JPH11131325A - Polyurethane-based elastic fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject fiber excellent in durability such as light resistance, chlorine resistance and hot water resistance, and useful in swimming suits, supporters, by using a hydroxyl-terminated saturated hydrocarbon-based polymer as a polymeric polyol. SOLUTION: This polyurethane-based elastic fiber is obtained by using, as polymeric polyol, pref. 20 wt.% (based on the polyurethane) of a hydroxyl- terminated saturated hydrocarbon-based polymer, for example, with an average molecular weight of 500-8,000 and average functional number of 1.5-2.6, having polyisobutylene, hydrogenated polybutadiene or hydrogenated polyisoprene as the main skeleton.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane-based elastic fiber having excellent durability such as light resistance, chlorine resistance and hot water resistance, and more particularly to swimwear, lingerie, foundation, underwear, and the like. Clothing field such as sportswear, socks field such as pantyhose and socks, medical field such as supporters, bandages, masks, pulp base cloth, taping, etc., industrial materials field such as car seats, chair upholstery, packaging materials, hair The present invention relates to a polyurethane-based elastic fiber that can be used in general goods fields such as nets and handicrafts.

[0002]

2. Description of the Related Art Polyurethane elastic fibers have hitherto been produced mainly by a wet or dry spinning method. In other words, this fiber having a polyurethane urea structure has excellent elastic properties and excellent elongation recovery properties, but since polyether diol is used as a soft segment component, chlorine resistance and light resistance are poor. The disadvantage is that it is very poor.

[0003] If the chlorine resistance is poor, the stretchability of the swimsuit is impaired by chlorine for disinfecting the pool, and the dirt on the underwear using polyurethane elastic yarn is bleached with a chlorine bleach to cause significant embrittlement and wear. There is a problem that it becomes impossible or that it is embrittled by chlorine in tap water during long-term home washing. Further, with respect to light resistance, if this property is poor, there is a problem that yellowing due to light and elongation and elongation recovery inherent in the elastic yarn do not develop over time.

As a method for improving the chlorine resistance, for example, a method of adding magnesium oxide or aluminum oxide described in JP-B-61-35283, or a method of improving the chlorine resistance,
Japanese Patent No. 3444 discloses a method of adding zinc oxide, and the like. However, since these metal oxides are difficult to uniformly disperse in a dope for dry (wet) spinning, as a result, the resulting elastic yarn has There are disadvantages in that unevenness in chlorine resistance occurs, and that metal oxides are liable to adhere to the spinneret, and as a result, yarn breakage is likely to occur and productivity is significantly reduced.
Further, in a post-processing step such as dyeing, since these metal oxides fall off, for example, when passing through a treatment bath, there arises a problem that desired chlorine resistance cannot be obtained.

As a method for improving light resistance, a method of adding a benzotriazole-based, benzphenone-based, or salicylic acid-based ultraviolet absorber has hitherto been known. The problems of solubility in the dope for yarn protection, adhesion to the spinneret, problems of yarn breakage, and the fact that these additives are extremely expensive are one of the causes of the high cost of urethane elastic yarns. .

[0006] On the other hand, production by the melt spinning method has recently been increasing due to low cost and good transparency. However, polyurethane elastic yarns obtained by the melt spinning method have disadvantages in that they are inferior in heat resistance and hot water resistance to elastic yarns obtained by the dry spinning method. For example, it has been pointed out that those produced using polyester diol are inferior in hot water resistance, alkali resistance, and mold resistance.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide light resistance, chlorine resistance,
An object of the present invention is to provide a polyurethane-based elastic fiber having excellent durability such as hot water resistance.

[0008]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have found that by using a saturated hydrocarbon polymer having a hydroxyl group at the terminal, it is excellent in light resistance, chlorine resistance and hot water resistance. It has been found that polyurethane elastic fibers can be obtained. That is, the present invention is a polyurethane-based elastic fiber characterized in that a saturated hydrocarbon-based polymer having a hydroxyl group at a terminal is used as a polymer polyol.

It is desirable to use a saturated hydrocarbon polymer having a hydroxyl group at a terminal as a polymer polyol in an amount of 20% by weight or more in polyurethane, but it can also be used in combination with another polymer polyol. The average molecular weight of the saturated hydrocarbon polymer having a hydroxyl group at the terminal is 500.
It is preferably from 8,000 to 8,000. Furthermore, the average functionality of the saturated hydrocarbon polymer having a hydroxyl group at the terminal is 1.5.
~ 2.6 is preferred.

