JPH0684285B2 - Pesticide carrier - Google Patents

Description

TECHNICAL FIELD The present invention relates to a pesticide carrier, and more particularly to a pesticide carrier mainly containing barium sulfate.

(Prior art) Currently, as a pesticide carrier, many fine powders of mineral substances such as kaolinite, talc, silica sand, calcium carbonate, gypsum, diatomaceous earth, coal stone, calcite, bentonite, acid clay, zeolite, and aluminum oxide are used. It is used. These carriers are used as pesticide formulations in powders, granules, wettable powders and the like for increasing the amount and for diluting.

However, the physical and chemical properties and biological effects of pesticide formulations as well as the overall properties such as the prevention of environmental pollution depend largely on these carriers. For example, not only is it difficult for the fine powder part of the carrier to drift and scatter when the powder is used, making it difficult for the drug to reach the root of the rice plant, but it may also drift and scatter around the operators and the spraying area, adversely affecting the environment and the human body. is there. In order to improve these properties, the particle composition has been expanded, and for example, improvements have been made to powders with a reduced buoyancy, which are obtained by blending a mineral carrier having an average particle size of 20 μm or more and substantially 46 μm or less. It can not be said.

In addition, due to labor saving in agriculture in recent years, demand for mixed preparations containing several pesticides is high, but when the pesticide is in a liquid state,
It is a conventional method to add an oil-absorbing powder in order to powderize the liquid raw material. Alternatively, even a solid drug substance may cause a melting point lowering phenomenon due to coexistence with a liquid auxiliary agent or another liquid drug substance, and part or all of the solid drug substance may be dissolved.

When the amount of liquid in the formulation is large as described above, the amount of the oil-absorbent powder compounded inevitably increases, leading to a decrease in the apparent specific gravity of the formulation. The following problems can be considered as a problem of the preparation having a reduced apparent specific gravity.

Since the volume per unit weight increases, the packaging volume increases, which is not economical for transportation and the like, and is difficult for consumers to use.

As a dust, it is easy to drift and scatter due to wind and rising air during spraying.

It causes physical deterioration due to degassing during storage.

In the spraying device of the forced feeding mechanism of the screw conveyor type, it takes a long time to spray the same weight, which affects the sprayability.

It is difficult to reach the root of the plant and the control effect is likely to decrease.

Further, as a chemical property, with respect to the mineral carrier, there is concern that the active ingredient may be decomposed depending on the pesticide due to moisture, pH, particle size (surface area), heavy metals, impurities, surface activity, ion exchange capacity, polar adsorption and the like. The absolute factors that affect these properties are currently unknown, and it is thought that the chemical reaction proceeds due to catalysis, but it is difficult to suppress the degradation in the formulation because the degradation mechanism is particularly complicated in the above-mentioned mixed formulation. It is not easy to search for decomposition inhibitors.

(Problems to be Solved by the Invention) The present invention has been made to solve these conventional problems, and its purpose is in the form of a pesticide powder, which causes less drift and scattering, is easy to reach the stock origin, and is sprayed. It is intended to provide a pesticide carrier that has good properties and achieves miniaturization of packaging, and to provide a pesticide carrier that further improves the stability of a pesticide formulation that is easily decomposed during storage.

(Means for Solving Problems) The pesticide carrier of the present invention is characterized by containing barium sulfate powder.

The barium sulfate powder used in the present invention may be either barium sulphate sulphate obtained by crushing natural barium sulphate ore (barite) and hydrating or precipitated barium sulphate obtained as a precipitate by a chemical reaction. Composition BaSO ₄ , molecular weight 2
It is a powder of the compound of 33.43.

The pesticide carrier of the present invention may be a mixture of a conventional carrier and an auxiliary agent with barium sulfate.

Examples of the carrier include clays such as kaolinite group, montmorillonite group, and attapulgite group, talc, diatomaceous earth, calcium carbonate, calcium sulfate, potassium sulfate, sodium sulfate, ammonium sulfate, aluminum oxide, pyrophyllite, permiqueurite,
Examples include dolomite, phospholime, slaked lime, magnesium lime, and the like.

