JP2002249925A - Antibacterial polyamide fiber having excellent resistance to washing, antibacterial polyamide crimped textured yarn, antibacterial polyamide woven or knitted fabric and method for producing antibacterial polyamide fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antibacterial polyamide fiber and an antibacterial polyamide crimped textured yarn exhibiting a good antibacterial activity, slightly causing discoloration (color development) even when an alkali treatment is carried out, causing remarkably slight lowering of the antibacterial activity after washing and having excellent resistance to washing, and to provide a method for producing the antibacterial polyamide fiber. SOLUTION: This antibacterial polyamide fiber has excellent resistance to washing and is characterized as comprising a polyamide resin containing 0.1-5.0 mass% of zinc oxide fine particles and having <=2.5 color difference ΔE before and after the alkali treatment and >=2.2 bacteriostatic activity value after 50 washings.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber made of a resin containing an antibacterial agent, which has a small discoloration (coloring) even when subjected to an alkali treatment, and has excellent washing resistance and an antibacterial polyamide fiber. It relates to a manufacturing method.

[0002]

2. Description of the Related Art There have been proposed a large number of antibacterial fibers in which synthetic fibers such as polyamide fibers such as nylon 6 contain powder having antibacterial properties. Among them,
Silver-based inorganic substances are widely used as antibacterial agents, and phosphate-based antibacterial agents carrying silver ions, zeolite-based antibacterial agents carrying silver ions, and calcined hydroxyapatite products carrying silver ions Antibacterial agents and the like are used.

[0003] Fibers containing such a silver-based inorganic antibacterial agent have good antibacterial properties and excellent durability, but the sizing agent applied to improve the weaving property is washed away in a step before dyeing. Therefore, when the alkali treatment is performed, silver, which is an antibacterial component, is oxidized and discolored (colored). As a result, the antibacterial property is reduced. Was.

Therefore, in order to prevent discoloration and improve the whiteness and sharpness of the fiber, an antibacterial agent treated with a discoloration inhibitor such as sodium percarbonate, sodium hypochlorite, or an azole compound having no mercapto group is used. A conductive fiber has been proposed in JP-A-4-50376, JP-A-6-264360, and JP-A-6-272173.
However, these fibers cannot sufficiently avoid discoloration (coloring) when subjected to alkali treatment only by treatment with a discoloration inhibitor, and the treatment is complicated, and the whiteness and sharpness of clothing and the like are reduced. However, there is a problem that it is difficult to use it for an application that requires the above.

In order to solve these problems, the present inventors disclosed in Japanese Patent Application Laid-Open No. Hei 11-293521 that an alkali treatment was carried out by adding zinc oxide fine particles whose surfaces were coated with a coupling agent. An antibacterial polyamide fiber with little discoloration (coloring) even when performed is proposed. This fiber is an excellent antibacterial fiber with little coloring after alkali treatment. However, in the production of this fiber, the antimicrobial agent tends to bleed out to the fiber surface during spinning, and the distribution of the antimicrobial agent in the obtained fiber becomes uneven (particularly localized on the surface). There was something. For this reason, there was a problem that the antibacterial agent dropped off from the fiber surface after extensive washing, and the sustainability of the antibacterial performance was not sufficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above problems, exhibits good antibacterial properties, has little discoloration (coloring) even after alkali treatment, and has a reduced antibacterial property after washing. An object of the present invention is to provide an antibacterial polyamide fiber and an antibacterial polyamide crimped yarn having extremely low washing resistance and a method for producing the same.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention has the following (1) to (4). (1) It is made of a polyamide resin containing 0.1 to 5.0% by mass of zinc oxide fine particles, has a color difference ΔE of 2.5 or less before and after alkali treatment, and has a bacteriostatic activity value of 2 after 50 washings. 2. An antibacterial polyamide fiber excellent in washing resistance, characterized by being 2 or more. (2) A crimped antibacterial polyamide yarn obtained by crimping the antibacterial polyamide fiber according to (1). (3) An antibacterial polyamide woven or knitted fabric which is knitted and woven using at least a part of the antibacterial polyamide fiber according to (1) or the crimped antibacterial polyamide yarn according to (2). (4) A polyamide resin chip containing zinc oxide fine particles of 0.1 to 5.0% by mass is adjusted to have a water content of 0.01 to 0.2% by mass, and then melt-spun, and within 400 mm from the nozzle surface. (1) The method for producing an antibacterial polyamide fiber according to (1), wherein

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the polyamide constituting the fiber of the present invention include nylon 6, nylon 66, nylon 69, and nylon 46.
And the like, or copolymers or blends thereof. Then, as long as the effects of the present invention are not impaired, the composition may contain a matting agent, a modifying agent, an antistatic agent, a pigment, and the like.

The antibacterial agent contained in the fiber of the present invention is zinc oxide fine particles. The zinc oxide fine particles have a bactericidal and antibacterial action in addition to the action of absorbing and deodorizing ultraviolet rays. It is considered that the bactericidal and antibacterial properties of the zinc oxide fine particles are exhibited by high affinity with sulfur, which is one of the chemical properties of zinc oxide. Specifically, it is presumed that zinc oxide fine particles act in some way on the thiol group of the enzyme present in the cell membrane of the fungus to reduce the activity of the fungus.

In the present invention, it is preferable that the surface of the zinc oxide fine particles is coated with a coupling agent. This is because zinc oxide has photocatalytic activity and may cause photodegradation when contained in a resin.

The photocatalytic activity of the zinc oxide fine particles is a reaction on the surface of the particles, and attempts have been made to suppress the activity by treating the surface of the particles. For example, a microencapsulated surface treatment for cutting off contact with oxygen or water has been performed, and the zinc oxide fine particles subjected to this treatment optically have the properties of zinc oxide, but have a chemical property. Had the problem of losing the properties of zinc oxide.

Therefore, in the present invention, in order to suppress the photocatalytic activity, which is a drawback of zinc oxide fine particles, and to have the properties of zinc oxide both optically and chemically, the surfaces of the particles are coupled. It is preferable to use one coated with an agent.

The coupling agent is not particularly limited, but a silane coupling agent is preferable. For example, a silane coupling agent KBM-4 manufactured by Shin-Etsu Chemical Co., Ltd.
03, KBM-503.

Further, as coupling agents other than the silane coupling agent, coupling agents such as titanium-based, aluminum-based, zirconium-based, and zircoaluminate-based coupling agents can be mentioned.

