JP2000290836A - Polyurethaneurea elastic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethaneurea elastic fiber having excellent resistance to embrittlement due to chlorine for a long term even under an acidic condition (pH 3-6) in dyeing and even after the dye-fixing treatment with a tannin solution (pH 3-4.5). SOLUTION: This polyurethaneurea elastic fiber contains hydrotalcite with an adhesional phosphate (ester) on its surface in an amount of 0.5-10 wt.% based on the weight of the polyurethaneurea elastic fiber itself, and is produced by a method characterized by the solution spinning of a polyurethaneurea dope in which hydrotalcite with the adhesional phosphate (ester) on its surface is blended in an amount of 0.5-10 wt.% based on the weight of a polyurethaneurea composition. The hydrotalcite with the adhesional phosphate (ester) on its surface can prevent the polyurethaneurea dope from choking a filter. The polyurethaneurea elastic fiber containing the above hydrotalcite shows excellent resistance to embrittlement due to chlorine even after dyeing treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane urea elastic fiber having excellent chlorine embrittlement resistance.

[0002]

2. Description of the Related Art Conventionally, polyurethane urea elastic fibers obtained by extending the chain length of an isocyanate-terminated prepolymer prepared with an organic diisocyanate and a high molecular weight diol with a diamine are known, and are knitted with polyamide fibers or polyester fibers. It is used as a stretchable material in many fields, such as foundations, socks, pantyhose, and sportswear.

However, when a clothing product using polyurethane urea elastic fiber is exposed to chlorine bleach, or when a swimwear using polyurethane urea elastic fiber is repeatedly exposed to sterilizing chlorine water having an effective chlorine concentration of 0.5 to 3 ppm, It is known that the elastic function of the polyurethane urea elastic fiber is remarkably reduced and the yarn is broken. In the case of apparel products comprising polyamide fibers and polyurethane urea elastic fibers, the discoloration of the dye is caused.

[0004] As a measure for improving the chlorine embrittlement resistance, a method of adding 0.1 to 1 µm of zinc oxide to improve the chlorine embrittlement resistance of a polyether-based polyurethane elastic fiber which is not degraded by microorganisms (Japanese Patent Publication No. JP-A-60-43444), a method of adding a hydrotalcite compound (JP-A-59-133248), and a method of adding magnesium oxide or aluminum oxide having a particle size of 5 μm or less (JP-B-61-35283). A method of adding a solid solution of magnesium oxide and zinc oxide having a thickness of 0.05 to 3 μm (JP-A-6-81215) is disclosed.
There were the following problems.

In a swimsuit made of polyamide fiber and polyurethane urea elastic fiber, the dye of the polyamide fiber is dyed with an acid (pH 3 to 6) in order to prevent the dye of the polyamide fiber from discoloring due to chlorine contained in the water of the swimming pool. After that, a dye fixing treatment (pH 3 to 4.5) with a tannin solution is performed. By the acid dyeing and the dye fixing treatment of the dye dyed on the polyamide fiber by the tannin solution, the above-mentioned chlorine embrittlement resistance improving agent added to the polyurethane urea elastic fiber is eluted from the fiber to improve the chlorine embrittlement resistance. The decline was seen.

Further, when these additives are added to a spinning solution of polyurethane urea, secondary agglomeration occurs and clogging of a spinning filter and breakage of yarn during spinning increase. JP-A-3-292364 discloses a method of coating a surface of hydrotalcite with a fatty acid to prevent secondary aggregation, but it is insufficient. JP-A-10-
JP-A-168657 discloses that hydrotalcite and / or other basic metal aluminum hydroxy compounds coated with a polyorganosiloxane or a mixture of a polyorganosiloxane and a polyorganohydrogensiloxane are less likely to undergo secondary aggregation. But still not enough.

[0007] WO 98/36112 states that
It includes divalent metal M ^{2 +} and aluminum, 0.5-10 weight composite oxide particles divalent metal M ^{2 +} molar ratio of to aluminum is 1-5 to polyurethaneurea%
An elastic fiber characterized by being contained is disclosed.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for dyeing under acidic conditions (pH 3 to 6) or a dye fixing process using a tannin solution (pH 3 to 4.5) after dyeing. It is an object of the present invention to provide a polyurethane urea elastic fiber having excellent chlorine embrittlement resistance over a long period of time.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that hydrotalcite having a phosphate ester attached to its surface is 0.5 to 10% by weight based on the total weight of polyurethane urea elastic fibers. % Of polyurethane urea elastic fiber with excellent chlorine embrittlement resistance and extremely small amount of filter clogging due to secondary agglomeration of hydrotalcite and thread breakage during spinning and aging. I found it.