As an auxiliary agent, oil-absorbing fine powder such as white carbon (hydrous silicic acid), ionic surfactant such as lignin sulfonate, alkylallyl sulfonate, or nonionic surfactant such as ethylene oxide addition, polyvinyl alcohol, carboxy It is possible to use various physical property improving agents such as methyl cellulose, starch, binder such as dextrin, alkyl phosphates, higher fatty acids or metal salts thereof, and decomposition inhibitors.

The pesticide carrier of the present invention can be used for all kinds of active ingredients such as insecticides, fungicides, herbicides, and examples thereof include, but are not limited to, the following.

O, S-Dimethyl-N-acetyl-phosphoroamidothioate [acephate] 1,3-bis (carbamoylthio) -2- (N, N-dimethylamino) propane hydrochloride [cartap] O, O-dimethyl- O-3,5,6-Trichloro-2-pyridylphosphorothioate [chlorpyrifosmethyl] dimethyl-S- (N-methylcarbamoylmethyl) dithiophosphate [dimethoate] (2-isopropyl-4-methylpyrimidyl-6-)-diethylthio Phosphate [Diazinon] Dimethylmethylcarbamoylethylthioethyl phosphorothiolate [Vamidothione] Dimethyldicarbetoxyethyldithiophosphate [Marathon] 2-sec-Butylphenyl-N-methylcarbamate [BPMC] 2-Chloro-1- (2 , 4-Dichlorophenyl (vinyl dimethyl phosphate [dimethylbinphos] 2-methoxy-4H-1,3,2-beta Zone dioxaphosphorin2-
Sulfide [salithione] 2-chloro-1- (2,4,5-trichlorophenyl) vinyl dimethyl phosphate [CVMP] dimethyldichlorovinyl phosphate [DDVP] dimethyl (3-methyl-4-nitrophenyl) thiophosphate [MEP ] O, O-Dimethyl-O- [3-methyl-4- (methylthio) phenyl] thiophosphate [MPP] Metatryl-N-methylcarbamate [MTMC] Diisopropyl-1,3-dithiolane-2-ylidene-malonate [isobrothio Orchid] 5-methyl-1,2,4-triazolo [3,4-b] benzothiazole [tricyclazole] 4,5,6,7-tetrachlorophthalide [phthalide] 3-allyloxy-1,2-benzoiso Thiazole-1,1-dioxide [Probenazole] 3'-isopropoxy-2-methylbenzanilide [Mepronil] O-ethyl-S, S-diphenyldithiophosphate [EDDP] O, O- Diisopropyl-S-benzylthiophosphate [IB
P] Kasugamycin-hydrochloride [Kasugamycin] Validamycin A [Validamycin] Polyoxin complex [Polyoxin] 2,4-bis (ethylamino) -6-methylthio-1,3,5-triazine [cimetrin] S-ethylhexahydro- 1H-azepine-1-carbothioate [molinate] 2-chloro-2 ', 6'-diethyl-N- (butoxymethyl)
Acetanilide [butachlor] 2- (β-naphthyloxy) propionanilide [Naproanilide] 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-pyrazolyl-p-toluenesulfonate [pyrazolate] Sp-chlorobenzyl Diethylthiocarbamate [Benchocarb] Furthermore, the pesticide carrier of the present invention exhibits a particularly large stabilizing effect on certain active ingredients such as the following.

Such an active ingredient is a compound having a property of being easily hydrolyzed by an acid, and examples thereof include a compound group represented by the following general formula, but are not limited thereto.

In the formula, X represents a halogen atom, R represents a cycloalkyl group having 5 to 6 carbon atoms, and Y represents an oxygen atom or a sulfur atom.

Where X is (A is a halogen atom, lower alkyl group n = 1 to 3) A benzothiazole group or a thiadiazole group, Y is a lower alkyl group, a lower alkoxy group, Indicates.

R ₁ and R ₂ represent a hydrogen atom, a lower alkyl group or a lower alkoxy group.

Where X is Wherein Y is -CH = or a nitrogen atom, R ₁ is a methyl group or a methoxy group, R ₂ is a chlorine atom or a methyl group, a methoxy group,
R ₃ is a chlorine atom, a bromine atom, a nitro group, a lower alkyl group,
Lower alkoxy group, -COOR ₆ , -SO ₂ R ₆ or Indicates. R ₄ , R ₅ , R ₆ and R ₇ represent a hydrogen atom or a lower alkyl group.

