JP2000282328A - Polyurethane-based elastic yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane-based elastic yarn having excellent yellowing resistance to light, a gas such as NOx, etc., a chlorine bleaching agent, etc., no reduction in durability to a chlorine bleaching agent, a hypochlorite, etc., suitably useful for a swimming suit, etc. SOLUTION: This polyurethane-based elastic yarn is a polyurethane-based elastic yarn containing a hindered amine-based stabilizer and an inorganic additive. The hindered amine-based stabilizer is a poly(N,N-diethyl-β- aminoethylmethacrylate) having a repeating unit of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyurethane-based elastic fiber. More specifically, it has excellent resistance to deterioration of yarn properties due to chlorinated water,
The present invention relates to a polyurethane-based elastic fiber having excellent resistance to yellowing due to x gas, chlorine and the like and suitable for swimwear used in swimming pools and the like.

[0002]

2. Description of the Related Art In general, polyurethane elastic fibers have a problem that they often turn yellow when exposed to atmospheric conditions due to their chemical structure.

[0003] Japanese Patent Publication No. 36-19491 (US Pat. No. 2,998,939) discloses a technique for preventing discoloration of polyurethane-based elastic fibers by using a tertiary aliphatic amine having a molecular weight of 280 or more. ing. However, when exposed to chlorine bleach contained in pool water and the like, polyurethane-based elastic fibers discolor,
In addition, there is a problem that the yarn properties deteriorate.

[0004]

SUMMARY OF THE INVENTION In view of the problems of the prior art, the present invention does not discolor the yarn to yellow by light, a gas such as NOx, or a chlorine bleaching agent, and uses a chlorine bleaching agent or a hypochlorite. An object of the present invention is to provide a polyurethane-based elastic fiber which is preferably used for swimwear, in which physical properties of the yarn are not deteriorated by chlorate or the like.

[0005]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the polyurethane-based elastic fiber of the present invention is a polyurethane-based elastic fiber containing a hindered amine-based stabilizer and an inorganic additive, wherein the hindered amine-based stabilizer has a repeating unit represented by the following formula (I). (NN-diethyl-β-aminoethyl methacrylate).

[0006]

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[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyurethane-based elastic fibers according to the present invention are those formed from a long-chain polyurethane polymer containing at least 85% by weight of a segmented polyurethane.

The polyurethane segment of the polyurethane polymer used in the present invention comprises a soft segment (a) such as a long-chain polyether segment, a polyester segment or a polyether ester segment, an isocyanate and a diamine or diol as a chain extender. And hard segment (b), which is a relatively short-chain segment obtained by the above reaction.

As the soft segment (a) of such a polyurethane polymer, 1) tetramethylene glycol,
A polyether segment that is a polymer or copolymer obtained from 3-methyl-1,5-pentanediol, tetrahydrofuran, 3-methyltetrahydrofuran, or the like;
2) ethylene glycol, tetramethylene glycol,
Polyester segment obtained from a diol such as 2,2-dimethyl-1,3-propanediol and a dibasic acid such as adipic acid and succinic acid; 3) poly- (pentane-
1,5-carbonate) diol, poly- (hexane-
Polyetherester segments obtained from (1,6-carbonate) diol and the like can be used, and among them, polyether segments obtained from tetramethylene glycol are preferable.

In the present invention, the polyurethane polymer is subjected to a polyaddition reaction of a hydroxyl-terminated soft segment precursor with an organic diisocyanate (capping reaction).
Can be obtained by extending the chain with an amine chain extender or a diol chain extender.

In the present invention, the organic diisocyanate used for the polyurethane polymer includes bis- (p-isocyanatophenyl) -methane (hereinafter abbreviated as MDI), tolylene diisocyanate (hereinafter abbreviated as TDI), and bis- (p-isocyanatophenyl) -methane. (4-isocyanatocyclohexyl)-
Methane (hereinafter abbreviated as PICM), hexamethylene diisocyanate, 3,3,5-trimethyl-5-methylenecyclohexyl diisocyanate and the like can be used, and among them, MDI is preferable.

Various diamines such as ethylenediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine and the like are preferably used as amine chain extenders for forming polyurethaneurea.

The amine chain extender is not limited to one kind of diamine, but may be composed of plural kinds of amines. Chain terminators can be included in the reaction mixture to help control the final molecular weight of the polyurethaneurea. Usually, a monofunctional compound having active hydrogen as a chain terminator, such as diethylamine, can be used.

It is also preferable to use a diol as the chain extender. For example, ethylene glycol, 1,
3-propanediol, 4-butanediol, neopentyl glycol, 1,2-propylene glycol, 1,
4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-bis (β-hydroxyethoxy) benzene, bis (β-hydroxyethyl) terephthalate, paraxylylene diol and the like can be used. The diol chain extender is not limited to only one type of diol, and may be composed of a plurality of types of diols. Further, it may be used in combination with a compound containing one hydroxyl group that reacts with an isocyanate group. In this case, various methods such as a melt polymerization method and a solution polymerization method can be employed for obtaining such a polyurethane, and the method is not limited. Regarding the formulation of polymerization,
There is no particular limitation, and for example, a method of synthesizing a polyurethane by simultaneously reacting a polyol, a diisocyanate, and a chain extender composed of a diol can be adopted, and any method may be used. Further, it is preferable to add another stabilizer within a range that does not impair the effects of the present invention.

