JP2007320927A - Binder for agrochemical granule water-dispersible agent and agrochemical granule water-dispersible agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a binder which is used for dispersing agrochemical granules in water and gives granules having good strengths and having good dispersibility and good collapsibility in water, when added to the water. <P>SOLUTION: This binder for dispersing agrochemical granules in water comprises carboxymethyl inulin having an etherification degree of 0.7 to 1.5 and giving an anhydrous carboxymethylinulin 10% aqueous solution viscosity of ≤300 mPa/s. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a binder for agrochemical granule wettable powder and an agrochemical granule wettable powder using the binder.

  Pesticide granule wettable powder does not contain an organic solvent and is granular, so it is highly safe for workers because it does not cause dust when preparing a pesticide spray solution or when spraying pesticides. It is. Moreover, since the active ingredient concentration is high and the specific gravity of the preparation is large, it is compact. Furthermore, it has excellent characteristics such as fluidity is better than conventional wettable powders, so there is little adhesion remaining on the container, paper containers can be used, and disposal of containers after use is easy. ing.

  As described above, in order to prevent powdering, it is necessary that the preparation does not contain fine powder and that fine powder is not generated during production or transportation, and a strong granule is required. And in order to manufacture such a strong agricultural chemical granule wettable powder, a water-soluble binder is used. Generally, agrochemical granule wettable powder disintegrates in water and becomes primary particles and is dispersed. However, with conventional binders, if strong granules are obtained, disintegration / dispersion in water On the other hand, when granules having good disintegration and dispersibility in water are obtained, there is a problem that strong granules cannot be obtained. In addition to the binder, a large amount of surfactant must be added. Therefore, there has been a demand for a binder that is strong and that gives granules with good disintegration in water and dispersibility when added to water.

  Conventionally, polyvinyl alcohol (see Patent Document 1), sodium salt of carboxymethyl cellulose (see Patent Document 2), and the like have been used as binders in agrochemical granule wettable powders. It is known that it has excellent properties and water dispersibility. However, when polyvinyl alcohol is used, there is a problem that it is difficult to obtain a low-viscosity product, and when sodium carboxymethyl cellulose is used, although it is excellent in disintegration in water, it is still sufficient. There was a problem that was not.

JP 11-228305 A JP-A-2005-41833

  An object of the present invention is to provide a binder for an agrochemical granule wettable powder that has a strength and is capable of obtaining granules that are disintegratable and dispersible in water when added to water.

  The present invention relates to a bond for agrochemical granule wettable powder containing a carboxymethylinulin (hereinafter referred to as CMI) metal salt having a degree of etherification of 0.7 to 1.5 and a 10% aqueous solution viscosity of an anhydride of 300 mPa · s or less. It relates to the agent.

  The present invention also relates to an agrochemical granule wettable powder containing the binder.

  The blending amount of the binder is preferably 0.1 to 20% by weight in the wettable powder.

  When the binder of the present invention is used, a pesticidal granule wettable powder which is strong and particularly excellent in water disintegration and dispersibility when added to water can be obtained.

  The present invention relates to a binder for an agrochemical granule wettable powder containing a CMI metal salt having a degree of etherification of 0.7 to 1.5 and a 10% aqueous solution viscosity of an anhydride of 300 mPa · s or less.

  The degree of etherification of the CMI metal salt is 0.7 to 1.5, preferably 0.8 to 1.0, and more preferably 0.85 to 0.95. When the degree of etherification is less than 0.7, insoluble matter tends to remain in the aqueous solution. On the other hand, when the degree of etherification is more than 1.5, there is no particular problem, but there is a large amount of salt produced as a by-product salt, and the degree of difficulty in purifying to high purity tends to increase.

  The viscosity of a 10% aqueous solution of CMI metal salt anhydride is 300 mPa · s or less. When the viscosity of the 10% aqueous solution is greater than 300 mPa · s, the water disintegration force due to the hydration force accompanying the viscosity tends to be deteriorated. The lower limit of the 10% aqueous solution viscosity is not particularly limited, but is preferably 20 mPa · s or more from the viewpoint of maintaining hydration power.

  Specific examples of the CMI metal salt include CMI sodium (hereinafter referred to as CMI-Na), CMI potassium, CMI ammonium, CMI lithium and the like. Among these, CMI-Na is preferable from the viewpoint of easy procurement of raw materials.

