DE4100786A1 - Modifying properties of textiles - Google Patents

Abstract

A process for modifying the properties of textiles, comprises applying to the textile substrate (I) initiator(s) (II) which decompose(s) into radicals and/or ions by physical treatment, carrying out such treatment simultaneously and/or subsequently, and reacting the resulting radicals and/or ions with (I) itself, a substance (III), applied thereto and/or a gas surrounding (I). The gas is a reactive gas, pref. oxygen, N2O, ozone, CO2, ammonia, SO2, SiCl4, CCl4, CF3Cl, CF4, CO, Me3SiOSiMe3 and/or hydrogen, an inert gas, pref. nobel gas(es) and/or nitrogen and/or a mixt. thereof; (III) is a radically- and/or ionically-polymerisable substance, pref. oligomerisable and/or polymerisable hydrocarbon or a copolymer, mixed polymer, oligomer or mixed oligomer thereof and/or a deriv. thereof, pref. based on acrylic acid and/or styrene and/or salts or derivs. thereof; (II) is a persulphate (esp. K and/or ammonium), a peroxide (esp. dibenzoyl or di-tert.-butyl peroxide, cumene hydroperoxide, cyclohexanone peroxide or cyclohexylsulphonylacetyl peroxide), an azo cpd. (esp. AIBN) and/or an initiator based on benzpinacol, di-isopropyl percarbonate and/or tert.-butyl peroctoate, or a redoc system, esp. K persulphate/Na hyposulphite, H2O2/FeSO4, cumene hydroperoxide/polyamine and/or benzoylperoxide/N-dimethylaniline; (I) is swollen with a swelling agent before and/or during application of (II); the physical treatment involves heating, irradiation with light or with alpha-, beta- or gamma-rays.

Description

The present invention relates to a sewing thread with the Features of the preamble of claim 1 and a Process for producing such a sewing thread with the Features of the preamble of claim 13.

To in the manufacture of sewing threads, such. B. in the primary and secondary spinning, winding, twisting or the like. and to prevent yarn breakage during the actual sewing, It is known to sew on the different threads in the Bear processing levels. For example as the block waxing the sewing thread z. B. at Rewinding with an appropriate solid finish, at which it is in particular paraffin or a wax, in Brought in contact. This will transport from the Sewing thread taken on a certain amount of the finish is mechanically bound to the surface of the yarn.

It is also known to sew the sewing threads by an aqueous Dispersion or emulsion of a solid or liquid finish to lead, so that after the evaporation of the  Water a corresponding amount of surface finish of the yarn is deposited. You can also use one Apply finish from a long liquor. Here, the appropriate finishing agent dissolved, dispersed in water or emulsified. With such a solution, dispersion or Emulsion is then the sewing thread, preferably in the on form as a cheese, treated so that also, as above, the finish on the surface of the yarn is deposited.

In addition to the additives, there are other connections known that mechanically abge on the surface of the yarn be stored in order to specifically change the yarn properties other. For example, there is the possibility of sewing threads to be flame-retardant, for which purpose certain organic phosphorus compounds or special organic Nitrogen compounds on the surface of the yarn be mechanically deposited. By applying special It is also organic nitrogen compounds possible to decompose the yarn by microorganisms prevent. Fluorocarboxylic acid derivatives can also be used on the Surface of the yarns are deposited in layers thereby making these yarns water-repellent.

The equipment described above, which is the most diverse connections, for example around oligomeric or polymeric compounds, allow the processing properties or other properties properties of the yarns treated with this to change. However, all these equipment have in common that it in the form of a more or less coherent Layer or in the form of individual concrete particles deposited on the surface of the yarn and / or partially in the yarn spaces are stored, so that the be knew equipment at most a mechanical fixation  is present on or in the yarn. This mechanical fixation is but not permanently, so the equipment for example removed more or less during the use of the yarn becomes. This in turn leads to the fact that already at the manufacturer development of the yarns undesirable, for example, on deflection elements Deposits of the equipment are formed. This Ab storage then often leads to damage to the outer layers of the yarn, unless regularly used by the corresponding machine parts are removed. About that in addition often occurs when such Equipment the problem on that the equipment over the Yarn size or yarn length is not uniform is applied, whereby the desired property changes accordingly is different, which consequently represents a loss of quality.

The present invention is based on the object equipped sewing thread of the specified type is available places that have a particularly high abrasion resistance.

This task is accomplished with a sewing thread with the characteristic Feature of claim 1 solved.

According to the invention, a sewing thread, in particular a Sewing thread containing synthetic fibers, described, the one about equipment provided on the yarn surface points, which specifically changes the yarn properties will. This is the sewing thread according to the invention Equipment chemically bound to the yarn material.

The sewing thread according to the invention has a number of advantages on. So it was found that one of them Equipment chemically bound to the yarn material in particular is permanently and firmly attached to the yarn material. This particularly applies to such embodiments of the inventions  sewing thread according to the invention, in which the equipment over a covalent bond is bound to the yarn material. The In this case, equipment is only broken down disruption of the chemical bonds within the yarn polymer chains or by destruction this covalent bond removable. Usually points but also one about ionic bonds to the yarn equipment bound material the required permanence on, so that these ionically bound equipment also the one required in the manufacture of the sewing thread Process steps as well as the actual sewing itself not be rubbed off undesirably, as at the beginning state of the art listed is very easily possible. Furthermore, those so chemically bound to the yarn material Equipment both over the yarn length and over the The yarn size is particularly evenly distributed, because here for example differences in roughness of the yarn surface, a different one in block paraffining Effect paraffin absorption, do not matter. Rather is in the sewing thread according to the invention, the number of reactive Centers preferably on the surface of the sewing thread ent outgoing to the chemical connection of the previously described Effect equipment. As a result, the fiction has moderate sewing thread due to the particularly uniform Ver division of the equipment always at each thread section the sel ben properties. The sewing according to the invention can also be done Manufacture yarn particularly environmentally friendly, since there is only one such concentration of equipment is used that he is required to respond to the previously mentioned Saturate centers and train them with these chemical compound (covalent or ionic) to react. As a result, even with an application a such equipment from a long fleet, suspended or emulsified equipment almost quantitative pulls on the respective yarn material, so that the off  Armor residual concentration in the fleet after application the equipment is almost zero and therefore appropriate smaller amounts of equipment get into wastewater. Wei depending on the selected one Equipment, targeted and permanent property changes adjust gene in the sewing thread according to the invention, wherein these properties are still present when Repeatedly assembled parts accordingly cleans or washed as well as extreme use under were thrown. Likewise, because of the chemical bond the equipment in the sewing thread according to the invention none at all Migration problems occur during storage, so that for example a deterioration in fastness properties of Colorings due to storage in the invention Sewing thread does not occur, which is the case with the known threads fit appropriate, promoting the migration of dyes Avivagen are equipped, has occurred repeatedly.

