MXPA00001258A - Process for shaping polymer mixtures into filaments - Google Patents

Abstract

A process is disclosed for producing pre-oriented filaments from polyester-based polymer mixtures by spinning polymer mixtures at a drawing-off speed v of at least 2500 m/min, a second amorphous, thermoplastically deformable copolymer with a glass transition temperature of more than 100°C being added to the polyester. The process is characterised in that the ratio between the viscosity of the molten copolymer and the viscosity of the molten polyester equals 1:1 to 10:1 (measurement parameters as described), that the amount of copolymer added to the polyesters equals at least 0.05 wt%, that the maximum amount M of copolymer added to the polyester is dependent on the drawing-off speed v and that the value of M is M=[1/1600 . v(m/min) - 0,8].

Description

PROCEDURE FOR FORMING FILAMENTS TO POLYMERIC MIXTURES DESCRIPTION OF THE INVENTION The present invention relates to a process for the preparation of filaments previously oriented from polymer blends based on polyester prepared in the melt, using a thermoplastically deformable amorphous copolymer with a vitreous transition temperature greater than 100. ° C by spinning the molten polymer blends with a speed v of at least 2500 m / minute. The spinning of polymer blends is known from many documents: EP 0 035 796 A (Teijin) describes synthetic fibers including polyester and polyamide, which contain 1-15% by weight of a polysulfone polymer with a high glass transition temperature TG. > 150 ° C. The additive remains in a spherical shape in the matrix and influences the surface structure of the filaments and the friction of the threads. The spinning speed is 2000-5500 m / min. EP 0 041 327 B (ICI) presents PET or PA-6.6 fibers, which contain 0.1-10% by weight of another polymer with anisotropic properties (LCP types). The spinning speeds are from 1000 to 5000 m / min. A reduction of the speed (USS: wind up speed suppression) is obtained by means of REF .: 32751 a greater stretch of yarn rupture and with this a greater proportion of stretching and increase of the productivity. EP 0 080 274 B (ICI) refers to fibers of PET, PA-6.6 or PP, which contains 0.1-10% by weight of another polymer, which is in the melt with an average particle size of 0.5- 3 μm and during spinning of the melt are deformed into fibrils. The speeds of spinning are at 2000 to 6000 m / min, reaching a reduction in speed (WUSS) of at least 20% average of greater extension of tear or lower double rupture of the yarn (PET) and with this higher proportions of stretch and increase in productivity. Preferred additive polymers are polyethylene glycol or PA-6.6 for PET or polyolefins for PA-6.6. The effect reacts strongly on the production parameter as, yield, spinning temperature, type of mix or type of extrusion. A transfer to production facilities with different capacities, types of equipment or titling programs is difficult due to this sensitivity. We attribute the negative tendency to an inadequate additive with a too low viscosity, a low vitrification point and the tendency to crystallization. JP 56-91013 A (Teijin) presents a non-stretched polyester yarn, wherein the addition of 0.5-10% by weight of a styrene polymer, produces a better productivity by increasing the yarn breaking stretch at speeds between 850 -8000 m / min, preferably > 2500 m / min and proportions of stretching correspondingly higher. The requirements of the polymer blend and the unstretched yarn 5 for texturing are not presented. EP 0 047 464 B (Teijin) refers to an unstretched polyester yarn, wherein by means of the addition of 0.2-10% by weight of a polymer of the type (-CH2-CR1R2) n as poly (4-methyl) -l-pentene) or polymethylmethacrylate, is obtained a better productivity increase the stretch of yarn rupture at speeds between 2500-8000 m / min and proportions of stretching correspondingly higher., It requires a fine and uniform dispersion of the additive polymer, by means of mixing, having to be the diameter particle < 1 μm to avoid the formation of fibrils. Indicative of the effect must be the combination of three properties, 1 the chemical additive structure, which does not allow the stretching of the additive molecules, the low mobility and the compatibility of the polyester and the additive. Measures serve to increase productivity. The requirements for texturing are not presented. EP 0 631 638 B (AKZO) describes fibers predominantly of PET, containing 0.1-5% by weight of an imidated polymethacrylic acid alkyl ester of 50-25%. The fibers obtained at speeds of 500 - 10,000 t - - ~ attM - »-« a-- > ^^^ | g || j j m / min, and subsequently stretched have a high initial modulus. Spinning at very high temperatures (such as 8000 m / min) should be possible with the usual thread break values. Up to 8,000 m / min, partially oriented yarns are obtained, which have not yet been stretched to their final value, and can later be processed, for example, with textured yarns. In the examples for industrial yarns the influence on the module does not go unnoticed, in general the resistances obtained are smaller, which is a considerable disadvantage for that product. In the case of textile applications, mainly unstretched yarns are described. The corresponding undrawn yarns from a spinning speed of 6000 m / min show breaking stretches < 65.3% this due to high vitrification (shrinkage by cooking < 6.5%) can not be subjected to texturing. The spinning of polymer blends to form synthetic yarns has the object in the case of a certain spinning speed to obtain a greater breaking stretch in the yarns than without the modification by means of the additional polymer. Therefore, a greater proportion of stretch must be possible for the preparation of the final yarn, which produces a greater productivity of the spinner. According to EP 0 041 B there is an increase in production = fl + E '/ lOO) - (i + E / 100). 