JPH02131402A - Water-base liquid bioactive composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of keeping the stability of bioactive component, storable over a long period without causing agglomeration and coagulation of dispersed particles and useful as an agricultural chemical by adding fine powder of halloysite-base inorganic silicate to a specific water- base liquid composition. CONSTITUTION:The objective composition is produced by compounding (A) a water-base liquid composition containing water as the dispersion medium and composed of fine powder of a water-insoluble or scarcely soluble bioactive substance such as fungicide, insecticide, herbicide and plant growth regular, a thickener and a surfactant with (B) 0.1-10wt.% (based on the composition A) of fine powder of a halloysite-base inorganic silicate expressed by the chemical formula, e.g., halloysite or endellite which is a hydrated aluminum silicate mineral forming halloysite by losing a part of water at about 50 deg.C. The particle diameter of the halloysite powder is about 10-1mum. The composition has physical stability to keep high fluidity and chemical stability to keep the stability of the active component. The active component can be stably maintained in the composition.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to sterilization, insecticidal, weeding, etc. The present invention relates to an aqueous liquid bioactive composition that secures the stability of bioactive ingredients such as plant growth regulators and maintains the formulation stability of the composition.

[Conventional technology]

Conventionally, pest control agents (insecticides, fungicides, etc.), herbicides.
For formulation of biologically active compositions such as plant growth regulators, emulsions.
There are wettable powders, powders, granules, vJ cloudy agents, etc., and these formulation types are used depending on the purpose of use.

In particular, aqueous suspensions use water as a diluent, so compared to emulsions using organic solvents or powders, granules, and permanent agents using fine mineral powder, they are more susceptible to phytotoxicity to plants, It is characterized by reducing various health and safety problems for workers caused by scattering of powder during use.

However, bioactive compositions in the form of aqueous suspensions have many problems in terms of formulation technology. For example, physical properties often deteriorate during storage due to phenomena such as sedimentation of dispersed particles in a suspending agent, formation of a strong sediment layer at the bottom of the container after sedimentation, and aggregation of dispersed particles. This poses a serious problem to the quality of the product and causes a loss of product value.

In order to eliminate such drawbacks, various efforts have been made in the past. For example, petroleum resin as an aqueous suspension agent. Coumaron resin,
Technology using ester gum etc. (Japanese Patent Application Laid-Open No. 52-14862
5), technology using polyvinyl alcohol (Japanese Unexamined Patent Publication No. 61-126001), a polymer of unsaturated carboxylic acid, styrene sulfonate, and a formalin condensate of a sulfonated polycyclic aromatic compound. technology (Unexamined Japanese Patent Publication No. 6)
2-126101), technology using abaculgite and bentonite as water-soluble polymers (Japanese Patent Laid-Open No. 62-8
No. 7501) and the like are disclosed.

[Problem to be solved by the invention]

In the above-mentioned conventional technology, the key point of the aqueous suspension agent is how to prevent the suspended particles from agglomerating, settling, and solidifying. Therefore, the question is how to find a material or method for thickening and preventing sedimentation that is suitable for these purposes.

Most of these techniques use a specific organic polymer compound and add it to a specific viscosity to provide physical stability to the suspended particles.

However, it is still difficult to achieve sufficient physical stability of suspended particles using only organic polymer compounds. Therefore, a technique has been disclosed in which clay minerals are added to these thickeners as an anti-agglomeration, sedimentation and caking agent (Japanese Patent Application Laid-Open No. 1987-87501). However, the clay minerals disclosed in this technique are They are generally alkaline.

On the other hand, most biologically active substances, for example, the active ingredients of pesticides such as insecticides, bactericidal, herbicidal, and plant growth regulators, are unstable in alkaline conditions, and in order to maintain the stability of their ingredients, neutral The requirement was that it be slightly acidic.

Therefore, there is a need for formulations that have both the physical stability of aqueous suspensions and the chemical stability of the active ingredients used.

The object of the present invention is to provide an aqueous suspension composition that meets this need and has both the chemical stability of biologically active ingredients and the physical stability of the formulation.