Depending on the desired change in properties of the sewing thread depends on the selection of the respective Aus armor. For example, should the staining behavior of such synthetic yarn materials that are inherently are difficult to dye, are improved, it is sufficient if you have fairly short chain equipment on the yarn material binds chemically, but is characterized by a high Number of functional groups. About these, additional function chemically bound to the yarn material Small groups then succeed in for example with ionic dyes, with a relative to paint with little effort. Such equipment will for example with polyolefin fibers or the relatively heavy dyeable aromatic polyamides preferred.

However, should the running behavior of the sewing threads during the Manufacture or subsequent processing, d. H. when sewing,  can be improved, for this purpose such Aus use armor, preferably a molecular weight have between 80 and 1500, the chemical structure such connections depending on the desired Eigen Changes in shaft can vary as follows is still described.

On the other hand, if the sewing thread according to the invention is intended, for example against extreme stresses caused by chemical or mechanical influences, are protected such sewing thread in particular high molecular weight equipment on, the molecular weight of such equipment preferably between 1500 and 1 80,000, in particular varies between 20,000 and 80,000. In addition to the chemical connection of the equipment to the yarn material can this equipment then triple with each other be offset dimensionally, so that a corresponding fixed and / or liquid coating on the surface of the yarn resulting in the outer layers of the Garnes surrounds and so prevents the previously described Attack the actual yarn material.

The number of copies of the equipment also depends on the yarn according to the invention according to the particular desired change of business. Usually the equipment varies in a height between 0.01 wt.% and 20 wt.%, preferably in a height between 0.5% and 10% by weight.

The layer thickness of the appli on the surface of the sewing thread graced and chemically bound to the yarn material armor also varies depending on the ge desired change in properties and the one used Product. So it is possible, for example, the equipment to be provided only selectively on the surface of the sewing thread, so that such equipment, for example  wise to improve the equipment described above staining behavior, not a closed layer forms on the surface of the yarn. Polymer equipment on the other hand, especially the niedermo listed above molecular and / or high molecular weight equipment usually the surface of the sewing thread according to the invention nes with a closed or almost closed solid or liquid layer, this layer fiction appropriate sewing thread covered on the outside and preferably a layer thickness between about 100 nm and about 0.1 nm, between about 20 nm and about 2 nm.

As already described above, the sewing thread according to the invention has an equipment which is bound to the polymeric chains of the thread material via an ionic or preferably via a covalent chemical bond. This presupposes that the polymeric chains of the yarn material as such have appropriate reactive centers or such reactive centers are produced before the equipment is connected to the yarn material. The first option includes in particular those sewing threads which are made of polyamide 6, 6, polyamide 6, modified polyacrylonitrile and / or cellulose acetate fibers or filaments or contain these fibers or filaments. The aforementioned polymers already have appropriate functional groups here, such as, in particular, NH ₂ , OH and / or COOH groups. These polymer-specific groups can then react with corresponding groups of the armor to form the appropriate chemical bond and fix the equipment to the yarn material, so that in such an embodiment of the sewing thread according to the invention the chemical bonding of the armor is either ionic or, in particular, covalently via appropriate amide and / or ester groups.

If, on the other hand, the polymers forming the sewing thread do not have such reactive centers for the attachment of the equipment, it is necessary to first generate the like reactive centers, in particular on the surface of the sewing thread. This can in particular be achieved by preferably partially splitting the polymer chains of the yarn material present on the surface of the sewing thread by suitable methods, preferably by hydrolysis, a low-temperature plasma treatment, a corona treatment and / or by chemical radical formers and thus creates reactive centers, which are either corresponding functional groups, such as OH, COOH and / or NH ₂ groups, or from which the aforementioned functional groups are produced. Furthermore, it is possible, in particular by a low-temperature plasma treatment, a corona treatment and / or by a treatment with initiators, radi cal and / or ions preferably to produce on the surface of the yarn material, which then with the appropriate equipment with the formation of React chemical bond or form functional groups, for example by reaction with oxygen, carbon dioxide and / or sulfur dioxide.

Assign the polymeric chains that the inventive Form sewing thread or in the sewing thread according to the invention are already present, the ones described above reactive functional groups or become Group prepared according to the aforementioned method, so it is particularly useful to use these functional Groups with such equipment to react to bring that one to the functional groups of yarn has polymer-tuned reactive group. This then leads to an embodiment of the sewing thread according to the invention, where the equipment through the chemical reaction between the functional group of the yarn polymer with the reactive  group of equipment covalently and / or ionically to the yarn material is bound.

In particular, these equipments then have a reactive group pen heterocyclic ring systems, especially triazine Derivatives, cyanuric halides, pyrimidine derivatives, such as in for example 2, 4, 5, 6 tetrahalopyrimidine or 2, 4, 6 Trihalopyrimidine, quinazoline derivatives, in particular 2, 4-dihalo-quinazoline, quinoxaline derivatives, in particular 2, 3-dichloro-quinoxaline and / or pyridazone derivatives, in particular their 1-aryl-4,5-dihalopyridazone-6. Furthermore are in the case of the heterocyclic ring systems, the derivatives of Imidazole, tiazole, isothiazole and corresponding Pyrimidine derivatives, such as quinoline or Pyridizine derivatives.