100% (i + E / 100) with E / E 'the unmodified / modified rupture stretches. A verification of the formula shows that the effect in case of high stretch increases (E'-E) is very large. Stretches that are too high and with this a reduced degree of orientation of the yarn are not suitable for production in fast texturing processes. One way to increase productivity is described in EP 0 080 274 B by means of the magnitude WUSS > twenty%. At a spinning speed at least 20% greater the same stretch of break is obtained in fact than at the correspondingly lower speeds with unmodified polymer. The data on movement in the spinner at higher speeds and in the subsequent elaboration as well as the properties of the final yarns thus produced are not offered. It has been shown that the average particle sizes claimed > 0.5 μm are not suitable for the commercial production of the mixture, since this type of particle distribution leads to multiple capillary and yarn breaks. The increase in production is based on an increase in the profitability of the production process. This is reduced by the worsening of production and more expensive high-speed devices. Of essential influence are the additional costs of the additive polymer, so that depending on the aggregate amount gives up to a zero value for profitability. Also the existence of additive polymers in the market has an important role. For these reasons, many of the additives described in the literature are eliminated for large-scale reactions. The producer or presenter of the procedure must consider the entire production reaction and can not stop at increasing the production of a partial stage (for example spinning). Subsequent processes should not be impaired. In particular, it is a main objective of the invention not to reduce the conditions of subsequent processing in the following stages, preferably to improve them and that despite the higher spinning speed. Thus, in the state of the art of polymer blends, high breaking stretches are mentioned also for high spinning speeds, which are characterized by a strong reduction in the degree of orientation. Of this type of yarn it is known that they are not stable to storage and can not be used and worked in friction texturing processes at high speeds. The breaking stretches given in cases of high spinning speeds of less than 70% indicate again the high degree of vitrification, which reduces the resistance obtainable in the texturing process. The task of the present invention is to provide a process for the production of polyester-based polymer blends with an extraction speed >; 2500 m / min to form suitable filaments previously oriented, preferably suitable for longitudinal texturing, in which the aforementioned disadvantages do not arise. In particular, the costs of the additive added to the polyester must be as low as possible, that is, the additive must be cheap, and the aggregate quantity must be kept low. The spinning of the polyester mixture should lead to an increase in production compared to the unmodified matrix polymers and allow high-speed spinning in the longitudinal texturing process. The solution of this task is carried out according to the invention by means of a method according to the characteristics of the claims. This process is characterized in that the ratio of the melt viscosity of the copolymer to the viscosity of the polyester melt is 1: 1 to 10: 1, because the amount added to the polyester of the copolymer is at least 0.05% (based on to polyester) and maximum corresponds to an amount M, where M is given by the formula M = [1/1600. V (m / min) -0.8] [% weight] In accordance with the invention, a copolymer is added to the polyester in an amount of at least 0.05%, the copolymer being amorphous and continuously insoluble in the polyester matrix. Essentially, these two polymers are not compatible with each other and form two phases that can be differentiated microscopically. In addition, the copolymer must have a vitreous transition temperature (determined by means of DSC with a heating rate of 10 ° C / min) greater than 100 ° C and must be thermoplastically deformable. 10 The melt velocity of the copolymer should be selected in such a way that the ratio of its melt viscosity extrapolated to the zero measurement time, measured at an oscillation rate of 2.4 Hz and a temperature that is equal to the melting temperature of polyester 34.0 ° C (for polyethylene terephthalate 290 ° C) in relation to that of polyester, measured under the same conditions, is between 1: 1 and 10: 1. This is the melt viscosity of the copolymer is at least equal to or preferably greater than that of the polyester. Only by selecting a range of For the specific viscosity for the additive (copolymer) or for the selection of a specific viscosity ratio of the additive and polyester, the optimum degree of effectiveness is achieved. In the case of a viscosity ratio optimized in this way, it is possible to minimize the amount of the additive, with which the profitability of the procedure and particularly advantageous manufacturing properties are achieved. Surprisingly the viscosity ratio determined as ideal according to the invention, for the use of polymer blends for the preparation of synthetic filaments above the range which is indicated as advantageous for the mixture of two polymers. Contrary to the state of the art, polymer blends with high molecular weight copolymers could be spun excellently. Due to the high flow activation energy of the additive polymers, the viscosity ratio is drastically increased after the polymer mixture leaves the spinning nozzle in the field of yarn formation. By the selection of proportions of By virtue of suitable viscosity, a particularly narrow particle size distribution of the additive is obtained in the polyester matrix and by the combination of the viscosity proportions with a flow activation energy clearly higher than that of the polyester (PET approximately 60 kJ / mol ) , this is of more than 80 kJ / mol, preferably more than 100 kJ / mol, the necessary fibril structure of the additive in the spinning is obtained. The high vitreous transition temperature compared to polyester ensures a rapid solidification of this structure of fibrils in the yarn. The size of particle maximum additive polymer is found é ^^^^ &: directly at the exit of the spinning nozzle at approximately 1000 nm, while the average particle size is 40 nm or less. Preferably, the ratio of the viscosity of the melt of the copolymer to that of the polyester is below the aforementioned conditions between 1.4: 1 and 8: 1. In particular, a ratio of melt viscosities between 1.7: 1 and 6.5: 1 is preferred. Under these conditions, the average particle size of the additive polymer is 220-350 nm. The amount of copolymer to be added to the polyester is at least 0.05% by weight. For many applications, quantities less than 1.5% are sufficient, at extraction speeds greater than 35000 and up to 6000 m / min and more, or frequently less than 1.0%, which is an important cost advantage. The maximum amount to be added of the additive polymer according to the invention in relation to that of the polyester corresponds to the quantity M, where M is defined depending on the spinning speed v by means of the following formula: M = [1/1600 . v (m / min) - 0.8] [% by weight] In the range of the spinning speed from 3500 to 6000 m / min the maximum amounts of additives from 1.39 to 2.95% by weight are presented.

