JPH0826497B2 - Antibacterial wool blend fabric - 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 wool-blend fabric which retains excellent antibacterial / deodorant properties at a high level and is excellent in washing durability, and in particular, antibacterial wool-blend socks. Etc. are useful.

[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 as a composite type antibacterial zeolite substituted with.

The metal-substituted zeolite obtained by substituting one or more of these metals is compounded in a polymer by a usual method, molded into a fiber or a film, and then mixed with other fibers, if necessary, to obtain a cloth. It is then dyed and finished into an antibacterial textile product.

Since these conventional antibacterial polyamide fibers have excellent resistance to abrasion and the like, they are also used for socks such as socks.

[0006] In socks, it is generally practiced to cross-knit polyamide fibers and natural fibers, to combust, or to mix and spin them to exert their advantages. For example, there is a wool-blend sock that uses wool fibers and polyamide fibers in combination.

[0007]

However, when polyamide fibers made of antibacterial zeolite are mixed in the wool-blended socks by a usual method and used, the antibacterial properties of the antibacterial zeolite are lost and sufficient antibacterial properties are obtained. A wool-blend socks product that exhibits the above performance could not be obtained.

Therefore, the present invention is mainly intended to solve the above-mentioned drawbacks of the prior art and to provide a wool-blended fabric which exhibits antibacterial / deodorant performance at a sufficient level and excellent in washing durability. It has a purpose.

Another object of the present invention is to provide a wool mixed fabric which exhibits excellent antibacterial and deodorant performance even when dyed with an acid dye or finished.

[0010]

In order to achieve this object, the wool-blended fabric of claim 1 is a wool-blended fabric comprising antibacterial polyamide fiber containing silver-substituted zeolite and wool fiber, and at least the wool fiber. A resin thin film is formed on the surface of the fiber, and the mixing ratio of the antibacterial polyamide fiber is 10% by weight or more.

Further, in the wool-blended fabric of claim 2, the antibacterial polyamide fiber is 0.01 to 0.01% with respect to the fiber.
20% by weight of silver-substituted antibacterial zeolite and 0.001-
It is characterized in that it contains 1.0% by weight of a sparingly water-soluble copper compound, and that the sparingly water-soluble copper compound in the fiber exists independently of the zeolite.

The antibacterial polyamide fiber used in the present invention is
It is a polyamide fiber to which antibacterial properties are imparted by dispersing and containing silver-substituted zeolite.

Examples of the silver-substituted zeolite 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. 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. Further, 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.

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 incorporated into the fiber varies depending on the amount of silver substituted, but is generally 0.0
1-20% by weight is suitable. Among them, 0.05-5
Weight% is preferable, and 0.1 to 1 weight% is particularly preferable. If the blending amount is too small, the antibacterial effect is insufficient. On the contrary, if it is too much, it will be difficult to fiberize it,
Further, since the coloring becomes large, the color tone of the dyed fiber is restricted, and the commercial value is remarkably reduced.

When the silver-substituted zeolite is mixed with the fiber,
It may be during the polymerization of the synthetic fiber raw material or before the spinning, but above all, addition at the stage before the completion of the polymer polymerization such as before the polymerization or during the polymerization (addition at the time of polymerization) causes the zeolite particles to be finely dispersed uniformly in the polymer. Preferred for.

It is preferable that the polyamide fiber containing the silver-substituted zeolite is further blended with a sparingly water-soluble copper compound as a compound that is present in an independent state and is not supported on the zeolite particles.

The fact that the copper compound exists in the polymer in a state independent of the zeolite means that the copper compound does not exist in the state where the metal is substituted (supported) in the zeolite but exists as a copper compound different from the zeolite particles. Means. 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. It 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 should be blended during the polymerization, and the copper compound should be blended with the polyamide before spinning in the form of powder, dispersion or solution. Good. On the other hand, in the method of polymerizing the silver-substituted zeolite and the copper compound together in the raw material monomer in the stage before the polymerization, the copper compound is metal-substituted in the zeolite during the polymerization, and is adsorbed. In order to independently present the copper compound, it is necessary to add a large amount of the copper compound in anticipation of the amount taken into the zeolite, and this large amount of the copper compound easily causes coloration or discoloration with time of the fiber obtained. Therefore, it is not preferable.