  Inulin, which is a raw material of the CMI metal salt used in the present invention, is contained in 15 to 60% by weight in the rhizomes of Asteraceae plants such as Jerusalem artichoke and dahlia, and is composed mainly of D-fructose represented by the following general formula. It is a polysaccharide of about 5000 to 6300 (n is about 20 to 35), 20 to 30 residue fructose (furanose type) is polymerized by β-2,1 bond with sucrose as a receptor, and glucose is reduced at the reducing end. It is a polysaccharide present and is not particularly limited.

  The method for producing a CMI metal salt comprises a step in which raw inulin is alkali-treated with an alkali metal compound in a hydrous organic solvent, and then etherified by adding a carboxymethyl etherifying agent to the alkali-treated inulin. is there.

The amount of the alkali metal compound added when the raw material inulin is alkali-treated is preferably 0.5 to 10 mol, more preferably 0.5 to 3.0 mol, per mol of D-fructose unit of inulin. When the addition amount of the alkali metal compound is smaller than 0.5 mol, the alkali amount is insufficient and the etherification reaction tends to be difficult. On the other hand, when the addition amount of the alkali metal compound is larger than 10 mol, there is a tendency to promote the side decomposition of the etherifying agent.
The addition amount of the carboxymethyl etherifying agent is preferably 0.8 to 2.0 per mole of D-fructose unit of inulin. When the addition amount of the carboxymethyl etherifying agent is less than 0.8 mol, there is a tendency that CMI having an etherification degree of 0.7 or more cannot be obtained. On the other hand, when the added amount of the carboxymethyl etherifying agent is larger than 2.0 mol, there is a tendency that CMI having a degree of etherification of 1.5 or less cannot be obtained.

  The present invention also relates to an agrochemical granule wettable powder containing the binder.

  The agrochemical granule wettable powder contains a binder, an agrochemical active ingredient, a surfactant and a bulking agent.

  The blending amount of the binder is preferably 0.1 to 20% by weight in the wettable powder, more preferably 0.1 to 10% by weight, and further preferably 1 to 8% by weight. If the blending amount of the binder is less than 0.1% by weight, the disintegration property in water is good, but the strength of the granules cannot be obtained, and there is a tendency for powdering due to the disintegration of granules during transportation. . On the other hand, when the blending amount of the binder is larger than 20% by weight, there is a tendency that it is not economical and the granule is solidified and hardly disintegrates in water.

  The pesticide active ingredient is not particularly limited, and every year, insecticides, fungicides, herbicides, plant growth regulators, attractants, repellents, insecticides, exhibitions described in the Agricultural Handbook published by the Japan Plant Protection Association All of the dressings are listed. When the pesticide raw material is solid, the suspension of the pesticide spray solution is improved when used as it is or after being pulverized with an inorganic extender. In addition, when the liquid is used by being adsorbed on a mineral filler or the like, the productivity is improved. The pesticide raw material is used after being pulverized wet or dry depending on the granulation method.

  1-95 weight% is preferable in a wettable powder, 2-70 weight% is more preferable in the wettable powder, and 5-20 weight% is further more preferable. If the blending amount of the pesticide raw material is less than 1% by weight, the pesticide effect tends not to be exhibited. On the other hand, when the blending amount of the agrochemical raw material is larger than 95% by weight, the agrochemical effect is obtained, but there is a tendency that the shape as a granule cannot be maintained due to insufficient binders.

  Surfactants are added to promote the disintegration and dispersion of the granules in water and increase the suspension. The type is not particularly limited, and anionic surfactants such as carboxylate, sulfate, sulfonate, and phosphate, polyoxyethylene, polyoxyalkylene, polyhydric alcohol, and ether Nonionic surfactants such as ester type, amphoteric surfactants, cationic surfactants and the like can be mentioned. Moreover, you may use many types together. Among these, it is preferable to use an anionic surfactant, a nonionic surfactant, or a combination of both. Preferred surfactants include formalin condensate of naphthalene sulfonate, formalin condensate of alkyl naphthalene sulfonate, lignin sulfonate, polyacrylate, alkylaryl sulfonate, polyoxyethylene alkyl ether, polyoxy Ethylene styryl phenyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block polymer, alkyl naphthalene sulfonate, alkyl benzene sulfonate, alkyl sulfo succinate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, And polyoxyethylene styryl phenyl ether sulfate, polyoxyethylene alkylaryl sulfate, and mixtures thereof. .