Preferably, in order to obtain an especially good profitability, the upper limit of the amount of additive to be used for extraction speeds greater than 2900 m / min, is defined by the magnitude M +, where * = [1/1650. (m / min) -1.73] [% by weight] Thus are presented for spinning speeds of 3500 to 6000 m / min, additive amounts of between 0.39 and 1.91% by weight. For extraction rates greater than 4200 m / min, the amount of additive polymer that is added to the polyester is preferably at least the same magnitude N, however at least equal to 0.05% by weight, where N = [1/3510. (m / min) -1.14] [% by weight]. For extraction speeds of 4200 to 6000 m / min, the minimum amount between 0.057 and 0.57% by weight is found. By maintaining the above-mentioned preferred viscosity ratios of the additive polymer to the polyester, the amount to be used of the copolymer in relation to the polyester preferably corresponds to the quantity P, where P = P * + 0.2% by weight, however at least equal to 0.05% by weight and where for extraction rates greater than 3900 m / min P * = [1 / 2270.v (m / min) -1.45] [% by weight]. The amount of the additive used in the preferred case for spinning speeds of 3900 to 6000 m / min, is ^ -3. * ^ * to ém t? M ^ - found between 0.07 and 1.39% by weight. For spinning speeds between 2500 m / min and the minimum spinning speeds specified here for M +, N and P are valid only for the minimum and maximum quantities given in claim 1, while for higher spinning speeds additionally preferred are the amounts mentioned above. Obviously these formulas are also valid for spinning speeds above 6000 m / min up to approximately 12000 m / min. Suitable fiber-forming matrix polymers are thermoplastically deformable polyesters, such as, for example, polyethylene terephthalate (PET), polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate. The preferred ones are homopolymers. However, the copolymers of these polyesters with a fraction of up to 15 mol% of common comonomers, such as, for example, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, isophthalic acid and / or adipic acid are also considered.

Additionally, additives for polymers are suitable, such as catalysts, stabilizers, optical brighteners and matifiers. The polyester can also contain a reduced fraction (maximum 0.5% by weight) of a branching component, also for example acids polyfunctional, such as trimellitic acid, pyromellitic acid, -.-. , - + ¿| e ^^^ gáí¡ ?? gLwtaí3 ¡a ¡á ¡.. -.? 32 ^ *? > The following are trivaled to hexavalent alcohols, such as trimethylolpropane, pentaerythritol, dipentaerythritol, glycerin or corresponding hydroxy acids. The mixture of the additive polymer (copolymer) with the polymer matrix is carried out by means of solid addition to the matrix polymer chips at the inlet of the extruder with a chip mixer or gravimetric dosing or alternatively by melting the additive polymer, dosing by means of a gear pump and feeding in a melt stream of the matrix polymer. The preparation of a homogeneous distribution is then carried out by mixing in the extruder and / or by means of a static or dynamic mixer. Advantageously by means of the specific selection of the mixer and the duration of the mixing process, a defined particle distribution is fixed, before the melt is conveyed by means of product distribution conduits to the spinning points and nozzles of the product. yarn. Mixers have been recommended with a tear rate of 16 to 128 sec "1 and a dwell time in the mixer of at least 8 seconds, thus the product with a tear rate (s_1) and a dwell time at 0.8 power. (in seconds) it should be 250 to 2500 preferably 300 to 600. Here the tear rate is defined by means of 'É GGH rate tear in the empty tube (sll-1) by the factor of the mixer factor being a characteristic dimension mixer-type mixer. For Sulzer-SMX mixers that factor is for example approximately 7-8. The tear rate? in the empty tube it is calculated in the following way Y = 4. 10a.F [s "1] 7T. 6 .R3.60 and the dwell time T (S) according to T - F V2.?. d. 60 where F = quantity extracted from the polymer (g / min) V2 = internal volume of the empty tube (cm3) R = diameter of the empty tube (mm) E = fraction of the empty volume (in Sulzer-SMX types 0.84 to 0.88) d = nominal density of the polymer mixture in the melt (approximately 1.2 g / cm3) Both the mixture of both polymers as well as the subsequent spinning of the polymer mixture is carried out at temperatures depending on the matrix polymer, in the range of 220 to 320 ° C. The preparation of synthetic filaments of the polymer blends according to the invention by means of the fast spinning with extraction speeds > 2500 m / min is made using known spinners. Here the filter pack according to the known state of the art is provided with filtering devices and / or bulk filtering means (for example iron powder). The melted polymer mixture after tearing and filtering is pressed into the nozzle pack by means of perforations in the nozzle plate. In the subsequent cooling zone, the melt threads are cooled by means of cold air below their softening temperature, in such a way that they are prevented from sticking or adhering to the thread conductor. The conformation of the cooling zone is not critical, as long as an air current is guaranteed that penetrates the skein of filaments. In this way, the nozzle plate can be found directly below a zone of rest in the air to accelerate cooling. Cold air can be conducted through transverse and radial blow from an air conditioning system or removed from the environment by a cooling tube through self-suction. After cooling the filaments are wound into skeins and coated with spinning oil. For this, lubricators are used, to which the spinning oil is fed in the form of an emulsion by means of dosing pumps. Prepared threads move advantageously , * »Í? in an interlaced direction to improve thread cutting. management and security organs can also be used before the wire reaches the winding-added and there Devane on coil bodies in packets. The peripheral speed of the yarn package is regulated automatically and is equal to the winding speed. The yarn removal speed can be greater than the winding speed due to its changing movement, by 0.2 to 2.5%. Optionally they can be used after preparation or before winding galets. The peripheral speed of the first system of galets is called extraction speed. Other galets can be used to tension or relax. The incompatibility of both polymers causes the additive polymer immediately occur after the output of the polymer blend of the spinneret, including circular or deformed longitudinally in the matrix