JPH05320500A - Polyurethane composition and fiber made therefrom - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in mildew resistance by adding a compound containing a 4-thiazolyl group of a specified formula, a benzophenone compound, a hindered amine compound, and a phenolic compound to a polyurethane. CONSTITUTION:This composition excellent in mildew resistance is obtained by adding 0.01-1.0wt.% compound containing at least one 4-thiazolyl group of formula I (wherein R<1> and R<2> are each H, alkyl or halogen), 0.01-1wt.% hindered amine compound containing at least one piperidinyl group of formula II (wherein R<3> to R<6> are each alkyl) and having a molecular weight of 1000 and 0.01-1.0wt.% benzo-phenone compound containing at least one benzoylhydroxyphenyl group of formula IV and having a molecular weight of 10000 or above to a polyurethane and melt-kneading the obtained mixture.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to polyurethane compositions and fibers comprising them. In particular, excellent antifungal, yet light resistance, NO _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 them, polyurethane produced by using an aromatic isocyanate such as 4,4'-diphenylmethane diisocyanate as an isocyanate component is excellent in mechanical performance. However, this type of polyurethane has a drawback that it is easily discolored when exposed to sunlight or artificial light. In addition, polyurethane is generally susceptible to deterioration due to mold, and as time passes, NO
There is a drawback that it gradually turns yellow due to outdoor exposure to _X gas, automobile exhaust gas, etc., and contact with chemical substances such as chlorine bleach and organic solvents, and mechanical properties such as strength and elongation deteriorate. is doing.

In order to improve the above-mentioned drawbacks of polyurethane, various attempts have been made to add an antifungal agent and a light resistance improver to the polyurethane. For example, 2nd and 6th
It has been proposed to add to the polyurethane a lightfastness stabilizer consisting of a low molecular weight hindered amine compound having a hindered piperidine ring in which each position is substituted with two alkyl groups. However, when a polyurethane blended with a low molecular weight hindered amine compound is used, when a film or tube is produced by extrusion molding,
There are drawbacks such that infusible impurities are attached to the die to cause defects in the product, and the spinneret becomes dirty during fiber spinning, resulting in yarn breakage. Moreover, while using the obtained polyurethane product, the light resistance improver bleeds out on the product surface and the appearance is impaired, or the light resistance improver is dropped from the product and the light resistance is significantly reduced. There are drawbacks.

[0005] Moreover, when used in combination fungicide and light resistance improving agents to the polyurethane, or generally tend to cancel each other out the effect inherent their formulations, and anti-NO _X gas polyurethane is impaired, In many cases, the heat coloring becomes so intense that the intended purpose cannot be achieved.

[0006]

From the above point of view, the present inventors have found that even if an antifungal agent and a light resistance improver are used in combination, both properties work effectively and the above-mentioned drawbacks do not occur, and the antifungal property is , Light discoloration resistance,
Heat discoloration resistance, NO _X gas resistance has been studied for the purpose of obtaining chemical and polyurethane resins and fibers made therefrom have excellent weather resistance.

As a result, the present inventors have found that in polyurethane, a compound having at least one 4-thiazolyl group,
It has been found that the above object can be achieved by incorporating three kinds of compounds of a specific hindered amine compound having a molecular weight of 1000 or more and a specific hindered phenol compound having a molecular weight of 500 or more. Further, the present inventors is blended in addition to more molecular weight 10000 or more specific benzophenone compound of the three compounds above, light discoloration resistance, heat discoloration resistance, NO _X gas resistance, chemical resistance and It has been found that characteristics such as weather resistance are further improved.

That is, the present invention is based on the
(A) the following formula (I);

[0009]

[Chemical 5] (In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or a halogen atom), a compound having at least one 4-thiazolyl group, (b) the following formula (II);

[0010]

[Chemical 6] (In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ 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, (c ) The following formula (III);

[0011]

[Chemical 7] (In the formula, R ⁷ and R ⁸ each independently represent an alkyl group), which has at least one dialkylhydroxyphenyl group and has a molecular weight of 500 or more, and a hindered phenolic compound having a molecular weight of 500 or more. IV);

[0012]

[Chemical 8] 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, the above-mentioned compound having at least one 4-thiazolyl group (hereinafter referred to as "4-thiazolyl group-containing compound") (a), hindered amine compound
It is necessary to incorporate the three components of (b) and the hindered phenolic compound (c) into the polyurethane, and even if one of them is omitted, the above-mentioned mold resistance, light resistance,
It is not possible to obtain a polyurethane composition or fiber excellent in various properties such as NO _x gas resistance, weather resistance, heat discoloration resistance, and organic solvent resistance. Further, the polyurethane composition and fiber of the present invention may further contain the above-mentioned benzophenone compound (d) in addition to the above-mentioned three kinds of compounds, whereby the performance thereof, particularly the weather resistance thereof, can be improved. Further improve.

