JPH081003B2 - Antibacterial and deodorant stockings - 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 and deodorant stocking which has excellent antibacterial and deodorant properties which are maintained at a high level even after being dyed and finished and which is excellent in washing durability. 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]

These conventional antibacterial polyamide fibers are used in stockings because of their excellent resistance to abrasion and the like.

However, with the conventional antibacterial polyamide fiber, a phenomenon was observed in which the antibacterial effect was greatly diminished in the stocking dyeing step and the finishing step such as softening and water repellent finishing.

The degree of reduction of this antibacterial effect varies depending on the type of dye or post-processing agent used and the processing / finishing conditions thereof, but especially when dyed with an acid dye such as a metal dye. It had a remarkable killing effect, and even the desired antibacterial effect was almost lost.

Further, in stockings, in order to improve comfort when worn, finish processing such as softening, antistatic processing, and water repellent processing is performed, and the antibacterial effect is also reduced by these finishing processing.

The phenomenon in which these antibacterial effects are diminished (deactivation phenomenon) is fatal in the case of a support type stocking in which polyurethane fibers are used together with polyamide fibers, because the amount of polyamide fibers capable of exerting the antibacterial effect is small. Have an adverse effect.

The problem of this antibacterial deactivation phenomenon can be covered to some extent by adding a large amount of antibacterial zeolite in anticipation of the effect reduction due to it, but the combination of zeolite is effective for the transparency of the fiber, Since it tends to cause deterioration of color tone and deterioration of yarn-forming property and post-processability, it is desirable to minimize the amount of the compounding agent.

Therefore, the present invention overcomes the above-mentioned drawbacks of the prior art, can significantly suppress the antibacterial deactivation phenomenon in dyeing and finishing, and minimizes the amount of antibacterial zeolite compounded. The main purpose is to provide stockings that can exhibit excellent antibacterial and deodorant performance even if they are kept to a minimum.

Another object of the present invention is to provide a stocking capable of exhibiting excellent antibacterial / deodorant performance by specifying the conditions under which the antibacterial polyamide fiber is used in the stocking.

[0013]

In order to achieve this object, the antibacterial / deodorant stocking according to claim 1 is a stocking dyed with an acid dye and finished, which is 0.01 to 20% by weight. Silver-substituted zeolite particles and 0.001 to 1.0% by weight of poorly water-soluble copper compound
The sparingly water-soluble copper compound contained in the fiber in a dispersed state
Is characterized in that the antibacterial polyamide fiber existing independently of zeolite is used in at least the sole portion at a mixing ratio of 30% by weight or more.

The antibacterial / deodorant stocking of claim 2 is further characterized in that the leg portion is interwoven with the antibacterial polyamide fiber and the covering elastic yarn.

In the present invention, the copper compound blended in the polyamide fiber needs to exist independently of the silver-substituted antibacterial zeolite particles.

[0016] The present in the polymer in a state independent of a poorly water-soluble copper compound Gaze zeolite, rather than a state in which the copper compound is a metal-substituted (carried) in the zeolite, Po
In the limmer, it means that they exist as copper compound particles different from the zeolite particles. In this case, in a solvent such as zeolite particles or copper compound does not decompose dissolve the fibers and separate the zeolite particles and the copper compounds from the solution, when added in a polymer substantially the same copper <br/> The compounds can be separated in substantially the same amount .

In order for the copper compound and the zeolite particles to exist independently, the copper compound may be added to the polyamide containing the silver-substituted zeolite particles dispersed therein 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 silver ions and copper ions are compositely adsorbed, or they are manufactured separately. In the case of a composite type use such as that used in antibacterial zeolite particles in which silver-adsorbed zeolite and copper-adsorbed zeolite are mixed, the presence of the copper compound in the polymer is not independent of the silver-substituted zeolite. The object of the present invention cannot be achieved only by itself.
Further, both the silver-substituted zeolite and the copper compound, even when polymerized after blending in the raw material monomer in the stage before the polymerization, it is difficult to coexist in the polymer in an independent state due to the interaction of the two, The object of the present invention cannot be achieved by itself.

