JPH05156151A - Polyurethane composition and fiber made therefrom - Google Patents

Abstract

PURPOSE:To prepare a polyurethane compsn. excellent in softness, heat resistance, weatherability, discoloration resistance, etc., by compounding a specific polyurethane with a hindered phenol compd. having a specified mol.wt. CONSTITUTION:A polyurethane prepd. by reacting a high-molecular diol, a chain extender, and an org. diisocyanate component at least a part of which is an NCO-terminated prepolymer having pendant piperidine rings with 2- and 6-positions each substd. by two alkyl groups, an average mol.wt. of 1,500 or higher, and an average number of NCO groups in the molecule of 1.8-3 is compounded with a hindered phenol compd. having a dialkylphenol group of the formula (wherein R<1> and R<2> are each alkyl) and a mol.wt. of 500 or higher to give the objective polyurethane compsn., which is excellent in softness, heat resistance, weatherability, discoloration resistance, etc., and gives a fiber having a high elasticity unattainable by other kinds of fiber.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to polyurethane compositions and fibers comprising them. Specifically, the present invention relates to a polyurethane composition and polyurethane fiber having excellent flexibility, heat resistance, weather resistance, discoloration resistance, and the like.

[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. Among them, polyurethane fiber is called spandex, and because it has excellent elasticity that other fibers do not have, it is used for sports clothing such as swimwear and ski wear, underwear,
Widely used as medical materials such as stockings, elastic bandages and artificial blood vessels. However, polyurethane molded articles and fibers are exposed to sunlight, NO
_{x It} has a drawback that it gradually turns yellow due to outdoor exposure to 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. In particular, the polyurethane fiber having a soft segment of polyether diol such as polytetramethylene glycol has poor light resistance due to the low light resistance of the ether bond.

Various attempts have been made to improve the above-mentioned drawbacks of polyurethane. For example, it is known that a matting agent such as titanium oxide is blended in a large amount with a polyurethane molded article, fiber or the like to aim at the effect of shielding sunlight, but when colored with a dye or pigment, it becomes whitish and deep. There is a drawback that it does not become a color and it becomes of low quality.

Further, a stabilizer such as a light resistance stabilizer or an ultraviolet absorber made of a 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 is used in polyurethane. It has also been conventionally added to. However, when the hindered amine compound is simply added, there is a problem that a blooming phenomenon of moving to the surface of the polyurethane occurs and the hindered amine compound is easily dropped from the polyurethane. Further, when producing polyurethane fibers by the dry spinning method or the wet spinning method, the solubility of the stabilizer in the stock solution for spinning is not good, or the stabilizer is detached from the fiber during desolvation during spinning. However, in the case of the melt spinning method, there are drawbacks such that the stabilizer volatilizes and adheres to the spinneret to generate stains and cause yarn breakage.

Therefore, in order to solve the above problems, there has been proposed a method of chemically bonding a hindered amine compound containing a hindered piperidine ring to polyurethane for fibers and films. As a conventionally proposed method of chemically bonding a hindered amine compound, a method of using the hindered amine compound as a terminal terminating agent during the production of polyurethane, and using the hindered amine compound as a chain extender to form a hindered piperidine ring in a hard segment portion of polyurethane. There is a method of introducing in a side chain form, and a method of introducing the hindered piperidine ring itself into the main chain of polyurethane.
JP-A-53-39395 and JP-A-55-1840
No. 9, etc., and the above method is disclosed in JP-A-53-129.
No. 4 publication.

However, in the case of the above method, the hindered amine compound acts as a terminal terminating agent, which is an obstacle in increasing the degree of polymerization of polyurethane.
In particular, when a large amount of hindered amine compound is used in order to further improve the weather resistance and discoloration resistance of polyurethane, it is impossible to produce polyurethane having a desired degree of polymerization because the polyurethane is terminated at an extremely low degree of polymerization. There are drawbacks and the amount of hindered amine compound used is limited.

Further, in the case of the above method, the presence of a bulky hindered piperidine ring as a side chain in the hard segment portion hinders the formation of a crosslinked structure due to hydrogen bonding between the hard segments, so that the polyurethane is essentially Has the drawback that the excellent mechanical properties such as, for example, elastic recovery, tensile strength, etc. are liable to be deteriorated and the heat resistance is easily lost.

In the case of the above method, the polyurethane main chain is cleaved by light at the nitrogen atom portion of the piperidine ring in the polyurethane main chain, similarly to the radical scavenging mechanism known as the light stabilization mechanism of the hindered amine compound. Therefore, there is a drawback in that the light resistance of the polyurethane is not improved, and when exposed to light, the main chain is likely to be broken and the mechanical strength is likely to be lowered.

