JPH0394827A - Composition and kit for microcapsule and production of microcapsule - Google Patents

Abstract

PURPOSE:To prepare a stable microcapsule composition by incorporating an emulsifier and a polyisocyanate compd. having a cationic group in the molecule forming a coating film by the reaction with water and which does not react with the emulsifier as the essential components. CONSTITUTION:An emulsifier and a polyisocyanate compd. having a cationic group in the molecule capable of forming a coating film by the reaction with water and which does not react with the emulsifier are incorporated as the essential components to prepare a microcapsule composition. A component to be microcapsuled is further added to the composition to prepare a microcapsule composition. The microcapsule composition and water are mixed and agitated to produce a microcapsule. A cationic surfactant, a nonionic surfactant, etc., are exemplified as the emulsifier, and agricultural chemicals, perfumes, paints, cosmetics, etc., as the component to be microcapsuled.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industry 1] The present invention relates to a composition for casozel.

In more detail, for example, when applying commercially available Kakusou nato; 1) Adding it to the rli. cloth solution with the active ingredients and stirring and mixing 6, the pesticide 1 active ingredient is incorporated. F1 to form the microphone L1 capsule
tlJ HoZJ - Concerning the crude product for the functional ma, iku 0 cazocell 4-. The present invention also provides the microscopic capsule composition,
1. Concerning the composition of the mic-eye casosel citrus, which is made of the buzel-forming component, and the mic, which is made of the compositions described above. , [Conventional technique] Previously, Microcazorel was '+171 ri's 兇i. x} f. −j is changed to a more manageable form (
．． : Stabilizes unstable substances, increases safety in the use of dangerous substances, etc. (7) Increases the effect of , Please pay close attention to it (ii3, For example, pesticides are one example (; Shiteko's microphone I.iX
The significance of 1 force -l' tru is as follows.

In other words, as is well known, the IBA drug is very effective.
9: To δ, there is a heavy official "c". Therefore, the spatula agent・Improve the medicinal effect and prevent the spread of medicinal substances to crops. ￥ Efficacy can be achieved, so C゛ exists,, this l: 2nd time 1', 7 pear-type development fil}
One of the results of this research is the recent study of IIP 11 power 1 cell technology 1jf'
J has not been developed yet. This agricultural mulberry
Iku 11 Turnip Hill is a pesticide with active ingredients in a film.
-1-Lee J and: }This J, R, Defeat ``Improve the safety of J Ministry and make it possible to gradually improve the efficacy of medicine. drug discovery J
We hope to achieve a purposeful and labor-saving dispersion method using conventional techniques related to the encapsulation of agricultural chemicals.
C is the H method (Japanese Patent Publication No. 53-38325Q, Japanese Patent Application Laid-open No. 58-1
/ I43 Old Month Bulletin), and poorly water-soluble pesticides
a. 7 by polyurethane 7 formed by 0 interfacial reaction)]
] Encapsulation method (special report) Ai624700:3
;Refer to the official gazette> etc. are published here.

However, until now, the above-mentioned pesticide V-Ik-D encapsulation technology has been applied to G5l and other ingredients in the MIC lJ force 1' cell technology (a3~'ct), which has been formed -/Ikrll
In order to isolate the capsules, complicated separation of the culms is necessary, and there remains the problem that the cost is also high. 1] There is a problem with the leaching of Li active ingredients from the capsule, and in reality, the conventional technology is to separate the cell from the microphone. ! vinegar'
1, 2 As it is as a slurry preparation - Rirudui for C publication)
The shape of the slurry (problem to be solved by the invention) is often the same as when it is prepared and stored in this slurry.
Problems such as precipitation of J-capsules and freezing at low temperatures persist, and also problems such as dispersibility of the capsules being poor (or lack of) when diluting them with water during production, etc. There were some problems and the improvement was 9!

Zoko C' The present inventors have developed a technique for converting 7 iku 11 forces.
・React with emulsifier and water (form a film!T-
The compound (hereinafter referred to as a film-forming compound) that
X: Prepare a combined phase composition and LB, Shikawa 0, ) 1
I devised a Puno method in which this was mixed with components such as pesticides in a solvent such as water, and encapsulated with microphone 11.

However, there is no problem when using this product immediately after preparation, but there is a certain amount of storage time.
If you try to use it after a period of time has passed, it may gel during the storage period or the precipitate may sludge, and when it is diluted with 7 liters of water, the emulsification is insufficient. It was revealed that there is a problem that microencapsulation does not proceed well.

