JPS6310921B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a powder composition for agricultural and horticultural use that has good physical properties such as dispersibility, dust-shedding property, and fluidity. Conventionally, powders have the advantage that they are relatively easy to formulate not only alone but also as a mixture, are easy to spray, are reliable, and can be used even in places with poor water availability. However, on the other hand, since fillers and other additives are blended, the above-mentioned physical properties often deteriorate during dispersion due to compression during storage. As a result, uniform dispersion is hindered, leading to problems such as a decline in work efficiency and efficacy, and the development of phytotoxicity.Therefore, there is an increasing demand for the development of agricultural and horticultural powder compositions with good physical properties. Various techniques for improving the physical properties of such powders have been proposed.
(See Publication No. 5440),

[Formula] and

Powder for agricultural and epidemic prevention (specially (see Publication No. 38-24900) and a compound obtained by esterifying some or all of the above compounds with an alkylene oxide, or a compound obtained by neutralizing the above compound with a basic substance, for agricultural and epidemic prevention purposes with good fluidity. Powder composition (see Japanese Patent Publication No. 40-21440), (R ₁ O) ₃ P or (R ₂ O) ₂ POH (wherein R ₁ is an alkyl group or benzyl group, R ₂ is an alkyl group, a phenyl group or a benzyl group), a stable and fluid organic phosphate ester composition (see Japanese Patent Publication No. 45-9199);

A method for improving organophosphorus insecticides by adding a compound represented by the formula: (wherein R is an alkyl group having 1 to 4 carbon atoms and may be the same or different) (See Publication No. 45-9200),
An organic phosphorus powder containing a polyoxyethylene alkyl ether phosphate or a polyoxyethylene alkyl allyl phosphate monoester and diester, which has both a dispersion effect and a decomposition prevention ability (see Japanese Patent Publication No. 46-42399), general formula

[Formula] or

[Formula] (wherein, R is a higher alkyl group or a higher alkylaryl group, Z is an oxygen or sulfur atom, and n is an arbitrary integer) is a salt of an organic phosphorus compound obtained by neutralizing the compound with a basic substance. Powder composition with good fluidity (Tokukosho)
47-3279), general formula

