JPH07111004B2 - Dyeed antibacterial synthetic fiber and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial synthetic fiber capable of maintaining the antibacterial performance of an antibacterial synthetic fiber by silver-substituted antibacterial zeolite particles at a high level even after dyeing, and a method for producing the same. is there.

[0002]

2. Description of the Related Art It is known that fibers containing an antibacterial zeolite substituted with silver ions and products obtained therefrom exhibit excellent antibacterial activity against microorganisms such as bacteria and fungi ( JP-B-63-5401
No. 3, etc.).

Further, in addition to silver ions, divalent metal ions such as copper ions and zinc ions also have considerable antibacterial properties and heat resistance, although they are less effective than silver ions, so that they are zeolite at the same time as silver ions. Often used in composite antibacterial zeolite adsorbed on.

The metal-substituted zeolite in which one or more of these metals are adsorbed is compounded in a polymer by a usual method, molded into a fiber or a film, and then subjected to a dyeing finishing process.

[0005]

However, the conventional method has a phenomenon that the antibacterial effect is greatly diminished by dyeing or finishing. The degree of reduction of this antibacterial effect varies depending on the dye used, the post-processing agent, and these processing conditions, but especially when dyed with a kind of acid dye such as a metal-containing dye or an acid dye (narrow sense). There was even a significant decrease in the antibacterial effect, and the initial antibacterial effect was almost lost.

Therefore, the present invention solves the above-mentioned drawbacks of the prior art and can significantly suppress the antibacterial deactivation phenomenon in dyeing and finishing, and a silver-substituted zeolite antibacterial synthetic fiber, And to provide a method for producing the same.

[0007]

In order to achieve this object, the present invention relates to 0.01 to 20% by weight of silver-substituted antibacterial zeolite and 0.001 to 1.0% by weight of sparingly soluble in water. A fiber containing a copper compound, wherein the sparingly water-soluble copper compound in the fiber exists independently of the zeolite, and the fiber is an antibacterial synthetic fiber dyed with a dye.

This antibacterial synthetic fiber is obtained, for example, by adding a silver-substituted antibacterial zeolite at a stage before the polymerization of the polymer is completed, and adding a sparingly water-soluble copper compound to the polymer before spinning. , 0.01 for polymer
~ 20 wt% silver-substituted antibacterial zeolite and 0.001-
A polymer composition containing 1.0% by weight of a sparingly water-soluble copper compound, which is then spun into a fiber and then produced by a dyeing method. The copper compound needs to exist independently of the zeolite.

The fact that the poorly water-soluble copper compound exists in the polymer in a state independent of the zeolite means that the copper compound does not enter the zeolite in the state of being metal-substituted,
It means that they exist as copper compound particles different from the zeolite particles. In this case, the fibers are dissolved in a solvent that does not decompose the zeolite particles and copper compounds, and when the zeolite particles and the copper compound are separated from the solution, substantially the same copper compound as when added to the polymer is substantially used. They can be separated in the same amount.

In order for the copper compound and the zeolite particles to exist independently, the silver-substituted zeolite particles are added at a stage before the polymerization of the polymer is completed, such as before or during the polymerization of the polymer, and further the copper compound is added. It may be added to the polymer before spinning in the form of powder, dispersion or solution.

On the other hand, a silver compound and a copper compound are mixed with an unsubstituted zeolite to form composite type antibacterial zeolite particles in which both silver ions and copper ions are adsorbed, or they are manufactured separately. In the case of a composite type use in which a silver-substituted antibacterial zeolite and a copper-substituted antibacterial zeolite are mixed and used, the presence of the copper compound in the polymer is not in a state independent of the zeolite. Can not be achieved. Incidentally, when the silver-substituted zeolite and the copper compound are both polymerized after being mixed into the raw material monomer in a stage before the polymerization, the copper compound is metal-substituted in the zeolite during the polymerization, and is adsorbed, so that it is incorporated into the zeolite. Since it is necessary to add a large amount of a copper compound in excess of the above amount, coloring of the obtained fiber and discoloration with time tend to occur, which is not preferable. Examples of the silver-substituted zeolite used in the present invention include the following.