polymer. Preferably it is the length / diameter ratio > 2. The best conditions are presented when the average particle size (arithmetic mean) d50 < 400 nm, and the particle fraction > 1000 nm in a sample average was less than 1%. It was possible to determine the influence on these particles of the delay in spinning by analytical methods. New investigations of the yarns according to the Jg ^ ^^ ^^ j gg Ü ^ g ^^ jég procedure TEM (transmission electron microscopy) showed that there is a structure in the form of fibrils. The average diameter of the fibrils was estimated at approximately 40 nm. The length / diameter ratio of the fibrils was >; 50. The longitudinal / diameter ratio of the fibrils or additive particles after leaving the spinning nozzle is too large in diameter or the size distribution is very uneven, which is the case in insufficient proportions of viscosity, so loses the effect The effect of the rollers described in the literature could not be obtained with the additive polymer according to the invention. The evaluation of the microscopic studies of transversal and longitudinal cuts of the fibers indicate that the spinning tension is conducted on the additive fibrils that are formed and the polymeric matrix remains without tension. In this way, the deformation of the matrix is obtained under conditions which result in a reduction of the orientation and reduced crystallization when spinning under a vacuum. In a timely manner, the evaluation of the effect on the formation of yarns and the processing conditions is carried out. Furthermore, for the effectiveness of the additives according to the invention, a flow activation energy of the copolymers of at least 80 kJ / mol is required, as well as a higher flow activation energy to the polyester matrix. Only under these conditions is it possible to solidify the additive fibrils of the polyester matrix and to admit a considerable fraction of the stress present. Thus it is possible to achieve the desired capacity increase of the spinner. In a known manner, the spinning structure is essentially formed in the extraction zone below the spinning nozzle. The length of the extraction zone varies by means of unmodified polymers by means of the speed of extraction of the yarn. Typical values for precasting at conventional extraction speeds of at least 2500 m / min for lengths of approximately 300 mm, preferably for POY a > 250 mm to < 700 mm In the method according to the invention, the extraction zone is extended compared to conventional spinning machines. The bridging behavior of the filaments observed at high speeds is reduced. The changes in the speed of the yarns along the extraction path take a value corresponding to the conventional POY produced at 3200 m / min. The process according to the invention is equally suitable for the rapid spinning of POY yarns with a POY filament title of > 3 dtex to 20 dtex and more, as well as filament titers POY < 3 dtex, especially microfilaments with 0.2 to 2.0 dtex. For the further processing of the yarn in a longitudinal texturing process at high speeds, the following is important: the yarns according to this invention as pre-yarn for longitudinal texturing, usually called POY, are produced with extraction speeds of > 2500 m / min, preferably > 3500 m / min, especially '4000 m / min. These threads must have a physical structure that is characterized by a 10 degree of specific orientation and a reduced crystallization. For this characterization, the characteristic magnitudes of the stretch of rupture, the double rupture, the degree of crystallization and the shrinkage by cooking have been verified. The polymeric mixture according to the invention is characterized by a breaking stretch of the PET (POY) yarn of at least 85% and maximum 180%. The shrinkage by baking is 32-69%, the double breaking is found between 0.03 and 0.075. The crystallinity was less than 20% and the tear strength was at least 17 20 cN / tex. Preferably, the breaking stretch of the PET yarns is between 85 and 160%. Particularly advantageous proportions are obtained, when the breaking stretch of the PET yarns is between 109 and 146%, the breaking strength simultaneously is at least 22 cN / tex and the maximum Uster value is 0.7%.

^^^ Hg | The longitudinal texturing is done according to the type of filament title at different speeds, where for filaments of normal size > 2 dtex per filament (final title) speeds are used > 750 m / min 5 preferably > 900 m / min. For microfilaments and fine titles (final title) < dtex speeds are preferred between 400 and 750 m / min. The procedure can be used with this title and especially with microfilaments between 0.15 and 1.10 dtex (final title) per filament. 10 The stretching ratios to be used are found for the yarns specified between 1.35 and 2.2 where for a degree of reduced orientation, stretching proportions are preferred in the upper range and vice versa. In case of longitudinal texturing it is modified the proportion of stretch by means of variations in tension (surging) depending on the speed of work. Especially preferred are stretch ratios according to the formula: Stretch ratio = 5, 10"4 .w (m / min) + b 20 where w = longitudinal texturing speed in m / min b = constant lying between 1.15 and 1.5 The additive polymers to be added to the polyester according to the invention, insofar as they possess the properties mentioned above, present a chemical composition * «» ** different. Preferably three different types of copolymers are used, that is 1. A copolymer, which has the new monomer units: A = Acrylic acid, methacrylic acid or CHa = CR COORA where R is an H atom or a CH3 group and R1 is an alkyl radical with from 1 to 15 carbon atoms or a cycloalkyl radical with from 5 to 12 carbon atoms or an aryl radical with from 6 to 14 carbon atoms, B = styrene or styrenes substituted with alkyl having from 1 to 3 atoms carbon, wherein the copolymer consists of 60 to 98% by weight of A and 2 to 40% by weight of B, preferably 83 to 98% by weight of A and 2 to 17% by weight of B, and especially preferred of 90 to 98% by weight A and 2 to 10% by weight B (total = 100% by weight). A copolymer containing the following monomer units: C = styrene or styrene substituted with alkyl having from 1 to 3 carbon atoms, D = one or more of the monomers of formula I, II or III M? ^^ jismuMí satgsi S? Si Wherein Rl t Ra and R3 are each an atom of H, or an alkyl radical with 1 to 15 carbon atoms or a cycloalkyl radical with 5 to 12 carbon atoms or a aryl radical with 6 to 14 carbon atoms, wherein the copolymer consists of 15 to 95% by weight of C and 2 to 80% by weight of D, preferably 50 to 90% by weight C and 5 to 50% by weight D and especially preferred from 70 to 85% by weight in C and 15 to 30% by weight D, the total of C and D being equal to 100%. 