JP3108530B2 - Method for producing dyed polyurethane fibers or textile products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dyed polyurethane fiber or a fiber product comprising the same and a method for producing the same. More specifically, light fastness, color fastness, NO _x
The present invention relates to a dyed product of a polyurethane fiber or a fiber product particularly excellent in gas property and fastness to chlorine and a method for producing the same.

[0002]

2. Description of the Related Art Due to its excellent elasticity, polyurethane fibers are widely used as sports materials such as swimwear and ski wear, medical materials such as underwear, stockings, elastic bandages, etc. by being mixed with other fibers. I have. However,
Polyurethane fibers are difficult to dye evenly in a skein or cheese shape, and are used without dyeing in the case of the first dyeing method. In that case, when fabrics such as knitted fabrics are manufactured by mixing such undyed polyurethane fibers with pre-dyed polyester fibers or other fibers, the undyed polyurethane fibers are stretched when the fabric is stretched. A so-called slimming phenomenon that looks white appears, and the commercial value becomes extremely low.

[0003] In view of the above, polyurethane fibers are generally dyed after knitted fabric or the like, but in this case, polyurethane fibers are not sufficiently dyed with a dye other than the disperse dye. However, when a polyurethane fiber is deeply dyed at a high temperature and a high pressure of, for example, 120 to 130 ° C. using a disperse dye, the dyeing fastness of the polyurethane fiber, particularly, the dyeing fastness to light becomes poor and cannot be put to practical use. In practice, the dyeing of polyurethane fibers with disperse dyes is actually limited to light color dyeing under normal pressure (for example,
Japanese Patent Publication No. 140137/1992), a dyed polyurethane fiber which is dyed in a deep color and has excellent color fastness has not been obtained.

[0004]

An object of the present invention is to provide a polyurethane fiber which, when dyed with a disperse dye, has excellent color fastness, especially light fastness, and is dyed in any color from dark to light. Or to obtain a dyed product of a textile product comprising the same.

[0005]

The inventors of the present invention have continued their research to solve the above-mentioned problems. As a result, the polyurethane fiber is composed of a polyester polyurethane based on a specific polyester diol and has a specific hindered amine in the polyurethane. The above-mentioned problems are solved by using a fiber comprising a polyurethane compound blended with a phenolic compound, a hindered phenolic compound, and, if desired, a specific benzophenone-based compound. The present invention was completed by finding that a polyurethane fiber dyed to a desired color tone and a dyed product of a fiber product comprising the same could be obtained.

That is, the present invention relates to a method for producing a dyed polyurethane fiber or a fiber product comprising the same, wherein (i) the polyurethane constituting the fiber or the fiber product has the following formula (I):

[0007]

Embedded image (Wherein, R ¹ has a carbon number of 6 to 1 having one methyl branch)
An alkylene group of 0 and R ² represent a divalent organic group), with an organic diisocyanate and, if necessary, a chain extender with a polymer diol mainly composed of a polyester diol mainly composed of a unit represented by the following formula: And (ii) in the polyurethane, (a) the following formula (II);

[0008]

Embedded image (Wherein, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group) and a hindered amine compound having at least one group containing a piperidine ring and having a molecular weight of 1,000 or more, (b ) Formula (III) below;

[0009]

Embedded image (Wherein R ⁷ and R ⁸ each independently represent an alkyl group). A hindered phenol compound having a molecular weight of 500 or more and having at least one dialkylhydroxyphenyl group represented by the following formula (C): Equation (I
V);

[0010]

Embedded image A benzophenone-based compound having at least one benzoylhydroxyphenyl group and a molecular weight of 10,000 or more, and (iii) dyeing the polyurethane fiber or textile product with a disperse dye. A method for producing a dyed polyurethane fiber or a fiber product comprising the same. The present invention further includes a polyurethane fiber dyed with the disperse dye obtained by the above method or a fiber product comprising the same.

In the present invention, the term "polyurethane fiber or a fiber product comprising the same" refers to the polyurethane fiber itself, a yarn, a cloth, a semi-finished product, a final product (eg, clothing, underwear, pantyhose, etc.) obtained by using the fiber. Etc.). Polyurethane fibers and textile products composed thereof may be those formed solely of polyurethane, or natural fibers such as cotton, hemp, wool and silk and / or synthetic resins such as polyester, polyamide, polyolefin, acrylic and polyvinyl alcohol. Or composite or mixed with synthetic fibers,
In short, any fiber or fiber product in which at least a part of the fiber or the fiber product is formed of polyurethane is included.