The zeolite before substitution with silver is an aluminosilicate having a three-dimensional skeleton containing SiO ₂ and Al ₂ O ₃ as main components, and either natural zeolite or synthetic zeolite can be used. Typical examples are Chabazite and Clinoptilolite.
lite), erionite, Faujasite, mordenite and other natural zeolites; A type, X type, Y type, mordenite type, pentasil type, ferrierite type, beta type, ZSM-5 Mold,
Synthetic zeolites such as ZSM-11 type are suitable. Zeolites having a high SiO ₂ / Al ₂ O ₃ molar ratio of, for example, 15 or more are preferred in order to suppress coloration in melt spinning and enhance particle dispersibility.

These zeolites may be silver-substituted zeolites by substituting silver ions with alkali or alkaline earth metals in the zeolite by an ion exchange reaction. Specifically, it may be treated with a solution of a water-soluble silver compound. The silver-substituted zeolite used in the present invention may be a composite type antibacterial zeolite in which other metal ions (copper, zinc, etc.) are simultaneously substituted with silver ions. Even when this composite type antibacterial zeolite is used, the presence of the copper compound existing in the polymer in a state independent of the zeolite is necessary for achieving the object of the present invention.

The substitution amount of silver ion depends on the structure of zeolite,
Depending on the SiO ₂ / Al ₂ O ₃ molar ratio, etc.
A range of 20% by weight is common.

The amount of the silver-substituted zeolite incorporated into the synthetic fiber varies depending on the amount of silver substituted, but generally 0.01 to 20% by weight based on the fiber is suitable. Among them, 0.05 to 5% by weight is preferable, and 0.1 to 1 is particularly preferable.
Weight percent is preferred. If the blending amount is too small, the antibacterial effect is insufficient. On the other hand, if the amount is too large, it becomes difficult to form a fiber, and since the coloring becomes large, the color tone of the dyed fiber deteriorates and the commercial value remarkably decreases.

The method of blending the silver-substituted zeolite with the synthetic fiber may be either during the polymerization of the synthetic fiber raw material or before the spinning. Among them, the polymer before the polymerization of the polymer or during the polymerization may be used. Addition at a stage before the completion of the polymerization is preferable for uniformly finely dispersing the zeolite particles in the polymer.

The sparingly water-soluble copper compound is prepared by mixing water 1 at 20.degree.
As dissolution amount for 00g it is expressed by the following copper compound 100mg, a no or only trace amount not soluble copper compound in water, cuprous chloride, cuprous iodide, a halogen such as bromide cuprous copper; typified by an organic acid copper such as cheap Ikikosando; copper carbonate, inorganic copper, such as copper oxide.

The optimum sparingly water-soluble copper compound depends on the type of the base polymer forming the synthetic fiber, and specifically, it may be selected mainly because it can be dissolved or finely dispersed in the polymer. For example, in the case of polyamide, copper halide, especially copper iodide, is optimal.

The compounding amount of the copper compound is 0.
It may be 001 to 1.0% by weight. Above all, 0.0
05 to 0.5% by weight is preferable, and 0.01 to 0.
1% by weight is preferred. If the blending amount is too small, it is difficult to suppress the deactivation of the antibacterial property of the dyed fiber. On the other hand, if the amount is too large, it causes a great trouble such as yarn breakage during the production of the synthetic fiber, and the coloring is remarkable, which impairs the commercial value of the dyed fiber.

In order to assist the dissolution and dispersion of these copper compounds in the polymer and to stabilize the polymer,
An auxiliary agent may be added at the same time, but this auxiliary agent is not essential in order to exert the intended effect by the addition of the copper compound. Examples of the auxiliary include alkali halides represented by potassium iodide, sodium iodide, potassium bromide, and sodium bromide. Among them, potassium halide is preferable.

The content of the alkali halide may be generally 0.001 to 1.0% by weight based on the fiber. Further, 0.01 to 0.1% by weight is preferable. Actually, it may be blended in the same number of moles as the copper compound. The alkali halide is effective in stabilizing the copper compound in the polymer and suppressing coloring of the polymer by the copper compound.

As a method of blending the copper compound with the polymer before spinning, an optimum method may be selected according to the characteristics of the copper compound. For example, a copper compound that can be pulverized to such an extent that fiber formation is not hindered can be blended with a fiber raw material polymer (pellet) in a powder form and sufficiently mixed before being subjected to spinning. For the copper compound that can be dissolved in the solvent, a method in which the concentrated solution in which the copper compound is dissolved is sprinkled on the polymer and then dried can be used.

