JPS6115166B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an elastic yarn that has excellent unwinding properties and is stabilized. More specifically, the present invention relates to an elastic yarn that is stabilized against deterioration and discoloration caused by outside air conditions and microorganisms such as mold, and has improved unwinding properties. related to elastic yarns. Synthetic elastomers such as polyurethane elastomers have excellent abrasion resistance, oil resistance, cold resistance, chemical resistance, mechanical strength, etc., and are therefore widely used in the form of threads, films, and other molded products. However, on the other hand, it not only has drawbacks such as deterioration and discoloration due to outside air conditions and microorganisms, but also has problems in handling and use, such as poor unwinding properties due to stickiness when wound with elastic thread on a bobbin. I have a problem. In order to prevent deterioration and discoloration caused by microorganisms, it is possible to add antibacterial agents in post-processing or to incorporate them into polymers, but depending on the type, it may reduce the physical properties of the elastic yarn or cause hygienic problems. There are not many effective methods known, such as those that have the same properties, or are effective for other materials but not for elastic yarns. Furthermore, even if it is an effective antibacterial agent, there are problems with durability when used in post-processing, and when compounded into polymers, there are problems due to thermal decomposition and evaporation during spinning, and problems with scum formation in the yarn path, etc. However, there are drawbacks such as poor unwinding properties after spinning, and no satisfactory product is known. As a result of extensive research into additives that do not have the above drawbacks, the inventors have arrived at the elastic yarn of the present invention. That is, the present invention is an elastic yarn characterized by containing 0.001% by weight or more of a cyclic thiohydroxy acid metal compound represented by the following general formula [] and/or [].

【formula】

[Formula] (However, M ₁ represents an alkali metal, and M ₂ represents a polyvalent metal.) The elastic thread according to the present invention is resistant to deterioration and discoloration caused by outside air conditions and microorganisms without impairing the excellent physical properties of the polymer itself. It has excellent resistance to water, and has the advantage that it has almost no adverse effects even when exposed to high temperature and high humidity atmospheres for long periods of time. It is also characterized by its excellent durability. Furthermore, in addition to the fact that there are no troubles during the spinning stage, it also has the great advantage that, quite surprisingly, the unwinding property after winding the bobbin is improved compared to the case without additives. The reason why such an excellent effect is obtained is not yet clear, but it is presumed that the additives contained in the elastic yarn in a finely dispersed state contribute to the improvement in unwinding property. The elastic threads used in the present invention include polyurethane elastic, polyester elastic, polycarbonate elastic, polyamide elastic, etc., which are spun by dry spinning, melt spinning, etc., depending on the polymer, and stretched as desired. An example is an elastic yarn obtained by heat treatment or the like. Alternatively, it may be a composite yarn obtained by composite spinning an elastic body and an inelastic body.
To explain polyurethane elastic material in more detail,
Examples include polymers obtained by reacting polymer diols, organic diisocyanates, and bifunctional active hydrogen compounds with a molecular weight of 400 or less, usually having a molecular weight of 500 or more, preferably 1,000 to 8,000. Examples of polymer diols include at least polyether glycols such as polytetramethylene ether glycol and polyethylene/propylene ether glycol, and glycols such as ethylene glycol, 1,4-butanediol neobentyl glycol, and 1,6-hexanediol. Polyester glycols, polycaprolatone glycol, and polyhexamethylene obtained by reacting one type with at least one dicarboxylic acid such as adipic acid, suberic acid, azelaic acid, sebacic acid, β-methyladipic acid, and isophthalic acid. In addition to dicarbonate glycol, one type of polymer diol of polyhydrocarbon diol, or a mixture or copolymer of two or more types thereof is exemplified. In addition, as an 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 include dicyclohexylmethane diisocyanate and isophorone diisocyanate, and one type or a mixture of two or more of these can be used. Bifunctional active hydrogen compounds include ethylenediamine, 1,2-propylenediamine, hexamethylenediamine, xylylenediamine, 4,4'-diphenylmethanediamine, hydrazine, 1,4-
Diamine piperazine, ethylene glycol, 1,
Examples include 4-butanediol, 1,6-hexanediol, and water, which may be used alone or in combination of two or more. The method for producing a polymer is not particularly limited, and usually a prepolymer having isocyanate groups at both ends is produced by reacting a polymer diol with an organic diisocyanate in the presence or absence of a solvent (reaction accelerator, reaction Inhibitors, etc. can be used)
It is then obtained by chain elongation with a difunctional active hydrogen compound in a solution state. Alternatively, it may be produced by reacting each component in one stage, or by dividing each component and reacting in several stages. A monofunctional compound such as a monoamine can also be used as a terminal capper at the end or middle of the polymerization reaction. In addition, as a polyester-based elastic body, a polyester-based elastic body whose hard segment is an aromatic polyester such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene terephthalate/isophthalate, and whose soft segment is polyether glycol, polyester glycol, or polycaprolactone glycol. is exemplified. A metal compound of a cyclic thiohydroxy acid represented by the general formula is blended into such an elastic body and spun by a conventional method. The cyclic thiohydroxy acid used is 2-mercaptopyridine N oxide, which is sometimes referred to as 1-hydroxypyridine-2-ion, 2-pyridineethyl-1-oxide, or 1-hydroxypyrithione. General formula [],
M ₁ shown in [ ] is an alkali metal such as sodium and potassium, and M ₂ is a polyvalent metal such as calcium, magnesium, zinc, iron, copper, and cadmium, and especially alkali metals, Zn, and Cd. A four-coordinated polyvalent metal is preferred. In the case of an alkali metal, it is a cyclic thiohydroxy acid salt, and in the case of a polyvalent metal, it is a chelate compound in which two molecules of a cyclic thiohydroxy acid are coordinated. In order to incorporate it into the elastic yarn, it is preferable to add it to the polymer or polymer dope at any step before spinning. The content of the compound is 0.001% by weight or more, preferably about 0.01 to 1% by weight, based on the elastic yarn. The elastic yarn of the present invention may further contain or adhere to various additives such as light stabilizers, thermal oxidative deterioration inhibitors, gas-resistant discoloration inhibitors, dyes and pigments, metallic soaps, oil agents, and antibacterial agents other than the present invention. can be done. The present invention improves yarn unwinding properties and running smoothness, as well as improves stability against deterioration or discoloration caused by microorganisms, but polyurethane elastomers using polyester diol as the polymer diol, which is particularly susceptible to microorganisms, and polyester The effect is remarkable on elastic yarns. Hereinafter, the present invention will be explained with reference to examples, where parts in the examples mean parts by weight. In addition, the mold resistance test and the unwinding property test in the examples were carried out by the following method. 1 Mold resistance test Pour the following medium containing a sterilizing agent into a 9 cm diameter shear dish, and immediately before the medium solidifies, add an elastic thread fabric (2
cm x 2 cm) on the medium, and then
An aqueous dispersion of Fusarium SP (phytopathogenic fungus) was sprayed on top, followed by a 10-day culture test. Medium Pepton 4.0 parts Yeast extract 2.0 Malt extract 2.0 Glucose 5.0 Agar 8.0 Water 1000ml PH 6.0 After the culture test, mold resistance was determined as follows.