In the present invention, the polyurethane constituting the fiber and the fiber product is obtained by adding a polymer diol mainly composed of a polyester diol mainly composed of the unit represented by the above formula (I) to an organic diisocyanate and, if necessary, an organic diisocyanate. It must be a polyurethane obtained by reacting a chain extender. Here, the “polyester diol mainly composed of the unit represented by the formula (I)” means that at least 50 mol%, preferably at least 70 mol% of the repeating units constituting the polyester diol are represented by the formula (I). Means that the unit is

Further, in the present invention, the above-mentioned polyester diol mainly comprising the unit represented by the formula (I) is
It is desirable that the polyester diol satisfies the following formulas 1 and 2.

[0014]

## EQU1 ## 6 ≦ Cn / En ≦ 10

[0015]

Where, in the above formulas (1) and (2), Cn is the number of carbon atoms contained in the ester bond (-COO-) from the total number of carbon atoms constituting the polyesterdiol molecule. En = total number of ester bonds (—COO—) contained in the polyesterdiol molecule Mn = total number of methine groups contained in the polyesterdiol molecule [where the methine group is represented by the following formula (V): Group)

[0016]

Embedded image (Wherein, and, mean a bond bonded to another carbon atom)

When a polyester diol satisfying the above formula (1) is used, the hot water resistance, cold resistance and elastic recovery of the polyurethane obtained therefrom become particularly good. Further, when a polyester diol satisfying the above formula 2 is used, the heat resistance and elastic recovery of the polyurethane obtained therefrom also become good. In particular, it is more preferable to use a polyester diol in which the value of Expression 2 is in the range of 0.03 to 0.10.

[0018] The alkylene group R ¹ having 6 to 10 carbon atoms having one methyl group in the unit of formula (I), 2- or 3-methyl pentamethylene group, 2-
Or 3-methylhexamethylene group, 2-, 3- or 4-methylheptamethylene group, or 2-, 3- or 4-methyloctamethylene group, and among them, 3-methylpentamethylene group and The 4-methylheptamethylene group is preferred in terms of hot water resistance and cold resistance of the polyurethane fiber obtained.

Examples of the divalent organic group R ² include a divalent aliphatic group, an alicyclic group and an aromatic group. The organic group R ² is a divalent group having 4 to 12 carbon atoms. Is preferred. Preferred examples of the group R ² include a tetramethylene group, a pentamethylene group, a hexamethylene group,
Examples thereof include an alkylene group having 4 to 12 carbon atoms such as a heptamethylene group, an octamethylene group, and a decamethylene group; and an arylene group having 6 to 12 carbon atoms such as a phenylene group and a naphthylene group.

The polyester diol described above has the formula: H
A diol represented by the formula: O—R ¹ —OH (wherein R ¹ is the group described above); and HOOC—R ² —COOH (where R ^{2 is}
Is a group described above), and optionally a small amount of other copolymerization components (e.g., ethylene glycol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
Together with 10-decanediol) in a manner known per se, followed by polycondensation.

In particular, 3-methyl-
A linear fatty acid having 9 to 12 carbon atoms such as azelaic acid, sebacic acid and 1,10-decanedicarboxylic acid as a dicarboxylic acid component using a diol containing 1,5-pentanediol in an amount of 50 mol% or more. When using a polyester diol obtained using an aromatic dicarboxylic acid,
Even at a low temperature of −10 ° C., a polyurethane excellent in elastic recovery can be obtained.

In the present invention, it is preferable that 50% by weight or more, especially 80% by weight or more of the high molecular weight diol used for producing the polyurethane is composed of the above-mentioned polyester diol, whereby the light fastness is improved. In addition, fibers and fiber products having excellent color fastness can be obtained. Examples of other polymer diols that can be used in combination with the polyester diol described above include polyester diols other than those described above, polycarbonate diols,
Examples thereof include polyether diols and polyether ester diols. These other high molecular diols are preferably used in a proportion of 50% by weight or less, particularly preferably 20% by weight or less.

