JP2001323156A - Thermoplastic polyurethane resin composition and polyurethane elastomer fiber made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplatic polyurethane resin composition excellent in heat resistance, hot-water resistance, elastic recovery, elongation, etc. SOLUTION: Provided is thermoplastic polyurethane resin composition prepared by compounding 100 pts.wt. (A) thermoplastic polyurethane resin obtained by reacting a polyol with an organic diisocyanate and a chain extender in a ratio satisfying the formula 1: 1.00<=b/(a+c)<=1.10, wherein a is the number of moles of the polyol; b is the number of moles of the organic diisocyanate; and c is the number of moles of the chain extender with 0.1-3.0 pts.wt. (B) processing stabilizer containing (X9 a dialkylhydroxyphenyl-containing phenolic compound represented by formula I, wherein R1 is a 3-20C branched alkyl; and R2 is an alkyl or formula II, wherein R3 is a 3-20C branched alkyl; and R4 is an alkyl and (Y) a phosphorus compound in a ratio satisfying the formula: 0.1<=x/y<=10, wherein x is the weight of the phenolic compound X; and y is the weight of the phosphorus compound Y.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyurethane resin composition and an elastic fiber comprising the thermoplastic polyurethane resin composition. The thermoplastic polyurethane resin composition of the present invention has heat resistance, hot water resistance, elastic recovery,
Excellent in various properties such as elongation, in the production of polyurethane elastic fibers by the melt spinning method, there is little generation of deteriorating products when staying in the melt, and there is long-time spinning stability and excellent uniformity without unevenness of fineness. To give polyurethane elastic fibers.

[0002]

2. Description of the Related Art Known methods for producing polyurethane elastic fibers include dry spinning, wet spinning, and melt spinning. Among them, the polyurethane elastic fiber obtained by the melt spinning method has been used in recent years because of its excellent heat setting property, abrasion resistance and transparency, and low production cost. However, polyurethane elastic fibers obtained by the melt spinning method are compared with polyurethane urethane fibers obtained by the dry spinning method,
Hard hard segments were hardly formed, and heat resistance and hot water resistance were not sufficient.

[0003] Therefore, as a method for improving various properties of a polyurethane elastic fiber obtained by a melt spinning method, a method in which the molar ratio of isocyanate groups to hydroxyl groups is excessively long has been proposed. ,
Japanese Patent Publication No. 44-7960 discloses that an excessively high molar ratio of isocyanate groups can provide excellent elastic properties at high temperatures. JP-A-8-337629 discloses that a polyurethane having excellent heat resistance and melt moldability can be obtained by increasing the molar ratio of an isocyanate group to a hydroxyl group, and JP-A-9-49120. Japanese Patent Application Laid-Open Publication No. H11-157, discloses that a polyurethane elastic fiber having excellent properties such as heat resistance, hot water resistance and elastic recovery can be obtained by the same method.

[0004] On the other hand, it is known that a thermoplastic polyurethane resin is liable to undergo thermal degradation accompanying the decomposition of isocyanate groups during melt molding. To prevent this thermal degradation, JP-A-8-81624 is disclosed. Discloses a thermoplastic polyurethane resin composition to which a phenolic heat-resistant processing stabilizer is added.

[0005] However, when the present inventors produced a thermoplastic polyurethane resin composition and a polyurethane elastic fiber according to the methods described in the examples of these publications, it was found that problems occurred during continuous production. That is, during continuous operation for a long time, due to low thermal stability derived from the isocyanate group, a thermally degraded product is generated in a spinning head in which the thermoplastic polyurethane resin composition stays in a molten state, and thread breakage occurs. The phenomenon that occurs frequently occurs,
That sufficient spinning stability for a long time is not ensured,
It became clear that problems such as an increase in unevenness in the size of the obtained polyurethane elastic fibers occurred with the elapse of the operation time. Therefore, it is desired to solve these problems from an industrial viewpoint.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide not only excellent properties such as heat resistance, hot water resistance, elastic recovery property and elongation, but also the effect of the melt spinning during melt spinning. It is an object of the present invention to provide a thermoplastic polyurethane resin composition and a polyurethane elastic fiber comprising the thermoplastic polyurethane resin composition, which is capable of obtaining a homogeneous fiber with less generation of a degraded product and excellent spinning stability over a long period of time.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a thermoplastic polyurethane resin in which the molar ratio of isocyanate groups to hydroxyl groups is excessive has been conventionally known. It was clarified that the problem of insufficient spinning stability during long-term operation was caused by the formation of thermally degraded products due to stagnation of the thermoplastic polyurethane resin, and the problem was identified by specific processing. The present inventors have found that the problem can be solved by adding a stabilizer, and have completed the present invention.

