JPS6366101A - Exterminating granule composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition capable of suppressing environmental pollution, having high effects on organisms, readily preservable and transportable, having improved degradation property and dispersibility, containing a finely granulated exterminating agent and a specific dispersant as essential components, consisting of granules having specific particle diameters and bulk specific gravity. CONSTITUTION:The titled composition comprising granules which contains a finely granulated exterminating agent comprising >=50wt% particles having <=0.5mu particle diameter and one or more dispersants selected from (A) a water- soluble or water-dispersible polymer having a monomer consisting of an unsaturated caboxylic acid and a derivative thereof as an essential component, (B) a (co)polymer of a styrenesulfonate, (C) a condensate of formalin and a sulfonated polycyclic aromatic compound which may contain a hydrocarbon group as a substituent or a salt thereof and (D) an alkali metallic salt of phosphoric acid, as essential components, and has 0.1-5mm average particle diameter and 0.25-1.30g/cm<2> bulk specific gravity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a biocidal granule composition, and more particularly, a biocidal granule composition, which has high biological efficacy, is easy to store and transport, and is easy to apply. The present invention relates to a biocidal granule composition with excellent disintegration properties and dispersibility.

[Conventional technology]

The dosage forms of biocides used today include powders, emulsions, irrigation agents, granules, and flowables, among which granules are important for labor-saving pest and weed control systems. In addition to fulfilling its role, it is safe, convenient, and can be applied with little loss, so it is used as a pesticide for soil treatment and water surface treatment.
It is a rational dosage form that has become widely used as herbicides, insecticides, fungicides, etc.

Ordinary granules contain various biocide active ingredients as active ingredients, inorganic mineral powders such as bentonite, talc, clay, kaolin, and calcium carbonate as carriers, and starch 1, fIJ vinyl alcohol, and Seratin-CM as binders.
It is made into granules by adding C5 sodium fulginate.

In some cases, a nonionic surfactant or an anionic surfactant is added to improve disintegration and dispersibility, and a carboxylic acid polymer is added to further improve spreadability.

Several granulation methods have been mentioned, but in the case of solid raw materials, after dry pulverization using a Zoetomizer, etc., a carrier, a binder, an appropriate amount of water, etc. are added, and a wet material is added, followed by extrusion. It is often manufactured using methods such as grains.

[Problem that the invention seeks to solve]

However, even if the granules produced by this method have excellent disintegration and spreadability, the biocidal active substance has a large particle size of 10 to 60 μm, making it difficult for plants, insects, etc. The problem was that the penetrating power was weak and a sufficient biocidal effect could not be obtained.

[Means for solving problems]

Therefore, as a result of extensive research, the present inventors found that if a dispersion of biocidal drug substance is stirred with 5 ml or less of rigid media, particles with a particle size of 0.5 μ or less can be reduced to 50 w.
t% or more, and if the resulting micronized biocidal drug substance is used as an active ingredient, the biological effect is high and the hard caking at the bottom due to natural sedimentation of the biocidal drug substance can be obtained. discovered that a suspension pesticide formulation with excellent long-term stability without thickening could be obtained, and filed a patent application (Japanese Patent Application Laid-Open No. 61-63601). However, as a result of further research into granulation, we found that by making the micronized biocide with a specific dispersant to a specific particle size and high density, it is possible to improve handling efficiency. The present inventors have discovered that a granule composition can be obtained that can suppress environmental pollution caused by the scattering of powder, is easy and convenient to store and transport, and has good disintegration and dispersion properties when added to water, and has completed the present invention. .

That is, the present invention provides a micronized biocide containing 50% by weight or more of particles having a particle size of 0.5 μ or less, and the following (1).
~(4), (1) A water-soluble or water-dispersible polymer containing as an essential component one or more selected from the monomer group consisting of unsaturated carboxylic acids and derivatives thereof, (2) Styrene sulfone (co)polymer of acid salt, (3
) a formalin condensate of a sulfonated polycyclic aromatic compound which may have a hydrocarbon group as a substituent, or a salt thereof; (4) an alkali metal phosphate; one or more dispersants selected from the following. A granular material containing as an essential component, the average particle size of the granular material is 0.1 to 5.
The present invention provides a biocidal granule composition characterized by having a bulk specific gravity of 0.25 to 1.3017♂.

