JP2625508B2 - Stabilized polyurethane - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to stabilized polyurethanes. More specifically, the present invention relates to a polyurethane having excellent light resistance, NOx resistance, chlorine resistance, and heat resistance.

2. Description of the Related Art Polyurethane is a polymer obtained from polyisocyanate, polyhydroxy compound and polyfunctional active hydrogen compound as raw materials, and since its properties are excellent in elasticity, elastomers, foams, leather, and elastic yarns are used. Widely used for coating materials. However, polyurethane has problems of heat resistance, oxidation resistance, and light resistance. Deterioration and discoloration occur especially during molding and use of products, and therefore, the use of stabilizers such as antioxidants and light stabilizers. Without a doubt, many stabilizers and combinations thereof have been developed and proposed.

Particularly when polyurethane is produced and used for elastic yarn, its stability is required to be higher. That is, polyurethane elastic yarn requires a long process such as spinning, heat treatment, scouring, bleaching, dyeing, post-treatment, and processing, and in terms of utilization, it is worn and washed repeatedly as fiber or clothing. Since it is returned, it is desired to have a high stability which is susceptible to deterioration and coloring and does not suffer from deterioration and coloring due to the conditions of the multi-step process. When used for clothing, coloring or discoloration caused by daily use impairs the beauty itself and lowers its value.

Conventionally, various stabilizers and combinations thereof have been proposed for polyurethane stabilization, but none of polyurethanes satisfy all the stability in light resistance, NOx resistance, chlorine resistance, and heat resistance. Equal to. In particular, there is no polyurethane which is stable to NOx gas for a long time and does not discolor or discolor.

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a polyurethane excellent in various stability, particularly a polyurethane suitable as an elastic yarn.

Other objects of the present invention are light resistance, NOx resistance, chlorine resistance,
An object of the present invention is to provide a stabilized polyurethane having excellent heat resistance.

Still another object of the present invention is to provide a stabilized polyurethane which has very little deterioration, discoloration or coloring even when exposed to a NOx gas atmosphere for a long time.

Still another object of the present invention is to provide a stabilized polyurethane in which the whiteness of the polyurethane is impaired or the compatibility of the additive is improved by adding and combining the stabilizer.

Still other objects of the present invention will become more apparent from the following description.

According to the study of the present inventors, the object of the present invention is to provide a polyurethane (A) having the following general formula (I) However Shikichu, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ²
Represents a t-butyl group, a sec-butyl group or a neopentyl group, a phenolic compound represented by the following formula, (B) a benzotriazole ultraviolet absorber, (C) a hindered amine light stabilizer, and (D) a general formula (II) ) However, in the formula, R ^{3 to} R ⁴ are the same or different and have 1 to 4 carbon atoms.
And X represents a divalent hydrocarbon group having 15 or less carbon atoms. It has been found that this is achieved by a stabilized polyurethane containing a semicarbazide compound represented by the following formula:

According to the present invention, various combinations of the above-mentioned stabilizers (A) to (D) are excellent in various stability in the production process of polyurethane, particularly polyurethane elastic yarn, and in the stage of its use. No deterioration, discoloration or coloring is observed, and in particular, there is an excellent advantage that no stability is lost even when exposed to a NOx atmosphere for a long time.

 Hereinafter, the present invention will be described in more detail.

The polyurethane in the present invention may be any one obtained by a usual method, but it is suitable as an elastic yarn, and the polyurethane used therefor is preferably used. Hereinafter, the polyurethane that can be used in the present invention will be described, but this is merely an example, and the present invention is not limited thereto. Polyurethanes are generally obtained by reacting diisocyanates with polymers having two or more terminal hydroxyl groups, in particular polyesters, polyols, optionally with polyfunctional active hydrogen compounds.

