JPS6149281B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a solidified emulsion and a method of using the same. The solidified emulsion herein refers to a solid drug in which an emulsion is supported on a carrier, and forms a stable emulsion when mixed with water. Moreover, in this specification, agricultural use does not only mean agricultural use in a narrow sense, but also includes agricultural use in a broad sense, including trees and agricultural and forestry products. Agricultural and epidemic prevention drugs are usually sold and used as preparations containing active ingredients mixed with various auxiliaries. Depending on the dosage form, the formulation is usually powder,
It is classified into granules, tablets, wettable powders (suspensions), emulsions, liquids, etc. Wettable powders, emulsions and solutions are generally diluted in water to form suspensions, emulsions and solutions, respectively, at the time of use, and are generally sprayed using a sprayer. Since these use water as a carrier, they are more complicated to spray than powders, granules, etc., but because the droplet size of the sprayed droplets is large and there are fewer particles that drift and scatter, there is less contamination of the active ingredient outside the target environment. Among these formulations that use water as a carrier, liquid formulations and emulsions are more preferable formulations because they are more quickly decomposed and detoxified than wettable powders after the onset of their effects. However, when water is used as a carrier, active ingredients that are sparingly soluble or insoluble in water cannot be prepared as a liquid formulation, so they must be used as a wettable powder or emulsion. Wettable powders have their active ingredients supported on a solid carrier, so they can be handled as solids until they are diluted with water for application. On the other hand, an emulsion is a solution prepared by adding a surfactant and, if necessary, an organic solvent or water to an active ingredient, and is handled as a liquid. However, liquids have various disadvantages compared to solids in terms of packaging, handling, etc.
It would be extremely advantageous if the emulsion could be solidified. Attempts have been made to solidify emulsions. For example, a method of solidifying emulsions by adsorbing them to diatomaceous earth is known. However, the product obtained by this method is intended for spraying as is, and it is not yet known to dilute the solidified emulsion with water and spray it as a stable emulsion. The present inventor investigated a method of solidifying an emulsion that can form a stable emulsion when diluted with water, and found that an emulsion in which the emulsion is occluded in cellulose powder is suitable for this purpose, and completed the present invention. did. The present invention will be explained in detail below. The solidified emulsion according to the present invention is basically a solution obtained by adding an emulsifier and an organic solvent as necessary to the active ingredient, which is occluded in cellulose powder. It is solidified. The organic solvent dissolves the active ingredient to form a solution, which allows the active ingredient to be absorbed into the cellulose powder, and when the resulting solidified emulsion is mixed with water, the droplets containing the active ingredient dissolved therein are uniformly dispersed in the water. It has the effect of dispersing into the liquid and producing an emulsion. Therefore, if the active ingredient is in liquid form and can be easily absorbed into cellulose powder by itself, and can form a stable emulsion when mixed with water under the action of an emulsifier, organic solvents should not be used. Not good enough to use. As the organic solvent, any organic solvent used in producing the emulsion of the active ingredient can be used, and the amount used is preferably as small as possible within the range that achieves the above purpose. The emulsifier functions to form a stable emulsion when the solidified emulsion is mixed with water. As the emulsifier, any one used in producing an emulsion of the active ingredient or its organic solvent solution can be used, and the amount used is basically the same as in the case of producing an emulsion. Note that depending on the type of emulsifier, the emulsion may become slightly viscous, but this does not pose a problem for occluded in cellulose powder. As is well known, cellulose powder is mainly composed of α-cellulose obtained from plants, and various types are commercially available for use as fillers, admixtures, carriers, and the like. There are various shapes such as fibrous and crystalline, and there are also various particle sizes and colors, and an appropriate one may be used depending on the purpose.
