JP2017501023A - Polymer fine capsule containing functional substance and method for producing the same - Google Patents

Abstract

The present invention relates to a fine capsule having a structure in which various synthetic and natural functional substances have a diameter of 1 to less than 500 nm and are contained in a number of fine inner capsules existing inside a polymer fine capsule. Excellent heat resistance and durability by adjusting the thickness of the outermost shell of the fine capsules thus produced by using the amount of crosslinking agent, the amount of added monomer, reaction temperature and reaction time By applying a processing agent in a state where the polymer microcapsules are dispersed in an organic solvent by mixing or dispersing the polymer microcapsules with a water-soluble binder, In addition to reducing the portion that cannot be applied to the fiber because it is destroyed by heat during the processing of the fiber, the polymer microcapsule containing the functional substance applied to the fiber is heated and frictioned due to its structural stability. Since the functional substance contained therein at a time even if damage is applied to the capsule by a stimulus such as washing is not released, functional fiber having a stable sustained release is produced.

Description

  The present invention relates to a polymer microcapsule containing a functional substance and a method for producing the same, and more specifically, a large number of microcapsules inside a polymer microcapsule having a size accommodated in a binder layer applied to a fiber. The inner capsule is distributed, the fine inner capsule contains various synthetic and natural functional substances, and the thickness of the outermost shell is added in the amount of the crosslinking agent in the manufacturing process of such a polymer microcapsule. Breakage of polymer capsules during fiber processing by providing fine capsules with many core-shell structure increased using changes in monomer amount, initiator amount, reaction temperature and reaction time The present invention relates to a fine capsule containing a functional substance that suppresses as much as possible and maintains functionality for a long time when applied to a fiber, and a method for producing the same.

  Until now, functional processing of textile products has been performed by mixing functional materials with the adhesive on the surface of the fiber and applying them to the microcapsules. The treatment was to volatilize the applied functional material or to develop functionality in the fiber by the release of the functional material due to the collapse of the microcapsules.

  In particular, functional fiber products using microcapsules use a microcapsule larger than the binder layer having a thickness of 1 to 3 μm as a functional substance carrier, which impairs the durability of capsules such as friction and washing. The microcapsules are easily disintegrated due to various factors, and the structure of the manufactured microcapsules is a single wall structure, so that the functional substance contained therein is released at once and rapidly. Therefore, there is a disadvantage that the period of providing functionality becomes very short.

  Examples of related research include a method in which a functional composition is made into a mixed emulsion of a fragrance and a binder and added to a carpet to give a fragrance function (Korea Patent Registration No. 10-0110057), acrylic resin or A method for producing an aromatic fiber material by adding a fragrance to a microcapsule made of urethane resin and coating the fiber fabric together with a binder resin (Korea Patent Application No. 10-2000-0086197), synthetic insect repellent Is then emulsified and then incorporated into microcapsules using a polymer condensation reaction, and then mixed with a binder and sprayed onto a fiber fabric to thermally fix it (Korea Patent Application No. 10-2002-0079616), etc. Is mentioned.

  The microcapsules manufactured in the above research have a size exceeding 1 to 3 μm which is the thickness of a normal fiber binder coating layer, and the functional substance in the microcapsule is contained in a capsule having a single-wall structure. Because of its structure, when the capsule breaks or is damaged due to physical damage such as heat, friction, and washing during processing, the internal substance is released at once and the duration of the functional substance Is extremely short, and there is a drawback that it is insufficient for use in the production of functional fiber products in which the duration and durability of functional materials are required to be at least 2 years.

  Moreover, the fact that the thickness of the outermost wall of the polymer particles containing the functional substance produced by the existing method cannot be adjusted appropriately enough to have sufficient durability also causes the above-mentioned durability problem. It has been pointed out as the cause.

  In the present invention, the functional substance contained in the capsule is abruptly released due to damage and collapse of the polymer capsule caused by various causes such as heat, friction and washing, which have been pointed out as conventional problems. In order to prevent this, polymer fine capsules of a size that can be accommodated inside the binder layer applied to the fiber are prepared. The object is to produce polymer microcapsules contained in each microcapsule.

  In addition, the thickness of the outermost wall of the manufactured polymer microcapsules is increased by using the change in manufacturing conditions such as the amount of crosslinking agent added, reaction temperature and reaction time, excellent thermal stability, durability, Another object is to produce polymer microcapsules having sustained release properties.

