JPH05320499A - Polyurethane composition and fiber made therefrom - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in light fastness by adding a hindered amine compound, a hindered phenolic compound and a benzophenone compound to a polyurethane. CONSTITUTION:This resin composition is prepared by adding 0.01-1wt.% hindered amine compound containing at least one piperidinyl group of formula I (wherein R<1> to R<4> are each alkyl) and having a molecular weight of 1000 or above, 0.01-1wt.% hindered phenolic compound containing at least one dialkyldihydroxyphenyl group of formula II (wherein R<5> and R<6> are each alkyl) and having a molecular weight of 500 or above, and 0.01-1wt.% benzophenone compound containing at least one benzoylhydroxyphenyl group of formula II to a polyurethane. This composition is spun into a polyurethane fiber excellent in light fastness, heat discoloration resistance, NOx resistance, etc., for example, by melt spinning.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to polyurethane compositions and fibers comprising them. Specifically, light resistance and N resistance
O _X gas resistance, weather resistance, heat discoloration resistance, excellent polyurethane composition in solvent resistance and the like and to polyurethane fibers.

[0002]

2. Description of the Related Art Polyurethane has excellent mechanical properties and is easy to mold and process. Therefore, various injection-molded products, extrusion-molded products such as hoses, tubes, films and sheets, fibers, artificial leather, etc. It is used for a wide range of purposes. Polyurethane fibers, in particular, have excellent elasticity not found in other fibers and are therefore widely used as sports clothing such as swimwear and ski wear, underwear, stockings, medical materials such as elastic bandages and artificial blood vessels. ing.

Among the polyurethanes, 4,
Polyurethanes produced by using aromatic isocyanates such as 4'-diphenylmethane diisocyanate as an isocyanate component have particularly excellent mechanical performance and occupy an important position. Polyurethanes based on these aromatic isocyanates are exposed to sunlight. It also has the drawback of discoloring when exposed to artificial light.

Various proposals have been made to add a light resistance improver to polyurethane for the purpose of improving the above-mentioned drawbacks of polyurethane using an aromatic isocyanate. For example, it is known that a matting agent such as titanium oxide is blended in a large amount with a polyurethane molded product or fiber to aim at the effect of shielding sunlight, but it becomes whitish when colored with a dye or pigment. However, there is a drawback that the color is not deep and the quality is low.

It is also possible to add to the polyurethane a light resistance stabilizer consisting of a low molecular weight hindered amine compound having a piperidine ring in which the 2-position and the 6-position are each substituted with two alkyl groups, that is, a hindered piperidine ring. Proposed. However, when a polyurethane blended with a low molecular weight hindered amine compound is used,
When manufacturing films, tubes, etc. by extrusion molding, infusible impurities may adhere to the die and cause defects in the product, or the spinneret may become dirty and cause fiber breakage during fiber spinning. There is a drawback. Moreover, while using the polyurethane product obtained from it, the light resistance improver bleeds out on the product surface and the appearance is impaired, or the light resistance improver falls off from the product and its light resistance is significantly reduced. There is a drawback. From this point of view, the fact is that a satisfactory light resistance improver for polyurethane has not been obtained yet.

Further, it has been proposed to use an aliphatic isocyanate or an alicyclic isocyanate instead of the aromatic isocyanate, but there is a drawback that the mechanical performance of the obtained polyurethane is deteriorated, which is also sufficiently satisfactory. I can't get a polyurethane product.

[0006]

From the above point of view, the present inventors have found that the die part and the die part are not contaminated during extrusion molding or spinning, and there is no bleed-out or drop-off from the product, light resistance and N resistance.
O _X gas resistance, weather resistance, heat discoloration resistance, we have studied for the purpose of obtaining various performance superior polyurethane compositions and fibers made therefrom, such as organic solvent resistance.

As a result, the polyurethane has a molecular weight of 1
It has been found that the above object can be achieved by blending three kinds of a specific hindered amine compound having a molecular weight of 000 or more, a specific hindered phenol compound having a molecular weight of 500 or more, and a specific benzophenone compound having a molecular weight of 10,000 or more. completed.

