JPH10337465A - Production of aqueous suspended emulsion unnecessitating solvent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the cost, to enable formulating a medicine without requiring an organic solvent even when an emulsion system is coexisted with a suspension system, and to have excellent storage stability in the obtained formulation and to have extended release property and a property lessening damage from the medicine. SOLUTION: In this method, oily substance for forming a boundary with water, a high polymer surfactant and a low polymer surfactant are added to water, and while they are stirred and mixed, the system is raised the temp. to convert the phase, then again lowered the temp. and continued to stir and mix to produce an emulsion unnecessitating the solvent. Next, a solid effective component, the high polymer surfactant and the low polymer surfactant are added, stirred and mixed to obtain an aqueous suspended emulsion unnecessitating the solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an aqueous suspension containing a solvent-free emulsion stably.

[0002]

2. Description of the Related Art In various fields such as medicines, agricultural chemicals and paints, sustained release and diffusibility are functions that are greatly desired. For example, as for the sustained-release property, a coacervation method in microencapsulation technology (JP-A-59-2306)
35, JP-A-59-159177), a submerged drying method, a phase separation method and a spray-drying method (JP-A-59-172653 and JP-A-59-162943). In addition, there is an agrochemical formulation method utilizing microencapsulation technology for the purpose of extending the residual effect by the sustained release effect or stabilizing the agrochemical active ingredient. For example, gelatin having a water-soluble polymer as a film (for example, JP-A-50-99969, etc.), polyamide, polyurethane, polyurea, polyester (JP-A-54-13)
5671), polyvinyl acetate, polyvinyl ether (JP-A-55-92136), polyurethane-polyurea (JP-A-54-91591), polyamide-polyurea (JP-A-48-4643), resin prepolymer -A method for producing a microencapsulated pesticide using a water-soluble cationic urea resin (Japanese Patent Application Laid-Open No. 2-29642) has been proposed. Further, there is a method for producing an aqueous suspension of microcapsules (Japanese Patent Publication No. 7-64682). However, the microencapsulation and the like are complicated in any of the formulations. In addition, the performance is unstable due to the difference in the film thickness or the breaking ratio after the preparation.

[0003] On the other hand, for the diffusivity, various suspension preparation techniques can be mentioned. Above all, a method in which a hydrophobic solid pesticide is wet-ground in water or a hydrophilic medium and suspended in the medium as hydrophilic ultrafine particles (Japanese Patent Publication No. 46-20519),
It comprises a solid pesticide that is hardly soluble in water or a system that simultaneously contains a solid pesticide that is hardly soluble in water and a water-soluble solid pesticide, a surfactant, a water-soluble polymer, and water.
Suspended pesticides of 00 cp (JP-B-58-2440)
No.), pesticide insoluble or hardly soluble in water or organic solvents,
Suspended pesticide consisting of surfactant, xanthan gum and water (JP-A-57-58601), suspended pesticide consisting of water-insoluble or sparingly soluble pesticide, surfactant, water-soluble biopolymer and water (JP-A-2-111703),
Aqueous suspension preparations using a herbicide active ingredient or a pesticide biocidal active ingredient and a surfactant (JP-B-7-47521, JP-B-7-4752)
No. 2, Japanese Patent Publication No. 64-7041, Japanese Patent Publication No. 63-5880
No. 2, Japanese Patent Publication No. 6-78202).

Further, at the time of production, which the conventional emulsion had,
An aqueous emulsion formulation has been reported in which the problem of flammability during transportation and storage has been improved (JP-A-9-5).
No. 2810), and described as a polyoxyethylene / polyoxypropylene block polymer as an emulsifier. In addition, when containing two or more active ingredients,
An emulsified suspension formulation (suspoemulsion formulation) has also been reported as a method for the case where the physicochemical property difference between the active ingredients is large (JP-A-6-92801, Patent No. 593886). It is described therein that formulation in this dosage form has generally been considered to be difficult.

[0005]

As a sustained-release preparation for the purpose of prolonging the residual effect, it is difficult to prepare a pesticide utilizing microencapsulation technology. The difference comes out. Therefore, it is very difficult to always maintain a constant sustained release. Further, when such microencapsulation is used for a suspension preparation, there is a high possibility that the film will be broken during the preparation.
In addition, the cost is high.

On the other hand, a pesticide suspension formulation for the purpose of diffusibility is prepared by using a hardly water-soluble solid as a raw material in the presence of a surfactant and water.
Grinding and crushing with a rigid body is required, which is troublesome. Further, since the emulsion requires an organic solvent, the emulsion is likely to have an adverse effect on the environment, and the problem of crystallization of the active ingredient during storage remains. Organic solvents are also essential in improved microemulsion formulations. In a suspoemulsion formulation in which an emulsification system and a suspension system are mixed, it is essential to make suspension particles finer and to add a thixotropic agent in order to prevent layer separation and hard caking. When the preparation obtained for the purpose of diffusibility as described above is sprayed on a paddy field in the field of agrochemicals, the active ingredient is rapidly diffused, and extension of the residual effect can hardly be expected.

The present invention is not expensive and does not require an organic solvent even when emulsified and suspended systems are mixed.
It can be formulated without the necessity of micronization and the addition of thixotropic agent, and the obtained formulation has excellent storage stability, and the composite particles are stable even when diluted with a large amount of water such as spraying in water Accordingly, it is an object of the present invention to provide a method for producing an aqueous suspension containing a solvent-free oil-in-water emulsion which also has a sustained release property. Further, the production method can be used in a wide range of fields such as agrochemicals, medicines, foods, and cosmetics.

[0008]

Means for Solving the Problems The present inventors diligently studied to solve the above-mentioned problems, and completed the present invention.
That is, the present invention relates to (1) (a) water, (b) an oily substance forming an interface with water, comprising an oily active ingredient and / or an oily liquid, (c) a polymer surfactant, and (d) ) Add a low molecular surfactant, stir and mix while keeping the temperature below 40 ° C. (2) Then, raise the temperature inside the system while continuing stirring and mixing, and continue until the inside of the system is uniformly gelled.
(3) The temperature is further raised to change the phase of the system into a W / O emulsion. (4) After the phase inversion, the system is cooled down to the temperature before gelation, (5) (e) a part of the solid water-insoluble solid active ingredient is added, and (6) stirring and mixing while maintaining the temperature at 40 ° C or lower.
(7) Next, (f) a water-insoluble solid active ingredient and (g) a polymeric surfactant are added, and the mixture is further stirred and mixed while maintaining the temperature at 40 ° C. or lower. (8) (h) Adding at least one low molecular surfactant having an average molecular weight of at least 400 smaller than the average molecular weight of the molecular surfactant (g) and 1100 or less, and stirring and mixing while maintaining the temperature at 40 ° C or less. A method for producing an aqueous suspension-type solvent-free emulsion, which is a feature.

In the method for producing an aqueous suspension-type solvent-free emulsion according to the present invention, the step (5) of adding a part of the hardly water-soluble solid active ingredient immediately after the phase inversion can be omitted.

