JPH0441714A - Polyurethane-urea elastic fiber - Google Patents

Abstract

PURPOSE:To obtain the subject fiber, having specific physical properties and excellent in chlorine, water and fungal resistance and elastic recovery ratio, etc., by polymerizing a specified polymer diol with an organic diisocyanate and a diamine. CONSTITUTION:The objective elastic fiber is obtained by polymerizing (A) a polymer diol composed of a polyester diol, expressed by formula I (R<1> is bifunctional organic group and >=50mol% thereof is group expressed by formula II; (n) is 4-10), satisfying formulas III and TV [the total number of carbon atoms is the total number of the residual carbon atoms after removing carbon atoms contained in ester bonds in the component (A)] and having 1000-3500 number-average molecular weight, (B) an organic diisocyanate at 1.4-2.8 molar ratio of the components [(B)/(A)] and (C) a diamine. The aforementioned elastic fiber is composed of a polyurethane urea and satisfies >=60% hot water-resistant strength retention, >=0.8 instantaneous elastic recovery ratio and >=90% elastic recovery ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to polyurethaneurea elastic fibers.

[Prior art]

Wet spinning, dry spinning, or melt spinning are generally used to produce polyurethane elastic fibers.

Conventionally, polyurethane used as elastic fiber has been manufactured using polyether diol, but it has poor chlorine resistance, light resistance, and heat resistance.

In addition, elastic fibers made from polyurethane produced using polyester diol have poor water resistance and mold resistance.

% 3-methyl-1,
A polyurethane using 5-bentanediol has been described and can be used in both dry and wet processes! ! JP-A-60-173117, which suggests that it can be made into fibers, describes elastic fibers made of polyurethane using polyester diols from hexamethylene glycol and 1,10-decanediol. However, when using long-chain diols that do not have such branches, elastic recovery is not possible.

Fibers with excellent heat resistance cannot be obtained.

! 2.2.4-Ma9 is 2 in JP-A-47-713.
, 4.4- Elastic fibers made of polyurethane using trimethylhexanediol and adipic acid polyester diol are disclosed in U.S. Pat.
．． 5-hexanediol or 2,2-dimethyl-1
, 3-propanediol, an elastic material made of polyurethane made from polyester diol was disclosed in JP-A-63-
No. 97617 describes an elastic fiber made of polyurethane using a polyester diol derived from (2,2-dimethy/I/-1,3-propane, dodecanedioate) glycol. If a polyester diol containing a diol having two or more methyl groups is used, fibers with excellent heat resistance, elastic recovery properties, and cold resistance cannot be obtained.

[Problem to be solved by the invention]

The purpose of this invention is chlorine resistance, water resistance, and mold resistance.

Elastic recovery, power feeling (small stress relaxation), heat resistance.

Niruru provides polyurethane elastic WR fibers that have excellent hot water resistance and high elongation.

[TI the assignment! Means for deciding

The present invention is an elastic fiber made of polyurethane urea obtained by polymerizing a polymeric diol (c), an organic diincyanate (B), and a diamine (q), which is composed of a structural unit of the general formula as a core polymeric diol (4), and has a structural unit of the general formula R1 in the middle is a divalent organic group.

CH3 More than 50 mole is -CH2-CH2-CH-CH2
~CHz-, n is a U number of 4 to 10, and has a number average molecular weight of 100 that satisfies the following conditions (1) and (2).
A polyurethaneurea in which a polyester diol of 0 to 3500 is used and a molar ratio of organic diincyana-1-(B)/polymer diol 4 of 1.4 to 2.8,
It is a polyurethaneurea elastic fiber characterized by satisfying the following conditions (1), (11), and Cm).