That is, the present invention provides a polymer polyol,
The organic diisocyanate and the chain extender are represented by the following formula (1); 1.00 ≦ b / (a + c) ≦ 1.10 (1) (where a is the number of moles of the polymer polyol, and b is the organic diisocyanate) , And c represents the number of moles of the chain extender) in 100 parts by weight of the thermoplastic polyurethane resin (A) obtained by reacting at a ratio satisfying the following general formula (I) or (II). );

[0009]

Embedded image (In the formula, R ¹ represents a branched alkyl group having 3 to 20 carbon atoms, and R ² represents an alkyl group.)

Embedded image (In the formula, R ³ represents a branched alkyl group having 3 to 20 carbon atoms, and R ⁴ represents an alkyl group.)

A phenolic compound (X) containing at least one dialkylhydroxyphenyl group represented by the formula:
And the phosphorus compound (Y) is represented by the following formula (2): 0.1 ≦ x / y ≦ 10 (2) (where x represents the weight of the phenol compound (X),
y represents the weight of the phosphorus compound (Y). A) a thermoplastic polyurethane resin composition containing 0.1 to 3.0 parts by weight of a processing stabilizer (B) containing the resin in a ratio satisfying the requirement (1), and a polyurethane elastic fiber comprising the same.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The thermoplastic polyurethane resin (A) comprises a polymer polyol, an organic diisocyanate and a chain extender represented by the following formula (I): 1.00 ≦ b / (a + c) ≦ 1.10 (I) The number of moles of the molecular polyol, b is the number of moles of the organic diisocyanate, and c is the number of moles of the chain extender). The value of b / (a + c) is 1.00
When it is less than 1, the molecular weight of the thermoplastic polyurethane resin is low, and various properties such as heat resistance and hot water resistance of the polyurethane elastic fiber obtained therefrom are inferior. Also, b /
When the value of (a + c) exceeds 1.10, the melt viscosity decreases due to the decrease in the molecular weight of the thermoplastic polyurethane resin, and not only poor spinning occurs, but also the polyurethane elastic fiber obtained therefrom lacks homogeneity. It will be.
From the viewpoint of the mechanical properties such as the strength and elastic recovery properties of the thermoplastic polyurethane resin, and the resulting polyurethane elastic fiber obtained therefrom, and the durability such as abrasion resistance and hydrolysis resistance, the value of b / (a + c) is: It is preferably 1.01 or more, and more preferably 1.02 or more. Further, from the viewpoint of spinning stability of the polyurethane elastic fiber, b /
The value of (a + c) is preferably 1.07 or less,
More preferably, it is 1.05 or less.

The high molecular weight polyol has an average molecular weight of 5
It is preferable to use those having a molecular weight of
It is more preferred to use those of ~ 4000. Examples of the polymer polyol include a polyester polyol, a polyether polyol, a polycarbonate polyol, and a polyether ester polyol. Among them, the polyether polyol and the polyester polyol are preferable. These polymer polyols are
They may be used alone or in combination of two or more.

Examples of the polyether polyol include polyether diols and glycols (eg, ethylene glycol, ethylene glycol, propylene oxide, trimethylene oxide, tetrahydrofuran, methyltetrahydrofuran, etc.) obtained by ring-opening polymerization of cyclic ethers. Propylene glycol, 1,
4-butanediol, neopentyl glycol, 1,6
-Hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,
9-nonanediol, 1,10-decanediol, etc.)
And polyether polyols obtained by the polycondensation of These may be used alone or in combination of two or more.

The polyester polyol in the present invention can be produced by a known polycondensation method using an esterification method or a transesterification method using a polycarboxylic acid, a polyol and other components as required.

