KR101691644B1 - The functional material containing the Polymeric microcapsules and its manufacturing method - Google Patents

Abstract

In the present invention, microcapsules having various microcapsules having a diameter of less than 1 to 500 nanometers and containing a large number of microcapsules inside the polymer microcapsules are prepared, and the microcapsules The outer shell thickness is controlled by varying the amount of crosslinking agent, the amount of monomer added, the reaction temperature, and the reaction time to produce a polymer microcapsule having excellent heat resistance and durability, mixing it with a water-soluble binder, The polymer microcapsules are dispersed in dimethylacetamide (DMSO), methyl ethyl ketone (MEK), methanol, ethanol, isopropyl alcohol and tetrahydrofuran (THF) The dispersed state of the processing agent is applied to the fiber to destroy it by heat during the processing of the conventional fiber, Polymer microcapsules containing the functional material applied to the fibers are not only reduced in size but also contain functional substances contained in the capsules even if the capsules are damaged due to stimulation such as heat, friction or washing owing to their structural stability Functional fibers having a stable sustained release property are produced.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer microcapsule containing a functional material,

The present invention relates to a polymer microcapsule containing a functional material and a method for producing the same, and more particularly, to a method of manufacturing a polymer microcapsule having a size capable of entering into a binder layer applied to a fiber, The microcapsules may contain various synthetic and natural functional materials. In the process of preparing the polymer microcapsule, the thickness of the outermost shell may be increased by varying the amount of the crosslinking agent, the amount of the monomer to be added, the amount of the initiator, Microcapsules containing a functional material that minimizes the breakage of the polymer capsules during fiber processing by providing a microcapsule having a many core-shell structure and maintains the functionality for a long time when applied to fibers, and a method for producing the same .

Functional processing of textile products has been performed by mixing functional materials with adhesive on the surface of fibers or by incorporating functional materials into microcapsules and then treating them with fibers with various adhesives so that the applied functional material is volatilized or the microcapsules collapse So that the functionalities are expressed in the fibers.

Among them, the functional fiber product using microcapsules has been used as a supporting material for functional materials, because microcapsules having a size larger than that of the binder layer having a thickness of 1 to 3 micrometers have been used as a carrier for the functional materials. Therefore, various factors that hinder the durability of capsules such as friction, The microcapsules are easily disintegrated, and the structure of the microcapsules produced is a single wall structure, so that the functional materials contained in the microcapsules are rapidly discharged at once, thus shortening the period of providing the functionalities.

Examples of related studies are as follows: a functional composition is prepared by adding a mixed emulsion of a fragrance and a binder to a carpet to impart a directional function (Patent Registration No. 10-0110057); a method of adding a fragrance to microcapsules made of an acrylic resin or a urethane resin (Patent Application No. 10-2000-0086197), and a method of producing a directional fiber material by coating with a binder resin together with a binder resin (Patent Application No. 10-2000-0086197). After the emulsion of the synthetic insoluble material is incorporated into microcapsules by polymer condensation reaction, And a method of spray-fixing the fabric to the fabric (Patent Application No. 10-2002-0079616).

The microcapsules prepared in the above studies have a size exceeding 1 to 3 micrometers, which is the thickness of a general fiber binder coating layer, and the functional material in the microcapsule is contained in a capsule having a single wall structure, And washing, the release of the internal substance occurs at the same time, so that the duration of the functional substance becomes very short. Therefore, the functional substance is required to have at least two years of duration and durability And it was insufficient to be used in the manufacture of textile products.

In addition, the fact that the outermost wall thickness of the polymer particles containing the functional material prepared by the conventional method can not be adjusted adequately to have sufficient durability is also pointed out as a cause of the durability problem mentioned above.

In order to prevent rapid release of the functional material contained in the capsules due to damage and collapse of the polymer capsules caused by various causes such as heat, friction, washing and the like, which have been pointed out as problems in the prior art, The present invention is directed to a polymer microcapsule having a size capable of entering into a polymer microcapsule, wherein a large number of microcylindrical capsules are distributed in the polymer microcapsule, so that functional microcapsules are contained in each microcapsule.

In addition, the outermost wall thickness of the prepared polymer microcapsules is increased through changes in the production conditions such as the amount of crosslinking agent added, the reaction temperature, and the reaction time to produce polymer microcapsules having excellent thermal stability, durability and sustained release properties. There is a purpose.

