JP5227718B2 - Rice seedling box coated granules - Google Patents

Description

  The present invention is not likely to cause phytotoxicity to young seedlings even if applied to rice seedling boxes, and increases the elution amount of the agrochemical active ingredient after transplanting rice seedlings into the rice seedling box, which shows excellent medicinal effects. It relates to the agent.

When using agricultural chemicals, from the viewpoint of labor saving and reduction of environmental burden, it is desired to reduce the usage amount or frequency of agricultural chemicals and to advance the application time. In response to these demands, in paddy rice cultivation, pesticides used in Honda are applied to seedling boxes at the time of sowing seeds, and rice seedlings are transplanted to Honda, and seedling box processing is performed to demonstrate the effects of the agricultural chemicals. When transplanting seedlings into Honda, a simultaneous transplanting process in which an attachment is attached to the rice planting machine and the agricultural chemicals are buried in the soil in the vicinity of the seedlings is performed. However, when normal granular pesticides are applied during this period when the seedlings are young, the pesticidal active ingredients or adjuvants are eluted or released into the water or soil in a short time, which is likely to cause phytotoxicity and is effective. Has a drawback such as a shorter duration.
In order to solve these problems, a preparation for the purpose of controlling the dissolution of an agrochemical active ingredient and prolonging the dissolution period or a production method thereof have been studied. For example, in order to enhance the sustained release, (1) a resin using a water-soluble polymer (polyacrylic acid) having gelling ability (Patent Document 1), (2) an adsorption carrier (acid clay, White carbon) (Patent Document 2), (3) Paraffin wax (Patent Document 3), (4) Alcohol wax (Patent Document 4), (5) Divalent or higher Using inorganic metal salts (Al, Cr, CO, Cu, Fe, Mg, Zn salts) (Patent Document 5), (6) using a water-soluble organic acid salt and an adsorptive carrier (Patent Document 6) ), (7) Those using carboxymethyl cellulose (Patent Document 7) are known. However, these methods are not always satisfactory because the obtained sustained release effect is small.

  In addition, for the purpose of long-term elution control, a preparation that covers the surface of particles containing an agrochemical active ingredient has been developed, but when a coating with low water resistance and weather resistance is used, sustained release As a result, the amount of coating necessary to obtain the required amount increases, and there is a problem economically and efficiently. On the other hand, a granule with a large amount of film to obtain sustained release and a granule with a film with too strong water resistance and weather resistance are effective even when it is time to show efficacy. A sufficient amount of elution was not obtained and the effect was often insufficient.

In order to solve the problem of insufficient effect that can occur in such coated granules, the function of starting the elution of pesticide components after a certain period of time, keeping the elution amount of pesticide active ingredients low for a certain period of time after treating the pesticide granules That is, an agrochemical granule having a timed elution control function has been proposed. As such agrochemical granules having a timed elution control function, for example, (1) coated agrochemical granules coated with a multilayer coating composed of a superabsorbent swellable substance layer and an olefin polymer layer, and an alkali substance layer, Coated pesticide granules coated with a multilayer coating such as a coated pesticide granule coated with a multilayer coating comprising an olefin resin and an alkaline water-soluble polymer (Patent Document 8, Patent Document 9, Patent Document 10), and (2) Coated agrochemical granules (Patent Document 11, Patent Document 12, Patent Document 13, Patent Document 14, Patent Document 15) in which an agrochemical granule containing a water-swellable substance is coated with a thermoplastic resin film are known. .
However, the coated agrochemical granule in which a film is formed with a multilayer film has the disadvantages that the number of production steps is larger than that in the case of coating with a single layer film, and the cost is increased.
In addition, with a coated agrochemical granule coated with a pesticide granule containing a swellable substance with a resin film, if there is even a pinhole or crack in the film, water will suddenly enter and the film will be destroyed. Agrochemical active ingredients are eluted rapidly. For this reason, a complete coating is required, and as a result, a great deal of labor is required for product management. In addition, stimuli-responsive granules using swelling substances exhibit the desired effect under certain conditions, but their functions do not work well if conditions such as temperature, water temperature, irrigation amount, and hardness change. There was a problem that elution control could not be controlled, resulting in phytotoxicity and insufficient efficacy.

JP 58-219103 A JP 58-8003 A JP 63-35504 A Japanese Patent Laid-Open No. 11-292706 Japanese Patent Publication No. 6-76282 JP-A-8-175903 JP 2001-233706 A JP-A-6-9303 JP-A-6-9304 JP-A-6-80514 JP-A-9-67206 Japanese Patent Laid-Open No. 9-97608 JP-A-9-268103 JP-A-11-322503 JP 2001-192305 A

  In view of the conventional problems as described above, the present invention provides a pesticide even if a granule is applied to a seedling box during the rice seedling period from seeding of rice seed pods to a seedling box until transplanting of seedlings to Honda. Rice that exhibits excellent medicinal effects by controlling the elution and release of active ingredients without causing any phytotoxicity and taking into the rice plant after the transplantation of Honda where the medicinal effects are required. It aims at providing the coated granule for nursery box application.

The present inventors diligently studied to solve the above problems. As a result, the granular material containing the pesticidal active ingredient is polymerizable unsaturated monomer excluding the polymerizable unsaturated monomer having a hydrolyzable silyl group and the polymerizable unsaturated monomer having the hydrolyzable silyl group. It has been found that when a copolymer with a monomer is coated with an aqueous resin composition obtained by dissolving or dispersing in a water, an excellent elution control effect can be obtained, and the present invention has been completed. That is, the gist of the present invention is as follows.
(1) a) Agrochemical active ingredient having a solubility in water (20 ° C.) of 0.01 g / L or more, b) lauryl sulfate, c) anionic surfactant excluding lauryl sulfate, d) orthophosphoric acid, e) An anhydrous mirabilite and f) a granular material containing a solid support, g) a polymerizable unsaturated monomer having a hydrolyzable silyl group, and a polymerizable unsaturated monomer having the hydrolyzable silyl group Coated granules for rice seedling box application, which is coated with an aqueous resin composition obtained by dissolving or dispersing a copolymer with a polymerizable unsaturated monomer in water,
(2) The polymerizable unsaturated monomer excluding the polymerizable unsaturated monomer having a hydrolyzable silyl group and the polymerizable unsaturated monomer having the hydrolyzable silyl group is an aqueous resin composition g). It is obtained by dissolving or dispersing a copolymer with one or more selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms as the body in water. A coated granule for rice seedling box application as described in (1) above,
(3) A water-based resin composition g) is 3-methacryloxypropyltrimethoxysilane as a polymerizable unsaturated monomer having a hydrolyzable silyl group and a polymerizable unsaturated monomer having the hydrolyzable silyl group. (1) to (1), wherein a copolymer of (meth) acrylic acid, methyl methacrylate and n-butyl acrylate is dissolved or dispersed in water as a polymerizable unsaturated monomer excluding the body. 2) coated granule for rice seedling box application according to any one of
(4) After applying the rice seedling box application coated granule according to any one of the above (1) to (3) to the seedling box, disintegrating the film of the granule by a transplanting operation from the rice seedling box to Honda By this, it is related with the dissolution control method of the coated granule characterized by increasing the elution amount of the agrochemical active ingredient to Honda.

When the rice seedling box application coated granule of the present invention is carried out, the following effects are brought about. That is,
(1) Even if an agrochemical active ingredient having a relatively high water solubility with a solubility in water (20 ° C.) of 0.01 g / L or more is used, no phytotoxicity occurs during the seedling raising period.
(2) In addition, since it is a so-called stimulus-responsive pesticide formulation whose elution amount is rapidly increased by external force generated by transplantation into Honda, after elution of the drug is increased without impairing the drug efficacy due to the loss of the drug during the seedling raising period, etc. Can exhibit excellent medicinal effects. Therefore, when applied to seedling boxes with high solubility in water, agrochemical active ingredients that could not be expected to have a long-term control effect due to runaway, or pesticides that could not be applied at high concentrations or seedling boxes due to chemical damage It is possible to treat the active ingredient in a seedling box. Therefore, according to the present invention, it is possible to save labor by expanding and expediting the application period and to stabilize the effect by increasing the dosage.
(3) Furthermore, the stimulus-responsive agrochemical formulation according to the present invention does not require troublesome operations such as a multi-layer coating process, and does not require the management of swelling properties when a swelling substance is used. The effect is also high.

Next, the rice seedling box coated granule and the method for controlling the release of the coated granule according to the present invention will be described in more detail.
a) About Agrochemical Active Ingredient The agrochemical active ingredient that can be used in the present invention has a solubility in water (20 ° C.) of 0.01 g / L or more and is usually used for rice cultivation. More than one species may be used in combination. Examples of such pesticidal active ingredients include the following.
Insecticides include organophosphorus, carbamate (eg benfuracarb), pyrethroid, nereistoxin (eg cartap), neonicotinoid (eg thiamethoxam), chloronicotinoid, phenylpyrazole and benzoyl Phenylurea insecticides, natural insecticides and the like can be mentioned.