[Formula] (where n is the same or different integer from 2 to 5, a and b
are the same or different and are 0 or an integer of 1 to 3, and c is an integer of 1 to 3. (see publication) and metal soaps such as calcium stearate, diisopropyl acid phosphate (manufactured by Nippon Kagaku Kogyo Co., Ltd.,
A stable agricultural fungicide (PAP) added (Tokukosho)
41-4110) etc. are known. In these prior art, phosphoric acid esters, higher fatty acids and their salts, esters, and other compounds are added to the powder, but depending on the type of filler added to the powder, physical properties may be improved. They are ineffective, some are expensive, and there are difficulties in using them. In particular, calcium carbonate and magnesium carbonate, which are the bulking agents that are the subject of the present invention, have a strong aggregation property in fine powder, making it difficult to use them as bulking agents for agricultural chemical powders using conventional techniques. The disadvantage is that the more it increases, the stronger its cohesive force becomes. On the other hand, calcium carbonate is a cheap and extremely easily available bulking agent, and when used in powders of inorganic copper compounds or organic copper compounds, calcium carbonate, as well as magnesium carbonate, suppress copper elution due to their alkalinity and have the effect of reducing chemical damage. It is also known that there are some particles, and the smaller the particle size, the higher the effect. As a technique for improving the physical properties of pesticide powder using calcium carbonate as an extender, the above-mentioned PAP is added as a powder spitting property improver to calcium carbonate as a base.
In addition, a stable agricultural and horticultural powder containing an organic phosphate ester pesticide as an active ingredient
28981) and calcium carbonate as a base, to which a monobasic saturated aliphatic carboxylic acid having 3 to 9 carbon atoms, a monobasic aromatic carboxylic acid, acrylic acid or oleic acid or the like may be added to improve dispersibility. Non-medical powders made by adding acid anhydrides or salts have been proposed (see JP-A-54-86622), but even with these techniques, due to the unique aggregation properties of calcium carbonate, , only those with large particle size, that is, weak cohesive force, can be used.
At present, its use is extremely limited. The present invention was made in view of the current situation, and its purpose is to provide a material containing calcium carbonate and/or magnesium carbonate as a bulking agent, and which has good physical properties such as dispersibility, powder discharging property, and fluidity. An object of the present invention is to provide a powder composition for agricultural and horticultural use. To summarize the present invention, the agricultural and horticultural powder composition of the present invention contains an agricultural and horticultural chemical, calcium carbonate and/or magnesium carbonate, and 5% by weight or less of polysiloxane based on the total amount of the composition. It is characterized by: The present inventors have focused on the above points and have conducted intensive research on various agricultural and horticultural chemicals using calcium carbonate and/or magnesium carbonate as bulking agents. Adding a small amount of organopolysiloxane (hereinafter referred to as polysiloxane), which is generally used in industry as a brake oil, electrical insulation oil, impregnating oil, polishing agent, cosmetic ingredient, mold release agent, antifoaming agent, etc. The present invention was achieved by discovering that the physical properties of the agrochemical powder, that is, the dispersion condition, were significantly improved. Regarding organosilicon compounds such as polysiloxane, conventionally,
There are some examples where it is used as an emulsifier for agricultural chemicals or as an antifoaming agent for hydrating powders, but in this case, the purpose of use is to dissolve polysiloxane in water or add it to suppress foaming when preparing chemical solutions. It is. In contrast, in the present invention, when calcium carbonate and/or magnesium carbonate are used together as a bulking agent in various agricultural and horticultural chemicals, such as a single pesticide or a mixture of two or more pesticides, a small amount of polysiloxane is added. By doing this, agrochemical powders with excellent physical properties can be obtained, but if necessary, talc, clay (clays include general powder clay and powder clay from which fine powder has been removed),
Pyrofluorite, white carbon, diatomaceous earth, etc. may also be added. In the present invention, the above white carbon (oil-absorbing hydrated sodium silicate)
It is appropriate to adsorb the polysiloxane onto a fine powder carrier such as diatomaceous earth, pulverize it together with the agricultural chemical raw material and the above-mentioned extender, and mix it uniformly. Examples of polysiloxanes applicable to the present invention are listed below using structural formulas. Among the above polysiloxanes, excluding those with structures () to (), those whose addition has a particularly remarkable effect of improving physical properties have a degree of polymerization m or n of 50 to 50.
It has been found that a value of 300, preferably 86 to 100, has the most stable effect, and as it goes outside this range, the effect tends to decrease. Further, these polysiloxanes may be added alone or in combination of two or more. The amount of these polysiloxanes added is 5% by weight or less, preferably 0.03% by weight based on the total amount of the composition.
It is appropriate to set the content to 2% by weight. Even if the amount added exceeds 5% by weight, the effect of improving physical properties will not be improved significantly, and it will not be economically advantageous. Next, the agricultural and horticultural chemicals that can be applied to the present invention are not particularly limited and are wide-ranging. Examples of insecticides include O,O-dimethyl-O-(4-methylthio-m-tolyl)phosphorothionate ( MPP),