In order to solve the above problems, an aspect of the present invention is to prepare an aqueous solution by dissolving 0.2 to 3.0% by weight of an emulsifier in 54 to 86% by weight of distilled water, based on the total weight of a solution of a polymer microcapsule comprising a micelle- Adding 5 to 30% by weight of a monomer, 5 to 40% by weight of a functional material, 0.1 to 5% by weight of a crosslinking agent and 0.1 to 5% by weight of a co-solvent to prepare a monomer solution, mixing the aqueous solution and the monomer solution Followed by mixing for 1 to 30 minutes using a homogenizer or an ultrasonic crusher to form micelles; Mixing the mixed solution in which the micelles have been formed in a nitrogen atmosphere at a ratio of 97 to 99.9: 0.1 to 3.0 in terms of a weight ratio of the radical initiator, and stirring the mixture at 10 to 85 ° C for 1 to 10 hours at 200 to 1000 rpm A polymeric microcapsule, and a polymeric microcapsule.

In another aspect of the present invention, there is provided a method for manufacturing a polymer microcapsule, comprising the steps of: preparing a polymer microcapsule having a plurality of microcapsules inside the polymer microcapsule and a functional material in the inner capsule, And a functional material having a size that can be inserted into the polymer microcapsule.

Another feature is that the polymeric microcapsule and the water-soluble acrylic binder are mixed in a volume ratio of 1: 9 to 5: 5, and the polymer microcapsule solution is mixed with an organic solvent at a volume ratio of 1: 9 to 6: 4 Which is produced by mixing and dispersing the fibers.

Since the microcapsules containing the functional additive are distributed in the polymer microcapsule having a size capable of entering into the binder layer applied to the fibers, the present invention having various characteristics such as heat, friction, The polymer microcapsules and the microcapsules are gradually degraded or broken due to the structural stability, so that the duration of the functional material contained therein can be stably increased.

In addition, by increasing the thickness of the outermost wall of the prepared polymer microcapsule through changes in the amount of cross-linking agent, reaction temperature, and reaction time, the polymer microcapsule can have improved durability and excellent thermal stability and durability Of course, it is also possible to control the release rate and duration of the contained material.

In addition, since the polymer microcapsule according to the present invention can be applied to various binders for fibers and organic solvents, it can be easily applied to various fabric manufacturing processes. Therefore, various functional fiber fabrics having excellent durability and functional duration can be produced.

Brief Description of the Drawings Figure 1 is a comparative drawing of polymer microcapsules prepared in the present invention and previously reported polymer capsules
2 is a view showing a process for producing a polymer microcapsule according to the present invention;
3 is an electron micrograph of the polymer microcapsules prepared in Example 1
4 is an electron micrograph of the polymer microcapsules prepared in Example 2
5 is an electron micrograph of the polymer microcapsules prepared in Example 3
6 is an electron micrograph showing the difference between Example 1 and Example 5 in which the outermost wall thickness of the polymer microcapsule is thickened
7 is an electron micrograph of the polymer microcapsules prepared in Example 5
FIG. 8 is a graph showing particle size distribution showing the average size of the polymer microcapsules prepared in Example 6
9 is a particle size analysis chart showing the average size of the polymer microcapsules prepared in Example 7
10 is a photograph of a coating agent for fibers in which the water-soluble acrylic binder and the polymer microcapsules prepared in Example 8 are mixed
11 is a photograph showing a polymer microcapsule solution in a state of being dispersed in DMF solvent in a working agent for fibers dispersed in various organic solvents prepared in Example 9
12 is an electron micrograph showing the adhesive layer and the applied state of the fabric coated with the water-soluble acrylic binder mixed with the functional polymer microcapsules having excellent thermal stability and high durability,
13 is a photograph showing that the polymer microcapsules prepared in the present invention are precipitated by adding methanol to recover the polymer microcapsules from water
14 is a photograph showing that the polymer microcapsule prepared in the present invention is salted by adding a saturated aqueous solution of sodium chloride to recover the polymer microcapsules separated from water

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

As shown in FIG. 1, a polymer microcapsule containing a functional material according to the present invention includes a plurality of microcapsules containing various synthetic and natural functional materials in a polymer microcapsule having a size capable of entering into a binder layer applied to fibers, Shell structure in which an inner capsule is distributed, and an outermost wall thickness of the polymer microcapsule is adjusted. The polymer microcapsules thus prepared are mixed and dispersed in various water-soluble binders and organic solvents to be applied to the fibers. At this time, the diameter of the polymer microcapsule is 50 to 500 nanometers.

