JPH05125140A - Polyurethane, polyurethane fiber and polyester-carbonatediol using the polyurethane - Google Patents

Abstract

PURPOSE:To provide a polyurethane excellent in the heat resistance, stress relaxation, cold resistance, hydrolysis resistance, elongation and elastic recovery factor by polymerizing a specific polymeric diol and a chain extender with an organic diisocyanate. CONSTITUTION:(A) A polymeric diol containing as a main component a polyestercarbonatediol comprising structural units of formulas I, II, III and IV in an I/II molar ratio of 65/35 to 35/65 and in a III/IV molar ratio of 98/2 to 85/15 and having a number-average mol.wt. of 1000-3500 and (C) a chain extender such as 1,4-butanediol are polymerized with (B) an organic diisocyanate such as 4,4'-diphenylmethane diisocyanate to provide the objective polyurethane having an inherent viscosity of >=0.2 l/g. The polyurethane is spun by a dry spinning method, a wet spinning method, etc., to give polyurethane fibers.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyurethane, a fiber comprising the polyurethane, and a polyester carbonate diol which gives the polyurethane.

[0002]

2. Description of the Related Art Polyurethanes such as polyester-based polyurethane, polyether-based polyurethane, polycarbonate-based polyurethane, polyester-carbonate-based polyurethane and the like are known, and their elasticity has been proposed to be used as an elastic fiber. For example, in JP-A-48-101496, 3-methyl-1,5-
It is disclosed that polyurethane using a polyester diol composed of pentane diol and dicarboxylic acid can be used as the elastic fiber. JP-A-61-185520
Japanese Patent Laid-Open Publication No. 2003-242242 discloses that a polyurethane using an polyester fiber obtained by reacting a diol mixture with 3-methyl-1,5-pentanediol containing 50% by weight or more of 1,9-nonanediol with dicarboxylic acid is used as an elastic fiber. It is described that it can be used. In addition, Japanese Examined Japanese Patent Sho 59-3
JP 7288 describes a polyurethane elastomer using a polyester carbonate diol from 1,10-decane dicarboxylic acid and a polycarbonate diol.

[0003]

Polyurethane elastic fibers are desired to have high elongation, excellent elastic recovery, cold resistance and hydrolysis resistance. For the purpose of not lowering the heat resistance, from the viewpoint of improving the power feeling of so-called elastic fiber, it is excellent in stress relaxation and heat resistant from the viewpoint of being able to be mixed with fibers such as polyester fibers that are used in high-temperature dyeing methods. It is desired to have excellent properties.
The elastic fibers produced from the known polyurethanes as exemplified above do not necessarily fully satisfy all of these performances. An object of the present invention is to provide a polyurethane which gives fibers which are excellent not only in all of hydrolysis resistance, elastic recovery, cold resistance and elongation but also in stress relaxation and heat resistance. ..

Further, an object of the present invention is to secondly provide a fiber comprising the polyurethane having excellent performance, and thirdly, to provide a polyester carbonate diol useful as a raw material for producing the polyurethane. It is in.

[0005]

Means for Solving the Problems When the polyurethane made of a specific polyester carbonate diol is used as a fiber, the present inventors have made it possible to obtain heat resistance, stress relaxation resistance, cold resistance, hydrolysis resistance, elongation and elastic recovery property. The present invention has been completed by finding that the polyurethane fiber is excellent in all of them.

The present invention is, firstly, a polyurethane obtained by polymerizing a polymeric diol, an organic diisocyanate and a chain extender, and the following structural units (I), ( II), (III)
And (IV), and the (I) / (II) molar ratio is 65
/ 35-35 / 65, and the (III) / (IV) molar ratio is 98 / 2-85 / 15.
A polyurethane having a logarithmic viscosity of 0.2 dl / g or more obtained by using 3500 polyester carbonate diol (however, the logarithmic viscosity is 0.5 g of a sample.
N-butylamine was dissolved in an N, N-dimethylformamide solution containing 1% by weight of n-butylamine so that the concentration became / dl.
It is a value measured using an Ubbelohde viscous tube after standing at 5 ± 5 ° C. for 24 hours).