In the formula, R ₁ and R ₂ are the same or different from each other, a hydrogen atom, a C _{1 to} C ₈ alkyl group, an allyl group, a C ₅ or C ₆ cycloalkyl group,
Benzyl group, phenyl group or formula (Wherein Y represents a halogen atom, a lower alkoxy group, a trifluoromethyl group or a lower alkyl group, and Z represents a hydrogen atom, a halogen atom or a lower alkyl group) and represents a substituted phenyl group.

In the formula, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group, a formyl group,
An alkenyl group, a thioalkyl group, or an optionally substituted alkoxy group, an acyl group, a carbamoyl group,
A dialkyl- or cycloalkyl group or a phenylthio group is shown.

Next, the compounds of the above formulas (I) to (V) will be specifically mentioned, but the compounds are not limited thereto.

1- (4-chlorobenzyl) -1-cyclobenzyl-3-phenylurea (Compound A) 1- (α, α-Dimethylbenzyl) -3- (paratolyl) urea (Compound B) N-[(4-methoxy- 6-Methylpyrimidin-2-yl) amicarbonyl] -1- (2-chlorophenyl) methanesulfonamide (Compound C) 2-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl-aminosulfonylmethyl] benzoate Acid methyl ester (Compound D) N-[(4,6-dimethoxytriazin-2-yl) aminocarbonyl] -4-dimethylsulfamoyl-5-methylpyrazole-3-sulfonamide (Compound E) N-[( 4,6-Dimethylpyrimidin-2-yl) aminocarbonyl] -3-methyl-5-ethylsulfonylpyrazole-4-
Sulfonamide (Compound F) 2-tert-Butylimino-3-isopropyl-5-phenyl-
Tetrahydro-1,3,5-thiadiazin-4-one (Compound G) 2H-1,3-thiazin-tetrahydro-2- (nitromethylene) (Compound H) Amount of barium sulfate used as a pesticide carrier of the present invention Is 10 to 100% by weight of the entire carrier, preferably 30 to 1
It is 00% by weight.

The pesticide carrier of the present invention can be used in the form of preparations such as powders, granules, wettable powders and the like, and the preparation composition can be obtained by, for example, the following production method, but is not limited thereto.

(A) Dust and wettable powder Barium sulfate, active ingredients and other carriers, and auxiliary agents are mixed and ground.

(B) Granules Barium sulfate, the active ingredient, other carriers and auxiliary agents are mixed and pulverized, and then granulated by kneading and granulation to obtain granules.

Alternatively, granules obtained by removing the active ingredient from the above formulation and granulating the granules can be obtained by adsorbing the active ingredient.

The amount of the active ingredient compounded is 0.01 to 80% by weight, preferably 0.1 to 50% by weight, based on the whole pharmaceutical composition.

(Examples) The present invention will be described in more detail with reference to Examples. In the following examples, "parts", "%" are all "parts by weight",
"% By weight" is shown.

Example 1 20 parts of chlorpyrifosmethyl, 20 parts of BPMC, 30 of mepronil
Parts, 40 parts of white carbon, 390 parts of clay and 500 parts of barium sulfate were uniformly mixed and pulverized to obtain a mixed powder containing chloropyrifosmethyl 2%, BPMC 2% and mepronil 3%.

Example 2 20 parts of MEP, 20 parts of BPMC, 30 parts of mepronil, 30 parts of IBP, 60 parts of white carbon, 40 parts of clay and 800 parts of barium sulfate were uniformly mixed and pulverized to obtain 2% of MEP, 2% of BPMC, 3% of mepronil and 3% of IBP. A mixed powder containing it was obtained.

Example 3 Compound A 15 parts, MPP 20 parts, EDDP 25 parts, white carbon 40
Parts and 900 parts of barium sulphate are uniformly mixed and crushed to obtain compound A
A mixed powder containing 1.5%, MPP2% and EDDP2.5% was obtained.

Example 4 10 parts of compound H, 20 parts of dimethylvinphos, 30 parts of white carbon, 200 parts of aluminum oxide, 340 parts of clay and 400 parts of barium sulfate are uniformly mixed and pulverized to obtain compound H1%,
A mixed powder containing 2% of dimethylvinphos was obtained.

Example 5 10 parts of compound G, 20 parts of chlorpyrifosmethyl, 20 parts of white carbon, 650 parts of clay and 300 parts of barium sulfate are uniformly mixed and pulverized to obtain a mixed powder containing 1% of compound G and 2% of chlorpyrifosmethyl.