As the polyol used in the production of the polyester polyol, those generally used in the production of polyester can be used. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propane Diols, 2-methyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol, 1,3
-Butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-
Pentanediol, 1,6-hexanediol, 1,7
-Heptanediol, 1,8-octanediol, 2-
Methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1,9-nonanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl-1,9- Aliphatic diols having 2 to 15 carbon atoms such as nonanediol and 1,10-decanediol;
Alicyclic diols such as cyclohexanediol, cyclohexanedimethanol and cyclooctanedimethanol;
Diols having two hydroxyl groups per molecule such as aromatic dihydric alcohols represented by 1,4-bis (β-hydroxyethoxy) benzene and trimethylolpropane;
Examples thereof include polyols having three or more hydroxyl groups per molecule, such as trimethylolethane, glycerin, 1,2,6-hensantriol, pentaerythritol, and diglycerin. In producing the polyester polyol, these polyols may be used alone or in combination of two or more. Among these, 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8
-Octanediol, 2,7-dimethyl-1,8-octanediol, 2-methyl-1,9-nonanediol,
It is preferable to use an aliphatic diol having 5 to 12 carbon atoms and having a methyl group as a side chain, such as 2,8-dimethyl-1,9-nonanediol.

As the polycarboxylic acid used in the production of the polyester polyol, polycarboxylic acids generally used in the production of polyesters can be used. For example, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, methylsuccinic acid, 2-methylglutaric acid,
3-methylglutaric acid, trimethyladipic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,
Aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as 7-dimethyldecandioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, dimer acid and hydrogenated dimer acid; terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid Aromatic dicarboxylic acids such as trimellitic acid, pyromellitic acid and the like; and trifunctional or higher polycarboxylic acids; and ester-forming derivatives thereof. These polycarboxylic acids may be used alone or in combination of two or more. Among these, aliphatic dicarboxylic acids having 6 to 12 carbon atoms are preferable, and adipic acid, azelaic acid, and sebacic acid are more preferably used.

The polycondensation reaction for producing the polyester polyol can be carried out in the presence of a catalyst. In this case, a titanium catalyst, a tin catalyst or the like is preferably used. Examples of titanium-based catalysts include titanic acid,
Examples thereof include tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, and more specifically, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate, and tetrastearyl titanate such as tetrastearyl titanate. Titanium acylate compounds such as alkoxytitanium compounds, polyhydroxytitanium stearate, and polyisopropoxytitanium stearate; titanium chelate compounds such as titanium acetyl acetate, triethanolamine titanate, titanium ammonium lactate, and titanium ethyl lactate; . Examples of the tin catalyst include dialkyltin diacetate, dialkyltin dilaurate, dialkyltin bismercaptocarboxylate, and more specifically, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bis (3-mercapto Ethoxybutyl propionate) and the like.

When a titanium-based catalyst is used, its amount can be adjusted according to each situation and is not particularly limited.
Generally, it is preferably from about 0.1 to 50 ppm, more preferably from about 1 to 30 ppm, based on the total weight of the reactants used to make the polyester polyol. In addition, when a tin-based catalyst is used, its use amount can be adjusted according to each situation and is not particularly limited, but is generally about 1 to 200 ppm based on the total weight of the reaction components used for producing the polyester polyol. And more preferably about 5 to 100 ppm.

In the case of a polyester polyol produced using a titanium-based catalyst, it is necessary to deactivate the titanium catalyst contained in the polyester polyol, and use a polyester polyol containing a titanium catalyst which has not been deactivated. To produce thermoplastic polyurethane resin,
The properties such as heat resistance of the thermoplastic polyurethane resin are inferior.

Examples of the method for deactivating the titanium-based catalyst contained in the polyester polyol include: (1) a method in which the polyester polyol is brought into contact with water while heating;
Examples of the method include a method of treating a polyester polyol with a phosphorus compound such as phosphoric acid, a phosphoric ester, a phosphorous acid, and a phosphite. In the case of the above method (1) in which water is brought into contact with water, for example, water is added to the polyester polyol in an amount of 1% by weight or more, and the water is added to 70 to 15
The heating may be performed at a temperature of 0 ° C., preferably 90 to 130 ° C. for about 1 to 3 hours. The deactivation treatment by heating at that time may be performed under normal pressure or under pressure. If the pressure of the system is reduced after the deactivation treatment, the water used for the deactivation can be smoothly removed from the polyester polyol.

As the polycarbonate polyol used in the present invention, those obtained by reacting a low molecular polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate and diaryl carbonate can be used. As the low molecular polyol constituting the polycarbonate diol, the polyols exemplified above as the constituent components of the polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, and the like. Examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

Examples of the polyester polycarbonate polyol include those obtained by simultaneously reacting a low molecular weight polyol, a polycarboxylic acid and a carbonate compound, and a polyester polyol and a polycarbonate polyol synthesized respectively in advance by the above-described method, and then, the carbonate polyol is synthesized. Those obtained by reacting with a compound or reacting with a low molecular weight polyol and a polycarboxylic acid can be used.