Polymers having two or more terminal hydroxyl groups used for the production of polyurethanes (referred to as "polyhydroxy polymers") are substantially linear and have a molecular weight ranging from about 600 to about 7,000. Things are appropriate. Further, the melting point of such a polymer is about 65 ° C. or less, preferably about
Those below 50 ° C. are advantageously used.

Examples of the polyhydroxy polymer include at least an aliphatic glycol having 2 to 10 carbon atoms such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and neopentylene glycol. A glycol component comprising one and at least one aliphatic dicarboxylic acid having 2 to 10 carbon atoms such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and cyclohexanedicarboxylic acid. And a polyester diol as a dicarboxylic acid component is preferred. The polyester diols include those in which an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, or hydroxybenzoic acid is used as a copolymer component. Further, the polyhydroxy polymer includes a polyol or polyester such as polytetramethylene ether diol and polycaprolactone diol.

On the other hand, examples of the polyisocyanate which is reacted with the polyhydroxy polymer to form a polyurethane include, for example, 2,4-toluylene diisocyanate (TDI), 4,4 '
-Diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), 1,4-phenylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (HMDI), naphthalene diisocyanate, xylylene diisocyanate ( XDI) is used, but preferred diisocyanates are TDI, MDI, HD
I, HMDI, XDI, etc.

When a polyurethane polymer is obtained, for example, diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, xylylenediamine, 4,4'-diaminodiphenylmethane, and hydrazine; diols such as ethylene glycol and 1,4-butanediol ;
Water; at least one polyfunctional active hydrogen compound such as dihydrazide, carbon dihydrazide, and hydrazides such as β-aminopropionic acid hydrazide may be further used.

The (A) phenolic compound added to the polyurethane in the present invention is a compound having two spiro rings represented by the above general formula (I). In the general formula (I), R ¹ has 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-, iso- or ter-butyl group.
And preferably a methyl group or a ter-butyl group. R ² is a t-butyl group, a sec-butyl group or a neopentyl group. Specific examples of the phenolic compound (A) of the general formula (I) include the following.

3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy]-
1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis {2- [3- (3,5-di-t-butyl-4-)
[Hydroxyphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,
5] undecane, 3,9-bis {2- [3- (3-iso-butyl-4-hydroxy-5-methylphenyl) propionyloxy] 1,
1'-dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis {2- [3- (3-neopentyl-4-hydroxy-5-methylphenyl) propionyl Oxy]
1,1'-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis {2- [3- (3-tert-butyl-5-ethyl-4) -Hydroxyphenyl) propionyloxy] 1,
1'-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

These phenolic compounds (A) are usually used in an amount of 0.1 to 5% by weight, preferably 0.2 to 3% by weight, based on the polyurethane.
Is added in the range of

As the (B) benzotriazole-based ultraviolet absorber, those generally added as an ultraviolet absorber of various polymers are used. Specifically, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2
-(3-t-butyl-5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole,
-[2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (3-t
-Butyl-5-methyl-2-hydroxyphenyl) -5
-Chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amino-2-hydroxyphenyl) Benzotriazole, 2- (3-sec-
Butyl-5-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-dineopentyl-2-
(Hydroxyphenyl) benzotriazole, 2- (4-
Octyloxyphenyl-2-hydroxy) benzotriazole. These (B) benzotriazole-based ultraviolet absorbers are generally used in an amount of 0.
It is used in the range of 1 to 5% by weight, preferably 0.2 to 3% by weight.

Examples of the hindered amine light stabilizer (C) include bis (2,2,6,6-tetramethyl-4-piperidyl) adipate and bis (2,2,6,6-tetramethyl-4) dibenzylmalonate. -Piperidyl), 2- (3,5-di-t-butyl-)
4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), dimethyl succinate-1- (2-hydroxyethyl) -4-
Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl ] [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [[2,2,6,6-tetramethyl-4-piperidylimino)], bis (3,5-di-t-butyl-4-hydroxybenzyl) malone Acid-bis (2,2,6,6-tetramethyl-
4-piperidyl), 3,5-di-t-butyl-4-hydroxy-hydroquinamic acid-2,2,6,6-tetramethyl-4-piperidyl, 1,3,8-triaza-2-oxo -3
Phenyl-4-imino-7,7,9,9-tetramethyl-spiro [4,5] decane, hexamethylene-bis (1,3,8-triaza 2,4-dioxo-7,7,9, 9-tetramethyl-3-
Il-spiro (4,5) decane) and the like. It is desirable that the hindered amine light stabilizer (C) is used in an amount of 0.1 to 5% by weight, preferably 0.2 to 3% by weight, based on the polyurethane.