The saturated hydrocarbon polymer having a hydroxyl group at a terminal includes a polymer having a main skeleton of polyisobutylene, a polymer having a main skeleton of hydrogenated polybutadiene, and a polymer having a main skeleton of hydrogenated polyisoprene. Certain such polymers can be used.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The polyurethane used in the present invention is a compound synthesized from a polymer polyol, an organic polyisocyanate and a chain extender.

The polymer constituting the skeleton of the saturated hydrocarbon polymer having a terminal hydroxyl group used in the present invention is (1) an olefin having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene. The compound is polymerized as a main monomer, (2) a diene compound such as butadiene or isoprene is homopolymerized, or the olefin compound and the diene compound are copolymerized and then hydrogenated. Obtainable.

Of the polymers obtained by these methods, isobutylene-based polymers, hydrogenated polybutadiene-based polymers or hydrogenated polyisoprene-based polymers are easy to introduce a functional group into the terminal and control the molecular weight. The polymer is desirable as the polymer forming the skeleton of the saturated hydrocarbon polymer having a hydroxyl group at the terminal used in the present invention.

The method for polymerizing a saturated hydrocarbon polymer having a hydroxyl group at a terminal is as follows: (1) a method of directly introducing a hydroxyl group into a terminal by cationic polymerization using H ₂ O ₂ as an initiator; A living anion polymerization method in which a living polymer having a structure in which an alkali metal is bonded to a terminal using an anion polymerization catalyst and then reacting with a monoepoxy compound, formaldehyde, or the like is used. (3) An alkenyl group is introduced into a terminal after living cationic polymerization. Further, a method of hydroxylating the terminal by using a hydroboration method and the like are known. In the present invention, a polymer polymerized by the method (3) (hereinafter, referred to as a “living polymerization method”) is preferable because the average functionality is easily controlled as described later.

The method for introducing an alkenyl group into a saturated hydrocarbon polymer in the living polymerization method includes, for example, the following method. That is, a compound having a halogen atom as an initiator and a chain transfer agent, in which a carbon atom to which the halogen atom is bonded to an aromatic ring carbon and / or a compound in which the carbon atom is a tertiary carbon atom is used. Then, after cationically polymerizing a cationically polymerizable monomer containing isobutylene using a Lewis acid as a catalyst, an allyl group-terminated isobutylene-based polymer is obtained by adding allyltrimethylsilane to the polymerization system. Can be. Further, as another method, an alkenyl group is added to the main chain or side chain by adding a non-conjugated diene such as 1,9-decadiene or an alkenyloxystyrene such as p-hexenyloxystyrene to the polymerization system. A method for producing an isobutylene-based polymer having a terminal is exemplified.

The initiator and chain transfer agent used in the present invention include, for example, those represented by the following general formula (1).

[0017]

Embedded image [In the formula, R ¹ represents an aromatic ring group or a substituted or unsubstituted aliphatic hydrocarbon group. R ² and R ³ may be the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. However, when R ¹ is an aliphatic hydrocarbon group, R ² and R ³ are not simultaneously hydrogen atoms. X is a halogen atom, an R ⁴ COO— group (R ⁴ is a hydrogen atom or
5 to 5 alkyl groups. ) Or R ⁵ O-group (R ⁵ represents a.) Of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n is an integer of 1 or more and 8 or less. ]

The compound represented by the general formula (1) includes, for example, a compound represented by the following general formula (2). AYn (2) wherein A represents a group having 1 to 4 aromatic rings. Y is a compound represented by the following general formula (3). n is an integer of 1 or more and 8 or less. ]

[0019]

Embedded image [Wherein, R ⁶ and R ⁷ are the same or different and each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. X is a halogen atom, an R ⁴ COO— group (R ⁴ is a hydrogen atom or
5 represents an alkyl group. ) Or R ⁵ O-group (R ⁵ represents a.) Of a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]

In the compound represented by the general formula (2), 1
A, which is a group having 4 to 4 aromatic rings, is
It may be formed or non-condensed. This
Examples of the group having an aromatic ring such as
Phenyl group, biphenyl group, naphthyl group, anthracene
Group, phenanthrenyl group, pyrenyl group, Ph- (C
H _Two)_p-Ph group (Ph is a phenyl group, p is 1 to 10
It is an integer. ), Etc., having these aromatic rings
Is a straight-chain and / or branched aliphatic carbon having 1 to 20 carbon atoms.
Functionality such as hydride group, hydroxyl group, ether group and vinyl group
It may be substituted with a group having a group.

