JP4514219B2 - Spreading agent for water-floating pesticide composition and water-floating pesticide composition - Google Patents

Description

  The present invention relates to a spreading agent for water-floating pesticide compositions and a water-floating pesticide composition. Water-floating pesticide compositions molded into various shapes are used as throw-in pesticide formulations that control pests and weeds that occur mainly in places where water is present, such as paddy fields, rush fields, and wetlands. . Such water-floating pesticide compositions are required to spread over a wide range in a short time without being affected by the growing plant leaves and stems when applied to the water surface due to their properties. Therefore, a spreading agent is used. The present invention relates to a spreader for such a water-floating pesticide composition and a water-floating pesticide composition using the same.

  Conventionally, as a spreading agent for a water surface floating type agricultural chemical composition, a surfactant having a high interfacial tension reducing ability such as an acetylene derivative (for example, see Patent Documents 1 to 3) and a sulfonic acid surfactant (for example, Patent Documents 4 to 4) 8), polyhydric alcohol fatty acid esters (for example, see Patent Document 9), alkylene oxide adducts of alkyl alcohols and derivatives thereof (for example, see Patent Document 10), and the like.

However, these conventional spreading agents for water-floating pesticide compositions, for example, in the case of an acetylene derivative, can give appropriate spreading properties to a water-floating pesticide composition prepared by using this, but are expensive. In the case of a sulfonic acid surfactant, there is a problem that the spreadability that can be imparted to the water-floating pesticide composition prepared using the surfactant is extremely insufficient. In the case of alkylene oxide adducts and derivatives thereof, there is a problem that the spreadability imparted when the surface-floating pesticide composition prepared using these is stored for a long period of time becomes insufficient.
JP-A-6-336403 JP-A-9-118602 JP 2000-95603 A JP-A-7-82102 Japanese Patent Laid-Open No. 7-23003 JP-A-10-81603 JP-A-10-182303 JP 2001-278701 A JP 2003-238307 A JP 2000-351701 A

  The problem to be solved by the present invention is that it can economically impart excellent extensibility to a water surface floating type agricultural chemical composition prepared using the same, and even when the prepared water surface floating type composition is stored for a long period of time. The present invention provides a spreader for water-floating pesticide compositions that can maintain excellent spreadability, and a water-floating pesticide composition having such properties.

  Therefore, as a result of studies to solve the above-mentioned problems, the present inventors have found that it is correctly and suitably used a specific diol compound as a spreading agent.

  That is, the present invention is a spreader for water-floating pesticide compositions characterized by comprising one or two or more selected from alkanediols having 6 to 10 carbon atoms and alkanediol derivatives represented by chemical formula 1 below. Concerning.

In chemical formula 1,
R: Residue obtained by removing all hydroxyl groups from an alkanediol having 6 to 10 carbon atoms A ¹ and A ² : (poly) oxy composed of a total of 1 to 7 oxyethylene units and / or oxypropylene units, respectively Residues obtained by removing all hydroxyl groups from (poly) alkylene glycol having an alkylene group

  Further, the present invention contains a total of 90% by mass or more of the above-mentioned spreading agent for floating surface agricultural chemical composition, agrochemical medicinal component, floating aid and extender, and the spreading for the floating surface agricultural chemical composition. 0.1 to 10% by weight of a spreading agent, 0.1 to 80% by weight of the agrochemical medicinal ingredient, 1 to 80% by weight of the floating aid and 1 to 80% by weight of the extender The present invention relates to a water surface floating type agricultural chemical composition.

  First, the spreader for water surface floating type agricultural chemical composition according to the present invention (hereinafter simply referred to as the spreader of the present invention) will be described. The spreading agent of the present invention comprises one or two or more selected from alkanediols having 6 to 10 carbon atoms and alkanediol derivatives represented by Chemical Formula 1.

  The alkanediol having 6 to 10 carbon atoms used as the spreading agent of the present invention is 1) a linear alkanediol having 6 to 10 carbon atoms such as hexanediol, heptanediol, octanediol, nonanediol, decanediol, etc. 2) C6-C10 branched alkanediols such as 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol Among them, branched alkanediols having 8 to 10 carbon atoms are preferable, and 2-butyl-2-ethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol are more preferable.

