DE1669474A1 - Process for the production of elastic polyurethane fibers - Google Patents

Description

W 12866/66 15 / pö

Kurashiki Rayon Co., Ltd., Kurashiki City, Japan

Process for the production of elastic polyurethane fibers

The invention relates to a method for producing elastic polyurethane threads or fibers with lower adhesive properties between yarns and between single threads than those of conventional products.

The elastic polyurethane fiber is a synthetic textile fiber that has been used in recent years due to its very high elasticity, good dyeability and spinnability into yarns with a finer denier than the usual rubber yarns, which have similar elasticity has received increasing attention. However, the fiber possesses Disadvantages insofar as regardless of the spinning process used, i.e. wet, dry, semi-melt or Melt spinning, the product so sticky or sticky

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is that the yarns wound on a bobbin have adhesion not only among yarns but also among filaments, so that there are great difficulties as a result occur during the continuous and smooth unwinding of the yarn from the bobbin.

Various attempts have been made to overcome these difficulties. One of the attempts includes sprinkling or spraying talc or other similar inorganic substances over the product what however leads to various disturbances, since talc in the form of fine powder from the yarn in the course of knitting, Knitting or weaving emerges and, although effective in preventing adhesion between twisted multifilament yarns is, the treatment for sticking single filament yarns to one another fails.

The object of the invention is to produce elastic polyurethane fibers or threads with a limited adhesive effect from a special spinning solution, which differs from the known technology, in which an elastic polyurethane fiber is treated with an adhesion-preventing agent - e.g. talc - with a high adhesive effect. at other known spinning processes, m-cresol, nitrobenzene, toluene, ethyl acetate, benzyl alcohol,

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chlorinated hydrocarbons, or the like. to the solvent mixture for the polyurethane polymer. Again, however, these methods fail in terms of manufacture elastic polyurethane fibers with lower adhesive properties, although they modify the viscosity of the Allow spinning solution or a slowing down of the coagulation speed of the threads.

The object of the invention is achieved by adding special additives to the spinning solution.

Contains the spinning solution for use in practicing the method according to the invention a polyurethane elastomer and one or more compounds consisting of carboxylic acid esters with a content on aliphatic hydrocarbon groups with 4 to 50 carbon atoms, amides, nitriles, alcohols, aldehydes, Ketones, amines, urethanes, urea compounds (üreiden) and sulfonic acid esters (all here as additives designated).

The elastic polyurethane fibers made according to the invention are not only limited in their adhesive property, but gain a remarkably increased one Daylight resistance, the lack of which is one of the greatest

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Disadvantages of ordinary polyurethane fibers have been is.

A spinning solution composed of a polyurethane elastomer and one or more of the above-mentioned additives according to of the invention can be achieved either by mixing and dissolving a solution or an emulsion of the additives be prepared in a solution of the polyurethane elastomer. It is also possible to use a solution of the additives to mix and dissolve in an emulsion of the polyurethane elastomer or to add an emulsion of the additives therein mix and disperse. The amount of additives to be blended in the polyurethane elastomer is usually 0.01 to 50%, preferably 0.5 to 20% by weight, based on the weight of the elastomer. When the crowd is below 0.01%, the purposes of the invention are not achieved. An amount over 50% is not appropriate, as it can lead to yarn breakage during spinning. An amount in the range of 20 to 50% would be acceptable of the invention, since spinning is somewhat less smooth within this range, but in general Threads with less adhesive properties and improved daylight resistance can be obtained. Eire made from polyurethane elastomers and additives according to the invention Spinning solution is spun by any conventional method, i.e. by NaB, dry, semi-melt

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"or melt spinning, creating an elastic polyurethane fiber or elastic polyurethane filaments with limited Adhesive property and improved daylight resistance can be obtained.

Polyurethane elastomers useful in the method according to the invention are reaction products of high molecular weight glycols with a molecular weight of 500 to 5000 such as Polyesters, polyethers, polyether esters and polyacetals with polyisocyanate and chain extenders such as diamine, Diol or water.

Suitable polyesters to be used according to the invention and having a molecular weight of 500 to 5000 are through Polycondensation of an aliphatic dicarboxylic acid such as adipic acid and sebacic acid with a glycol such as ethylene glycol, Propylene glycol, butylene glycol, pentamethylene glycol, Polyesters made from hexamethylene glycol and cyclohexane glycol; or by ring opening polymerization of lactone obtained polycaprolactam. Polyalkylene glycols are used as polyethers with a molecular weight of 500 to 5000 Suitable as polyethylene glycol, polypropylene glycol or polybutylene glycol · As a polyether ester with a molecular weight from 500 to 5000 are those suitable by polycondensation of an aliphatic dicarboxylic acid such as Adipic acid, sebacic acid or succinic acid with one

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Glycol such as diethylene glycol, triethylene glycol or tetraethylene glycol can be obtained.