In addition to the heterocyclic ring systems, the equipment also bound to the yarn material via such reactive groups be those that are caused by the elimination of water, acids or other compounds, for example in alkaline aq ger fleet, form vinyl groups. Here are in particular to name the β-substituted ethane derivatives, these slightly under due to the electron-attracting β-substituents Formation of the corresponding vinyl compound acid or Split off water and for the same reason accordingly then quickly with functional groups of the yarn polymers respond as follows through the reaction equation I is shown as an example.  

Formula I.

with X = halogens, OSO₃H, OPO₃H, OSO₂R, OSO₂-Ar-CH₃,
with Ar = aryl
and Y = O, SO₂, CO, NH, SO₂NH, NHSO₂, CONH, NHCO, CH₂S.

Furthermore, the equipment as a reactive group epoxy, Ethylene imine, sultone, isocyanate, isothiocyanate, sulfone and / or sulfofluoride groups, which then under Formation of a covalent bond with the functional ones Groups of the polymer forming the yarn react like this described above for the β-substituted ethane derivatives ben is.

There is also the possibility of an ionic and / or preferably radical chain cleavage of the yarn polymers and thereby create free bond valences fen, which then with corresponding radical and / or ionically polymerizable equipment can be saturated. In contrast to the above be written possibility of the direct connection of the equipment to the polymer chain of the yarn.  

As already stated above, the Selection of equipment according to the desired Property changes.

Thus, a further embodiment of the invention Yarn on equipment that contains hydrocarbons, oligomeric or polymeric hydrocarbon, hydrocarbon Copolymers of materials, co-oligomers, mixed oligomers, -Mixtures and / or derivatives of these compounds includes.

This includes in particular those listed below Links: Oligomeric or polymeric alkylenes, especially ethylene, Propylene, isobutylene, butadienes, isoprene, methylstyrenes, Xylylene, as well as halogen derivatives of the aforementioned verb dungen, in particular vinyl chloride, vinylidene chloride, Tetrafluoroethylene, trifluorethylene, vinyl fluoride, Vinylidene fluoride, pentafluorostyrene, 2,2,3,3-tetra fluoropropyl methacrylate and / or cooligomerizate polymers risate, mixed oligomer and / or mixed polymer previously mentioned compounds, in particular the Mischoli polymer or polymer of tetrafluoroethylene Perfluoropropylene; Tetrafluoroethylene-perfluoroalkylvinyl ether; Tetrafluoroethylene-ethylene; Trifluorochloroethylene Ethylene and hexafluoroisobutylene vinylidene fluoride. Both Cooligomers or copolymers are in particular those corresponding co-compounds of tetrafluoroethylene and Perfluoropropylene, tetrafluoroethylene and perfluoroalkyl vinyl ether, tetrafluoroethylene and ethylene cooligomers or Ethylene copolymers and hexafluoroisobutylene vinylidene fluoride to call.  

Another embodiment of the sewing thread according to the invention provides that this is a chemically bound equipment points, the oligomeric and / or polymeric compounds of Acrylic acid, acrylic acid, cooligomerisates, copolymers, Copolymers, mixed oligomers and / or derivatives and / or salts thereof.

In the case of the acrylates, in particular methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert. -Butyl acrylate, hexyl acrylate, 2- ethylhexyl acrylate and lauryl acrylate. These acrylates can then be cooligomerized or co-polymerized with suitable comonomers, such as, for example, methyl methacrylate, ethylene methacrylate, n-butyl methacrylate, acrylonitrile, styrene, 1,3-butadiene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, vinil fluoride and / or vinylidene fluoride. Furthermore, further monomers, in particular acrylic acid, methacrylic acid, acrylamide, methacrylamide and / or salts of the aforementioned two acids, can be present in the oligomeric or polymeric chain of the equipment. Such monomers, which have functional groups, can also be provided in the equipment, these being in particular monomers containing carboxyl groups, such as, for example, maleic acid and / or itaconic acid; monomers containing hydroxyl groups, such as, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, propylene glycol methacrylate and / or butanediol monoacrylate; n-Hydroxy methyl group-containing monomers, such as N-hydroxymethylacrylamide and / or N-hydroxymethyl methacrylamide; and / or monomers containing sulfonic acid, in particular 2-acrylamido-2-methylpropanesulfonic acid. These monomers then make it possible to cross-link the equipment three-dimensionally during and / or after it has been linked to the polymer chains of the sewing thread. Corresponding ethers, in particular ethyl diglycol acrylate, amines, in particular tert-butylaminomethacrylate, dimethylaminoethyl acrylate, diethylamino-ethyl methacrylate and / or diethylamino ethyl acrylate, epoxides, in particular glycidyl methacrylate; and / or halogen / hydroxyl group-containing monomers, in particular 3-chloro-2-hydroxypropyl acrylate.

Another embodiment of the sewing thread according to the invention provides that the equipment is oligomeric and / or polymeric Compounds of styrene, styrene co-oligomerisate, copoly merisates, mixed oligomerisates, mixed polymers and / or Derivatives and / or salts thereof. Here are special in addition to the polystyrene or polymethyl already mentioned styrene in particular the cooligomerisate and / or copolymers sate of styrene and / or methylstyrene with acrylonitrile and / or of styrene and / or methylstyrene with butadiene call.

Furthermore, the chemical bonded to the yarn material Equipment consist of organosilicon compounds or have them. This is then preferred as to oligomeric or polymeric silicones that are based on silicon atom are substituted accordingly. Here, the chemical bonding of these silicones preferably via the Silicon atom or reactive provided on the silicon atoms groups reached, these reactive groups the above have the chemical structure described. By an ent speaking chemical reaction between functional groups of the yarn polymers and the reactive groups is then the organosilicon equipment via a covalent bond the Garrn material fixed.

The present invention also has the object reasons, a process for producing the previously described to provide available sewing thread.  

