JPH0949120A - Polyurethane elastic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To smoothly obtain a polyurethane elastic fiber, excellent in various characteristics such as heat, wet heat and hot water resistances, elastic recovery and homogeneity of fibers and effectively usable in various applications under stable spinning conditions while suppressing a pressure rise in a spinning pack with time. SOLUTION: (A) A polyester polyol having 0.08-0.17 ester group concentration, 2.01-2.08 average number of functional groups of hydroxyl groups, 1000-5000 number-average molecular weight and <=70J/g crystallization enthalpy (▵H) is reacted with (B) an organic diisocyanate and (C) a chain extender so as to satisfy the formula 1.00<=(b)/[(a)+(c)]<=1.10 [(a), (b) and (c) are each the number of mol of the polyester polyol, organic diisocyanate and chain extender]. This polyurethane elastic fiber is then produced from the resultant polyurethane according to the melt spinning.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyurethane elastic fiber and a method for producing the same. More specifically, the present invention relates to polyurethane elastic fibers which are excellent in various properties such as heat resistance, moist heat resistance, hot water resistance, elastic recovery, homogeneity of fibers, and in the case of the method of the present invention, In addition, it is possible to extremely smoothly produce the high-quality polyurethane elastic fiber having the above-mentioned various properties in a stable spinning state while suppressing the pressure increase of the spinning pack over time.

[0002]

2. Description of the Related Art As a method for producing a polyurethane elastic fiber, methods such as a dry spinning method, a wet spinning method and a melt spinning method are known. Among them, the polyurethane elastic fiber obtained by the melt spinning method is excellent in heat setting property, abrasion resistance and transparency, and the production cost is low. However, the polyurethane elastic fiber obtained by the melt spinning method is less likely to form a strong hard segment than the polyurethane elastic fiber obtained by the dry spinning method, and thus tends to be inferior in heat resistance and wet heat resistance.

Therefore, various methods for improving the heat resistance and wet heat resistance of the polyurethane elastic fiber obtained by the melt spinning method have been proposed in the past. A method for forming a crosslinked structure is known, and for example, Japanese Patent Application Laid-Open No. Sho 4
In JP-A 8-58095, JP-B-50-10630, and JP-A-6-294012, a hard segment portion of polyurethane is crosslinked by using a trifunctional or higher polyfunctional chain extender such as trimethylolpropane. Forming a structure is disclosed. However, the above-mentioned conventional polyurethane having a crosslinked structure formed in the hard segment portion is not yet sufficient in heat resistance, and therefore the heat resistance of polyurethane elastic fiber obtained therefrom is not sufficiently satisfactory.

In addition to the above-mentioned conventional method, a secondary hydroxyl group (2) is used for the purpose of obtaining a polyurethane elastic fiber excellent in residual strain and dynamic elasticity (resilience).
Hydroxyl polyester obtained by reacting dicarboxylic acid with glycol having primary hydroxyl group) and polyhydric alcohol having 3 or more functional groups and a chain extender are reacted with organic diisocyanate to produce polyurethane, and melt spinning is performed using the polyurethane. A method for producing a polyurethane elastic fiber has been proposed (Japanese Patent Publication No. 42-3958).
Issue). However, the polyurethane elastic fiber obtained by this method is inferior in heat resistance, and the purpose of obtaining a polyurethane elastic fiber excellent in heat resistance cannot be achieved. Moreover, the present inventors
Polyurethane and polyurethane elastic fibers were produced according to the method described in the examples of the publications, and the resulting polyurethane elastic fibers were not only poor in heat resistance, but also wet heat resistance, hot water resistance, etc. It turned out to be inferior to the property of.

Furthermore, in Japanese Patent Publication No. 43-7426, Japanese Patent Application Laid-Open No. 2-127515, Japanese Patent Application Laid-Open No. 3-241013, and Japanese Patent Application Laid-Open No. 4-11011, a prepolymer compound containing a polyfunctional polyol is used as a polyurethane. A polyurethane or polyurethane elastic fiber having a crosslinked structure may be produced by adding a prepolymer compound containing a bifunctional polyol (diol) to a polyurethane produced by melting or by using a polyfunctional polyol at the time of fusion. Has been described. However, according to the methods described in these publications, it is difficult to uniformly mix the prepolymer compound with the polyurethane, and as a result, the composition of the polyurethane becomes nonuniform, and the fiber obtained by spinning is homogeneous. It lacks sex. Further, Japanese Patent Publication No. 42-5251 proposes a method of producing polyurethane by using a polyol having a hydroxyl functional group greater than 2, and a method of producing polyurethane elastic fiber by a wet chemical spinning method. When the spinning method is used, the homogeneity and abrasion resistance of the yarn tend to be poor.

Under the circumstances as described above, the present inventors have found that a polyester diol obtained by reacting a diol containing 3-methyl-1,5-pentanediol and an aliphatic dicarboxylic acid component having 6 to 12 carbon atoms. Is used together with an organic diisocyanate and a chain extender to produce polyurethane, and fibers are produced from the polyurethane,
The polyurethane elastic fiber obtained thereby was found to be excellent in various properties such as chlorine resistance, water resistance, mold resistance, elastic recovery, heat resistance, hot water resistance, and elongation. Kaihei 3-22031). And
As a part of the present inventors' research on this polyurethane elastic fiber, in order to further improve various performances, particularly hydrolysis resistance, hot water resistance, and moist heat resistance, polyurethane As a polyester diol used for formation, an attempt was made to use one having a lower ester group concentration. As a result, when the ester group concentration of the polyester diol is decreased, the pressure increase of the spin pack is likely to occur over time, stable spinning becomes difficult, and the homogeneity of the obtained polyurethane elastic fiber tends to decrease. It turned out to be.

Further, the inventors of the present invention have an average number of hydroxyl functional groups of 2.00 obtained by reacting a diol mixture consisting of 1,9-nonanediol and a specific diol having a branched carbon chain structure with a dicarboxylic acid. When a polyester diol is reacted with a polyisocyanate at a molar ratio of active hydrogen atoms / NCO groups of 1 to produce a polyurethane, the resulting polyurethane has hydrolysis resistance and flexibility at low temperatures. We found that it was excellent and filed an application first (Japanese Patent Laid-Open No. 61-18552).
No. 0). The inventors of the present invention produced polyurethane elastic fibers using the polyurethane obtained by this method, and although polyurethane elastic fibers excellent in hydrolysis resistance and flexibility at low temperature were obtained, stability during melt spinning was obtained. , It was found that there is still room for improvement in the homogeneity of the obtained polyurethane elastic fiber.

[0008]

Under the circumstances described above, the present inventors:
Compared with the conventional polyurethane elastic fiber described above, for the purpose of obtaining a polyurethane elastic fiber further excellent in various properties such as heat resistance, moist heat resistance, hot water resistance, elastic recovery property, fiber homogeneity, An object of the present invention is to develop a method capable of smoothly producing a polyurethane elastic fiber having excellent various properties during spinning, particularly during melt spinning, while preventing a pressure increase of a spin pack over time and maintaining good spinning stability. As a result, various studies have been repeated.

As a result of research conducted by the present inventors, in the polyurethane described in the examples of Japanese Patent Publication No. 42-3958, the ester group concentration of the hydroxyl polyester (ie, polyester polyol) used for forming the polyurethane is It is as large as 0.24, which brings about a decrease in heat resistance, hot water resistance, and moist heat resistance of polyurethane, and by extension, polyurethane elastic fiber formed therefrom, and moreover, in the invention described in this publication,
It has been found that a hydroxyl polyester for producing polyurethane (that is, a polyester polyol) is formed by using a glycol having a secondary hydroxyl group, which causes a decrease in heat resistance of the obtained polyurethane. Further, as a result of further study by the present inventors, the above-mentioned Japanese Patent Application Laid-Open No. 61-18552 by the present inventors.
In the invention of Japanese Patent No. 0, the cross-linked structure is not formed in the polyurethane because the average number of hydroxyl functional groups of the polyester polyol is 2, which means that when an attempt is made to produce a fiber using the polyurethane, It was found that the stability during spinning and the homogeneity of the polyurethane elastic fiber obtained by spinning were reduced.

