JPH05163614A - Antimicrobial polyamide fiber - Google Patents

Abstract

PURPOSE:To obtain the subject fiber, containing specific amounts of an insoluble copper compound and an oxime compound, excellent in durability in washing and antimicrobial and deodorant properties without yellowing and embrittling even by treatment with hydrogen peroxide and useful for clothes, etc. CONSTITUTION:The objective fiber containing a water-insoluble copper compound such as cuprous chloride in an amount of 20-200ppm expressed in terms of copper based on the weight of the polymer and an oxime compound such as cyclohexanone oxime in an amount of 0.01-0.1wt.% based on the weight of the polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial polyamide fiber having an excellent antibacterial effect.

[0002]

2. Description of the Related Art Synthetic fibers are widely used for clothing, bedding interiors, etc., but in recent years, pantyhose and leg products having strong antibacterial properties have been strongly demanded. Conventionally, a method of applying or spraying a compound having an antibacterial activity to natural or synthetic fibers or impregnating a fiber with a compound solution has been known. However, such a method has a non-persistent effect, and it is attached. There is a drawback that the drug is easily removed by washing, and various attempts have been made to maintain the persistence of efficacy even by washing.

However, powders (0.1 to 10% by weight) of metals or metal compounds (oxygen oxides, chlorides and thiocyanates of silver, copper and zinc) and liquid polyester compounds (0.1 to 10%). In an antibacterial inner layer made of a thermoplastic polymer (JP-A-2-182902) having an amount of 0.1% to 10% by weight of a metal or metal compound dispersed therein, coloring of the polymer is remarkable. However, it has the drawback that it cannot be used for fluorescent white or light dyeing. Further, a liquid mixture prepared by coating the surface of a metal oxide such as titanium oxide with silver, copper or zinc metal and then blended and mixed in a dispersion medium such as polyester is blended by pressing into a molten thermoplastic polymer. 2-22921
No. 4), the addition of a metal oxide coated titanium oxide such as titanium oxide impairs the transparency of the polymer, and is not suitable for pantyhose and leg products which are particularly required to have transparency.

In the case of socks and inner products such as slips and petticoats, hydrogen peroxide solution treatment (exposure process)
In some cases, the polyamide fiber containing a metal such as a copper compound has a fatal defect of being significantly yellowed and brittle during the processing step.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide fiber which is excellent in antibacterial durability and does not yellow or become brittle even when treated with a hydrogen peroxide solution.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a water-insoluble copper compound is contained in an amount of 20 to 200 ppm with respect to the polymer in terms of copper and an oxime compound with respect to the polymer weight. The present invention has been found out that a combined use of 0.01 to 0.1% results in a polyamide fiber having excellent antibacterial durability without yellowing or embrittlement due to treatment with hydrogen peroxide.

The polyamide fiber in the present invention is a practical homopolymer containing 95% by weight or more of polyhexamethylene adipamide polymerized from hexamethylenediamine and adipic acid, or a homopolymer consisting of polycapramide polymerized from ε-caprolactam. Polymer is a typical example,
Although it can be obtained by a known polymerization method, a homopolymer, a copolymer, or a mixture of each polymer can be used. The cross-sectional shape may be a round shape, a Y-shape, an L-shape triangle, a rectangle, a pentagon, a hollow shape, a star shape, or an irregular shape such as an irregular shape on the outer peripheral portion of the yarn cross section obtained by weight reduction processing. Further, additives which are usually added to polyamide, such as stabilizers and antistatic agents, may be included.

In order to obtain a polyamide fiber having excellent antibacterial durability, a water-insoluble copper compound is used in the present invention. Copper sulfate,
With water-soluble copper compounds such as copper nitrate and cupric oxide, water-insoluble copper compounds elute from the thread when washed,
That is, cuprous chloride, copper iodide, cuprous oxide, copper thiocyanate and the like are used. Particularly preferably, copper iodide is used.

