DE2228800A1 - Multi-component textile continuous thread - Google Patents

Description

DR, BERG DIFI -.-: NG. STAPF PATENT LAWYERS 9 9 7P RHfI

β MUNICH 8O. MAUERKIRCHERSTR. 48 L £. C. UV

Attorney's file 22 516 ^{13 (}

Monsanto Company
St. Louis, Missouri / USA

"Multi-component Iextile continuous thread"

The invention relates to multicomponent textile filaments and in particular a spirally crimped composite continuous textile thread. The manufacture of multicomponent Iextile filaments by combining two or more polymeric materials with different shrinkage or Heat retraction properties have been known for many years. The union of the materials comes about that they are at or near the point of formation of the continuous thread without intimate intermingling in such a way that brings together the materials above a certain

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Period of time at least partially tied to one another in their longitudinal direction. This results in a so-called Side by side arrangement of different polymers in a composite fiber. In a second method for When different polymers are combined to form a continuous thread, the polymers are initially used in the spinning station brought together in such a way that a continuous Arrangement of the polymers in the form of an eccentric core with a jacket surrounding it. In both arrangements the pasers are latently curable. The crimp can be made by stretching the filament and develop relaxation afterwards. This creates a torsion-free, non-directional spiral crimp.

When choosing the different polymers, consider the most favorable properties in terms of their association and the optimal properties of the continuous thread, many factors have to be taken into account. There have already been Process described in which two-component continuous filaments composed of elastomeric and hard polymeric components are spun under such conditions that the adhesion between the components during the subsequent stretching and relaxation is abruptly lifted. Compartment for the fractional release of the adhesion the components separate from one another, with the harder continuous filament component separating in an undirected or random manner loops around the elastomeric continuous thread part. From it

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results in a woolly structure with the appearance of spun yarn. There is also the production of two-component continuous filaments known by melt spinning, one component being a spruce elastomer and the other Component is a thermoplastic elastomer made from polyester urethanes and the like. With the appropriate Choice of elastomers and non-elastomers Component "the components remain essentially adhered to one another State. Made from polyester urethanes However, elastomers have the disadvantage that they yellow strongly when exposed to light.

Rubbers and elastomers made from natural or synthetic rubbers usually need one before they can be used chemical vulcanization, whereby they are thermosetting and insoluble by crosslinking. the However, thermosetting products are not suitable for melt spinning and can therefore not be combined with use a thermoplastic polymer to make composite fibers.

According to the invention, a thermoplastic thread is used for melt or solution spinning of a two-component continuous filament Non-elastomeric and one not exposed to light appreciably yellowing, thermoplastic, non-vulcanized rubber-like product. Use.

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The invention thus creates novel and versatile multicomponent continuous textile threads, the components of which are formed from special materials. One component is a hard, relatively inelastic, flexible thermoplastic polymer. The other component is a non-vulcanized thermoplastic elastomer of the general formula ABA, wherein A is a non-elastic thermoplastic polymer block with an average molecular weight between 2,000 and 100,000 and a glass transition temperature (Tg) of about 90 ⁰ C and B is an elastomeric polymer block with a Average molecular weight of about 25,000 to 1,000,000 and a glass transition temperature of below about 20 ^° C. The hard polymer, in the form of a separately drawn continuous thread, has a maximum elastic elongation of about $ 50 and the thermoplastic elastomer component has a maximum elongation of more than $ 100, preferably $ 100 to $ 800. The main polymer chain of the elastomer consists essentially of continuously linked carbon atoms. The two components are either side-by-side or as an eccentrically sheathed * ¹ core over the length of the fiber. The thermoplastic elastomer represents between about 20 and 80% by weight of the fiber structure. Furthermore, a continuous thread can be produced from a dispersion of the two components. For this purpose, the polymers are mixed with one another in a suitable manner. The mixture is then melted and

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extruded, resulting in a composite fiber in which the one component in the form of microfibrils is embedded in the other matrix component. To achieve the crimp the microfibrils should preferably be arranged eccentrically in the continuous threads. Such an endless thread can be exposed to light without the elastomeric component being appreciably stronger Yellowing experiences as the hard component.

The invention also extends to multicomponent filaments knitted hosiery and tricot goods, as well as woven, knitted or otherwise made therefrom manufactured textile products.