O,O-dimethyl-O-(4-nitro-m-tolyl)phosphorothionate (MEP), O,O-diethyl-O-(2-isopropyl-4-methyl-6
-pyrimidyl) phosphorothioate (diazinon), S-[1,2-bis(ethoxycarbonyl)
Ethyl]O,O-dimethylphosphorothiorothionate (Marathon), S-[α-(ethoxycarbonyl)benzyl]O,O-dimethylphosphorothiothionate (fuentate), O,O-dimethyl-S-( Phthalimidomethyl) phosphorothiolothionate (PMP), O,O-dimethyl-2,
2,2-trichloro-1-hydroxyethylphosphonate (DEP), 2,2-dichlorovinyl O,
O-dimethylphosphate (DDVP), 2-chloro-1-(2,4-dichlorophenyl)vinyl O,
O-diethyl phosphate (CVP), O-(p-
methylthiophenyl) O,O-dipropyl phosphate (propaphos) and S-[5-methoxy-
Organophosphorus insecticides such as 2-oxo-2,3-dihydro-1,3,4-thiadiazolyl-(3)-methyl]O,O-dimethylphosphorothiolothionate (DMTP), 1-naphthyl-N- Methyl carbamate (NAC), m-tolyl-N-methyl carbamate (MTMC), 3,4-xylyl-N-methyl carbamate (MPMC), o-sec-butylphenyl-N-methyl carbamate (BPMC), o-cumenyl- N-methyl carbamate (MIPC) and S-methyl-N-(methylcarbamoyloxy)
Carbamate insecticides such as thioacetimidate (methomyl), S,S-6-methylquinoxaline-2,3-diyldithiocarbonate (chinomethionate), N'-(4-chloro-o-tolyl)-
Acaricides such as N,N-dimethylformamidine (chlorphenamidine), 2,2,2-trichloro-1,1-bis(p-chlorophenyl)ethanol (Kersene), and tricyclohexyltin hydroxide (Plictran) Other examples include S,S'-[2-(dimethylamino)trimethylene]bis(thiocarbamate) (cartap).
In addition, as bactericidal agents, for example, inorganic copper compounds such as basic copper chloride, basic copper sulfate, and cuprous hydroxide;
Organic copper compounds such as 8-quinolinol copper, organic arsenic agents such as iron methanarsonate, zinc ethylene bisdithiocarbamate (zineb), manganese ethylene bisdithiocarbamate (maneb), bis(dimethylthiocarbamoyl) disulfide (TMTD) and organic sulfur agents such as bis(dimethyldithiocarbamoyl)ethylenediamine, inorganic sulfur agents such as colloidal sulfur, and compounds such as tetrachloroisophthalonitrile (TPN) and 4,5,6,7-tetrachlorophthalide (futhalide). In addition to chlorine-based disinfectants and organophosphorus disinfectants such as S-benzyl-O,O-diisopropylthiophosphate (IBP), 2,3-dichloro-1,4-naphthoquinone (Ziclon), N-(trichloromethylthio )-4-
Cyclohexene-1,2-dicarboximide (captan), 2,3-dicyano-1,4-dithianthraquinone (dithianone), phenazine-
5-oxide, 5-methyl-1,2,4-triazolo(3,4-b)benzothiazole (tricyclazole) and 2-methyl-3'-isopropoxybenzanilide (mepronil), 1-(4-chlorobenzyl) )-1-cyclopentyl-3-phenylurea (Pencyclone), and can also be applied to antibiotics such as Blasticidin S and polyoxin. These agricultural chemical ingredients can be formulated individually depending on the purpose, but formulations can also be made by combining two or more types. Moreover, the mixing order of each component is not particularly limited. Next, the present invention and its effects will be explained using Examples, Comparative Examples, and Test Examples, but the present invention is not limited by these in any way. Note that parts in the text indicate parts by weight. Example 1 The above structural formula () (m
0.5 part of a polysiloxane represented by 90) was adsorbed and mixed, and 10 parts of cuprous hydroxide and 59.5 parts of calcium carbonate were added to bring the total amount to 100 parts, and the mixture was pulverized using an impact pulverizer. The mixture was further mixed uniformly to obtain a powder composition. Example 2 2 parts of S-benzyl-O,O-diisopropylthiophosphate and 0.1 part of polysiloxane represented by the above structural formula () (where m is 100) were mixed, and the mixture was adsorbed and mixed with 1.5 parts of white carbon. After that, 2 parts of 4,5,6,7-tetrachlorophthalide and 94.4 parts of calcium carbonate were added to make the total amount 100 parts, and the mixture was mixed, and then pulverized using an impact pulverizer.
The mixture was further mixed uniformly to obtain a powder composition. Example 3 O,O-dimethyl-O-(4-methylthio-m
-tolyl) phosphorothionate 2 parts, o-sec-
2 parts of butylphenyl-N-methyl carbamate and 2 parts of polysiloxane represented by the above structural formula () (m is 80) are mixed, this is adsorbed and mixed on 2 parts of white carbon, and then calcium carbonate is added.
After adding 35.5 parts and 56.5 parts of Sickleite CA to make the total amount 100 parts, it was crushed using an impact crusher.
The mixture was further mixed uniformly to obtain a powder composition. Example 4 2 parts of O-(2-isopropyl-4-methyl-6-pyrimidyl)-O,O-diethylthionophosphate and 1.5 parts of the above structural formula () (where m is 85)
This was adsorbed and mixed with 1 part of magnesium carbonate, and further 0.4 parts of iron methanarsonate, 1.5 parts of m-tolyl-N-methylcarbamate, and 93.6 parts of calcium carbonate were added to bring the total amount to 100 parts. The entire amount was pulverized using an impact pulverizer and further mixed uniformly to obtain a powder composition. Example 5 2 parts of O-(p-methylthiophenyl)O,O-dipropyl phosphate and 1 part of polysiloxane represented by the above structural formula () were adsorbed and mixed with 4 parts of white carbon, and further 5-methyl- 1, 2,
After adding 1 part of 4-triazolo(3,4-b)benzothiazole, 10 parts of diatomaceous earth, and 82 parts of calcium carbonate to make the total amount 100 parts, the mixture was pulverized using an impact pulverizer and further mixed uniformly. A powder composition was obtained. Example 6 Polysiloxane represented by the above structural formula ()
0.5 part was adsorbed and mixed with 30 parts of white carbon, and further, 30 parts of tetrachloroisophthalonitrile, 10 parts of calcium carbonate, and 29.5 parts of magnesium carbonate were added to make the total amount 100 parts, and the mixture was pulverized using a jet pulverizer. A powder composition was obtained by uniformly mixing. Example 7 2 parts of S-benzyl-O,O-diisopropylthiophosphate and 1.5 parts of the above structural formula () (m is 75) were adsorbed and mixed with 3.5 parts of white carbon, and further 2-methyl-3-iso 3 parts propoxybenzanilide, 20 parts talc and 70 parts calcium carbonate
