JP2779643B2 - Composition and kit for microcapsule, and method for producing microcapsule - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a composition for microcapsules. More specifically, for example, when applying a commercially available pesticide or the like, for a long-term storable microcapsule used to form a microcapsule containing the pesticidal active ingredient by adding to the spraying liquid together with the active ingredient and stirring and mixing. Composition. The present invention also relates to a composition for microcapsules comprising the composition for microcapsules and a component to be microencapsulated, and a kit for microcapsules comprising both of the above compositions.

[Conventional technology]

Conventionally, microcapsules have been attracting attention as having effects such as changing the apparent physical properties of substances to make them easier to handle, stabilizing unstable substances, and increasing the safety in using dangerous substances. ing.

For example, looking at the significance of this microcapsule using pesticides as an example, the following points can be pointed out.

That is, as is well known, the medicinal effect is naturally important for pesticides, but the dosage form is also extremely important for practical use. This is because by making the dosage form appropriate, it is possible to enhance the safety for pesticide sprayers, prevent the occurrence of phytotoxicity to crops, and achieve the sustained or delayed efficacy of the drug. For this reason, research on the development of agricultural chemicals has been actively conducted, and as one of the results, the microencapsulation technology for agricultural chemicals has recently been developed and attracted attention. This pesticide microcapsule, by coating the pesticide active ingredient with a film, improves the safety of the sprayer and enables the sustained release of the medicinal effect, and realizes more purposeful and labor-saving spraying of the pesticide. Expected.

As a conventional technique for microencapsulation of the pesticide, there is a method of microencapsulating a pyrethroid insecticide or an organophosphorus insecticide with a polyurethane resin (Japanese Patent Publication No.
JP-A-53-38325 and JP-A-58-144304) and a method of microencapsulating a poorly water-soluble pesticide with a polyurea formed by an interfacial reaction between a polyisocyanate solution and an aqueous polyamine solution (Japanese Patent Laid-Open No. 62-67003). Has been already published.

However, up to now, even in the microcapsulation technology of other components including the above-mentioned pesticide microcapsulation technology, a complicated separation step is required to isolate the formed microcapsules, and cost is reduced. In addition, there is still the problem that the active ingredient is exuded from the isolated microcapsules. Many are in the form of being used as pharmaceuticals.

[Problems to be solved by the invention]

However, this slurry formulation also has a problem that the microcapsules settle during storage or freeze at a low temperature.In addition, when the capsules are broken during production or when diluted with water at the time of use, dispersibility is poor. There are problems such as
Improvement was desired.

Therefore, the present inventors studied a microencapsulation technique, and prepared a composition in which a compound that forms a film by reacting with an emulsifier and water (hereinafter referred to as a film-forming compound) was prepared and mixed, We tried to devise a method of adding this to a solvent such as water together with components such as pesticides and microencapsulating it.

However, there is no problem when the composition for microcapsules is used immediately after preparation, but if the composition is used after a certain storage period, gelation or precipitation occurs during the storage period. It was also found that there was a problem that when added to water or the like, emulsification was insufficient and microencapsulation did not proceed well.

[Means for solving the problem]

The present inventors have further studied to solve the above-mentioned problems, and as a result, by preventing the emulsifier and the film-forming compound from reacting with each other, or by selecting such a combination, a long term The present invention has been found that microcapsules which are stable and contain an active ingredient when added to a spray liquid are easily formed.

That is, the present invention provides a composition for microcapsules in which a non-reactive emulsifier and a compound capable of forming a film by reacting with water are mixed and integrated as essential components.

The present invention also provides a composition for microcapsules containing the above composition for microcapsules and a component to be microencapsulated as essential components. This composition is added to an appropriate amount of liquid such as water at the time of use, and mixed and stirred to be used as microcapsules containing the components to be microencapsulated.

Further, the present invention provides a simple method for producing microcapsules using the composition for microcapsules, and a kit for microcapsules comprising a combination of the composition for microcapsules and a component to be microencapsulated.

The components to be microencapsulated according to the present invention include, for example, pesticides,
Fragrances, paints, liquid crystals, repellents for pests and rats, fertilizers, cosmetics, pigments, inks, inducers, foaming agents, flame retardants, rust inhibitors,
It is mainly composed of a fungicide and the like, and these components are easily microencapsulated by adding them to a solvent such as water together with the above-mentioned composition for microcapsules at the time of use.

 Hereinafter, the present invention will be described in detail.

In the present invention, it is important that the emulsifier and the film-forming compound used do not react with each other.

