JP6739129B1 - Spreading agent for waterborne floating pesticide composition and pesticide composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-floating pesticide composition which gives excellent spreadability when a granular pesticide composition prepared in combination with an agrochemical active ingredient is applied to the water surface and gives a water-floating pesticide composition which disintegrates over the entire water surface. Provide a product extender. SOLUTION: The spreader for waterborne floating pesticide composition of the present invention is HO-R1-O-G1-H (wherein R1 is an alkylene group having 6 to 14 carbon atoms, and G1 is -). (R5O) is a divalent group represented by s-, R5 is an alkylene group having 2 or 3 carbon atoms, s is an integer of 1 to 10, and when s is 2 or more, -( R5 in R5O)s- may all be the same or different.). [Selection diagram] None

Description

The present invention provides a granular pesticide composition that is contained together with a pesticide active ingredient (pesticide active ingredient) and is applied to the water surface of farmland, and is for a waterborne floating pesticide composition that sufficiently spreads the pesticide active ingredient on the water surface. Regarding extender.

For example, in order to obtain a sufficient effect of the pesticide sprinkled on the paddy field, that is, to disperse the pesticide sprinkled on the entire paddy field without localizing the pesticide, the pesticide active ingredient is used in combination with a spreading agent. The agricultural chemicals (agrochemical composition) of are widely used. The spreading agent is required to have a long spreading distance and a high spreading speed after contact with water.

Patent Document 1 discloses a water-floating particle nucleus containing an active ingredient of an agricultural chemical, one or more selected from calcined vermiculite, foamed perlite, foamed shirasu and cork, acetylene alcohol and acetylene diol, and alkylene oxides thereof. Water-floating pesticide solid agents containing one or more water surface-extending agents selected from the surfactants added to the water-soluble paper, and the active ingredients are dispersed in water. Alternatively, a soluble pesticide formulation for paddy field is disclosed.
In Patent Document 2, (RCOO) _m X(OH) _n (R: an aliphatic hydrocarbon group having 6 to 9 carbon atoms, X: a monovalent to tetravalent aliphatic hydroxy compound having 2 to 8 carbon atoms, and A residue excluding a hydroxyl group, m is an integer of 1 to 3, n is an integer of 0 or 1 to 3 and is an integer satisfying 1≦m+n≦4) and its phosphoric acid ester salt or sulfuric acid ester salt. Disclosed is a spreader for waterborne floating agrochemical compositions, which comprises at least one or two or more of the following:
Patent Document 3 discloses an alkanediol having 6 to 14 carbon atoms and HO-A ¹ -O-R-O-A ² -OH (R: a residue obtained by removing all hydroxyl groups from an alkanediol having 6 to 14 carbon atoms). , A ¹ , A ² : a residue obtained by removing all hydroxyl groups from a (poly)alkylene glycol having a (poly)oxyalkylene group composed of 1 to 7 oxyalkylene units having 2 to 4 carbon atoms in total). Disclosed is a spreader for waterborne floating agrochemical compositions, which comprises one or more selected from the alkanediol derivatives shown.
Patent Document 4, a pesticidal active ^{_{ingredient, HO- (A 1 -O) m}} -X 1 - (O-A 2) n -OH (X 1 is a divalent saturated hydrocarbon group having 6 to 14 carbon atoms And A ¹ and A ² each represent an alkylene group having 2 to 4 carbon atoms, m and n each represent an integer, and the sum of m and n is any integer of 1 to 7, When m is an integer of 2 or more, each A ¹ is the same or different, and when n is an integer of 2 or more, each A ² is the same or different. Disclosed is a water-floating pesticide granular composition containing phosphoric acid or a salt thereof and a flotation aid and a bulking agent.
Further, in Patent Document 5, R ¹ COO-(AO) _n -R ² (R ¹ : a linear alkyl group having 6 to 9 carbon atoms or a branched alkyl group having 6 to 9 carbon atoms, AO: carbon number 2 oxyalkylene group, n: an integer of 3 to 4, R ² : an ester compound represented by a linear alkyl group having 1 to ² carbon atoms). Spreading agents are disclosed.

JP-A-6-336403 JP, 2003-238307, A JP, 2007-39344, A JP, 2009-114102, A JP, 2008-100261, A

An object of the present invention is to include a pesticidal active ingredient together with the pesticidal active ingredient, for example, to preferably give a granular pesticidal composition, and to apply the pesticidal active ingredient to the water surface of an agricultural land to sufficiently spread the pesticide active ingredient on the water surface. The purpose of the present invention is to provide a spreading agent for a water surface floating type agrochemical composition as an agent. Another object of the present invention is to provide a water-floating pesticide composition which is applied to the water surface of farmland and has excellent spreadability of the pesticide active ingredient on the water surface after application.