(I) -OC (= O) -O-

[0008] (II) -O-C (= O) - (CH 2) 7 -
C (= O) -O-

[0009] _{(III) -CH 2 -CH 2 -CH} (CH 3) -
CH ₂ -CH ₂ -

[0010] _{(IV) - (CH 2)} 9 -

The present invention is secondly a polyurethane fiber comprising the polyurethane, and thirdly the above polyester carbonate diol.

The above-mentioned polyester carbonate diol used for producing the polyurethane of the present invention has the structural unit (I),
A polymeric diol composed of (II), (III) and (IV) as essential structural units, and the ends of the structural units (III) and (IV) are bonded to the structural unit (I) or (II), respectively. Is.

The structural units (II) and (III) in the above polyester carbonate diol used for producing the polyurethane of the present invention mainly contribute to the improvement of stress relaxation property and elongation of the fiber obtained from the polyurethane of the present invention. In addition, the structural unit (IV) mainly contributes to improvement in heat resistance of the obtained polyurethane.

The (I) / (II) molar ratio in the polyester carbonate diol is 65 / 35-35 / 65, and the (III) / (IV) molar ratio is 98 / 2-85.
/ 15. Within this range, a polyurethane having remarkably excellent heat resistance, stress relaxation property and elongation can be obtained.

The number average molecular weight of the polyester carbonate diol of the present invention is 1000 to 3500, more preferably 1500 to 3000. When it is less than 1000, the heat resistance and elastic recovery of the obtained polyurethane are lowered, and when it is more than 3500, the spinnability of the polyurethane is lowered.

The method for producing the polyester carbonate diol is not particularly limited. For example, 3-
A glycol mainly containing methyl-1,5-pentanediol and 1,9-nonanediol, a dicarboxylic acid mainly containing azelaic acid or an ester thereof and a carbonate compound are charged at the same time, and an esterification reaction and / or an esterification reaction are conducted according to a known production method. Alternatively, a polyester carbonate diol can be produced by transesterification. Alternatively, a polyester diol or a polycarbonate diol may be synthesized in advance, and a carbonate compound or a dicarboxylic acid may optionally be reacted in the presence of glycol to synthesize.

As the carbonate compound used for producing the polyester carbonate diol, dialkyl carbonate such as diethyl carbonate, diaryl carbonate such as diphenyl carbonate, alkylene carbonate such as ethylene carbonate and the like are preferable.

Suitable organic diisocyanates used in the synthesis of the polyurethane of the present invention include aliphatic, alicyclic or aromatic organic diisocyanates, specifically 4,4'-diphenylmethane diisocyanate, p- Molecular weight of phenylene diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, etc. 500
The following diisocyanates are exemplified. Particularly preferred is 4,4'-diphenylmethane diisocyanate.

The chain extender used in the synthesis of the polyurethane of the present invention is a chain growth agent commonly used in the polyurethane industry, that is, a low molecular weight compound having a molecular weight of 400 or less and containing at least two functional groups capable of reacting with isocyanate. , Ethylene glycol, 1,4-butanediol, propylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,
4-bis (2-hydroxyethoxy) benzene, 1,4
Diols such as cyclohexanediol, bis (β-hydroxyethyl) terephthalate, xylylene glycol; ethylenediamine, propylenediamine, isophoronediamine, hydrazine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodicyclohexylmethane, dihydrazide, Examples include diamines such as piperazine and xylylenediamine. These compounds may be used alone or in admixture of two or more. Preferred chain extenders are 1,4-butanediol and 1,4-bis (2-
Hydroxyethoxy) benzene and the like can be mentioned.