As another compound represented by the general formula (1)
Is also a compound represented by the following general formula (4).
You. BZm (4) [wherein B is a substituent having 4 to 40 carbon atoms, preferably 9 to 20 carbon atoms.
Represents a substituted or unsubstituted hydrocarbon group. Z is tertiary carbon
A halogen atom bonded to an atom, R⁸COO- group (R⁸Is
It represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ) Or
R⁹O-group (R ⁹Is a hydrogen atom or an alkyl having 1 to 5 carbon atoms
Represents a hydroxyl group. ). m is an integer of 1 to 4. ]

The compound represented by the general formula (4) includes
For example, those having a functional group other than Z such as a vinyl group and a silyl group can be used.

Further, examples of the compound represented by the general formula (1) include oligomers having an α-halostyrene unit. Examples of the oligomer having an α-halostyrene unit that can be used as an initiator / chain transfer agent include:
For example, an oligomer of α-chlorostyrene, an oligomer obtained by copolymerizing α-chlorostyrene and a monomer copolymerizable therewith, and the like can be mentioned.

The compound represented by the general formula (1) is not limited to these. These compounds may be used alone or in combination of two or more.

In the present invention, among the compounds represented by the general formula (1), a halogen atom, an R ⁴ COO— group (R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) or R ⁵ O- group (R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) those having two or more, or a halogen atom, R ⁴ COO- group or R ⁵ O- groups and other reactive functionalities The use of a compound having a group as an initiator and a chain transfer agent is very effective because the degree of functionalization of the resulting polymer can be increased.

Usually, as the specific compound represented by the above general formula (1), oligomers of α-chlorostyrene and the following compounds are used, but are not limited thereto.

[0027]

Embedded image [In the formula, X is a halogen atom, an R ⁴ COO— group (R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) or R
Represents a ⁵ O-group (R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ]

[0028]

Embedded image [In the formula, X is a halogen atom, an R ⁴ COO— group (R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) or R
Represents a ⁵ O-group (R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ]

Preferred among these compounds are the following compounds.

[0030]

Embedded image

[0031]

Embedded image

Further, the following compounds containing a CH ₃ COO— group are also preferable compounds.

[0033]

Embedded image

[0034]

Embedded image

Further, the following compounds containing a CH ₃ O-group are also preferable compounds.

[0036]

Embedded image

These compounds are components used as an initiator, and in the present invention, one kind or a mixture of two or more kinds is used. The number average molecular weight of the resulting isobutylene-based polymer can be arbitrarily set by adjusting the amounts of these compounds used.

In the present invention, the amount of the compound represented by the above general formula (1) is usually in the range of 0.01 to 20% by weight of the cationically polymerizable monomer containing isobutylene, preferably 0.1 to 0.2% by weight. It is in the range of 1 to 10% by weight.

The Lewis acid used as the cationic polymerization catalyst component has a general formula MXa (where M is a metal atom,
X is a halogen atom, a is an integer and is a valence of a metal atom), for example, BCl ₃ , AlC
l ₃ , SnCl ₄ , TiCl ₄ , VCl ₅ , FeC
l ₃ and BF _3, but are not limited thereto. Among these Lewis acids, TiCl ₄ , B
Cl ₃ , SnCl ₄ , BF _{3 and the} like are preferable, and TiCl ₄ is particularly preferable. The amount of the Lewis acid is 0.1 to 0.1 mol per mol of the initiator / chain transfer agent.
It is preferably 10 times, more preferably 2 to 5 times.

A hydroxyl group can be introduced into the terminal of the saturated hydrocarbon polymer having an alkenyl group introduced into the terminal obtained by the above method by a known method such as hydroboration.

The molecular weight of the polymer is 500 to 3
0000, but the number average molecular weight is 500
About 10,000 to about 10,000 are preferable, and especially 500 to 80
A viscous liquid having a fluidity of about 00 is preferable from the viewpoint of easy handling. If the number average molecular weight is less than 500, the elongation of the fiber will be reduced, and if it exceeds 30,000, the elongation and recovery of the fiber will be poor, which is not preferable.