That is, the present invention is a polyurethane urea elastic fiber containing 0.5 to 10% by weight of hydrotalcite having a phosphate ester attached to the surface thereof, based on the weight of the polyurethane urea elastic fiber. Hereinafter, the present invention will be described in detail. The coating with a phosphate ester is described in WO 98/36112, but the coating of phosphate on hydrotalcite is not described. Surprisingly, however, this phosphate coating on hydrotalcite significantly reduces filter clogging due to secondary agglomeration of hydrotalcite, breakage during spinning and thread breakage during aging, and polyurethane urea elasticity due to tannin liquid. It shows excellent chlorine embrittlement resistance because it hardly falls off from the fiber.

The hydrotalcite of the present invention is, for example,
Described in JP-B-46-2280, by mixing the aluminum source material, magnesium source material was heated reaction, when former two ingredients containing no CO _2, the method of adding CO ₂ or carbonate Is obtained by
The amount of hydrotalcite added may be an amount that satisfies the chlorine embrittlement resistance required for the product, and is preferably 1 to 10% by weight, more preferably 2 to 6% by weight, based on the weight of all polyurethane urea elastic fibers. % By weight.

The phosphoric acid ester used in the present invention may be any of a monoester type, a diester type and a mixture thereof. However, the linear or branched alkyl group attached to one ester has 4 to 30 carbon atoms. Are preferred. Examples of phosphate esters include butyl acid phosphate, 2-ethylhexyl acid phosphate,
Lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, di-2
-Ethylhexyl phosphate, oleyl acid phosphate and the like. More preferably, the straight or branched alkyl group attached to one ester has 8 to 20 carbon atoms, and stearyl acid phosphate is most preferred.

As a method for attaching the phosphate ester, for example, there is the following method. (1) a method of directly heating hydrotalcite and a phosphate ester, (2) a method of directly spraying or mixing a phosphate ester dissolved in an organic solvent onto hydrotalcite and removing the organic solvent, and (3) a method of removing the phosphate ester. And (4) a method in which a phosphate ester is added to and mixed with a polyurethane urea solution containing hydrotalcite.

The amount of the phosphoric acid ester attached is preferably 0.1% by weight or more based on the hydrotalcite. When the content is less than 0.1% by weight, good effects are hardly exhibited, and 10% by weight
Even if it exceeds, the effect is hardly improved. When the phosphate ester is attached to the surface of hydrotalcite at the stage of the spinning dope before spinning the polyurethane urea elastic fiber,
In addition to the effect of further improving the chlorine embrittlement resistance after the tannin solution treatment, it also has the effect of suppressing the secondary aggregation of hydrotalcite in the spinning solution, so that filter clogging of the spinning solution is reduced, and during spinning. It also has the effect of reducing yarn breaks.

The polyurethane urea elastic fiber of the present invention comprises:
A chain extender having a polyfunctional active hydrogen atom and a terminal blocking agent having a monofunctional active hydrogen atom in an isocyanate-terminated prepolymer prepared with an organic diisocyanate and a substantially linear polymer diol; Polyurethane urethane polymer composition obtained by reacting a urethane group in a molecule obtained by one-step or multi-step reaction with an additive, if necessary, and a hydrotalcite having a phosphate ester attached to the surface. The polyurethane urea spinning solution containing is produced by dry spinning, wet spinning, or the like.

Another method for preparing the polyurethane urea elastic fiber is as described above, in which an isocyanate-terminated polymer comprising a substantially linear polymer having hydroxyl groups at both ends and having a molecular weight of 600 to 5,000 and an organic diisocyanate. And a chain extender having a polyfunctional active hydrogen atom and a terminal terminator having a monofunctional active hydrogen atom. In this case, the hydrotalcite having a phosphate ester adhered to the surface may be added at any stage before spinning.

The polymer diol which is one of the raw materials for producing the polyurethaneurea of the present invention is a substantially linear polymer having a molecular weight of 400 to 3,000 having hydroxyl groups at both ends. Polyether diols such as oxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol, and copolymerized polyalkylene ether diols having linear or random ether bonds of 1 to 8 carbon atoms Is mentioned.

