JPH0931858A - Adhesion of hinokitiol to fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for fixing hinokitiol to fibers, enabling the wide utilization of antimicrobial cellulosic fibers by strongly fixing the hinokitiol to the cellulosic fibers and facilitating post-processing treatments. SOLUTION: A cellulose reaction type N-methylol urea resin or urethane resin, or a silk protein produced by hydrolyzing silk under a high pressure is mixed with hinokitiol microcapsules or hinokitiol-adsorbed ceramic fine particles. Cellulosic fibers are immersed in the produced dispersion of the microcapsules or ceramic fine particles, squeezed in a dehydration rate of 60-100%, and subsequently thermally dried to fix the hinokitiol microcapsules or the hinokitiol-adsorbed ceramic fine particles to the cellulose fibers. The hinokitiol-adsorbed cellulose fibers are useful for rhinitis, etc., appearing as the syndromes of pollinosis, when used as a mask, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for fixing hinokitiol to fibers, and more particularly to a method for fixing hinokitiol to cellulosic fibers.

[0002]

2. Description of the Related Art Hinoki thiol, a natural compound contained in the essential oil of Taiwan cypress, has long been known to have antibacterial and antifungal and deodorant effects. Has been used for. Conventionally, for example, JP-A-2-307913 is known as a method for using hinokitiol as an antibacterial fiber.

According to this method, a resin containing an ethylene-vinyl acetate copolymer as a main component and a thermoplastic resin are composite-spun, and the spinning raw yarn or drawn yarn is dipped in a vegetable oil in which hinokitiol is dissolved to prepare a solution. Is absorbed by an ethylene-vinyl acetate copolymer. That is, this manufacturing method is
Utilizing the property that ethylene-vinyl acetate copolymer absorbs a large amount of vegetable oils and the property that hinokitiol dissolves in vegetable oils to some extent, hinokitiol is added to ethylene-vinyl acetate copolymer together with vegetable oils. By absorbing and holding the fiber, the fiber has an antibacterial effect.

[0004]

However, the above-mentioned conventional method for producing antibacterial fiber has the property that the ethylene-vinyl acetate copolymer absorbs a large amount of vegetable oils and takes in oil into the fiber. Even if you try to use this method for cellulosic fibers, because the cellulosic fibers originally do not absorb vegetable oils, oil adheres to the fiber surface and becomes sticky. There was a problem that it could not be processed.

Therefore, the present invention provides a fiber fixing method which strongly fixes hinokitiol to cellulosic fibers and enables processing after fixing.

[0006]

Means for Solving the Problems That is, the method for fixing hinokitiol to a fiber according to the present invention is a method in which hinokitiol is added to a fibrin-reactive N-methylol urea resin or urethane resin or a protein substance obtained by hydrolyzing silk under high pressure. Microcapsules or ceramic fine particles adsorbing hinokitiol are mixed to form a dispersion liquid of microcapsules or ceramic fine particles. Cellulosic fibers are immersed in this dispersion liquid, then squeezed to a dehydration rate of 60 to 100%, and dried. This is characterized in that microcapsules of hinokitiol or ceramic fine particles adsorbing hinokitiol are fixed to cellulosic fibers by heating.

In the present invention, hinokitiol, which has no affinity for cellulosic fibers, is microencapsulated with an emulsifier, or hinokitiol is adsorbed on porous ceramic fine particles, and this is used as a fiber-reactive N-methylolurea resin solution or This is to uniformly disperse in a urethane resin solution or silk protein solution, and to impregnate cellulosic fibers in this dispersion to fix microcapsules or ceramic fine particles of hinokitiol.

Resin and silk protein are fixed to the cellulosic fiber by a chemical reaction, and at the same time, hinokitiol microcapsules or ceramic fine particles are encapsulated in the resin and silk protein. In particular, cellulosic fibers have a high water content and have many voids in the fiber structure. Therefore, not only the above-mentioned chemical reaction between the cellulose fibers and the resin or silk protein, but also the resin or silk protein causes voids in the fiber structure. By entering, it physically adheres to the fiber, and as a result, stronger adhesion of hinokitiol can be obtained.

Hinokitiol C ₁₀ H used in the present invention
₁₂ O ₂ is also called 4-isopropyltropolone and is a natural compound mainly contained in Taiwan cypress wood in the form of a red iron complex salt. It is extracted from the essential oil obtained by steam distillation of Taiwan cypress wood and dissolves well in organic solvents.

