JPH09302062A - Stabilized polyurethaneurea polymer solution and elastic yarn made of polyurethaneurea polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethaneurea polymer solution having a stable solution viscosity. SOLUTION: This solution is obtained by adding 0.2-3.0wt.% organic amine salt to a polyurethaneurea polymer solution obtained by reacting an organic diamine compound and an organic sec. monoamine compound with an intermediate polymer having isocyanate groups at both ends and obtained by reacting a polymer diol having hydroxyl groups at both ends and a number-average molecular weight of 600-6,000 with a molar excess of an organic diisocyanate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane urea polymer solution having excellent solution viscosity stability, particularly to prevent the hard segment from physically aggregating even after the polymer solution is stored for a long period of time to increase the viscosity of the solution. The present invention relates to a polyurethane urea polymer solution that suppresses the above and an elastic yarn made of the polyurethane urea polymer.

[0002]

2. Description of the Related Art A polyurethaneurea polymer solution obtained by chain-extending an intermediate polymer having a polymer diol and an organic diisocyanate compound having isocyanate groups at both ends with an organic diamine compound and a small amount of a secondary monoamine compound is known. It is used for the production of fibers and films because it is formed by a dry method or a wet method into an elastic molded body having a high degree of elasticity and strength. However, this polyurethaneurea polymer solution has a drawback that it exhibits structural viscosity with time after polymerization and the viscosity of the solution increases. Such drawbacks adversely affect molding of the polyurethaneurea polymer solution. Several proposals have been made so far as means for improving the stability of the viscosity of such a polyurethane urea polymer solution over time. For example, JP-A-7-179
No. 547, a method for producing a polyurethaneurea polymer solution by carrying out a chain extension reaction using an organic diamine compound and a small amount of a secondary monoamine compound on an intermediate polymer composed of a polymer diol and an organic diisocyanate compound, It is described that a polyurethane solution with improved stability of solution viscosity can be produced by adding a carboxylic acid or carbon dioxide gas to an intermediate polymer solution after the completion of the polymer reaction and then performing a chain extension reaction. However, the polyurethane urea polymer solution produced by this method has a drawback in that the isocyanate end group of the intermediate polymer causes a side reaction with the carboxylic acid or carbon dioxide gas, and a satisfactory polymer cannot be obtained. It is known that when an inorganic salt such as lithium chloride is added to a polyurethane urea polymer solution, the solution viscosity is stable over time, but the polymer solution added with the inorganic salt was obtained by dry spinning. Since the inorganic salts of the elastic yarn remain in the elastic yarn, many problems may occur such as deterioration of the physical properties of the elastic yarn and generation of rust in a portion in contact with the metal during use of the elastic yarn. Therefore, when elastic yarn is obtained by the above method,
After spinning, there is no choice but to take measures such as a water washing process for removing the inorganic salts from the elastic yarn.

[0003]

As described above, the conventional polyurethaneurea polymer solution has various problems in its molding and use. The present invention solves the above-mentioned conventional problems by performing a chain extension reaction using an organic diamine compound and an organic secondary monoamine compound, and adding an organic amine salt to a polyurethane urea solution after completion of the polymerization reaction. , To obtain a polyurethane urea solution having a stable solution viscosity.

[0004]

In order to achieve the above object, the invention described in claim 1 has a number average molecular weight of 600.
-6000, a polymer diol having hydroxyl groups at both ends and an excess mole of an organic diisocyanate compound are reacted to obtain an intermediate polymer having isocyanate groups at both ends, which is reacted with an organic diamine compound and an organic secondary monoamine compound. It is characterized by being obtained by adding 0.2 to 3.0% by weight of an organic amine salt to the obtained polyurethane urea polymer.

The polyurethane-urea polymer solution having the above-mentioned constitution is a polyurethane-urea polymer solution which is excellent in stability of solution viscosity over time and which is suitable for producing a polyurethane-urea elastic body even when stored as a solution for a long time. is there.

In the invention described in claim 2, the intermediate polymer, the organic diamine compound and the organic secondary monoamine compound are reacted with each other, and the state after the completion of the reaction is such that the amount of the amino group is in excess of the amount of the isocyanate group. It is characterized in that

The polyurethaneurea polymer solution of the present invention having the above-mentioned constitution can be obtained by a stable chain extension reaction, and the obtained polymer solution can be prepared by physically aggregating the hard segment. Thickening is suppressed.