Disinfectants include inorganic copper agents, organic copper agents, inorganic sulfur agents, organic sulfur agents, melanin biosynthesis inhibitors (such as pyroxylone), organophosphorus, benzimidazole, dicarboximide, acid amide, and triazole. Imidazole, methoxyacrylate, strobilurin, anilinopyridine, dithiolane, quinoxaline, aminopyrimidine, phenylpyrrole, triazine, cyanoacetamide, anilide, guanidine, and antibiotics Etc.
The specific agrochemical active ingredients contained in these are, for example, “Agricultural Chemicals Handbook 2005” (issued on October 11, 2005 by the Japan Plant Protection Association), “SHIBUYA INDEX 8th Edition” (December 1998) Issued on the 15th), “The Pesticide Manual Fourteenth Edition” (British Crop Protection Council).

The pesticidal active ingredient used in the present invention is not limited to the above, and pesticidal active ingredients other than those described above can be used if necessary.
The addition amount of these pesticidal active ingredients is usually 0.01 to 90 parts by weight, preferably 0.1 to 50 parts by weight, and more preferably 0.5 to 30 parts by weight in 100 parts by weight of the preparation.

b) About lauryl sulfate Examples of lauryl sulfate that can be used in the present invention include sodium lauryl sulfate, ammonium lauryl sulfate, and triethanolamine lauryl sulfate.
The amount of lauryl sulfate added to the preparation is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight per 100 parts by weight of the preparation.

c) Anionic Surfactant Excluding Lauryl Sulfate Anionic surfactant other than lauryl sulfate is not particularly limited, and examples thereof include sodium oleate, potassium oleate, sodium dodecylbenzenesulfonate, Sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, alkyl phosphate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl ether sodium sulfate, polyoxyethylene alkyl ether sodium ether, polyoxyethylene alkyl ether sodium triethanolamine, lignin Examples thereof include sodium sulfonate and calcium lignin sulfonate.
The addition amount of the anionic surfactant excluding lauryl sulfate in the preparation is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight in 100 parts by weight of the preparation.
However, the ratio of lauryl sulfate to anionic surfactant excluding lauryl sulfate is preferably 1: 0.2 to 1:10. If the ratio is out of these ranges, the coating is disrupted by the transplantation operation. In this case, the pesticidal active ingredient is not sufficiently diffused and is localized, which tends to cause insufficient medicinal effects and phytotoxicity.
Further, in the use of an anionic surfactant other than lauryl sulfate, there is no problem even if one or more of these are used in combination.

d) About orthophosphoric acid The orthophosphoric acid that can be used in the present invention is not particularly limited as long as it is commercially available such as a special grade of phosphoric acid (purity 85% or more, Kanto Chemical Co., Inc.). The amount of orthophosphoric acid added to the preparation is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight per 100 parts by weight of the preparation. Orthophosphoric acid has the effect of reducing phytotoxicity that may occur due to rapid uptake of agrochemical active ingredients and the like when the coating is disrupted by transplantation.

e) Anhydrous mirabilite An anhydrous mirabilite that can be used in the present invention is not particularly limited as long as it is commercially available as anhydrous sodium sulfate such as sodium sulfate special grade (purity 99% or more, Kanto Chemical Co., Ltd.). is not. However, the content of anhydrous sodium sulfate in the present invention is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight in 100 parts by weight of the preparation. Anhydrous mirabilite has an action of accelerating the disintegration of the particulate matter in the film when the film is disintegrated by the transplantation operation.

f) Solid Carrier Examples of the solid carrier that can be used in the present invention include a water-insoluble solid carrier and a water-soluble solid carrier.
Examples of water-insoluble carriers include clay, silica sand and pulverized products thereof, diatomaceous earth, bentonite, talc, dikelite, sericite, acid clay, activated clay, quartzite, pumice, zeolite, vermiculite, white carbon, shirasu balloon, etc. Examples include inorganic carriers such as pulverized glassy powder, and organic carriers such as cellulose, pulp, rice bran, wood flour, starch, and soybean flour.
Examples of the water-soluble carrier include ammonium sulfate, potassium chloride, calcium carbonate, urea, glucose, sucrose, fructose, and lactose. The solid carrier is not limited to these, and one or more of these may be used in combination.
The amount of the solid carrier added to the preparation is usually 0.5 to 99 parts by weight, preferably 5 to 95 parts by weight per 100 parts by weight of the preparation.

g) Aqueous Resin Composition The aqueous resin composition that can be used in the present invention comprises a polymerizable unsaturated monomer having a hydrolyzable silyl group and a polymerizable unsaturated monomer having the hydrolyzable silyl group. It can be obtained by dissolving or dispersing a copolymer obtained by copolymerizing the polymerizable unsaturated monomer to be removed in water. Examples of the polymerizable unsaturated monomer having a hydrolyzable silyl group include a polymerizable unsaturated monomer containing a silyl group represented by the following general formula (1).

［式中、Ｒ_１、Ｒ_２、Ｒ_３は同一又は異なって、ハロゲン原子、アルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アシルオキシ基、ヒドロキシル基、アミノ基、アミノオキシ基またはアルキルチオ基を示す。但し、Ｒ_１〜Ｒ_３のうち少なくとも１つは、ハロゲン原子、アルコキシ基またはヒドロキシル基を示す。Ｘは、ビニル基、エポキシ基（３−グリシドキシプロピル基、２−（３、４−エポキシシクロヘキシル）エチル基など）、スチリル基、アミノ基（３−アミノプロピル基、Ｎ−（２−アミノエチル）−３−アミノプロピル基、３−（Ｎ−フェニル）アミノプロピル基など）、ウレイド基、クロロプロピル基、アクリロキシ基、メタクリロキシ基（３−メタクリロキシプロピル基など）、メルカプト基（３−メルカプトプロピル基など）、スルフィド基、イソシアネート基（３−イソシアネート基など）およびこれらの基を含有するアルキル基を示す。］
加水分解性シリル基は、通常、Ｒ_１〜Ｒ_３のうち少なくとも1つがハロゲン原子、アルコキシ基またはヒドロキシル基を有する。

[Wherein R ₁ , R ₂ and R ₃ are the same or different and are each a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyloxy group, a hydroxyl group, an amino group, an aminooxy group or An alkylthio group is shown. However, at least one of R _{1 to} R ₃ represents a halogen atom, an alkoxy group, or a hydroxyl group. X is vinyl group, epoxy group (3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, etc.), styryl group, amino group (3-aminopropyl group, N- (2-amino) Ethyl) -3-aminopropyl group, 3- (N-phenyl) aminopropyl group, etc.), ureido group, chloropropyl group, acryloxy group, methacryloxy group (such as 3-methacryloxypropyl group), mercapto group (3-mercapto) A propyl group), a sulfide group, an isocyanate group (such as a 3-isocyanate group) and an alkyl group containing these groups. ]
In the hydrolyzable silyl group, at least one of R _{1 to} R ₃ usually has a halogen atom, an alkoxy group or a hydroxyl group.

Among the silyl groups represented by the formula (1), R _{1 to} R ₃ halogen atoms, alkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, acyloxy groups, hydroxyl groups, amino groups, aminooxy groups, alkylthios Groups include those shown below.
The halogen atom includes, for example, fluorine, chlorine, bromine and iodine, and is usually a chlorine atom.
Alkyl groups include, for example, C1-10 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl groups.
The aryl group includes, for example, a C6-10 aryl group such as a phenyl group, and the aralkyl group includes, for example, a C7-10 aralkyl group such as a benzyl group.
Alkoxy groups include, for example, C1-16 alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy groups. Preferred alkoxy groups are C1-4 alkoxy groups, particularly methoxy groups and ethoxy groups. Alkoxy groups also include, for example, alkoxy-alkoxy groups such as methoxyethoxy groups.
The aryloxy group includes, for example, a C6-10 aryloxy group such as a phenoxy group. Acyloxy groups include, for example, C2-6 acyloxy groups such as acetyloxy, propionyloxy, and butyryloxy groups.
The amino group includes, for example, an amino group which may have a substituent such as a dimethylamino group, and the aminooxy group may have a substituent such as a dimethylaminooxy group. Good aminooxy groups are included. Alkylthio groups include, for example, C1-6 alkylthio groups such as methylthio and ethylthio groups.
Examples of the polymerizable unsaturated monomer having a hydrolyzable silyl group include compounds represented by the following general formulas (2) to (13).

