JPH09170147A - Polyurethane fiber/polyamide fiber mixed and knitted fabric excellent in resistances to yellowing and brittleness - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane/polyamide mixed and knitted fabric, excellent resistances to yellowing and brittleness and capable of permanently sustaining the effects. SOLUTION: This polyurethane fiber/polyamide fiber mixed and knitted fabric is obtained by mixing and knitting polyurethane fibers with polyamide fibers containing 0.05-3.0wt.% trialkyl-substituted triazine derivative having at least one sterically hindered amino group or an alkyl-substituted amino group and further a group reactive with hydroxyl group and/or amino group. Thereby, the polyurethane-fiber containing mixed and knitted fabric is capable of permanently and economically improving resistances to yellowing and brittleness at the time of not only storing merchandise but also repetitive wearing in knitted fabric merchandise under severe use environmental conditions.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyurethane fiber / polyamide fiber interwoven knitted fabric product which is excellent in yellowing resistance and embrittlement resistance even during long-term storage and under severe use conditions (sports / casual use). It is provided.

[0002]

2. Description of the Related Art Polyurethane fiber / polyamide fiber interwoven knitted fabric is useful for sports and swimwear inner wear, but the polyurethane fiber becomes brittle (cuts polyurethane fibers during long-term storage and during severe wear and use). However, there was a problem that it was exposed to the surface of the knitted fabric) or turned yellow. As a countermeasure for these problems, various methods have been proposed in which various antioxidants and light stabilizers are applied at the polymer polymerization stage of polyamide fibers or polyurethane fibers, at the fiber production stage or at post-treatment stages such as dyeing. However, a polyurethane fiber / polyamide fiber interwoven fabric having sufficient embrittlement resistance and yellowing resistance has not been proposed.

As a measure for improving such a problem, a method of adding an ordinary hindered phenol type or hindered amine type antioxidant at the stage of producing the yarn, or a copper compound, for example,
A method of adding a copper halide, a copper salt complex compound, a benzotriazole-based or benzophenone-based organic light-proofing agent at the yarn production stage or the dyeing processing stage is known, but the former ordinary antioxidant is added. It was difficult to obtain sufficient embrittlement resistance because the antioxidant fell off and disappeared during the dyeing process or during severe wear and use.
Further, in the latter method of adding a copper compound in the raw yarn manufacturing step, metallic copper is likely to be deposited during spinning, while a method of adding an organic light-proofing agent such as a benzotriazole type or benzophenone type in the raw yarn manufacturing stage. Has a drawback that the spinning operability is likely to be remarkably reduced because heat is easily dissipated.
It is difficult to impart economical and excellent embrittlement resistance and yellowing resistance.

Another proposal, Japanese Patent Laid-Open No. 7-54273, discloses a method of arranging α-oxycarboxylic acid around amino end groups of nylon. However, although some yellowing is improved by this method as well, a polyurethane fiber / polyamide fiber interwoven knitted fabric product having sufficient embrittlement resistance and yellowing resistance has not been proposed.

[0005]

DISCLOSURE OF THE INVENTION The present invention is intended for use in sports products which are used under severe environmental conditions such as a lot of perspiration during exercise in addition to natural / artificial light such as ultraviolet rays and fluorescent lights, and during storage and storage. The purpose is to permanently improve embrittlement resistance and yellowing resistance after repeated wearing.

[0006]

That is, the present invention provides a nitrogen-containing group having at least one sterically hindered amino group or alkyl-substituted amino group and having a hydroxyl group and / or a group reactive with an amino group. A knitted and knitted fabric composed of a polyurethane fiber containing a compound and a polyamide fiber.

In the present invention, a nitrogen-containing compound having a group reactive with a hydroxy group and / or an amino group and imparting embrittlement resistance to polyurethane fibers and polyamide fibers is one or more steric compounds. Trimesic acid trialkylamides having a hindered amino group or one or more alkyl group-substituted amino groups, pyromellitic acid tetraalkylamides, alkylamide-substituted triazines having one or more (alkyl) amino groups, and the like. A compound having at least one group reactive with a group and / or an amino group. From the viewpoint of resistance to embrittlement, a trialkylamide-substituted triazine derivative having at least one sterically hindered amino group and a group reactive with a hydroxy group and / or an amino group is particularly preferable. The group reactive with a hydroxy group and / or an amino group is preferably of a type capable of covalently bonding with a terminal amino group of polyurethane fiber, and examples thereof include an active chlorine group and a fluorine group.