[Means to solve the problem]

The present inventors have conducted further studies to solve the above problems, and found that by preventing the emulsifier and film-forming compound from reacting with each other, or by selecting a combination that results in such a combination, The present invention was achieved by discovering that it is stable and that microcapsules containing the active ingredient are easily formed when added to a spray solution.

In other words, the present invention provides a composition for microcapsules in which an emulsifier that does not react with each other and a polyisocyanate compound having a cation group in the molecule as a compound capable of forming a film by reacting with water are mixed and suspended as essential components. This is what we provide.

The present invention also provides a composition for microcapsules which contains the above-mentioned composition for microcapsules and a component to be microencapsulated as essential components. At the time of use, this composition is added to an appropriate amount of a liquid such as water, and mixed and stirred to form microcapsules containing the components to be microencapsulated.

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

The microencapsulated components of the present invention include e-medicines, fragrances, paints, liquid crystals, repellents for pests and rats, fertilizers, cosmetics, pigments, inks, inducers, foaming agents, flame retardants, rust preventives, and preventive agents. The main ingredient is a fungicide, etc., and when used, these ingredients can be easily microencapsulated by adding them to a solvent such as water together with the above-mentioned composition for microcapsules.

The present invention will be explained in detail below.

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

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

Specific examples of each are shown below.

Emulsifier (1) Cavion surfactant used in the present invention; For example, primary amine salt, secondary amine salt, tertiary amine salt, modified amine salt, tetraalkyl quaternary ammonium salt, modified 1-realkyl Quaternary ammonium salt, ]・
Realkyl benzyl quaternary ammonium salt, modified trialkyl pencil quaternary ammonium salt, alkyl benzyl quaternary ammonium salt,
Pyridinium salts, modified alkyl viridinium salts, alkyl quinolinium salts, alkyl sulfonium salts, alkyl sulfonium salts, etc. are used.

(2) Nonionic surfactant; For example, polyA xyethylene alkyl ether, polyoxyethylene ester, polyoxypropylene alkyl ether, polyA xyethylene sorbitan fatty acid ester, polyoxyethylene styrylphenyl ether, etc. are used. These compounds are used in a form in which the terminal primary or secondary OH group of the polyA xyalkylene chain of these compounds is chemically blocked by a known method to prevent reaction with the isocyanate group possessed by the film-forming compound. .

(3) Double-sided surfactant: For example, lecithin, alkylaminocarboxylate, alkyldimethylbetaine, alkylhydroxyethylbetaine, etc. are used.

(4) Anionic surface active agent; For example, alkyl lylphate, polyoxyethylene alkyl ether sulfate-1, polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene polyoxypropylene block polymer sulfate,
Alkanesulfonate, dialkyl sulfosuccinate, alkylaryl sulfone-1~, fatty acid salt, funnel oil, polyoxyethylene alkyl ether phosphate,
Polyoxyethylene alkyl allyl ether phosphate, alkyl phosphate, etc. are used.

Note that (1) to (4) above may be used in combination as appropriate. 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 capable of forming a film by reacting with water, and is a polyisocyanate compound having a thionic group in its molecule. The compound can be produced by known methods. For example, after introducing a tertiary amino group by reacting a polyisocyanate compound having three or more isocyanate groups with an alcohol having a tertiary amino group, alkyl sulfates such as dimethyl sulfate and diethyl tta, methyl iodide, iodide It can be easily produced by reacting with an alkylating agent such as an alkyl halide such as probyl, methyl chloride, probyl chloride, methyl bromide, and probyl bromide and quaternizing it. Examples of the polyisocyanate compounds used in producing this compound include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, toridine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Modified diphenylmethane diisocyanate, triphenylmethane triisocyanate, undecane triisocyanate, hexamethylene triisocyanate, polymethylenepoI no phenyl isocyanate, etc., and these compounds and polyhydric alcohols, polyether polyols, polyester polyols, polycarbonate polyols , acrylic polyols, or polybutadiene polyols. Examples of the alcohols having a tertiary amine group include diethylethanolamine, dimethylethanolamine, dimethylhexynolamine, and dimethylbutanolamine.

