 6

Compound a-6 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that the amount of ethylene oxide used was changed from 4 moles to 8 moles.

Synthesis example 7

Compound a-7 (see table 1) was obtained by the same operation as in synthesis example 1, except that 2, 4-diethyl-1, 3-pentanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and the amount of ethylene oxide used was changed from 4 moles to 6 moles.

Synthesis example 8

1 mol of 2, 4-diethyl-1, 3-pentanediol and 0.3g (6 mmol equivalent to the raw material) of potassium hydroxide powder as a catalyst were added, and then the inside of the autoclave was sufficiently replaced with nitrogen gas. Then, the temperature of the reaction system was maintained at 130 to 150 ℃ while stirring them, 1 mol of propylene oxide was introduced thereinto, and after aging at the same temperature for 1 hour, 1 mol of ethylene oxide was introduced thereinto at 130 to 150 ℃ and aging at the same temperature for 1 hour was carried out to complete the addition polymerization. After completion of the reaction, the same operation as in Synthesis example 1 was carried out to obtain Compound A-8 (see Table 1).

Synthesis example 9

Compound a-9 (see table 1) was obtained by the same operation as in synthesis example 1, except that 2-methyl-1, 8-octanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and the amount of ethylene oxide used was changed from 4 moles to 5 moles.

Synthesis example 10

Compound a-10 (see table 1) was obtained by the same procedure as in synthesis example 1, except that 2-methyl-1, 8-octanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and 7 moles of propylene oxide were used instead of 4 moles of ethylene oxide.

Synthesis example 11

Compound a-11 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that the amount of ethylene oxide used was changed from 4 moles to 6 moles.

Synthesis example 12

Compound A-12 (see Table 1) was obtained by performing the same operation as in Synthesis example 1, except that 6 moles of propylene oxide were used instead of 4 moles of ethylene oxide

Synthesis example 13

Compound a-13 (see table 1) was obtained by the same operation as in synthesis example 1, except that 2-ethyl-1, 3-hexanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and the amount of ethylene oxide used was changed from 4 moles to 5 moles.

Synthesis example 14

Compound a-14 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that 1, 8-octanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and a mixture of 3 moles of ethylene oxide and 5 moles of propylene oxide was used instead of only 4 moles of ethylene oxide.

Synthesis example 15

Compound a-15 (see table 1) was obtained by the same operation as in synthesis example 1, except that 1, 9-nonanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and the amount of ethylene oxide used was changed from 4 moles to 5 moles.

Synthesis example 16

Compound a-16 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that the amount of ethylene oxide used was changed from 4 moles to 9 moles.

Synthesis example 17

Compound a-17 (see table 1) was obtained by performing the same operation as in synthesis example 4, except that the amount of ethylene oxide used was 4 moles and the amount of propylene oxide used was 5 moles.

Synthesis example 18

Compound a-18 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that the amount of ethylene oxide used was changed from 4 moles to 1 mole.

Synthesis example 19

Compound a-19 (see table 1) was obtained by the same procedure as in synthesis example 1, except that 1, 10-decanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and a mixture of 4 moles of ethylene oxide and 1 mole of propylene oxide was used instead of only 4 moles of ethylene oxide.

Synthesis example 20

Compound a-20 (see table 1) was obtained by the same operation as in synthesis example 1, except that 1, 12-dodecanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and the amount of ethylene oxide used was changed from 4 moles to 8 moles.

Synthesis example 21

Compound a-21 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that 1, 6-hexanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol.

Synthesis example 22

1 mol of 1, 10-decanediol and 0.3g (6 millimolar equivalents based on the starting material) of potassium hydroxide powder as a catalyst were added, and then the inside of the autoclave was sufficiently replaced with nitrogen. Then, the temperature of the reaction system was maintained at 130 to 150 ℃ while stirring them, 5 moles of ethylene oxide were introduced thereinto, and after aging at the same temperature for 1 hour, 4 moles of propylene oxide were introduced thereinto at 130 to 150 ℃ and aging at the same temperature for 1 hour was carried out to complete the addition polymerization. After completion of the reaction, the same operation as in Synthesis example 1 was carried out to obtain Compound A-22 (see Table 1).

Synthesis example 23

1 mol of 1, 2-tetradecanediol and 0.3g (6 millimolar equivalents based on the raw material) of potassium hydroxide powder as a catalyst were added, and then the inside of the autoclave was sufficiently replaced with nitrogen gas. Then, the temperature of the reaction system was maintained at 130 to 150 ℃ while stirring them, 2 moles of propylene oxide were introduced thereinto, and after aging at the same temperature for 1 hour, 4 moles of ethylene oxide were introduced thereinto at 130 to 150 ℃ and aging at the same temperature for 1 hour to complete the addition polymerization. After completion of the reaction, the same operation as in Synthesis example 1 was carried out to obtain Compound A-23 (see Table 1).