In the micronized biocide according to the present invention, it is necessary that particles having a particle size of 0.5 μm or less account for 50 wt% or more, and it is further preferable that the overall average particle size is 0.5 μm or less. In particular, particles with a particle size of 0.5 μ or less
It is preferable that the total average particle size is 0.4 μm or less at wt% or more.

The biocide according to the present invention includes any biocide that is insoluble in water and solid at room temperature, regardless of its type. Furthermore, by making any biocide into microparticles according to the present invention, excellent biological effects that were hitherto unimaginable can be obtained. Furthermore, two or more types of biocides having different structures can also be used in combination.

As a biocide that is insoluble in water and solid at room temperature, benlate (methyl-1-(butylcarbamoyl)-
2-benzimidazole carbamate, bamboo galen (3
-Hydroxy-5-methylinxazole), Fushiwan (diinzolovir 1,3-dithiolane 2-yliben malonate), Colatop (1#1, 5,6-tetrahydro-4H-pyrrolo[3,2,1 -ij]Quinoline-4
-one), oryzemate (3-allyloxy-1,2-penzisothiazole 1,1-dioxide), beam (5-methyl-1,2,4-)lyazole (3,4-b
) - benzothiazole), etc.: For herbicides, nip (2
, 4-zochlorophenyl + p-nitrophenyl ether), Mo (p-nitrophenyl-2,4,6-)lichlorphenyl ether), chlormethoxynil (2,4-dichlorophenyl 3'-methoxy-4'-di trophenyl ether) natonosophenyl ether herbicides; carbamate herbicides such as SUE f (methyl-3,4-zochlorocarbanilate);
Urea herbicides such as dimethylpencil)-3-(p-tolyl)urea]; triazine herbicides such as cymasin (2-chloro-4,6-bis(ethylami)-113,5-)riazine); and Uripest (α-(2-naphthoxy)zolopionanilide), Sunbird (4-(2-naphthoxy)zolopionanilide),
, 4-dichloropendiyl) 1,3-dimethyl-5-pyrazolyl p-toluenesulfone)), 7' retilachlor (2-chloro-27, 61-diethyl-N-(2-
zorotooxyethyl)acetanilide), pasagran (3
-Isozorovir-2,1,3-benzo-thiazoacin-
4-one 2,2-dioxide); insecticides such as DDT (1,1,1-trichlor-2,2-bis())
Organochlorine insecticides such as Q-Lachlorphenyl-nitank; organophosphorus insecticides with aromatic rings such as Kaya Ace (/Q-Lazomethylsulfamylphenylzoethylphosphorothionate); Dena? Carbamate insecticides such as (1-naphthyl-methylcarbamate); O,S-dimethyl N-acetylphosphoramidothioate)%NOQdan(1,3-bis(
carpamoylthio)-2-(N,N-dimethylamino)
-7'' o-Q-hydrochloride), and the like.

The micronized biocide according to the present invention is easily produced by stirring a dispersion of the biocide with rigid media having a particle size of 0.5 μ or less.

The dispersants (1) to (4) used in the present invention are specifically those described below, and may of course be added at the time of crushing the biocide. These dispersants #-i [j alone or 2
Species or gold are used in combination.

(1) A water-soluble or water-dispersible polymer containing one or more monomers selected from the monomer group consisting of unsaturated carboxylic acids and their derivatives as an essential component 0 Used in the production of polymer (1) Monomers include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid,
Unsaturated dicarboxylic compounds such as maleic acid M1 Derivatives thereof, such as alkyl esters (such as methyl esters) of the above-mentioned acids, alkali gold maple salts (such as soda salts), ammonium salts and organic amine salts I J - (such as triethanolamine salts) , there are mixtures of these. In addition to these monomers, copolymerizable monomers such as vinyl acetate, imbutylene, diisobutylene, and styrene can also be added as copolymerization components.

The method of polymerizing these monomers is conventionally known. Although there are no particular restrictions on the ratio of monomer components and the degree of polymerization of the polymer, it is necessary that the polymer be at least water-soluble or water-dispersible.

