JPS60173117A - Elastic yarn - Google Patents

Abstract

PURPOSE:Elastic yarn having improved elasticity, chemical resistance, strength, etc., obtained by reacting a polymer diol with an organic diisocyanate to give an intermediate polymer, reacting the polymer with a specific amount of an amino compound, spinning the reaction product, winding it, heat-treating it. CONSTITUTION:(i) A polymer such as polyoxyethylene glycol, etc. having 500- 6,000 molecular weight is reacted with (ii) excess mole of an organic diisocyanate such as p-phenylene diisocyanate, etc. to obtain a terminal isocyanate group-containing middle polymer. Then, this intermediate polymer is reacted with an amino compound in an amount to satisfy the equation (A is equivalent of isocyanate group in the middle polymer; B is equivalent of polyfunctional amino compound; C is equivalent of monofunctional amino compound), to give a polymer. Then, the polymer is spun, wound, heat-treated at 50-100 deg.C for >=2hr, to give the desired high-molecular weight elastic yarn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to elastic fibers, and its purpose is to provide polyurethane elastic fibers with excellent elastic properties, chemical resistance, strength, etc.

In general, polyurethane elastomers are produced by reacting a polyhydroxy compound such as polyester or polyether having hydroxyl groups at the ends with an excess molar amount of organic diisocyanate to produce a linear polyurethane intermediate polymer having essentially isocyanate groups at both ends. After producing a substantially linear segmented polyurethane by reacting the intermediate polymer with a diamino compound having an active hydrogen that can easily react with incyanate groups in an inert organic solvent, molding and then By removing the solvent, polyurethane elastomer molded products such as films and threads having elastic properties are formed. In addition to elastic properties, other important properties of polyurethane elastomers include physical properties such as chemical resistance, strength, and abrasion resistance, as well as light resistance. In particular, in order to obtain elastic fibers with excellent elastic properties, chemical resistance, physical properties, etc., it is necessary to spin segmented polyurethane having a high logarithmic viscosity. However, in order to produce elastic fibers by spinning a famous polymer with a high logarithmic viscosity, the polymer solution has a high viscosity, so there are operational disadvantages such as the need to lower the solution concentration or slow the spinning speed. Not only does it have a negative effect, but it also does not produce the expected effect.

According to Japanese Patent Publication No. 40-3717, when a polymerization reaction is carried out using an intermediate polymer having an isocyanate end and an excess amount of a difunctional or monofunctional compound having an active hydrogen, an excellent polymer (with an intrinsic viscosity of about 0.6-1.2) and a solution are obtained. However, it is still difficult to obtain elastic fibers with satisfactory physical properties using this method alone.

The present inventors have achieved the present invention as a result of intensive research in order to solve the above-mentioned drawbacks and obtain an elastic fiber with excellent elastic properties and strength. That is, the present invention has a molecular weight of 500 to 6000.
A polymer diol and an excess of molar organic diincyanate are reacted to obtain a medium M polymer having terminal incyanate groups, and a polymer obtained by reacting the intermediate polymer with an amount of an amino compound satisfying the following formula, An elastic fiber characterized by being made to have a high molecular weight by heat treatment at a temperature of 50 to 100°C for 2 hours or more after spinning and winding.

1.5≦(B+C-A)/C≦5.0 (wherein: equivalent of isocyanate group in intermediate polymer, B: equivalent of polyfunctional amino compound, C: equivalent of monofunctional amino compound) Equivalent) The polyurethane elastomer in the present invention contains a polymer diol, a polyfunctional isocyanate, and optionally water,
An intermediate polymer having substantially isocyanate groups at both ends is produced by reacting a low molecular weight glycol, etc., and the resulting intermediate polymer is usually mixed with a polyfunctional amino compound and a monofunctional amino compound in an inert organic solvent. It is a polyurethane urea polymer obtained by reacting with a compound.

The polymer diol used is a substantially linear polymer diol having a number average molecular weight of 500 to 6,000, such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol. ,
Polyether diol such as polyoxypropylenetetramethylene glycol, one or more dibasic acids such as adipic acid, sepacic acid, maleic acid, itaconic acid, azelaic acid, and mantanic acid, and ethylene glycol, 1.2
-Propylene glycol, 1, 3-propylene glycol, 2,2-dimethyl-1,3-propanediol, 1
．． 4-butanediol, 2,3-butanediol, hexamethylene glycol, diethylene glycol, 1,1
Polyester diol, poly-C-caprolactone, polyvalerolactone, etc. obtained from one or more glycols such as 0-decanediol, 1,3-cyclohexane dimetatool, and 1,4-cyclohexane dimetatool. Examples include polylactone diols, polyesteramide diols, polyether-ester diols, polycarbonate diols, and the like.