The average functionality of the saturated hydrocarbon polymer having a terminal hydroxyl group used in the present invention is 1.5 to 1.5.
2.6, preferably 1.8 to 2.3. Here, "average functionality" means the average number of active hydrogen atoms per molecule. Such an active hydrogen atom is associated with a hydroxyl group in the case of a polyol. The average functionality is 1.5
If it is less than 1, the degree of polymerization of the polyurethane resin decreases, and the mechanical properties of the fiber tend to deteriorate. Conversely, if it exceeds 2.6, the crosslinking points increase during the polymerization of the polyurethane resin, and the spinning stability tends to decrease, and the mechanical properties and productivity of the fiber tend to decrease, which is not preferable.

In the present invention, as the polymer polyol, the above-mentioned saturated hydrocarbon polymer having a hydroxyl group at a terminal and another polymer polyol can be used in combination. However, it is preferable to use a saturated hydrocarbon polymer having a hydroxyl group at a terminal as a high molecular polyol in the polyurethane in an amount of 20% by weight or more. If it is less than 20% by weight, the light resistance, chlorine resistance and hot water resistance, which are the objects of the present invention, tend to decrease, which is not preferred.

Other high molecular polyols include dihydroxy polyesters, dihydroxy polycarbonates, dihydroxy polyethers and the like.

Examples of the dihydroxy polyesters include at least one of ethylene glycol, propylene glycol, 1,6-hexanediol, 1,4-butanediol, and neopentyl glycol, and succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid. Examples thereof include those obtained by reacting at least one of dicarboxylic acids such as acid, sebacic acid, β-methyladipic acid, and isophthalic acid.

Examples of the dihydroxy polycarbonates include polycaprolactone glycol.

Examples of the dihydroxy polyethers include polytetramethylene glycol, polyethylene glycol,
Polypropylene glycol and the like.

The organic polyisocyanate used in the present invention has at least two isocyanate groups in the molecule.
Known aliphatic, aromatic and alicyclic organic polyisocyanates. For example, organic diisocyanates include 4,4′-diphenylmethane diisocyanate, p
-Phenylene diisocyanate, toluylene diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane- Examples include 1,4-diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated methylene diphenyl diisocyanate, and the like.

As the organic triisocyanate, 3 mol / mol of trimethylolpropane or glycerin can be used.
and l tolylene diisocyanate.

Preferred organic isocyanates have a molecular weight of 2
It is a thing of 00-500, and 4,4'- diphenylmethane diisocyanate is especially preferable. These organic polyisocyanates may be used alone or as a mixture.

Examples of the chain extender used in the present invention include low molecular weight compounds having a molecular weight of 400 or less and having at least two hydrogen atoms capable of reacting with an isocyanate group, ie, polyhydric alcohols and polyamines. Can be

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, Examples include 1,12-dodecanediol, ethoxylated hydroquinone, 1,4-cyclohexanediol, trimethylolpropane, glycerin, sorbitol and the like. Preferred polyhydric alcohols have a molecular weight of 50 to 2
50 aliphatic diols.

As polyvalent amines, hydrazine, 1,1,
2-diaminoethane, 1,3-diaminopropane, 1,
4-diaminobutane, 1,5-diaminopentane, 1,
6-diaminohexane, 3,3′-dichloro-4,4 ′
-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane and the like. These chain extenders may be used alone or as a mixture.

The polyurethane resin used for the polyurethane elastic fiber of the present invention can be produced by a known method. For example, there is a so-called "one-shot" method in which a polymer polyol, an organic polyisocyanate, a chain extender and other additives are simultaneously mixed and reacted at a high temperature. Another method is a so-called "prepolymer" method in which a high molecular polyol is first reacted with an organic polyisocyanate to synthesize an isocyanate-terminated prepolymer, and then this prepolymer is reacted with a chain extender. Furthermore, it is also possible to use a variant of the above method, in which the chain extender is first reacted with the organic polyisocyanate and then the resulting product is reacted with the polymeric polyol. In the production of the polyurethane resin, a catalyst can be used if necessary.

The average molecular weight of the obtained polyurethane is generally 5,000 to 500,000, preferably 10,000 to 500,000.
It is in the range of 400,000. If it is smaller than 5000, the mechanical properties are poor, and if it is larger than 500,000, the spinnability is poor.