As to be used in the method according to the invention Polyisocyanate are aromatic diisocyanates such as naphthylene diisocyanate, diphenylmethane diisocyanate and diphenyl diisocyanate and toluene diisocyanate are suitable. Aliphatic diisocyanates such as hexamethylene diisocyanate are also used.

As additives for use in the method according to the invention one or more of the various compounds mentioned below are used. Among the connections most will be those who have lower affinity for water because of its ability to retain its adhesive property of the product and to increase its resistance to daylight is preferred. You can of course in a mixture, e.g. as a natural wax.

The additives to be used in the method according to the invention include the following:

Esters of carboxylic acids containing aliphatic hydrocarbon groups with 4 to 50 carbon atoms such as octyl caproate, tetradecyl caproate, pentadecyl caproate, Heptyl enanthate, octyl enanthate, hexyl caprylate, heptyl caprylate, Octyl caprylate, amyl pelargonate, heptyl pelargonate, heptyl

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caprylate, heptyl undecanate, vinyl laurate, heptyl laurate, Dodecyl laurate, octadecyl laurate, heptyl myristate, heptyl palmitate, Octyl palmitate, dodecyl palmitate, cetyl palmitate, Octadecyl palmitate, melissyl palmitate, and monoalcohol esters such as methyl, ethyl, propyl, isoacyl, tert-butyl, heptyl, octyl, hexadecyl, heptadecyl, octadecyl, Oleyl, hexacosyl, allyl and the respective cholic acid esters of stearic acid, petroselinic acid, octadecenoic acid (Octadessenic acid), oleic acid, elaidic acid and ricinoleic acid. Also included are esters of dibasic mono- or dicarboxylic acids such as mono- or diesters of sebacic acid, Glycerol esters of the aforementioned carboxylic acid, esters of oxycarboxylic acid and esters of carboxylic acid such as Methyl ester of 2-oxystearic acid.

Aliphatic alcohols that can be used are such as nonyl alcohol, caprylic alcohol, lauryl alcohol, myristyl alcohol, Cetyl alcohol, stearyl alcohol, eicosanol, decanol-2, tridecanol-2, melissyl alcohol or such unsaturated Alcohols such as 10-ündecenol-l, 1,2-tridecenol-l, oleic alcohol, Elaidyl alcohol, linoleyl alcohol or linolenyl alcohol or diols such as octanediol, nonanediol, decanediol and eicosanediol;

such aliphatic aldehydes as butyl aldehyde, hexyl aldehyde, octyl aldehyde, nonyl aldehyde, dodecyl aldehyde or the like.?

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those ketones containing the above-described aliphatic hydrocarbon groups such as methyl butyl ketone, Methyl hexyl ketone, ethyl butyl ketone, dinonyl ketone or. like-1

such aliphatic nitriles as capronitrile, oenanthonitrile, caprylonitrile, pereralgonitrile , undecanenitrile, myristyl nitrile, pentadecanenitrile, palmityl nitrile, margalonitrile, stearyl nitrile, oleyl nitrile or the like;

such aliphatic amides as hexylamide, heptylamide, octylamide, Nonylamide, decylamide, undecylamide, laurylamide, stearic acid amide, Oleic acid amide, renolic acid amide, (renolic acid amide), or their acylsulfanylamides or oxyethylamides;

such aliphatic amines as hexylamine, heptylamine, octylamine, tridecylamine, tetradecylamine, pentydecylamine, hexadecylamine, dococylamine (dococyl amine) , diamylamine, diheptylamine, didecylamine, didodecylamine, dihexadecylamine, trioctadecylamine, trioctadecylamine, trioctadecylamine, trioctadecylamine, trioodecylamine, trioctadecylamine, trioctadecylamine, trioctadecylamine, trioctadecylamine, trioctadecylamine , N, N-dimethylhexylamine, Ν, Ν-diethylpalmitylamine, trilaurylamine, tristearylamine, N-tridecylaniline, N-unecyl-N-methylaniline, N-palmityl-N-methylaniline, 1,8-diaminoctane, 1,6-oxypalmitylamine or . the like;