This object is achieved by a method with the characterizing features of claim 13 solved.

In the method according to the invention for producing the standing described sewing thread, which is a chemical to the Having yarn material tied equipment is produced in the yarn and / or centers reactive on its surface, where these reactive centers are radicals, Ions and / or functional groups, such as this has already been described above. Simultaneously or after The generation of the reactive centers then becomes the end armor and / or the monomers making up the equipment and / or oligomers to form the chemical bond reacted with the sewing thread.

To the reactive centers in the yarn and / or on the yarn There are several ways to create a surface.

This is a first embodiment of the invention Procedure before that these reactive centers by a chemical attack on the polymer chains of Garnma terials are formed. Exist or include example as the polymeric chains of the yarn material polyester or Cellulose acetate, so the aforementioned reactive Centers are created by using these polymers, especially in alkaline, hydrolyzed. The one here emerging COOH or OH groups can then with such equipment as that described above Contain reactive groups, forming a covalent Bond between the yarn polymer and the equipment to the Fix the thread material.

Of course, the method according to the invention is also applicable to such yarn polymers that are inherently  have reactive centers, such as polyamides. Here either the Ver drive or the first process step listed can be done in addition to the concentration the reactive centers in the yarn or on its surface enlarge.

Furthermore, in the method according to the invention instead of the previously described functional groups or in addition to the functional groups previously described on the surface of the yarn and / or in the yarn itself as reactive centers preferably generate radicals and / or ions will. This generation of radicals or ions can again by chemical means, in particular through a Treatment of the yarns with one or more initiators and / or by physical means, in particular by a Low-temperature plasma treatment or corona treatment, respectively.

In order to generate radicals chemically in the process according to the invention, the yarns are treated with an initiator and / or an initiator mixture, in particular persulfate initiators, preferably potassium persulfate; Peroxide initiators, preferably dibenzoyl peroxide, cumene hydroperoxide, cyclohexanone peroxide and / or di tert. -Butyl peroxide; Azo compounds, preferably Azodiiso butyronitrile and / or 4,4'-azo-bis ( 4- cyanopentanoic acid chloride); and / or tert. -Butyl peroctoate is used.

To the formation of the radicals previously described on the To be yarn surface and / or in the yarn spaces accelerate, sees another embodiment of the he inventive method before that before and / or at Treatment with the aforementioned initiators using the yarn a swelling agent is treated. This will make the  Accessibility of the initiators to the polymeric chains of the Yarn material increased, resulting in a correspondingly lower con concentrations at initiators and / or the Aus loot at radical reactive centers can be increased.

The selection of the swelling agent depends on the respective material of the polymer.

It is particularly suitable in the Ver drive when you activate the previously described Initiators brought about by a redox system, being here for as redox systems especially potassium persulfate / sodium hyposulfite; Hydrogen peroxide / iron (II) sulfate; Cumene hydroperoxide / polyamine and / or benzoyl peroxide / N-dimethyl aniline can be used. It was found that the necessary for the destruction of these redox systems Temperature was significantly reduced, so accordingly lower temperatures are required to remove the ent to generate speaking radicals or ions.

As already explained above, the radicals and / or ions, preferably also by physical means, especially by a low-temperature plasma treatment or a corona treatment can be created, according to the conditions for this are described in detail below are.

Basically, the method according to the invention is to be firmly established hold that you can both the chemical described above Treatment to generate the reactive centers as well Temperature plasma treatment described below or corona treatment on the individual yarn with a pre given continuous speed by the ent speaking chamber is performed, or on a single Yarn layer, can perform.  

However, it is particularly suitable if the invention procedures and in particular the low temperature Plasma treatment or corona treatment on the pile and before preferably carried out on the winding former, since it is in particular especially with low-temperature plasma treatment it is necessary to evacuate the corresponding yarn Introduce or remove the chamber again, see above that in the treatment in the pile or in the winding body Sealing problems do not play a decisive role. About It was surprisingly found that even if the radicals and / or the ions through a low temperature Plasma treatment or corona treatment in the pile be the equipment over the yarn length and over seen the yarn size very evenly on the yarn material is chemically bound.

To be a special in the inventive method even distribution of the low-temperature Plasma treatment or corona treatment generated radicals or ions over the yarn length and over the yarn circumference ensure another embodiment of the he sees inventive method before that from each creates a pile of sewing thread and this pile during the low-temperature plasma treatment or Corona treatment with a gas flowing through it.

A further improvement in distribution and in particular also a further acceleration of the invention The method is used in another embodiment of the inventive method achieved in that from the Sewing thread a pile, in particular a winding body, too next manufactures. Then an initiator of the standing type ad- and / or absorbed on the sewing thread, for this purpose the pile or the winding body of  a gaseous initiator or an initiator mixture or an aqueous solution, dispersion or emulsion of Initia tor or initiator mixture is flowed through. after the individual layers of yarn of the pile or the winding body so with the initiator or a mixture of initiators the same are moderately occupied, the initiator is destroyed or the initiator mixture and thus the formation of Radicals or ions through the low-temperature plasma treatment lung or corona treatment.

The previously described embodiment variant of the fiction method, which is the sole application of the Initiator for the formation of reactive centers on the yarn polymer leads accordingly by reaction with geeig liquids or gases, such as water, Oxygen, carbon dioxide or sulfur dioxide, in function le groups can be converted may vary be changed that after the manufacture of the heap kes or the winding body together with the initiator or the equipment described above to the initiator mixture evenly absorbs or absorbs the yarn. This will then the pile or the winding body with a mixture, be standing from the initiator or the initiator mixture and the Equipment, in the form of a gas mixture or ent flows through speaking solution, emulsion or dispersion and then the pile or the winding body of the Nieder temperature plasma treatment b between corona treatment fen.

