JP7779178B2 - Polyester fiber and woven/knitted fabrics using the same - Google Patents

Description

The present invention relates to polyester fibers that have excellent washing durability and antiviral properties, and to polyester woven and knitted fabrics made from such fibers.

In recent years, interest in environmental hygiene has grown, and there is a growing demand for materials used in clothing to have functions such as antiviral properties.

A fiber fabric having antibacterial, antiviral, and antiallergenic properties has been proposed (Patent Document 1), but has problems such as a hard texture and poor water absorbency due to the use of a binder.
While various agents such as metal ions and cationic surfactants have been proposed as antiviral agents, a product containing a quaternary ammonium halide has been proposed as an antiviral product with excellent washing durability (Patent Document 2). However, a product with even better washing durability is desired.

JP 2011-246859 A International Publication No. 2016/009928

The object of the present invention is to provide a polyester fiber having excellent washing durability and antiviral properties, and a polyester woven or knitted fabric made therefrom.

The present inventors have conducted extensive research to achieve the above object, and as a result, have found that the use of a polyester-based water-absorbing agent in a woven or knitted fabric using polyester fibers dramatically improves the washing durability of the antiviral performance when a quaternary ammonium halide is used.
That is, the present invention has the following configuration.
The woven or knitted fabric contains polyester-based fibers, and a quaternary ammonium halide and a polyester-based water-absorbing agent are attached to the polyester-based fibers.
In a preferred embodiment, the woven or knitted fabric has an antiviral activity value of 3 or more according to JIS L 1922:2016 after 50 washes according to the standard washing method (40°C) in accordance with the washing method for SEK-marked textile products.
Furthermore, as a woven or knitted fabric, it is a preferred embodiment that the water absorbency is within 3 seconds when evaluated by the dropping method of JIS L 1907 (2010 method) after 50 washes using the standard washing method (40°C) in accordance with the washing method for SEK-marked textile products.
The woven or knitted fabric preferably contains polyester fibers in an amount of 50% by mass or more, and more preferably 80% by mass or more.
The present invention also relates to polyester fibers to which a quaternary ammonium halide and a polyester water-absorbing agent are attached.

According to the present invention, the polyester-based water-absorbing agent is absorbed into the polyester fiber, and the antiviral agent is also absorbed into the polyester-based water-absorbing agent, which significantly prevents the antiviral agent from falling off after washing, making it possible to provide antiviral woven and knitted fabrics and polyester-based fibers with dramatically improved washing durability.