For that purpose, it is necessary to select and use those which do not react with each other, or to chemically block the groups (reactive groups) involved in the reaction in advance if they have reactivity.

 The specific examples are shown below.

Emulsifier used in the present invention (1) Anionic surfactant; any one usually used for emulsification can be used.
For example, alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene polyoxypropylene block polymer sulfate, alkane sulfonate, dialkyl sulfosuccinate,
Alkyl allyl sulfonate, fatty acid salt, funnel oil, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ether phosphate, alkyl phosphate and the like.

(2) Cationic surfactants; for example, primary amine salt, secondary amine salt, tertiary amine salt, modified amine salt, tetraalkyl quaternary ammonium salt, modified trialkyl quaternary ammonium salt, triamine Alkyl benzyl quaternary ammonium salts, modified trialkyl benzyl quaternary ammonium salts, alkyl pyridinium salts, modified alkyl pyridinium salts, alkyl quinolinium salts, alkyl phosphonium salts,
Alkyl sulfonium salts and the like are used.

(3) Nonionic surfactant; For example, polyoxyethylene alkyl ether, polyoxyethylene rosin ester, polyoxypropylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene butyryl phenyl ether and the like are used. These are used in such a manner that the terminal primary or secondary OH group of the polyoxyalkylene chain of these compounds is chemically blocked by a known method, if necessary, to prevent the reaction with the isocyanate group of the film-forming compound.

(4) Double-sided surfactants: For example, lecithin, alkylaminocarboxylate, alkyldimethylbetaine, alkylhydroxyethylbetaine and the like are used.

Note that the above (1) to (4) may be used in appropriate combination. Usually, a mixture of an anionic surfactant and a nonionic surfactant is preferably used. The amount of these emulsifiers is usually 1 to 50 parts by weight, preferably 3 to 20 parts by weight.

Film-forming compound used in the present invention The film-forming compound used in the present invention is a compound as shown below which can react with water to form a film.

(1) Isocyanate compound: The following diisocyanates or polyisocyanates, or urethane prepolymers obtained by reacting diols or polyols with diisocyanates or polyisocyanates are used alone or as a mixture of two or more.

Examples of diisocyanates and polyisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, triphenylmethane triisocyanate, undecane triisocyanate,
Hexamethylene triisocyanate, lysine ester triisocyanate, polymethylene polyphenyl isocyanate and the like.

Examples of diols and polyols include polyhydric alcohols such as ethylene glycol, propylene glycol, hexanediol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, and sucrose, and ethylene oxide, propylene Examples include polyether polyols to which an alkylene oxide such as an oxide is added, polyester polyols such as ethylene adipate, diethylene adipate, and butylene adipate, and polycarbonate polyols, acrylic polyols, and polybutadiene polyols.

(2) Mixture of ketimine and epoxy resin; diamine and epoxy produced by the reaction of ketimine and water react to form a polymer film.

(3) alkyl α-cyanoacrylate; water acts as a catalyst to form a polymer film.

Among the above (1) to (3), particularly preferred is the isocyanate compound (1).

Next, a method of blocking a reactive group when the emulsifier and the film-forming compound have reactivity will be described.

First, as an example, the case of a terminal hydroxyl group of a nonionic surfactant will be described. To block this, a known etherification method, esterification method, urethanation method, tertiary
It can be carried out by a method appropriately selected from the OH conversion method and the like.

Of these, the etherification method can be usually carried out by reacting a nonionic surfactant with an alkyl halide such as methylene chloride or methyl iodide. In addition, the esterification is usually a non-ionic surfactant acetic acid, monocarboxylic acids such as propionic acid, oxalic acid, succinic acid, malonic acid, maleic acid, dicarboxylic acids such as adipic acid, tricarboxylic acids such as citric acid or these. The reaction can be carried out by reacting a carboxylic acid anhydride. Of urethane is reacted with non-ionic surfactants such as monoisocyanates such as methyl isocyanate, ethyl isocyanate, propyl isocyanate and phenyl isocyanate, and polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate and triphenylmethane triisocyanate. Can be performed.
Can be carried out, for example, by adding isobutylene oxide to a nonionic surfactant.

Anionic surfactants other than nonionic surfactants, cationic surfactants and amphoteric surfactants have few reactive groups, but in the case of salts having hydroxyl groups such as monoethanolamine salts, the above is described above. It can also be carried out by using a blocking method, or by using a metal salt such as a Na, K, Da salt, or an ammonium salt.

On the other hand, blocking the film-forming compounds can also render them non-reactive.