In order for the two process variants described above in low-temperature plasma treatment or corona loading to treat an uneven treatment effect prevent and in particular an undesirable local Zer To avoid disruption of the yarn polymers, the set initiator or the initiator mixture used and  the conditions of the low-temperature plasma treatment or Corona treatment, such as B. pressure, temperature, power, Power density and frequency, so to behave on each delnde yarn matched that at the low temperature plasma treatment or corona treatment only the previous one evenly applied initiator or the initiator mixture disintegrates.

Also preferred in the two previously described Procedures the pile or the winding body of flows through a suitable gas, this measure also contributes to the fact that the individual layers of the pile or of the winding body are not treated unevenly.

Usually in the method according to the invention Low temperature plasma treatment with a vacuum between 5 Pa and 500 Pa. Particularly good results can be achieved by low-temperature plasma treatment at a vacuum between 20 Pa and 300 Pa, preferably between 70 Pa and 200 Pa.

Another embodiment of the invention The process provides that at low temperature Plasma treatment during a first treatment period Vacuum between about 5 Pa and about 120 Pa, preferably between about 20 Pa and 120 Pa, and during one itself followed by a second treatment period between about 80 Pa and about 250 Pa, preferably between about 100 Pa and about 200 Pa. This will make him is enough that the winding body or the pile is particularly good is flowed through with the gas, which is the uniformity of the Generation of radicals or ions on the surface or in the spaces between the threads. Especially in the Cases in which the first treatment period immediately after the second treatment period, and before  all things when you have the first and second treatment Period alternating several times and immediately after each other other repeated, the winding body or the pile flows particularly well, so that an uneven Ra dical formation over the thickness of the winding body or Haufwerkes is completely excluded.

In the embodiment of the invention described above according procedure, in which two successive Be periods of action in a different vacuum be carried out, one can transition from the first Treatment period to the second treatment period and from the second treatment period to the first treatment Design the period so that the vacuum in each loading action period abruptly stops. A special one Gentle treatment of the winding body or the pile however, enables a further embodiment of the inventions method according to the invention, in which the vacuum in the first Treatment period continuously in the vacuum of the second Treatment period and the vacuum in the second treatment period into the vacuum of the first Treatment period transferred so that the pressure during the Total treatment is increased or decreased sinusoidally.

Particularly good and even results in relation to the Ion or radical formation is achieved with the invention according to the method whenever the residence time of the first and second treatment periods between 10 seconds and 160 seconds, preferably between 20 Se customers and 60 seconds, varies.

In order to make the method according to the invention particularly reproducible with regard to the formation of ions or radicals, sees another embodiment of the invention Procedure before that at the beginning of the low-temperature plasma  treatment a vacuum is set at a pressure that is less than the pressure at the low temperature plasma treatment. This makes foreign gases more uncontrolled Compositions usually removed almost quantitatively. Then the gas leading to the winding body or the pile flows through until the desired one Pressure for low temperature plasma treatment reached is.

Usually the frequency is at low temperature tur plasma treatment between 1 MHz and 20 MHz, where particularly good results in terms of the number of generated radicals at a frequency of 13.56 MHz be enough.

In addition, you can in the inventive method the low-temperature plasma treatment even with one Frequency of 27.12 MHz, 40.68 MHz and / or 81.36 MHz lead, but it is also possible during the never the temperature plasma treatment the frequencies in the previous change mentioned areas or to different Set values within the aforementioned ranges.

The performance in the method according to the invention is preferably between 200 W and 600 W.

The power density at low-temperature plasma treatment varies between 2 W / dm ³ and 25 W / dm ³ , the volume information relating to the volume of the autoclave used in each case. However, the power density is preferably between 8 w / dm ³ and 14 w / dm ³ , in particular at 12.5 W / dm ³ .

Particularly good results with regard to the yield of ions and / or radicals which are formed on the yarn polymers can also be achieved in the process according to the invention with a low-temperature plasma treatment which is carried out at a frequency of 2.45 GHz and a pressure between 10 ^-1 Pa and 1000 Pa, preferably between 70 Pa and 120 Pa, and at a power density between 0.1 W / dm ³ and 5 W / dm ³ , preferably between 1.5 W / dm ³ and 3 W / dm ³ , is carried out.

The parameters are listed beforehand, which can then be used are when the radicals or the ions that make up the reactive Form centers for chemical bonding of the equipment, formed by a low temperature plasma treatment will.

If, on the other hand, the reactive centers are to be formed by a corona treatment, this corona treatment is carried out at a pressure which is at normal pressure and / or slightly above and / or slightly below normal pressure. Thus, in the method according to the invention, the corona treatment is preferably carried out at a pressure between 86.659 · 10 ³ Pa and 133.32 · 10 ³ Pa, in particular at a pressure between 93.325 · 10 ³ Pa and 113.324 · 10 ³ Pa. As with the low-temperature plasma treatment, the corona treatment always achieves particularly good results with regard to an even distribution and the number of radicals or ions if a pressure between 86.659 · 10 ³ Pa and during a first treatment period 99.99 x 10 ³ Pa and a pressure between 99.99 x 10 ³ Pa and 133.32 x 10 ³ Pa during a second treatment period. This is particularly true if the corona treatment is carried out in the pile or in the winding body. As an explanation for this, it is assumed that the pressure change flows through the winding body or the pile particularly well and uniformly, so that a correspondingly uniform distribution of the radicals or ions also results. Preferably, the first treatment period immediately follows the second treatment period, it being advisable to repeat this treatment cycle, consisting of the first and second treatment periods, several times alternately.

As before with the low-temperature plasma treatment described, you can see the pressure change between the first and the second treatment period abruptly. Here can however, there is a risk that the abrupt pressure change of the winding body or the pile in unwanted Way laid, so that especially with relatively soft Bobbins or soft packed piles, d. H. such Coils or piles in which the Shore hardness is low, at the transition from the first treatment period for the second treatment period a continuous printer elevation and at the transition from the second treatment period in the first treatment period a continuous pressure lowering is carried out. This pressure increase or pressure lowering can then be carried out sinusoidally, whereby for the first period and the second period preferably each because treatment times between 10 seconds and 160 seconds the, especially between 20 seconds and 60 seconds to get voted.