Examples of the silver-substituted zeolite used in the present invention include the following.

The zeolite before substituting 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. Zeolite having a high SiO ₂ / Al ₂ O ₃ molar ratio of, for example, 14 or more is preferable in order to suppress coloration in melt spinning and improve 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. It may be a composite type antibacterial zeolite in which other metal ions (copper, zinc, etc.) are simultaneously substituted together with silver ions. Even when this composite type antibacterial zeolite is used, the copper compound which exists independently in the polymer is necessary for achieving the object of the present invention.

The substitution amount of silver ions 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 silver-substituted zeolite blended into the fiber varies depending on the amount of silver substituted, but is generally 0.01-.
20% by weight is suitable. Furthermore, 0.05 to 5% by weight
Is preferred. If this amount is too small, the antibacterial effect is insufficient. On the other hand, if the amount is too large, the spinnability and the post-processability are greatly deteriorated, and the transparency and deterioration of the color tone due to the coloring are increased, and the commercial value is lost.

When the silver-substituted zeolite is added to the fiber,
If it is before the compounding time of the copper compound, it may be during the polymerization of the synthetic fiber raw material or before the spinning, but above all, addition during the polymerization is preferable because the zeolite particles are finely dispersed uniformly in the polymer.

As the copper compound, cuprous chloride and cupric chloride can be used.
Poorly water-soluble, such as copper carboxylate such as cheap Ikikosando; inorganic copper, such as copper carbonate, copper oxide; copper, copper halide, such as iodide cuprous, bromide cuprous, cupric bromide Copper compounds are used. Among them, a substance that can be dissolved or finely dispersed in a polymer is preferable, and, for example, copper halide, particularly copper iodide is most preferable.

The compounding amount of the copper compound is 0.00 based on the fiber.
It may be 1 to 1.0% by weight. Further 0.005-
0.5% by weight is preferred. If the amount is too small, less than 0.001% by weight, it is difficult to suppress the deactivation of the antibacterial property of the dyed fiber. On the contrary, if the amount exceeds 1.0% by weight,
At the time of producing synthetic fibers, it causes serious troubles such as yarn breakage, and coloring becomes remarkable, so that the commercial value of the dyed fibers is impaired.

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. This alkali halide 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.

This copper compound and further its auxiliary agent are added before spinning to a polyamide in which a silver-substituted zeolite is pre-blended in a polymerization step or the like. The addition method is optimal depending on the properties of the copper compound. Just select the method. For example, a copper compound which can be finely pulverized to the extent that it does not hinder fiber formation can be blended into a fiber raw material polymer 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.

As the polyamide of the antibacterial polyamide fiber used in the present invention, for example, polyε-caprolactam (nylon 6) and polylaurolactam (nylon 12) are used.
Examples thereof include polyamides derived from lactams, or polyamides derived from diamines and dicarboxylic acids represented by polyhexamethylene adipamide (nylon 66). In addition, a polyamide obtained by copolymerizing a copolymerizable diamine-dicarboxylic acid and a lactam with these polyamides may be used.

These polyamides may be combined with usual additives such as heat-resistant agents, light-resistant agents, dispersants and antistatic agents, as long as they are compounds which do not reduce the effect by reacting with copper ions or silver ions. It may be contained.

These polyamides may be melt-spun and drawn by an ordinary spinning method to obtain antibacterial polyamide fibers. According to the high speed spinning method, the stretching can be substantially omitted.

The antibacterial polyamide fiber thus obtained is a straight yarn which is not crimped, or
The crimped yarn, which has been crimped such as false twisting, may be used for knitting stockings.

The knitting of the stockings using the antibacterial polyamide fiber may be carried out by the following method, and in any method, 30% by weight based on the whole knitting yarn of the part where the antibacterial polyamide fiber is used. It is necessary to use the antibacterial polyamide fiber in the above mixing ratio in order to obtain a desired antibacterial / deodorant effect.