Specific examples of the triazine derivative of the present invention include 2-chloro-4,6-bis (2,2,6,6-tetramethylpiperidyl-4-amino) triazine and the like. Content of 0.05 to polyurethane fiber according to the desired embrittlement resistance level.
It is 3.0% by weight, more preferably 0.1 to 2.0% by weight. If this content is less than 0.05% by weight, the effect becomes insufficient in terms of embrittlement resistance,
If it exceeds 3.0% by weight, it is not economically preferable. As a method for incorporating the triazine derivative of the present invention, in the case of dry spinning, it is possible to add it in a prepolymer damp, and in the case of melt spinning, it is possible to blend it in a polymerization stage or immediately before spinning. Also, no deterioration in spinning operability was observed, and there was no effect on the dope stability, yarn breakage, fluff, loop, or yarn physical properties.

The polyurethane fiber in the present invention is a polyurethane filament obtained by polymerizing a high molecular diol, an organic diisocyanate and a chain extender, and a spinning method is a dry method or a melting method.

The polyamide fibers in the present invention are synthetic fibers such as nylon-6 and nylon-66, and wool,
It is a natural fiber such as silk, and preferably nylon-6 or nylon-66 can be used. A usual melting method is applied as a spinning method. In addition, the polyamide-polymer is an additive that is usually added, for example, a matting agent,
It may contain a stabilizer, an electrostatic agent and the like. The cross-sectional shape and fineness of the fiber are appropriately selected according to the application.

In the present invention, the finished fabric has a pH of 4.0.
It is preferable to adjust the pH of the finished fabric to 4.0 to 6.0, but it is possible to add a non-volatile acid to the fabric during dyeing.
Specific examples of the non-volatile acid include citric acid, malic acid, oxalic acid, tartaric acid and the like, and citric acid is particularly preferably used. As a treatment method, a solution containing 1% to 10% by weight of citric acid with respect to the weight of the dough is used at 50 ° C to 8 ° C.
Treatment at a temperature of 0 ° C. for 30 minutes to 60 minutes can be mentioned. When the fabric pH of the finished cloth is lower than 4.0, the effect of preventing yellowing is sufficient, but it may cause inflammation such as skin damage to the human body. Further, when the fabric pH of the finished fabric is higher than 6.0, the effect of preventing yellowing tends to be insufficient.

The polyurethane fiber / polyamide fiber interwoven knitted fabric of the present invention can be applied with any mixing method, mixing ratio and knitting method. In addition, as applications, sports,
Functional materials for clothing such as swimwear and innerwear are mentioned.

The polyurethane fiber / polyamide fiber interwoven knitted fabric of the present invention is dyed with an acid dye or a metal-containing dye after ordinary scouring and presetting to give a finished fabric pH of 4.0.
It is preferable to adjust to ~ 6.0. In addition, although electrostatic processing, softening processing, resin processing, or the like may be performed as finishing processing, it is preferable to adjust the finish dough pH to 4.0 to 6.0.

According to the present invention, special nitrogen having excellent heat resistance stability and excellent radical accelerating effect as compared with usual antioxidants and organic light-proofing agents which tend to cause deposition of metal copper and heat scattering during the spinning stage. Since the compound is used, the spinning operability of the polyurethane fiber is not deteriorated at all, and the target yellowing resistance and embrittlement resistance are obtained. Also, the finish dough pH is 4.0.
The yellowing resistance can be further improved by adjusting the amount to be about 6.0. The yellowing resistance and embrittlement resistance of such a polyurethane fiber / polyamide fiber interwoven knitted fabric product are permanent, and it is a functional clothing material suitable for sportswear applications under severe wearing conditions.

[0015]

EXAMPLES The present invention will be specifically described with reference to the following examples. In the examples, all% indicate weight%. The characteristics of the polyurethane fiber-containing mixed knitted fabric of the present invention were evaluated by the following methods.

1. Finished Dough pH According to the method defined in JIS-L1096, the pH of the dough extract was measured with a pH meter (manufactured by Horiba Ltd.).

2. Yellowing resistance In accordance with the method specified in JIS-L0855, after the exposure test with nitrogen oxide gas, the yellowing degree is (poor) 1 to 5 grade (good).
It was visually determined by.

3. Heat resistance Dry heat 150 ℃ × 50 hours after heating, yellowing degree (poor) 1
It was visually evaluated as grade 5 (good).

4. Light resistance In accordance with the method specified in JIS-L-2-0842, 6
After irradiation with an ultraviolet ray fader for 3 × 40 hours, discoloration and fading was evaluated on a JIS scale scale in grades 1 to 5.