  The blending amount of the surfactant is preferably 1 to 30% by weight in the wettable powder, more preferably 1 to 10% by weight, and further preferably 3 to 8% by weight. If the surfactant is less than 1% by weight, the manufacturability tends to be poor, and the disintegration property in water tends to be poor. is there.

  The bulking agent is a mineral, such as clay, talc, calcium carbonate, diatomaceous earth, zeolite, bentonite, acid clay, activated clay, attapulgus clay, white carbon (silica), and titanium dioxide. Examples include sodium chloride, ammonium sulfate, sodium sulfate, glucose, lactose, and sucrose.

  The blending amount of the extender is preferably 0 to 97.9% by weight in the wettable powder, more preferably 12 to 96% by weight, and still more preferably 20 to 70% by weight. When the blending amount of the extender is larger than 97.9% by weight, the blending amounts of the agrochemical raw material component, the surfactant component, the binder component and the like tend to decrease.

  In addition to the above-described components, a dispersant, a decomposition inhibitor, a stabilizer, a solvent, a pH adjuster, a foaming agent, a preservative, and the like can be added to the granular wettable powder of the present invention.

  The granule wettable powder of the present invention contains a CMI metal salt as a binder, but a binder other than the CMI metal salt may be used in combination. Specifically, CMC-Na, xanthan gum, polyvinyl pyrrolidone (PVP), etc. are mentioned.

  The particle size of the agricultural granule wettable powder of the present invention is preferably 0.3 to 3 mm, and more preferably 0.5 to 1.5 mm. If the particle size is less than 0.3 mm, powdering tends to occur and the productivity tends to deteriorate. On the other hand, when it is larger than 3 mm, the disintegration property in water tends to deteriorate.

  The method of adding the binder of the present invention is not particularly limited, and differs depending on the granulation method of the granule hydrate. The binder powder may be added to the raw material powder, or the binder aqueous solution may be used as the raw material powder. In addition, in the case of a method of dry granulating the slurry, it may be added to the slurry.

  Further, the production method of the agrochemical granule wettable powder of the present invention is not particularly limited, and is spray-dried granulation, fluidized bed granulation, freeze-drying, bread-type rolling granulation, extrusion granulation, mixed stirring granulation, and Examples include compression granulation. Of these, fluidized bed granulation, spray drying granulation, extrusion granulation, and bread type rolling granulation method are preferred from the viewpoint of economy and physical properties of the preparation.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

Production Examples 1-2
<Method for producing CMI-Na>
In 1500 g of a water-containing organic solvent in which water: isopropyl alcohol (hereinafter referred to as IPA) was mixed at a weight ratio of 20:80, sodium hydroxide was dissolved in the amount shown in Table 1, and the obtained alkaline solution was dissolved in a 5-liter biaxial kneader. The reactor was charged. While stirring the kneader, 500 g of inulin (manufactured by SENSUS, Frufit HD) (weight average molecular weight: 5400, polymerization degree: 30) was added, and the mixture was stirred at 30 ° C. for 40 minutes to perform an alkali reaction.

  Monochloroacetic acid in the amount shown in Table 1 was dissolved in a water-containing organic solvent (water: IPA = 20: 80% by weight), the temperature was adjusted to 25 ° C., and then added over 10 minutes. Subsequently, an etherification reaction was carried out at 78 ° C. for 120 minutes. After completion of the reaction, the reaction mixture was cooled to 50 ° C. and neutralized with a 50 wt% acetic acid aqueous solution.

  The obtained CMI-Na was heated at 80 ° C. to 105 ° C. for 60 to 120 minutes to increase the solid content concentration to 40 to 70%. Further, the paste-like reaction product was poured into 20 times methanol, stirred for 30 minutes at 600 rpm, allowed to stand, and the supernatant methanol was removed, followed by centrifugation at 200 rpm / 10 minutes. After 20 times of methanol was added to the crude CMI-Na and the same operation was repeated twice, the crude CMI-Na was dried under reduced pressure and pulverized to obtain a 180 μm pass CMI-Na powder.

  The moisture value of the obtained CMI-Na, the 10% aqueous solution viscosity, and the degree of etherification were measured by the following methods.

<Analysis method of CMI-Na>
(1) Moisture value Samples 1 to 2 g were precisely weighed in a weighing bottle, dried in a dryer at 105 ± 0.2 ° C for 2 hours, and the moisture value was determined from the weight loss by drying according to the following equation.

