JP2010209001A - Aqueous suspension preparation for home gardening - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous suspension preparation for home gardening excellent in redispersibility and storage stability. <P>SOLUTION: The aqueous suspension preparation for home gardening excellent in redispersibility and storage stability contains three active components of clothianidin and fenpropathrin as agricultural chemical insecticidal components and mepanipyrim as an agricultural chemical bactericidal component, and a water-swellable carboxymethyl cellulose or a sodium salt thereof as a redispersibility improving agent. There is used a water-swellable carboxymethyl cellulose or a sodium salt thereof which has a degree of carboxymethyl substitution per glucose residue of 0.05-0.5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous suspension formulation for home gardening. More specifically, pesticides that are effective against home garden arts, such as semi-Lepidopterous insects and phosphorus lepidopterous insects, and pesticides that are effective against home powders such as powdery mildew and black spot disease. The present invention relates to an aqueous suspension preparation for home gardening that can be sprayed as it is without dilution with water. Specifically, re-dispersibility containing clothianidin and fenpropatoline as agricultural chemical insecticidal components, mepanipyrim as active ingredients, and water-swellable carboxymethyl cellulose or a sodium salt thereof as a re-dispersion improver. The present invention also relates to an aqueous suspension preparation for home gardening having excellent storage stability.

  Conventionally, insecticides, fungicides, and insecticides that are diluted with water as agricultural chemicals for general farmers have been sold. In addition, pesticides for home gardening that are diluted with water are also sold. However, since it takes time and effort to dilute with water, pesticides, fungicides and insecticides that can be sprayed without dilution are now available. Bactericides have become the mainstream pesticide for home gardening.

JP 2004-155672 A Japanese Patent Laid-Open No. 4-9307 JP 2006-225277 A

  Under such technical background, the present inventors have emphasized the importance of home gardening as an insecticidal active ingredient in order to develop an aqueous preparation for home gardening that can be sprayed as it is without dilution with water, and particularly suitable as a hand spray type. Phenpropatoline, which has a fast-acting insecticidal effect, and clothianidin, which has a repellent-effective insecticidal effect, are selected for the semi-lepidopterous insects and phosphorus-mothing pests. An aqueous formulation of a three-component mixed insecticide that selected mepanipyrim, which has bactericidal effects on rudon powdery mildew and black spot disease, was examined.

  Of the three active ingredients, clothianidin is water-soluble, so there is no particular problem, but phenpropatoline and mepanipyrim are insoluble in water, so that they can be stably and uniformly retained in the preparation in an aqueous medium. It tried to make it contain. As a result, fenpropatoline could be solubilized by selecting an appropriate surfactant, but mepanipyrim was difficult to solubilize. Therefore, an attempt was made to prepare mepanipyrim as a suspension preparation in the form of fine particles suspended in an aqueous medium. In aqueous suspension formulations, initially suspended mepanipyrim settles over time during storage, so it is necessary to re-disperse mepanipyrim by shaking the formulation container immediately before application, but mepanipyrim has poor redispersibility. It was confirmed that the settled mepanipyrim formed a hard cake and was not redispersed by shaking the container. In order to improve the redispersibility, an attempt was made to use a redispersion improver.

  Conventionally, it is known to contain silica or hydrous aluminum silicate for the purpose of improving the redispersibility and storage stability of an aqueous suspension preparation. Examples of using silica include at least one active ingredient selected from agrochemical active ingredients, industrial / household antiseptic and fungicidal active ingredients, surfactant, silica, and water for improving redispersibility. There is an aqueous suspension preparation (JP 2004-155672 A; Patent Document 1). The hydrous aluminum silicate contains, for example, sulfur as an active ingredient, and includes a naphthalene sulfonic acid anionic surfactant, an unsaturated carboxylic acid polymer anionic surfactant, and a colloidal hydrous aluminum silicate. And a suspension agricultural fungicide composition containing water and water are disclosed (Japanese Patent Laid-Open No. 4-9307; Patent Document 2).