When 4,4'-diphenylmethane diisocyanate is used as the organic diisocyanate and 1,4-butanediol and / or 1,4-bis (2-hydroxyethoxy) benzene is used as the chain extender, heat resistance is improved. A polyurethane which gives fibers having particularly excellent properties in elastic recovery and elongation is obtained.

The composition ratio of the polymeric diol (A), the organic diisocyanate (B) and the chain extender (C) used in the production of the polyurethane of the present invention is (B) /
The molar ratio of [(A) + (C)] is in the range of 0.9 to 1.2,
In particular, the range of 0.95 to 1.15 is preferable.
Within this range, a polyurethane fiber having particularly excellent heat resistance, elastic recovery and elongation can be obtained.

Regarding the method for producing the polyurethane of the present invention, a known technique of urethanization reaction can be adopted, but among them, it is preferable to carry out melt polymerization in a state in which a solvent is not substantially present, and particularly a multi-screw screw. It is preferable to carry out continuous melt polymerization using a die extruder.

The temperature of the melt polymerization is not particularly limited, but is 20
It is preferably 0 ° C. or higher and 260 ° C. or lower. By keeping the temperature at 260 ° C. or lower, the heat resistance of the obtained polyurethane can be improved, and by keeping the temperature at 200 ° C. or higher, a thermoplastic polyurethane excellent in spinnability can be obtained.

The polyurethane of the present invention has an inherent viscosity of 0.2 dl / g or more measured by the above method. When the logarithmic viscosity is less than 0.2 dl / g, the elastic recovery of the obtained fiber is lowered. When it is 1.6 dl / g or less, good spinnability can be maintained, so the logarithmic viscosity is preferably 0.2 to 1.6 dl / g. More preferably, it is 0.6 to 1.4 dl / g.

The polyurethane of the present invention is substantially

(S) A divalent group in which two hydrogen atoms have been removed from the hydroxyl groups at both ends of the molecule of the above-mentioned polymer diol such as polyester carbonate diol;

(T) General formula derived from organic diisocyanate

--CO--NH--R--NH--CO--

(In the formula, R represents a divalent organic group)

A divalent group represented by:

(U) a divalent group in a form in which two hydrogen atoms capable of reacting with isocyanate are removed from a molecule of a low molecular weight compound (chain extender);

It is considered to be composed of

The polyurethane of the present invention can be made into fibers by a spinning method that can be adopted in ordinary production of polyurethane fibers such as a dry spinning method, a wet spinning method and a melt spinning method. The melt spinning method is preferable because it can be made into a fine denier, for example, a method in which the polyurethane obtained by polymerization is once pelletized and then subjected to melt spinning, and the melt of the polyurethane obtained by melt polymerization is solidified without solidification. A method of spinning through a spinneret can be adopted. From the viewpoint of spinning stability, the latter polymerization direct binding spinning method is desirable.

Polymer diol (A), organic diisocyanate (B) and chain extender (C) are added to (B) / [(A) +
(C)] is spun into a polyurethane obtained by polymerization in an isocyanate excess system such that the molar ratio is 1.02 to 1.15, or a polyisocyanate compound or a blocked polyisocyanate compound is added to the polyurethane during spinning. By adding and mixing (B) / [(A) +
When the amount of alohanate bonds in the polyurethane is increased by spinning the polyurethane in an isocyanate excess state such that the molar ratio of (C)] corresponds to 1.02 to 1.15, heat resistance and elasticity are further increased. A polyurethane fiber having excellent recoverability and high elongation can be obtained.

The polyurethane fiber of the present invention is dissolved in a solution of n-butylamine 0.5N in N, N-dimethylformamide, and the amount of alohanate bond determined by back titration is 0.001 to 0.1 mmol / g. Especially, the elastic recovery may be particularly good.

In addition to the polyurethane of the present invention, the polyurethane fiber of the present invention may be mixed with other polymeric substances such as polyurethane, or may be blended with additives such as organic substances or inorganic substances. ..

