JPH07268772A - Hollow fiber containing drug - Google Patents

Abstract

PURPOSE:To produce a chemical-containing hollow fiber excellent in durability by immersing a hollow fiber having a specified fineness, a specified strength, etc., in a solution containing a perfume, an antibacterial agent, an antifungal agent, etc. CONSTITUTION:This hollow fiber excellent in durability of chemicals and slow release properties of the chemicals is produced by immersing a hollow fiber having 7 to 150mum single yarn fineness, 1 to 7g/denier strength and 3 to 60% percentage of hollowness in a solvent solution containing a perfume, an anti-bacterial and fungal agent, a repellent, an insecticide, an attractant, an electrolyte and a chemical such as a metal, e.g. hinokitiol, respectively dissolved in their corresponding good solvents at room temperature for 24hr and allowing the chemicals to adhere to the hollow fiber so that a great part of the chemicals may stay in the hollow part of the hollow fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a drug-containing hollow fiber in which a drug is gradually released and released.

Such drug-containing hollow fibers are fragrances, antibacterial
It can be used as a fungicide, repellent, insecticide, rodenticide, insecticide, etc.

In particular, since the composition is fibrous and the content of the drug can be increased, it can be used as a woven or knitted fabric, a non-woven fabric or the like, which has a long duration and can be freely shaped.

[0004]

2. Description of the Related Art As fragrances, antibacterial and antifungal agents, repellents, insecticides, rodenticides, insecticides, etc., maintenance-type ones have been commercialized. The most typical method is to encapsulate a drug in microcapsules and attach the drug-encapsulated microcapsules to the surface of the fiber. This method can be applied to many drugs, but since the drug inside is released due to the destruction of the microcapsules, the effect tends to be reduced in a relatively short time after the start of use, more than 5 times. It is difficult to obtain durability that can withstand the washing of
Further, for the same reason, it is general that the microcapsules are attached after the form of the final product is processed, and there are many manufacturing restrictions.

The idea of incorporating the drug into the hollow fibers to measure the sustained release of the drug so that the drug is transdermally absorbed is disclosed in JP-B-3-71406 and JP-B-62-50447.

However, it is essential that the hollow fibers mentioned here have microporous holes in the hollow peripheral wall in the cross-sectional direction of the fibers. That is, the purpose of using such a microporous hollow fiber is to consider that the drug in the hollow fiber can be sustainedly released when it is transdermally absorbed by a human rather than when the drug is simply dispersed in the adhesive layer. It is based.

However, it is difficult for such microporous hollow fibers to gradually release the drug over a long period of time, for example, over several days. In particular, volatile drugs such as liquids readily volatilize through the microporous pores. Further, regardless of whether it is a solid or a liquid, if the drug-containing hollow fiber that is a good solvent for the drug is immersed, the drug will be easily eluted. In particular, if the drug-containing hollow fiber is not coated with a pressure-sensitive adhesive layer having an action of suppressing the release of the drug to some extent or a support made of a film-like material such as a film, the drug is easily eluted. , It is difficult to make one that is stable and sustainable.

An example of putting a drug into such a hollow fiber and gradually releasing it is described in J. Clin. Periodontology 1970, 6 , 83-.
As also shown in 92, the material of the hollow fiber used in this case is also cellulose acetate, and it is well known that this has innumerable micropores in the peripheral wall of the hollow fiber,
Utilizing this property, it is also applied to artificial dialysis.

Further, as in this J. Clin. Periodontology example, when the diameter of the hollow fiber is as large as 200 μm,
It is not difficult to incorporate the drug into the hollow fibers. That is, in the case of a hollow fiber having a large diameter, the liquid can be passed from one cross section of the fiber by, for example, pump pressure. When the diameter of the hollow fiber becomes small, it becomes theoretically extremely difficult to pass the liquid through such a method. The pressure loss when flowing the liquid in the pipe is simply the Fanning equation (1)

[0010]

[Equation 2]

It is well known that it is represented by In this equation, 1 is the length of the pipe, and 1 is the diameter of the pipe. From this equation, it can be seen that the pressure loss Δp is proportional to 1 / D. When flowing liquid through normal piping, for example, the inner diameter is 2.5c
If m and the length is 10 m, then 1 / D = 400. However, in J. Clin. Periodontology, l = 1 m and D = 200 μ (= 0.02 cm). Therefore, 1 / D = 50000. That is, 1 in the normal case
There are 20 times more difficult. Of course, such high pressure pumps are usually not available, so the Fanning formula
The bar (average outflow rate), that is, the outflow rate may be set to 1/10 or less.