[0010] Of the above-described aqueous suspension generation and emulsion / aqueous suspension mixing steps (steps 7 to 8), only the aqueous suspension generation step is performed in another system, and the emulsion generation step (step 1) is performed. After the step 6) is completed, the aqueous suspension formed in another system is mixed, and thereafter, the emulsion / aqueous suspension mixing step of (step 7 to step 8) is performed.
This is a method of producing an aqueous suspension-type solvent-free emulsion in which stirring and mixing are carried out at 0 ° C. or lower.

Further, the present invention is an aqueous suspension-type solvent-free emulsion obtained by the above-mentioned production method.

In the present invention, the solid active ingredient is incorporated into the oily substance by the step (5) of adding a part of the hardly water-soluble solid active ingredient immediately after the phase inversion. An aqueous suspension-type solvent-free emulsion wherein contact of the solid active ingredient with water is reduced.

In the method for producing an aqueous solvent-free emulsion of the present invention, an oily substance is essential. This oily substance is a component of the emulsion, and is not used in the conventional emulsion production method. It does not act as a solvent. Therefore, the oily liquid used as the oily substance is not usually used as an organic solvent, so that an adverse effect on the environment due to the organic solvent can be prevented.

In the method for producing an aqueous suspension-type solvent-free emulsion of the present invention, the phase is inverted to obtain a fine microemulsion. The microemulsion obtained by this phase inversion alone or, when a part of a poorly water-soluble solid active ingredient is added immediately after phase inversion, with the solid particles incorporated in the microemulsion, is mixed with a low molecular surfactant. It forms strong composite particles by interaction with a polymeric surfactant. These strong composite particles cannot be obtained simply by mixing and using a high-molecular surfactant and a low-molecular surfactant as in the prior art. Further, the solid active ingredient added after the formation of the strong composite particles is completed is coated with the high molecular surfactant and the low molecular surfactant added later to form the composite particles.
The rigid composite particles described above are also further coated on the outside to form double composite particles.

[0015] The aqueous suspension-type solvent-free emulsion obtained by the production method of the present invention is stable in the composite particles, so that creaming is unlikely to occur and storage stability is excellent, so that the emulsion and the aqueous suspension can be mixed. It is made possible. In addition, in the conventional emulsion, the surfactant concentration is reduced by dilution with water, and the emulsion is rapidly destroyed. However, the emulsion does not occur in the aqueous suspension-type solvent-free emulsion of the present invention. It can survive in a stable manner. Therefore, it is possible to exhibit a sustained release property while maintaining the diffusibility, and at the same time, to reduce the phytotoxicity. In this case, the cost does not increase as in a capsule. In the case of conventional emulsions, such sustained release cannot be expected.

In the method for producing a solvent-free emulsion in the form of an aqueous suspension according to the present invention, when handling a plurality of active ingredients, even if there is a large difference in the physicochemical properties between the active ingredients, the emulsion and the aqueous suspension may be used. Liquid mixed preparations are possible, and no organic solvent is required. The composite particles of the present invention are stably suspended in water even if they have a large particle size of, for example, 100 to 1000 μm. This aqueous suspension-type solvent-free emulsion can be used in cosmetics raw materials, dyes, pigments, food raw materials, pharmaceuticals, agricultural chemicals, hygiene chemicals, household chemicals, office chemicals, civil engineering, and the like, as long as the above characteristics can be exploited. It can be applied to fields such as materials and industrial chemicals.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The type of the oily active ingredient of the present invention is not particularly limited, but the following types of active ingredients can be exemplified. As cosmetic raw materials, for example, organic fatty acids such as oleic acid, olive oil, petrolatum, benzyl benzoate and the like can be used. Food ingredients include, for example, vegetable edible oils and animal edible oils. Pharmaceuticals include, for example, methyl salicylate, clofibrate, diphenhydramine and dimercaprol. Sanitary chemicals include, for example, bath salts, insect repellents and animal repellents. As daily medicine,
For example, fragrances, deodorants, deodorants, toiletry products, paint vehicles, and the like can be used.

As agricultural chemicals, for example, ethyl 4-
[4- (4-trifluoromethylphenoxy) phenoxy] -2-pentenoate, butyl 2- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy]
Propionate, N-benzyl-N-isopropylpiparamide, N, N-diallyl-2-chloroacetamide, S-ethyl N, N-diethylcarbamate, S-
4-chlorobenzyldiethylthiocarbamate, S-benzyl N-ethyl-N- (1,2-dimethylpropyl) thiocarbamate, S-ethyl N, N-hexamethylene-thiocarbamate, S-ethylhexahydro-
1H-azepine-1-carbothioate, O-ethyl-
O- (3-methyl-6-nitrophenyl) secondary butyl phosphoramidothioate, (1RS, 2SR,
4SR) -1,4-epoxy-p-mens-2-yl-
2-methylbenzyl ether, 4-octanoyloxy-
3,5-dibromobenzonitrile, 2-chloro-2 ',
6'-diethyl-N- (n-propoxyethyl) -acetanilide, N-butoxymethyl-2-chloro-2 ',
6′-diethylacetanilide, (S-ethyl N,
N-hexamethylene-thiocarbamate, (2-chlorobenzylthio) -5-propyl1,3,4-oxadiazole, 2- (1,2-dimethylpropylamino) -4
-Ethylamino-6-methylthio-1,3,5-triazine, hexachloroacetone, ethyl 4- (4-chloro-2-methylphenoxy) butyrate, butyl 2-methyl-4-chloro-phenoxyacetate, tris [ 2
-(2,4-dichlorophenoxy) ethyl] -phosphite, 2- (2-chlorophenyl) methyl-4,4-
Dimethyl-3-isoxazolidinone or the like can be used.

The type of the solid active ingredient of the present invention is not particularly limited, but the following types of active ingredients can be exemplified. Cosmetic raw materials include, for example, titanium dioxide, talc and ultraviolet absorbers. Examples of the dye include a disperse dye and an oil-soluble dye. Examples of the pigment include inorganic pigments such as carbon black, graphite, ultramarine, and red bean, and organic pigments such as azo pigments, phthalocyanine pigments, and quinacridone pigments. Food raw materials include, for example, flour, starch and powdered milk. Examples of the drug include benzalkonium chloride, aspirin and erythromycin. As a sanitary chemical,
There are bath salts, insect repellents and animal repellents. Household chemicals include fragrances, deodorants and deodorants. As the office chemical, for example, a color former for pressure-sensitive copying paper / thermosensitive recording paper, a material for ink and correction fluid, and the like can be used. Civil engineering building materials include silica, gypsum and cement. Examples of industrial chemicals include activated carbon, ceramics, and parahydroxybenzoic acid.

