JPH03281518A - Polyurethane and polyurethane elastic yarn - Google Patents

Abstract

PURPOSE:To obtain the title polymer useful as an elastic yarn having excellent chlorine resistance, water resistance, mildew resistance, elastic recovery, heat resistance and freeze resistance, by polymerizing a polymer diol such as polyester and polycarbonate with an organic diisocyanate and a chain extender. CONSTITUTION:(A) A polyester diol comprising a repeating unit shown by formula I (R<1> is group wherein >=50mol% of the group is organic group shown by formula II; (n) is 4-10), satisfying relationship shown by formula III and formula IV and having 1,000-3,500 number-average molecular weight is polymerized with (B) a polymer diol which comprises a polycarbonate diol having structural units shown by formula V ((m) is 6-10), formula VI, formula VII, etc., bonded through carbonate bond, having molar ratios of units shown by formulas (VI+VII)/units shown by formulas (V+VI+VII) and of units shown by formulas (V+VI)/units shown by formulas (V+VI+VII) of 0.1-1.0, 1,000-3,000 number- molecular weight and has a weight ratio of the component A/component B of (10/90) to (80/20), an organic diisocyanate and a chain extender to give the objective polymer having 0.2-1.6dl/g logarithmic viscosity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyurethane and polyurethane elastic fines.

[Prior art]

Conventionally, polyester-based polyurethane, polyether-based polyurethane, polycarbonate-based polyurethane, etc. have been known as polyurethane, but 4? 1977-
Publication No. 101496 discloses a polyurethane using a polyester diol consisting of Kr13-meru-1,5-bentanediol and dicarboxylic acid. Also,! ￥
! 2-methyl-18-
A polyurethane using a polycarbonate diol similar to octanediol has been described.

! ! s Publication No. 2-33382 and Japanese Patent Publication No. 2-33
Publication No. 384 describes 2-methyl-1,8 octanediol, the polyester diol used and 2-methyl-1,8 octanediol.
A polycarbonate diol using -octanediol or 3-methyl-1,5bentanediol is disclosed, and a polyurethane using a mixed 2ol of this polyester diol and polycarbonate diol as a polymer diol is disclosed. However, when this polyurethane is used to make elastic fibers, fibers with excellent elastic recovery properties at low temperatures cannot be obtained.
Publication No. 17311773117 Sameethylene glycol,
1. Polyester diols from 10-decane diol have been described which are more elastic than polyurethanes. However, if a long chain diol without such branching is used, fibers with excellent elastic recovery properties cannot be obtained.

Ma7t*! 2.2.4-
U.S. Pat.
, No. 192 discloses an elastic polyurethane IIC (polyurethane made from a polyester diol using 2,5-hetobasic diol or muc-dimethyl-1,3-propanediol), and JP-A-63-97617 discloses describes elastic fibers made of polyurethane incorporating polyester diols from (2,2-,; methyl-1,3-propane, dodecanoate) glycol. However, when such polyester diols are used, fibers with excellent heat resistance, elastic recovery properties, and cold resistance cannot be obtained.

JP-A-1-190717 describes polyurethane elastic fibers made of polyurethane using polycarbonate diol using 1.6-hexanediol and 1.5-bentanediol. However, the delicacy obtained by this method is not satisfactory in terms of elongation. The purpose of the present invention is to provide a polyurethane elastic fiber that is excellent in all the properties of 1M4 and has high elongation.

The object of the present invention is to provide a polyurethane elastic material which has low strength in a low elongation region and has poor strength in a high elongation region.

The present invention provides a polyurethane for use in producing the polyurethane elastic material.

[Means for Solving the Problems] The present invention provides a polyurethane obtained by polymerizing a polymeric diol, an organic diincyanate, and a cast lengthening agent, wherein the polymeric diol has a general formula.

(In the formula, R'!d represents an organic group in which 50 or more molar groups are Hs -CH2-Ck* -CH-CH2-CH2-, and n represents a Jl number of 4 to 10.) Number average molecule f 1000~ that is i from the return unit and that satisfies the following relational expressions (3) and (1)
3,500 polyester diols (A) and at least 41 ffiO structural units selected from the group consisting of the following structural units (r), (ff), (Iff) (i.e., the diol and the remaining OH groups except for the two OH groups). C(ff) + (
III) )/C(1) +(II) +(II))
is mo/l/ratio from 0.1 to 1.0, and C(1
)+(II))/l:(1)+(II)+(I[I)]
is 0.1 or more and 1.0 or less in molar ratio, number average molecular weight 1
000 to 3000 polycarbonate diol (B), and the weight ratio (A) / (B) it 1
The polyurethane is characterized by being a polymeric diol having a k of 0/90 to 80/20, and having a logarithmic viscosity of 0.2 dllt or more and 1.6 dl/f or less.