Among the polyisocyanate compounds having a cationic group in the molecule produced as described above, the following compounds (a) to (f) were used in the examples described later. It should be noted that the present invention is of course not limited to these compounds.

(a) Polyisocyanate 0 shown by the following v4 formula
(tentatively named urethane prepolymer ^J) (b) A polyisocyanate compound represented by the following II4 formula ("
(Tentatively named "Urethane Prebolymer B") (C) A polyisocyanate compound represented by the following structural formula (Tentatively named "Urethane Prebolymer 10") 0 (d) A polyisocyanate compound represented by the following structural formula (r) Tentatively named Polymer DJ〉(fat”
(e) A polyisocyanate compound represented by the following structural formula (tentatively named "urethane prepolymer E") (e) A polyisocyanate compound represented by the following structural formula (tentatively named "urethane prepolymer E") Next, an emulsifier and a coating film A method of blocking a reactive group when the forming compound has reactivity will be explained.

First, we will explain the case of the terminal hydroxyl group of a nonionic surfactant as an example. In order to block this, there are known methods such as ■ etherification method, ■ esterification method, ■ urethanization method, and ■ 3@O
This can be carried out by an appropriately selected method such as the oral method.

Among these, the etherification method (2) 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 of This can be carried out by reacting anhydrides of these carboxylic acids. For the urethanization of (2), nonionic surfactants include monoisocyanates such as methyl isocyanate, ethyl isocyanate, probyl isocyanate, phenyl isocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triincyanate, etc. This can be carried out by reacting polyisocyanates.

The tertiary O dioxidation (2) can be carried out, for example, by adding isobutylene oxide to a nonionic surfactant.

Few cationic surfactants, amphoteric surfactants, and anionic surfactants other than nonionic surfactants have reactive groups, but in the case of salts with hydroxyl groups such as monoethanolamine salts, the above-mentioned This can also be done by using a blocking method or by using metal salts such as Na, K, Ca salts, ammonium salts, etc.

On the other hand, the film-forming compounds can also be made non-reactive with each other by blocking them.

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

Blocking agents used in this method include methanol, ethanol, phenol, ethyl mercabutane, hydrocyanic acid, diethyl malonate, ε-cubic lactam, sodium bisulfite, acetylacetone, and the like. When these blocked urethane prepolymers are heated to above their respective cleavage temperatures, isocyanate groups are liberated and the film-forming ability is restored.

Therefore, if the component to be microencapsulated is sensitive to heat, it is preferable to select one from those with a low degree of cleavage. To produce the microcapsule composition of the present invention, usually 0.05 parts by weight of an emulsifier is added to 1 part by weight of the film-forming compound.
Add ~100 parts by weight, preferably 0.5 to 10 parts by weight,
It can be manufactured by mixing and stirring. Mixing entrainment can be carried out by a commonly used stirrer,
The temperature during mixing may also be room temperature.

Furthermore, if the viscosity of the film-forming compound or emulsifier used is high, an appropriate amount of an organic solvent may be added if necessary. In this case, the organic solvent used is a drug active ingredient,
Any material that dissolves the emulsifier, film-forming compound, etc. and does not react with the film-forming compound may be used. For example, aliphatic hydrocarbons such as hebutane, n-hexane, cyclohexane, octane, and isooctane, halogenated hydrocarbons such as chloroform, carbon tetrachloride, trichlorethylene, and benzene chloride, isobutyl ketone, diethyl ketone, and methyl ede. ketones such as dipropyl ketone and dipropyl ketone; esters such as ethyl acetate, butyl acetate, isoamyl acetate, and ethyl propionate; ethers such as butyl ether and isopropyl ether; Aromatic hydrocarbons such as silylethane, dimethylformamide, dimethyl sulfoxide, etc. can be used.

When the composition for microcapsules of the present invention is, for example, a pesticide as the component to be microencapsulated, the commercially available pesticide can be used by simply purchasing a commercially available pesticide and adding it and the composition to the spray solution and stirring at the time of use. The encapsulated microcapsules are easily formed, and the liquid containing them can be used as is by dispersing it into waste cloth using a spraying device.

In order to produce a composition for microcapsules containing the component to be microencapsulated of the present invention, the film-forming compound is usually added in an amount of 0.05 to 100 parts by weight per part by weight of the component to be microencapsulated, for example, an agricultural chemical active ingredient. part, preferably 0,
5 to 20 parts by weight, and 0.0 parts by weight of emulsifier. WA can be produced by adding 0.5 to 50 parts by weight, preferably 0.5 to 10 parts by weight, and mixing and stirring.