That is, it becomes non-reactive by, for example, reacting a blocking agent with the urethane prepolymer to form a blocked urethane prepolymer.

Examples of the blocking agent used in this method include methanol, ethanol, phenol, ethyl mercaptan, hydrocyanic acid, diethyl malonate, ε-caprolactam, sodium bisulfite, acetylacetone and the like. These blocked urethane prepolymers release isocyanate groups when the temperature exceeds the respective cleavage temperature, and the film forming ability is restored.

Therefore, when the component to be microencapsulated is weak to heat, it is preferable to select from those having a low degree of cleavage.
In order to produce the composition for microcapsules of the present invention, the emulsifier is usually used in an amount of 0.05 to 1 part by weight of the film-forming compound.
It can be produced by adding 100 parts by weight, preferably 0.5 to 10 parts by weight, and mixing and stirring. Mixing and stirring can be performed by a commonly used stirrer, and the temperature during mixing may be room temperature.

When the viscosity of the film-forming compound or emulsifier used is high, an appropriate amount of an organic solvent may be added if necessary. As the organic solvent used in this case, any organic solvent may be used as long as it dissolves the agricultural chemical active ingredient, the emulsifier, the film-forming compound, and does not react with the film-forming compound. For example, heptane, n-
Hexane, cyclohexane, octane, isooctane,
Aliphatic hydrocarbons such as chloroform, carbon tetrachloride, trichloroethylene, benzene chloride and the like, ketones such as isobutyl ketone, diethyl ketone, methyl ethyl ketone, dipropyl ketone, ethyl acetate, butyl acetate, acetic acid Esters such as isoamyl and ethyl propionate, ethers such as butyl ether and isopropyl ether, aromatic hydrocarbons such as benzene, toluene, xylene and phenylxylylethane, dimethylformamide, dimethyl sulfoxide and the like can be used. .

The composition for microcapsules of the present invention, for example, when the component to be microencapsulated is a pesticide, purchases a commercially available pesticide, and encloses the commercial pesticide simply by adding it and the composition to the spray liquid at the time of use and stirring. A microcapsule is easily formed, and a liquid containing the microcapsule can be easily sprayed by a spraying device.

In order to produce a composition for microcapsules containing the component to be microencapsulated according to the present invention, the component to be microencapsulated, for example, 1 part by weight of the pesticidally active ingredient is usually added.
0.05-100 parts by weight of the film-forming compound, preferably 0.5-20 parts by weight, and 0.05-50 parts by weight of the emulsifier, preferably 0.5-1 part by weight.
It can be produced by adding 0 parts by weight and mixing and stirring. Mixing and stirring can be performed by a commonly used stirrer, and the temperature during mixing may be room temperature.

As the component to be microencapsulated, any component can be used as long as it does not react with the film-forming compound. Therefore, the pesticidal active ingredient can be appropriately selected from herbicides, fungicides, insecticides, plant growth regulators and the like.

Next, the mechanism of microencapsulation when the composition for microcapsules of the present invention is used will be described.

When the composition for microcapsules of the present invention is added to a pesticide spray liquid prepared by a usual method, the composition is emulsified and dispersed as microdroplets of several microns or less in the pesticide spray liquid. Next, the fine droplets of the composition generated in the spray liquid and the droplets or particles containing the pesticidal active ingredient in the spray liquid are united. Thus, it is presumed that droplets containing both the pesticidal active ingredient and the film-forming compound are newly produced, and a film is formed at the interface between the newly produced droplets and water to produce microcapsules containing the pesticidal active ingredient.

The amount of the composition for microcapsules of the present invention is usually 0.02 to the spray liquid containing the components to be microencapsulated.
% (V / V) to 10% (V / V), preferably 0.05% (V / V)
2% (V / V).

The thickness of the microcapsules can be adjusted by the amount of the film-forming compound or the amount of the microcapsule composition of the present invention.

When an isocyanate-based compound is used as the film-forming compound in the present invention, the film-forming speed of the microcapsules when diluted with water can be increased by using a catalyst. In this case, the catalyst can be added in advance to the composition for microcapsules, or can be added by adding the composition for microcapsules to water when the composition is added to water to form microcapsules.

In the case of a composition for agrochemical microcapsules, a catalyst can be put therein, or it can be put into it at the time of microencapsulation.

The film forming speed can be adjusted by the amount of the catalyst added (see Example 25), and is usually used in the range of 0.1 to 10% by weight based on the composition for microcapsules.