As a result of diligent research, the present inventor found that the pesticidal active ingredient was sufficiently spread when the granular material prepared by using the pesticidal active ingredient in combination with the specific diol compound was sprinkled on the water surface.
The present invention is shown below.

The spreader for waterborne floating agrochemical compositions of the present invention is characterized by containing a compound represented by the following general formula (1).
^{HO-R 1 -O-G 1} -H (1)
(In the formula, R ¹ is an alkylene group having 6 to 14 carbon atoms, G ¹ is a divalent group represented by —(R ⁵ O) _s —, and R ⁵ has 2 carbon atoms. Or 3 is an alkylene group, s is an integer of 1 to 10, and when s is 2 or more, all R ⁵ _{s in} —(R ⁵ O) _s — may be the same or different. )
The water-floating pesticide composition spreading agent of the present invention may further contain a compound represented by the following general formula (2).
^{H-G 2 -O-R 2} -O-G 3 -H (2)
(In the formula, R ² is an alkylene group having 6 to 14 carbon atoms, G ² is a divalent group represented by —(OR ⁷ ) _t —, and R ⁷ has 2 or 3 carbon atoms. It is an alkylene group, t is an integer of 1 to 10, and when t is 2 or more, R ^{7 s} in -(OR ⁷ ) _t- may be the same or different, and G ³ is -. (R ⁹ O) is a divalent group represented by _u −, R ⁹ is an alkylene group having 2 or 3 carbon atoms, u is an integer of 1 to 10, and when u is 2 or more, _{^{- (R 9 O) u -}} R 9 in all be the same or may be different).

The water-floating pesticide composition of the present invention is characterized by containing a pesticide active ingredient and the above-mentioned water-floating pesticide composition spreader of the present invention.
The water-floating pesticide composition of the present invention may further contain a filler.

According to the present invention, when a granulated product (water-floating pesticide composition) prepared by using a spreading agent for a water-floating pesticide composition in combination with a pesticide active ingredient (water-floating pesticide composition) is spread on the water surface, the pesticide active ingredient is sufficiently spread. The effect of spreading is obtained. Therefore, the waterborne floating pesticide composition of the present invention is useful for application to agricultural land having a water surface. Further, since the spreader for waterborne floating agrochemical compositions of the present invention is excellent in the granulation property of the agrochemical active ingredient, the granular waterborne floating agrochemical composition can be easily applied to the water surface.

It is a schematic diagram of the container used for spreadability evaluation of the agricultural chemical composition in [Example]. It is a schematic diagram explaining spreadability evaluation of the agrochemical composition in [Example]. It is a schematic diagram explaining the mode that the pesticide composition was thrown into the water surface in the spreadability evaluation of the pesticide composition in [Example].

The spreader for waterborne floating agrochemical compositions of the present invention contains a compound represented by the following general formula (1) (hereinafter referred to as "diol compound (A)").
^{HO-R 1 -O-G 1} -H (1)
(In the formula, R ¹ is an alkylene group having 6 to 14 carbon atoms, G ¹ is a divalent group represented by —(R ⁵ O) _s —, and R ⁵ has 2 carbon atoms. Or 3 is an alkylene group, s is an integer of 1 to 10, and when s is 2 or more, all R ⁵ _{s in} —(R ⁵ O) _s — may be the same or different. )

In the general formula (1), the structure of the alkylene group R ¹ is not particularly limited and may be linear or branched. The alkylene group for R ¹ has 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms, and more preferably 8 to 9 carbon atoms. From the viewpoint of water surface spreadability, the alkylene group R ¹ is preferably a branched alkylene group having 8 to 12 carbon atoms. Specific examples of preferable R ¹ are shown below.

Further, in the general formula (1), the alkylene group R ⁵ constituting G ¹ is an alkylene group having 2 or 3 carbon atoms, that is, an ethylene group or a linear or branched propylene group. Accordingly, ^{G 1} comprises an oxyethylene group _{(-C 2} H 4 O-) or an oxypropylene group _{(-C 3} H 6 O-).
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. If s is 2 or ^{more, - (R 5 O) S} - also all R ⁵ are the same in, may be different, if it contains both oxyethylene groups and oxypropylene groups, these groups It has a structure in which it is connected regularly or irregularly.

