EP2459785A1

EP2459785A1 - Method for producing spinnable and dyeable polyester fibers

Info

Publication number: EP2459785A1
Application number: EP10737320A
Authority: EP
Inventors: Pia Baum; Klaus Scheuermann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2009-07-31
Filing date: 2010-07-27
Publication date: 2012-06-06
Anticipated expiration: 2030-07-27
Also published as: US20120180232A1; CN102471942A; EP2459785B1; AU2010277618B2; AU2010277618C1; ES2535331T3; MX2012000799A; KR20120040234A; JP2013501152A; PL2459785T3; AU2010277618A1; JP5575240B2; KR101718565B1; BR112012001832A2; US10202712B2; CA2767371A1; MY160755A; ZA201201420B; CN102471942B; WO2011012598A1

Abstract

The present invention relates to a method for producing dyed polyester fibers (C) from a terephthalate polyester (A), at least one additive (B) containing polyester, and optionally at least one component (G). The additive contining polyester can be obtained by condensing the monomers of an aliphatic 1, ω-dicarbolic acid and an aromatic 1, ω-dicarbolic acid. Chain lengtheners (V) are optionally also used in the production of the additive (B) containing polyester. The components (A, B) and optionally (G) are mixed, melted in an extruder, and extruding by means of spinnerets for generating fiber. Said polyester fibers (C) are preferably used in the production of dyed textile material webs (F).

Description

Process for the preparation of spun and dyeable polyester fibers

The present invention relates to a process for the production of spun and dyeable polyester fibers from a terephthalate polyester and at least one polyester-containing additive.

Polyester (PES) are polymers with ester bonds - [- CO-O -] - in their backbone. Polyesters today are the large family of synthetic polymers (plastics), which include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). PET is one of the most important thermoplastic polyesters. It is used, for example, in fibers (microfibers) for textiles and nonwovens.

PES fibers are produced by the melt spinning process. The action of heat produces a melt which is extruded through spinnerets. The coloring of PES fibers is usually carried out by the use of disperse dyes, which are contained in the form of pigments in mostly aqueous formulation in emulsion paints. The dyeing process of PES fibers generally takes place after the exhaust or the Thermosolverfah- ren at temperatures of 130 ⁰ C or more. If the dyeing of a PES material is to be carried out at a lower temperature in order to be able to dispense, for example, with pressure vessels, then a so-called "carrier", ie a chemical substance which allows penetration of the dye into the fiber even at lower temperatures, must also be used. An example of a carrier for dyeing PES materials is described in EP 0 364 792 B1. JP-A 8074124 reports the preparation of a good dyeable polybutylene terephthalate fiber obtained by copolymerization with a comonomer of 0.5 to 5 mol%, based on all acid constituents in the fiber, of a sodium salt of sulfoisophthalic acid, 15 to 85 ppm of titanium and 0.02% to 2.0% by weight of the antioxidant phenol (hypo) phosphite Use of cationic dyeing agents that bind to the comonomer.

EP 1 217 024 B1 reports on spun and dyeable polyester resins such as polybutylene terephthalate. The polyester is here constructed from an alkyl diol, terephthalic acid and a complex comonomer which may contain a metal or alkyl phosphonium sulfone, trivalent aromatic rings and ester functional groups. The polymerization is carried out using a titanium catalyst. The incorporated comonomer is also the receptor site for a cationic stain. The coloring takes place at a temperature of 100 ^° C. The processes known from the prior art PES fibers to 100 ⁰ C are dyeable at temperatures are thus either rely on the use of carriers, or there must be used PES copolymers, which must be manufactured via complex polymerization. Another problem in polyester production or processing is that fibers of complex copolymers may have higher requirements in terms of spinnability or little variation in the fiber thickness is possible, the fibers are inflexible and, above all, that even standard polyester fibers only at very high Temperatures can be dyed light and washfast. The object is to provide a process for producing a PES material (for example, polyethylene terephthalate or polybutylene terephthalate as a base polyester), wherein the produced PES material does not have complex polymerization steps in the production, has good spinning properties and the produced PES material even at temperatures below 130 ⁰ C, preferably at and below 100 ⁰ C, light and fast wash without using a carrier.

This object is achieved by a process for the production of dyed polyester fibers (C), dyed yarns and / or dyed textile fabrics from components a) from 80 to 99% by weight, based on the sum of all constituents of the fibers

at least one terephthalate polyester (A),

b) 1 to 20% by weight, based on the sum of all constituents of the fibers, of at least one polyester-containing additive (B) obtainable from the monomers m

m1) aliphatic 1, ω-diol,

m2) aliphatic 1, ω-dicarboxylic acid,

m3) aromatic 1, ω-dicarboxylic acid, and

optionally at least one chain extender (V), and c) optionally at least one component (G) comprising the steps

I) mixing the components (A), (B) and optionally (G),

II) producing polyester fibers (C) from the mixture obtained in step I),

III) optionally further processing of the polyester fibers (C) into yarn (E) and / or textile fabric (F), and

IV) dyeing the polyester fibers (C), the yarn (E) and / or the textile fabric (F) at a temperature of <130 ° C. The production of PES fibers according to the invention, which takes place by fusing in particular PBT or PET and at least one polyester-containing additive (B), is distinguished by the fact that no complex polymerization processes are necessary, but only two or more components, ie at least (A) and (B) are mixed and fused together and the melt spun, the addition of the polyester-containing additive (B) often facilitating even the melt spinning process.