The coating amount of the coupling agent depends on the surface area of the zinc oxide fine particles.
It is preferable to set it to about mass%. Since the surface of the zinc oxide fine particles is coated with the coupling agent in this manner, the photocatalytic activity of the zinc oxide fine particles can be sufficiently suppressed without waste with a small amount of coating.
It is possible to maintain the functions of ultraviolet absorption, antibacterial, sterilization, and the like as they are. Therefore, fibers containing zinc oxide fine particles whose surface is coated with such a coupling agent,
Discoloration due to ultraviolet rays is prevented, and at the same time, effects such as antibacterial and sterilization are achieved.

In the present invention, when zinc oxide fine particles not subjected to the above-mentioned coupling treatment are used as the antibacterial agent, the photocatalytic activity excited by ultraviolet rays is high, and the deterioration of the polymer is easily promoted. It is desirable to add an organic ultraviolet absorber such as a phenol-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, or antioxidant to the fiber.

In the present invention, zinc oxide fine particles which are not subjected to the above-mentioned coupling treatment can also be suitably used, but this is achieved by employing the production method of the present invention as described later. This is because zinc fine particles can be uniformly distributed in the fiber. Generally, when zinc oxide fine particles are dispersed in a resin, the dispersibility is poor, and the larger the aggregation of the zinc oxide fine particles, the faster the resin deteriorates. However, since the zinc oxide fine particles are uniformly dispersed in the antibacterial fiber of the present invention, deterioration of the resin is suppressed, and even if zinc oxide fine particles not subjected to the coupling treatment are used, the color difference ΔE before and after the alkali treatment can be reduced by 2%. .5 or less.

In the fiber of the present invention, the content of the zinc oxide fine particles in the polyamide resin is 0.1 to 5.0% by mass,
Preferably it is 0.2 to 3.5% by mass, more preferably 0.1 to 3.5% by mass.
3 to 2.0% by mass. If the content is less than 0.1% by mass, fibers having sufficient antibacterial properties will not be obtained. If the content exceeds 5.0% by mass, yarn breakage will occur during spinning or drawing, or weaving will occur. Occasionally, thread breakage and fluff due to wear of guides, reeds, healds, etc. occur frequently, and the operability deteriorates. further,
Not only the antibacterial performance is saturated and the cost is increased, but also the yarn quality performance such as high elongation is reduced.

The zinc oxide fine particles are used in the process from spinning to winding to prevent problems such as guide abrasion and the like, to improve the processability, and to prevent the nozzle pack pressure from increasing. Average particle size 0.01 ~
Preferably, the thickness is about 5.0 μm.

Further, as long as the fiber of the present invention does not inhibit the manifestation of antibacterial properties, it may be provided with an anti-mite agent, a deodorant, etc. by post-processing, a water-repellent treatment, a moisture-permeable waterproofing. Processing or the like may be performed.

The fiber of the present invention has a color difference ΔE of 2.5 or less before and after the alkali treatment. When the surface of the zinc oxide particles is not coated with the coupling agent, the color difference ΔE before and after the alkali treatment is 2.5 or less, preferably 2.0 or less, more preferably 1.5 or less. When the zinc oxide fine particles surface-treated with the coupling agent as described above are used as the antibacterial agent, discoloration (coloring) can be further prevented, and the color difference ΔE before and after the alkali treatment can be reduced to 2.0 or less. , Preferably 1.5 or less, more preferably 1.0 or less. That is, this value is an index indicating that there is no discoloration (coloring) due to the alkali treatment, which is caused mainly by using a silver-based antibacterial agent.

Color difference Δ before and after alkali treatment in the present invention
E is the color difference ΔE between the antibacterial fiber after the alkali treatment and the antibacterial fiber before the alkali treatment, and the knitted fibers obtained by knitting the fibers before and after the alkali treatment are overlapped with each other, and a spectrophotometer is used. (Manufactured by Macbeth Co., Ltd., CE-3100).

The color difference ΔE before and after the alkali treatment is 2.5
If it exceeds, the degree of coloration of the fiber due to alkali treatment such as scouring treatment is large, the whiteness is reduced in the case of fibers containing no pigment or colorant, and the color is sharp in the case of colored fibers containing pigment or colorant. The properties are reduced, resulting in fibers of reduced quality. Further, the antibacterial property may be significantly reduced due to the reaction with the alkali, which is not preferable. Examples of pigments and colorants to be contained include carbon black (particularly preferred is a channel type), yellow pigment (for example, Yellow10G manufactured by Bayer), blue pigment (for example, cyanine blue manufactured by Dainichi Seika), and green pigment (for example, And red pigments (eg, Slen-based red manufactured by DIC), purple pigments (eg, Sandrin Violet BL manufactured by SANDOZ), and the like.

Next, the fiber of the present invention has a bacteriostatic activity value of 2.2 or more after 50 washings. In addition, the bactericidal activity value after 50 washings is preferably 0 or more. The bacteriostatic activity value after 50 washes is defined as the quantitative antibacterial test method (unified) of textile products determined by the New Product Evaluation Council for Textile Products (JAFET) using a knitted fabric made of antibacterial fibers or crimped yarn. Test method) According to the manual, Staphylococcus aureus (Staphylo
coccus aureus ATCC 6538P), and the number of bacteria was measured and calculated by the following formula. The samples were evaluated for untreated, alkali-treated, after 50 washes, and after weathering (untreated samples were directly weathered). The alkali treatment was carried out by boiling in a 0.1% aqueous sodium hydroxide solution for 30 minutes.
This is performed by the method of L 0217 103. The weathering treatment is J
Irradiation at 63 ° C. for 20 hours using a carbon arc fade meter according to IS L 0842 (fourth class irradiation)
I do. Bacteriostatic activity value = Log B-Log C Bactericidal activity value = Log A-Log C A: Average value of the number of bacteria collected immediately after inoculation of a standard cloth (unprocessed cloth). B: The average value of the number of bacteria collected after culturing the standard cloth (unprocessed cloth) for 18 hours is shown. C: Average value of the number of bacteria collected after culturing the work cloth for 18 hours.

The bactericidal activity value after 50 washes refers to a method for quantitatively testing the antibacterial activity of textile products determined by the Textile Product New Function Evaluation Council (JAFET) using antibacterial fibers or knitted fabric obtained by crimping yarn. (Unified test method) In accordance with the manual, Staphylococcus aureus ATCC
6538P) and Klebsiella pneumoniae (ATCC4352). Then, the bactericidal activity value after unwashed and washed 50 times is determined in the same manner as the above bacteriostatic activity value.