(D) The semicarbazide-based compound is represented by the general formula (II), wherein R ^{3 to} R ⁶ are the same or different and have 1 carbon atom.
To 4 alkyl groups, examples of which are methyl, ethyl, n- or iso-propyl, n-, sec-
Or t-butyl is shown, but methyl is preferred. X in the formula [II] is a divalent hydrocarbon group having 15 or less carbon atoms, and examples thereof include-(CH ₂ ) n-, (Where n is an integer of 10 or less, m is an integer of 3 or less, 1 is 0
And r represents an integer of 0 to 4).
Specific examples of these (D) semicarbazide light stabilizers include, for example, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide) and 4,4 ′-(methylenedi-p-phenylene) bis (N, N- Diethylsemicarbazide), 4,4'-
(Methylenedi-p-phenylene) bis (N, N-diethylsemicarbazide), 4,4 '-(methylenedi-p-phenylene) bis (N, N-di-i-propylsemicarbazide), α, α- (p- Xylylene) bis (N, N-dimethylsemicarbazide), 1,4-cyclohexylenebis (N, N
-Dimethylsemicarbazide) and the like. These (D) semicarbazide-based light stabilizers are advantageously compounded in an amount of 0.1 to 5% by weight, preferably 0.2 to 3% by weight, based on the polyurethane.

In the present invention, the compounds (A) to (D) are added to the polyurethane in combination, and the total of (A) to (D) is 0.4 to 10% by weight, preferably 0.8 to 5% by weight of the polyurethane.
It is desirably in the range of weight%. These (A) ~
(D) may be added together or separately. The timing of addition may be at any time during the production and molding of the polyurethane, but is preferably after the production of the polyurethane and before the molding.

The molding of the stabilized polyurethane according to the present invention depends on its purpose, but it can be carried out by dry, wet or melt molding to obtain fibers, films, leather, foam and the like. In particular, the present invention is preferably used as a fiber, that is, an elastic yarn. In the stabilized polyurethane of the present invention, addition of other additives generally used in the polyurethane, that is, pigments, dyes, stabilizers, extenders, and the like can be performed without any problem.

Thus, according to the present invention, a stabilized polyurethane having excellent light resistance, NOx resistance, chlorine resistance and heat resistance can be obtained by the combination of the above (A) to (D).

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

The term “parts in the examples” means “parts by weight” unless otherwise specified.

Also, during the execution, the stability test of the polyurethane was measured by the following methods.

・ Weather resistance test: Wind a 40 denier polyurethane fiber around an aluminum plate and irradiate it with Suga Test Machine UV long life weather meter for 20 hours.
The change (ΔE) was determined by measuring with a 1001DP colorimeter. The strength before and after the treatment was measured with a Tensilon tester, and the strength retention (%) was determined.

-NOx resistance test: A 40 denier polyurethane fiber was wound around an aluminum plate and treated with a NOx gas concentration of 650 ppm for 1 hour in accordance with JIS-L-0855-1976. I asked.

-Chlorine resistance test: A 40 denier polyurethane fiber was treated in an aqueous solution having a chlorine concentration of 30 ppm for 5 hours, and the ΔE value and the strength retention were similarly determined.

Heat resistance test: A 40 denier polyurethane fiber was stretched twice and fixed, and treated at 180 ° C. for 60 seconds. Similarly, the strength retention was determined.