As the spreading agent of the present invention, it is preferable to use one or two or more selected from alkanediol derivatives represented by Chemical Formula 1. In the alkanediol derivative represented by Chemical Formula 1, R in Chemical Formula 1 is a residue obtained by removing all hydroxyl groups from an alkanediol having 6 to 10 carbon atoms, and the above-mentioned alkanediol having 6 to 10 carbon atoms has been described above. Is the same. A ¹ and A ^{2 in} Chemical Formula 1 are all hydroxyl groups from a (poly) alkylene glycol having a (poly) oxyalkylene group composed of a total of 1 to 7 oxyethylene units and / or oxypropylene units. Excluded residues. In A ¹ and A ² in Chemical Formula 1, 1) a residue obtained by removing all hydroxyl groups from an alkylene glycol having one oxyethylene unit or oxypropylene unit, and 2) a total of 2 to 7 oxyethylenes each. A residue obtained by removing all hydroxyl groups from a polyalkylene glycol having a polyoxyalkylene group composed of units and / or oxypropylene units is included. Among them, as A ¹ and A ^{2 in} Chemical Formula 1, all the hydroxyl groups were removed from the polyalkylene glycol having a polyoxyalkylene group composed of a total of 2 to 6 oxyethylene units and / or oxypropylene units. A residue is preferable, and a residue obtained by removing all hydroxyl groups from polyethylene glycol having a polyoxyethylene group composed of 3 to 5 oxyethylene units is more preferable. When the polyoxyalkylene group is composed of two or more different oxyalkylene units, the bonding mode may be random bonding, block bonding, or both of them.

  The alkanediol derivative represented by Chemical Formula 1 as described above can be synthesized by a known method. For example, it can be synthesized by a method in which ethylene oxide or propylene oxide is successively added to alkanediol in the presence of a basic catalyst such as sodium hydroxide or potassium hydroxide.

  Next, the surface-floating pesticide composition according to the present invention (hereinafter simply referred to as the composition of the present invention) will be described. The composition of the present invention comprises the spreader, the agrochemical medicinal component, the floating aid and the extender of the present invention described above, and these are a total of 90% by mass or more, preferably 100% by mass. 0.1 to 10% by weight, preferably 1 to 9% by weight, and 0.1 to 80% by weight, preferably 1 to 50% by weight of a pesticide, 1 to 80% by mass of the agent, preferably 10 to 50% by mass, and 1 to 80% by mass of the extender, preferably 5 to 60% by mass.

  As the agrochemical medicinal component used in the composition of the present invention, various known herbicides, insecticides, fungicides and the like can be applied. For example, herbicides include 1- (diethylcarbamoyl) -3- (2,4,6-trimethylphenylsulfonyl) -1,2,4-triazole (cafentrol), 1- (α, α-dimethylbenzyl)- 3- (p-tolyl) urea (Dimron), 2-chloro-2 ′, 6′-diethyl-N- (2-butoxymethyl) acetanilide (butachlor), 2-chloro-2 ′, 6′-diethyl-N -(2-propoxyethyl) acetanilide (pretilachlor), α- (2-naphthoxy) propionanilide (naproanilide), 2-methylthio-4,6-bis (ethylamino) -S-triazine (cimethrin), S-tertiary butyl -3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazoline-2-one Oxadiazone), S- (2-methyl-1-piperidyl-caribonylmethyl-O, O-di-n-propyldithiophosphate (piperophos), 3-isopropyl-2,1,3-benzo-thiadianone- (4) -2 , 2-dioxide (bentazone), 2-methylthio-4-ethylamino-6- (1,2-dimethylpropylamino) -s-triazine (dimetamethrin), 3- (4,6-dimethoxypyrimidin-2-yl) Examples include -1-[(2-methoxycarbanylbenzyl) sulfonyl] urea (bensulfuron methyl).

  Further, as insecticides, 1-naphthyl-N-methylcarbamate (NAC), metharyl-N-methylcarbamate (MTMC), 2-isopropylphenyl-N-methylcarbamate (MIPC), 2-secondary butylphenyl-N-methyl Carbamate (BPMC), 3,4-xylyl-N-methylcarbamate (MPMC), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl (dibutylaminothio) methylcarbamate (carbosulfan), O -N-butyl-O '-(2,2-) dimethyl-2,3-dihydrobenzofuran-7-yl) -N, N'-thio-dicarbamate (furathiocarb), (RS) α-cyano-3-phenoxy Benzyl = (RS) -2,2-1- (4-ethoxyphenyl) cyclopropanecarboxyl Rato (cycloprotorin), 2-tert-butyl-butimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one (buprofezin), 2- (4-ethoxyphenyl) -2-methyl Propyl-3-phenoxybenzyl ether (ethofenprox), O, O-dimethyl-O- (methyl-4-nitrophenyl) thiophosphate (MEP), (2-isopropyl-4-methylpyrimidyl-6) -diethylthiophosphate (Diazinone), S, S ′-[2- (dimethylamino) trimethylene] bis-benzenethiosulfonate (bensulfap) and the like.