However, the inner diameter becomes small, for example, 20 μ
When the fiber is a long fiber and the length is 10 m, 1 / D
= 5 × 10 ⁶ , which proves that the difficulty is much greater.

[0013] In simple terms, no matter how large l / D becomes, if the outflow rate is reduced accordingly, the liquid can be enclosed in the hollow fiber by using the current ordinary pump.

However, in practice, it has been found difficult to adopt such a method for the following reason. In other words, there is a greater risk of pump failure if only the pressure is increased even though almost no liquid is flowing. In order to increase the amount of the liquid as much as possible, when a plurality of hollow fibers are arranged in parallel at the tip of the pump and it is attempted to let the liquid flow out to a plurality of fibers at the same time, the pipe wall may be broken in all the hollow fibers. This shouldn't be the case, but with the thin hollow fibers that are normally available, it's unlikely to be expected. When a liquid is sent from one end to a long hollow fiber for a very long time, the solvent gradually evaporates from the tube wall of the hollow fiber, the composition of the solution changes, and the precipitation of crystals occurs,
After all, the hollow fiber cannot be impregnated with the drug. Hollow fibers of very thin synthetic fibers are generally produced by re-melting a molten polymer discharged from a slit opening divided into 2 to 5, but such a fiber has long fibers. Since there is a defect in the hollow part in the part and the liquid leaks from this part, the whole cannot be impregnated with the liquid.

In other words, filling a relatively short hollow fiber having a large inner diameter with a chemical solution is advantageous in terms of pressure for liquid delivery.
It is also possible in terms of making hollow fibers with almost no defects.

However, when the diameter is small and the fibers are long fibers, it becomes extremely difficult from the viewpoint of pressure and the surface of forming hollow fibers, that is, the method of J. Clin. Periodontology is difficult and a special device is used. Is required. Moreover, J. C
The fiber obtained by the method of lin. Periodontology is a cellulose acetate fiber, and has a large thickness, so that the flexibility, strength, and sustained release required by the present invention cannot be satisfied.

In the case of Japanese Examined Patent Publication No. 3-71406, etc., since the through-holes that escape from the hollow portion of the hollow fiber to the outside are provided in the cross-sectional direction of the fiber, it is necessary to put the drug in the hollow portion of the hollow fiber.
It is easy because there is no need to insert it from the end face. However, at the same time, such a drug is likely to elute the drug in the hollow fiber, and the drug containing the drug in the hollow fiber is most of the drug easily eluted in the solvent when immersed in a good solvent for the drug, In the same manner as this, the drug is easily released even by washing or the like, so that the sustained drug-containing hollow fiber intended by the present invention cannot be obtained.

Due to these difficulties, a thin, long, hollow fiber having no through hole and containing a drug is a conjugate fiber having a so-called sheath-core structure which is co-extruded during the production of the hollow fiber. Most are manufactured as.

However, in such a conjugate fiber, it goes without saying that the drug filled inside the hollow fiber also
Since the same heat resistance as the material forming the hollow fiber is required, its application range is extremely limited. Moreover, in most cases, the drug contained in the hollow portion is not a polymer having so-called thread-forming property, and when the volume of the hollow portion becomes large, it becomes difficult to manufacture even by such a conjugate spinning method. Rather, it can be said that only a limited number of products can be obtained by conjugate spinning.

For this reason, the hollow fiber is thin and long, and has no through holes in the outer peripheral direction, and has a relatively large hollow ratio. For a fiber in which various drugs are contained in the hollow part of the hollow fiber by producing a hollow fiber which does not sufficiently contain, and then treating with the drug,
At present, it has hardly been commercialized, and little is known about its performance or the performance that such a drug-containing hollow fiber should have in order to maintain a sustained effect.

[0021]

Means for Solving the Problems That is, the present invention is a hollow fiber in which the thickness of a single yarn is 7 to 150 μm, the strength is 1 to 7 g / denier, and the hollow ratio is 3 to 60%. The drug is contained in a liquid or / and solid form by post-treatment of the fiber, and most of the drug is contained even when the drug-containing hollow fiber is immersed in a good solvent for the drug at room temperature for 24 hours. A drug-containing hollow fiber having solvent resistance so that it remains in the hollow portion of the hollow fiber.