As the agricultural chemicals, for example, the following compounds can be exemplified. 2,4-dichlorophenoxyacetic acid (2.4-D), 2-methyl-4-chlorophenoxyacetic acid (MCP), ethyl 2-methyl-4-chlorophenoxybutyrate (MCPB), 2,4-dichlorophenyl-
3-methoxy-4-nitrophenyl ether (chloromethoxynil), methyl 5- (2,4-dichlorophenyl) -2-nitrobenzoate (bifenox),
2,4,6-trichlorophenyl-4-nitrophenyl ether (CNP), 2-chloro-N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl-aminocarbonyl) benzenesulfone Amide, methyl = 2
-[3- (4-Methoxy-6-methyl-1,3,5-triazin-2-yl) ureidosulfonyl] benzoate, methyl = 2- [3- (4,6-dimethylpyrimidin-2-yl) Ureidosulfonyl] benzoate, ethyl 2- [3- (4-chloro-6-methoxypyrimidin-2-yl) ureidosulfonyl] benzoate, 1-
(4,6-dimethoxypyrimidin-2-yl) -3-
(3-ethylsulfonyl-2-pyridylsulfonyl) urea, 3- (6-methoxy-4-methyl-1,3,5-triazin-2-yl) -1-[-(2-chloroethoxy) phenylsulfonyl] Urea, methyl = 2- [3-
(4-Methoxy-6-methyl-1,3,5-triazin-2-yl) -3-methylureidosulfonyl] benzoate, methyl 3- [3- (4-methoxy-6-methyl-1,3 , 5-Triazin-2-yl) ureidosulfonyl] thiophen-2-carboxylate, 1-
(4,6-dimethoxypyrimidin-2-yl) -3-
(3-trifluoromethyl-2-pyridinylsulfonyl) urea, 2- (4,6-dimethoxypyrimidine-2-
Yl-carbamoylsulfamoyl) -N, N-dimethylnicotinamide, 3- (4,6-dimethoxy-1,
3,5-triazin-2-yl) -1- [2- (2-methoxyethoxy) phenylsulfonyl] urea, 2- [3
-(4,6-bis (difluoromethoxy) -pyrimidin-2-yl) ureidosulfonyl] benzoic acid = methyl,
Methyl = 2-[(4-ethoxy-6-methylamino-
1,3,5-triazin-2-yl) carbamoylsulfamoyl] benzoate, methyl 2- [3- (4,
6-dimethoxypyrimidin-2-yl) ureidosulfonylmethyl] benzoate (bensulfuronmethyl),
Ethyl = 5- [3- (4,6-dimethoxypyrimidine-
2-yl) ureidosulfonyl] -1-methylpyrazole-4-carboxylate (pyrazosulfuron), N-
(2-chloroimidazole [1,2-a] pyridine-3
-Yl-sulfonyl) -N '-(4,6-dimethoxy-
2-pyrimidyl) urea (imazosulfuron), 2,4
-Bis (ethylamino) -6-methylthio-1,3,5
-Triazine (simethrin), 2,4-bis (isopropylamino) -6-methylthio-1,3,5-triazine (promethrin), 2- (1,2-dimethylpropylamino) -4-ethylamino-6 Methylthio-1,
3,5-triazine (dimetamethrin), 4- (2,4
-Dichlorobenzoyl) -1,3-dimethyl-1H-pyrazol-5-yl-p-toluenesulfonate (pyrazolate), 4- (2,4-dichlorobenzoyl)-
1,3-dimethyl-5-phenacyloxy-1H-pyrazole (pyrazoxifene), 4- (2,4-dichloro-3-methylbenzoyl) -1,3-dimethyl-5
(4-methylphenacyloxy) -1H-pyrazole (benzophenap), 5-tert-butyl-3-
(2,4-dichloro-5-isopropoxyphenyl)-
1,3,4-oxadiazol-2 (3H) -one (oxadiazone), 2- (2,4-dichloro-3-methylphenoxy) -propionanilide (clomeprop), 2- (2-naphthyloxy) propion Anilide (naproanilide), 3-isopropyl-1H-2,
1,3-benzothiadiazin-4- (3H) one-2,
2-dioxide (bentazone), 3- (3,4-dichlorophenyl) -1,1-dimethylurea (diuron)
2 ′, 3′-dichloro-4-ethoxymethoxybenzanilide and 3,5-xylyl = N-methylcarbamate and the like.

The above-mentioned pesticidal active ingredient may be added, if necessary, to 1
They can be used alone or as a mixture of two or more, and the mixing ratio in the case of mixing can be arbitrarily selected.

The type of the oily liquid of the present invention is not particularly limited, but the following types of oily liquids can be exemplified. Examples of vegetable oils include cottonseed oil, flaxseed oil, corn oil, peanut oil, olive oil, castor oil, palm oil, almond oil, avocado oil, jojoba oil and the like. Animal oils include, for example, perhydrosqualene and whale oil. Mineral oils include, for example, liquid paraffin, petrolatum oil, spindle oil and machine oil. Examples of synthetic oils include oleic acid, chlorinated paraffin, methyl naphthalene, glycerin monolaurate, 1-phenyl-1-xylylethane, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, tri-n-butyl phosphate, citrate Examples thereof include acetyl tributyl acid, cetyl myristate, isopropyl stearate, decyl palmitate, hexyl laurate, and propylene glycol dicaprylate. Silicone oils include cyclomethicones, polymethylsiloxanes and dimethiconols. Fluorinated oils include perfluoroethers and fluorinated silicones

The polymer surfactant of the present invention has a molecular weight of 110
The type is not particularly limited as long as it has 0 to 700,000, and the following types of polymer surfactants can be exemplified. (1) Poly-4-vinylpyridine type cationic surfactant (2) Graft copolymer of cationic derivative of linear polysaccharide and olefin monomer (3) Copolymer of cationic monomer and nonionic monomer (for example, (4) Poly (2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride) (5) Poly (dimethylaminoethyl methacrylate) (6) Acrylic acid polymerization (7) Copolymers of maleic anhydride and acrylic acid and their salts with alkali metals, amines and ammonia (8) Copolymers of itaconic acid and acrylic acid And salts thereof with alkali metals, amines and ammonia (9) Alkali metal salt of honed styrene-maleic anhydride copolymer (10) Alkali metal salt of polyvinyl sulfonic acid (11) Alkali metal salt of polystyrene sulfonic acid (12) Polymethacryloyloxypropyl sulfonic acid (13) Polyepoxysuccinic acid (14) Formalin condensate of sodium naphthalene sulfonate (15) Melamine-sulfonic acid formalin condensate (16) Copolymer of alkylaminoalkyl (meth) acrylamide and (meth) acrylic acid alkylacrylamide or acrylonitrile (17) fatty acid dextrin (18) carboxymethyl cellulose (19) polyvinyl alcohol (20) polyoxyethylene (hereinafter abbreviated as POE)-
Polyoxypropylene (hereinafter abbreviated as POP) block polymer (21) Ethylenediamine-POE / POP block polymer (22) POE-POP triblock polymer

Two or more of these polymeric surfactants may be used. In this case, the same ionic one or a combination of the same ionic one and nonionic one must be used. Further, the polymer surfactant added in the first step of the present production method and the polymer surfactant added in the seventh step after the emulsion formation step is completed,
They may be the same or different. Among these polymeric surfactants, particularly preferred is POE (Polymerization number 2).
-400) -POP (polymerization number: 2-200) block polymer.

In the present invention, when selecting a low molecular surfactant, the ionicity of the high molecular surfactant used at the same time must be considered. For example, when the high molecular surfactant used contains an anionic high molecular surfactant, an anionic low molecular surfactant or a nonionic low molecular surfactant, or an anionic low molecular surfactant And a combination of a nonionic low-molecular surfactant must be used. When a cationic high molecular surfactant is contained, a cationic low molecular surfactant or a nonionic low molecular surfactant, or a cationic low molecular surfactant and a nonionic low molecular surfactant are used. Must be used.

