KR20020091229A - Biodegradable foam having high oil-absorbing ability and floating on water surface, process for producing the same, and composition containing the same - Google Patents

Abstract

0.1-5 parts by mass of the crosslinking agent was added and mixed to 95.0-99.0 parts by mass of the starch-containing material, and the diameter of the foam treated with the extruder was 1-5 times the diameter, 1-20 mL / g in volume, and 0.3- Foam having five times oil absorption, suspended in water for more than 10 minutes.

Description

Biodegradable Sleep Floating Foam Having High Absorption Capacity, Method for Manufacturing The Same and Composition Containing The Same {BIODEGRADABLE FOAM HAVING HIGH OIL-ABSORBING ABILITY AND FLOATING ON WATER SURFACE, PROCESS FOR PRODUCING THE SAME, AND COMPOSITION CONTAINING THE SAME}

Conventionally, there exist some which were disclosed by Unexamined-Japanese-Patent No. 7-32441 and 9-296076 as a technique regarding the foam which extruded the thing containing starch.

Among them, Japanese Patent Application Laid-Open No. 7-32441 discloses a edible biodegradable cushioning material which uses starch as a raw material, is excellent in flexibility and elasticity, has edibility and biodegradability, and can be used as a buffer material for foamed styrol substitutes. A method is disclosed. Further, Japanese Laid-Open Patent Publication No. 9-296076 discloses a starch resin capable of decomposing living organisms and a method for producing the same. However, since they contain starch, they are biodegradable. They are oil-absorbent and do not float in water, and because they do not have a crosslinking agent added to the present invention, they are expanded and adjusted so that they do not have small bubbles. .

Moreover, as a technique regarding a starch foam containing an agricultural chemical, there exist some which were disclosed by Unexamined-Japanese-Patent No. 5-502437 and patent 2785490. Among them, Japanese Patent Application Laid-open No. Hei 5-502437 discloses a technique of using crosslinked starch or crosslinking at the time of extrusion treatment, which indicates insolubilization of starch. It is not intended to increase oil absorption. The same applies to Patent No. 2785490. Since oily ingredients such as pesticides and starch ingredients are mixed and processed by an extruder, the specific gravity becomes lighter due to the assistance of oily ingredients, and it is considered to float on water. As a result, the gelatinization of the starch particles is suppressed to form a molded article that is hardly compatible with water. Therefore, oily components such as pesticides contained therein are less likely to be released into the water, and the early effects as pesticides are lowered.

On the contrary, post-mixing of the foam and the pesticide like the pesticide composition of the present invention is because the pesticide is adsorbed on the surface and the bubble portion of the foam, so that the oily components adhered to the surface easily fall off from the foam (oil content). It replaces with water, and the foam swells by the water which slowly penetrates, and the oily component which penetrated and absorbed to the inside is also released to the outside in a short period of time, so that the drug appears early.

In addition, in the technique disclosed in these, since the pesticide itself is subjected to high pressure and high temperature treatment in an extruder, there is a possibility of decomposition or volatiles, and thus there is a problem of environmental pollution. In particular, when crosslinking agents are mixed, the possibility of denaturation becomes higher.

Conventionally, the starch foam obtained by treating the starch with an extruder is excellent in water absorption because it is a porous structure having a large bubble, but there is a problem that the starch foam itself is dissolved in water, and even if a water-repellent substance is added to the water, the oil absorption ability is high. A foam could not be obtained. In addition, there was no foam having a high absorption capacity, biodegradability, and sleep-suspending foam.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biodegradable sleep-floating foam having a high absorption capacity treated with an extruder as a main component, a method for producing the same, and a pesticide composition containing the biodegradable sleep-floating foam, a method for producing the same, and a method of using the same. . Background Art Conventionally, oily liquid substances such as fats and oils and organic solvents are often powdered according to their use, and powdered liquid substances have been attempted in various fields, including food, feed, medicine, and pesticides. Since the foam of the present invention may contain an oily liquid material, it is applicable in the above field, and among these, it is to provide a pesticide composition having excellent properties of containing the pesticide in the foam.

1 is a sample treatment position and a water sampling position in Test Example 2.

Disclosure of the Invention

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve such a subject, the present inventors added and mixed 0.1-5 mass parts of crosslinking agents to 95.0-99.0 mass parts of starch-containing substances, and the diameter of the foam processed by the extruder was 1-5 times of diameter, and volume Is 1 to 20 ml / g, has a oil absorption capacity of 0.3 to 5 times its own weight, and is a foam suspended in water for 10 minutes or more, and a starch-containing substance and starch (starch-containing substance: starch = 0 to 80: 100 to 20) 1 to 30 parts by mass of the thermal coagulant and 0.1 to 5 parts by mass of the crosslinking agent are added and mixed to 45 to 95 parts by mass, and the diameter of the foam treated with the extruder is 1 to 5 times the die diameter, and the volume is 1 to 20. It is found that a foam having an oil absorption capacity of 0.3 to 5 times its own weight and floating in water for 10 minutes or more can be produced, and that the foam can powder an oily liquid substance. In addition, pesticides in the foam of the present invention Is a granule which absorbs an oily substance and, in some cases, coats the powdered solid pesticide or its premix or the fine powder of the solid carrier, which is sleep-floating and can easily release the oily active ingredient in a short time. The present invention was completed by finding that it can be obtained.

The starch-containing substance used in the present invention includes corn, corn flour, corn grits, rice, rice flour, rice bran, sliced tapioca, sliced sweet potato, potato, sweet potato, soybean, green beans, bran, wheat, flour, chestnut, sorghum, etc. It means containing starch which can form a film after gelatinization. Examples of the starch include raw starch and processed starch. Specifically, raw starches such as potato starch, cornstarch, hyaluronic corn starch, sweet potato starch, tapioca starch, sago starch, rice starch, amaranthus starch and their processed starches (acid decomposition starch, oxidized starch, dealdehyde) Starch, etherified starch (carboxymethyl starch, hydroxyalkyl starch, cationic starch, methylolated starch, etc.), esterified starch (acetic acid starch, phosphate starch, succinic acid starch, octenyl succinic acid starch, maleic acid starch, higher fatty acid esterification Starch, etc.), cross-linked starch, grafted starch, wet heat-treated starch, etc. Preferably, soft-film starches, such as oxidized starch, acid-treated starch and slightly crosslinked starch, are preferable. Starch tends to be difficult to foam with an extruder, of which flour, corn grits and corn flour are preferred. Is classified as a minute, soft flour is especially preferred.

Lipids can be added to the mixture prior to pressure extraction with the extruder of the present invention. Lipids used in the present invention include triglycerides (fats and oils that are glycerides of fatty acids. They include liquid fatty oils and solid fats at room temperature), waxes (esters of fatty acids and higher alcohols, petroleum waxes such as petrolatum and paraffin). Furthermore, simple lipids such as sterols and esters of vitamins A and D, phospholipids which may contain nitrogen, glycolipids having sugars as constituents, and sulfolipids having sulfuric acid groups or sulfo groups therein (sulfur lipids) Complex lipids such as those having CP bonds, fatty acids considered to be precursors or metabolites of the above two, higher alcohols, sterols, hydrocarbons such as carotenoids and squalene, and fat-soluble vitamins. Lipids. Among these, fatty acids are glycerides of fats and oils (lard, semi-sweet, palm kernel oil, palm oil, soybean oil, olive oil, safflower oil, peanut oil, rapeseed oil, white fertilized oil, corn oil, cottonseed oil, rice oil, sesame oil, sunflower Oil, castor oil, cacao oil, linseed oil, tung oil, perilla oil, marine animal oil), waxes such as petrolatum and paraffin are suitably used.

To extrude with an extruder, thermoplastic is required. To make starch thermoplastic, water must be added and gelatinized. However, since the foam luxury by adding water to the starch contains a lot of water, the foam should be further dried to increase the oil absorption capacity which is the object of the present invention. By adding a small amount of lipids, the amount of water added can be minimum or no addition, and the foam with low moisture can be extruded smoothly. In addition, a thin lipid film is formed on the surface of the foam, the oil absorption capacity of the foam can be significantly improved to increase the floating capacity for water.

The amount of lipid added is 0.1 to 8 parts by mass. However, when using starch-containing materials such as corn flour, corn grits, and flour containing raw lipids, or processed starches such as octenyl succinic acid starch and higher fatty acid esterified starch, the addition amount may be limited. Can be.

Emulsifier can be added to the mixture before the pressure extraction by the extruder of the present invention. As the emulsifier used in the present invention, nonionic surfactants having an appropriate HLB value, anionic surfactants such as soaps, polymer materials such as proteins, and the like, glycerin fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, and propylene are used. It is preferable that it is recognized as a food additive, such as glycol fatty acid ester, lecithin, calcium stearoyl lactate, sodium oleate, morpholine fatty acid salt, and polyoxyethylene higher aliphatic alcohol.

In the present invention, the emulsifier is considered to enhance the emulsification properties of the starch-containing substance, starch and lipids, and consequently, it is believed that the emulsifiers contribute to increase the oil absorption capacity and water flossability by increasing the bubbles inside and the surface.

The addition amount of an emulsifier is 0.1-5 mass parts.

