JP2000110026A - Polyurethane elastic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane elastic fiber having excellent elastic recovery, slight reduction in elastic recovery after passing through a heat setting process, useful in the state of a covering yarn or a bare yarn by making the yarn have one component of a chain extender, being a specific isocyanurate compound. SOLUTION: This polyurethane elastic fiber comprises (A) a polymer polyol such as polytetramethylene glycol, etc., (B) an organic polyisocyanate such as 4,4'-diphenylmethane diisocyanate, etc., and (C) a chain extender such as ethylene glycol, etc. One component of the chain extender is a compound of a formula I (R is a bifunctional alkylene group and may contain an aromatic ring, a halogen group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond or the like; X is a hydroxyl group or an amino group containing an active hydrogen) such as a compound of formula II, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastic fiber having an excellent elastic recovery property, and particularly to a cloth or the like in which the elastic fiber is woven, characterized in that the elastic recovery property after the heat setting step is small. And a polyurethane elastic fiber. More specifically, a polyurethane elastic fiber comprising a polymer polyol, an organic polyisocyanate, and a chain extender, wherein one component of the chain extender is a compound having an isocyanurate ring. It relates to elastic fibers.

[0002]

2. Description of the Related Art Conventionally, high molecular diols, organic diisocyanates and low molecular diols have been used for the production of polyurethane elastic fibers, but the elastic recovery of polyurethane elastic fibers produced therefrom has been used. Sex is not always satisfactory. In particular, when the polyurethane elastic fiber is woven into a cloth or the like and passes through a heat setting step, the elastic recovery of the polyurethane elastic fiber after the heat setting is not satisfactory.

As an elastic fiber, polyurethane urea using a low molecular weight diamine instead of a low molecular weight diol is widely used. Polyurethane urea has better elastic recovery than polyurethane, but after passing through the heat setting step, the elastic recovery is still reduced.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polymer polyol, an organic polyisocyanate, and a chain extender which are excellent in elastic recovery and lower in elastic recovery after passing through a heat setting step. Is to provide a polyurethane elastic fiber having a small size.

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and studies, and as a result, have reached the present invention. That is, the present invention is a polyurethane elastic fiber comprising a polymer polyol, an organic polyisocyanate, and a chain extender, wherein one component of the chain extender is a compound represented by the following general formula (1). It is a polyurethane elastic fiber characterized by the above.

[0006]

Embedded image (In the above formula, R represents a divalent alkylene group, but may contain an aromatic ring, a halogen group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, etc. X Represents a hydroxyl group or an amino group having active hydrogen.)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The high molecular weight polyol used in the present invention includes polyether polyols typified by polytetramethylene ether glycol and polyester polyols typified by polybutylene adipate. , Polycaprolactonepolyol, polyesterpolycarbonatepolyol exemplified by a reaction product of a polyesterglycol such as polycaprolactone with an alkylene carbonate, etc., and ethylene carbonate as ethylene glycol. −
Propylene glycol, butylene glycol, neopentyl glycol, and other polyvalent alcohols,
Then, the obtained reaction mixture was reacted with an organic dicarboxylic acid such as adipic acid, azelaic acid, and sebacic acid,
And 1,4-butanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol,
Examples thereof include a polycarbonate resin obtained by a transesterification reaction of a polyhydroxyl compound such as 1,8-octanediol and an aryl carbonate, for example, diphenyl carbonate. These may be used alone or in combination of two or more.

[0008] Organic polyisocyanates include:
4,4'-diphenylmethane diisocyanate, 1,5
-Naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate,
Aromatic diisocyanates such as 2,6-tolylene diisocyanate; benzylic diisocyanates such as m-xylylene diisocyanate and p-xylylene diisocyanate
Aliphatic diisocyanate, such as hexamethylene diisocyanate, and 1,4-cyclohexane diisocyanate
G, 4,4'-dicyclohexylmethane diisocyanate
And alicyclic diisocyanates such as isophorone diisocyanate. These may be used alone or in combination of two or more.

One component of the chain extender is a compound represented by the following general formula (1). Specifically, tris (2-hydroxyethyl) isocyanurate [the following formula (2)] (2-aminoethyl) isocyanurate
[Formula (3)], tris (2-hydroxypropyl) isocyanurate [Formula (4)], tris (2-
(2-hydroxyethoxy) ethyl) isocyanurate [formula (5) below] and the like. These may be used singly or as a mixture of two or more as one component of a chain extender.