In a method for producing the invention Multi-component filaments become either of the two components by melt or by solution spinning - using conventional composite spinning devices for Formation of a side-by-side arrangement or an eccentric core-shell arrangement pxtruded. Suitable for this numerous known spinneret arrangements for the Melt or solution spinning »After the extrusion from the spinneret, the composite continuous filament or the composite filament becomes coagulated in a spinning bath or the liquid extrudate solidified by treatment with a cooling gas. To improve the molecular orientation and to achieve the desired tensile strength and the for

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The shrinkage stress required will be the crimp Stretched fibers. The crimp then develops when the stretching forces disappear, i.e. when the Paser. The size of the shrinkage forces causing the crimp can be increased still further, and the shrinkage of the fibers reduced in boiling water, by removing the fibers subjected to a heat treatment following the stretching, in which they are heated under low tensile stress and then cooled. Depending on the spinning technique used Other follow-up treatments may also be necessary.

One of the for the production of the continuous filaments according to the invention components used is a relatively inelastic, hard thermoplastic polymer, for example a synthetic polymer such as

1. a polyamide called nylon in the form of a long-chain synthetic polycarbonamide with repeating imide groups as integral parts of the polymer chain. Examples are polymeric hexamethylene adipamide (nylon 66), polymeric epsilon-caprolactam (nylon 6) polymers of 1,4-cyclohexyl dimethylamine and adipic acid (GBMA 6) or lauric acid (CBMA 12), polymers made from bis (p-aminocyclohexylamine) and azelaic acid (PACM 9) or lauric acid (PACM 12), polymeric p-benzamide and numerous mixed polyamides ,

2. linear polyesters made from a fiber-forming substance

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on the basis of any long-chain synthetic Polymers of at least 85% by weight of an ester of a dihydric alcohol and an alicyclic or aromatic one Dicarboxylic acid, for example terephthalic acid. Examples of dihydric alcohols include ethylene glycol, 1,4-butanediol and 1 ^ -cyclohexanedimethanol, as well as Mixed polyesters and polyester amides,

3. polyurethanes,

4. polyuret offe,

5. Polycarbonates and addition polymers such as

6. Acrylates from a fiber-forming substance of at least 85 wt. <- $ acrylonitrile units,

7. modified acrylates based on fiber-forming Substances with less than 85 and at least 35 wt .- $ acrylinitrile units,

8. Crystalline polymeric hydrocarbons, the fiber-forming substance of which is at least 85% by weight of ethylene, propylene or contains other olefin units,

9. Vinyl chloride, vinylidene chloride, vinyl acetate, and many copolymers of the same. Also included are laser-forming agents Materials such as viscose and cellulose derivatives, for example cellulose acetate.

Fibers made solely from the above relatively inelastic polymers have a maximum elongation at break from $ 50. The preferred "hard" fibers stretch about $ 20 to $ 40 without breakage and have one

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Initial module from 18 "to 85 g / den. The non-post-treated "Hard" fibers can achieve the molecular orientation two to ten times the original length can be stretched.

The unvulcanized elastomeric block copolymer used can be expressed by the general formula

A-B-A

reproduce. Here, A denotes a block that is glassy or crystalline at the use temperatures for textile material and liquid at melt spinning temperatures, and B denotes an elastomeric block at the use temperatures for textile material, the main polymer chain of which consists of carbon atoms continuously connected to one another. The block A may be a thermoplastic polymer respected any normally provided the main chain of the molecule-constituting atoms are carbon atoms and, block A has a glass or crystallization temperature of about 9O ⁰ C or above. Examples include polystyrene, poly (methyl methacrylate), polypropylene, polymeric aC -methylatyrene, 4-vinylbiphenyl, p-tert-butylstyrene, acenaphthene, diisopropylstyrene, 2,4,6-trimethylstyrene, aC- vinyl! Naphthalene, etc. The Block B can be any linear polymer normally regarded as elastomeric at room temperature, for example polyisoprene, polybutadiene, polyisobutylene, smells thereof and mixtures of ethylene and propylene, etc. The elastic properties

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in-it-solution creeping and recovery from the Solution or with heating and cooling essentially completely restored. Preparations and production of block copolymers of the general formula A-B-A are described in U.S. Patent 3,265,765.