When hinokitiol is microencapsulated, various surfactants are used for emulsification, and high molecular surfactants are particularly desirable. Further, as a resin for encapsulating the fine particles of hinokitiol into microcapsules, a formalin polycondensation resin such as a melamine resin or a urea resin is desirable. On the other hand, since hinokitiol is adsorbed by a large number of micropores provided in the ceramic fine particles, the ceramic fine particles need to be porous, but the kind thereof is not limited.

The fibrin-reactive N-methylol urea resin acts as a binder for fixing hinokitiol, which has no affinity for cellulosic fibers, such as glyoxal resin, dimethylol ethylene urea,
3. dimethylol, methylated dimethylol urethane, hexamethylol melamine, dimethylol propylene urea, dimethylol dihydroxyethylene urea, tetramethylol acetylenediurea, Methoxy 5. Dimethyl propylene urea, dimethylol alkyl carbamate, etc. can be used.

In the present invention, a urethane resin can also be used as a binder, for example, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc. are used.

When the hinokitiol microcapsules are dispersed in the above-mentioned fibrin reactive N-methylol urea resin or urethane resin, the dispersibility can be enhanced by using a catalyst such as ammonium chloride.

The silk protein substance can be produced by, for example, using waste eyebrows as a raw material, reacting this with a nonionic surfactant and a proteolytic enzyme, decomposing and removing sericin protein, and further hydrolyzing with an organic acid. it can. When dispersing microcapsules or ceramic fine particles of hinokitiol in the silk protein substance, dispersibility can be enhanced by adding a cationic or nonionic silicone resin.

The cellulosic fibers according to the present invention include:
In addition to natural fibers such as cotton fiber and hemp fiber, chemical fibers such as viscose rayon, cupra rayon and acetate are targeted. Further, although hinokitiol can be fixed directly to the spun filament, hinokitiol can be fixed after the filament is woven into a fabric or nonwoven fabric.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Next, a method for fixing hinokitiol microcapsules to cellulosic fibers will be described. First, hinokitiol is dispersed in an emulsifier and a formalin polycondensation resin to prepare hinokitiol microcapsules. The microcapsules are then placed with water in a resin or silk protein material and mixed to disperse the hinokitiol in the resin or silk protein material. The cellulosic fiber is immersed in the dispersion liquid of the microcapsules thus prepared and immersed for 5 to 10 minutes to impregnate the resin or the silk protein substance. Then, this impregnated fiber is pulled out of the solution and is subjected to a dehydrator to dehydration rate of 60 to 10
Dehydrate to 0%. After dehydration, the fibers are dried at about 80-100 ° C and further heated at 150-160 ° C for about 3 minutes,
The resin or silk protein material reacts and solidifies on the fiber to form a resin layer or silk protein material layer on the surface of the fiber. At this time, the hinokitiol microcapsules are tightly fixed to the fiber by being enclosed in the resin layer or the silk protein substance layer in a uniformly dispersed state.

In FIG. 1, a protective layer 2 such as a resin or a silk protein substance is fixed on the surface of a cellulosic fiber 1, and hinokitiol microcapsules 3 are enclosed in the protective layer 2 in a uniformly dispersed state. It shows the situation. FIG. 2 shows the structure of the microcapsule 3 in which the peripheral surface of hinokitiol 4 is wrapped with a film 5 of formalin polycondensation resin.

Next, the chemical formula in the case where the fibrin reactive N-methylol urea resin or urethane resin reacts with the cellulosic fibers is shown below.

[0019]

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[0020]

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[0021]

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[0022]

【Example】

(Example 1) A fiber fixing method of hinokitiol with a fiber-reactive N-methylol urea resin. First, a dispersion liquid of microcapsules is prepared by using a glyoxal resin as the fiber-reactive N-methylol urea resin. The drug for preparation is as follows. Hinokitiol 20% Emulsion 20 g Glyoxal resin 50 g Ammonium chloride 5 g Water 1 l Gauze is immersed in the resin solution prepared in this way and left to cool for 5-10 minutes, and then dehydration rate of 65-65 using a dehydrator or the like. Gauze is dehydrated to 100%, dried at 80 to 100 ° C, and further dried at 150 to 160 ° C for 3 days.
After heat treatment for a minute, the hinokitiol microcapsules were fixed to the gauze.