The diol compound (A) contained in the spreading agent for a water-borne floating agrochemical composition of the present invention may be only one type, or may be two or more types.

The method for producing the diol compound (A) is not particularly limited. A preferred production method comprises a step of reacting an alkanediol having 6 to 14 carbon atoms with at least one selected from ethylene oxide and propylene oxide in the presence of a catalyst (hereinafter, referred to as "reaction step"). Is. Hereinafter, this manufacturing method will be described.

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

A catalyst is used in the reaction step. The catalyst is not particularly limited, but it is preferably a basic compound because the desired product can be efficiently obtained. The basic compound may be either an inorganic compound or an organic compound, and examples of the inorganic compound include potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate and lithium carbonate. Examples of the organic compound include CH ₃ ONa, C ₂ H ₅ ONa, CH ₃ OLi, C ₂ H ₅ OLi, CH ₃ OK, C ₂ H ₅ OK and the like. The amount of the catalyst used is preferably 0.1 to 10 mmolequivalent based on 1 mol of the alkanediol.

The reaction step is carried out in a pressure reactor such as an autoclave while the temperature of the reaction system is preferably 100°C to 170°C, more preferably 130°C to 150°C while stirring the raw materials. Ethylene oxide or propylene oxide can be added while changing the order, the ratio, etc. in order to obtain a diol compound having a desired structure.

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

The spreader for waterborne floating agrochemical compositions of the present invention further comprises a compound represented by the following general formula (2) (hereinafter referred to as “diol compound (B)”) in order to improve spreadability. Can be included.
^{H-G 2 -O-R 2} -O-G 3 -H (2)
(In the formula, R ² is an alkylene group having 6 to 14 carbon atoms, G ² is a divalent group represented by —(OR ⁷ ) _t —, and R ⁷ has 2 or 3 carbon atoms. It is an alkylene group, t is an integer of 1 to 10, and when t is 2 or more, R ^{7 s} in -(OR ⁷ ) _t- may be the same or different, and G ³ is -. (R ⁹ O) is a divalent group represented by _u −, R ⁹ is an alkylene group having 2 or 3 carbon atoms, u is an integer of 1 to 10, and when u is 2 or more, _{^{- (R 9 O) u -}} R 9 in all be the same or may be different).

In the general formula (2), the structure of the alkylene group R ² is not particularly limited and may be linear or branched. The alkylene group in R ² has 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms. From the viewpoint of water surface spreadability, the alkylene group R ² is preferably a branched alkylene group having 8 to 12 carbon atoms. Specific examples of preferable R ² are shown below.

Further, in the general formula (2), the alkylene group R ⁷ constituting G ² is an alkylene group having 2 or 3 carbon atoms, that is, an ethylene group or a linear or branched propylene group. Thus, ^{G 2} is an oxyethylene group containing _(-OC 2 _{H 4} - -) or oxypropylene group _(-OC 3 _{H 6).}
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, all R ^{7 s} in -(OR ⁷ ) _t- may be the same or different, but when both oxyethylene groups and oxypropylene groups are contained, these groups have a regular structure. It has a structure in which it is connected in a continuous or irregular manner.

Further, in the general formula (2), the alkylene group R ⁹ constituting G ³ is an alkylene group having 2 or 3 carbon atoms, that is, an ethylene group or a linear or branched propylene group. Thus, ^{G 3} includes an oxyethylene group _{(-C 2} H 4 O-) or an oxypropylene group _{(-C 3} H 6 O-).
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. If u is 2 or more, - (R 9 ^O) u _- even R ⁹ are all the same in, may be different, if it contains both oxyethylene groups and oxypropylene groups, these groups It has a structure in which it is connected regularly or irregularly.

The method for producing the diol compound (B) is not particularly limited. A preferred production method is a production method including a step of reacting an alkanediol having 6 to 14 carbon atoms with at least one selected from ethylene oxide and propylene oxide in the presence of a catalyst composed of a basic compound. In this case, the amount of the catalyst used is preferably 10 to 100 millimoles, and more preferably 15 to 50 millimoles, based on 1 mol of the alkanediol.

When the spreading agent for a floating agrochemical composition of the present invention contains the diol compound (B), the content ratio of the diol compound (A) and the diol compound (B) is 100% by mass in total. In this case, it 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%, respectively. It is% by mass.