Based on the above-mentioned various findings,
As a result of further studies, in producing an elastic fiber by using a polyurethane obtained by reacting a polyester polyol, an organic diisocyanate and a chain extender, as the polyester polyol, the ester group concentration (number of ester bonds in the polyester polyol / The total number of carbon atoms in the polyester polyol) is 0.08
~ 0.17, the average number of hydroxyl functional groups is 2.01 to 2.0
8, a number average molecular weight of 1000 to 5000 and a crystallization enthalpy (ΔH) of 70 J / g or less are used, and the number of moles of organic diisocyanate: (total number of moles of polyester polyol and chain extender) is 1: 1. .00-
When polyurethane elastic fibers are produced by reacting these components in the range of 1.10 to form polyurethane, heat resistance, wet heat resistance, hot water resistance, elastic recovery,
The present invention has been completed by finding that polyurethane elastic fibers, which are more excellent in various properties such as fiber homogeneity, can be produced extremely smoothly while preventing a pressure increase of the spinning pack over time during spinning and maintaining good spinning stability. .

Accordingly, the present invention provides a polyurethane elastic fiber comprising (i) a polyurethane formed from a polyester polyol, an organic diisocyanate and a chain extender; (ii) the polyester polyol used for forming the polyurethane constituting the fiber. However, the following requirements ~; ester group concentration (number of ester bonds in polyester polyol / total number of carbon atoms of polyester polyol) is 0.08 to 0.17; hydroxyl group average number of functional groups is 2.01 to 2.08; number average A polyester polyol having a molecular weight of 1000 to 5000; and a crystallization enthalpy (ΔH) of 70 J / g or less; and (iii) the polyurethane constituting the fiber is represented by the following formula (1);

[0012]

## EQU3 ## where 1.00 ≦ b / (a + c) ≦ 1.10 (1) where a = the number of moles of the polyester polyol, b = the number of moles of the organic diisocyanate, and c = the number of moles of the chain extender. The above polyester polyol,
A polyurethane elastic fiber obtained by reacting an organic diisocyanate and a chain extender;

The present invention provides (A) the following requirements
Ester group concentration (number of ester bonds in polyester polyol / total number of carbon atoms in polyester polyol) is 0.08 to 0.17; hydroxyl group average functional group number is 2.01 to 2.08; number average molecular weight is 1000 to 5000; And a crystallization enthalpy (ΔH) of 70 J / g or less; (B) an organic diisocyanate; and (C) a chain extender;

[0014]

## EQU4 ## 1.00 ≦ b / (a + c) ≦ 1.10 (1) In the formula, a = the number of moles of the polyester polyol b = the number of moles of the organic diisocyanate c = the number of moles of the chain extender Melt-spinning is performed using the polyurethane obtained by reacting the above-mentioned compound, or the polyester polyol, the organic diisocyanate and the chain extender are reacted so as to satisfy the above mathematical expression (1) to form polyurethane. A method for producing a polyurethane elastic fiber, which comprises performing melt spinning.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The polyurethane constituting the polyurethane elastic fiber of the present invention is a polyurethane formed by using a polyester polyol, an organic diisocyanate and a chain extender, and the polyester polyol used for forming the polyurethane first has the above-mentioned requirements (ester). It is necessary that the group concentration satisfies 0.08 to 0.17). When the ester group concentration of the polyester polyol is less than 0.08, the resulting polyurethane elastic fiber has low cold resistance and elastic recovery, and further, the pressure rise of the spinning pack over time is remarkable during the production of the fiber, and the fiber is stable. Spinning becomes impossible and the resulting polyurethane elastic fiber lacks homogeneity. On the other hand, the ester group concentration of the polyester polyol used for forming the polyurethane constituting the polyurethane elastic fiber is 0.17.
When it exceeds, the heat resistance, hot water resistance, and moist heat resistance of the resulting polyurethane elastic fiber are significantly reduced. From the viewpoint that the spinning stability and the above-mentioned various properties are further improved, the ester group concentration of the polyester polyol is 0.11 to 0.1.
It is preferably in the range of 6. Here, in the present invention,
The “ester group concentration” of the polyester polyol is a value obtained by dividing the number of ester bonds in the polyester polyol by the total number of carbon atoms of the polyester polyol as described above.

Furthermore, in the present invention, the polyester polyol used for forming the polyurethane constituting the polyurethane elastic fiber has the above-mentioned requirements (the average number of hydroxyl functional groups is 2.0).
It is necessary to satisfy 1 to 2.08). When the average number of hydroxyl functional groups of the polyester polyol is less than 2.01, the molecular weight of the polyurethane constituting the polyurethane elastic fiber does not become high, and the heat resistance and wet heat resistance of the resulting polyurethane, and thus the polyurethane elastic fiber, deteriorate. When the polyester polyol does not satisfy the requirements, even if the polyester polyol satisfies the above requirements (ester group concentration 0.08 to 0.17), the polyurethane formed using the polyester polyol is spun. At the same time, the pressure increase of the spinning pack over time becomes remarkable and stable spinning cannot be performed, the homogeneity of the fiber is reduced, and particularly in the case of polyurethane formed using a polyester polyol having an ester group concentration of 0.12 or less. That is remarkable. On the other hand, when the average number of hydroxyl functional groups of the polyester polyol exceeds 2.08, the hot water resistance of the resulting polyurethane elastic fiber is lowered, and further, a heat-deteriorated product is generated during spinning, which deteriorates the spinning processability and the resulting polyurethane elasticity. Deterioration of fiber quality occurs. The average number of hydroxyl functional groups of the polyester polyol is 2.015 to
2.060 is more preferable from the viewpoint of spinning stability and physical properties of the obtained polyurethane elastic fiber. In addition,
The “average number of hydroxyl functional groups” of the polyester polyol in the present invention means the average of the polyester polyols used in the production of polyurethane (when they are regarded as an aggregate of each polyester polyol molecule). It means the number of hydroxyl functional groups.

The reason why the above-mentioned various problems are caused when the average number of hydroxyl functional groups of the polyester polyol deviates from 2.01 to 2.08 is not clear, but it is presumed as follows. That is, in the present invention, in order to improve the cold resistance, hot water resistance, heat resistance, moist heat resistance and the like of the polyurethane elastic fiber, and to suppress the pressure increase over time of the spinning pack during spinning, as described above. Ester group concentration is 0.0
Spinning is performed using a polyurethane formed from a polyester polyol having a concentration of 8 to 0.17, and in the polyurethane obtained using a polyester polyol having such an ester group concentration, particularly an ester group concentration of 0.16 or less, The compatibility between the hard segment and the soft segment constituting the polyurethane molecule is reduced, and as a result, the pressure increase of the spinning pack over time tends to occur during spinning, and the unevenness of the fiber thickness and the inhomogeneity of the fiber easily occur. Become. However, in the present invention, by using a polyester polyol having an average number of hydroxyl functional groups of 2.01 to 2.08, the molecular weight of the polyurethane obtained from the polyester polyol becomes suitable for fiber production, As the pressure of the spinning pack does not rise with time during spinning, the spinning stability is improved, the homogeneity of the resulting polyurethane elastic fiber is increased, and the properties such as heat resistance and wet heat resistance are also improved. Presumed. Further, when the average number of hydroxyl functional groups of the polyester polyol exceeds 2.08, in the polyurethane obtained by using the polyester polyol, the entanglement of the molecular chains of the soft segment increases excessively, and the mobility of the hard segment also decreases. It is presumed that the aggregation in the hard segment is reduced, the hot water resistance, the heat resistance and the like are reduced, and further the spinning temperature needs to be increased, so that the thermal decomposition reaction of the polyurethane is likely to occur.