In the present invention, the significance of adopting the bacteriostatic activity value and the bactericidal activity value after 50 washings as a reference is as follows. That is, even if a fiber in which the antibacterial agent is coated on the fiber surface or a fiber in which the antibacterial agent is localized on the fiber surface in the post-processing step as in the related art, at most several times to 10 times
Since the antibacterial property is remarkably reduced by washing about the number of times, it is difficult to use it especially for clothing applications where the number of washings is large. On the other hand, the number of washings of 50 times in the present invention is significantly improved in washing resistance as compared with the conventional method (compared to several times to 10 times in the conventional method,
50 times), and the value of 50 washes is judged, for example, from the fact that the number of washings in the SEK evaluation by the Council for Evaluation of New Functions of Textile Products (JAFET) was at most 50 times (clothing, bedding, etc.). It can be said that it has sufficient washing resistance even in the application.

Examination of the antibacterial effect and the deodorant effect (Evaluation standard WG report of the antibacterial and deodorant processing subcommittee of the Evaluation Committee for New Functions of Textile Products) shows that when the bacteriostatic activity value is 2.2 or more, the odor caused by the indigenous bacteria on the skin is reduced. The occurrence is suppressed. Therefore, in the present invention, a bacteriostatic activity value of 2.2 or more, which is an index for exhibiting a substantial antibacterial effect when used for clothing, is employed.

When the bacteriostatic activity value after 50 washings is smaller than 2.2, the antibacterial properties decrease after multiple washings, and the fibers cannot maintain the antibacterial properties. For this reason, it is difficult to use it for clothing or medical applications that require washing resistance. In the antibacterial fiber of the present invention, the bacteriostatic activity value after 50 washings is 2.2 or more, particularly preferably 3.0 or more, and more preferably 4.0 or more.

The antibacterial fiber of the present invention preferably has a bactericidal activity value of 50 or more after 50 washings. The bactericidal activity value is a bacteriostatic processing evaluation determined by JAFET. When this value is 0 or more, the growth of bacteria on the fiber is suppressed. For this reason, it can be suitably used for applications aimed at improving living environments (living, life) and care environments (health, medical). The bactericidal activity value after 50 washes was 1.
It is more preferably 0 or more, and still more preferably 2.0 or more.

Further, in the antibacterial fiber of the present invention,
2 used in the method for measuring the bactericidal activity value shown above
It also has a bactericidal effect against Escherichia coli, Pseudomonas aeruginosa, and MRSA as well as various kinds of bacteria, and the bactericidal activity value after 50 washes of these bacteria measured and evaluated in the same manner as above was also 0.
The bactericidal activity value is preferably 1.0 or more, and more preferably 2.0 or more. In particular, those having a bactericidal activity value of 0 or more against MRSA in addition to Staphylococcus aureus and Klebsiella pneumoniae can be suitably used for applications aimed at improving the medical environment such as medical institutions.

In the fiber of the present invention, 50
The bacteriostatic activity value and the bactericidal activity value after washing show good values,
This is because the antibacterial agent (fine zinc oxide particles) can be uniformly distributed in the fiber by employing the production method of the present invention as described below. Thereby, the antibacterial agent is not localized on the fiber surface and does not fall off from the fiber surface, and the fiber has antibacterial properties excellent in washing resistance (persistence).

[0032] In the antibacterial polyamide fiber of the present invention, it is preferable that the cross-sectional shape of the fiber is an irregular cross-section having an irregularity of 20 to 60%. By adopting such an irregular cross-sectional shape, the surface area of the filament is increased, so that the antibacterial performance is improved. Further, it is advantageous for cooling the discharged yarn from the nozzle surface described later, and the solidification point can be made closer to the nozzle surface. Therefore, the effect of the antibacterial fiber of the present invention and the effect of the zinc oxide fine particles are sufficiently exhibited, and the antibacterial property and the sustainability thereof are improved. As a result, the content of the zinc oxide fine particles can be reduced, so that the cost can be reduced.

The degree of irregularity in the fiber of the present invention means a numerical value (%) obtained by dividing the diameter of the inscribed circle in the cross-sectional shape of the filament by the diameter of the circumscribed circle and multiplying by 100. Examples of such a shape include a polygonal shape such as a triangle or a square, a multi-leaf cross-sectional shape having a large number of irregularities, and a rice-shaped or well-shaped shape.

And, in the fiber of the present invention,
Irrespective of not being irregular, it may have a hollow part,
In order to avoid yarn breakage and fluffing during weaving, a core-sheath structure in which zinc oxide fine particles are contained in the core may be used.

Further, the fiber of the present invention may be a short fiber or a long fiber, and the long fiber may be a multifilament or a monofilament, and both the short fiber and the long fiber have a single fiber fineness of 0.5 to 2300 dtex.

Next, a method for producing the antibacterial fiber of the present invention will be described. In the production method of the present invention, a polyamide resin chip containing 0.1 to 5.0% by mass of zinc oxide fine particles or zinc oxide fine particles whose surfaces are coated with a coupling agent is manufactured, and the moisture content of the chips is reduced. 0.0
Melt spinning is performed by adjusting the amount to be 1 to 0.2% by mass, preferably 0.03 to 0.15% by mass, and more preferably 0.05 to 0.10% by mass. When manufacturing a polyamide resin chip containing 0.1 to 5.0% by mass of zinc oxide fine particles, not only a method of preparing a chip containing this amount of zinc oxide fine particles in advance, but also a method of preparing zinc oxide fine particles. A method of blending with a polyamide resin chip, a method of producing a polyamide resin chip containing zinc oxide fine particles at a high concentration in advance, and a method of blending this chip with ordinary polyamide can be employed. However, in any case, the water content of the resin chip to be used is adjusted so as to be within the above range.

In order to keep the moisture content of the resin chip within the above range, the resin chip may be dried at about 90 to 160 ° C.
The moisture content in the resin chip is involved in the coloring and discoloration of the obtained polyamide fiber. This is presumably because polyamide fibers are susceptible to degradation such as hydrolysis in a molten state. As the moisture content increases, coloring and discoloration of the obtained fibers after alkali treatment increase. That is, in the fiber before the alkali treatment, even if there is no difference in coloring and discoloration, the fiber after the alkali treatment becomes more colored and discolored as the moisture content of the chip increases. Therefore, in order to keep the moisture content of the resin chip within the above range, 90%
What is necessary is just to dry at about 160 degreeC.

When the moisture content of the chip exceeds 0.2% by mass, the coloring and discoloration of the obtained fiber after the alkali treatment become large, and it becomes difficult to reduce the color difference ΔE before and after the alkali treatment to 2.5 or less. Chip moisture content is 0.01% by mass
If it is less than 1, the step of drying the chips becomes longer, the cost becomes higher, and the physical properties such as the high elongation of the obtained fiber tend to be reduced.