This water-insoluble copper compound is added in the step of polymerizing a polymer, or after it is once made into chips and then sprinkled on the chips. The amount of addition is 20 to 2 based on the weight of the polymer in terms of copper.
It is necessary to set it to 00 ppm, and copper iodide is most suitable from the viewpoint of color tone. From the viewpoint of antibacterial performance, 200 ppm is sufficient, and if the content exceeds 200 ppm, the color tone of the thread becomes poor, which is not preferable. If it is less than 20 ppm, the antibacterial performance varies, so a minimum of 20 ppm is required. The oxime compound used in the present invention includes cyclohexanone oxime,
There are acetoxime, dimethylglyoxime, 9-fluorenone oxime, and the like, and it is recommended that the chips be sprinkled on the chips and then contained. The addition amount is preferably 0.01 to 0.1% based on the weight of the polymer in order to prevent yellowing and embrittlement of the polyamide due to the treatment with hydrogen peroxide solution.

The polyamide fiber of the present invention can be produced by a usual method for producing a polyamide fiber, for example, once spinning at a winding speed of 1000 to 1500 m / min,
The yarn may be drawn, or a so-called high-speed spinning yarn in which a yarn discharged at a high speed of 3500 m / min or more is directly wound or wound while being drawn as necessary. Is also good.

In order to obtain a transparent yarn, it goes without saying that additives such as a matting agent are not added, but it is necessary that the yarn has a spun form or polymer composition in which spherulite generation is suppressed. In particular, when the polyamide fiber is polyhexamethylene adipamide, since the crystallization rate is high, a spinning form in which water is rapidly quenched before the polymer is solidified to suppress the generation of spherulites is taken. good. In the case of a normal spinning form, polyhexamethylene adipamide is mixed with polycapramide in a ratio of 5/20% by weight, or a copolymerization ratio of polymers N66 and N6 copolymerized with polycapramide is 90% by weight: 10% by weight to 80% by weight. %: It is preferable to use 20% by weight.

The polyamide fiber thus obtained is used as a companion yarn (tomoto) of pantyhose, or is used as pantyhose as FTY by covering polyurethane elastic yarn, or after false twisting, polyurethane elastic yarn is used. Used as covered elastic yarn in pantyhose, or as back yarn for socks.

[0013]

EXAMPLES The present invention will be described in detail below with reference to examples. The physical properties are evaluated by the following measuring methods. 1) Antibacterial bacteria count method The bacteria count for evaluating antibacterial properties is measured by the following processing effect evaluation test manual for antibacterial and deodorant processed products / bacteria count method (Textile Products Sanitary Processing Council, 1988) ..

The following bacteria were suspended in a sterilized liquid broth, 0.2 ml of this liquid was inoculated (the number of bacteria was 280,000), and the mixture was cultured at 37 ° C. for 18 hours and then taken out. The viable cell count on the test piece before and after culturing is measured, and the increase / decrease value and difference in increase / decrease value of the bacterial count are calculated by the following formula. If the difference between the increase and decrease is 1.6 or more, it is recognized as having antibacterial property. Test bacterium: Staphylococcus aureus AT
CC 6539 (IFO 12732) Test piece sample: 0.2 g Culture temperature / time: 37 ° C x 18 hours Washing method: JIS 0217 103 Increase / decrease in number of bacteria = Log ₁₀ {Number of viable bacteria on the test piece after 18 hours of culture} ÷ {Number of viable cells immediately before culturing} In the above formula, the number of viable cells immediately before culturing is also referred to as the number of rooted cells.

Difference in increase / decrease in number of bacteria = Increase / decrease in number of bacteria of unprocessed sample−
Increase / decrease in bacterial count of processed sample Use standard white cloth as unprocessed sample. The halo method potato dextrose agar medium is sterilized and cooled to 50 ° C. 5 ml of the adjusted spore suspension is mixed with 100 ml of the main medium, and 15 to 20 ml is immediately poured into a Petri dish to prepare a plate medium. After solidification, a circular test piece with a diameter of about 28 mm is stuck on the medium. This was cultured at 28 ± 2 ° C for 7 days,
The width of the transparent growth inhibition zone (halo) around the sample produced after culturing is measured to confirm the growth condition on the sample piece.

Test bacterium: Trichophyton mentagrophytes (IFO 5466) test piece sample: circle with a diameter of about 28 mm Culture temperature / time: 28 ± 2 ° C. for 7 days Washing method: According to JIS 0217 103 Evaluation method: Display Evaluation-No growth is observed on the sample.