As long as these conditions are satisfied, there is no problem even if two or more low molecular surfactants are used in combination. Further, the low-molecular surfactant added in the first step of the present production method and the low-molecular surfactant added in the eighth step after the emulsion formation step is the same or different. Good. However, the low molecular weight surfactant used in the eighth step must be at least 400 smaller than the average molecular weight of the high molecular weight surfactant added in the seventh step and have an average molecular weight of 1100 or less.

Examples of the anionic low molecular surfactant include, but are not particularly limited to, alkyl sulfates such as sodium lauryl sulfate, triethanolamine lauryl sulfate and potassium lauryl sulfate, lignin sulfonate,
Alkyl aryl sulfonic acids such as alkyl benzene sulfonic acid salt and alkyl naphthalene sulfonic acid, and salts thereof, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, disodium lauryl sulfosuccinate, lauryl polyoxyethylene alkyl sulfosuccinate Disodium and sulfosuccinates such as dioctyl sodium sulfosuccinate, lauryl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl ether phosphate, polyoxyethylene styrenated phenol ether sulfate, etc. Can be used.

Examples of the cationic low-molecular surfactant include alkyltrimethylammonium halide salts such as lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryltrimethylammonium bromide, and stearyltrimethylammonium bromide. Alkyl dimethyl benzyl ammonium halide salts such as lauryl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, tri (polyoxyethylene) stearyl ammonium chloride, stearyl pentaethoxy ammonium chloride, and chloro- [2-hydroxy -3-
(Trimethylammonio) propyl] hydroxyethylcellulose and the like can be used.

Examples of the nonionic low molecular surfactant include alkylol amides such as lauric acid diethanolamide, lauric acid myristic acid diethanolamide, myristic acid diethanolamide, and polyoxyethylene stearic acid amide, polyoxyethylene octyl phenyl ether, Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonyl phenyl ether and polyoxyethylene dinonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether Oxyethylene alkyl ether, polyethylene glycol monooleate, polyethylene glycol dioleate, monostearyl Polyethylene glycol fatty acid esters such as polyethylene glycol acid, polyethylene glycol distearate, etc., decaglyceryl monocaprylate, glyceryl monostearate, sorbitan monocaprylate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate Sorbitan fatty acid esters such as sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate; monoolein Acid polyoxyethylene sorbit, tetraoleic acid polyoxyethylene sorbite, etc. Polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl such as sorbitol fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether (block), polyoxyethylene polyoxypropylene glycol, and ethylenediamine tetrapolyoxyethylene polyoxypropylene There are aryl ethers, polyoxyethylene styrenated phenol ethers, polyoxyethylene alkyl esters, and polyoxyethylene styrenated phenol ether polymers.

In the process for producing an aqueous suspension-type solvent-free emulsion according to the present invention, the effect is enhanced by using a viscosity modifier, a preservative and deodorant, an antifoaming agent, an excipient and the like as a solid auxiliary additive. However, it is needless to say that the effect is exhibited even without using.

Examples of the viscosity modifier include xanthan gum, guar gum, tragacanth gum, gum arabic, casein, dextrin, carboxymethyl cellulose, carboxymethyl starch sodium salt, sodium alginate, hydroxyethyl cellulose, carboxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, Examples include, but are not limited to, polyvinyl alcohol, polyacrylic acid and its derivatives, colloidal hydrous magnesium silicate, colloidal hydrous aluminum / magnesium, and the like, or a mixture of two or more of these. It can also be used.

Examples of the preservative and antiseptic include butyl p-oxybenzoate, sorbitanic acid and potassium sorbate, and these can be used alone or in combination of two or more.

As the defoaming agent, generally used silicone type, fatty acid type and mineral oil type are used.
It is not limited to these.

As the excipient, generally used excipients, for example, carplex, aerosil and the like can be mentioned.

Other auxiliary additives include antifreezing agents such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether and methanol, and inorganic and organic salts as suspension stabilizers. There are antioxidants, UV inhibitors and the like as stabilizers of the active ingredient.
Species or two or more species can be used in combination.

In the method for producing an aqueous suspension-type solvent-free emulsion of the present invention, a method for producing an ordinary aqueous suspension preparation may be used without any special method or equipment. When stirring and mixing the added components in the preparation process, the purpose of use and the required residual effect period are changed by variously changing the type of stirring device, the stirring speed, the shape of the stirring blade, the stirring time, the stirring temperature, etc. Can be prepared. As the stirring device, for example, a homomixer, a homogenizer, a Dynomill or the like can be used.

The process for producing an aqueous suspension-type solvent-free emulsion of the present invention can be carried out in the following steps. First, with respect to (a) water, (b) an oily substance which forms an interface with water, comprising an oily active ingredient or / and an oily liquid, (c) a polymer surfactant, and (d) a low molecular interface The activator is added, and the mixture is stirred and mixed at 3000 to 15000 rpm for 3 to 20 minutes with a homomixer or the like while maintaining the temperature at 40 ° C. or lower. Second, 30
The temperature in the system is increased while stirring and mixing at 00 to 15000 rpm, and the process is continued until the inside of the system is uniformly gelled. In this case, the gelation temperature is determined by the physical properties and quantitative ratio of each component added to the system. After confirming that the inside of the system has gelled, thirdly, the temperature is further raised to change the inside of the system into a W / O emulsion. In this case, the physical properties of the low molecular surfactant of the component (d) most influence the phase inversion temperature. Fourth, the inside of the system after the phase inversion is cooled to a temperature before gelation. Fifth, (e) a part of the solid water-insoluble solid active ingredient is added, and (6) stirring and mixing while maintaining the temperature at 40 ° C. or lower.
(7) Next, (f) a water-insoluble solid active ingredient and (g) a polymeric surfactant are added, and the mixture is further stirred and mixed while maintaining the temperature at 40 ° C. or lower. (8) (h) Add at least one low molecular surfactant having an average molecular weight of at least 400 smaller than the average molecular weight of the molecular surfactant (g) and 1100 or less, and stir and mix while maintaining the temperature at 40 ° C or less.

The step (5) of adding a part of the hardly water-soluble solid active ingredient immediately after the phase inversion can be omitted. The solid active ingredient (e) and the solid active ingredient (f) of the step (7) may be pulverized before being added.

Of the above-described aqueous suspension generation and emulsion / aqueous suspension mixing steps (Steps 7 to 8), only the aqueous suspension generation step is performed in another system, and the emulsion formation step (Step 1) is performed. After completion of Step 6), the aqueous suspension formed in another system is mixed, and the mixture is stirred while maintaining the temperature at 40 ° C. or lower, which corresponds to the emulsion / aqueous suspension mixing step in Step 7 to Step 8. -It is also possible to carry out mixing.

The oily substance (component (b)) may be any oily substance that forms an interface with water, and does not require any performance as an organic solvent. The oily substance may be an oily active ingredient alone or an oily liquid alone, or a mixture of an oily active ingredient and an oily liquid. The amount of the oily substance to be added is 1 to 30% by weight, preferably 4 to 20% by weight based on the whole aqueous suspension-type solvent-free emulsion.

The amount of the polymeric surfactant (component (c)) to be added is 0.5 to 20% by weight, preferably 4 to 10% by weight, based on the total amount of the aqueous suspension-type solvent-free emulsion.