The preferred A-B-A block copolymer is a polystyrene-polybutadiene-polystyrene block copolymer (S-B-S), in which the molecular weights of S and B as well as the relative Weight percentage of S are limited. Another suitable A-B-A block copolymer is a polystyrene-isoprene-polystyrene block copolymer (S-I-S) with a limited molecular weight of S and I and a relative weight fraction from S. With a high A-block proportion of, for example more than $ 50, the elastomers have an irreversible yield point with very little elongation. With a low A— Leave block proportion, for example less than 10 J6 no fibers form from the elastomers. The most appropriate range for the block molecular weights is for polystyrene between about 10,000 and 20,000 and for Polybutadiene or polyisoprene between about 40,000 and 80,000.

Fibers made solely from the above relatively elastic polymers have an elongation at break of at least 100 #. When the tensile stress is released, the

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Elongation can essentially be completely canceled. The elastic fiber can preferably be stretched up to <100> ■ without breaking and has a module, ie one for stretching the fiber by 100 ^! _t .> required tensile force of about 0.01 to 0.1 g / den. The two components, that is to say the hard component and the elastomeric ABA block mixed polymer, are preferably extruded in a side-by-side arrangement through individual spinnerets. With this arrangement, the crimp is given a higher retraction force. However, L ¹ S is also possible to extrude the two components through separately adjacent spinnerets and to combine them in the still liquid state shortly after exiting the spinnerets. For a crimp with a lower retraction force, a core arrangement can be produced from the polymers, the core having to be arranged eccentrically with respect to the longitudinal axis of the loop thread. The two constituents can be present in approximately the same weight ratio, but also in weight ratios between 20 ": i.0 and ^ O: 20, " ■ . A strong crimp is guaranteed if at least 30 , - of the cross-section of the spun fiber through the ABA block nischpolymers are formed.! After the extrusion, the composite continuous filament should be stretched. After stretching, the non-continuous filament can then be heated under a low tensile load. Depending on the type of polymer selected, the components can possibly become one during the stretching and the heat treatment from-

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BATH ORIGINAL

solve each other. The polymer interface can have a third tooth arrangement, which dissolves the Components prevented from each other. With a core-sheath composite the problem of detachment does not appear to occur.

The invention is based on some embodiments. examples explained in more detail.

example 1

The example illustrates the preparation of an A-B-A block copolymer according to Example T of FIG U.S. Patent 3,265,765.

60 parts of styrene are dissolved in 1 400 parts of benzene and heated to 40 ⁰ C, after which 0.003 mole of sec-butyl lithium Eatalysator be added. The reaction mixture is polymerized in a reactor at about 40 ^° C. until all of the styrene has been converted to polymer. 450 parts of isoprene are then added to the reaction mixture until the isoprene monomer has been completely absorbed. Then 60 parts of styrene are added and the mixture is polymerized further until no more monomer is present. The product is a styrene-isoprene-styrene block copolymer with thermoplastic elastomeric properties. The StyrolTilock has a glass transition temperature of about 90 ⁰ C and the isoprene block, such a below 20 ⁰ C.

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Example 2

This example shows an embodiment of the invention. As a hard, relatively inelastic component is polyethylene having a density of 0.96 and a melting point of 12 ⁰ C. The elastic component is the SI-S block copolymer produced according to Example 1. The two polymers are melted separately and extruded under pressure through a nozzle in a spinneret. The streams of molten polymers, which are initially conducted separately, combine in the spinning head and emerge from this as a composite continuous thread with side-by-side arrangement of the components with approximately the same weight percentage. The continuous thread is cooled and then stretched by hand. The drawn continuous thread has a spiral crimp after relaxation.

Example 3

In this example the hard component is polymeric

£ -Gaprolactam with a formic acid viscosity of 20. The elastic component is a gemäi; prepared to Example 1 SIS ~ I ^T ischpolymeres, but with a 30, j 'increased total styrene content. The two polymers are separately melted and extruded under pressure through a spinneret into a spinning head ^1. The initially separate stivouos of the 'schnolnen new polymers' unite in the spinning head and also appear: as a pre-bunched continuous thread with soite-nn ~ gpite-.' IUordnm \ j dm *

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rornponont.on at otv / a the same weight proportion of the same the end. The enrollment thread is then cooled and hand-operated stretched to about three times its length. The relaxed, stretched one jjndlosfaden has a spiral crimp. That stretched Yarn has a denier of 25. This is made on a normal boat machine with double yarn feed knitted in a Danien stocking. The stocking is acid dyed using conventional techniques and dry shaped. The finished ieinstrump has favorable holding and Support properties for "the leg.