Dyeing of polymer compositions containing, in addition to the standard polyesters, such as PET or PBT, at least one of said polyester-containing additives (B), has the effect of using a disperse dye according to the exhaust process at temperatures below 130 ⁰ C and even only 100 ⁰ C can run.

The polyester fibers, yarns and textile fabrics produced by the process according to the invention are distinguished by intensive and uniform dyeability. They also have a wide range of applications in the color spectrum, good rubfastness and very good wash fastness.

In comparison to the previous polyester fibers, which can be dyed without great expenditure on equipment only from temperatures of 130 ^° C., the use of the polyester fiber (C) according to the invention for the dyeing process means a simplification of the machine technology. In addition, the energy consumption is reduced and it saves time. In addition, the inventive method has a gentle effect on the material to be dyed. The polyester fibers (C) are smooth and soft both before and after dyeing.

More specifically, the following is to be accomplished for the invention:

In step (I), the components (A), (B) and optionally (G) are mixed. This takes place according to the invention preferably in the melt. In step (II), polyester fibers (C) are prepared from the mixture obtained in step (I). According to the invention, the mixture obtained in step (I) is preferably melted in an extruder, extruded through spinnerets and spun on to produce the polyester fibers (C). The fibers obtained are still undyed.

Depending on requirements, the polyester fibers (C) in step (III) can be further processed into yarn (E) and / or textile fabrics (F) before the polyester fibers (C) or the yarn (E) or the textile fabric produced therefrom (F) is dyed at a temperature <130 ⁰ C. According to one embodiment of the invention, the polyester fibers (C) are spun into a yarn (E) in step (III). From the yarn (E) or the polyester fiber (C), a textile fabric (F) can also be produced in step (III) before the dyeing is carried out in step (IV). Of course, the fibers can be dyed first and then further processed into yarn (E) and / or textile fabrics (F) or from the undyed polyester fibers (C) first yarn (E) are made, this the first dyed and then textile fabrics getting produced.

Initially, undyed fibers consisting essentially of polyester are produced by intensive mixing of the components terephthalate polyester (A) and at least one polyester-containing additive (B) and optionally one or more components (D) in the melt and subsequent spinning.

The undyed polyester fibers (C) comprise after completion as far as possible a terephthalate polyester (A) as the main component and at least one polyester-containing additive (B), wherein (B) before fiber production in a further preferred embodiment, up to 7 wt.% - Based on the Sum of all components of the respective component - at least one chain extender (V), which is in particular 1, 6-hexamethylene diisocyanate may contain. In a particularly preferred embodiment, the terephthalate polyester (A) is selected from polyethylene terephthalate (PET) or polybutylene terephthalate (PBT). The polyester fibers (C) contain preferably 80 to 99% PBT or PET, more preferably PET is used, particularly preferably a polyester of terephthalic acid and ethylene glycol is used as a textile fiber. An example of a commercially available PBT is Ultradur B 4520® from the manufacturer BASF SE in Ludwigshafen. The terephthalate polyester (A) is generally a polyester having a melting point of 200 to 280 ⁰ C, another example are textile fibers such as Dralon Trevira.

The polyester-containing additives (B) can be prepared from monomers m which have at least two different dicarboxylic acid units m2) and m3). This total of monomers m - based on the total weight of the polyester-containing additive (B) - contains, for example, at least 5 to 80% phthalic acid units and 20 to 95% units of aliphatic 1-ω-dicarboxylic acids having 4 to 10 carbon atoms. In a further, preferred embodiment of the invention, the monomers m1): m2): m3) are present in a molar ratio of 2: 1: 1.

The polyester-containing additives (B) used according to the invention for the preparation of the polyester fibers (C) comprise at least the carboxylic acids described and a diol unit. To prepare the polyester-containing additive (B), the monomers m are subjected to a polymerization step. It happens that a certain amount of monomer is not polymerized, that is, "free" in the polyester-containing additive (B), which optionally has influence on the polyester fiber (C) prepared from (B).

The total amount of the carboxylic acid units m2) and m3), which are free or polymerized in the polyester-containing additive (B), is at least 50%.

In a preferred embodiment, the aromatic 1, ω-dicarboxylic acid m3) is terephthalic acid.