In addition, the spreader for waterborne floating agrochemical compositions of the present invention may further contain a binder, a disintegration promoter, a dispersant, an emulsifier, a liquid medium (water, glycol, paraffin oil, etc.), a stabilizer, if necessary. Other ingredients such as

The water-floating pesticide composition spreader of the present invention is applied to the water surface of farmland, and is suitable as a raw material for producing a granular water-floating pesticide composition having excellent spreadability of the pesticide active ingredient on the water surface after application. is there.

The waterborne floating agrochemical composition of the present invention is characterized by containing an agrochemical active ingredient and the above-mentioned spreader of the present invention.
The agrochemical active ingredient is not particularly limited as long as its activity is not impaired by coexistence with water. Examples include herbicides, insecticides, acaricides, nematicides, antiviral agents, plant growth regulators, fungicides, attractants, repellents and the like. These pesticidal active ingredients may be either water-soluble or water-insoluble. The pesticidal active ingredient contained in the waterborne floating pesticide composition of the present invention may be only one kind or two or more kinds.
The content ratio of the agrochemical active ingredient and the spreader is not particularly limited.

The waterborne floating pesticide composition of the present invention further contains other components such as a filler, a binder, a disintegration accelerator, a dispersant, an emulsifier, a liquid medium (water, glycol, paraffin oil, etc.), a stabilizer and the like. be able to.

The waterborne floating pesticide composition of the present invention preferably contains a filler as another component. As a filler, clay, silica stone, 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, foaming Powders or particles such as sex shirasu, microspheres and carboxymethyl cellulose can be used.

When the waterborne floating agrochemical composition of the present invention contains a filler, the agrochemical active ingredient, the spreader of the present invention (the total amount of the diol compound (A), or the diol compound (A) and the diol compound ( The total amount of B)) and the content ratio of the extender are preferably 0.1 to 80% by mass, 0.1 to 10% by mass and 10 to 97% by mass, respectively, when the total of these is 100% by mass. %, more preferably 0.2 to 70% by mass, 0.5 to 8% by mass and 20 to 95% by mass.

The water-floating pesticide composition of the present invention may be a mixture having no shape in which the respective components are mixed in the same state (hereinafter, referred to as “first pesticide composition”). It may be a granular molded product (granulated product) obtained by using the pesticide composition. In the case of the granulated product, the liquid medium may or may not be contained.
When the waterborne floating pesticide composition of the present invention is applied to the water surface of an agricultural land, it is preferably a granulated product.

The water-floating pesticide composition of the present invention can be sprayed by a method such as hand spraying, mechanical spraying, and transfer spraying as in the case of ordinary pesticide granules, but so-called frame spraying sprayed from ridges, banks, etc. It can also be packaged in water-soluble paper and thrown from ridges or banks. The water-soluble paper used for throwing application is a film or sheet having solubility or dispersibility in water, and is formed from, for example, polyvinyl alcohol or a derivative thereof, pullulan, sodium salt of carboxymethyl cellulose, cellulose, polyethylene oxide or a derivative thereof. Examples thereof include a film or sheet, and among them, a film or sheet formed from polyvinyl alcohol or a derivative thereof is preferable.

When producing the above-mentioned granulated product, the first pesticide composition can be processed using, for example, an extrusion molding machine, a screw molding machine, a roll molding machine, a blade molding machine, or the like. Since the above-mentioned spreader of the present invention is excellent in the formability and shape stability of the granulated product, the granular waterborne floating pesticide composition obtained is easy to handle.

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

1. Raw material of spreader for waterborne floating pesticide composition 1-1. Diol compound (A)
The compounds A-1 to A-25 and a-1 to a-4 obtained in the following Synthesis Examples 1 to 29 were used.

Synthesis example 1
After charging 160.3 g (1 mol) of 2-butyl-2-ethyl-1,3-propanediol in an autoclave and adding 0.3 g of potassium hydroxide powder (6 mmol equivalent to the raw material) as a catalyst, the autoclave The inside was sufficiently replaced with nitrogen gas. Next, while stirring these, while maintaining the temperature of the reaction system at 130°C to 150°C, 176 g (4 mol) of ethylene oxide was injected under pressure to start the addition polymerization reaction. Then, it was aged at the same temperature for 1 hour to complete the addition polymerization reaction. Then, the catalyst of the reaction system was neutralized with phosphoric acid, and then the reaction product was separated and collected by liquid chromatography. When the obtained reaction product was subjected to LC-MS analysis, it was found to be a compound represented by the following formula. Hereinafter, this compound is shown as A-1 (see Table 1).
ESI-MS: m/z=337 (M+H) ⁺

Synthesis example 2
Compound A-2 was obtained by performing the same operation as in Synthesis Example 1 except that 4 mol of propylene oxide was used instead of 4 mol of ethylene oxide (see Table 1).