  Therefore, first, the use of silica as a redispersion improving agent was examined. As a result, the settled mepanipyrim was not redispersed even when the container was shaken 200 times or more, and improvement in redispersibility was not confirmed. Next, the use of hydrous aluminum silicate as a redispersion improver was attempted. As a result, the redispersibility was improved, but it was confirmed that the primary particles of mepanipyrim aggregated to form secondary aggregated particles having a diameter of about 1 mm. When secondary agglomerated particles are produced, the secondary agglomerated particles settle during application of the preparation, so that the active ingredient concentration in the applied chemical solution changes (decreases) over time, resulting in unstable medicinal properties, and leaves with agglomerated particles attached There are problems such as the possibility of causing chemical damage to the surface and the possibility of clogging the hand spray nozzle.

  Accordingly, an object of the present invention is to provide an aqueous suspension preparation for home gardening that includes fenpropatoline and clothianidin as insecticidal active ingredients and mepanipyrim as a bactericidal active ingredient and has excellent redispersibility and storage stability.

  The present inventors have intensively studied to solve the above problems. As a result, the use of water-swellable carboxymethyl cellulose having a specific degree of carboxymethyl substitution per glucose residue or its sodium salt as a redispersion improver makes it possible to use an aqueous suspension having excellent redispersibility and storage stability. The present invention was completed by finding that a turbid preparation can be obtained.

That is, the present invention provides the following aqueous suspension formulation for home gardening.
1. It is characterized by containing three kinds of ingredients, clothianidin and fenpropatoline, which are agricultural chemical insecticides, and mepanipyrim, which is an agricultural chemical bactericidal ingredient, and water-swellable carboxymethyl cellulose or its sodium salt as a redispersion improver. An aqueous suspension formulation for home gardening with excellent dispersibility and storage stability.
2. The house gardening according to 1 above, wherein the clothianidin concentration is 0.004 to 0.008% by mass, the fenpropatoline concentration is 0.005 to 0.010% by mass, and the mepanipyrim concentration is 0.013 to 0.020% by mass. Aqueous suspension formulation.
3. 3. The aqueous garden preparation for home gardening according to 1 or 2 above, wherein mepanipyrim has an average particle size of 2 to 13 μm.
4). 4. The aqueous suspension preparation for home gardening according to any one of 1 to 3 above, wherein the degree of carboxymethyl substitution per glucose residue of water-swellable carboxymethylcellulose or a sodium salt thereof is 0.05 to 0.5.
5). 5. The aqueous suspension formulation for home gardening according to any one of 1 to 4 above, wherein the concentration of water-swellable carboxymethylcellulose or a sodium salt thereof is 0.05% by mass or more and less than 0.2% by mass.

According to the home gardening aqueous suspension preparation of the present invention, the following effects can be obtained.
(1) If the preparation is allowed to stand, mepanipyrim precipitates but does not hard-cake, so it can be easily redispersed by shaking the container.
(2) Mepanipyrim primary particles do not aggregate and have excellent storage stability.
(3) Even if the preparation is sprayed on the leaves of plants, it does not get dirty.

Hereinafter, the aqueous suspension preparation for home gardening according to the present invention will be described in detail.
The active ingredient of the aqueous suspension preparation of the present invention is effective against hemipod pests and phosphorus lepidopterous insects that are regarded as important in home gardening, especially fenpropatrin which has a fast-acting insecticidal effect and residual insecticidal effect. A clothianidin and mepanipyrim that has bactericidal effects on powdery mildew and black spot disease, which are regarded as important in home gardening.