That is, the present invention relates to
(A) the following formula (I);

[0011]

[Chemical 4] (In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent an alkyl group) and a hindered amine compound having a molecular weight of 1000 or more and having at least one group containing a piperidine ring, (b) Formula (II) below;

[0012]

[Chemical 5] (In the formula, R ⁵ and R ⁶ 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, and (c) the following formula ( III);

[0013]

[Chemical 6] And a benzophenone-based compound having a molecular weight of 10,000 or more and having at least one benzoylhydroxyphenyl group represented by the following. And this invention includes the polyurethane fiber manufactured from the above-mentioned polyurethane composition.

In the present invention, it is necessary that the above-mentioned hindered amine compound (a), hindered phenol compound (b) and benzophenone compound (c) are contained in the polyurethane. even it lacks one above light resistance, nO _X gas resistance, weather resistance, heat discoloration resistance, it is impossible to obtain an excellent polyurethane composition and fiber to various performance, such as organic solvent resistance.

Further, in the polyurethane composition of the present invention,
Hindered amine compound (a), hindered phenol compound (b) and benzophenone compound (c)
0.01% each based on the weight of polyurethane
It is desirable to add in the range of ˜1% by weight. Each is 0.
If the amount is less than 01% by weight, the light resistance is not sufficiently improved and the color is easily discolored by light. On the other hand, if the amount exceeds 1% by weight, problems such as turbidity of the polyurethane and bleed-out of the stabilizer tend to occur.

The above-mentioned hindered amine compound (a)
As the compound, any compound having a molecular weight of 1000 or more and having at least one group containing the piperidine ring represented by the above formula (I) in the molecule may be used.
The molecular weight of the hindered phenolic compound (a) is 100.
When it is 0 or more, bleed-out to the polyurethane surface can be prevented. The hindered amine compound (a) preferably has a molecular weight in the range of 1,500 to 10,000. Hindered amine compounds (a)
As a typical example of, the following formula (IV);

[0017]

[Chemical 7] (Wherein R ¹ , R ² , R ³ and R ⁴ are the same as above,
R ⁷ 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)
A compound having a molecular weight of 1000 or more represented by

The group represented by the above formula (I) and the formula (I
V) in the compound represented by R ¹ , R ² , R ³ and R
Each of ⁴ 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 (IV), when R ⁷ 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, etc. 2
It can be a valent group. Also, without limitation, one or both of A and B is a group having 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.), an isocyanate group contained in the polyurethane By the reaction, the hindered amine compound (a) can be chemically bound and contained in the polyurethane, and the bleed-out resistance thereof can be further improved. In the compound of formula (IV), 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 it is added before the completion of the polyurethane production reaction, the hindered amine compound (a) is used. Has a high molecular weight of 1000 or more, the number of moles added can be kept low relative to the amount added, and as a result, the rate of end-termination reaction during the polyurethane production reaction can be lowered, and the molecular weight of polyurethane can be increased. be able to.

In the compound represented by the above formula (IV), the group R ⁷ has the formula;-(CH ₂ ) p-O-CO- (CH ₂ ) q-C.
It is preferably a group represented by OO- (in the formula, p and q each represent an integer of 2 to 4), and specific examples of such a hindered amine compound (a) include the following formula (V). ;

[0022]

[Chemical 8] (In the formula, n is preferably a number of 4 to 20). The compound represented by the formula (V) can be produced, for example, by a polycondensation reaction of 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 (II) in the molecule and having a molecular weight of 500 or more. It doesn't matter. Among them, those in which R ⁵ and R ⁶ in the dialkylhydroxyphenyl group of the above formula (II) are each a methyl, ethyl, propyl or t-butyl group are particularly preferable.

Although not limited, preferred examples of the hindered phenol compound (b) are that the polyurethane composition after blending the hindered phenol compound (b) has a good color tone. Is the following formula (VI);

[0025]

[Chemical 9] 3,9-bis [2- {3- (3-t-butyl-4) represented by
-Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, and further tetrakis [methylene-3- (3,5) -Di-t-butyl-4-hydroxyphenyl) propionate] methane, triethyleneglycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6
-Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like can be mentioned.