A synthetic fiber containing a silver-substituted zeolite and a sparingly water-soluble copper compound in a state independent of the zeolite is dyed with a dye, for example, an acid dye such as a metal-containing dye or an acid dye (in a narrow sense). There is no particular limitation as long as it is a synthetic fiber that is possible. For example, fibers made of polyamide, polyester, polyacrylonitrile, or a copolymer thereof can be mentioned, and the present invention is particularly suitable for polyamide fibers.

Suitable polyamides include poly ε-caprolactam (nylon 6), polylaurolactam (nylon 12), polyamides from diamines and dicarboxylic acids such as polyhexamethylene adipamide (nylon 6).
6) etc. are mentioned. Further, polyamides obtained by copolymerizing these polyamides with copolymerizable diamine-dicarboxylic acid and lactams can also be used.

These synthetic fibers may be combined with usual additives such as heat-resistant agents, light-resistant agents, dispersants and antistatic agents, so long as they are compounds that do not react with copper ions or silver ions to diminish their effects. It may be contained.

The production of synthetic fibers from these polymers can be carried out by the usual methods suitable for the polymers. That is, methods such as melt spinning, wet spinning, and dry spinning may be used.

The antibacterial synthetic fiber obtained by spinning is in the state of filament yarn as it is, in the state of textured yarn subjected to false twisting or fluid processing, of the coated elastic yarn used for covering the polyurethane elastic yarn. Used in the production of a fabric in the state or in the form of stapled spun yarn, it is a fabric product such as tricot, circular knit, woven fabric, and tufted fabric depending on the application.

[0028] In the steps up to the formation of these fabrics, the antibacterial synthetic fibers are other synthetic fibers such as ordinary polyamide fibers, polyester fibers, acrylic fibers;
Mixed with natural fibers such as wool (for example, mixed fibers, mixed spinning,
Although it may be used by knitting, mixed weaving, etc., it is preferable to design the cloth so that the mixing ratio of the antibacterial synthetic fiber of the present invention in the cloth product is 15% or more. When the mixing ratio is as low as less than 15%, it is difficult to exert a sufficient antibacterial effect in the final product.

As described above, the final product is prepared by a method according to the application, but at any stage until the final product is prepared,
It is dyed by a usual method and, if necessary, finished.

As the dye, a dye generally used in synthetic fibers, that is, a disperse dye, an acid dye, a basic dye,
Direct dyes can be used. In particular, the present invention is effective when using an acid dye class such as a metal-containing dye having a metal complex salt structure or an acid dye (in a narrow sense).

The acid dyes (abbreviated as "acid dye" in the present invention) are acid dye bath dyes used for dyeing polyamide fibers and the like, and are represented by, for example, a metal-containing dye and an acid dye (in a narrow sense). To be done.

The metal-containing dyes are generally chromium,
It is a metal complex salt dye in which a metal atom of copper, cobalt, iron or the like and a dye molecule are coordinate-bonded, and a mordant dye, an acid mordant dye or the like can be used in addition to the usual metal-containing acid dye.

The metal-containing dye is a 1: 2 type metal-containing dye, for example, "Irgalan Ye" manufactured by Ciba-Geigy Co., Ltd. of Japan.
llow GRL ”,“ Irgalan Red 4GL ”,“ Irgalan Blue 3
GL ”,“ Irgalan Brown 2GL ”,“ Irgalan Black BGL
"; Kayakalan Yellow GL" manufactured by Nippon Kayaku Co., Ltd.,
"Kayakalan Brown GL", "Kayakalan Red BL", "Ka
yakalan Olive GL ”,“ Kayakalan Black BGL ”;“ Lanafast Khaki GL ”,“ Lanafa ”manufactured by Mitsui Toatsu Dyes Co., Ltd.
st Brown BL ”,“ Lanafast Gray BGL ”;“ Lannyl Blue 3G ”,“ Lannyl Brown ”manufactured by Sumitomo Chemical Co., Ltd.
R ”,“ Lannyl Black BG ”, etc., or 1: 1 type gold-containing dye, for example,“ Neol ”manufactured by Nippon Ciba Geigy Co., Ltd.
an Yellow E-2R ”,“ Neolan Red GRE ”,“ Neolan Blu
e 3R ”,“ NeolanGreen E-3GL ”,“ Neolan Brown E-5G
L ”,“ Neolan Black WA ”;“ Sumilan Black WA ”made by Sumitomo Chemical Co., Ltd .;“ Palatin Fast Yellow ELN ”made by BASF Japan Ltd.,“ Palatin Fast Red G ”
REN ”,“ Palatin Fast Violet SRN ”,“ Palatin Fa
st Blue GGN ”,“ Palatin Fast Green BLN ”,“ Pala
tin Fast Black WAN ”and so on.