As described above, the polyurethane fiber of the present invention is excellent in heat resistance, stress relaxation property, cold resistance, hydrolysis resistance and elastic recovery property and has a large elongation.

[0038]

The present invention will be described in the following examples.

The hydrolysis resistance, elastic recovery property, strength and elongation, heat resistance, stress relaxation property, logarithmic viscosity, ¹ H-NMR and DSC in Examples and Comparative Examples were measured by the following methods.

Hydrolysis resistance The tensile strength retention rate (%) of the sample was measured and evaluated before and after hot water treatment at 100 ° C. for 24 hours.

Elastic recovery property At 25 ° C. or −10 ° C., the sample was stretched by 200% and held for 10 minutes, the tension was removed, and the recovery rate (%) of the yarn length after standing for 3 minutes was evaluated. ..

[Strength and Elongation] Measured according to JIS L-1013.

-Stress relaxation property The sample was heated to 200 at a tension rate of 500 mm / min at 20 ° C.
The stress immediately after the% elongation (this is referred to as a) and the stress after holding as it is for 10 minutes (this is referred to as b) were measured, and the stress relaxation rate (%) was calculated by the following formula.

Stress relaxation rate (%) = [(ab) / a] ×
100

Heat resistance (melt drip, MD) 1 ° C./in a state where a load of 1/3000 g / d is applied to the sample
Evaluation was made by the temperature (° C.) at which the sample was cut by heating at a rate of minutes.

Logarithmic viscosity (ηinh) A sample was dissolved in an N, N-dimethylformamide solution containing 1% by weight of n-butylamine so as to have a concentration of 0.5 g / dl, and the sample was allowed to stand at 25 ± 5 ° C. for 24 hours. After that, it measured using the Ubbelohde viscosity tube.

¹ H-NMR GSX-270 manufactured by JEOL Ltd. was used as a measuring device, and tetramethylsilane was measured as an internal standard.

Using DS-Mettler TA-4000 and DSC30,
First, the sample is heated and held at 100 ° C for 3 minutes, then at 10 ° C.
/ Min and kept at -100 ° C for 1 minute. Next 10
The temperature was raised to 100 ° C at ° C / min. During this heating process, the melting point (mp), enthalpy of fusion (ΔHm) and glass transition point (Tg) were measured.

The compounds used in Examples and Comparative Examples are indicated by abbreviations, and the relationship between the abbreviations and compounds is shown in Table 1.
It is as follows.

[0050]

[Table 1]

Example 1 (Production of Polyester Carbonate Diol) MPD691 g, ND104 g, AZ66 under a nitrogen stream.
A mixture of 8 g and EC213 g was heated and reacted at 200 ° C. while distilling off ethylene glycol (EG) and water produced from the reaction system, and after almost distilling off EG and water, it was removed under reduced pressure of 1 to 5 mmHg. Further polycondensation was recommended. As a result, a polyester carbonate diol (a) having the following physical properties was obtained.

Acid value: 0.05 mg KOH / g

Hydroxyl value: 54.8 mg KOH / g

Number average molecular weight: 2049 (based on hydroxyl value)

DSC (heating rate 10 ° C./min);

M. p. : -17 ° C

ΔHm: 3.2 cal / g

Tg: -61 ° C

¹ H-NMR (CDCl ₃ , 270 MH
z), (multiplicity, relative intensity): δ 4.17 (m, 3.
9), δ 4.10 (m, 5.9), δ 3.66 (m,
1.0), δ2.28 (t, 5.9), δ1.78-
1.42 (m, 22.0), δ1.32 (m, 13.
3), δ 0.96 (m, 7.4)

Example 2 (Production of Polyester Carbonate Diol) MPD691 g, ND104 g, AZ56 under nitrogen stream.
100 g of a mixture of 5 g and DPC 643 g
The mixture was heated to 180 to 200 ° C. under reduced pressure of 0 mmHg, and reacted while distilling off the produced phenol and water. After distilling off most of phenol and water, 1-5mmH
Further polycondensation was promoted under reduced pressure of g. As a result, a polyester carbonate diol (b) having the following physical properties was obtained.

