JPH01207350A - Polyurethane composition - Google Patents

Abstract

PURPOSE:To obtain a polyurethane composition having excellent color change resistance in gas, light resistance, heat resistance, etc., containing a specific phenolic compound, benztriazole ultraviolet light absorber, hindered amine antioxidant and hydrazine derivative. CONSTITUTION:A polyurethane composition comprising (A) polyurethane, (B) a phenolic compound shown by formula I (R1 is t-butyl, sec-butyl or neopentyl group), preferably 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and (C) C1: a benztriazole ultraviolet light absorber, C2: a hindered amine antioxidant and C3: a hydrazine derivative containing one or more groups shown by formula II (R1 is H or methyl; R3 is H, monofunctional or bifunctional organic group) and obtained by blending the component A with 0.1-5 pts.wt. component B and 0.2-10wt.% sum of components B and C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to stabilized polyurethane compositions. More specifically, the present invention relates to a polyurethane elastomer composition that is stabilized against deterioration and discoloration caused by sunlight, heat, sterilizing chlorine, combustion gas, and the like.

Polyurethanes obtained from polyisocyanates, relatively low molecular weight polymer diols, and low molecular weight polyfunctional active hydrogen compounds have excellent mechanical properties and are easy to process, so they can be used in foams, elastomers, paints, synthetic leathers, fibers, etc. Although it has a wide range of uses, it is essential to use some co-stabilizers to prevent deterioration during processing and to impart durability.

However, the combination of stabilizers, especially phenolic antioxidants, which are highly effective, can often cause products to discolor due to combustion gas or chlorine, so consideration should be given to their selection in addition to effectiveness. There are many. Among them, 4,
Polyurethane elastomer obtained from diisocyanates such as 4'-diphenylmethane diisocyanate, polyether diols such as polytetramethylene ether diol, or polyester diols such as polyethylene adipate diol, and low molecular weight bifunctional active hydrogen compounds such as ethylene diamine, propylene diamine, and butane diol. In particular, the primary condition for stabilizers used in clothing fibers, tapes, etc. is that they have durability against processing steps such as scouring, bleaching, dyeing, and heat treatment leading to the final product, as well as home washing during the practical stage. However, it must not cause discoloration such as yellowing, which impairs aesthetic appearance.

Furthermore, in addition to the polyurethane elastomer itself, the stabilizer must not cause discoloration of the mating fibers used together with the polyurethane in textile products, especially nylon fibers.

The present inventors have completed the present invention as a result of intensive research aimed at overcoming such constraints and imparting excellent stability to polyurethane products.

That is, the present invention provides polyurethane with general formula (I) (wherein,
R represents a group selected from a t-butyl group, a 5ee-butyl group, and a neopentyl group), (a) a benztriazole-based ultraviolet absorber, (b) a hindered amine-based antioxidant, and (c) In the molecule, the general formula (II)\ (wherein R2 represents a group selected from hydrogen and a methyl group, and R3 represents a group selected from hydrogen and a monovalent or divalent slave group) An object of the present invention is to provide a polyurethane composition containing a compound selected from hydrazine derivatives having at least one group represented by .).

According to the present invention, the light stability, chlorine resistance,
Gas yellowing resistance, heat resistance, etc. can be significantly improved. It also has the characteristic that when the fibers formed from the composition of the present invention are mixed with other fibers, such as nylon fibers, they do not cause discoloration of the nylon fibers. Furthermore, it has many advantages in industrialization, such as no trouble occurring during the molding process or post-processing of the molded product, and no decrease in physical properties or whiteness.

Examples of the phenolic compound represented by the general formula (I) of the present invention include 1,3.5-)lis(4-t-butyl-3
-Hydroxy-2,6-dimethylbenzyl) isotheateric acid, 1,3.5-tris(4-sec-butyl-3
-Hydroxy-2゜6-dimethylbenzyl) isotheateric acid, 1゜3.5-)lis(4-neopentyl-3-
Examples include hydroxy-2,6-dimethylbenzyl)intheatal acid. Particularly preferred from the viewpoint of production and effectiveness is 1,3.5-tris(4-t-butyl-3-hydroxy-2,8-dimethylbenzyl)intheatal acid. The blending amount of these phenolic compounds is usually 0.1 to 10% by weight, preferably 0.5 to 3% by weight based on the polyurethane.