Mixing can be carried out using a commonly used stirrer, and the temperature during mixing may be room temperature.

Note that any component to be microencapsulated can be used as long as it does not react with the film-forming compound. Therefore, the agricultural chemical active ingredients can be appropriately selected from herbicides, fungicides, insecticides, plant growth regulators, etc., and used.

Next, the microencapsulation mechanism when using the composition for microcapsules of the present invention will be explained.

When the composition for microcapsules of the present invention is added to a pesticide spray solution prepared by a conventional method, the microcapsule composition emulsifies and breaks down into minute droplets of several microns or less in the pesticide solution. Next, the minute droplets of the composition formed in the sprayed liquid and the droplets or particles containing the agricultural chemical active ingredient in the sprayed liquid are combined.

It is presumed that in this way, new droplets containing both the pesticide active ingredient and the film-forming compound are generated, and a film is formed at the interface between the newly generated droplet and water to produce microcapsules containing the pesticide active ingredient.

The amount of the composition for microcapsules of the present invention to be added is usually 0.00 to 100% of the liquid containing the component to be microencapsulated. (
}2% (V/V) ~ 10% (V/V), better <ha0
．． 05% (V/V) to 2% (V/V).

Further, the film thickness of the microcapsules can be adjusted by adjusting the amount of the film-forming compound or the amount of the microcapsule composition of the present invention added.

When an isocyanate compound is used as a film-forming compound in the present invention, the rate of film formation on 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 it can be added into the composition when the composition for microcapsules is added to water to produce microcapsules.

In the case of a composition for agricultural chemical microcapsules, a catalyst can be contained therein, or may be contained therein at the time of microencapsulation.

The rate of film formation can be adjusted by adjusting the amount of catalyst added, and is usually 0.00% for the microcapsule composition.
It is used within the range of 1 to 10% by weight.

Such catalysts include triethylamine, N,N,N,
Amines such as N-tetramethyl-1,3-butanediamine, lauryldimethylamine, triethylenediamine,
Organic tin compounds such as dibutyltin dilaurate, dibutyltin di(2-edylhexoate), and stannous oleate are used alone or in combination of two or more.

In addition, particularly when a urethane prepolymer is used as the film-forming compound, the film formation rate can also be adjusted by changing the hydrophilicity/hydrophobicity balance (1-IL B ) of the urethane prepolymer.

(Effects of the Invention) The composition for microcapsules of the present invention can be stored for a long period of time, and microcapsules containing the component to be microencapsulated are easily formed by simply adding it to a liquid such as water at the time of use. It has the characteristic that a liquid containing it can be prepared and used as it is. In addition, the composition for microcapsules containing the component to be microencapsulated of the present invention, for example, the composition for microencapsulated pesticide preparations, can be stored for a long period of time like the above-mentioned composition for microcapsules, and can be added to the spray solution at the time of use. It has the characteristics that a pesticide microcapsule formulation containing the pesticide active ingredient can be easily formed by simply doing this, a spray containing the same can be prepared, and it can be destroyed as it is. Therefore, by using the agrochemical microcapsule preparation of the present invention, safe, effective, and labor-saving agrochemical spraying that has been desired can be realized.

[Example] The present invention will be specifically explained below using Examples and Comparative Examples. In addition, the test method in the following examples and comparative examples was performed by the method shown below.

Storage stability test method; During preparation, microcapsule compositions stored at 40°C for 1 week or 3 months were visually observed to check for coloration, precipitation, and gelation, and those without were evaluated as good.

Emulsification test: A part of the microcapsule composition used for the storage stability test was mixed and diluted 1000 times with 3 degree hard water at 20°C, and the emulsion stability was visually determined after 2 hours.

Method for quantifying isocyanate groups: Prepare a solution of 0.1N di-n-butylamine in acetone. 25 ml of this solution is placed in an Erlenmeyer flask, and 10 g of an i ooo times diluted solution of the composition for microcapsules of the present invention is accurately weighed and added thereto. After standing for 20 minutes at room temperature, 100 d of isopropyl alcohol was added, and bromophenol blue was used as an indicator. Titrate with IN hydrochloric acid to determine the reaction rate of unreacted isocyanate groups.