  The feature of the present invention for solving the above-mentioned problems is that a process for producing an aqueous solution by dissolving 0.2 to 3.0% by weight of an emulsifier in 70 to 89% by weight of distilled water based on the total weight, A process for producing a monomer solution by adding and mixing 5 to 30% by weight of a body, 5 to 40% by weight of a functional substance, 0.1 to 5% by weight of a crosslinking agent and 0.1 to 5% by weight of a coemulsifier And mixing the aqueous solution and the monomer solution and then mixing for 1 to 30 minutes using a homogenizer or an ultrasonic crusher to form micelles, and radical initiation in the mixed solution in which the micelles are formed And mixing the agent at a weight ratio of 98-99.9: 0.1-2.0, followed by stirring at 200-1000 rpm for 1-10 hours at 10-85 ° C. The present invention relates to a method for producing a polymer microcapsule containing an active substance.

  In addition, another feature of the present invention is that a large number of fine inner capsules are distributed in the polymer fine capsules manufactured by the manufacturing method, and a functional substance is contained in the inner capsules. The polymer microcapsule is in a polymer microcapsule containing a functional material having a dimension that is inserted into a binder layer applied to the fiber.

  Furthermore, still another feature of the present invention is that a functional fiber coating agent in which the polymer microcapsules and a water-soluble acrylic binder are mixed at a volume ratio of 1: 9 to 5: 5 and water in the polymer microcapsule solution. In the processing agent for fibers produced by mixing and dispersing with an organic solvent at a volume ratio of 1: 9 to 6: 4.

  In the present invention having the above-described features, since the fine inner capsule containing the functional additive is distributed inside the polymer fine capsule having a size accommodated in the binder layer applied to the fiber, heat, Excellent durability against various irritation and destruction factors such as friction and washing, and because of the structural stability, the polymer fine capsule and the fine inner capsule are gradually broken or broken, It has the effect that the duration of the functional substance contained in is stably increased.

  In addition, the thickness of the outermost wall of the prepared polymer microcapsules is increased by using changes in the amount of cross-linking agent, reaction temperature, reaction time, etc., so as to have improved durability, compared with existing microcapsules. In addition to having excellent thermal stability and durability, it is also possible to adjust the release rate and duration of the contained substances.

  Furthermore, since the polymer microcapsules according to the present invention can be applied to various fiber binders and organic solvents, they can be easily applied to various textile manufacturing processes. Therefore, there is an effect that various functional fiber fabrics having excellent durability and functional duration can be manufactured.

FIG. 1 is a diagram comparing a polymer microcapsule manufactured in the present invention with a previously reported polymer capsule. FIG. 2 is a diagram showing a manufacturing process of a polymer microcapsule according to the present invention. FIG. 3 is an electron micrograph of the polymer microcapsules produced in Example 1. FIG. 4 is an electron micrograph of the polymer microcapsules produced in Example 2. FIG. 5 is an electron micrograph of the polymer microcapsules produced in Example 3. FIG. 6 is an electron micrograph showing a difference between Example 1 and Example 5 in which the thickness of the outermost wall of the polymer microcapsule was increased. FIG. 7 is an electron micrograph of the polymer microcapsules produced in Example 5. FIG. 8 is a particle size analysis diagram showing the average dimensions of the polymer microcapsules produced in Example 6. FIG. 9 is a particle size analysis diagram showing the average dimensions of the polymer microcapsules produced in Example 7. FIG. 10 is a photograph of a coating agent for fibers in which the water-soluble acrylic binder and polymer microcapsules produced in Example 8 were mixed. FIG. 11 is a photograph showing polymer microcapsule solutions dispersed in a dimethylformamide (DMF) solvent among the fiber processing agents dispersed in various organic solvents produced in Example 9. is there. FIG. 12 is an electron microscope showing an adhesive layer of a fabric applied after mixing the functional polymer fine capsules having excellent thermal stability and high durability produced in Example 8 with a water-soluble acrylic binder, and the application state. It is a photograph. FIG. 13 is a photograph showing that methanol was added and precipitated in order to separate and collect the polymer microcapsules produced in the present invention from water. FIG. 14 is a photograph showing salting out by adding a saturated aqueous sodium chloride solution in order to separate and recover the polymer microcapsules produced in the present invention from water.

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

  As shown in FIG. 1, the polymer microcapsule containing the functional substance according to the present invention has various synthetic and natural functions inside the polymer microcapsule having a size accommodated in the binder layer applied to the fiber. The polymer fine capsule has a Manny core-shell structure in which a large number of fine inner capsules containing the active substance are distributed, and the thickness of the outermost wall of the polymer fine capsule is adjusted to improve the durability of the produced polymer fine capsule. The polymer fine capsules thus produced are mixed and dispersed in various water-soluble binders and organic solvents and applied to the fibers. At this time, the polymer fine capsule has a diameter of 50 to 500 nm.