  In the preparation of the present invention, mepanipyrim that needs to be suspended in an aqueous medium has an average particle diameter of 2 to 13 μm, preferably 2 to 3 μm. If the average particle size is less than 2 μm, the amount of mepanipyrim placed on the foliage after application of the drug is reduced, so that the residual effect is lowered. On the other hand, when it exceeds 13 μm, mepanipyrim is difficult to cover the foliar surface tightly after spraying the drug, so the medicinal effect is expected to be unstable, and from the pharmaceutical viewpoint, the precipitation rate of mepanipyrim increases. This makes it difficult to maintain dispersion and increases the time and effort required to shake the container. In the present specification, the average particle size of mepanipyrim is a value measured by a laser diffraction particle size distribution analyzer (SALD-7000, manufactured by Shimadzu Corporation).

  The amount of active ingredient used (concentration in the preparation) may be in a range that exhibits the desired insecticidal and bactericidal effects when used for home gardening. That is, it is usually 0.004 to 0.008 mass%, preferably about 0.008 mass% for clothianidin, and 0.005 to 0.010 mass%, preferably about 0.010 mass for fenpropatoline. % And mepanipyrim is 0.013 to 0.020% by mass, preferably about 0.020% by mass. The above-mentioned concentration range of each component is an appropriate concentration range recognized in the registration of agricultural chemicals showing medicinal effects against pests regarded as important in home gardening. Outside the above concentration range, it is unsuitable as a home gardening pesticide that is applied as it is without dilution.

  Carboxymethylcellulose or a sodium salt thereof (hereinafter sometimes abbreviated as CMC) used as a redispersion improving agent in the present invention is water-insoluble and has water swellability. Water-swellable CMC can be obtained by lightly carboxymethylating cellulose (JP 2006-225277 A; Patent Document 3). As an index of the degree of solubility of CMC in water or water swellability, there can be mentioned the degree of substitution of carboxymethyl groups per glycol residue (degree of etherification, hereinafter sometimes abbreviated as CM-DS). The CM-DS of CMC used in the present invention is 0.05 to 0.5, preferably 0.2 to 0.3. When the CM-DS is less than 0.05, the degree of swelling of the water-swellable CMC becomes insufficient, and the water-swellable CMC itself also forms a hard cake, and the tendency for excellent redispersibility to be hardly obtained is increased. Further, if CM-DS exceeds 0.5, the solubility in water increases, and it becomes difficult to form a bulky precipitated layer with fluidity, so it becomes difficult to suppress the formation of hard cake, and good re- The tendency to become difficult to obtain dispersibility increases.

  Further, the amount (concentration) of CMC used in the present invention is in the range of 0.05% by mass or more and less than 0.2% by mass, preferably about 0.1% by mass. When the CMC concentration is less than 0.05% by mass, the redispersibility becomes poor. When the CMC concentration is 0.2% by mass or more, the redispersibility remains good, but the foliage on the plant leaves becomes noticeable.

The home gardening aqueous suspension preparation of the present invention can be produced by a conventional method. An example of the manufacturing method is shown below.
After dissolving the fenpropatoline drug substance in an organic solvent, a surfactant is mixed, an appropriate amount of water is added dropwise to this, and the solution (liquid A) subjected to phase inversion emulsification and the clothianidin drug substance as a solvent (ethanol, etc.) The solution (liquid B) dissolved in the solution, mepanipyrim drug substance, surfactant and antifoaming agent are dispersed in water and then wet pulverized to prepare a solution (liquid C) having mepanipyrim as a predetermined average particle size. . An aqueous suspension preparation can be produced by adding and mixing the prepared liquid A, liquid B and liquid C to a dispersion obtained by dispersing water-swellable sodium carboxymethylcellulose in water. As water, tap water, ion exchange water, distilled water, filtered water, sterilized water, or the like is used.

  In the home gardening aqueous suspension preparation of the present invention, a surfactant and a conventional solvent, antifreezing agent, antifoaming agent, antiseptic, antioxidant, thickener and the like used when preparing the agrochemical preparation are optionally added. Can be added.