The polyurethanes used in the present invention include 4,4'-diphenylmethane diisocyanate, 114' unilene diisocyanate, 2,4-tolylene diisocyanate,
naphthalene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate,
One type of diisocyanate such as 4,4'-dicyclohexylmethane diisocyanate and xylylene diisocyanate, or a mixture thereof, preferably 4,4'-diphenylmethane diisocyanate and a diisocyanate having a molecular weight of 600 to 7,000 and having hydroxyl groups at both ends. Substantially linear polymers such as polytetramethylene ether diol, polycaprolactone diol, and one of the glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.
species or a mixture thereof and one or a mixture of aliphatic dicarboxylic acids such as succinic acid, geltaric acid, adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, β-methyladipic acid, hexahydroterephthalic acid, and Part is a polyester diol having a melting point of 60°C or less, preferably 40°C or less, prepared from a dicarboxylic acid which may also contain an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid, or a mixture thereof. Functional active hydrogen compounds such as hydrazine, ethylene diamine, 1,2-propylene diamine, hexamethylene diamine, quinrylene diamine, polyamines such as 4°4'-diaminodiphenylmethane, 4,4'-diphenylmethane disemiconsite, β- It is an elastic polymer having urethane bonds in the molecule obtained by reacting one or a mixture of aminopropionic acid hydrazide, carposihydrazide, water, ethylene glycol, 1,4-butanediol, etc.

In addition, the effects of the present invention are obtained by combining the phenolic compound represented by the general formula (I), the benztriarysyl type ultraviolet absorber, the hindered amine type antioxidant, and the general formula (n) \ (wherein, N R2 is hydrogen and a methyl group. (R1 represents a group selected from hydrogen and a monovalent or divalent radical) in combination with a hydrazine derivative having at least one group in the molecule. Synergistically enhanced.

As a benztriazole ultraviolet absorber, 2-(
2'-Hydroxy-3'-t-butyl-5'-methylphenyl)benztriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)penstriazole, 2-(2'-hydroxy-3'-5ee-butyl-5'-t-butylphenyl)benztriazole,2-(2'-hydroxy-3',5'-di-neopentylphenyl)benztriazole, 2- (2'- Hydroxy-3',5'-di-t-butylphenyl)-
Examples include 5-chlorobenztriazole and 2-(2'-hydroxy-4'-octyloxyphenyl)benztriazole.

As a hindered amine antioxidant, bis(2,2,8
, 6-tetramethyl-4-piperidyl)adipate, 3
, 5-di-t-butyl-4-hydroxy-hydrocinnamic acid-2'+2'te', e'-tetramethyl-4
'-piperidyl ester, bis(3,5-di-t-butyl-4-hydroxybenzyl)malonic acid-bis(2,2
,8゜6-tetramethyl-4-piperidyl) ester,
Dibenzylmalonic acid-bis(2,2,8,8-tetramethyl-4-piperidyl) ester, 1,3°8-triaza-2-oxo-3-phenyl-4-imino-7,7,
9,9-tetramethyl-spiro(4,5)decane, hexamethylene-bis[1°3.8-1-diaza-2,4-
Dioxo-7,7゜9.9-tetramethyl-3-yl-
spiro[4°5]decane), P,P'-diphenylmethane-bis(4-oxo-2,2,6,El-tetramethyl-piperidyl)carbamate, and the like.

Particularly preferred is bis(3,5-di-t-butyl-4-
hydroxybenzyl) malonate bis-(2゜2.6.8
-tetramethyl-4-piperidyl)-ester and bis(2,2,6,6-tetramethyl-4-piperidyl)
It is adipate.

As a hydrazine derivative having at least one group represented by the general formula (■) in the molecule, Ct 1H23cONH
NH2, H2NNHCO(CI2)4CON■NH2,CII
H23CONHN (,CH3)2, CI 7H23C
ONHN (C:Ha)2,CH3NHNHCOCO
NHNHCH3, (CH+)2NNHCOCONHN
(CH3)2, HOCH2CH2NHCOCONHN
HCH2CH20H1 and (where n is a positive integer and the average value is 1-5.

) can be mentioned. Particularly preferred is the reaction product of bisphenol A diglycidyl ether of formula (III) with lauric acid hydrazide.

When the compound of Cholera is contained in polyurethane in combination with the phenol compound of the general formula (I), the compound of the general formula (I)
) The content of the phenolic compound represented by formula (I) is 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the polyurethane, and the compound represented by general formula (I) and the benztriazole ultraviolet absorber , a hindered amine antioxidant and at least one group represented by the general formula (n) in the molecule.
The total content of at least one compound selected from the hydrazine derivatives contained in the polyurethane is 0.2 to 0.2 to
10% by weight, preferably 1-5% by weight.