6≦Total return prime number/Ester condensation number≦9・・・・・・・・・
・Cl3.03≦Methine fF number/total return prime number≦0.1
In the song (2) (here, the full translation prime number is the total number of carbons remaining after excluding the carbons contained in the ester bonds in the polymer diol) Hot water resistance strength retention rate (withdrawal ≧60...・・・・・・
...(1) Instantaneous elastic recovery rate ratio ≧0,8 ...
・・・・・・・・・(n) (11 at 200% elongation
Ratio of instantaneous elastic recovery rates at 0'C and 20'C) Elastic recovery rate (%) ≧90 ・・・・・・・・・
... (lit) (After being left at 300% elongation for 24 hours, difficult removal, elastic recovery rate after 5 minutes) When diol and dicarboxylic acid components are used as long chain raw materials for polymeric diols, they are resistant to hydrolysis. sex.

The resulting polyurethane elastic fiber has improved mold resistance, but is significantly inferior in elastic recovery, cold resistance, and elongation.

Adipic acid, azelain! i%sebashin vote.

1. Polyurethane elasticity l# using polyester diol copolymerized with 10-decanedicarboxylic acid, etc., and direct diol such as 1,4-butanediol, 1,6-hexane glycol, etc.! , Usua has extremely poor elastic recovery, cold resistance, and elongation. In order to improve this property, when propylene glycol, neopentyl glycol, or the like is used in the diol component, the heat resistance, hydrolysis resistance, and hot water resistance of the resulting polyurethane elastic fiber are reduced. Elastic fibers made from polyurethane with the composition of the present invention have all the above-mentioned contradictions improved, and are not only excellent in hydrolysis resistance, mildew resistance, heat resistance, and cold resistance, but also in elastic recovery, elongation, and power feeling. The properties of the elastic fibers are very good even after hot water treatment at 130° C. for 90 minutes.

The polymeric diol^ used in the present invention consists of structural units of the general formula, in which R1 is a divalent organic group, and CH
3 The 50 mol or more is -CH2-Q(2-CH-CH2
It is a polyester diol in which -CH2- is an integer of LnFi4 to IO. In the polyester diol molecule, at least 50 molar proportion of R1 in CH3 is -CH2-CH2-C)
By being 1-CH2-CH2-, an elastic fiber with good low-temperature elastic recovery properties and elongation can be obtained.

This polyester diol uses a diol component containing 3-methyl-1,5-bentanediol as an essential component, and dicarboxylic acid components such as adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, and 1,10-decanedicarboxylic acid. Preferably 4 to 10 methylene chains such as r/i
It is obtained by using aliphatic dicarboxylic acids of 7 to IO. In any case, for the combination of diol and dicarboxylic acid, 6≦total carbon number/number of ester bonds≦
It is essential that the number is within the range of 9. If it is less than 6, the hot water resistance and cold resistance will be greatly reduced, and if it is larger than 9, the elastic recovery property will be severely reduced, and the cold resistance and elongation will be reduced. Preferably, Fi6≦total carbon number/number of ester bonds≦8.5.

Furthermore, in the present invention, the number of methine groups/total carbon number of the polyester diol is 0.03 times larger.

It is important that it be smaller than 0 or 1. If it is less than 0.03, elastic recovery properties, especially low-temperature elastic recovery properties, will be poor.

On the other hand, if it is greater than 0.1, heat resistance, strength, and elastic recovery properties will be poor.

4 Preferred dicarboxylic acids in terms of performance are azelaic acid,
sebacic acid ml, 10 7” candicarboxylic acid,
When produced by a dry or wet spinning method, particularly preferred are azelaic acid and sebacic acid. Of course, a small amount of dicarboxylic acid in which n in the general formula of the dicarboxylic acid is outside the range of 4 to 10 may be added.

Examples of diols that can be copolymerized with 3-methyl-1,5-bentanediol include 1.10-decanediol, 1.9-nonanediol, 1.8-octanediol, and 1.6-hexanediol. , 1.5-bentanediol, 1.4-7'tanediol, etc., but are not limited to these in any way.

However, the influence of the molecular weight of the polyester polyol is also large, and a range of 1000 to 3500 is preferable. More preferable? ′
i, 1500-2500 ruru. When δ is less than 1,000, heat resistance, low-temperature elastic recovery, and elongation decrease.

When it is 3,500 or more, elastic recovery properties decrease.