According to the present invention, a drug is gradually released and released, and a fragrance, an antibacterial / antifungal agent, a repellent, an insecticide, a rodenticide,
We have conducted extensive studies to develop a highly safe industrial fiber material that can be used as an insect attractant, etc., and has good handleability. As a result, the stability of the drug in the textile products, that is, the stability of washing resistance, abrasion resistance, weather resistance, etc., the safety of drug such as skin irritation, the sustainability and the effective release amount of the drug It was concluded that it is best to allow the drug to be contained inside the hollow fiber, that is, the hollow part, from the viewpoints of the amount retained, the variety of product shapes, and the aesthetics.

In addition, a wide variety of drugs ranging from liquid drugs having a low boiling point and a problem of thermal stability to inorganic substances having a high boiling point, particularly, drugs containing many complex compounds having special medicinal effects are used for textile products. There are many problems with such methods as the conjugate spinning method, which is carried out in the hollow fiber spinning process that requires a large-scale device and strict condition control in order to quickly and reliably meet the needs of It was found that a method of producing a hollow fiber and incorporating a drug into this hollow fiber is preferable. The hollow fibers required here preferably have a single yarn thickness of 7 to 150 μm. Fiber thickness is 1
If it is 50 μm or more, the flexibility of the fiber is lacking, so that the use as a fiber is significantly limited. Further, the content of the drug to be contained becomes unnecessarily large. Decreasing the hollowness of the fibers to reduce this content increases the wall thickness of the hollow fiber tube, which results in an undesirably slow release of the drug. That is, the release of the drug in this case means that the drug diffuses and moves in the material of the hollow fiber, passes through the tube wall, and is released.

Further, in such a thick hollow fiber, if the hollow ratio of the hollow fiber is kept high and the amount of the drug to be put in the hollow portion is reduced, as a result, the drug can be dispersed almost uniformly in the hollow fiber. It becomes difficult and thus the properties of the obtained drug-containing hollow fiber are also unfavorable.

Further, if the thickness of the single yarn is less than 7 μm, it becomes difficult to obtain a hollow rate for containing a sufficient amount of the drug.

Further, the single yarn is easily cut during the production or use, and as a result, the release of the drug becomes unstable. That is, when the single yarn is cut, the drug leaks from the cut surface and the releasability increases.

Therefore, in consideration of flexibility as a fiber, appropriate drug holding property and drug releasing property, the preferable fiber thickness is 7 to 150 μm, and more preferable thickness is 10 to 100 μm. Furthermore, as a material containing a drug and having excellent moldability, 10 to 60 μ is particularly preferable.
m.

The strength and elongation of the hollow fiber are also important. That is, the fiber has a strength of 1 to 7 g / denier and an elongation of 10
300% is preferable. Hollow fibers tend to have lower strength than ordinary fibers. For example, for hollow cellulosic fibers used for artificial kidneys, the strength is often less than 1 g / denier.

However, with such a low strength fiber,
Applications are significantly limited. In addition, there are inconveniences in the operation of incorporating the drug. In the case of the drug-containing hollow fiber of the present invention, if the fiber is cut during use, it may cause a significant hindrance to the retention and release properties of the drug, and the importance of the problem due to the strength becoming too weak is important. large. The same applies to the elongation, and when the elongation is low at less than 10%, the yarn is likely to break during handling.

Therefore, the preferred strength is 1 to 7 g / denier and the elongation is 10 to 300%.

The hollow ratio of the hollow fiber is related to the thickness of the single yarn of the hollow fiber, and is related to the amount of drug held, the drug release property, the stability against yarn cutting, and the stability of the hollow shape during the production of the hollow fiber. It also has to do with sex. A preferable hollow ratio is 3 to 60%.

However, in order for the drug-containing hollow fiber of the present invention to be sufficient, and to have the necessary drug holding property and sustained release property, the average hollow ratio (Rh) of such hollow fibers and the average of the tube wall are required. It is preferable that the thickness (t) simultaneously satisfies the following equations (2), (3), and (4).