Further, in the method of the present invention, the solidification point needs to be within 400 mm from the nozzle surface. In the present invention, the distance from the nozzle surface to the solidification point has a very large effect on the dispersion state of the antimicrobial agent inside the fiber of the obtained fiber. Here, the solidification point is a point at which the fiber diameter of the yarn discharged from the nozzle becomes substantially constant at first, that is, a point at which the yarn is solidified. The method of calculating the distance from the nozzle surface to the solidification point is the value of the single yarn for a monofilament, and the average value of each single yarn for a multifilament.

The solidification point under normal spinning conditions is in the range of 600 to 2,000 mm, depending on the single yarn fineness. In the present invention, it is necessary to cool and solidify so that the solidification point is within 400 mm from the nozzle surface by employing the method described below. That is, by setting the solidification point to within 400 mm from the nozzle surface, the time of cooling and solidification of the molten polyamide discharged from the nozzle hole is shortened, and the antibacterial agent can be prevented from bleeding out to the fiber surface, The antibacterial agent is not localized on the fiber surface, and the fiber can be uniformly contained in the fiber.

Since the antibacterial agent is not localized on the fiber surface and can be made into fibers uniformly dispersed in the fiber, the antibacterial agent does not fall off from the fiber surface, and the duration of the antibacterial performance is extended. , Resulting in excellent washing resistance. Furthermore, since the antibacterial agent is not localized on the fiber surface and can be made into fibers uniformly dispersed in the fiber, deterioration of the resin is suppressed, and even if zinc oxide fine particles not subjected to coupling treatment are used. And the color difference ΔE before and after the alkali treatment can be 2.5 or less.

The closer the solidification point is to the nozzle surface, the more the antimicrobial agent can be prevented from bleeding out to the fiber surface and the antimicrobial agent can be uniformly dispersed in the fiber. preferable.

As a method for keeping the solidification point within 400 mm, the polymer temperature at the time of discharging from the nozzle hole is kept low, and the cooling air blowing temperature for cooling the molten polyamide discharged from the nozzle hole is lowered. And means for increasing the blowing air volume and cooling the yarn with a liquid medium such as water.

When the means for suppressing the polymer temperature at the time of discharge from the nozzle hole is adopted, the polymer temperature at the time of discharge is preferably 235 to 255 ° C., more preferably 250 ° C. or lower, more preferably 245 ° C. or less. It should be below ° C. Under normal spinning conditions, the polymer temperature often exceeds 255 ° C. For example, at 258 ° C., under normal cooling conditions, it is difficult to keep the solidification point within 400 mm, and the antibacterial agent may bleed out to the fiber surface. is there. On the other hand, when the polymer temperature at the time of discharge is lower than 235 ° C., yarn breakage is likely to occur during spinning due to the generation of undissolved substances and the like.

In the case of cooling with cooling air, the temperature of the cooling air is preferably set to 10 ° C. or less. Cooling air temperature is 1
If it exceeds 0 ° C., it is difficult to keep the solidification point within 400 mm.

The greater the amount of cooling air blown, the more advantageous for cooling, which is preferable. The blowing speed of the cooling air is preferably 1.5 to 2.
It is preferably 5 m / min, more preferably 1.
7 to 2.3 m / min. If the wind speed exceeds 2.5 m / min, yarn breakage tends to occur during spinning, which is not preferable.
Under normal conditions, the wind speed is less than 1.5 m / min,
If it is less than 1.5 m / min, the cooling becomes insufficient and the solidification point becomes 40
In some cases, it is difficult to set the thickness within 0 mm.

When the fibers are cooled and solidified, the size of the single-fiber fineness is involved, and the smaller the single-fiber, the larger the surface area, which is advantageous for cooling. Therefore, if the single-fiber fineness is less than 3.3 dtex, cooling by cooling air is adopted, and if the single-fiber fineness is 3.3 to 100 dtex, the cooling efficiency is high. It is preferable to employ cooling by a nozzle type liquid medium. Further, in the case of a fiber having a single-fiber fineness of more than 100 dtex, it is preferable to employ a method of dipping in a liquid bath or a method of spraying with a spraying device, which has higher cooling efficiency, as described later.

Next, a cooling means using a liquid medium will be described. As a cooling medium, a liquid medium such as water or an oil agent is used. When the liquid medium is used for cooling, it is more efficiently cooled than the cooling air due to the specific heat, so that the single yarn fineness is 3.3.
Solidification point of 400 mm even for fibers with dtex or more
It becomes easy to be within.

Specifically, a roller type liquid medium supply means as shown in FIG. 1 or a slit nozzle type liquid medium supply means as shown in FIG. 2 is provided within 400 mm from the nozzle surface, preferably
It is preferable that the yarn is provided within 350 mm to cool and solidify the yarn. These roller type or slit nozzle type liquid medium supply means have a spinning speed of 10 times as compared with a method of dipping in a liquid bath described later or a method of spraying with a spraying device or the like.
Since the speed can be increased to 00 m / min or more, it is more preferable from the viewpoint of productivity.

In the roller type liquid medium supply means shown in FIG.
The liquid 5 in the liquid bath 6 is supplied to the roller 4 and applied to the yarn 1 (before solidification). In the slit nozzle type liquid medium supply means shown in FIG. 2, the oil agent supplied from the liquid supply pipe 3 to the liquid application nozzle 2 is applied to the yarn 1 (before solidification). In addition, a method of immersing in a liquid bath or a method of applying a liquid medium by a spray device or the like may be used. These cooling means described above may be used alone or two or more means may be used in combination. Further, the cooling may be performed in combination with the cooling air blowing device.

The liquid medium referred to here is preferably, for example, water, polyalkyl glycol, or a spinning oil containing mineral oil, organic acid, ethers and the like.
You may mix and use. The liquid medium may contain various additives such as a finishing agent.

As the temperature of the liquid medium is lower, the cooling effect of the yarn is higher.
The temperature is preferably 0 ° C, more preferably -10 to
The temperature is 30 ° C, more preferably 0 to 10 ° C.

When the antibacterial fiber of the present invention is produced by such a method, the antibacterial agent does not bleed out to the fiber surface during spinning. The distribution of the agent is also uniform. For this reason, the antibacterial agent does not fall off from the fiber surface even after extensive washing, the antibacterial property is maintained, and the clothing use where washing resistance is required,
Further, it can be suitably used for medical purposes. In addition, the antibacterial agent is not localized on the fiber surface, and can be a fiber uniformly dispersed in the fiber,
Even if zinc oxide fine particles not subjected to the coupling treatment are used because the deterioration of the resin is suppressed, the color difference ΔE before and after the alkali treatment can be obtained.
Can be set to 2.5 or less. Further, the fiber of the present invention has a high antibacterial property after the weathering treatment, and the bacteriostatic activity value after the weathering treatment is 2.2 or more. Although the reason for this is not clear, it is presumed that the antimicrobial agent is not localized on the fiber surface and is uniformly distributed, so that deterioration of the antimicrobial agent due to weathering treatment is also suppressed.