4≦Total number of carbons/Number of star bonds≦11...Song (S) 0.
03≦Number of methine groups/Total number of carbon atoms≦0.2...Song (1
) (Here, the total number of carbon atoms means the total number of carbons remaining after excluding carbons contained in ester bonds and carbonate bonds in the straw molecule diol.) -1: (?Hz1m
-・・・・・・(1) (Here, m is 6 to 10!Il
〒H3 -CH2CJI-(CHz)5-CI(z-...
...CII) CH3 -CH2-CH2-CI-CH2-CHz-...
... C [[I] Also, the present invention I''i is a polyurethane elastic fiber made from the polytalethane.

The polymer diol component used in the present invention has molecules tt,
ooo~3,500 polyester diol and a polycarbonate diol with a molecular weight of 1,000~3,000.

The polyester diol used in the present invention contains 50 or more moles of 3-methyl-1,5-bentanediol as a diol component! Diol is used, and the dicarboxylic ingredients are adipic acid, pimeline, speric acid,
By using aliphatic dicarboxylic acids having 4 to 10 methylene chains such as azelaic acid, mono(sinic acid, 1.10-decane dicarboxylic acid), any Vζ can be obtained with diol, decane dicarboxylic acid, etc. 1,9 ancestors (・Two points, 4≦all carbons/number of ester bonds≦11, adding 14 is 2・su, and if it is smaller than 4,
Endurance? The decrease in water resistance and cold resistance is large, and if the thickness is larger than 111, the decrease in elastic recovery is X, resulting in a decrease in cold resistance and elongation.

Furthermore, the number of methine groups in BoIJ ester diol/total carbon 1!17510.03 or more and 0.2 or less is 1
It is essential. Represents l'--CH-J bonded to three carbon atoms different from the methine length referred to in the present invention. 0. F
) If it is smaller than 3, the elastic recovery property, especially the low temperature elastic recovery property, will be poor. If it is larger than -50.2, heat resistance 1 strength and elastic recovery properties will be poor. In general, preferred dicarboxylic acids are azelaic acid, 7.3ffi, and 1,10-decanedicarboxylic acid, and when produced by a melt-spinning method, particularly preferably azelaino i! 12. It is sebacic acid. Dicarboxylic acids other than the above-mentioned aliphatic dicarboxylic acids may be used in small amounts.

However, when 3-methyl-1,5-bentanediol in the diol component is less than 50 molt, it is low temperature! II chronic injection and 1 degree of elongation were both poor. Diols that can be used together with 3-methyl-1,5-bentanediol include l,10-decanediol, 1°9-nonanodiol, l,8-xcutanodiol, 1,6-bundiol, , 5-bentanediol, 1,4-butanediol, etc., but are not limited to these in any way.

Further, the influence of the molecular weight of the polyester polyol is also large, and a number average molecular weight in the range of 1txooo to 3,500 is required. More preferably, it is 1500-2500. 10
If it is less than 00, heat resistance, low-temperature elastic recovery, and elongation will decrease. If it is larger than 3500, the elastic recovery property will be lowered and when using the melt spinning method.

Spinneret dirt and filter clogging are likely to occur, which shortens continuous spinning operation time.

The polyester diol used in the present invention may be produced by any method. For example, it can be produced by methods similar to those known in the art used in the production of polyethylene terephthalate or polybutylene terephthalate, ie transesterification or direct esterification followed by melt polycondensation reaction.

The polycarbonate diol used in the present invention contains at least one structural unit from the group consisting of the structural units (1), (n), and (II).

Compounds that provide the group represented by (1) include 1.6-
Hexanediol, 1.7-hebutanediol, 1.8
-Octanediol, 1,9-nonanediol.

1.10-Decanediol is mentioned, preferably a
1,9-nonanediol.

Examples of compounds that provide the group represented by (II) include 2-methyl-1,8-octanediol, ([[)
Compounds that provide the group represented by include 3-methyl-1,
5-bentanediol is mentioned. In the present invention, C(1[)+(IN))/[: (
The molar ratio of 1) + (summer) + (1)] should be 0.1 or more and 1.0 or less.

((1) + (II) ) / ((1) + (ri) ten (1)
](D molar ratio d O, 1 or more and 1.0 or less.C(
II) + (1) E / [” (1) + (II) +
When the molar ratio of (Jl) ) becomes 0.1, the elastic recovery property decreases and the elongation decreases.