Examples of the sparingly water-soluble copper compounds, for example, cuprous chloride, cuprous iodide, copper halide such as bromide cuprous; copper carbonate, inorganic copper, such as copper oxide; From Ikikosando And copper carboxylate. Among them, those which can be dissolved or finely dispersed in polyamide are preferable, and for example, copper halide, particularly copper iodide is most suitable.

The compounding amount of the copper compound is 0.00 with respect to the fiber.
It may be 1 to 1.0% by weight. Further 0.005-
0.5 wt% is preferable, and 0.01 to 0.1 wt% is particularly preferable. 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, a great trouble such as yarn breakage is induced during the production of the synthetic fiber, and coloring becomes remarkable, so that the commercial value of the dyed fiber is likely to be impaired.

The effect of the combined addition of the copper compound is that the composite type antibacterial zeolite particles in which silver ions and copper ions are compositely replaced or the antibacterial zeolite particles in which silver-substituted zeolite and copper-substituted zeolite are mixed and used are used. It is difficult to exert such a composite type, and even when these composite type antibacterial zeolites are used, it is preferable to include a copper compound in a state independent of the silver-substituted zeolite.

In order to assist the dissolution and dispersion of these copper compounds in the polymer and to stabilize the polymer,
You may mix | blend an auxiliary agent further. 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 is generally 0.
It is preferable to add 001 to 1.0% by weight, more preferably 0.01 to 0.1% by weight, and it is actually preferable to add it in the same number of moles as the copper compound. This alkali halide aims to stabilize the copper compound in the polymer,
It is effective in suppressing the coloring of the polymer due to the copper compound.

This copper compound and further its auxiliary agent may be added before spinning to a polyamide in which a silver-substituted zeolite is preliminarily blended in a polymerization step or the like. The addition method is as follows.
The optimum method may be selected according to the characteristics of the copper compound.
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 added with usual additives such as heat-resistant agents, light-resistant agents, dispersants and antistatic agents, as long as they are compounds that do not react with copper ions or silver ions to reduce their effects. 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 filament yarn which is not crimped, a crimped yarn which has been crimped such as false twisting, or a staple, which is used. It may be used as a spun spun yarn or the like. At this time, other fibers may be mixed and used.

On the other hand, the wool fiber constituting the wool mixed fabric of the present invention needs to be present in the wool mixed fabric with a resin thin film formed on the fiber surface.
Wool fibers on which this resin thin film is formed are polyamide resin, urethane resin, melamine resin, acrylate resin, epoxy resin, organic chlorine resin, silicone resin, glycazole resin, polyarylate, urea. -A resin such as a formaldehyde resin or a polyamide-epichlorohydrin resin, which is resin-processed with a resin adhesion amount (solid content) of about 0.5 to 5 wt% owf, more preferably about 1 to 3 wt% owf. Good. According to this resin adhesion amount, the film thickness is 0.025 to 0.25.
A resin thin film having a thickness of about μm, more preferably about 0.05 to 0.15 μm is formed. If the coating thickness of this resin thin film is too thin, the desired effect intended by the present invention cannot be sufficiently exhibited. On the other hand, if it is too thick, the soft feel and feel of the obtained fiber or cloth will be impaired and the commercial value will be reduced.