[0033]

[Equation 3]

Where D is the average diameter of the hollow fibers (μ
m) t is the average thickness of the hollow fiber tube wall (μm) Rh is expressed in%, where the hollow fiber tube wall is the difference between the outer radius and the inner radius when the cross section of the hollow fiber is circular. However, when the cross section is irregular such as a triangle or a star, the average tube wall thickness is shown. The thickness of the tube wall is related to the releasability of the contained drug, and the effect of sustained release decreases as the thickness decreases, so the thickness is preferably 1.5 μm or more.

That is, in order for the drug-containing hollow fiber of the present invention to have a sufficient sustained-release property, it is required that the drug-containing hollow fiber is easily released even when immersed in a good solvent for the drug. I won't. Even if it is immersed in a good solvent for 24 hours, most of the drug must remain in the hollow portion.
To that end, t is greater than or equal to 1.5 μm and the hollow fibers must not be porous in the cross-sectional direction.

Further, when the thickness of the tube wall becomes large, the sustained release property of the drug deteriorates, so the maximum value is 30 μm.

As a material for forming the hollow fiber of the present invention, a known fiber material can be used. In the present invention, the drug is impregnated in a liquid state by a post-treatment or is dissolved in a solvent to impregnate it in a liquid state. It is necessary to have solvent resistance and stability. Polyolefin such as polyethylene and polypropylene, polystyrene, polyester such as polystyrene and polyethylene terephthalate, polyamide such as nylon 6 and nylon 6.6, polyacryl such as polyacrylonitrile. Etc. are particularly preferable.

In the present invention, such hollow fibers are formed into a fabric such as a woven fabric, a knitted fabric or a non-woven fabric by using the hollow fibers alone or in combination with other fibers, and then the hollow portion of the hollow fibers is impregnated with a drug. By doing so, a product that is particularly stable, uniform, and excellent in sustained release can be manufactured at low cost. The fabric weight of such a fabric can be changed up to 5 to 300 g / m ² , depending on the required amount of drug release and the application. In addition, the hollow fiber as a long fiber of 10 m or more wound in a hobbin shape (paper tube or the like), or a thread wound in a ring shape, which is impregnated with a drug in a so-called kaseki- It becomes a hollow long fiber, and by using this as a fabric such as a woven fabric, a knitted fabric, a non-woven fabric, etc. alone or with other fibers, the amount of the drug used and the amount of the drug released by adjusting the amount of the hollow fiber used for the fabric. It is particularly preferable that a product having a new function can be manufactured by a conventional method using a conventional loom or knitting machine in a conventional manner.

That is, one of the purposes of the present invention is to easily produce fiber materials having various functions. In the present invention, firstly, one hollow fiber contains one specific drug. This object can be achieved by using the drug-containing hollow fiber thus prepared.

Secondly, when one specific hollow fiber containing one drug is used, the performance of the resulting fiber product is also limited, but one drug and / or two or more different hollow fibers are used. By combining fibers impregnated with different drug contents, a wider range of performances than those obtained with one can be obtained.

Thirdly, when two or more different drugs are impregnated into one and / or two or more different hollow fibers, a fiber product having two or more functions is obtained. In addition, different drugs can be mixed in one hollow fiber and / or can be separated and present in one hollow fiber as required, so that the degree of freedom can be significantly increased in terms of stability and release of drugs. You can do it.

That is, when impregnating hollow fibers with any drug, it is necessary to devise the impregnation conditions, the washing conditions, the drying conditions, etc., starting with the selection of the solvent. Especially when two or more drugs are used in combination, It is difficult to find common points among drugs, and it is necessary to consider confounding such as a long-term reaction of two or more drugs. However, in the method of the present invention, each drug is used individually and optimally. This is because it is only necessary to produce them under various conditions and mix them as needed when making them into a fiber product, and the diversification of their functions is significantly enhanced. By using a plurality of drug-containing hollow fibers imparting different special functions, rather than simply knitting different yarns, many drawbacks of the conventional techniques can be solved at once, which leads to industrial problems. The range of use can be significantly increased.