Example 6 200 parts of compound C, 100 parts of white carbon, 30 parts of sodium lauryl sulfate, 20 parts of polyoxyethylene nonylphenyl ether, 100 parts of diatomaceous earth and 550 parts of barium sulfate are uniformly mixed and pulverized to contain 20% of compound C. A wettable powder was obtained.

Example 7 Compound F (250 parts), white carbon (200 parts), sodium alkylnaphthalenesulfonate (20 parts), polyoxyethylene sorbitan monolaurate (30 parts), clay (200 parts) and barium sulfate (300 parts) were uniformly mixed and ground to give compound F (25%). A wettable powder containing was obtained.

Example 8 70 parts of compound B, 30 parts of polyvinyl alcohol, 100 parts of bentonite, 300 parts of talc and 500 parts of barium sulfate are uniformly mixed and pulverized, and then an appropriate amount of water is added and kneaded. This was granulated with a granulator equipped with a screen having a hole diameter of 0.8 mm, and the granulated product was dried and then sized to obtain a granule containing Compound B 7%.

Example 9 Compound D 2.5 parts, sodium carboxymethyl cellulose
After uniformly mixing and pulverizing 10 parts, 197.5 parts of bentonite, 400 parts of clay and 390 parts of barium sulfate, a granule containing Compound D 0.25% was obtained according to the method of Example 8.

Example 10 1 part of compound E, 25 parts of alpha starch, 27 bentonite
After uniformly mixing and pulverizing 4 parts, 200 parts of clay and 500 parts of barium sulfate, a granule containing compound E 0.1% was obtained according to the method of Example 8.

Reference Example 1 The barium sulfate of Example 1 was replaced with clay to obtain a mixed powder containing chlorpyrifosmethyl 2%, BPMC 2% and mepronil 3%.

Reference Example 2 The barium sulfate of Example 2 was replaced with clay, and MEP2%,
A mixed powder of 2% BPMC, 3% mebronil and 3% IBP was obtained.

Reference Example 3 Compound A was prepared by substituting clay for barium sulfate in Example 3.
A mixed powder of 1.5%, MPP2% and EDDP2.5% was obtained.

Reference Example 4 The barium sulfate of Example 3 was replaced with calcium sulfate,
A mixed powder of compound A 1.5%, MPP 2% and EDDP 2.5% was obtained.

Reference Example 5 900 parts of barium sulfate of Example 3 was mixed with 10 parts of epoxy glyceride.
Parts and clay 890 parts, Compound A 1.5%, MPP2
%, EDDP 2.5% was obtained.

Reference Example 6 Barium sulfate in Example 4 was replaced with calcium sulfate,
A mixed powder containing 1% of compound H and 2% of dimethylvinphos was obtained.

Reference Example 7 The barium sulfate of Example 4 was replaced with clay to prepare compound H2
%, And dimethyl vinphos 2% were obtained.

Reference Example 8 Compound G1 was prepared by substituting clay for barium sulfate in Example 5.
%, And chloropyrifosmethyl 2% were obtained.

Reference Example 9 The barium sulfate of Example 6 was replaced with calcium carbonate,
A wettable powder containing 20% of compound C was obtained.

Reference Example 10 The barium sulfate of Example 7 was replaced with clay to obtain the compound F2
A wettable powder containing 5% was obtained.

Reference Example 11 Compound B7 was prepared by substituting clay for barium sulfate in Example 8.
A granule containing 10% was obtained.

Reference Example 12 Compound D was prepared by substituting clay for barium sulfate in Example 9.
A granule containing 0.25% was obtained.

Reference Example 13 Compound E was prepared by substituting clay for barium sulfate in Example 10.
A granule containing 0.1% was obtained.

(Effects of the Invention) Next, test examples and test results of the samples prepared in Examples 1 to 10 and Reference Examples 1 to 13 will be shown.

Test Example 1 Powder Physical Properties Test The physical properties (apparent specific gravity, dusting property, and floating property) of the powders manufactured according to the examples and reference examples were tested. The test method is as follows, and the test results are shown in Table 1.