In order to eliminate undesirable foreign gases during the corona treatment, such as water vapor or dust particles from the air humidity, which can lead to an uncontrolled, non-reproducible corona discharge and continue to undesirably saturate the radicals or ions formed, it is recommended to set a pressure before the start of the corona treatment which is lower than the pressure during the corona treatment and then to set the required treatment pressure by supplying a defined amount of gas. In this case, the autoclave used for the corona treatment is preferably evacuated, in particular to a pressure between 1000 Pa and 10,000 Pa, so that subsequently the respective gas which flows through the winding body or the pile or in which the corona treatment is carried out, can be supplied to adjust the pressure in the autoclave to a value between 86.659 · 10 ³ Pa and 133.32 · 10 ³ Pa.

Of course you can also use the corona treatment Carry out normal pressure, only here for is that the corona treatment may be turned on gas also passed through the winding body or the pile flows.

Previously, in the method according to the invention both Low temperature plasma treatment as well as with the corona Treatment of a gas has been mentioned that wraps the flows through the body or the pile. The selection of each current gas depends on the achievable Effect. For example, by the low temperature Plasma treatment or corona treatment on the surface radicals or ions are generated from the yarn, this is how it works one preferably with an inert gas, such as Nitrogen and / or noble gases, otherwise the danger be stands that these radicals or ions with the gas and not, as desired, with the equipment or the yarn polymer react.

However, if the corona or low-temperature plasma treatment is used to generate functional groups on the yarn polymers or to destroy the initiator applied beforehand, a reactive gas is preferably used here, so that this gas or the radicals or ions formed in the process Gases react with the yarn polymer itself or with corresponding radicals or ions of the yarn polymer, as a result of which either the functional groups chemically bonded to the yarn polymer are formed directly or those bonded to the yarn polymer are formed which are converted into corresponding functional groups. Reactive gases which can be used are, for example, O ₂ , N ₂ O, O ₃ , CO ₂ , NH ₃ , SO ₂ , SiCl ₄ , CCl ₄ , CF ₃ Cl, CF ₄ , SF ₆ , hexane methyl disiloxane, CO and / or H ₂ , where these gases can exist both as individual gases and as gas mixtures.

The total treatment time for the invention Procedures in both low temperature plasma treatment as well as in the corona treatment depending on the ge desired effects and the set power density between about 2 minutes and about 30 minutes, preferably between about 5 minutes and about 20 minutes.

Particularly good results are achieved with the invention appropriate procedure if one before the Corona or Nieder temperature plasma treatment the material to a perfo rier sleeve, preferably on a perforated metal sleeve, wound in a bobbin.

In order to produce the radicals or Ions and thus even properties of an ent equipped yarns talking about the thickness of the wrap body or pile, it is recommended especially with very dense packages or Piles, alternately the winding body or the pile to flow through from outside to inside and from inside to outside men. Is in the inventive method according to the previously described embodiment worked, in which a first Treatment period with reduced pressure from a second Treatment period with a correspondingly increased pressure is carried out, it is advisable during the first loading the winding body or the pile of  inside out and during the second treatment period the winding body or the pile from the outside in or reverse flow through.

Basically, in the method according to the invention any suitable starting material, such as e.g. B. Polyamide, polyester, polypropylene and / or polyacrylic nitrile fibers, each alone or as a mixture with each other or use with other synthetic and / or natural fibers. Regarding the thread construction of the sewing thread used it should be noted that for this purpose every usual sewing thread construction tion can be used because in the invention Process the chemical bonding of the equipment predominantly on the surface or in the yarn gaps. Examples of such sewing thread constructions are Core yarns, multifilament yarns and filament fiber yarns too name that can be twisted if necessary. Of others are the known intermingled yarns as well as the well-known wound yarns, the titer of the aforementioned sewing threads in sizes order between 50 dtex · 2 (total titre 100 dtex) and 1200 dtex · 3 (total titre 3600 dtex).

After preferably in the inventive method the yarn surface and / or in the accessible yarn spaces between the reactive centers have been created these reactive centers to train the chemically attached to the Equipment bound with yarn material with appropriate Aus armor implemented. Basically, this comes as an end equipment such equipment that is either the Reactive described at the beginning of the claimed sewing thread have groups, which then with the functional groups of the yarn polymer react. However, be considered reactive Centers of the yarn polymer formed radicals or ions, so these can either be taken with a suitable gas  Training of a corresponding functional group react or vice versa with appropriate equipment be set, which is the level above if equipment listed for the yarn material is involved, either via radicals or ions to the yarn material can be coupled or the ionically and / or radically oli are gomerizable or polymerizable. This ionic or radical coupling or oligomerization or polyme rization with training of the actual equipment can according to the pre-radiation technique or by an equal early irradiation and connection. At the front radiation technology are first on the surface or in the interstices of the corresponding sewing thread Radicals or ions generated, which then in a second Reaction stage with the appropriate equipment for Response. The desired chemical bond the equipment can also be achieved in that the process steps described above simultaneously be performed.

Advantageous developments of the yarn according to the invention and the equipment according to the invention are in the sub claims specified.

The method according to the invention is described below with the aid of two exemplary embodiments explained in more detail.

example 1

A Nm 25/2 polyester core sewing thread was first used with a Treated 2% sodium hydroxide solution at 98 ° C for 15 minutes. Here through swelling and improvement of Accessibility of the surface.  

The sewing thread was then rinsed with water. Thereafter, the sewing yarn thus pretreated with a 1 M was Kaliumper sulfate solution impregnated (liquor pick-up 100 wt.%) And heated under nitrogen to a temperature of about 80 ⁰ C.

The sewing thread was then immersed in an aqueous emulsion leads, as an emulsifier anionic surfactants based on Alkyl sulfates and a mixture of isobutyl acrylate, Contains styrene and acrylic acid. After that, the sewing thread squeezed to a liquor intake of 100% by weight and stored under nitrogen at 40 ° C for 5 minutes.

