JP2001159025A - Elastic fiber having excellent bleedout resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastic fiber free from bleedout of an additive. SOLUTION: This elastic fiber comprises the elastic fiber having 8.0-13.5 solubility parameter and the additive having 8.0-13.5 solubility parameter. The content of the additive is adjusted to <=2.0 wt.% based on the weight of the fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an elastic fiber,
More specifically, the present invention provides an elastic fiber used for exhibiting performance and improving quality of the elastic fiber, in which bleed-out of various additives is suppressed.

[0002]

2. Description of the Related Art Conventionally, various additives such as an antioxidant, an ultraviolet absorber and an anti-yellowing agent have been employed in elastic fibers, particularly spandex fibers, to improve the quality of products.
The history of this quality improvement research is old. However, even if an additive that satisfies the performance is found, the additive may bleed out during the processing step, during storage of the product, or after the product has been manufactured, and may not be adopted.
In this case, the investigation time until the final stage requires a long time.
In addition, when the additive bleeds out to the post-processing step, particularly the aging roller, creel stand, knitting needle of a knitting machine, etc., it takes a lot of time and labor to remove the scum, and improvement is desired. . In particular, there is a strong demand for simplification of work due to recent labor situations. Thus, it has been desired to improve the quality of spandex fibers, shorten the development time, improve handling by eliminating the briout, and improve the product quality.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks, and its object is to provide an elastic fiber,
Especially in the selection of additives in the production of spandex fibers, maintain the initial performance of antioxidation, yellowing, ultraviolet absorption, etc., and at the same time, reasonably anticipate post-processing handling and bleed-out, and anti-bleed-out properties It is intended to provide an elastic fiber excellent in the above.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have accomplished the present invention. That is, the present invention relates to a bleed-out resistant resin in which the solubility parameters of the elastic fiber and the additive are each in the range of 8.0 to 13.5, and the additive is contained in an amount of 2.0% by weight or less based on the weight of the fiber. It is an elastic fiber with excellent properties.

[0005] When the solubility parameter is out of this range, the post-processability becomes a problem even if the effects such as antioxidation, yellowing and ultraviolet absorption can be confirmed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The elastic fiber in the present invention means an elastic fiber such as a polyurethane-based, polyester-based, or polyolefin-based fiber, and is preferably a polyurethane-based fiber, and is generally called a spandex fiber. The spandex fiber in the present invention is a polymer composed of a soft segment and a hard segment. Soft segments include polyethylene adipate glycol, polyethylene propylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, polynonamethylene adipate glycol, oxalic acid, succinic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, and isophthalic acid. Acids, polyester glycols such as polymers obtained by condensation polymerization of dibasic acids such as terephthalic acid and glycols, polyethylene ether glycol, propylene ether glycol, polytetramethylene ether glycol, polyethylene propylene ether glycol, polyhexamethylene Examples include polyether glycols such as ether glycol and polycaprolactone glycol. The molecular weight of the soft segment is 4
00 or more is desirable.

The hard segment consists of a reaction product of one or more organic diisocyanates and a chain extender such as a diol or a diamine. The ratio of the soft segment to the hard segment is not particularly limited as long as it is in the range of 0.5 to 4.0 in terms of the molar ratio for polymerization, and the solubility parameter of the polymer obtained therefrom is about 10.0.

[0008] The polymer of the spandex fiber of the present invention is synthesized by a conventional method, and may be either a melt type or a solution type. Melt type is used when polymer is dissolved just before spinning.
In the case of the solution type, a predetermined amount of each additive is added at the end of the polymerization.

As the additives, there are various functionalizing agents, the functions of which are various, such as antioxidation, yellowing prevention, ultraviolet absorption, flame retardancy, antifungal, antibacterial, coloring and the like. The solubility parameter is 8.0 to 1 common to the agents.
3.5, preferably 9.0 to 13.3. This calculation is based on Polymer Engineering Science, Vol. 14, NO. Follow page 2,147. Calculate the solubility parameter of the additive with the desired performance, confirm that it falls within the scope of the claims, and determine the minimum addition amount of the performance manifestation by experimental evaluation. However, no matter how much the solubility parameter is within the scope of the claims, if the added amount is 2.0% by weight or more, bleed-out occurs due to the large added amount. The amount of additive added is 0, depending on the passability of the post-processing step and the quality of the product.
If it is 0 to 1.5, preferably 0.0 to 1.2% by weight, there is no bleed out.

The polymer composition obtained by adding the additives is spun by a usual method. That is, for the melt type, melt spinning is performed by a normal method, and for the solution type, dry or wet spinning is performed by a normal method, and the spandex fiber is wound. At the time of winding, an oil for normal post-processing is applied by any spinning method.

In the present invention, the solubility parameters of the base polymer are cited from the Polymer Handbook, and the solubility parameters of the additives are as described in Polymer Engineering Science Vol. 14, No. 21, page 147, R, F and Fader. Cited in the paper of Zu.