As the organic diisocyanate used in the production of the thermoplastic polyurethane resin in the present invention, any of the organic diisocyanates conventionally used in the production of ordinary thermoplastic polyurethane resins may be used. For example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dichloro-4,
Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate and toluylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hydrogenated xylylene diisocyanate and the like Aliphatic or alicyclic diisocyanates can be mentioned.
These organic diisocyanates may be used alone or in combination of two or more. Among them, 4,
It is preferred to use 4'-diphenylmethane diisocyanate. Further, a tri- or higher functional polyisocyanate compound such as triphenylmethane triisocyanate may be added in a small amount as necessary.

As the chain extender used in the production of the thermoplastic polyurethane resin in the present invention, any of the chain extenders conventionally used in the production of ordinary thermoplastic polyurethane resins may be used. It is preferable to use a low molecular weight compound having a molecular weight of 300 or less and having two or more active hydrogen atoms capable of reacting with a group in the molecule. Examples of the low molecular weight compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6
-Hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol,
Diols such as bis (β-hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, propylenediamine, xylylenediamine,
Examples include diamines such as isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, adipic dihydrazide, and isophthalic dihydrazide; and amino alcohols such as aminoethyl alcohol and aminopropyl alcohol. These low molecular weight compounds may be used alone or in combination of two or more. Among them, aliphatic diols having 2 to 10 carbon atoms are preferably used, and 1,4-butanediol is more preferably used from the viewpoint of obtaining a thermoplastic polyurethane resin having excellent heat resistance and hot water resistance.

The process for producing the thermoplastic polyurethane resin in the present invention is carried out by using the above-mentioned polymer diol, diisocyanate, chain extender and, if necessary, other components. Either can be used. For example, it can be produced by a method such as a prepolymer method or a one-shot method using a known urethanization reaction technique such as melt polymerization or solution polymerization. Above all, it is preferable to produce a thermoplastic polyurethane resin by carrying out melt polymerization under conditions substantially free of a solvent, since the polymerization can be carried out easily and smoothly. It is more preferable to carry out by a continuous melt polymerization method using a screw type extruder, because productivity is increased. In the production of a thermoplastic polyurethane resin, a polyurethane-forming reaction can be carried out using a tin-based urethanization catalyst.In particular, the tin-based urethanization catalyst is converted to a tin atom based on the total weight of the thermoplastic polyurethane resin raw material. When the thermoplastic polyurethane resin is produced at a ratio of 0.5 to 50 ppm in terms of, a thermoplastic polyurethane resin having a high molecular weight can be obtained. As the tin-based urethanization catalyst at that time, for example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bis (ethoxybutyl ester of 3-mercaptopropionate) and the like can be mentioned.

In the present invention, the following general formula (I) or (II) is used for the thermoplastic polyurethane resin (A):

Embedded image (In the formula, R ¹ represents a branched alkyl group having 3 to 20 carbon atoms, and R ² represents an alkyl group.)

Embedded image (In the formula, R ³ represents a branched alkyl group having 3 to 20 carbon atoms, and R ⁴ represents an alkyl group.)

A phenolic compound (X) containing at least one dialkylhydroxyphenyl group represented by the formula (X)
Stabilizer (B) containing phosphorus and a phosphorus compound (Y)
Is blended.

The phenolic compound (X) contains at least one dialkylhydroxyphenyl group represented by the above formula (I) or (II). In the above general formulas (I) and (II), R ¹ and R ³ each represent an isopropyl group, an isohexyl group, a t-butyl group, a t-butyl group,
-Pentyl group, neopentyl group, dibutyl octyl group,
A branched alkyl group having 3 to 20 carbon atoms such as a diethyldecyl group; R ² and R ⁴ each represent a methyl group,
Ethyl group, butyl group, isopropyl group, isohexyl group, t-butyl group, t-pentyl group, neopentyl group,
It represents an alkyl group such as a dibutyloctyl group and a diethyldecyl group. Among them, R ¹ and R ³ are preferably an isopropyl group, an isohexyl group, a t-butyl group, a t-pentyl group, and a neopentyl group, respectively.
A butyl group and a t-pentyl group are more preferred. Also, R ²
And R ⁴ are each preferably a branched alkyl group having 1 to 20 carbon atoms, more preferably an isopropyl group, an isohexyl group, a t-butyl group, a t-pentyl group or a neopentyl group, and more preferably a t-butyl group or a t-butyl group. A pentyl group is more preferred.