Specific examples include acrylic acid polymers, methacrylic acid polymers, copolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and acrylic acid methyl ester, and copolymers of acrylic acid and vinyl acetate. Polymers, copolymers of acrylic acid and maleic acid, copolymers of maleic acid and imptile, copolymers of maleic acid and styrene, and combinations of these with alkali metals, ammonia, and organic amines. Salt is an example. Two or more kinds of these polymers can also be used.

(2) (Co)polymer of styrene sulfonate A polymer of styrene sulfonate can be easily produced by polymerizing styrene sulfonate or by sulfonating polystyrene. The styrene sulfonate polymer has a skeleton represented by the following formula.

S (JsM molecular weight is 1000 or more, preferably 10000-300
Ten thousand. M is alkali metal salts such as Li, Na, etc., alkylamines, alkanolamines, etc. 1! Taste.

Moreover, the polymer of styrene sulfonic acid may be a copolymer of styrene sulfonate and other monomers. Such a copolymer can be easily produced by copolymerizing styrene sulfonate and other monomers or by sulfonating a copolymer of styrene and other monomers.

In the case of copolymerization, it may be used within a range that does not impair the effects of the present invention.

As the monomer to be copolymerized, alkyl acrylate,
Hydrophobic monomers such as alkyl methacrylate, vinyl alkyl ether, vinyl acetate, ethylene, solopyrene, butylene, butadiene, zoisoptylene, vinyl chloride, vinylidene chloride, acrylonitrile, styrene, and acrylic acid, methacrylic acid, maleic acid, fumaric acid , maleic anhydride, vinyl alcohol, acrylamide, methacrylamide, diacetone acrylamide, N-vinylpyrrolidone, 2-acrylic 7)-2-methylzolonoQ sulfonic acid, methalylsulfonic acid, and other hydrophilic monomers. used.

(3) Formalin condensates of sulfonated polycyclic aromatic compounds that may have hydrocarbon groups as substituents or salts thereof 0 Specifically, petroleum sulfonic acid derivatives, lignin sulfonic acid derivatives, naphthalene sulfonic acid derivatives, etc. It is a formalin condensate of

The above compound (3) according to the present invention is, for example, naphthalene,
Alkyl-substituted 7-talenes, anthracenes, alkyl-substituted anthracenes, lignin, petroleum residues containing aromatic rings, etc., are sulfonated using a conventional method, followed by a salt-forming reaction, and then formalin condensation. It will be done. In this case, the degree of condensation is preferably 1.2 to 30,
More preferably, it is 1.2-10. Here, when the degree of condensation is 1.2 or less, the effect of condensation is small;
When it exceeds 0, the molecular weight becomes high, which causes practical problems in terms of solubility and the like.

Various types of polycyclic aromatic compounds can be used, but preferably lignin, naphthalene, or alkylnaphthalene having 1 to 6 carbon atoms may be used, and of course, a mixture thereof may be used. .

As salts, alkali metals such as sodium and potassium, alkaline earth metals such as calcium, amines, ammonium salts, etc. can be used.

(4) Examples of alkali metal phosphates include sodium tritylyphosphate, potassium birophosphate, sodium birophosphate, sodium hexametaphosphate, monobasic sodium phosphate, dibasic sodium phosphate, and tertiary sodium phosphate, and the like. One or more types from among these may be used.

The ratio of the micronized biocide and the above-mentioned dispersant in the composition of the present invention is dispersant/micronized biocide (weight ratio) = 1/1 to 1.
150, preferably 1/6 to 1/40.

In addition, as dispersants other than the above, nonionic surfactants,
An anionic surfactant may be used in combination. Nonionic surfactants and anionic surfactants include Fi, specifically those shown in (5) and (6) below. These dispersants can be used alone or in combination of two or more, but adding them at the time of pulverization is undesirable as it may cause problems such as foaming, so it is desirable to add them at the time of granulation. 0 to 20% by weight, preferably 1 to 20% by weight
It is 10-fold leaves.

(5) What are some examples of nonionic surfactants? Lioxyethylene (hereinafter referred to as POE) alkyl (carbon number 6-2
2) Ether, POE alkyl (4 to 18 carbon atoms) phenol ether, ? Lioxiderovirene? Lyoxyethylene (block or random) alkyl ether, P
Examples include OE phenylphenol ether, POE styrenated phenol ether, and OE) lipensylphenol ether.