The organic diisocyanate which is one of the raw materials for producing the polyurethaneurea of the present invention is, for example, an aliphatic, alicyclic or aromatic diisocyanate which is dissolved or liquid under the reaction conditions. Everything can be applied.
For example, methylene-bis (4-phenyl isocyanate), methylene-bis (3-methyl-4-phenyl isocyanate), 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, m- and p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate, m- and p
-Phenylene diisocyanate, 4,4'-dimethyl-
1,3-xylylene diisocyanate, 1-alkylphenylene-2,4 and 2,6-diisocyanate, 3-
(Α-isocyanatoethyl) phenyl isocyanate, 2,6-diethylphenylene-1,4-diisocyanate, diphenyl-dimethylmethane-4,4-diisocyanate, diphenylether-4,4′-diisocyanate, Naphthylene-1,5-diisocyanate,
1,6-hexamethylene diisocyanate, methylene-
Bis (4-cyclohexyl isocyanate), 1,3-
And 1,4-cyclohexylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.

Preferred is methylene-bis (4-phenylisocyanate). Examples of the chain extender having a polyfunctional active hydrogen atom, which is one of the raw materials for producing the polyurethaneurea of the present invention, include, for example, polyamines such as hydrazine, polyhydrazide, polyol, ethylenediamine, propylenediamine, hydroxylamine, and water. Etc. can be used.

As a terminal stopper having a monofunctional active hydrogen atom, which is one of the raw materials for producing the polyurethaneurea of the present invention, for example, dialkylamine such as diethylamine is used. These chain extenders and terminal stoppers may be used alone or in combination of two or more. The polyurethane urea composition, if desired, an organic or inorganic compounding agent having a specific chemical structure useful for known polyurethane urea compositions, for example, a gas yellowing inhibitor, an ultraviolet absorber, an antioxidant, Calcium stearate, magnesium stearate, polytetrafluoroethylene, organopolysiloxane, polyester-modified silicon, polyether-modified silicon, amino-modified silicon, and the like can be used alone or in any combination as needed.

The polyurethane urea elastic fiber of the present invention comprises:
It may be used as it is as a bare yarn, or it may be coated with a conventionally known fiber such as polyamide fiber, polyester fiber or cotton, and used as a coated elastic fiber.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto. (Measurement method of elongation at break) 20 ° C., 6 ° C. with a tensile tester (Model UTM-III-100 manufactured by Orientec Co., Ltd.)
1000% /
The elongation at break is measured at a tensile speed of one minute.

(Method of Evaluating Chlorine Embrittlement Resistance of Yarn) <Assumed Nylon Cross-Knitting Dyeing> 190 ° C. under 50% elongation
× Prepare a yarn set by dry heat setting for 1 minute. Irgala
n Black BGL200 (manufactured by Bayer Corporation) 2
% Owf, 12 g of ammonium sulfate was dissolved in 9 liters of ion-exchanged water, and the set yarn was dyed under a 50% elongation in a dye bath adjusted to pH 4 with acetic acid.
Set dry heat at 0 ° C for 1 minute.

The above dyeing set was completed with a solution obtained by adding 4.5 g of tannic acid (HIFIX SA, manufactured by Dainippon Pharmaceutical Co., Ltd.) and 2.7 g of acetic acid to 6 liters of ion-exchanged water.
The raw yarn is immersed under 50% yarn length, heated from 25 ° C. to 80 ° C. at a rate of 1 ° C./min, and the treatment is continued for 20 minutes. <Evaluation of chlorine embrittlement resistance performance assuming a swimming pool> Dilute sodium hypochlorite solution with ion-exchanged water to obtain an effective chlorine concentration of 3 ppm, and use chlorine water adjusted to pH 7 with a buffer solution of citric acid and sodium hydrogen phosphate. In a bath adjusted to a temperature of 30 ° C, 50% of the original yarn that has been subjected to
It is immersed at an interval of 6 hours for one cycle under elongation, and the change in the breaking strength is tracked over time, and the retention is calculated by comparing the strength before immersion treatment.

Evaluation of chlorine embrittlement resistance at time τ 1/2 at which the strength retention rate becomes 50% (Method of evaluating filter clogging property of spinning stock solution) Polyurethane urea spinning stock solution having a diameter of 10 mm and a constant flow rate of 3 liter / Hr. The solution was passed through a 10 μm NASLON filter (manufactured by Nippon Seisen Co., Ltd.) and the liquid sending pressure P (0.1 mm) after 0.1 hr.
The pressure increase rate Pr represented by the following equation (1) is measured from the liquid sending pressure P (2.0 Hr) after 1 Hr) and 2 Hr.