As the phenolic compound (X), for example, 3,9-bis [2- {3- (3-t-butyl-4-
[Hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,4,8,10-
Tetraoxospiro [5.5] undecane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate, 2-t-butyl-6-
(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1-
(2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 1,6-hexanediol-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], triethylene glycol-bis [3
-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 2,6-di- t-butyl-4-methylphenol and the like, among which 3,9-
Bis [2- {3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy {-1,1-
Dimethylethyl] -2,4,8,10-tetraoxospiro [5.5] undecane, tetrakis [methylene-3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-t) -Pentylphenyl) ethyl] -4,
6-di-t-pentylphenyl acrylate and N,
N'-hexamethylenebis (3,5-di-t-butyl-
4-hydroxy-hydrocinnamamide) is preferred.

The above-mentioned phosphorus compound (Y) is not particularly limited as long as the object of the present invention can be achieved. For example, triphenyl phosphite, tris (2,4-di-t- Butylphenyl) phosphite, trisnonylphenylphosphite, diphenylisodecylphosphite, cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetraylbis (2,4-di-t
-Butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4)
-Methylphenyl) phosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octylphosphite, 2-[｛2,4,8,10-tetrakis (1,1-dimethylethyl) Dibenzo [d, f] [1,
3,2] dioxaphosphepin-6-yldioxy]
-N, N-bis [2-[{2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f]
[1,3,2] dioxaphosphepin-6-yldioxy] -ethyl] ethanamine and the like, among which tris (2,4-di-t-butylphenyl) phosphite and cyclic neo Pentanetetraylbis (2,4-di-t-butylphenyl) phosphite,
Cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite,
2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and 2-[{2,4,4
8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl} oxy] -N, N-bis [2-[{2 ,
4,8,10-tetrakis (1,1-dimethylethyl)
Dibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl {oxy] -ethyl] ethanamine is preferred.

The weight ratio of the phenol compound (X) to the phosphorus compound (Y) in the processing stabilizer (B) is represented by the following formula (2): 0.1 ≦ x / y ≦ 10 (2) Represents the weight of the phenolic compound (X),
y represents the weight of the phosphorus compound (Y). Satisfies.
When the value of x / y is less than 0.1, the NOx gas discoloration property of the thermoplastic polyurethane resin composition decreases, and when it exceeds 10, the spinning stability of the thermoplastic polyurethane resin composition deteriorates, and The unevenness of fineness of the polyurethane elastic fiber increases. The value of x / y is preferably in the range of 0.5 to 5 from the viewpoint of durability such as thermal stability.

The compounding amount of the processing stabilizer (B) in the present invention is in the range of 0.1 to 3.0 parts by weight based on 100 parts by weight of the thermoplastic polyurethane resin (A). If the amount of the processing stabilizer (B) is less than 0.1 part by weight, the resulting thermoplastic polyurethane resin composition cannot sufficiently suppress the deterioration of the thermoplastic polyurethane resin composition during the stagnation, and can provide long-time spinning stability. Absent. On the other hand, if it exceeds 3.0 parts by weight, various properties such as heat resistance are reduced, and the bleed out of the processing stabilizer to the surface of the obtained polyurethane elastic fiber becomes remarkable. The amount of the processing stabilizer (B) is preferably in the range of 0.2 to 2.0 parts by weight from the viewpoints of the effect of improving processability and heat resistance.

The processing stabilizer (B) can be added, for example, during or after the polymerization of the thermoplastic polyurethane resin (A). Further, if necessary, a heat stabilizer, an antioxidant, an ultraviolet absorber, a lubricant, a coloring agent, a hydrolysis inhibitor, a crystal nucleating agent, a weathering agent, which are usually used in producing a thermoplastic polyurethane resin composition. Various additives such as improvers, fungicides, EB crosslinking agents, and other resins such as polyolefin resins, styrene resins, vinyl chloride resins, ethylene-vinyl acetate copolymer resins, polyamide resins, polyester resins, and polymethyl methacrylate resins. They may be added as appropriate.