Such catalysts include triethylamine, N, N, N, N-
Amines such as tetramethyl-1,3-butanediamine, lauryldimethylamine and triethylenediamine, and organic tin compounds such as dibutyltin dilaurate, dibutyltin di (2-ethylhexoate) and stannous oleate alone or Mix and use two or more types.

In particular, when a urethane prepolymer is used as the film-forming compound, the film-forming speed can also be adjusted by changing the hydrophilic-hydrophobic balance (HLB) of the urethane prepolymer (see Example 24).

〔The invention's effect〕

The composition for microcapsules of the present invention can be stored for a long period of time, and microcapsules containing components to be microencapsulated can be easily formed by simply adding them to a liquid such as water at the time of use, and a liquid preparation containing the same is prepared. It has the feature that it can be used as it is. Further, a composition for microcapsules containing the component to be microencapsulated according to the present invention,
For example, the composition for pesticide microencapsulated preparations can be stored for a long period of time in the same manner as the composition for microcapsules, and the pesticide microcapsule preparation containing the pesticide active ingredient can be easily formed by simply adding to the spray liquid at the time of use, It has the characteristic that a spray containing it can be prepared and can be sprayed as it is. Therefore, the use of the pesticidal microencapsulated preparation of the present invention realizes safe, effective and labor-saving pesticide spraying that has been conventionally desired.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples.
In addition, the test method in the following Examples and Comparative Examples was performed by the following method.

Storage stability test method: At the time of preparation, the composition for microcapsules was stored at 40 ° C. for one week and three months, and the composition for microcapsules was observed with the naked eye.

Emulsifiability test method: A part of the composition for microcapsules used in the storage stability test was taken, diluted 1000 times with 3 degrees hard water at 20 ° C, and then mixed.
The emulsion stability after the passage of time was visually judged.

Determination method of isocyanate group; A acetone solution of 0.1N di-n-butylamine is prepared.
25 ml of this solution is placed in an Erlenmeyer flask, and 10 g of a 1000-fold diluted solution of the composition for microcapsules of the present invention is precisely weighed and added. After leaving at room temperature for 20 minutes, isopropyl alcohol 100m
l and add 0.1N with bromophenol blue as indicator
Titrate with hydrochloric acid, calculate the ratio of unreacted isocyanate groups, and determine the reaction rate of isocyanate groups based on this value.

In addition, "part" indicating the amount of each component used in Examples means "part by weight".

Example 1 Acetic ester 50 of polyoxyethylene distyrylphenol ether (addition of 17.5 mol of ethylene oxide)
And 10 parts of an emulsifier comprising 50 parts of calcium dodecylbenzenesulfonate, 70 parts of polygrout O-1 (urethane prepolymer manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 20 parts of xylene, and the mixture is stirred to form a composition for microcapsules. (Hereinafter abbreviated as a composition) was prepared.

Example 2 Acetic acid ester 50 of polyoxyethylene distyrylphenol ether (addition of 17.5 mol of ethylene oxide)
And 10 parts of an emulsifier comprising 50 parts of calcium dodecylbenzenesulfonate, 50 parts of polygrout O-1 (urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 40 parts of xylene are mixed and stirred to prepare a composition. did.

Example 3 Acetic acid ester 50 of polyoxyethylene distyrylphenol ether (addition of 17.5 mol of ethylene oxide)
And 10 parts of an emulsifier comprising 50 parts of calcium dodecylbenzenesulfonate, 20 parts of polygrout O-1 (urethane prepolymer manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 70 parts of xylene are mixed and stirred to prepare a composition. did.

Comparative Example 1 Unblocked polyoxyethylene distyryl phenol ether (ethylene oxide 1
7.5 parts) and 10 parts of an emulsifier consisting of 50 parts of calcium dodecylbenzenesulfonate 50 parts, polyguldo O-1
20 parts (urethane polymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 70 parts of xylene were mixed and stirred to prepare a composition.
This composition and the compositions of Examples 1 to 3 were tested for storage stability and emulsifiability. Table 1 shows the results.
Shown in

As is clear from Table 1, the compositions of Examples 1 to 3 are stable, whereas the composition of Comparative Example 1 does not block the end of the nonionic surfactant used, and thus has a nonionic interface. It can be seen that the activator reacts with the urethane polymer, resulting in precipitation and a marked decrease in emulsifiability.