Examples of the drug used in the present invention include jasmine, rose, john kill, lavender, muscone, civetone, balsam, bergamot cinnamic aldehyde, vanillin, geraniol, linalool, citronellol, borneol, lavender, β-phenylethyl alcohol, Fragrances such as peppermint, eucalyptus, lemon, N-nonyl aldehyde, citral, cinnamic aldehyde, heliotrobin, lilial, 1-carvone, musk, camphor, yonone, ethylene brushlate, peppermint oil, galaxolide, linalyl acetate; sodium pyrithione, Benzalkonium chloride, benzethonium chloride, povidone iodine, α-bromocinnamaldehyde, alkyldi (aminoethyl) glycine hydrochloride, N,
Such as N-dimethyl-N'-phenyl-N '-(fluorodiomethylthio) sulfamide, clotrimazole, siabendazole, 2,2'-dihydroxy 5,5'-dichlorophenylmethane, hinokitiol, hiba oil Antibacterial and antifungal agents; repellents such as diethyl toluamide; organophosphorus compounds such as diazinon and phennitrothion; pyrethroid compounds such as allethrin and permethrin; carboxmate tricarboxylic isocyanurates such as provoxur and basser; monochloronaphthalene; creosote. , Acaricides such as capsaicin, insecticides, insecticides, rodenticides; pesticides such as pyrethrins, cycloheximide parathion, warfarin, methylbalathione; insecticides such as pheromones; electrolysis such as calcium chloride, magnesium chloride, sodium chloride Inorganic; metals such as mercury; conductive material, such as polyacetylene ethanol, methanol, acetic acid, ethyl acetate, amyl acetate, glycerol, polyethylene glycol, oils, organic substances such as a surfactant,
Examples thereof include water and dyes and pigments. Among these, for example, fragrances such as vanillin, jasmine, geraniol, and 1-menthol; antibacterial and antifungal agents such as sodium pyrithione, benzalkonium chloride, α-bromocinnamaldehyde, hinokitiol; repellents such as diethyltoluamide Can be mentioned as a preferable example.

In the present invention, such a drug is impregnated as it is when the drug is in a liquid state, or as in the case of a solid drug which is not in a liquid state, by dissolving it in a solvent for the drug.

When the drug is dissolved and used, the higher the concentration of the drug in the solvent is, the higher the impregnation amount per time can be. Therefore, the concentration is about 5 to 80%, which is close to the solubility of the drug in the solvent. Is preferably used. Usually its value is 20-6
It is 0%.

However, in the case where the drug is usually used in a solvent such as glycerin (using this solution as a stock solution), for example, a fragrance, the content of the stock solution in another solvent for decreasing the viscosity is 5 to 80. %. It is preferably 20 to 60%.

Further, the viscosity of the drug solution is important for sufficiently impregnating the hollow fiber with the drug solution, and the solvent, temperature and concentration are usually selected so that the solution is 5 centipoise or less. It is preferably 2 centipoise or less. It is particularly preferably 1 centipoise or less. When the viscosity is high, auxiliary means such as ultrahigh pressure, heat, vibration, vacuum, etc. are required to a higher degree.

In the present invention, it is necessary to impregnate the hollow fiber with the drug and / or the drug solution at least 10% or more of the hollow volume. After the impregnation, the hollow fiber is pulled up and the hollow fiber is used as a good solvent for the drug. After washing, the impregnated amount of the drug can be examined by quantifying the drug.

Further, the presence of undissolved drug solids or particulate impurities in the drug solution markedly hinders impregnation, so the solution should be filtered with a 200-mesh wire mesh, or it should be sufficiently filtered. Use a solution with low insoluble matter.

Usually, when a solution is used in the production, a filter made of wire mesh of about 50 mesh may be used for the purpose of protecting a machine such as a pump. Although it is rarely used for filtration, it is important in the present invention, and filtration with a fine filter of 200 mesh or more is preferable.

In the present invention, a drug solution having such a low viscosity is used to impregnate the hollow fiber with the drug by immersing the hollow fiber. Immersion is performed until a certain amount of impregnation is performed, but the effect of impregnation may be enhanced by physical stimulation such as taking out hollow fibers from the solution several times during immersion.
Further, when the heating, pressurization, depressurization, ultrasonic vibration or a combination thereof is used as an auxiliary means, the impregnation becomes easy. Room temperature to 200 ° C for heating, low pressure of 1 mmHg to 2000 kg / cm ^{2 for} pressurization / decompression.
Applicable up to ultra high pressure up to G. The effect can be particularly enhanced by combining these auxiliary means or changing the order.