As the resin used for this resin processing,
"Sumitex Resin" M-6 (Sumitomo Chemical Co., Ltd.)
Melamine-based resins such as "Melatex" (manufactured by Tokai Oil Industry Co., Ltd.); "Elastron" BAP (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Eraslen" 600 (manufactured by Tokai Oil Industry Co., Ltd.) ) Such as a urethane resin; an acrylic ester resin such as "PANTEX" ES-3 (manufactured by Shinba Co., Ltd.); "PANTEX" X-330 (Shinba Co., Ltd.)
Made of epoxy resin; "Basolan" DC (BA
Organochlorine resin such as SF; "Tasilon Soft" W
Special silicone rubber resin such as A (manufactured by BASF);
"Azoresin" U-65 (manufactured by Satota Kako Co., Ltd.), "Nissei Danset" F6-10 (manufactured by Nissei Kasei Co., Ltd.)
The glyoxal-based resin and the like are listed.

The resin processing may be carried out either before the wool fiber is mixed with the antibacterial polyamide fiber, at the yarn stage where both fibers are mixed, or at the stage after the wool mixed fabric is formed. Well, for example, the following method can be used.

One component of the polymerization raw material is contained in an aqueous solution in the wool fiber, and then the other polymerization raw material component is treated with a solvent liquid having no water compatibility to form an interfacial polymerized polymer on the fiber surface. There is a method of utilizing the interfacial polymerization phenomenon. For example, treatment with an aqueous solution of hexamethylenediamine, and then
There is a method of forming a nylon polymer on the fiber surface by treating sebacic acid chloride with a petroleum solvent solution. In the case of this method, a sufficient effect can be obtained even with an attached amount of about 1% by weight owf.

Also, a thin resin film is obtained by pretreatment with a halide such as 0.5% by weight bromate, and then resin treatment with polyarylate, urea-formaldehyde resin, polyamide-epichlorohydrin resin or the like. There is also a method of forming the on the wool surface. In the case of this method, it is preferable that the amount of adhesion is about 2 to 3% by weight owf.

Furthermore, the cloth is dipped in an aqueous polyurethane resin emulsion, and the cloth is immersed at 100 to 120 ° C. for 1 to 5 ° C.
You may use the resin processing method of drying in 150 minutes and curing in 150-180 degreeC and 1-3 minutes.

The wool-blended fabric may be woven or knitted by an ordinary method, but in order to obtain a desired antibacterial / deodorant effect,
It is necessary that the mixing ratio of the antibacterial polyamide fiber is 10% by weight or more, and further preferably 30% by weight or more. This mixing ratio is a weight ratio of the antibacterial polyamide fiber to the entire wool-blended fabric, and may be calculated by a usual method from the fabric constitution, the yarn constitution, and the fineness.

When the antibacterial property is imparted only to a part of the wool-blended fabric, the content of the antibacterial polyamide fiber in the fabric part to which the antibacterial property is imparted should satisfy the above value.

The wool mixed fabric is most commonly obtained, for example, by straight knitting or weaving a straight filament yarn, a crimped yarn, or a spun yarn containing an antibacterial polyamide fiber with a wool spun yarn to obtain a wool mixed fabric. Target. In this case, the wool spun yarn includes fibers other than wool, for example,
Unmodified polyamide fiber, polyester fiber, cotton, etc. may be contained at the same time.

The yarn containing the antibacterial polyamide fiber may be a covered elastic yarn obtained by covering around a polyurethane or polyester elastic fiber with a covering yarn containing the antibacterial polyamide fiber. .

Furthermore, staples made of antibacterial polyamide fibers may be mixed-spun with wool fibers to form spun yarns, and wool-blended fabrics may be knitted or woven from the spun yarns. In this case, other fibers may be mixed and spun.

When the present invention is applied to socks, it is effective to partially use a yarn containing an antibacterial polyamide fiber in a shoe covered portion such as a sole portion, a toe portion and a heel portion. In this case, in ordinary sock knitting, a means of knitting by partially adding a yarn containing an antibacterial polyamide fiber may be used.

The knitted and woven wool blended fabric is dyed with a dye such as an acid dye by a usual method, further finish-processed, and optionally set-processed to obtain a wool blended sock-like wool blended fabric product. Becomes

For dyeing this wool-blended fabric, for example, 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.