For example, there is a method of using polyamide fiber (straight yarn or crimped yarn) as it is as a knitting yarn of stockings. In this case, the antibacterial polyamide fiber may be used as a part of the knitting yarn, and may be knitted with another fiber such as a usual polyamide crimped yarn or a usual covering elastic yarn.

It is also possible to use an antibacterial polyamide fiber as a covering yarn for the covering elastic yarn and knit a stocking with the covering elastic yarn. In this case, it may be knitted with the antibacterial polyamide fiber yarn, or may be knitted with another fiber yarn, for example, another covering elastic yarn or a normal polyamide fiber yarn.

Among them, the method of using the polyamide antibacterial fiber yarn by knitting with the usual covering elastic yarn is suitable when the antibacterial fiber yarn is used for the leg portion. It is also effective to partially use only the part covered with the shoe, such as the toe, the toe and the heel. In this case, the usual stocking knitting,
A means of knitting by partially adding the antibacterial polyamide fiber may be used.

The covering twist number of the covering elastic yarn is about 2000 to 2500 t / m for both the upper twist and the lower twist for the double covering elastic yarn, and about 1500 to 2000 t / m for the single covering elastic yarn. Good.

The knitted stockings are dyed with an acid dye by a conventional method, further subjected to finish processing, and, if necessary, set in a foot pattern to give a stocking product.

As the dye used for dyeing, an acid dye, particularly a metal-containing dye having a metal complex salt structure is used. The acid dye is an acid dye bath dye used for dyeing polyamide fibers and the like, and examples thereof include a metal-containing dye, an acid dye (in a narrow sense), and an acid mordant dye.

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 gold-containing dye is a 1: 2 type gold-containing dye, for example, "Irgalan Ye" manufactured by Ciba-Geigy Co., Ltd. of Japan.
llow GRL "," Irgalan Red 4GL "," Irgalan Blue 3GL ",
"Irgalan Brown 2GL", "Irgalan Black BGL";"Kayakalan Yellow GL", "Kayakalan B" manufactured by Nippon Kayaku Co., Ltd.
rown GL ", Kayakalan Red BL", Kayakalan Olive GL ",
"Kayakalan Black BGL";"La from Mitsui Toatsu Dyestuff Co., Ltd.
nafast Khaki GL "," Lanafast Brown BL "," Lanafast G
rey BGL ";" Lannyl Blue 3 "made by Sumitomo Chemical Co., Ltd.
G "," Lannyl Brown R "," Lannyl Black BG ", etc.
Alternatively, a 1: 1 type gold-containing dye, for example, "Neolan Yellow E-2R", "NeolanRed GR" manufactured by Ciba Geigy Co., Ltd.
"E", "Neolan Blue 3R", "Neolan Green E-3GL", "Neolan
Brown E-5GL "," Neolan Black WA ";" Sumilan Black WA "by Sumitomo Chemical Co., Ltd .;" Palatin Fast Yellow ELN "," Palatin Fas "by BASF Japan Ltd.
t Red GREN "," Palatin Fast Violet SRN "," Palatin Fa
st Blue GGN "," Palatin FastGreenBLN "," Palatin Fas
t Black WAN "and so on.

Acid dyes (narrowly defined) include "Diacid Fast YellowR" and "Diacid Fast R" manufactured by Mitsubishi Kasei Co., Ltd.
ed 3BL "," Diacid Black ";" Ka "manufactured by Nippon Kayaku Co., Ltd.
yanol Yellow NFG "," Kayanol Red NBR "," Kayanol Blu
e NR "Mitsui Nylon Fa manufactured by Mitsui Toatsu Dyes Co., Ltd.
st Yellow 5G "," Mitsui NylonFast Red BB "," Mitsui
Nylon Fast Blue G "；" Nylosan Yell "made by Sand Co.
ow N-5GL "," Nylosan Red N-GZ "," Nylosan Blue N-GF
L "," Nylosan Navy N-RBL "; Sumitomo Chemical Co., Ltd.
"Suminol Milling Yellow 3G", "Suminol Milling R
ed G "," Suminol Milling Brown 3G "," Suminol Millin
g Black B ".