[0009]

From the above point of view, the inventors of the present invention have the drawbacks as in the above-mentioned prior art in which a matting agent or stabilizer such as titanium oxide is simply blended in polyurethane and the above-mentioned prior arts. No sunlight, NO _x gas, outdoor exposure to automobile exhaust gas, yellowing due to contact with chemical substances such as chlorine bleach or organic solvent and deterioration of mechanical properties, flexibility, heat resistance, Research has been conducted for the purpose of obtaining a polyurethane excellent in weather resistance and discoloration resistance and a fiber made of the same.

As a result, when producing polyurethane,
Without using the hindered amine compound containing a hindered piperidine ring as a terminal terminator or a chain extender, the hindered amine compound is incorporated as a side chain in a prepolymer type organic polyisocyanate having a molecular weight of a predetermined value or more, The prepolymer is used as at least a part of the organic diisocyanate used in producing a polyurethane, and a specific hindered phenolic compound having a molecular weight of 500 or more in the polyurethane thus produced, or the hindered phenol. The present invention has been completed by finding that the above object can be achieved by containing a specific compound and a specific benzophenone compound having a molecular weight of 1000 or more.

Accordingly, the present invention is directed to (a) a polyurethane obtained by using a polymeric diol, an organic diisocyanate and optionally a chain extender, wherein at least a part of the organic diisocyanate is at positions 2 and 6. A prepolymer-type organic compound having a piperidine ring-containing group in which each position is substituted with two alkyl groups in a pendant side chain, having an average molecular weight of 1500 or more and an average number of isocyanate groups of 1.8 to 3 In a polyurethane produced using polyisocyanate, (b) the following formula (I);

[0011]

[Chemical 4] (Wherein R ¹ and R ² each independently represent an alkyl group), and a hindered phenolic compound having a molecular weight of 500 or more and having at least one dialkylhydroxyphenyl group. Is a polyurethane composition.

The present invention also provides the above polyurethane (a) in the above hindered phenol compound (b), and (c) the following formula (II);

[Chemical 5] A benzophenone-based compound having a molecular weight of 1000 or more having at least one benzoylhydroxyphenyl group represented by

The present invention also includes a fiber produced from the above polyurethane composition containing a hindered phenolic compound or the above polyurethane composition containing a hindered phenolic compound and a benzophenone compound.

The above-mentioned "groups containing a piperidine ring in which 2-position and 6-position are each substituted with two alkyl groups, which are used for producing the above-mentioned polyurethane (a), are pendant in a side chain. "Prepolymer organic polyisocyanate having an average molecular weight of 1500 or more and an average number of isocyanate groups of 1.8 to 3" (hereinafter referred to as "piperidine side chain-containing prepolymer") has an average molecular weight of 1500 or more, preferably 1700. It has an average molecular weight of 10,000 to 10,000, a hindered piperidine ring is present in the prepolymer as a side chain in a pendant form, and the average number of isocyanate groups is 1.8 to 3, preferably 1.
Any material may be used as long as it is 9 to 2.8, and its manufacturing method and the like are not particularly limited.

In order to facilitate understanding of the content of the piperidine side chain-containing prepolymer used for producing the polyurethane (a), an example of a preferable production method thereof will be described below. However, of course, the piperidine side chain-containing prepolymer is not limited to the following.

[0016]Production example of piperidine side chain-containing prepolymer  (1) The number F of active hydrogen atoms such as hydroxyl groups is 2 <F <4
Polyester polyol, polyether polyol, etc.
Of the relatively high molecular weight polyols of
React with a salt (preferably organic diisocyanate)
And the average number of isocyanate groups is greater than 2, preferably
Isocyanate-terminated prepolymer of 2.2 to 3.8
To manufacture. (2) Isocyanate-terminated prepoly prepared in (1) above
Mer has one isocyanate-reactive active hydrogen atom
Substituted at the 2- and 6-positions with two alkyl groups each
A hindered amine compound containing a piperidine ring,
Isocyanate group of the isocyanate-terminated prepolymer
React a smaller amount than the equivalent amount, and average 1.8 to 3
Reacting isocyanate groups remain and hindered pi
Peridine ring as a side chain in a pendant form into a prepolymer
The above-mentioned piperid having an average molecular weight of 1500 or more, which is bonded
A gin side chain containing prepolymer is prepared.