Incorporation into polyurethane to obtain the composition of the present invention includes:
Although it can be added at any stage of producing polyurethane, it is preferable to mix it after the completion of polyurethane polymerization and before the molding stage.

The composition of the present invention may also contain other known stabilizers, pigments, dyes, extenders, etc.

The polyurethane composition thus obtained can be formed into fibers, tapes, films, etc. by dry, wet, or melt molding, and can also be used for foams, elastomers, synthetic leather, paints, etc., but especially for clothing fibers and It is used for tape applications.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the scope of these Examples.

Note that parts in the examples indicate parts by weight.

In addition, the method for measuring the characteristic values in the examples was as follows.

Gaspa test of polyurethane 0.5ry with a circular ventilation cylinder with a diameter of 8c11 at the top? Place a gas burner in the chamber and add propane gas to the
The sample was exposed for 10 hours while burning at a flow rate of 00 IIQ/min and maintaining the temperature at 60°C. b before and after this test
The value was measured using a ND-101 type color difference meter manufactured by Nippon Heavy Industries Co., Ltd., and expressed as a change (Δb). As for the nitrogen oxide gas exposure test, the test according to J I 5-L-0855-1978 was conducted once, and the b value was measured in the same manner as described above.

Polyester 40 denier polyurethane fibers are made from Inogen HC
After scouring the Ig/e aqueous solution of Kogyo Co., Ltd.'s nonionic activator) at 80°C for 20 minutes, irradiation was performed for 20 hours, 40 hours, 60 hours, and 80 hours with a fade-o-meter, and the strength was measured with a Tensilon meter. The irradiation time (T%) at which the intensity was reduced by half was determined from the change curve.

Polyurethane, test 40 denier polyurethane fiber with Inogen HC1g/
After scouring in Q aqueous solution at 80°C for 20 minutes, it was heated at 120°C for 24 hours in a circulating hot air dryer. The tenacity measured by a Tensilon measuring machine was expressed as a retention rate (%) with respect to the tenacity before treatment.

Mininiren,'s voice ゛Tes 40 denier polyurethane fiber Inogen HC1g/
After scouring at 80°C for 20 minutes in a σ aqueous solution, the effective chlorine concentration was 100 ppm, the bath ratio was 1:100, and the pH was 8.0.25.
It was treated for 24 hours at °C and air-dried. The tenacity measured by a Tensilon measuring machine was expressed as a retention rate (%) with respect to the tenacity before treatment.

Take 1 part of 24 filament 70 denier 6-nylon processed yarn and add 0.005% stabilizer to polyurethane.
It was uniformly impregnated with a solution of 5 parts of acetone and air-dried.

The nylon thread thus contaminated with stabilizer was subjected to a propane combustion gas exposure test for 5 hours and in the gas discoloration test for polyurethane samples described above.
-1976 Nitrogen oxide gas exposure test was conducted once. In addition to yellow, the discoloration was red, brown, green, purple, etc., and the degree of discoloration was visually judged and classified according to the following.

Grade 5: No difference from non-contaminated nylon thread.

Grade 4: Slight discoloration is observed compared to uncontaminated nylon thread.

Grade 3: There is a clear difference in discoloration compared to uncontaminated nylon thread.

Grade 2: The degree of discoloration is large.

Grade 1: Significant discoloration.

Example 1 1950 parts of polytetramethylene ether glycol having a molecular weight of 1950 and 500 parts of 4,4'-diphenylmethane diisocyanate were reacted at 70°C for 60 minutes to obtain a prepolymer having incyanate groups at both end groups. 4478 parts of dimethylformamide was added to this and dissolved to form a homogeneous solution.

This solution was cooled to 0°C, and a small amount of blue tint was obtained by dispersing it in dimethylformamide.
% paste was added thereto, and without further stirring, a solution of 74 parts of 1,2-propylene diamine dissolved in 983 parts of dimethylformamide was added quickly (and slowly at the end) to perform a chain extension reaction.1. 90% of the 2-propylene diamine solution was added to reach 2500 poise at 25°C. At this point 12 parts of monoethanolamine dissolved in 72 parts of dimethylformamide was added to eliminate free incyanate in the polymer solution. The viscosity of the polymer solution was then stabilized by adding 10 parts of acetic anhydride dissolved in 72 parts of dimethylformamide.The resulting solids content was 32%.
, A polymer solution with a viscosity of 2200 voids at 25°C is
Make it dope.