Acid dyes (narrowly defined) include "Diacid Fast YellowR" and "Diacid Fast manufactured by Mitsubishi Kasei Co., Ltd."
"Red 3BL", "Diacid Fast Black BR";"Kayanol Yellow NFG", "Kayanol Red NB" manufactured by Nippon Kayaku Co., Ltd.
"R", "Kayanol Blue NR";"Mitsui Nylon Fast Yellow 5G", "Mitsui NylonFa" manufactured by Mitsui Toatsu Dyes Co., Ltd.
st Red BB ”,“ Mitsui Nylon Fast Blue G ”;“ Nylosan Yellow N-5GL ”,“ Nylosan Red ”made by Sand Co.
N-GZ ”,“ Nylosan Blue N-GFL ”,“ Nylosan Navy NR
BL ”;“ Suminol Milling Yell ”manufactured by Sumitomo Chemical Co., Ltd.
ow 3G ”,“ Suminol Milling Red G ”,“ Suminol Mi
lling Brown 3G ”,“ Suminol Milling Black B ”and so on.

The dyed and obtained synthetic fiber of the present invention (and the cloth thereof) may be subjected to finishing processing such as water repellency, antistatic and softening processing, if necessary. Even when these finishing processes are performed, the incorporation of the copper compound in a state independent of the zeolite effectively acts, and the reduction of the antibacterial effect during the finishing process can be significantly suppressed.

The dyed or dyed fabric product which has been further finished may be sewn as required to be finished products such as hosiery such as stockings and socks, clothing such as lingerie, and the like, Further, it may be used as a final product by being used as a lining cloth for a human body wearing molded article such as shoes, a helmet, a hat and gloves. Alternatively, it may be used for upholstery articles such as rugs that require antibacterial properties. It should be noted that dyeing and finishing may be performed after the final product is formed.

[0037]

The copper compound, which is incorporated into the fiber independently of the zeolite, exerts a remarkable effect of significantly suppressing the deactivation of the antibacterial performance of the dyed fiber. This effect is obtained by the presence of the copper compound in a state independent of the zeolite.

On the other hand, in the case of using the composite type metal-substituted zeolite in which copper is added together with silver as a substitution metal in the zeolite, almost no antibacterial deactivation suppressing effect is obtained, and the antibacterial property of the dyed product is satisfactory. Difficult to hold.

When the copper compound is added together with the silver-substituted zeolite before the polymerization, the copper compound is metal-substituted and adsorbed in the zeolite during the polymerization, so that a predetermined amount of the copper compound is present independently. However, it is not preferable because it is necessary to add a large amount of copper compound in consideration of the amount taken into the zeolite, and the coloring of the fiber obtained by this large amount of copper compound and discoloration with time tend to occur.

Since the silver-substituted zeolite is far superior in antibacterial property to the zeolite containing only another antibacterial metal such as copper, the desired antibacterial effect can be obtained by using a small amount of this silver. When the polymer using the substituted zeolite is used as the fiber, there is a big problem that the antibacterial performance is deactivated by using the dyed fiber. This deactivation is
It is remarkable when dyed with an acid dye, especially a metal-containing dye.

It is considered that one of the causes is that silver ions gradually dissociated and released from the antibacterial zeolite particles are trapped by the sulfone group in the acid dye and the antibacterial performance cannot be exhibited. In the case of gold-containing dyes, the released silver ions are further substituted with metal ions (chromium ions, etc.) in the dye or formed by forming a complex with the residual charge site, and thus the antibacterial performance is remarkably reduced. it is conceivable that.