The high molecular weight diol used in the present invention, including the polyester diol mainly composed of the unit represented by the above formula (I) and other high molecular weight diols which can be used together as required, are all average molecular weights. Molecular weight 1000-3
It is preferably in the range of 500, especially 1500 to 3000. When the average molecular weight of the high molecular diol is smaller than 1000, the elastic recovery, heat resistance, hot water resistance and cold resistance of the obtained polyurethane decrease, while when it is higher than 3500, the elastic recovery, spinning stability and strength of the polyurethane are reduced. descend.

The polyurethane constituting the fiber and the fiber product of the present invention is obtained by reacting the above-mentioned polyester diol and optionally other polymer diol with an organic diisocyanate and optionally a chain extender and other components. It can be manufactured by doing.

The organic diisocyanate includes, but is not limited to, for example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,5
-A molecular weight of 500 such as naphthalene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate
The following organic diisocyanates may be mentioned, and these organic diisocyanates may be used alone or in combination of two or more. Particularly, organic diisocyanates having a molecular weight of 500 or less such as 4,4'-diphenylmethane diisocyanate It is preferred to use

As the chain extender, a low molecular weight compound having two active hydrogen atoms capable of reacting with an isocyanate group is preferably used. For example, ethylene glycol, propylene glycol, 1,4-butanediol, , 6
-Hexanediol, 1,9-nonanediol, 1,4
-Bis (β-hydroxyethoxy) benzene, 1,4-
Diols such as cyclohexanediol and xylylene glycol, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, 4,4′-diaminodiphenylmethane, tolylenediamine, 4,4 ′
And diamines such as diaminodicyclohexylmethane, and these chain extenders may be used alone or in combination.
More than one species can be used. Among them, diols having a molecular weight of 400 or less such as 1,4-butanediol and 1,4-bis (β-hydroxyethoxy) benzene are particularly preferable.

Particularly, as organic diisocyanate, 4,
Using 4′-diphenylmethane diisocyanate and 1,4-butanediol and / or 1,4-bis (β-hydroxyethoxy) benzene as a chain extender, reacting these with the above-mentioned polyester diol. Polyurethane fibers obtained are desirable because of their excellent heat resistance, elastic recovery and elongation.

In the production of polyurethane, it is possible to use both such that the molar ratio of organic diisocyanate: polymer diol is in the range of 1.5: 1 to 4.5: 1. It is preferable from the viewpoints of elastic recovery, heat resistance and cold resistance of the polyurethane fiber. Also,
At that time, the organic diisocyanate: (polymer diol +
Chain extender) in a molar ratio of 0.95: 1 to 1
When the ratio is in the range of 1.15: 1, the heat resistance, elastic recovery and elongation of the obtained polyurethane fiber are improved, which is desirable.

In producing the polyurethane used in the present invention, various known methods and apparatuses of a batch type or a continuous type can be employed. In particular, it is preferable to carry out the polymerization of the polyurethane in a molten state substantially in the absence of a solvent, and it is more preferable to carry out the continuous melt polymerization using an extruder such as a multi-screw type. The temperature at this time is not particularly limited, but it is usually preferable to perform the reaction in the range of about 200 to 260 ° C. By maintaining the temperature during polymerization at 260 ° C. or lower, the heat resistance and mechanical properties of the polyurethane are improved,
On the other hand, by maintaining the temperature at 200 ° C. or higher, a thermoplastic polyurethane having excellent melt spinnability can be produced.

In the present invention, the above-mentioned polyurethane constituting the fiber comprises a hindered amine compound (a) represented by the above formula (II) and a hindered phenol compound (b) represented by the above formula (III) And optionally a benzophenone-based compound (c) represented by the above formula (IV). The polyurethane is a hindered amine compound (a) and a hindered phenol compound (b), or the benzophenone compound (c) together with two of those compounds.
By containing the, even when the deep dyeing a textile consisting of polyurethane fibers and thereby disperse dyes, dyeing fastness, particularly good dyeing fastness to light, yet resistant NO _X gas resistance, salt Motokei Polyurethane fibers and fiber products excellent in various performances such as chemical resistance, weather resistance, and organic solvent resistance can be obtained.

The polyurethane fiber and the fiber product of the present invention contain the hindered amine compound (a) and the hindered phenol compound (b) in an amount of 0.05 to 0.8% by weight based on the weight of the polyurethane. It is desirable to contain. Each less and the dyeing fastness and light fastness is not sufficient than 0.05 wt%, liable to discoloration or fading by chemicals such as organic solvents and chlorine bleach, further light resistance and NO _X gas resistance Will also be lower. On the other hand, each is 0.
If the content is more than 8% by weight, cloudiness of polyurethane and bleed-out of those compounds are liable to occur.