Suitable organic diincyanates for use in the present invention include 4,4'-diphenylmethane diincyanate, p-p-diphenyl diincyanate, and 1,5-naphthylene diincyanate b4.4' Examples include one or a mixture of two or more organic diincyanates having a molecular weight of 500 or less, such as -dicyclohexylmethane diincyanate.

Particularly preferred is 4,4'-diphenylmethane diincyanate.

Diamines (chain extenders) used in the present invention include ethylene diamine, propylene diamine, inphorone diamine, hydrazine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, dihydrazide, piperazine, xylylene diamine. Examples include 181 low molecular weight diamines having a molecular weight of 400 or less, or a mixture of two or more thereof.

Particularly preferred is 4,4-diaminophenylmethane.

The polyurethane constituting the elastic fiber of the present invention is obtained by polymerizing these polymeric diol (3), organic diincyanate (B) and diamine (q).The ratio of organic diincyanate-1-(B) to polymeric diol A is (The molar ratio of 1.4 to 2.8 is elastic recovery, elongation, heat resistance,
From the viewpoint of cold resistance, it is not necessary, preferably 1.5 to 2.3
It is.

The polyurethane urea constituting the polyurethane urea elastic fiber of the present invention essentially consists of: 1) a divalent group in which two hydrogen atoms are removed from the hydroxyl groups at both ends of the polymeric diol molecule; (in the formula, B2 is 2 (Represents a divalent organic group) [Phase] It is thought to consist of a structural unit represented by -Ni-1-R3-NH- (in the formula, R3 represents a divalent organic group) derived from a diamine.

The composition ratio @/[■+@] of these residues is preferably in the range of 0.9 to 1.1 in terms of molar ratio. When the content is within this range, elastic fibers with excellent heat resistance, elastic recovery properties, and elongation can be obtained.

More preferably, ■/[■+■] is 0.95 to 1.05.

The polyurethane urea used in the present invention has a ηinh of 0.5
As mentioned above, it is preferably 0.7 or more and 1.5 or less, and by setting it within this range, excellent elasticity fibers with excellent elastic recovery properties and small stress relaxation can be obtained.

The logarithmic viscosity (n inh) is determined by dissolving the sample in dimethylacetamide and adding 0,5yl dl at a constant temperature of 30°C.
Measure it with an Utsperohde viscometer and calculate it using the following formula.

rl refl=t/t.

t: Solution flow time (seconds) tO: Solvent flow time (extract) C: Polymer production (f/#) The polyester diol used in the present invention may be produced by any production method. For example, by a method similar to the known methods used in the production of polyethylene terephthalate or polybutylene terephthalate, i.e. transesterification or direct esterification using a diol and a dicarboxylic acid or an ester-forming derivative thereof, followed by a condensation polycondensation reaction. Manufacturable.

As for the method of producing polyurethane by polymerizing a polymeric diol, an organic diincyanate, and a diamine, a known urethanization reaction technique can be employed.

Examples of solvents for polyurethane include N,N-dimethylformamide, N,N-dimethylacetamide, N-
Examples include methylpyrrolidone, dimethylsulfoxide, and the like.

In the present invention, organic polysiloxane and hindered phenol are added to the polyurethane urea.1. Hindered amines, ultraviolet absorbers, tertiary amine compounds, gas discoloration inhibitors, pigments such as titanium oxide, etc. can be added.

The polyurethane urea thus obtained can be made into fibers by conventionally known dry spinning methods or wet spinning methods.

The polyurethaneurea elastic fiber of the present invention has good hot water resistance, and the hot water resistance strength retention rate is 6 (1 or more, preferably 701 or more).

The vocal embroidery of the present invention also includes fibers that have a hot water resistance strength retention rate of 60 degrees or more at 120°C but less than 60 degrees at 135°C.

The elastic recovery rate is 90 inches or more. Furthermore, the elastic recovery rate at low temperatures is good, and the instantaneous elastic recovery rate ratio is at least FiO,S, more preferably at least 0.9.

It is practical for the polyurethane elastic fiber of the present invention to have an elongation of 500 inches or more, preferably 550 degrees or more.

