JPH04290539A - Microcapusle composite and production of it - Google Patents

Abstract

PURPOSE:To improve the various kinds of performance, a slow release property, the mechanical strength, the chemical durability, the physical durability, etc., of the microcapusle. CONSTITUTION:The paste which >=one kind of microcapusle particles being made a microcapusle from the material to be included are prepared by mixing with an oligomer or a polymer component consisting of >=1 kind of the components, is made particulate and the microcapsule composite is formed.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microcapsule composite containing a plurality of microcapsules and a method for producing the same.

0002

[Prior Art] Microcapsules encapsulating various substances, their manufacturing methods, and applied products are already known.Such microcapsules are used as sustained release agents in fragrances, deodorants, insecticides, pharmaceuticals, etc. It is used to hold. Furthermore, microcapsules containing reaction catalysts, crosslinking agents, etc. are used as components in reactive one-component resin compositions, and their range of applications is wide.

0003

[Problems to be Solved by the Invention] However, in such conventional microcapsules, it is difficult to control functions such as microencapsulation of the encapsulated substance and sustained release of the encapsulated shell substance, and to improve the surface of the microcapsule. Problems include the difficulty of satisfying both chemical and physical properties at the same time, and the lack of durability of applied products due to destruction of the microcapsule shell material caused by insufficient mechanical strength of the microcapsules. , no effective characteristics could be obtained. For this reason, there was a problem that it was difficult to apply it to industrial products.

0004

[Means for Solving the Problems] In order to solve these conventional problems, the present invention synthesizes microcapsules containing a desired encapsulated substance, and injects into the microcapsules a targeted controlled release agent. properties, mechanical strength, chemical durability,
A paste containing one or more types of microcapsules (hereinafter referred to as base paste) dispersed in an oligomer or polymer (hereinafter referred to as granulated material) that can satisfy each required performance in order to impart various performances such as physical durability. By newly forming particles using methods such as suspension polymerization,
The object of the present invention is to provide a microcapsule composite that can effectively control the sustained release time characteristics, surface physical properties, etc., and also allows the strength of the microcapsules to be improved and to be made into colored particles.

[0005]

[Example] The microcapsules encapsulated in the microcapsule complex of the present invention include fragrances, deodorants, adhesives, curing agents for adhesives, curing agents for paints, catalysts, insecticides, and bactericides. , pharmaceuticals, etc., and these encapsulated substances are selected depending on the purpose of the final product and are not particularly limited in type. These microcapsules are microcapsules obtained by conventional formulations, such as by interfacial polymerization of monomers in O/W (oil-in-water) or W/O (water-in-oil) emulsions. be.

[0006] The composition of the substance constituting the shell constituting the microcapsules is selected depending on the purpose of the final product, but is not particularly limited as long as it can be microencapsulated. In addition, the average particle size of the microcapsules is not particularly limited, but in order to synthesize a stable microcapsule complex and obtain a uniform particle size distribution in the next step of microcapsule complexation, the average particle size must be 0.3 to 100 μm is preferable.

The present invention is achieved by granulating the base paste containing the above-mentioned microcapsules.
The type of microcapsules is not limited, and several types of microcapsules may be used. In addition, when making microcapsules into a base paste, if you take into consideration the dispersibility of microcapsules in the granulating material used for the base paste and the coalescence and destruction of microcapsules during the dispersion process, it is possible to separate and dry the microcapsules. It is preferable not to do so.

For example, when using microcapsules obtained by the above-mentioned interfacial polymerization, if the microcapsules are obtained in an O/W emulsion, the oil component (generally an organic solvent) to be used may be appropriately adjusted. It is preferable that the base paste is obtained by dispersing the microcapsules in a lipophilic base paste granulated material by performing an operation that increases the concentration of the microcapsules in the dispersion medium without performing selective filtration, drying, or other such separation of the microcapsules. In addition, microcapsules are W/
When obtained in an O emulsion, it is preferable to similarly select a hydrophilic granulated material for the base paste to obtain the base paste. However, if the dispersion medium is replaced after microcapsule production, both lipophilic and hydrophilic base paste granules can be obtained without separating and drying the microcapsules.

Examples of resins that can be used as the granulated material of the base paste include oligomers and polymers such as polyester resins, polyurethane resins, polyether resins, acrylic resins, epoxy resins, polypropylene resins, and organosiloxane resins. There are no particular limitations on the composition of the granulated material, as long as it has an appropriate viscosity and can stably disperse the microcapsules in the granulated material. Further, the granulated material of the base paste is preferably a linear polymer, soluble in an appropriate solvent, and having a reactive functional group used for polymerization or three-dimensional crosslinking.