The present invention will be described in detail below.
The woven or knitted fabric of the present invention contains polyester-based fibers, which provide excellent adhesion of quaternary ammonium halides. From the viewpoint of excellent adhesion, the polyester-based fibers preferably account for 50% by mass or more, and more preferably 80% by mass or more, of the woven or knitted fabric. Examples of polyester-based fibers include, but are not limited to, aromatic polyester fibers such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate, and aliphatic polyester fibers such as polylactic acid and polyglycolic acid. Among these, fibers made of polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate are preferred because they have excellent mechanical properties and durability, and also have good color fastness due to their material properties.
As fibers other than polyester-based fibers, synthetic fibers such as polyamide, polyacrylic, polyurethane, etc., and blended yarns of synthetic fibers with natural fibers such as cotton, rayon, wool, silk, etc. As for the form of woven or knitted fabrics, polyester-based fibers can be used alone, or the above-mentioned fibers can be used in combination with each other to form interwoven or interknitted fabrics.
It is important that the woven or knitted fabric of the present invention has a quaternary ammonium halide attached thereto. Quaternary ammonium halide has the ability to strongly adsorb and denature the amino acids in the proteins that constitute viruses, thereby exerting a high antiviral effect.
Examples of quaternary ammonium halides include tetramethylammonium iodide, trimethyldecylammonium bromide, didecyldimethylammonium bromide, dimethyldidodecylammonium bromide, dodecyldimethyl-2-phenoxyethylammonium bromide, lauryltrimethylammonium bromide, cetyltrimethylammonium bromide, didecyldimethylammonium chloride, trimethylammonium chloride, trimethyldodecylammonium chloride, trimethyltetradecylammonium chloride, cetylpyridinium chloride, and trimethylhexadecylammonium chloride. Examples of the ammonium chloride include octadecyl ammonium chloride, trimethyloctadecyl ammonium chloride, didecyl monomethyl hydroxyethyl ammonium bromide, alkyl dimethyl hydroxyethyl ammonium chloride, alkyl trimethyl ammonium bromide, dioctyl dimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, octyl decyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium bromide, methyl benzethonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl pyridinium ammonium chloride, dialkyl methyl benzyl ammonium chloride, etc. Among these, didecyl dimethyl ammonium chloride is particularly preferably used because of its high affinity with polyester-based water-absorbing agents.
The amount of quaternary ammonium halide attached is preferably 0.01 to 10 parts by weight per 100 parts by weight of the woven or knitted fabric. If the amount is less than 0.01 part by weight, sufficient antiviral properties may not be obtained, while if the amount is more than 10 parts by weight, there is a concern that fastness may decrease. In the present invention, in addition to the quaternary ammonium halide, a polyester-based water-absorbing agent is attached to the woven or knitted fabric. This dramatically improves the durability of the antiviral properties provided by the quaternary ammonium halide. The concentration of the quaternary ammonium halide used is preferably 0.1 to 100 g/L.
Since anionic additives may inhibit the antiviral properties of quaternary ammonium halides, nonionic polyester water-absorbing agents are preferably used as polyester water-absorbing agents. Nonionic water-absorbing agents generally marketed as water-absorbing agents for polyester fibers are preferably used, and polyoxyethylene polyester resins are particularly preferred due to their high affinity with quaternary ammonium halides. Commercially available products include SR6200, Acriner N A99, and SR-N7015 (manufactured by Takamatsu Oil & Fat Co., Ltd.), "Nicepol" PR-86E (manufactured by Nicca Chemical Co., Ltd.), Meika Finish SRM-65 (manufactured by Meisei Chemical Industry Co., Ltd.), and Chlamical RX-10 (manufactured by Keihin Chemical Industry Co., Ltd.), which can achieve high antiviral activity values.
Various additives such as water absorbents other than polyester-based ones, water repellents, hard finishing agents, and stain-proofing agents can be blended, but it is preferable to select nonionic additives for these as well, as with polyester-based water absorbents.
Methods for attaching the quaternary ammonium halide to the woven or knitted fabric of the present invention include bath treatment, dry heat treatment, and wet heat treatment.
A preferred method for bath treatment is to place a woven or knitted fabric in a treatment solution containing a quaternary ammonium halide and circulate the treatment solution. Equipment for bath treatment that can be used includes jet dyeing machines, air jet dyeing machines, Jigger dyeing machines, winch dyeing machines, and beam dyeing machines. The bath treatment temperature is preferably 80 to 140°C, more preferably 110 to 140°C. The treatment time is preferably 10 to 120 minutes, more preferably 20 to 60 minutes.

Dry heat treatment methods include applying a treatment solution containing a quaternary ammonium halide to a woven or knitted fabric using a device such as a mangle, followed by drying and heat treatment. The device used to apply the treatment solution should be one that can apply the solution evenly to the woven or knitted fabric, and a typical mangle is ideal as a liquid application device. Application can also be done using a foam processing machine, printing, inkjet printing, spraying, coating, or other methods.

Drying and heat treatment equipment that can be used includes tenters, short loops, shrink surfers, and cylinder dryers, which can apply heat uniformly to woven and knitted fabrics.

The drying temperature is preferably 80 to 150°C. The treatment time is preferably 15 seconds to 5 minutes, more preferably 100 to 140°C and 30 seconds to 3 minutes. The heat treatment temperature after drying is preferably 80 to 200°C. The treatment time is preferably 15 seconds to 8 minutes, more preferably 130 to 190°C and 30 seconds to 5 minutes. If the treatment temperature is too low, the reaction may be insufficient and satisfactory washing durability may not be achieved. If the treatment temperature is too high, the quaternary ammonium halide may decompose. Furthermore, if a treatment solution is applied during dry heat treatment, the quaternary ammonium halide may draw out the dye, reducing rubfastness. Therefore, it is preferable to wash the fabric in water at 30 to 80°C for 30 seconds to 5 minutes.