The molecular weight of polyhydroxy compounds is usually 500 to 6000
It is about 1,000 to 5,000, preferably 1,000 to 5,000.

In addition to the polymer diol, examples of low-molecular glycols that can be used as desired include ethylene glycol, propylene glycol, and 1,4-butanediol, but the amount used is based on the total of the polymer diol, water, and low-molecular glycol. Water, low molecular weight glycol usually 10 mol%
The following ranges are preferred.

As the organic diisocyanate used in the present invention, any of aliphatic, alicyclic and aromatic diisocyanates which dissolve or are liquid under the reaction conditions can be used. For example, p-phenylene diisocyanate, bis(
4-isocyanatophenyl)methane, bis(3-methyl-4-isocyanatophenyl)methane, bis(4-
Isocyanate cyclohexyl) methane, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, etc.
The ratio of the molar amount of the organic diisocyanate to the molar amount of the polymer diol used in the present invention is 1:1.5 to 1 in consideration of desirable elastic properties and physical properties.
: 2.5, but is not particularly limited.

In addition, polyfunctional amino compounds include ethylenediamine, tetrapyrenediamine, trimethylenediamine, hexamethylenediamine, hydrazine, carbodihydrazide,
Adipic acid dihydrazide, sebacic acid dihydrazide, N
, N'bis(γ-amitube tetravir) -N,W-dimethylethylenediamine and the like can be exemplified.

As a monofunctional amine compound used at the same time, for example, l
Functional secondary amines include dimethylamine, methylethylamine, diethylamine, methyl-n-polyamine, methyl-isopropylamine, diisopropylamine, methyl-n-butylamine, methyl-isobutylamine, methyl-isoamylamine. etc.

Examples of inert organic solvents used in the present invention include solvents that dissolve the above-mentioned raw materials and dissolve or disperse the urethane polymer, such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. Known solvents may be used.

The reaction between an intermediate polymer and an amino compound is usually carried out by introducing a solution of the intermediate polymer dissolved in an inert organic solvent into an inert organic solvent containing a polyfunctional amino compound and a monofunctional amino compound. , a polyurethaneurea polymer is produced. Here a polyfunctional amino compound containing a molar excess of amine groups over the equivalents of incyanate groups in the intermediate polymer is reacted with a mixture of monofunctional amine compounds, and the end groups of the resulting polymer are reacted. is an amine 7 group or an alkyl group introduced by a monoamine. The concentration of the polymer solution at this time is preferably 30-40%, and the logarithmic viscosity of the polymer is 0.6-0.9 dll? The amount of the polyfunctional amino compound and the monofunctional amine compound to be added is adjusted so that the amount of the amino compound used is within the range shown by the following formula.

1.5≦(B+C-A)/C≦5.0 (wherein A: equivalent weight of isocyanate group in intermediate polymer, B: equivalent weight of polyfunctional amino compound, C′: monofunctional amino compound If the amount of the amino compound added is outside the above range, i.e. less than i, s, the viscosity of the polymer before spinning will be too low and the physical properties of the resulting elastic yarn will be poor; on the other hand, if it exceeds 5.0, the spinning will be poor. It becomes difficult to obtain the effects of subsequent heat treatment.

The obtained polymer solution is usually dry-spun using a conventional method.
After winding it up onto a bobbin, it is heat-treated at a temperature of usually 50 to 100°C, preferably 60 to 90°C, for 2 hours or more, preferably 3 to 24 hours. Thus, the logarithmic viscosity of the polymer constituting the yarn is x, xctt/ or more, preferably from 1.4 to
2.5 dt/f, improved physical properties such as cutting strength, elastic recovery rate, set rate, etc., and improved chemical properties such as chemical resistance. In particular, since a relatively low viscosity is required during spinning, it is possible to form yarn at a high spinning speed, and it is also a great advantage in industrialization that it is possible to obtain high molecular weight and improve physical properties by simple means after spinning. The increase in viscosity due to heat treatment is at least 0.2 or more, preferably 0.5 or more.