As shown in FIG. 2, the polymer microcapsules are prepared by dissolving 50 to 86% by weight of water and 0.2 to 3% by weight of an emulsifier based on the total weight of the solution, An aqueous solution manufacturing process for producing an aqueous solution; Polymeric microcapsule preparation solution composed of a mixture solution in which micelles are formed and a radical initiator is mixed with 5 to 30% by weight of a monomer, 5 to 40% by weight of a functional material, 0.1 to 5% by weight of a crosslinking agent, and 0.1 to 5% Solution preparation process; And mixing the aqueous solution and the monomer solution to form micelles; Mixing the radical initiator in a mixed solvent in which the micelle is formed in a nitrogen atmosphere at a ratio of 97 to 99.9: 0.1 to 3.0 by weight, and then stirring the mixture at 10 to 85 ° C for 1 to 10 hours at 200 to 1000 rpm. .

In this process, the amount of the crosslinking agent added to adjust the wall thickness of the outermost bark is 0.2 to 5 wt% based on the total weight of the solution of the microcapsule-containing mixed solution and the radical initiator, Deg.] C, and the reaction time is 2 hours to 10 hours.

Then, the polymer microcapsules prepared as described above are mixed with an acrylic binder to prepare a fiber coating agent, which is then applied to the fibers and heat-treated (100 to 300 ° C) to produce a functional fiber product comprising the functional fiber coating layer.

Alternatively, the polymer microcapsule solution may be subjected to a reduced pressure treatment to remove moisture, or methanol or various salts may be added thereto to precipitate or salting out the polymeric microcapsule solution, and then the polymeric microcapsule solution may be dried and dispersed in an organic solvent to prepare a fiber application agent. Then, the fiber coating agent is applied to the fiber and heat-treated to prepare a functional fiber product including the functional fiber coating layer.

In the above, the organic solvent is selected from DMF, dimethysulfoxide (DMSO), methyl ethyl ketone (MEK), methanol, ethanol, isopropyl alcohol, and tetrahydrofuran (THF).

Hereinafter, embodiments of the present invention will be described in detail.

Example 1: Preparation of polymeric microcapsules containing phytoncide

80 ml of distilled water and 0.2 to 3.0 g of sodium dodecyl sulfate (SDS) as an emulsifier were added to a round bottom flask and dissolved at room temperature to prepare an aqueous solution (aqueous system).

Further, 5 to 30 g of phytoncide oil, 0.1 to 2.0 g of crosslinking agent divinylbenzene (DVB) and 0.1 to 3.0 g of n-hexadecane (n-HD) are added to 5 to 20 g of the styrene monomer, A monomer solution (flow rate) was prepared.

Then, the emulsifier aqueous solution and the monomer solution prepared as described above were mixed at room temperature and then treated with a homogenizer at 8000 to 24000 rpm for 1 to 30 minutes to prepare a micelle-emulsified mixture.

Next, 98 g to 99.9 g of the emulsion mixture in which micelles are formed in a reaction vessel equipped with a mechanical stirrer, a condenser, a thermostat, and a nitrogen injecting apparatus and 0.1 to 2.0 g of a radical initiator AIBN (Azobisisobutyronitrile) Polymeric microcapsules containing phytoncide having a uniform size ranging from 200 to 400 nm in average particle size as shown in FIG. 3 were prepared by stirring at 300 to 1000 rpm for 10 hours.

Example  2: Citronella  Preparation of oil-containing polymer microcapsules

80 ml of distilled water and 0.1-3.0 g of sodium dodecylbenzenesulfonate (SDBS) as an emulsifier were added to a round bottom flask and dissolved therein at room temperature to prepare an emulsifier aqueous solution.

Also, 5 to 30 g of citronella oil, 0.1 to 1.0 g of crosslinking agent divinylbenzene (DVB) and 0.1 to 5.0 g of cetyl alcohol as a co-solvent are added to 10 to 30 g of a styrene monomer, followed by mixing and stirring to obtain citronella oil To prepare a monomer solution.

Then, the emulsifier solution and the monomer solution were mixed at room temperature and then treated with an ultrasonic shredder for 1 to 30 minutes to prepare an emulsion mixture in which micelles were formed.