[Means to solve the problem]

In order to solve these problems, the present inventors have attempted to agglomerate and precipitate suspended particles of an aqueous suspension composition. After intensive research to obtain a material that has anti-caking properties and maintains the stability of active ingredients, it was discovered that among inorganic silicates, halloysites are suitable for this purpose. They found this and completed the present invention.

The present invention uses water as a dispersion medium to produce fine powder of biologically active substances that are insoluble or poorly soluble in water. This is an aqueous liquid biologically active composition prepared by adding halloysite-based inorganic silicate fine powder to an aqueous liquid composition consisting of a thickener and a surfactant.

The halloysite-based inorganic silicate used in the present invention includes:
It is a hydrous silicate mineral of aluminum and has the same chemical formula as kaolin, but its crystal structure has different layers and is more disordered than kaolin.

Examples of the halloysite-based inorganic silicates include endeleite, hawaisite, and the like.

Endellite (Endellite, }Iydro
halloysite) is ^1. Si. 0, (leaf),・
It is a hydrated silicate mineral of aluminum, which has a chemical formula of 2 and 20, and loses some of its water to become halloysite at around 50°C. This substance is produced as gangue of metal deposits, rock alteration products due to hot spring action, or weathering products of volcanic ash. Many natural products contain a few percent of iron (Fezo*), and are produced as fine, wax-like aggregates. It is light brown and mostly isotropic.

Halloysite (}Ialloysite) is Al
2S+20s (DH) + aluminum hydrated silicate mineral, a type of kaolin (n = 1.56
0>, white powder mass, hardness 1-2. d-2.1, nearly isotropic, n = 1. 49 ~1. It has physical properties of 53, and unlike kaolin, the overlapping layers of its crystal structure are more disordered than kaolin.

The hawaisite-based inorganic silicate used in the present invention is preferably added as a fine powder with a particle size of about 10 to 1 μm in an amount of about 0.1 to 10% (by weight) based on the total amount of the suspension composition.

The biologically active ingredients of the present invention are mainly agricultural chemical active ingredients that are sparingly soluble or insoluble in water. The following are examples.

Sankel (nickel-dimethyldithiocarbamate).
Basic copper chloride, sulfur, maneb [ethylene bis(dithiocarbamic acid) manganese], polycarbamate agent [(bis-dimethyldithiocarbamic acid) ethylenepis(dithiocarbamic acid) dizinc], thiram [bis(dimethylthiorubamoyl) disulfide] , Daconyl (tetrachloroisophthalonitrile), Fusaride (4.5.6
．． 7-tetrachlorophthalide). EDDP (o-ethyl dithiophosphate = S, S diphenyl), hydrocyinxazole (3-hydroxy-5-methylinxazole), dithianone (2,3-dicyano-1,4-dithia,
1.4-dihydroanthraquinone), triflumizole ((E) 4-chloroα,α,α-trifluoro-N-
(1-(imidazol-1-yl)-2-propoxyethylidene]10-toluidine].Byleton C I
-(4-chlorophenoxy)-3.3-dimethyl-(IH-1.2.4-triazol-1-yl)-2-
butanone], isobrothiolane (diisoprobyl 1,3-dithiolane-2-ylidenemalonate), thiophanate methyl [4,4゜101phinylenebis(3-thioalophenic acid) dimethyl], and other bactericidal substances.

Carbaryl (1-naphthyl-N-methylcarbamate)
．． Tumaside (m-tri-N-methylcarbamate)
．． Mypsin (0-cumenyl-N-methylcarbamate)
．． Passa (0-Sec-butylphenyl-N-methylcarbamate), Sancide (0-impropoxyphenyl-N-methylcarbamate), Macbar (3.5-
-1-silyl-N-methylcarbamate). Bisit (dimethyl-4-methylthio-m-}lylphosfluorothionate), Sumithion (dimethyl-4-nitro-
m-}Rylphosphosothionate>. Diazinon (
diethyl-2-isobrobyl-4-methyl-6-pyrimidinylphosphorothionate), offnac (2.
3-dihydro-3-oise-2-phenyl-6-pyridazinyldiethylphosphorothionate), salithion (2.2-methoxy-48-1.3.2-penzodioxaphosphorine-2-sulfide), Acephate (
0,S-dimethyl-N-acetyl phosphoroamide thiolate), carbofuran (2.3-dihydro-2.2
-dimethyl-7-penzofuranyl methyl carbamate)
and other insecticidal substances.