Example 4 The above Examples 1 to 3 and Comparative Example 1 in which a commercially available pyridafenthion emulsion (Offnack R emulsion manufactured by Mitsui Toatsu Chemicals, Inc.) was diluted 500 times with water and stored at 40 ° C. for 3 months at a diluent. Each of the compositions was added with 0.1% (v / v), mixed and stirred to prepare a diluent. An aluminum plate having a diameter of 7 cm was immersed in the diluted solution for 1 minute. Take out and dry and treat the treated aluminum plate in a thermostat at 30 ° C. Take out the aluminum plate on a predetermined day, measure the amount of attached pyridafenthion by gas chromatography, and calculate the residual ratio when the value immediately after spraying is set to 100. Was. If the compositions of Examples 1 to 3 are microcapsules containing pyridafenthion,
This is because the encapsulated pyridafenthion is released in accordance with the disintegration rate of the capsule, and the residual ratio gradually decreases, and the residual ratio serves as an indicator of whether microcapsules are formed. Table 2 shows the results.

It is clear from the results in Table 2 (residual activity of the insecticide) that the composition for microcapsules of the present invention microencapsulates a commercially available insecticide.

Example 5 5% (v / v) of orange oil used as a fragrance
Add to and suspend in 0.1% (v / v) Tween 20 aqueous solution to obtain v). To this suspension, a composition prepared in the same manner as in Example 1 was added in the same volume as that of the orange oil, and the mixture was stirred and mixed to prepare a microcapsule suspension containing the orange oil.

Example 6 4-bromo-bisphenol used as a flame retardant is added to and suspended in a 0.1% (v / v) aqueous solution of Tween 20 so as to have a concentration of 10% (v / v). To this suspension, a composition prepared in the same manner as in Example 1 was added in the same amount as the 4-bromo-bisphenol, followed by stirring and mixing to prepare a microcapsule suspension containing 4-bromo-bisphenol.

Example 7 10 parts of an emulsifier consisting of 40 parts of pyridafenthion, 50 parts of an acetic acid ester of polyoxyethylene distyrylphenol ether (addition of 25 moles of ethylene oxide) and 50 parts of calcium salt of dodecylbenzenefluorate,
10 parts of MG10 (urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 40 parts of xylene were mixed and stirred to prepare a composition.

Example 8 10 parts of an emulsifier consisting of 40 parts of pyridafenthion, 50 parts of an acetic acid ester of polyoxyethylene distyrylphenol ether (addition of 25 mol of ethylene oxide) and 50 parts of calcium dodecylene sulfonic acid salt, disczol
A composition was prepared by mixing and stirring 5 parts of MG100 (urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 45 parts of xylene.

Example 9 10 parts of an emulsifier consisting of 40 parts of pyridafenthion, 50 parts of an acetic acid ester of polyoxyethylene distyrylphenol ether (addition of 25 mol of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, Discsol MG100 (Daiichi Kogyo Seiyaku) A composition was prepared by mixing and stirring 3 parts of urethane prepolymer (manufactured by Co., Ltd.) and 47 parts of xylene.

Comparative Example 2 An emulsifier 10 comprising 40 parts of pyridafenthion, 50 parts of polyoxyethylene distyrylphenol ether (25 mol of ethylene oxide added) not capped as an emulsifier and 50 parts of calcium dodecylbenzenesulfonate.
, 3 parts of Disczol MG100 (urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 47 parts of xylene were mixed and stirred to prepare a composition. This composition and Examples 7 to
The compositions of No. 9 were tested for storage stability and emulsifiability. Table 3 shows the results.

As is apparent from Table 3, the compositions of Examples 7 to 9 are stable, whereas the composition of Comparative Example 2 does not block the end of the nonionic surfactant in the liquid, so that the composition is nonionic. The surfactant reacts with the urethane prepolymer, and as a result,
It can be seen that precipitation occurs and the emulsifiability is significantly reduced.

Example 10 Prepared in the same manner as in Examples 7 to 9 above,
Each of the compositions stored for one month was diluted 1000-fold to prepare diluents. The residual ratio of pyridafenthion was determined for each diluent in the same manner as in Example 4, and the results are shown in Table-4.

It is clear from the results in Table 3 that the composition of the present invention is a microcapsule preparation containing a main drug component in a length that can be diluted and mixed with water at the time of use even after long-term storage.

Example 11 4 parts of polynactin complex, polyoxyethylene nonylphenol ether (addition of 30 mol of ethylene oxide)
Emulsifier consisting of 50 parts of acetic acid ester and 50 parts of calcium dodecylbenzenesulfonate, Disczol MD10
0 (urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 10 parts N-lauroylglutamic acid dibutylamide
2 parts and 69.8 parts of machine oil were mixed and stirred to prepare a suspension composition. This composition was tested in the same manner as in Comparative Example 1, and as a result, both the storage stabilizer and the emulsifiability showed good results.