The aliphatic 1-ω-dicarboxylic acids m2) may, for example, be succinic acid, glutaric acid, adipic acid or sebacic acid. In a particularly preferred embodiment of the invention, the aliphatic 1, ω-dicarboxylic M2) adipic acid.

In the first of these, the amount of terephthalic acid units and adipic acid units is 1: 1. The diols m1) are selected from the group of aliphatic, cycloaliphatic and / or polyether diols, wherein maximally 52% of aliphatic 1-ω-diols are present and the percentages are based on the total amount of all diols which are free in the polyester-containing additive or as Esters are present.

The aliphatic diols having 4 to 10 carbon atoms may be for example 1, 4-butanediol, 1, 5-pentanediol or 1, 6-hexanediol. In an advantageous embodiment of the invention, the aliphatic 1, ω-diol m1) 1, 4-butanediol.

At least one chain extender (V) can be used to prepare the polyester-containing additive (B). The at least one chain extender (V) is usually selected from compounds containing at least three ester-capable groups (V1) and selected from compounds containing at least two isocyanate groups (V2).

The compounds V1 preferably contain from three to ten functional groups which are capable of forming ester bonds. Particularly preferred compounds V1 have three to six functional groups of this type in the molecule, in particular three to six hydroxyl groups and / or carboxyl groups. Examples include:

Tartaric acid, citric acid, malic acid; Trimethylolpropane, trimethylolethane; pentaerythritol; polyethertriols; glycerol; trimesic; Trimellitic acid, anhydride; Pyromellitic acid, dianhydride and hydroxyisophthalic acid. The compounds V1 are generally used in amounts of 0.01 to 15, preferably 0.05 to 10, particularly preferably 0.1 to 4 mol%, based on the components m2 and m3. As component V2, one or a mixture of different isocyanates are used. It is possible to use aromatic or aliphatic diisocyanates. However, it is also possible to use higher functional isocyanates.

In the context of the present invention, an aromatic diisocyanate V2 is in particular toluylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, 2,2'-diisocyanate,

Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene-1,5-diisocyanate or xylylene diisocyanate understood. Of these, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate as component V2 are particularly preferred. In general, the latter diisocyanates are used as a mixture.

Trinuclear isocyanate V2 is also tri (4-isocyanophenyl) methane. The polynuclear aromatic diisocyanates are obtained, for example, in the preparation of mono- or binuclear diisocyanates.

In minor amounts, for example up to 5 wt .-%, based on the total weight of component V2, the component V2 may also contain urethione groups, for example, for capping the isocyanate groups.

In the context of the present invention, an aliphatic diisocyanate V2 is in particular linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example 1,6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane), Understood. Particularly preferred aliphatic diisocyanates V2 are 1,6-hexamethylene diisocyanate and isophorone diisocyanate.

Preferred isocyanurates include the aliphatic isocyanurates derived from alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example isophorone diisocyanate or methylenebis (4-isocyanatocyclohexane). The alkylene diisocyanates can be both linear and branched. Particular preference is given to isocyanurates which are

Hexamethylene diisocyanate based, for example, cyclic trimers, pentamers or higher oligomers of n-hexamethylene diisocyanate. In general, the component V2 is used in amounts of 0.01 to 5, preferably 0.05 to 4 mol%, particularly preferably 0.1 to 4 mol%, based on the sum of the molar amounts of m1, m2 and m3. The Tg value (in degrees C) denotes the glass transition temperature at which amorphous or crystalline polymers change from the hard-elastic or glassy state into the liquid or rubber-elastic state. A standard PES material has a Tg of about 80 ⁰ C. In a particularly preferred embodiment of the invention is the Tg value of the po- lyesterhaltigen additive (B) -50 to 0 ⁰ C, preferably between -45 and -10 ⁰ C and especially preferably between -40 and -20 ⁰ C.

By admixing the polyester-containing additive (B) to the terephthalate polyester (A) and the associated production of polyester fibers (C) with a reduced softening point, the dyeing at <130 ⁰ C, preferably <120 ⁰ C, more preferably <1 10th ⁰ C, most preferably <100 ⁰ C and particularly preferably <90 ⁰ C allows. A lowered glass transition temperature brings increased mobility into the PES chains; At the same time, any added colorant preferably penetrates into these soft segments of the fiber. Overall, an intense color result is achieved.

The distribution of the polyester-containing additive (B) in the terephthalate polyester (A) takes place uniformly and without droplets. The fibers obtained can easily be spun out very quickly. Depending on the desired application, different fiber thicknesses can be spun out in a textile fabric (F) to be produced from this later. For optimal mixing of (A) and (B), optional compatibilizers (R) can be used.