Examples of moist heat treatment include applying a treatment solution containing a quaternary ammonium halide to a woven or knitted fabric using a device such as a mangle, followed by moist heat treatment. Any moist heat treatment device can be used as long as it is capable of uniformly applying heat to the woven or knitted fabric, and atmospheric pressure steamers or high-pressure steamers can be used. The moist heat treatment temperature is preferably 80 to 140°C. The treatment time is preferably 15 seconds to 10 minutes. If the treatment temperature or treatment time for applying the quaternary ammonium halide is insufficient, the quaternary ammonium halide may not be sufficiently fixed to the woven or knitted fabric, resulting in poor antiviral properties. Furthermore, if the treatment temperature or treatment time is too long, the texture of the woven or knitted fabric may become hardened and its fastness may decrease.

The method for applying a polyester-based water-absorbing agent will now be described. The preferred method for applying a polyester-based water-absorbing agent is the exhaustion method using in-bath treatment. Specifically, a preferred method involves immersing a woven or knitted fabric in a treatment solution containing a polyester-based water-absorbing agent and circulating the treatment solution. Equipment for in-bath treatment can include jet dyeing machines, air jet dyeing machines, Jigger dyeing machines, winch dyeing machines, and beam dyeing machines. The bath treatment temperature is preferably 80 to 140°C, more preferably 110 to 140°C. The treatment time is preferably 10 to 120 minutes, more preferably 20 to 60 minutes.

Next, we will explain the dyeing process of woven and knitted fabrics. The dyeing process can be carried out in accordance with the dyeing process and conditions for general polyester blend woven and knitted fabrics, and can be carried out using known methods such as batch dyeing machines such as jet dyeing machines, air jet dyeing machines, jigger dyeing machines, winch dyeing machines, and beam dyeing machines, as well as continuous dyeing using the pad method, and textile printing using flat screens, rotary screens, inkjet printing, etc.

The quaternary ammonium halide and polyester-based water absorbing agent of the present invention adhere to the fibers, but it is preferable to treat the polyester-based water absorbing agent, which has high affinity with polyester fibers, in a bath before applying the quaternary ammonium halide. The polyester-based water absorbing agent is absorbed into the polyester fibers, and then the quaternary ammonium halide is applied, so that the quaternary ammonium halide is absorbed into the polyester fibers and also into the polyester-based water absorbing agent.
Because a polyester-based water-absorbing agent is attached, the fiber has excellent water absorption performance, and it is preferable that the water absorption performance be within 3 seconds when evaluated by the dropping method of JIS L 1907 (2010 method) after 50 washes. Since polyester-based fibers are hydrophobic, if a water-absorbing agent is not added, the water absorption performance is poor both initially and after 50 washes, and the antiviral washing durability is also insufficient. However, by adding a water-absorbing agent and a quaternary ammonium halide, it is possible to achieve high water absorption performance and antiviral performance. Here, the measurement method for 50 washes is the value obtained by the standard washing method (40°C) in accordance with the washing method for SEK-marked textile products.
The antiviral performance is preferably such that the antiviral activity value after 50 washes is 3 or more according to JIS L 1922:2016. The antiviral activity value after 50 washes is measured using a standard washing method (40°C) in accordance with the washing method for SEK-marked textile products. The polyester-based water-absorbing agent is absorbed into the polyester fiber, and then the quaternary ammonium halide is also absorbed into the polyester-based water-absorbing agent, so that shedding after washing is significantly suppressed and washing durability is excellent. In the absence of a polyester-based water-absorbing agent, the quaternary ammonium halide is partially absorbed into the polyester fiber and partially attached to the fiber surface, but the attached quaternary ammonium halide falls off after washing, making it impossible to impart excellent antiviral performance.
The woven or knitted fabric of the present invention is preferably used for clothing such as sportswear, loungewear, coats, blousons, blouses, shirts, skirts, slacks, indoor sportswear, pajamas, sleepwear, underwear, office wear, work clothes, food service wear, nursing wear, patient wear, care wear, school uniforms, and kitchen wear. It is also preferably used for miscellaneous goods such as aprons, towels, gloves, scarves, socks, hats, shoes, sandals, and bags. It is also preferably used for interior goods such as curtains, kotatsu covers, sofa covers, cushion covers, sofa coverings, and tablecloths. It is also preferably used for bedding such as futon coverings, sheets, futon covers, and pillowcases.