In the present invention, the polyester polyol used for forming the polyurethane constituting the polyurethane elastic fiber has the above-mentioned requirements (number average molecular weight of 1000 to 1000).
It is necessary to further satisfy 5000). When the number average molecular weight of the polyester polyol is less than 1,000, the resulting polyurethane elastic fiber has poor performance such as heat resistance, hot water resistance, and moist heat resistance. On the other hand, when the number average molecular weight is more than 5000, stability during spinning, The breaking strength and fiber homogeneity of the resulting polyurethane elastic fiber are reduced. Number average molecular weight of polyester polyol is 1500
It is preferably ˜3000.

Further, in the present invention, the polyester polyol used for forming the polyurethane constituting the polyurethane elastic fiber has the above-mentioned requirements [crystallization enthalpy (Δ
H) of 70 J / g or less] is required.
Crystallization enthalpy of polyester polyol (△ H)
Of more than 70 J / g, the resulting polyurethane,
As a result, the cold resistance of the polyurethane elastic fiber is significantly lowered, and when exposed to a low temperature, for example, an ambient temperature of -30 ° C or less, cracks and the like are likely to occur. Here, the enthalpy of crystallization of the polyester polyol (Δ in the present invention)
H) can be measured using a differential scanning calorimeter,
Specifically, it refers to a value obtained by the method described in the section of Examples below.

In the present invention, as long as the polyester polyol for forming the polyurethane constituting the polyurethane elastic fiber is a polyester polyol having the above-mentioned requirements to requirements, the type of polyester polyol and the manufacturing method are not particularly limited. Although not provided, the polyester polyol having the above requirements to requirements can be smoothly produced, preferably as described below.

[Preferred production method of polyester polyol used in the present invention] A polyester polyol is produced by reacting a dicarboxylic acid component with a polyol component mainly composed of a diol and containing a small amount of a trifunctional or higher functional polyol. At that time, the use ratio of the dicarboxylic acid component and the polyol component is such that the ester group concentration of the polyester polyol obtained by the reaction between them is 0.08 to 0.17 and the hydroxyl group average functional group number is 2.01 to 2 described above. It is necessary to carry out polycondensation in such a manner that the number average molecular weight of the polyester polyol obtained by the reaction between the two is in the range of 1,000 to 5,000 described above.

In the polycondensation reaction of the polyester polyol, the polyester group obtained has an ester group concentration in the range of 0.08 to 0.17 and the crystallization enthalpy (ΔH) is 70 J /
In order to achieve g or less, it is preferable to use a branched dicarboxylic acid component as a part or all of the dicarboxylic acid component and / or a branched primary diol as a part or all of the diol. . In that case, the content ratio of the branched chain dicarboxylic acid component and / or the branched chain primary diol is based on the total number of moles (total number of moles) of the dicarboxylic acid component and the diol used for forming the polyester polyol. The total molar number of the dicarboxylic acid component and the branched primary diol is preferably 10 mol% or more, more preferably 30 mol% or more, and further preferably 50 mol% or more.

When the total number of moles of the branched chain dicarboxylic acid component and the branched chain primary diol is less than 10 mol% based on the total number of moles of the dicarboxylic acid component and diol used for forming the polyester polyol, the polyester polyol is It becomes difficult to control the ester group concentration of 0.08 to 0.17 and it is difficult to control the crystallization enthalpy (ΔH) of the polyester polyol to 70 J / g or less. Polyurethane elastic fibers obtained by using such polyester polyols whose concentration and / or enthalpy of crystallization (ΔH) are out of the range of the present invention have poor heat resistance, hot water resistance, wet heat resistance, cold resistance and elastic recovery. It also tends to be inferior in sex. As long as the total number of moles of the branched dicarboxylic acid component and the branched primary diol is 10 mol% or more based on the total number of moles of the dicarboxylic acid component and the diol, the dicarboxylic acid component used for producing the polyester polyol Only contains a branched dicarboxylic acid component and the diol does not contain a branched primary diol, the dicarboxylic acid component does not contain a branched dicarboxylic acid component and only the diol has a branched chain 1 The primary diol may be contained, or the dicarboxylic acid component may contain a branched dicarboxylic acid component and the diol may contain a branched primary diol.

The above-mentioned branched dicarboxylic acid component preferably used for the production of polyester polyol has a branched saturated aliphatic hydrocarbon chain or a branched unsaturated aliphatic hydrocarbon chain, and both ends of the hydrocarbon chain. A branched chain dicarboxylic acid having 5 to 14 carbon atoms in which a carboxyl group is bound to each of the above and an ester-forming derivative thereof are preferably used. Preferred examples of such a branched dicarboxylic acid component include 2-methyl-succinic acid, 3
-Methyl glutaric acid, 2-methyl adipic acid, 3-methyl adipic acid, 3-methyl-pentanedioic acid, 2-methyl-octanedioic acid, 3,7-dimethyl sebacic acid, 3,8
-Dimethyl sebacic acid or an ester-forming derivative thereof may be mentioned, and these branched chain dicarboxylic acid components may be used alone or in combination of two or more kinds.

Further, in the production of polyester polyol, together with the above-mentioned branched dicarboxylic acid component,
Other dicarboxylic acid components consisting of a linear dicarboxylic acid component and a cyclic dicarboxylic acid component may be optionally used, and examples of such other dicarboxylic acid components include:
Linear dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid; aromatics such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and tetrabromophthalic acid Examples thereof include dicarboxylic acid; alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; or ester-forming derivatives thereof. These other dicarboxylic acid components may be used alone or in combination of two or more kinds. Good. Furthermore, as long as the polyester polyol satisfies the above requirements to requirements, a trifunctional or higher polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid or an ester-forming derivative thereof may be used in the production of the polyester polyol, if necessary. You may use a small amount.

As the above-mentioned branched primary diol preferably used for the production of polyester polyol, hydroxyl groups are bonded to both ends of the branched saturated aliphatic hydrocarbon chain or the branched unsaturated aliphatic hydrocarbon chain, respectively. A branched chain primary diol having 4 to 10 carbon atoms is preferably used. Preferred examples of such branched primary diols include 2-methyl-1,3-propanediol, neopentyl glycols, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octane. Examples thereof include diols. Among them, in order to further improve the hot water resistance, heat resistance, and moist heat resistance of the obtained polyurethane, and thus the polyurethane elastic fiber, a branched primary diol having a relatively long chain is used. Is preferably used, and 3-methyl-1,5-pentanediol and 2-methyl-1,8-octanediol are particularly preferably used. The branched primary diols may be used alone or in combination of two or more.

Further, in the production of the polyester polyol, other diols consisting of linear diols and cyclic diols may be used together with the above-mentioned branched primary diols, if necessary. Examples of diols are 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol and 1,9-.
Examples thereof include linear diols such as nonanediol and 1,10-decanediol; alicyclic diols such as cyclohexanediol. These other diols may be used alone or in combination of two or more kinds. May be.

In the production of the polyester polyol, in order to adjust the average number of hydroxyl functional groups of the polyester polyol to 2.01 to 2.08, as described above, a small amount of trifunctional or higher functional polyol together with the above-mentioned diol. Is preferably used. Examples of trifunctional or higher functional polyols used in combination with diols include glycerin, trimethylolpropane, butanetriol, hexanetriol, trimethylolbutane, trimethylolpentane, pentaerythritol, and the like.
These polyols may be used alone or in combination of two or more. Of the above-mentioned polyols, glycerin and trimethylolpropane are more preferably used.

The ratio of the diol used for the production of the polyester polyol to the trifunctional or higher functional polyol may vary depending on the number of functionalities of the polyol. In order to adjust the number of groups to 2.01 to 2.08, the molar ratio of diol: triol is preferably 100: 1 to 1000: 1. When tetraol is used as the trifunctional or higher functional polyol, In order to make the average number of hydroxyl functional groups of the polyester polyol 2.01 to 2.08, the molar ratio of diol: tetraol is 200: 1 to 2000: 1.
It is preferred that

In the production of the polyester polyol, the use ratio of the dicarboxylic acid component, the diol and the trifunctional or higher functional polyol is adjusted so that the average number of hydroxyl functional groups of the obtained polyester polyol is 2.01 to 2.08. It is necessary to carry out the reaction.