  Also, the method for producing the polymer fine capsule will be described. As shown in FIG. 2, an aqueous solution in which 50 to 86% by weight of water and 0.2 to 3% by weight of a water-soluble surfactant are dissolved based on the total weight. Manufacturing process of aqueous solution to produce a monomer, 5 to 20% by weight of monomer, 5 to 40% by weight of functional material, 0.1 to 5% by weight of cross-linking agent and 0.1 to 5% by weight of coemulsifier based on the total weight % Of the monomer solution, the process of mixing the aqueous solution and the monomer solution to form micelles, and the mixed solution in which the micelles are formed is radical based on the total weight in a nitrogen atmosphere. A polymer capsule is manufactured using a method including a step of polymerizing by adding 0.1 to 3 wt% of an initiator.

  In this process, in order to adjust the wall thickness of the outermost shell, the reaction is performed at a reaction temperature of 60 ° C. to 95 ° C. while adding a crosslinking agent at 0.2 to 5% by weight. The reaction time is 2 hours to 10 hours.

  The polymer fine capsules thus produced are mixed with an acrylic binder to produce a fiber coating agent, which is applied to the fiber and heat treated (100-300 ° C.) to form a functional fiber coating layer. The functional fiber product which has is manufactured.

  Alternatively, the polymer fine capsule solution is removed by removing the water by decompression, or recovered by precipitation or salting out by adding methanol or various salts, and then drying and dispersing in an organic solvent. A coating agent for fibers is produced. Also, a functional fiber product having a functional fiber coating agent layer is produced by applying the fiber coating agent to the fiber and heat-treating it.

  In the above, the organic solvent is any one selected from the group consisting of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), methyl ethyl ketone (MEK), methanol, ethanol, isopropyl alcohol, and tetrahydrofuran (THF).

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

Example 1: Production of phytoncide-containing polymer fine capsules A round bottom flask was charged with 80 ml of distilled water and 0.2 to 3.0 g of sodium dodecyl sulfate (SDS) as an emulsifier, and dissolved at room temperature to obtain an aqueous solution (aqueous system). ) Was manufactured.

  Also, 5 to 20 g of styrene monomer, 5 to 30 g of phytoncide oil, 0.1 to 2.0 g of divinylbenzene (DVB) as a crosslinking agent, and 0.1 of n-hexadecane (n-HD) as a co-emulsifier. ˜3.0 g was added and stirred to prepare a functional substance-containing monomer solution (oil system).

Next, the emulsifier aqueous solution and the monomer solution thus prepared were all mixed at room temperature, and then treated with a homogenizer at 8000 to 24000 rpm for 1 to 30 minutes to form an emulsified mixed liquid in which micelles were formed. Manufactured.

  Next, 98 g to 99.9 g of the emulsified mixed solution in which micelles are formed in a reaction tank provided with a mechanical stirrer, a condenser, a constant temperature device, and a nitrogen injection device, and azobisisobutyronitrile as a radical initiator (AIBN) 0.1-2.0 g was charged and stirred at 300-1000 rpm for 1-10 hours at 20-60 ° C., and as shown in FIG. A phytoncide-containing polymer fine capsule having a thickness was produced.

Example 2 Production of Citronella Oil-Containing Polymer Microcapsules A round bottom flask was charged with 80 ml of distilled water and 0.1-3.0 g of sodium dodecylbenzenesulfonate (SDBS) as an emulsifier, and dissolved at room temperature. An aqueous emulsifier solution was prepared.

  Moreover, 5-30 g of citronella oil, 0.1-1.0 g of divinylbenzene (DVB) as a crosslinking agent and 0.1-5.0 g of cetyl alcohol as a co-emulsifier are added to 10-30 g of styrene monomer. After mixing, the mixture was stirred to produce a citronella oil-containing monomer solution.

Subsequently, after mixing all the said emulsifier aqueous solution and monomer solution at normal temperature, it processed for 1 to 30 minutes using the ultrasonic crusher, and manufactured the emulsion liquid mixture in which the micelle was formed.