In the impregnation in the present invention, the viscosity of the solution is important, but the solvent used is also important. Such a solvent is selected in consideration of the solubility of the drug, the viscosity, the wettability with the fiber, the volatility, the economical efficiency, the safety and the like. In particular, wettability with fibers is important. Preferred solvents are ether, methanol, water, carbon disulfide, acetone, ethanol, isopropyl alcohol, acetic acid, ethyl acetate, methylene chloride, hexane, heptane, toluene, benzene, xylene, dimethylformamide, liquefied carbon dioxide gas, etc., It may be a mixture of these.

In particular, ether, acetone, methanol,
Ethanol, propylene glycol and water are preferred. When used at high pressure, liquefied carbon dioxide gas is also suitable because it dissolves organic drugs well. Furthermore, for the purpose of improving the wettability of the solvent,
When a surfactant is used in an amount of 0.1 to 10% with respect to these solvents, impregnation of the drug becomes easy. In addition to these acids and alkalis, sucrose and the like may be added to these liquids in order to change the pH and viscosity.

[0054]

According to the present invention, particularly excellent sustainability,
It is possible to obtain a drug-containing material which is easy to handle and can be formed into various shapes.

The drug-containing hollow fiber of the present invention alone or in combination with other fibers, film, resin or the like, clothes, bedding, ornaments, bags, building materials, civil engineering materials, electric parts,
It can be used as agricultural products, household products, medical products, health / beauty products, etc.

Hereinafter, the present invention will be described in more detail with reference to examples.

The antibacterial and antifungal properties of the present invention mean that bacteria are used for the antibacterial test and antifungal properties are those when fungi are used. According to the antibacterial property test of JIS1902-1990 textile products. I went. However, the fungus is Aspergillus niger
IFO4414 (black mold: A. niger), Penicillium citrinum IFO6026 (blue mold: P. niger)
bacterium, Staphylococcus aureus IAM12082 (Staphylococcus aureus:
S. aureus) was used. The medium used for the test was a potato dextrose agar medium for fungi and a normal agar medium for bacteria.

[0058]

【Example】

[Example 1] Mainly polyethylene terephthalate having an average outer diameter of 22 µm and an average inner diameter of 14 µm.
The average tube wall thickness is 4 μm, and the strength is 3.
A hollow fiber having a length of 1000 m and an elongation of 1% / denier of 33% and an average hollow ratio of about 40% was obtained.

On the other hand, a hinokitiol solution prepared by dissolving 20 parts of hinokitiol (non-Japanese Pharmacopoeia drug) in 80 parts of ethanol was prepared.

10 parts in 50 ml of the hinokitiol solution
After immersing 00 m of the hollow fiber, the hollow part of the hollow fiber was sufficiently impregnated with the hinokitiol solution for 7 days, the hollow fiber was pulled up, and air-dried at room temperature overnight. When hinokitiol in this hollow fiber was extracted with methanol and quantified by HPLC, 61 mg of hinokitiol was contained in 1 g of the hollow fiber.

An antibacterial / antifungal test was carried out on this hinokitiol-containing hollow fiber, and it was effective against both fungi and bacteria.

Also, the hinokitiol-containing hollow fiber had antibacterial and antifungal properties even after being left in running water at room temperature for 1 day.

Even after 1 day in running water, 43 mg of hinokitiol remained in this hollow fiber, and this product was also useful as an aromatic fiber.

Furthermore, 18 mg of hinokitiol remained in the hollow fiber even after being immersed in the ethanol solution for 1 day.

[0065]

[Comparative example]

[Comparative Example 1] A fiber obtained by performing the same test as in Example 1 using a fiber having an average diameter of about 22 µm and mainly made of polyethylene terephthalate had no antibacterial and antifungal properties.

[Comparative Example 2] The average outer diameter obtained by the method of the hollow fiber sample shown in the example of Japanese Examined Patent Publication No. 4-17931 was about 15 μm, the average inner diameter was about 6 μm, and a large number of them were formed on the tube wall. The same test as in Example 1 was carried out using the hollow fiber having the through hole.

When such a hollow fiber was used, the hinokitiol solution filled the hollow portion only by instantaneously immersing it in the hinokitiol solution. Although this product had sufficient antibacterial properties, hinokitiol was rapidly released, and thus it had a strong odor of nasal discharge.

The hinokitiol-containing hollow fiber had almost no residual amount of hinokitiol after immersion in ethanol, and did not show antibacterial or antifungal properties.