[Table] 2. Residual strength retention rate from mold resistance test The test piece obtained in the mold resistance test was loosened and made into yarn, and the residual strength was measured using an Autograph IM-100 manufactured by Shimadzu. Represents the remaining strength retention rate in comparison with strength. Residual strength retention rate = Tenacity of yarn after test / Tenacity of untreated yarn x 100 (%) 3. Measuring method of unwinding property A cheese wrapped with elastic yarn is placed on a feed roller, while the yarn is placed on a take-up roller. The rotation speed of the feed roller is fixed, and the rotation speed of the take-up roller is adjusted to such a speed that the filament is fed out at right angles to the axis of the feed roller. When the rotational speed of is A and the feed roller speed is B, it is expressed by the following formula. A-B/B×100=Unwinding property (%) Example 1 Methylenebis(4-phenyl isocyanate)
10 parts of polyester glycol having a molecular weight of 6000 were reacted at 80° C. for 60 minutes to obtain a prepolymer having terminal isocyanate groups, which was then dissolved in 80 parts of dimethylformamide. 1, which was dissolved in 80 parts of dimethylformamide while keeping this solution at 5°C.
1.4 parts of 2-propylene diamine was added and reacted. Obtained viscous polymer solution (viscosity at 20℃
Pyridine dithiol prepared as a slurry in dimethylformamide to 1200 poise.
1-oxide sodium salt, pyridine-2-thiol-1-oxide potassium salt, bis-1
Hydroxypyridine-2-thionate cadmium complex, bis-1-hydroxy, and pyridine-2-thionate zinc complex were added to the polymer at 0,
After adding 0.0001, 0.001, 0.01, 0.1, 1.0 weight percent and blending for 120 minutes, the pore diameter was 0.3 nmφ and the number of pores was 5.
The yarn is spun into an air stream heated to 250℃ through a spinneret, and when the solvent content reaches 0.5% or less, the yarn is bundled by mechanical false twisting and then an oil agent is applied. The weight is rolled up at 700m/min.
100g of cheese was obtained. The obtained yarn was knitted into a tube of approximately 10 cm using a circular knitting machine and used for testing. The mold resistance test and the residual strength retention rate by the mold resistance test were measured using the marked test pieces, and the results are shown in Table 1. In addition, the unwinding property was determined by spinning the yarn in the same manner.
Measurement was performed on the surface layer and inner layer of 400g rolled cheese.

【table】

[Table] As a result, the elastic yarn according to the present invention contains pyridine-
Elastic threads containing 2-thiol-1-oxide sodium salt exhibited excellent mold resistance. Furthermore, all of the elastic yarns according to the present invention had improved unwinding properties. In addition, Table 1 shows that the amount added (content) is 0.001% by weight.
This shows that the above amount is necessary, and it is particularly preferable to add 0.01% by weight or more. Although not shown in Table 1, the mold resistance showed excellent durability with virtually no change even after the yarn was treated with boiling water for 2 hours. On the other hand, in a comparative example in which the resin was added to an oil agent and treated during the spinning process, the mold resistance after boiling water treatment was first class, and the residual tenacity retention rate was 0%.

Claims (1)

[Scope of Claims] 1. An elastic thread containing 0.001% by weight or more of a cyclic thiohydroxy acid metal compound represented by the following general formula [] and/or []. [Formula] [Formula] (However, M ₁ represents an alkali metal, and M ₂ represents a polyvalent metal.) 2. Claim 1, in which the content of the metal compound in the cyclic thiohydroxy acid is 0.01 to 1% by weight. Elastic thread as described in section. 3. The elastic thread according to claim 1 or 2, wherein the elastic thread is a polyester-based polyurethane elastic thread.