As the metal-containing dye, a 1: 2 type metal-containing dye, for example, "Irgalan Ye" manufactured by Nippon Ciba Geigy Co., Ltd.
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 Fas
t Blue GGN ”,“ Palatin Fast Green BLN ”,“ Palat
in Fast Black WAN ”.

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 N";"Mitsui Nylon Fast Yellow5G", "Mitsui Nylon Fa" 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 NavyN-RB
L ”;“ Suminol Milling Yello ”made by Sumitomo Chemical Co., Ltd.
w 3G ”,“ Suminol Milling Red G ”,“ Suminol Mil
ling Brown 3G ”,“ Suminol Milling Black B ”and so on.

In addition to the dyeing process, the wool-blended fabric product of the present invention has a finishing process such as water repellency, antistatic and softening,
Antibacterial / deodorant processing may be applied.

The wool-blended fabric of the present invention may be dyed and finished at the stage of yarn before knitting and weaving.

In this case, for dyeing wool fibers, dyes such as chrome dyes, vat dyes, and reactive dyes can be used in addition to the above-mentioned acid dyes and metal-containing dyes.

For example, as vat dyes, "Mikethren Yellow 4GF" and "Mikethren" manufactured by Mitsui Toatsu Dye Co., Ltd.
"Orange R", "Mikethren Dark Blue BOA";"Nihonthrene Yellow 3GC", "Nihont" manufactured by Sumitomo Chemical Co., Ltd.
hrene Blue GCD ”,“ Nihonthrene Brown R ”; BAS
"Indanthren Yellow G", "In" made by F Japan Co., Ltd.
"danthren Red FBB", "Indanthren Olive MW";"Cibanone Yellow R", "Ci" manufactured by Ciba Geigy Co., Ltd.
Examples include banone Blue RS ”and“ Cibanone Olive B ”.

As reactive dyes, "Diacron Yellow 5G" and "Diacron Red B" manufactured by Mitsubishi Kasei Co., Ltd.
"," Diacron Blue 3R ";" Kay "manufactured by Nippon Kayaku Co., Ltd.
acion E Yellow E-S4R ”,“ Kayacion E Red E-53
"B", "Kayacion E Blue E-14B";"Lanasol Yellow 4G", "Lanasol Orange" manufactured by Ciba-Geigy Japan Ltd.
G ”,“ Lanasol Blue 3R ”and the like.

[0053]

The silver-substituted zeolite is far superior in antibacterial properties to zeolite containing other antibacterial metals such as copper, so that a desired antibacterial effect can be obtained even if used in a small amount. In the antibacterial polyamide fiber mixed with this silver-substituted zeolite, the silver ions gradually dissociated from the antibacterial zeolite particles and released act on the bacteria to exhibit antibacterial and deodorant properties.

This antibacterial property can be exerted against bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pneumococcus, Pseudomonas aeruginosa, and fungi such as Candida and Trichophyton. .

When this antibacterial polyamide fiber is made into a wool blended cloth by the conventional method, the antibacterial performance is greatly lost.
According to the method of the present invention, the deactivation of the antibacterial performance is suppressed, and a wool-blended fabric exhibiting excellent antibacterial / deodorant performance can be obtained.

This is because in the conventional wool blend fabric,
Most of the silver ions released from the antibacterial zeolite particles permeate into the wool fiber before they act on the fungus and are trapped by the active groups (peptide groups, etc.) in the wool fiber, thus free silver ions that act on the fungus. It is considered that the amount is greatly reduced and the antibacterial performance is significantly lost.

However, in the present invention, since the resin thin film is formed on the fiber surface of the wool fiber, the active groups in the wool fiber are inactivated, and the capture of silver ions by the active groups is greatly suppressed. It is considered that the amount of free silver ions acting on the bacteria can be maintained at a sufficient level.

The antibacterial effect is also reduced by dyeing with acid dyes or finishing.

However, when the wool-blended fabric according to claim 2 is used, the antibacterial performance can be maintained at an excellent level even when dyeing with acid dyes or finishing.