[Example 2] The same drug-free hollow fiber as in Example 1 was taken as 1000 m.

On the other hand, 30 parts of l-menthol was dissolved in 70 parts of methanol to prepare an l-menthol solution.

1000 ml in 50 ml of the menthol solution
m of the hollow fiber is soaked, the hollow part of the hollow fiber is sufficiently impregnated with the 1-menthol solution, and then the hollow fiber is pulled up,
Air dried overnight at room temperature.

When 1-menthol in this hollow fiber was extracted with methanol and quantified by the HPLC method, 1 mg of hollow fiber contained 84 mg of 1-menthol.

L from this l-menthol-containing hollow fiber
-The release amount of menthol was sustained release for more than 3 months. This tendency was hardly affected even when this 1-menthol-containing hollow fiber was treated for one day in running water.

[Example 3] Same as that used in Example 1, and having a basis weight of 38 g / m ^{2 made of} hollow fibers containing no drug.
The knitted fabric of 40 cm × 40 cm (about 6 g) was taken.

On the other hand, diethyltoluamide (DEET) 3
A DEET solution was obtained by dissolving 0 part in 70 parts of ethanol. The hollow fiber knitted fabric is dipped in 300 ml of the DEET solution, the hollow fiber is sufficiently impregnated with the DEET solution, the knitted fabric is pulled up from the solution, and the knitted fabric is passed through an ethanol solution containing no DEET to adhere to the surface of the knitted fabric.
After removing the, the cloth was air dried overnight.

On the other hand, add sugar water to a size of 15 cm × 20 cm.
Put it in a dish with a depth of 3 cm, and add this sugar water to a width of 60 c.
It was put in a net made of an insect-proof net of m × length 60 cm × height 50 cm.

Further, a mosquito test device was prepared in which about 1000 mosquitoes (Squid mosquitoes) were placed in this net.

The DEET-containing cloth obtained in this example was covered on the sugar water dish of the mosquito tester to examine how the mosquitoes stayed on the cloth. Also, for comparison, the fabric before being treated with DEET was similarly tested.

As for the DEET-treated cloth, a DEET-treated cloth laundry which was repeatedly washed with warm water at 40 ° C. for 5 minutes 10 times was also tested.

The result is that the degree of stopping of the mosquito on the cloth is DE
The number of ET-treated cloths, DEET-treated cloths, and laundry products was 0, whereas the untreated cloth was 58, and a clear repellent effect was observed.

[Comparative Example 3] The same test as in Example 3 was conducted using the hollow fiber used in Comparative Example 2.

The cloth obtained from the hollow fibers having through holes had a strong DEET odor even after air-drying. However, the mosquito repellent effect was sufficient.

However, after 10 times of washing, the result of the mosquito test device was not significantly different from that of the untreated cloth.

Example 4 Instead of the hollow fiber mainly made of polyethylene terephthalate of Example 1, nylon 6 was used, the average outer diameter was 20 μm, the average inner diameter was 8 μm, and the average tube wall thickness was 6 μm. Thus, a hollow fiber having a strength of 5.1 g / denier, an elongation of 58%, an average hollow ratio of about 16% and a length of about 1000 m was obtained.

When the hollow fibers were impregnated with hinokitiol in the same manner as in Example 1, the hollow fibers 1 were washed before washing.
23 mg of hinokitiol was contained per g.

Also, the hinokitiol content was 16 mg even after 1 day of running water. The hinokitiol-containing hollow fiber had antibacterial and antifungal properties both before and after washing.

[Comparative Example 4] A single yarn has an outer diameter of about 220 µm, an inner diameter of about 60 µm, and an average hollow ratio of about 7%.
The hollow fiber made of polypropylene of Example 1 was impregnated with hinokitiol by the method of Example 1. The hollow fiber obtained by this method did not show antibacterial and antifungal properties even though the fiber contained about 10 mg / g of hinokitiol.

Further, the hollow fiber was rigid and lacked in flexibility.

Example 5 A drug-containing hollow fiber containing 59 mg of vanillin per 1 g of hollow fiber was obtained in the same manner as in Example 1 except that vanillin was used instead of hinokitiol.

The drug-containing hollow fiber (A) obtained in Example 1, the vanillin-containing hollow fiber (B) and the drug-free hollow fiber (C) of this Example were knitted at a ratio of 30: 1: 69. Got the ground. This knitted fabric had a preferable vanillin odor different from that of the cloth of Example 1. At the same time, the fabric had antibacterial properties.