As the polyol with 2 <F <4 used in the above step (1), at least one low molecular weight polyol having three or more hydroxyl groups such as glycerin, trimethylolpropane and pentaerythritol is present. In addition, at least one low molecular weight polyol having 3 or more hydroxyl groups such as polyester polyol of 2 <F <4 produced by reacting an organic dicarboxylic acid and a low molecular weight diol, glycerin, trimethylolpropane, and pentaerythritol, At least one low molecular weight polyol having 3 or more hydroxyl groups such as polyester polyol of 2 <F <4, glycerin, trimethylolpropane and pentaerythritol produced by reacting a lactone compound together with glycol, ethylene oxide, Propylene The alkylene oxide of the side like reacted can be mentioned 2 <F <4 polyether polyol produced by. And, those polyester polyols and polyether polyols are usually about 300-
It is desirable to have an average molecular weight of 5000, especially about 500 to 3000.

Further, as the organic polyisocyanate used in the above step (1), it is preferable to use an organic diisocyanate, and as such an organic diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, 1 , 5-naphthalene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and the like can be mentioned, and it is preferable to use one kind or two or more kinds of these organic diisocyanates.

Then, the "hindered amine compound containing a piperidine ring having one isocyanate-reactive active hydrogen atom and each substituted with two alkyl groups at the 2- and 6-positions" used in the above step (2). As long as it has a total of four alkyl groups bonded to the 2- and 6-positions of the piperidine ring and has one isocyanate-reactive active hydrogen atom, it is known in this type of technique. Any of the hindered amine compounds mentioned above can be used, and a typical compound thereof is a compound represented by the following formula (III).

[0020]

[Chemical 6] (Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each an alkyl group, R ⁷ is a direct bond or a divalent group, A and B are each a monovalent group, and A and B Only one has an isocyanate-reactive active hydrogen atom and m is 1
The above is the number)

In the compound of the above formula (III), R ³ , R
Each of 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. When R ⁷ is a divalent group, it may be a divalent hydrocarbon group such as an alkylene group or an arylene group, or a divalent group having an ester bond, an ether bond, a thioether bond, an amide bond or the like. it can. Furthermore, one of A and B is a monovalent group having an isocyanate-reactive active hydrogen atom, preferably an amino group, a hydroxyl group, a carboxyl group, or another group having a hydroxyl group, an amino group or a carboxyl group.
Valent groups (eg aminomethyl group, hydroxymethyl group,
And the other one of A and B is a monovalent group having no isocyanate-reactive active hydrogen atom such as an alkyl group, an aryl group, an alkoxy group and an aryloxy group. Further, m is preferably 1 to 20.

Specific examples of the hindered amine compound contained in the compound represented by the formula (III) include the following formula (I
1-methyl-2,2,6,6-tetramethyl-4-hydroxypiperidine represented by V), 1-methyl-2,2,6,6-tetramethyl-4 represented by the following formula (V)
-Aminopiperidine, compounds represented by the following formula (VI), and the like can be given.

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9] (In the formula, n represents a number of 2 to 20)

In the piperidine side chain-containing prepolymer used in the present invention, the proportion of the hindered amine compound contained in the piperidine side chain-containing prepolymer is about 5 to 7.
0% by weight, preferably about 10 to 60% by weight,
It is preferable from the viewpoints of improving the weather resistance, light resistance, discoloration resistance, heat resistance and the like of polyurethane and maintaining good mechanical properties. Then, the reaction (2) for producing the piperidine side chain-containing prepolymer is usually carried out at a temperature of about 50 to 200 ° C, preferably about 70 to 160 ° C.

The polyurethane used for producing the polyurethane fiber of the present invention is produced by the one-shot method, the prepolymer method, or the other method using a polymer diol, an organic diisocyanate and optionally a chain extender. It can be manufactured by a method. At that time, the piperidine side chain-containing prepolymer produced above may be reacted at the same time when producing a polyurethane by the one-shot method or the prepolymer method, or after producing a polyurethane containing no hindered piperidine side chain. In addition, it may be reacted. Therefore, in the case of producing a polyurethane fiber, a piperidine side chain-containing prepolymer is added to the polyurethane and reacted at any stage until the spinning is completed to chemically bond the hindered piperidine side chain to the molecule of the polyurethane. May be.

In any of the above methods,
The bond ratio of the hindered piperidine ring in the finally obtained polyurethane is not particularly limited, but in consideration of the effect of improving light resistance and weather resistance and the economical efficiency, it is usually based on the total weight of the raw materials for polyurethane. , Piperidine side chain-containing prepolymer usage ratio is about 0.1-20%
It is desirable to manufacture the polyurethane as follows.

As the above-mentioned polymer diol used in the above one-shot method, prepolymer method or other method, it is preferable to use one having an average molecular weight of 500 to 5,000, preferably 1,000 to 3,000.
As the polymer diol, at least one kind of polyester diol, polycarbonate diol, polyether diol, polyether ester diol and the like can be used, but polyester diol and polycarbonate diol are particularly preferable.