  Next, 97 to 99.9 g of the mixture in which micelles were formed in a reaction vessel provided with a mechanical stirrer, a condenser, a thermostatic device and a nitrogen injecting device, and potassium persulfate (KPS) as a radical initiator in an amount of 0. Citronella oil containing particles having a uniform particle size of 300 to 500 nm as shown in FIG. 4 after being charged with 1 to 3.0 g and stirred at 200 to 1000 rpm for 1 to 10 hours at 50 to 80 ° C. Polymer fine capsules were produced.

Example 3 Production of Jasmine Oil-Containing Polymer Microcapsules Polymer microcapsules were produced in the same manner as in Example 1 except that 5-30 g of jasmine oil was used instead of phytoncide. The produced polymer microcapsules have a particle size of 200 to 400 nm and a uniform distribution as shown in FIG.

Example 4: Production of polymer microcapsules with increased outermost wall thickness of particles Under the same conditions as in Example 1, the amount of divinylbenzene (DVB) as a cross-linking agent was 3.0-5. Polymer fine capsules were produced in the same manner as in Example 1 except that 0 g was increased, the reaction temperature was raised to 85 ° C., and the reaction time was 2 to 10 hours. As shown in FIG. 6, it was confirmed by an electron micrograph that the outermost wall of the manufactured polymer microcapsule was thicker than that of Example 1.

Example 5: Production of phytoncide-containing polymer microcapsules Polymer microcapsules were produced in the same manner as in Example 1 except that an acrylic monomer was used instead of the styrene monomer of Example 1. did. The produced polymer fine capsules had a particle size of 50 to 200 nm as shown in FIG.

Example 6: Production of permethrin-containing polymer microcapsules A polymer was prepared in the same manner as in Example 1 except that 10 to 40 g of permethrin, a synthetic freslin insecticide, was added under the same conditions as in Example 1. Fine capsules were produced. When the average particle diameter of the manufactured polymer fine capsule was confirmed using a particle size analyzer, it was 200 to 300 nm as shown in FIG.

Example 7: Production of cypermethrin-containing polymer microcapsules Under the same conditions as in Example 2, 5-30 g of cypermethrin, which is a synthetic freslin insecticide, was added, and polymer was prepared in the same manner as in Example 2. Fine capsules were produced. The average particle size of the produced polymer fine capsules was 200 to 300 nm as shown in FIG.

Example 8: Production of polymer microcapsule solution mixed with water-soluble acrylic binder The phytoncide-containing polymer microcapsules produced in Example 4 were mixed with a water-soluble acrylic binder in a volume ratio of 1: 9 to 5: 5. Then, as shown in FIG. 10, a functional fiber coating agent having excellent thermal stability and high durability was produced.

Example 9: Production of a processing agent for fibers in which polymer fine capsules are dispersed in an organic solvent Polymer fine capsules produced in the same manner as in Example 1 described above were prepared in a volume ratio of 1: 9 to 6: In order to produce a processing agent for fibers by mixing and dispersing in 4, the water in the polymer microcapsule solution is a vacuum concentrator, a vacuum concentration device using a vacuum pump, a freeze-drying device, a centrifuge, etc. After the water was completely removed, the fiber processing agent was prepared by dispersing in various organic solvents. Examples of the organic solvent include dimethylformamide (DMF), methyl ethyl ketone (MEK), Examples thereof include dimethyl sulfoxide (DMSO).

  Of the fiber processing agents produced in Example 9, a photograph of the fiber processing agent in a state in which polymer fine capsules are dispersed in dimethylformamide (DMF) is shown in FIG.

Example 10: Production of a functional fiber to which the fiber processing agent produced in Example 8 was applied The fiber coating agent produced in Example 8 was applied to a polyester / cotton blend fabric with a thickness of about 3 μm. And after spraying and applying at a speed of 300 to 800 rpm, it was dried with hot air at 100 to 300 ° C. to form a binder layer coated with functional polymer fine capsules on the fabric.

  FIG. 12 shows a photograph of the fiber coated with the functional polymer microcapsules obtained in this way, obtained using an electron microscope.

  As shown in FIG. 12, the binder layer in the fiber coated with the functional fiber coating agent obtained in Example 8 formed a uniform coated surface where the functional polymer microcapsules were not exposed.

Example 11: Comparison of pick-up rates for comparing the difference in thermal stability due to the difference in the thickness of the outermost wall of the polymer microcapsules The polymer microcapsules produced in Example 1 and Example 4 were respectively used for fibers. After mixing with a binder, it was applied to cotton and dried with hot air at 100 to 300 ° C. Next, when the weight of the dried cotton was measured and a comparative experiment of thermal stability according to the pickup rate was performed, as shown in Table 1, the polymer microcapsules according to Example 4 having a thick outermost wall were mixed. The pickup rate of the applied coating agent for fibers shows a value 41% higher than that of the coating agent for fibers mixed with the polymer fine capsules according to Example 1 in which the outermost wall is thin.