Synthesis example 3
Compound A-3 was obtained in the same manner as in Synthesis Example 1 except that a mixture of 2 mol of ethylene oxide and 2 mol of propylene oxide was used instead of only 4 mol of ethylene oxide (see Table 1).

Synthesis example 4
After charging 160.3 g (1 mol) of 2-butyl-2-ethyl-1,3-propanediol in an autoclave and adding 0.3 g of potassium hydroxide powder (6 mmol equivalent to the raw material) as a catalyst, the autoclave The inside was sufficiently replaced with nitrogen gas. Then, while stirring these, while maintaining the temperature of the reaction system at 130°C to 150°C, 2 mol of ethylene oxide was press-fitted and aged at the same temperature for 1 hour, and then at 130°C to 150°C. 2 mol of oxide was injected under pressure and aged at the same temperature for 1 hour to complete the addition polymerization reaction. After the completion of the reaction, the same operation as in Synthesis Example 1 was performed to obtain compound A-4 (see Table 1).

Synthesis example 5
Compound A-5 was obtained in the same manner as in Synthesis Example 4 except that the order of press-fitting ethylene oxide (2 mol) and propylene oxide (2 mol) was reversed (see Table 1).

Synthesis example 6
Compound A-6 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide used was changed from 4 mol to 8 mol (see Table 1).

Synthesis example 7
2,4-diethyl-1,3-pentanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol, and the amount of ethylene oxide used was changed from 4 mol to 6 mol. The same operation as in Synthesis Example 1 was performed to obtain compound A-7 (see Table 1).

Synthesis example 8
After adding 1 mol of 2,4-diethyl-1,3-pentanediol and 0.3 g of potassium hydroxide powder (6 mmol equivalent to the raw material) as a catalyst, the inside of the autoclave was sufficiently replaced with nitrogen gas. .. Next, while stirring these, while maintaining the temperature of the reaction system at 130°C to 150°C, 1 mol of propylene oxide was press-fitted and aged at the same temperature for 1 hour, and then ethylene was added at 130°C to 150°C. 1 mol of oxide was injected under pressure and aged at the same temperature for 1 hour to complete the addition polymerization reaction. After the completion of the reaction, the same operation as in Synthesis Example 1 was performed to obtain compound A-8 (see Table 1).

Synthesis Example 9
Synthesis Example 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 mol to 5 mol. The same operation as in 1 was performed to obtain compound A-9 (see Table 1).

Synthesis example 10
2-Methyl-1,8-octanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol, and 7 mol of propylene oxide was used in place of 4 mol of ethylene oxide. Then, the same operation as in Synthesis Example 1 was performed to obtain a compound A-10 (see Table 1).

Synthesis Example 11
Compound A-11 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide used was changed from 4 mol to 6 mol (see Table 1).

Synthesis Example 12
Compound A-12 was obtained in the same manner as in Synthesis Example 1 except that 6 mol of propylene oxide was used instead of 4 mol of ethylene oxide (see Table 1).

Synthesis Example 13
Synthesis example except that 2-ethyl-1,3-hexanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol and the amount of ethylene oxide used was changed from 4 mol to 5 mol The same operation as in 1 was performed to obtain compound A-13 (see Table 1).

Synthesis Example 14
1,8-Octanediol was used instead of 2-butyl-2-ethyl-1,3-propanediol, and a mixture of 3 mol of ethylene oxide and 5 mol of propylene oxide was used instead of only 4 mol of ethylene oxide. Other than the same operations as in Synthesis Example 1 were performed to obtain compound A-14 (see Table 1).

Synthesis Example 15
Similar to Synthesis Example 1 except that 1,9-nonanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol and the amount of ethylene oxide used was changed from 4 mol to 5 mol. Operation was performed to obtain compound A-15 (see Table 1).

Synthesis Example 16
Compound A-16 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide used was changed from 4 mol to 9 mol (see Table 1).

Synthesis Example 17
Compound A-17 was obtained in the same manner as in Synthesis Example 4 except that the amount of ethylene oxide used was 4 mol and the amount of propylene oxide used was 5 mol (see Table 1).