+ Grow within 1/3 of the sample area. ++ Grow within 1/3 to 2/3 of the sample area. +++ Grow within 2/3 of the sample area. ++++ Grow on the entire surface of the sample area. In the above-mentioned evaluation method, the case of-indication is considered to have antibacterial properties.

2) Safety of Skin Disorders According to the patch test determination method (Kawai method) by microscopic observation of Japan Society for Industrial Dermatology, a patch test is carried out using 20 adult males and 20 females as a panel, and the determination is made by the following method. After applying the test sample and the control sample to the inner part of the upper arm of a healthy ancestor for 24 hours, peel off the sample and make a macroscopic judgment 30 minutes later. Observe the skin groove (B-stage). In the depressed skin groove, the sign (+) of the reactivity is emphasized, and in the subtraction of the test regime stimulation index and the control stimulation index, the
(Negative), 1B to 2B (quasi-negative), 3B (quasi-positive) 4B
Judgment is made in four stages of (negative). OB (negative), 1B ~
The case of 2B (quasi-negative) is recognized as effective.

3) Method of observing spherulites The cross section of the fiber is observed under a polarizing microscope, and it is judged by the number of spherulites. Example 1 An oxime compound (cyclohexanone oxime) was added to a polymer weight of 0.05 to a polyhexamethylene adipamide chip made by adding 238 ppm of copper iodide (copper conversion to polymer weight of 79 ppm) from the polymerization stage. %
After sprinkling, it was spun. When spinning is performed at 295 ° C., water is applied at a position 1 m immediately below the spinneret, and then an oil agent is applied to the second godet roll that rotates at 5700 m / min through the first godet roll that rotates at 3958 m / min. 15d / 5f and 7 at 5500m / min.
Wind up 0d / 20f Y-shaped cross-section yarn. At this time, the stretching ratio is 1.44 and the stretching temperature is 150 to 180 ° C.
(The yarns A15d and A70d are used.) Using the yarn A15d, a single-coated elastic yarn of polyurethane elastic yarn of 10d / 1f is obtained under the following conditions.

False Twisting Conditions Model Ishikawa Seisakusho SK-6 Processing Speed 700 m / min Spinning Speed Ratio 0.5 Processing Temperature 205 ° C. False Twist Drawing Ratio 1.07 Covering Conditions Draft Rate 3.00 Twist 2000 m / min S Twist , A support pantyhose is obtained using only a single-ply elastic yarn of Z twist (referred to as A pantyhose). Next, yarn A70d
Is used to obtain a single coating elasticity of a polyurethane elastic yarn of 20d / 2f under the following conditions.

False Twisting Conditions (Same as A15d) Covering Conditions (Same as A15d) This single-coated elastic yarn was used as a back yarn to make socks (A
Socks). Comparative Example 1 The same method as in Example 1 was carried out except that no oxime compound was added, and 15d / 5f and 70d / 20f Y-shaped yarns (yarns B15d, B70) were used.
d) Obtaining support pantyhose (B pantyhose) and socks (B socks) having only the single-coated elastic yarn.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the copper iodide and the oxime compound were not added, and 15d / 5f and 70d / 20f Y-shaped cross-section yarns (yarns C15d, C70d) were used. ), To obtain support pantyhose (C pantyhose) and socks (C sock) having only the single-coated elastic yarn.

[Example 2] Y of 15d / 5f and 70d / 20f was obtained in the same manner as in Example 1 except that water was not added to a portion 1m immediately below the spinning hole.
The thread of the mold section is wound up (threads D15d and D70d). Example 1 is also applied to the yarns D15d and D70d.
A support pantyhose (D pantyhose) and a sock (D sock) having only the single-coated elastic yarn are obtained in the same manner as in.