Next, the antiviral woven or knitted fabric of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(1) Antiviral Activity Value Testing was conducted in accordance with JIS L 1922:2016. Measurement was performed using the Plaque assay. The test virus used was Influenza A virus: A/Hong Kong/8/68 (H3N2) ATCC VR-1679. The antiviral activity was assessed for fabrics without washing (initial) and fabrics after 50 washes to determine whether they met the antiviral processing standard of 3 or higher established by the Japan Textile Evaluation Technology Council. The washing method was in accordance with the washing method for SEK-marked textile products, with standard washing (40°C) and high-temperature accelerated washing (80°C) performed a specified number of times, and the antiviral activity was measured for each.
(2) Water absorption (dropping method)
Evaluation was carried out in accordance with JIS L 1907 (2010).
The washing method was in accordance with the washing method for SEK mark textile products, with standard washing (40°C) and high-temperature accelerated washing (80°C) carried out a specified number of times each, and the water absorbency was measured for each.
(3) Washing fastness: Evaluated according to JIS L 0844 (A-2) (2011).
(4) Rubbing fastness: Evaluated according to JIS L 0849 (Gakushin-type method) (2013).
(5) Lightfastness: Evaluated in accordance with JIS L 0842 (2004).
[Example 1]
A twill fabric was woven with a warp density of 86 threads/2.54 cm and a weft density of 59 threads/2.54 cm using polyethylene terephthalate (PET) false twist textured yarns (167 dtex, 48 filaments) as the warp and weft yarns forming the ground weave of the fabric.

The dyeing process involved standard scouring at 95°C, drying at 130°C, and intermediate setting at 180°C. Next, a commercially available navy blue dye and 1% owf of a nonionic polyester water absorbent ("SR-N7015" manufactured by Takamatsu Oil & Fat Co., Ltd.) were added, and the fabric was dyed for 45 minutes at 130°C, reduction washed at 80°C, rinsed with hot water, dried, and heat-set at 150°C.

The fabric was then immersed in a 4 g/L aqueous solution of didecyldimethylammonium chloride, squeezed at 80% pickup, and dried in a pin tenter set at 130°C. Heat setting was then carried out for 1 minute at 185°C. The polyester fabric was then washed with water at 60°C for 1 minute and heat set for 1 minute in a pin tenter set at 170°C, yielding a fabric with a density of 107 x 67 threads/2.54 cm.
The resulting woven fabric was excellent in fastness, water absorbency, and antiviral activity, and also had good washing durability. The results are shown in Table 1.
[Example 2]
A matte fabric was woven using PET false twist textured yarn (84 dtex, 36 filaments) as the warp yarn and PET/cotton spun yarn (16 count, 65% polyester by mass/35% cotton by mass) as the weft yarn, with a warp density of 151 threads/2.54 cm and a weft density of 42 threads/2.54 cm.