Furthermore, the cellulose powder may contain some impurities such as ash, lignin, resin, etc. derived from raw materials. In the present invention, cellulose powder with a small particle size is generally used so as not to clog a sprayer when spraying the emulsion. Usually 90% or less is 177μ or less, preferably 46μ
A cellulose powder containing 90% or more of the following is used: Cellulose powder generally has a high absorption capacity for liquids, for example, 2 times its own weight.
Can absorb ~3 times more water or 1.5-2.5 times more oil. Therefore, by using cellulose powder, a solidified emulsion with a high active ingredient content can be obtained. Some examples of commercially available cellulose powders are as follows. No. 1 Soft tissue cellulose powder (trademark, KC Flotsuk W-300, product of Sanyo Kokusaku Pulp Co., Ltd.) Moisture 4.5%, ash content 0.3%, particle size 46 μ or less, 90% or more, white No. 2 Crystalline cellulose powder (trademark, Avicel, Asahi Kasei Kogyosha product) Moisture 5.8%, ash 0.08%, particle size 125μ or less 90%
Above, White No. 3 Soft tissue cellulose powder (trademark, Pulp Flock W-1, Sanyo Kokusaku Pulp Co., Ltd. product) Moisture 5.3%, Ash content 1.6%, Resin content 2.0%, Particle size
177μ or less, 90% or more, white No. 4 Short fibrous cellulose powder Moisture 7.5%, ash content 5.3%, lignin 10.5%, particle size 177μ or less 90% or more, brown Liquid material containing active ingredients is occluded in cellulose powder and solidified. To prepare an emulsion, it is sufficient to simply add an appropriate amount of cellulose powder to the liquid and stir.
In some cases, as shown in Examples below, water may be added to the emulsion to form a thick emulsion and occlude it. Operations such as drying the occluded material are generally not only unnecessary, but also sometimes harmful. This is because if the organic solvent is removed by drying, the active ingredient will precipitate, and there is a risk that a stable emulsion will not be formed when the obtained solidified emulsion is diluted with water. In addition to the above-mentioned components, the solidified emulsion of the present invention may also contain decomposition inhibitors, potency enhancers, fillers, etc. in accordance with conventional formulation methods. Examples of decomposition inhibitors used include isopropyl acid phosphate and epichlorohydrin, and fillers include inorganic powders such as sulfates, carbonates, chlorides, phosphates, and silicates, or urea, starch, sugar, and synthetic resins. Organic powder such as powder is used. Depending on the nature of the additives, these decomposition inhibitors, potency enhancers, bulking agents, and other additives may be added to the liquid containing the active ingredient before being occluded in the cellulose powder, or added to the liquid containing the active ingredient after being occluded in the cellulose powder. It may be added to cellulose powder. The solidified emulsion of the present invention can contain a high concentration of active ingredients due to the high absorbency of cellulose powder. On the other hand, in water, the absorbency of cellulose powder for the active ingredient or its organic solvent solution decreases, so when the solidified emulsion of the present invention is mixed with water, most of the active ingredient immediately turns into droplets from the cellulose powder. A stable emulsified suspension of cellulose is released and occludes a small amount of the active ingredient. Therefore, the solidified emulsion of the present invention can be diluted with water to a desired concentration and sprayed in the same manner as an emulsion from a general emulsion. Further, in the solidified emulsion of the present invention, the active ingredients are less likely to decompose during storage due to the inert nature of the cellulose powder. Furthermore, since the solidified emulsion of the present invention has appropriate wettability, it is hygienic because it does not generate dust when handled, and there is no need to contain an excessive amount of organic solvent, so it is safe from fire hazards and fire hazards when stored and used. It is also less dangerous in terms of environmental health. In other words, conventional emulsions use a large amount of organic solvent to adjust the concentration during production, so when they are diluted with water and sprayed, a relatively large amount of solvent is scattered along with the active ingredient into the surrounding environment, causing environmental pollution. make worse. In general, solvents are more or less toxic, flammable, and hygienic and fire hazards. In particular, when large amounts of chemicals are handled at once, such as in aerial spraying for forest control, complex pollution such as air pollution, water pollution, soil pollution, and odor pollution may occur, increasing unexpected risks.