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

As the polycarbonate diol, for example, at least one kind of dialkyl carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate, etc.) and low molecular weight 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, polyether diol obtained by ring-opening polymerization of cyclic ether (polyethylene oxide, polypropylene oxide, trimethylene oxide, tetrahydrofuran, etc.), glycol (ethylene glycol, propylene glycol, 1,4-) Butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5
-Pentane diol, 2-methyl-1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, etc.) are preferred.

As the polyether ester diol, those produced by reacting the above polyester diol with the above cyclic ether, those obtained by reacting the above polyester diol and polyether diol, and the like are used. You can

As the organic diisocyanate other than the above-mentioned piperidine side chain-containing prepolymer, 4,
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. Particularly, 4,4'-diphenylmethane diisocyanate is preferable.

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. For example, 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.

Use in the compositions and fibers of the present invention, whether by the one-shot method or the prepolymer method, and whether or not the organic diisocyanate contains the piperidine side chain-containing prepolymer during the reaction. In producing the polyurethane, various known batch-type or continuous-type methods and apparatuses can be adopted.
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 2
It is preferable to carry out the polymerization at a temperature of 60 ° C.
Keeping the temperature at 0 ° C or lower improves the heat resistance and mechanical properties of the polyurethane, while keeping it at 200 ° C or higher 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 the present invention, the hindered phenol having at least one dialkylhydroxyphenyl group represented by the formula (I) and having a molecular weight of 500 or more is added to the polyurethane having the side chain containing the hindered piperidine ring. Including a system compound. When the molecular weight of the hindered phenol compound is less than 500, it is easy to bleed out on the surface of the polyurethane, and the hindered phenol compound is lost from the polyurethane due to dry cleaning treatment or the like over time, and the stabilizing effect of the polyurethane is not exhibited. The molecular weight of the hindered phenolic compound is preferably in the range of 500 to 5000.

The hindered phenol compound may be any compound as long as it has a molecular weight of 500 or more and has at least one dialkylhydroxyphenyl group represented by the formula (I) in the molecule. Of which
Particularly preferred are those in which R ¹ and R ² of the dialkylhydroxyphenyl group in the formula (I) are each a methyl, ethyl, propyl or t-butyl group.

Although not limited, preferred examples of the hindered phenol-based compound include the following formula (VII) from the viewpoint that the color tone of the polyurethane composition after blending is good.

[0040]

[Chemical 10] 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 can be mentioned.

The content of the hindered phenolic compound in the polyurethane is usually preferably in the range of 0.001 to 1.0% based on the weight of the polyurethane, thereby preventing the turbidity of the polyurethane. It is possible to prevent yellowing and improve NO _X resistance by improving light resistance. Further, the timing of adding the hindered phenolic compound to the polyurethane is not particularly limited, and 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. When added after production, the hindered phenolic compound can be added at any stage during the production of preforms such as polyurethane pellets, or during production of molded products, fibers and other products from polyurethane.

In the present invention, the polyurethane having a hindered piperidine ring-containing side chain contains the above-mentioned hindered phenolic compound, whereby the light resistance, heat resistance, heat coloring resistance, NO _X resistance and weather resistance of the polyurethane are improved. The properties are further improved, and the yellowing and deterioration of mechanical properties can be prevented more effectively.

Further, in the present invention, at least one benzoylhydroxyphenyl group represented by the above formula (II) is contained in the above polyurethane having a hindered piperidine ring-containing side chain together with the above hindered phenol compound.
A benzophenone compound having a molecular weight of 1000 or more may be contained, whereby the light resistance can be further improved while maintaining the heat resistance coloring resistance and the NO _x resistance. When the molecular weight of the benzophenone compound is less than 1000, bleeding out easily occurs on the surface of the polyurethane, and the compound is likely to be lost from the polyurethane by the dry cleaning treatment or with the passage of time. The molecular weight of the benzophenone compound 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.

The benzophenone compound has a molecular weight of 10
Any one may be used as long as it is at least 00 and has at least one benzoylhydroxyphenyl group represented by the above formula (II) in the molecule. Among them, the benzoylhydroxyphenyl group represented by the formula (II) is represented by the following formula (VIII);

[0045]

[Chemical 11] (Wherein R ⁸ represents an alkylene group), a benzophenone compound existing in the form of a monovalent group, particularly R ⁸ in the monovalent group represented by the formula (VIII) DE is a carbon number. Benzophenone compounds having 1 to 4 alkylene groups are preferred.

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

[0047]

[Chemical 12] Where n ₁ and n ₂ are n ₁ + n ₂ ≧ 35 and n
₂ / (n ₁ + n ₂ ) ≧ 0.2.] 2-hydroxy-4- (methacryloyloxyethoxy) benzophenone / methyl methacrylate copolymer and the like.