Another sample of the stretched yarn is used as filler yarn used for a sap tissue, the chain of which consists of a thirteen-thread lIylon-66 yarn is made of 40 denier. The mesh is dyed acidic using conventional techniques. The dyed finished fabric has due to the crimp of the hill yarn an advantageous extensibility.

Example 4

In this example the hard polymer is polymeric hexaraethylene adipamide with. a formic acid viscosity of 3d, the elastic component is the SIS block copolymers produced in accordance with Example I, but with a 35 ^c '> increased styrene content. The two polymers are melted separately and extruded under pressure through a spinneret in a spinneret. The initially separate streams of the molten

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mers unite in the spinning head and emerge from this as a composite continuous thread with a side-by-side arrangement of the Components with approximately the same weight proportion of the same. The continuous thread is then cooled and manually adjusted to etv / a stretched three times. The relaxed stretched endless thread has a spiral crimp.

example 5

In this example the hard component is polyethylene terephthalate with an intrinsic viscosity of 0.64. The elastomeric component is one according to that described in Example 1 S-B-S block high-quality polymer produced by the method with 1,3-butadiene as the B block and a proportion by weight of styrene of 30;. ·. The two polymers are melted separately and in equal amounts under pressure extruded through a spinneret in a spinneret. The paser is then cooled and stretched by hand.

Example 6

This example uses a linear polyester urethane elastomer combined with nylon-6. The polyester urethane is made from a polyester with hydroxyl end groups from 1,4-butanediol and 4,4-diphenylmethane diisocyanate Adipic acid (molecular weight of 2,000) produced and chain-extended with 1,4-butanediol, with the -KCO / -OH ratio Is 1.01. The two polymers are melted separately and in equal amounts under pressure extruded through a spinneret in a spinneret. Of the

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Endless thread is cooled and mechanically triple Stretched length. The continuous thread obtained becomes your sunlight exposed, the elastomer turning a distinct yellow color within a few days, indicating degradation of the polymer indicates.

The continuous filaments mentioned in Example 2 were exposed to sunlight for an equal amount of time, but the elastomeric component will not turn yellow discolored.

According to the above examples, the hard polymer and the unvulcanized thermoplastic rubber although fed separately to the spinning head and kept separately in mutual contact in the finished continuous thread, however, advantageous results can also be achieved in the form of a heterogeneous mixture of the two Components are spun into a continuous thread, in which then one component in the form of microfibers in the other component is embedded as a matrix. To be the various polymers dry in the form of chips or powders mixed together, or one polymer becomes the other in the form of a concentrated dispersion clogged. The mixture is melted and formed into a composite .iindloc thread extruded. The microj'asem that form in the process have an average diameter of less than about; ' niri at lengths between about 100 Jum and a few / ioatiüioterti. The microfiber component can be between e.twa.

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Make up 10 and 40 w / y of the heterogeneous continuous thread,

A wide variety of additives can be added to the polymer components in order to impart certain desirable properties to them. To reduce the ability to flex light, for example, IIO can be added. Additives can also be used to improve the resistance to degradation by heat and light and to increase or. Reduction of the colorability of the components can be added. In addition, the use of additives can reduce the tendency towards electrostatic charging ^ ₀ H of textile products made from the continuous threads. Such antistatic additives are particularly suitable as a separate phase in the components diverged polyalkoxylated compounds of various types. In particular, certain polyalkoxylated saturated fatty acids, esters of hydroxy fatty acids and fatty acid amines are suitable. A particularly useful antistatic additive is a polyalkoxylated one. Triglyceride of a saturated hydroxy fatty acid having 12 to 30 carbon atoms, as described in US Pat. No. 5% -t- 104. The proportion of Polyalkoxyalkylengruppe in the glyceride is preferably in Ilolekulargewichtsbereich 1000-30000 and for example, an ethoxy, propoxy group od. The like, to be. The repeating alkylene oxide groups preferably represent at least one. 50 ^c _t j of the molecular weight of the glyccride. Furthermore, polyalkylene ethers such as ethylene oxide, propylene

oxide and the like, as well as condensation products. The concentration of the polyalkoxylated additives is about 1-10 Gev /.^.