Further, the benzophenone compound (c) may be any compound as long as it has at least one benzoylhydroxyphenyl group represented by the above formula (III) in the molecule and has a molecular weight of 10,000 or more. .. When the molecular weight of the benzophenone compound (c) is less than 10,000, bleeding out easily occurs on the surface of the polyurethane, and the benzophenone compound (c) is easily lost from the polyurethane by the dry cleaning treatment or with the passage of time. The molecular weight of the benzophenone compound (c) is preferably in the range of about 20,000 to 40,000, because the bleed-out phenomenon is further suppressed and the effect can be exhibited over a long period of time.

Among the benzophenone compounds (c), the benzoylhydroxyphenyl group represented by the above formula (III) is represented by the following formula (VII);

[0028]

[Chemical 10] (In the formula, R ⁸ represents an alkylene group), which is present in the form of a monovalent group, and in particular, R ⁸ in the monovalent group represented by the formula (VII) has a carbon number. Benzophenone compounds having 1 to 4 alkylene groups are preferred.

Although not limited thereto, preferred specific examples of the benzophenone compound (c) include the following formula (VIII);

[0030]

[Chemical 11] [Wherein n ₁ and n ₂ are numbers such that n ₁ + n ₂ ≧ 35 and n ₂ / (n ₁ + n ₂ ) ≧ 0.2] 2-hydroxy-4 Examples thereof include- (methacryloyloxyethoxy) benzophenone / methyl methacrylate copolymer.

The timing of adding the hindered amine compound (a), the hindered phenol compound (b) and the benzophenone compound (c) to the polyurethane is not particularly limited, and it may be added either during the production of the polyurethane or after the production of the polyurethane. Good. Generally, it is desirable to melt and add the polyurethane after the production of the polyurethane because the above-mentioned effects such as the light resistance are increased. When it is added after production, it can be added at any stage during the production of polyurethane pellets or during production of molded articles, fibers and other products from polyurethane. Further, the compounds (a) to (c) described above may be added simultaneously or sequentially, and when they are added sequentially, the order of addition may be any.

The polyurethane used as the base of the polyurethane composition of the present invention may be either a thermoplastic polyurethane or a thermosetting polyurethane, and the polyurethane may contain an organic polyisocyanate and a polyol, and if necessary, other chain extenders and the like. It can be produced by reacting the components with a one-shot method, a prepolymer method or another method. Further, the polyurethane fiber of the present invention is formed from a thermoplastic polyurethane, and the thermoplastic polyurethane can be produced by reacting an organic diisocyanate and a polymeric diol with a chain extender and other components, if necessary. ..

Non-limiting examples of organic polyisocyanates for polyurethane production include:
4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and other organic diisocyanates having a molecular weight of 500 or less can be mentioned. May be used alone or in combination of two or more, and a polyurethane obtained by using 4,4′-diphenylmethane diisocyanate is particularly preferable.

The polyol for producing polyurethane is not limited, but the average molecular weight is 500.
It is preferred to use ~ 5000, especially 1000-3000 polymeric diols. Examples of the polymer diol include polyester diol, polycarbonate diol, polyether diol, polyether ester diol, and the like, and polyurethane produced by using polyester diol and polycarbonate diol is particularly preferable.

In this case, as the polyester diol, at least one dicarboxylic acid (eg, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and a low-molecular diol (eg, ethylene glycol, propylene glycol) are used. 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1, 10-decane diol and the like), and polylactone diol such as polycaprolactone diol and polymethyl valerolactone diol obtained by ring-opening polymerization of a lactone compound.

As the polycarbonate diol, for example, at least one kind of dialkyl carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate, etc.) and low-molecular diol (for example, ethylene glycol, propylene glycol, 1,
4-butanediol, neopentyl glycol, 1,6
-Hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,
There may be mentioned a polycarbonate diol produced from at least one of 9-nonane diol and 1,10-decane diol.