The thermal coagulant used in the present invention refers to protein-based systems such as soy protein, wheat protein such as gluten, and milk proteins such as casein, and thermocoagulable polysaccharides such as cedlan and methyl cellulose. When the thermal coagulant is dissolved, it becomes a mesh-like polymer structure and solidifies by heating, and when treated with an extruder, it becomes a foam having a small bubble. The addition of the crosslinking agent forms a rigid foam.

The addition amount of a thermocoagulant is 1-30 mass parts.

As a crosslinking agent used in the present invention, phosphates such as sodium tripolyphosphate, sodium trimethaphosphate, phosphorus oxychloride, epichlorohydrin, polyepoxy compounds having two or more epoxy groups at the terminals, aldehydes such as formaldehyde and glyoxal Substances containing two or more functional groups capable of reacting with hydroxyl groups, proteins contained in polysaccharides such as starches, other starches and the like, and carboxyl groups (adipic acid, acrolein, bisethylene urea, diisocyanate, melamine resin, Polyvalent cation salts such as melamine formalin resin, amino resin, polyamine epichlorohydrin resin, water-soluble alkylated amino resin, water-soluble methylated melamine resin), potassium pyroantimonate, calcium salt and magnesium salt. Preferably, there is no toxicity such as food additives. These crosslinking agents are those which require and do not need a catalyst (heating only), but what is generally used (usually an alkali catalyst or an acid catalyst is added to achieve optimum pH) may be added to the catalyst required for the crosslinking reaction. As for addition amount, 0.1-5 mass parts is preferable.

In the present invention, it is believed that the crosslinking agent contributes to adjusting the diameter of the foam during foaming and also contributes to water flotation.

In the said various materials, each compounding mass becomes as follows. 0.1-5 mass parts of crosslinking agents, and the catalyst of the quantity required for crosslinking in 95.0-99.0 mass parts of starch containing materials. Starch-containing substance and starch (starch-containing substance: starch = 0 to 80: 100 to 20) 45 to 95 parts by mass, if necessary, 0.1 to 8 parts by mass of lipid, 0.1 to 5 parts by mass of emulsifier, thermocoagulant 1-30 mass parts, 0.1-5 mass parts of crosslinking agents, and the catalyst of the quantity required for crosslinking.

In addition, in this invention, a starch containing mass may contain other natural products or its derivatives, For example, natural products, such as a cellulose system, a protein system, and a natural gum system, or its derivatives are mentioned.

As a cellulose natural product or its derivative, cellulose derivatives, such as carboxymethylcellulose and its salt, methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, are mentioned, for example.

Examples of the protein-based natural products or derivatives thereof include gelatin obtained from animal bones, casein obtained from milk and salts thereof, gluten obtained from wheat, and the like.

Natural gum-based natural products or derivatives thereof include, for example, derivatives such as pectin, arginic acid and salts and esters thereof, pullulan, xanthan gum, wellan gum, guar gum, cadmium and the like.

The extruder which is the processing apparatus of this invention is demonstrated below.

Generally, an extruder is composed of a hopper, a feeder, a screw, a barrel, a die, a heating coil, a cleaning jacket, a driving motor, and has a single axis and a two axis, and suitably a two axis. In order to obtain the foam of the present invention, the barrel temperature is 60 to 250 ° C, preferably 80 to 160 ° C, the screw rotation speed is 50 to 300 rpm, preferably 70 to 200 rpm, and the die temperature 90 to 200 ° C, preferably 100 It discharges on the conditions of -150 degreeC and die discharge diameters 0.5-10 mm, Preferably it is 1-5 mm. The conditions should be selected so that the foam is a foam having a large number of small bubbles with a specific gravity of 10 times or less, preferably 1 to 5 times the die diameter.

The barrel temperature is involved in the gelatinization of the starch and the reactivity of the crosslinker. The screw rotation speed influences the discharge pressure and at the same time controls the size of the emulsified particles before discharge. Die temperature determines the foaming force and is responsible for the discharge of internal moisture. The die discharge diameter is appropriately adjusted according to the application used, and the conditions should be selected so that the foam becomes a foam having a large number of small bubbles with a specific gravity of 10 times or less, preferably 1 to 5 times the die diameter.

The foam of the present invention is produced 1 to 5 times the die diameter, so that many small continuous bubbles are formed and the foam has a large specific gravity. The foam has a volume of 1 to 20 ml / g, preferably 1 to 12.5 ml / g, 0.3 to 5 times its own weight, preferably 1 or more times of oil absorption capacity, and 10 minutes or more, preferably 1 Float in water for more than an hour.

Method of measuring volume: 20 g of sample (5 g for light) is placed in a 500 ml (1 l for light) volume measuring cylinder, and the scale (ml) of the measuring cylinder is read (take the average of the high and low values). . The volume is calculated by the following equation.

Volume (ml / g) = graduation value / 20 (or 5)

Absorption magnification measurement method: 10 g of a sample is put into a 200 ml wide-mouth glass jar, and a small amount of white glue is added dropwise. After dropping, the bottle is covered with a lid and the bottle is shaken by hand to spread the white glue uniformly on the sample. In addition, if white glue adheres to the inner wall of the bottle and the lubricity of white glue disappears from the sample surface, the lid is opened at that point, and the white glue is added dropwise, and the above operation is repeated. Even if shaken for 5 minutes after the dropping, the white glue oil adheres to the inner wall of the bottle and the lubricity of the white glue oil does not disappear on the sample surface. The oil absorption capacity is calculated by the following equation.

Oil absorption capacity (%) = [{total weight of loaded white oil (g)} ÷ {sample weight (10g)}] × 100

The foam of starch thus obtained can be used as a carrier for so-called jumbo or packs, which are separately packaged with a water-soluble film and put into the paddy or treated, or as a carrier for water-borne agrochemical granules that are scattered and treated in paddy fields without being separately packed. have. This formulation is useful as a manpower-saving pesticide with strong demands against the background of the recent agricultural situation, and in particular, it is possible to prepare granules containing liquid components at high concentrations, thereby reducing the amount of medicine per unit area. Since it is released into the water in a short time without sinking in the state occupied by the carrier, it has a characteristic that there is no fear of weakness or ineffectiveness.

Pesticide active ingredients used in the present invention are herbicides, insecticides, fungicides, plant regulators, etc. used for sleeping in rice fields, and are not particularly limited in their physical properties. For example, bensulfonmethyl , Azimsulphron, imazosulphron, pyrazosulfonethyl, ethoxysulphron, cynosulphron, cyclosulfamron, dimepiperate, mefenacet, pretilacror, molinate, pyributycarb, tenylchlor , Esprocarb, butamifos, bromobutide, dimelone, carfenstrol, sihalopopbutyl, benzophenad, pyrazolate, pyrazoxifen, benpresate, thiobencarb, cimet Lean, dimethamethrin, pentoxazone, edbenzanid, dithiofil, butachlor, oxadiargyl, naproanilide, cinmethylline, 2,4-D and its alkylesters or salts thereof, MCPA , MCPB and their alkyl esters or salts thereof, oxa Clomefon, pentrazamide, benzobicyclone, indanophane, cumylone, pyrazogil, anilophos, biphenox, piperophos, quinocramine, pyriminobacmethyl, clomecrob and betazone have.

The insecticidal active ingredient may be an insecticide having a penetrating property, and an insecticide effective for insects living on the water surface such as weeping weevil and rice leaf beetle. For example, silafluorophene, cycloprotrin, etofenprox, imidacroprid, Nitenpyram, acetamiprid, isoxation, ethylthiomethone, diazinone, thiocyclam, acetate, and benfuracarb.

The bactericidal active ingredient may be a bactericide effective for a penetrating bottle or a paperback disease having a penetrability, for example, teclophthalam, olibolite, azoxystrobin, carpropamide, pyroquilon, isoprothiolane, provenazole, Tifluzamide, cimeconazole, ifprobenfos, tricyclazole, fipronil, flutolanyl, fumetpyr, mepronyl, benomil, and 7-fluoro-1,2,5,6-tetra Hydro-4H-pyrrolo [3.2.1-ij] quinolin-4-one and the like.

Examples of plant regulators include maleic acid hydrazide and salts thereof, abscisic acid, calcium peroxide, inaben feed, palovabutrazole, uniconazole, triaptenol, and psychocells. Can be.

Pesticide active ingredient used in the present invention may be used one or two or more of the herbicides, insecticides, fungicides, plant control agents, can be blended two or more active ingredients of different action mechanisms or targets among herbicides. For example, a combination of two or more completely different objects such as herbicides, fungicides and insecticides is possible.

Among them, liquid elements such as butachlor, pretilachlor, anilofos, benpresate, sihalopopbutyl, dimethamethrin, benzulflonmethyl, pyrazosulflonethyl, azisulfulfone, ethoxysulfron, Sulfonylurea herbicides (manufactured by SU) such as imazosulphron, cynosulphron, and cyclosulfamlone, carpentrol, oxadiargyl, dimelone, oxadichromemepon, pentrazamide, benzobisichron, and indanopan , Insecticides such as pyriminobaekmethyl, pyrazogil, pyrazolate, benzophenab, insecticides such as silafluorophene, cycloprotrin, etofenprox, imidacloprid, nitenpyram, acetamiprid, isoxation, and teclo Fungicides such as phthalam, olivelite, azoxystrobin, carpropamide, pyroquilon, isoprothiolane, probenazole, tifluzamide, cimeconazole, and the like are particularly suitable. Suitably applied Can.