The invention described in claim 3 is characterized in that the organic amine salt is a salt composed of an organic diamine and an organic acid.

The polyurethaneurea polymer solution of the present invention having such a constitution is a polymer solution which suppresses the viscosity increase of the solution with time and has excellent stability.

In the invention described in claim 4, the polymer diol is polytetramethylene ether glycol having a number average molecular weight of 600 to 3000, the organic diisocyanate compound is diphenylmethane diisocyanate, the organic diamine compound is ethylenediamine, 1,2. −
Diaminopropane or a mixture thereof, wherein the organic secondary monoamine compound is diethylamine.

The polyurethaneurea polymer solution of the present invention having such a constitution is a polymer solution which can easily obtain an elastic yarn having excellent characteristics by dry or wet spinning.

The invention described in claim 5 is characterized in that it is obtained by dry or wet spinning a solution of a stabilized polyurethane-urea polymer.

The elastic yarn of the present invention having such a structure has excellent strength, and the needle does not rust when it is passed through a knitting machine or a loom.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The embodiments of the polyurethane urea polymer solution and the elastic yarn comprising the polyurethane urea polymer of the present invention will be described below in detail.

The polymer diol used in the present invention is polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol,
Polymer diols used for producing polyurethane elastic bodies such as polyethylene adipate diol, polypropylene adipate diol, and polycaprolactam can be used. The molecular weight of the polymer diol is
Those having a number average molecular weight of 600 to 6000 can be used, but those having a molecular weight of 600 to 3000 are preferable from the viewpoint of the physical properties of the polyurethane elastic body.

Examples of the organic diisocyanate compound used in the present invention include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate and 1,4-phenylene diisocyanate. Especially 4,
4'-diphenylmethane diisocyanate is preferred.

In the present invention, these polymer diols and an organic diisocyanate compound are usually mixed in a molar ratio of 1.5 to 3.0 so that the organic diisocyanate compound becomes excessive, and the mixture is heated at a temperature of 60 to 120 ° C. To obtain an intermediate polymer. At this time, two or more kinds of the polymer diol and the organic diisocyanate compound can be copolymerized, respectively, as long as the physical properties of the polyurethane elastic body obtained after the chain extension reaction are not impaired. It is also possible to copolymerize a small amount of a low molecular weight diol such as ethylene glycol, propylene glycol or butanediol in the intermediate polymer.

40% of the intermediate polymer thus obtained
It is cooled to below 0 ° C. and dissolved in a polar solvent to obtain an intermediate polymer solution. The solid content concentration of the intermediate polymer is generally 10 to 50% by weight, preferably about 20 to 30% by weight. Examples of the polar solvent used at this time include N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylenephosphylamide, dimethylsulfoxide and the like. A high molecular weight polyurethaneurea polymer solution can be obtained by reacting such an intermediate polymer solution with an organic diamine compound and an organic secondary monoamine. The reaction temperature is not limited, but is about -5 ° C to + 30 ° C.

Examples of the organic diamine compound used in the chain extension reaction include hydrazine, ethylenediamine,
Examples include 1,2,2-propylenediamine, 1,3-cyclohexanediamine, 4,4′-diaminodiphenylmethane, and the like or a mixture thereof. Ethylenediamine, 1,2-propylenediamine or a mixture thereof is preferable as a material that gives good physical properties.

The reaction with the organic secondary monoamine compound is carried out simultaneously with or before or after the reaction with the organic diamine compound. Examples of the organic secondary monoamine compound include diethylamine, diisopropylamine, di-n-butylamine, dicyclohexylamine and the like.

With respect to the polyurethane urea polymer thus obtained, 0.2 to 3.0% by weight of an organic amine salt is dissolved in a solid state or in a polar solvent and added to the polyurethane urea polymer solution, By mixing with a mixer or the like, physical aggregation of the hard segment portion of the polyurethane urea polymer solution is suppressed to suppress thickening of the solution, and a polyurethane urea polymer solution having a stable solution viscosity is obtained.