Furthermore, the elastic fibers referred to in the present invention are substantially continuous fibers or delicate bundles, and the unevenness of fineness when taking the length xoom is within ±15%, preferably Preferably within the same range.

The polyurethane urea elastic fiber thus obtained is used as a plain yarn by covering it with other fibers that were used as a bare yarn. Other fibers include polyamide fiber and cool.

Conventionally known fibers such as cotton and polyester fibers can be used, and among them, polyester fibers are used in the present invention.

That is, the polyurethaneurea elastic fiber of the present invention has 12
It is possible to dye at a temperature of 0°C or higher, and it can be used in combination with polyester delicate fibers, which could not be mixed with conventional polyurethane elastic fibers, and can be dyed at a temperature of 120°C or higher. It is made of yarn and fabrics such as polyester fibers and polyurethane urea elastic fibers.

The term "covered elastic yarn" in the present invention refers to a coated elastic yarn in which polyurethane urea elastic fiber is used as a core yarn and covered with other fibers, and the manufacturing method thereof includes, for example, covering with a twisting machine, covering with air entanglement. , covering by an n-spinning machine, etc., but is not limited to these.

The covered elastic yarn used in the present invention is preferably a yarn coated with polyurethane urea elastic fibers and other fibers in a ratio of 1:2 to 1:30.

Furthermore, the term "fabric" used in the present invention refers to woven fabrics, knitted fabrics, non-woven fabrics, paper, etc., and woven fabrics and knitted fabrics are preferred since various mechanical properties can be imparted depending on the weaving method.

In the fabric made of polyurethane urea elastic fiber and polyester fiber as used in the present invention, it is preferable that at least 30% or more of the surface (face yarn) of the fabric is polyester fiber. In the fabric of the present invention, if the polyurethane urea elastic fibers are placed in the center and are not exposed on the surface as much as possible, the fabric will be preferable in terms of light resistance and consumption performance.

Furthermore, it is practical that the fabric of the present invention contains 3% by weight or more of polyurethane urea elastic fines. Similarly, when using a covered elastic yarn, it is practical to use a weight of 5 weight or more. If it is less than this, there is a possibility that the elastic function of the fabric will deteriorate.

The fabric of the present invention may be a yarn whose shape is not limited, such as spun yarn, filament yarn, woven yarn, or processed yarn. The polyester fiber used in the present invention has repeating units of 9
It is preferable to use polyester in which 0 or more moles are ethylene terephthalate residues.

As the other fibers used in the present invention, IR cone having a fineness commonly used is used, but fibers having a fineness of 0.1 to 10 d are preferable.

The m-making machine is made using a conventional method, but as a single knit structure.

Power net, mesh, tulle, pile, satin,
tricot, lace, and jacquard (more than ia),
There are reversible jerseys, smooth, nanatsuku, pile, velor, mesh, and jacquard (all 9a), and the weaves and textures include satin and plain weave.

There are fills, double ridges, etc.

Industrial applications of the polyurethane urea elastic fine fiber of the present invention and coated elastic yarns, fabrics, etc. with other fibers include:
These include:

Clothing; swimwear, ski wear, cycling wear, leotards, lingerie, foundation, underwear; pantyhose, socks, supporter hats,
Gloves, power nets, bandages; strings for tennis rackets; base yarn for car seats for integral molding; metal-coated yarn for robot arms The present invention will be described in detail with reference to Examples below.

The measurement method adopted in the present invention will be explained.

<Measurement of molecular weight of polymeric diol> Measure the hydroxyl value and acid value of the polymeric diol and obtain them according to the conventional method.

<Hot water resistance strength retention rate> Polyurethane elastic fibers are combined with polyester fibers having a denier 2 to 5 times that of the fibers to form a simple (circular knit) fabric,
Relaxation treatment was performed in hot water at 95 to 98°C for 10 minutes, and the knitted fabric was air-dried and preset (180°C x 1 minute, f
JpIIIii, no tension) shi.