Next, 97 to 99.9 g of the above mixture in which micelles are formed in a reaction vessel equipped with a mechanical stirrer, a condenser, a thermostat and a nitrogen injecting apparatus and 0.1 to 3.0 g of KPS (potassium persulfate) as a radical initiator are introduced, And stirred at 200 to 1000 rpm for 10 hours to prepare a polymer microcapsule containing citronella oil having a uniform size ranging from 300 to 500 nanometers as shown in Fig.

Example  3: Jasmine ( Jasmine ) Preparation of oil-containing polymer microcapsules

5 to 30 g of jasmine oil was added instead of phytoncide under the same conditions as in Example 1 and proceeded in the same manner. As shown in FIG. 5, the prepared polymer microcapsules showed a uniform distribution of particle sizes ranging from 200 to 400 nm.

Example  4: Particle Outermost  Manufacture of polymer microcapsules with increased wall thickness

The outermost wall of the capsule prepared in the experiment in which the amount of DVB used as a crosslinking agent was increased from 3.0 to 5.0 g, the reaction temperature was raised to 85 ° C, and the reaction time was changed from 2 to 10 hours under the same conditions as in Example 1, As shown in FIG. 5B, electron microscopic photographs confirm that the fourth embodiment is thicker than the first embodiment.

Example  5: Preparation of polymeric microcapsules containing phytoncide

Acrylic styrene was substituted for the styrene monomer of Example 1, and the same procedure as in Example 1 was carried out. The particle size of the prepared polymer microcapsules was 50 to 200 nanometers in size as shown in FIG.

Example  6: Permethrin is a  Preparation of Microcapsules Containing Polymers

10 to 40 g of permethrin, which is a synthetic pressurized insecticide, was added under the same conditions as in Example 1, and the same procedure as in Example 1 was carried out. The average particle size of the prepared polymer microcapsules was measured by a particle size analyzer, and as shown in FIG. 8, it was measured at 200 to 300 nanometers.

Example  7: Cypher meslin ( Cypermethrin Preparation of polymer microcapsules containing

5 to 30 g of cipher meslin, which is a synthetic pressurized insecticide, was added under the same conditions as in Example 2, and the same procedure as in Example 2 was conducted. The average particle diameter of the prepared polymer microcapsules was measured at 200 to 300 nanometers as shown in Fig.

Example  8: Preparation of polymeric microcapsule solution mixed with water-soluble acrylic binder

The phytoncide-containing polymer microcapsules prepared in Example 4 were mixed with a water-soluble acrylic binder at a volume ratio of 1: 9 to 5: 5 to prepare a functional fiber coating agent having excellent thermal stability and high durability as shown in FIG. 10 .

Example  9: Preparation of a processing agent for fibers in which polymer microcapsules are dispersed in an organic solvent

The polymer microcapsules prepared as in Example 1 were mixed with an organic solvent at a volume ratio of 1: 9 to 6: 4 and dispersed. To prepare the polymer microcapsules as fiber processing agents, the water in the polymer microcapsule solution was transferred to a rotary evaporator, The water was completely removed using a vacuum concentration apparatus using a pump, a freeze-drying apparatus, a centrifugal separator, etc., and dispersed in various organic solvents to prepare a fiber processing agent

Examples of the organic solvent include dimethylformamide (DMF), methylethylketone (MEK), dimethylsulfoxide (DMSO), and the like.

Fig. 11 shows a photograph of a processing agent for fibers in which the polymer microcapsules in the processing agent for fibers prepared in Example 9 are dispersed in DMF.

Example  10: Example  Preparation of Functional Fiber Using Fabric Processing Agent Manufactured in 8

The fabric coating material prepared in Example 8 was spray-applied to the polyester / cotton blend fabric at a rate of about 3 micrometers and at a speed of 300 to 800 rpm, followed by hot-air drying at 100 to 300 ° C to obtain a binder coated with the functional polymer microcapsules A layer was formed on the fabric.

FIG. 12 shows a photograph of the thus-obtained functional polymer microcapsule-coated fiber obtained using an electron microscope.

As shown in Fig. 12, the binder layer of the fiber coated with the functional fiber coating material obtained in Example 8 formed a uniform coating surface free from exposure of the functional polymer microcapsules.