Synthesis Example 18
Compound A-18 was obtained in the same manner as in Synthesis Example 1 except that the amount of ethylene oxide used was changed from 4 mol to 1 mol (see Table 1).

Synthesis Example 19
1,10-decanediol was used instead of 2-butyl-2-ethyl-1,3-propanediol, and a mixture of 4 mol of ethylene oxide and 1 mol of propylene oxide was used instead of only 4 mol of ethylene oxide. Other than the same operations as in Synthesis Example 1 were carried out to obtain compound A-19 (see Table 1).

Synthesis example 20
Similar to Synthesis Example 1 except that 1,12-dodecanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol and the amount of ethylene oxide used was changed from 4 mol to 8 mol. Operation was performed to obtain compound A-20 (see Table 1).

Synthesis Example 21
Compound A-21 was obtained in the same manner as in Synthesis Example 1 except that 1,6-hexanediol was used instead of 2-butyl-2-ethyl-1,3-propanediol (Table 1). reference).

Synthesis Example 22
After adding 1 mol of 1,10-decanediol and 0.3 g of potassium hydroxide powder (6 mmol equivalent to the raw material) as a catalyst, the inside of the autoclave was sufficiently replaced with nitrogen gas. Then, while stirring these, while maintaining the temperature of the reaction system at 130°C to 150°C, 5 mol of ethylene oxide was press-fitted and aged at the same temperature for 1 hour, and then at 130°C to 150°C. 4 mol of oxide was injected under pressure and aged at the same temperature for 1 hour to complete the addition polymerization reaction. After the completion of the reaction, the same operation as in Synthesis Example 1 was performed to obtain compound A-22 (see Table 1).

Synthesis Example 23
After adding 1 mol of 1,2-tetradecanediol and 0.3 g of potassium hydroxide powder (6 mmol equivalent to the raw material) as a catalyst, the inside of the autoclave was sufficiently replaced with nitrogen gas. Then, while stirring these, while maintaining the temperature of the reaction system at 130°C to 150°C, 2 mol of propylene oxide was press-fitted and aged at the same temperature for 1 hour, and then ethylene was added at 130°C to 150°C. 4 mol of oxide was injected under pressure and aged at the same temperature for 1 hour to complete the addition polymerization reaction. After the completion of the reaction, the same operation as in Synthesis Example 1 was performed to obtain compound A-23 (see Table 1).

Synthesis Example 24
The same as 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 mol to 10 mol. Operation was performed to obtain compound A-24 (see Table 1).

Synthesis Example 25
Synthesis Example 1 except that 1,6-hexanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol and 1 mol of propylene oxide was used in place of 4 mol of ethylene oxide. Compound A-25 was obtained by performing the same operation as above (see Table 1).

Synthesis Example 26
Compound a-1 was obtained in the same manner as in Synthesis Example 1 except that a mixture of 6 mol of ethylene oxide and 6 mol of propylene oxide was used instead of only 4 mol of ethylene oxide (see Table 1).

Synthesis Example 27
Synthesis example 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 mol to 14 mol The same operation as in 1 was performed to obtain compound a-2 (see Table 1).

Synthesis Example 28
Similar to Synthesis Example 1 except that 1,4-butanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol and the amount of ethylene oxide used was changed from 4 mol to 6 mol. Operation was performed to obtain compound a-3 (see Table 1).

Synthesis Example 29
Compound a-4 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 reference).

1-2. Diol compound (B)
The compounds B-1 to B-4 obtained in the following Synthesis Examples 30 to 33 were used.

Synthesis Example 30
After charging 160.3 g (1 mol) of 2-butyl-2-ethyl-1,3-propanediol in an autoclave and adding 0.9 g of potassium hydroxide powder (18 mmol equivalent to the raw material) as a catalyst, the autoclave The inside was sufficiently replaced with nitrogen gas. Then, while maintaining the reaction temperature at 130° C. to 150° C. under stirring, 176 g (4 mol) of ethylene oxide was injected under pressure to cause an addition polymerization reaction, followed by aging at the same temperature for 1 hour to complete the addition polymerization reaction. Then, the catalyst was neutralized with phosphoric acid, and then by-products were separated by liquid chromatography to obtain a diol compound B-1 represented by the following formula (see Table 2).

Synthesis Example 31
2,4-diethyl-1,3-pentanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol, and the amount of ethylene oxide used was changed from 4 mol to 6 mol. The same operation as in Synthesis Example 30 was performed to obtain a diol compound B-2 (see Table 2).