The amount of the low molecular surfactant (component (d)) to be added is 0.5 to 20% by weight, preferably 0.5 to 10% by weight, based on the total amount of the aqueous emulsion without solvent.
It is.

In the step (5) of adding a part of the hardly water-soluble solid active ingredient immediately after the phase inversion, the solid active ingredient is incorporated into the oily substance, and the solid active ingredient in the obtained aqueous suspension is obtained. Contact with water can be reduced.
Therefore, if it is required to reduce the contact of the solid active ingredient in the aqueous suspension with water, this step (5)
Is required, and a portion of the solid active ingredient is treated in this step. If it is not necessary to reduce the contact with water, this step (5) is also unnecessary. The addition amount of the solid active ingredient is 0.1 to 6 with respect to the whole aqueous suspension solvent-free emulsion.
It is 5% by weight, preferably 0.1 to 35% by weight.

The average particle size of such an aqueous suspension-type solvent-free emulsion can be measured very easily with a measuring instrument, so that the average particle size can be easily grasped. As the measuring instrument, for example, a Coulter LS130 laser type (Nikkaki Co., Ltd.) can be mentioned.

[0045]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In addition, all the parts in the following formulation examples and comparative examples indicate parts by weight.

Formulation Example 1 In 46 parts of water, 3 parts of a POE (polymerization number 5) -POP (polymerization number 35) block polymer were added.
2 parts of POE (polymerization number 14) nonylphenyl ether,
Add 10 parts of cottonseed oil and use a homomixer at 5000 rpm
m, stirring and mixing at 40 ° C. or lower for 30 minutes, and then 1 part of a silicon-based antifoaming agent DK QB-8011 (trademark of Dow Corning Asia Co., Ltd.) was added, and the mixture was mixed with a homomixer at 5,000.
The temperature is increased to 55 ° C. and the mixture is stirred and mixed for 30 minutes. After confirming that the inside of the system was gelled uniformly, the temperature was further raised to 68 ° C., and the inside of the system was changed into a W / O emulsion. After confirming that the inside of the system has uniformly turned into a W / O emulsion, the inside of the system is cooled to a temperature before gelation. Thereafter, the mixture was stirred and mixed at 5,000 rpm and 40 ° C. or lower for 30 minutes using a homomixer to obtain a solvent-free oil-in-water emulsion. rear,
30 parts of 2 ', 3'-dichloro-4-ethoxymethoxybenzanilide were added, followed by POE (polymerization number 5) -P
3 parts of OP (polymerization number 35) block polymer, POE
(Polymerization number 14) After adding 2 parts of nonylphenyl ether again, the mixture is stirred and mixed at 8000 rpm and 40 ° C. or lower for 30 minutes using a homomixer. Next, 0.8 parts of POE (polymerization number 6) alkyl aryl ether, POE (polymerization number 8)
0.3 part of an alkylaryl ether, 1.4 parts of an alkylbenzene sulfonate, and 0.5 part of POE (polymerization number 6) alkyl ether are added, and 500 parts are mixed by a homomixer.
The mixture was stirred and mixed at 0 rpm and 40 ° C. or lower for 30 minutes to obtain an aqueous suspension-type solvent-free emulsion.

[Formulation Example 2] POE (polymerization number 10) -POP (polymerization number 30) block polymer 4 in 45 parts of water
Part, 2 of POE (polymerization number 16) nonylphenyl ether
Parts, 10 parts of flaxseed oil and 5000 with a homomixer
rpm, stirring and mixing at 35 ° C or less for 30 minutes.
QB-8011 (trademark of Dow Corning Asia Co., Ltd.)
And 5000 rpm, 51 parts by a homomixer.
The temperature was raised to 0 ° C and the mixture was stirred and mixed for 30 minutes. After confirming that the inside of the system was gelled uniformly, the temperature was further raised to 69 ° C., and the inside of the system was changed into a W / O emulsion. W /
After confirming that the phase has changed to an O emulsion, the inside of the system is cooled to a temperature before gelation. Then, use a homomixer for 500
The mixture was stirred and mixed at 0 rpm and 35 ° C. or lower for 30 minutes to obtain a solvent-free oil-in-water emulsion. Thereafter, 30 parts of 3- (3,4-dichlorophenyl) -1,1-dimethylurea was added, and subsequently, POE (polymerization number 5) -POP (polymerization number 3) was added.
5) After re-adding 3 parts of the block polymer and 2 parts of POE (polymerization number 14) nonylphenyl ether, the mixture is stirred and mixed with a homomixer at 8000 rpm at 40 ° C or lower for 30 minutes. Next, 0.8 parts of POE (polymerization number 6) alkyl aryl ether, 0.3 parts of POE (polymerization number 8) alkyl aryl ether, and 1.
4 parts, and POE (polymerization number 6) alkyl ether 0.5
5,000 rpm, 40 ° C. using a homomixer.
The mixture was stirred and mixed for 30 minutes below to obtain an aqueous suspension-type solvent-free emulsion.

[Formulation Example 3] 5 parts of POE (polymerization number 12) -POP (polymerization number 35) block polymer in 44 parts of water
Part, 2 of POE (polymerization number 18) nonylphenyl ether
Parts and 10 parts of corn oil and add 5000 with a homomixer.
stirring and mixing at 40 rpm or less for 30 minutes, and then DK
QB-8011 (trademark of Dow Corning Asia Co., Ltd.)
And 5000 rpm at 48 rpm with a homomixer.
The temperature was raised to 0 ° C and the mixture was stirred and mixed for 30 minutes. After confirming that the inside of the system was gelled uniformly, the temperature was further raised to 72 ° C., and the inside of the system was changed into a W / O emulsion. W /
After confirming that the phase has changed to an O emulsion, the inside of the system is cooled to a temperature before gelation. Then, use a homomixer for 500
The mixture was stirred and mixed at 0 rpm and 40 ° C. or lower for 30 minutes to obtain a solvent-free oil-in-water emulsion. Later, 2- [4- (2,
30 parts of 3-dichlorophenylcarbamoyl) phenoxy] propionic acid = sodium salt are added, followed by PO
3 parts of E (Polymerization number 5) -POP (Polymerization number 35) block polymer and 2 parts of POE (Polymerization number 14) nonylphenyl ether were added again, and then 8000 r using a homomixer.
Stir and mix at pm, 40 ° C or less for 30 minutes. Next, PO
0.8 parts of E (polymerization number 6) alkyl aryl ether, P
OE (number of polymerization 8) alkyl aryl ether 0.3 part,
1.4 parts of alkylbenzene sulfonate, and POE
(Polymerization number 6) 0.5 parts of an alkyl ether was added, and the mixture was stirred and mixed with a homomixer at 5,000 rpm and 40 ° C. or lower for 30 minutes to obtain an aqueous suspension-type solvent-free emulsion.