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリ−ル基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示す。Ｙ_１、Ｙ_２は同一または異なってフッ素、塩素、臭素又はヨウ素原子を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。）
このような化合物としては、例えば、ビニルトリクロロシラン、ビニルメチルジクロロシラン、ビニルジメチルクロロシラン、ビニルメチルフェニルクロロシラン、イソプロペニルトリクロロシラン、イソプロペニルメチルジクロロシランおよびイソプロペニルメチルフェニルクロロシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, and R ₅ represents a hydrogen atom or a methyl group. Y ₁ and Y ₂ are the same or different. A fluorine atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a, b, and c each represent an integer of a = 0-2, b = 0-3, c = 0-3, and a + b + c = 3.
Examples of such a compound include vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinylmethylphenylchlorosilane, isopropenyltrichlorosilane, isopropenylmethyldichlorosilane, and isopropenylmethylphenylchlorosilane.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリ−ル基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示す。Ｙ_１、Ｙ_２は同一または異なってフッ素、塩素、臭素又はヨウ素原子を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。ｎは１〜１２の整数を示す。）
このような化合物としては、例えば、アリルトリクロロシラン、アリルメチルジクロロシランおよびアリルジメチルクロロシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, and R ₅ represents a hydrogen atom or a methyl group. Y ₁ and Y ₂ are the same or different. Fluorine, chlorine, bromine or iodine atoms, a, b and c each represent an integer of a = 0 to 2, b = 0 to 3, c = 0 to 3, and a + b + c = 3, where n is 1 to 2. Indicates an integer of 12.)
Examples of such a compound include allyltrichlorosilane, allylmethyldichlorosilane, and allyldimethylchlorosilane.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリ−ル基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示す。Ｙ_１、Ｙ_２は同一または異なってフッ素、塩素、臭素又はヨウ素原子を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。ｎは１〜１２の整数を示す。）
このような化合物としては、例えば、２−（メタ）アクリロキシエチルトリクロロシラン、２−（メタ）アクリロキシプロピルトリクロロシラン、２−（メタ）アクリロキシエチルメチルジクロロシラン、３−（メタ）アクリロキシプロピルメチルジクロロシラン、２−（メタ）アクリロキシエチルジメチルクロロシラン、および３−（メタ）アクリロキシプロピルジメチルクロロシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, and R ₅ represents a hydrogen atom or a methyl group. Y ₁ and Y ₂ are the same or different. Fluorine, chlorine, bromine or iodine atoms, a, b and c each represent an integer of a = 0 to 2, b = 0 to 3, c = 0 to 3, and a + b + c = 3, where n is 1 to 2. Indicates an integer of 12.)
Examples of such compounds include 2- (meth) acryloxyethyltrichlorosilane, 2- (meth) acryloxypropyltrichlorosilane, 2- (meth) acryloxyethylmethyldichlorosilane, and 3- (meth) acryloxy. Examples thereof include propylmethyldichlorosilane, 2- (meth) acryloxyethyldimethylchlorosilane, and 3- (meth) acryloxypropyldimethylchlorosilane.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリ−ル基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。）
このような化合物としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリブトキシシラン、ビニルトリ（ヘキシルオキシ）シラン、ビニルトリ（オクチルオキシ）シラン、ビニルトリ（デシルオキシ）シラン、ビニルトリ（ドデシルオキシ）シラン、ビニルジメトキシメチルシラン、ビニルジエトキシメチルシラン、ビニルメトキシジメチルシラン、ビニルエトキシジメチルシラン、ビニルブトキシジメチルシラン、ビニルジフェニルエトキシシラン、イソプロペニルトリメトキシシラン、イソプロペニルトリエトキシシラン、イソプロペニルトリブトキシシラン、イソプロペニルトリ（ヘキシルオキシ）シラン、イソプロペニルトリ（オクチルオキシ）シラン、イソプロペニルトリ（オクチルオキシ）シラン、イソプロペニルトリ（デシルオキシ）シラン、イソプロペニルトリ（ドデシルオキシ）シラン、イソプロペニルジメトキシメチルシラン、イソプロペニルジエトキシメチルシラン、イソプロペニルメトキシジメチルシラン、イソプロペニルエトキシジメチルシラン、イソプロペニルブトキシジメチルシランおよびビニルトリス（２−メトキシエトキシ）シランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different. A C1-16 alkoxy group, a, b and c are each an integer of a = 0-2, b = 0-3, c = 0-3, and a + b + c = 3.
Examples of such compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltri (hexyloxy) silane, vinyltri (octyloxy) silane, vinyltri (decyloxy) silane, and vinyltri (dodecyloxy) silane. , Vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinylmethoxydimethylsilane, vinylethoxydimethylsilane, vinylbutoxydimethylsilane, vinyldiphenylethoxysilane, isopropenyltrimethoxysilane, isopropenyltriethoxysilane, isopropenyltributoxysilane, Isopropenyltri (hexyloxy) silane, isopropenyltri (octyloxy) silane, isopropenyltri (octyloxy) sila , Isopropenyltri (decyloxy) silane, isopropenyltri (dodecyloxy) silane, isopropenyldimethoxymethylsilane, isopropenyldiethoxymethylsilane, isopropenylmethoxydimethylsilane, isopropenylethoxydimethylsilane, isopropenylbutoxydimethylsilane and vinyltris (2-methoxyethoxy) silane and the like.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリ−ル基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示し、Ｒ_８はＣ１−１２アルキレン基またはフェニレン基を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。）
このような化合物としては、例えば、アリルトリメトキシシラン、ビニルデシルトリメトシキシラン、ビニルオクチルトリメトキシシラン、ビニルフェニルトリメトキシシラン、ビニルフェニルジメトキシメチルシラン、ビニルフェニルメトキシジメチルシラン、イソプロペニルフェニルトリメトキシシラン、イソプロペニルフェニルジメトキシメチルシランおよびイソプロペニルフェニルメトキシジメチルシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different. C1-16 an alkoxy group, _{R 8} is .a showing a C1-12 alkylene group or a phenylene group, b, c are each a = 0~2, b = 0~3, an integer of c = 0 to 3 A + b + c = 3.)
Examples of such compounds include allyltrimethoxysilane, vinyldecyltrimethoxysilane, vinyloctyltrimethoxysilane, vinylphenyltrimethoxysilane, vinylphenyldimethoxymethylsilane, vinylphenylmethoxydimethylsilane, and isopropenylphenyltrimethoxysilane. , Isopropenylphenyldimethoxymethylsilane, isopropenylphenylmethoxydimethylsilane, and the like.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリ−ル基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。ｎは１〜１２の整数を示す。）
このような化合物としては、例えば、２−（メタ）アクリロキシエチルトリメトキシシラン、２−（メタ）アクリロキシエチルトリエトキシシラン、３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルトリエトキシシラン、３−（メタ）アクリロキシプロピルメチルジメトキシシラン、３−（メタ）アクリロキシプロピルジエトキシメチルシランおよび３−（メタ）アクリロキシプロピルトリス（２−メトキシエトキシ）シランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different. C1-16 represents an alkoxy group, a, b and c each represent an integer of a = 0 to 2, b = 0 to 3, c = 0 to 3, and a + b + c = 3, n is an integer of 1 to 12 Is shown.)
Examples of such a compound include 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and 3- (meth). Acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyldiethoxymethylsilane, 3- (meth) acryloxypropyltris (2-methoxyethoxy) silane, etc. Can be mentioned.