In the case of producing the antibacterial polyamide fiber of the present invention, even in a two-step method in which a spun undrawn yarn is once wound and then drawn, the spun yarn is cooled and then wound at a speed of 100 m / min or more. It may be manufactured by a direct spin drawing method.

When the fiber of the present invention is produced by a two-step method of once winding and drawing after melt-spinning, 25 to 25
It is preferable to wind at a speed of about 1500 m / min and then to draw at a draw ratio of about 1.5 to 6.0 times. Depending on the type of yarn, it may be hot drawn or cold drawn at room temperature. In the case of stretching, the stretching is preferably performed at about 50 to 170 ° C.

In the case of manufacturing by the direct spinning and drawing method,
Without winding the melt spun yarn once, 100m /
It is manufactured by winding at a speed of at least minutes. At this time, it is preferable that the spinning speed is slower as the fiber having a larger single-fiber fineness is obtained. For example, when the single-fiber fineness is 0.6 to 3.3 dtex, the spinning speed is preferably 500 to 5000 m / min, and 3.3 to 100 m / min.
In dtex, 500 to 3000 m / min is preferable, and 10
When it exceeds 0 dtex, it is preferable to set it to 100 to 1500 m / min. Stretching may be performed before winding. In this case, it is preferable to perform thermal stretching at a magnification of about 1.1 to 3.0 times while heating to about 50 to 150 ° C.

Here, a process chart in the case of employing the direct spinning and drawing method as an example of the production method of the present invention will be described with reference to FIG. A cooling medium is applied to the yarn 1 spun from the spinneret 10 placed on the spin head 9 from the slit nozzle 2 to be cooled and solidified. At this time, cooling is performed using a cooling device 12 that blows cooling air. Thereafter, the film is wound by the winding device 14 via the take-up rollers 13a and 13b.

Further, an example of a process diagram for a monofilament will be described with reference to FIG. Monofilament 2 spun from spinneret 10 placed on spin head 9
1 was cooled in a liquid bath 15 and then taken up by a take-up roller 13.
A hot air heater 17 is provided between a plurality of stretching rollers 16 to perform hot stretching and heat setting.

In the case of the crimped yarn of the present invention, the fiber obtained as described above is subjected to a crimping process. Method, an indentation crimping method, a fluid indentation crimping method using a heated fluid, and the like. Above all, the false twisting method is preferred in terms of quality stability and cost.

As the false twisting machine, a general false twisting machine equipped with a pin type or disk type twisting device can be used. The false twisting conditions may be appropriately selected in a general condition range, and usually, the false twist coefficient represented by the product of the number of false twists (T / M) and the square root of the fiber fineness (d) is 1500.
It is preferable to set it in the range of 0 to 33000. However, the present invention is not limited to these as long as crimps can be obtained, and a two-stage heater false twisting in which heat treatment is continuously performed to suppress torque after false twisting may be performed.

The antibacterial polyamide woven or knitted fabric of the present invention is obtained by knitting and weaving using at least a part of the antibacterial polyamide fiber or the crimped antibacterial polyamide yarn of the present invention. That is, the antibacterial polyamide woven or knitted fabric of the present invention preferably uses the antibacterial polyamide fiber and / or crimped yarn of the present invention for all of the fibers constituting the woven or knitted fabric. If, if the antibacterial polyamide fiber and or crimped yarn of the present invention in advance,
A fiber entangled with other fibers, a ply-twisted yarn, or the like, which has been manufactured and woven or woven from such a mixed-filament yarn or a ply-twisted yarn, or the antibacterial polyamide fiber and / or crimped yarn of the present invention. May be mixed and knitted with other fibers.

The ratio of the antibacterial fiber or the crimped yarn in the woven or knitted fabric as described above may be appropriately selected depending on the required application such as antibacterial performance and feeling. In addition, the conditions such as the structure at the time of forming the woven or knitted material are not particularly limited, and may be performed by a conventional method.

The antibacterial polyamide fiber and crimped yarn of the present invention have a color difference ΔE of 2.5 or less before and after the alkali treatment, and have a whiteness when containing no pigment or colorant.
When they are contained, they are excellent in sharpness and have a long duration of antibacterial performance. Therefore, the woven or knitted fabric of the present invention in which these fibers or crimped yarns are partially or wholly used can be dyed in a desired color and used for applications in which washing resistance is required. Can be.

[0064]

Next, the present invention will be described specifically with reference to examples. In addition, the measurement of the characteristic value in an Example was performed as follows. (a) Strong elongation Measured in accordance with JIS L1090. (b) Antibacterial property Measured by the method described above. In addition, about the bactericidal activity value, the value using Escherichia coli, Pseudomonas aeruginosa, and MRSA was also measured. (c) Color difference ΔE before and after the alkali treatment was carried out as described above. (d) Weathering treatment The above treatment was performed. (e) Measurement of solidification point (position) Using a fiber diameter measuring device (460A / 5, manufactured by ZIMMER), the fiber diameter was measured at each position at intervals of 5 cm below the nozzle surface for 30 seconds, and the average value was calculated. And create a graph. The first point (distance from below the nozzle surface) at which the average value becomes constant (the average value is within ± 1%) is defined as the solidification point of the yarn.

Example 1 Relative viscosity (measured at a concentration of 1 g / dl using 96% sulfuric acid as a solvent and at a temperature of 25 ° C.) was 2.53, and zinc oxide fine particles (average particle size: 0.2 μm) were 1.0 as an antibacterial agent. A nylon 6 chip containing 0.5% by mass of 2 (2′-hydroxy-4′octoxyphenyl) benzotriazole (manufactured by Sumitomo Chemical Co., Ltd.) as an ultraviolet absorber;
After adjusting the moisture content of the chips to 0.10% by mass, the chips were supplied to an extruder-type melt extruder, and the spinning temperature was set to 255.
C. and was discharged from a spinneret having 24 spinning holes having a hole diameter of 0.3 mm. Cooling air is blown from a cooling device to cool and solidify the yarn, and after applying an oil agent with an oiling roller, winding is performed at a winding speed of 4000 m / min.
4 dtex / 24f antibacterial fiber was obtained.