After rinsing with water, the sewing thread thus equipped was ge dries and the sewing behavior is measured.

Example 2

The sewing thread mentioned in Example 1 was in a stick atmosphere of a low-temperature plasma treatment subjected to the conditions of low temperature Plasma treatment were as follows:

Pressure before the low-temperature plasma treatment: 5 Pa
Frequency: 13.56 MHz
Power density: 8 W / dm³
Pressure curve during plasma treatment: Figure 1
Duration of the first and second treatment period: 30 seconds each
Total treatment time: 4 minutes
Gas: nitrogen

Then the yarn with the previously described Emulsion treated under nitrogen and as in Example 1 described further processed. From this as well equipped sewing thread, the sewing behavior was examined.  

The results of the sewing behavior according to the above described embodiment are equipped yarns reproduced in Table 1 below.

In comparison, the sewing behavior became a standard sewing thread, which has the same structure, but with a Standard preparation is provided. This he too result is in table 1 in the column "standard sewing thread" reproduced.

Example 3

The sewing thread mentioned in Examples 1 and 2 was used as Opened 1 kg cheese. This cheese was initially with a 2% sodium hydroxide solution for 15 minutes at 98 ° C delt.

The cheese was then rinsed with water. After that was the cheese with a 1 M potassium persulfate solution treated at room temperature for 4 minutes.

Thereafter, a low-temperature plasma treatment was carried out under the conditions shown in Example 2, but deviating from this, the pressure was 20 Fa, the power density 25 W / dm ³ and the total treatment time was 6 minutes. Oxygen was used as the gas during this treatment.

The cheese was after the low temperature plasma treatment in an alkaline medium (pH: 8). After adding 0.5% sodium acetate and 1% acetic acid and 10% sodium sul The cheese was fat with a cationic dye (2%, type: Astrazon <colored.  

The spool was unwound and from the inner one samples were taken from the middle and outer layers. For this it should be noted that both visually and colorimetrically no differences in color depth or color tone existed between the three layers. Furthermore, the usual wet fastness measured. Neither the rub fastness nor perspiration and water fastness (heavy bean complaint) were objectionable. Comparative strength Measurements of the three layers showed that compared to the Starting material a loss in strength of 5% occurred was while the three layers were within each other Fault tolerance had the same strength.  

Table 1

The measurement results shown in Table 1 above represent mean values from 50 measurements clearly recognizable that the two sewing threads according to Example 1 and 2 the standard comparable in yarn construction sewing thread are clearly superior.

Microscopic examination of the sewing threads according to Example 1 and 2 show that a. on the surface of the sewing threads continuous layer of equipment with a layer thickness of about 10 nm was arranged. When trying to rewind it is found that the sewing threads according to Examples 1 and 2 caused no abrasion on thread deflecting elements, while such abrasion with the corresponding standard sewing thread occurred.

Claims (45)