Synthesis Example 32
2-Methyl-1,8-octanediol was used in place of 2-butyl-2-ethyl-1,3-propanediol, and 8 mol of propylene oxide was used in place of 4 mol of ethylene oxide. The same operation as in Example 30 was carried out to obtain a diol compound B-3 (see Table 2).

Synthesis Example 33
A diol compound B-4 was obtained in the same manner as in Synthesis Example 30 except that the amount of ethylene oxide used was changed from 4 mol to 10 mol (see Table 2).

2. Preparation of Spreading Agent for Water Floating Agrochemical Composition Examples 1-1 to 1-31 and Comparative Examples 1-1 to 1-8
A spreading agent for a waterborne floating pesticide composition was obtained using only the diol compound (A) obtained above or the diol compounds (A) and (B) (see Table 3). The ones obtained in Examples 1-1 to 1-31 were used as water-floating pesticide composition extenders C-1 to C-31, and those obtained in Comparative Examples 1-1 to 1-8. , And the spreading agents for waterborne floating pesticide compositions c-1 to c-8.

3. Production and Evaluation of Water-Floating Agrochemical Composition A water-floating agricultural chemical composition spreading agent obtained above, the following agrochemical active ingredient and extender, and a small amount of water are used to form a granular water-floating agricultural chemical composition. An agrochemical composition was produced. Then, the evaluation was performed assuming application to farmland having water surface.
(Pesticide active ingredient)
Z-1: Kafenstrol Z-2: Bensulfuron methyl Z-3: Daimlon Z-4: Pretilachlor Z-5: Diazinon Z-6: Tricyclazole (extending agent)
J-1: Clay powder J-2: Calcium carbonate powder J-3: Potassium chloride powder J-4: Talc 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 particles J-11: Wood powder J-12: Cork powder J-13: Effervescent Shirasu powder J-14: Microsphere J-15: Carboxymethylcellulose powder

Example 2-1
After uniformly mixing 20 parts of cafenstrol (Z-1), 31 parts of clay (J-1), 10 parts of bentonite (J-5), and 35 parts of hollow glass (J-10) The mixture, 4 parts of the extender (C-1) and a small amount of water were sufficiently kneaded. Then, the obtained kneaded product was subjected to extrusion molding using a basket type granulator ("KAR-75" manufactured by Tsutsui Rikagaku Kikai Co., Ltd.) equipped with a screen having an opening of 1.0 mm. Then, the molded product was dried at 50° C. in a thermostat and sized to a length of 2 to 4 mm to produce a cylindrical granular water-surface floating pesticide composition (see Table 4).

0.2 g of both the water-borne floating pesticide composition immediately after production and the water-borne floating pesticide composition stored at 54° C. for 4 weeks was used as a sample, and tap water (depth: 2 cm) was stored in the container shown in FIG. ) And spread distance, spread speed, spreadability and collapse state were evaluated by the following methods. The container 1 of FIG. 1 is made of stainless steel having a length of 20 cm, a width of 100 cm, and a depth of 4 cm, and is provided with a partitioning portion 3 to divide the inside into a length corresponding to 90 cm from one end side.

(1) Spreading distance The distance that the granular material floated on the water surface and moved within 2 minutes after the sample was put in the X mark in FIGS. 2 and 3 (when folded back at the Δ mark in FIGS. 2 and 3, A maximum of 200 cm) was measured. This operation was performed 5 times, and the average of the distances was evaluated according to the following criteria.
(Evaluation criteria)
◎: 170 cm or more ○: 130 cm or more, less than 170 cm ×: less than 130 cm

(2) Spreading speed The time required for the granular material floating on the water surface to spread to the Δ mark was measured after the sample was put in the X marks in FIGS. 2 and 3. The measurement was performed 5 times, the spreading rate was calculated from the average value by the following calculation formula, and evaluated according to the following criteria.
Spreading speed (cm/sec)=100 (cm)/required time (sec)
(Evaluation criteria)
◎: 6 cm/sec or more ○: 4 cm/sec or more and less than 6 cm/sec ×: less than 4 cm/sec

(3) Spreadability After the sample was put in the mark X in FIGS. 2 and 3, the state of collapse was visually observed and evaluated according to the following criteria.
(Evaluation criteria)
◎ ◎: Spreading irregularly, rotating violently during grain collapse ◎: Spreading irregularly, rotating during grain collapse ○: Spreading irregularly, not rotating during collapse ×: Expanded linearly, did not rotate when collapsed