When the copper compound is not contained, the silver ion released from the antibacterial zeolite particles is trapped by the sulfone group in the acid dye, and the antibacterial performance cannot be exhibited. In this case, the silver ion is further substituted with a metal ion (chromium ion or the like) in the dye or formed by forming a complex with the residual charge site, and thus the antibacterial performance is lowered, but the copper compound as claimed in claim 2 is used. When the copper compound is contained, 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 or forms a stable complex with the residual charge site, and thus the released silver ion is trapped. It is considered that the deactivation phenomenon of the silver ion antibacterial action due to the groups in these dyes is prevented. This effect is obtained by the presence of the copper compound in a state independent of the zeolite.

On the other hand, this effect can hardly be obtained by using a composite metal-substituted zeolite in which copper is added together with silver as a substitution metal in the zeolite. This is presumably because when copper ions are supported on zeolite in the same manner as silver ions, the copper ions can be eluted in a very small amount during dyeing.

[0062]

EXAMPLES 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.

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 70 denier, 24 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 and mixed, and melted similarly. An antibacterial nylon 6 filament yarn was obtained by spinning (No. 2).

Furthermore, after drying the same antibacterial nylon 6 pellets, 0.08% by weight of powdered cuprous bromide and 0.08% by weight of potassium bromide were added and mixed, and Melt spinning was performed to obtain an antibacterial nylon 6 filament yarn (No. 3).

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, nylon 6 was prepared in the same manner as above except that neither silver-substituted zeolite nor copper compound was added.
A filament yarn was obtained (No. 4).

The obtained (antibacterial) nylon 6 filament yarn was subjected to Woolly false twisting by a usual method to obtain a processed yarn.

Using these processed yarns as back yarns and undyed wool spun yarns (52th count) as front yarns, knitting was carried out under the condition that the mixing ratio of (antibacterial) nylon 6 filament yarns was 35%, and knitting of men's socks was carried out. did.

The obtained men's socks were treated with water-based polyurethane resin "Elastron" BAP (Daiichi Kogyo Seiyaku Co., Ltd.).
The resin thin film having a resin adhesion amount (solid content) of 2.0 wt% was formed on the surface of the fiber by immersing the resin thin film in a water solution.

The resulting sock knitted fabric was mixed with 1: 2 type gold-containing dye "Kayakalan Black BGL" (manufactured by Nippon Kayaku Co., Ltd.).
After dyeing with 8% owf, "Softener TO" (manufactured by Takamatsu Yushi Co., Ltd.) 3.0% owf, 50 ° C, 10 minutes, softening was performed to obtain a wool-blend socks product.

For comparison, a wool-blend sock product was obtained by similarly dyeing and softening without the resin processing.

The resulting wool-blend socks product, and
The antibacterial performance of the sock knitted fabric before dyeing and finishing was evaluated by the following shake flask method.

A test bacterium (Staphylococcus aureus Sta
phylococcus aureus 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.

[0076]

[Table 1]

As shown in Table 1, even when the antibacterial nylon 6 yarn is knitted in dark blue (Nos. 1 to 3), a wool-blend sock product which exhibits excellent antibacterial performance only by being resin-processed should be obtained. I was able to.

The antibacterial performance was not obtained when nylon 6 yarn containing no antibacterial zeolite was used (No. 4).

Example 2 Antibacterial nylon 6 having the same composition as No. 2 in Example 1
Melt spinning from polymer as usual, 30 denier,
An antibacterial nylon 6 filament yarn of 10 filaments was obtained.

The obtained antibacterial nylon 6 filament yarn was subjected to Woolly false twisting by a usual method to form a crimped yarn, and then 1: 2 type metal-containing dye "Kayakalan Black BGL" (Nippon Kayaku Co., Ltd.) (Made by Meisei Chemical Industry Co., Ltd.) 3% owf after dyeing with 0.8% owf
Fix treatment at 80 ° C. for 20 minutes, and then “Sofuna-TO” (manufactured by Takamatsu Yushi Co., Ltd.) 3.0% owf, 50
Softening was performed at 10 ° C for 10 minutes to obtain an antibacterial nylon yarn-dyed yarn.