In addition, all "parts" used in the examples to indicate the usage amount of each component mean "parts by weight."

Example 1 Acetate ester of polyoxyethylene distyryl phenol ether (addition of 17.5 moles of ethylene oxide) 5
A liquid composition was prepared by mixing 10 parts of an emulsifier consisting of 0 parts and 50 parts of calcium dodecylbenzenesulfonate, 70 parts of urethane prepolymer A, and 20 parts of xylene.

Example 2 Acetate ester of polyoxyethylene distyryl phenol ether (addition of 17.5 moles of ethylene oxylide) 5
0 parts and dodecylbenzenesulfonic acid cal. 50 sium salts
10 parts of emulsifier consisting of 50 parts of urethane prepolymer A50
1 part and 40 parts of xylene were mixed and stirred to prepare a liquid composition.

Example 3 Acetate ester of polyoxyethylene distyryl phenol ether (addition of 17.5 moles of ethylene oxide) 5
A liquid composition was prepared by mixing and stirring 10 parts of an emulsifier consisting of 0 parts and 50 parts of calcium dodecylbenzenesulfonate, 20 parts of urethane prepolymer A, and 70 parts of xylene.

Comparative Example 1 Polyoxyethylene distyryl phenol ether (ethylene oxide 17
．． A liquid composition was prepared by mixing and stirring 10 parts of an emulsifier consisting of 50 parts of 5 mole addition), 50 parts of calcium dodecylbenzenesulfonate, 20 parts of urethane prepolymer A, and 70 parts of xylene.

Table 1 shows the storage stability and emulsifying test results for Examples 1 to 3 and Comparative Example 1.

Q: Good It can be seen that since the nonionic surfactant and the urethane prepolymer were not blocked, the nonionic surfactant and the urethane prepolymer reacted, resulting in precipitation, and the emulsifying property was significantly reduced.

Experimental Example 1 The above-mentioned Examples 1 to 3 were stored at 40°C for 3 months in a diluted solution prepared by diluting a commercially available pyridafuenthione emulsion (Ofnac emulsion manufactured by Sanfu Toatsu Kagaku Co., Ltd.) 500 times with water. The liquid composition of Comparative Example 1 was added at 0.1% (V/V
> was added and mixed and stirred to prepare a diluted solution. An aluminum plate with a diameter of 7 cm was immersed in this diluted solution for 1 minute. The aluminum plate treated after drying was stored in a constant temperature bath at 30°C, and the aluminum plate was taken out on a specified day and the amount of attached pyridafenthion was measured using gas chromatography. I asked for it.

The results are shown in Table-2. All numerical values are percentages.

Table 2 The results of Table 2 show that the microencapsulated liquid composition of the present invention microencapsulates a commercially available insecticide.
This is clear from the residual effectiveness of insecticides.

Example 4 Orange oil used as a fragrance was added to 5% (V/
V) 0.1% (V/V) ding WEEN 20
Add to aqueous solution and suspend. A solution composition prepared in the same manner as in Example 1 was added to this suspension in the same volume as the orange oil, and mixed with stirring to prepare a microcapsule suspension containing orange oil.

Implementation VA5 Add 0.1% TWEEN to 10% (V/V) of 4-promobisphenol used as a flame retardant.
The solution composition prepared in Example 1 was added in the same amount as 4-bromobisphenol and mixed with stirring to prepare a microcapsule suspension containing 4-bromobisphenol.

Example 6 40 parts of pyridafenedione, 10 parts of an emulsifier consisting of 50 parts of acetate ester of polyoxyethylene distyryl phenol ether (added with 25 moles of ethylene oxymonide) and 50 parts of calcium dodecylbenzenesulfonate, urethane prepolymer A liquid composition was prepared by mixing and stirring 810 parts of xylene and 40 parts of xylene.

Example 7 40 parts of pyridafenthion, 10 parts of an emulsifier consisting of 50 parts of acetate of polyoxyethylene distyryl phenol ether (added with 25 moles of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, 85 parts of urethane prepolymer, and 45 parts of xylene. A liquid composition was prepared by mixing and stirring the following parts.

Example 8 40 parts of viridafenethione, 10 parts of an emulsifier consisting of 50 parts of acetate of polyoxyethylene distyryl phenol ether (addition of 25 moles of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, 83 parts of urethane prebolimer, and A liquid composition was prepared by mixing and stirring 47 parts of xylene.