The amount of the benzophenone compound compounded in the polyurethane is usually 0.1% based on the weight of the polyurethane.
It is preferably in the range of 01 to 1.0%. When the amount of the benzophenone-based compound added is within the above range, the stabilizing effect of the benzophenone-based compound, particularly the light resistance improving effect, can be sufficiently exerted without causing bleeding out and the like. Further, the timing of adding the benzophenone compound 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, and it is generally desirable to add it during the melting of the polyurethane after the production of the polyurethane.

From the above, the polyurethane composition of the present invention excellent in flexibility, heat resistance, weather resistance, discoloration resistance and the like can be obtained. In the production of the polyurethane composition of the present invention and the above-mentioned polyurethane having a hindered piperidine ring-containing side chain used therein, a catalyst, an activator, an antifoaming agent and other stabilizers which are commonly used in the art. Any component such as a colorant such as a dye or a pigment, a filler, a flame retardant, and a lubricant can be used as necessary.

Since the polyurethane composition of the present invention is generally thermoplastic and has excellent moldability and processability, it is possible to apply the techniques commonly used for thermoplastic polyurethane, such as tubes, films, It can be effectively used for the production of various products such as extrusion molded products such as sheets, shoe soles by injection molding and other molding and other various molded products, synthetic leather, artificial leather, fibers and the like.

Among them, the polyurethane composition of the present invention is suitable for the material of polyurethane fiber, and in producing the polyurethane fiber of the present invention, for example, any method such as melt spinning method, dry spinning method and wet spinning method can be used. The method can be adopted, and the melt spinning method which does not use a solvent or water is particularly preferable.

In producing the polyurethane fiber, as described above, the piperidine side chain-containing prepolymer,
The hindered phenol-based compound and the benzophenone-based compound can be added at the time of producing the polyurethane, or at any stage until the spinning is completed after the production of the polyurethane. The polyurethane fiber of the present invention has excellent properties such as heat resistance, weather resistance and discoloration resistance as well as mechanical properties such as elastic recovery and elongation.

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. Further, in the following examples, the strength, light resistance, outdoor exposure test, NO _x resistance, color tone and heat resistance of polyurethane film, and the strength and elongation of polyurethane fiber, light resistance strength retention rate, and NO _x resistance are as follows. It was measured by the method.

<< Strength of Polyurethane Film >> Polyurethane film (thickness: 0.1 m) produced in each of the following examples.
For m), the strength was measured using an autograph manufactured by Shimadzu Corporation.

[Light resistance test of polyurethane film]
The polyurethane film (thickness of 0.
1 mm), carbon arc type manufactured by Suga Test Instruments Co., Ltd.
At a temperature of 83 ° C using a Fade meter FAL-5
Irradiation with ultraviolet light for 40 hours, its light yellowing resistance and strength
The retention rate was investigated. The light yellowing resistance is shown below by the degree of browning.
The evaluation was carried out according to the following five-level evaluation.Criteria for evaluation of light yellowing resistance  5 ... No discoloration (colorless) 4 ... Slightly yellowish 3 ... Yellow discoloring 2 ... Yellow to brown discoloring 1 ... Brown discoloring In addition, strength retention is Shimadzu Autograph of
Measure the strength of the polyurethane film using
It was calculated from Equation 1.

[0056]

[Formula 1] Strength retention rate (%) = (strength after ultraviolet irradiation / strength before ultraviolet 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.

[0058]

[Formula 2] Strength retention rate (%) = (strength after outdoor exposure / strength before outdoor exposure) × 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, and the strength retention before and after this treatment was compared with that of the above strength retention. It was determined according to the formula.

<< Color Tone of Polyurethane Film >> Each of the following
Degree of coloring of polyurethane composition pellets produced in the example
Is then prepared by hot pressing as described in Example 1.
The color tone of the produced film having a thickness of 0.1 mm was evaluated.Color evaluation criteria  5 ... No discoloration (colorless) 4 ... Slightly yellow discoloration 3 ... Yellow discoloration 2 ... Yellow-brown discoloration 1 ... Brown discoloration

<Heat resistance of polyurethane film> The dynamic viscoelasticity of a polyurethane film having a thickness of 0.1 mm, a width of 5 mm and a length of 30 mm was measured, and the storage elastic modulus ratio at 100 ° C. and 130 ° C. It was calculated by The dynamic viscoelasticity was measured by a dynamic viscoelasticity measuring device DVE-4 manufactured by Rheology.

[0062]

## EQU00003 ## Storage modulus ratio = (storage modulus at 130.degree. C./1
Storage modulus at 00 ° C) x 100

<< Strength and Elongation of Polyurethane Fiber >> JIS L
The strength and elongation was determined according to -1013.