On the other hand, in the case of the dyed fiber according to the present invention in which the copper compound is contained independently of the zeolite, the copper ion from the copper compound becomes the sulfonic group of the acid dye or the metal ion of the metal-containing dye. It is considered that since a stable complex is formed with the substituted or residual charge site, trapping of released silver ions is significantly reduced and the antibacterial action of silver ions is not obstructed.

Further, the antibacterial fiber of the present invention, even when worn in the final product, is a contaminant (dust, dust, etc.) during wearing.
Reduction of antibacterial performance due to human secretions, cosmetics, etc.) can be suppressed. This effect is also similar to the above, the copper ion from the copper compound in the fiber acts on the contaminant,
It is considered that the antibacterial effect of silver ions will not be disturbed.

As in the production method of claim 2, the method of adding the silver-substituted antibacterial zeolite at a stage before the polymerization of the polymer is completed, and adding the sparingly water-soluble copper compound to the polymer before spinning. For example, a dyed fiber in which a copper compound is incorporated in the fiber independently of the silver-substituted zeolite can be obtained, and a dyed antibacterial fiber according to the present invention can be obtained by a method that can be easily carried out industrially. You can

[0045]

Example 1 Example 1 Mordenite-type zeolite particles (SiO ₂ / Al ₂ O ₃
The molar ratio of 17) was treated with an aqueous silver nitrate solution to obtain silver-substituted antibacterial zeolite particles containing 7.5% by weight of silver ion.

The obtained silver-substituted zeolite particles were added in an amount of 0.3% by weight before the polymerization of nylon 6 and polymerized in a usual manner to obtain 98% sulfuric acid relative viscosity 2.75 antibacterial nylon 6 pellets. It was

After drying the obtained antibacterial nylon 6 pellets, powdery copper compounds (cuprous iodide, bromide 1
0.05% by weight of copper or copper benzoate),
After thoroughly mixing and drying, melt-spin as usual 3
Nylon 6 filament yarns of 0 denier and 6 filaments were obtained (No. 1, 2, 3).

The obtained No. 1 fiber was dissolved in a phenol / methanol mixed solvent (3: 1) and the copper compound was separated. As a result, the same copper iodide as when it was added was used at substantially the same molar ratio. Could be separated.

Also, with the same modified nylon 6 pellets,
0.05% by weight powdered cuprous iodide and 0.05% by weight
Was mixed, dried and melt-spun in the same manner as above to obtain a nylon 6 filament yarn (N
o.4).

For comparison, nylon 6 filament yarn mixed with only silver-substituted zeolite was added in the same manner as above except that no copper compound was added, and copper iodide alone was added in the same manner as above except that no silver-substituted zeolite was added. Nylon 6 filament yarn blended with was obtained (No.
5, 6).

Further, as a comparison, a nylon 6 filament yarn was obtained by the same method as above except that neither silver-substituted zeolite nor copper compound was added (No. 7).

These filament yarns were warped and knitted in the usual manner to knit a 32-gauge half tricot, and then a 1: 2 type gold-containing dye "Kayakalan Black BGL".
(Manufactured by Nippon Kayaku Co., Ltd.) stained with 0.8% owf.
"Dimafix" ESH (manufactured by Meisei Chemical Industry Co., Ltd.)
It was fixed in.

The half tricot from the No. 2 filament yarn is "Su: 1: 1 type gold-containing dye".
milan Black WA ”(Sumitomo Chemical Co., Ltd.) 0.8% ow
It was also stained with f. and fixed as above. Also,
Acid dye "Nylusan Blue N-GFL" (Sand Co., Ltd.)
Manufactured), 0.8 wt% owf., 98 ° C, 60 minutes.

The dyed knitted fabric and the knitted fabric before dyeing were evaluated for antibacterial performance by the following shake flask method.

A test strain (Staphylococcus aureus Sta
phylococcus aereus IFO12732) suspension buffer was added, shaken in a closed container at 150 times / min for 1 hour, and the viable cell count after shaking was measured. The difference (%) was calculated.