Most of the active ingredients of these pesticides are floated on the surface of the rice paddies when they are put into the paddy field, and after they have been widely spread on the surface, they are easily dispersed, emulsified or dissolved in the water, or floated on the surface without sinking. It needs to spread throughout. In the case of a compound that is poorly soluble in water, if the active ingredient floats on the water surface for a long time, it may be driven to one side by the wind, and the local presence of the active ingredient may be accelerated. Therefore, the active ingredient is dispersed in water by blending an appropriate wetting and dispersing agent. It is preferable to emulsify or dissolve. To this end, if necessary, an appropriate extender or auxiliary agent is blended, and the active ingredient is granulated so that the active ingredient is easily wetted with water and emulsified and dispersed.

The compounding ratio of the active pesticide active ingredient used in the present invention is not particularly limited, but considering economical efficiency and manpower reduction, it is preferable that the ratio is high in a range that does not cause processing problems. Usually, it is 0.1 to 80% in agrochemical granules, Preferably it is 0.3 to 70%, More preferably, it is 0.5 to 60%.

The granular pesticide composition having floating property in the water of the present invention preferably disperses, emulsifies, or dissolves the active ingredient in water quickly after expanding the water, may be disintegrated when administered in water, and is non-degradable. The disintegratable one is suitable because the active ingredient of the pesticide is eluted in a short time. In order to make the granular pesticide composition disintegratable, the granular pesticide composition having floating property on the water surface of the present invention may contain a starch-containing material or an enzyme acting on the starch.

Examples of enzymes used in the present invention include amyloglucosidase, α-amylase, β-amylase, and isoamylase.

Amyloglucosidase is a starch degrading enzyme produced by bacteria or filamentous fungi. It acts on α-1,4 and α-1,6 bonds of starch and separates glucose from the non-reducing end of glucose chain by one molecule. It is an exo type enzyme.

α-amylase is a starch dehydrogenase produced by bacteria and filamentous fungi, and is rich in heat resistance and pH safety. An enzyme that hydrolyzes α-1,4 bonds of glucose polysaccharides having three or more α-1,4 bonds, an endo type that breaks down at least five oligosaccharides to produce glucose, maltose and oligosaccharides. It is an enzyme. The starch or its derivatives are randomly cleaved and decomposed into oligosaccharides at once, so the viscosity-lowering ability is excellent.

β-amylase is a starch degrading enzyme obtained from malt, also called malt amylase. Recently, it is also obtained from bacteria and filamentous bacteria. It is an exo type enzyme that generates β-maltose in order at the non-reducing end of the glucose chain of α-1,4-glucan such as starch, glycogen and dextrin. Produced in malt is a mixture with α-amylase.

Isoamylase is present in yeast, rice, potatoes, silkworms, malt and the like. It is an endo type enzyme that acts on α-1,6-glycosidic bonds in starch-based polysaccharides such as amylopectin and glycogen and generates amylose-like polysaccharides comprising only α-1,4 bonds.

In the case where the granular pesticide composition having floating property on the water surface of the present invention contains a cellulose-based natural product or a derivative thereof, there is a cellulase as an enzyme acting thereon. This enzyme is a complex enzyme composed of at least three kinds of enzymes, and has many hemicellulase activities that act on hemicellulose, a polysaccharide of five-saccharide sugars. Cellulase hydrolyzes β-1,4 glucan bonds in cellulose and produces soluble polymers and D-glucose. Cellulase is a complex enzyme and has the following activities.

C ₁ activity: an enzyme that destroys natural cellulose.

C _x1 activity: Endoglucanase that produces cellodextrin, cellotriose, and cellobiose, isolated from fungi such as Aspergillus.

C _x2 activity: degrades cellodextrin produced from C _x1 and produces glucose.

When the granular pesticide composition having floating property on the water surface of the present invention contains a protein-based natural product or a derivative thereof, examples of the enzyme acting thereon include bacterial proteases, filamentous fungal proteases, papain and pepsin.

Bacterial proteases are enzymes produced from B. subtilis and classified into neutral and alkaline proteases at their working pH. It acts on proteins and peptides and is used in baking, dry cleaning and household detergents.

Fungal proteases include those of Aspergillus origin, Rhizopus origin, Streptomyces origin, and the like. In Japan, it has been used for a long time to break down soy protein for the production of soybean and soy sauce. Most of them are shown as a mixture of exo type proteases and endo type proteases, and the content of amylase varies depending on the strain. In addition, cellulase, phosphatase, RNA enzyme, pectinase and the like coexist depending on the strain.

Papain is made from papaya fruit and is used to prevent turbidity in beer. Hydrolyzing the binding sites of basic amino acids, leucine, glycine and the like, such as peptides, amides and esters, and immature papua is used as a raw material.

Pepsin hydrolyzes peptide bonds adjacent to L-amino acid residues of an aromatic or dicarboxylic acid system. It does not work on esters or amides. It works at extremely low pH, such as pH 1.8 to 2.5.

In addition, proteolytic enzymes used as anti-inflammatory drugs include trypsin, chymotrypsin, plasmin, seaprose, ceratiopeptidase, bromelain and the like.

When the granular pesticide composition having floating property on the water surface of the present invention contains pectin, an enzyme acting on it is pectinase. It is used as a fermentation refining agent for horses, and as a clarifier for juice and wine. Pectin degrading enzyme is generally called pectinase and is a generic name of a group of enzymes involved in the hydrolysis of pectin substances, protofectinase, pectin esterase, pectin / pectin hydrase, polygalactronase, pectitriase This includes. These also have an end type and an exo type, respectively.

When the granular pesticide composition having floating property on the water surface of the present invention contains arginic acid and derivatives such as salts and esters thereof, the enzymes acting thereon include arginase and arginate antipyretic enzymes. Arginase is present in digestive fluids such as abalone, seashells, cattle, scaly breams and produces oligouronides, mannuronic acids, di or triuronides. Arginic acid dissociation enzyme is present in Pseudomonas, and it decomposes and decomposes arginic acid, and produces the small sugar which makes uronic acid which has an unsaturated bond the non-reducing terminal.

When the granular pesticide composition having floating property on the water surface of the present invention contains pullulan, the enzymes acting thereon include flulanase and isofluranase. Flulanase hydrolyzes α-1,6 bonds of pullulan, amylopectin and glycogen, and generates linear polysaccharides such as maltriose and amylose. It acts as an endo type to pullulan. Isofluranase hydrolyzes the α-1,4 glucoside bond on the reducing end side adjacent to the α-1,6 glucoside bond of pullulan and generates isophanose.

When the granular pesticide composition having floating property on the water surface of the present invention contains polysaccharides and mucopolysaccharides, hyaluronidase is an enzyme acting thereon.

In this way, the enzyme acting on the natural polymer substance or its derivatives acts randomly on the binding site of the polymer chain and suddenly decomposes into a low molecular weight polymer (endo type), and the end binding site of the polymer chain. It acts on and separates the components one by one (exo type). In this application, an endo type enzyme is preferable among these.

Although exo-type enzymes do not interfere, they act only on the ends of natural products or derivatives thereof, and therefore take a long time to decompose these natural products or derivatives that act as binders (which take time to disintegrate and disperse the agent). There is this.

In the present application, suitable among these starch-containing substances and combinations of starches and enzymes acting on them are α-amylases wherein the starch-containing substances and starches are corn flour, corn grits or wheat flour and the enzyme is an endo type. Or a combination of isoamylase, more preferably a combination of α-amylase or isoamylase, wherein the natural product or derivative thereof is wheat flour and the enzyme is an endo type.

The amount of enzyme varies greatly depending on the type of starch-containing substance and starch, the amount of the compound, the type of enzyme, its titer, etc., and is usually 0.001 to 10 parts by mass in the surface-suspension type agrochemical preparation of the present invention. Preferably it is 0.002-5 mass parts, More preferably, it is 0.01-3 mass parts. In addition, by adjusting the compounding amount of the enzyme, the dissolution or disintegration time of the pesticide preparation in water can be controlled.

The shape of the granular pesticide composition of the present invention may be cylindrical or irregular.

Pesticide active ingredients are ground to a particle size sufficient to exhibit biological activity in the case of solids. If necessary, other grinding aids, wetting agents, dispersants, etc. may be added to dry pre-pulverization with a hammer mill or jet mill to form a premix containing a high concentration of the pesticide active ingredient. It may also be ground.

In the case of wet grinding, when an oily substance is used as a medium, the carrier may be absorbed as it is. However, when water is used, it is dried using a suitable dryer such as a spray dryer, and dried by a hammer mill or a jet mill. When pulverized, it can be handled in the same manner as the dry premix.

In order to prepare granules, a pesticide active ingredient is coated on a foam prepared according to the present invention using a suitable nonvolatile liquid substance, or the pesticide active ingredient is dissolved in a suitable solvent and absorbed into a foam of the present invention prepared in advance. Obtain the desired floating pesticide granules.

In the case of the coating method, for example, the foam of the present invention prepared in advance is injected into a stirring mixer, a non-volatile liquid substance is added to wet the surface, and then a solid pesticide active ingredient, or if necessary, water surface. What is necessary is just to add the powder premix containing a retarder and another adjuvant, and to stir again, and to coat the surface of a granule. Instead of nonvolatile liquid substances, pesticides in liquid or liquid form may be used.