<< Light resistance strength retention of polyurethane fiber >>
Polyurethane fiber produced in each of the following examples
A carbon arc type fade meter FAL- manufactured by Suga Test Instruments Co., Ltd., which was wound on a frame under a tension of 0 g / denier.
The strength retention was determined by irradiating with ultraviolet ray at a temperature of 83 ° C. for 20 hours using a No. 5 type. The strength retention rate was calculated from the following Equation 4 using an autograph manufactured by Shimadzu Corporation.

[0065]

[Formula 4] Strength retention rate (%) = (strength after ultraviolet irradiation / strength before ultraviolet irradiation) × 100

<< Polyurethane fiber NO _x resistance test >> 40
Denier polyurethane elastic fiber with NO ₂ gas concentration of 6
The sample was treated in air increased to 50 ppm for 1 hour, and the strength retention before and after this was determined according to the above formula of strength retention.

The compounds used in each example are as shown by the following abbreviations. MPD : 3-methyl-1,5-pentanediol BD : 1,4-butanediol TMP : trimethylolpropane AD : adipic acid AZ : azelaic acid PMAZ : polyester of average molecular weight 2000 obtained by reacting MPD and AZ Diol MDI : 4,4'-diphenylmethane diisocyanate stabilizer (a) : 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (hindered amine compound) stabilizer (b ) represented by the above formula (IV) ) : Hindered phenolic compound stabilizer represented by the above formula (VII) (c) : Benzophenone compound represented by the above formula (IX) (n ₁ / n ₂ = 50/50; average molecular weight 3000)
0)

Reference Example 1 [Production of Trifunctional Polyester] 134 parts of TMP, 460 parts of MPD, 603 parts of AZ and 0.05 part of titanium tetraisopropoxide were passed under nitrogen at normal pressure while the produced water was distilled at 210 ° C. Esterification was performed while leaving. When the acid value reached about 50, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. As a result, a trifunctional polyester triol (polyester A) having a hydroxyl value of 168, an acid value of 0.5 and an average molecular weight of 1000 was obtained.

Reference Example 2 [Production of Trifunctional Polyester] TMP, MPD, AD and titanium tetraisopropoxide were used to carry out a condensation reaction in the same manner as in Reference Example 1 to give a hydroxyl value of 198 and an acid. Value 0.5 and average molecular weight 85
A trifunctional polyester triol of 0 (Polyester B) was obtained.

Reference Example 3 [Production of Piperidine Side Chain-Containing Prepolymer] 100 parts of polyester A was placed in a reaction vessel sealed with nitrogen, and 75 parts of MDI was added while maintaining at 90 ° C. to give 40 parts.
After reacting for 1 minute, 13.7 parts of stabilizer (a) was added to 1
After the reaction for time, the average number of functional groups (average number of isocyanate groups) is 2.2, and the amount of binding (content) of the stabilizer (a) is
Of 7.3% by weight of piperidine side chain-containing prepolymer (Prepolymer C; average molecular weight 1921) was produced.

Reference Example 4 [Production of Piperidine Side-Chain-Containing Prepolymer] 85 parts of polyester B was placed in a reaction vessel sealed with nitrogen, 75 parts of MDI was added while maintaining at 90 ° C., and the mixture was reacted for 40 minutes. , 13.7 parts of stabilizer (a) was added and reacted for 1 hour, and the average number of functional groups (average number of isocyanate groups) was 2.2, and the binding amount (content) of stabilizer (a)
Of 7.9% by weight of piperidine side chain-containing prepolymer (Prepolymer D; average molecular weight 1771) was produced.

Examples 1 to 4 [Production of Polyurethane Film] A mixture containing PMAZ and BD shown in Table 1 below in a ratio shown in Table 1 and heated to 80 ° C. and MDI heated to 50 ° C. were melted. It is continuously fed to a twin-screw extruder by a metering pump, and further, the piperidine side chain-containing prepolymers (prepolymers C to D) shown in Table 1 heated to 130 ° C. are continuously fed by a static mixer to be continuously fed. Melt polymerization was carried out, and the produced polyurethane was extruded into water in a strand shape and cut into polyurethane pellets.

When the above pellets were dehumidified and dried at 80 ° C. for 20 hours and melt-extruded by a twin-screw extruder, the stabilizer (b) or the stabilizer (b) and the stabilizer (b) were added from the middle of the cylinder.
(c) was added and mixed in the proportions shown in Table 1 to obtain a polyurethane composition in the form of pellets. The pelletized polyurethane composition was dehumidified and dried at 80 ° C. for 20 hours and then dried at a temperature of
A film having a thickness of 0.1 mm was prepared by hot-pressing with, and the strength, light resistance, heat resistance, NO _x resistance and color tone were measured, and the outdoor exposure test was conducted by the above-mentioned method. The results are shown in Table 1.