Experimental example Azoic diazo component 22 (Showa Kako Kako
Blue VR Salt) 0.5 part, emulsifier consisting of 50 parts of acetic acid ester of polyoxyethylene nonylphenol ether (addition of 20 moles of ethylene oxide) and 50 parts of calcium salt of dodecylbenzenesulfonic acid, Disksol MG100
(Urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
10 parts and 79.5 parts of xylene were mixed and stirred to prepare a liquid composition. Next, an emulsifier 10 consisting of 0.5 parts of β-naphthol (manufactured by Wako Pure Chemical Industries, Ltd.), 50 parts of acetic acid ester of polyoxyethylene nonylphenol ether (addition of 20 mol of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate.
And 89.5 parts of xylene were mixed and stirred to prepare a composition. 1 ml of each of these two compositions was mixed with 3 ml at 20 ° C.
It was added to 1000 ml of hard water and stirred. After 15 minutes, the emulsion in the diluent turned red. This means that the azoic diazo component 22 in the two compositions and β-naphthol reacted, and that the two emulsions were combined in water to form microcapsules containing the active ingredient. It is an indirect proof.

Example 12 "Preparation of composition capable of easily producing a microcapsule preparation containing soybean oil as a main component for use as an enamel remover" 80 parts of soybean oil (main component), polyoxyethylene distyrylphenol ether (ethylene) 50 parts of an acetic acid ester of 25 mol of oxide), 10 parts of an emulsifier composed of 50 parts of calcium dodecylbenzenesulfonate and 10 parts of Disksol MG100 (urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are mixed and stirred to form a composition. Prepared.

Example 13 "Preparation of composition for the purpose of improving the fluidity of chill-type titanium dioxide used as a pigment and allowing easy production of a microcapsule preparation containing this as a main component" Other than using rutile-type titanium dioxide as a main component Was prepared in exactly the same manner as in Example 12.

Example 14 “Preparation of composition capable of easily producing microcapsule preparation containing citronellal used as a perfume as a main component” Preparation was performed in exactly the same manner as in Example 12 except that citronellal was used as a main component.

Example 15 "Preparation of a composition for the purpose of masking effect of 4-bromoethane used as a flame retardant and capable of easily producing a microcapsule preparation containing this as a main component" Except that the main component was 4-bromoethane, Prepared exactly as in Example 12.

Example 16 "Preparation of composition capable of easily producing a microcapsule preparation containing cholesteric liquid crystal used for liquid crystal printing as a main component" A cholesteric liquid crystal composed mainly of 20 parts of cholesterol chloride and 80 parts of cholesterol nonanoate was used. Other examples
Prepared exactly as in 12.

Test Example The compositions of Examples 12 to 16 were tested in the same manner as in Comparative Example 1, and it was confirmed that all of them had good storage stability and emulsifiability.

Example 17 12 parts of a polynactin complex, 10 parts of an emulsifier comprising 50 parts of an acetic acid ester of polyoxyethylene distyrylphenol ether (addition of 35 mol of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, and 0 parts of a polygrout
-1 (Urethane polymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
10 parts and 68 parts of chlorobenzene were mixed and stirred to prepare a composition. Table 5 shows the results of tests on the storage stability and the emulsifiability of the composition.

Comparative Example 3 Polyoxyethylene distyryl phenol ether (ethylene oxide) having no terminal blocking as an emulsifier
A composition was prepared in the same manner as in Example 17, except that an emulsifier consisting of 50 parts (35 mol addition) and 50 parts of calcium dodecylbenzenesulfonate was used. Table 5 shows the test results of storage stability and emulsifiability.

As is clear from Table 5, the composition of Example 17 is stable, while the composition of Comparative Example 3 has no nonionic surfactant in the emulsifier because the nonionic surfactant is not blocked. It can be seen that the agent reacts with the urethane prepolymer, resulting in precipitation and a marked decrease in emulsifiability.

Example 18 2 parts of etofenprox, 10 parts of an emulsifier consisting of 50 parts of methyl ether of polyoxyethylene nonylphenol ether (addition of 15 mol of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, Urethane polymer manufactured by Kogyo Pharmaceutical Co., Ltd.)
15 parts and 73 parts of xylene were mixed and stirred to prepare a composition. The test results of storage stability and emulsifiability of this composition were good at the time of preparation, after one week and after three months.

Example 19 10 parts of an emulsifier composed of 40 parts of pyridafenthion, 50 parts of an acetic acid ester of polyoxyethylene distyrylphenol ether (addition of 35 moles of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, 10 parts of tolylene diisocyanate, and xylene 40 The components were mixed and stirred to prepare a composition. Table 6 shows the test results of storage stability and emulsifiability of this composition.