  As the surfactant, a nonionic surfactant, an anionic surfactant, or the like can be used. Examples of the nonionic surfactant include polyoxyalkylene allyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene allyl phenyl ether, polyoxyethylene styryl phenyl ether, and polyoxyethylene alkylphenyl. Ether formaldehyde condensate, polyoxyethylene-polyoxypropylene block polymer, polyoxyethylene-polyoxypropylene block polymer alkylphenyl ether, sorbitan fatty acid ester (eg, sorbitan monooleate, sorbitan laurate), polyoxyethylene fatty acid ester, poly Oxyethylene sorbitan fatty acid ester, polyoxyethylene caster oil ether, polyethylene group Call fatty esters, polyethylene glycol fatty acid ester. Examples of the anionic surfactant include alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene benzyl (or styryl) phenyl ether sulfate, and polyoxyethylene-polyoxypropylene block polymer. Sodium, calcium or ammonium salts of sulfuric acid; alkyl sulfonates, dialkyl sulfosuccinates, alkylbenzene sulfonic acids (eg, calcium dodecylbenzene sulfonate), mono- or di-alkyl naphthalene sulfonic acids, naphthalene sulfonic acid formaldehyde condensation , Lignin sulfonic acid, polyoxyethylene alkyl phenyl ether sulfonic acid or polyoxyethylene alkyl ether sulfosuccinate Sodium, calcium, ammonium or alkanolamine salts of polyoxyethylene alkyl ether phosphate, polyoxyethylene, mono- or di-alkyl phenyl ether phosphate, polyoxyethylene benzyl (or styryl) phenyl ether phosphate, polyoxyethylene Examples include salts such as sodium or calcium salts of benzyl (or styryl) phenyl ether phosphate or polyoxyethylene-polyoxypropylene block polymer phosphate.

As the solvent, for example, a high boiling point solvent having a boiling point of 200 ° C. or higher, preferably 200 ° C. to 500 ° C. can be used. Specifically, triallyl diethane (boiling point 340 to 405 ° C.), phenyl xylyl ethane (boiling point 290 to 305 ° C.), dimethylpropylnaphthalene (boiling point 294 to 290 ° C.), which is preferably used for the purpose of a dissolution aid. 315 ° C.), a mixture of dimethyl succinic acid, dimethyl glutaric acid, and dimethyl adipic acid (boiling point 200-235 ° C .; structural formula H ₃ COOC— (CH ₂ ) n—COOCH ₃ (n = 2 to 4)), N , N-dimethyldecanamide (boiling point 250 ° C.), methylnaphthalene (boiling point 226 to 286 ° C.), and the like.

  Examples of the antifreezing agent include ethanol, ethylene glycol, propylene glycol, ethyl cellosolve, butyl carbitol, 3-methyl-methoxybutanol and the like.

  Antifoam E-20 (silicone emulsion, Kao Corporation, trade name), antifoam C (Dow Corning, trade name), antifoam C emulsion (Dow Corning, trade name) ), Rhodosyl 454 (Rhodia, trade name), Rhodosyl Antiform 432 (Rhodia, trade name), TSA730 (Toshiba Silicone, trade name), TSA731 (Toshiba Silicone, trade name), TSA732 (Toshiba Silicone) ), Silicone type antifoaming agents such as YMA6509 (Toshiba Silicone Co., Ltd., trade name), and fluorine type antifoaming agents such as Fluorowet PL80 (Clariant Co., Ltd., trade name).

  Examples of preservatives include Priventol D2 (chemical name: benzyl alcohol mono (poly) hemiformal), PROXEL GXL (S) (chemical name: 1,2-benzisothiazolin-3-one, 20%), biohope, and the like. Biohope L (chemical name: organic nitrogen sulfur compound, organic bromine compound), bestside-750 (chemical name: isothiazoline compound, 2.5-6.0%), 5-chloro-2-methyl- 4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, sodium benzoate, potassium sorbate, sodium dehydroacetate, parachlorometa Examples include xylenol and 2,6-dimethylphenol.

  Antioxidants include tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (Tominox TT (Api Corporation, trade name), IRGANOX1010 and IRGANOX1010EDS. (Ciba Japan Co., Ltd., trade name)), butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), propyl gallate, and vitamin E, mixed tocopherol, α-tocopherol, ethoxyquin, ascorbic acid, etc. Is mentioned.