Comparative Examples 1 and 2 The amounts of PMAZ and M shown in Table 1 were used without using the piperidine side chain-containing prepolymer.
Examples 1 to 2 on a twin-screw extruder using DI and BD
Polyurethane pellets were produced in the same manner as in 4. When the pellets are dehumidified and dried at 80 ° C. for 20 hours and melt-extruded by a twin-screw extruder, the stabilizer (a) and the stabilizer (b) are added from the middle of the cylinder, or the stabilizer (a) and the stabilizer are stabilized. The three components, agent (b) and stabilizer (c), were added in the proportions shown in Table 1 and mixed, and a pelletized polyurethane composition was obtained in the same manner as in Example 1. How this from pelletized polyurethane composition in the same manner as in Example 1 to prepare a film having a thickness of 0.1 mm, its strength, light resistance, heat resistance, measured as well as outdoor exposure test of resistance to NO _x resistance and color tone above Went by. The results are shown in Table 1.

[0075]

[Table 1]  Example Comparative example 1 2 3 4 1 2 Raw material for polyurethane  PMAZ usage amount (molar ratio) 1.00 1.00 1.00 1.00 1.00 1.00 MDI usage amount (molar ratio) 2.90 2.90 2.90 2.90 3.00 3.00 BD usage amount (molar ratio) 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Prepolymer species CDC D − − Used Amount (molar ratio) 0.090 0.090 0.090 0.090 − −Stabilizer content (wt% ) (A) 0.40 0.40 0.40 0.40 0.40 0.40 (b) 0.40 0.40 0.40 0.40 0.40 0.40 (c) 0 0 0.20 0.20 0 0.20Strength (kg / cm) 480 500 520 470 180 200Light resistance test  Lightfastness 4.5 4.5 4.5 4.5 4.5 4.5 Strength retention (%) 92 89 89 90 48 56Heat resistance (ratio of storage modulus ) 95 94 92 93 72 73NO _x resistance (strength retention) (% ) 87 90 91 88 82 83Color tone 5 5 5 5 5 5Outdoor exposure test (strength retention rate) 78 74 88 86 70 83(%)

In Table 1, the content of the stabilizer (a) in Examples 1 to 4 is the amount of the stabilizer incorporated in the polyurethane molecule as the piperidine side chain-containing prepolymer.
The amount of (a) is shown.

From the results shown in Table 1 above, from the polyurethane composition of the present invention in which a hindered phenol type compound or a hindered phenol type compound and a benzophenone type compound are further contained in a polyurethane containing a hindered piperidine ring side chain. The films of Examples 1 to 4 thus obtained have strength, light resistance, heat resistance, and NO resistance as compared with the films obtained from the polyurethane compositions of Comparative Examples 1 and 2 in which the polyurethane molecule does not contain a hindered piperidine ring. _It can be seen that the _x property and the weather resistance are all excellent. Also, Table 1
From the results, it can be seen that the weather resistance (outdoor exposure test) is further improved when both the hindered phenol compound and the benzophenone compound are contained in the polyurethane containing the hindered piperidine ring side chain.

Examples 5 to 8 Polyurethane pellets were produced using the piperidine side chain-containing prepolymer in the same manner as in Examples 1 to 4, and the pellets were dehumidified and dried at 80 ° C. for 20 hours. Stabilizer (b) or stabilizer from the middle of the cylinder during melt extrusion by the axial extruder
(b) and the stabilizer (c) were added and mixed in the proportions shown in Table 2 to obtain a polyurethane composition in the form of pellets.

The pelletized polyurethane composition was blended with 80
After dehumidifying and drying at 20 ° C. for 20 hours, using a conventional spinning machine with a single-screw extruder, the spinning temperature is 235 ° C., the spinning speed is 650 m / min,
Apparent draft rate 847, spinning tension 0.1g /
d, spinning at a yarn feeding speed difference of 25 m / min, 40 denier / 1
A polyurethane raw yarn of filament was obtained. 8 of this yarn
After aging at 0 ° C. for 48 hours, the obtained fibers were measured for light resistance, strength and elongation and NO _x resistance, and subjected to an outdoor exposure test by the methods described above. The results are shown in Table 2.