Formulation Example 4 Five parts of a POE (polymerization number 5) -POP (polymerization number 35) block polymer was added to 43 parts of water.
3 parts of POE (polymerization number 14) nonylphenyl ether,
Add 10 parts of olive oil and 5,000 with a homomixer
stirring and mixing at 40 rpm or less for 30 minutes, and then DK
QB-8011 (trademark of Dow Corning Asia Co., Ltd.)
Is added at 5000 rpm and 46 with a homomixer.
The temperature was raised to 0 ° C and the mixture was stirred and mixed for 30 minutes. After confirming that the inside of the system was gelled uniformly, the temperature was further raised to 74 ° C., and the inside of the system was changed into a W / O emulsion. W /
After confirming that the phase has changed to an O emulsion, the inside of the system is cooled to a temperature before gelation. Then, use a homomixer for 500
The mixture was stirred and mixed at 0 rpm and 40 ° C. or lower for 30 minutes to obtain a solvent-free oil-in-water emulsion. Later, 2-anilino-3
30 parts of -methyl-6-dibutylaminofluoran were added, followed by POE (polymerization number 5) -POP (polymerization number 3).
5) After re-adding 3 parts of the block polymer and 2 parts of POE (polymerization number 14) nonylphenyl ether, the mixture is stirred and mixed with a homomixer at 8000 rpm at 40 ° C or lower for 30 minutes. Next, 0.8 parts of POE (polymerization number 6) alkyl aryl ether, 0.3 parts of POE (polymerization number 8) alkyl aryl ether, and 1.
4 parts, and POE (polymerization number 6) alkyl ether 0.5
5,000 rpm, 40 ° C. using a homomixer.
The mixture was stirred and mixed for 30 minutes below to obtain an aqueous suspension-type solvent-free emulsion.

[Formulation Example 5] 4 parts of POE (polymerization number 5) -POP (polymerization number 30) block polymer was added to 45 parts of water,
3 parts of POE (polymerization number 14) nonylphenyl ether,
Add 4 parts of soybean oil and use a homomixer at 5000 rpm,
Stir and mix at 40 ° C or less for 30 minutes, then DK QB-
8011 (a trademark of Dow Corning Asia Co., Ltd.)
Add 4 parts of ethylene glycol, and add 5 parts with a homomixer.
The mixture was heated to 000 rpm and 45 ° C., and stirred and mixed for 30 minutes. After confirming that the inside of the system was gelled uniformly, the temperature was further raised to 72 ° C., and the inside of the system was changed into a W / O emulsion. After confirming that the inside of the system was uniformly transformed into a W / O emulsion, the inside of the system was cooled to a temperature before gelation, and when the temperature inside the system reached 50 ° C, 2 ′, 3′-dichloro Add 5 parts of 4-ethoxymethoxybenzanilide. Then, cool and use a homomixer at 8000 rpm at 40 ° C or less.
Stir and mix for 0 minutes. Next, 30 parts of 3- (3,4-dichlorophenyl) -1,1-dimethylurea and 3 parts of POE (polymerization number 5) -POP (polymerization number 35) block polymer
Part, 2 of POE (polymerization number 14) nonylphenyl ether
After adding 8000 rpm, use a homomixer at 8000 rpm, 40
Stir and mix at below 30 ° C for 30 minutes. Next, 0.8 parts of POE (number of polymerization 6) alkyl aryl ether, 0.3 parts of POE (number of polymerization 8) alkyl aryl ether, 1.4 parts of alkylbenzene sulfonate, and POE (number of polymerization 6)
0.5 part of an alkyl ether was added, and the mixture was stirred and mixed at 5,000 rpm and 40 ° C. or lower for 30 minutes using a homomixer to obtain an aqueous suspension in the form of a solvent-free emulsion. [Formulation Example 6]
POE (polymerization number 5) -POP (polymerization number 3) was added to 45 parts of water.
0) 4 parts of the block polymer, 3 parts of POE (polymerization number 14) nonylphenyl ether, and 4 parts of soybean oil were added, and the mixture was stirred and mixed with a homomixer at 5,000 rpm for 30 minutes at 40 ° C or lower, and then DK QB- 8011 (a trademark of Dow Corning Asia Co., Ltd.) and ethylene glycol 4
Then, the mixture is heated to 5,000 rpm and 45 ° C. with a homomixer, and stirred and mixed for 30 minutes. After confirming that the inside of the system was gelled uniformly, the temperature was further raised to 72 ° C., and the inside of the system was changed into a W / O emulsion. After confirming that the inside of the system was uniformly transformed into a W / O emulsion, the inside of the system was cooled to a temperature before gelation, and when the temperature inside the system reached 50 ° C, 2 ′, 3′-dichloro Add 5 parts of 4-ethoxymethoxybenzanilide. After cooling, use a homomixer for 80
The mixture was stirred and mixed at 00 rpm and 40 ° C. or lower for 30 minutes to obtain a solvent-free emulsion. In another container, add 3- (3,4-
30 parts of dichlorophenyl) -1,1-dimethylurea,
After adding 3 parts of POE (Polymerization number 5) -POP (Polymerization number 35) block polymer and 2 parts of POE (Polymerization number 14) nonylphenyl ether, the mixture was mixed at 8000 r with a homomixer.
Stir and mix at pm, 40 ° C or less for 30 minutes. Next, PO
0.8 parts of E (polymerization number 6) alkyl aryl ether, P
OE (number of polymerization 8) alkyl aryl ether 0.3 part,
1.4 parts of alkylbenzene sulfonate, and POE
(Polymerization number 6) 0.5 part of alkyl ether was added, and the mixture was stirred and mixed at 5,000 rpm and 40 ° C. or lower for 30 minutes with a homomixer to obtain an aqueous suspension, mixed with the solvent-free emulsion previously prepared, and further homogenized. 500 by mixer
The mixture was stirred and mixed at 0 rpm and 40 ° C. or lower for 30 minutes to obtain an aqueous suspension-type solvent-free emulsion.

[Comparative Example 1] 3 parts of a POE (polymerization number 5) -POP (polymerization number 35) block polymer was added to 84 parts of water.
2 parts of POE (polymerization number 14) nonylphenyl ether,
1 part of DK QB-8011 (Dow Corning Asia Co., Ltd.) and 10 parts of cottonseed oil were added, and the mixture was stirred and mixed with a homomixer at 10,000 rpm for 30 minutes at 40 ° C. or less.
An oil-in-water emulsion was obtained. Thereafter, 30 parts of 2 ′, 3′-dichloro-4-ethoxymethoxybenzanilide was added, and subsequently, POE (polymerization number 5) -POP (polymerization number 3) was added.
5) 3 parts of the block polymer and 2 parts of POE (polymerization number 14) nonylphenyl ether were added again, and the mixture was stirred and mixed with a homomixer at 8000 rpm at 40 ° C. or lower for 30 minutes to obtain an aqueous suspension.

[Comparative Examples 2] to [Comparative Example 3] Preparations were made in the same manner as in Comparative Example 1, and the same raw materials were used as in Formulation Examples 2 to 3. In Comparative Examples 1 to 3, the same raw materials as in Formulation Examples 1 to 3 were used, respectively, but the manufacturing process employed a conventional method.

Next, results of tests performed to demonstrate the usefulness of the present invention are shown in Test Examples. [Test Example 1] 5 of the preparations obtained in each preparation example and each comparative example
One month after the observation at 0 ° C., the appearance was “creaming” (O /
In the W emulsion, the oil droplet particles have a density lower than that of water, so that the oil droplet particles rise due to buoyancy and gather at the upper portion to exhibit a creamy state). The results are shown in [Table 1]. It can be seen that the aqueous suspension-free solvent-based emulsion of the present invention exists more stably for a long period of time as compared with a conventional emulsion preparation and a mixed preparation of an aqueous suspension.