Comparative Example 4 Polyoxyethylene distyryl phenol ether (ethylene oxide) having no terminal blocking as an emulsifier
A composition was prepared in the same manner as in Example 19, except for using an emulsifier consisting of 50 parts (addition of 35 mol) and 50 parts of calcium salt of dodecylbenzenesulfonic acid. Table 6 shows the test results of storage stability and emulsifiability of this composition.

As is clear from Table 6, the composition of Example 19 is stable, whereas the composition of Comparative Example 4 reacts with the nonionic surfactant and tolylene diisocyanate, resulting in precipitation and emulsifying properties. It can be seen that is significantly reduced.

Example 20 Isobutylene oxide adduct of 40 parts of tripropyl isocyanate (TPIC) and polyoxyethylene nonylphenol ether (addition of 10 mol of ethylene oxide)
10 parts, 15 parts of 1,4-butane diisocyanate, and 35 parts of kerosene were mixed and stirred to prepare a composition. This composition had good storage stability and emulsifiability.

Example 21 A composition was prepared by mixing and stirring 50 parts of dichlorvos, 5 parts of ethyl cyanoacrylate, 10 parts of acetic acid ester of polyoxyethylene benzylphenol ether (addition of 30 mol of ethylene oxide) and 35 parts of xylene. This composition had good storage stability and emulsifiability.

Example 22 10 parts of oxadiazon, 3 parts of ketimine obtained by reacting ethynediamine and acetone, 6 parts of epoxy resin (diglycosidyl ether of bisphenol A), and polyoxyethylene distyryl phenol ether (35 mol of ethylene oxide added) ), 50 parts of an acetic ester, 50 parts of calcium dodecylbenzenesulfonate, and 10 parts of an emulsifier, and 71 parts of xylene were mixed and stirred to prepare a composition.

 This composition had good storage stability and emulsifiability.

Example 23 40 parts of diazinon, methyl ether 50 of polyoxyethylenated castor oil (addition of 50 moles of ethylene oxide)
20 parts of emulsifier consisting of 1 part by weight and 50 parts of calcium dodecylbenzenesulfonate, 10 parts of Monotack 700 (urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and xylene
30 parts of a mixed solvent consisting of 50 parts and 50 parts of benzene chloride was mixed and stirred to prepare a composition. The test results of storage stability and emulsifiability of this composition were good at the time of preparation, after 1 hour and after 3 months.

After the preparation, the reaction rate of the isocyanate group was determined with time according to the above-mentioned method for determining the isocyanate group in the above composition after 3 months at room temperature, and this was used as an index of the rate of formation of the microcapsule film.

Table 7 shows the measurement results of the reaction rates of the isocyanate groups.

Table 7 and observation with an electron microscope confirmed that when the composition for microcapsules of the present invention was diluted with water, the film-forming compound and water reacted to form microcapsules.

Example 24 8 parts of tetradiphone, 50 parts of acetic ester of polyoxyethylene distyrylphenol (addition of 25 mol of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate
The emulsifier consisting of 20 parts, 10 parts of polygrout W-1 (urethane prepolymer manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a hydrophilic urethane polymer, and 62 parts of xylene were mixed and stirred to prepare a composition. The reaction rate of the isocyanate group was measured for this composition in the same manner as in Example 23, and was used as an index of the film formation rate of the microcapsules. Table-Measurement results
FIG.

When Example 23 is compared with this example, it is clear that the composition of this example has a higher film formation rate. This suggests that the film formation rate can be increased by using a highly hydrophilic urethane prepolymer as the film forming compound, and by changing the hydrophilic-hydrophobic balance (HLB) of the urethane prepolymer, It is possible to adjust the film formation speed. The storage stability and emulsifiability of the composition of this example were good.

Example 25 10 parts of an emulsifier consisting of 40 parts of glyphosate, 50 parts of methylene urethane compound of polyoxyethylene distyrylphenol ether (addition of 15 moles of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, 10 parts of polyoxypropylene glycerin ether and After adding 10 parts of urethane prepolymer produced by the reaction of methylene diisocyanate, and 0 parts, 0.1 parts, 1 part and 5 parts of dibutyltin dilaurate as a catalyst, respectively, adding xylene to each to make the total amount 100 parts, and then stirring. Then, four kinds of compositions having different amounts of the catalyst were prepared.