As the solvent used when the polyurethane polymer is made into a solution, N, N-dimethylacetamide (hereinafter abbreviated as DMAc), dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and the like can be used. , DMAc are the most commonly used solvents.

As the solution concentration of the polyurethane polymer,
Usually a solution concentration of the polyurethane polymer of 30 to 40% (based on the total weight of the solution), especially 35 to 38%, is preferred for the dry spinning process for obtaining filament yarns of polyurethane elastic fibers.

In the present invention, a method for spinning polyurethane elastic fibers from a polyurethane polymer is not particularly limited. For example, 1) a method for spinning polyurethane elastic fibers using a diol as a chain extender is used. ,
A melt spinning method, a dry spinning method, a wet spinning method, or the like can be employed. In addition, as a method of spinning polyurethane-based elastic fibers using 2) an amine as a chain extender, a dry spinning method can be usually employed.

The polyurethane elastic fiber of the present invention contains a hindered amine stabilizer.

In the present invention, it is preferable to use poly (NN-diethyl-β-aminoethyl methacrylate) having a repeating unit represented by the following formula (I).

[0020]

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If the hindered amine-based stabilizer is not contained, there is a problem that the durability to gas such as NOx and light is deteriorated.

The hindered amine stabilizer is preferably contained in an amount of 0.5% by weight or more and 5% by weight or less based on the polymer solid.

The hindered amine-based stabilizer is preferably placed in a slurry containing other additives, and stirred so as to be uniformly dispersed in the solvent with the other additives. Alternatively, a slurry containing the other additives and a slurry containing the hindered amine-based stabilizer are separately prepared, and separately added to the polymer, or prepared by any method as long as the dispersibility in the polymer is not impaired. Good.

The polyurethane-based elastic fiber of the present invention contains an inorganic additive.

As the inorganic additive in the present invention, it is preferable to use a mineral mixture of zinc oxide, huntite and hydromagnesite.

Huntite has a general formula of Mg ₃ Ca (CO ₃ )
Refers to those represented by _4, hydro magnesite formula _{Mg 4 (CO 3) 4 ·} Mg (OH) refers to those represented by ₂ · 4H ₂ O.

The inorganic additive such as a mineral mixture of zinc oxide, huntite and hydromagnesite is preferably contained in an amount of 1.5% by weight to 5% by weight based on the polymer solid.

In the present invention, the mineral mixture of zinc oxide, huntite and hydromagnesite is preferably a fine powder from the viewpoint of process stability, and has a mean particle size in the range of 0.1 to 1 μm. Is preferred.

In the present invention, when a mineral mixture of zinc oxide, huntite and hydromagnesite is pulverized, a mineral mixture of zinc oxide, huntite and hydromagnesite is added to the polymer from the viewpoint of process stability. By then, it is preferable to mix the solvent with other additives, for example, a thickener, to prepare a slurry, and pulverize the slurry with a vertical or horizontal mill or the like.

It is preferable that the inorganic additive is put into a slurry containing the hindered amine-based stabilizer and stirred with the hindered amine-based additive and other additives so as to be uniformly dispersed in the solvent.

Also, a slurry containing a hindered amine and a slurry containing an inorganic additive are separately prepared,
Separate addition to the polymer also occurs as long as the dispersibility in the polymer is not compromised.

[0032]

The polyurethane elastic fiber of the present invention will be described below in detail with reference to examples.

The evaluation method according to the present invention will be described. [Chlorine yellowing resistance] A sample card in which 10 g of a polyurethane-based elastic fiber was wound around a Teflon plate was prepared, and this was set to 40 ±
It is immersed in a chlorine solution having a chlorine concentration of 600 ppm at a constant temperature of 2 ° C. for 30 minutes, washed with pure water for 10 minutes, air-dried, and then dried with a color master (D25 DP-9000).
"B" color was measured using a signal processor) and the degree of yellowing was evaluated by the difference Δb before and after the treatment. [Sunshine yellowing resistance] A sample card was prepared by winding 10 g of a polyurethane-based elastic fiber around a stainless steel plate, and this was used as a sunshine weather meter (WEL-SUN-).
HCH B type Suga Test Machine Co., Ltd.) for 40 hours, and measure the “b” color using a color master (D25 DP-9000 type signal processor). evaluated. [NO ₂ gas yellowing resistance] A sample card was prepared by winding 10 g of a polyurethane-based elastic fiber around a stainless steel plate, and using a Scott tester, a gas obtained by mixing NO ₂ gas to a specified concentration (7 ppm) was mixed. Exposure alone for 40 hours, measure "b" color using a color master (D25 DP-9000 signal processor),
The degree of yellowing was evaluated by the difference Δb before and after the treatment. [Chlorine durability] Water temperature 25 ° C, pH 7.5, chlorine concentration 1p
The polyurethane-based elastic fiber stretched 25% in a thermostatic chamber adjusted to pm was immersed for 96 hours, and before and after the chlorination, the strength at the time of stretching 200% and the strength at the time of thread cutting were measured using a commercially available universal tensile tester. The retention was measured.