[0056]

[Table 1]

[0057]

[0058]

[Table 2]

[0059] As shown in Table 1, in the case of the present invention (Nos. 1 to 4) in which a copper compound existing independently of zeolite was blended, excellent antibacterial properties could be exhibited even after dyeing. On the other hand, in the case of fibers containing only silver-substituted zeolite (No.
5) showed an excellent antibacterial property in the undyed knitted fabric,
The antibacterial property was greatly diminished by the dyeing, and the antibacterial property was hardly shown after the dyeing. When the silver-substituted zeolite was not blended (Nos. 6 and 7), antibacterial properties could not be obtained even with the undyed knitted fabric. In addition, as shown in Table 2, the degree of deactivation of antibacterial performance due to the use of dyed fibers varies depending on the type of dye, but in any case, the combined addition of a copper compound suppresses the deactivation of antibacterial performance. It was possible to show a remarkable effect on.

Example 2 Nylon 6 was prepared in the same manner as No. 4 of Example 1 except that modified nylon 6 having a sulfuric acid relative viscosity of 2.72 in which the addition amount of silver-substituted zeolite was 0.2% by weight was used. A filament yarn was obtained (No. 10). With respect to the obtained fiber, substantially the same amount of copper iodide as when it was added could be separated by the same dissolution separation method as in Example 1.

As a comparison, Y-type zeolite having a SiO ₂ / Al ₂ O ₃ molar ratio of 5.0 was treated with silver nitrate and an aqueous solution of copper sulfate to obtain silver and copper at 5.8 wt% and 6.2, respectively.
A composite metal-substituted zeolite having a weight% substitution was obtained, and 0.3% by weight of the zeolite was added before the polymerization of nylon 6 in the same manner as in Example 1, and a modified nylon 6 pellet having a relative sulfuric acid viscosity of 2.72 was obtained. Got Then, melt-spinning was performed in the same manner as in Example 1 without blending the copper compound to obtain a nylon 6 filament yarn (No. 11).

Half tricots were knitted and dyed from these filament yarns in the same manner as in Example 1 to obtain a dyed knitted fabric. The antibacterial properties were evaluated, and the results are shown in Table 3.

[0063]

[Table 3]

[0064] As shown in Table 3, in the case of the fiber (No. 10) obtained by adding the silver-substituted zeolite at the time of polymerization and polymer-blending the copper compound powder, since the copper compound exists independently of the zeolite, It was possible to show excellent antibacterial properties even after dyeing.

On the other hand, in the case of using the composite metal-substituted zeolite in which copper was also substituted in the zeolite together with silver (No. 11), the antibacterial activity was largely inactivated by dyeing, and after dyeing, almost no It did not show antibacterial performance.

Example 3 As a silver-substituted zeolite, S
A composite metal in which mordenite type zeolite having an iO ₂ / Al ₂ O ₃ molar ratio of 17.0 is treated with silver nitrate and an aqueous solution of copper sulfate to substitute 2.0% by weight of silver and 4.0% by weight of copper, respectively. A substituted zeolite was obtained, and 0.7% by weight of the substituted zeolite was added before the polymerization of nylon 6 in the same manner as in Example 1 to obtain a modified nylon 6 pellet having a relative sulfuric acid viscosity of 2.72. Then, similarly to No. 4 of Example 1, copper iodide and potassium iodide were added and mixed, and melt-spun to obtain a nylon 6 filament yarn (No. 12).

The obtained filament yarn was knitted into half tricots and dyed in the same manner as in Example 1 to obtain a dyed knitted fabric. Then, the antibacterial property was evaluated.

The difference in the bacterial reduction rate in the dyed knitted fabric was 86.
%, Showing excellent antibacterial properties.

Example 4 0.05% by weight was added to the modified nylon 6 obtained in Example 1.
Copper bromide and 0.05% by weight potassium bromide are added,
Example 1 except 40 denier and 13 filaments
An antibacterial nylon 6 filament yarn was obtained in the same manner as in.

A half tricot was knitted using 100% of the obtained antibacterial nylon 6 filament yarn (No. 1
3).

Further, this antibacterial filament yarn was supplied to the back of a half tricot, and a normal nylon 6 filament yarn was supplied to the back to knit a half tricot having a mixing ratio of the antibacterial nylon yarn of 50% (No. 14).

Further, as a comparison, a half tricot using 100% of ordinary nylon 6 filament yarn was also knitted (No. 16).

The resulting tricot knitted fabric was treated with 0.5% of "Nylosan Blue N-GFL" (manufactured by Sand Co.) which is an acid dye.
After dyeing with owf., "Sun Life E-7" (manufactured by Nichika Chemical Co., Ltd.) 3% owf.
It was soft-finished with "Sofuna-TO" (manufactured by Takamatsu Yushi Co., Ltd.).