In the polyurethane composition of the present invention, the 4-thiazolyl group-containing compound (a), the hindered amine compound (b) and the hindered phenol compound (c) are used.
0.01% each based on the weight of polyurethane
It is desirable to add in the range of 1.0 wt%. Polyurethane When each is less than 0.01 wt%, mildew resistance, light resistance, improvement in such resistance NO _X gas property becomes liable to discolor by light is not sufficient, whereas when each exceeds 1.0 wt% And the problem of bleeding out of these compounds is likely to occur. In particular, it is more preferable that the total amount of the three compounds added is 0.1 to 1.5% by weight. When the above-mentioned benzophenone-based compound (d) is further blended, it is added in an amount of 0.01 to 0.01 based on the weight of the polyurethane.
The amount of 1.0% by weight is desirable from the viewpoint of the stabilizing effect of the benzophenone compound (d) and the prevention of bleed-out.

The 4-thiazolyl group-containing compound (a) may be any compound having at least one 4-thiazolyl group represented by the above formula (I) in the molecule. Among them, especially the following formula (V);

[0016]

[Chemical 9] (In the formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group or a halogen atom), and the benzimidazole compound represented by the formula has low skin irritation and the like. And is highly safe to the human body and excellent in heat resistance. Particularly, in the benzimidazole compound represented by the above formula (V), the groups R ⁹ , R
^A compound in which ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are all hydrogen atoms, that is, 2- (4-thiazolyl) benzimidazole is preferable.

The 4-thiazolyl group-containing compound (a) has an excellent antifungal effect, excellent heat resistance, does not heat-color even when kneaded in polyurethane, and has a hindered amine compound (b) and a hinder. de phenolic compound (c) does not lead to a loss of light discoloration resistance and nO _X gas discoloration of the polyurethane composition formulated.

The above-mentioned hindered amine compound (b) is a compound having a molecular weight of 1000 or more and at least one group containing a piperidine ring represented by the above formula (II) in the molecule. Any of them will do. When the molecular weight of the hindered phenol compound (b) is 1000 or more, bleed-out on the polyurethane surface can be prevented. The molecular weight of the hindered amine compound (b) is 1500 to 10,000.
It is preferably within the range. A typical example of the hindered amine compound (b) is the following formula (VI);

[0019]

[Chemical 10] (Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are the same as above,
R ¹⁵ 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 (II) and the formula (V
In the compound represented by I), R ³ , R ⁴ , R ⁵ and R
Each of 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 ¹⁵ 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 (b) can be chemically bound and contained in the polyurethane, and the bleed-out resistance thereof can be further improved. In the compound of 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 (b) and it is added before the completion of the polyurethane production reaction, the hindered amine compound (b) 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 (VI), the group R ¹⁵ 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 (b) include the following formula (VI
I);

[0024]

[Chemical 11] (In the formula, n is preferably a number of 4 to 20). The compound represented by the formula (VII) 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 (c)
The compound may be any compound as long as it has at least one dialkylhydroxyphenyl group represented by the above formula (III) in the molecule and has a molecular weight of 500 or more.
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 particularly preferable.

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

[0027]

[Chemical formula 12] 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,1 represented by
0-tetraoxaspiro [5.5] undecane, further tetrakis [methylene-3- (3,5-di-t-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] and the like.

Further, the above-mentioned benzophenone compound (d) which is an optional component is 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 of them will do. When the molecular weight of the benzophenone compound (d) is less than 10,000, bleeding out easily occurs on the surface of the polyurethane, and the benzophenone compound (d) is likely to be lost from the polyurethane by the dry cleaning treatment or with the passage of time. The benzophenone compound (d) has a molecular weight of about 20,000.
The range of up to 40,000 is preferable because the bleed-out phenomenon can be further suppressed and the effect can be exhibited over a long period of time. Among the benzophenone compounds (d), the benzoylhydroxyphenyl group represented by the above formula (IV) has the following formula (IX);

[0029]

[Chemical 13] (Wherein R ¹⁶ represents an alkylene group), a benzophenone compound existing in the form of a monovalent group, particularly R ¹⁶ in the monovalent group represented by the formula (IX) 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 (d) include the following formula (X);

[0030]

[Chemical 14] [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 4-thiazolyl group-containing compound (a), the hindered amine compound (b), the hindered phenol compound (c) and the optional benzophenone compound (d) are added to the polyurethane at any time. Alternatively, it may be either during the production of the polyurethane or after the production of the polyurethane. Generally, it is desirable to melt and add the polyurethane after the production of the polyurethane because the above-mentioned antifungal property, light resistance and other effects 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 above-mentioned compounds (a) to (c) and optionally (d) 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 1000-4000 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,
Spinning technology etc. can be applied. The polyurethane composition of the present invention is used for producing various products such as extruded products such as tubes, films and sheets, shoe soles by injection molding and other molding and other various molded products, synthetic leather, artificial leather, fibers and the like. It is particularly suitable for manufacturing products that are used or stored in a hot and humid environment where molds are prone to grow. Also, when using thermosetting polyurethane,
It is possible to obtain various thermosetting molded products, adhesives, paints and the like.