The polyester polyol used for producing polyurethane may be a single polyester polyol or 2
Even a mixture of two or more polyester polyols,
Alternatively, a mixture of a polyester diol and a polyester polyol may be used. In short, when viewed as the whole polyester polyol (aggregate of polyester polyols), a polyester polyol satisfying the above requirements to requirements may be used.

The method for producing the polyester polyol having the requirements 1 to 3 is not particularly limited, and the above-mentioned dicarboxylic acid component, diol, trifunctional or higher functional polyol, and, if necessary, trifunctional or higher functional carboxylic acid component are used.
It can be produced by a known polycondensation method using an esterification reaction or a transesterification reaction.

The polycondensation reaction in producing the polyester polyol can be carried out in the presence of a catalyst, and in this case, a titanium-based catalyst or a tin-based catalyst is preferably used. Examples of titanium-based catalysts include titanic acid, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, and more specifically, tetraisopropyl titanate and tetra-n-.
Butyl titanate, tetra-2-ethylhexyl titanate, tetraalkoxy titanium compounds such as tetrastearyl titanate, titanium hydroxylate compounds such as polyhydroxy titanium stearate, polyisopropoxy titanium stearate, titanium acetyl acetate, triethanolamine titanate, titanium ammonium Examples thereof include titanium chelate compounds such as lactate, titanium ethyl lactate, and titanium octylene glycol. Examples of tin catalysts include dialkyltin diacetate, dialkyltin dilaurate, dialkyltin bismercaptocarboxylic acid ester salt, and the like. More specifically, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bis (3 -Mercaptopropionic acid ethoxybutyl ester) salt and the like.

When a titanium-based catalyst is used, the amount used can be adjusted according to each situation and is not particularly limited, but generally it is about 0. 0 based on the total weight of the reaction components used for producing the polyester polyol. It is preferably from 1 to 50 ppm, more preferably from about 1 to 30 ppm. Also, when a tin-based catalyst is used, the amount thereof can be adjusted according to each situation and is not particularly limited, but it is generally about 1 to 200 ppm based on the total weight of the reaction components used for producing the polyester polyol. Is preferable, and about 5 to 100 ppm is more preferable.

In the polyester polyol produced by using the titanium-based catalyst, it is necessary to deactivate the titanium-based catalyst contained in the polyester polyol, and the polyester containing the non-deactivated titanium-based catalyst is required. When polyurethane is produced using a polyol, the polyurethane, and thus the polyurethane elastic fiber formed therefrom, tends to have inferior properties such as hot water resistance, dry heat resistance, and moist heat resistance.

Examples of the method for deactivating the titanium-based catalyst contained in the polyester polyol include (1) a method of bringing the polyester polyol into contact with water under heating; (2) a polyester polyol containing phosphoric acid, a phosphoric acid ester, and Examples thereof include a method of treating with a phosphorus compound such as phosphoric acid and phosphorous acid ester. Then, in the case of the method (1) of contacting with water, for example, water of 1% by weight or more is added to the polyester polyol to obtain 70 to 150.
The heating may be performed at a temperature of 90 ° C., preferably 90 to 130 ° C. for about 1 to 3 hours. Then, the deactivation treatment by heating at that time may be performed under normal pressure or under pressure. When the system is depressurized after the deactivation treatment, the water used for the deactivation is smoothly removed from the polyester polyol. be able to.

In the present invention, a polyester polyol having the above-mentioned requirements is used, and the polyester polyol, the organic diisocyanate and the chain extender are represented by the following formula (1);

[0038]

1.00 ≦ b / (a + c) ≦ 1.10 (1) In the formula, a = the number of moles of the polyester polyol, b = the number of moles of the organic diisocyanate, and c = the number of moles of the chain extender. It is necessary that the polyurethane elastic fiber of the present invention is formed from the polyurethane obtained by reacting with the polyurethane. When the above-mentioned value of b / (a + c) at the time of forming polyurethane is less than 1.00, the polyurethane elastic fiber obtained from it has a low molecular weight of the polyurethane constituting the fiber, so that the hot water resistance, heat resistance, It becomes inferior in moist heat resistance. On the other hand, b /
When the value of (a + c) exceeds 1.10, the spinning stability at the time of producing a polyurethane elastic fiber is lowered, and the obtained polyurethane elastic fiber lacks homogeneity. The above-mentioned value of b / (a + c) when forming polyurethane is preferably 1.01 to 1.07 from the viewpoint of spinning stability, various properties of the obtained polyurethane elastic fiber, and the like.

As the above-mentioned organic diisocyanate used in the production of the polyurethane elastic fiber of the present invention, any of the organic diisocyanates conventionally used in the production of polyurethane for elastic fibers can be used, and particularly, those having a molecular weight of 5 are used.
Those of 00 or less are preferably used. Examples of such organic diisocyanates include 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, toluylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dichloro-4,4'-.
Aromatic diisocyanates such as diphenylmethane diisocyanate, xylylene diisocyanate, toluylene diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, aliphatic or alicyclic diisocyanates such as hydrogenated xylylene diisocyanate, etc. These organic diisocyanates may be used alone or in combination of two or more kinds. Among them, 4,4'-diphenylmethane diisocyanate and / or p-phenylene diisocyanate are preferably used. Also, a trifunctional or higher functional polyisocyanate compound such as triphenylmethane triisocyanate may be used in a small amount, if necessary.

As the chain extender used for producing the polyurethane elastic fiber of the present invention, any chain extender conventionally used for producing polyurethane for elastic fiber can be used, and it is not particularly limited. However, a low molecular compound having two active hydrogen atoms reactive with an isocyanate group in the molecule and having a molecular weight of 300 or less is preferably used. Examples of such chain extenders include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,9-nonanediol; 1,4-bis (β-hydroxyethoxy). ) Benzene, 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate, aromatic ring-containing diol such as xylylene glycol; hydrazine, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, piperazine derivative, phenylenediamine Diamines such as tolylenediamine and xylenediamine; dihydrazides such as adipic acid dihydrazide and isophthalic acid dihydrazide; amino alcohols such as aminoethyl alcohol and aminopropyl alcohol. These chain extenders may be used alone or in combination of two or more kinds. Among them, it is preferable to use 1,4-butanediol because a polyurethane elastic fiber excellent in hot water resistance, heat resistance, and elastic recovery can be obtained.

In producing polyurethane, a polyurethane-forming reaction can be carried out using a tin-based urethane-forming catalyst, and in particular, the tin-based urethane-forming catalyst is converted into tin atoms based on the total weight of the raw materials for polyurethane. When a polyurethane is produced with a ratio of 0.5 to 5 ppm, a polyurethane having a high molecular weight can be obtained, and when a fiber is produced using such a polyurethane, good spin-up windability is obtained, and Less sticking between fibers. Further, by producing a fiber using such a high molecular weight polyurethane, a polyurethane elastic fiber having excellent mechanical properties typified by tensile strength and elongation recovery and heat resistance can be obtained. Examples of the tin-based urethane-forming catalyst in that case include dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin bis (3-mercaptopropionic acid ethoxybutyl ester) salt.

The reason why the above-mentioned excellent effects are obtained by using the tin-based urethane-forming catalyst is not completely clear, but it is presumed that the reason is as follows. That is, in a polyurethane obtained by using a polyester polyol satisfying the above requirements of an ester group concentration of 0.08 to 0.17 and the number average molecular weight of 1000 to 5000, a hard segment and a soft segment constituting a polyurethane molecule are formed. The low compatibility between the isocyanate group and the hydroxyl group caused by thermal dissociation after melt spinning, and the reactivity between the isocyanate group and water is low due to the hydrophobic effect. Therefore, the molecular weight of the polyurethane constituting the fiber is low. However, by using a tin-based urethane-forming catalyst, the recovery of the molecular weight of the polyurethane can be increased, and as a result, polyurethane with excellent properties such as hot water resistance, heat resistance, moist heat resistance, mechanical properties, etc. Elastic fibers are also obtained It is presumed that. However, when the amount of the tin-based urethane-forming catalyst used exceeds 5 ppm in terms of tin atom based on the raw material for polyurethane, the hot water resistance of the polyurethane elastic fiber obtained from such polyurethane,
It tends to have low heat resistance and low heat and humidity resistance.