The mixture was mixed to make a total amount of 100 parts, and then ground using an impact grinder and further mixed uniformly to obtain a powder composition. Example 8 S-[5-methoxy-2-oxo-2,3-dihydro-1,3,4-thiadiazolyl-(3)-methyl]O,O-dimethylphosphorothiolothionate
15 parts, the above structural formula () (m is 80 and n is 70)
After adding and mixing 0.5 parts of polysiloxane represented by, 15 parts of white carbon, 15 parts of magnesium carbonate, and 54.5 parts of calcium carbonate, the mixture was pulverized using a jet-type pulverizer, and further mixed uniformly to obtain 100 parts of flow dust powder composition. I got it. Example 9 O,O-diethyl O-(2-isopropyl-4
- 3 parts of methyl-6-pyrimidyl) phosphorothioate and 4 parts of polysiloxane represented by the above structural formula () are adsorbed and mixed on 4 parts of white carbon, and 89 parts of calcium carbonate are added and mixed, and the entire amount is impact-pulverized. The mixture was pulverized using a machine and mixed uniformly to obtain 100 parts of a powder composition. Example 10 2 parts of S-benzyl-O,O-diisopropylthiophosphate and the above structural formula () (m=90)
After mixing 1 part of polysiloxane represented by
Add magnesium carbonate and mix by adsorption to bring the total amount to 100%.
Department. This was pulverized using an impact pulverizer and further mixed uniformly to obtain a powder composition. Example 11 20 parts of calcium carbonate was added with the above structural formula () (m is
88) was adsorbed and mixed, and further 1-(4-chlorobenzyl)-1
1.5 parts of -cyclopentyl-3-phenylurea and 77.7 parts of Siegrite CA were added to bring the total amount to 100 parts, and the mixture was pulverized using an impact pulverizer and further mixed uniformly to obtain a powder composition. Comparative Example 1 (With no polysiloxane added) After mixing 10 parts of cuprous hydroxide, 30 parts of magnesium carbonate, and 60 parts of calcium carbonate, the entire amount was pulverized using an impact pulverizer, and then mixed uniformly to form a powder. Composition
Got 100 copies. Comparative Example 2 (When the amount of polysiloxane added exceeds 5%) 2 parts of O-(p-methylthiophenyl)O,O-dipropyl phosphate and 6.5 parts of polysiloxane represented by the above structural formula () were added. This is adsorbed and mixed with 4 parts of white carbon, and further 5-
Methyl-1,2,4-triazolo(3,4-b)
1 part of benzothiazole, 10 parts of diatomaceous earth and 76.5 parts of calcium carbonate were added and mixed to make the total amount 100 parts.The entire amount was pulverized using an impact pulverizer and further mixed uniformly to obtain a powder composition. Comparative Example 3 (With no addition of polysiloxane) S-[5-methoxy-2-oxo-2,3-dihydro-1,3,4-thiadiazolyl-(3)-methyl]-O,O-dimethylphosphorothi After mixing 15 parts of orothionate, 15 parts of magnesium carbonate, 15 parts of white carbon, and 55 parts of calcium carbonate, the entire amount was pulverized using a jet-type pulverizer and further mixed uniformly to obtain 100 parts of a flow dust powder composition. . Comparative Example 4 (With no addition of polysiloxane) O,O-diethyl-O-(2-isopropyl-
After adsorbing and mixing 3 parts of 4-methyl-6-pyrimidyl) phosphorothioate with 4 parts of white carbon and further mixing with 93 parts of calcium carbonate, the entire amount was pulverized with an impact pulverizer and further mixed uniformly to obtain a powder composition of 100 parts. I got the department. Comparative Example 5 (With no addition of polysiloxane, with addition of PAP) O,O-dimethyl-O-(4-methylthio-m
-tolyl) phosphorothionate 2 parts, o-sec-
2 parts of butylphenyl-N-methyl carbamate and diisopropyl acid phosphate (PAP)
Mix 0.5 parts, adsorb and mix with 2 parts of white carbon, and then add 35 parts of calcium carbonate and Siegrite.
After mixing 58.5 parts of CA, the entire amount was pulverized using an impact pulverizer and further mixed uniformly to obtain 100 parts of a powder composition. Comparative Example 6 (With no addition of polysiloxane) After adsorbing and mixing 2 parts of S-benzyl-O,O-diisopropylthiophosphate with 2 parts of white carbon, and further mixing 96 parts of magnesium carbonate,
The entire amount was pulverized using an impact pulverizer and mixed uniformly to obtain 100 parts of a powder composition. Comparative Example 7 (Clay alone with addition of polysiloxane) The above structural formula () (m
0.8 part of a polysiloxane represented by
After 1.5 parts of 1-cyclopentyl-3-phenylurea was added to bring the total amount to 100 parts, the mixture was pulverized using an impact pulverizer and further mixed uniformly to obtain a pulverized composition. Test Example 1 The physical properties of each powder composition obtained in the above Examples and Comparative Examples were measured by the following method. (1) Dispersibility Measures the amount of powder dispersed within a certain amount of time while a certain amount of air passes through a glass filter. (Measurement method: Pesticide production technology, 1964, 11
(Refer to No., p. 29) (2) Powder discharging property Determine the amount of powder discharging over a certain period of time under certain conditions using a hand-cranked powder duster. (Measurement method) Weigh 200g of the sample, put it in a Kyoritsu-type Midget standard duster, rotate it at a speed of 150 times per minute, spit out the powder for 1 minute, and weigh the remaining powder. (Calculation method) Sample weight (g) - Powder residue (g)
= Amount of powder discharged (g) (3) Fluidity Vibration is applied to the powder using a vibrator, and a fixed amount of 20 g of sample is dropped from the mesh of the device, and the falling time is defined as fluidity. (Measurement method: see Pesticide Production Technology, 1971, No. 24, p. 43) The test results obtained are shown in Table 1 below.