(2) Viscosity of 10% aqueous solution About 28 g of sample was precisely weighed in a 300 ml tall beaker, and the amount of dissolved water required to obtain a 10% aqueous solution obtained by the following formula was added and dispersed with a glass rod. In addition, the water | moisture content utilized the water | moisture value of said (1).

The aqueous solution was allowed to stand for a whole day and night, and stirred with a magnetic stirrer for about 5 minutes to obtain a complete solution, and then placed in a constant temperature water bath at 25 ° C. for 30 minutes to bring the solution to 25 ° C. Thereafter, the mixture was gently stirred with a glass rod, an appropriate rotor and guard of a BM type viscometer were attached, and the scale after 3 minutes was read at a rotational speed of 60 rpm.
Viscosity (mPa · s) = Reading scale x Coefficient

(3) Degree of etherification About 1 g of carboxymethylinulin was precisely weighed, wrapped in filter paper, placed in a magnetic crucible, and incinerated at 60 ° C. The resulting sodium hydroxide was titrated with 0.1N sulfuric acid using phenolphthalein as an indicator, and the degree of etherification was determined using the amount of sulfuric acid A (ml) required for neutralization titration and the titer f ₃ of 0.1N sulfuric acid. Was calculated.

Example 1
<Manufacture of pesticide granule wettable powder>
While mixing the components shown below with a mixer, 30 parts by weight of water was added to prepare a humidified powder.
Calcium carbonate 70 parts by weight CMI-Na obtained in Production Example 1 2 parts by weight Sodium lauryl sulfate 10 parts by weight Sodium polyacrylate (40% aqueous solution) 5 parts by weight Powdered silica 15 parts by weight

  Further, it was extruded from a screen having an aperture of 0.5 mm using an extrusion granulator. After drying it at 70 ° C. for 3 hours, it was coarsely pulverized and sized with a sieve to 0.5 to 0.8 mm to obtain an agrochemical granule wettable powder. Each physical property was evaluated by the following methods. The measurement results are shown in Table 2.

<Evaluation>
1. Load at the time of disintegration The obtained agricultural chemical granule wettable powder was loaded using a KOMURA medal S type tester (manufactured by Yamato Kagaku Co., Ltd.), and the load [kg] at the time of breakage was read.

2. Number of disintegrations 100 ml of hard water was put into a 100 ml stoppered cylinder, 1.0 g of agrochemical granule wettable powder was added, and the inverted mixing test was repeated, and the number of inversions when the granules disintegrated was measured.

3. Dispersion State The state of the dispersion liquid was visually confirmed to evaluate uniformity.

Example 2
An agrochemical granule wettable powder was produced in the same manner as in Example 1 except that CMI-Na obtained in Production Example 1 was replaced with CMI-Na obtained in Production Example 2, and the same as in Example 1. Each physical property value was measured by the method. The measurement results are shown in Table 2.

Comparative Examples 1-3
As carboxymethylcellulose (hereinafter referred to as CMC) showing the degree of etherification and 10% aqueous solution viscosity shown in Table 2, CMC (A) (Fine Gum HE-Li, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Comparative Example 1)), CMC (B) (Serogen 5A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Comparative Example 2)) and CMC (C) (Serogen F-907A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Comparative Example 3)) Agrochemical granule wettable powder was prepared in the same manner as in Example 1 except that it was used as a sample, and each physical property was measured. The measurement results are shown in Table 2.

  From Examples 1 and 2, when CMI-Na having a specific degree of etherification and a 10% aqueous solution viscosity is used as a binder, there is no turbidity and solid matter, the dispersion state is good, and the number of disintegrations is small. It can be seen that an agrochemical granule wettable powder excellent in disintegration in water can be obtained. This is considered to be because shape retention was maintained by an appropriate caking force by using CMI-Na as a binder.

  On the other hand, from Comparative Examples 1 to 3, when CMC is used as the binder, the dispersion state is good, but since the number of disintegrations is large, the disintegration property in water is inferior compared with CMI-Na used in the examples. As a result.

Claims (3)

A binder for pesticidal granule wettable powders containing a carboxymethylinulin metal salt having a degree of etherification of 0.7 to 1.5 and a 10% aqueous solution viscosity of an anhydride of 300 mPa · s or less. An agrochemical granule wettable powder comprising the binder according to claim 1. The agrochemical granule wettable powder according to claim 2, wherein the amount of the binder is 0.1 to 20% by weight in the wettable powder.