Example 12: Method of adding methanol to polymer microcapsules and precipitating, then filtering and drying to disperse in an organic solvent Various amounts of the polymer microcapsule solutions prepared in Examples 1 and 4 After methanol was added and precipitated, this was recovered by filtration under reduced pressure. Next, this was dried to produce powdery polymer microcapsules from which methanol had been removed, and then dispersed in various organic solvents such as dimethylformamide (DMF) to disperse the polymer microparticles dispersed on the organic solvent. A capsule solution was produced. A photograph of the polymer microcapsules precipitated in methanol is shown in FIG.

Example 13: Method of adding salt aqueous solution to polymer fine capsule, recovering by salting-out treatment and filtration, drying and dispersing in organic solvent Polymer fine capsule produced in Example 1 and Example 4 Polymer fine capsules produced by adding aqueous solutions in which various salts such as sodium chloride and magnesium sulfate were dissolved to the solution were salted out, and then recovered by filtration under reduced pressure. Next, this was dried to produce a powdery polymer microcapsule, and then dimethylformamide (DMF), dimethylsulfoxide (DMSO), methyl ethyl ketone (MEK), methanol, ethanol, isopropyl alcohol, tetrahydrofuran (THF) A polymer microcapsule solution loaded with phytoncide in a state of being dispersed in any one, preferably dimethylformamide (DMF) and dispersed on an organic solvent, was prepared. A photograph of the salted out polymer microcapsules is shown in FIG.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims of the present invention, and these are also within the scope of the right of the present invention. It goes without saying that.

Claims (7)

A process of producing an aqueous emulsifier solution by dissolving 0.2 to 3.0% by weight of an emulsifier in 70 to 89% by weight of distilled water;
Monomer solution is prepared by adding and mixing 5 to 30% by weight of monomer, 5 to 40% by weight of functional substance, 0.1 to 5% by weight of crosslinking agent and 0.1 to 5% by weight of coemulsifier. The process of
After mixing the aqueous emulsifier solution and the monomer solution, a process of forming micelles by homogenizing for 1 to 30 minutes using a homogenizer or an ultrasonic crusher;
A radical initiator is mixed in a weight ratio of 98 to 99.9: 0.1 to 2.0 with the mixed solution in which the micelles are formed, and then stirred at 10 to 85 ° C. for 1 to 10 hours at 200 to 1000 rpm. Process,
The manufacturing method of the polymer microcapsule containing the functional substance characterized by including this.   The thickness of the outermost shell of the polymer microcapsule is adjusted by adding the cross-linking agent at 0.2 to 5% by weight at a reaction temperature of 60 to 85 ° C. and a reaction time of 2 to 10 hours. The manufacturing method of the polymer microcapsule containing the functional substance of Claim 1 characterized by the above-mentioned.   A large number of fine inner capsules are distributed in the polymer fine capsule, the functional substance is contained in the fine inner capsule, and the polymer fine capsule includes a functional substance having a size of 50 to 500 nm. Polymer fine capsule.   A functional fiber coating agent, wherein the polymer microcapsules and the water-soluble acrylic binder according to claim 3 are mixed in a volume ratio of 1: 9 to 5: 5.   It removes the water in the polymer fine capsule solution manufactured by the manufacturing method of Claim 1, and mixes and disperse | distributes with an organic solvent by volume ratio 1: 9-6: 4, It is characterized by the above-mentioned. A processing agent for fibers.   After adding methanol to the polymer microcapsule solution produced by the production method according to claim 1 and precipitating it, this is recovered by filtration under reduced pressure, and dried to obtain a powdery form from which methanol has been removed. A processing agent for fibers, which is produced by producing polymer fine capsules and then dispersing the mixture in an organic solvent at a volume ratio of 1: 9 to 6: 4. An aqueous solution in which any one salt selected from the group consisting of sodium chloride and magnesium sulfate is added to the polymer microcapsule solution produced by the production method according to claim 1 to salt out the polymer microcapsules. Thereafter, this is recovered by filtration under reduced pressure, and dried to produce powdery polymer microcapsules, which are then dispersed in an organic solvent at a volume ratio of 1: 9 to 6: 4. Characteristic processing agent for fibers.

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