  Examples of the thickener include PVP K-15 (chemical name: polyvinylpyrrolidone), xanthan gum, polyvinyl alcohol, guar gum, carboxyvinyl polymer, and the like.

  Next, the present invention will be described more specifically with reference to examples, comparative examples, and test examples. However, the present invention is not limited to these examples. In addition, in the following example, a part represents a mass part. The components used in the formulations of Examples and Comparative Examples are as follows.

1) Active ingredient
(1) clothianidin: Sumitomo Chemical Co., Ltd., purity 98%,
(2) Fenpropatoline substance: manufactured by Sumitomo Chemical Co., Ltd., purity 92.4%,
(3) Mepanipyrim drug substance: Kumiai Chemical Industry Co., Ltd., purity 99.1%.

2) Redispersion improver
(1) Sodium carboxymethyl cellulose (CM-DS: 0.2 to 0.3): Sunrose SLD-F1 (manufactured by Nippon Paper Chemicals Co., Ltd.)
(2) Sodium carboxymethyl cellulose (CM-DS: 0.65-0.75): Sunrose APP-84 (manufactured by Nippon Paper Chemicals Co., Ltd.)
(3) Silica: Carplex # 101 (manufactured by DSL Japan),
(4) Hydrous aluminum silicate: Kunipia-F (Kunimine Industry Co., Ltd.).

3) Surfactant
(1) Polyoxyalkylene allyl phenyl ether: New Calgen CP-120 (manufactured by Takemoto Yushi Co., Ltd.),
(2) Alkylbenzenesulfonic acid metal salt: New Calgen AD-85-C (manufactured by Takemoto Yushi Co., Ltd.).

4) Antioxidant Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane: Tominox TT (manufactured by API Corporation).

5) Solvent
(1) ion exchange water,
(2) Phenylxylylethane: Nisseki Hyzol SAS-296 (manufactured by Nippon Oil Corporation),
(3) Ethanol: General alcohol 99 degree synthesis (made by Nippon Alcohol Sales Co., Ltd.).

6) Preservative sodium benzoate (manufactured by Aioka Chemical Co., Ltd.).

7) Antifoaming agent:
Silicone emulsion: Antifoam E-20 (manufactured by Kao Corporation).

Example:
Fenpropatrin drug substance (0.0108 parts) and Tominox TT (0.003 parts) were dissolved in Nisseki Hyzol SAS-296 (0.03 parts), and then Newkalgen CP-120 (0.043 parts) and Newkalgen AD-85-C ( 0.066 parts) was mixed, and an appropriate amount of water was added dropwise thereto to prepare a solution (liquid A) subjected to phase inversion emulsification. In addition, a solution (solution B) was prepared by dissolving clothianidin base (0.00816 parts) in general alcohol 99 degree synthesis (2 parts). Further, mepanipyrim drug substance (0.0202 parts), Newkalgen CP-120 (0.001 parts), and Antifoam E-20 (0.000133 parts) were placed in ion-exchanged water, dispersed, and then wet pulverized to obtain an average particle size. A solution (solution C) of 2.0 μm was prepared. After dispersing and dissolving Sunrose SLD-F1 (0.1 part) and sodium benzoate (0.1 part) in ion-exchanged water (remaining amount in which the total amount of the blended components is 100 parts), liquid A, liquid B, and C The liquid was added and further mixed to prepare an aqueous suspension formulation.

Comparative Examples 1-6:
The aqueous suspension preparations of Comparative Examples 1 to 6 were prepared in the same manner as in the Examples, using the components whose blending ratios (formulations) were listed in Table 1.

Test Example 1:
50 mL of each of the preparations of Examples and Comparative Examples 1 to 4 was placed in a 50 mL capacity glass bottle and stored for 3 months at −5 ° C., room temperature, and 40 ° C. The number of falls required to completely redisperse the sediment was measured to confirm the presence or absence of aggregation. The results are shown in Table 2.