In the case of the absorption method, for example, the foam of the present invention prepared in advance is injected into a stirring mixer, and a method of absorbing the pesticide active ingredient or its rich oil premix which is liquefied by liquid or solvent is added. In the pesticide active ingredient powder or oil premix, a sleep expanding agent and, if necessary, other auxiliaries may be combined.

In the case of producing granules by coating or absorption method, it is preferable to add the last one after coating or absorbing the active ingredient or other auxiliary agent in order to maximize the effect. In this way, the coating or absorption step may be divided into two or more steps.

The stirring mixer to be used is preferably selected from a group having low crushing granules to be mixed at low speed, such as cement mixers, Smith mixers, tote bottles, outer mixers, ribbon blenders, rotary blenders, and V-type mixers.

Regarding the granularity of granules, when the particle size is small, it is easy to sink in water, and the scattering granules are susceptible to wind resistance. On the contrary, when the particle size is larger than 20mm, it is easy to be driven to one side by the wind, and it takes time to dissolve the liquid active ingredient absorbed in the center, so that it may settle at one side and cause the ubiquity of the active ingredient of pesticide. have. Usually, 90% or more falls into the division of 0.71 mm-15 mm, Preferably it is preferable that 40% or more falls into the division of 1 mm-10 mm.

In order to obtain a pesticide granule having a good flotation property in the water surface of the present invention, the active ingredient of the pesticide, the foam of the present invention, a sleep spreader used to spread widely in the water surface, and other auxiliary agents can be prepared.

The sleep expanding agent of the present invention is formulated to expand the pesticide solids in the surface of water. For example, sodium salts, potassium salts of polymerized carboxylic acids such as acrylic acid and maleic acid, styrenesulfonic acid, vinyl groups, etc. Polysorbs of carboxylic acid type or sulfonic acid type such as ammonium salts; Soaps such as sodium oleate and potassium stearate; Mono or dialkyl sulfosuccinates and surfactants in which alkylene oxide is added thereto, sodium dodecylbenzene sulfonate, alkyl sulfates, α-olefin sulfonates, α-sulfofatty acids, α-olefin fatty acid salts, and oleylmethyltau Anionic surfactants such as a ride salt; Polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether, polyoxyethylene aryl aryl ether, polyoxyethylene alkyl ester, alkyl ester of polyoxyethylene sorbitan, alkyl ester of sorbitan, silicone surfactant, acetylene surfactant, Various nonionic surfactants such as a fluorogenic surfactant; Polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether, polyoxyethylene aryl aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester and the like are used as esters of phosphoric acid or sulfuric acid, and in some cases, neutralized with an appropriate alkali. Surfactants; Fluorine-based surfactants; Various cationic surfactants; Zwitterionic surfactants; Various esters and ethers of glycols such as ethylene glycol, propylene glycol, butanediol and polymers thereof; High boiling point solvents of liquid paraffins, naphthenes or aromatics; Mineral oils such as low viscosity polybutene, silicone oil and machine oil; Various animal and vegetable oils; Various resins such as rosin; Camphor; αpinene; Camphor; Naphthalene; Hydrophobic silica and the like can be used, and suitably mono or dialkyl sulfosuccinates and surfactants in which alkylene oxide is added thereto, α-olefin sulfonates, α-sulfofatty acids, α-olefin fatty acid salts, and oleyls. Methyl taurate salts, alkyl sulfates, acetylene surfactants, silicone surfactants, fluorine surfactants, ethers or esters of glycols and alkyl esters of carboxylic acids, and more preferably α-olefin sulfonates and ethers of α-olefin fatty acid salts, acetylene surfactants and glycols. Some of these sleep extenders may be used as dispersants, binders, granulation enhancers, or emulsifiers.

Mono or dialkyl sulfosuccinates and surfactants in which alkylene oxides are added thereto are monoalkyl sulfosuccinates as well as dialkyl sulfosuccinates commonly used in pesticides, and mono- or poly-alkylenes in advance. oxide manufactured with a (C ₂ ~ C ₄₎ an additional one alkyl ethers, salts of what comprises reacting a sulfosuccinate per one molecule, one molecule or two molecules.

These are, for example, New call 291PG (manufactured by Nihon New Kazai Co., Ltd.), neo call SWCE, neo call SWC, neo call YSK (manufactured by Daiichi-Kyosei Seikaku Co., Ltd.), New Kargen EP-70G (Takemoto YUOPON SDS (manufactured by Shioshigi Seiyaku Co., Ltd.), Ferrex OT-P (manufactured by Kao Kagushiki Kaisha), air roll CT-1 (manufactured by Tobo Kagaku Kogyo Co., Ltd.) ), Genoa boa SB1970J (manufactured by Hekistojapan Co., Ltd.), Repul 860K, Repul 870E (manufactured by Lion Co., Ltd.), (Dioctylsulfosuccinate sodium), Ferrex TR (Kao Kagoshi Co., Ltd.) Sodium tridecyl sulfosuccinate), Ferex CS (manufactured by Kao Kagushi Co., Ltd.) (sodium dicyclohexyl sulfosuccinate), ripearl NTD (manufactured by Lion Co., Ltd.) (sodium uji sulfosuccinate), New call 292PG (Nihon New Kazaa) (Manufactured by IKABushiki Kaisha) (diethylhexyl ethoxy It is marketed by brand names, such as sodium sulfosuccinate) and zero fon ACR / 4 (made by Rhodia Geronazo) (sodium salt of the lauryl ethoxy half ester of sulfosuccinic acid).

α-olefins sulfonates are salts of sulfonates based on crude oil (petroleum), which are highly biodegradable, very safe for skin and eyes, stable against acid alkali, and excellent in hard water resistance. has a friendly environment, characterized by, for example, an α- olefin sulfonate salts of C ₁₂ ~ C _16.

There is no restriction | limiting in particular as a salt of (alpha)-olefin sulfonate, For example, sodium, potassium, calcium, ammonium, various amine salts, etc. are mentioned, A sodium, ammonium, or a calcium salt is preferable.

Specific examples of the α-olefinsulfonate salt include, for example, Liporan LB-440, Liporan LB-840, Liporan PJ-400, K Liporan PJ-400, Liporan PB-800, Dt-95 Kaisha), M-3801, M-3801G (made by Daiichi Kyo Seiyaku Co., Ltd.), a postapa OSB (made by Heki Stojapan Japan Co., Ltd.), etc. are mentioned.

α- sulfo fatty acid salt can be cited as a sulfonated natural oil as a raw material for, for example, an α- sulfo fatty acid salt of a C ₁₀ ~ C _14.

Although there is no restriction | limiting in particular as a salt of (alpha)-sulfofatty acid salt, For example, sodium, potassium, calcium, ammonium, various amine salts, etc. are mentioned, A sodium, ammonium, or a calcium salt is preferable.

Specific examples of the α-sulfofatty acid salt include, for example, FA-615B, FA-616B, FA-617B (manufactured by Lion Corporation), acid base, acid base FM-2 (manufactured by Nihon Yushi Corporation), and the like. Can be mentioned.

The α-olefin fatty acid salt is a carboxylic acid reacted with an α-olefin. For example, a salt of laurylthiopropionic acid obtained by reacting 3-mercaptopropionic acid with an α-olefin of C ₁₂ is NovaSalt SA-66T or Nova. It is commercialized as Salt SA-66TE (manufactured by Nippon Yushi Co., Ltd.).

The oleylmethyltauride salt is a salt obtained by reacting oleic acid chloride with N-methyltaurine. The salt is not particularly limited, and examples thereof include sodium, calcium, potassium and ammonium salts, and sodium or calcium salts. This is preferable.

Specific examples of the oleyl methyl taurate salt include, for example, Diafon T powder (manufactured by Nippon Yushi Co., Ltd.), Postapon T powder (manufactured by Hekisuto Japan Co., Ltd.), Arkopon T powder (Hekisuto Japan Co., Ltd.) Bushing Co., Ltd.) etc. are mentioned.

As for alkyl sulfate, lauryl sulfate is marketed under the brand name of Emulsion 10 powder (made by Kaoga Co., Ltd.), and a monogen powder (made by Daiichi-kyo Kogyo Co., Ltd.).

Acetylene-based surfactants include acetylene alcohol, acetylene diol, and surfactants in which alkylene oxide is added thereto.

Acetylene alcohol is a compound represented by general formula HOC (R ¹ ) (R ² ) -C ≡CH (wherein R ¹ and R ² are the same or different and represent an alkyl group of C ₁ to C _8. ) It is commercially available under the trade name of Orffin P that ¹ is a methyl group and R ² is isobutyl group, or suffinol 61, R ¹ and R ² are all methyl groups, orpin B, R ¹ is a methyl group, and R ² is an ethyl group.

Acetylenediol is represented by the general formula HOC (R ¹ ) (R ² ) -C≡C-CR ¹ R ² OH (R ¹ and R ² are the same or different and represent an alkyl group of C ₁ to C _8. ) A compound wherein R ¹ is a methyl group and R ² is an ethyl group; safinol 82; R ¹ is a methyl group; and R ² is an isobutyl group; safinol 104; R ¹ is an ethyl group; and R ² is a butyl group; safinol DF110, R It is marketed under the brand name of orpin Y that ¹ and R <^2> are both methyl groups.