If the molar ratio of ((I)+(n))/((1)+(n)+(1)) is less than 0.1, water resistance, mold resistance, and cold resistance will decrease. Preferably [(■)+1))/I:(1)+
(II) + (■)] is 00.3 or more C (1) + (II
) ]/l: (1) + (f[) + (If) ) is 0
．． It is 3 or more.

Further, the molecular weight of the polycarbonate has a large influence, and a number average molecular weight of 1,000 to 3,000 is required.

If it is less than 1000, not only elastic recovery, cold resistance, and elongation but also heat resistance will be poor. If it is larger than 3,000, the elastic recovery property decreases, and when using the melt spinning method, staining of the spinneret, filter clogging, etc. are likely to occur, and the continuous spinning operation time is shortened.

Diols other than the above-mentioned raw material diols may also be used in the synthesis of polycarbonate diols as long as they are in small amounts.

The carbonate compound used in producing the polycarbonate diol used in the present invention is preferably +2 dialkyl carbonate, diaryl carbonate, or alkylene carbonate.
Legality is not particularly limited. For example, known methods used in the production of polycarbonate from diphenyl carbonate and bisphenol A and methods similar to 1j11,
That is, it can be produced by transesterification.

The polymer diol used in the present invention is the above polyester diol (A) and the above polycarbonate diol CB.
) is a mixture of The mixing ratio of (A) and CB) is the weight ratio f
(A)/(B) = 10/90 to 80/20.

If A is less than 10% by weight, the elongation will decrease, and if B is less than 20% by weight, the hot water resistance will decrease.

Other polymeric diols can be used as long as they do not substantially reduce the O effect of the present invention.

Suitable organic diincyanates for use in the present invention include aliphatic, cycloaliphatic or aromatic organic diincyanates, specifically 4,4'-diphenylmethane diincyanate, p-phenylmethane diincyanate, Incyanate, toluylene diincyanate, t, S-naphthylene diincyanate, xylylene diincyanate,
Examples include diisocyanates having a molecular Ik of 500 or less, such as hexitemethylene diincyanate, inphorone diincyanate, and 4,4'-dicyclohexylmethane diincyanate-F. Preferred is 4,4'-diphenylmethane diincyanate.

The chain extenders used in the present invention include chain extenders commonly used in the polyurethane industry, ie, low-molecular compounds with molecules of 1t400 or less containing at least 2 hydrogen atoms capable of reacting with incyanate, such as ethylene glycol, 1.4 -butanediol, phlopylene glycol, 1,6-hequinanediol, 3-methyl-1,
Diols such as 5-bentanediol, 1,4-bis(2-hydroxyethoxy)benzene, 1,4-cyclohexanediol, bis(β-hydroxyethyl)terephthalate, xylene glycol, ethylenediamine, propylenediamine, inphoronediamine.

Human lysine, 4,4'-diaminodiphenylmethane, 4
．． 4'-Diamino dicyclo to silmethane, dihydracite, piperazine, =? Examples include cyanogens such as silylene diamine.

These compounds may be used alone or in combination of two or more. The most preferred chain extenders are 1,4-butanediol or 1,4-bis(2-hydroxyethoxy)benzene.

In particular, when producing elastic fibers from thermoplastic polyurethane by melt spinning, the organic diincyanate used to synthesize the thermoplastic polyurethane is 4,4'-diphenylmethane diincyanate, and the chain extender is 1,4-butanediol and/or Alternatively, by selecting 1,4-bis(2-hydroxyethoxy)benzene, excellent performance in heat resistance, elastic recovery, and elongation can be obtained.

As for the method for producing the polyurethane of the present invention, known urethanization reaction techniques can be employed. According to the research conducted by the present inventors, it has been found that it is preferable to perform melt polymerization in the substantial absence of an inert solvent, and that continuous 'IJ@polymerization using a multi-screw extruder is particularly preferable. did.

The temperature at which melt polymerization occurs is not particularly limited, but is 200°C or higher2.
The temperature is preferably 40°C or lower. By keeping the temperature below 240°C, M resistance increases, and by keeping the temperature above 200°C, it becomes possible to produce a thermoplastic polyurethane with excellent spinnability.

The polyurethane of the present invention has an ηinb of 0.2 or more and 1.6#
/f or less is 6. yinh is 0.2dll? If it is smaller than 1.6d12/f, the elastic recovery property will be lowered, and if it is larger than 1.6d12/f, the spinnability will be poor. Preferably 0.3 to 1.4
It is 纒/f.

m-molecular diol (X), organic diincyanate (Y), chain extender (
In the composition ratio of Z), (Y)/[(X)+(Z)
) has a molar ratio of 0.9 to 1.2 t! range, especially 0.95~
A range of 1.15 is preferred. In this range, heat resistance,
Polyurethane elastic fibers with excellent elastic recovery and elongation can be obtained.