In order to obtain the stocking product of the present invention, in addition to dyeing processing, finishing processing such as water repellency, antistatic and softening processing is performed. Even when these finishing processes are performed, the incorporation of the copper compound in an independent state with the silver-substituted zeolite effectively acts, and the reduction of the antibacterial effect during the finishing processes can be significantly suppressed.

[0044]

The copper compound, which is incorporated into the fiber independently of the silver-substituted zeolite, exerts a remarkable effect of significantly suppressing the deactivation of the antibacterial performance in the stockings that have been dyed and finished. This effect is obtained when the copper compound exists independently of the antibacterial zeolite. On the other hand, the use of a composite metal-substituted zeolite in which copper is put together with silver as a substitution metal in the zeolite, or a method of adding a copper compound together with the zeolite at the time of polymerization, an antibacterial deactivation suppressing effect is hardly obtained. , It is difficult to keep the antibacterial property of stocking products at a satisfactory level.

Since the silver-substituted zeolite is far superior in antibacterial property to the zeolite containing other antibacterial metal such as copper, the desired antibacterial effect can be obtained by using a small amount thereof. When a polymer using zeolite is used as a fiber, there is a big problem that the antibacterial performance is deactivated by dyeing and finishing with an acid dye.

One of the causes is considered to be that the silver ions gradually dissociated from the antibacterial zeolite particles and released 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.

In the case of the antibacterial polyamide fiber of the present invention in which the copper compound is contained independently of the silver-substituted zeolite, the copper ion from the copper compound is substituted with the sulfone group of the acid dye or the metal ion of the metal-containing dye. Alternatively, it is considered that since a stable complex is formed with the residual charge site, trapping of released silver ions is significantly reduced, and the antibacterial action of silver ions is not obstructed.

On the other hand, when copper ions are supported on zeolite in the same manner as silver ions, only a trace amount of the copper ions is eluted during dyeing, so that the silver ions react with the dye and are deactivated. It is difficult to prevent. Further, even if copper ions are added together with silver zeolite during the polymerization of polyamide, most of them are supported by the zeolite and cannot exist in the fiber in a state independent of the zeolite, thus failing to achieve the object. Particularly in the case of nylon 6, since there is a step of washing the polymerized polymer with water to remove unpolymerized monomers and oligomers, most of the added copper ions are eluted and do not remain in the polyamide.

When this antibacterial polyamide fiber is used in at least the sole portion in a mixing ratio of 30% by weight or more, a sufficient antibacterial and deodorizing effect can be exhibited even in a stocking that has been dyed and finished.

In particular, when the antibacterial polyamide fiber yarn is used as the yarn for interlacing with the ordinary covering elastic yarn, it is easy to cover the drawback that the color tone of the antibacterial polyamide fiber is slightly deteriorated by the blended silver-substituted zeolite. It is effective for obtaining a desired antibacterial / deodorant effect without impairing aesthetic properties such as transparency and color tone of the leg portion.

[0051]

Example: Mordenite type zeolite particles (SiO ₂ /
An Al ₂ O ₃ 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 ions.

0.3% by weight of the obtained silver-substituted zeolite particles was added before the polymerization of nylon 6, and the mixture was polymerized in the 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, 0.05% by weight of powdery cuprous iodide was added and mixed well, and melt-spun in the usual manner to obtain 15 denier, 5 An antibacterial nylon 6 filament yarn of filament was obtained (No. 1).

After drying the same antibacterial nylon 6 pellets, 0.05% by weight of powdery cuprous iodide and 0.05% by weight of potassium iodide were added, mixed and melted in the same manner. An antibacterial nylon 6 filament yarn was obtained by spinning (No. 2).

When these antibacterial fibers were dissolved in a phenol / methanol mixed solvent (3: 1) to separate the copper compound, the same copper iodide as when added was separated at substantially the same molar ratio. did it.

For comparison, the same antibacterial nylon 6 pellet was spun into the same antibacterial nylon 6 filament yarn and the silver-substituted zeolite was added in the same manner as above except that cuprous iodide and potassium iodide compound were not added. Only the copper iodide was added to the nylon 6 pellets which were not prepared, and the nylon 6 filament yarn was obtained by spinning in the same manner as above (Nos. 3 and 4).