[0026] A small pressure rise rate means that clogging is small. (Method of measuring recovery rate of circular knitted fabric) A circular knitted fabric cut into a strip having a length of 20 cm and a width of 5 cm in a fiber knitting direction is adjusted to a gripping interval of 10 cm of a tensile tester, and a gripping portion is marked with a mark pen. Note that 80% elongation repeat 3
The recovery rate after the test is measured. The circular knitted fabric after immersion is measured after washing with water and drying.

[0027]

EXAMPLE 1 A spinning dope (b) in which 4% by weight of uncoated hydrotalcite was added to a spinning dope (a), and hydrotalcite coated with 2.0% by weight of stearic acid based on the weight of hydrotalcite 4% by weight of site
The added spinning dope (c), the spinning dope (d) added with 4% by weight of hydrotalcite coated with 2.0% by weight of butyl acid phosphate based on the weight of hydrotalcite, based on the weight of hydrotalcite 2.0
A spinning solution (e) containing 4% by weight of hydrotalcite coated with 4% by weight of lauryl acid phosphate, and hydrotalcite coated with 2.0% by weight of stearyl acid phosphate based on the weight of hydrotalcite. Stock spinning solution (f) containing 1% by weight, stock solution spinning solution (g) containing 4% by weight of hydrotalcite coated with 2.0% by weight of stearyl acid phosphate based on the weight of hydrotalcite, A spinning dope (h) was prepared by adding 8% by weight of hydrotalcite coated with 2.0% by weight of stearyl acid phosphate to the weight.

Dry spinning is carried out according to a conventional method using the spinning stock solutions (a) to (h), and each of them is 40d / 4f.
Produced polyurethane urea elastic fibers A to H. Table 1 shows the behavior of clogging during each spinning (pressure rise rate Pr), spinning stability, and chlorine embrittlement resistance of the fiber.

[0029]

[Table 1]

As shown in Table 1, it can be seen that the clogging of the hydrotalcite coated with the phosphate ester is suppressed, so that a yarn excellent in chlorine embrittlement resistance can be stably spun. Here, the spinnability means whether or not the yarn can be stably spun without yarn breakage.
：: good, Δ: slightly poor, ×: poor.

[0031]

Example 2 Each of the yarns A, C, G, and H of Example 1 was circularized with a circular knitting machine having nylon 50d / 17f, each having 54 feeders, 28 gauges, 2,916 needles, and a 3.4-inch diameter. After knitting the knitted fabric and setting it at 190 ° C. for 1 minute, 2% owf IrgalanBlack BGL2
00 (manufactured by Bayer Corp.) and pH adjusted with ammonium sulfate and acetic acid.
Dyeing at 95 ° C. for 30 minutes in a dye bath adjusted to 4.
Tannic acid (HIFIX SA, Dainippon Pharmaceutical Co., Ltd.)
Circular knitted fabric finished with the above dyeing set is immersed in a bath containing 0.75 g / l and 0.45 g / l acetic acid, and the temperature is raised from 25 ° C to 80 ° C at a rate of 1 ° C / min. The treatment was continued for 20 minutes. After that, 180 ° C
X Dry heat setting for 1 minute. Finished fabric is width 135c
m, length 50 m, mixing ratio of polyurethane urea elastic fiber was 18%, and basis weight was 280 g / m (m basis weight).

In order to determine the residual amount of the chlorine embrittlement improving agent in the polyurethane urea fiber in the dyeing step, about 1 g of the polyurethane urea fiber was pulled out from the circular knitted fabric and determined by the atomic absorption method. The chlorine embrittlement resistance of these circular knitted fabrics was evaluated by the following method. A circular knitted fabric cut into a strip of 20 cm in length and 5 cm in width in the direction of weaving fibers in a chlorine water bath adjusted to pH 7, temperature 30 ° C., and effective chlorine concentration 3 ppm. And evaluated by the recovery rate after repeating 80% elongation three times with a tensile tester.

Table 2 shows the residual amount of the chlorine embrittlement improving agent and the recovery rate after immersing the knitted fabric in chlorine water.

[0034]

[Table 2]

It can be seen that hydrotalcite having a phosphate ester adhered to the surface is suppressed from being eluted from the fiber under acidic conditions, and has good chlorine embrittlement resistance.

[0036]

According to the present invention, the hydrotalcite having a phosphate ester attached to the surface thereof suppresses filter clogging of the polyurethane urea spinning solution. The polyurethane urea elastic fiber containing the hydrotalcite of the present invention shows excellent chlorine embrittlement resistance even after the dyeing treatment.

Claims (1)

[Claims] 1. A polyurethane urea elastic fiber containing 0.5 to 10% by weight of hydrotalcite having a phosphate ester attached to its surface, based on the total weight of the polyurethane urea elastic fiber.