（式中、Ｒ_４はＣ１−１０ アルキル基、Ｃ６−１０アリール基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。ｎは１〜１２の整数を示す。）
このような化合物としては、例えば、３−（アリルオキシカルボニル−ｏ−フェニレン−カルボキシ）プロピルトリメトキシシラン、３−（アリルオキシカルボニル−ｏ−フェニレン−カルボキシ）プロピルジメトキシメチルシラン、３−（アリルオキシカルボニル−ｏ−フェニレン−カルボキシ）プロピルメトキシジメチルシラン、３−（イソプロペニルメチレンオキシカルボニル−ｏ−フェニレン−カルボキシ）プロピルトリメトキシシラン、３−（イソプロペニルメチレンオキシカルボニル−ｏ−フェニレン−カルボキシ）プロピルジメトキシメチルシランおよび３−（イソプロペニルメチレンオキシカルボニル−ｏ−フェニレン−カルボキシ）プロピルメトキシジメチルシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different, and 16 represents an alkoxy group, a, b and c each represent an integer of a = 0-2, b = 0-3, c = 0-3, and a + b + c = 3, n represents an integer of 1-12. .)
Examples of such compounds include 3- (allyloxycarbonyl-o-phenylene-carboxy) propyltrimethoxysilane, 3- (allyloxycarbonyl-o-phenylene-carboxy) propyldimethoxymethylsilane, 3- (allyloxy). Carbonyl-o-phenylene-carboxy) propylmethoxydimethylsilane, 3- (isopropenylmethyleneoxycarbonyl-o-phenylene-carboxy) propyltrimethoxysilane, 3- (isopropenylmethyleneoxycarbonyl-o-phenylene-carboxy) propyldimethoxy Examples include methylsilane and 3- (isopropenylmethyleneoxycarbonyl-o-phenylene-carboxy) propylmethoxydimethylsilane.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリール基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示し、Ｒ_９はフェニレン基またはフェニルメチル基を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。）
このような化合物としては、例えば、３−（ビニルフェニルアミノ）プロピルトリメトキシシラン、３−（ビニルフェニルアミノ）プロピルトリエトキシシラン、３−（ビニルベンジルアミノ）プロピルトリメトキシシランおよび３−（ビニルベンジルアミノ）プロピルトリエトキシシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different, and 16 represents an alkoxy group, R ₉ represents a phenylene group or a phenylmethyl group, a, b, and c each represent an integer of a = 0-2, b = 0-3, c = 0-3, and a + b + c = 3 Will be.)
Examples of such compounds include 3- (vinylphenylamino) propyltrimethoxysilane, 3- (vinylphenylamino) propyltriethoxysilane, 3- (vinylbenzylamino) propyltrimethoxysilane and 3- (vinylbenzyl). And amino) propyltriethoxysilane.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリール基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。）
このような化合物としては、例えば、３−［ビニルフェニレンメチレン（エチレンジアミノ）]プロピルトリメトキシシランおよび３−［イソプロペニルフェニレンメチレン（エチレンジアミノ）]プロピルトリメトキシシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different, and 16 represents an alkoxy group, a, b, and c are integers of a = 0 to 2, b = 0 to 3, and c = 0 to 3, respectively, and a + b + c = 3.
Examples of such a compound include 3- [vinylphenylenemethylene (ethylenediamino)] propyltrimethoxysilane and 3- [isopropenylphenylenemethylene (ethylenediamino)] propyltrimethoxysilane.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリール基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。ｎは１〜１２の整数を示す。）
このような化合物としては、例えば、２−（ビニルオキシ）エチルトリメトキシシラン、３−（ビニルオキシ）プロピルトリメトキシシラン、４−（ビニルオキシ）ブチルトリエトキシシランおよび２−（イソプロペニルオキシ）エチルトリメトキシシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different, and 16 represents an alkoxy group, a, b and c each represent an integer of a = 0-2, b = 0-3, c = 0-3, and a + b + c = 3, n represents an integer of 1-12. .)
Examples of such compounds include 2- (vinyloxy) ethyltrimethoxysilane, 3- (vinyloxy) propyltrimethoxysilane, 4- (vinyloxy) butyltriethoxysilane, and 2- (isopropenyloxy) ethyltrimethoxysilane. Etc.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリール基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示し、Ｒ_１０は−ＣＨ_２Ｏ−又は−ＣＨ_２ＯＣＯ−を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。ｎは１〜１２の整数を示す。）
このような化合物としては、例えば、３−（アリルオキシ）プロピルトリメトキシシラン、１０−（アリルオキシカルボニル）デシルトリメトキシシラン、３−（イソプロペニルメチレンオキシ）プロピルトリメトキシシランおよび１０−（イソプロペニルメチレンオキシカルボニル）デシルトリメトキシシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different, and 16 represents an alkoxy group, R ₁₀ represents —CH ₂ O— or —CH ₂ OCO—, a, b and c are each an integer of a = 0 to 2, b = 0 to 3 and c = 0 to 3; A + b + c = 3, where n is an integer from 1 to 12.)
Examples of such compounds include 3- (allyloxy) propyltrimethoxysilane, 10- (allyloxycarbonyl) decyltrimethoxysilane, 3- (isopropenylmethyleneoxy) propyltrimethoxysilane and 10- (isopropenylmethylene). And oxycarbonyl) decyltrimethoxysilane.

（式中、Ｒ_４はＣ１−１０アルキル基、Ｃ６−１０アリール基又はＣ７−１０アラルキル基を示し、Ｒ_５は水素原子又はメチル基を示し、Ｒ_６、Ｒ_７は同一または異なってＣ１−１６アルコキシ基を示す。ａ、ｂ、ｃはそれぞれａ＝０〜２、ｂ＝０〜３、ｃ＝０〜３の整数を示し、ａ＋ｂ＋ｃ＝３となる。ｎは１〜１２の整数を示し、ｍは１〜１２の整数を示す。）
このような化合物としては、例えば、３−［（メタ）アクリロキシエチレンオキシ］プロピルトリメトキシシランおよび３−［（メタ）アクリロキシエチレンオキシ］プロピルジメトキシメチルシランなどが挙げられる。

(Wherein R ₄ represents a C 1-10 alkyl group, a C 6-10 aryl group or a C 7-10 aralkyl group, R ₅ represents a hydrogen atom or a methyl group, and R ₆ and R ₇ are the same or different, and 16 represents an alkoxy group, a, b and c each represent an integer of a = 0 to 2, b = 0 to 3, c = 0 to 3, and a + b + c = 3, n represents an integer of 1 to 12. M represents an integer of 1 to 12.)
Examples of such a compound include 3-[(meth) acryloxyethyleneoxy] propyltrimethoxysilane and 3-[(meth) acryloxyethyleneoxy] propyldimethoxymethylsilane.

  The polymerizable unsaturated monomer having a hydrolyzable silyl group may be a divinyl group-containing compound such as divinyldimethoxysilane, divinyldiethoxysilane, and divinyldi (β-methoxyethoxy) silane. The polymerizable unsaturated monomer having a hydrolyzable silyl group can be used alone or in combination of two or more. Preferable silyl group-containing monomers include, for example, vinyl monomers containing alkoxysilyl groups from the viewpoints of handleability, economy, and suppression of side reactions.

  Examples of the polymerizable unsaturated monomer excluding the polymerizable unsaturated monomer having a hydrolyzable silyl group include (meth) acrylic monomers, aromatic vinyls, unsaturated carboxylic acids, vinyl esters, Halogen-containing vinyls, vinyl ethers (eg, vinyl ethyl ether), vinyl ketones (eg, methyl vinyl ketone), vinyl heterocycles (eg, N-vinyl compounds such as N-vinyl pyrrolidone, N-vinyl imidazole), Vinyl pyridine, etc.), olefinic monomers (eg, ethylene, propylene, etc.), allyl compounds (eg, allyl esters such as allyl acetate, etc.) and the like. These polymerizable unsaturated monomers excluding the polymerizable unsaturated monomer having a hydrolyzable silyl group can be used alone or in combination of two or more.

Examples of the (meth) acrylic monomer that is a polymerizable unsaturated monomer excluding a polymerizable unsaturated monomer having a hydrolyzable silyl group include (meth) acrylate, (meth) acrylamides, ( (Meth) acrylonitrile and the like are included.
Examples of (meth) acrylate include alkyl (meth) acrylate [for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, C1-18 alkyl (meth) acrylate such as lauryl (meth) acrylate], cyclo Alkyl (meth) acrylate [for example, cyclohexyl (meth) acrylate, etc.], aryl (meth) acrylate [[for example, phenyl (meth) acrylate, etc.], aralkyl (meth) acrylate [for example, Benzyl (meth) acrylate], hydroxyalkyl (meth) acrylate [for example, 2-hydroxyethyl, 2-hydroxypropyl (hydroxy-C2-4 alkyl (meth) acrylate such as (meth) acrylate)], glycidyl (meth) Acrylates, dialkylamino-alkyl (meth) acrylates [e.g., di-C1-4 alkylamino-C2-4 alkyl (meta) such as 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, etc. ) Acrylate, etc.].

  Examples of (meth) acrylamides include (meth) acrylamide, hydroxyalkyl (meth) acrylamide [for example, N-hydroxy-C1-4 alkyl (meth) acrylamide such as N-methylol (meth) acrylamide], alkoxyalkyl, and the like. (Meth) acrylamide [for example, N-C1-4 alkoxy-C1-4 alkyl (meth) acrylamide such as N-methoxymethyl (meth) acrylamide], diacetone (meth) acrylamide and the like are included.

Preferable (meth) acrylic monomers include, for example, (meth) acrylate [for example, C1-18 alkyl (meth) acrylate, hydroxy-C2-4 alkyl (meth) acrylate, glycidyl (meth) acrylate, C1-4 Dialkylamino-C2-4 alkyl (meth) acrylate and the like], (meth) acrylamides and the like.
More preferable (meth) acrylic monomers include C2-10 alkyl acrylate (eg, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), C 1-6 alkyl methacrylate (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc.). , Hydroxy-C2-3 alkyl (meth) acrylate, glycidyl (meth) acrylate, C1-3 dialkylamino-C2-3 alkyl (meth) acrylate, and the like.

Examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids [for example, ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid], unsaturated polycarboxylic acids [for example, maleic acid, fumaric acid, etc. Acids, ethylenically unsaturated polyvalent carboxylic acids such as itaconic acid, or acid anhydrides thereof (such as maleic anhydride) or esters (for example, monoalkyl esters of divalent carboxylic acids such as monomethyl maleate and monobutyl maleate) Etc.] are included.
Preferred unsaturated carboxylic acids include, for example, monocarboxylic acids such as (meth) acrylic acid, polyvalent carboxylic acids such as maleic acid, or acid anhydrides or esters thereof.
Aromatic vinyls include, for example, styrene, α-methylstyrene, vinyl toluene, and styrene is often used.
Vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl versatate (VeoVa, etc.) and the like.
Examples of the halogen-containing vinyls include vinyl chloride and vinylidene chloride .