Further, as the polyether diol, cyclic ethers (ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, etc.)
Polyether diol and glycol (ethylene glycol, propylene glycol, obtained by ring-opening polymerization of
1,4-butanediol, neopentyl glycol,
1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc.) Polyether diol is preferred.

As the chain extender, it is preferable to use a low molecular weight compound having two active hydrogen atoms capable of reacting with an isocyanate group, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1 , 6
-Hexanediol, 1,9-nonanediol, 1,4
-Bis (β-hydroxyethoxy) benzene, 1,4-
Cyclohexanediol, diols such as xylylene glycol, ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, 4,4′-diaminodiphenylmethane, tolylenediamine, 4,4 ′
Diamines such as diaminodicyclohexylmethane may be mentioned, and only one of these chain extenders or 2
More than one species can be used. Among them, 1,4-butanediol and 1,4-bis (β-hydroxyethoxy) benzene are particularly preferable.

Various known batch or continuous processes and equipment may be employed in making the polyurethanes used in the compositions and fibers of the present invention. In particular, it is preferable to carry out the polymerization of polyurethane in a molten state in the substantial absence of a solvent, and it is more preferable to carry out continuous melt polymerization using an extruder such as a multi-screw type. The temperature at that time is not particularly limited, but is usually about 200 to 26.
It is preferable to carry out the polymerization at a temperature of 0 ° C.
Keeping the temperature below 0 ° C. improves the heat resistance and mechanical properties of the polyurethane, while keeping it above 200 ° C. makes it possible to produce a thermoplastic polyurethane having excellent melt spinnability. At this time, it is preferable that the ratio (R value) of the isocyanate group to the active hydrogen atom in the raw material is in the range of 1.0 to 1.1.

In producing the polyurethane composition and fiber of the present invention, catalysts, activators, defoamers, other stabilizers, coloring agents such as dyes and pigments, fillers, etc. which are commonly used in the art. Any components such as flame retardants, lubricants, foaming agents and the like can be used as required.

When thermoplastic polyurethane is used as the polyurethane in the composition of the present invention, molding / processing which is usually adopted for thermoplastic polyurethane,
For the production of various products such as extrusion molding products such as tubes, films and sheets, shoe soles by injection molding and other molds and other various molding products, synthetic leather, artificial leather, fibers, etc. The polyurethane composition of the present invention can be effectively used for the above. Further, when thermosetting polyurethane is used, various thermosetting molded products, adhesives, paints, etc. can be obtained.

Among the above, the polyurethane composition of the present invention is suitable as a material for polyurethane fibers, and in producing the polyurethane fiber of the present invention, for example, a melt spinning method, a dry spinning method, a wet spinning method and the like are used. Any method can be adopted, and a melt spinning method using no solvent or water is particularly preferable.

The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited thereto. Moreover, parts in the following examples represent parts by weight. Furthermore, in the following examples, the light resistance (light fastness and strength retention) of the polyurethane film, outdoor exposure test (strength retention), solvent extraction resistance (light fastness and strength retention after solvent extraction) and resistance NO _x property (strength retention rate), strength / elongation of polyurethane fiber, light resistance (strength retention rate), outdoor exposure test (strength retention rate), solvent extraction resistance (strength retention rate after solvent extraction) and NO resistance _{The x} property (strength retention rate) was measured by the following method.

<< Light Resistance Test of Polyurethane Film >> (1) Lightfastness of Polyurethane Film: Polyurethane film (thickness 0.1 mm) produced in each of the following examples
On the other hand, a carbon arc fade meter FAL-5 type manufactured by Suga Test Instruments Co., Ltd. was used to irradiate ultraviolet rays at a temperature of 83 ° C. for 40 hours, and the light yellowing resistance and strength retention thereof were examined. The light yellowing resistance was evaluated by the following five-level evaluation of the degree of browning. Criteria for evaluation of light yellowing resistance 5 ... No discoloration 4 ... Slightly yellow discoloration 3 ... Discoloration to yellow 2 ... Discoloration from yellow to brown 1 ... Discoloration to brown

(2) Strength retention rate: The strength of the polyurethane film was measured using an autograph manufactured by Shimadzu Corporation and calculated from the following formula 1.