A universal tensile tester (INSTRON 11)
22 type, 4500 type) repeats four times of tension and recovery at an elongation of 300%, the strength at the point where the elongation reaches 200% at the fifth load is defined as T + 200, and the tensile is performed until the test yarn is cut at the sixth time. The strength at the time of cutting was defined as TB. Example 1 Bis- (p-isocyanatophenyl)-
A mixture of methane / tetramethylene ether glycol (number average molecular weight 1800) = 1.58 / 1 (molar ratio) was reacted in a conventional manner at 90 ° C. for about 3 hours to obtain a capped graphate containing 2.22% of an isocyanate moiety. Equol was prepared. This capped glycol was diluted with N, N-dimethylacetamide (DMAc). Next, a DMAc solution containing ethylenediamine and diethyleneamine was added to the DMAc solution of capped glycol, mixed at room temperature using a commercially available high-speed stirrer, chain-extended, and DMAc having a solid content of 35% by weight in the polymer was added. A solution was obtained.

Further, the content is 3% with respect to the polymer solid separately.
wt% zinc oxide (Kadox-15, New Jersey Zinc Company) in 1.5 wt%
% Phenolic stabilizer (paracresol /
A slurry of divinylbenzene copolymer) was prepared using a hindered amine-based stabilizer (NN-diethyl-β-aminoethyl methacrylate (FHM, manufactured by Sanyo Chemical Industry Co., Ltd.)) so as to be 0.5 wt%. .

A horizontal mill is filled with glass beads, and the zinc oxide-containing slurry is mixed with an average particle size of zinc oxide of 0.1 to 0.1.
Milling was performed to 1 μm. This slurry was added to the polymer solids so that each of the above-mentioned additives was in a specified liquid amount to obtain a polyurethane polymer solution.

The polyurethane polymer solution was subjected to a polyurethane elastic fiber (40D, 40D) by an ordinary dry spinning method.
4 filaments).

The obtained polyurethane elastic fiber had excellent yellowing resistance to chlorine water and also excellent yellowing resistance to light and NO ₂ gas. .

Further, from the viewpoint of strength, the steel had extremely excellent durability against chlorine.

The results are shown in Table 1. [Example 2] A mineral mixture of huntite and hydromagnesite (Ultracarb U3, De) as an additive for improving the chlorine water resistance so that the content becomes 4 wt%.
rby, Microfine Min from England
erals Ltd)), except that polyurethane-based elastic fibers were obtained under the same conditions as in Example 1.

The obtained polyurethane elastic fiber had excellent yellowing resistance to chlorine water and also excellent yellowing resistance to light and NO ₂ gas. .

Further, from the viewpoint of strength, the steel had extremely excellent durability against chlorine.

Table 1 also shows the results. Comparative Example 1 A polyurethane elastic fiber was obtained under the same conditions as in Example 1 except that the hindered amine-based stabilizer was not used.

The resulting polyurethane-based elastic fibers had poor yellowing resistance to chlorine water, light, and NO ₂ gas.

The results are shown in Table 1. Comparative Example 2 A polyurethane elastic fiber was obtained under the same conditions as in Example 1 except that zinc oxide was not used.

The obtained polyurethane-based elastic fiber was extremely poor in durability against chlorine, for example, the yellowing resistance to chlorine water and the strength of the yarn breakage could not be measured within the treatment time in view of the strength.

Table 1 also shows the results. Comparative Example 3 A polyurethane elastic fiber was obtained under the same conditions as in Example 2 except that the hindered amine stabilizer was not used.

The obtained polyurethane-based elastic fiber was made of NO
_The yellowing resistance to _two gases and chlorine water was poor. Comparative Example 4 A polyurethane elastic fiber was obtained under the same conditions as in Example 1 except that the hindered amine-based stabilizer and the inorganic additive were not used.

The obtained polyurethane elastic fiber was NO
_{In view} of the yellowing resistance to gas ₂ and chlorine water, and the strength, yarn breakage occurred within the treatment time, and the durability to chlorine water was so poor that the strength could not be measured.

[0050]

[Table 1]

(-Indicates that measurement was impossible due to yarn breakage during processing or measurement.)

[0052]

According to the present invention, light, gas such as NOx,
It is possible to provide a polyurethane-based elastic fiber which has excellent yellowing resistance to chlorine bleach and the like and can be suitably used for swimwear without reducing the durability to the chlorine bleach or hypochlorite. .

Claims (3)

[Claims] 1. A polyurethane elastic fiber containing a hindered amine stabilizer and an inorganic additive, wherein the hindered amine stabilizer has a poly (NNN-) having a repeating unit represented by the following formula (I). Diethyl-β-aminoethyl methacrylate). Embedded image 2. The polyurethane elastic fiber according to claim 1, wherein said inorganic additive is zinc oxide. 3. The polyurethane elastic fiber according to claim 1, wherein said inorganic additive is a mineral mixture of huntite and hydromagnesite.