(4) Disintegration state After the sample was put into the mark X in FIGS. 2 and 3, the state of the powder disintegrated and dispersed in water was visually observed from above and evaluated according to the following criteria.
(Evaluation criteria)
◯: No agglomeration of powder, uniformly dispersed on the entire water surface Δ: Agglomeration of some powders was observed, or uneven distribution of powders was observed ×: Most powders Aggregation was observed, or uneven distribution of powder was noticeable

Examples 2-1 to 2-31 and Comparative Examples 2-1 to 2-16
Extrusion molding was performed in the same manner as in Example 2-1 using the raw materials shown in Tables 4 to 8 to produce a cylindrical granular water surface floating pesticide composition. After that, various evaluations were performed. The results are also shown in Tables 4 to 8.

In Tables 4 to 6, Examples 2-1 to 2-31 are examples of agrochemical compositions containing the spreading agent for waterborne floating agrochemical compositions containing the diol compound (A) according to the present invention, The spread distance, spread speed, spreadability and collapsed state were all good. Of these, particularly Examples 2-1 to 2-13, as the diol compound (A) according to the present invention, R ¹ in the above formula (1) is an alkylene group having 8 or 9 carbon atoms, and s is This is an example using a compound that is an integer of 2 to 8, and the above performance was at a higher level.
On the other hand, Comparative Examples 2-1 to 2-8 in Table 7 and Table 8 are examples of pesticide compositions containing the spreading agent for waterborne floating pesticide compositions that does not contain the diol compound (A) according to the present invention. Yes, sufficient performance was not obtained.

The spreading agent for waterborne floating agrochemical compositions of the present invention is preferably used in combination with an agrochemical active substance, a bulking agent and the like to suitably form, for example, a granulated product of a waterborne floating agrochemical composition. When this granulated product is sprinkled on an agricultural land having a water surface, the pesticide active ingredient can be sufficiently spread. Therefore, the waterborne floating pesticide composition of the present invention is useful for application to agricultural land having a water surface.

Claims (8)

A spreading agent for a waterborne floating agrochemical composition, which comprises a compound represented by the following general formula (1).
^{HO-R 1 -O-G 1} -H (1)
(In the formula, R ¹ is an alkylene group having 6 to 14 carbon atoms, G ¹ is a divalent group represented by —(R ⁵ O) _s —, and R ⁵ has 2 carbon atoms. Or 3 is an alkylene group, s is an integer of 1 to 10, and when s is 2 or more, all R ⁵ _{s in} —(R ⁵ O) _s — may be the same or different. ) In the compound of the general formula (1), R ¹ is an alkylene group having 8 to 12 carbon atoms, and the spreading agent for waterborne floating agrochemical compositions according to claim 1. In the compound of the general formula (1), R ¹ is an alkylene group having 8 or 9 carbon atoms, and s is an integer of 2 to 8. Spreading agent. Furthermore, the spreader for waterborne floating agrochemical compositions according to any one of claims 1 to 3, which further comprises a compound represented by the following general formula (2).
^{H-G 2 -O-R 2} -O-G 3 -H (2)
(In the formula, R ² is an alkylene group having 6 to 14 carbon atoms, G ² is a divalent group represented by —(OR ⁷ ) _t —, and R ⁷ has 2 or 3 carbon atoms. It is an alkylene group, t is an integer of 1 to 10, and when t is 2 or more, R ^{7 s} in -(OR ⁷ ) _t- may be the same or different, and G ³ is -. (R ⁹ O) is a divalent group represented by _u −, R ⁹ is an alkylene group having 2 or 3 carbon atoms, u is an integer of 1 to 10, and when u is 2 or more, _{^{- (R 9 O) u -}} R 9 in all be the same or may be different). The content ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2) is such that the total content of these compounds is 100% by mass. The compound represented by the formula (4) is 40 to 99% by mass, and the compound represented by the general formula (2) is 1 to 60% by mass, the spreading agent for a waterborne floating pesticide composition according to claim 4. .. A water-floating pesticide composition comprising an agrochemical active ingredient and the spreading agent for water-floating pesticide composition according to any one of claims 1 to 5. The waterborne floating pesticide composition according to claim 6, further comprising an extender. The content ratio of the pesticidal active ingredient, the water-floating pesticide spreader and the extender is 0.1 when the total content of these ingredients is 100% by mass. The water-floating pesticide composition according to claim 7, wherein the water-floating pesticide composition extender is 0.1 to 10 mass %, and the extender is 10 to 97 mass %. Stuff.

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