As the polymerizable unsaturated monomer excluding the polymerizable unsaturated monomer having a hydrolyzable silyl group, usually a hard monomer [for example, a glass transition temperature of 80 to 80 of methyl (meth) acrylate, styrene, etc. Monomer component forming a homopolymer of about 120 ° C. (especially 90 to 105 ° C.)] and soft monomer [for example, glass transition temperature of acrylic acid C2-10 alkyl ester etc. −85 to 10 ° C. (especially −85 It is often used in combination with a monomer component that forms a homopolymer of about -20 ° C.
On the other hand, as a polymerizable unsaturated monomer excluding a polymerizable unsaturated monomer having a hydrolyzable silyl group, a monomer component having an ionic functional group such as a carboxyl group or an amino group [for example, dialkylamino- When an alkyl (meth) acrylate or the like] is used, an aqueous resin composition can be obtained without using an emulsifier.
Thus, when using a hard monomer, a soft monomer, and an ionic group-containing monomer as a polymerizable unsaturated monomer excluding a polymerizable unsaturated monomer having a hydrolyzable silyl group, the blending ratio is particularly limited. Although not, for example, 10 to 90% by weight of hard monomer (for example, 15 to 85% by weight, preferably 20 to 80% by weight, more preferably 25 to 75% by weight, particularly 30 to 70% by weight), soft monomer 10 to 90% by weight (for example, 15 to 85% by weight, preferably 20 to 80% by weight, more preferably 25 to 75% by weight, especially 30 to 70% by weight) and ionic group-containing monomers 0 to 80% by weight (for example, 0 to 70% by weight, preferably 0 to 60% by weight, more preferably 0 to 50% by weight, especially 0 to 40% by weight).

The aqueous resin composition used in the present invention is polymerizable unsaturated monomer excluding the polymerizable unsaturated monomer having a hydrolyzable silyl group and the polymerizable unsaturated monomer having a hydrolyzable silyl group as described above. A copolymer obtained by copolymerizing a monomer is used. When copolymerizing each of these polymerizable unsaturated monomers, the proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the total polymerizable unsaturated monomer is 0.5 wt% to 50 wt%. %, In particular 0.5% to 20.0% by weight. If the ratio of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the total polymerizable unsaturated monomer is less than the above range, the water resistance, solvent resistance and adhesion of the cured coating film deteriorate. May cause problems. On the other hand, if this range exceeds the above range, there may be a problem that the polymerization stability and storage stability of the aqueous resin composition are lowered.
In the present invention, the coating amount (parts by weight) of the aqueous resin composition is preferably 0.5 to 40 parts by weight, and more preferably 1.0 to 20 parts by weight. The width of the coating amount is appropriately determined in consideration of the water solubility of the pesticidal active ingredient to be used and the degree of chemical damage to rice during the seedling raising period.
Further, the ratio of the content (parts by weight) of the aqueous resin composition and anhydrous sodium sulfate is preferably 1: 0.01 to 1: 0.5.

In carrying out the present invention, a surfactant other than an anionic surfactant, a stabilizer for an agrochemical active ingredient, a binder, an organic solvent, an auxiliary agent, and the like can be added as necessary.
Examples of surfactants other than the anionic surfactant that can be used in the present invention include nonionic surfactants, cationic surfactants, and double-sided surfactants. For example, nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene stynyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkylate, polyoxyethylene phenyl ether polymer , Polyoxyethylene alkylene aryl phenyl ether, polyoxyethylene alkylene glycol, polyoxyethylene polyoxypropylene block polymer and the like. Examples of the cationic surfactant include alkyl trimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, and alkyl pyridinium salts. Examples of the double-sided surfactant include dialkyldiaminoethylbetaine and alkyldimethylbenzylbetaine. However, the surfactants other than the anionic surfactant that can be used in the present invention are not limited to these examples, and there is no problem even if one or more types are used in combination.

  Examples of binders that can be used in the present invention include natural, semi-synthetic and synthetic polymers. Examples of natural products include starch, pullulan, sodium alginate, dextran, mannan, pectin, tragacanth gum, curdlan, sorbitol, guar gum, roast cast bean gum, gum arabic, xanthan gum, gelatin, casein and the like. Examples of the semi-synthetic system include dextrin, soluble starch, oxidized starch, pregelatinized starch, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like. Examples of the synthetic system include polyvinyl alcohol, polyacrylamide, sodium polyacrylate, polyvinyl pyrrolidone, polyethylene glycol, ethylene-acrylic acid copolymer, maleic anhydride copolymer, and the like. The binder in this invention is not restricted to these illustrations, and even if it uses 1 type or 2 types or more together, there is no problem.

  Examples of organic solvents that can be used in the present invention include Solvesso 150 (trade name, manufactured by Exxon Chemical Co., Ltd.), Hysol E, Hysol F (trade name, manufactured by Nippon Oil Corporation), Cactus Solvent P100, Cactus Solvent P150, and Cactus. Alkylbenzene solvents such as Solvent P187, Cactus Solvent P200 (trade name manufactured by Nippon Mining Co., Ltd.), Alkene 56N, Alkene 60NH, Alkene L (trade name manufactured by Nippon Petrochemical Co., Ltd.), Cactus Solvent 220, Cactus Solvent P240 ( Product name manufactured by Nippon Mining Co., Ltd.), Solvesso 200 (product name manufactured by Exxon Chemical Co., Ltd.), purified methylnaphthalene (manufactured by Sumikin Kako Co., Ltd.), diisopropyl naphthalene (product name "KMC-113", manufactured by Kureha Chemical Industry Co., Ltd.) A) Kirunaphthalene solvent, isoparaffin (trade name “Isosol 300” manufactured by Nippon Petrochemical Co., Ltd.), paraffinic solvents such as liquid paraffin and n-paraffin, naphthesol (manufactured by Nippon Petrochemical Co., Ltd.), Exsol (manufactured by Exxon Chemical Co., Ltd.) Naphthenic solvents, such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl Alcohol solvents such as acetate and 3-methyl-1,3-butanediol, alkylpyrrolidone solvents such as N-methylpyrrolidone, n-octylpyrrolidone and n-dodecylpyrrolidone, DuPont DBE (DuPont strain) Company name), ditridecyl phthalate, diisodecyl adipate, didecyl phthalate, didecyl phthalate, dialkyl phthalate (C10 to C12), trimet and tri-2-ethylhexyl acid, trinormal alkyl trimellitic acid (C8 C10) Polybasic acid ester solvents such as tri-2-ethylhexyl trimellitic acid, trialkyl trimellitic acid (C9), triisodecyl trimellitic acid, dioleyl adipate, isobutyl oleate, methyl palm fatty acid, methyl laurate, palm Fatty acid esters such as fatty acid methyl, isopropyl palmitate, isotridecyl stearate, 2-ethylhexyl stearate, lauryl oleate, decyl oleate, aromatic hydrocarbon solvents based on diallyl ethane, triaryl Solvents such as aromatic hydrocarbon solvents based on dietane, and vegetable oils such as rice bran oil fatty acid methyl ester, rapeseed oil, soybean oil, castor oil, cottonseed oil, and corn oil can be mentioned. It is not limited, and there is no problem even if one of these is used or two or more are used in combination.

  Adjuvants that can be used in the present invention include stabilizers such as antioxidants, UV inhibitors, and crystal precipitation inhibitors, sorbic acid, potassium sorbate, p-chloro-m-xylenol, p-butyl oxyoxybenzoate, and the like. And anti-corrosion agent, and pH adjusters such as citric acid, calcium carbonate and magnesium carbonate.

The coated granule for rice seedling box of the present invention comprises an agrochemical active ingredient having a solubility in water (20 ° C.) of 0.01 g / L or more, lauryl sulfate, anionic surfactant excluding lauryl sulfate, orthophosphoric acid It is obtained by granulating a granular material containing anhydrous mirabilite and a solid carrier and coating the granular material with a resin. The method may be a method usually used in the formulation of agricultural chemicals.
In obtaining the coated granules for rice seedling box of the present invention, the granules before coating with the resin may be obtained by the granulation method of the core particles, such as extrusion granulation method, rolling Examples thereof include a granulation method, a rolling fluidized granulation method, a fluidized bed granulation method, a compression granulation method, a stirring and mixing granulation method, a coating granulation method, and a tableting method. When obtaining a cylindrical granulated product, an extrusion granulation method is preferable, and when obtaining a spherical granulated product, a rolling granulation method and a stirring and mixing granulation method are preferred.

In the extrusion granulation method, first, an agrochemical active ingredient, lauryl sulfate, an anionic surfactant excluding lauryl sulfate, orthophosphoric acid, anhydrous sodium sulfate and a solid carrier, and if necessary, a binder and other interfaces. Add the activator, organic solvent and auxiliary agent, and mix uniformly using a juice mixer, hammer mill, Redige mixer or ribbon mixer. Water and / or an aqueous solution or dispersion of a binder is added to this mixture and kneaded using a double-arm kneader or a ribbon mixer.
Next, this kneaded product is granulated using an extrusion granulator such as a basket type granulator or a screw type granulator. The extrusion hole diameter (screen diameter) during granulation is usually in the range of 0.3 to 5 mm, preferably 0.5 to 2 mm. After the obtained granulated product is sized using a Malmerizer or the like, the granulated product used in the present invention is obtained by drying using a fluidized dryer or a bed-type dryer and then sieving.

