KR100330927B1 - Solid or semi-solid paraquat preparations and production method thereof - Google Patents

Abstract

Solid or semisolid paraquat preparations are provided. In the non-liquid paraquat preparation of the present invention, the liquid paraquat dichloride is used as a raw material, and dried under reduced pressure, pulverized, and firstly powdered, and further, a surfactant, an extender, and optionally a vomiting agent, a odorant, a thickener, a pigment, etc. It can be prepared in the form of various solid or semisolid preparations in the form of granules or gels.

Description

Solid or semi-solid paraquat agent and manufacturing method thereof {SOLID OR SEMI-SOLID PARAQUAT PREPARATIONS AND PRODUCTION METHOD THEREOF}

The present invention relates to a solid or semi-solid paraquat (1,1'-dimethyl-4,4'-bipyridinium) formulation and a process for preparing the same. Paraquat is a non-selective herbicide that kills plants with leaf blueberries. Paraquat was introduced in the form of dichloride under the trade name Gramoxone by Zeneca, and registered in Korea with Gramoxone solution (24.5%) in 1970 in Korea. This pesticide

1) It is fast-acting enough to confirm the efficacy within 1 hour after spraying on weeds;

2) the soil half-life is long and the soil half-life is 200 ~ 500 days, but the adsorption fixed to the soil is inactivated;

3) classified as moderately toxic, but fatal to mammals, especially humans, making regeneration almost impossible with drinking more than 10 ml;

4) It is characterized by low cost.

Paraquat itself is insoluble in water and is used in the form of ammonium salt, chlorine salt and sodium salt to dissolve it in water.

Toxicity of paraquat dichloride was determined by oral toxicity LD ₅₀ value of rat 157 mg / kg, mouse 104 mg / kg, dog 25-50 mg / kg, cat 40-50 mg / kg, cow 50-75 mg / kg, sheep 50 ~ 75 mg / kg, human 30 mg / kg and transdermal toxicity LD ₅₀ value of rabbit 236 ~ 500mg / kg ulcers in the digestive tract, diarrhea, vomiting, rectum and jaundice. In Korea, it is classified as a general toxicity grade, and Japan is designated as poison, and the United States is designated as inhalation toxicity.

The commercial method of paraquat liquids is to dilute the stock solution 400 times with water to spray 120 to 150 liters (stock solution 300ml) on 300 pyeong.

However, since the formulation of the paraquat is a liquid formulation, according to consumer organizations and the Korean Major Council, about 1,000 people per year are reported to die by poisoning paraquat by mistake or for the purpose of suicide.

Therefore, it is an object of the present invention to change the formulation of paraquat so that the user cannot drink this high concentration of this toxic pesticide. In other words, because the formulation is a liquid (stock liquid), it is easy to drink because it is convenient to drink. It can be a big help in prevention.

Accordingly, it is an object of the present invention to provide paraquats in solid or semi-solid, i.e., hydrated, powdery, such as water-soluble, water-soluble granules, semi-solid, such as granular watering agents, or gels.

It is another object of the present invention to provide a process for preparing solid or semi-solid paraquat preparations.

It is another object of the present invention to provide solid or semi-solid paraquat preparations in various formulations.

In order to achieve the above object, in the present invention, paraquat, which has been produced only as a liquid, is formulated in a solid form in the form of a water soluble, a hydrate, a granular water soluble, a granular water soluble, a gel, and the like. Such solid paraquat may be diluted with water when used.

The paraquat large chloride raw material according to the present invention can be used in the form of crystalline powder or concentrate. First, in order to solidify the liquid paraquat dichloride, in the present invention, the paraquat dichloride raw material is dried under reduced pressure to crystallize, and then pulverized and powdered. Drying under reduced pressure at about 550 to 650 mmHg atmospheric pressure and then dried by heating to 70 ~ 80 ℃. Grinding is carried out using a ball mill to pass more than 98% through 300 ~ 350 mesh.

In addition, the concentrate of the concentrated liquid is concentrated by drying the paraquat dichloride liquid under the reduced pressure under reduced pressure, but unlike the obtaining of the crystalline powder of the raw material, drying for a short time before it is completely dried and crystallized, that is, until it becomes sticky. Get it done. In this case, powdering is carried out by admixing the paraquat dichloride concentrate to an adsorbent, followed by fine grinding under the powder conditions. As the adsorbent, white carbon is preferable.