[0054]

[Table 1] Formulation stability test results Preparation example Comparative example 1 2 3 4 5 1 2 3 With or without creaming ク リ 〇 〇 〇 〇 × × × (50 ° C for 1 month)

[0055]

EFFECT OF THE INVENTION The solvent-free emulsion of the present invention is not expensive in cost, enables mixing of the emulsion with the aqueous suspension, and can be formulated without the need for an organic solvent. , The resulting formulation has excellent storage stability,
It maintains a stable emulsion after being put in water at the time of use, and has the characteristics of a sustained-release preparation and the property of reducing phytotoxicity. Further, the present production method can be used not only in the field of agrochemicals but also in a wide range of fields such as medicines, foods, cosmetics, sanitary medicines, household medicines, office supplies, and civil engineering construction materials.

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[Procedure amendment]

[Submission date] August 31, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0002

[Correction method] Change

[Correction contents]

[0002]

2. Description of the Related Art In the fields of medicine, agricultural chemicals, etc., its sustained release and diffusibility are functions that are greatly desired. For example,
As for the sustained release, the coacervation method (JP-A-59-230635, JP-A-59-159177), the in-liquid drying method, the phase separation method and the spray drying method (JP-A-59-172653, JP-A-59-1
62943). In addition, there is an agrochemical formulation method utilizing microencapsulation technology for the purpose of extending the residual effect by the sustained release effect or stabilizing the agrochemical active ingredient. For example, gelatin (for example, Japanese Patent Application Laid-Open No. 50-99969, etc.) coated with a water-soluble polymer, polyamide, polyurethane,
Polyurea, polyester (JP-A-54-135671)
No.), polyvinyl acetate, polyvinyl ether (JP-A-5
5-92136), polyurethane-polyurea (Japanese Patent Application Laid-Open No. 54-91591), polyamide-polyurea (Japanese Patent Application Laid-Open No.
8-4643), and a method for producing microencapsulated pesticides using a resin prepolymer-water-soluble cationic urea resin (Japanese Patent Application Laid-Open No. 2-29642). Further, there is a method for producing an aqueous suspension of microcapsules (Japanese Patent Publication No. 7-64682). However, the microencapsulation and the like are complicated in any of the formulations. In addition, the performance is unstable due to the difference in the film thickness or the breaking ratio after the preparation.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

Further, at the time of production, which the conventional emulsion had,
An aqueous emulsion formulation has been reported in which the problem of flammability during transportation and storage has been improved (JP-A-9-5).
No. 2810), and described as a polyoxyethylene / polyoxypropylene block polymer as an emulsifier. In addition, when containing two or more active ingredients,
An emulsified suspension formulation (suspoemulsion formulation) has also been reported as a method for the case where the physicochemical property difference between the active ingredients is large (JP-A-6-92801, Patent No. 2593886). It is described therein that formulation in this dosage form has generally been considered to be difficult.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction contents]

[Formulation Example 5] 4 parts of POE (polymerization number 5) -POP (polymerization number 30) block polymer was added to 45 parts of water,
3 parts of POE (polymerization number 14) nonylphenyl ether,
Add 4 parts of soybean oil and use a homomixer at 5000 rpm,
Stir and mix at 40 ° C or less for 30 minutes, then DK QB-
8011 (a trademark of Dow Corning Asia Co., Ltd.)
Add 4 parts of ethylene glycol, and add 5 parts with a homomixer.
The mixture was heated to 000 rpm and 45 ° C., and stirred and mixed for 30 minutes. After confirming that the inside of the system was uniformly gelled, the temperature was further raised to 72 ° C., and the inside of the system was changed into a W / O emulsion. After confirming that the inside of the system was uniformly transformed into a W / O emulsion, the inside of the system was cooled to a temperature before gelation, and when the temperature inside the system reached 50 ° C., 2 ′, 3′-dichloromethane was dissolved. 5 parts of -4-ethoxymethoxybenzanilide were added. Then, cool and use a homomixer at 8000 rpm at 40 ° C or less.
Stir and mix for 0 minutes. Next, 30 parts of 3- (3,4-dichlorophenyl) -1,1-dimethylurea and 3 parts of POE (polymerization number 5) -POP (polymerization number 35) block polymer
Part, 2 of POE (polymerization number 14) nonylphenyl ether
After adding 8000 rpm, use a homomixer at 8000 rpm, 40
The mixture was stirred and mixed at 30 ° C. or lower for 30 minutes. Next, 0.8 parts of POE (number of polymerization 6) alkyl aryl ether, 0.3 parts of POE (number of polymerization 8) alkyl aryl ether, 1.4 parts of alkylbenzene sulfonate, and POE (number of polymerization 6)
0.5 part of an alkyl ether was added, and the mixture was stirred and mixed at 5,000 rpm and 40 ° C. or lower for 30 minutes using a homomixer to obtain an aqueous suspension-type solvent-free emulsion. [Formulation Example 6] POE (Polymerization number 5) -POP in 45 parts of water
(Polymerization number 30) 4 parts of block polymer, 3 parts of POE (polymerization number 14) nonylphenyl ether and 4 parts of soybean oil were added, and the mixture was stirred and mixed with a homomixer at 5000 rpm and 40 ° C. or lower for 30 minutes. Add 1 part of DK QB-8011 (trademark of Dow Corning Asia Co., Ltd.) and 4 parts of ethylene glycol, and use a homomixer at 5000 rpm.
m, the temperature was raised to 45 ° C., and the mixture was stirred and mixed for 30 minutes. After confirming that the inside of the system was gelled uniformly, the temperature was further raised to 72 ° C., and the inside of the system was changed into a W / O emulsion. After confirming that the inside of the system was uniformly transformed into a W / O emulsion,
The system was cooled to a temperature before gelation, and when the temperature of the system reached 50 ° C., 5 parts of 2 ′, 3′-dichloro-4-ethoxymethoxybenzanilide was added. Thereafter, the mixture was cooled and stirred and mixed with a homomixer at 8000 rpm at 40 ° C. or lower for 30 minutes to obtain a solventless emulsion. In another container, 3
30 parts of-(3,4-dichlorophenyl) -1,1-dimethylurea, POE (polymerization number 5) -POP (polymerization number 3)
5) After adding 3 parts of the block polymer, 2 parts of POE (polymerization number 14) nonylphenyl ether, and 65 parts of water, the mixture was stirred and mixed at 8000 rpm at 40 ° C. or lower for 30 minutes using a homomixer. Next, 0.8 parts of POE (number of polymerization 6) alkyl aryl ether, 0.3 parts of POE (number of polymerization 8) alkyl aryl ether, 1.4 parts of alkylbenzene sulfonate, and 0 parts of POE (number of polymerization 6) alkyl ether 0 .5 parts and 5000 rpm with a homomixer.
Stir and mix at 40 ° C or lower for 30 minutes to obtain an aqueous suspension, mix with the solvent-free emulsion prepared above, and further stir and mix with a homomixer at 5000 rpm at 40 ° C or lower for 30 minutes to obtain an aqueous suspension. A solvent-free emulsion was obtained.