(6) As anionic surfactants, lignin sulfonate, alkylbenzene sulfonate, alkyl sulfone salt, POE alkyl sulfonate% POE furkylphenyl nityl sulfonic acid in, POE alkyl phenyl ether phosphate ester salt, POE phenylphenol ether sulfonate, POE phenylphenol ether phosphate ester salt, naphthalene sulfonate, naphthalene sulfonic acid pomarine condensate, 1 (
) E tribenzylphenol ether sulfonate,
POE) lipensylphenylphenol ether phosphate ester salt, etc. are used.

There are several methods for producing the biocidal granule composition of the present invention, for example: (1) containing one or more compounds selected from the above micronized biocide and dispersant (1) to (4) A mineral carrier and, if necessary, (5) and (6) are added to the aqueous slurry (hereinafter referred to as micronized biocide slurry).
One or more compounds selected from: and a binder, etc.? In addition, after mixing, a method of manufacturing by a known method such as a transfer granulation method or an extrusion granulation method, a micronized biocide slurry containing a dispersant of (4) to (4), or a
5), a method in which one or more of the compounds selected from (6) is added to the mineral carrier and then granulated together with a binder etc., or ■ Spraying of the micronized biocide slurry A preferred method is to dry the powder, add a mineral carrier, a binder, etc. to the resulting powder, and then granulate it.

The mineral carriers used here include waxite, talc, kaolin, calcium carbonate, bentonite, silica powder, limestone powder, acid clay, gravel earth powder, gypsum, pumice powder,
Shellfish powder, mica powder, colloidal hydrated sodium silicate, etc., and their blending ratio in the granular biocide composition is 50
~98.4% by weight is preferred.

Specific examples of binders include natural water-soluble polymers such as xanthan gum, xanfuro, pectin, gum arabic, and guar gum; methylated products, carboxyalkylated products, and hydroxyalkylated products of cellulose or starch derivatives (methyl cellulose, Semi-synthetic polymers such as oxymethylcellulose, hydroxymethylcellulose, etc., or synthetic polymers such as dense acrylate, limalate, polyvinyl alcohol, broken vinyl pyrrolidone, or polygenine sulfonate, etc. can be mentioned.

The blending ratio of the binder in the granular biocide composition is 0.1 to 1
0% by weight, especially 0.5-5% by weight is preferred.

In the composition of the present invention, other ingredients may be added as necessary within a range that does not impair the effects of the present invention. It is also possible to add an anti-aggregation agent such as a lyoxyethylene-polyoxyderobylene block polymer, or an anti-decomposition agent such as epichlorohydrin, phenyl glycidyl ether, allyl glycidyl ether, and the like.

An example of the biocidal granule composition of the present invention described above is as follows.

) (1) to (4) dispersant 0.1 to 15
CC) (5), (6) dispersant 0-20
〇) Mineral carrier 50-98,4 ■ Binder 0.1-1° [F] Others (anti-agglomeration agent, anti-decomposition agent, etc.) 0-7 [Effects of the invention] Biocidal granule composition of the present invention Because things are granular, they can be stored,
It has excellent stability and is extremely easy to handle and transport without scattering. Furthermore, the biocide has been made into fine particles, and its biological effect is significantly enhanced compared to conventional biocides with large particle sizes, and it also contains the dispersants α) to (4) above. Because of this, it has excellent disintegration properties and biocide dispersibility after application.

〔Example〕

Next, the present invention will be explained with reference to Preparation Examples, Examples, and Test Examples, but the present invention is not limited to these Examples.

<Preparation Example 1> Preparation Sample 1: 20 parts by weight of BEAM (bactericide) powder, 460 parts by weight of a water-soluble copolymer salt represented by the formula (the molecular weight of the compound of the above formula is 680,000), and 76 parts by weight of water. and 0.1
200 parts by weight of ~0.2 u glass beads (media) are mixed (media/dispersion liquid volume ratio = 67/33) L, and the disk is rotated in a sand grinder for 12 hours.