Acid value: 0.05 mg KOH / g

Hydroxyl value: 55.1 mg KOH / g

Number average molecular weight: 2035 (based on hydroxyl value)

DSC (heating rate 10 ° C./min);

M. p. : -19 ° C

ΔHm: 2.0 cal / g

Tg: -60 ° C

¹ H-NMR (CDCl ₃ , 270 MH
z), (multiplicity, relative intensity): δ 4.17 (m, 4,
9), δ 4.10 (m, 5.1), δ 3.66 (m,
1.0), δ 2.28 (t, 5.1), δ 1.78 ~
1.42 (m, 22.3), δ1.32 (m, 12.
7), δ 0.96 (m, 7.8)

Examples 3 and 4 and Reference Examples 1 to 5 (Production of polyester carbonate diol) Example 1 or 2 except that the diol component, dicarboxylic acid component and carbonate compound shown in Table 2 were used. Similarly, polyester carbonate diols c to i shown in Table 2 were obtained.

Reference Example 6 (Production of Polyester Carbonate Diol) According to the method described in JP-B-59-37288, 100 to 100 parts of DEC354g and HD708g were prepared.
After reacting at 120 ° C for 15 hours to obtain a polycarbonate diol, HD427g and DA920g are added, and 2
React at 00-220 ° C for 8 hours, then 30-50m
The reaction was carried out under reduced pressure at mHg to obtain polyester carbonate diol j.

Reference Example 7 (Production of Polyester Carbonate Diol) A mixture of 354 g of MPD, 480 g of ND and 976 g of AZ was heated and reacted at 220 ° C. while distilling off water produced from the reaction system, and after almost distilling off water, 1
Further polycondensation was promoted under reduced pressure of ˜5 mmHg. As a result, the polyester diol k shown in Table 2 was obtained.

Reference Example 8 (Production of Polycarbonate Diol) MPD354g, ND480g and DPC1180g
The mixture consisting of 18 under a reduced pressure of 100 to 80 mmHg.
The mixture was heated to 0 to 200 ° C. and reacted while distilling off the produced phenol. After distilling off most of the phenol, 1
Further polycondensation was promoted under reduced pressure of ˜5 mmHg. As a result, the polycarbonate diol 1 shown in Table 2 was obtained.

[0073]

[Table 2]

Example 5 (Production of Polyurethane and Fiber) A mixture of polyester carbonate diol a and BD heated to 30 ° C. and MDI heated to 50 ° C. were added as shown in Table 3 to polyester carbonate diol / MDI / The molar ratio of BD used is 1 / 3.15 / 2
The amount of was continuously charged into a twin-screw extruder rotating in the same direction by a metering pump to carry out continuous melt polymerization. At this time, the inside of the extruder was divided into three regions of a front part, a middle part and a rear part, and the temperature of the middle part (polymerization temperature) was adjusted to 23
It was set to 0 ° C. The resulting polyurethane was extruded continuously into water in strands and then pelletized with a pelletizer.

The pellets were vacuum dried at 80 ° C. for 10 hours, and the spinning temperature was 235 ° C. using a spinning machine equipped with a single screw extruder.
Spinning speed 800m / min, spinning tension 0.08g
/ D, and 70 denier / 2 filament polyurethane fiber was obtained. When this fiber was heat-treated at 80 ° C. for 20 hours and its performance was measured, the results shown in Table 4 were obtained. The data of ¹ H-NMR measured by using this polyurethane fiber as a sample is shown below.