[0046]

## EQU1 ## Strength retention rate (%) = (strength after UV irradiation / strength before UV irradiation) × 100

<< Outdoor exposure test of polyurethane film >>
The polyurethane film (thickness 0.1 mm) manufactured in each of the following examples was left for 20 days outdoors in a well-lit environment, the strength of the film was measured before and after this, and the following formula 2 was used.
The strength retention rate was obtained more.

[0048]

[Formula 2] Strength retention rate (%) = (strength after outdoor exposure / strength before outdoor exposure) × 100

<< Solvent Extraction Resistance Test of Polyurethane Film >> The polyurethane film (thickness 0.1 mm) produced in each of the following examples was soaked in Perkren at 70 ° C. for 5 hours at a bath ratio of 1: 1000, and then 50 ° C. The lightfastness of the product dried for 1 hour was irradiated with ultraviolet rays at a temperature of 83 ° C. for 40 hours using a carbon arc type fade meter FAL-5 manufactured by Suga Test Instruments Co., Ltd. In addition to the evaluation according to the modification evaluation standard, the strength retention rate after ultraviolet irradiation was measured in the same manner as above.

<< Test of Polyurethane Film for NO _x Resistance >> The polyurethane film (thickness 0.1 mm) produced in each of the following examples was treated for 2 hours in the air in which the concentration of NO ₂ gas was increased to 650 ppm, The strength retention rate at that time was determined according to the above formula of the strength retention rate.

<< Measurement of Strength and Elongation of Polyurethane Fiber >> JI
The toughness was determined according to SL-1013.

<< Measurement of light resistance strength retention of polyurethane fiber >> The polyurethane fiber produced in each of the following examples was
What was wound on the frame under the tension of 1000 g / denier,
Carbon arc type fade meter F manufactured by Suga Test Instruments Co., Ltd.
The AL-5 type was irradiated with ultraviolet rays at a temperature of 83 ° C. for 20 hours, and the strength retention thereof was calculated by the following mathematical formula 3.

[0053]

[Formula 3] Strength retention rate (%) = (strength after ultraviolet irradiation / strength before ultraviolet irradiation) × 100

<< Outdoor exposure test of polyurethane fiber >> The polyurethane fiber produced in each of the following examples was left outdoors in the sunlight for 20 days, the strength of the fiber before and after this was measured, and the strength retention rate was calculated by the above-mentioned formula 3. I asked.

<< Solvent Extraction Resistance Test of Polyurethane Fibers >>
Polyurethane fiber produced in each of the following examples
A bath ratio of one wound on a frame under a tension of 0 g / denier was 1:
50 after immersing in 1000 ° C. perklen for 5 hours at 1000
It was dried at ℃ for 1 hour, and at 83 ℃ by using a carbon arc type fade meter FAL-5 type manufactured by Suga Test Instruments Co., Ltd.
The sample was irradiated with ultraviolet rays at the temperature of 40 hours, and the strength retention rate after irradiation of the ultraviolet rays was measured in the same manner as above.

<< NO _x resistance test of polyurethane fiber >> 4
A 0 denier polyurethane elastic fiber was treated for 1 hour in air with an NO ₂ gas concentration increased to 650 ppm, the strength before and after this was measured, and the strength retention was determined according to the above strength retention formula. ..

The compounds used in each example are shown in Table 1 below.
It is represented by the symbol shown in.