The polyurethane elastic fiber can be produced by melt-spinning the thermoplastic polyurethane resin composition of the present invention. As the melt spinning method, a method in which the thermoplastic polyurethane resin composition of the present invention is prepared in advance and melt-spinning is performed using the same, and the processing stabilizer (B) is added while forming the thermoplastic polyurethane resin (A) as described above. And a method in which the thermoplastic polyurethane resin composition thus formed, which is still in a molten state, is directly spun from a spinneret as it is.

The melt spinning temperature is preferably 260 ° C. or lower, more preferably 220 to 250 ° C., in view of the physical properties of the obtained fiber and the ease of the melt spinning operation. Then, in order to further improve the performance of the polyurethane elastic fiber obtained after the melt spinning, it is preferable to perform a heat aging treatment at 50 to 100 ° C. There are no particular restrictions on the type or type of spinning device used for melt spinning, and the melt spinning device used for producing polyurethane elastic fibers can be used.

In the polyurethane elastic fiber of the present invention, the degree of polymerization of the thermoplastic polyurethane resin constituting the fiber is not particularly limited. However, from the viewpoint of heat resistance and hot water resistance of the polyurethane elastic fiber, the polyurethane elastic fiber contains 1% by weight of n-butylamine. The polyurethane elastic fiber is dissolved in an amount of 0.5 g / dl in N, N-dimethylformamide
The degree of polymerization is preferably such that the logarithmic viscosity measured at 30 ° C. is 0.5 dl / g or more, particularly 0.7 d
The degree of polymerization is more preferably 1 / g or more. In particular, when a polyurethane elastic fiber is to be dissolved in N, N-dimethylformamide containing 1% by weight of n-butylamine, it has a high degree of polymerization such that it does not dissolve at all or only partially dissolves. When the polyurethane elastic fiber of the present invention is formed from a plastic polyurethane, a polyurethane elastic fiber having more excellent heat resistance and hot water resistance can be obtained.

The single fiber fineness of the polyurethane elastic fiber of the present invention is not particularly limited and can be appropriately determined depending on its use and the like.
It is preferable to keep it at about 0 denier. Further, the polyurethane elastic fiber of the present invention may be in the form of a monofilament or a multifilament, and in the case of a multifilament, the number of filaments, the total denier, and the like are not particularly limited and may be appropriately determined. Can be. Further, the cross-sectional shape of the polyurethane elastic fiber of the present invention is not particularly limited, and may be any of a round shape, a square shape, a hollow shape, a triangle shape, an elliptical shape, a flat shape, a multilobe shape, a V shape, a T shape, an array shape, and any other shape. Can have irregular cross section. In producing various products using the polyurethane elastic fiber of the present invention, the polyurethane elastic fiber of the present invention may be used alone or in combination with other fibers in an appropriate form.

The use of the polyurethane elastic fiber of the present invention is not particularly limited and can be used for various uses. By utilizing its elastic properties, sports goods such as swimwear, outerwear, cycling wear and leotard; lingerie Accessories such as pantyhose, socks, supporters, hats, gloves, etc .; medical supplies such as bandages and artificial blood vessels; gut for tennis rackets, vehicle seats for integrated molding, robot arms It can be effectively used for non-clothing products such as metal-coated materials. Among these, the polyurethane elastic fiber of the present invention is characterized by its excellent heat resistance, hot water resistance, elongation, elastic recovery, uniformity of yarn, etc.
It can be used very effectively for applications such as clothing.

[0039]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. The raw materials and processing stabilizers used in the examples and comparative examples are represented by the abbreviations shown in Table 1 below.

[0040]

[Table 1]

In Examples and Comparative Examples, unevenness of fineness of polyurethane elastic fiber, logarithmic viscosity, heat resistance, and NOx resistance
The property was measured or evaluated by the following method.

[Polyurities of polyurethane elastic fiber] Uster
Using Eveness Tester (made by USTER), take-up speed 100 at the measurement slit according to the total fineness of the yarn.
m / min (feed rate 50 m / min). 20
The measurement was carried out at any five locations of the measurement sample, with the measurement being performed twice per minute, and a fineness variance exceeding ± 25% was called imocov, and the number of imocovs in a given yarn length was counted.