DCPA (3,4-dichloropropionanilide),
DCMU l”3- (3.4-dichlorophenyl)-
1.1-dimethylurea], cymetrine [2.4-bis(ethylamino)-6-methylthio-1.3.5-}riazine]. birazole} (4- (2,4-dichlorobenzyl-1,3-dimethylvirazol-5-yl p
−} herbicidal substances such as luenesulfonate].

These biologically active ingredients may be used alone or in combination of two or more to form an aqueous aqueous suspension agrochemical, as in the case of ordinary aqueous aqueous suspension agrochemicals. The amount of these bioactive ingredients to be mixed depends on the intended use. Although it is appropriately selected depending on the conditions of use, it is usually contained in an amount of about 5 to 60% (by weight).

In addition to the above-mentioned components, the aqueous liquid composition of the present invention contains a thickener and a surfactant that are normally contained in the same composition.

Thickeners include xanthan gum, gum arabic, and guar gum. Plant-derived polymer substances such as gelatin, carboxyalwal cellulose. Semi-synthetic polymeric substances such as hydroxyalkyl cellulose, synthetic polymeric substances such as polyvinyl alcohol and polyacrylates, which are generally used as thickeners for aqueous liquid compositions, are used, and the amount used also varies. The amount used in the same composition, e.g. 0.001
-10% (by weight) is used as appropriate.

Examples of surfactants include polymeric nonionic surfactants and nonionic phosphate anionic surfactants. Naphthalene polycondensation type anionic activator, sorbitan ester type nonionic activator,
The types of active ingredients that are generally used as surfactants for aqueous liquid compositions, such as reduced-type nonionic surfactants and mixtures thereof, are as follows: They are appropriately selected and used depending on the purpose of use of the composition, usage conditions, etc.

In addition, other antifreeze agents such as ethylene glycol and propylene glycol, and preservatives such as paraformaldehyde may be added as appropriate.

Next, examples of the present invention and test results of the fluidity (physical stability) of the composition of the present invention after being left under heating for a long period of time, and the residual rate of the active ingredient (chemical stability) are shown below. show. The present invention is not limited to these examples.

〔Example〕

Example 1 Fine powder of Carhal ['(1-naphthyl-N-methylcarbamate) insecticidal active substance] with an average particle size of about 10μ 32
Parts by weight are halloysite with an average particle size of 10μ0.1 parts by weight, white carbon 1.7 parts by weight, and Solbol 374.
1 (manufactured by Toho Chemical Industry ■, surfactant) 4.0 parts by weight,
0.1 part by weight of xanthan gum was dissolved in water and dispersed using a homomixer to obtain 100 parts by weight of a carbaryl aqueous liquid composition.

Example 2 A carbaryl aqueous liquid composition of 100 parts by weight was prepared in the same manner as in Example 1 except that 0.3 parts by weight of halloysite was used instead of 0.1 parts by weight of halloysite.
Parts by weight were prepared.

Example 3 Carbaryl aqueous liquid composition 10 parts by weight was prepared in the same manner as in Example 1 except that 1.0 parts by weight of halloysite was used instead of 0.1 parts by weight of halloysite.
0 parts by weight were prepared.

Example 4 100 parts by weight of a carbaryl aqueous liquid composition was prepared in the same manner as in Example 1 except that 3.0 parts by weight of hawaisite was used instead of 0.1 parts by weight of halloysite.

Example 5 In Example 1, instead of using 0.1 part by weight of halloysite, 10. Carbaryl aqueous liquid composition 10 was prepared in the same manner as in Example 1 except that 0 parts by weight was used.
0 parts by weight were prepared.

Example 6 In Example 1, instead of using 0.1 parts by weight of Hawaiisite, 15. Carbaryl aqueous liquid composition 10 was prepared in the same manner as in Example 1 except that 0 parts by weight was used.
0 parts by weight were prepared.