Comparative Example 2 40 parts of pyridafenethione, 10 parts of an emulsifier consisting of 50 parts of non-end-capped polyoxyethylene distyryl phenol ether (25 moles of ethylene oxide added) and 50 parts of dodecylbenpine sulfonic acid calcium salt, urethane. A composition was prepared by mixing and stirring 83 parts of prebolimer and 47 parts of xylene.

The storage stability and emulsifying test results for Examples 6 to 8 and Comparative Example 2 are shown in Table 3.

Table 3 As is clear from Table 3, the liquid compositions of Examples 6 to 8 are stable, whereas the liquid composition of Comparative Example 2 blocks the ends of the nonionic surfactant in the liquid. It can be seen that since there is no nonionic surfactant, the nonionic surfactant reacts with the urethane prebolimer, resulting in precipitation, and the emulsifying property is significantly reduced.

Experimental Example 2 Prepared in the same manner as in Examples 6 to 8 above, and then heated at 40°C.
A diluted solution was prepared by diluting the composition stored for a month 1000 times. Regarding this diluted solution, the residual rate of viridafentione was determined in the same manner as in Experimental Example 1. The results are shown in Table 4. What? Oh, the numbers are in %.

Table 4 It is clear from the results in Table 4 that even after long-term storage, the composition of the present invention can be used as a microcapsule preparation containing the active ingredient simply by diluting and mixing with water.

Example 9 10 parts of flufenoxuron, 10 parts of an emulsifier consisting of 50 parts of acetate ester of polyoxyethylene nonylphenol ether (addition of 20 moles of ethylene oxylide) and 50 parts of calcium dodecylbenvinsulfonate, urethane prebolymer CIO part, N -0.2 part of lauroylglutamic acid dibutylamide and 69.8 parts of xylene were mixed and stirred to prepare a suspension-like liquid composition.

Experimental example 3 Azoitsuku diazo component 22 (Showa Kako lKa
ko Blue VR Salt) 0.5 part, emulsifier ion consisting of 50 parts of acetate ester of polyoxyethylene nonylphenol ether (added with 20 moles of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, urethane polymer CIO part, and xylene 79. A liquid composition was prepared by mixing and stirring 5 parts. Next, 0.5 part of β-naphthol (manufactured by Wako Pure Chemical Industries, Ltd.), polyoxyethylene nonylphenol ether (ethylene oxide 2
10 parts of an emulsifier consisting of 50 parts of acetate ester (0 mol addition) and 50 parts of calcium dodecylbenzenesulfonate;
and 89.5 parts of xylene were mixed and stirred to prepare a liquid composition. Each of these two liquid compositions 1-,
It was added to 1,000 rIJi of 3 degree hard water at 20°C and stirred. After 15 minutes, the emulsion in the diluent took on a red color.

This means that the azoic diazo component 22 and β-naphthol in the above two compositions reacted, and the two emulsions coalesced in water to form microcapsules containing herbal drug ingredients. This is an indirect proof.

Example 10 "Preparation of a composition capable of easily producing a microcapsule preparation containing soybean oil as a microencapsulated component for use as an enamel remover" Soybean oil (main component) 80 parts, polyoxyethylene distyryl A composition was prepared by mixing and stirring 10 parts of an emulsifier consisting of 50 parts of acetate ester of phenol ether (25 moles of ethylene oxylide added), 50 parts of calcium dodecylbenzenesulfonic acid salt, and urethane prepolymer CTOS.

Example 11 "Preparation of a composition that can easily produce a microcapsule formulation that encapsulates Rudil-type titanium dioxide as a component to be microencapsulated for the purpose of improving the fluidity of Rudil-type titanium dioxide used as a liquid additive" Component to be microencapsulated It was prepared in exactly the same manner as in Example 12, except that rutile titanium dioxide was used.

Example 12 "Preparation of a composition that can easily produce a microcapsule formulation that encapsulates citronellal, which is used as aromatic rice, as a component to be microencapsulated" Same as Example 10 except that citronellal was used as the component to be microencapsulated. Prepared in the same manner.

Example 13 "Preparation of a composition that can easily produce a microcapsule formulation containing 4-promoethane, which is used as a flame retardant, as a microencapsulated component for the purpose of masking effect" Microencapsulated component It was prepared in exactly the same manner as in Example 10, except that 4-bromoethane was used.