[Logarithmic viscosity of polyurethane elastic fiber] n-
A sample was dissolved in an N, N-dimethylformamide solution containing 1% by weight of butylamine to a concentration of 0.5 g / dl, and the falling time of the polyurethane solution at 30 ° C. was measured using an Ubbelohde viscometer. The logarithmic viscosity was determined by the following equation. Logarithmic viscosity = [ln (t / t ₀ )] / c (where, t is the falling time (seconds) of the polyurethane solution, t ₀
Represents the flow time (second) of the solvent, and c represents the concentration (g / dl) of the polyurethane solution. )

[Heat resistance of polyurethane elastic fiber] A sample made of polyurethane elastic fiber was 200%
It is fixed in the stretched state and heat-treated at 140 ° C. for 1 minute using a hot-air drier, and the heat retention index at the time of elongation at 300% based on the yarn length before the treatment is calculated by the following formula. And Strength retention at 300% elongation (%) = (M / M ₀ ) × 1
00 (where M represents the 300% modulus after the treatment and M ₀ represents the 300% modulus before the treatment)

[NOx Resistance of Polyurethane Elastic Fiber] A sample made of polyurethane elastic fiber was subjected to NO ₂ gas concentration of 650.
The treatment was performed for 1 hour in the air increased to ppm, and the strength before and after the treatment was measured, and the strength retention was determined according to the following formula of the strength retention. Strength retention (%) = (strength after treatment) / (strength before treatment)

Example 1 (1) In a twin-screw extruder rotating in the same direction having a diameter of 30 mm and an L / D of 36, a polymer polyol heated to 80 ° C., BD, and MDI heated to 50 ° C. And the phenolic compound (x1) and the phosphorus compound (y1) were simultaneously and continuously supplied at a rate shown in Table 2 by a metering pump at a rate shown in Table 2 to reduce the cylinder temperature of the extruder. After generating a thermoplastic polyurethane resin composition by continuous melt polymerization at 260 ° C.,
It is extruded into water in a strand form from a die and cut to produce pellets of the thermoplastic polyurethane resin composition.
Vacuum dried for 4 hours.

(2) The pellets of the thermoplastic polyurethane resin composition obtained in the above (1) are supplied to a usual spinning apparatus equipped with a single screw extruder, and the spinning temperature is 200 to 240.
At a cooling air dew point of 10 ° C. and a spinning speed of 500 m / min., Melt-spun into a monofilament, wound up on a bobbin, and polyurethane elastic fiber (monofilament).
(40 d / f). Here, the operation was performed for a maximum of 5 days for the evaluation of spinning stability, but after 5 days, there was no pressure increase in the spinning nozzle pack, and the spinning pack showed a service life of 5 days or more and good spinning stability. I was

(3) The polyurethane elastic fiber obtained in the above (2) was aged for 10 days at room temperature under a relative humidity of 60%.

(4) Irregularity, logarithmic viscosity, heat resistance and NOx resistance of the aged polyurethane elastic fiber obtained in (3) above
The properties were measured or evaluated by the methods described above, and were as shown in Table 3 below.

[0050]

[Table 2]

[0051]

[Table 3]

Examples 2 to 11 (1) A thermoplastic polyurethane was prepared in the same manner as in Example 1 except that the polymer polyol, the chain extender, the organic diisocyanate and the processing stabilizer were used in the composition and ratio shown in Table 2 above. Pellets of the resin composition were produced, and then vacuum-dried in the same manner as in Example 1.

(2) Using each of the pellets of the thermoplastic polyurethane resin composition obtained in the above (1), melt spinning was carried out in the same manner as in Example 1 to produce polyurethane elastic fibers (monofilaments). The spin pack life was as shown in Table 3 above.

After the polyurethane elastic fiber obtained in the above (2) was aged, the unevenness of fineness, logarithmic viscosity, heat resistance and NOx resistance were measured or evaluated in the same manner as in Example 1. However, it was as shown in Table 3.

Comparative Examples 1 to 7 (1) A thermoplastic polyurethane was prepared in the same manner as in Example 1 except that the polymer polyol, the chain extender, the organic diisocyanate and the processing stabilizer were used in the composition and ratio shown in Table 2 above. Pellets of the resin composition were produced, and then vacuum-dried in the same manner as in Example 1.

(2) Using the pellets of the respective thermoplastic polyurethane resin compositions obtained in the above (1), melt spinning was carried out in the same manner as in Example 1 to produce polyurethane elastic fibers (monofilaments). The spin pack life was as shown in Table 3 above.