The polyurethane of the present invention consists essentially of (&) 2 hydroxyl groups at both ends of the polymeric diol molecule.
Round 21ili group with @ hydrogen atom removed; (b)
General formula derived from organic diincyanate (in the formula, R2 represents a divalent organic straw) (C) 2 in the form of a low molecular compound (chain extender) from which two hydrogen atoms are removed, which reacts with the incyanate molecule. It is thought to consist of a structural unit represented by the following valence group:

The polyurethane thus obtained is spun into fibers by conventionally known dry spinning methods, wet spinning methods, melt spinning methods, and the like.

Among these, the melt spinning method is preferable because it can make the denier fine. Specifically, the polyurethane is pelletized and then melt-spun, or the thermoplastic polyurethane obtained by melt polymerization is directly passed through a spinneret and spun. The method is adopted. From the viewpoint of spinning stability, direct polymerization spinning is preferred.

In addition, polymeric diol (X), relaxed diincyanate (
Y), the composition ratio of the chain extender (Z), (Y)/(
(X) + (Z) ) t7) -t= k ratio 7>!
Polyurethane polymerized with excess isyanate of 1.02 to L15, or polyincyanate compound or sealing wax polyincyanate compound added to polyurethane during spinning, ij polymerization, (Y)/I:(X)+(Z)
By spinning a polyurethane with an excess of incyanate at a molar ratio of tii, o of 2 to 1,15, polyurethane elastic fibers having excellent heat resistance, elastic recovery properties, and high elongation can be obtained.

Furthermore, the uninvented polyurethane elastic fiber can be obtained by spinning the above-mentioned incyanate-excess polyurethane, dissolving the iron ring in a solution of 0.5N n-butylamine in N,N-dimethylformamide, and obtaining an aHanate binding amount 0.001 to 0.1 mmojl/
f), the fiber can have excellent elastic recovery properties. The polyurethane elasticity 111 of the present invention contains no polymers or other organic substances other than the above-mentioned polyurethane! ! A substance may be added.

As described above, the polyurethane of the present invention has excellent heat resistance, cold resistance, water resistance, and elastic recovery, and has high elongation and good chlorine resistance.

This will be explained below using examples.

It hydrothermal properties (strength flavoring ¥9, elastic recovery rate, ηjnb) in the same four examples were measured by the following method.

・Hot water resistance (strength retention rate) Measure tensile strength retention after hot water treatment of sample at 130°C for 90 minutes.

・Elastic recovery After stretching the sample by 200% and holding for 10 minutes.

After removing the tension and leaving it for 3 minutes, the elastic cycle 81 was measured at 25°C.
and measured at -10°C.

・Strong elongation Measured according to JIS t, -1 ota.

・Logarithmic viscosity (ηfnh) The sample was heated to a concentration of 0.5 G/dL (/c,
It was dissolved in N,N-dimethylformamide containing 1% by weight of n-butylamine, left at room temperature for 24 hours, and then measured using an Utsurohde viscosity tube.

The compounds used are indicated using abbreviations, and the relationship between the abbreviations and compounds is as shown in Table 1.

Table reference example 1 (Production method of polyester diol) 3-methyl-1,5-bentanediol 1531' and azefinic acid 1880f (MPD/AZ molar ratio: 1
．． 3/1) was subjected to esterification at a temperature of about 195° C. while passing nitrogen gas under normal pressure and distilling off the water content. Just in case the acid value of the polyester decreased to about 1 or less, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction. Thus, the hydroxyl value was 44.9. A polyester diol (hereinafter referred to as polyester a) having an acid value of 0.23 was obtained. This polyester.

It was liquid at room temperature and had a molecular weight of 2,500.

Reference Examples 2 to 7 Polyesters (polyester b -g) was obtained.

Reference Example 8 (Manufacture of polycarbonate diol) Mixture of 2-methyl-1,8-octanediol (MOD) and 1,9-nonanediol (ND) under nitrogen flow %
(Ratio to MOD/ND: 50150) 1730F
and diphenylcarbonate-1-2140f] was heated, and phenol was distilled off from the reaction system at 200°C. The temperature was gradually raised to 210-220°C, and after most of the phenol had been distilled off, vacuum was applied and the temperature was heated to 6-10°C.
The remaining phenol was completely distilled off at 210-220° C. under vacuum. As a result, a polycarbonate diol (polycarbonate h) having a molecular weight of 2000 was obtained.