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such aliphatic sulfonic acid esters as methyloctadecanesulfonate; and

such aliphatic ureals or urethanes including monoureids of the carboxylic acids mentioned such as lauric acid monoureide, tridecanolic acid monoureid, myristic acid monoureide, palmitic acid monoureide, stearic acid monoureide, oleic acid monoureide, elaidic acid monoureide, linolenic acid monoureide, linolenic acid monoureide, linolenic acid monoureide, laurecyl alcohol alcohol, linolenic acid monoureide, linolenic acid monoureide, laurecyl alcoholic alcohol, lauric acid monoureide, linolenic acid monoureide, alcoholic , Stearyl alcohol, nonandecyl alcohol, 10-undecenol-l- (10-undesenol-l-,) 1,1-dodecenol-1-, 1,2-tridecenol-C-, oleyl alcohol, Eraidyl alcohol, decanediol, heptadecanediol -, Octadecanediol urethanes or similar urethanes of higher alcohols, a-naphthyl urethane or phenyl urethane or hexyl urethane, tetramethylene di urethane, hexamethylene di urethane and other higher urethanes of various types of alcohols such as methyl alcohol, ethyl alcohol and octyl alcohol.

The invention is illustrated in more detail by means of the following examples.

example 1

A spinning solution consisting of 2 parts of methyl oleate, 88 parts of dimethylformamide and 10 parts of polyurethane elastomer

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with an intrinsic viscosity of 0.82 dl / g in dimethylformamide at 30 ° C and consisting of a polyester with two terminal hydroxyl groups and a molecular weight of 2660 from adipic acid and a mixture of ethylene glycol and propylene glycol at a molar ratio of 70:30, diphenylmethane diisocyanate and methylenedianiline were in water at 30 ° C through a nozzle with 100 Holes with a diameter of 0.08 mm each are extruded at a speed of 6 cm / min and onto a spool wound up at a speed of 10 m / min after washing with water. The fiber thus obtained showed complete Separation not only among yarns but also among single threads and was cut into staple fibers.

On the other hand, if a solution consisting of 10 parts Polyurethane elastomer, 0.001 part methyl oleate and 89.9 parts dimethylformamide were used as the spinning solution, the sticking was not prevented particularly effectively.

Example 2

One of 4 parts of stearic acid amide, 76 parts of dimethylformamide and 20 parts of polyurethane elastomer with an intrinsic viscosity of 0.72 dl / g in dimethylformamide at 30 ° C and consisting of polybutylene glycol with a molecular weight of 1 134, diphenylmethane diisocyanate and ethylene

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diamine was passed into a spinning column kept at 175 ° C extruded a nozzle with 20 holes each 0.1 mm in diameter at a speed of 16 cm / min and wound on a spool at a speed of 200 m / min. The fiber thus obtained showed neither under Yarns still sticking under single threads.

Example 3

One of 25 parts of polyurethane elastomer with an intrinsic viscosity of 0.96 dl / g in dimethylformamide 30 ° C, composed of polycaprolactam with a molecular weight of 1240, toluene diisocyanate and ethylene glycol, 2 parts of palmityl alcohol and 73 parts of tetrahydrofuran The spinning solution produced was spun in the same manner as described in Example 2. After winding the fiber showed no adhesion either under single filaments or under yarns.

Example 4

12 parts of polyurethane elastomer having an intrinsic viscosity of 0.82 dl / g in dimethylformamide at 30 ⁰ C, composed of polypropylene glycol, diphenylmethane diisocyanate and Tetramethylendianilin a solution "A" were dissolved in 88 parts of dimethylformamide to manufacture. Meanwhile, 30 parts of phenyl urethane were made from cetyl alcohol in 40 parts of water with 30 parts of one from one

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Nonion-anion mixture existing surfactant emulsified and the thus prepared emulsion became the solution "A" in an amount of 5% by weight based on the Amount of the solution "A" was added, whereby a spinning solution was obtained.

The spinning solution was spun in the same manner as in Example 1, whereupon the obtained fiber was complete Separation showed not only between yarns but also between monofilaments. The fiber had tensile strength of 0.64 g / den and an elongation at break of 490%. After exposure to a fadeometer for 40 hours, the showed Fiber has a tensile strength of 0.38 g / den and an elongation of 250%.

A fiber obtained by adding 5% by weight of nitrobenzene to the solution "A" as a control showed a remarkable one Adhered between the monofilaments and had a tensile strength of 0.59 g / den and an elongation of 495%. When exposed to a fadeometer, it had a tensile strength of 0.21 g / den and an elongation of 170%.