Examples of functional groups include hydroxyl groups, glycidyl groups, carbonyl groups, nitrile groups, carboxyl groups, amino groups, alkoxysilyl groups, isocyanate groups, and ethylenic double bonds. In order to polymerize or crosslink polymerize the granulated material of the base paste, a method may be considered in which a crosslinking agent or a reaction catalyst that reacts with these functional groups is blended into the base paste. Further, at this time, it is also possible to disperse various additives such as coloring pigments, extender pigments, ultraviolet absorbers, and reaction catalysts in the base paste depending on the purpose. Furthermore, by appropriately diluting with water or a hydrophilic solvent if the base paste system is aqueous, or with a lipophilic solvent if the base paste system is non-aqueous, the particle size of composite microencapsulation in the next step can be adjusted. You can adjust efficiency etc.

The particles granulated from the base paste obtained above constitute a microcapsule composite containing a plurality of microcapsules. Examples of granulation methods at this time include solution polymerization, suspension polymerization, etc.
The granulation method is not particularly limited. However, in consideration of ease of granulation and safety, suspension polymerization is preferred.

[00012] When obtaining composite microcapsules by suspension polymerization, a suitable dispersion aid is required in the dispersion medium, such as polyvinyl alcohol, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose. Examples include polyethylene glycol, poly(meth)acrylate, seratin, and polyethyleneimine. These dispersion aids are selected depending on the characteristics, dispersion ability, etc. of the granulated material.

[00013] The base paste obtained above is dispersed in a dispersion medium containing a dispersion aid etc. by strong stirring, and the reaction is allowed to proceed by heating while stirring.
Polymerized or three-dimensionally crosslinked particles are obtained. This particle is a microcapsule complex containing multiple microcapsules. The obtained microcapsule complex is separated by centrifugation, filtration, etc., and if necessary, washed with a solvent and dried.

[00014] The present invention will be explained below using Examples, but the present invention is not limited to these Examples. Note that numerical values without specific units represent parts by weight. Example 1 [Synthesis of microcapsules] (1) Prescription of microcapsule inclusions and shell-forming components
10% by weight aqueous solution of polyvinyl alcohol 10 Hexamethylene diamine 6
water soluble fragrance
84

Total 100 (2)
Formulation of dispersion medium for microcapsule formation
Carbon tetrachloride
200 Sorbitan monooleate
0.5

Total 200.5

000
15] Add the composition obtained in (1) to the composition in (2), stir with a homomixer at 5000 rpm for 5 minutes,
Emulsified and dispersed. While further stirring this dispersion at 200 rpm, 30 parts by weight of an aromatic polyisocyanate (Sumidur L-75; manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added dropwise at a temperature of 30°C over 1 hour, and further at the same temperature and under the same stirring conditions. Stirring was continued under pressure for 24 hours. The product was collected by filtration and air-dried at room temperature for one day to obtain 120 parts by weight of microcapsules with a particle size of 10 μm to 100 μm.

[Synthesis of composite microcapsules] (3)
Base paste formulation The above microcapsules
50
Acrylic polyol (OHV 25mgKO
H/g) 20 Ethyl acetate

42 Dibutyltin dilaurate
0.5 Coronate EH (manufactured by Nippon Polyurethane Co., Ltd.)
3

Total 115.5 (4
) Prescription of dispersion medium 10% by weight aqueous solution of polyvinyl alcohol
300

[00017] (4
300 parts by weight of the dispersion solvent obtained by ) was put into a 1 liter separable flask equipped with a reducing device and heated to 25
℃ and under forced stirring with a disper, (3)
100 parts by weight of the base paste composition obtained by
It was dropped in 0 minutes. Forced stirring was continued for another 20 minutes, and then the temperature was raised to about 95° C. over 15 minutes, and the reaction was continued for 120 minutes. The product was collected by filtration, washed several times with tap water and air-dried at room temperature.
70 parts by weight of microcapsule composites of ~200 μm were obtained.