(Example 2) A method for fixing fibers of hinokitiol with a silk protein material. First, a silk protein material was prepared by the following method. Waste cocoon with nonionic surfactant 1g / l and proteolytic enzyme 5
Oxygen reaction was performed for 60 minutes at g / l, pH 9 to decompose and remove the sericin protein in the waste eyebrows. By this decomposition and removal, the fibrous disintegrated refuse eyebrows are further treated with 0.1 to 5 M organic acid at 70 to 98 ° C for 1 to 3 hours to decompose the acid of the protein and centrifuge the undecomposed residue. Alternatively, it was removed by filtration. Next, 5 g of proteolytic enzyme was added to the supernatant.
/ L was enzymatically reacted at pH 7 for about 0.2 hours, and the decomposed solution was purified by ultrafiltration to obtain a silk protein substance having a molecular weight of about 10,000.

When hinokitiol is fixed using the silk protein material, a microcapsule dispersion is first prepared using the following chemicals, and 5 gauze is added to the dispersion.
After soaking for 10 minutes, squeezing to a dehydration rate of 60 to 100%, drying and steaming at 120 ° C. Silk protein material 30-50g Hinokitiol microcapsules 20g Cationic silicone agent 2-5g Water 1l

When the gauze obtained in Examples 1 and 2 above is viewed under an electron microscope, a protective layer of resin or silk protein substance is formed on the surface of each fiber constituting the gauze as shown in FIG. And the protective layer is formed in the gap between the adjacent fibers. Then, the microcapsules are held in a state of being enclosed in these protective layers. Even if the microcapsules are trapped in resin or the like, the scent of hinokitiol is still present, but by rubbing this gauze by hand, a stronger scent is emitted. This is because the film of the microcapsules enclosing hinokitiol is broken and hinokitiol is exposed.

In the above-mentioned embodiment, the hinokitiol microcapsules are fixed to the fibers, but the ceramic fine particles to which the hinokitiol is adsorbed can also be fixed to the fibers by the same means as in the first and second embodiments.

Next, use of the cellulosic fibers to which the hinokitiol is fixed will be described. The present inventor has discovered that rhinitis, which is a symptom of hay fever, can be effectively prevented when the fiber is used as a mask. For example, just by impregnating hinokitiol into gauze (the entire mask or the part that directly contacts the mouth), rhinitis can be reduced,
The onset of rhinitis can be effectively prevented. Further, not limited to gauze, non-woven fabric or filter paper may be impregnated with hinokitiol and then sandwiched between gauze masks that are overlapped with each other to exert the rhinitis effect of hinokitiol. When the scent becomes light, hinokitiol breaks the film and gives a new scent just by rubbing the gauze, so it can be used for washing and repeated use.

[0026]

As described above, according to the method for fixing hinokitiol fiber according to the present invention, hinokitiol can be firmly fixed to the cellulosic fiber and can be repeatedly used by washing and the like. Since, when hinokitiol is fixed, oil or the like does not adhere to the fiber surface, there is an effect that various post-processing can be performed. Therefore, the cellulosic antibacterial fiber can be widely applied, and when it is used in a mask or the like, it has an effect of effectively acting on rhinitis or the like which is a symptom of pollinosis.

[Brief description of drawings]

FIG. 1 is an enlarged cross-sectional view showing a state in which hinokitiol is fixed on the surface of a fiber.

FIG. 2 is an enlarged sectional view showing hinokitiol microcapsules.

[Explanation of symbols]

 1 Cellulose Fiber 2 Protective Layer 3 Micro Capsule 4 Hinokitiol 5 Film

Claims (1)

[Claims] 1. A hinokitiol microcapsule or ceramic fine particles adsorbing hinokitiol are mixed with a fibrin-reactive N-methylolurea resin or urethane resin, or a silk protein substance obtained by hydrolyzing silk under high pressure, and mixed with microparticles. As a dispersion liquid of capsules or ceramic fine particles, cellulosic fibers are soaked in the dispersion liquid, squeezed to a dehydration rate of 60 to 100%, dried and heated, and microcapsules of hinokitiol or ceramic fine particles having hinokitiol adsorbed thereto are treated with cellulose. A method for fixing hinokitiol fiber, which is characterized in that it is fixed to a base fiber.