1. Sewing thread, in particular synthetic fiber-containing sewing thread, provided with a yarn properties changing and predominantly on the surface of the yarn provided equipment, characterized in that the equipment is chemically bound to the yarn material. 2. Sewing thread according to claim 1, characterized in that the equipment is a low molecular weight equipment and a Has molecular weight between 80 and 11500. 3. Sewing thread according to claim 1, characterized in that the equipment is a high molecular equipment and a Molecular weight between 11,500 and 1 80,000. 4. Sewing thread according to one of the preceding claims, characterized characterized that it is the equipment at a height between 0.01% by weight and 20% by weight, preferably at a level between 0.5% by weight and 10% by weight.   5. Sewing thread according to one of the preceding claims, characterized characterized that the equipment the surface of the yarn completely or almost completely in one layer thickness between 100 nm and 0.1 nm, preferably 20 nm and 2 nm covers. 6. Sewing thread according to one of the preceding claims, characterized characterized that the equipment by a chemical Reaction of reactive centers of equipment with reactive Centers of the yarn material to the yarn material chemically is bound. 7. Sewing thread according to claim 6, characterized in that the equipment via at least one heterocyclic ring system, a β-substituted ethane derivative, an epoxy, a Ethyleneimine, a sultone and / or a sulfone group Amino, hydroxy and / or carboxyl groups of the Garm material is bound. 8. Sewing thread according to one of the preceding claims, characterized characterized that the reactive centers of equipment and / or the reactive centers of the yarn material radicals and / or ions. 9. Sewing thread according to one of the preceding claims, characterized characterized that the equipment hydrocarbons, oligomeric and / or polymeric hydrocarbons, coal water copolymers of copolymers, co-oligomers, mixed oligo merisates, copolymers and / or derivatives of these ver bonds included. 10. Sewing thread according to one of the preceding claims, characterized characterized in that the equipment oligomeric and / or polymeric compounds of acrylic acid, acrylic acid co  oligomerizates, copolymers, mixed oligomerizates, -Mixtures and / or salts and / or derivatives of includes the aforementioned compounds. 11. Sewing thread according to one of the preceding claims, characterized characterized in that the equipment oligomeric and / or polymeric compounds of styrene, its derivatives, co oligomerizates, copolymers, mixed oligomerisates, Copolymers and / or salts and / or derivatives thereof Connections includes. 12. Sewing thread according to one of the preceding claims, characterized characterized that the equipment is networked. 13. A method for producing a sewing thread according to a of the preceding claims, characterized in that one reactive centers in the yarn and / or on its surface generated and that one with or after the yarn with the equipment and / or the mono constituting the equipment mers and / or oligomers to form the chemically the yarn material bound equipment can react. 14. The method according to claim 13, characterized in that radicals and / or ions on the Surface of the yarn and / or generated in the yarn. 15. The method according to claim 13 or 14, characterized records that a pile of yarn, in particular a winding body, and then the reactive Centers. 16. The method according to any one of claims 13 to 15, characterized characterized in that the radicals and / or ions by treatment of the yarn with at least one initiator generated.   17. The method according to any one of claims 13 to 16, characterized characterized in that one can treat radicals by treating the Yarns with a persulfate, especially potassium persulfate a peroxide, an azo compound and / or tert. - Butyl peroctoate produced. 18. The method according to claim 16 or 17, characterized records that the yarns before and / or during treatment swells with the initiator by adding a swelling agent. 19. The method according to any one of claims 13 to 18, characterized characterized in that the reactive centers by a Low temperature plasma treatment or a corona treatment action generated. 20. The method according to any one of claims 13 to 19, characterized characterized in that from the sewing thread a pile, ins special a winding body, that one makes the off armor together with the initiator on the sewing thread ad and / or absorbed and that one subsequently destroys the Initiator and for the formation of radicals and / or ions the low temperature plasma treatment or corona treatment lung. 21. The method according to any one of the preceding claims, characterized in that the heap or Winding body during low-temperature plasma treatment or the corona treatment with a gas flows through. 22. The method according to any one of claims 19 to 21, characterized characterized in that the low-temperature plasma treatment at a pressure between 5 Pa and 500 Pa, in particular between 20 Pa and 300 Pa, preferably between 70 Pa and 200 Pa.   23. The method according to any one of claims 19 to 22, characterized characterized in that at low-temperature plasma treatment during a first treatment period Pressure between 5 Pa and about 120 Pa, preferably between 20 Pa and about 120 Pa, and during one of these closing second treatment period a pressure between 80 Pa and about 250 Pa, preferably between about 100 Pa and about 200 Pa. 24. The method according to claim 23, characterized in that the first treatment period immediately after the second Treatment period follows. 25. The method according to claim 23 or 24, characterized records that the first and second treatment periods repeated several times alternately. 26. The method according to any one of claims 23 to 25, characterized characterized that one for the first and second treatment period between 10 seconds and 160 seconds, preferably between 20 seconds and 60 seconds. 27. The method according to any one of claims 19 to 26, characterized characterized that one at the beginning of the low temperature plasma treatment sets a pressure that is less than the pressure during the low temperature plasma treatment and that you then the gas until the required treatment pressure. 28. The method according to any one of claims 19 to 27, characterized characterized in that the low-temperature plasma treatment at a frequency between 1 MHz and 20 MHz, preferred  at 13.56 MHz, and / or at a frequency of 27.12 MHz, 40.68 MHz and / or 81.36 MHz. 29. The method according to any one of claims 19 to 28, characterized characterized in that the low-temperature plasma treatment at a power between 200 W and 600 W. 30. The method according to any one of claims 19 to 27, characterized in that the low-temperature plasma treatment at a frequency of 2.45 GHz, at a pressure between 10 Pa and 1000 Pa, preferably between 70 Pa and 120 Pa, and at a power density between 0.1 w / dm ³ and 5 W / dm ³ , preferably between 1.5 W / dm ³ and 3 W / dm ³ . 31. The method according to claim 19 or 20, characterized in that the reactive centers are prepared by a corona treatment of the yarns and that the corona treatment at a pressure between 86.659 × 10 ³ Pa and 133.32 × 10 ³ Pa , preferably at a pressure between 93.325 × 10 ³ Pa and 113.324 × 10 ³ Pa. 32. The method according to claim 31, characterized in that in the corona treatment during a first treatment period a pressure between 86.659 × 10 ³ Pa and 99.99 × 10 Pa and during a second treatment period a pressure between 99.99 × 10 ³ Pa and 113.324 × 10 ³ Pa. 33. The method according to claim 32, characterized in that the first treatment period immediately after the second Treatment period follows.   34. The method according to claim 32 or 33, characterized records that the first and second treatment periods repeated several times alternately. 35. The method according to any one of claims 32 to 34, characterized characterized that one for the first and second treatment period between 10 seconds and 160 seconds, preferably between 20 seconds and 60 seconds customers. 36. The method according to any one of claims 32 to 35, characterized characterized that one before the start of the corona treatment sets a pressure that is less than the pressure during the corona treatment and that afterwards the Gas until the selected treatment pressure is reached feeds. 37. The method according to any one of claims 19 to 36, characterized characterized in that the gas is an inert gas, preferably a noble gas, a mixture of noble gases and / or nitrogen, starts. 38. The method according to any one of claims 19 to 36, characterized in that the gas is a reactive gas, in particular O ₂ , N ₂ O, O ₃ , CO ₂ , NH ₃ , 502, SiCl ₄ , CCl ₄ , CF ₃ Cl , CF ₄ , 5F ₆ , Hexanmethyldisiloxan, CO and / or H ₂ selects. 39. The method according to any one of claims 19 to 38, characterized characterized in that the yarns between 2 minutes and Treated for 30 minutes. 40. The method according to any one of claims 20 to 39, characterized characterized in that the yarns are perforated Sleeve, preferably a perforated metal sleeve wraps.   41. The method according to any one of claims 20 to 40, characterized characterized in that the pile or the winding body alternately from outside to inside and from inside to outside flows with the gas. 42. The method according to any one of claims 19 to 41, characterized characterized in that after the corona or Low temperature plasma treatment turns the yarns off armor that has reactive centers. 43. The method according to any one of claims 13 to 41, characterized characterized that one such equipment as Aus armor selects the hydrocarbons, hydro fabric oligomers, copolymers, copolymers, -Mixed oligomerizates and / or derivatives of these compounds includes. 44. The method according to any one of claims 13 to 42, characterized characterized that one such equipment as Aus armor selects the oligomeric and / or polymeric compound solutions of acrylic acid, acrylic acid copolymers, -Co oligomerisates, copolymers, mixed oligomerisates and / or salts and / or derivatives of these compounds. 45. The method according to any one of claims 13 to 44, characterized characterized that one such equipment as Aus armor selects the oligomeric and / or polymeric compound styrene copolymers, styrene copolymers, oligomerizates, Copolymers, mixed oligomers and / or derivatives and / or salts of these compounds. 46. The method according to any one of the preceding claims,  characterized in that the equipment as one aqueous solution, emulsion and / or dispersion on the sewing applies yarn.