In the stirring and mixing granulation method, first of all, an agrochemical active ingredient, lauryl sulfate, anionic surfactant excluding lauryl sulfate, orthophosphoric acid, anhydrous sodium sulfate and solid carrier, binder as required, other surface activity Add agents, solvents, and adjuvants and mix evenly using a juice mixer, hammer mill, Redige mixer or ribbon mixer. The mixture is stirred and fluidized by rotating the stirring blade in the granulation vessel of the stirring and mixing granulator. The aqueous mixture or aqueous dispersion of water and / or a binder is dropped or sprayed onto the rolling mixture, and the particles are grown to an appropriate size and granulated. The granulated material used in the present invention is obtained by taking out this granulated material, drying it using a fluidized bed dryer or a bed type dryer, and then sieving it.
The granular material obtained by the rolling granulation method or the rolling fluidized bed granulation method is spherical, and the diameter or maximum diameter of the granular material used in the present invention is usually 0.1 to 20 mm, preferably 0.5. Those in the range of ˜15 mm are preferred.

  In the tableting method, a predetermined amount of the granular material obtained by the extrusion granulation method may be subjected to compression compression using a tableting machine as it is, and may be shaped and granulated. Agrochemical active ingredients and lauryl sulfate, lauryl sulfate Add the anionic surfactant other than salt, orthophosphoric acid, anhydrous sodium sulfate and solid carrier, and if necessary, the binder, other surfactants, solvents and adjuvants, and mix the powder directly in the tablet press. It is good also as a granulation by shaping and granulating by pressure-compression. The form of the granular material in this case is determined by the shape of the mortar and punch of the tableting machine, and they are obtained in various shapes and sizes such as a circular plate shape, an oval plate shape, a square plate shape, and an oval shape. Any of them can be used in the present invention, but those having a diameter or a maximum diameter of usually 0.1 to 30 mm, preferably 0.5 to 20 mm are preferable.

  Next, if the granular material obtained by said method is coat | covered with an aqueous resin composition, the rice seedling box application | coating granule of this invention can be obtained. Such a coating method is not particularly limited. For example, the aqueous resin composition is continuously or intermittently applied to a fluidized bed under a heated air stream, or to a granular material that is rolling on a rotating pan or rotating drum. By spraying or dripping onto a rice cake and drying, a coated granule for rice seedling box application in which the granular material is coated with a resin is obtained.

  The applied amount of the rice seedling box application coated granule of the present invention when applied to the seedling box is 10 to 200 g, preferably 25 to 100 g, per seedling box (usually 0.18 square meters).

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following examples and comparative examples, “parts” means “parts by weight”. The aqueous resin compositions A to E described in the following examples and comparative examples are applied mutatis mutandis in Tables 1 to 4.
[Example 1]
<Preparation of core particles>
Kasugamycin (antibiotic antibiotic) 2.0 parts, sodium lauryl sulfate 2.0 parts, calcium lignin sulfonate 5.0 parts, orthophosphoric acid 0.5 parts, anhydrous sodium sulfate 0.5 parts and clay 83.0 parts The total amount was 93.0 parts, and the mixture was mixed uniformly with a hammer mill (Fuji Powdal Co., Ltd.). 11.0 parts of water was added to this mixture and kneaded with a double arm kneader (manufactured by Fuji Powder Co., Ltd.).
Next, this hydro-kneaded product was granulated by an extrusion granulator equipped with a basket type screen having a pore diameter of 1.0 mm. The obtained granulated material was dried with a fluidized bed dryer (Fuji Paudal Co., Ltd.) and then sieved with a sieve having a diameter of 1.7 mm to 850 μm to obtain a granular material.
<Preparation of aqueous resin composition>
Into a 2 liter reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, add 219 parts of isopropyl alcohol and add 0.62 part of azobisisobutyronitrile as a catalyst while stirring. Dissolved and warmed to 80 degrees Celsius. As a polymerizable unsaturated monomer having a hydrolyzable silyl group, 3-methacryloxypropyltrimethoxysilane (trade name KMB-503, manufactured by Shin-Etsu Chemical Co., Ltd.) is 4.94 parts, and methyl methacrylate is 135.7. A copolymer component consisting of 98.7 parts of n-butyl acrylate and 7.39 parts of acrylic acid was mixed and dropped into the reaction vessel using a dropping funnel over about 4 hours. After completion of the dropping, 1.25 parts of azobisisobutyronitrile as an additional catalyst was dissolved in 25 parts of isopropyl alcohol and dropped into the reaction vessel, and the reaction was maintained for 2 hours. After completion of the polymerization, 6.95 parts of 25% aqueous ammonia was added into the reaction vessel while stirring, and 705 parts of water was dropped into the reaction vessel over about 2 hours to emulsify. After emulsification, isopropyl alcohol was evaporated using a rotary evaporator to obtain an aqueous resin composition A. The solid content of the aqueous resin composition A was 35% by weight. Moreover, the ratio of the polymerizable unsaturated monomer which has a hydrolysable silyl group in the copolymerization component of this aqueous resin composition A is 2.0 weight%.
<Coating of core resin with water-based resin composition>
93.0 parts of the granular material is put into a rolling fluidized bed coating apparatus “Multiplex MP-01” (manufactured by POWREC Co., Ltd.), and 20.0 parts of the aqueous resin composition A and 40.0 parts of water are mixed together. The liquid was sprayed onto the granules.
After the coated granular material is taken out from the coating apparatus, it is dried by a fluidized bed dryer, and rice in which 93.0 parts of the granular material is coated with 7.0 parts of the solid content of the aqueous resin composition A is obtained. A coated granule for nursery box application was obtained.

[Example 2] At the time of preparation of the aqueous resin composition of Example 1, 1.25 parts of addition amount of 3-methacryloxypropyltrimethoxysilane (trade name KMB-503 manufactured by Shin-Etsu Chemical Co., Ltd.), Except for the addition amount of methyl methacrylate being 142.59 parts, the aqueous resin composition B (solid content 35% by weight, hydrolyzable silyl group in the copolymerization component was determined in accordance with the aqueous resin composition method of Example 1). The ratio of the polymerizable unsaturated monomer having was 0.5 wt%). Using this aqueous resin composition B, a granular material was coated in the same manner as in Example 1 to obtain a rice seedling box coated granule coated with 7.0 parts of the solid content of the aqueous resin composition B.
[Example 3] At the time of preparation of the aqueous resin composition of Example 1, 55.7 parts of 3-methacryloxypropyltrimethoxysilane (trade name KMB-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added. Except for the addition amount of methyl methacrylate being 116.56 parts, the aqueous resin composition C (solid content 35% by weight, hydrolyzable silyl group occupying in the copolymerization component was determined in accordance with the aqueous resin composition method of Example 1. The ratio of the polymerizable unsaturated monomer having was 20.0% by weight). Using this water-based resin composition C, a granular material was coated in the same manner as in Example 1 to obtain a rice seedling box coated granule coated with 7.0 parts of the solid content of the water-based resin composition C.

[Example 4] When preparing the aqueous resin composition of Example 1, 4.04 parts of 3-methacryloxypropyltrimethoxysilane (trade name KMB-503, manufactured by Shin-Etsu Chemical Co., Ltd.) as a copolymerization component , 111.1 parts of methyl methacrylate, 80.8 parts of n-butyl acrylate, and 6.06 parts of acrylic acid were mixed to obtain 4.67 parts of sodium alkylallylsulfosuccinate (trade name Eleminol JS-2 manufactured by Sanyo Chemical Co., Ltd.). Was pre-emulsified by dropping it into an aqueous solution dissolved in 58.47 parts of deionized water. On the other hand, 157 parts of deionized water was placed in a 2 liter reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, nitrogen inlet tube and thermometer, and stirred with sodium alkylallylsulfosuccinate (manufactured by Sanyo Chemical Co., Ltd.). The product name Eleminol JS-2) 2.34 parts was added and dissolved, and 0.77 parts ammonium persulfate was further added and dissolved. After heating the reaction vessel to 60 degrees Celsius, the pre-emulsion and 53 parts of a 0.68 wt% sodium thiosulfate aqueous solution were dropped into the reaction vessel using a dropping funnel over about 4 hours. After completion of the dropwise addition, the reaction was further maintained for 2 hours, and the water-based resin composition D (solid content 40% by weight, the proportion of the polymerizable unsaturated monomer having a hydrolyzable silyl group in the copolymerization component was 2.0). % By weight). Using this water-based resin composition D, a granular material was coated in the same manner as in Example 1 to obtain a rice seedling box coated granule coated with 7.0 parts of the solid content of the water-based resin composition D.