Synthesis example 24

Compound a-24 (see table 1) was obtained by the same operation as in synthesis example 1, except that 1, 2-tetradecanediol was used in place of 2-butyl-2-ethyl-1, 3-propanediol and the amount of ethylene oxide used was changed from 4 moles to 10 moles.

Synthesis example 25

Compound a-25 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that 1, 6-hexanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and 1 mol of propylene oxide was used instead of 4 mol of ethylene oxide.

Synthesis example 26

Compound a-1 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that a mixture of 6 moles of ethylene oxide and 6 moles of propylene oxide was used instead of only 4 moles of ethylene oxide.

Synthesis example 27

Compound a-2 (see table 1) was obtained by the same operation as in synthesis example 1, except that 2-ethyl-1, 3-hexanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol, and the amount of ethylene oxide used was changed from 4 moles to 14 moles.

Synthesis example 28

Compound a-3 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that 1, 4-butanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and the amount of ethylene oxide used was changed from 4 moles to 6 moles.

Synthesis example 29

Compound a-4 (see table 1) was obtained by performing the same operation as in synthesis example 1, except that 1, 2-hexadecanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol.

[ Table 1]

1-2. diol compound (B)

The compounds B-1 to B-4 obtained in the following synthetic examples 30 to 33 were used.

Synthesis example 30

160.3g (1 mol) of 2-butyl-2-ethyl-1, 3-propanediol was charged into an autoclave, 0.9g (18 mmol equivalent to the raw material) of potassium hydroxide powder as a catalyst was added, and the inside of the autoclave was sufficiently replaced with nitrogen. Then, the reaction temperature was maintained at 130 to 150 ℃ with stirring, 176g (4 mol) of ethylene oxide was introduced thereinto under pressure to conduct addition polymerization, and the reaction mixture was aged at the same temperature for 1 hour to complete the addition polymerization. Then, the catalyst was neutralized with phosphoric acid, and the by-product was separated by liquid chromatography to obtain a diol compound B-1 represented by the following formula (see table 2).

Synthesis example 31

A diol compound B-2 (see table 2) was obtained in the same manner as in synthesis example 30, except that 2, 4-diethyl-1, 3-pentanediol was used instead of 2-butyl-2-ethyl-1, 3-propanediol and the amount of ethylene oxide used was changed from 4 moles to 6 moles.

Synthesis example 32

The same operation as in synthesis example 30 was carried out except for using 2-methyl-1, 8-octanediol instead of 2-butyl-2-ethyl-1, 3-propanediol and using 8 moles of propylene oxide instead of 4 moles of ethylene oxide, to obtain diol compound B-3 (see table 2).

Synthesis example 33

Diol compound B-4 (see table 2) was obtained in the same manner as in synthesis example 30, except that the amount of ethylene oxide used was changed from 4 moles to 10 moles.

[ Table 2]

TABLE 2

2. Preparation of spreading agent for water surface floating type pesticide composition

Examples 1-1 to 1-31 and comparative examples 1-1 to 1-8

Using only the diol compound (a) obtained above or using the diol compounds (a) and (B), a spreading agent for a water-floating agricultural chemical composition was obtained (see table 3). The substances obtained in examples 1-1 to 1-31 were used as the water-surface floating type agricultural chemical composition spreaders C-1 to C-31, and the substances obtained in comparative examples 1-1 to 1-8 were used as the water-surface floating type agricultural chemical composition spreaders C-1 to C-8.

[ Table 3]

TABLE 3

3. Production and evaluation of Water surface Floating type pesticidal composition

The above-obtained spreading agent for a water-surface floating type agricultural chemical composition, the following agricultural chemical active ingredient and extender, and a small amount of water were used to produce a granular water-surface floating type agricultural chemical composition. Then, evaluation was performed assuming application to agricultural land having a water surface.

(pesticidal active ingredient)

Z-1: cafenstrole (cafenstrole)

Z-2: bensulfuron-methyl (Londax Power)

Z-3: weeding method (Daimuron)

Z-4: pretilachlor (Pretilachlor)

Z-5: diazinon (Diazinon)

Z-6: tricyclozole (Tricyclazole)

(extenders)

J-1: clay powder

J-2: calcium carbonate powder

J-3: potassium chloride powder

J-4: talcum powder

J-5: bentonite powder

J-6: diatomaceous earth powder

J-7: lactose powder

J-8: starch powder

J-9: white carbon powder

J-10: hollow glass particle

J-11: wood flour

J-12: cork powder

J-13: foaming white sand powder

J-14: microspheres

J-15: carboxymethyl cellulose powder

Example 2-1

After 20 parts of cafenstrole (Z-1) and 31 parts of clay (J-1) and 10 parts of bentonite (J-5) are uniformly mixed with 35 parts of hollow glass (J-10), the mixture is thoroughly mixed with 4 parts of a spreader (C-1) and a small amount of water. Next, the resulting kneaded mixture was subjected to extrusion molding using a basket pelletizer (KAR-75, manufactured by Kazuki Kaisha, chemical Co., Ltd.) equipped with a wire mesh having a pore diameter of 1.0 mm. Then, the molded product was dried at 50 ℃ in a thermostat, and the length of each particle was adjusted to 2 to 4mm, thereby producing cylindrical granular water-floating pesticide compositions (see table 4).