  Furthermore, as the bactericidal agent, 5-methyl-1,2,4-triazolo (3,4-b) benzothiazole (tricyclazole), dimethyl 4,4- (o-phenylene) bis-3-thioallophanate (Topgin M), O, O-diisopropyl-S-benzylthiophosphate (IBP), 3-allyloxy-1,2-benzisothiazole-1,1-dioxide (propenazole), O-ethyl-S, S-diphenyldithiophosphate ( EDDP), diisopropyl-1,3-dithiolane-2-ylidene-malonate (isoprothiolane), 3-isopropoxy-2-methylbenzanilide (mepronil), (E, Z) -4,6-dimethyl-2- [1 -(O-Tolyl) -1-ethylidene-hydrazino] pyrimidine (ferimzone), 1- (4-c Robenjiru) -1-cyclopentyl-3-phenyl urea (pencycuron), and the like.

  As the floating aid used in the composition of the present invention, any of various known inorganic floating aids and organic floating aids can be applied. For example, examples of the inorganic floating aid include foamed shirasu, foamed pumice, foamed perlite, and hollow glass. Examples of organic floating aids include waxy substances derived from animals and plants, paraffin wax, cork, wood powder, foamed synthetic resin, synthetic resin powder such as polyethylene powder and polypropylene powder, and the like. Among these, as the floating aid, foamed shirasu, hollow glass, and foamed synthetic resin are preferable.

  As the extender used in the composition of the present invention, various known inorganic powders, low-molecular water-soluble compounds, synthetic resin powders, and organic powders can be applied. For example, examples of the inorganic powder include bentonite, talc, clay, diatomaceous earth, amorphous silicon dioxide, calcium carbonate, and magnesium carbonate. Examples of the low molecular weight water-soluble compound include sodium sulfate, ammonium sulfate, potassium chloride, urea and the like. Furthermore, examples of the synthetic resin powder include vinyl chloride, chlorinated polyethylene, and chlorinated polypropylene. Furthermore, examples of the organic powder include sugars such as glucose, fructose, sucrose, and lactose, carboxymethylcellulose and salts thereof, starch and derivatives thereof, microcrystalline cellulose, wood flour, rice bran, bran, and rice straw. Of these, inorganic powders and low-molecular water-soluble compounds are preferred as the bulking agent.

  The composition of the present invention as described above can be prepared by a known method. For example, 1) a method in which the spreader, the agrochemical medicinal component, the floating aid, the extender and water of the present invention are kneaded with a stirring mixer, then granulated using a granulator, and dried. 2) the present invention A kneading agent, a spreading aid, a bulking agent and water, and then granulating with a granulator, impregnating and adsorbing the agrochemical medicinal component to the granulated product, etc. Is mentioned. Here, as the stirring mixer, a nauta mixer, a ribbon blender, a rotary blender, a V-type mixer, etc. can be applied, and as a granulator, an extrusion granulator, a mixing granulator, a rolling granulator, a fluidizer A layer granulator or the like can be applied.

  The composition of the present invention can be sprayed by methods such as hand sowing spraying, mechanical spraying, and transfer spraying, as in the case of ordinary agricultural chemical granules, but it can also be used as a so-called frame spraying sprayed from a cocoon or shore. It can also be packaged in water-soluble paper and thrown from a ridge or shore. Water-soluble paper used for casting 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. In particular, a film or sheet formed from polyvinyl alcohol or a derivative thereof is preferable.

  The composition of the present invention includes a binder, a granulating property improver, a disintegrant, a dispersant, an emulsifier in addition to the spreader, the agrochemical medicinal component, the floating aid and the extender of the present invention as described above. Further, a solvent or the like can be used in combination.

  The present invention described above can economically impart excellent extensibility to a water-floating pesticide composition, and has such excellent spreadability even if the prepared water-floating pesticide composition is stored for a long period of time. There is an effect that it can be held.

  Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to the examples. In the following examples and the like, unless otherwise indicated, parts are parts by mass and% is% by mass.