To examine the film formation rate of each of these, Example 23 was used.
Measure the reaction rate of the isocyanate group in the same manner as
It was used as an index of the film formation rate of the microcapsules.

Table 9 shows the measurement results.

As is clear from Table-9, the film formation rate of the microcapsules can be adjusted by the amount of the catalyst added.

In these compositions, it was confirmed that good microcapsules were formed by observing the formed microcapsules with an electron microscope. In addition, the test results of storage stability and emulsifiability of these compositions are as follows:
All three months were good.

Example 26 20 parts of triadimefon, 20 parts of diphenylmethane diisocyanate, 1 part of lauryl dimethylamine as a catalyst,
An emulsifier consisting of 50 parts of a propionate of polyoxyethylene tristyryl phenol ether (addition of 25 moles of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate was added to 10 parts of dimethylformamide in an amount of 5 parts each.
Parts, 10 parts, and 20 parts, and xylene was further added to make the total amount 100 parts, followed by stirring to prepare three types of compositions having different amounts of the emulsifier added. 25 of these compositions
After diluting and emulsifying 1000-fold with water at a temperature of 30 ° C., 30 minutes later, the resulting microcapsules were observed with an electron microscope to examine the average particle size. The results are shown in Table-10.

From the above results, it can be seen that microcapsules having a small particle size are produced by increasing the amount of the emulsifier.

In addition, the test results of the storage stability and the emulsifying property of the composition of this example were good at the time of preparation, after one week, and after three months.

〔Example of use〕

10 g of the composition of Example 24 was added to 10 water and stirred. After leaving this to stand for about 15 minutes, a sufficient amount of the prepared capsule suspension was sprayed on a cabbage seedling cultivated in a greenhouse by potting using a commercially available stainless steel shoulder sprayer. At the time of spraying, there was no clogging, and both the spraying state and the wet state of the cabbage were good.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 19/52 C09K 19/52 (72) Inventor Yuki Kataoka 7-7 Yuigaoka, Misato-cho, Misato-cho, Ikoma-gun, Nara Prefecture (72) Inventor Kazuto Jinno 11 Kashihara-Enohonmachi, Nishikyo-ku, Kyoto-shi, Kyoto (56) References JP-A-58-40142 (JP, A) JP-A-57-99332 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B01J 13/02

Claims (12)

(57) [Claims] An essential component is an emulsifier which is dissolved in an organic solvent which does not react with a compound capable of forming a film by reacting with water and which does not react with each other and a compound capable of forming a film by reacting with water. A composition for microcapsules. 2. A composition for microcapsules comprising the composition for microcapsules according to claim 1 and a component to be microencapsulated as essential components. 3. The composition for microcapsules according to claim 1, wherein the compound capable of forming a film by reacting with water is one or more compounds selected from diisocyanate, polyisocyanate and urethane prepolymer. Stuff. 4. A compound capable of forming a film by reacting with water,
The composition for microcapsules according to claim 1 or 2, which is a mixture of a ketimine and an epoxy resin or an alkyl α-cyanoacrylate. 5. An emulsifier comprising one or two or more surfactants selected from anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. The composition for microcapsules according to claim 1 or 2, which is an emulsifier that does not react with a compound capable of forming a film by reacting with water. 6. An emulsifier wherein a reactive group which reacts with a compound capable of forming a film by reacting with water present in the compound is blocked.
The composition for microcapsules according to the above. 7. The microencapsulated component is a pesticide, a fragrance,
The composition according to any one of claims 2 to 6, which is a component selected from paints, liquid crystals, repellents, fertilizers, cosmetics, pigments, inks, inducers, foaming agents, flame retardants, rust inhibitors, and fungicides. Composition for microcapsules. 8. A microcapsule, characterized in that the composition containing the component to be microencapsulated, the composition for microcapsules according to any one of claims 1 to 3, and water are mixed and stirred. Production method. 9. The composition to be microencapsulated is a pesticide, a fragrance,
The method for producing microcapsules according to claim 8, which is a component selected from paints, liquid crystals, repellents, fertilizers, cosmetics, pigments, inks, inducers, foaming agents, flame retardants, rust inhibitors, and fungicides. 10. The method for producing a microencapsulated agricultural chemical preparation according to claim 8, wherein the microencapsulated component is an agricultural chemical active ingredient. 11. A microcapsule kit comprising a combination of a composition containing a component to be microencapsulated and the microcapsule composition according to any one of claims 1 or 3 to 6. 12. The kit for preparing microcapsules for agricultural chemicals according to claim 11, wherein the component to be microencapsulated is an active ingredient for agricultural chemicals.