After the polyurethane elastic fiber obtained in the above (2) was aged, the unevenness of fineness, logarithmic viscosity, heat resistance, and NOx resistance were measured or evaluated in the same manner as in Example 1. However, it was as shown in Table 3.

As shown in Table 3, the thermoplastic polyurethane resin composition and the polyurethane elastic fiber satisfying the constitutional requirements of the present invention not only have a long spin pack life and good spinning stability, but also have a fineness unevenness. Various properties such as logarithmic viscosity, heat resistance and NOx resistance are also excellent. On the other hand, as shown in Table 3, the polyurethane elastic fiber of Comparative Example 1 having a smaller b / (a + c) than the polyurethane elastic fibers of Examples 1 to 11 has a lower molecular weight (logarithmic viscosity) and thus has a higher heat resistance. In Comparative Example 2 which is inferior in property and b / (a + c) is large, the life of the spinning pack is shortened and the fineness unevenness of the obtained polyurethane elastic fiber increases. In Comparative Example 3 in which the amount of the processing stabilizer was small, there was a problem in the life of the spinning pack and in the unevenness of the obtained polyurethane elastic fiber. In Comparative Example 4, in which the amount of the processing stabilizer was large, bleeding from the fiber surface was observed. There is a problem that is severe. In Comparative Example 5 in which the ratio (x / y) of the phenolic compound to the phosphorus compound was too large, in which only a phenolic compound was added as a processing stabilizer, the life of the spinning pack and the unevenness of fineness of the obtained polyurethane elastic fiber were poor. It is. Comparative Example 6 in which the ratio (x / y) of the phenolic compound to the phosphorus compound is too small
Then, in addition to the same problem as in Comparative Example 5, the NOx resistance also deteriorates. In Comparative Example 7 using a phenolic compound having no dialkylhydroxyphenyl group represented by the general formula (I) or (II), the desired (5 days or more) spin pack life was not reached.

[0059]

The thermoplastic polyurethane resin composition of the present invention and the polyurethane elastic fiber comprising the same have excellent properties such as heat resistance, hot water resistance, elastic recovery and elongation. It can be used effectively for applications. Further, the thermoplastic polyurethane resin composition of the present invention is excellent in processing stability at the time of melt spinning because the retention deterioration during the melt processing is small. Therefore, the obtained polyurethane elastic fiber is excellent in homogeneity.

Claims (5)

[Claims] 1. A polymer polyol, an organic diisocyanate and a chain extender represented by the following formula (1): 1.00 ≦ b / (a + c) ≦ 1.10 (1) The number of moles, b is the number of moles of the organic diisocyanate, and c is the number of moles of the chain extender.) 100 parts by weight of the thermoplastic polyurethane resin (A) obtained by reacting at a ratio satisfying the following. Formula (I) or (II) of the formula: (In the formula, R ¹ represents a branched alkyl group having 3 to 20 carbon atoms, and R ² represents an alkyl group.) Wherein R ³ represents a branched alkyl group having 3 to 20 carbon atoms, and R ⁴ represents an alkyl group. A phenolic compound (X) containing at least one dialkylhydroxyphenyl group represented by the formula: 0.1 ≦ x / y ≦ 10 (2) (where x represents the weight of the phenolic compound (X),
y represents the weight of the phosphorus compound (Y). A) a thermoplastic polyurethane resin composition comprising 0.1 to 3.0 parts by weight of a processing stabilizer (B) containing satisfies the ratio satisfying (1). 2. The dialkylhydroxyphenyl group represented by formula (I) or (II), wherein R ¹ or R ³ in the formula is a t-butyl group or a t-pentyl group. Thermoplastic polyurethane resin composition. 3. The phenolic compound is 3,9-bis [2
-{3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxospiro [5.5] undecane, Tetrakis [methylene-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, n-octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-t) -Pentylphenyl) ethyl] -4,
6-di-t-pentylphenyl acrylate and N,
N'-hexamethylenebis (3,5-di-t-butyl-
The thermoplastic polyurethane resin composition according to claim 2, which is at least one compound selected from the group consisting of 4-hydroxy-hydrocinnamamide). 4. The value of b / (a + c) is 1.02 to 1.0.
The thermoplastic polyurethane resin composition according to any one of claims 1 to 3, wherein the composition is within the range of 7. 5. A polyurethane elastic fiber comprising the thermoplastic polyurethane resin composition according to any one of claims 1 to 4.