Examples of organic amine salts suitable for use in the present invention include monoamines such as methylamine, ethylamine, propylamine and butylamine, ethylenediamine, 1,2-propylenediamine, 1,2-cyclohexanediamine, 1,3. -Primary amines represented by diamines such as cyclohexanediamine, dimethylamine,
Diethylamine, dipropylamine, dibutylamine,
Examples thereof include salts of primary and secondary amines such as secondary amines such as dicyclohexylamine with acidic substances as shown below. Examples of the acidic substance include formic acid, acetic acid,
Examples thereof include aliphatic carboxylic acid salts having 2 to 10 carbon atoms such as propionic acid, aromatic carboxylic acid salts such as benzoic acid, naphthoacetic acid and phenylacetic acid, or hydrochlorides. In particular, ethylenediamine diacetate and diethylamine acetate are preferably used. Most of these organic carboxylates of amines can be removed by molding at high temperature.

[Evaluation of Stability of Viscosity of Polyurethane Urea Polymer Solution with Time] Immediately after the polymerization of the polymer solution and after putting it in a closed container in a thermostat at 30 ° C. for 7 days, the solution viscosity was measured and its change was measured. Find out. The stability over time is shown by the following numerical values.・ Viscosity change rate (%) = {(viscosity after leaving for 7 days (poise)-
Viscosity immediately after polymerization (poise) / Viscosity immediately after polymerization (poise)} × 100 Solution viscosity measurement: The polymer solution was placed in a constant temperature bath at 30 ° C., and the solution temperature was kept constant, followed by rotation viscometer (JIS. Z
8803-78).

The following problems in polymer solution production can be identified from the above-mentioned rate of change in viscosity. 50% change in viscosity
Within the following range, the stability of the polymer solution is good and there is no problem in production. When the viscosity change rate is in the range of 50 to 100%,
The stability is slightly inferior, but it is within the operable range in the molding process. When the viscosity change rate is 100 to 200%, the operation stability becomes poor, and problems such as pipe clogging and filter back pressure increase occur. When the viscosity change rate is 200% or more, it is difficult to process the polymer solution. From the above,
When the viscosity change rate of the polymer solution is 100% or less,
It is considered that stable operation is possible, and it is preferable to suppress the rate of change in viscosity to 50% or less.

[0025]

The present invention will be described in the following examples.
These examples illustrate the invention and are not intended to limit it in any way. In addition, a part shows a weight part in an Example.

Example 1 180 parts of polytetramethylene ether glycol having a number average molecular weight of 1825, 4,
4′-Diphenylmethane diisocyanate (42.5 parts) was charged into a polymerization reactor, and the mixture was heated and stirred at 85 ° C. After heating and stirring for 80 minutes, heating was stopped, 406 parts of N, N-dimethylacetamide was added, and the reaction mixture was dissolved while cooling. When the internal temperature reached 10 ° C, a solution of 3.7 parts of ethylenediamine and 0.31 part of diethylamine in 76.8 parts of N, N-dimethylacetamide was gradually added dropwise with stirring. The viscosity of the polymer solution thus obtained was 2257 poise. 0.5% by weight of ethylenediamine diacetate was added to the polymer solution, stirred for 10 minutes, and the viscosity was measured again. As a result, it was 2238 poise. The polymer solution to which this salt was added was allowed to stand in a constant temperature bath at 30 ° C. for 7 days, and the viscosity was measured. As a result, the viscosity change rate was 1788 poise, the viscosity change rate was −20%, and the stability with time was good.

Example 2 A 2273 poise organic amine salt-added polymer solution was prepared in the same manner as in Example 1 except that 0.2% by weight of ethylenediamine diacetate was added to the polymer solution as an organic amine salt. Obtained. The temporal stability was evaluated in the same manner as in Example 1. The viscosity change rate was 68%, and the stability was slightly inferior to that of Example 1, but there was no effect on the moldability of the polymer solution.

Example 3 93.6 parts of polytetramethylene ether glycol having a number average molecular weight of 1800,
21.5 parts of 4'-diphenylmethane diisocyanate was charged into a polymerization reactor, and heated and stirred at 70 ° C. After heating and stirring for 80 minutes, heating was stopped, 225 parts of N, N-dimethylacetamide was added, and the reaction mixture was dissolved while cooling. When the internal temperature reached 10 ° C, 1.4 parts of ethylenediamine, 0.8 part of 1,2-propylenediamine,
A solution of 0.25 parts of diethylamine dissolved in 30 parts of N, N-dimethylacetamide was gradually added dropwise with stirring. The polymer solution thus obtained has a viscosity of 22.
It was 57 poise. 0.2% by weight of ethylenediamine diacetate was added to the polymer solution thus obtained, stirred for 10 minutes, and the viscosity was measured again. As a result, it was 2399 poise. The polymer solution to which the organic amine salt was added was allowed to stand for 7 days in a thermostat at 30 ° C., and the stability with time was evaluated. As a result, the rate of change in viscosity was 52%, and the stability with time was good.