In step (I) of the process according to the invention, it is also possible to mix one or more components (G) with components (A) and (B). The component (s) (G) are processing aids such as lubricants, process aids and waxes, additives such as compatibilizers, UV and light stabilizers, heat stabilizers, dyes and pigments, flame retardants, antioxidants, plasticizers, metal oxides such as titanium oxides, optical brighteners and fillers. Their proportion is generally from 0 to 20% by weight, preferably from 0 to 10% by weight, based on the total weight of the mixture obtained in step (I) or of undyed fibers prepared therefrom, this being at least 0 , 1 wt .-% of component (G), if present. The inventive method is characterized in that the polyester-containing additive (B) preferably has a number average molecular weight M _w of 50,000 to 300,000 g / mol. The preparation of the polyester-containing additive (B) used according to the invention, typical reaction conditions and catalysts are known in principle to the person skilled in the art. The dicarboxylic acids used for the preparation of (B) m2) and m3) can be used in a manner known in principle as free acids or in the form of conventional derivatives such as esters. Typical esterification catalysts can be used. E is also equivalent to chain length re (V), such as HMDI (1,6-hexamethylene diisocyanate) used in the preparation of (B). In an advantageous variant of the reaction, polyester diol units can first be presynthesized, which can then be linked together by means of a chain extender (V). By choosing the building blocks and / or the reaction conditions, the properties of the polyester can be easily adapted by a person skilled in the art to a specific requirement profile.

Of course, a mixture of several different polyester-containing additives (B) can be used.

According to the invention, the undyed polyester fibers (C) comprise 1 to 20% by weight, preferably 5 to 10% by weight and for example 6% by weight of at least one such polyester-containing additive (B), based on the sum of all constituents of the undyed fiber. steps

Undyed, substantially polyester fibers are prepared by mixing at least the components terephthalate-polyester (A) and polyester-containing additive (B) by mixing, melting and spinning.

For this purpose, terephthalate polyester (A) and polyester-containing additive (B) are preferably metered into the mixing unit using appropriate metering devices, for example as granules. Of course, it is also possible to use a premixed granules.

The components (A) and (B) and optionally further polymers and / or additives and auxiliaries (component (D)) are first mixed intensively with one another by heating to the melt by means of suitable equipment. For example, kneaders, single-screw extruders, twin-screw extruders or other mixing or dispersing apparatus can be used. Single-screw extruders are preferred. sets, because by length and type of screw, temperature and residence time in the extruder, even in the single screw extruder, a homogeneous mixing can be achieved.

The temperature for mixing is selected by the person skilled in the art and depends on the nature of the components (A) and (B). The terephthalate polyester (A) and the other polyester-containing additive (B) should on the one hand sufficiently soften, so that mixing is possible. On the other hand, they should not be too thin, because otherwise sufficient shear energy input can no longer take place and, under certain circumstances, thermal degradation is also to be feared. As a rule, the mixing at a temperature of 250 Produkttempe- is ⁰ C to 290 ⁰ C, preferably at 280 ⁰ C, without the invention being restricted thereto.

After mixing, the undyed polyester fiber (C) is obtained from the melt by extrusion, which is then spun directly. In this case, the molten mass is pressed in a manner known in principle by one or preferably several nozzles, such as a perforated nozzle, for example a 24-hole nozzle with a normal screen, and a nozzle pressure of, for example, 28 to 32 bar, corresponding polyester fibers ( C) (filaments) are formed. Proven for direct spinning of the mixtures used according to the invention has a regulator temperature of 280 ⁰ C. The fibers or filaments should have a diameter of less than 0.7 microns in the rule. Preferably, the diameter is 0.5 to 0.2 microns, without the invention being limited thereto. As a rule, the polyester fibers (C) consist of several filaments with total yarn titres of 125 to 127 dtex (dtex = g / 10km fiber). It is of course also possible to produce Gesamtgarntiter from 1 to 300 d / tex.

In a proven embodiment, the extruder speed is for example at 50 rpm, the godet speed at 300 rpm and the winding speed at 600 rpm. The hotplate has for example, 100 ⁰ C at a draft of 1: 2 (50: 100 m / min). The polyester fibers (C) produced according to the invention by the process described above can also be processed into textile fabrics (F) and dyed. The polyester fibers (C) may also first be dyed and then further processed into yarn (E) and / or textile fabrics (F). It is also possible to first produce yarn (E) from the polyester fibers and to dye this. From the dyed yarn (E) then optionally textile fabric (F) can be produced.

According to a preferred embodiment of the invention, the polyester fibers (C), the yarn (E) and / or the textile fabric (F) are treated prior to dyeing with a stabilizing emulsifier. The process according to the invention is distinguished in particular by the fact that the process for producing a dyed textile fabric (F) starting from polyester fiber (C) preferably comprises the steps d) spinning the polyester fiber (C) into a yarn (E),

e) further processing of the yarn (E) into a textile fabric (F), f) treatment of the textile fabric (F) with a stabilizing effect

emulsifier,

g) dyeing the textile fabric (F) comprises.