Both the water-surface floating type agricultural chemical composition immediately after production and 0.2g of the water-surface floating type agricultural chemical composition stored at 54 ℃ for 4 weeks were used as samples, and the samples were put into tap water (depth 2cm) stored in a container shown in fig. 1, and the spreading distance, spreading speed, spreading property, and disintegration state were evaluated by the following methods. The vessel 1 of fig. 1 is made of stainless steel having a longitudinal length of 20cm, a lateral length of 100cm and a depth of 4cm, and the inside thereof is divided into two parts by providing the partition 3 with a length corresponding to 90cm from one end side.

(1) Spreading distance

After the sample was put into the water surface at the x mark of fig. 2 and 3, the distance that the granular material floated on the water surface and moved within 2 minutes was measured (maximum 200cm in the case of folding back at the Δ mark of fig. 2 and 3). This operation was performed 5 times, and the average value of the distances was evaluated according to the following criteria.

(evaluation criteria)

Very good: over 170cm

O: 130cm or more and less than 170cm

X: below 130cm

(2) Speed of spreading

After the sample was put into the place marked by x in fig. 2 and 3, the time required for the granular material floating on the water surface to spread until marked by Δ was measured. The measurement was performed 5 times, and the development rate was calculated from the average value thereof according to the following calculation formula and evaluated according to the following criteria.

The spreading speed (cm/s) is 100 (cm)/required time(s)

(evaluation criteria)

Very good: 6 cm/sec or more

O: 4 cm/sec or more and less than 6 cm/sec

X: less than 4 cm/sec

(3) Spreading property

After the sample was put into the x mark of fig. 2 and 3, the appearance at the time of disintegration was visually observed and evaluated according to the following criteria.

(evaluation criteria)

Very excellent: spread with irregular movement and rotate sharply when the granules disintegrate

Very good: spread with irregular movement and rotate when the granules are disintegrated

O: spread with irregular movement and not rotate when disintegrating

X: spread in a straight line without rotating during disintegration

(4) Disintegrating state

After the sample was put into the x mark of fig. 2 and 3, the appearance of the powder disintegrated and dispersed in water was visually observed from above, and evaluated according to the following criteria.

(evaluation criteria)

O: no powder aggregation and uniform dispersion on water surface

And (delta): some of the visible powder aggregates or some of the visible powder is unevenly distributed

X: most of the powder is visibly aggregated or the powder is visibly unevenly distributed

Examples 2-2 to 2-31 and comparative examples 2-1 to 2-16

Using the raw materials shown in tables 4 to 8, a cylindrical granular water-surface floating type agricultural chemical composition was produced by extrusion molding in the same manner as in example 2-1. Thereafter, various evaluations were performed. The results are also shown in tables 4 to 8.

[ Table 4]

TABLE 4

[ Table 5]

TABLE 5

[ Table 6]

TABLE 6

[ Table 7]

TABLE 7

[ Table 8]

TABLE 8

In tables 4 to 6, examples 2-1 to 2-31 are examples of the agricultural chemical composition containing the spreading agent for a water-surface floating type agricultural chemical composition containing the diol compound (a) of the present invention, and are good in all of the spreading distance, spreading speed, spreading property and disintegration state. Wherein, in particular, in examples 2-1 to 2-13, R in the above formula (1) is used¹As an example of the diol compound (A) of the present invention, a compound which is an alkylene group having 8 or 9 carbon atoms and s is an integer of 2 to 8 is mentioned, and the above properties are at a higher level.

On the other hand, comparative examples 2-1 to 2-8 in tables 7 and 8 are examples of the agricultural chemical composition containing the spreading agent for a water-surface floating type agricultural chemical composition not containing the diol compound (a) of the present invention, and sufficient performance was not obtained.

Industrial applicability

The above-mentioned spreading agent for a water-surface-floating agricultural chemical composition of the present invention is used in combination with an agricultural chemical active material, an extender and the like to form a water-surface-floating agricultural chemical composition, and is suitable for forming granules, for example. Further, if the granules are sprayed on agricultural land having a water surface, the active ingredients of agricultural chemicals can be spread sufficiently. Therefore, the water-surface floating type pesticidal composition of the present invention is useful for application to agricultural land having a water surface.