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Claims (19)

[Claims] 1. The single yarn has a thickness of 7 to 150 μm and a strength of 1.
~ 7g / denier, hollow fiber having a hollow ratio of 3 ~ 60%, the hollow portion is made to contain a liquid or / and solid drug by a post-treatment of the hollow fiber, and the drug is a hollow containing the drug. A drug-containing hollow fiber having solvent resistance such that most of the fiber remains in the hollow portion of the hollow fiber even when the fiber is immersed in a good solvent for the drug at room temperature for 24 hours. 2. The drug according to claim 1, wherein the drug comprises one or more drugs selected from perfume, antibacterial / antifungal agent, repellent, insecticide, rodenticide, insect attractant, attractant, electrolyte, metal and the like. Hollow fiber containing drug. 3. The hollow fiber according to claim 1, wherein the drug is hinokitiol. 4. The drug-containing hollow fiber according to claim 1, wherein two or more hollow fibers having different thickness, strength, elongation and hollowness of a single yarn are used in combination. 5. The drug-containing hollow fiber according to claim 1, wherein the drug-containing hollow fiber and a drug-free fiber are used in combination. 6. The drug-containing hollow fiber according to claim 5, wherein the ratio of the drug-containing hollow fiber is 2 to 60%. 7. The drug-containing hollow fiber according to claim 5, wherein the ratio of the drug-containing hollow fiber is 2 to 33%. 8. The drug-containing hollow fiber according to claim 1, wherein two or more hollow fibers having different drug contents are used in combination for the same drug. 9. The drug-containing hollow fiber according to claim 1, wherein two or more drug-containing hollow fibers each containing a different drug are used in combination. 10. The drug-containing hollow fiber according to claim 9, wherein at least one drug-containing hollow fiber is a drug-containing hollow fiber for the purpose of aromaticity, and is additionally used with a drug-containing hollow fiber for the purpose of functions other than aroma. Hollow fiber. 11. The drug-containing hollow fiber according to claim 1, wherein the hollow fiber is a long fiber having a length of 10 m or more. 12. The drug-containing hollow fiber according to claim 1, wherein the hollow fiber is a long fiber having no holes penetrating in the outer peripheral direction. 13. The drug-containing hollow fiber according to claim 1, which is a drug not intended for percutaneous absorption. 14. The hollow fiber has a basis weight of 5 to 300 g.
The drug-containing hollow fiber according to claim 1, which is the whole or a part of the fabric having a diameter of / m ² . 15. When the average hollow ratio (Rh%) of the hollow fibers having an average diameter (D μm) and the average thickness (t μm) of the tube wall are defined, the following (a), (b), (c), (d) 3. The drug-containing hollow fiber according to claim 1, which simultaneously satisfies the conditions of 1). [Equation 1] 16. The method for producing a drug-containing hollow fiber according to claim 1, which is carried out by any one of the following methods, or two or more operations, or a combination thereof. (B) A single solution of the drug or a uniform solution of the solvent, and the viscosity of the solution is 5 centipoise or less. (B) The hollow fiber is immersed in a liquid drug or drug solution for 30 minutes or more. (C) The hollow fiber and the liquid drug or drug solution are brought into contact with each other under reduced pressure. (D) Ultrasonic vibration or / and an ultrahigh pressure of 100 kg / cm ² G or more is applied while the hollow fibers are immersed in a liquid drug or drug solution. 17. The drug solution obtained by adjusting a liquid or solid drug so as to be compatible with the drug or adjusted to a drug concentration of 50% or less with a solvent in which the drug is dissolved. The method for producing a drug-containing hollow fiber according to claim 1, which is obtained by removing most of the solvent from the drug-containing hollow fiber obtained by the method. 18. The solvent for dissolving a drug contains, as a main component, any one of ether, acetone, methanol, ethanol, propylene glycol or a mixture thereof.
A method for producing a drug-containing hollow fiber as described above. 19. A hollow fiber is immersed in a drug-containing solution to impregnate the hollow part of the hollow fiber with the drug solution, and then the hollow fiber is taken out from the drug-containing solution. A solvent that dissolves the drug,
The method for producing a drug-containing hollow fiber according to claim 17, wherein the hollow fiber is washed.