For this purpose, the undyed polyester fibers (C), for example, spun a second time to obtain a yarn (E). The yarn (E) can then be processed, for example, on a circular knitting machine to form a textile fabric (F) analogous to process step e). Processes for producing textile fabric fabrics (F) from fibers (C) or yarns (E) are known in principle to the person skilled in the art.

The undyed polyester fibers (C), yarns (E) and textile fabrics (F) are pretreated by surfactants, for example consisting of an anionic and a nonionic surfactant, at a weight ratio of textile material to the dye formulation (liquor ratio) of for example, 1: 20 treated at elevated temperature. Essentially, a stabilizing emulsifier is used for this pretreatment.

The undyed, pretreated polyester fibers (C), yarns (E) and textile fabrics (F) are dyed by treating them with a formulation comprising at least water and a dye. An aqueous formulation for coloring textile materials is also referred to by the person skilled in the art as a "liquor".

In one embodiment, the inking g) or IV) takes place at a temperature below 130 ° C, preferably at <120 ⁰ C, more preferably <1 10 ⁰ C, most preferably <100 ⁰ C and particularly preferably <90 ⁰ C.

Preferably, the emulsion paint in addition to the formulation and the disperse dye comprises only water. However, small amounts of water-miscible organic solvents may also be present. Examples of such organic solvents include monohydric or polyhydric alcohols, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol or glycerin. Furthermore, it may also be ether alcohols. Examples include monoalkyl ethers of (poly) ethylene or (poly) propylene glycols such as ethylene glycol monobutyl ether. The amounts of such, different from water solvents should, however, usually 20 Wt .-%, preferably 10 wt .-% and particularly preferably 5 wt .-%, with respect to the sum of all solvents of the formulation or liquor does not exceed.

As dyes in the formulation, for dyeing PES fibers (polyester fibers (C)), yarns (E) and textile fabrics (F), it is possible in principle to use all known dyes which are suitable for dyeing polyester fibers. The inventive method is characterized in particular by the fact that in the inking process g) or (IV) preferably a disperse dye and optionally a dispersing aid is used.

Disperse dyes are dyes having a low water solubility which are used in disperse, colloidal form for dyeing, in particular for dyeing fibers and textile materials These may be different chromophores or mixtures of the chromophores, in particular, azo dyes or anthraquinone dyes, quinophthalone, naphthalimide, naphthoquinone or nitro dyes The nomenclature of dyes is known to those skilled in the art Further details on disperse dyes and further examples are also detailed in, for example, "Industrial Dyes", Editor Klaus Hummer, Wiley-VCH, Weinheim 2003, pages 134-158 shown.

Of course, mixtures of different emulsion paints can be used. In this way, mixed colors can be obtained. Preference is given to those emulsion paints which have good fastness properties and in which trichromaticity is possible.

The amount of (disperse) dyes in the formulation will be determined by one skilled in the art according to the desired application.

The formulation may include other adjuvants beyond solvents and dyes. Examples include typical textile auxiliaries, such as dispersants and leveling agents, acids, bases, buffer systems, surfactants, complexing agents, defoamers or stabilizers against UV degradation. Preferably, a UV absorber can be used as an aid.

For dyeing, preference is given to using a weakly acidic formulation, for example having a pH of 4.5 to 6, preferably 5 to 5.5. All types of textile materials (D) can be produced from the polyester fibers (C), yarns (E) and textile fabrics (F) produced by the process according to the invention. The term "textile materials" (D) is intended to include all materials throughout the textile manufacturing chain, including all types of finished textile goods, such as all types of clothing, home textiles such as carpets, curtains, blankets or upholstery fabrics or industrial or industrial technical textiles or domestic applications such as rags or wipes for cleaning or covering umbrellas.The term also includes the starting materials, ie fibers for textile use such as filaments or staple fibers and semi-finished or intermediate products such as yarns, fabrics, knits, knitted fabrics, nonwovens Fillers and flakes for textiles such as cushions or soft toys, or as packaging material are also included according to the invention Processes for producing textile materials from yarns and / or fibers are known in principle to a person skilled in the art.