3. A copolymer containing the following monomer units: E = acrylic acid, methacrylic acid or CH 2 = CR-COOR 'wherein R is an H atom or a CH 3 group and R 1 an alkyl radical having from 1 to 15 carbon atoms or a cycloalkyl radical with from 5 to 22 carbon atoms or an aryl radical with from 6 to 14 carbon atoms, t. F = styrene or styrene substituted with alkyl having from 1 to 3 carbon atoms, G = one or more monomers of formula I, II or III wherein R 2 R 2 and R 3 are each an H atom, or an alkyl radical with 1 to 15 carbon atoms or a cycloalkyl radical with 5 to 12 carbon atoms or an aryl radical with 6 to 14 carbon atoms, H = one or more ethylene-unsaturated monomers copolymerizable with E and / or F and / or G, of the group consisting of Q'-methylstyrene, vinyl acetate, esters of acrylic acid, esters of methacrylic acid, which are different from E , vinyl chloride, vinylidene chloride, halogen substituted styrenes, vinyl ethers, isopropenyl ethers and dienes, wherein the copolymer consists of 30 to 99% by weight of E, 0 to 50% by weight of F, > 0 q 50% by weight of G and 0 to 50% by weight of H, preferably 45 to 97% by weight of E; 0 to 30% in 15 weight of F, 3 to 40% in weight of G and 0 to 30% in weight of H and especially preferred of 60 to 94% in weight of E, 0 to 20% in weight of F, 6 to 30% by weight of G and 0 to 20% by weight of H, the sum of E, F, G and H being equal to 100%. It is treated here in component H of an optional component. While they saw advantages to be achieved according to the invention already by copolymers, which present components from groups E to G can be achieved, the advantages to be obtained according to the invention are also presented, if the copolymer structure which has to be applied according to the invention shares other monomers of the group H. The component H is preferably selected in such a way that it has no disadvantageous effect on the properties of the copolymer according to the invention. Component H and others can therefore be used to modify the properties of the copolymers in any way, for example by increasing or improving the properties of flowability if the copolymer is heated to the melting temperature, if he The copolymer is heated to the melting temperature, or to reduce a remaining color in the copolymer or by the use of polyfunctional monomers, in this way and a certain degree of crosslinking is introduced into the copolymer. In addition, it can be selected in such a way that a copolymerization of the components E to G is mainly possible or supported only, as in the case of MSA and MMA that are not copolymerized, but by the addition of a third component with styrene HE copolymerize without problem. Suitable monomers for this purpose include, inter alia, vinyl ester, acrylic acid ester, for example methyl acrylate and ethyl acrylate, methacrylic acid ester, differing from methacrylate methyl, for example butyl methacrylate, methacrylate ethylhexyl, vinyl chloride, vinylidene chloride, styrene, a-methylstyrene and the different styrene isopropenyl vinyl ester, dienes, such as, for example, 1,3-butadiene and divinylbenzene. The color reduction of the copolymer can be achieved, for example, preferably by application of an electron-rich monomer, such as, for example, vinyl ether, vinyl acetate, styrene or Q-methyl styrene. The manufacture according to the invention of The copolymer to be applied, is in lf known, can be manufactured in substances, solutions, suspensions or emulsions by polymerization. An auxiliary indication is found with respect to the polymerization of substance in Houben Weyl, volume E20, part 2 (1987) pages 1145ff.

Notes on the solution polymerization can also be found on page 1136. The technique of suspension polymerization is also described on page 1156, while the emulsion polymerization is also introduced there and explained on page 1150 Especially preferred are within the framework of the invention pearl polymerized, whose particle size remains in a particularly favorable field. Especially preferred are the copolymers to be used by mixing in the melt of the polymers of fiber in the form of particles with an average diameter of ? - »¡«? 6 < ? iMfe? < Ítet & fiMfat »-l« * 0.1 to 1.0 mm. However, larger or smaller beads or granules could be used. The polymers according to the invention can contain other additives as constituent parts, as are usual for thermoplastic molding compositions and for improving the properties of the polymer. As such, there may be mentioned: anti-static, anti-oxidants, flame protection agents, lubricants, colorants, light stabilizers, polymerization catalysts and / or organic phosphites. These additional substances are used in customary amounts, preferably in amounts of up to 10% by weight, preferably less than 1% by weight with reference to 1005 by weight of the copolymer. The imidizing copolymer types 2 and 3 can also be produced from monomers both from the monomers with the use of a monomeric imide and also by a total or preferably partial imideization of one of the corresponding maleinic acid derivatives. These additive polymers are obtained, for example, by a total or partial reaction of the corresponding copolymer in the melt phase with ammonia or an alkyl or arylamine, for example aniline (Encyclopedia of Polymer Science and Engineering Vol 16 (1989), Wiley Verlag page 78) . copolymers according to the invention as well, as long as they are presented, g | The initial non-imidized copolymers are commercially available or producible by a process known to the person skilled in the art. For polymerization blends from polyethylene terephthalate with an intrinsic viscosity of about .055 to .075 dl / g and type 1 copolymers, 2 or 3, copolymers with a viscosity number in the range of 70 to 130 cm 3 / g are preferred. The process according to the invention allows that by the addition of a copolymer to the polyester the pulling speed in the manufacture of yarn by spinning can be increased with respect to the state of the art, while the stretch ratio in the texturing of the stretch it can be maintained. With this increases the capacity of 1 production device directly proportional to the speed of pulling or taking. Since the capacity of the spinning position is proportional to the product from the stretch ratio and the picking speed, it is the capacity gain in the loom: Capacity gain = (Wl.vl / WO.vO) 100 (%) where W 1 = proportion of stretch with additive W0 s > proportion of stretch