The results of evaluating the antibacterial performance of the obtained half tricot in the same manner as in Example 1 are shown in Table 4.

[0075]

[Table 4]

[0076] As shown in Table 4, even if other fibers were mixed with the antibacterial fiber, an excellent antibacterial product could be obtained.

A hunting hat was manufactured by a usual method using the obtained antibacterial tricot No. 14 as a lining cloth and an acrylic fiber cloth as a surface material. The obtained hunting hat was continuously worn for one month, but the degree of sweatiness was slight as compared with the conventional product.

Further, the antibacterial tricot No. 14 was used for lining synthetic leather ski gloves to manufacture ski gloves. I wore the obtained ski gloves for one season,
The degree of offensive odor and mold caused by sweat was less than that of conventional products.

Example 5 The silver substitution amount in the silver-substituted antibacterial zeolite was 8.5% by weight, and the amount of the silver substitution antibacterial zeolite in the fiber was 0.
An antibacterial polyamide filament yarn was produced (No. 16) in the same manner as in No. 4 of Example 1 except that the amount was 5% by weight, and further 40 denier and 10 filaments were used.

After knitting a 30-gauge half tricot from the obtained antibacterial filament yarn in the usual manner,
1: 2 type gold-containing dye "Lannyl Brown R" (Sumitomo Chemical Co., Ltd.) 1% owf. Dye, then "Dimafix" ESH (Meisei Chemical Co., Ltd.) 3% owf Fixed with., And finally "Lanotex" PMS
(Takamatsu Yushi Co., Ltd.) was used for a soft finish.

When the antibacterial properties of the obtained cloth were evaluated in the same manner as in Example 1, the difference in bacterial reduction ratio was 82% before dyeing and 79% after dyeing and finishing, showing excellent antibacterial performance.

The antibacterial cloth thus obtained was used as an inner lining, and a cotton canvas material having a soft vinyl chloride coating was used as an outer material, and ladies' shoes were used as an inner lining by a usual method.

When the obtained women's shoes were continuously worn for 10 days, 10 hours a day, the degree of offensive odor was slight after 10 days' wear compared to the conventional products.

[0084]

INDUSTRIAL APPLICABILITY The antibacterial fiber according to the present invention is dyed with almost no deactivation of the antibacterial effect even when it is dyed with an acid dye such as a metal-containing dye or further finished. It can also exhibit excellent antibacterial performance as a textile product. This antibacterial fiber exhibits excellent antibacterial performance against bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pneumococcus, Pseudomonas aeruginosa, and fungi such as Candida and Trichophyton. it can.

Therefore, according to the present invention, a dyeing treatment can be performed.
In addition, various textile products that must be finished (such as lingerie, clothing such as underwear, socks such as stockings and socks, helmets, shoes, gloves, and other items worn on the human body such as hats) It is useful as an antibacterial fiber used for products such as lining cloth, upholstery, etc.). In particular, it is extremely useful when dyeing with an acid dye such as a metal-containing dye is required.

Further, the dyed antibacterial fiber can be industrially easily produced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D06P 5/22 F (56) References JP-A-1-250413 (JP, A) JPB 63 -54013 (JP, B2)

Claims (3)

[Claims] 1. A fiber containing 0.01 to 20% by weight of silver-substituted antibacterial zeolite and 0.001 to 1.0% by weight of a sparingly water-soluble copper compound with respect to the fiber. A dyed antibacterial synthetic fiber, characterized in that a sparingly water-soluble copper compound exists independently of zeolite and the fiber is dyed with a dye. 2. The dyed antibacterial synthetic fiber according to claim 1, wherein the dye is an acid dye. 3. A silver-substituted antibacterial zeolite is added at a stage before the polymerization of the polymer is completed, and a sparingly water-soluble copper compound is added to the polymer before spinning, whereby 0.01 to 20 relative to the polymer is added. Dyeing characterized by forming a polymer composition containing 1% by weight of silver-substituted antibacterial zeolite and 0.001 to 1.0% by weight of a poorly water-soluble copper compound, spinning it into fibers, and then dyeing it. For producing a synthetic antibacterial fiber.