On the other hand, the wool spun yarn (52 count) was dyed in the same manner as in the case of the above-mentioned antibacterial nylon 6 filament yarn, further treated with an aqueous solution of hexamethylenediamine, and then treated with a chloride produced by sebacin. A wool-spun yarn-dyed yarn that was resin-processed with an adhesion amount (solid content) of 1.0 wt%.

By the obtained antibacterial nylon yarn-dyed yarn and wool spun yarn-dyed yarn, the mixing ratio of the antibacterial nylon yarn-dyed yarn is
Knit to be 5%, 30%, 50%, 70%,
Men's socks products were obtained (No.5-8).

About the obtained sock product, Example 1
The antibacterial performance was evaluated in the same manner as.

[0084]

[Table 2]

As shown in Table 2, when the mixture ratio of the antibacterial nylon 6 yarn is 10% or more (No. 6 to 8),
Although excellent antibacterial performance was exhibited, sufficient antibacterial performance was not obtained when the mixing ratio was too small (No. 5).

Example 3 The same antibacterial nylon 6 pellet as No. 2 in Example 1 was dried and then melt-spun in the same manner without adding cuprous iodide or potassium iodide, and then the antibacterial nylon 6 was obtained. 6 filament yarn was obtained (No. 9).

For comparison, nylon 6 pellets to which no silver-substituted zeolite was added, 0.05 wt% of powdered cuprous iodide was added and mixed well, and similarly spun into nylon 6 filament yarn. Was obtained (No. 10).

The obtained (antibacterial) nylon 6 filament yarn was subjected to Woolly false twisting by a usual method to obtain a processed yarn.

These processed yarns and the same wool spun yarns used in Example 1 were knitted under the condition that the mixing ratio of the (antibacterial) nylon 6 filament yarn was 35% to knit men's socks, Similarly, resin processed, dyed and soft finished.

For comparison, dyeing and softening were performed without resin processing.

Example 1 was carried out on the obtained men's socks.
The antibacterial performance was evaluated in the same manner as.

[0092]

[Table 3]

As shown in Table 3, when the nylon 6 yarn containing silver-substituted zeolite was used and processed with resin, excellent antibacterial performance was exhibited, but in other cases, sufficient antibacterial performance was obtained. There wasn't.

[0094]

According to the present invention, the antibacterial / deodorant performance can be maintained at a sufficient level even as a fabric product mixed with wool, and therefore, the excellent antibacterial / deodorant performance can be maintained at a high level, and It is possible to easily obtain an antibacterial wool mixed fabric product having excellent washing durability.

Further, according to the invention of claim 2, it is possible to obtain a wool mixed fabric which exhibits excellent antibacterial / deodorant performance even when dyed with acid dyes or finished.

The wool-blended fabric according to the present invention can be generally applied to the wool-blended fabric in which the antibacterial polyamide fiber is mixed with wool, and is particularly useful for wool-blended socks such as wool-blown socks. In addition, it can be applied to wool tights plating, wool mixed gloves, and the like.

Continuation of the front page (56) Reference JP-A-3-206147 (JP, A) JP-A-2-61132 (JP, A) JP-A-1-139805 (JP, A) JP-A-54-151669 (JP , A) JPB 63-54013 (JP, B2)

Claims (2)

[Claims] 1. A wool mixed fabric comprising antibacterial polyamide fiber containing silver-substituted zeolite and wool fiber, wherein a resin thin film is formed on at least the fiber surface of said wool fiber, and said antibacterial polyamide fiber An antibacterial wool blend fabric having a blending ratio of 10% by weight or more. 2. The antibacterial polyamide fiber contains 0.01 to 20% by weight of the silver-substituted antibacterial zeolite and 0.001 to 1.0% by weight of a sparingly water-soluble copper compound, and The antibacterial wool-blend fabric according to claim 1, wherein the sparingly water-soluble copper compound in the fiber exists independently of the zeolite.