Example 1 2000 parts of polytetramethylene glycol having a molecular weight of 2,000
500 parts of 4,4'-diphenylmethane diisocyanate was mixed and reacted at 90 ° C. for 60 minutes to synthesize a prepolymer having isocyanate groups at both ends. After adding and dissolving 5833 parts of dimethylacetamide, the mixture was cooled to 0 ° C., and a small amount of a blue pigment and 1.75 parts of titanium oxide were added. While stirring the solution, a solution obtained by dissolving 54 parts of ethylenediamine in 1746 parts of dimethylacetamide was added dropwise over about 1 hour to carry out a chain extension reaction. Thereafter, a solution of 12.9 parts of di-n-butylamine in 121.6 parts of dimethylacetamide was added at a time to eliminate free isocyanate groups in the polymer solution. The solid content in the obtained polymer solution is
At 25%, the viscosity at 30 ° C. is 2000 poise.

To this polymer solution was added 3,9-bis {2- [3- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10
12.8 parts of tetraoxaspiro [5,5] undecane (hereinafter referred to as compound A-1) and 2- (5-methyl-2-hydroxyphenyl) benzotriazole (hereinafter referred to as compound B-
1), 12.8 parts of bis (2,2,6,6-tetramethyl-4-piperidyl) adipate (hereinafter referred to as compound C-1) and 1,6-hexamethylenebis (N, N 12.8 parts of dimethylsemicarbazide (hereinafter referred to as compound D-1) was added, and the mixture was discharged into an atmosphere at 200 ° C. to spin a 40-denier fiber.

This fiber was subjected to a weather resistance test, a NOx resistance test, a chlorine resistance test, and a heat resistance test. The results are shown in Table 1. In addition, Table 2 shows the values of the respective additives in terms of percentages by weight based on the weight of the polyurethane.

Comparative Example 1 The same test as in Example 1 was performed, except that nothing was added to the polymer solution of Example 1. The results are shown in Table 1.

Example 2 Except that 4,4 '-(methylenedi-p-phenylene) bis (N, N-dimethylsemicarbazide) (hereinafter referred to as compound D-2) was used instead of compound D-1 in Example 1, An experiment was performed in the same manner as in Example 1. Table 1 shows the results.
And the mixing ratio is shown in Table 2.

Example 3 In Example 1, the above compound D was used instead of compound D-1.
Except that Compound-2 is used and 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole (hereinafter referred to as Compound B-2) is used in place of Compound B-1. The experiment was performed as in Example 1. The results are shown in Table 1, and the mixing ratio is shown in Table 2.

Comparative Example 2 An experiment was performed in the same manner as in Example 1 except that only the compound A-1 was added to the polymer solution of Example 1. The results are shown in Table 1, and the mixing ratio is shown in Table 2.

Comparative Example 3 In Example 2, pentaerythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (hereinafter referred to as compound X) was used instead of compound A-1. The experiment was carried out in the same manner as in Example 2 except for the above. The results are shown in Table 1 and the blending ratio is shown in Table 2.

Comparative Example 4 In Example 2, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (hereinafter referred to as compound Y) was used in place of compound A-1, Otherwise, the experiment was performed in the same manner as in Example 2. The results are shown in Table 1, and the mixing ratio is shown in Table 2.

Claims (1)

(57) [Claims] (1) A polyurethane having the following general formula (I): In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, and R ² represents t-
A phenolic compound represented by the following formula, which represents a butyl group, a sec-butyl group or a neopentyl group, (B) a benzotriazole-based ultraviolet absorber, (C) a hindered amine-based light stabilizer, and (D) a general formula (II) shown below. In the formula, R ^{3 to} R ⁶ represent the same or different alkyl groups having 1 to 4 carbon atoms, and X represents a divalent hydrocarbon group having 15 or less carbon atoms. A stable compound containing a semicarbazide compound represented by Polyurethane.