Polyurethane The method for producing polyurethane for elastic fibers is not particularly limited, and any of the methods conventionally used for producing polyurethane for elastic fibers can be used. For example, known methods such as melt polymerization and solution polymerization can be used. It can be produced by a method such as a prepolymer method or a one-shot method using a urethane-forming reaction technique. Among them, it is preferable to carry out melt polymerization under conditions where substantially no solvent is present to produce polyurethane, from the viewpoint that polymerization can be carried out easily and smoothly, and particularly the melt polymerization is carried out with a screw type extruder. When the continuous melt polymerization method used is used, the productivity is increased, which is preferable.

In producing the polyurethane elastic fiber of the present invention using the above-mentioned polyurethane,
A melt spinning method, a dry spinning method, a wet spinning method and the like can be adopted, and among them, the melt spinning method is preferably used from the viewpoints of physical properties, simplicity, and productivity of the obtained polyurethane elastic fiber. In the case of producing a polyurethane elastic fiber by melt spinning, (i) a polyurethane is produced in advance by using a polyester polyol, an organic diisocyanate and a chain extender having the above-mentioned requirements to requirements in a ratio satisfying the above mathematical expression (1). In advance, a method of melt spinning using the polyurethane; (ii) melt polymerization using a polyester polyol, an organic diisocyanate, and a chain extender having the above-mentioned requirements 1 to 3 in a ratio satisfying the above mathematical expression (1). A method in which the polyurethane which is still in a molten state formed by forming the polyurethane is directly spun out directly from the spinneret; The melt spinning temperature is preferably 250 ° C. or lower from the viewpoints of physical properties of the obtained fiber and easiness of melt spinning work.
More preferably, it is 200 to 240 ° C. Then, the polyurethane elastic fiber obtained after spinning is heated to 50 to 100 ° C.
It is preferable that the heat aging treatment is performed at the temperature because the performance is further improved. There are no particular restrictions on the type or type of spinning device used for melt spinning, and a melt spinning device conventionally used for producing polyurethane elastic fibers can be used.

The polyurethane elastic fiber of the present invention comprises a light stabilizer, a heat stabilizer, an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, an antifungal agent, a colorant, a flame retardant, and an improved weather resistance, if necessary. One or two or more kinds of additives such as agents may be contained. The method of adding the above-mentioned additive to the polyurethane elastic fiber is not particularly limited, and for example, it may be added during polymerization of polyurethane, during melt kneading when producing pellets or the like from the polyurethane obtained by polymerization, during melt spinning, etc. You can

In the polyurethane elastic fiber of the present invention, the degree of polymerization of the polyurethane constituting the fiber is not particularly limited, but from the viewpoint of dry heat resistance and wet heat resistance of the polyurethane elastic fiber, N containing 1% by weight of n-butylamine, N-
The degree of polymerization is such that the polyurethane elastic fiber is dissolved in dimethylformamide in an amount such that the concentration becomes 0.5 dl / g, and the logarithmic viscosity measured at 30 ° C. becomes 0.5 dl / g or more. It is particularly preferable that the degree of polymerization is 0.7 dl / g or more. Especially,
When polyurethane elastic fiber is dissolved in N, N-dimethylformamide containing 1% by weight of n-butylamine, it is not dissolved at all, or only a part thereof is dissolved. When the polyurethane elastic fiber of the invention is formed, dry heat resistance,
It is possible to obtain a polyurethane elastic fiber having more excellent resistance to moist heat.

The single fiber fineness of the polyurethane elastic fiber of the present invention is not particularly limited and can be appropriately determined according to the application, etc., but the single fiber fineness is generally 10 to 10.
It is preferably about 0 denier. Further, the polyurethane elastic fiber of the present invention may be in the form of a monofilament or in the form of a multifilament. In the case of a multifilament, the number of filaments, the total number of denier, etc. are not particularly limited and are appropriately determined. be able to. Further, the cross-sectional shape of the polyurethane elastic fiber of the present invention is also not particularly limited, round cross-section, square, hollow,
It can be triangular, elliptical, flat, multi-lobed, V-shaped, T-shaped, array-shaped, or any other irregular cross-section.
In manufacturing 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 application of the polyurethane elastic fiber of the present invention is not particularly limited and it can be used for various purposes. Taking advantage of its elastic properties, for example, sports equipment such as swimwear, ski wear, cycling wear, leotards; Clothing such as lingerie, foundation, underwear; wearing pantyhose, socks, supporters, hats, gloves, etc .; power nets; medical supplies such as bandages and artificial blood vessels; tennis racket gut, vehicle seat fabric for integral molding It can be effectively used for non-clothing products such as metal-coated yarns for robot arms. Among them, the polyurethane elastic fiber of the present invention is extremely effective for use in sports goods, clothing, etc. by taking advantage of its excellent heat resistance, moist heat resistance, hot water resistance, elastic recovery property, yarn homogeneity and the like. Can be used.

[0049]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, the number average molecular weight of polyester polyol, enthalpy of crystallization (ΔH), spinning stability when producing polyurethane elastic fiber, logarithmic viscosity of polyurethane elastic fiber, heat resistance, hot water resistance, moist heat resistance, elastic recovery Rate and fiber homogeneity were measured or evaluated as follows.

1. Number average molecular weight of polyester polyol: The number average molecular weight of the polyester polyol was calculated based on the hydroxyl value measured according to JIS K1577.

2. Crystallization enthalpy (ΔH) of polyester polyol: differential scanning calorimeter [Rigaku Thermal Analysis manufactured by Rigaku Electric Co., Ltd.]
Station TAS10 "] was used to measure the crystallization enthalpy (ΔH) of the polyester polyol.
The sample amount is about 10mg, and under nitrogen stream (100ml
/ Min) under the conditions shown in Table 1 below, and the crystallization enthalpy (ΔH) from the peak area in step 3
I asked.

[0052]

[Table 1] Starting temperature Ending temperature Ending temperature holding time Temperature rising / falling speed (° C) (° C) (min) (° C / min) Step 1 room temperature → 100 3 100 Step 2 100 → -100 1 10 Step 3 -100 → 100 0 10

3. Spinning stability during the production of polyurethane elastic fibers: Using a single-screw extruder, as in the following Examples or Comparative Examples, at a spinning temperature of 200 to 240 ° C., continuously spinning for 1 week to perform melt spinning, at which time The pressurization of the spinning pack (Sandmesh # 60-80) was measured with a pressure gauge, and the spinning stability was evaluated according to the evaluation criteria shown in Table 2 below.

[0054]

[Table 2] Evaluation criteria for spinning stability ○: the step-up of the spinning pack is almost no (step-up is 4kg / cm ² or less), it is possible to continuous operation △: if there is a step-up of the spinning pack (step-up is less than 8kg / cm ² beyond the 4kg / cm ^2), Continuous operation is difficult x: The pressure of the spinning pack is too high (pressurization is 8 kg / cm ² or more) and continuous operation is impossible.

4. Logarithmic viscosity of polyurethane elastic fiber: A sample made of polyurethane elastic fiber has a concentration of 0.5 g / d.
It was dissolved in N, N-dimethylformamide containing 1% by weight of n-butylamine so that the concentration became 1 and the mixture was added at 20 ° C. for 24 hours.
After standing for 30 hours, use an Ubbelohde viscometer to measure 30
The falling time at ° C was measured, and the logarithmic viscosity of the polyurethane elastic fiber was calculated by the following mathematical formula.

[0056]

[Equation 6] Logarithmic viscosity of polyurethane elastic fiber = {ln (t
/ T ₀ )} / c In the formula, t = falling time (second) of the sample solution t ₀ = falling time (second) of N, N-dimethylformamide solution (blank solution) containing 1% by weight of n-butylamine c = Sample concentration in sample solution (g / dl)

5. Heat resistance of polyurethane elastic fiber: A sample made of polyurethane elastic fiber is heated at a rate of 3 ° C./min in a state of being stretched 100%, and the temperature at which the polyurethane elastic fiber is cut is determined to obtain the heat resistance of the polyurethane elastic fiber. It was used as an index.