Example 2, Comparative Examples 1-2 The antibacterial agent content, the moisture content of nylon 6 chips, the temperature of the discharged polymer, the position of the solidification point, the blowing temperature of the cooling air and the air volume were variously changed as shown in Table 1. did. Otherwise, Example 1
The same as above.

Example 3 and Comparative Example 3 Sandolin violet BL (manufactured by SAN-DOZ) as a pigment was added to a nylon 6 chip in an amount of 0.01% by mass.
The content of the antibacterial agent, the moisture content of the nylon 6 chip, the temperature of the discharged polymer, the position of the solidification point, the blowing temperature of the cooling air and the air volume were variously changed as shown in Table 1. Otherwise, Example 1
The same as above.

Example 4 A spinneret having 24 trilobal-shaped spinning holes was used, and the content of the antibacterial agent was changed as shown in Table 1.
Except for this, in the same manner as in Example 1, an antibacterial fiber of 44 dtex / 24f having a triangular cross section having a degree of irregularity of 33% was obtained.

Table 1 shows the evaluation of the strength, elongation, antibacterial property and color difference before and after the alkali treatment of the fibers obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

[0070]

[Table 1]

As is clear from Table 1, the antibacterial fibers obtained in Examples 1 to 4 are excellent in the thread properties such as high elongation and the evaluation of the antibacterial properties (bacteriostatic activity value and bactericidal activity value). , A small color difference before and after alkali treatment, and a high evaluation of antibacterial properties after 50 washings and weathering treatments, it can be favorably used for applications requiring whiteness, sharpness and washing resistance. Was. Further, the fibers of Examples 1 to 4 were produced by the direct spinning and drawing method, but did not suffer from guide wear and the like, and could be produced with good operability. On the other hand, Comparative Example 1 did not have an antibacterial property because it did not contain an antibacterial agent. In Comparative Example 2, since the antibacterial agent content was too high, yarn breakage occurred during spinning or drawing, and fibers could not be obtained. In Comparative Example 3, melt spinning was performed in a state where the water content in the chips was high, and the solidification point could not be set to a position within 400 mm from the nozzle surface, so the color difference of the obtained fibers before and after alkali treatment was high, Further, the antibacterial performance after 50 washings was sharply reduced.

Examples 5 to 6, Comparative Example 4 The content of the antibacterial agent was changed as shown in Table 2, and the spinning hole was changed to 3
A spinneret having four pieces was used. Otherwise in the same manner as in Example 1, a 70 dtex / 34f antibacterial polyamide fiber was obtained. Next, a feed roller, a false twist heater, a pin type false twist twisting device, a delivery roller,
Using a false twisting machine equipped with a winding device in order, various false twisting conditions were changed as shown in Table 2 to carry out processing to obtain a crimped yarn. Table 2 shows the evaluation of the strength, elongation, antibacterial property, and color difference before and after the alkali treatment of the obtained crimped yarn.

[0073]

[Table 2]

As is clear from Table 2, the antibacterial crimped yarns obtained in Examples 5 to 6 have excellent yarn properties such as high elongation, high evaluation of antibacterial properties, and alkali treatment. Since the color difference between before and after was small and the antibacterial property after 50 washings and after the weathering treatment was high, it could be favorably used for applications requiring whiteness, clarity and washing resistance. On the other hand, Comparative Example 4
Did not have antibacterial properties because it did not contain an antibacterial agent.

Example 7 Using the fiber of Example 1 as a warp and a weft, a warp density of 14
A plain woven fabric having 0 threads / 2.54 cm and a weft density of 108 threads / 2.54 cm was woven. The antibacterial properties of this plain fabric and the color difference before and after the alkali treatment were measured and evaluated. These evaluations and measurements were performed not only in Example 7 but also in Example 8 described below.
Also in Nos. To 10, the evaluation and measurement methods described above, which were performed on the knitted fabric, were performed on the woven fabric.

Example 8 Using the crimped yarn of Example 5 as a warp and a weft, a warp density of 114 yarns / 2.54 cm and a weft density of 86 yarns / 2.54c
m plain weave fabrics. Other than that was the same as Example 7.

Example 9 Using the fiber of Example 1 for the warp and the fiber of Comparative Example 1 for the weft, warp density 140 / 2.54 cm, weft density 108
Book / 2.54cm plain woven fabric (56% of antibacterial fiber)
Weaved. Other than that was the same as Example 7.

Example 10 An interlaced mixed yarn obtained by subjecting the crimped yarn of Example 5 and the crimped yarn of Comparative Example 4 to air entanglement using an interlacer JD-1 manufactured by DuPont was used as a weft. Using the crimped yarn of Comparative Example 4 as a warp, a plain woven fabric with a warp density of 114 yarns / 2.54 cm and a weft density of 62 yarns / 2.54 cm (mixing ratio of antibacterial crimped yarn of 26%) was woven. Other than that was the same as Example 7.

Example 11 Using the fibers of Example 1, a tricot knit was obtained with a mesh structure.

Example 12 Using the fiber of Example 1 and the fiber of Comparative Example 1, mixed knitted fabric (tubular knitting, mixing ratio of antibacterial fiber: 65
%).

The woven fabrics of Examples 7 to 10 and Examples 11 to 12
Table 3 shows the evaluation results of the antibacterial property with the knitted fabric and the color difference before and after the alkali treatment.

[0082]

[Table 3]

As is evident from Table 3, the woven or knitted fabric using all or a part of the antibacterial fiber or the crimped antibacterial yarn of the present invention has a high antibacterial property and a small color difference before and after the alkali treatment. In addition, since the antibacterial properties after 50 washings and after the weathering treatment were high, they could be favorably used for applications requiring whiteness, sharpness and washing resistance.

Example 13 Zinc oxide fine particles (Z-NOUVE, Mitsui Kinzoku Co., average particle size 0.2 μm) having a relative viscosity of 2.53 and having a surface coated with a silane coupling agent as an antibacterial agent A nylon 6 chip containing 0.1% by mass was used. After adjusting the moisture content of the chips to 0.07% by mass, the chips are fed to an extruder-type melt extruder, melted at a spinning temperature of 248 ° C., and have a spinneret having 24 spinning holes having a hole diameter of 0.3 mm. More. The cooling air is blown from the cooling device under the conditions shown in Table 4 to cool and solidify the yarn, and after applying an oil agent with an oiling roller, the winding speed is 4000.
Winding was performed at m / min to obtain an antibacterial fiber of 44 dtex / 24f.

Examples 14 and 15, Comparative Examples 5 and 6 Except that the contents of the antibacterial agent, the moisture content of the nylon 6 chip, the temperature and amount of cooling air blown, and the position of the solidification point were variously changed as shown in Table 4. Was performed in the same manner as in Example 13.