When the benzophenone compound (c) is further contained, the benzophenone compound (c) is added based on the weight of the polyurethane.
Again, it is desirably 0.05 to 0.8% by weight. By including the benzophenone-based compound (c) at such a ratio, the color fastness and light fastness of polyurethane fibers and fiber products are further improved.

The above hindered amine compound (a)
May be any as long as it has a molecular weight of 1000 or more and has at least one group containing a piperidine ring represented by the above formula (II) in the molecule. When the molecular weight of the hindered amine compound (a) is 1,000 or more, bleed out to the surface of the polyurethane fiber can be prevented. The molecular weight of the hindered amine compound (a) is preferably in the range of 1,000 to 5,000. Representative examples of the hindered amine compound (a) include the following formula (VI):

[0034]

Embedded image (Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are the same as above;
R ⁹ is a direct bond or a divalent group, A and B are each a monovalent group, and m is a number of 1 or more.
Can be mentioned.

The group represented by the above formula (II) and the group represented by the formula (V
In the compound represented by I), R ³ , R ⁴ , R ⁵ and R
⁶ is preferably a lower alkyl group having 1 to 4 carbon atoms, and particularly preferably all of the 4 alkyl groups are methyl groups.

In the compound represented by the formula (VI), when R ⁹ is a divalent group, a divalent hydrocarbon group such as an alkylene group or an arylene group, or an ester bond, an ether bond or a thioether bond Having an amide bond or the like
Can be a valence group. Also, but not limited to, one or both of A and B may have an isocyanate-reactive active hydrogen atom, such as an amino group,
When it is a hydroxyl group, a carboxyl group, or another monovalent group having a hydroxyl group, an amino group or a carboxyl group (for example, an aminomethyl group, a hydroxymethyl group, an aminoethyl group, etc.), the isocyanate group contained in the polyurethane The reaction allows the hindered amine compound (a) to be chemically bonded and contained in the polyurethane, thereby further improving the bleed-out resistance. In the compound of the formula (VI), m
Is 4 or more, the molecular weight is often 1000 or more, and m is preferably 4 to 20.

In the present invention, when the above-mentioned compound having an isocyanate-reactive active hydrogen atom is used as the hindered amine compound (a) and is added before the completion of the polyurethane production reaction, the hindered amine compound (a) Having a high molecular weight of 1000 or more, the number of moles added can be kept low with respect to the added amount. As a result, the rate of the terminal termination reaction during the polyurethane production reaction can be reduced, and the molecular weight of the polyurethane is increased. be able to.

[0038] In the compounds represented by formula (VI), group R ⁹ has the formula _{;-( CH 2) p-O-} CO- (CH 2) q-C
It is preferably a group represented by OO- (wherein p and q each represent an integer of 2 to 4). Specific examples of such a hindered amine compound (a) include the following formula (VI)
I);

[0039]

Embedded image (Wherein, n preferably represents a number of 4 to 20). The compound represented by the formula (VII) can be produced, for example, by a polycondensation reaction between dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine. it can.

Next, the hindered phenol compound (b) is a compound having at least one dialkylhydroxyphenyl group represented by the above formula (III) in the molecule and having a molecular weight of 500 or more. Any may be used. Among them, those in which R ⁷ and R ⁸ in the dialkylhydroxyphenyl group of the above formula (III) are each a methyl, ethyl, propyl or t-butyl group are more preferred.

Although not limited, preferred specific examples of the hindered phenolic compound (b) include, for example, a good color tone of the polyurethane fiber after the compounding of the hindered phenolic compound (b). , The following formula (VIII):

[0042]

Embedded image 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,1
0-tetraoxaspiro [5.5] undecane, further tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane;
Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate].

The benzophenone-based compound (c) to be added as desired may be a compound having at least one benzoylhydroxyphenyl group represented by the above formula (IV) in the molecule and having a molecular weight of 10,000 or more. Any may be used. When the molecular weight of the benzophenone-based compound (c) is less than 10,000, it easily bleeds out to the surface of the polyurethane fiber, and is easily lost from the polyurethane fiber or fiber product over time by dry cleaning treatment. The molecular weight of the benzophenone-based compound (c) is preferably in the range of about 20,000 to 40,000 because the bleed-out phenomenon can be further suppressed and the effect can be exhibited for a long period of time.