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 mold resistance of polyurethane film (strength retention rate),
Light resistance (light fastness and strength retention), outdoor exposure test
(Strength retention rate), NO _x resistance (strength retention rate) and color tone,
And mold resistance, light resistance (light fastness and strength retention) of polyurethane fiber, outdoor exposure test (strength retention),
The NO _x resistance (strength retention rate) and color tone were measured or evaluated by the following methods.

<Moldproofing test of polyurethane film>
On a glucose peptone agar culture medium, a 0.1 mm-thick polyurethane film produced in each of the following examples was attached, and a mixed spore suspension of 5 types of mold was inoculated, and the temperature was 30 ° C.
After culturing at a humidity of 90 to 95% for 2 weeks, the strength of the polyurethane film was measured by an autograph manufactured by Shimadzu Corporation, and the strength retention rate (%) was calculated by the following mathematical formula 1. In addition, in this test, the molds described in JIS Z2911-1960 "Mold resistance test", that is, Alpergillus niger ATCC9642, Penicillium luteum ATCC9644, Rhizopus niglycans S.
N. 32, Trichoderma T-1 ATCC 9645 and Ketomium globosum ATCC 6205 were used.

[0045]

[Formula 1] Strength retention rate (%) = (strength after culture / strength before culture) × 100

<< Light Resistance Test of Polyurethane Film >> (1) Lightfastness of Polyurethane Film: Polyurethane film manufactured in each of the following examples (thickness 0.1 mm)
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 mathematical formula 2.

[0048]

## EQU00002 ## 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 outdoors in a well-lit environment for 20 days, and the strength of the film was measured before and after this, and the following formula 3 was used.
The strength retention rate was obtained more.

[0050]

[Formula 3] Strength retention rate (%) = (strength after outdoor exposure / strength before outdoor exposure) x 100

<< NO _x resistance test of polyurethane film >> 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 NO ₂ gas concentration was increased to 650 ppm, The strength retention rate at that time was determined according to the above formula of the strength retention rate.

<< Evaluation of Color Tone of Polyurethane Film >> Polyurethane film (thickness 0.1
The color tone of (mm) was evaluated according to the following criteria based on the color tone of the 0.1 mm-thick polyurethane film produced in the same manner except that no antifungal agent and stabilizer were added. Evaluation criteria of color tone ○ ・ ・ ・ Color tone similar to that without additive × ・ ・ ・ Significant coloration compared to the case without additive

<Moldproofing Test of Polyurethane Fiber> Glucose peptone agar culture medium with 40 denier polyurethane fiber produced in each example wound around a glass plate was attached, and the same as in the case of the above-mentioned polyurethane film. Inoculated with a mixed spore suspension of 5 molds at a temperature of 30
After culturing for 2 weeks at 90 ° C and a humidity of 90 to 95%, the strength of the polyurethane fiber was measured by an autograph manufactured by Shimadzu Corporation, and the strength retention rate (%) was calculated by the above mathematical formula 1.

<< Lightfastness Test of Polyurethane Fibers >> Polyurethane fibers produced in the following examples were used at 5/1000 g /
What was wound on the frame under the tension of denier was irradiated with ultraviolet rays at a temperature of 83 ° C. for 20 hours using a carbon arc type fade meter FAL-5 type manufactured by Suga Test Instruments Co., Ltd. to obtain its light fastness (light resistance). (Yellowing) and strength retention were investigated.
The strength retention rate was calculated from the above mathematical formula 2 by measuring the strength of the polyurethane fiber using an autograph manufactured by Shimadzu Corporation. Further, the light fastness (light yellowing resistance) was evaluated by the following five-level evaluation of the degree of browning.

Criteria for evaluation of light fastness (light yellowing resistance) 5 ... No discoloration 4 ... Slightly yellow discoloration 3 ... Yellow discoloration 2 ... Yellow-brown discoloration 1 ... Brown discoloration

<< Outdoor Exposure Test of Polyurethane Fibers >> The polyurethane fibers produced in the following examples were left outdoors for a period of 20 days, and the strength of the fibers before and after this was measured to maintain the strength according to the above mathematical formula 3. I asked for the rate.

[0057] "anti-NO _x resistance test of polyurethane fibers" 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. ..

<< Evaluation of color tone of polyurethane fiber >> The color tone of the polyurethane fiber produced in each of the following examples is based on the color tone of the polyurethane fiber produced in the same manner except that no antifungal agent and stabilizer are added. The evaluation criteria were the same as those used for the "evaluation criteria for color tone".

