JPH07107204B2 - Polyester urethane elastic yarn - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyester-based urethane elastic yarn, and particularly to a polyester-based urethane elastic yarn having improved moisture aging resistance and mildew resistance.

(Prior Art) Polyester-based urethane elastic yarns have excellent mechanical properties and elastic recovery properties and are therefore used in various clothing fields. However, the polyester-based urethane elastic yarn has drawbacks such that the polymer is hydrolyzed in a wet state and is deteriorated by microorganisms to impair the excellent mechanical properties and elastic recovery of polyurethane.

To improve the moisture aging resistance of polyester-based urethane elastic yarns, use a polylactone-based or polycarbonate-based polyester diol, or use a polyester diol hydrophobized by lowering the ester bond concentration, and use the polymer end of polyurethane. Attempts and the like to crosslink are known. However, in the case of the polyester-based urethane elastic yarn obtained from these conventional techniques, not only the cost becomes high, but also the improvement of the moisture aging resistance is insufficient, and the elastic recovery property is usually lowered, and yet. There is no known satisfactory method. In the field of urethane elastomers and coatings, attempts have been made to improve adhesion and water resistance by using silyl compounds as one component of polyurethane for curable adhesives. However, even when this method is used, the improvement of the moisture aging resistance is not sufficient, and there is a drawback that the characteristics of the elastic yarn are significantly impaired. On the other hand, with regard to deterioration due to microorganisms, attempts to impart antibacterial and antifungal properties by incorporating antibacterial and antifungal compounds have been reported in Chemistry of Antibacterial and Antifungal (Sankyo Publishing, Horiguchi), JP Sho
Although it has been proposed in 59-211678 and the like, there is a problem that it falls off due to selection etc. and lacks in durability performance, and a satisfactory method is not yet known.

(Problems to be Solved by the Invention) The present invention relates to the above-mentioned conventional drawbacks of polyester-based urethane elastic yarns, that is, polyester-based urethane elastic yarns provided with antibacterial and antifungal properties that are excellent in moisture aging resistance and durability. Is intended to be provided.

(Means for Solving Problems) The inventors of the present invention have arrived at the present invention as a result of earnest research to solve these problems. That is, the present invention is a prepolymer obtained by reacting 1, polyester diol and an excess mole of organic diisocyanate with the general formula: A polyester-based urethane elastic yarn obtained by yarn-proofing a polyester-based polyurethane elastic body chain-extended with a bifunctional active hydrogen compound containing a diaminosilyl compound represented by The polyester-based urethane elastic yarn is characterized by containing.

According to the present invention, excellent moisture aging resistance and antibacterial and antifungal properties can be imparted without deteriorating the physical properties and performance of the polyester urethane elastic yarn.

The polyester-based urethane elastic yarn referred to in the present invention has a molecular weight of
A prepolymer is prepared by reacting a polyester diol having a melting point of 60 to 6000, preferably 600 to 8000, and a melting point of 60 ° C. or less with an organic diisocyanate in an excess amount. 0.5 to 10.0 mol% based on the previous bifunctional active hydrogen compound
Preferably 2.0 to 6.0 mol% and antibacterial and antifungal compound 20
~ 1000ppm, for example, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine 20 to 1000ppm based on all components
It is preferably obtained by adding 50 to 500 ppm and then spinning.

As polyester diol, ethylene glycol,
1,4-butanediol, neopentyl glycol, 1,6-
Polyester glycols comprising one or more glycols such as hexanediol and one or more dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, β-methyladipic acid and isophthalic acid , Voricaprolactone glycol, polyhexamethylene dicarbonate glycol, etc., or two of these
Examples thereof include a mixture or copolymer of two or more kinds.

Further, as the organic diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4 ′-
Examples thereof include dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like, or a mixture of two or more thereof. In the present invention, the excess mole means that the ratio of the mole amount of polyester diol and the mole amount of organic diisocyanate is 1: 1.3 to 1: 3.5, preferably 1: 1.5 to 3.0.