Reference Examples 9 to 13 Polycarbonate diols shown in Table 3 (polycarbonate i-m
) was obtained.

Table 2 Table 3 Example 1 Mixture of polyester islands and polycarbonate g (weight ratio: polyester island/polycarbonate g = 50150
), BDO heated to 30°C, and MDI heated and melted to 50°C in an amount such that the molar ratio of polymer diol/MDI/BD used is 1/3.15/2 in a quantitative bonder in the same direction. The mixture was charged into a rotating two-wheel screw extruder in a continuous manner, and continuous melt polymerization was performed. At this time, the inside of the extruder was divided into three zones, a front section, a middle section, and a rear section, and the temperature of the middle section (11 temperature) was set at 230°C. The produced polyurethane is continuously extruded into water in the form of strands,
Then, it was formed into pellets using a pelletizer.

The pellets were vacuum-dried for 80"010 hours, and spun at a spinning temperature of 235°C using a spinning machine equipped with a single-screw extruder.

Spinning speed 800m/rnin, apparent draft rate 847
゜Yarn feeding speed difference 3s m/mj4. Spinning tension 0.
A polyurethane fiber having a density of 70 denier/2 filaments was obtained by spinning at 0.08 f/d. When this fiber was heat treated at 80°C for 20 hours and its physical properties were measured, favorable results were obtained as shown in Table 1 and Figure 1.

Examples 2 to 6 In the same manner as in Example 1, polyurethane having the composition shown in Table 4 was synthesized, pelletized, and spun to produce polyurethane elastic fibers. As shown in Table 4, favorable results were obtained.

Comparative Examples 1 to 4 In the same manner as in Example 1, polyurethane having the composition shown in Table 2 was synthesized, pelletized, and spun to obtain polyurethane elastic fibers. Good strength and elongation, hot water resistance, and elastic recovery were not obtained.

Hereinafter, gold platinum [@+ of the invention] As is clear from the above examples, the polyurethane of the present invention has high elongation and excellent elastic recovery properties, as well as hot water resistance and cold resistance. Excellent.

1st J**a The relationship between the strength and elongation in the elastic range MK of the elastic fibers of Example 1, the elastic fibers from the polyester diol of Comparative Example 1, and the polycarbonate diol of Comparative Example 2 is shown.

The elastic fiber of Example 1 of the present invention has very excellent properties as an elastic fiber, having low strength and easy stretching in the low elongation region, and high strength and difficult to stretch in the high elongation region. .

[Brief explanation of drawings]

FIG. 1 is a diagram showing the relationship between the strength up to breakage of the nine-elastic brewed fibers obtained in Example 1, Comparative Example 1, and Comparative Example 2 and the sacred ceremony.

Claims (3)

[Claims] (1) A polyurethane obtained by polymerizing a polymeric diol, an organic diisocyanate, and a chain extender, in which the polymeric diol has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (formula K, R ^1 represents an organic group of which 50 mol% or more is ▲a mathematical formula, a chemical formula, a table, etc.▼, n is an integer from 4 to 10), and consists of repeating units shown by the following (s) and ( A number average molecular weight of 1000 to 35 that satisfies the relational expression t)
00 polyester diol (A) and at least one structural unit selected from the group consisting of the following structural units (I), (II), and (III), having a structure in which they are connected via a carbonate bond, [(II)+(III)]/[(I)+
(II)+(III)] is 0.1 or more and 1.0 or less in molar ratio, and [(I)+(II)]/[(I)+(II)+(
III)] is composed of a polycarbonate diol (B) having a number average molecular weight of 1000 to 3000 in a molar ratio of 0.1 to 1.0, and the weight ratio (A)/(B) is 10
/90 to 80/20, and has a logarithmic viscosity of 0.2 dl/g or more and 1.6 dl/g or less. 4≦Total carbon number/Number of ester bonds≦11 (s
)0.03≦number of methine groups/total number of carbon atoms≦0.2...
...(t) (Here, the total number of carbon atoms means the total number of carbons remaining after excluding carbons contained in ester bonds and carbonate bonds in the polymer diol) -(CH
＿２）＿m－・・・・・・・・・(I) (Here, m is an integer from 6 to 10. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
(III) [However, the logarithmic viscosity is calculated using N,N-
This is a value measured using an Ubbelohde viscosity tube after dissolving in dimethylformamide and leaving it at room temperature for 24 hours. ] (2) The polyurethane according to claim 1, wherein the structural unit (I) is a nonamethylene group. (3) A polyurethane elastic fiber made of the polyurethane according to claim 1 or 2.