The paraquat dichloride raw material thus obtained may be contained in an amount of 5 to 42.2% in the final formulation in consideration of the dilution factor (200 to 1,000 times).

Since paraquat dichloride is insoluble in water, it is made water-soluble by adding salts such as ammonium salt, chlorine salt, sodium salt, etc., with surfactants and extenders, and optionally thickeners, vomiting agents, odorants, pigments, antifreeze agents and other auxiliaries. It can be added and formulated in various forms. At this time, the paraquat dichloride is used to be concentrated and dried to 70 ~ 76%. Paraquat is adsorbed and fixed to the soil and is easily inactivated, so it is not recommended to use clay mineral as an extender. As the extender, minerals such as kaolin, bentonite, talc, diatomaceous earth, calcium carbonate, quartz, mica, starch, polysaccharides, water and the like can be used.

Surfactants include polyoxyethylene alkyl aryl ethers such as polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl aryl sulfates, sodium lignosulfate, ethoxylated tallow amines, and the like. Can be used.

In addition, xanthan gum or dextrin may be used as a thickener as an optional ingredient, and especially in the case of preparing a gel preparation, propylene glycol is added as an antifreeze agent and water is used as an extender to prevent freezing or low fluidity at low temperatures. Can be used. In addition, pigments can be added so that users do not easily misunderstand them as ordinary drinks. The color of the pigment is not particularly limited, and may be any color that may draw attention to the user, such as blue, yellow, and red.

In addition, since the purpose of the present invention is to prevent eating paraquat due to poisoning suicide or misdiagnosis, it is important to add malodorants and nausea so as not to pass through the esophagus. Pyridine compounds may be used as odorants, motherwort, bark bark, amino propyl triazolo pyrimidone, etc. may be used as antiemetic agents. On the other hand, in order to reduce the toxicity of paraquat, it is possible to reduce the content of paraquat and to prepare a powder, granular, gel-like preparation in combination with other non-selective solid herbicides.

The following provides specific examples of the present invention, but the scope of the present invention is not limited to these examples. In the following examples all percentages are by weight.

Raw Material Preparation Example 1 Preparation of Powdered (Crystal) Paraquat Dichloride Agent

1 L of a dark brown paraquat dichloride liquid (42%) was heated to 75 ° C under reduced pressure at a pressure of 600 mmHg and dried to obtain dark brown crystals. This was milled using a ball mill to allow at least 98% to pass through the 325 mesh. The paraquat dichloride crystal powder (75.8%) thus obtained was used as a starting material.

Raw Material Preparation Example 2 Preparation of Concentrated Paraquat Dichloride Agent

1 L of the dark brown paraquat dichloride liquid (42%) was dried by heating to 75 ° C. under reduced pressure to 600 mmHg atmosphere, but only before the paraquat dichloride was completely crystallized, ie, until it became a sticky concentrate. The resulting paraquat dichloride concentrate (60%) may be adsorbed on white carbon, powdered under the conditions of Preparation Example 1, as illustrated in Example 7, and then mixed with other ingredients.

Example 1 Preparation of Hydration

Original Paraquat Dichloride Powder (75.8%) 27.7%

Surfactants polyoxyethylene alkyl aryl ether polymers

1.0% of themed formulations

Polyoxyethylene Alkyl Aryl Sulfate 7.0%

Antiemetic Amino Propyl Triazolo Pyrimidone 0.05%

Odor Pyridine 0.1%

Extender Talc Remaining

1 kg of a paraquat hydrate was obtained at the above ratio.

Example 2. Preparation of Gel Forms

Original Paraquat Dichloride Powder (75.8%) 27.7%

Surfactant polyoxyethylene alkyl phenyl ether

5.0% of themed formulations

Antifreeze Propylene Glycol 7.0%

Thickener Xanthan Gum 0.5%

Antiemetic Amino Propyl Triazolo Pyrimidone 0.05%

Odor Pyridine 0.1%

Extender water level

1 kg of the gelled paraquat formulation was prepared in this proportion.