Ethylenediamine, 1,2 as bifunctional active hydrogen compounds
-Propylenediamine, hexamethylenediamine, xylylenediamine, 4,4'-diphenylmethanediamine,
Examples thereof include hydrazine, 1,4-diaminopiperazine, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, water and the like, or a mixture of two or more thereof. Diamines are particularly preferred.

The polymer solution obtained by chain extension may be terminated by a conventional method with a monofunctional active hydrogen compound or the like.

As a solvent for polyurethane, N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea,
Hexamethylphosphonamide and the like can be mentioned.

Usually, 1.5 to 3.0 mol of organic diisocyanate is reacted with 1 mol of polymer diol in the presence or absence of a solvent to obtain a prepolymer having isocyanate groups at both ends. In this case, a catalyst that accelerates the reaction of a tertiary amine or a tin compound or an acidic negative catalyst can be used. Then, a chain extension reaction is carried out with a bifunctional active hydrogen compound in a solution state to obtain a polyurethane solution.

The method for obtaining these polymers is not essential to the present invention, and the polymer diol, the organic diisocyanate and the bifunctional active hydrogen compound can be reacted at the same time, or each of them can be divided and reacted in several stages. You can also

The antifungal agent used in the present invention is shown in the following 2, 3,
5,6-Tetrachloro-4- (methylsulfonyl) pyridine for all components It is characterized by containing 50 to 500 ppm, preferably 100 to 250 ppm. If the content is less than 50 ppm, satisfactory antifungal performance cannot be obtained, and if it exceeds 500 ppm, the elastic yarn is colored and the quality deteriorates. The present antifungal agent is added at a stage after the termination, but the method is not particularly limited and may be added at the same time as other additives.

The diaminosilyl compound used in the present invention is (A is a C _{2 to} C ₆ alkylene group, X and R are C _{1 to} C ₄ alkyl groups, and n is 0 to 1), and for all difunctional active hydrogen used as a chain extender, 0.5-10.0 mol%
Preferably, it is characterized by being copolymerized at 2.0 to 6.0 mol%. When the copolymerization rate is 0.5 mol% or less, desired moisture aging resistance cannot be imparted. On the other hand, when the copolymerization rate is 10.0% mol% or more, the stability of the polymer solution is lowered, which causes a problem in operation. According to the present invention, excellent moisture aging resistance and antibacterial and antifungal properties can be imparted without impairing the characteristics of the polyester urethane elastic yarn.

In the present invention, addition of hindered phenols, hindered amines, ultraviolet absorbers, tertiary amine compounds, gas discoloration inhibitors, pigments such as titanium oxide, etc., which are usually added to polyurethane, does not hinder, Can be used together.

The polyester-based urethane polymer solution obtained from the present invention can be spun by a conventional spinning method and is not limited at all. The spun yarn is temporarily burned and an oil agent is applied. The type of oil agent is not particularly limited, but in addition to commonly used dimethylpolysiloxane, diorganopolysiloxane in which a part of the methyl group is substituted with other alkyl group or phenyl group, epoxy group, amino group, vinyl group, etc. Organopolysiloxanes such as introduced modified polysiloxanes and oils containing mineral oil as a main component are preferable. Particularly, straight oil mainly composed of organopolysiloxane is particularly suitable for polyurethane using polyester diol as a soft component.

The polyester-based urethane elastic yarn of the present invention is preferably crosslinked by heating in the steps after spinning. Particularly, it is preferable to carry out the steps of scouring and dyeing.

Action It is not clear why the antibacterial and antifungal agent used in the present invention can impart excellent durability performance, but it is considered that the diaminosilyl compound used in the present invention has some influence. It is quite surprising that no endurance performance is obtained when the diaminosilyl compound is not used and when the antibacterial and antifungal agents other than the present invention are used.

The present invention is described below with reference to examples, but the present invention is not limited thereto. The evaluation of the moisture aging property and antifungal property in the present invention was carried out by the following methods.