Example 14 "Preparation of a composition that can easily produce a microcapsule formulation containing cholesteric liquid crystal used in liquid crystal printing as a component to be microencapsulated" Same as Example 10 except that cholesteric liquid crystal was used as the component to be microencapsulated. Prepared in exactly the same manner.

Experimental Example 4 The compositions of Examples 10 to 14 were tested in the same manner as in Experimental Example 1, and it was confirmed that they all had good storage stability and emulsifying properties.

Example 15 Polynactin complex 12? J5, polyoxyegul distyryl phenol ether (ethylene oxylide 3
10 parts of an emulsifier consisting of 50 parts of acetate ester (addition of 5 moles) and 50 parts of calcium dodecylbenzenesulfonate;
10 parts of urethane prepolymer D, and 6 parts of benzene chloride
A composition was prepared by mixing and stirring 8 parts. Table 5 shows the results of the storage stability and emulsifying properties of the composition.

Comparative Example 3 Polyoxyethylene distyryl phenol ether (ethylene oxide 3
Example 17 except that an emulsifier consisting of 50 parts of 5 molar addition and 50 parts of calcium dodecylbenzenesulfonate was used.
A composition was prepared in the same manner as described above. The storage stability and emulsifying test results are shown in Table 5.

Table 5 O: Good ×: Bad As is clear from Table 5, the composition of Example 15 is stable, whereas the composition of Comparative Example 3 is It can be seen that since the terminals were not blocked, the nonionic surfactant and the urethane prepolymer reacted, resulting in precipitation, and the emulsifying property was significantly reduced.

Example 16 2 parts of Ethofene Blocks, 10 parts of an emulsifier consisting of 50 parts of methyl ether of polyoxyethylene nonylphenol ether (added with 15 moles of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, 15 parts of urethane prepolymer E, and xylene. A composition was prepared by mixing and stirring 73 parts.

The storage stability and emulsifying properties of this composition were tested at the time of preparation, one week later, and three months later, all of which were good.

Example 17 Pyridafenethion 401, 10 parts of an emulsifier consisting of 50 parts of acetate ester of polyoxyethylene disdyryl phenol ether (added with 35 moles of ethylene oxide) and 50 parts of calcium dodecylbenzenesulfonate, 10 parts of urethane prepolymer F, and 40 parts of xylene were mixed and stirred to prepare a composition. Table 6 shows the test results for storage stability and emulsifying properties of this composition.

Comparative Example 4 Example 17 except that an emulsifier consisting of 50 parts of non-end-capped polyoxyethylene disdyryl phenol ether (added with 35 moles of ethylene oxinoid) and 50 parts of dodecylbenzenesulfonic acid calcium salt was used. A composition was prepared in the same manner as above.The storage stability and emulsifying property test results of this composition are shown in Table 6.

As is clear from Table 6, the composition of Example 17 is stable, but in the composition of Comparative Example 2, the nonionic surfactant and the urethane prebolymer react, resulting in precipitation and emulsification. It can be seen that the performance is significantly reduced.

Example 18 40 parts of triprobyl isocyanate (TPIC), 108 parts of isobutylene A kylide adduct of polyoxyethylene nonylphenol ether (ethylene oxylide 10-E addition), 5 parts of urethane prepolymer CI, and 35 parts of kerosene were mixed and stirred. A composition was prepared.The storage stability and emulsifying properties of this composition were good.

Example 19 40 parts of diazinon, 50 parts of methyl ether of polyoxyethylated castor oil (added with 50 moles of ethylene oxynoid), and 5 parts of dodecylbenzenesulfonic acid calcium salt
A composition was prepared by mixing and stirring 20 parts of an emulsifier consisting of 0 parts, 10 parts of urethane prevolmer 10, and 30 parts of a mixed solvent consisting of 50 parts of xylene and 50 parts of benvyne chloride.

The storage stability and emulsifying properties of this composite product were tested at the time of preparation, after 1 hour, and after 3 months, all of which were good.

After 3 months at room temperature after preparation, the reaction rate of isocyanate groups was determined over time according to the method for quantifying isocyanate groups described above, and this was used as an index of the film-form rate of microcapsules.