The temperature inside the sand grinder is 20-25°C. Furthermore, by pressurizing this, 60 parts by weight of the atomized beam dispersion liquid is obtained. In addition, if the media is completely washed twice with 70 parts by weight of water, 98i weight of the beam can be recovered.

This atomized beam is 0.5μ as shown in Table 1.
The particle size distribution consists of 80% by weight of particles having the following particle sizes:

Table 1 Preparation sample 2: 30 parts by weight of X-Goni (herbicide), 3.5 parts by weight of a water-soluble copolymer salt represented by the formula (the molecular weight of the compound of the above formula is 380,000), 66 parts by weight of water. 5 parts by weight and 0.1-0.2
Mix 180 parts by weight of 1 jl of glass peas (media) (media/dispersion liquid volume ratio = 69/3], ) L,
, the disc was rotated for a total of 10 hours in a sand grinder. The temperature inside the sand grinder is 20-25°C. When this is filtered under pressure, 70 parts of micronized X-Gol dispersion is obtained.

As shown in Table 2, this micronized X-Goni is
The particle size distribution consists of 90% by weight of particles having a particle size of 0.05 μm or less.

Preparation sample 3: 25 parts by weight of Bunabon (insecticide), 3.51 parts by weight of a water-soluble copolymer salt represented by the formula (the molecular weight of the compound of the above formula is 480,000), 71.5 parts by weight of water, and 0 .1~0.2111 glass beads (media) 1
80 parts by weight Totally mixed moisturized media/dispersed liquid volume ratio = 69/3
1) In the sand grinder, cut the disc into 1
Rotate for 5 hours. The temperature inside the sand grinder is 2
The temperature is 0 to 25°C. When this is further filtered under pressure, 75 parts by weight of a micronized Bunabon dispersion is obtained.
The particle size distribution consists of 87% by weight of particles having a particle size of less than μ.

Preparation Sample 4 30 parts by weight of nioxamyl (insecticide) powder, 4.5 parts by weight of a water-soluble copolymer salt represented by the formula (the molecular weight of the compound of the above formula is 220,000), 65 parts by weight of water, and 0.1 parts by weight of water. 187 parts by weight of ~0.2 U of glass beads (media) are mixed (media/dispersion liquid volume ratio = 5015 (4)) and the disk is rotated in a sand grinder for 8 hours.

The temperature inside the sand grinder is 20-25°C. Furthermore, when this is filtered under pressure, micronized oxamyl dispersion 4 is obtained.
5 parts by weight are obtained.

As shown in Table 2, this micronized oxamyl was 0.
Particles having a particle size of 5 microns or less consist of a 70 weight - 0 particle size distribution.

Table 2 (Example) After adjusting the moisture content of the micronized biocide obtained in Preparation Samples 1 to 4, a predetermined amount of mineral powder and other ingredients were added, and extrusion granulation was performed according to the recipe shown below. As a comparative formulation example, biocidal granule compositions were prepared using a normal raw material that had not been micronized.

beam 4 dispersant
O,S bentonite
91, 2 broken vinyl alcohol
2? Lioxyethylene 0(4)nonylphenol ether 1 Formulation example 2: (wt%) XGoni 7 Dispersant
0.8 bentonite
90.2IJ Sodium Kuninsulfonate 2 Formulation Example 3: Dispersant 0.7 Calcium Carbonate 61.3 Clay
30? lipinyl alcohol
2 lauryl phosphate diethanolamine salt 2 Formulation example 4: Dispersant 0.2 clay
95.8 Sodium monolyacrylate 2 Sodium sialkyl sulfosuccinate 1 Comparative formulation example 1: (wt%) Beam 4 Bentonite 93-rivinyl alcohol 2-oxyethylene (IG nonylphenyl ether 1 Comparative formulation example 2: (wt%) ) XGoni 7 Bentonite 90 Sodium ricninsulfonate 3 Comparative formulation example 3: (% male) Denane 5 Calcium carbonate 61 Clay
30bori vinyl alcohol
2 lauryl phosphate ester zoethanolamine salt
2 Oxamyl 1 Clay 95 Sodium lyacrylate 2 Sodium dialkyl sulfosuccinate 2 <Test Example 1> Using Formulation Example 1 obtained in Example and Comparative Formulation Example 1, all biological tests were conducted in the following manner. The results are shown in Table 3.