without additive Vi = Winding speed of the spindle thread with additive V0 = Winding speed with spindle thread without additive Typically Vo remains in the area of 2500 to 3500 m / min and WO correspondingly to the spinning speed according to known state of the art between 1.35 and 2.2. The dependencies according to the invention M, M *, P and N, indicate that the amounts of additive can not be independently selected from the picking speed, if the objective, pre-oriented, low crystalline is to be reached, for the right filaments of stretch texturing made of polymer mixture. Here, on the one hand, a degree of orientation that is too low, for example the extension of a very high tear, and on the other hand a very high degree of orientation with which an crystallization induced by spinning. For the different extraction speeds and the additive concentrations with which the filaments are manufactured, the proportion of stretch in the stretch texturization was obtained, the dependencies M *, P * and N represent proportions of constant stretch to be linear. From here there is a special advantage of this procedure. The filament manufacturer can, at each desired extraction speed, select the quantity of additive and adjust it, which is obtained by a proportion of optimal stretch for those processing conditions. the texturing of the section is carried out with that in optimal, selectable conditions. The values of the properties given in the following examples and the text are obtained as follows: The distribution of additive particles; Fused or swollen strings are torn apart in fluid nitrogen with a sharp chisel. The investigation of the breaking surfaces is carried out by means of scanning electron microscopy and then analytical evaluation of figure under the basic establishment of an elliptical stamping (similar to a sphere) where the length, the width are evaluated and from this the average diameter. The wire speeds are determined by means of nanometer - Laser Doppler using a diode laser with 10 mW of power, TSI GmbH, Aachen / Al, type LS 50 M. With this method a laser beam is divided and the two partial rays are lead to the cut in the object to be measured, the interference frequency is measured in the rear scatter field and the displacement of the interference frequency of the object speed is calculated, the wire speed is measured at several distances below the spinning nozzle. The variation of the speed until reaching the speed defined by the extraction apparatus ^^^^^ j ^ i ^^^ j ^^ y ^^^^ j ^^^^ traction characterizes the spinning delay zone, as a measure the length between the speed points is defined as lOOOm / min and 90 % final speed in millimeters. Usually the lag length is more than 100 mm. With high spinning speeds, it can be shortened to approximately 100 mm, where the thread wrapping is presented; the variation of the yarn speed in the downstream zone of approximately 1750 m / min is then performed almost in the form of dots. The intrinsic velocity is determined in a solution of 0.5 g of polyester in 100 ml of a mixture of phenol and 1,2-dichlorobenzene (3: 2 parts by weight) at 25 ° C. The viscosity number VZ (also Satudinger function) is the variation of relative viscosity referred to the concentration of a solution of 0.5% solution of copolymers in chloroform in reference to the solvent, where the time of passage in the Ubelohde viscosimeter with hanging spherical level. Type Schotto no 53203 and Oc capillary in accordance with DIN 51562 at 25 °. Solvent serves as chloroform VZ = (1 / to-1). 1 / c where t = Time of passage of the polymer solution in seconds to- time of passage of the solvent in seconds c = concentration in g / 100 ccm. For the determination of the melting viscosity (initial viscosity) the polymer was dried in vacuo at a water content less than or equal to lOOOppm (minor polyester) or equal 50ppm). , Next the granulate was put in a reometro -placa- sphere, type UM100, Physica Messtechnik GmbH, Germany, under nitrogen accumulation on the hardened measuring plate. Here the measuring sphere (MK210) after the melting of the sample, this is after of about 30 seconds, it is placed on the measuring plate. The measurement is started again after another heating period of 60 seconds (measurement time = 0 seconds). The measurement temperature was 290 ° C for polyethylene terephthalate and additive polymer, to which added polyethylene terephthalate, or is equal to the melt temperature (method here) of the polyester considered to be plus 34.0 ° C. The measurement temperature determined corresponds to the typical processing or spinning temperature of each polyester. The amount of The sample is selected in such a way that the Reometro space is completely filled. The measurement was made in oscillation with the frequency 2.4 Hz 9 corresponding to a cut-off rate of 15 sec "1) and a deformation amplitude of 0.3, and the amount of complex viscosity was determined as a function of the measurement time. After the The initial viscosity was calculated by a linear regression at the zero measurement time. For the determination of the melting temperature of the polyester first the polyester sample was melted at 310 ° C for one minute and directly afterwards it was stretched to room temperature. Then the melting temperature was determined by DSC measurement (Differential Scanning Calorimetry) with a heating rate of 10 ° per minute. The pretreatment and the measurement were performed under nitrogen accumulation The energy of flow activation (E) is a measure) for the rate of variation of the null viscosity depending on the variation of the measurement temperature, where the null viscosity is the extrapolated viscosity at the cut-off rate 0. The zero viscosity measurement is carried out at temperatures in the field from 240 to 280 ° with a reometro-high-pressure capillary, type reografo 2002, Gottferte GmbH Buchen / Germany and the evaluation of agreement with the three-parameter law of Carreu- Winter. Then the energy of activation of flow by means of the law of Arrhenius from the null viscosity according to M. Pahl and associates, Praktische Rheologie der Kunststoffe und Elastomere, VDI Verlag Dusseldorf (1995) pages 256 et seq. The properties of mechanical resistance are tested in a tensile test apparatus in a space length of 200mm, a pretensioning force of 0.05 cN / dtex and a test speed of 2000 mm / min. The cooking shrinkage was conditioned at room temperature and before 10 minutes in water of 95 + -1 ° C was determined from the treated fibers. The double breaking was measured as described in DE 195 19 898 A and the uster values as described