The surfactant in which alkylene oxide is added to the acetylene alcohol or acetylene diol is, for example, a surfactant in which ethylene oxide and / or propylene oxide is added to the acetylene alcohol or acetylene diol. As the addition of alkylene oxide, for example, the addition of ethylene oxide to safinol 104 is commercially available as the safinol 400 series.

In addition, powdered premixes of crushed sapinol 104 (wax type) and amorphous silicon dioxide at a weight ratio of 40:60 are used in the ratio of sapinol 104S, sapinol DF110 (wax type) and amorphous silicon dioxide at a ratio of 40:60. A powdered premix which is mixed and ground is sold under the trade name of Safinol DF110S (all manufactured by Aero Products, sold by Nisshin Chemical Co., Ltd.).

The silicone-based surfactant introduces polyethylene oxide or polypropylene oxide or both thereof into a part of the methyl group of the terminal and / or the side chain of methyl or dimethylpolysiloxane, and in some cases, a polyether-modified compound in which the terminal hydroxyl group is ether or esterified with an alkyl group. As nonionic surfactants containing silicone oil as a main component, for example, Seal Guard Series (manufactured by Dow Corning Silicone Co., Ltd.), Silhouette Series (manufactured by Nippon Unicar Corp.), Silicone Oil KF Series (Shin-Etsu Chemical Co., Ltd.) It is marketed under brand names, such as Shikisha Co., Ltd., and Genetic (made by Helena Chemical Co., Ltd.).

Fluorine-based surfactants are surfactants in which part or all of the hydrogen atoms of a common anionic, nonionic, cationic or zwitterionic surfactant are substituted with fluorine atoms, and are known to have excellent surface tension lowering force. (Made by Daikin Kogyo Co., Ltd.), mega pack series (made by Dainippon Inkigagaku Kogyo Co., Ltd.), Futgent series (manufactured by Co., Ltd.), saffron series (Asahi Glass Co., Ltd.) And F-Top (Tochem Products Co., Ltd.).

Ethers and esters of glycols are ethylene glycol, propylene glycol, butanediol, and ethers or esters in which one or both of the terminal hydroxyl groups of these polymers are substituted with a suitable alkyl or carboxylic acid group, and specifically, hexyl glycol (HeG , Ethylene glycol monohexyl ether, Nihon New Kazai Co., Ltd., hexyl diglycol (HeDG, diethylene glycol monohexyl ether, Nihon New Kazai Co., Ltd.), 2-ethylhexyl glycol (EHG, ethylene glycol mono 2) -Ethyl hexyl ether, Nihon New Kazai Co., Ltd., 2-ethylhexyl diglycol (EHDG, diethylene glycol mono 2-ethylhexyl ether, Nihon New Kazai Co., Ltd.) etc. are sold.

Alkyl esters of carboxylic acids include carboxylic acids such as palm oil fatty acid, lauric acid, oleic acid, lactic acid or methyl of polybasic carboxylic acids such as maleic acid, citric acid, fumaric acid, adipic acid, glutaric acid, phthalic acid, Alkyl esters such as ethyl, propyl, butyl, hexyl, ethylhexyl, lauryl, oleyl and the like, specifically, Exepal MC (methyl fatty acid, Kao Kagushi Kaisha), Exepal M-OL (methyl oleate, gaoga) Bushishi Co., Ltd., Binisaiza 30 (Isobutyl Oleate, Kaogakishiki Co., Ltd.), Vinisasai 124 (Dialkyl phthalate, Kaogakishiki Kaisha), Butyl Lactate (Kabushishikaga Musashinogaku Kogen Kyusho), etc. It is sold under the brand name of.

The amount of the sleeping retardant used in the present invention varies depending on the formulation and formulation of the pesticide active ingredient, the type and the method of adding the sleeping retardant, and the type and amount of the other ingredients. It is-30%, Preferably it is 0.3-20%, More preferably, it is 0.5-10%.

The pesticide solid agent of the present invention may be blended with other auxiliaries such as nonvolatile liquid substances, emulsifiers, dispersants, wetting agents, diluents, water repellents, particle growth inhibitors, and stabilizers.

In order to dilute, coat or impregnate the solid, semi-solid or liquid pesticide active ingredient at room temperature, a nonvolatile liquid substance can be used if necessary. The nonvolatile liquid substance may be one having a property of uniformly coating and impregnating the active ingredient of the pesticide into the foam of the present invention without adversely affecting the pesticide active ingredient, such as particle growth and decomposition, and having a high boiling point, low toxicity and a flash point. It is preferable that the specific gravity is high, and low in viscosity at low viscosity. Generally, the pesticide active ingredient has a specific gravity of 1 or more. In such a case, in order to keep emulsified particles in water for as long as possible and to spread them widely in rice fields, a solvent having a specific gravity smaller than 1 and having a low viscosity is often used. Examples thereof include mineral oils such as low viscosity liquid paraffin, isoparaffin, machine oil, polybutene, paraffinic, naphthenic and aromatic high boiling point solvents; Vegetable oils such as palm oil, soybean oil, and rapeseed oil; Animal oils such as whale oil and sardine oil; Silicone oil and its derivatives; Mono or polyhydric carboxylic acids such as oleic acid, lactic acid, palm oil fatty acid, maleic acid, fumaric acid, phthalic acid, adipic acid and various esters thereof; Plasticizers such as various esters of phosphoric acid such as tributyl phosphate and trischloroethyl phosphate; lactones such as ε-caprolactone and γ-butyrolactone; N-methylpyrrolidone; And various liquid surfactants. Preferably, they are low viscosity liquid paraffin, machine oil, isoparaffin, or various alkyl esters, and specifically, super oil series, smile P series (Nihonseki Yugaku Chemical Co., Ltd.). Liquid paraffins, such as the liquid paraffin No series (manufactured by Chuo Chemical Co., Ltd.); Machine oils such as Daphni Oil Series (manufactured by Idemitsu Kosan Co., Ltd.); Isoparaffins, such as isopa series and isosol series (made by Nihon Seki Yugaku Co., Ltd.), etc. are mentioned, You may mix and use 2 or more types of these.

The amount of the nonvolatile liquid substance used in the present invention varies depending on the type of active ingredient of pesticide, the type of other auxiliary agent, the amount of compounding, etc., as long as it does not affect the stability or physical properties of the pesticide solids over time. good. The compounding quantity is generally 1 to 60%, preferably 2 to 50%, more preferably 3 to 40%.

The emulsifier used in the present invention is used as necessary to emulsify a liquid pesticide active ingredient or a solution of the pesticide active ingredient in water, and is selected and used in the same manner as selecting an emulsifier of a conventional emulsion according to the pesticide active ingredient or solvent. Can be.

The compounding quantity of the emulsifier used by this invention is generally 0.01 to 30%, Preferably it is 0.03 to 15%.

The dispersant used in the present invention is used to suspend and disperse the pesticide active ingredient in water, for example, lignin sulfonate, (alkyl) naphthalene sulfonate and its condensate, phenol sulfonate and its condensate, styrene sulfonate Condensates, salts of condensates of maleic acid and styrenesulfonic acids, salts of carboxylic acid condensates such as acrylic acid and maleic acid, alkylbenzenesulfonates, salts of lauryl sulfate, salts of polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylaryl And anionic surfactants such as salts of ether sulfate, polyoxyethylene alkyl ether phosphate esters and salts thereof, polyoxyethylene alkylaryl ether phosphate esters and salts thereof, and phosphate salts such as sodium tripolyphosphate and sodium hexametaphosphate. Moreover, a suitable thing can also be selected even if it is a nonionic, cationic, and zwitterionic surfactant. Many of these dispersants are useful as wetting agents.

The compounding amount of the dispersing agent and the wetting agent used in the present invention is generally from 0.01 to 30%, preferably from 0.1 to 20%, more preferably from 0.2 to 15%.

The diluent used in the present invention is a diluent for preparing a rich premix of solid pesticide active ingredients, and is generally a carrier of pesticides such as bentonite, talc, clay, diatomaceous earth, amorphous silicon dioxide, calcium carbonate, magnesium carbonate and the like. In addition to mineral powders used as powders, various resin powders such as chloride, vinylidene chloride, polyethylene and polypropylene, sugars such as glucose, sugar and lactose, starch and derivatives thereof, microcrystalline cellulose, wood powder, sawdust, rice bran, bran and chaff powder And organic materials such as coffee beans, coconut shell powder, activated carbon, cellulose powder, licorice powder, water-soluble inorganic salts such as sodium sulfate, ammonium sulfate, potassium chloride, and urea.

The compounding quantity of the extender used by this invention is generally 0.1 to 80%, Preferably it is 0.2 to 50%, More preferably, it is 0.5 to 20%.

The water-repellent used in the present invention is mainly formulated to suppress the elution of the active ingredient of the pesticide, spread as widely as possible to the surface of the water when the active ingredient of the pesticide active ingredient is high, and to dissolve in water, for example magnesium stearate And fatty acids such as calcium stearate, higher alcohols such as stearyl alcohol, higher fatty acids such as stearic acid, silicone oils and derivatives thereof, fluorine-based surfactants, cationic surfactants, hydrophobic silica, liquid paraffin, and machine oils. .

Although the compounding quantity of the water repellent used by this invention changes with the kind and physical property of an active pesticide active ingredient, the compounding quantity is generally 0.05 to 10%, Preferably it is 0.1 to 5%.