Example 7 In Example 1, instead of using halloysite 0.1 overlap, halloysite 20. Carbaryl aqueous liquid composition 100 was prepared in the same manner as in Example 1 except that 0 parts by weight was used.
Parts by weight were prepared.

Test example 1) Test sample a. Example 1 (sample number 1), example 2 (sample number 2), example 3 (sample number 3). Carbaryl aqueous liquid compositions (compositions of the present invention) of Example 4 (Sample No. 4), Example 5 (Sample No. 5), Example 6 (Sample No. 6), and Example 7 (Sample No. 7).

mouth. Carbaryl 32.0 heavy base section, white carbon 1
．． 7 parts by weight, 4.0 parts by weight of Solbol 3741, 0.1 part by weight of xanthan gum, and the balance was water, and the same method as in Example 1 was used to prepare 100 parts by weight of carbaryl aqueous liquid composition. Control composition) (Sample No. 8)
.

C. Carbaryl 320 parts by weight, bentonite 3.0 parts by weight, white carbon 1.7 parts by weight, Solbol 37 parts by weight
41 100 parts by weight of carbaryl aqueous liquid composition was prepared in the same manner as in Example 1 using 4.0 parts by weight of xanthan gum, 0.1 parts by weight of xanthan gum, and the balance was water. Number 9).

2. Carbaryl 32.0 parts by weight, kaolin 3.0 parts by weight, white carbon 1.7 parts by weight, Solpol 374
100 parts by weight of carbaryl aqueous liquid composition was prepared in the same manner as in Example 1 using 14.0 parts by weight of xanthan gum, 0.1 parts by weight of xanthan gum, and the balance as water. , carbaryl 32.0 parts by weight, diatomaceous earth 3.0 parts by weight, white carbon 1.7 parts by weight, Solpol 3741
100 parts by weight of carbaryl aqueous liquid composition was prepared in the same manner as in Example 1 using 4.0 parts by weight of xanthan gum, 0.1 parts by weight of xanthan gum, and the remainder water (control) (sample number 11) 2 ) Test method A. Viscosity was measured using a B-type viscometer [B-type viscometer B 8 M60Hz (manufactured by Tokyo Keiki).

degree of separation and fluidity after being left at 60°C for 2 weeks Separation degree in a sealed container when each test sample was placed in a sealed container in a constant temperature bath at 60°C and left standing for 2 weeks [Separated liquid (Height of transparent liquid/height of total liquid XIOO) was measured.

Fluidity was determined in the next step by tilting the container and observing the fluidity with the naked eye.

Good: Flows easily when tilted.

Acceptable: Difficult to flow.

Impossible; does not flow.

C. Separation degree and fluidity after being left at 50℃ for 2 weeks.Put each test sample in a sealed container in a constant temperature bath at 50℃, and measure the degree of separation in the sealed container when left standing for 2 weeks. , the fluidity was observed. The measurement of separation degree and observation of fluidity are as described in the previous section.
I followed.

two. pH The pH of a mixed suspension of 20 g of each test sample and 80 mg of water was measured using a glass electrode.

Ho. Component Stability The residual rate of carbaryl was measured when each test sample was left at 50° C. for one month.

3》Test results It was as shown in Table 1.

As is clear from the above results, the composition of the present invention is superior to each control composition in terms of fluidity and component stability.

〔Effect of the invention〕

The aqueous liquid composition of the present invention has good physical stability with good fluidity that does not cause solidification or condensation of dispersed particles even when stored for a long period of time, and chemical stability that maintains the stability of the active ingredient. It is an extremely useful composition, especially when used as an agricultural chemical.

Patent applicant: Mikasa Chemical Industry Co., Ltd. Representative Riki Nii (and 2 others) -l;

Claims (1)

[Claims] 1. Halloysite-based inorganic silicate fine powder is added to an aqueous liquid composition containing water as a dispersion medium, a fine powder of a biologically active substance that is insoluble or poorly soluble in water, a thickener, and a surfactant. An aqueous liquid bioactive composition comprising: 2. An aqueous liquid bioactive composition in which the amount of the halloysite-based inorganic silicate fine powder according to claim 1 added is 0.1 to 10% (by weight).