in EP 0 346 641. The determination of the stretching force was performed with a Dynafil M apparatus from Textechno, Monchengladbach / Germany to a hot tube temperature of 200 ° and a test speed of 100 m / min. The crystallinity (K) was calculated from the rho density according to K (%) = (1.455, j 1.938 / ¿0.123) (100) where the density was obtained in short knotted pieces of wire, at 23 ° according to the density gradient method * in CCl4 / n heptane). The characteristic curling values of the textured filament skeins (nominal titre up to 500 dtex) were obtained according to DIN 53840, part 1. The coloration depth was determined with a dark blue dyed cloth TERASIL GRL-C 200% (CIBA -GEIGY, Basel / Switzerland for comparison of measurement of color remission with a reflection photometer according to DIN 54001. EXAMPLE 1: (Comparison) Polyethylene terephthalate with an intrinsic viscosity N? Ntr = 0.64 dl / g (corresponds to an initiation viscosity) 250 Pa.s) and a remaining water content of less than 50 ppm was melted in a conical extruder and at a temperature of 296 ° C by a product line with 15 static mixing elements, Type SMX, nominal width DN 15, from Sulzer AG, Zurich / Switzerland and hollow tube sections - to guarantee a technically relevant residence time or the duration of the thermal melt charge - by means of a gear metering pump through a spinneret adapter is led to the spinneret pack. The spinning yarns that come out of the perforations of the nozzle plate are taken to a conventional blowhole and cooled by a transverse blow, where the air velocity was adjusted to 0.45 m / sec. At a distance of 1200 mm below the spinning nozzle, the yarns cooled by means of an oiled rod are joined in a bundle and supplied with an emulsion-water spinning oil, where the amount of preparation applied to the yarns was 0.355 in reference to the weight of J ^ S-faith ** »the threads. The bundle of threads was pulled by means of two garts or driven draw rollers knotted in S-shape and wound in a winding aggregate of Bermag AG Remscheid / Germany type SW7 with a bi-rotor change in sleeves to the packages of skein. The spindle traction speed was set lower, so that a voltage of lOcN was produced between galets and in windrower. The nominal title of the yarn produced in this way was 84/34 dtex. The pulling speed was adjusted to 3200 m / min where a polymer amount of 41.4 g / min is supplied to the spinning nozzle. The characteristic data of the spinning yarn are presented in Table 1: TABLE I: Reference POY CV = coefficient of variation EXAMPLE 2; The spinning system according to Example 1 was amplified by means of a dosing device consisting of a melt extruder and a gear metering pump. With this dosing system, the additive was melted with a residual water content of less than 1000 ppm in the form of granulate and as a melt was dosed by adding it to the concentration of 1.0 5 by weight in the molten PET stream and by means of a mixer The static mixer was mixed in a dwell time in the mixer of 44 sec. the polymer mixture is threaded in It is similar to those of Example 1 at a temperature of 296 ° C. In the additive from the comparison test no 2 was the commercial product Delpet 80N from Asahi Kasei / Japan, a polymethyl methacrylate with a viscosity number VZ = 61.2 ccm / g. The spinning speed of the yarn was in any case constant at 5000m / min. The polymer step was 63g / min, whereby a mean melt residence time of about 7.5 min was obtained up to the entry into the spinneret pack. In a further comparison test (No. 3) the Delpet 80 additive was not dosed to the PET melt stream in a concentration of 1.8% by weight and under the same conditions it was spun. In other tests (No. 4-9), mixtures of polymers according to the invention were spun under the same conditions, but the amount of the corresponding copolymer was only 0.65% by weight. The additives were products of Degussa AG, Hanau / Germany and 91.2% by weight of methacrylate by weight (MMA) and different viscosity numbers (according to Table 2). In the essay no. Under similar conditions a polymer mixture was made at a temperature of only 286 ° C, processed and spun. The characteristic data for these and the tests previously ; _h ^ -il¡aa.fr;, A mentioned are given in Table 2a and 2b. TABLE 2a 10 ^^^^^^^^^^^^^^ TABLE 2b: polyester melt (= 1) ** Flow activation energy In the increase of the viscosity number of the aggregate additive polymer is shown first an increase in the extent of tearing, that is, a maximum improvement of the economy is observed by the addition of the copolymer with a viscosity number of about 105 ccm / g. In the addition of the additive with an even higher viscosity number the economy of the process slowly recedes.

In contrast to EP 47 464 B the exposed additive achieves with the copolymers according to the invention viscosity numbers in the range of 91 to 118 ccm / g approximately the same capacity-increasing effect dn a drastically reduced amount of additive. This reduction of the additive is not only economically advantageous, but also represents an important technical advantage, other complications of the processing process such as glue of the additive connections that are found on the surface of the wires to the hot metal surfaces of the heater. texturization aggregates are markedly diminished-if - as in the context of the present invention - the admixture of the added additive arrives to decrease. It also represents the boundary surface between the additive connections and the polyester matrix because of the incompatibility of both materials a place of failure in the transmission of mechanical stresses to the skein, which can lead with high concentrations of additive to capillary breaks. This effect is more impressive the greater the amount of additive and the textural behavior as well as the tear resistance of the textured skein. In trials no 6 and no 9, despite the Fif]] i! ? mm? ^. thermal preload drastically changed from the melt mixture by the application of a spinning temperature of 286 ° C to 296 ° C which reaches the tear extension, that is the additive according to the invention is characterized by a good thermostability in a large field of technically relevant temperature EXAMPLE 3 In other tests, other polymer mixtures were spun under equal conditions to Example 2, where the addition of the corresponding additive was 0.72% by weight The additives were copolymers of Degussa AG, Hanau / Germany with 8.8% by weight of styrene, 86.2% by weight MMA and 5% by weight of N-cyclohexylmaleninide, and different viscosity numbers which also contain data characteristic of the spinning yarns.