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

Table 7 Table 7 and electron microscope observation 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 20 40 parts of glypholate, polyoxyethylene distyryl phenol ether (15 moles of ethylene oxide added)
10 parts of an emulsifier consisting of 50 parts of methylene urethanide and 50 parts of calcium dodecylbenzenesulfonate, 10 parts of urethane prebolymer B, and O parts, 0.1 part, 1 part, and 5 parts of dibutyltin dilaurate as catalysts, respectively. 1 part, and add xylene to each to bring the total amount to 100 parts.
% and then stirred to prepare four types of compositions with different amounts of catalyst added.

In order to investigate the film formation rate of each of these, Example 19
The reaction rate of isocyanate groups was measured in the same manner as
This was used as an index of the rate of film formation on microcapsules.

The measurement results are shown in Table-8.

Table 8 As is clear from Table 8, the rate of film formation on the microcapsules can be adjusted by changing the amount of catalyst added.

Furthermore, by electron microscopic observation of the microphone-mouth capsules produced with these compositions, it was confirmed that good microcapsules were produced.

The storage stability and emulsifying properties of these compositions were tested at the time of preparation, one week later, and three months later, all of which were good.

Example 21 20 parts of triadimefon, 20 parts of urethane prevolimer-F, 1 part of lauryl dimethylamine as a catalyst, 50 parts of propionic acid ester of polyoxyethylene tristyrylphenol ether (25 moles of ethylene oxide added) and dodecyl to 10 parts of dimethylformamide. 5 parts of each emulsifier consisting of 50 parts of bempine snolephonic acid calcium salt.
After adding xylene to make the total amount 100 parts, three types of compositions with different amounts of emulsifier were prepared by stirring. These compositions were diluted and emulsified 1,000 times with water at 25°C, and after 30 minutes, the resulting microcapsules were observed using an electron microscope to determine the average particle size.

The results are shown in Table-9.

Table 9 From the above results, it can be seen that by increasing the amount of emulsifier blended, microcapsules with smaller particle diameters are produced.

The storage stability and emulsifying properties of the composition of this example were tested at the time of preparation, one week later, and three months later, all of which were good.

〔Example of use〕

10 g of the composition of Example 17 was added to 101 of water and stirred. After this was left to stand for about 15 minutes, a sufficient amount of the prepared capsule suspension was applied to cabbage seedlings grown in pots in a greenhouse using a commercially available stainless steel shoulder sprayer. There was no clogging at the time of spraying, and both the state of fallen cloth and the state of wetness of the cabbage were good.

Claims (1)

[Scope of Claims] 1. A composition for microcapsules comprising as essential components an emulsifier that does not react with each other and a polyisocyanate compound having a cationic group in the molecule as a compound capable of forming a film by reacting with water. 2. A composition for microcapsules comprising the composition for microcapsules according to claim 1 and the component to be microencapsulated as essential components. 3. The emulsifier is one or more surfactants selected from cationic surfactants, nonionic surfactants, amphoteric surfactants, and anionic surfactants, and is reactive with water. 3. The composition for microcapsules according to claim 1, wherein the composition is an emulsifier that does not react with a compound capable of forming a film. 4. The composition for microcapsules according to claim 1 or 2, wherein the emulsifier is an emulsifier in which a reactive group that reacts with a compound capable of reacting with water present in the compound to form a film is blocked. thing. 5. The component to be microencapsulated is a component selected from pesticides, fragrances, paints, liquid crystals, repellents, fertilizers, cosmetics, pigments, inks, inducers, foaming agents, flame retardants, rust preventives, and fungicides. The composition for microcapsules according to any one of claims 2 to 5. 6. Production of microcapsules by mixing and stirring a composition containing a component to be microencapsulated, the composition for microcapsules according to any one of claims 1, 3, or 4, and water. Method. 7. The components to be microencapsulated are selected from pesticides, fragrances, paints, liquid crystals, repellents, fertilizers, cosmetics, pigments, inks, inducers, foaming agents, flame retardants, rust preventives, and fungicides. The method for producing microcapsules according to claim 6. 8. The method for producing a microencapsulated pesticide preparation according to claim 6, wherein the component to be microencapsulated is an active ingredient of a pesticide. 9. A kit for microcapsules comprising a combination of a composition containing a component to be microencapsulated and the composition for microcapsules according to claim 1, claim 3, or claim 4. 10. The kit for agrochemical microcapsule formulation according to claim 9, wherein the component to be microencapsulated is an agrochemical active ingredient.