[0010]

Embedded image (In the above formula, R represents a divalent alkylene group, but may contain an aromatic ring, a halogen group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, etc. X Represents a hydroxyl group or an amino group having active hydrogen.)

[0011]

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[0012]

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[0013]

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[0014]

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The chain extender which can be used in combination with the chain extender of the general formula (1) includes ethylene glycol
Propylene glycol, 1,4-butanediol,
1,6-hexanediol, 1,4-bis (hydroxyethoxy) benzene, 1,3-bis (hydroxyethoxy) benzene, 1,2-bis (hydroxyethoxy) benzene, cyclohexanedimethanol, bis (2 -Hydroxyethyl) terephthalate, bis (2-hydroxyethyl) isophthalate, bis (2-hydroxyethyl) phthalate, low molecular weight diols such as 2,2-bis (4- (hydroxyethoxy) phenyl) propane, ethylenediamine, Low molecular diamines such as 1,2-propylenediamine and 1,4-diaminobenzene are exemplified.

In the present invention, the ratio of the high molecular weight polyol to the chain extender can be variously changed depending on the molecular weight of each and the desired physical properties of the polyurethane. Also, for the total number of moles of both,
The ratio of the number of moles of the organic polyisocyanate is 0.80 to 1.
It is preferably in the range of 25, more preferably 0.95 to 1.15. If the ratio is too small, a sufficient high molecular weight polymer cannot be obtained, and the elastic recovery property is unfavorably reduced. If the ratio is too large, the adhesiveness on the surface is increased and the productivity is undesirably reduced.

In the present invention, since a polyfunctional isocyanurate compound is used as a chain extender, the obtained polyurethane has a structure having a chemical crosslinking point in a hard segment portion. Generally, polyurethane is
The soft segments are constrained by the cohesive force of the hydrogen bonds of the hard segments, exhibiting rubber-like properties, but the elastic recovery is improved if strong chemical bonds are added to the hydrogen bonds as the cohesive forces of the hard segments. I do. Further, the isocyanurate structure itself is a rigid and heat-resistant structure, and is considered to be very effective for agglomeration of hard segments. Therefore, it is presumed that the elastic fiber of the present invention has a small decrease in elastic recovery after passing through the heat setting step.

When producing the polyurethane which is a raw material of the polyurethane elastic fiber of the present invention, it can be produced by using a known urethane technology such as a melting method and a solution method.
For example, a polymer polyol and a chain extender are added in an amount of about 40 to 10
After preheating to 0 ° C., the mole number of the organic polyisocyanate is 0.80 to 1.25 based on the total mole number of these mixtures.
After adding the organic polyisocyanate in the amount shown below and stirring vigorously in a short period of time, the mixture is left at about 50 to 180 ° C. under nitrogen to obtain a polyurethane. Further, a method of obtaining a polyurethane via a urethane prepolymer can also be used. If necessary, other trifunctional components such as triol and triisocyanate may be used in combination.

In the production of polyurethane, a catalyst or a catalyst generally used in the production of polyurethane is used.
Activators, defoamers, lubricants, UV absorbers, stabilizers such as anti-yellowing agents, pigments, antistatic agents, surface treatment agents, flame retardants, fungicides, reinforcing agents as required Can be used.

The polyurethane elastic fiber of the present invention can be produced by a spinning method such as melt spinning, dry spinning, and wet spinning. For example, the spinning apparatus and spinning conditions for the melt spinning method may vary depending on the content of the polyurethane, the thickness of the target fiber, the polymerization method, and the like. It is supplied to a spinning device, and a spinning temperature of 180 to 240 ° C and a spinning speed of 1000 m /
The spinning is preferably performed at a speed of at most 600 m / min. The apparent draft rate is 50 or more, preferably 1
It is better to be 00 or more. In addition, the spinning tension when the spun yarn is wound on a bobbin by a winder is 0.
1 g / d or less, preferably 0.05 g / d or less.

The wound yarn is hardened under low humidity.
It is preferable to perform a heat treatment near the glass transition temperature of the hard segment to sufficiently advance the phase separation between the hard segment and the soft segment. In general, polyurethane elastic fibers having a thickness of about 5 to 100 denier / filament can be obtained by these methods, but the polyurethane elastic fibers used in the present invention have a denier in the range of 15 to 100. It is suitable, preferably 40-80. These elastic fibers are used in the form of a covering yarn or a bare yarn.

[0022]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Parts in the examples are parts by weight. Further, in the following examples, the elastic recovery rate was measured by the following method.