The polyurethane resin thus obtained can be fiberized by a known dry spinning method, wet spinning method, or melt spinning method. Among them, the melt spinning method is a preferable spinning method from the viewpoint of quality, production cost and environment.

At an appropriate stage of the resin production and spinning process, pigments, dyes,
Needless to say, additives such as fillers, lubricants, stabilizers, antioxidants, flame retardants, antistatic agents and surface treatment agents can be used as required.

[0058]

EXAMPLES The present invention will be specifically described below with reference to examples.
The present invention is not limited to the following embodiments.

(Production Example 1) A stirring vessel, a three-way cock, and a vacuum line were attached to a 1-liter pressure-resistant glass autoclave (polymerization vessel), and the polymerization vessel was heated at 100 ° C. for 1 hour while evacuating with a vacuum line. After drying to room temperature, the three-way cock was opened and the pressure in the polymerization vessel was returned to normal pressure with nitrogen. Then, while flowing nitrogen from one of the three-way cocks, methylene chloride 18 dried by molecular sieve treatment was added to the polymerization container using a syringe.
0 ml and 348 ml of n-hexane were introduced. Subsequently, a solution of 44.8 mmol of p-bis (α-chloroisopropyl) benzene (the following compound A) in 10 ml of methylene chloride was added.

[0060]

Embedded image

Next, 112.8 g of isobutylene dehydrated by passing through a column filled with barium oxide.
After connecting a liquefied gas sampling tube made of pressure-resistant glass with a needle valve enclosing the
It was immersed in a 0 ° C. dry ice-acetone bath and cooled for 1 hour while stirring the inside of the polymerization vessel. After cooling, the inside of the reactor was depressurized by a vacuum line, and then the needle valve was opened to introduce isobutylene from the pressure-resistant glass liquefied gas sampling tube into the polymerization vessel. Next, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks. After cooling for 1 hour with stirring, the polymerization vessel was kept at -70 ° C.

Next, 7.11 g of TiCl ₄ (37.5 m
mol) was added from a three-way cock using a syringe to initiate polymerization, and after 1 hour, 12.27 g (107.5 mmol) of allyltrimethylsilane was added.
After a further 8 hours of reaction, the catalyst was deactivated by pouring the reaction mixture into water. Thereafter, the organic layer was washed with pure water three times and then separated, and methylene chloride, n-hexane and allyltrimethylsilane were distilled off under reduced pressure to remove the isobutylene polymer having a double bond at the terminal.
18 g were obtained.

Next, 100 g of the isobutylene polymer having a double bond at the terminal was dissolved at 21 ° C. in 2 liters of dry THF. 9-borabicyclo [3.3.1] nonane (hereinafter abbreviated as "9-BBN") under an argon stream.
400 ml of a 0.5 mol THF solution of (9-B
The isobutylene polymer THF solution was added dropwise to the BN amount (20 mmol) at 21 ° C. in 37 minutes. 25 reaction solutions
C., and reacted at the same temperature for 5 hours. To the reaction solution, 266 ml of a 3N aqueous sodium hydroxide solution was added dropwise, followed by dropwise addition of 80 ml of a 30% aqueous hydrogen peroxide solution.
After the reaction solution was stirred at 25 ° C. for 14 hours, potassium carbonate 100
g was added. The reaction compound was concentrated under reduced pressure to 410 g,
3 L of n-hexane was added and dissolved. After sufficiently washing the organic layer with water, the solvent was distilled off under reduced pressure to obtain an isobutylene polymer having a terminal hydroxyl group.

(Production Example 2) The amount of compound A was 5.19 g.
(22.4 mmol), allyltrimethylsilane 6.1
110 g of an isobutylene polymer having a double bond at a terminal was obtained in the same manner as in Production Example 1 except that the amount was changed to 3 g (53.76 mmol).

Next, 100 g of the isobutylene polymer having a double bond at its terminal was dissolved in 2 liters of dry THF at 21 ° C. Under an argon stream, 0.5 of 9-BBN
The above isobutylene polymer THF solution was added dropwise to 200 ml of the mol THF solution (10 mmol in 9-BBN amount) at 21 ° C. in 37 minutes. The reaction solution was heated to 25 ° C. and reacted at the same temperature for 5 hours. 133 ml of a 3N aqueous sodium hydroxide solution was added dropwise to the reaction solution, followed by 30
Forty milliliters of aqueous hydrogen peroxide were added dropwise. After the reaction solution was stirred at 25 ° C. for 14 hours, 50 g of potassium carbonate was added. The reaction mixture was concentrated under reduced pressure to 410 g, and dissolved by adding 3 L of n-hexane. After sufficiently washing the organic layer with water, the solvent was distilled off under reduced pressure to obtain an isobutylene polymer having a terminal hydroxyl group.