[Example 5] A rice seedling box was prepared according to the preparation method of Example 1 except that 0.5 parts of polyvinyl alcohol and 82.5 parts of clay were added as binders during the preparation of the granular material of Example 1. An applied coated granule was obtained.
[Examples 6 and 7] Except that the solid carrier of Example 1 was zeolite and lactose, it was prepared according to the preparation method of Example 1 to obtain rice seedling box coated granules.
[Examples 8 and 9] Example 1 except that the amount of orthophosphoric acid added in Example 1 was 0.1 or 1.0 part and the amount of clay added was 83.4 parts or 82.5 parts, respectively. Thus, a coated granule for rice seedling box application was obtained.
[Example 10] The amount of orthophosphoric acid added in Example 1 was 2.0 parts, the amount of anhydrous sodium sulfate added was 2.0 parts, and the amount of clay added was 80.0 parts. Prepared according to the preparation method to obtain coated granules for rice seedling box application.
[Example 11] A rice seedling box was prepared according to the preparation method of Example 1 except that the amount of anhydrous sodium sulfate of Example 1 was 3.0 parts and the amount of clay was 80.5 parts. An applied coated granule was obtained.

[Example 12] Rice seedlings were prepared according to the preparation method of Example 1 except that the addition amount of sodium lauryl sulfate in Example 1 was 0.5 part and the addition amount of clay was 84.5 parts. Box-coated granules were obtained.
[Example 13] Preparation was performed according to the preparation method of Example 1, except that the amount of calcium lignin sulfonate in Example 1 was 0.5 part and the amount of clay was 87.5 parts. A coated granule for nursery box application was obtained.
[Example 14] The procedure was carried out except that the addition amount of sodium lauryl sulfate in Example 1 was 5.0 parts, the addition amount of calcium lignin sulfonate was 3.0 parts, and the addition amount of clay was 82.0 parts. Prepared according to the preparation method of Example 1 to obtain rice seedling box coated granules.
[Example 15] A rice seedling box application was prepared according to the preparation method of Example 1 except that 5.0 parts of anionic surfactant excluding lauryl sulfate of Example 1 was sodium dodecylbenzenesulfonate. Coated granules were obtained.
[Example 16] Rice seedlings were prepared according to the preparation method of Example 1 except that the anionic surfactant excluding lauryl sulfate of Example 1 was changed to 5.0 parts of naphthalenesulfonic acid formalin condensate. Box-coated granules were obtained.
[Example 17] Except that the sodium lauryl sulfate of Example 1 was changed to 2.0 parts of ammonium lauryl sulfate, it was prepared according to the preparation method of Example 1 to obtain rice seedling box coated granules.

[Example 18] According to the preparation method of Example 1, except that 12.0 parts of the pesticide active ingredient of Example 1 was 12.0 parts of pyrokilone (melanin biosynthesis inhibitor) and 73.0 parts of clay was added. Prepared and obtained rice seedling box coated granules.
[Example 19] 12.0 parts of pyroxylone as an agrochemical active ingredient of Example 1, 2.0 parts of ammonium lauryl sulfate as sodium lauryl sulfate, and 5.0 sodium dodecylbenzenesulfonate as an anionic surfactant excluding lauryl sulfate. And the amount of clay added was 73.0 parts except that the amount was adjusted according to the preparation method of Example 1 to obtain rice seedling box coated granules.
[Example 20] According to the preparation method of Example 1, except that the active ingredient of agricultural chemical of Example 1 is 4.0 parts of cartap (nereistoxin insecticide) and the amount of clay added is 81.0 parts. Thus, a coated granule for rice seedling box application was obtained.
[Example 21] A rice seedling box application coating was prepared according to the preparation method of Example 1 except that the agricultural chemical active ingredient of Example 19 was 4.0 parts by cartap and the addition amount of clay was 81.0 parts. A granule was obtained.
[Example 22] A coated granule for rice seedling box application, prepared according to the preparation method of Example 1 except that 2.0 parts of thiamethoxam (neonicotinoid insecticide) was used as the agrochemical active ingredient of Example 1. Got.
[Example 23] A rice seedling box coating was prepared according to the preparation method of Example 1 except that the pesticide active ingredient of Example 19 was 2.0 parts of thiamethoxam and the addition amount of clay was 83.0 parts. A granule was obtained.

[Comparative Example 1] Prepared according to the preparation method of Example 1, except that the anionic surfactant excluding lauryl sulfate of Example 1 was not added and the amount of clay added was 88.0 parts. Then, a coated granule for rice seedling box application was obtained.
[Comparative Example 2] Prepared according to the preparation method of Example 1 except that lauryl sulfate of Example 1 was not added and the amount of clay added was 85.0 parts. Got.
[Comparative Example 3] Prepared according to the preparation method of Example 1 except that the orthophosphoric acid of Example 1 was not added and the amount of clay added was 83.5 parts. Obtained.
[Comparative Example 4] Prepared according to the preparation method of Example 1 except that anhydrous sodium sulfate of Example 1 was not added and the amount of clay added was 83.5 parts. Obtained.
[Comparative Example 5] A rice seedling box was prepared according to the preparation method of Example 1 except that 5.0 parts of sodium dodecylbenzenesulfonate was used as the anionic surfactant excluding lauryl sulfate of Comparative Example 3. An applied coated granule was obtained.

[Comparative Example 6] A rice seedling box was prepared according to the preparation method of Example 1 except that 5.0 parts of sodium dodecylbenzenesulfonate was used as the anionic surfactant excluding lauryl sulfate of Comparative Example 4. An applied coated granule was obtained.
[Comparative Example 7] The preparation method of Example 1 except that the anionic surfactant except for lauryl sulfate of Example 1 was replaced with 5.0 parts of a nonionic surfactant polyoxyethylene alkyl ether. To obtain a coated granule for rice seedling box application.
[Comparative Example 8] Except that the sodium lauryl sulfate of Comparative Example 1 was changed to 2.0 parts of ammonium lauryl sulfate, it was prepared according to the preparation method of Example 1 to obtain rice seedling box coated granules.
[Comparative Examples 9-10] Except that the sodium lauryl sulfate of Comparative Examples 3-4 was 2.0 parts ammonium lauryl sulfate, it was prepared according to the preparation method of Example 1 to obtain rice seedling box coated granules. .
[Comparative Example 11] A rice seedling box was prepared according to the preparation method of Example 1 except that 12.0 parts of the pesticide active ingredient of Comparative Example 1 was 12.0 parts, and the addition amount of clay was 78.0 parts. Coated granules were obtained.

[Comparative Example 12] A rice seedling box was prepared according to the preparation method of Example 1 except that 12.0 parts of pesticide active ingredient in Comparative Example 2 was used and 75.0 parts of clay was added. Coated granules were obtained.
[Comparative Example 13] Prepared in accordance with the preparation method of Example 1 except that 12.0 parts of pesticide active ingredient in Comparative Example 3 and 73.5 parts of clay were added, and applied to rice seedling box Coated granules were obtained.
[Comparative Example 14] A rice seedling box was prepared according to the preparation method of Example 1 except that 12.0 parts of the pesticide active ingredient of Comparative Example 4 was changed to 12.0 parts and the addition amount of clay was 73.5 parts. Coated granules were obtained.
[Comparative Example 15] This was carried out except that 3-methacryloxypropyltrimethoxysilane (trade name KMB-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was not added during the preparation of the aqueous resin composition of Example 1. In the same manner as in Example 1, an aqueous resin composition E (solid content: 35% by weight, excluding a polymerizable unsaturated monomer having a hydrolyzable silyl group) was obtained. Using this aqueous resin composition E, granules were coated in the same manner as in Example 1 to obtain a rice seedling box coated granule coated with 7.0 parts of the solid content of the aqueous resin composition E.
[Comparative Example 16] A rice seedling box was prepared according to the preparation method of Example 1 except that 12.0 parts of the pesticide active ingredient of Comparative Example 15 was changed to 12.0 parts and the addition amount of clay was 73.0 parts. Coated granules were obtained.

[Comparative Example 17] Prepared according to the preparation method of Example 1 except that the agricultural chemical active ingredient of Comparative Example 15 was set to 4.0 parts of Cartap and the addition amount of clay was set to 81.0 parts. Coated granules were obtained.
[Comparative Example 18] Except that the agricultural chemical active ingredient of Comparative Example 15 was 2.0 parts of thiamethoxam, it was prepared according to the preparation method of Example 1 to obtain rice seedling box coated granules.
[Comparative Example 19] Rice seedlings were prepared according to the preparation method of Example 1 except that the aqueous resin composition was not coated in the preparation method of Example 1 and the amount of clay added was 90.0 parts. A box application granule was obtained.
[Comparative Example 20] A rice seedling box was prepared according to the preparation method of Example 1 except that the agrochemical active ingredient of Comparative Example 19 was 12.0 parts of Pyroxylone and the addition amount of clay was 80.0 parts. A granule was obtained.
[Comparative Example 21] Prepared according to the preparation method of Example 1 except that the agricultural chemical active ingredient of Comparative Example 19 was 4.0 parts by weight and the addition amount of clay was 88.0 parts. A granule was obtained.