(Test method) Three-leaf stage rice (variety Nihonbare) was transplanted into a 40m x 606n plastic bat and grown in a greenhouse. rice is 7
When the plants grew to the ~8 leaf stage, the water depth was adjusted to 1.5 cfn, and the beam granules of Prescription Example 1 and Comparative Prescription Example 1 were applied in predetermined amounts (7 cfn).

The average particle diameter of the beam particles of Comparative Prescription Example 1 is 10.31! Met. Fifteen hours after the chemical application, a rice blast fungus spore suspension was sprayed. After dispersing the spores, store them in a greenhouse for 5 days.
The number of lesions on 10 Tsutomura leaves was investigated, and the p control value was calculated using the following formula.

Table 3: Value as effective content <Test Example 2> Using all of Formulation Example 2 and Comparative Formulation Example 2 obtained in the Example, a biological test was conducted in the following manner.

The results are shown in Table 4.

(Test method) Put paddy soil in a 40 ctyt x 60 cm silastic vat, add paddy water to a water depth of 3 cInVc, mix and let stand, then sow pine viper and wild grass, and plant paddy rice seedlings (variety: Nipponbare). After 5 days, all prescribed amounts of X-Go 2 granules of Example 2 and Comparative Formulation Example 2 were treated, and the samples were kept in a flooded state at a water depth of 1, 5e:In for 14 days, and the occurrence of aspergillus and phytotoxicity was observed.

In addition, the particle size of the X-Go 2 particles of Comparative Prescription Example 2 is 11
, 8μ.

Test Example 3 in Table 4 Using Formulation Example 3 and Comparative Formulation Example 3 obtained in the Examples, a biological test was conducted in the following manner. The results are shown in Table 5.

(Test method) 40 rice seedlings (cultivar Nihonbare) at the 5-leaf stage were transplanted.
cm x 60 cm glass pad with water depth 1
, 5α, Prescription Example 3 and Comparative Prescription Example 3
Dena? Each predetermined amount of granules was processed. Dena in comparative prescription example 3? The particle size of the particles was 9.5μ. 24 hours after the chemical treatment, 10 leafhopper larvae per plant were released, and after being stored in a greenhouse for 24 hours, the mortality rate was examined.

Table 5 (Test Example 4) Using Formulation Example 4 and Comparative Formulation Example 4 obtained in the Examples, a biological test was conducted in the following manner. The results are shown in Table 6.

(Test method) Soil inhabited by root-knot nematodes was placed in a 6-inch pot, and a predetermined amount of the oxamyl granules of Formulation Example 4 and Comparative Formulation Example 4 were applied. The particle size of the oxamyl particles of Comparative Prescription Example 4 was 11.8μ. After the chemical treatment, the seeds of Kiyuushi are sown and further.

After 30 days, the mushrooms were dug and the number of IO1 root knots was measured to determine the effectiveness.

Evaluation criteria: 5: No root knots 4: 1 to 5 galls occur on one root 3: 6 to 10 galls occur on one root 2: 1 root 11 to 15 of them occur on one root 1... 16 to 20 of them occur on one root 6 Table of Test Example 5> Water (340 once hard water) was poured into a Petri dish with a diameter of 15 and a depth of 2 cm to a depth of 1 crn. Prescription example 1
~4. Granules 19 of Comparative Formulation Examples 1 to 4 were gently placed in the center of a petri dish, and the area of expansion over time was determined. The results are shown in Table 7.

Table 7 that's all

Claims (1)

[Claims] 1. A micronized biocide containing 50% by weight or more of particles having a particle size of 0.5μ or less, and the following (1) to (4), (1)
A water-soluble or water-dispersible polymer containing as an essential component one or more monomers selected from the monomer group consisting of unsaturated carboxylic acids and their derivatives; (2) (co)polymer of styrene sulfonate; , (3) a formalin condensate of a sulfonated polycyclic aromatic compound that may have a hydrocarbon group as a substituent or a salt thereof, (4) an alkali metal phosphate salt, or one or more selected from the following. A granular material containing a dispersant as an essential component, and the average particle size of the granular material is 0.1 to 5.
A biocidal granule composition having a bulk specific gravity of 0.25 to 1.30 g/cm^3.