Example 16 Sandolin Violet BL (manufactured by Sandoz) was added as a pigment to a nylon 6 chip in an amount of 0.01% by mass, and the content of the antibacterial agent, the moisture content of the nylon 6 chip, and the position of the solidification point are shown in Table 1. The same procedures as in Example 13 were carried out, except for various changes as shown.

Examples 17 to 19, Comparative Example 7 The content of the antibacterial agent, the moisture content of nylon 6 chips, the temperature and amount of cooling air blown, the position of the solidification point, and the temperature of the discharged polymer were variously changed as shown in Table 4. A 78 dtex / 24f fiber was obtained in the same manner as in Example 13 except for the above.

Example 20, Comparative Example 8 To a nylon 6 chip, 0.1% by mass of yellow 10G (manufactured by BAYEL) was added as a pigment, the content of an antibacterial agent, the moisture content of the nylon 6 chip, and the cooling air blowing temperature were measured. 78 dtex in the same manner as in Example 13 except that the air flow rate, the position of the solidification point, and the temperature of the discharged polymer were variously changed as shown in Table 4.
/ 24f fiber was obtained.

Table 4 shows the evaluation of the strength, elongation, antibacterial property and color difference before and after the alkali treatment of the fibers obtained in Examples 13 to 20 and Comparative Examples 5 to 8.

[0090]

[Table 4]

Example 21 A nylon 6 chip having a content of 1.0% by mass of surface-coated zinc oxide fine particles having the same relative viscosity as that used in Example 13 was used. 0.1
After adjusting to 0% by mass, the mixture is fed to an extruder-type melt extruder and melted at a spinning temperature of 255 ° C. to have a pore diameter of 0.3 m
m was spun from a spinneret having 34 spin holes. A roller-type liquid medium supply means shown in FIG. 1 was provided at a position 390 mm below the surface of the base (solidification point). At this time,
The temperature of the water was 25 ° C. and the amount applied was 5 ml / min. Subsequently, after applying oil to the solidified yarn with an oiling roller, the yarn is wound at a winding speed of 3000 m / min.
An antibacterial fiber of 5 dtex / 34f was obtained.

Example 22, Comparative Example 9 The content of the antibacterial agent, the moisture content of the nylon 6 chip, and the position of the solidification point were changed as shown in Table 5. Otherwise, Example 2
Same as 1.

Examples 23 to 24, Comparative Example 10 Instead of the roller-type liquid medium supply means, a slit nozzle type liquid medium supply means shown in FIG. 2 was used, and water at 10 ° C. was applied at 10 ml / min. . Further, the content of the antibacterial agent, the moisture content of the nylon 6 chip, and the position of the solidification point were changed as shown in Table 5. Other than that was the same as Example 21.

Table 5 shows the evaluation results of the strength, elongation, antibacterial property, and color difference before and after the alkali treatment of the fibers obtained in Examples 21 to 24 and Comparative Examples 9 to 10.

[0095]

[Table 5]

Example 25 A nylon 6 chip containing 1.0% by mass of surface-coated zinc oxide fine particles having the same relative viscosity as that used in Example 13 was used. After adjusting to mass%, the mixture was supplied to an extruder-type melt extruder, melted at a spinning temperature of 255 ° C., and discharged from a spinning hole having a hole diameter of 2.0 mm. After cooling the spun monofilament in a water bath placed 20 mm below the nozzle surface, the monofilament was stretched 5.3 times in total by a conventional method, heat set, and 1120 dt.
ex antibacterial monofilament was obtained.

Examples 26 to 27 and Comparative Examples 11 to 12 The content of the antibacterial agent, the moisture content of the nylon 6 chip and the position of the solidification point were changed as shown in Table 6. Otherwise, Example 2
Same as 5.

Table 6 shows the evaluation results of the strength, elongation, antibacterial property and color difference before and after the alkali treatment of the monofilaments obtained in Examples 25 to 27 and Comparative Examples 11 to 12.

[0099]

[Table 6]

As apparent from Tables 4 to 6, Example 13
The antibacterial fibers obtained in Examples 24 to 24 and the antibacterial monofilaments obtained in Examples 25 to 27 have excellent thread properties such as high elongation, a small color difference before and after alkali treatment, and after 50 washings and weathering treatment. Since the evaluation of antibacterial properties afterwards was high, it could be favorably used for applications requiring whiteness, sharpness and washing resistance. Further, the fibers and monofilaments of Examples 13 to 27 were produced by the direct spinning and drawing method, but could be produced with good operability without abrasion of the guide. On the other hand, in Comparative Examples 5 to 8, the cooling conditions and the like were not optimal, and the solidification point could not be set to a position within 400 mm from the nozzle surface.
After 50 washings, the antibacterial performance was sharply reduced, and the antibacterial properties after the weathering treatment were also considerably reduced. Comparative Examples 9 to 12
Is that the position of the roller or slit type liquid medium supply means and the position of the cooling bath (solidification point) were not within 400 mm from the nozzle surface, so that the antibacterial performance before alkali treatment was high, but the antibacterial performance after 50 washes was similarly high. The antibacterial properties after the weathering treatment were also considerably reduced.

Examples 28 to 29, Comparative Example 13 The content of the antibacterial agent was changed as shown in Table 7, and a spinneret having 34 spinning holes was used. Otherwise, Example 1
In the same manner as in 3, a fiber of 78 dtex / 34f was obtained.
A false twisting machine equipped with a feed roller, a false twist heater, a pin type false twist twisting device, a delivery roller, and a winding device in this order was used for the obtained antibacterial polyamide fiber. The processing was performed by changing the processing conditions variously to obtain a crimped yarn. Table 7 shows the strength, elongation, antibacterial properties, and color difference before and after the alkali treatment of the obtained crimped yarn.

[0102]

[Table 7]

As is clear from Table 7, Examples 28 to 2
The antibacterial fiber obtained in 9 has excellent yarn properties such as high elongation, a small color difference before and after alkali treatment, and a high evaluation of antibacterial properties after 50 washings and weathering treatments. It can be favorably used for applications requiring water resistance and washing resistance. On the other hand, Comparative Example 13 had no antibacterial property because it did not contain an antibacterial agent.

Example 30 Using the fiber of Example 13 as a warp and a weft, a warp density of 1
40 / 2.54cm, weft density 108 / 2.54cm
Was woven. The antibacterial properties of this plain fabric and the color difference before and after the alkali treatment were measured and evaluated. These ratings,
The measurement was performed on a woven fabric instead of the evaluation and measurement method described above on a knitted fabric.