(1) Moisture aging property: The elastic yarn was left for 2 weeks in an atmosphere of 70 ° C. and 95% RH, and the tenacity retention rate and the polymer viscosity before and after the leaving were measured.

S ₀ : Strength before being left in an atmosphere of 70 ° C and 95% RH (g) S: 〃 〃 Strength after being left for 2 weeks ・ Polymer viscosity (ηinh) = logeηr / c C; 0.3 g / 100 ml DMA, 30 ° C. DMA; Dimethylacetamide (2) Antifungal Mold Resistance Test In accordance with JIS-Z-2911-6.2.2 (Test for textile products, wet method). In the test, a knitted fabric made of a polyester-based urethane elastic yarn was used, and after scouring and bleaching, a sample after 20 HL cycles was evaluated.

Example 1 A polyester diol having hydroxyl groups at both terminals and a molecular weight of 4000 (adipic acid: ethylene glycol: 1,4.butanediol = 1.00: 0.64: 0.55 molar ratio) and 4,4′-diphenylmethane diisocyanate were used. A 50% dimethylacetamide was added to the polymer produced at a molar ratio of 1: 2.5 to carry out a prepolymer reaction, and then 1,2-propylenediamine /
Chain extension was carried out with a diamine consisting of N-β (aminoethyl) γ-aminopropyltrimethoxysilane (97.0 / 3.0 mol%), followed by termination with diethylamine. Further, 1% of antioxidant and 150 ppm of 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine were added, stirred and mixed to obtain a polyurethane solution having a viscosity of 1800 poise at a polymer concentration of 30%. . Then, dry spinning was performed by a conventional method to obtain 55 denier polyurethane elastic yarn.

Examples 2 to 9 1,2-Propylenediamine / N-β (aminoethyl) γ-
Aminopropyltrimethoxysilane mol% is 100/0, 9
Polymerization was carried out in the same manner as in Example 1 using a diamine solution consisting of 9/1, 97/3, 95/5, 91/9, 88/12, 93/7 and 100/0. After termination of the terminals, the antifungal agent shown in Table 1 was added together with 1% of the antioxidant, and the mixture was stirred and spun to give a 55 denier polyurethane elastic yarn.

Example 10 Using a polyester diol (molecular weight 4000, adipic acid: 1,6-hexanediol: neopentyl glycol = 1.4: 1: 0: 0: 0.4 molar ratio) instead of the polyester diol in Example 1, a chain extender was used. Polymerization was carried out in the same manner as in Example 1 except that the diaminosilyl compound was not added to the above diamine, the antifungal agent shown in Table 1 was added, and the mixture was stirred and spun to give a polyurethane elastic yarn of 55 denier. The tenacity of the spun yarns obtained from Examples 1-10 was 53-55 g.

The moisture aging resistance and antifungal performance of the polyester urethane elastic yarns obtained from Examples 1 to 10 are shown in Table-2.

As is clear from the results in Table 2, both the moisture aging resistance and the antifungal performance are remarkably improved by the present invention.

(Effect of the Invention) According to the present invention, no special device for improving the hydrolysis resistance of the polyester diol itself (for example, changing the polymer composition) is required, and excellent moisture aging resistance can be obtained. Therefore, the cost advantage in manufacturing is very large. Moreover, it also has antifungal performance with excellent durability. The polyester-based urethane elastic yarn obtained from the present invention has excellent moisture aging resistance and mildew resistance.

Claims (1)

[Claims] 1. A prepolymer obtained by reacting a polyester diol with an excess molar amount of an organic diisocyanate is represented by the general formula: In a polyester urethane elastic yarn obtained by spinning a polyester polyurethane elastic body chain-extended with a bifunctional active hydrogen compound containing a diaminosilyl compound, the urethane elastic yarn contains a fungicidal and antifungal compound. Polyester urethane elastic yarn characterized by being.