[5] Complex embrittlement A: Artificial sweat (JIS sweat test D liquid component) 40 ° C. × 0.5 hours B: Artificial lipid 40 ° C. × 0.5 hours C: Bleaching treatment (chlorine-based highter) JIS 103 method D: Household Laundry JIS 103 method E: UV rays F.I. O. M. Irradiation 63 ° C. × 5.0 hours F; Repeated 2000% 20% elongation 2000 times Expansion / contraction fatigue tester A → F cycle 3 times, then 2. in the wale direction.
A test piece of 5 cm × 10 cm was sampled, 80% elongation length was repeated 3 times by a constant velocity type tensilon, stress at 80% elongation at the third time was measured, and stress retention rate was calculated by the following formula. (80% elongation stress of 3-cycle treated sample) / (80% elongation stress of untreated sample) × 100

Example 1 2-Chloro-4,6-bis (2,2,6,6-tetramethylpiperidyl-4-amino) triazine [SANDOFIL A
NCHOR DWL (manufactured by Sand Co.)] was added to a polyurethane prepolymer damp in an amount equivalent to 1.0%, and then 40 denier obtained by ordinary dry spinning. 4 filament spandex yarn and 50 denier. After using nylon-6 filament of 12 filaments as a two-weight recot knitted knitted fabric, after scouring by a conventional method, preset at 190 ° C. for 30 seconds,
A jet dyeing machine for milling type blue acid dyes (Ka
yanol Milling Turquoise Blue 3G, manufactured by Nippon Kayaku Co., Ltd.)
After dyeing in a dyeing solution containing 1.0% by weight of fiber, a leveling agent, and a pH adjusting agent at 95 ° C. for 30 minutes, 6.0% by weight of citric acid and 60 ° C. for 30 minutes were treated with a jet dyeing machine. , Fix agent (Hifix 45, manufactured by Dainippon Pharmaceutical Co., Ltd.) 3% fiber weight%,
Fixing treatment was carried out at 80 ° C for 20 minutes in a solution containing 0.3 g / of an auxiliary agent (Plender-P, manufactured by Dainippon Pharmaceutical Co., Ltd.), and a finishing set at 170 ° C for 40 seconds was performed to prepare a polyurethane fiber / polyamide fiber mixture. A knitted fabric dyed product was obtained. The performance of the obtained fabric is shown in Table 1.

Comparative Example 1 Instead of the specific nitrogen compound of Example 1, an antioxidant (Cy
anox1790: tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -5-triazine-
2,4,6-trione) in the same manner as in Example 1 except that a spandex yarn added with 1.0% by weight was used,
Under the same conditions, a polyurethane fiber / polyamide fiber interwoven knitted fabric dyed product was obtained. The performance of the obtained fabric is shown in Table 1.

Comparative Example 2 Instead of the specific nitrogen compound of Example 1, an antioxidant (Cy
anox 1790) was used in the same method and under the same conditions as in Example 1 except that a spandex yarn added with 1.0% by weight was used and citric acid treatment was not performed during dyeing.
A polyurethane fiber / polyamide fiber interwoven knitted fabric dyed product was obtained. The performance of the obtained fabric is shown in Table 1.

[0024]

[Table 1]

[0025]

INDUSTRIAL APPLICABILITY The polyurethane fiber / polyamide fiber interwoven knitted fabric of the present invention is excellent in radical accelerating effect, good in heat resistance, and extremely excellent in light resistance. Not only can polyurethane fibers be obtained, but also excellent yellowing resistance and embrittlement resistance, which are the original purposes, can be obtained. Further, the specific nitrogen compound of the present invention is strongly chemically bonded to the terminal amino groups of the polyurethane fiber and further the polyamide fiber, and thus has excellent durability of such performance. Therefore, in addition to natural / artificial light such as ultraviolet rays and fluorescent lights, knitted fabric products that are subject to severe environmental conditions, such as sweating during exercise, are resistant to yellowing and brittleness during repeated wear as well as during product storage. It is possible to realize a knitted knitted fabric with improved chemical properties that is permanently and economically improved.

Claims (4)

[Claims] 1. A compound having at least one sterically hindered amino group or alkyl-substituted amino group, and having a hydroxyl group and / or
Alternatively, a polyurethane fiber / polyamide fiber composite excellent in yellowing resistance and embrittlement resistance, characterized in that it is composed of a polyurethane fiber containing a nitrogen-containing compound having a group reactive to an amino group and a polyamide fiber. Knitted fabric. 2. A nitrogen-containing compound having at least one sterically hindered amino group and having a hydroxyl group and / or a group reactive with an amino group is a triazine derivative, and the derivative is used for polyurethane fibers. 0.05 ~
The polyurethane fiber / polyamide fiber interlaced knitted fabric according to claim 1, wherein the content is 3.0% by weight. 3. The fabric pH after dyeing and finishing is 4.0 to 6.
The polyurethane fiber / polyamide fiber interwoven knitted fabric according to claim 1, characterized in that the number is 0. 4. The polyurethane fiber / polyamide fiber interwoven knitted fabric according to claim 3, which is treated with citric acid during dyeing.