Comparative Example 1 As a comparative example, a polymer solution was obtained in the same manner as in Example 1 except that no organic amine salt was added, and then stability with time was evaluated in the same manner as in Examples 1 to 3. It was The viscosity change rate was 339%, and unlike Examples 1 to 3, almost no fluidity was observed and it was impossible to process. Table 1 shows a comparison of the viscosity change rates of Examples 1 to 3 and Comparative Example 1.

[0030]

[Table 1]

Example 4 The 0.5 wt% ethylenediamine diacetate-added polyurethaneurea polymer solution obtained in Example 1 was dry-spun by a conventional method and processed into a 40-denier yarn. Then, the breaking strength and the elongation were measured by a tensile tester and found to be 0.
9 g / d, 502%, 190 at 200% elongation
No phenomenon of fusing was observed even when heated to ℃. Also,
No rust was observed even when the yarn was passed over the knitting needle and the knitting needle was left as it was for 5 days. As described above, there were no problems in physical properties and use.

Comparative Example 2 As a comparative example, polymerization was carried out in the same manner as in Example 1 except that 0.3% by weight of lithium bromide was added in place of the ethylenediamine diacetate, and 2318 poise of inorganic salt was added. A combined solution was obtained. This polymer solution was evaluated for stability of solution viscosity with time in the same manner as in Examples 1 to 3 and Comparative Example 1. The viscosity change rate was −2%, and the stability over time was good. This polymer solution was spun in the same manner as in Example 4, processed into a 40 denier yarn and then subjected to the same physical property evaluation. The breaking strength was 0.7 g / d and the breaking elongation was 398.
%, And the phenomenon of fusing when heated to 190 ° C. in a 200% stretched state was confirmed. In addition, when this yarn was passed over the knitting needle and the knitting needle was left as it was, 5
Rust occurred on the knitting needles during the day. Thus, lithium bromide remained in the yarn after molding, causing problems in physical properties and use. Table 2 shows a comparison of the viscosity change rates of Example 4 and Comparative Example 2, and Table 3 shows a comparison of the physical properties of the yarns.

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

The polyurethaneurea polymer solution described in claim 1 is excellent in stability of solution viscosity over time. The polyurethane urea polymer solution according to the second aspect can perform a stable chain extension reaction, and the obtained polymer solution can suppress thickening of the solution due to physical aggregation of hard segment portions. The polyurethane-urea polymer solution described in claim 3 suppresses the viscosity increase of the solution with time, and has excellent stability. The polyurethaneurea polymer solution described in claim 4 can be easily dry- or wet-spun to obtain an elastic yarn having excellent properties. The elastic yarn obtained from the polyurethaneurea polymer according to claim 5 has excellent strength, and the needle does not rust when passing through a knitting machine or a loom.

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Claims (5)

[Claims] 1. An organic diamine compound is added to an intermediate polymer having isocyanate groups at both ends obtained by reacting a polymer diol having a number average molecular weight of 600 to 6000 and having hydroxyl groups at both ends with an excess mole of an organic diisocyanate compound. 0.2 to 3.0 with respect to a polyurethane urea polymer solution obtained by reacting an organic secondary monoamine compound with
A stabilized polyurethaneurea polymer solution obtained by adding a weight% of an organic amine salt. 2. An intermediate polymer, an organic diamine compound, and an organic secondary monoamine compound are reacted, and the state after the reaction is in a state where the amount of amino groups is in excess of the amount of isocyanate groups. The stabilized polyurethaneurea polymer solution according to claim 1. 3. The stabilized polyurethaneurea polymer solution according to claim 1, wherein the organic amine salt is a salt composed of an organic diamine and an organic acid. 4. The polymer diol has a number average molecular weight of 600.
To 3000 polytetramethylene ether glycol, the organic diisocyanate compound is diphenylmethane diisocyanate, the organic diamine compound is ethylenediamine, 1,2-propylenediamine or a mixture thereof, and the organic secondary monoamine compound is diethylamine. The stabilized polyurethaneurea polymer solution according to claim 1, 2 or 3. 5. An elastic yarn made of a polyurethane urea polymer, which is obtained by dry or wet spinning the solution of the stabilized polyurethane urea polymer according to claim 1, 2, 3 or 4.