Among the benzophenone compounds (c), the benzoylhydroxyphenyl group represented by the above formula (IV) has the following formula (IX):

[0045]

Embedded image (Wherein R ¹⁰ represents an alkylene group) a benzophenone-based compound which is present in the form of a monovalent group represented by the formula (IX), particularly, R ¹⁰ in the monovalent group represented by the formula (IX) Benzophenone-based compounds (c) which are 1-4 alkylene groups are preferred.

Although not limited, preferred specific examples of the benzophenone-based compound (c) include the following formula (X):

[0047]

Embedded image Wherein n ₁ and n ₂ are numbers such that n ₁ + n ₂ ≧ 35 and n ₂ / (n ₁ + n ₂ ) ≧ 0.2. -(Methacryloyloxyethoxy) benzophenone / methyl methacrylate copolymer.

The timing of adding the hindered amine compound (a), the hindered phenol compound (b) and the optionally added benzophenone compound (c) to the polyurethane is not particularly limited. Either may be later. In general, it is desirable to melt and add the polyurethane after the production of the polyurethane, since the above-mentioned effects such as light resistance are increased. When it is added after production, it can be added at the time of producing polyurethane pellets or at any stage of producing fibers from polyurethane. The above-mentioned compounds (a) and (b) or (a) to (c) may be added simultaneously or sequentially, and when added sequentially, the order of addition may be any.

In producing the polyurethane fiber of the present invention, other polymers, catalysts, activators, other stabilizers, coloring agents such as dyes and pigments, fillers, and flame retardants commonly used in the art are used. Arbitrary components such as a lubricant and the like can be used as needed.

In producing polyurethane fibers from the above-mentioned polyurethane blended with a hindered amine compound (a), a hindered phenol compound (b) and, if desired, a benzophenone compound (c), for example, a melt spinning method or a dry spinning method Any method such as a wet spinning method can be employed, and a melt spinning method using no solvent or water is particularly preferable.

In the present invention, the polyurethane fiber obtained as described above or a fiber product comprising the same is dyed with a disperse dye. For dyeing, any of dyes, dye baths, dyeing methods, dyeing conditions, dyeing equipment, post-treatment methods and the like which are usually used when dyeing polyurethane fibers or fiber products with a disperse dye can be used. Dyeing can be performed by directly dyeing the polyurethane fiber obtained by spinning with a disperse dye, or by mixing the polyurethane fiber with other fibers as necessary, yarns, knitted fabrics, clothing, and underwear. , Stockings and the like, and the products may be dyed with a disperse dye.

Before dyeing the polyurethane fiber obtained by the melt-spinning method or the like, the transition from a temperature 50 ° C. lower than the glass transition temperature of the hard segment (segment based on the chain extender) in the polyurethane under low humidity. Preliminarily performing heat treatment at a temperature within a range of 20 ° C. higher than the temperature is preferable because the elastic recovery rate of the polyurethane fiber can be improved.

As described above, the conditions for dyeing with a disperse dye are not particularly limited.
It is preferable to employ a high-temperature and high-pressure dyeing method of 0 ° C. or more, particularly 110 ° C. or more, whereby polyurethane fibers and fiber products which are deeply dyed and have extremely good dyeing fastness can be obtained.

The type of the disperse dye used in the present invention is not particularly limited, and examples thereof include an aminoazo disperse dye, a quinone disperse dye, and a nitroarylamine disperse dye. Karon Red E-RPD (Sumikaron Red RPD) (manufactured by Sumitomo Chemical Co., Ltd.)] and the like. In dyeing, if the content of the disperse dye in the polyurethane fiber is in the range of 0.01 to 0.6% by weight based on the weight of the polyurethane, it is sufficient without deteriorating the mechanical properties of the polyurethane fiber. It is preferable because it can be dyed. After dyeing with a disperse dye, reduction washing is preferably performed to promote fixing of the dye.

[0055]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited thereto. Parts in the following examples represent parts by weight. Further, in the example below,
Before and after solvent extraction treatment of polyurethane fiber before dyeing, light resistance strength retention rate, NO _x gas resistance, and content of disperse dye of polyurethane fiber knitted fabric after dyeing, polyurethane fiber knitted fabric after dyeing The light fastness and the chlorine fastness before and after the solvent extraction treatment were measured or evaluated by the following methods.