Example 2 [Synthesis of microcapsules] was the same as in Example 1. [Synthesis of composite microcapsules] (3) Prescription of base paste The above microcapsules

50 Polycaprolactone diol (OHV 56mgKOH/g) 30
Ethyl acetate

30 Dibutyltin dilaurate
1 Coronate EH (manufactured by Nippon Polyurethane Co., Ltd.)
15

Total 126 (4) Dispersion medium formulation Polyvinyl alcohol 10% by weight aqueous solution
300

00
[019] 300 parts by weight of the dispersion solvent obtained in (4) was placed in a 1 liter separable flask equipped with a reductor and kept at 25°C, and under forced stirring with a disper, the dispersion solvent obtained in (3) was added. 100 parts by weight of the base paste composition was added dropwise over 10 minutes. Forced stirring was continued for another 20 minutes, and then the temperature was raised to about 95° C. over 15 minutes, and the reaction was continued for 60 minutes. The product was filtered, washed several times with tap water,
When air-dried at room temperature, 80 parts by weight of a microcapsule composite containing many microcapsules and having a particle size of 30 to 100 μm was obtained.

Application Example 1 [Coating composition] The microcapsule composite obtained in Example 2 was classified into particle sizes of 30 to 100 μm.
The weight part is polyester polyol (OHV 160
mgKOH/g Burnock D6-439 manufactured by Dainippon Ink Co., Ltd.) was dispersed in 30 parts by weight, and 5 parts by weight of ethyl acetate, 10 parts by weight of methyl isobutyl ketone, and 0.1 part by weight of dibutyltin dilaurate were added to form a matte paint. I got something. 4 parts by weight of an isocyanate prepolymer (Sumidur N-75 manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to 30 parts by weight of this coating composition, diluted with an appropriate organic solvent, and spray-painted on an ABS substrate. 2 at 70℃
After drying for 0 minutes, a matte coating film was obtained.

[0021] This coating film was a matte coating film with an uneven pattern and had the scent of the perfume used in the microcapsules. Even after this coated plate was left at 30° C. and 50 RH% for one month, it still had this scent.

Comparative Example The microcapsules used in Example 2 had a particle size of 30 to 10
20 parts by weight of the material classified to 0 μm were dispersed in 30 parts by weight of polyester polyol (OHV 160mgKOH/g Burnock D6-439 manufactured by Dainippon Ink Co., Ltd.), 5 parts by weight of ethyl acetate, and 10 parts by weight of methyl isobutyl ketone.
parts by weight and 0.1 part by weight of dibutyltin dilaurate were added to obtain a matte coating composition. 4 parts by weight of an isocyanate prepolymer (Sumidur N-75 manufactured by Sumitomo Bayer Urethane Co., Ltd.) was added to 30 parts by weight of this coating composition, diluted with an appropriate organic solvent, and spray-painted on an ABS substrate. The coating was dried at 70° C. for 20 minutes to obtain a matte coating.

[00023] This coating film had the scent of the perfume used in the microcapsules, but the coating film surface formed an uneven surface. When this coated plate was left for one month at 30° C. and 50 RH%, the fragrance of the fragrance used in the microcapsules had disappeared.

[00024]

[Effect of the invention] As explained above, according to this invention,
To synthesize microcapsules that can encapsulate a specified substance, and to impart various desired performances such as sustained release properties, mechanical strength, chemical durability, and physical durability to one or more types of these microcapsules. The sustained release time characteristics,
This is a microcapsule composite that makes it possible to effectively control surface properties, improve microcapsule stability, and make it possible to form colored particles. As a result, it has become possible to easily apply the microcapsules to industrial products, which was difficult to do with conventional microcapsules, and to provide microcapsules with new functions.

Claims (4)

[Claims] [Claim 1] A microorganism characterized in that it is made by granulating a paste made by mixing one or more types of microcapsule particles in which a substance to be encapsulated is microencapsulated with an oligomer or polymer component consisting of one or more types of components. capsule complex. 2. The microcapsule complex according to claim 1, wherein the substance to be encapsulated has hydrophilicity or lipophilicity. [Claim 3] The substance to be included is selected from fragrances, deodorants, adhesives, adhesives, curing agents, paint curing agents, catalysts, insecticides, bactericidal agents, and pharmaceuticals. The microcapsule complex according to claim (1) or (2). 4. One or more types of microcapsule particles microcapsulating a substance to be encapsulated are dispersed in an oligomer or polymer component consisting of one or more types of components to form a paste, which contains a plurality of the microcapsule particles. A method for producing a microcapsule composite, comprising granulating the paste as follows.