Example 11: Comparison of pick-up rate for comparing the thermal stability difference according to the difference of the outermost wall thickness of polymer microcapsules

The polymeric microcapsules prepared in Example 1 and Example 4 were mixed with a binder for fibers, respectively, and then applied to a cotton pad, followed by hot air drying at 100 to 300 ° C. Then, the weight of the dried cotton was measured to determine the thermal stability according to the pick- As shown in Table 1. As shown in Table 1, the picking rate of the fiber application agent mixed with Example 4 having the thickest outer shell thickness was 41% higher than that of the fiber application agent mixed with Example 1 in which the outermost shell was thinner Respectively.

Example  12: The polymer microcapsules were precipitated by the addition of methanol Filtering  And drying it and dispersing it in an organic solvent

Various amounts of methanol were added to the polymer microcapsule solution prepared in Example 1 and Example 4 to precipitate and then recovered by filtration under reduced pressure. Thereafter, the microcapsules were dried to prepare methanol-removed powdery polymer microcapsules, and dispersed in various organic solvents such as dimethylformamide (DMF) to prepare polymer microcapsule solutions dispersed in an organic solvent. A photograph of the polymer microcapsules precipitated in methanol is shown in Fig.

Example  13: Polymer microcapsules were treated with saline solution By filtering  Recovering, drying and dispersing in an organic solvent

The polymer microcapsules prepared by adding an aqueous solution prepared by dissolving various salts such as sodium chloride and magnesium sulfate to the polymer microcapsule solution prepared in Example 1 and Example 4 were salted out and then recovered by filtration under reduced pressure . The polymer microcapsules were then dried to obtain polymer microcapsules in the form of powders, followed by the addition of dimethylformamide (DMF), dimethysulfoxide (DMSO), methyl ethyl ketone (MEK), methanol, ethanol, isopropyl alcohol, tetrahydrofuran (DMF) to prepare a polymer microcapsule solution loaded with phytoncide in a state of being dispersed in an organic solvent. A photograph of the salted polymer microcapsules is shown in Fig.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

Preparing a solution of a polymeric microcapsule composed of a mixed solution in which micelles are formed and a radical initiator; dissolving 0.2 to 3.0% by weight of an emulsifier in 54 to 86% by weight of distilled water based on the total weight of the solution;
And 5 to 40% by weight of a monomer, 0.1 to 5% by weight of a crosslinking agent, and 0.1 to 5% by weight of a co-polymerization initiator, based on the total weight of the mixed solution and the radical initiator, To prepare a monomer solution,
Mixing the aqueous solution with the monomer solution, and mixing the mixture with a homogenizer or an ultrasonic wave shaker for 1 to 30 minutes to form micelles;
Mixing the mixed solution in which the micelle is formed in a nitrogen atmosphere at a ratio of 97 to 99.9: 0.1 to 3.0 in terms of a weight ratio of the radical initiator, and stirring the mixture at 10 to 85 ° C for 1 to 10 hours at 200 to 1000 rpm Wherein the polymeric microcapsule comprises a functional material. The method according to claim 1, wherein the crosslinking agent is added in an amount of 0.2 to 5% by weight based on the total weight of the polymer microcapsule preparation solution composed of the micelle-containing mixed solution and the radical initiator, and the reaction temperature is 60 to 85 ° C and 2 to 10 hours Wherein the thickness of the outermost shell of the polymer microcapsule is controlled by adjusting the thickness of the outermost shell of the polymer microcapsule. The method of manufacturing a polymer microcapsule according to claim 1, delete delete The process according to claim 1, wherein water is removed from the polymer microcapsule solution prepared by the method of claim 1, and the mixture is mixed with an organic solvent at a volume ratio of 1: 9 to 6: 4. Methanol was added to the polymer microcapsule solution prepared according to the preparation method of the present invention to precipitate and recovered by filtration under reduced pressure. The methanol microcapsules were dried to prepare polymer microcapsules in powder form. The polymer microcapsules were dissolved in an organic solvent at a volume ratio of 1: To 6: 4. ≪ / RTI > The polymer microcapsule solution prepared by the method of claim 1 is dissolved in a salt selected from sodium chloride and magnesium sulfate to cause the polymer microcapsules to be salted out and recovered by filtration under reduced pressure, Wherein the polymeric microcapsules are prepared by dispersing the polymeric microcapsules in a volume ratio of 1: 9 to 6: 4 in an organic solvent phase.

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