<< Measurement of Light-Resistance Strength Retention Ratio of Polyurethane Fiber Before Dyeing Before Solvent Extraction Treatment >> The undyed polyurethane fiber (40 denier) produced in each of the following examples was 5/1.
In a state of being wound on a frame under a tension of 000 g / denier, a carbon arc type fade meter FA manufactured by Suga Test Instruments Co., Ltd.
UV irradiation was performed for 20 hours at a temperature of 83 ° C. using an L-5 type, and the strength retention was calculated from the following Equation 3.

[0057]

## EQU3 ## Intensity retention (%) = (strength after UV irradiation / strength before UV irradiation) × 100

<< Measurement of Light-Resistant Strength Retention Rate of Polyurethane Fiber Before Dyeing After Solvent Extraction Treatment >> The undyed polyurethane fiber (40 denier) produced in each of the following examples was 5/1.
After being immersed in a park ratio of 1: 1000 at 70 ° C. for 5 hours and dried at 50 ° C. for 1 hour under a tension of 000 g / denier, the carbon arc type fade meter manufactured by Suga Test Instruments Co., Ltd. 83 ° C using FAL-5 type
At 20 ° C. for 20 hours, and the intensity retention was calculated from the above equation (3).

<< Test of NO _x resistance of polyurethane fiber before dyeing >> The polyurethane fiber (40 denier) before dyeing produced in each of the following examples was subjected to air for 1 hour in air in which the NO ₂ gas concentration was increased to 650 ppm. After processing, the strength before and after this was measured, and the strength retention was calculated by the following equation (4).

[0060]

## EQU4 ## Strength retention (%) = (Strength after NO ₂ gas treatment / N
(Strength before O ₂ gas treatment) × 100

<< Measurement of Disperse Dye Content of Knitted Fabric of Polyurethane Fiber after Dyeing >> The maximum absorbance of the dyeing solution before and after dyeing was measured with a spectrophotometer, and the content of the disperse dye was calculated by the following formula 5. did.

[0062]

## EQU5 ## Disperse dye content (% by weight) = (Wd / Wpu) .times. (1
−Ad / Ao) × 100 where Wd = weight of the dye in the initial dyeing solution Wpu = weight of the polyurethane constituting the knitted fabric Ad = maximum absorbance of the dyeing solution after dyeing Ao = maximum absorbance of the initial dyeing solution

<Evaluation of light fastness of dyed polyurethane fiber knitted fabric before solvent extraction treatment> The dyed polyurethane knitted fabrics manufactured in the following examples were subjected to JIS L-08.
The light fastness was determined according to 42 "Carbon Arc Third Exposure Method".

<Evaluation of light fastness of dyed polyurethane fiber knitted fabric after solvent extraction treatment> The dyed polyurethane knitted fabrics manufactured in the following examples were subjected to a bath ratio of 1: 1000 at 70%.
C. for 5 hours, and then dried at 50.degree. C. for 1 hour. The light fastness was determined according to JIS L-0842 "Carbon Arc Third Exposure Method".

<< Evaluation of chlorine fastness of dyed polyurethane fiber knitted fabric >> Chloride fastness of dyed polyurethane knitted fabrics manufactured in the following examples according to JIS L-0856 "Strong test method". I asked.

The compounds used in each example are shown in Table 1 below.
Are represented by the abbreviations shown below.

[0067]

[Table 1]

<Examples 1 to 6> 80 ° C. containing the polymer diols and BDs shown in Table 4 below in the proportions shown in Table 4
The mixture heated to 50 ° C. and the MDI heated to 50 ° C. are continuously supplied to a twin-screw extruder by means of a metering pump, and while the various compounds shown in Table 4 are mixed in the middle of the cylinder at the ratio shown in Table 4. Continuous melt polymerization was carried out, and the obtained polyurethane composition was extruded into water in a strand shape and cut to produce polyurethane pellets.

The above pellets were vacuum dried at 80 ° C. for 20 hours and spun at a spinning temperature of 230 ° C. and a spinning speed of 500 m / min using a straight oil at a spinning machine of a single screw extruder.
A polyurethane fiber of 40 denier / 2 filaments was obtained. This fiber was aged at 80 ° C. for 48 hours. Light resistance strength retention rate before and after the solvent extraction process and resistance to NO _X gas resistance of the polyurethane fibers before dyeing obtained in the above were measured by the aforementioned method. The results are shown in Table 5 below.