6. Hot water resistance of polyurethane elastic fiber: A sample of polyurethane elastic fiber was used in a wooden frame.
Fix it in the state of 0% elongation and use a hot air dryer to 140
After dry heat treatment at ℃ for 2 minutes, use an autoclave to immerse it in hot water at a temperature of 130 ℃ for 30 minutes, then take it out of the autoclave and measure its stress while keeping the elongation at 200%. (Instron 4501 manufactured by Instron Co., Ltd.) was used to measure the stress (R) (g / 80d) at that time, which was used as an index of hot water resistance.

7. Moisture and heat resistance of polyurethane elastic fiber: Sample made of polyurethane elastic fiber at 70 ° C, 95% RH
Under a relative humidity of 5 weeks, the breaking strength of the polyurethane elastic fiber before and after the test is measured according to JIS-L-1013, and the retention ratio of the breaking strength after the test to the breaking strength before the test is calculated by the following mathematical formula. Then, it was used as an index of moist heat resistance.

[0060]

Equation 7] retention of breaking strength (%) = (T / T 0) × 100 where, T = breaking strength of the sample after the test (g / d) T ₀ = breaking strength of the test before the test (g / D)

8. Elastic recovery rate of polyurethane elastic fiber:
A sample made of polyurethane elastic fibers was held at room temperature for 2 minutes in a state of being stretched by 300%, the elastic recovery rate after leaving for 2 minutes after removing the tension was calculated by the following mathematical formula.

[0062]

Equation 8] elastic recovery (%) = {1- (L -L 0) / L 0} × 100 where, L = length of the sample after standing for 2 minutes after the tension is removed (mm) L ₀ = Length of sample before extension (mm)

9. Homogeneity of polyurethane elastic fibers: length 50 from polyurethane elastic fibers obtained by melt spinning
m sample is taken, and a thickness measuring instrument (Kesokuki Even) manufactured by Keisokuki Kogyo Co., Ltd. is taken along the length direction of the sample.
(Nest Tester Model KEP-80C)
Was slid to measure the thickness irregularity of the fiber, and the homogeneity of the polyurethane elastic fiber was evaluated according to the evaluation criteria shown in Table 3 below.

[0064]

[Table 3] Criteria for evaluating homogeneity of polyurethane elastic fiber ◯: Fiber thickness unevenness is within 1% Δ: Fiber thickness unevenness is over 1% and less than 3% ×: Fiber thickness The spot is 3% or more

In the following examples, compounds may be represented by abbreviations, and the relationship between abbreviations and compounds is as shown in Table 4 below. The number average molecular weights of the polyester polyols shown in Table 4 below are 2
000.

[0066]

[Table 4]

Reference Example 1 [Production of PMAz] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g and azelaic acid (AZ) 4058 g
Was charged into a reactor, and an esterification reaction was carried out at 200 ° C. under normal pressure while distilling the produced water out of the system. When the acid value of the reaction product reached 30 or less, 90 mg of tetraisopropyl titanate was added as a titanium-based esterification catalyst, and the reaction was continued while gradually reducing the pressure from 200 mmHg to 100 mmHg for polycondensation. When the acid value of the reaction product became 1.0 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the polycondensation reaction. As a result, a PMA having a number average molecular weight of 2000 and a hydroxyl group average number of functional groups of 2.00
6210 g of z (hereinafter referred to as PMAz-A) was obtained. (2) 1000 of PMAz-A obtained in (1) above
g to 100 ° C., 30 g (3% by weight) of water was added thereto and heated for 2 hours with stirring to deactivate the titanium-based esterification catalyst, and then water was distilled off under reduced pressure. Titanium-based esterification catalyst deactivated PMAz was obtained (hereinafter PMAz
Az-B). (3) The PMAz-B obtained in (2) above is 100
It was heated to ℃, 6ppm of dibutyltin diacetate as a tin-based urethane conversion catalyst (2pp as tin metal
m) was added and stirred for 1 hour. As a result, PMAz containing a tin-based urethane-forming catalyst and deactivating the titanium-based esterification catalyst was obtained (hereinafter referred to as PMAz-C).

Reference Example 2 [Production of PMTAz] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g, trimethylolpropane (TMP) 2
0.5 g and 4008 g of azelaic acid (AZ) were charged into a reactor, and an esterification reaction and a polycondensation reaction were carried out in the same manner as in (1) of Reference Example 1 to give a number average molecular weight of 2000.
And 6180 g of PMTAz having an average number of hydroxyl functional groups of 2.05 (hereinafter referred to as PMTAz-A ₁ ) were obtained. (2) Using PMTAz-A ₁ obtained in (1) above,
In the same manner as in (2) of Reference Example 1, the titanium-based esterification catalyst was deactivated, and the titanium-based esterification catalyst was deactivated PMTA.
z was obtained (hereinafter referred to as PMTAz-B ₁ ).

Reference Example 3 [Production of PMTAz] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g, trimethylolpropane (TMP) 3
2.4 g and 3978 g of azelaic acid (AZ) were charged into a reactor, and an esterification reaction and a polycondensation reaction were performed in the same manner as in (1) of Reference Example 1 to give a number average molecular weight of 2000.
And hydroxyl average functionality 2.08 PMTAz (hereinafter this is referred PMTAz-A ₂₎ was obtained 6165G. (2) Using the PMTAz-A ₂ obtained in (1) above,
In the same manner as in (2) of Reference Example 1, the titanium-based esterification catalyst was deactivated, and the titanium-based esterification catalyst was deactivated PMTA.
z was obtained (hereinafter referred to as PMTAz-B ₂ ). (3) Using PMTAz-B ₂ obtained in (2) above,
A tin-based urethane-forming catalyst was added in the same manner as in (3) of Example 1 to obtain PMTAz containing the tin-based urethane-forming catalyst and deactivated the titanium-based esterification catalyst (hereinafter referred to as PMTAz- that C _2).

Reference Example 4 [Production of PMTAz] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g, trimethylolpropane (TMP) 6
0.1 g and 3910 g of azelaic acid (AZ) were charged into a reactor, and an esterification reaction and a polycondensation reaction were performed in the same manner as in (1) of Reference Example 1 to give a number average molecular weight of 2000.
And hydroxyl average functionality 2.15 PMTAz (hereinafter this PMTAz-A ₃₎ was obtained 6125G. (2) Using the PMTAz-A ₃ obtained in (1) above,
In the same manner as in (2) of Reference Example 1, the titanium-based esterification catalyst was deactivated, and the titanium-based esterification catalyst was deactivated PMTA.
It was obtained z (hereinafter this is referred PMTAz-B _3).

Reference Example 5 [Production of PMAd] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g and adipic acid (AD) 3214 g were charged into a reactor, and an esterification reaction was carried out at 200 ° C. under normal pressure while distilling off the produced water out of the system. When the acid value of the reaction product became 30 or less, 90 mg of tetraisopropyl titanate was added as a titanium-based esterification catalyst,
While gradually reducing the pressure from 200 mmHg to 100 mmHg, the reaction was continued to cause polycondensation. The acid value of the reaction product is 1.
When it became 0 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the polycondensation reaction. As a result, a PMAd having a number average molecular weight of 2000 and a hydroxyl group average functional group number of 2.00
(Hereinafter, referred to as PMAd-A) 5468 g was obtained. (2) 1000 of PMAd-A obtained in (1) above
g to 100 ° C., 30 g (3% by weight) of water was added thereto and heated for 2 hours with stirring to deactivate the titanium-based esterification catalyst, and then water was distilled off under reduced pressure. PMAd deactivated titanium-based esterification catalyst was obtained (hereinafter referred to as PM
Ad-B).

Reference Example 6 [Production of PMTAd] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g, trimethylolpropane (TMP) 1
7.7 g and adipic acid (AD) 3180 g were charged in a reactor, and an esterification reaction and a polycondensation reaction were performed in the same manner as in (1) of Reference Example 1 to give a number average molecular weight of 2000 and a hydroxyl group average functional group number of 2.05. 5450 g of PMTAd (hereinafter referred to as PMTAd-A) was obtained. (2) Using the PMTAd-A obtained in (1) above, the titanium-based esterification catalyst is deactivated in the same manner as in (2) of Reference Example 1 to deactivate the titanium-based esterification catalyst.
Was obtained (hereinafter referred to as PMTAd-B).