Example 5

It became a spinning solution of 15 parts of polyurethane elastomer with a basic viscosity in dimethylformamide

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at 30 ° C of 0.89 dl / g, consisting of a polyethylene adipate with hydroxyl end groups and a molecular weight from 1980, diphenylmethane diisocyanate and 1,4-butanediol, 4.5 parts of stearyl nitrile and 80.5 parts of dimethylformamide. The spinning solution thus obtained was in a at 180 ° held spinning column through a nozzle with 60 holes, each 0.09 mm in diameter at a speed of 16 cm / min extruded and wound on a spool at a speed of 250 m / min. The threads received had a tensile strength of 0.58 g / denier and an elongation of 330% and had during exposure to a fadeometer 30 hours a tensile strength of 0.44 g / den and an elongation of 285%.

The fibers obtained showed no adhesion either under yarns or under single threads.

Example 6

A spinning solution of 10 parts of polyurethane elastomer with an intrinsic molar viscosity in dimethylformamide was obtained at 30 ° C of 0.98 dl / g, composed of polyester with hydroxyl end groups and a molecular weight of 4190 and consisting of sebacic acid and a mixture of ethylene glycol and propylene glycol in a molar Ratio of 80/20, 0.7 parts octylaldehyde and 89.3

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Parts of dimethylacetamide. The thus obtained Solution was spun in the same manner as in Example 1. Pipes were obtained in this way which did not adhere between individual threads.

On the other hand, if the same procedure was carried out, but with the modification that the same amount of ethyl acetate, a known additive, used in place of octylaldehyde, found sticking not only between Single threads, but also between yarns wound on a bobbin.

Example 7

A solution "B" was made of 12 parts of polyurethane elastomer with an intrinsic viscosity in dimethylformamide at 30 ° C of 0.80 dl / g and consisting of diphenylmethane diisocyanate, ethylene glycol and a polyether ester with hydroxyl end groups and a molecular weight of 2300, composed of diethylene glycol and adipic acid and 88 parts of dimethylformamide. On the other hand, a mixture of 20 parts of methyl octadecanesulfonate and 40 parts of water was added in an amount of 5% by weight to the solution "B ¹ * to prepare a spinning solution. When this solution was spun in the same manner as in Example 2, fibrous m which showed no adhesion under yarns and under monofilaments were obtained.

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As a comparative experiment, a known additive, namely benzyl alcohol, was added to the solution ^W B ^W in an amount of 5% by weight. The obtained fibers showed remarkable inter-filament adhesion. When subjected to a fadeometer for 5 hours, they were colored deep yellow.

Example 8

The same procedure as in Example 2 was repeated, but with the modification that 0.7 parts of monoure eid stereate and 89.3 parts of dimethylformamide were used in place of methyl oleate. Fibers were obtained which showed no adhesion between monofilaments. Furthermore, there was essentially no yarn breakage.

Example 9

The same procedure as in Example 1 was repeated, but with the modification that 0.5 parts of ethyl butyl ketone and 89.5 parts of dimethylformamide in place of methyl oleate were used. Fibers were obtained which had a somewhat stronger adhesion between monofilaments than fibers obtained according to Example 2 showed.

Example 10

The same procedure as in Example 2 was repeated, but with the modification that 0.3 parts of octylamine

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and 79.7 parts of dimethylformamide in place of stearic acid amide were used. Fibers were obtained which had a somewhat stronger adhesion between individual threads than that according to FIG Example 2 showed fibers obtained.

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Claims (4)

Claims 1. A process for the production of elastic polyurethane fibers with low adhesive properties under yarns and under single threads, characterized in that a spinning solution with the addition of 0.01 to 50% by weight of esters of carboxylic acids with aliphatic hydrocarbon groups with 4 to 50 carbon atoms, amides, Nitriles, alcohols, aldehydes, ketones, amines, urethanes, sulphonic acid esters or mixtures thereof to form a polyurethane elastomer and then spinning the spinning solution » 2. The method according to claim 1, characterized in that the spinning solution is spun wet. 3. The method according to claim I or 2, characterized in that one uses a polyurethane elastomer composed of a polyester, polyisocyanate and diol. 4. The method according to claim 3, characterized in that a Pclyurethanelastomeres is used, which is composed of a polyester of ethylene glycol, propylene glycol and adipic acid and diphenylmethane diisocyanate and iifchyienglykol. 'or containing these hydrocarbon groups 109832M605