Test category 1 (synthesis of spreading agent)
Examples 1 to 8 and Comparative Examples 1 to 3 {Synthesis of spreading agents (A-1) to (A-8) and (a-1) to (a-3)}
After charging 160.3 g (1 mol) of 2-butyl-2-ethyl-1,3-propanediol into an autoclave and adding 1 g of potassium hydroxide powder as a catalyst, the inside of the autoclave was sufficiently substituted with nitrogen. While maintaining the reaction temperature at 130 to 150 ° C. with stirring, 264 g (6 mol) of ethylene oxide was injected to carry out an addition polymerization reaction, followed by aging at the same temperature for 1 hour to complete the addition polymerization reaction. After neutralizing the catalyst with phosphoric acid, by-products are separated by molecular distillation, and R in Chemical Formula 1 is a residue obtained by removing all hydroxyl groups from 2-butyl-2-ethyl-1,3-propanediol. And from the alkanediol derivative represented by Chemical Formula 1 when A ¹ and A ² are residues obtained by removing all hydroxyl groups from a polyethylene glycol having a polyoxyethylene group composed of a total of three oxyethylene units. Thus, the spreader (A-1) of Example 1 was obtained. Similarly, the spreading agents (A-2) to (A-8) of Examples 2 to 8 and the spreading agents (a-1) to (a-3) of Comparative Examples 1 to 3 were synthesized. The contents of each spreading agent synthesized above are summarized in Table 1.

In Table 1,
* 1: Indicated by alkanediol used as raw material to form R EO: oxyethylene unit PO: oxypropylene unit

Test Category 2 (Preparation of composition)
Examples 9 to 41 and Comparative Examples 4 to 12
2 parts of the spreading agent (A-1) synthesized in Test Category 1, 20 parts of Caventrol as an agrochemical medicinal ingredient, 33 parts of hollow glass as a floating aid, 9 parts of bentonite and 36 parts of clay as a bulking agent, 40 parts of water was added to the mixture and kneaded thoroughly. The obtained kneaded product was formed by using a basket type granulator equipped with a screen having an opening of 1.0 mm, cut, and dried by a fluidized bed dryer at 50 ° C. The obtained dried product was sized to about 3 mm in length to prepare the composition of Example 9. Similarly, compositions of Examples 10 to 41 and Comparative Examples 4 to 12 were prepared. The contents of each composition prepared above are summarized in Tables 2 and 3.

In Tables 2 and 3,
Percentage:%
A-1 to A-8, a-1 to a-3: Spreading agents shown in Table 1 synthesized in Test Category A-9: 2-butyl-2-ethyl-1,3-propanediol A- 10: 2,4-diethyl-1,5-pentanediol A-11: 2-methyl-1,8-octanediol A-12: 1,10-decanediol A-13: 1,6-hexanediol a- 4: 1,4-butanediol a-5: 1,16-hexadecanediol a-6: ethylene glycol monononanate a-7: α-2-ethylhexyl-ω-hydroxy-dioxyethylene a-8: Surfynol 104 (manufactured by Air Products)
a-9: sodium 1,2-bis (2-ethylhexyloxycarbonyl) ethanesulfonate

Z-1: Café Troll Z-2: Daimron Z-3: Butachlor M-1: NAC
M-2: Diazinon K-1: Propenazole K-2: Tricyclazole G-1: Hollow glass (trade name CEL-STAR Z-27 manufactured by Tokai Kogyo Co., Ltd.)
G-2: Foamed Shirasu (trade name Shirasu Balloon manufactured by Calceid)
I-1: Mixture of bentonite (trade name Kunigel V1 manufactured by Kunimine Kogyo Co., Ltd.) / Clay (trade name Showa fine powder clay manufactured by Showa Mining Co., Ltd.) = 20/80 (weight ratio) I-2: white carbon (manufactured by Tokuyama Co., Ltd.) (Trade name Tokusir NR) / bentonite (trade name Kunigel V1 manufactured by Kunimine Kogyo Co., Ltd.) / Clay (trade name Showa fine powder clay manufactured by Showa Mining Co., Ltd.) = 10/20/70 (weight ratio) I-3: White Carbon (trade name Tokuseal NR manufactured by Tokuyama Co., Ltd.) / Bentonite (trade name Kunigel V1 manufactured by Kunimine Kogyo Co., Ltd.) / Calcium carbonate (trade name heavy calcium carbonate manufactured by Maruo Calcium Co., Ltd.) = 10/20/70 (weight ratio) I-4: Bentonite (trade name Kunigel V1 manufactured by Kunimine Kogyo Co., Ltd.) / Calcium carbonate (trade name Heavy Carbonate Carbonate manufactured by Maruo Calcium Co., Ltd.) Siumu) = 20/80 (mixture H-1 weight ratio): alkylnaphthalene sulfonic acid metal salt (manufactured by Takemoto Yushi Co. trade name NEWKALGEN BX-C)
H-2: Naphthalenesulfonic acid formaldehyde condensate metal salt (Brand name New Calgen PS-P manufactured by Takemoto Yushi Co., Ltd.)