Reference Example 7 [Production of PMSb] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g and sebacic acid (Sb) 4332 g were charged in a reactor, and an esterification reaction and a polycondensation reaction were performed in the same manner as in (1) of Reference Example 1 to give a number average molecular weight of 20.
00, and PMSb having an average number of hydroxyl functional groups of 2.05 (hereinafter referred to as PMSb-A) 6452 g were obtained. (2) Using the PMSb-A obtained in (1) above, the titanium-based esterification catalyst was deactivated in the same manner as in (2) of Reference Example 1 to obtain PMSb in which the titanium-based esterification catalyst was deactivated. (Hereinafter referred to as PMSb-B).

Reference Example 8 [Production of PMTSb] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g, trimethylolpropane (TMP) 2
1.3 g and 4274 g of sebacic acid (Sb) were charged into a reactor, and an esterification reaction and a polycondensation reaction were carried out in the same manner as in (1) of Reference Example 1 to give a number average molecular weight of 2000 and a hydroxyl group average functional group number of 2.05. 6705 g of PMTSb (hereinafter referred to as PMTSb-A) was obtained. (2) Using the PMTSb-A obtained in (1) above, the titanium-based esterification catalyst is deactivated in the same manner as in (2) of Reference Example 1 to deactivate the titanium-based esterification catalyst.
Was obtained (hereinafter referred to as PMSb-B).

Reference Example 9 [Production of PBAd] (1) 3000 g of 1,4-butanediol (BD) and 4156 g of adipic acid (AD) were charged in a reactor,
The esterification reaction was carried out under normal pressure at 200 ° C. while distilling the produced water out of the system. When the acid value of the reaction product reached 30 or less, 90 mg of tetraisopropyl titanate was added as a titanium-based esterification catalyst, and the reaction was continued while gradually reducing the pressure from 200 mmHg to 100 mmHg for polycondensation. When the acid value of the reaction product became 1.0 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the polycondensation reaction. As a result, PBAd having a number average molecular weight of 2,000 and an average number of hydroxyl functional groups of 2.00 (hereinafter referred to as PBAd
6080 g was obtained. (2) 1000 of PBAd-A obtained in (1) above
g to 100 ° C., 30 g (3% by weight) of water was added thereto and heated for 2 hours with stirring to deactivate the titanium-based esterification catalyst, and then water was distilled off under reduced pressure. PBAd deactivated titanium-based esterification catalyst was obtained (hereinafter referred to as PBd
Ad-B).

<< Reference Example 10 >> [Production of PBTAd] (1) 3000 g of 1,4-butanediol (BD),
Trimethylolpropane (TMP) (19.8 g) and adipic acid (AD) (4115 g) were charged into a reactor, and an esterification reaction was carried out at 200 ° C. under atmospheric pressure while distilling off the produced water out of the system. When the acid value of the reaction product reached 30 or less, 90 mg of tetraisopropyl titanate was added as a titanium-based esterification catalyst, and 200 mgHg to 1 was added.
While gradually reducing the pressure to 00 mmHg, the reaction was continued to cause polycondensation. When the acid value of the reaction product became 1.0 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the polycondensation reaction. As a result, PBTAd having a number average molecular weight of 2000 and a hydroxyl group average functional group number of 2.05 (hereinafter referred to as PBTA
6275 g was obtained. (2) 100 of PBTAd-A obtained in (1) above
0g is heated to 100 ℃, to this 30g water (3% by weight)
Was added and heated with stirring for 2 hours to deactivate the titanium-based esterification catalyst, and then water was distilled off under reduced pressure to obtain PBTAd with deactivated titanium-based esterification catalyst (hereinafter referred to as PBTAd. -B).

Reference Example 11 [Production of PNAd] (1) 3000 g of 1,9-nonanediol (ND) and 2318 g of adipic acid (AD) were charged in a reactor,
The esterification reaction was carried out under normal pressure at 200 ° C. while distilling the produced water out of the system. When the acid value of the reaction product reached 30 or less, 90 mg of tetraisopropyl titanate was added as a titanium-based esterification catalyst, and the reaction was continued while gradually reducing the pressure from 200 mmHg to 100 mmHg for polycondensation. When the acid value of the reaction product became 1.0 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the polycondensation reaction. As a result, PNAd having a number average molecular weight of 2000 and a hydroxyl group average functional group number of 2.00 (hereinafter referred to as PNA
4680 g was obtained. (2) 1000 of PNAd-A obtained in (1) above
g to 100 ° C., 30 g (3% by weight) of water was added thereto and heated for 2 hours with stirring to deactivate the titanium-based esterification catalyst, and then water was distilled off under reduced pressure. PNAd deactivated titanium-based esterification catalyst was obtained (hereinafter referred to as PN
Ad-B).

Reference Example 12 Production of PNTAd (1) 3000 g of 1,9-nonanediol (ND),
Trimethylolpropane (TMP) (15.4 g) and adipic acid (AD) (2287 g) were charged in a reactor, and an esterification reaction was carried out under normal pressure at 200 ° C. while distilling off the produced water out of the system. When the acid value of the reaction product reached 30 or less, 90 mg of tetraisopropyl titanate was added as a titanium-based esterification catalyst, and 200 mgHg to 1 was added.
While gradually reducing the pressure to 00 mmHg, the reaction was continued to cause polycondensation. When the acid value of the reaction product became 1.0 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the polycondensation reaction. As a result, PNTAd having a number average molecular weight of 2000 and a hydroxyl group average number of functional groups of 2.05 (hereinafter referred to as PNTA
4667 g was obtained. (2) 100 of PNRAd-A obtained in (1) above
0g is heated to 100 ℃, to this 30g water (3% by weight)
Was added and heated with stirring for 2 hours to deactivate the titanium-based esterification catalyst, and then water was distilled off under reduced pressure to obtain PNTAd in which the titanium-based esterification catalyst was deactivated (hereinafter referred to as PNTAd). -B).

Reference Example 13 Production of PEPTAd (1) 2000 g of ethylene glycol (EG), 409 g of propylene glycol (PG), 18.9 g of trimethylolpropane (TMP) and adipic acid (AD)
4544 g was charged into a reactor, and an esterification reaction and a polycondensation reaction were performed in the same manner as in (1) of Reference Example 1 to obtain PEPTAd having a number average molecular weight of 2000 and a hydroxyl group average functional group number of 2.05 (hereinafter referred to as PEPTAd-A). 5)
575 g were obtained. (2) Using PEPTAd-A obtained in (1) above,
In the same manner as in (2) of Reference Example 1, the titanium-based esterification catalyst was deactivated, and the titanium-based esterification catalyst was deactivated PEPT.
Ad was obtained (hereinafter referred to as PEPTAd-B)

Reference Example 14 Production of PMTAz (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g, trimethylolpropane (TMP)
4.1 g and 4048 g of azelaic acid (AZ) were charged into a reactor, and an esterification reaction and a polycondensation reaction were carried out in the same manner as in (1) of Reference Example 1 to give a number average molecular weight of 2000.
And (this hereinafter referred PMTAz-A ₄₎ PMTAz hydroxyl average functionality 2.01 was obtained 6206G. (2) Using PMTAz-A ₄ obtained in (1) above,
In the same manner as in (2) of Reference Example 1, the titanium-based esterification catalyst was deactivated, and the titanium-based esterification catalyst was deactivated PMTA.
z was obtained (hereinafter referred to as PMTAz-B ₄ )

Reference Example 15 [Production of PMTAz] (1) 3-Methyl-1,5-pentanediol (MP
D) 3000 g, trimethylolpropane (TMP) 3
6.5 g and 3968 g of azelaic acid (AZ) were charged into a reactor, and an esterification reaction and a polycondensation reaction were carried out in the same manner as in (1) of Reference Example 1 to give a number average molecular weight of 2000.
And 6164 g of PMTAz having an average number of hydroxyl functional groups of 2.09 (hereinafter, referred to as PMTAz-A ₅ ). (2) Using the PMTAz-A ₅ obtained in (1) above,
In the same manner as in (2) of Reference Example 1, the titanium-based esterification catalyst was deactivated, and the titanium-based esterification catalyst was deactivated PMTA.
z was obtained (hereinafter referred to as PMTAz-B ₅ )

The ester group concentration, the average number of hydroxyl functional groups and the crystallization enthalpy (ΔH) of the polyester polyols obtained in Reference Examples 1 to 15 were as shown in Table 5 below.