The dyeing process was carried out with intermediate setting in the same process as in Example 1. Next, 1% owf of a nonionic polyester water absorbent ("SR-N7015" manufactured by Takamatsu Yushi Co., Ltd.) was added simultaneously with the commercially available navy blue dye, and the PET false twist textured yarn was dyed at 130°C for 45 minutes, reduction washed at 80°C, and rinsed with hot water. Next, cotton was dyed with the commercially available navy blue dye at 100°C for 30 minutes, rinsed with water, dried, and heat set at 150°C.
The fabric was then immersed in a 5 g/L aqueous solution of didecyldimethylammonium chloride, squeezed at a pickup of 60%, and dried in a pin tenter set at 130° C. Heat setting was then carried out for 1 minute at 185° C. The polyester fabric was then washed with water at 60° C. for 1 minute and heat set in a pin tenter set at 170° C. for 1 minute to obtain a fabric with a density of 160 × 48 threads/2.54 cm.
The resulting woven fabric was excellent in fastness, water absorbency, and antiviral activity, and also had good washing durability. The results are shown in Table 1.
[Example 3]
A smooth knit fabric was obtained on a 28-gauge double circular knitting machine using PET false twist textured yarns of 84 dTec 72 filaments and 84 dTec 48 filaments.
In the dyeing process, after relaxation scouring by the usual method, a commercially available fluorescent dye and a nonionic polyester water absorbent ("SR-N7015" manufactured by Takamatsu Yushi Co., Ltd.) were added at 1% owf, and the PET false twist textured yarn was dyed at 120°C for 30 minutes, rinsed with hot water, dried, and heat set at 150°C.
Thereafter, the knitted polyester fabric was immersed in an aqueous solution of 3 g/L of didecyldimethylammonium chloride, squeezed at a pickup of 90%, and then dried in a pin tenter set at 130° C. Next, heat setting was performed for 1 minute at 185° C. Furthermore, this polyester knitted fabric was washed with water at 60° C. for 1 minute and heat setting was performed for 1 minute in a pin tenter set at 170° C. to obtain a knitted fabric.
The obtained knitted fabric was excellent in fastness, water absorbency, and antiviral activity, and also had good washing durability. The results are shown in Table 1.
[Example 4]
Using a 28-gauge double circular knitting machine, PET false twist textured yarns of 84 decitec 72 filaments and 84 decitec 48 filaments were knitted in a smooth weave.
The dyeing process was carried out according to the dyeing method for ordinary polyester circular knit fabrics up to relaxed scouring. Next, 1% owf of a nonionic polyester water absorbent ("SR-N7015" manufactured by Takamatsu Yushi Co., Ltd.) was added together with a commercially available fluorescent dye, and the polyester was dyed at 120°C for 30 minutes, washed with hot water, and then
Thereafter, the knitted polyester fabric was immersed in an aqueous solution of 3 g/L of dimethyldidodecylammonium bromide, wrung at 90% pickup, and then dried in a pin tenter set at 130° C. Next, heat setting was performed for 1 minute at 185° C. Furthermore, this polyester knitted fabric was washed with water at 60° C. for 1 minute, and heat setting was performed for 1 minute in a pin tenter set at 170° C. to obtain a knitted fabric.
The obtained knitted fabric was excellent in fastness, water absorbency, and antiviral activity, and also had good washing durability. The results are shown in Table 1.
[Comparative Example 1]
The same treatment as in Example 1 was carried out, except that the nonionic polyester-based water-absorbing agent was not added. The obtained woven fabric had insufficient water absorbency and antiviral activity. The results are shown in Table 1.
[Comparative Example 2]
The same treatment as in Example 2 was carried out except that the nonionic polyester-based water-absorbing agent was not added. The obtained woven fabric had insufficient water absorbency and antiviral activity. The results are shown in Table 1.
[Comparative Example 3]
The same treatment as in Example 3 was carried out except that the nonionic polyester-based water-absorbing agent was not added. The obtained knitted fabric had insufficient water absorbency and antiviral activity. The results are shown in Table 1.
[Comparative Example 4]
The same treatment as in Comparative Example 3 was carried out, except that the concentration of didecyldimethylammonium chloride was changed to 1 g/L of aqueous solution. The obtained knitted fabric had insufficient water absorbency and antiviral activity. The results are shown in Table 1.

Claims (4)

A woven or knitted fabric containing polyester fibers, wherein a nonionic polyester water-absorbing agent and a quaternary ammonium halide are adhered to the polyester fibers, and the woven or knitted fabric has an antiviral activity value of 3 or more in accordance with JIS L 1922:2016 after 50 washes by a standard washing method (40°C), and a water absorbency of 3 seconds or less when evaluated by the dropping method of JIS L 1907 (2010 method) after 50 washes by a standard washing method (40°C) . The woven or knitted fabric according to claim 1, wherein the polyester fiber is contained in the woven or knitted fabric in an amount of 50% by mass or more. The woven or knitted fabric according to claim 1 or 2, wherein the polyester fiber is contained in the woven or knitted fabric in an amount of 80% by mass or more. 4. The woven or knitted fabric according to claim 1, wherein the nonionic polyester water-absorbing agent is a polyoxyethylene polyester resin.