Test category 3 (composition evaluation)
A stainless steel rectangular container with a length of 200 cm, a width of 10 cm, and a depth of 4 cm is used. Cylindrical obstacles with a diameter of 2.5 cm and a length of 5.5 cm are spaced at 10 cm intervals in the center of the inner bottom along the vertical direction of the container. A total of 19 bottles were installed, and water was poured into the container to a depth of 2 cm. 0.2 g of the surface-floating pesticide composition prepared in Test Category 2 was added from the center of one end in the longitudinal direction of the container, and its extension distance, extension speed, and extension situation were evaluated as follows (Evaluation 1). . Similarly, also about the water-floating type agrochemical composition preserve | saved at 54 degreeC for 4 weeks, the expansion distance, the expansion speed, and the expansion condition were evaluated as follows (evaluation 2). The results are summarized in Table 4 and Table 5.

-Evaluation of expansion distance: The vertical distance which expanded in 2 minutes after input was measured. The measurement was performed 5 times, and the average value was evaluated according to the following criteria.
Evaluation criteria:
◎: 170 cm or more ○: 150 cm or more, less than 170 cm △: 130 cm or more, less than 150 cm ×: less than 130 cm

-Evaluation of spreading speed: The time required for the charged composition to spread to 100 cm in the longitudinal direction was measured. The measurement was performed 5 times, and the spreading speed was calculated from the average value by the following formula, and evaluated according to the following criteria.
Expansion speed (cm / sec) = 100 (cm) / Required time (sec)
Evaluation criteria:
◎: 6 cm / second or more ○: 5 cm / second or more, less than 6 cm / second △: 3 cm / second or more, less than 5 cm / second
X: Less than 3 cm / sec

・ Evaluation of the spread state: The state in which the charged composition spreads was observed and evaluated according to the following criteria.
Evaluation criteria:
◎: Expands very violently while spreading ripples on the water surface and has excellent spreadability ○: Spreads slightly while spreading ripples on the water surface and has good spreadability △: No ripples on the water surface , Ripples slightly spread just before the grain collapses, and the spreadability is slightly bad. ×: No ripples are generated on the water surface.

Claims (6)

A spreader for a surface-floating pesticide composition, comprising one or two or more selected from alkanediols having 6 to 10 carbon atoms and alkanediol derivatives represented by the following chemical formula 1:

(In chemical formula 1,
R: Residues obtained by removing all hydroxyl groups from an alkanediol having 6 to 10 carbon atoms A ¹ and A ² : (poly) oxy each composed of a total of 1 to 7 oxyethylene units and / or oxypropylene units Residue obtained by removing all hydroxyl groups from (poly) alkylene glycol having an alkylene group)   The spreader for water surface floating type agricultural chemical compositions according to claim 1, comprising one or more selected from alkanediol derivatives represented by Chemical Formula 1. In the alkanediol derivative represented by Chemical Formula 1, R is a residue obtained by removing all hydroxyl groups from a branched alkanediol having 8 to 10 carbon atoms, and A ¹ and A ² are each 2 to 6 in total The water-floating pesticide according to claim 1 or 2, wherein the residue is a residue obtained by removing all hydroxyl groups from a polyalkylene glycol having a polyoxyalkylene group composed of oxyethylene units and / or oxypropylene units. Spreading agent for composition. In the alkanediol derivative represented by Chemical Formula 1, R in Chemical Formula 1 was obtained by removing all hydroxyl groups from 2-butyl-2-ethyl-1,3-propanediol or 2,4-diethyl-1,5-pentanediol. It is a residue, and when A ¹ and A ² are residues obtained by removing all hydroxyl groups from polyethylene glycol having a polyoxyethylene group composed of 3 to 5 oxyethylene units. The spreader for water surface floating type agricultural chemical compositions according to claim 1 or 2.   A total of 90% by mass or more of the spreading agent for water-floating pesticide composition according to any one of claims 1 to 4, an agrochemical medicinal component, a floating aid and a bulking agent, and the water-floating pesticide 0.1 to 10% by mass of a spreader for the composition, 0.1 to 80% by mass of the agrochemical medicinal component, 1 to 80% by mass of the floating aid, and 1 to 80% by mass of the extender A water-floating pesticide composition comprising:   The water-floating pesticide composition according to claim 5, comprising a total of 100% by mass of a spreader for a water-floating pesticide composition, a pesticide medicinal component, a floating aid and a bulking agent.