Predetermined temperature (any temperature from 120 to 135℃ Ti!L
) with hot water under pressure for 60 minutes under disperse dye staining conditions, air-dried to release the silk, and only the polyurethane urea elastic fibers were taken out. The retention rate was determined by measurement.

<Measurement of strong elongation> Strength and elongation were determined according to JIS L-1013.

<Instantaneous elastic recovery ratio> - The instantaneous elastic recovery ratio of 200% elongation at 10° C. and 20° C. was determined, and the ratio thereof was determined.

Instantaneous elastic recovery refers to the ability to recover immediately after elongation to 5200 cm, holding it for 2 minutes, and removing the stress (JISL-10
96).

Instantaneous elastic recovery rate = 100x(n!/, -(n -1/n
A) (n is elongation ratio. 2: initial length, !L: length after stress release. elongation and unloading speed is 500x/min) W14
Instantaneous elastic recovery rate ratio = Instantaneous elastic recovery rate at -10℃/20℃
Elastic recovery rate during f14 (Elastic recovery rate) Elastic fibers were stretched by 300 and held in the stretched state for 24 hours. Thereafter, the stress was removed and the elastic recovery rate was measured after being left for 5 minutes. The initial length is 45I0, the chemotactic compound is indicated using an abbreviation, and the relationship between the abbreviation and the compound is as follows. (Table 1) Table 1 Reference Example 1 (Manufacture of polyester diol) 3-Methyl-1,5-bentanediol 1534F and azelain! 11880f (MPD/AZ molar ratio:
1.3/1) under normal pressure while passing v1 elementary gas to about 195
Esterification was carried out while distilling off the water of condensation at a temperature of .degree. When the acid value of the polyester becomes about 1 or less, the degree of vacuum is gradually increased using a vacuum bonder to complete the reaction. In this way, a polyester diol (hereinafter referred to as polyester a) having a hydroxyl value of 56 and a divalent value of 0.23 was obtained. This polyester was liquid at room temperature and had a molecular weight of 2,000.

Reference Examples 2 to 14 A hydroxyl value of 56 was prepared in the same manner as in Reference Example 1 except that the acid component and the diol component were each listed in Table 2.
Thus, polyesters (polyesters b to n) having acid values and molecular weights shown in Table 2 were obtained.

Example 1 1 mol of polyester C (polyester silica with a molecular weight of 2000 from SA and MPD) was added with 1.8 mol of 4.4-diphenylmethane diincyanate and 80
The reaction was carried out at ℃ for 90 minutes. The prepolymer having incyanates at both terminals was cooled to 60° C. and mixed with N,N-dimethylacetamide to form a 30-volume solution. Then, with vigorous stirring, a solution of 0.8 mol of 4,4-diamino-diphenylmethane dissolved in N,N-dimethylacetamide was added to obtain a spinning stock solution of 2000 voids (30° C.) at 30% concentration.

After vacuum defoaming of this polymer solution according to the usual method,
The yarn was extruded into a spinning cylinder in which heated air at 180°C was flowed through a nozzle with 5 holes, and the yarn was spun at a spinning speed of 500 while applying an oil agent mainly composed of dimethylpolysiloxane to the yarn at a rate of 7 times.
It was rolled up for 7 minutes to obtain a 40 denier polyurethane urea elastic fiber. Its physical properties are favorable as shown in Table 3.

Examples 2 to 8 Polyurethane flares shown in Table 3 were synthesized from polyester dials having the compositions shown in Table 2 in the same manner as in Example 1, and spun in the same manner as in Example 1. The physical properties of the obtained nine-elastic wax showed excellent values as shown in Table 3.

Comparative Example 1 80 consisting of polyester C and 1.4 butanediol
℃ heated mixture and 4,4' heated and melted at 50℃
-diphenylmethane diincyanate (MDI) and 5
The compositions shown in Table 3 were continuously supplied to a twin-screw extruder using a metering pump to carry out continuous melt polymerization, and the resulting polyurethane was extruded into water in the form of a strand and cut into pellets.