The textile materials (D) can be produced exclusively from the polyester compositions used according to the invention. Of course, they can also be used in combination with other materials, such as natural fibers. A combination can be made at various stages of production. For example, filaments of a plurality of polymers with a defined geometric arrangement can already be produced at the stage of melt spinning. In the manufacture of yarn, fibers of other polymers may be incorporated, or fiber blends may be made of staple fibers. Furthermore, various yarns can be processed together, and finally, fabrics, knits, or the like comprising the polyester compositions of the present invention can be joined to chemically dissimilar fabrics. According to preferred textile materials (D) comprise in particular textile materials for sports and leisure clothing, carpets or nonwovens. The treatment of the textile materials (D) with the aqueous dye formulation can be carried out by conventional dyeing methods, for example by dipping in the formulation (for example after the exhaustion process), spraying the formulation, printing dyeing or applying the formulation by means of suitable equipment. They can be continuous or discontinuous processes. Dyeing apparatuses are known to the person skilled in the art. The dyeing may, for example, be carried out batchwise with chaff skids, yarn dyeing apparatuses, unit beam dyeing apparatuses or jets or continuously by padding, padding, spraying or foam application methods with suitable drying and / or fixing equipment. The weight ratio of textile materials (D) to the dye formulation (also referred to as liquor ratio) and in particular the dye itself is determined by the skilled person depending on the desired application. As a rule, a weight ratio of textile materials (D) / dye formulation of from 1: 5 to 1:50, preferably 1:10 to 1:50, and also preferably from 1: 5 to 1:20, particularly preferably 1:10, has proven useful based on the textile material without the invention being set to this range. The amount of dye in the formulation is preferably from about 0.5 to 5 wt .-%, preferably 1 to 4 wt .-%, based on the textile material. According to the invention, the textile materials are heated during and / or after the treatment with the dye formulation to a temperature above the glass transition temperature Tg of the polyester fibers, but below their melting temperature. This can preferably be carried out by heating the entire formulation to the relevant temperature and immersing the textile materials in the formulation. The glass transition temperature Tg of the polyester fibers depends on the type of polymer composition used and can be measured by methods known to those skilled in the art.

However, one can also treat the textile materials with the formulation at a temperature below Tg, optionally dry and subsequently heat the treated textile materials to a temperature above Tg. Of course, combinations of both approaches are possible.

The temperature in the treatment depends naturally on the type of polyester composition used and the dye used. Temperatures of 90 to 145 ^° C., preferably 95 to 130 ^° C., have proven useful.

The duration of the dyeing process is determined by the person skilled in the art, depending on the type of polymer composition, formulation and the dyeing conditions. It is also possible to change the temperature as a function of the duration of treatment. For example, at intervals of 2 to 3 ° C / min in aqueous liquor initially heated to 100 ⁰ C, then held for about 25 to 35 minutes, the temperature and then at a distance of 2 to 3 ° C / min to 70 ⁰ C and then cooled to 30 ⁰ C.

The dyeing may be followed by a customary aftertreatment, for example with detergents or oxidative or reductive-acting secondary cleaning agents or fastness improvers. Such post-treatments are known in principle to the person skilled in the art. A possible after-wash can be combined with hydrogen sulphite and NaOH. For example, carried out at 70 ⁰ C, followed by warm water and cold rinsing and acidification.

In an alternative embodiment of the invention, the undyed textile materials (D) can also be printed. Naturally, only those textile materials (D) which have a sufficient surface area are suitable for printing. For example, nonwovens, nonwovens, woven fabrics, knitted fabrics, knitted fabrics or films can be printed. Preferably, fabrics are used for printing. Processes for printing textile materials (D), for example with disperse dyes, are known in principle to the person skilled in the art.

Dyeing and printing can be combined with each other, for example by first dyeing a textile material (D) in a specific color and then imprinting a pattern, logo or the like.

A further subject of the present invention is the use of the fibers (C), yarns (E) and textile fabrics (F) produced by the inventive process described in detail above for the production of textile materials (D) and textile fabrics, in particular for the production of fibers, Yarn, fillers, flakes, woven, knitted, knitted, nonwovens, nonwovens, decorative and technical textiles and carpets.

In an advantageous embodiment of the invention, the polyester fibers (C) are used for the production of dyed or undyed pure or mixed fibers for clothing, home or utility textiles.

The following examples are intended to explain the invention in more detail. Example 1 Production of a Polyester Fiber (C) and Processing into a Yarn (E) Containing Polyester-Containing Additives (B)

For the experiments, a polyester (PBT granules) (A) [X%] with Y% of a polyester-containing additive (B), consisting of the monomers 1, 4-butanediol (50 mol%), adipic acid (25 mol -%) and terephthalic acid (25 mol%, prepared according to WO 98/12242), mixed and fused in an extruder. The homogeneous melt was then extruded through the hole dies and the polyester fiber (C) was obtained in the form of filaments spun on. The spinning machine used contained a 24-hole nozzle (24 / 0.2) with a normal sieve (50μ). The temperature was 280 ⁰ C on all regulators and the nozzle pressure was 28-32 bar. The extruder speed was set to 50 rpm, the godet speed was 300 rpm, and the winding speed was 600 rpm.

The stretching ratio was 1: 2 (50/1 OOM / min) and the temperature of the hot plate was 100 ⁰ C. The spun polyester fibers (C) were then in a second spinning to form a yarn (E) is spun.

Table 1 shows the ratios of polyester (PBT) (A) to polyester-containing additive (B) and the yarn yield point (E) obtained therefrom.

Table 1 :

Anschießend could from the yarns (E) on a circular knitting machine, a textile fabric (F) are created.