Number average of the polymers obtained in Production Examples 1 and 2
Molecular weight Mn and molecular weight distribution (Mw / Mn: where Mw is heavy
Weight average molecular weight) was determined by the GPC method. Also 300M
Hz ¹Protons belonging to each structure by H-NMR analysis
(Protons derived from initiator: 6.5 to 7.5 ppm, poly
Proton from end of mer: 3-4 ppm) resonance signal
By measuring and comparing the strength of
(Fn: the number of hydroxyl groups per molecule). The result
It is shown in Table 1.

[0067]

[Table 1]

(Example 1) 21.2 parts by weight of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was equipped with a stirrer based on 100 parts by weight of the polyisobutylene polyol obtained in Production Example 1. Charge the reactor, 8
The reaction was carried out at 0 ° C. for 2 hours to obtain a prepolymer having an isocyanate at a terminal. Next, the prepolymer and 1,
4-Butanediol (hereinafter abbreviated as “BD”) was heated to 80 ° C., and a twin-screw extruder (at the tip) was heated by a metering pump so that the weight ratio of prepolymer / BD was 121.2 / 3.76. (Nozzle temperature: 200 ° C.), continuous melt polymerization was performed, and the produced polyurethane was extruded into water in the form of a strand, cut, and pelletized. This pellet was vacuum-dried at 90 ° C. for 24 hours, and a spinning temperature of 200 ° C. and a spinning speed of 100 were measured using a melt spinning machine having a single screw extruder.
A polyurethane elastic yarn of 50 denier was obtained at m / min.

Example 2 As in Example 1, Production Example 2
A prepolymer was obtained by using 100 parts by weight of the polyisobutylene polyol obtained in 1) and 21.2 parts by weight of MDI. Next, the prepolymer and the BD were each heated to 80 ° C.
To the prepolymer / B by weight ratio with a metering pump.
It is supplied to a twin-screw extruder (nozzle temperature at the tip is 200 ° C.) so that D = 121.2 / 5.76, continuous melt polymerization is performed, and the produced polyurethane is extruded into water in a strand form, cut and pelletized. did. This pellet was vacuum-dried at 90 ° C. for 24 hours, and the spinning temperature was 200 ° C. and the spinning speed was 100 m / mi using a melt spinning machine having a single screw extruder.
With n, a 50 denier polyurethane elastic yarn was obtained.

(Example 3) 21 parts by weight of MDI was charged into a reactor equipped with a stirrer based on 100 parts by weight of hydrogenated polyisoprene having a hydroxyl group at a terminal (trade name: Epole: manufactured by Idemitsu Petrochemical Co., Ltd.). For 2 hours to obtain a prepolymer having a terminal isocyanate. Next, the prepolymer and the BD were each heated to 80 ° C., and the prepolymer / BD = 1 in a weight ratio by a metering pump.
The mixture was supplied to a twin-screw extruder (tip temperature: 200 ° C.) so as to obtain 21 / 3.8, continuous melt polymerization was performed, and the produced polyurethane was extruded into water in a strand shape, cut and pelletized. The pellets were vacuum-dried at 90 ° C. for 24 hours, and 50 denier polyurethane elastic yarn was obtained at a spinning temperature of 200 ° C. and a spinning speed of 100 m / min using a melt spinning machine having a single screw extruder. The typical physical property values of Epole are as follows. (Idemitsu Petrochemical: from Epol technical data) Hydroxyl group content (meq / g) 0.90 Average molecular weight (VPO measurement) 2500