The pellets were vacuum dried at 80°C for 20 hours, and then spun at a spinning temperature of 235°C and a spinning speed of 6 using an ordinary spinning machine equipped with a single-screw extruder.
Spun at 50m/min, 40 denier polyurethane IIi! I got the answer. When this tltm was heat treated at 80'C for 4 g hours7 and its physical properties were measured, it was found that the elastic recovery rate was poor.

Comparison J2-9 Polyurethane N1. The performance was evaluated by combining them. elastic recovery,
There are problems with the elastic recovery rate ratio between II and 2, the hot water resistance strength and medical waiting rate, and the elongation.

Below is the blank space Example 9 The polyurethane urea elastic wire obtained in Example I, Teijin jPIl! Using a single covering machine manufactured by *, the draft rate was set to 3.5 times, and the cover yarn was a regular polyester filament drawn yarn (drawn to 3.6 times after spinning at 1200 m/min), a 75 d/36 briny T-type irregular yarn. A covered yarn was prepared by twisting f at a number of twists of 600 times/m. This covered thread (b)
wrapped in gauze and heated to 130°C under virtually no load.
Boiled in hot water for 90 minutes. After boiling, vacuum dry in a desiccator, untwist, and take out only the polyurethane elastic thread.
When a retention wheel with elastic recovery was determined, it was found to be 99% good.

Example work 0 The polyurethane elastic fiber obtained in Example 1.

POY-Indolo One-way twisted 75d polyester processed yarn and 28G smooth texture II
A completed. After relaxing the Ia knitted fabric in hot water for 95℃
×1 minute, hot air, no rope L, disperse dye Re5olin B
lue FBL (Friend of Bayer) 1.0chowf,
Level dyeing agent Tohon Ruto (Toho Kagaku #) 1.0P/μ,
Regulator Ultra MT (manufactured by Mihejima Kagaku Co., Ltd.) 1.0f/1
The dye was adjusted to 5.0 and dyed at 130°C for 60 minutes in a nine dye bath. After dyeing, it was finished using a pin tenter at 150°C for 1 minute.

The finished product had good elasticity and color consistency.

After finishing, the knitted fabric was released and its strength, elongation, and elastic recovery rate were measured.

There was little decrease in strength, elongation, and elastic recovery rate, and the hot water resistance and strength retention rate were good at 87 mm.

This knitted fabric was cut and sewn to make a swimsuit, and the needle base fastness of this swimsuit (JIS 0842 Carbon Arg 3rd grade)
jl! (light method) is grade 5, and chlorine fastness (JIS
0844 strong test method) Grade 5 for discoloration and fading, showing good color fastness.

Special fraud applicant RiRashi Co., Ltd.

Claims (2)

[Claims] (1) Polymeric diol (A), organic diisocyanate (
It is an elastic fiber made of polyurethane urea obtained by polymerizing B) and diamine (C), and the polymer diol (A) is composed of the structural unit of the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and it has the formula The middle R^1 is a divalent organic group, and 50 mol% or more of it is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n is an integer from 4 to 10, and the following (1),
Number average molecular weight 1000-350 that satisfies the condition (2)
0 polyester diol is used, and the molar ratio of organic diisocyanate (B)/polymer diol (A) is 1
．． 4 to 2.8 polyurethaneurea elastic fiber, which satisfies the following conditions (I), (II), and (III). 6≦Total carbon number/Number of ester bonds≦9 (1)
0.03≦Number of methine groups/Total number of carbon atoms≦0.1...
(2) (Here, the total number of carbons is the total number of carbons remaining after excluding carbons contained in ester bonds in the polymer diol) Hot water resistance strength retention rate (%) ≧ 60...・・・・・・
...(I) Instantaneous elastic recovery rate ratio ≧0.8...
......(II) (Ratio of instantaneous elastic recovery rates at -10°C and 20°C at 200% elongation) Elastic recovery rate (%) ≧90... (I
II) (After standing for 24 hours with 3005 elongation, remove the stress,
Elastic recovery rate after 5 minutes) (2) The polyurethaneurea elastic fiber according to claim 1, wherein n is 7 to 10 in the general formula (includes numerical formula, chemical formula, table, etc.).