【table】

[Table] As is clear from Table 1, the powder composition of the present invention is superior in fluidity, dispersibility, and powder discharging properties (physical properties) as compared to that of the comparative example. Test Example 2 Using the powder compositions of Example 5 of the present invention and Comparative Example 2, their control effects against rice and leafhopper were compared. That is, using the rice variety Haruyuki, 3 kg was sprayed per 10 a area, and on the day of spraying, 1 day, 3 days, 5 days, and 7 days after spraying, 1
Four points (each point 50 x 50 cm) were examined for live and dead leafhoppers using a suction scanner. The results obtained are shown in Table 2 below.

[Table] As is clear from Table 2, the powder composition of Comparative Example 2, which has poor powder discharging properties, has a biological effect that is lower than that of the powder composition of the present invention in Example 5 due to the non-uniform powder discharging property. Even worse than that. As explained above, according to the present invention, by adding a small amount of polysiloxane to an agricultural and horticultural powder composition containing calcium carbonate and/or magnesium carbonate as an extender, dispersibility, powder discharging properties, and fluidity can be improved. It is possible to significantly improve the physical properties such as

Claims (1)

[Claims] 1. A powder composition for agricultural and horticultural use, characterized in that it contains an agricultural and horticultural chemical, calcium carbonate and/or magnesium carbonate, and 5% by weight or less of polysiloxane based on the total amount of the composition.