Example 31 Using the crimped yarn of Example 28 as a warp and a weft, a warp density of 114 / 2.54 cm and a weft density of 86 / 2.54
cm plain weave. The antibacterial property of this plain fabric and the color difference before and after the alkali treatment were measured and evaluated in the same manner as in Example 30.

Example 32 Using the fiber of Example 13 as a warp and the fiber of Comparative Example 13 as a weft, warp density 140 / 2.54 cm, weft density 108
Book / 2.54cm plain woven fabric (56% of antibacterial fiber)
Weaved. The antibacterial property of this plain fabric and the color difference before and after the alkali treatment were measured and evaluated in the same manner as in Example 30.

Example 33 The crimped yarn of Example 28 and the crimped yarn of Comparative Example 13 were subjected to an air entanglement treatment using an interlacer JD-1 manufactured by DuPont to obtain an entangled mixed yarn. This entangled blended yarn is used as the weft, and the crimped yarn of Comparative Example 13 is used as the warp.
cm of plain woven fabric (mixture ratio of antibacterial crimped yarn: 26%). The antibacterial property of this plain fabric and the color difference before and after the alkali treatment were measured and evaluated in the same manner as in Example 30.

Example 34 Using the fiber of Example 13, a tricot knit was obtained in a mesh structure. The antibacterial property of this tricot knit and the color difference before and after the alkali treatment were measured and evaluated in the same manner as in Example 30.

Example 35 Using the fiber of Example 13 and the fiber of Comparative Example 13, a cross-knitted fabric (mixed knitting, 65% of antibacterial fiber) was obtained in a mock rhodia structure. The antibacterial property of this mixed knitted fabric and the color difference before and after the alkali treatment were measured and evaluated in the same manner as in Example 30.

The woven fabrics of Examples 30 to 33 and Examples 34 to 3
Table 8 shows the results of evaluating the antibacterial property and the color difference before and after the alkali treatment with the knitted fabric No. 5.

[0111]

[Table 8]

As is evident from Table 8, the woven or knitted fabric using the antibacterial fiber or the antibacterial crimped yarn of the present invention for all or a part thereof has a high antibacterial property and a small color difference before and after the alkali treatment. It could be used favorably for applications requiring whiteness and sharpness.

[0113]

The antibacterial polyamide fiber and the crimped antibacterial polyamide yarn of the present invention, which are excellent in washing resistance, have almost no discoloration (coloring) and no reduction in antibacterial properties even after alkali treatment, and furthermore, have a high resistance to washing. It has good antibacterial properties with excellent washability, excellent elongation, and can be suitably used for applications requiring whiteness and sharpness. And according to the manufacturing method of the antibacterial polyamide fiber of the present invention, the above-mentioned fiber and crimped yarn can be obtained with good operability.
Furthermore, since the antibacterial polyamide woven or knitted fabric of the present invention uses at least a part of the antibacterial polyamide fiber or the crimped antibacterial polyamide yarn of the present invention, it exhibits good antibacterial properties excellent in washing resistance. However, even when the alkali treatment is performed, there is almost no discoloration (coloring) or decrease in antibacterial properties, and the composition can be suitably used for applications requiring whiteness and sharpness.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one embodiment of a roller type liquid medium supply means used in the production method of the present invention.

FIG. 2 is a schematic view showing an embodiment of a slit nozzle type liquid medium supply means used in the production method of the present invention.

FIG. 3 is a partial schematic process drawing showing one embodiment of the production method of the present invention.

FIG. 4 is a partial schematic process drawing showing another embodiment of the production method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Yarn 2 Slit nozzle 3 Liquid supply pipe 4 Roller 5 Liquid 6 Liquid bath 9 Spin head 10 Spinneret 12 Cooling device 13 Take-up roller 14 Winding device 15 Liquid bath 16 Drawing roller 17 Hot air heater

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) D03D 15/00 D03D 15/00 E D04B 1/16 D04B 1/16 1/20 1/20 21/00 21 / 00 B 21/18 21/18 (72) Inventor Minoru Fujii 4-3-1 Kutaro-cho, Chuo-ku, Osaka-shi F-term in Unitika Fiber Co., Ltd. (Reference) 4L002 AA06 AB00 AB04 AC00 BB01 CA01 DA05 EA00 4L035 AA02 AA09 BB36 BB54 DD02 EE11 EE20 FF08 FF10 GG03 JJ05 JJ30 KK01 KK03 KK05 LC01 LC02 4L036 MA06 MA20 MA24 MA33 PA05 UA08 UA26 4L048 AA24 AA56 AB07 AB21 BA01 DA01 DA13 DA15

Claims (8)

[Claims] 1. A zinc oxide fine particle of 0.1 to 5.0% by mass.
It is made of a polyamide resin and has a color difference ΔE of 2.5 or less before and after alkali treatment and a bacteriostatic activity value of 2.2 or more after 50 washings, and is excellent in washing resistance. Antibacterial polyamide fiber. 2. The antibacterial polyamide fiber excellent in washing resistance according to claim 1, wherein the bactericidal activity value after 50 washings is 0 or more. 3. The zinc oxide fine particles, wherein the surface of the particles is coated with a coupling agent, and the color difference ΔE before and after the alkali treatment is 2.0 or less.
An antibacterial polyamide fiber having excellent washing resistance as described. 4. The fiber has a cross-sectional shape of an irregularity of 20 to 60.
The antibacterial polyamide fiber excellent in washing resistance according to claim 1, wherein the antibacterial polyamide fiber has an irregular cross-sectional shape. 5. An antibacterial polyamide crimped yarn obtained by crimping the antibacterial polyamide fiber excellent in washing resistance according to claim 1, 2, 3 or 4. 6. An antibacterial polyamide fiber excellent in washing resistance according to claim 1, 2, 3 or 4, or knitted and woven using at least a part of the antibacterial polyamide crimped yarn according to claim 5. Antibacterial polyamide woven / knitted fabric. 7. A zinc oxide fine particle of 0.1 to 5.0% by mass.
The moisture content of the containing polyamide resin chip is 0.01 to
5. The antibacterial polyamide fiber having excellent washing resistance according to claim 1, wherein the fiber is melt-spun after being adjusted to 0.2% by mass and solidified within 400 mm from the nozzle surface. Method. 8. A polyamide resin chip containing 0.1 to 5.0% by mass of zinc oxide fine particles whose surface is coated with a coupling agent and having a moisture content of 0.01 to 0.2% by mass.
And then melt-spun to adjust
The method for producing an antibacterial polyamide fiber excellent in washing resistance according to claim 3 or 4, wherein the antibacterial polyamide fiber is solidified within 00 mm.