Example 3 From the polymerization stage, copper iodide was added to 45
A mixture of 90 parts by weight of AH salt and 10 parts by weight of ε-caprolactam was prepared by a conventional method in the presence of 0 ppm (copper conversion: polymer weight 150 ppm), oxime compound (α-benzoin oxime): polymer weight 0.1%. Polymerization by heating gives a copolymer of nylon 66 and nylon 6. Then, this polymer is melt-spun at 280 ° C.
After passing 1560 got roll for 3560 m / min, 570
15d / 5 at 5500m / min after feeding to a second Gotett roll rotating at 0m / min and then applying an oil agent.
Wind up the f and 70d / 20f Y-shaped cross-section yarns. still,
The draw ratio is 1.60. (The yarns E15d and E70d are used.) For the yarns E15d and E70d, the support pantyhose (E pantyhose) and the socks (E socks) having only the single-coated elastic yarn are obtained in the same manner as in Example 1.

COMPARATIVE EXAMPLE 3 The same method as in Example 3 was carried out except that no oxime compound was added.
5d / 5f and 70d / 20f Y-shaped cross-section yarn (thread F
15d, F70d), and support pantyhose (F pantyhose) and socks (F socks) having only a single-coated elastic yarn are obtained.

Comparative Example 4 The same method as in Example 3 was repeated except that copper iodide and oxime compound were not added, and 15d / 5f and 70d / 20f Y-shaped cross-section yarns (yarns G15d and G70d) were used. , Support pantyhose (G pantyhose) and socks (G socks) with only single-coated elastic yarn are obtained.

Example 4 When blending 80 parts by weight of a chip of polyhexamethylene adipamide having a relative viscosity of sulfuric acid of 2.5 and 20 parts by weight of a chip of a polycapramide having a relative viscosity of sulfuric acid of 2.4, a copper-converted polymer was used. 45 ppm by weight of copper iodide and 0.3% by weight of polymer of oxime compound (9-fluorenone oxime) are added. The blended chips are spun according to Example 3. (The yarns are H15d and H70d.) For the yarns H15d and H70d, the support pantyhose (H pantyhose) and the socks (H socks) having only the single-coated elastic yarn are obtained in the same manner as in Example 1.

Comparative Example 5 The same method as in Example 4 was carried out except that no oxime compound was added.
Y-shaped cross-section yarns (yarns I15d, I70d) of 15d / 5f and 70d / 20f, support pantyhose (I pantyhose) and socks (I socks) having only single-coated elastic yarn are obtained.

[Comparative Example 6] The same procedure as in Example 4 was carried out except that copper iodide and oxime compound were not added, and 15d / 5f and 70d / 20f Y-shaped cross-section yarns (yarns J15d, J70d) were used. ), So as to obtain support pantyhose (J pantyhose) and socks (J socks) having only the single-coated elastic yarn.

The yarns A to J pantyhose thus obtained,
Sox treated with hydrogen peroxide is 35% hydrogen peroxide
The test piece is immersed in 5 g / l hyper 3 g / l at 80 ° C. for 5 minutes and subsequently at 95 ° C. for 30 minutes. After that, it is washed with water for 10 minutes and air dried. Table 1 shows the occurrence of spherulites for the yarns A to J, and the support pantyhose and socks of A to J are transparent, antibacterial and deodorant, and the strength retention rate of the yarn after treatment with hydrogen peroxide solution and the antibacterial and deodorant are shown. The sex (evaluation by Trichophyton) is shown in Tables 2 and 3. However, the strength was measured by pulling out polyamide fiber from pantyhose.

The mixing ratios of the copper iodide-added yarns in the support pantyhose and the socks having only the single-coated elastic yarn obtained by using the yarns to which copper iodide was added in the above Examples and Comparative Examples were 82% and 16%, respectively. there were.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

EFFECTS OF THE INVENTION The antibacterial polyamide fiber of the present invention has an excellent antibacterial effect and yellows even when treated with hydrogen peroxide.
It does not become brittle and retains its excellent antibacterial effect. The antibacterial polyamide fiber of the present invention having such performances can be industrially easily manufactured and can be freely switched to many kinds by using ordinary synthetic fiber manufacturing conditions, facilities and equipment.

Claims (1)

[Claims] 1. A polyamide fiber containing a water-insoluble copper compound in a copper equivalent weight of 20 to 200 ppm and an oxime compound in an amount of 0.01 to 0.1% by weight of the polymer.