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

[0060]

[Table 1]

Examples 1 to 6 [Production of Polyurethane Film] A mixture containing the polymeric diol and BD shown in Table 2 below in the proportions shown in Table 2 and heated to 80 ° C. and heated to 50 ° C. and melted. MDI was continuously supplied to a twin-screw extruder by a metering pump to carry out continuous melt polymerization. At that time, the temperature of the extruder is set to 80 ° C. at the raw material supply port, 120 ° C., 220 ° C., 220 ° C., 200 at the extrusion port in the next section.
C., 200.degree. C. and 195.degree. C. were set. Further, the screw rotation speed of the extruder was set to 250 times / minute. The generated polyurethane was extruded into water in a strand shape from an extrusion port and cut into polyurethane pellets.

When the above pellets were dehumidified and dried at 80 ° C. for 20 hours and melt-extruded at 210 ° C. by a twin-screw extruder, various stabilizers were added from the middle of the cylinder at a ratio shown in Table 2 and mixed, A polyurethane composition in the form of pellets was obtained. This pelletized polyurethane composition was heated at 80 ° C for 2
After dehumidifying and drying for 0 hours, it is hot-pressed to produce a film with a thickness of 0.1 mm, and it is mildewproof (strength retention rate), light resistance (fastness to light and strength retention rate), outdoor exposure test (strength retention rate). ), NO _x resistance (strength retention rate) and color tone were evaluated by the methods described above. The results are shown in Table 3.

Comparative Examples 1 to 11 Same as Examples 1 to 6 except that no antifungal agent and / or stabilizer was added or the various additives shown in Table 2 were mixed in the proportions shown in Table 2. Then, a polyurethane film was prepared and the test was conducted in the same manner. The results are shown in Table 3.

[0064]

[Table 2]

[0065]

[Table 3]

From the results shown in Table 3 above, the 4-thiazolyl group-containing compound (a), the hindered amine type compound (b) and the hindered phenol type compound (c), or the three of them and the benzophenone type compound (d). Example 1 obtained from the polyurethane composition of the present invention blending
Films of ~ 6 are mildewproof, lightfastness, outdoor exposure test
It can be seen that (weather resistance), NO _x resistance and color tone are all excellent. On the other hand, 4-thiazolyl group-containing compound (a) (antifungal agent) and one or more of stabilizers (b) and (c) are lacking, or other stabilizers are added. Comparative Examples 1 to 11 obtained from polyurethane composition
It can be seen that all or some of the above-mentioned properties are inferior in the film No. 3 and the film does not have a sufficiently satisfactory performance.

<Examples 7 to 11> Polyurethane pellets prepared by blending various additives in the same manner as in Examples 1 to 6 so as to have the composition 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 at 80 ° C. for 48 hours, the obtained fiber has mold resistance, light resistance (light fastness and strength retention), outdoor exposure test (strength retention), NO _x resistance (strength retention). ) And the color tone were evaluated by the method described above. The results are shown in Table 5 below.

[0068]

[Table 4]

[0069]

[Table 5]

From the results in Table 5 above, the 4-thiazolyl group-containing compound (a), the hindered amine-based compound (b) and the hindered phenol-based compound (c), or three of them and the benzophenone-based compound (d) were used. ) And the polyurethane fibers of Examples 7 to 11 of the present invention are excellent in antifungal property, light resistance, outdoor exposure test (weather resistance), NO _x resistance and color tone. Recognize. On the other hand, 4-thiazolyl group-containing compound (a) (antifungal agent) and one or more of the stabilizers (b) and (c) are lacking or other stabilizers are added. It can be seen that the fibers of Comparative Examples 12 to 18 obtained from the polyurethane composition are inferior in all or some of the above-mentioned properties and do not have sufficiently satisfactory performance.

[0071]

EFFECT OF THE INVENTION 4-Thiazolyl Group-Containing Compound Above
(a), a hindered amine-based compound (b) and a hindered phenol-based compound (c), or a polyurethane composition of the present invention containing the three, and a benzophenone-based compound (d). fibers made is mildew resistance, light resistance, NO _X gas resistance, weather resistance, and all characteristics of the heat discoloration resistance and the like.

Claims (2)

[Claims] 1. In a polyurethane, (a) the following formula (I); (In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or a halogen atom), a compound having at least one 4-thiazolyl group, (b) the following formula (II); [Chemical 2] (Wherein each of R ³ , R ⁴ , R ⁵ and R ⁶ 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, (c ) The following formula (III); (In the formula, R ⁷ and R ⁸ each independently represent an alkyl group), which has at least one dialkylhydroxyphenyl group and has a molecular weight of 500 or more, and a hindered phenolic compound having a molecular weight of 500 or more. IV); 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.