<< Measurement of Elastic Recovery Rate >> An elastic fiber having a sample length of 5 cm was stretched at a constant speed of 1000% / min by 300% using a tensile tester, and then relaxed at the same speed.
150% elongation stress during elongation and 15 during relaxation
The stress at 0% elongation was measured and determined from the following equation. Elastic recovery rate (%) = (stress at 150% elongation of relaxation process / stress at 150% elongation of extension process) × 100

Example 1 360 parts of polybutylene adipate (abbreviated as PBA) having a hydroxyl group at both terminals and having a number average molecular weight of 2,000 as a high molecular weight polyol, and tris (2-hydroxyethyl) isocyanurate as a chain extender 1.72 (abbreviated as THEI)
And 1,4-butanediol (abbreviated as BD) 19.21
Then, 100 parts of diphenylmethane diisocyanate (abbreviated as MDI) (NCO / OH = 0.99) was added as an organic polyisocyanate to polymerize the polyurethane. The obtained polyurethane is spun at a spinning temperature of 215 ° C. and a spinning speed of 600 m / min using a spinning machine of a single screw extruder,
Denier and monofilament elastic fibers were obtained. The elastic recovery rate of this polyurethane elastic fiber was measured. In addition, as a process corresponding to the heat setting process, the same elastic recovery rate was measured using a sample after performing a process of holding the elastic fiber in an atmosphere of 140 ° C. for 1 minute in a state of being stretched by 100%. Was done. Table 1 shows the results.

Examples 2 and 3 1.72 parts of THEI were used as a chain extender, and Example 2: tris (2-hydroxypropyl) isocyanurate (T
2.00 parts, Example 3: Tris (2-
(2-Hydroxyethoxy) ethyl) isocyanurate (abbreviated as THEEI) The same procedure as in Example 1 was carried out except that the amount was changed to 2.59 parts. Table 1 shows the results.

Examples 4, 5, and 6 The ratio of the amount of BD / THEI added and the spinning temperature were as follows:
9.74 parts / 0.17 parts, 208 ° C., Example 5:19.
60 parts / 0.57 parts, 213 ° C., Example 6: 18.41
Parts / 4.02 parts The same procedure as in Example 1 was carried out except that the temperature was changed to 221 ° C. Table 1 shows the results.

Example 7 Polytetramethylene glycol having a number average molecular weight of 2000 and having hydroxyl groups at both terminals (PTM) was used as a high molecular weight polyol.
G) (abbreviated as G). Table 1 shows the results.

Comparative Example 1 PBA having a number average molecular weight of 2,000 as a high molecular weight polyol
360 parts, BD 19.8 parts as chain extender, MDI 100 parts as organic polyisocyanate (NCO / OH =
1.00) to polymerize the polyurethane. Spinning temperature of the obtained polyurethane with a spinning machine of a single screw extruder 207 ° C,
Spinning was performed at a spinning speed of 600 m / min to obtain a 20-denier, monofilament elastic fiber. This polyurethane elastic fiber was measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Examples 2 and 3 THEI was used as a chain extender. Comparative Example 2: Trimethylo-
0.88 parts of lupropane (abbreviated as TMP), Comparative Example 3:
Example 1 was repeated except that the amount was changed to 0.87 part of 1,3,5-cyclohexanetriol (abbreviated as CHT). Table 1 shows the results.

[0030]

[Table 1]

As is clear from Table 1, the polyurethane elastic fiber of the present invention has excellent elastic recovery and a small decrease in elastic recovery after passing through the heat setting step.

[0032]

According to the present invention, a polyurethane elastic fiber having good elastic recovery even after passing through the heat setting step can be obtained, and the field of application can be greatly expanded, contributing to the industry. It is.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J034 BA08 CA04 CA05 CA14 CA15 CA16 CA17 CC03 CC35 CC62 DA01 DB03 DF02 DF12 DF16 DF22 DG06 HA07 HC03 HC12 HC13 HC17 HC22 HC46 HC52 HC64 HC67 HC71 HC73 RA09 4L035 BB31 EE01 FF08MH02

Claims (1)

[Claims] 1. A polyurethane elastic fiber comprising a polymer polyol, an organic polyisocyanate, and a chain extender, wherein one component of the chain extender is a compound represented by the following general formula (1). A polyurethane elastic fiber, characterized in that: Embedded image (In the above formula, R represents a divalent alkylene group, but may contain an aromatic ring, a halogen group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, etc. X Represents a hydroxyl group or an amino group having active hydrogen.)