注１）ＨＣはハードケーキングを示す。
注２）再分散性とはガラス瓶底に沈降した成分が容器の転倒によりすべて剥がれることを示す。
注３）凝集とは一次粒子（約２μｍ）が集合して二次粒子（約１ｍｍ以上）を形成することを示す。

Note 1) HC indicates hard caking.
Note 2) Redispersibility means that all the components that have settled on the bottom of the glass bottle are peeled off by overturning the container.
Note 3) Aggregation means that primary particles (about 2 μm) aggregate to form secondary particles (about 1 mm or more).

  From the results of Table 2, Comparative Example 1 without the addition of a redispersion improver, Carplex # 101, Kunipia-F, Sunrose APP-84 (CMC / CM-DS 0.65 to 0.75) as a redispersion improver. Each of Comparative Example 2, Comparative Example 3 and Comparative Example 4 added had poor redispersibility and aggregation (storage stability) or both. On the other hand, in the example in which Sunrose SLD-F1 (CM-DS 0.2 to 0.3) was added as a redispersion improver, both redispersibility and storage stability were good.

Test example 2:
50 mL of each formulation of Example, Comparative Example 5 and Comparative Example 6 was placed in a 50 mL capacity glass bottle and stored for 3 months at −5 ° C., room temperature, and 40 ° C. The number of falls required to completely redisperse the sediment was measured to confirm the presence or absence of aggregation. Moreover, each formulation was sprayed on the rose by hand spray, and the fouling of the leaf surface was evaluated. The results are shown in Table 3.

  From the results shown in Table 3, Comparative Example 5 in which 0.05% by mass of Sunrose SLD-F1 was added as a redispersion improver tended to be slightly worse in redispersibility, but was within an acceptable range. In Comparative Example 6 in which 0.2% by mass of Sunrose SLD-F1 was added as a redispersion improving agent, the redispersibility was good, but the stain on the rose leaf surface was conspicuous. On the other hand, in the example in which 0.1% by mass of Sunrose SLD-F1 was added as a redispersion improver, stain on the rose leaf surface was not confirmed while maintaining good redispersibility.

  The preparation of the present invention has a bactericidal effect on powdery mildew and black spot disease, such as fenpropatoline, which has a fast-acting insecticidal effect against hemipods and phosphorus-worms, clothianidin, which has a residual insecticidal effect An aqueous formulation containing mepanipyrim as an active ingredient and containing water-swellable carboxymethylcellulose or its sodium salt as a redispersion improver and can be sprayed as it is without diluting with water. Redispersibility and storage stability It is useful as a home gardening preparation with excellent properties.

Claims (5)

  It is characterized by containing three kinds of ingredients, clothianidin, phenpropatoline, an agricultural chemical insecticide, and mepanipyrim, an agricultural chemical bactericidal ingredient, and water-swellable carboxymethyl cellulose or its sodium salt as a redispersion improver. An aqueous suspension formulation for home gardening with excellent dispersibility and storage stability.   The home gardening according to claim 1, wherein the clothianidin concentration is 0.004 to 0.008 mass%, the fenpropatoline concentration is 0.005 to 0.010 mass%, and the mepanipyrim concentration is 0.013 to 0.020 mass%. Aqueous suspension formulation.   The aqueous suspension preparation for home gardening according to claim 1 or 2, wherein mepanipyrim has an average particle diameter of 2 to 13 µm.   The aqueous suspension formulation for home gardening according to any one of claims 1 to 3, wherein the degree of carboxymethyl substitution per glucose residue of water-swellable carboxymethyl cellulose or a sodium salt thereof is 0.05 to 0.5.   The aqueous suspension formulation for home gardening according to any one of claims 1 to 4, wherein the concentration of water-swellable carboxymethylcellulose or a sodium salt thereof is 0.05% by mass or more and less than 0.2% by mass.