The particle growth inhibitor or stabilizer used in the present invention may be blended if necessary depending on the nature of the active ingredient of the pesticide. In addition, a pigment | dye, bitter agent, and other various adjuvant can be mix | blended as needed.

Since the pesticide granules of the present invention need to be dispersed, emulsified or dissolved in water promptly after the pesticide granules are expanded in water, the amount of wetting agent, dispersant, emulsifier, etc. is adjusted.

It is preferable that the pesticide granules of this application obtained in this way show the favorable sleep-sustainability of 5 points or more of the electrostatic potential index by the method shown below.

The `` Accuracy Indices '' refers to the quantification of sleep aggression of sleeping pesticide solids in the range of 0 to 15 (out of 15), and the higher the score, the better the sleep integrity. Preferably 5 or more, more preferably 7 or more, and more preferably 9 or more. The test method for sleep integrity is as follows.

25 liters of tap water is placed in a gutter of 4 m in length and 14 cm in width, and the water temperature is adjusted to 20 ° C. Assuming that an obstacle (float) on the front surface of the water is assumed, 2 g of Smithelco (manufactured by Smithkinbusan Co., Ltd., powdered rice husk) is treated to be uniform on the surface of the water. After stationary, 280mg of pesticide solids are added at 10cm from one end of the gutter, 1.5m at the point of injection of each pesticide solids after input, the longest reach from the point of input, and the expansion state after 5 minutes. The visual inspection was carried out with each other, and the results were determined according to the evaluation criteria shown in Table 1 below, and the evaluation points of the respective items were summed to obtain respective reliability indexes.

Evaluation Items and Evaluation Criteria Evaluation item Criteria Score 1.5m reach time 2 minutes or more 1 minute or more, less than 2 minutes 30 seconds or more, less than 1 minute 20 seconds or more, less than 30 seconds 10 seconds or more, less than 20 seconds less than 10 seconds 012345 Longest Reach Less than 0.5 m More than 0.5 m Less than 1.0 m More than 1.0 m More than 1.5 m Less than 1.5 m More than 2.0 m Less than 2.0 m More than 2.5 m More than 2.5 m More than 3.0 m Less than 3.0 m More than 3.5 m More than 3.5 m 01234567 5 minutes after treatment Expanded tip returns to treatment point Return more than 1m from longest point return Less than 1m from longest point Not return from longest point 0123 Perfect score 15

The pesticide granules exhibiting the surface-floating properties of the present invention thus obtained may be scattered in the paddy field using a hand or a suitable granulator as it is, or may be separately packed and packaged in a paper or sheet containing a water-soluble paper, and introduced into the paddy and treated. In the case of granules having good sleep stability, even if they are not uniformly placed in paddy fields or uniformly processed using a granulator, the granules are naturally expanded in the water surface just by performing so-called liquid treatment along the vicinity of the paddy field. The same effect as that of processing can be obtained. In the case of separate packaging with a receiving paper, if the granulating agent does not have sleep stability, the granulating agent may not sufficiently expand even if the receiving paper is dissolved in water. Thus, a granulating agent having good expandability is preferable.

Here, the receiving paper is composed of a water-soluble film or sheet and has a property of dissolving or dispersing in cold water to release the granules therein. Examples of the material include polyvinyl alcohol (PVA), cellulose such as sodium salt of carboxymethyl cellulose, polyether such as polyethylene oxide, polysaccharide such as pullulan, and the like in the present invention. You may use either. These include not only the board | substrate-shaped paper or the embossed film normally used, but the sheet | seat which consists of water-soluble nonwoven fabrics which consist of these materials. The water-soluble nonwoven fabric includes not only the water-soluble nonwoven fabric but also the sheet which consists of a laminated material which laminated the water-soluble film suitable for a water-soluble nonwoven fabric.

Among these materials, PVA in which the film itself is electrostatic is particularly preferable. Preferable PVA is about 1000-2000 degree of polymerization, about 85 to 95% of degree of saponification (soaping), and also includes what copolymerized a small amount of carboxylic acid, sulfonic acid, etc. in a polymer. If the degree of polymerization of PVA is too high or the degree of susceptibility is too high, it is difficult to dissolve in cold water, which is not preferable. Moreover, in order to improve the physical property and stability of PVA, you may contain a plasticizer, a stabilizer, a pigment | dye, etc. which are added to a normal PVA film.

As for the thickness of these water-soluble films or sheets, 20-100 micrometers is preferable. When the thickness is 20 µm or less, the strength may be insufficient and the fracture may be easily caused, causing problems in use as a packaging material. Moreover, when it becomes 100 micrometers or more, it will take time to melt | dissolve in water, and it will not become a profitable measure because a price becomes high. Preferably it is 30-60 micrometers, More preferably, it is 35-50 micrometers.

The weight of one sachet is usually 10 to 200 g, preferably 20 to 100 g, more preferably 25 to 70 g in view of the ease of feeding. With this weight, even children, women and elderly people can easily put it in the target point within 15m. If it is too heavy, it is difficult to put in, so it is not easy to process a large area, and under this, it is not possible to reach the target point under the influence of the wind.

As the shape of the separated packaging, a rectangle having a side of 1 to 30 cm or a square is generally used, but it is not limited to these, and even if it is a polygon, a circle, a sphere, a cylinder or the like, there is no problem at all. As a method of separating and packaging, each side may be sealed with a paste. Ultrasonic waves, high frequency, and heat seals may be used, and heat sealing is suitable in view of workability.

As a method of heat sealing, the method of thermocompression bonding at 3-100 kg / cm linear pressure, for example using a heat sealing machine at the temperature 20-150 degreeC lower than melting | fusing point of a receiving paper can be used.

Since the pesticide granules of the present invention are extensively expanded on the surface of water and the spread of the active ingredient of pesticides reaches a wide range, it is not necessary to put them far in the ordinary paddy field, and drop them on the surface of the surface of the rice paddies in the vicinity of the rice paddies in the vicinity of 2-3 m. Is enough.

If the number of separated pavements put into the paddy field is too large, it will not reduce manpower and it is economically disadvantageous. Usually, by dropping 1-30 pieces per 10 a, sufficient biological effects can be exerted. It is 1-20 pieces.

The separated packaging of the obtained solid agent is enveloped in a bag or a box such as a paper bag, a resin bag or an aluminum foil bonding, or a resin bag in which aluminum or silica is deposited, and thus is stable over time with respect to moisture absorption. Therefore, it is not necessary to pay attention to hygroscopicity, but since the receiving paper is torn off when the water touches, it is preferable to use an exterior with proper waterproofing.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in more detail in Examples and Test Examples, but the present invention is not limited to these Examples.

(Example 1)

The high pressure process was performed with the extruder by the raw material formulation prescription shown in following Table 2. The properties of the obtained composition are shown in Table 3. In addition, oil separability in Table 3 is shown by the symbol, and is shown by (double-circle), (circle), or x in order from a thing with good oil separability.

In addition, the operating conditions of the extruder (single screw extruder α100 manufactured by Shiro EPM Co., Ltd.) are rotation speed: 80 to 160 rpm, inner diameter and barrel ratio L / D: 12, raw material input amount: 40 to 80 kg / hr, pressure: 30 to 50 kg. / Cm <2>, Die opening diameter: 2.5 mm (1.5 mm of sample numbers 4 and 12), 10 holes in series, barrel temperature: 80-90 degreeC, die temperature: 80 degreeC-120 degreeC.

Sample Number Starch-containing substances Crosslinking agent 1 (comparison) 234 Corn Grits (100) Corn Grits (97) Corn (98) Soybeans (98) Sodium tripolyphosphate (3) sodium tripolyphosphate (1) + sodium trimethphosphate (1) sodium tripolyphosphate (1) + sodium trimethphosphate (1) () Shows the mass part of compounding quantity.

Sample Number volume Foam outer diameter Oil absorption magnification Floating time Oil separability 1 (comparison) 234 80976 20 mm7 mm5 mm3 mm 0.11.52.02.5 1 hour 6 hours 20 hours 22 hours × ◎◎◎

(Example 2)

In the same manner as in Example 1, the high pressure treatment was performed with an extruder by the raw material blending prescription shown in Table 4 below. The properties of the obtained composition are shown in Table 5.

Sample Number Starch Starch-containing substances Geology Emulsifier Thermal coagulant Crosslinking agent 5 (comparative) Cornstarch (100) 0 0 0 0 0 6 (comparative) Oxidized Starch (100) 0 0 0 0 0 7 Starch Oxide (82) 0 Palm oil (2) Sucrose Fatty Acid Ester (1) Soy Protein (10) Sodium Tripolyphosphate (5) 8 Oxide Starch (50) Cornrichz (42.5) Palm oil (1) Sucrose Fatty Acid Ester (0.5) Soy Protein (3) Sodium Tripolyphosphate (3) 9 (comparative) Hydroxypropylated Starch (97) 0 0 0 0 Sodium trimetaphosphate (3) 10 Hydroxypropylated Starch (87) 0 0 0 Gluten (10) Sodium trimetaphosphate (3) 11 Hydroxypropylated Starch (82) 0 Baekkyo oil (4) Glycerin Fatty Acid Ester (1) Gluten (10) Sodium trimetaphosphate (3) 12 Hydroxypropylated Starch (50) Soybeans (40.5) Vaseline (1) Glycerin Fatty Acid Ester (0.5) Gluten (3) Sodium trimetaphosphate (3) () Shows the mass part of compounding quantity.