Example 3: Preparation of Granular Hydrating Agent

Original Paraquat Dichloride Powder (75.8%) 27.7%

Surfactant Sodium Lignosulfonate 10.0%

Ethoxylated tallow amine 5.0%

Thickener Xanthan Gum 0.5%

Dextrin 1.0%

Antiemetic Amino Propyl Triazolo Pyrimidone 0.05%

Odor Pyridine 0.1%

Extender kaolin 5%

Talc Level

1 kg of paraquat granular hydrate was obtained in the said ratio.

Example 4: Preparation of Hydrating Agent

Original Paraquat Dichloride Powder (75.8%) 27.7%

Surfactant Polyoxyethylene Polyoxypropylene Alkyl Ether

Thematic formulation 7%

Extender Calcium Carbonate Residue

1 kg of paraquat hydration was made in this proportion.

Example 5: Preparation of Hydrating Agent

Original Paraquat Dichloride Powder (75.8%) 17.0%

Surfactant polyoxyethylene aryletheralkyl sulfosuccinate

Themed formulation 5.0

Colorant Blue Pigment 0.1%

Extender Talc 20.0%

Calcium Carbonate

1 kg of paraquat hydration was prepared in this proportion.

Example 6: Preparation of Hydrating Agent

Original Paraquat Dichloride Powder (75.8%) 68.6%

Surfactant polyoxyethylene aryletheralkyl sulfosuccinate

Themed formulation 10.0%

Colorant Yellow Pigment 0.2%

Extender Sodium Sulphite Residue

1 kg of paraquat hydration was prepared in this proportion.

Example 7: Preparation of Hydrating Agent

Original Paraquat Dichloride Concentrate (60%) 27.7%

Surfactant polyoxyethylene aryletheralkyl sulfosuccinate

5.0% of themed formulations

Colorant Blue Pigment 0.1%

Supplement White Carbon 10%

Vomiting agent aminopropyl triazolo pyrimidone 0.05%

Odor Pyridine 0.1%

Extender Talc Remaining

1 kg of paraquat hydrate was prepared by mixing and grinding in the above ratio.

Paraquat preparations, which are toxic herbicides according to the invention, can be prepared as solid or semisolid formulations rather than conventional liquid formulations. Since the paraquat preparation according to the present invention can be simply diluted in water during use while maintaining herbicidal efficacy, the paraquat formulation is not inferior in terms of usability and efficacy as compared to the conventional liquid paraquat, and due to the conventional paraquat formulation is liquid. It is possible to significantly reduce the risk that a user may die by accident or intentional poisoning.

Claims (5)

The paraquat dichloride powder obtained by drying the liquid paraquat dichloride under reduced pressure and then pulverized or the concentrate, the surfactant, the extender and the optional ingredient in the concentrated liquid dried under reduced pressure until it becomes a sticky state, as an emetic agent, odorant, thickener, pigment and antifreeze agent Solid or semi-solid paraquat formulation containing one or more components selected from. The solid or semi-solid paraquat preparation according to claim 1, which has a granular or gel-like formulation such as a hydrating agent, a powdery phase such as a water soluble agent, a water-soluble granule, and a granular hydrating agent. The liquid paraquat dichloride was decompressed in the range of 550 to 650 mmHg, warmed and dried at 70 to 80 ° C., and then pulverized to pass through at least 98% through 300 to 350 mesh to obtain crystalline powdered paraquat dichloride, followed by powder paraquat dichloride. A process for producing a solid or semi-solid paraquat preparation according to claim 1, characterized in that it is mixed with at least one component selected from extenders, surfactants and optionally vomiting agents, odorants, antifreeze agents, pigments and thickeners. Paraquat dichloride and solid non-selective herbicides are mixed and finely powdered, and extenders, surfactants and optionally nausea, odorants, pigments, thickeners, etc. are added to prepare powdery, granular, gelous solid or semisolid paraquat mixtures. How to. The liquid paraquat dichloride was decompressed in the range of 550 to 650 mmHg, warmed to 70 to 80 ° C. until a sticky concentrate was obtained, and then adsorbed to an adsorbent and then ground to pass through at least 98% through 300 to 350 mesh. A process for producing the solid or semi-solid paraquat preparation according to claim 1, characterized in that the powdered paraquat dichloride obtained is mixed with at least one component selected from extenders, surfactants and optionally nausea, odorants, antifreezes, pigments and thickeners. .