The solution of the polyurethane elastomer of the present invention may optionally further contain gas anti-yellowing agents, stabilizers such as ultraviolet absorbers, barium sulfate, magnesium silicate, calcium silicate, inorganic fine particles such as zinc oxide, calcium stearate, etc. Magnesium stearate 1 Anti-blocking agents such as polytetrafluoroethylene and organopolysiloxane, antifungal agents, and other compounding agents can be appropriately blended. In addition, along with the post-spinning oil agent, a fungicide having affinity for fibers, such as 2-(4-
47 Zolylbenzimidazole, N-dimethyl-N'-
It is also possible to add phenyl-(N'-fluorodichloromethylthio)sulfamide or the like and fix it to the fibers by heat treatment.

The present invention will be explained below with reference to Examples, and the characteristic values of the threads in the Examples were determined by the following method.

In addition, parts in the examples are based on weight.

Strength and elongation, elastic recovery, and set rate were measured using a tensile tester.

(1) Strength (f/d) is the cutting strength when elongated at a speed of 1000%/min.

(2) Elongation (%) is the cutting elongation when elongated at a speed of 1000%/min.

(3i Elastic recovery rate (%) is 3 at a speed of 1000%/min.
This is the (1-(unrecovered rate)) xioo% value after removing the tension after 00% elongation and leaving it for 1 minute.

(4) Set rate (%) is 0 to 3 at a speed of 1000%/min.
This value is the residual elongation rate of the yarn length after repeating 00% elongation five times, and is expressed by the following formula.

Set rate (%) = (L-LO)/LOX100 (where, Lo is the original sample length, L is the sample length after repeated elongation) (5) Logarithmic viscosity is expressed as tn (n/no)/C .

n is the viscosity of the dilute solution of the segmented polyurethane and 11G is the viscosity of the solvent at the same temperature. C is solution 1
d7! It is the concentration expressed in f number of polyurethane per unit. The logarithmic viscosity in the examples is a value measured in dimethylacetamide at 30°C (C=O, af/di)
.

Example 1 260 parts of 4,4'-diphenylmethane diisocyanate was added to 1000% polytetramethylene glycol of several thousand equivalents -7-ji1980, heated to 70°C and reacted for 60 minutes. Next, 1250 parts of dimethylacetamide was added to prepare an intermediate polymer solution, and the mixture was cooled to 15°C.

This intermediate polymer solution was mixed with 1,2-propylenediamine 3
9.6 parts of diethylamine, 2.7 parts of diethylamine, and 1150 parts of dimethylacetamide were gradually added thereto to obtain a polymer solution. The viscosity of the solution is 1620 poise at 30 °C, and the logarithmic viscosity of the polymer is 0.81 di/r
Met. This polymer solution was dry spun using a conventional method to obtain a 40 denier multifilament elastic yarn. This filament was heated at 80° C. for 24 hours while wound on a bobbin. The logarithmic viscosity of the polymer after heating is 1.72 dt/
f, and the physical properties of the elastic yarn before and after heating are shown in Table 1. In addition, addition of an amino compound as used in the present inventionff1B
+C-A/C was 2.88.

1. By the method of the present invention, the cutting strength and elastic recovery rate were greatly improved, and the set rate was also improved. In addition, the heating temperature is 4
At 0°C, almost no change was observed in the physical property values before heating.

Examples 2-3 Polytetramethylene glycol shown in Table 2, 4.4'
A polymer solution was obtained in the same manner as in Example 1 using the -diphenylmethane diisocyanate/diol molar ratio, diamine and monoamine, and dry spinning was performed to obtain a 40 denier multifilament elastic yarn. 70% of the obtained elastic yarn
The physical properties obtained after heating at °C for 12 hours are shown in Table 3.

Table 2 Table 3 According to the present invention, elastic yarns with excellent physical properties were obtained.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] A polymer obtained by obtaining an intermediate polymer having terminal isocyanate groups and reacting the intermediate polymer with an amine compound in an amount satisfying the following formula is spun and wound, and then heated at a temperature of 50 to 100 ml. ℃
An elastic fiber characterized by being made to have a high molecular weight by being heat-treated for two or more times. 1.5≦(B+C-A)/C≦5.0 (wherein: the equivalent of the isocyanate group in the intermediate polymer, B: the equivalent of the polyfunctional amine compound, C: the equivalent of the monofunctional amino compound) equivalent)