Sample Number volume Foam outer diameter Oil absorption magnification Floating time Oil separability 5 (Compare) 6 (Compare) 789 (Compare) 101 112 110120851301075 20 mm30 mm5 mm5 mm35 mm8 mm8 mm3 mm 0.10.21.32.00.10.30.62.0 30 minutes 10 minutes 12 hours 15 hours 5 minutes 1 hour 5 hours 15 hours ○○ ◎◎ × ○○ ◎

(Example 3)

Butachlor original (ai 90%) 43.75 parts, EHDG (diethylene glycol mono2-ethylhexyl ether, manufactured by Nihon New Kazai Co., Ltd.) 3.00 parts, NE-2609 (polyoxyethylene polycyclic phenyl ether, Nihon New Kazaga) 1.50 parts of Bushiki Co., Ltd. and 1.50 parts of DBC (70% of calcium dodecylbenzenesulfonate, the Nihon New Kazai Co., Ltd.) were mixed to obtain an oil premix. In addition, 0.95 parts of ethoxysulphone original (ai 98.8%), 7.90 parts of Roca HELP 439 (Perlite, Mitsui Ginjo Kogyo Co., Ltd.), and M-3801G (sodium olefin sulfonate, Daiichigo Kyase Seiyakuga) 0.50 parts of the company was mixed, and ground by a hammer mill to obtain a powder premix. 38.40 parts of the foam of sample No. 8 of Example 2 were injected into the outer mixer, 49.75 parts of oil premix was added, mixed and absorbed, followed by mixing and coating of 9.35 parts of powder premix, followed by 2.50 parts of Loca HELP 439. The mixture was coated to obtain an agrochemical granule of the present invention containing 37.50% butachlor and 0.85% ethoxysulfur. 40 g of the obtained granules were separated and packaged with Hyceron C-200 (a PVA film having a thickness of 40 µm and manufactured by Nichigo Film Co., Ltd.) to obtain a preparation for paddy field of the present invention. This formulation is applied at a rate of 5 packs per 10a of rice paddies.

(Example 4)

43.75 parts of butachlor origin and 3.00 parts of EHDG were mixed to obtain an oil premix. Separately, 0.95 parts of ethoxysulfone element, 6.40 parts of Loka help 439, Barney Rex N (sodium lignin sulfonate, manufactured by Nippon Seishi KK) and GEROPON SDS (sodium dioctyl sulfosuccinate, Shionogi Seiyaku Kabu) Shikisha) 1.00 parts were mixed and ground by a hammer mill to obtain a powder premix. 41.40 parts of the foam of sample No. 7 of Example 2 were injected into the outer mixer, 46.75 parts of oil premix was added and mixed, absorbed, and then mixed and coated with 9.35 parts of powder premix, and then 2.50 parts of Loca HELP 439 was added. The mixture was coated to obtain an agrochemical granule of the present invention containing 37.50% butachlor and 0.85% ethoxysulfur. 40 g of the obtained granules were separated and packaged with Hysrone C-200 to obtain a preparation for paddy field of the present invention. This formulation is applied at a rate of 5 packs per 10a of rice paddies.

(Example 5)

29.17 parts of butachlor origin, 3.00 parts of EHDG, 1.50 parts of NE-2609 and 1.50 parts of DBC were mixed to obtain an oil premix. Separately, 0.64 parts of ethoxysulphone original material, 5.26 parts of Loca help 439 and 0.33 parts of M-3801G were mixed, and ground by a hammer mill to obtain a powder premix. 54.60 parts of the foam of sample No. 2 of Example 1 were injected into the outer mixer, 35.17 parts of oil premix was added and mixed, and then absorbed. Then, 6.23 parts of powder premix was added and mixed, and 4.00 parts of LocaHelp 439 was added again. The mixture was coated to obtain an agrochemical granule of the present invention containing 25.00% butachlor and 0.57% ethoxysulfur. This formulation is applied in the vicinity of paddy field at the rate of 300 g per paddy field 10a.

(Example 6)

Manufacture of foam carrier

In the raw material blending prescription shown in Table 6 below, a foam carrier was produced using a twin screw extruder. Table 7 shows the physical properties of the obtained foam carrier.

In addition, the conveying conditions of the extruder (Swine EPM Co., Ltd. twin-screw extruder α100) are rotational speed: 80-160 rpm, inner diameter and barrel ratio L / D: 12, raw material input amount: 40-80 kg / hr, pressure: 30-50 kg / Cm <2>, die opening diameter: 1.5 mm, series 10 holes, barrel temperature: 80-90 degreeC, die temperature: 80-120 degreeC.

Foam carrier prescription Sample Number Natural products or derivatives thereof Crosslinking agent One Power component (98) Sodium trimetaphosphate (2) 2 Kongritz (98) Sodium trimetaphosphate (2) 3 Starch oxide (50) + corn (38) + serogen EP ^* (5) Sodium Tripolyphosphate (3) + Gluten (3) + Palm Oil (1) ^* Carboxymethylcellulose sodium salt and Dai-Ichigo Kyaseiya Co., Ltd. product () show the mass part of compounding quantity.

Physical properties of foam carrier Sample Number volume Foam outer diameter Oil absorption magnification Floating time Underwater decay One 11 3 mm 1.5 20 hours Non-destructive 2 9 5 mm 1.5 6 hours Non-destructive 3 7 3 mm 1.8 18 hours Non-destructive

(Example 7)

Pesticide formulations containing force component and α-amylase and preparations for paddy field

Butachlor original (ai 90%) 43.75 parts, EHDG (diethylene glycol mono2-ethylhexyl ether, manufactured by Nihon New Kazai Co., Ltd.) 3.00 parts, NE-2609 (polyoxyethylene polycyclic phenyl ether, Nihon New Kazaga) 0.50 parts of DBC (calcium dodecylbenzenesulfonate 70%, manufactured by Nihon New Kazai Co., Ltd.) 0.50 parts of Bushiki Kaisha and BioCryptase M8 (α-amylase, manufactured by Yamato Chemical Co., Ltd.) 0.20 The parts were mixed to obtain an oil premix. Separately, 0.95 parts of ethoxysulfone element (ai 98.8%), Roca help 439 (powder type ferrite, manufactured by Mitsui Ginjo Kogyo Co., Ltd.) 5.40 parts, Banirex N (sodium lignin sulfonate, Nippon Seishi Co., Ltd.) ) 1.00 parts and 2.00 parts of GEROPON SDS (sodium dioctylsulfosuccinate, Shionogi Seiyaku Co., Ltd.) were mixed and ground by a hammer mill to obtain a powder premix.

40.20 parts of the foam of sample No. 1 of Example 6 were injected into the outer mixer, 47.95 parts of oil premix was added and mixed and absorbed, 9.35 parts of powder premix was added and mixed, and then 2.50 parts of Roca help 439 was mixed. It coat | covered and obtained the pesticide granules of this invention containing 37.50% of butachlor and 0.85% of ethoxysulphron. 40 g of the obtained granules were separated and packaged with Hyceron C-200 (a PVA film having a thickness of 40 µm and manufactured by Nichigo Film Co., Ltd.) to obtain a preparation for paddy field of the present invention. This formulation is applied at a rate of 5 packs per 10a of rice paddies.

(Example 8)

Pesticide formulations containing Cornrichz and α-amylase and preparations for paddy field

In Example 7, except for changing the foam carrier of Sample No. 1 of Example 6 to the foam carrier of Sample No. 2 of Example 6, buttachlor was 37.50% and ethoxysulfur in the same manner as in Example 1. The pesticide granules of the present invention containing 0.85% of pron were obtained. 40 g of the obtained granules were separated and packaged with Hysrone C-200 to obtain a preparation for paddy field of the present invention. This formulation is applied at a rate of 5 packs per 10a of rice paddies.

(Example 9)

Pesticides containing rice flour, α-amylase and protease and preparations for paddy field

In Example 7, the same procedure as in Example 7 was repeated except that 0.20 parts of biocristase M8 was changed to 0.10 parts of biocristase M8 and 0.10 parts of protein AS10 (protease, manufactured by Yamato Chemical Co., Ltd.). Thus, the pesticide granules of the present invention containing 37.50% butachlor and 0.85% ethoxysulfur were obtained. 40 g of the obtained granules were separated and packaged with Hysrone C-200 to obtain a preparation for paddy field of the present invention. This formulation is applied at a rate of 5 packs per 10a of rice paddies.

(Example 10)

Pesticide formulations containing starch oxide, corn flour, serogen EP, α-amylase and cellulase and preparations for paddy fields

In Example 7, 0.20 parts of biocristase M8 was changed to 0.10 parts of biocristase M8 and 0.10 parts of cellulose (cellulase, manufactured by Hankyu Bio Industry Co., Ltd.), and also the sample number 1 of Example 6 A pesticide granule of the present invention containing 37.50% butachlor and 0.85% of ethoxysulfuron was obtained in the same manner as in Example 7, except that the foam carrier of Example 6 was changed to the foam carrier of Sample No. 3 of Example 6. . 40 g of the obtained granules were separated and packaged with Hysrone C-200 to obtain a preparation for paddy field of the present invention. This formulation is applied at a rate of 5 packs per 10a of rice paddies.