Next, the polyurethane fiber obtained above was knitted with a 20-gauge tubular knitting machine, dyed under the dyeing conditions shown in Table 2 below, and then reduced and washed under the reducing washing conditions shown in Table 3 below. To prepare a knitted fabric made of polyurethane fibers dyed with a disperse dye.

[0071]

[Table 2]

[0072]

[Table 3]

The content of the disperse dye, the light fastness and the light fastness before and after the solvent extraction treatment of the knitted fabric made of polyurethane fiber obtained above were measured or evaluated by the methods described above. The results are shown in Table 5 below.

Comparative Examples 1 to 7 As shown in Table 4 below, except that polymer diol, MDI and BD were used, and the types and amounts of various compounds were changed as shown in Table 4, In the same manner as in Examples 1 to 8, a polyurethane fiber and a knitted article comprising the same were produced and dyed. Various properties were measured or evaluated in the same manner as in Examples 1 to 8. The results are shown in Table 5 below.

[0075]

[Table 4]

[0076]

[Table 5]

From the results shown in Table 5, the polymer diol mainly composed of the polyester diol represented by the above formula (I) was reacted with an organic diisocyanate and, if necessary, a chain extender to obtain a polymer diol. The polyurethane fibers of Examples 1 to 8 obtained by blending the above-mentioned hindered amine compound (a), hindered phenol compound (b) and optionally benzophenone compound (c) in the obtained polyurethane, and the polyurethane fibers obtained therefrom. was textiles, light resistance and excellent resistance to NO _X gas resistance, yet be capable of deeply stained by disperse dyes, are excellent in fastness properties and salt-containing fastness after dyeing. In contrast, polyurethanes based on polyester diols which do not contain the compounds (a) and (b) at all, lack one of them or do not contain the units of the formula (I) Comparative Example 1 using
7-polyurethane fiber and knitting made therefrom are inferior in light resistance and / or resistance to NO _X gas resistance, yet when deeply stained by disperse dye, it can be seen that less dye fastness and salt-containing fastness after dyeing .

[0078]

According to the present invention, a polyurethane obtained by reacting an organic diisocyanate and, if necessary, a chain extender with a polymer diol having a specific polyester diol as a main component mainly comprising the unit represented by the above formula (I). The polyurethane fiber of the present invention obtained by blending the above-mentioned hindered amine compound (a), the hindered phenol compound (b) and optionally the benzophenone compound (c) and a fiber product comprising the same have light resistance and excellent resistance to NO _X gas resistance, yet be capable of deeply stained by disperse dye, dyeing fastness after dyeing and is excellent in salt tolerance containing fastness, further heat resistance, weather resistance, characteristics such as solvent resistance And is extremely useful for various applications.

Continuation of the front page (56) References JP-A-3-220333 (JP, A) JP-A-4-185713 (JP, A) JP-A-60-81371 (JP, A) JP-A-5-25783 (JP, A) , A) JP-A-4-57978 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06P 3/26 D06P 1/645 D06P 1/651

Claims (2)

(57) [Claims] 1. A method for producing a dyed polyurethane fiber or a fiber product comprising the same, wherein (i) the polyurethane constituting the fiber or the fiber product has the following formula:
(I); (Wherein, R ¹ has a carbon number of 6 to 1 having one methyl branch)
An alkylene group of 0, and R ² represents a divalent organic group), with an organic diisocyanate and, if necessary, a chain extender with a polymer diol mainly composed of a polyester diol mainly composed of a unit represented by the following formula: And (ii) in the polyurethane, (a) a compound represented by the following formula (II): (Wherein, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group) and a hindered amine compound having at least one group containing a piperidine ring and having a molecular weight of 1,000 or more, (b ) The following formula (III): (Wherein, R ⁷ and R ⁸ each independently represent an alkyl group). A hindered phenolic compound having a molecular weight of 500 or more and having at least one dialkylhydroxyphenyl group represented by the following formula (C): Equation (I
V); A benzophenone-based compound having at least one benzoylhydroxyphenyl group and a molecular weight of 10,000 or more, and (iii) dyeing the polyurethane fiber or fiber product with a disperse dye. A method for producing a dyed polyurethane fiber or a fiber product comprising the same. 2. A polyurethane fiber dyed with the disperse dye obtained by the method of claim 1, or a fiber product comprising the same.