Claims (16)

[Claims] (1) (a) water, (b) an oily substance which forms an interface with water, comprising (b) an oily active ingredient and / or an oily liquid, (c) a polymer surfactant, and (d) )
A low-molecular surfactant is added, and the mixture is stirred and mixed while maintaining the temperature at 40 ° C. or lower. (2) Then, the temperature in the system is increased while stirring and mixing are continued, and the mixture is continued until the inside of the system is uniformly gelled. 3) The temperature is further raised to change the phase of the system into a W / O emulsion.
(4) After the phase inversion, cool the inside of the system to the temperature before gelation, (5)
(E) adding a portion of a solid water-insoluble solid active ingredient,
(6) Stir and mix while maintaining the temperature at 40 ° C. or lower. (7)
Next, (f) a sparingly water-soluble solid active ingredient and (g) a polymer surfactant are added, and the mixture is further stirred while being kept at 40 ° C. or lower.
Mixing, (8) (h) followed by the polymeric surfactant described above
(g) adding at least one low-molecular surfactant having an average molecular weight of at least 400 and an average molecular weight of 1100 or less, and stirring and mixing while maintaining the temperature at 40 ° C or less. A method for producing an aqueous suspension-type solvent-free emulsion. 2. The process of claim 1, wherein the step (5) of adding a part of the hardly water-soluble solid active ingredient immediately after the phase inversion is omitted. Method. 3. In the above-mentioned aqueous suspension generation and emulsion / aqueous suspension mixing step (steps 7 to 8),
Only the aqueous suspension generation step is performed in another system, and after the emulsion formation step (Step 1 to Step 6) is completed, the aqueous suspension generated in another system is mixed, and then (Step 7 to Step 8) Equivalent to the emulsion and aqueous suspension mixing step,
The method for producing an aqueous suspension-type solvent-free emulsion according to claim 1 or 2, wherein stirring and mixing are performed while maintaining the temperature at 40 ° C or lower. 4. The aqueous solution according to claim 1, wherein the oily active ingredient is a cosmetic raw material, a food raw material, a pharmaceutical, an agricultural chemical, a sanitary chemical, a household chemical, an office chemical, or an industrial chemical. A method for producing a suspension-type solvent-free emulsion. 5. The hardly water-soluble solid active ingredient (e, f ingredient) is a cosmetic raw material, a dye, a pigment, a food raw material, a pharmaceutical, an agricultural chemical, a sanitary chemical, a household chemical, an office chemical, a civil engineering building material. 4. The method for producing an aqueous suspension-type solvent-free emulsion according to claim 1, which is an industrial chemical. 6. The method according to claim 1, wherein the oily liquid is at least one selected from vegetable oils, animal oils, mineral oils, synthetic oils, silicone oils and fluorinated oils.
4. The method for producing an aqueous suspension-type solvent-free emulsion according to 2 or 3. 7. The polymer surfactant (component c) and the polymer surfactant (component g) may be the same or different, have a molecular weight of 1100 or more, and have a cationic polymer interface. Surfactant, anionic polymer surfactant, nonionic polymer surfactant, mixture of cationic polymer surfactant and nonionic polymer surfactant, or anionic polymer surfactant and nonionic polymer surfactant The method for producing an aqueous suspension-type solvent-free emulsion according to claim 1, 2 or 3, comprising at least one selected from a mixture with a molecular surfactant. 8. The low molecular surfactant (d component) and the low molecular surfactant (h component) may be the same or different, and may be a cationic low molecular surfactant or an anionic low molecule. Surfactant, nonionic low molecular surfactant,
1 selected from a mixture of a cationic low molecular surfactant and a nonionic low molecular surfactant, or a mixture of an anionic low molecular surfactant and a nonionic low molecular surfactant
4. The method for producing an aqueous suspension-type solvent-free emulsion according to claim 1, which comprises at least one species. 9. The high molecular surfactant (c and g components) comprises at least one selected from a cationic high molecular surfactant and a nonionic high molecular surfactant, and the low molecular surfactant is The method for producing an aqueous suspension-type solvent-free emulsion according to claim 1, 2 or 3, comprising one or more selected from a cationic low molecular surfactant and a nonionic low molecular surfactant. 10. The polymer surfactant (c and g components)
Comprises at least one member selected from an anionic high-molecular surfactant and a nonionic high-molecular surfactant, and the low-molecular surfactant is selected from an anionic low-molecular surfactant and a nonionic low-molecular surfactant. Consisting of one or more
The method for producing an aqueous suspension-type solvent-free emulsion according to claim 1, 2 or 3. 11. The aqueous suspension according to claim 1, wherein the amount of the oily substance to be added is 1 to 30% by weight based on the total amount of the aqueous suspension-type solvent-free emulsion. A method for producing a solvent-free emulsion. 12. The hardly water-soluble solid active ingredient (e, f)
The component (1) is added in an amount of 0.1 to 65% by weight based on the total amount of the aqueous suspension-type solvent-free emulsion.
6. The method for producing an aqueous suspension-type solvent-free emulsion according to 2, 3, or 5. 13. The amount of the polymeric surfactant to be added is from 0.5 to the entire aqueous suspension-type solvent-free emulsion.
8. The method for producing an aqueous suspension-type solvent-free emulsion according to claim 1, wherein the amount is 20% by weight. 14. The amount of the low molecular surfactant added to the aqueous suspension-type solvent-free emulsion as a whole is from 0.5 to 0.5.
9. The method for producing an aqueous suspension-type solvent-free emulsion according to claim 1, which is 20% by weight. 15. (1) (a) water, (b) an oily substance which forms an interface with water, composed of an oily active ingredient and / or an oily liquid, (c) a polymeric surfactant, and (d) ) Add a low molecular surfactant, stir and mix while keeping the temperature below 40 ° C. (2) Then, raise the temperature inside the system while continuing stirring and mixing, and continue until the inside of the system is uniformly gelled.
(3) The temperature is further raised to change the phase of the system into a W / O emulsion. (4) After the phase inversion, the system is cooled down to the temperature before gelation, (5) (e) a part of the solid water-insoluble solid active ingredient is added, and (6) stirring and mixing while maintaining the temperature at 40 ° C or lower.
(7) Next, (f) a water-insoluble solid active ingredient and (g) a polymeric surfactant are added, and the mixture is further stirred and mixed while maintaining the temperature at 40 ° C. or lower. (8) (h) Adding at least one low molecular surfactant having an average molecular weight of at least 400 smaller than the average molecular weight of the molecular surfactant (g) and 1100 or less, and stirring and mixing while maintaining the temperature at 40 ° C or less. Characterized by being produced by a method for producing an aqueous suspension-type solvent-free emulsion,
Aqueous suspension type solvent-free emulsion. 16. The solid active ingredient is incorporated into the oily substance by the step (e) of adding a part of the hardly water-soluble solid active ingredient immediately after the phase inversion, and the solid active ingredient in the obtained aqueous suspension is obtained. The aqueous suspension-type solvent-free emulsion produced by the method for producing an aqueous suspension-type solvent-free emulsion according to claim 15, wherein the contact of the component with water is reduced.