Experimental Example 1

The integrity index of the granules obtained in Examples 3 to 5 and the floating property of the granules were examined. The results are shown in Table 8. As shown in Table 8, the sleep-floating granules according to the present invention were suspended in water for about 24 hours after being added to water, and then gradually began to sink, and most of the granules settled after 48 hours. In addition, these granules had a high electrostatic index, which showed good diffusion on the surface. The granules of these examples were free of particles that settled immediately after addition in water, and also exhibited good electrostatic properties.

EXAMPLES Suspension and Sustainability Index of Granules Test Granule Sleep Flotation Probability index Example 3 Example 4 Example 5 No granules settle down until after 24 hours. After that, it slowly began to sink, and after 48 hours most granules had settled down. After that, it slowly began to sink, and after 48 hours most granules had settled down. After that, it began to sink slowly, and after 48 hours most granules settle. 111012

(Test Example 2)

Dissolution Test

Under conditions of room temperature 20 ° C., 10 liters of constant water (depth of about 5 cm) was put in a poly container having a dimension of 60 cm in width x 34 cm in height x 10 cm in height (area 2040 cm 2), and the water temperature was adjusted to 20 ° C. The sample is accurately weighed about 40 mg for Examples 3 and 4 and about 60 mg for Example 5 and processed at the center. After 24 hours of treatment, water was sampled at three points on the diagonal of the container as shown in Fig. 1, and the granules suspended in water or suspended in the water were collected. The active liquid concentration in water and the active ingredient in the granules were analyzed by high performance liquid chromatography, and the dissolution rate of the active ingredient in water and the residual ratio of the active ingredient in the granules were determined. The results are shown in Table 9. All of the samples of Examples 3 to 5 exhibited a dissolution rate of almost 100% in both ethoxysulfone and butachlor after one day of treatment, and almost no residual of the active ingredient was found in the granules.

Dissolution test result Test Granule Ethoxysulfron Butachlor Concentration in water (ppm) n = 3 Average Water dissolution (%) Residual rate in granules (%) Concentration in water (ppm) n = 3 Average Water dissolution (%) Residual rate in granules (%) Example 3 0.030.030.03 0.03 100 0 1.401.451.44 1.43 95 One Example 4 0.030.030.03 0.03 100 0 1.321.441.42 1.39 93 2 Example 5 0.030.030.03 0.03 100 0 1.441.361.39 1.40 93 4 Theoretical values for concentration in water are ethoxysulphron: 0.03 ppm and butachlor: 1.50 ppm.

Experimental Example 3

Collapsible test

Under conditions of room temperature 20 ° C., 500 mL of 3 degree hard water was placed in a 500 mL capacity beaker, and the water temperature was adjusted to 20 ° C. The pesticide preparations of Examples 7 to 10 and the foam carriers of Sample Nos. 1 to 3 of Example 6 were each placed in three particles of a beaker, and the disintegration time of the particles was observed. The results are shown in Table 10.

Collapsible test number Test Agent or Carrier Decay time in water 1234567 Pesticide Preparation Example 7 Pesticide Preparation Example 8 Pesticide Preparation Example 9 Pesticide Preparation Example 9 Pesticide Preparation Example 6 Foam Carrier Example 6 Foam Carrier Example 6 Foam Carrier Example 6 Sample No. 3, foam carrier 20 minutes 30 minutes 15 minutes 10 minutes

Although all the foam carriers of Example 6 were non-collapsed, the pesticide preparations of Examples 7-10 containing these foam carriers and enzymes collapsed within 30 minutes of treatment.

According to the present invention, a foam which floats on the surface of water and is excellent in oil absorption capacity is obtained. Such a foam can be used, for example, as a carrier for a pesticide sprayed on a paddy field or a paddy field, and can contain a high concentration of a liquid element, thereby greatly reducing the amount of medicine to be treated in the paddy field. This technology, along with the aging of farms, contributes to the recent agriculture, which requires a reduction in manpower.

Claims (20)

0.1-5 parts by mass of the crosslinking agent was added and mixed to 95.0-99.0 parts by mass of the starch-containing material, and the diameter of the foam treated with the extruder was 1-5 times the diameter, 1-20 mL / g in volume, and 0.3- Foam having five times oil absorption, suspended in water for more than 10 minutes. Starch-containing substance and starch (starch-containing substance: starch = 0 to 80: 100 to 20) 1 to 30 parts by mass of thermocoagulated substance and 0.1 to 5 parts by mass of crosslinking agent are added to 45 to 95 parts by mass, and mixed with an extruder. A foam having a diameter of 1 to 5 times the die diameter, a volume of 1 to 20 ml / g, an oil absorption capacity of 0.3 to 5 times its own weight, and floating in water for 10 minutes or more. The foam according to claim 2, wherein the mixture before treating with an extruder contains 0.1 to 8 parts by mass of lipid and 0.1 to 5 parts by mass of an emulsifier. A method of producing a foam having a diameter of 1 to 5 times the diameter of the foam, 1 to 20 ml / g in volume, 0.3 to 5 times the oil absorption capacity, and floating in water for 10 minutes or more. 0.1-5 mass parts of crosslinking agents are added-mixed with 95.0-99.0 mass parts of a substance, and it press-extracts and processes at die temperature of 100-150 degreeC with an extruder, The manufacturing method of the foam characterized by the above-mentioned. A method of producing a foam in which the diameter of the foam is 1 to 5 times the die diameter, the volume is 1 to 20 ml / g, the oil absorption capacity of 0.3 to 5 times its own weight, and is suspended in water for 10 minutes or more. Substances and starches (starch-containing substances: starches = 0 to 80: 100 to 20) 1 to 30 parts by mass of thermocoagulant and 0.1 to 5 parts by mass of crosslinking agent are added and mixed to 45 to 95 parts by mass, and the die temperature is 100 Process for producing a foam, characterized in that the pressure extraction at -150 ℃ processing. The method for producing a foam according to claim 5, wherein the mixture before pressurization with an extruder contains 0.1 to 8 parts by mass of lipid and 0.1 to 5 parts by mass of an emulsifier. The foam according to any one of claims 1 to 3, which absorbs 0.2 to 7 times the amount of oil pesticides or high boiling point organic solvent solutions of pesticides, and further grinds the solids of pesticides as necessary. A sleep-floating granular pesticide composition having fluidity by coating a powder of a solid material which does not contain a premix or a pesticide pulverized with a solid carrier of water and a pesticide. 8. The sleep-floating granular pesticide composition according to claim 7, further comprising a sleep expanding agent. 7. The sleep enhancer according to claim 6, wherein the sleep enhancer comprises an α-olefin sulfonate, an α-sulfofatty acid salt, an α-olefin fatty acid salt, an oleylmethyltauride salt, a mono- or di-alkylsulfosuccinate salt and an alkylene oxide thereto. It is 1 type, or 2 or more types chosen from the high boiling point solvent chosen from the added surfactant, alkyl sulfate, acetylene type, silicone type, fluorine type surfactant, ether or ester of glucol, and alkyl ester of carboxylic acid. Sleep-floating granular pesticide composition. 10. The sleep-floating granular pesticide composition according to any one of claims 7 to 9, wherein the sleep spreading number is 5 or more. The liquid pesticide composition according to any one of claims 7 to 10, wherein the active ingredient of the agrochemical consists of butachlor, pretilachlor, anilophos, benpresate, sihalopopbutyl, dimethamethrin, or bensulphron. Sleep-floating granular pesticides, characterized in that it contains one or two or more of sulfonylurea herbicides selected from methyl, pyrazosulfurethyl, azimsulfur, ethoxysulfur, imazosulfron, and cynosulfron. Composition. The sleep-floating granular pesticide composition according to any one of claims 7 to 11, which contains a starch-containing substance or an enzyme acting on starch. 13. The sleep-floating granular pesticide composition according to claim 12, wherein the starch-containing substance or starch is corn flour, corn grits or wheat flour, and the enzyme is amyloglucosidase, α-amylase, β-amylase or isoamylase. The sleep-sustaining granular pesticide composition according to any one of claims 7 to 13, which contains cellulase, bacterial protease, filamentous fungal protease, papain, pepsin or pectinase. The sleep-sustaining granular pesticide composition according to any one of claims 12 to 14, wherein the enzyme is an endo type enzyme. The foam according to any one of claims 1 to 3, which absorbs 0.2 to 7 times the amount of an oily pesticide agent or a high boiling point organic solvent solution of the pesticide, further grinds the solid agent of the pesticide, if necessary. A method for producing a water-floating granular pesticide composition having a fluidity by coating a powder of a solid carrier which does not contain a premix or a pesticide pulverized with a solid carrier of water and a pesticide. A pesticide composition for paddy fields, wherein the sleeping-floating granular pesticide composition according to any one of claims 7 to 15 is separately packed and packaged with a water-soluble film or sheet. 18. The agrochemical composition for paddy fields according to claim 17, wherein the water-soluble film or sheet is a water-soluble film or sheet made of polyvinyl alcohol or a derivative thereof. A method for treating rice field pesticides, comprising: dispersing the surface-floating floating granular pesticide composition according to any one of claims 7 to 15 directly in a rice field. 19. A method for treating paddy field pesticides, comprising treating the paddy grain composition of any one of claims 17 or 18 with the paddy field.