Example 1 (1) Obtained in (2) of Reference Example 2 heated to 80 ° C. in a twin-screw extruder having a diameter (φ) = 30 mm and L / D = 36 rotating in the coaxial direction. The obtained PMTAz-B ₁ , 1,4-butanediol (BD) heated to 80 ° C., and 4,4′-diphenylmethane diisocyanate (MDI) heated and melted at 50 ° C. were mixed in the proportions (molar ratios) shown in Table 6 below. ) Is continuously supplied with a metering pump to keep the cylinder temperature of the extruder at 260 ° C. and continuously melt-polymerize to produce polyurethane, which is then extruded into water in a strand form from a die and cut to form polyurethane pellets. The polyurethane pellets produced were vacuum dried at 80 ° C. for 20 hours. (2) The dry polyurethane pellets obtained in the above (1) are supplied to a usual spinning machine equipped with a single-screw extruder, and spinning temperature is 200 to 240 ° C., cooling air dew point temperature is 10 ° C., spinning speed is 500 m / min. Melt-spun into a monofilament under the conditions, and this was wound on a bobbin to produce polyurethane elastic fiber (monofilament) (40 d / f). The spinning stability at this time was evaluated by the above-mentioned method, and was as shown in Table 6 below. (3) Under the condition that the polyurethane elastic fiber obtained in the above (2) is wound on a bobbin, under low humidity (dew point = about −
(30 ° C.) at a temperature of 80 ° C. for 20 hours, and further at room temperature under a relative humidity of 60% for 10 days. (4) The logarithmic viscosity, heat resistance, hot water resistance, wet heat resistance, elastic recovery rate and fiber homogeneity of the aged polyurethane elastic fiber obtained in (3) above were measured or evaluated by the above-mentioned method. The results are shown in Table 6.

Examples 2 to 8 (1) The polyester polyols shown in Table 6 below were used, and the polyester polyols and MD were used.
(1) of Example 1 except that the polyester polyol, MDI and BD were used in amounts such that the above-mentioned use ratios [b / (a + c)] of I and BD were the values shown in Table 6.
Polyurethane pellets were prepared in the same manner as above and then dried. (2) Using the respective polyurethane pellets obtained in (1) above, melt spinning was performed in the same manner as in (2) of Example 1 to produce polyurethane elastic fibers (monofilaments).
Was manufactured, and its spinning stability was as shown in Table 6. (3) The polyurethane elastic fiber obtained in (2) above is aged in the same manner as in (3) of Example 1, and then its logarithmic viscosity, heat resistance, hot water resistance, moist heat resistance, elastic recovery rate and fiber homogeneity. When the sex was measured or evaluated by the method described above, it was as shown in Table 6 below.

Comparative Examples 1 to 14 (1) Polyester polyols shown in Table 7 below were used, and polyester polyols and MD were used.
(1) of Example 1 except that the polyester polyol, MDI, and BD were used in amounts such that the above-mentioned use ratios [b / (a + c)] of I and BD were the values shown in Table 7.
Polyurethane pellets were prepared in the same manner as above and then dried. (2) Using the respective polyurethane pellets obtained in (1) above, melt spinning was performed in the same manner as in (2) of Example 1 to produce polyurethane elastic fibers (monofilaments).
Was manufactured, and its spinning stability was as shown in Table 7. (3) The polyurethane elastic fiber obtained in (2) above is aged in the same manner as in (3) of Example 1, and then its logarithmic viscosity, heat resistance, hot water resistance, moist heat resistance, elastic recovery rate and fiber homogeneity. When the sex was measured or evaluated by the method described above, it was as shown in Table 7 below.

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[Table 5]

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[Table 6]

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[Table 7]

From the results shown in Tables 5 to 7, the above-mentioned requirements-requirements [that is, the ester group concentration is 0.08-0.1].
7, hydroxyl group average functional group number 2.01 to 2.08, number average molecular weight 1000 to 5000 and crystallization enthalpy (△
H) requirement of 70 J / g or less], and the ratio of the total number of moles a of the polyester polyol and the number of moles c of the chain extender to the number b of moles of the organic diisocyanate is used in the above formula (1). )
[That is, 1.00 ≦ b / (a + c) ≦ 1.10] so that the polyester polyol, 4,4′-
Examples 1-8 formed from polyurethanes obtained by reacting diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD) (chain extender)
It can be seen that the polyurethane elastic fiber (1) can be produced with good spinning stability and is excellent in all properties such as heat resistance, hot water resistance, wet heat resistance, elastic recovery rate and fiber homogeneity.

On the other hand, the polyester polyol used for producing the polyurethane does not satisfy any one or more of the above requirements to requirements, and / or the polyester polyol with respect to the number of moles b of the organic diisocyanate. In the case of Comparative Examples 1 to 14 in which the ratio of the total number of moles a and the total number of moles c of the chain extender does not satisfy the above-mentioned formula (1), the polyurethane elastic fibers obtained there are heat resistant, hot water resistant, It can be seen that one or more of moist heat resistance, elastic recovery rate and fiber homogeneity are inferior in properties, or spinning stability is inferior.

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EFFECT OF THE INVENTION The polyurethane elastic fiber of the present invention is excellent in various properties such as heat resistance, moist heat resistance, hot water resistance, elastic recovery property and fiber homogeneity, and is effective for many applications by utilizing these properties. Can be used for In the case of the method of the present invention, while suppressing the pressure increase of the spinning pack over time, in a stable spinning state, a high-quality polyurethane elastic fiber having the above-mentioned various properties can be obtained with extremely good processability. It can be manufactured smoothly.

Claims (2)

[Claims] 1. A polyurethane elastic fiber comprising (i) a polyurethane formed from a polyester polyol, an organic diisocyanate and a chain extender; (ii) the polyester polyol used for forming the polyurethane constituting the fiber is Requirements ~; Ester group concentration (number of ester bonds in polyester polyol / total number of carbon atoms in polyester polyol) is 0.08 to 0.17; hydroxyl group average functional group number is 2.01 to 2.08; number average molecular weight is 1000 to 5000; and a crystallization enthalpy (ΔH) of 70 J / g or less; and (iii) the polyurethane constituting the fiber is represented by the following formula (1); b / (a + c) ≦ 1.10 (1) In the formula, a = the number of moles of the polyester polyol. b = the number of moles of an organic diisocyanate, c = the number of moles of a chain extender, and the above polyester polyol,
A polyurethane elastic fiber, which is a polyurethane obtained by reacting an organic diisocyanate and a chain extender. 2. (A) The following requirements ~; the ester group concentration (the number of ester bonds in the polyester polyol / the total number of carbon atoms in the polyester polyol) is 0.08 to 0.17; the average number of hydroxyl functional groups is 2.01 to 2.08; a polyester polyol satisfying a number average molecular weight of 1000 to 5000; and a crystallization enthalpy (ΔH) of 70 J / g or less; (B) an organic diisocyanate; and (C) a chain extender; Formula (1); ## EQU2 ## 1.00 ≦ b / (a + c) ≦ 1.10 (1) In the formula, a = number of moles of polyester polyol b = number of moles of organic diisocyanate c = number of moles of chain extender Melt-spinning is carried out using a polyurethane obtained by reacting the polyester polyol, organic diisocyanate and Method for producing a polyurethane elastic fiber characterized in that the chain extender is reacted so as to satisfy Equation (1) above perform melt spinning while forming a polyurethane.