For comparison, a nylon 6 filament yarn was obtained in the same manner as above except that neither silver-substituted zeolite nor copper compound was added (No. 5).

The obtained (antibacterial) nylon 6 filament yarn is used as a yarn for knitting with an ordinary single covering elastic yarn, and is knitted by feeding the same number of 2 yarns at a time and feeding by 4 yarns. The leg part of the type pantyhose (including the toe part) is knitted. The nylon 6 false twisted textured yarn (30 denier, 6 filaments) was used for the panty portion. The mixing ratio of the (antibacterial) nylon 6 filament yarn in the leg portion of the obtained pantyhose was 45%.

For comparison, a yarn for interlaced knitting of the leg portion is used.
A pantyhose was produced in the same manner as described above except that the No. 2 antibacterial nylon 6 filament yarn and the No. 5 nylon 6 filament yarn were used for each yarn feeding (No. 12). The mixing ratio of the antibacterial nylon 6 filament yarn in the leg portion of the obtained pantyhose was 2
It was 3%.

The resulting stockings were treated with 1: 2 type gold-containing dye "Kayakalan Brown GL" (manufactured by Nippon Kayaku Co., Ltd.),
Stained with 0.8% owf., Then "Sunlife E-7"
(Nichika Chemical Industry Co., Ltd.) was subjected to a fix treatment, and then softening was performed using “Sofuna-TO” (Takamatsu Yushi Co., Ltd.) to obtain product stockings.

The resulting product stockings and their dyeing
With respect to the stockings before finishing, the antibacterial performance was evaluated by the following shake flask method.

Test cloths (Staphylococcus aureus Sta
phylocococcus 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.

[0063]

[Table 1]

As shown in Table 1, in the case of the present invention (Nos. 1 and 2) in which the copper compound not supported on the silver-substituted zeolite coexisted in the fiber (Nos. 1 and 2), the antibacterial activity was inactivated by dyeing and finishing. Almost none, excellent antibacterial performance was demonstrated.

On the other hand, no copper compound was allowed to coexist.
In the case of No. 3, the antibacterial performance was excellent before dyeing, but the antibacterial performance was significantly reduced by dyeing and finishing, and the antibacterial performance in the product stocking was as follows: No.4,
It was about the same as 5).

When only copper compound is contained (No. 4)
No antibacterial performance was exhibited, and the copper compound exhibited an antibacterial deactivation prevention effect only when it was made to coexist with a silver-substituted zeolite.

Further, in the case of No. 12 stocking in which the mixing ratio of the antibacterial nylon fiber specified in the present invention was too small, sufficient antibacterial and deodorant effects could not be obtained.

Furthermore, the stockings of the present invention (No. 1,
Regarding 2), a wearing test was carried out under the condition that stockings were worn and women's shoes made of cowhide were worn. As a result, no unpleasant odor was observed even after wearing for about 10 hours.

[0069]

EFFECTS OF THE INVENTION According to the present invention, since the deactivation phenomenon of antibacterial property in dyeing and finishing can be significantly suppressed, excellent antibacterial and deodorant performance is obtained even if the amount of antibacterial zeolite is minimized. In addition, the desired antibacterial / deodorant stocking product can be obtained without impairing the aesthetics (transparency, color tone, etc.) of the leg part most required for stockings.

Claims (2)

[Claims] 1. A stocking dyed with an acid dye and finished, comprising 0.01 to 20% by weight of silver-substituted zeolite particles and 0.001 to 1.0% by weight of a sparingly water-soluble copper compound. Dispersed and contained in the fiber
An antibacterial / deodorant stocking, characterized in that the antibacterial polyamide fiber in which the sparingly water-soluble copper compound exists independently of zeolite is used in at least a sole portion in a mixing ratio of 30% by weight or more. 2. The antibacterial / deodorant stocking according to claim 1, wherein the leg portion is interwoven with the antibacterial polyamide fiber and the covering elastic yarn.