Example 2: Pretreatment before a Dyeing Process

For the pretreatment of the textile fabric (F) before the dyeing process, this was first concentrated with Kieralon Jet B® conc. (1 g / L) and a liquor ratio of 1:20 for 20 minutes at 60 ⁰ C in a standard apparatus. Example 3: Dyeing process

The dyeings were carried out by adding the knitted pieces prepared as described with the addition of commercial disperse dyes (for example DianixDeepRed SF) in an amount of 2% by weight, based on the amount of undyed textile used, and 1 g / L of Basojet XP® as CO Color additive in desalted water at pH 5 to 5.5 in a standard dyeing apparatus of initially 30 ⁰ C within 30 to 40 minutes to 100 ⁰ C (or 115 ⁰ C) left. The ratio of textile fabric (F), ie polyester-containing knitted fabric (dry) in kilograms to the volume of the treatment bath in liters, the so-called liquor ratio, was 1:10 in an aqueous medium. After staining was cooled at rates of 2.5 ° C / min to 70 ⁰ C, then to 30 ⁰ C.

For further washing was washed with 4 g / L of hydrogen sulfite and 2 g / L NaOH (100%) for 10 minutes at 70 ⁰ C, then was rinsed warm and cold with water and acidified with acetic acid.

Table 2 gives a list of the different blended fabrics, the color temperature and the color strengths (washed and unwashed).

Experiments 1, 2, 3 and 4 show in comparison that the color strength increases with increasing content of (B) (polyester-containing additive). At 8% of (B) almost the same color intensity is achieved as in experiment 6 (= prior art, 1 14% vs. 1 12%, which is within the error range). At a dyeing temperature of 100 ⁰ C almost the same color intensity is achieved in the additivierten variant as in the unadditivierten PBT at 130 ⁰ C. Thus, it was shown that the dyeing in an open system at 100 ⁰ C is possible and coloring comparable results can be achieved as previously at 130 ⁰ C.

Table 2: The dyed knits 1, 5 and 6 (100% PES material) were with

100% color intensity assumed as comparison sample.

Example 4: Wash fastness test

The washing fastness test was carried out according to "ISO 105-C06-A1 S, 40 ⁰ C" (without steel balls). Experiments 1 to 6 were washed and tested for water-fastness. The numbering of the experiments resulting from the shown in Table 2 experiments.

Table 3:

The washfastness and lightfastness of the textile materials were rated with grades of 1 to 5, the bleeding of the dyed substance and thus the dyeing of the textiles wool, polyacrylate, polyester, polyamide, cotton and viscose was tested. The higher the value, the lower the staining of the various textiles, which indicates less bleeding of the dyed polyester fiber knit.

Compared to PAC and VIS, but also PES and CO, the colored substance is absolutely washfast and only Wo and PA were slightly discolored. Example 5:

Polyethylene terephthalate having an intrinsic viscosity (I.V.) of 0.65 dl / g was reacted with and without the addition of 5.5% by weight of a polyester-containing additive (B) from the monomers 1, 4.

Butanediol (50 mol%), adipic acid (25 mol%) and terephthalic acid (25 mol%) (prepared according to WO 98/12242) in analogy to Example 1 to polyester fibers (C) processed. In each case, a multifilament polyester fiber with additive (B) (according to the invention) and without additive (comparison) was prepared. The fibers according to the invention and not according to the invention were partially drawn (POY = partially oriented yarn) after production and completely drawn and swirled (FDY = fully draw yarn). The POY and FDY methods are known to the person skilled in the art and can be read, for example, by Hans-J. Koslowski. "Dictionary of Man-made Fibers", Second edition, Deutscher Fachverlag, 2009. Table 4 shows the stretch titers for the four yarns. Subsequently, textile fabrics (F) were produced from the yarns (E) on a circular knitting machine.

Table 4:

The polyester fibers thus obtained were now dyed with different dyes. For dyeing, commercially available dyestuffs from DyStar Texilfarben GmbH & Co Germany were used, the red dye was Dianix Rubin CC, the yellow dyestuff was Dianix Yellow CC, the blue dyestuff was Dianix blue CC , The dye was used in each case in an amount of 2% by weight based on the amount of fabric to be dyed, and 1 g / L Basojet XP ^® as a co-additive color in deionized water. For dyeing, the temperature was increased at a heating rate of 2.5 ° C / min to 100, 105 and 130 ⁰ C and held for only 40 min at this temperature. It was then cooled at a cooling rate of 2.5 ° C / min to 70 ⁰ C. It was attenuated reductive - alkaline treated and then neutralized. These aftertreatment methods are known to the person skilled in the art.