[Comparative Example 22] A rice seedling box was prepared according to the preparation method of Example 1 except that the active ingredient of Comparative Example 19 was 2.0 parts of thiamethoxam and the addition amount of clay was 90.0 parts. A granule was obtained.
[Comparative Example 23] In place of the aqueous resin composition A of Example 1, 14.0 parts of Polysol SH-502 (50% vinyl acetate resin, Showa Polymer Co., Ltd.) and 28.0 parts of water were mixed. A rice granule for coated rice seedling box application was prepared according to the preparation method of Example 1 except that the solution was used, and coated with 7.0 parts of vinyl acetate resin.
[Comparative Example 24] In place of the aqueous resin composition A of Example 1, 14.0 parts of Polysol P-3 (ethylene / vinyl acetate resin 50%, Showa Polymer Co., Ltd.) and 28.0 parts of water were combined. Except that the dissolved liquid was used, a coated granule for rice seedling box application was obtained according to the preparation method of Example 1 and coated with 7.0 parts of ethylene / vinyl acetate resin.
[Comparative Example 25] In place of the aqueous resin composition A in Example 1, 23.3 parts of Superflex 126 (30% polyurethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 46.6 parts of water were mixed. Except that the liquid was used, a coated granule for rice seedling box application was obtained according to the preparation method of Example 1 and coated with 7.0 parts of polyurethane resin.
[Comparative Example 26] A rice seedling box application was prepared according to the preparation method of Example 1, except that 12.0 parts of the pesticide active ingredient of Comparative Example 23 was 12.0 parts and the addition amount of clay was 73.0 parts. Coated granules were obtained.

[Comparative Example 27] Prepared according to the preparation method of Example 1 except that 12.0 parts of pesticide active ingredient of Comparative Example 25 and 73.0 parts of clay were added, and applied to rice seedling box Coated granules were obtained.
[Comparative Example 28] Prepared according to the preparation method of Example 1 except that the pesticide active ingredient of Comparative Example 23 was Cartap 4.0 parts and the amount of clay added was 81.0 parts. Coated granules were obtained.
[Comparative Example 29] Prepared according to the preparation method of Example 1 except that the pesticide active ingredient of Comparative Example 25 was 4.0 parts by weight and the amount of clay added was 81.0 parts. Coated granules were obtained.
[Comparative Example 30] Except that the agricultural chemical active ingredient of Comparative Example 23 was 2.0 parts of thiamethoxam, it was prepared according to the preparation method of Example 1 to obtain rice seedling box coated granules.
[Comparative Example 31] Except that the agricultural chemical active ingredient of Comparative Example 25 was 2.0 parts of thiamethoxam, it was prepared according to the preparation method of Example 1 to obtain rice seedling box coated granules.

Next, the utility of the rice seedling box application granules of the present invention will be shown by test examples.
[Test Example 1] Paddy rice phytotoxicity test 4 L of culture soil was placed in a seedling box, and 180 g of seed meal (variety: Koshihikari) and 50 g of the prepared granular pesticide composition were treated. 20 days after sowing (corresponding to the time of transplantation to Honda), the growth of the seedlings and the extent of root elongation of rice seedlings were investigated, and the degree of phytotoxicity was tested in the field test method for fungicides such as rice and wheat (May 1990) ) Evaluation was made according to the following evaluation standards based on the Japan Plant Protection Association). The results are shown in Tables 1 to 2 (Invention Zones 1 and 2) and Tables 3 to 5 (Comparative Zones 1 to 3).
[Evaluation criteria for phytotoxicity in the growth of above-ground rice seedlings]
3: Height equivalent to untreated section (90% or more compared to untreated section).
2: Slightly inferior to the growth of the untreated plot, but no problem (89-80% of the untreated plot).
1: Variation in growth is observed (79-50% of the untreated area).
0: A phytotoxicity that is a practical problem (49% or less of the untreated area).
[Evaluation criteria for phytotoxicity of rice seedling root elongation]
3: Growth equivalent to the untreated group (90% or more compared to the untreated group).
2: Slightly inferior to the growth of the untreated plot, but no problem (89-80% of the untreated plot).
1: Variation in growth is observed (79-50% of the untreated area).
0: A phytotoxicity that is a practical problem (49% or less of the untreated area).

[Test Example 2] Rice body concentration confirmation test for drugs Using rice seedlings grown in the same manner as in Test Example 1, after sampling the above-ground part (excluding roots) of the seedlings immediately before transplanting, the remaining part was transplanted into a rice planting machine ( It was transplanted to Honda at SPJ400 (4 rows planted by Kubota Corporation). 10 days after transplantation, 20 days later, the top 3 leaves of the seedling (the part where the drug absorbed after transplantation is accumulated) are sampled, extracted by adding extraction solvent to 5.0 g of the sampled seedling, and purified by column Quantitatively by high performance liquid chromatography (HPLC) or gas chromatography (GC) (if decomposed products are produced, quantify the decomposed products and add them to pesticide active ingredients). The drug concentration in the body was calculated. The results are shown in Tables 1 to 2 (Invention Zones 1 and 2) and Tables 3 to 5 (Comparative Zones 1 to 3).

<Description of Table 1 to Table 5>
In Examples 1 to 23, the level of paddy rice growth (the degree of phytotoxicity) is equivalent to that of the untreated zone, and there is no problem. In addition, due to the effect of the present invention, the concentration of drug uptake in rice plants tends to increase by about 2 to 3 times 10 days after transplantation compared to immediately before transplantation.
Among the components necessary for the present invention, Comparative Example 2 and Comparative Example 12 excluding lauryl sulfate, Comparative Example 1, Comparative Example 7, Comparative Example 8 and Comparative Example excluding an anionic surfactant excluding lauryl sulfate In Example 11 and Comparative Example 4, Comparative Example 6, Comparative Example 10, and Comparative Example 14 excluding anhydrous mirabilite, the drug uptake concentration is reduced to about ½ after 10 days of transplantation compared to immediately before transplantation.
In Comparative Example 3, Comparative Example 5, Comparative Example 9, and Comparative Example 13 excluding orthophosphoric acid, the drug uptake concentration after transplantation does not increase and the degree of rice growth is slightly inferior.
In Comparative Examples 15 to 18 in which the polymerizable unsaturated monomer having a hydrolyzable silyl group is removed from the aqueous resin composition and Comparative Examples 19 to 22 in which the aqueous resin composition is not coated, it is not necessary in terms of medicinal effect. During the seedling period, the drug is released and eluted at a high concentration, and the drug uptake concentration immediately before transplantation is increased. As a result, the degree of rice growth is significantly inferior.
Among Comparative Examples 23 to 31 coated with other commercially available resins, in Comparative Example 23, Comparative Example 24, Comparative Example 26, Comparative Example 28 and Comparative Example 31 using vinyl acetate resin or ethylene / vinyl acetate resin, The elution / release of the drug during the seedling period cannot be controlled, and the degree of rice growth is significantly inferior. In Comparative Example 25, Comparative Example 27, Comparative Example 29, and Comparative Example 31 using a polyurethane resin, there is no problem in the growth degree (degree of chemical damage) of paddy rice, but the uptake concentration of the drug after transplantation does not increase.

Claims (4)

  a) Agrochemical active ingredient having a solubility in water (20 ° C.) of 0.01 g / L or more, b) lauryl sulfate, c) anionic surfactant excluding lauryl sulfate, d) orthophosphoric acid, e) anhydrous The granular material containing mirabilite and f) a solid carrier, g) a polymerizable property excluding the polymerizable unsaturated monomer having a hydrolyzable silyl group and the polymerizable unsaturated monomer having the hydrolyzable silyl group A coated granule for rice seedling box application, which is coated with an aqueous resin composition obtained by dissolving or dispersing a copolymer with an unsaturated monomer in water.   The aqueous resin composition g) is a polymerizable unsaturated monomer excluding a polymerizable unsaturated monomer having a hydrolyzable silyl group and a polymerizable unsaturated monomer having the hydrolyzable silyl group ( A copolymer with one or more selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl group is dissolved or dispersed in water. The coated granule for rice seedling box application according to claim 1.   The aqueous resin composition g) excludes 3-methacryloxypropyltrimethoxysilane as a polymerizable unsaturated monomer having a hydrolyzable silyl group and the polymerizable unsaturated monomer having the hydrolyzable silyl group. A copolymer of (meth) acrylic acid, methyl methacrylate, and n-butyl acrylate as a polymerizable unsaturated monomer is dissolved or dispersed in water. Coated granules for rice seedling box application as described.   After applying the rice seedling box application coated granule according to any one of claims 1 to 3 to the seedling box, disintegrating the coating of the granule by a transplanting operation from the rice nursery box to Honda, the agricultural chemical to Honda A method for controlling the elution of a coated granule, which comprises increasing the elution amount of an active ingredient.