[0058]

[Table 1]

Examples 1 to 6 [Production of Polyurethane Film] Mixtures containing the polymeric diols and BD shown in Table 2 below in the proportions shown in Table 2 and heated to 80 ° C. and heat-melted to 50 ° C. MDI was continuously supplied to a twin-screw extruder by a metering pump to carry out continuous melt polymerization, and the produced polyurethane was extruded into water in a strand form and cut to produce polyurethane pellets. When the above pellets were dehumidified and dried at 80 ° C. for 20 hours and melt-extruded by a twin-screw extruder, various stabilizers were added in the proportions shown in Table 2 from the middle of the cylinder and mixed to obtain a pelletized polyurethane composition. Got The pelletized polyurethane composition was dehumidified and dried at 80 ° C. for 20 hours, and then hot pressed to a thickness of 0.1 mm.
To produce the film, the evaluation of light resistance, outdoor exposure test, the evaluation of solvent extraction resistance and NO _x resistance was performed by the method described above. The results are shown in Table 3.

Comparative Examples 1 to 10 Polyurethane films were prepared in the same manner as in Examples 1 to 6 except that no stabilizer was added or the various stabilizers shown in Table 2 were mixed in the proportions shown in Table 2. Then, the test was conducted similarly. The results are shown in Table 3.

[0061]

[Table 2]

[0062]

[Table 3]

From the results shown in Table 3 above, the stabilizers (a) and (b ₁ )
Alternatively, it is obtained from the polyurethane composition of the present invention in which the three components (b ₂ ) and (c), that is, the hindered amine compound (a), the hindered phenol compound (b) and the benzophenone compound (c) are blended. was film of examples 1-6, light resistance, weather resistance (weathering test), are excellent in all of solvent extraction resistance and NO _X gas resistance. On the other hand, those stabilizers 3
The film of Comparative Examples 1 to 10 obtained from a polyurethane composition lacking one or more of the above-mentioned ones or blended with other stabilizers has light resistance, weather resistance (outdoor exposure test), resistance All of solvent extraction and NO _x gas resistance are inferior, or some of their performances are inferior, especially solvent extraction and NO _x gas resistance are inferior. Recognize.

<Examples 7 to 11> Polyurethane pellets prepared by blending various stabilizers in the same manner as in Examples 1 to 6 so as to have the compositions shown in Table 4 below at 80 ° C.
After dehumidifying and drying for 0 hour, the spinning temperature was 225 ° C., the spinning speed was 500 m / min, and the apparent draft rate was 8 using a spinning machine with a single-screw extruder.
47, spinning tension 0.1 g / d, yarn feeding speed difference 25
The fiber was spun at m / min to obtain a polyurethane fiber having 40 denier / 1 filament. After aging this fiber for 48 hours at 80 ° C., the strength / elongation, light resistance, outdoor exposure test, solvent extraction resistance and NO _x resistance of the obtained fiber were evaluated by the methods described above. The results are shown in Table 5 below.

[0065]

[Table 4]

[0066]

[Table 5]

From the results shown in Table 5 above, the polyurethane fibers of Examples 7 to 11 of the present invention containing the three components of the hindered amine compound (a), the hindered phenol compound (b) and the benzophenone compound (c) were prepared. In comparison with the polyurethane fibers of Comparative Examples 11 to 17 lacking one or more of the three stabilizers, or containing other stabilizers, light resistance and outdoor exposure test (weather resistance) is excellent in all of solvent extraction resistance and NO _X gas resistance, it is found particularly solvent extraction resistance and NO _X gas is good.

[0068]

The polyurethane composition of the present invention containing the hindered amine compound (a), the hindered phenol compound (b) and the benzophenone compound (c) and the fiber comprising the same have a light resistance and a NO resistance. Excellent in all properties such as _X gas resistance, weather resistance, heat discoloration resistance and solvent resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Hirai 1621 Sakata, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd.

Claims (2)

[Claims] 1. In a polyurethane, (a) the following formula (I); (Wherein each of R ¹ , R ² , R ³ and R ⁴ independently represents an alkyl group), a hindered amine compound having a molecular weight of 1000 or more and having at least one group containing a piperidine ring, ) The following formula (II); (In the formula, R ⁵ and R ⁶ 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, and (c) the following formula ( III); A benzophenone compound having a molecular weight of 10,000 or more and having at least one benzoylhydroxyphenyl group represented by: 2. A polyurethane fiber produced from the polyurethane composition of claim 1.