1,3.5-) squirrel (4-t-
butyl-3-hydroxy-2,6-synthylbenzyl)
In addition to blending 0.32 parts of isotheateric acid, 2- (2'
-Hydroxy-3',5'-geneobentylphenyl)benztriazole (abbreviation UV-1), bis(3,5
-di-t-butyl-4-hydroxybenzyl) malonic acid-bis(2,2,8,E3-tetramethyl-4-piperidyl) ester (abbreviation HA-2), and the following formula (where n is positive A lauric acid hydrazide bisphenol A diglycidyl ether reaction product (abbreviation: HD-2), which is represented by the integer of ) and has an average value of n of 1.4, was blended and placed in an atmosphere of 200°C from a 4-hole orifice. Dope was discharged into the fiber at a rate of 5.6 g/min, followed by spinning, drying, temporary twisting, oiling, and winding at a rate of 400 m/min to obtain a 40 denier fiber.

This fiber was subjected to a gas discoloration test, a light resistance test, a heat resistance test, and a chlorine resistance test.

These results are shown in Table 1 together with Comparative Examples 1-5.

Comparative Examples 1 to 5 In place of 1,3,5-tris(4-butyl-3-hydroxy-2,6-synthylbenzyl)in cyanuric acid in Example 1, Comparative Example 1), 1,3 without any additive was used. ．．
5-tris(3,5-diC-butyl-4-hydroxypendel)incyanuric acid (Comparative Example 2), 4.4'-
Butylidene-bis(2-t-butyl-5-methylphenol) (Comparative Example 3), pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxy-hydrocinnamic acid) ester (Comparative Example 4) ), 1, 3
．． 5-) Re-methyl-2,4,6
-) 0.32 each of lis(3,5-di-t-butyl-4-hydroxypendel)benzene (Comparative Example 5)
A comparative sample of Example 1 was prepared by dry spinning under the same conditions as in Example 1 to obtain a 40 denier fiber.

These results are shown in Table 1 together with the results of Example 1.

The polyurethane fibers prepared from the composition of the present invention exhibited excellent gas yellowing resistance, chlorine resistance, and good light resistance and heat resistance. On the other hand, the polyurethane fibers produced from the comparative composition had poor gas yellowing resistance and chlorine resistance. Further, in Comparative Example 3, even if the blended amount of the stabilizer was doubled, the effect was negligible and not only did it have the disadvantage of whitening of the fibers.

Examples, Comparative Examples Example 1. Dusly yarns were made from the 40 denier polyurethane fiber obtained in Comparative Example 3 and nylon yarn, and subjected to a propane combustion gas exposure test in a nylon fiber contamination gas discoloration test.

The manufacturing conditions for the Dasly yarn were as follows: 70 denier/24 filament 6-nylon pro-deust textured yarn and polyurethane fiber drafted 3.8 times were combined and twisted at 650 turns/m. .

The results of the gas discoloration test for these Dasly yarns are shown in the table.

Table 4 (Effects of the Invention) According to the present invention, polyurethane fibers with excellent gas discoloration properties, light resistance, heat resistance, and chlorine resistance are obtained, and even when used together with nylon fibers, they have good gas discoloration properties.

Claims (1)

[Claims] (1) Polyurethane has the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a group selected from t-butyl group, sec-butyl group, and neopentyl group) The phenolic compound shown, (a) benztriazole ultraviolet absorber, (b) hindered amine antioxidant, and (c) general formula (II) in the molecule ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_2 represents a group selected from hydrogen and a methyl group, and R_3 represents a group selected from hydrogen and a monovalent or divalent organic group.) Hydrazine having at least one group represented by A polyurethane composition containing a compound selected from derivatives. The content of phenolic compounds is 0.0 compared to polyurethane.
The total content of phenolic compounds and compounds selected from (a) benztriazole ultraviolet absorbers, (b) hindered amine antioxidants, and (c) hydrazine derivatives is 1 to 5% by weight. 0 for
．． 4. A polyurethane composition according to claim 3, wherein the amount is 2 to 10% by weight. The polyurethane composition according to claim 1, wherein the phenolic compound is 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid. Hindered amine antioxidants are bis(3,5-di-t-
butyl-4-hydroxybenzyl)malonate bis-(2
, 2,6,6-tetramethyl-4-piperidyl)-ester, and bis(2,2,6,6-tetramethyl-4-piperidyl)adipate. The hydrazine derivative is bisphenol A diglycidyl ether represented by the formula (III) ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, n is a positive integer, and the average value is 1 to 5.) A polyurethane composition according to claim 1, which is a reaction product of lauric acid hydrazide and lauric acid hydrazide.