(Example 4) To 100 parts by weight of a hydrogenated polybutadiene having a hydroxyl group at a terminal (trade name: GI2000: manufactured by Nippon Soda Co., Ltd.), 26 parts by weight of MDI was charged into a reactor equipped with a stirrer, and heated at 80 ° C The reaction was carried out for 2 hours to obtain a prepolymer having an isocyanate at a terminal. Next, the prepolymer and the BD were each heated to 80 ° C., and the prepolymer / BD = 1 in a weight ratio by a metering pump.
The mixture was supplied to a twin-screw extruder (nozzle temperature at the tip of 200 ° C.) so that the ratio became 26 / 4.76, continuous melt polymerization was performed, and the produced polyurethane was extruded into water in a strand shape, cut and pelletized. The pellets were vacuum-dried at 90 ° C. for 24 hours and, using a melt spinning machine having a single screw extruder,
A 50 denier polyurethane elastic yarn was obtained at a spinning temperature of 200 ° C and a spinning speed of 100 m / min. GI2000
Are as follows. (Nippon Soda: NIS
From SO-PB technical data. ) Hydroxyl value (KOHmg / g) 47.9 Iodine value (amount of iodine absorbed by 100 g of polymer) 11.4 Average molecular weight 2100

Example 5 100 parts by weight of a hydrogenated polybutadiene having a hydroxyl group at a terminal (KLP L2203: manufactured by Shell Japan KK) was added to 100 parts by weight of MDI.
3.1 parts by weight was charged into a reactor equipped with a stirrer and reacted at 80 ° C. for 2 hours to obtain a prepolymer having an isocyanate at a terminal. Next, each of the prepolymer and the BD was heated to 80 ° C., and a twin-screw extruder (nozzle temperature at the tip was 200 ° C.) by a metering pump so that the weight ratio of the prepolymer / BD became 123.1 / 5.14. The resulting polyurethane was extruded into water in the form of a strand, cut and pelletized. The pellets were vacuum-dried at 90 ° C. for 24 hours, and a spinning temperature of 200 ° C. and a spinning speed of 10 were measured using a melt spinning machine having a single screw extruder.
A polyurethane elastic yarn of 50 denier was obtained at 0 m / min. The representative physical properties of KLP L2203 are as follows. (Shell Japan: KRATON LIQUI
From D technical data. ) Hydroxyl group content (pieces / molecule) 1.92 average molecular weight (Mw) 3200

Example 6 50 parts by weight of the polyisobutylene polyol obtained in Production Example 1 and 50 parts by weight of polycaprolactone (molecular weight: 2,000) were added to 23.
6 parts by weight were charged into a reactor equipped with a stirrer and reacted at 80 ° C. for 2 hours to obtain a prepolymer having an isocyanate at a terminal. Next, this prepolymer and BD were each treated with 8
The mixture was heated to 0 ° C., fed to a twin-screw extruder (nozzle temperature at the tip of 200 ° C.) by a metering pump so that the weight ratio became prepolymer / BD = 123.6 / 4.25, and continuous melt polymerization was performed. The resulting polyurethane was extruded into water in the form of a strand, cut and pelletized. 90 pellets
C. for 24 hours under vacuum, and using a melt spinning machine having a single screw extruder, a spinning temperature of 200.degree.
In 50 minutes, a polyurethane elastic yarn of 50 denier was obtained.

Example 7 30 parts by weight of the polyisobutylene polyol obtained in Production Example 1 and 70 parts by weight of polytetramethylene glycol (molecular weight: 2,000) were mixed with MDI.
Was charged into a reactor equipped with a stirrer and charged at 80 ° C.
For 2 hours to obtain a prepolymer having a terminal isocyanate. Next, the prepolymer and the BD were heated to 80 ° C., respectively, and a twin-screw extruder (nozzle temperature at the tip was 200 ° C.) by a metering pump so that the weight ratio of the prepolymer / BD was 125.8 / 4.9. The resulting polyurethane was extruded into water in the form of a strand, cut and pelletized. The pellets were vacuum-dried at 90 ° C. for 24 hours, and a spinning temperature of 200 ° C. and a spinning speed of 10 were measured using a melt spinning machine having a single screw extruder.
A polyurethane elastic yarn of 50 denier was obtained at 0 m / min.

(Comparative Example 1) 100 parts by weight of polytetramethylene ether glycol (molecular weight: 2,000)
Charge 26 parts by weight of DI into a reactor equipped with a stirrer,
For 2 hours to obtain a prepolymer having a terminal isocyanate. Next, the prepolymer and the BD were heated to 80 ° C., respectively, and supplied to a twin-screw extruder (tip nozzle temperature: 200 ° C.) by a metering pump so that the weight ratio of the prepolymer / BD was 126 / 4.7. Then, continuous melt polymerization was performed, and the resulting polyurethane was extruded into water in a strand shape, cut, and pelletized. This pellet is 9
Vacuum dried at 0 ° C. for 24 hours, using a melt spinning machine having a single screw extruder, a spinning temperature of 200 ° C. and a spinning speed of 100 m.
/ Min yielded a 50 denier polyurethane elastic yarn.