Comparative Examples 3 to 4 The amounts of PMAZ and M shown in Table 2 were used without using the piperidine side chain-containing prepolymer.
Examples 5 to 5 with a twin screw extruder using DI and BD
Polyurethane pellets were produced as in 8. When the pellets are dehumidified and dried at 80 ° C. for 20 hours and melt-extruded by a twin-screw extruder, the stabilizer (a) and the stabilizer (b) are added from the middle of the cylinder, or the stabilizer (a) and the stabilizer are stabilized. The three components, agent (b) and stabilizer (c), were added and mixed in the proportions shown in Table 1, and a polyurethane composition in pellet form was obtained in the same manner as in Example 1. Polyurethane fibers were produced from the pelletized polyurethane composition in the same manner as in Examples 5 to 8, and the light resistance, the strength and elongation and the NO _x resistance were measured, and the outdoor exposure test was performed by the above-mentioned methods. The results are shown in Table 2.

[0081]

[Table 2]  Example Comparative example 5 6 7 8 3 4 Raw material for polyurethane  PMAZ dose (molar ratio) 1.00 1.00 1.00 1.00 1.00 1.00 MDI usage (molar ratio) 2.90 2.90 2.90 2.90 3.00 3.00 BD usage (molar ratio) 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Prepolymer species C CDD − − Usage (Molar ratio) 0.090 0.090 0.090 0.090 − −Stabilizer content (wt% ) (A) 0.40 0.40 0.40 0.40 0.40 0.40 (b) 0.40 0.40 0.40 0.40 0.40 0.40 (c) 0 0 0.20 0.20 0 0.20Strength (g / d ) 1.3 1.4 1.4 1.2 0.8 0.8Elongation (% ) 520 480 500 510 500 490Light resistance test  Lightfastness 4.5 4.5 4.5 4.5 4.5 4.5 Strength retention (%) 92 88 87 89 43 55NO _x resistance (strength retention) (% ) 90 92 93 94 86 84Outdoor exposure test (strength retention rate) 76 74 87 89 70 82(%)

In Table 2, the content of the stabilizer (a) in Examples 5 to 8 is the stabilizer incorporated in the polyurethane molecule as the piperidine side chain-containing prepolymer.
The amount of (a) is shown.

From the results of Table 2 above, it was obtained from a polyurethane composition containing a hindered phenol type compound or a hindered phenol type compound and a benzophenone type compound in a polyurethane containing a hindered piperidine ring side chain. The polyurethane fibers of Examples 5 to 8 of the present invention are Comparative Examples 3 to 4 obtained from polyurethane compositions containing no hindered piperidine ring in the polyurethane.
It can be seen that the polyurethane fiber is superior in strength and elongation to the polyurethane fiber, and is also excellent in all of light resistance, NO _x resistance and weather resistance. Furthermore, from the results in Table 2, when both the hindered phenol compound and the benzophenone compound are contained in the polyurethane containing the hindered piperidine ring side chain, the weather resistance (outdoor exposure test) is further improved. I understand.

[0084]

Industrial Applicability The polyurethane composition of the present invention and the polyurethane fiber produced from the polyurethane composition can be exposed to sunlight, NO _x gas,
It has very little yellowing due to outdoor exposure to automobile exhaust gases, contact with chemicals such as chlorine bleach and solvents, and has excellent heat resistance and mechanical properties such as strength and elongation. In the polyurethane composition and fiber of the present invention, since the hindered amine stabilizer is side-chained and chemically bonded to the soft segment of the polyurethane, problems such as bleed-out on the polyurethane surface and dropping from the polyurethane do not occur. Further, in the present invention, when both the hindered phenol compound and the benzophenone compound are contained in the polyurethane containing the hindered piperidine ring side chain, the weather resistance is further improved.

Claims (3)

[Claims] 1. A polyurethane obtained by using (a) a polymeric diol, an organic diisocyanate and, if necessary, a chain extender, wherein at least a part of the organic diisocyanate has 2- and 6-positions of 2 respectively. Prepolymer-type organic polyisocyanate having an average molecular weight of 1500 or more and an average number of isocyanate groups of 1.8 to 3 and having a pendant group containing a piperidine ring substituted with 4 alkyl groups is used. (B) the following formula (I); (Wherein R ¹ and R ² each independently represent an alkyl group), and a hindered phenolic compound having a molecular weight of 500 or more and having at least one dialkylhydroxyphenyl group. A polyurethane composition. 2. A polyurethane obtained by using (a) a polymeric diol, an organic diisocyanate and optionally a chain extender, wherein at least a part of the organic diisocyanate has 2- and 6-positions respectively. Prepolymer-type organic polyisocyanate having an average molecular weight of 1500 or more and an average number of isocyanate groups of 1.8 to 3 and having a pendant group containing a piperidine ring substituted with 4 alkyl groups is used. In the polyurethane produced by (b), the following formula (I); (In the formula, R ¹ and R ² 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 ( II); A benzophenone compound having at least one benzoylhydroxyphenyl group and having a molecular weight of 1000 or more; 3. A polyurethane fiber produced from the polyurethane composition according to claim 1 or 2.