In addition, airtight containers such as bottles, cans, and drums made of glass, tin, iron, or synthetic resin are normally used as storage containers for emulsions, and disposal of empty containers after use is difficult due to cleaning, crushing, etc. Sufficient care must be taken to avoid environmental pollution. However, the solidified emulsion of the present invention can be stored in a sealed container such as a so-called bag, which is mainly made of sheet materials such as paper, metal foil, or synthetic resin, which is convenient and economical in handling. In addition, empty containers after use can be safely disposed of relatively easily, such as by burning or burying them in the ground. The solidified emulsion of the present invention thus has the characteristics of both an emulsion and a wettable powder. The advantages of the solidified emulsion of the present invention described above can be summarized as follows. (1) Formulation is very simple, as the liquid containing the active ingredient is simply absorbed into the cellulose powder by stirring and mixing. (2) Due to the inert nature of cellulose powder, the active ingredients are less likely to decompose during storage, which has the advantage of saving resources. (3) Although it has the characteristics of an emulsion, it is solid and is not flammable, so there is very little risk of fire hazards, especially when handling or storing it. (4) Since it is also solid, containers such as paper bags can be used, making it convenient and economical to handle, and the containers can be easily disposed of after use. (5) In use, since the cellulose powder absorbs liquid appropriately, there is almost no dust generation when preparing the spray solution, making it highly safe in terms of handling and health and hygiene. (6) Despite its solid form, diluted liquid with water becomes an emulsion, which is much more stable than the so-called suspension of wettable powders. (7) Compared to conventional emulsions, the formulation contains no or less organic solvents, making it extremely safe from a health standpoint. As described above, the product of the present invention has a completely unique dosage form and is excellent in terms of environmental pollution, fire disasters, and health and hygiene. Examples of the present invention are listed below. The aging rate, emulsification rate, suspension rate and dissolution rate described in the examples are measured by the following method. Change rate: Percentage of the initial concentration of the active ingredient decomposed during storage of the compound in a sealed container (aluminum foil bag) at 40°C for 30 days. Emulsification rate: Pour 2.5 g of the compound into a 250 ml measuring cylinder and add water to make 250 ml. and let stand for 15 minutes. Next, repeat the handstand 30 times per minute to disperse and emulsify. After standing still for another 15 minutes, remove 30ml of the upper layer liquid.
was aspirated using 6 types of chemical analysis paper,
Measure the amount of component in 10ml of liquid. The percentage of this component amount to the component amount contained in 0.1 g of the blend is defined as the emulsification rate. Suspension rate: Take 2.5 g of the mixture in a 250 ml measuring cylinder, add water to make 250 ml, and let stand for 15 minutes. Next, repeat the inversion 30 times per minute to disperse and emulsify. After leaving it as it is for 24 hours, take 10ml from the center of the measuring cylinder, measure the amount of ingredients contained in it, and measure the amount of this mixture.
The suspension ratio is the ratio to the amount of component contained in 0.1g. Dissolution rate: This is carried out when using a liquid-absorbing and soluble solid composition, and the same operation as for the above emulsification rate is performed to determine the dissolution rate. Note that the symbols in the examples have the following meanings. PAP Isopropyl acid phosphate Decomposition inhibitor EC Epichlorohydrin Decomposition inhibitor E' Emulsifier No.1 Polyoxyalkylene alkylene allyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene sorbitan alkylate, alkylbenzene sulfon Among the mixtures of acid salts, the one with the best composition and specific gravity emulsifying properties was selected. No. 2 Sulfated castor oil No. 3 Polyoxyalkylene alkyl allyl ether No. 4 Benzalkonium chloride In addition, unless otherwise specified, agricultural chemicals or epidemic prevention drugs with the following formulation ratios contain an emulsifier and, if necessary, an emulsifier in the active ingredient. A solution is created by adding a solvent, to which cellulose powder (abbreviated as CP) and optionally a filler are added, and the mixture is stirred using a portable kneader to occlude the solution and solidify. Unless otherwise specified, percentages are percentages by weight (as a control, differences in the amounts of chemicals used were shown using conventional emulsions, etc.). Example 1 Water-insoluble liquid insecticide MEP (dimethyl-3-
Methyl-4-nitrophenyl phosphorothioate)