(1) Apparent specific gravity test Correctly from the upper edge of a metal cylindrical container with an inner diameter of 50 mm and a capacity of 100 ml.
Hold a mesh of 80 mesh standard sieve on 0 cm, place the sample on the sieve mesh, and gently tap it off with a supple flat brush of 20 mm in length and 30 mm in width. Then continue until the cone rises from the upper edge of the cylinder. The rising portion was dropped off with a slide glass, and the weight of the sample in the cylinder was measured.
The apparent specific gravity was calculated by the following formula.

(2) Discharge property test Discharge weight (Xg) per minute at an opening of 5/10 of a test machine (standard test machine manufactured by Kyoritsu Agricultural Machinery Co., Ltd.) for standard powder (a product distributed by JIS Talc Industry Association) Ask. Also, the apparent specific gravity at 5/10 is obtained, and the index at each opening is obtained.

Next, put the sample powder up to the top line of the tank, cover it and adjust the metering lever to 5/10. Place a container, which has been weighed in advance, under the discharge port and discharge accurately for 30 seconds, and measure the weight. Index, discharge volume for 1 minute is calculated by the following formula, and the corrected discharge volume is calculated from this,
This was made into dusting property.

(3) Floating property test Floating property index was measured by absorbing the suspended dust in water 5 minutes after the dust was dispersed in the floating measurement box and measuring the transmittance of the dust suspension with a spectrophotometer. And

Calculation Floating index = 100-Transmittance Floating index measurement (unit: nm) (Test conditions) Sample amount: 10g Standard dusting tester rotation speed: 700 rpm Leaving time: 30 seconds Leaving time: 5 minutes Absorption tube water amount: 75 ml Suction rate: 30 l / min for 1 minute Dust box inner pressure: ₂ mmH ₂ O Transmittance measurement liquid length: 610 nm The attached drawing is the principle diagram of the flotation measuring device, in which 1 is a blower, 2 is a sample filling machine, and 3 is Floating measurement box, 4 is an absorption tube, 5 is a deaeration hole, 6 is a cloth, and 7 is an ejection port.

Test Example 2 Stability Test over Time Each of the agents of Examples and Reference Examples was placed in a kraft bag and stored in a thermo-hygrostat kept at 40 ° C. and 70% relative humidity for 30 days and 60 days.

Table 2 shows the residual rate of each active ingredient after 30 days and 60 days.

The residual rate (%) was calculated from the following formula.

Test Example 3 Blight Blight Control Test A powder blight control test was carried out using the powders of Examples 1, 2 and 3 and Reference Examples 1, 2, 3, 4, and 5.

Method 3 stems of 3 stems were transplanted with a white porcelain pot with a diameter of 9 cm,
Dust was applied to the grown 7-8 leaf stage paddy rice (cultivar: Kinnanfu), and the leaf sheath of the paddy rice was inoculated with the leaf spot fungus cultivated in a flat potato medium 3 days after the application, and the wet leaf was placed in a greenhouse. Keep it in the room,
After 8 days, the length of the blotch spot formed on the rice leaf sheath was measured. In addition, this test was implemented by repeating 5 pots. The control value was calculated by the following formula.

The test results are shown in Table 3.

From the above results, by using the pesticide carrier of the present invention, the physical properties of the powder are improved and the reachability to the plant is also improved, which is effective in controlling the pests of the plant and is also excellent in stabilizing the active ingredient. It has been found that it has an effect.

As is clear from the above description, by using the pesticide carrier of the present invention, the following effects can be achieved.

When spraying pesticide powder, there is little drift and scattering, which reduces the impact on the sprayer and the human body, and at the same time reduces environmental pollution, leading to improved safety.

By increasing the apparent specific gravity of the powder, the dusting property is improved and the dispersibility is improved.

It is easy to reach the strain origin and shows a stable effect on the pests of the strain origin.

Since the volume per unit weight is reduced, the packaging volume is reduced, which not only reduces the packaging cost and transportation cost but also makes it easier for consumers to use.

Since it has a stabilizing effect on the active ingredient, it has excellent storage stability and a stable control effect even after long-term storage.

[Brief description of drawings]

The attached drawing shows the principle diagram of the floating property measuring device for pesticide carriers. In the figure, 1 ... Blower, 2 ... Sample filling machine, 3 ... Floating measurement box, 4 ... Absorption tube, 5 ... Degassing hole, 6 ... Cloth, 7 ...
... Spout

Claims (1)

[Claims] 1. A pesticide carrier comprising barium sulfate powder.