¹ H-NMR (DMF, 270 MHz),
(Multiplicity, relative intensity): δ9.4 (m, 1.2), δ
7.45 (m, 2.5), δ 7.1 (m, 2.5), δ
4.1 (m, 7.0), δ 3.8 (m, 1.0), δ
2.25 (m, 3.0), δ 1.8 to 1.1 (m, 2)
3.0), δ 0.9 (m, 4.5)

Examples 6 to 8 (Production of Polyurethane and Fiber) In the same manner as in Example 5, polyurethane was synthesized from the polyester carbonate diol b, c or d shown in Table 2 with the composition shown in Table 3, pelletized, A polyurethane fiber was obtained by spinning and heat treatment. The evaluation results shown in Table 4 were obtained.

Comparative Examples 1 to 8 (Production of Polyurethane and Fiber) Polyester carbonate diols e to j, polyester diol k or polycarbonate diol 1 shown in Table 2 were used to prepare polyurethanes having the compositions shown in Table 3 in the same manner as in Example 5. Polyurethane fibers were obtained by synthesizing, pelletizing, spinning and heat treating. The evaluation results shown in Table 4 were obtained.

[0079]

[Table 3]

[0080]

[Table 4]

The fibers of the present invention obtained in Examples 5 to 8 have an MD (melt drip for heat resistance evaluation) improved by about 10 ° C. as compared with the fibers obtained in Comparative Examples 1 to 8. When mixing with polyethylene terephthalate (PET) fibers, MD is used to enable application of the high temperature dyeing method.
Is preferably 160 ° C. or higher, but Examples 5-8
The fiber obtained in (1) fully satisfies this.

The fibers of the present invention obtained in Examples 5 to 8 have a stress relaxation rate of about 10% lower than that of the fibers obtained in Comparative Examples 1 to 8 and are excellent in stress relaxation. It is clear. Such improvement in stress relaxation improves the power feeling of the elastic fiber and greatly contributes to the high performance of the elastic fiber.

[0083]

As is apparent from the above examples, the polyurethane of the present invention has excellent elongation, elastic recovery, hydrolysis resistance and cold resistance, as well as heat resistance and stress relaxation resistance. give. Further, the polyester carbonate diol of the present invention is useful as a raw material for producing such an excellent polyurethane.

Claims (3)

[Claims] 1. A polyurethane obtained by polymerizing a polymer diol, an organic diisocyanate and a chain extender, wherein the following structural units (I), (II) and (III) are mainly used as at least a part of the polymer diol. And (IV), the molar ratio of (I) / (II) is 65 / 35-35 / 6.
5, and the (III) / (IV) molar ratio is 98/2 to 85
Polyurethane having a logarithmic viscosity of 0.2 dl / g or more obtained by using a polyester carbonate diol having a number average molecular weight of 1000 to 3500 of 15/15 (provided that the logarithmic viscosity is a sample at a concentration of 0.5 g / dl. As described above, it is a value measured by using an Ubbelohde viscous tube after dissolving it in a N, N-dimethylformamide solution containing 1% by weight of n-butylamine and leaving it at 25 ± 5 ° C. for 24 hours. (I) -O-C (= O) -O- (II) -O-C (= O) - (CH 2) 7 -C (= O) -
_{O- (III) -CH 2 -CH 2} -CH (CH 3) -CH 2 -CH
_{2 - (IV) - (CH} 2) 9 - 2. A polyurethane fiber made of the polyurethane according to claim 1. 3. The following structural units (I), (II),
(III) and (IV), the molar ratio of (I) / (II) is 65 / 35-35 / 65, and the molar ratio of (III) / (IV) is 98 / 2-85 / 15. Some number average molecular weight 10
00-3500 polyester carbonate diol. (I) -O-C (= O) -O- (II) -O-C (= O) - (CH 2) 7 -C (= O) -
_{O- (III) -CH 2 -CH 2} -CH (CH 3) -CH 2 -CH
_{2 - (IV) - (CH} 2) 9 -