(Comparative Example 2) With respect to 100 parts by weight of polycaprolactone (molecular weight: 2,000), 26 parts by weight of MDI was charged into a reactor equipped with a stirrer and reacted at 80 ° C. for 2 hours to obtain a prepolymer having an isocyanate terminal at the end. Obtained. Next, the prepolymer and the BD were each heated to 80 ° C., and the prepolymer / BD = 1 in a weight ratio by a metering pump.
The mixture was supplied to a twin-screw extruder (nozzle temperature at the tip of 200 ° C.) so as to obtain a ratio of 26 / 4.7, and continuous melt polymerization was performed. The resulting polyurethane was extruded into water in a strand shape, cut and pelletized. The pellets were vacuum-dried at 90 ° C. for 24 hours, and 50 denier polyurethane elastic yarn was obtained at a spinning temperature of 200 ° C. and a spinning speed of 100 m / min using a melt spinning machine having a single screw extruder.

Table 2 shows the characteristics of the saturated hydrocarbon polymers having a hydroxyl group at the terminal used in Examples and Comparative Examples.

[0078]

[Table 2]

Further, the elastic yarns obtained in Examples and Comparative Examples were evaluated by the following methods. (Tensile strength of fiber) The obtained filament was measured by a chemical fiber filament test method (JIS L-1013). (Light Resistance Test) The obtained elastic yarn was carbon arc 68
Irradiation was conducted for 40 hours under the condition of ° C., and the tensile strength and elongation before and after the irradiation were measured, and evaluated by the retention. (Heat-resistant water (boiling water) resistance test) The obtained elastic yarn was immersed in boiling water for 12 hours, the tensile strength and elongation before and after the treatment were measured, and the retention was evaluated. (Chlorine resistance test) The obtained elastic yarn was immersed in a 2% aqueous solution of sodium hypochlorite at 25 ° C for 72 hours, the tensile strength and elongation before and after the treatment were measured, and the retention was evaluated. . Table 3 shows the evaluation results.

[0080]

[Table 3]

As is clear from Table 3, in Examples using a saturated hydrocarbon polymer having a hydroxyl group at a terminal, which is a feature of the present invention, light resistance, chlorine resistance and hot water resistance are extremely excellent. You can see that. Conversely, in Comparative Examples in which no saturated hydrocarbon polymer having a hydroxyl group at the terminal was used, it was found that light resistance, chlorine resistance, and hot water resistance were very poor.

[0082]

As described above, according to the present invention, it is possible to provide a polyurethane elastic fiber having extremely excellent durability such as light resistance, chlorine resistance and hot water resistance. That is, it is achieved by melt-spinning a polyurethane resin obtained by polymerizing a saturated hydrocarbon polymer having a hydroxyl group at a terminal, an organic polyisocyanate and a chain extender. Thus, the present invention can be applied to fields that have not been used because of poor durability in the past, or where the market has not expanded.

Claims (7)

[Claims] 1. A polyurethane elastic fiber characterized by using a saturated hydrocarbon polymer having a hydroxyl group at a terminal as a high molecular polyol. 2. The polyurethane-based elastic fiber according to claim 1, wherein the polyurethane contains at least 20% by weight of a saturated hydrocarbon polymer having a hydroxyl group at a terminal. 3. The polyurethane-based elastic fiber according to claim 1, wherein the saturated hydrocarbon polymer having a hydroxyl group at a terminal has an average molecular weight of 500 to 8,000. 4. The polyurethane system according to claim 1, wherein the saturated hydrocarbon polymer having a hydroxyl group at the terminal has an average functionality of 1.5 to 2.6. Elastic fiber. 5. The polyurethane elastic fiber according to claim 1, wherein the main skeleton of the saturated hydrocarbon polymer having a hydroxyl group at a terminal is polyisobutylene. 6. The polyurethane-based elastic fiber according to claim 1, wherein the main skeleton of the saturated hydrocarbon polymer having a hydroxyl group at the terminal is hydrogenated polybutadiene. 7. The polyurethane-based elastic fiber according to claim 1, wherein the main skeleton of the saturated hydrocarbon polymer having a hydroxyl group at the terminal is hydrogenated polyisoprene.