The color strength of the dyed textiles was determined visually. The results are shown in Table 5. The color depth reached at the respective dyeing temperature is based on the color result of the pure polyester fiber at 130 ⁰ C. Table 5:

The results from Table 5 clearly show that textiles produced by the process according to the invention have a significantly higher color strength at lower dyeing temperatures than the comparison fibers which do not contain the polyester-containing additive and have to be dyed to achieve a satisfactory dyeing result at higher temperatures. Example 6:

The color fastness of the textiles from the fibers 5-1 to 5-4 was tested in various test methods. In each case, a standardized test fabric, which side by side strips of triacetate, cotton, polyamide fibers, polyester fibers, polyacrylic fibers and viscose fibers, each sewn onto a sample of the dyed textile and subjected to the test. Subsequently, the staining of the different types of fiber contained in the sewn standard fabric sample was visually determined. Different test methods were used. The sublimation test according to ISO 105 PO1 determines the dry heat fixation fastness (except ironing) of the dyed fabric. The perspiration fastness (acid) according to ISO 105 E04 and the perspiration fastness (alkaline) according to ISO 105 E04 determine the change of the dye caused by perspiration. Furthermore, the fastness to washing at 60 ⁰ C and the abrasion according to ISO 105 were tested according to ISO 105 X12 PO1. The results are summarized in Table 6. The rating follows a scale of 1 to 5, the higher the value, the lower the staining of the tissue contained in the standard fabric sample. From this it is possible to conclude on the color fastness of the tested textile.

Table 6:

As is clear from Table 6, show the dyed according to the invention at lower temperatures textiles with the component (B) as good color fastness properties as the textiles of pure PET, which were dyed at 130 ⁰ C.

Thus, the objects of the invention were achieved:

Preparation of an easily spinnable polyester fiber (C)

Production of a scratch-resistant, soft polyester fiber (C)

Dyeing of the produced polyester fiber (C) in the open system possible (no

Pressure vessels required),

Use of non-type carriers is eliminated

Energy saving due to lower water temperature in the dyeing process,

Time saving in the process as heating and cooling takes a long time

inexpensive

very good coloring result

high wash and lightfastness

Claims

claims

1. A process for the preparation of dyed polyester fibers (C), dyed yarn (E) and / or dyed textile fabric (F) from the components a) 80 to 99 wt .-% - based on the sum of all constituents of the fibers

at least one terephthalate polyester (A),

m1) aliphatic 1, ω-diol,

m2) aliphatic 1, ω-dicarboxylic acid,

m3) aromatic 1, ω-dicarboxylic acid, and

I) mixing components (A), (B) and optionally one or more components (G),

II) producing polyester fibers (C) from the mixture obtained in step I),

IV) dyeing the polyester fibers (C), the yarn (E) and / or the textile fabric (F) at a temperature of <130 ° C.

2. The method according to claim 1, characterized in that in step II), the mixture obtained in step I) is melted in an extruder and extruded through spinnerets and spun on.

3. The method according to claim 1 or 2, characterized in that in step III) the polyester fibers (C) to a yarn (E) are spun.

4. The method according to claim 3, characterized in that in step III) the polyester fibers (C) and / or the yarn (E) are further processed to form a textile surface fabric.

5. The method according to any one of claims 1 to 4, characterized in that the polyester fibers (C), the yarn (E) and / or the textile fabric (F) are treated prior to dyeing with a stabilizing emulsifier.

6. The method according to any one of claims 1 to 5, characterized in that the terephthalate P o I y e s t e r (A) a is selected p o l y e t h y e r e t e r e p h t h a la t and / or polybutylene terephthalate.

7. The method according to any one of claims 1 to 6, characterized in that the monomers m1): m2): m3) in the molar ratio 2: 1: 1 are present.

8. The method according to any one of claims 1 to 7, characterized in that up to 7 wt .-% of the at least one chain extender (V) can be used.

9. The method according to claim 8, characterized in that the chain extender (V) is 1, 6-hexamethylene diisocyanate.

10. The method according to any one of claims 1 to 9, characterized in that the aliphatic 1, ω-diol m1) 1, 4-butanediol.

1 1. A method according to any one of claims 1 to 10, characterized in that the aliphatic 1, ω-dicarboxylic M2) adipic acid.

12. The method according to any one of claims 1 to 11, characterized in that the aromatic 1, ω-dicarboxylic acid m3) terephthalic acid.

13. The method according to any one of claims 1 to 12, characterized in that the polyester-containing additive (B) has a number average molecular weight M _n of 50,000 to 180,000 g / mol.

14. The method according to any one of claims 1 to 13, characterized in that the glass transition temperature of the polyester-containing additive (B) between -50 ⁰ C and 0 0C, preferably between -45 ⁰ C and -10 ⁰ C and particularly preferably between -40 ⁰ C and -20 ⁰ C is located.

15. The method according to any one of claims 1 to 14, characterized in that in the inking process (IV), a disperse dye and optionally a dispersing aid is used.

16. Use of the dyed polyester fibers (C), dyed yarn (E) and / or dyed textile fabric (F) prepared by the process according to any one of claims 1 to 15 for the production of textile materials (D).