- 19 (claims)

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Claims (1)

ΐ a t e η t a η s ρ r ii before: 1. Continuous-component textile continuous thread, characterized in that one component is formed from one: -] relatively inelastic, hard polymer which, in front of a separately drawn fiber, has a maximum elastic elongation of about 50%. ' and a second component is formed from a non-vulcanized elastomeric copolymer of the general jj'ormel ABA, whose block B has a glass transition temperature below about 20 ΰ and whose block Λ has a temperature of over about 90 ⁰ C, the Ilisch polymer being an im has a polymer main chain consisting essentially of continuously interconnected carbon atoms, and in the form of a separately stretched fiber has a maximum elastic elongation of over about 100; J. 2. Spirally crimped two-component textile iJndlosfäden according to claim 1, characterized in that A is a non-elastomeric, monovinylaromatic hydrocarbon polymer block with an average molecular weight of 10,000 to 20,000 and a glass transition temperature of about 90 ⁰ O, that B is an elastomeric polymer block of a conjugated diene with an average molecular weight of 40,000 to & 0,000 and a glass transition temperature below about 20 ⁰ O. The main polymer chain of the copolymer consists essentially of continuously interconnected carbon atoms and the Hischpolytr.ere in the form of a separately drawn fiber has an elastic elongation of about 100 to about 100%, the total proportion 209852/1123 _ _zo _ mi block Λ about 10 to 50 wt.;. ' of the mixed polymer " . '5>. Lindless thread according to claim 1 or 2, characterized in that it is produced by the melt spinning process. 4. Continuous thread according to .spruch 3 »characterized in that that the "two components in side-by-side" arrangement are arranged along the length thereof. 5. Jündlosfaden according to claim 3 _}, characterized in that the two components are arranged in an eccentric Haute1-Kern-Anoruuung along the length thereof. 6. Paser according to one of claims 1 to 5, characterized in that that the elastomeric copolymer makes up about 20 to OO G-ew. ', - of the Yerbund filament. 7. knitted fabric, characterized in that it consists of liindlosfäden geraäß one of claims 1 to 6 is made, ■>. Material, characterized in that it contains continuous threads according to one of Claims 1 to 6. 9. continuous thread according to claim 3> characterized in that üai'i is the hard polymer fiber-forming lIylon-66. 10. _ · Λΐ (Πor: thread according to Anrsprvieh; 3, characterized in, da "'Iu ;: havio ιόΙλ.ιηϊγο fnnerbiidciiüen fiylon-G int. 209852/1123 7228800 11. Endless thread according to claim 3> characterized in that that the hard polymer is fiber-forming polypropylene. 12. Continuous thread according to claim 5, characterized in that the hard polymer is fiber-forming polyethylene terephthalate. 13. Endless thread according to at least one of claims 1 to 12, characterized in that the polymer block A by Polymerization of a monomer, namely of styrene, -Me thy I-styrene, 4-vinylbiphenyl, p-tert-butylstyrene, azenaphthene, Diisop: pylstyrene, 2,4 | 6-! I! Rimethylstyrene and / or vinylnaphthalene is made. Η. Spirally crimped two-component textile continuous thread produced by melt spinning, characterized in that one component eir. relatively inelastic hard. Polymer is which in the form of a separately scattered fiber has a maximum elastic elongation of 50 io and that the second component is a non-vulcanized styrene-butadiene-styrene block copolymer, the styrene segments of which have a G-las temperature of over 9O ⁰ O and its Butadienb lock of such has at 2O ⁰ O, wherein the mixing polymers having an elastic elongation of about 100 to 800. $ and the polystyrene content was about 10 to 50 wt. constitutes i of the mixed polymer. - 22 - 209857/1123 15. Endless thread according to claim 14, characterized in that the hard polymer fiber-forming liylon-66, Hylon-6, Is polyethylene terephthalate or polypropylene. 16. Spirally crimped two-component textile filament produced by melt spinning, characterized in that one component is a relatively inelastic hard polymer which, in separately drawn fiber form, has a maximum elastic elongation of about $ 50 and that the second component is a is unvulcanized styrene-isoprene-styrene block copolymer, the polystyrene segments of which have a glass transition temperature of over 90 C and whose isoprene segments a temperature of below 20 ⁰ C, the block copolymer having an elastic elongation of about 100 to 800 $ and the polystyrene content therein makes up about 10 to 50% by weight of the interpolymer. 17. Endless thread according to claim 1, characterized in that that the components are mixed with one another heterogeneously, so that one component as a matrix and another component in the form of microfibers. 18. Continuous thread according to claim 1, characterized in that it contains about 1 to 10 $ of a poly (alkylene ether) compound with a high molecular weight, the recurring alkylene oxide groups of which make up at least 50 fo the molecular weight. * ,,, o- ■ ' 209852/112?