[0012]

The present invention will be described below with reference to examples. In the following, the part indicating the amount of use means part by weight. Example 1 A prepolymer was obtained by reacting 10 parts of methylene bis (4-phenylisocyanate) with 30 parts of polytetramethylene glycol having a molecular weight of 1500 at 80 ° C for 60 minutes, and dissolved in 90 parts of dimethylcetamide. And 1.33 parts of 1,3-propylenediamine with N, N '
A solution dissolved in 12 parts of dimethylacetamide was added to carry out a chain extension reaction. . The additives shown in Table 1 were added to the obtained viscous polymer solution (viscosity at 20 ° C .: 1200 poise), and the mixture was stirred and mixed for 60 minutes.

The obtained polymer solution is supplied with a pore size of 0.15
through a spinneret having a diameter of 30 mm and a number of holes into a stream heated to 250 ° C., and forming the formed filamentous form having a solvent content of 1%.
After converging by mechanical false twist when it becomes below,
The oil was applied and wound up at 200 m / min to obtain 500 g of cheese. Table 1 shows the evaluation results of the obtained elastic fibers.

In the bleed-out test, the 280 denier yarn obtained above was stored at 45 ° C. for 6 months. That is, when a razor blade is applied to the yarn unwound at 10 m / min and wound up to 30 m / min, the presence or absence of a substance adhering to the razor is visually observed and determined. Collected and the substance was identified by IR spectrum.

Example 2 292 parts of adipic acid, 124 parts of ethylene glycol and 181 parts of 1,4-butanediol were charged into a 1 L flask and heated at 210 ° C. under atmospheric pressure and under a nitrogen atmosphere for 2 hours. Then, 0.02 part of titanyl ammonium oxalate and 0.025 part of triphenyl phosphite were added, and the mixture was heated at 210 ° C.
And gradually reduce the pressure to 0.2 mmHg in 2 hours.
Heated for an additional 2 hours under a pressure of 0.2 mmHg. Per Polymer 10 ⁶ g, and a 680 equivalents of hydroxyl groups and 4.8 equivalents of carboxyl groups, mp copoly 32 to 35 ° C. - was obtained (ethylene butylene) adipate.

100 parts of this copolyester (0.034
2 mol), 21.4 parts (0.0856 mol) of 4,4′-diphenylmethane diisocyanate and 0.09 part (0.005 mol) of water were placed in a 1-L polymerization flask, and stirred with N, N′-dimethyl. 80 parts of acetamide was added to make a homogeneous solution. The solution is then heated to 50 ° C.
Reaction was carried out for 60 minutes to obtain an intermediate. When the residual isocyanate groups of the obtained intermediate polymer were quantified, 4.6 × 10
^-4 equivalents of NCO / g. Next, 220 parts of N, N'-dimethylacetamide was added to make a homogeneous solution, which was then cooled to 10 ° C. and 3.2 parts of 1,2-diaminopropane (0.0432 parts).
Mol) in 30 parts of N, N'-dimethylacetamide was added over 30 minutes. The intrinsic viscosity of the obtained polymer was 1.28 dl / g. Then, various additives were added to the solution, and the mixture was stirred for 60 minutes and mixed uniformly. The obtained polymer solution was dry-spun in a usual manner to obtain 280 denier / 1
A 5f multifilament was obtained. The obtained elastic fibers were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[0017]

[Table 1]

[0018]

[Table 2]

NO. 1: Tris (3,5-di-t-butyl-4-hydroxylbenzyl) isocyanurate (Johoku Chemical Co., Ltd.) NO. 2: stearic acid NO. 3: polydiethylaminoethyl methacrylate NO. 4: Tinuvin-770 (manufactured by Ciba-Geigy Corporation) NO. 5: N-methylstearylamide NO. 6: Tinuvin-144 (manufactured by Ciba-Geigy) NO. 7: Stearyl alcohol NO. 8: Stearylamide NO. 9: 1,5-dimethyl-3-ethyl-3-azapentanediol NO. 10: p-chloromethylstyrene-p-cresol NO. 11: lauric acid hydrazide bisphenol-
A-Diglycidyl ether reactant NO. 12: Irganox-1010 (manufactured by Ciba-Geigy Corporation) NO. 13: Irganox RA1010 (manufactured by Ciba-Geigy Corporation) NO. 14: Tinuvin-328 (manufactured by Ciba-Geigy) NO. 15: Tinuvin-327 (manufactured by Ciba-Geigy) NO. 16: Irganox-1024 (manufactured by Ciba-Geigy) NO. 17: bis (N, N'-dimethyl-hydrazinocarboxylamino-4-phenyl) methane NO. 18: Cyanox-1790 (manufactured by Nippon Cyanamid)

As described above, the effect of generating scum was confirmed by the difference in solubility parameter. Further, as a result of analyzing the generated scum by IR spectrum, it was identified that the scum was the same as the added scum.

[0021]

In the present invention, by considering the solubility parameter of the elastic fiber and the additive, an appropriate additive without bleed-out and the amount of the additive can be estimated, and functions such as yellowing and coloring can be obtained. It is very effective in quality improvement activities aiming at and has high industrial value.

Claims (1)

[Claims] The solubility parameter of the elastic fiber and the additive is:
Elastic fibers excellent in bleed-out resistance, each having a range of 8.0 to 13.5 and containing an additive in an amount of 2.0% by weight or less based on the weight of the fiber.