【table】

[Table] In the table, 3 is for epidemic prevention, Control 1 is a hydrating agent, Control 2 is a conventional emulsion formulation, MAL is lauryl methacrylate deodorant, SiO ₂ white carbon average particle size 5
Example 2 Water-insoluble liquid disinfectant EDDP (ethyl diphenyl dithiophosphate)

[Table] Example 3 Water-insoluble solid insecticide BPMC (2-
Secondary-butyl-N-methylcarbamate)

【table】

[Table] Example 4 Water-insoluble liquid insecticide diazinon (2-isopropyl-4-methylpyrimidyl-6-diethylthiophosphate)

【table】

【table】

[Table] Example 5 Water-insoluble liquid insecticide marathon (dimethyl dicarbethoxyethyl dithiophosphate)

[Table] Example 6 Water-insoluble liquid insecticide DDVP (dimethyl dichlorovinyl phosphate)

[Table] Example 7 Water-insoluble liquid herbicide molinate (5-ethylhexahydroazepine-1-carbothioate),
Water-insoluble solid herbicide simetrine (2-methylthio-4,6-bisethylamino-S-triazine), water-insoluble liquid herbicide MCPB (2-methyl-
ethyl 4-chlorophenoxybutyrate)

[Table] Example 8 Water-insoluble liquid fungicide EDDP (ethyl-diphenyldithiophosphate), water-insoluble liquid insecticide
MPP (dimethyl-3-methylthiophenylthiophosphate)

[Table] Example 9 Water-insoluble solid insecticide, salithion (2-methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide)

[Table] Anone and isophorone are solvent examples 10 Water-insoluble liquid insecticide orthodichlorobenzene, water-insoluble liquid fungicide metacresol, water-soluble solid fungicide benzalkonium chloride Solidification method is orthodichlorobenzene, metacresol, E , fragrance and dye are mixed to form a homogeneous solution, CP is added to this, stirred and occluded.

【table】

[Table] Example 11 Water-insoluble liquid insecticide Allethrin, water-insoluble solid insecticide Phthalfurin, water-insoluble liquid insecticide
MEP (dimethyl-3-methyl-4-nitrophenylphosfluorothioate)

[Table] Example 12 For reference, changes in emulsification rate depending on the mixing ratio of cellulose powder and white carbon (SiO ₂ ) in the method of the present invention were tested. This results in SiO ₂
It was found that in the case of 36% cellulose powder, the emulsification rate could be maintained within a practical range even if up to 4% was mixed. The results are shown as a graph in the drawing. Reference example: Change in emulsification rate due to CP and SiO ₂ mixing ratio Marathon: dimethyl dicarbethoxyethyl dithiophosphate

【table】

【table】 [Brief explanation of the drawing]

The drawing is a graph showing the relationship between the ratio of the added amounts of cellulose powder and white carbon used in the method of the present invention on the emulsification rate.

Claims (1)

[Claims] 1. A liquid product obtained by mixing an active ingredient that is sparingly soluble or insoluble in water or its organic solvent solution with an amount of an emulsifying agent that can stably emulsify the active ingredient or solution in water. A solidified emulsion for agriculture or epidemic prevention, which is obtained by occluded by cellulose powder having a particle size of 177μ or less. 2. The solidified emulsion for agricultural or epidemic prevention purposes according to claim 1, characterized in that the liquid is a mixture of a liquid active ingredient and an emulsifier. 3. The solidified emulsion for agricultural or epidemic prevention purposes according to claim 1, characterized in that the liquid is a solution of a solid active ingredient in an organic solvent mixed with an emulsifier. 4. A solidified emulsion for agricultural or epidemic prevention purposes according to any one of claims 1 to 3, characterized in that it contains an agent for preventing decomposition of an active ingredient. 5. A solidified emulsion for agricultural or epidemic prevention purposes according to any one of claims 1 to 4, characterized in that it contains an efficacy enhancer of an active ingredient. 6. A solidified emulsion for agricultural or epidemic prevention purposes according to any one of claims 1 to 5, characterized in that it contains an extender. 7 Stabilized by mixing with water a solidified emulsion obtained by occluded in cellulose powder, of which 90% or more has a particle size of 177μ or less, containing a liquid substance containing a sparingly soluble or insoluble active ingredient or its organic solvent solution and an emulsifier. 1. A method for applying an emulsion for agricultural or epidemic prevention purposes, which comprises producing an emulsion and applying this to a target object. 8. A method for applying an emulsion for agricultural use or epidemic prevention according to claim 7, characterized in that the liquid is a mixture of a liquid active ingredient and an emulsifier. 9. The method for applying an emulsion for agricultural or epidemic prevention purposes according to claim 7, wherein the liquid is a solution of a solid active ingredient in an organic solvent mixed with an emulsifier. 10. A method for applying an agricultural or epidemic prevention emulsion according to any one of claims 7 to 9, characterized in that the solid emulsion contains an active ingredient decomposition inhibitor. 11. A method for applying an agricultural or epidemic prevention emulsion according to any one of claims 7 to 10, characterized in that the solidified emulsion contains an efficacy enhancer of the active ingredient. . 12. A method for applying an agricultural or epidemic prevention emulsion according to any one of claims 7 to 11, characterized in that the solidified emulsion contains an extender.