Comparison tests 10 and 17 and tests 11, 16 confirm again the existence of an applied optimum of the additive viscosity in reference to the increasing effect of the capacity or extent of tearing. In the zone of viscosity numbers from 61 to about 100 ccm / g, the economy of the firstly almost linear process increases with the viscosity number. In the area of VZ = l00ccm / g up to the viscosity number of approximately ll5ccm / g it improves the economy but only slightly. Above this optimum the economy decreases again slightly to a viscosity number of approximately 130 ccm / g. In VZ = l74ccm / g a clear negative effect with reference to the capacity is presented. The test number 11 produces a POY with a small tear extension smaller than the usual tests, and therefore remains in the boundary zone of the invention. EXAMPLE 4 In test number 18, in the spinning system of example 2, a pack of nozzles with a spinneret plate with 17 perforations was used instead of 34. Under otherwise unchanged conditions, 0.65% was mixed. by weight of the additive according to the invention, with 8.8% by weight of styrene and 91.2% by weight of MMA of the viscosity number VZ = 98.5ccm / g and the polymer mixture with an amount of polymer of 63g / min, of a extraction for spinning of 5,000m / min, and a spinning temperature of 296 ° C, were spun to a thread with the nominal title 84 / 17dtex. In another test (19), under otherwise unchanged conditions a spinneret plate with 72 perforations, perforation diameter O.lOmm, L = with 2, and a polymer mixture with the same additive as in the test 18 at a spinning speed of 5,000m / min, spinning a yarn with a nominal title 84 / 72dtex. Finally, a plate of spinning nozzles with 120 perforation diameter perforations 0.13mm, L = 2d, and with an addition of 0.65% by weight of the same additive, as above and a polymer amount of 58g / min and a speed were used. of extraction of spinning of 4500m / min, spinning a thread with nominal title 84/120 (test 20). The characteristic data of all the spinning yarns are shown in table 4. ^^^ m ^^ ... ^^^^ á ^^ ki Table 4 Comparative Example 5 Polyethylene terephthalate with an intrinsic viscosity ^ nr = 0.64dl / g (corresponding to an initial viscosity of 250Pa.s) and a remaining water content of less than 50ppm, was melted in a conical extruder with a part of mixed LTM, 3D type 4E 4 24 D from Barmag AG, Remscheid / Germany and with a temperature of 290 ° C, by means of a gear metering pump through a product line with 7 static mixing elements, type SMX , from Sulzer AG, Zurich / Switzerland and an empty tubular section (to guarantee a technically large relevant dwell time) was conducted to another gear dosing pump designated as spinning pump, at the output of that spinning pump the fused in 6 partial streams with one step between them equal. Each of these partial streams led through a spinneret adapter with two - static, type SMX DN10, from Sulzer AG, Zur_eh / Switzerland to a pack of spinning nozzles. The spinning pack contained the following structure in cutting and filtering media in the melt flow direction: steel volume-sand with a granulate 350 to 500 μm, support plate, second cloth filter with 20 μ 230 spinning plate with 34 perforations, perforation diameter 0.23mm, L = 2DD, and a plate diameter of 80mm, corresponding to a filtering surface of 40cmA With a varied polymer pitch, a pressure of 110-190 bar was presented. The threads that came out of the spinneret perforations were cooled with a transverse blow in a conventional blowhole, where the air speed was adjusted to 0.55m / min. At a distance of I500mm below the spinneret, the spinning yarns cooled by means of an oiled rod were joined and water, spinning oil was supplied where the amount of preparation applied to the yarns was about 0.35%. The bundle of threads was pulled by means of two garts or driven draw rollers knotted in an S-shape and wound in a winding aggregate of the firm Barmag AG, Remscheid / Germany type CW8 T-920/6, with Bi-change. rotor in 6 sleeves for bundles of skein. The spinning speed was defined by the peripheral speed of the rollers or Galets. The winding speed was adjusted approximately 1% lower so that between the Galet and the winding there was a tension of approximately 10cm. The nominal title of the manufactured yarns of that type was 84 / 34dtex. The speed of extraction or traction was 3,200m per minute, where an amount of polymer per nozzle of 44g / min, was adjusted, which resulted in an average dwell time of the melt until the entry into the spinning pump. approximately 15 min. In a second test, the extraction rate was raised to 5,000 / min, and simultaneously a polymer amount of 63g / min was set for each spinning nozzle with an average dwell time of about llmin. The data of the spinning yarns are presented in table 5, as the average value of the 6 reels of each test.

TABLE 5 The spinning yarns were further elaborated from the comparison tests El and E2 were placed in a Barmak extrusion machine type FK6-S900 equipped with the & added Barmak type 7 disc with PU polyurethane discs, H6 configuration 1-4-1, D / Y = 1. 84, heating temperature 1 and 2 = 195/160 ° C at a speed of 800m / min or heating temperature 1 and 2 = 210/160 ° at a speed of 800 m / min. The heating temperature 1 and 2 = 210/160 ° C at a speed of lOOOm / min. TABLE 6 Results of the texturing of the stretch or line of the test Do not . The - E2 + = positive 0 = lavorable with conditions; - = negative Example of comparison The corresponds to the state of the art, as regards the properties of the spun yarn as well as the line texturing. In the increase of the spinning speed to 5,000m / min, problems in the form of breaks and yarn tension defects appear in the line texturing, and the proportion of the section applied must be strongly reduced. Also the achievable resistance is low. The reason for this is the high degree of crystallization of the spin yarn POY, and is characterized by a correspondingly low tear extension and the interlacing behavior in spinning. EXAMPLE 6 In the spinning system according to example 5 and under the same conditions of spinning, polyethylene terephthalate chips or chips were added an additive polymer according to the invention, with a water content remaining less than 100 ° C in particular shape in the form of pearls, with an average diameter of the pearls with approximately 0.2mm in different concentrations. For this, the additive was applied in doses by means of a solid dosing device with mandrel drive type GRD 76 from Gericke, Rielasmgen / Germany, with the desired dosage rate by means of dosing tubes in the stream of the PET pellets, in the pull zone of the melt extruder. The additive polymer was a product of Degussa, AG Hanau / Al. type Degalan (M.R.) PVPMS, corresponding to a copolymer according to the invention with the following composition: 8.8% by weight styrene, 91.2% by weight MMA, No. of viscosity VZ = 98.5ccm.g.

The proportion of the melt viscosities of the additive to the polyester according to this invention was 4.8, and the residence time of the polymer mixture in the mixing zone 8S (7 mixing elements as in ex. 5). The spin extraction speed was constantly adjusted to 5,000m / min. The polymer passage in each spinneret was 63g / min. The nozzle pressure was in the range of 145 to 150 bar. Table 7 contains the 10 characteristic data as average value of the 6 coils of each of the tests. In the comparison examples E3 and E4 is the amount of additive lower than the amount N defined at the beginning, and with this so low, that there is precisely a clear difference with respect to the unmodified skein, but the amount of additive does not achieves to reduce the crystallinity and entanglement in the required measure, so that favorable properties of subsequent processing are guaranteed. In contrast, the tests E5 to E8 are in accordance with the invention. TABLE 7 sa > .,. - * * »" '. Faith *, »»! T. permanence min 11 11 11 11 11 11 7 7 7 7 7 7 No. SMX 290 290 290 290 290 290 5000 5000 5000 5000 5000 5000 5000 Spinning thread ° C 0.12 0.17 0.41 0.77 0.97 1.47 129.7 128.6 128.7 127.2 129.3 129.4 Take velocity m / min 70.4 73.4 90.3 118.1 139.9 167.0 Additive const% on p 3.1 3.5 2.5 2.2 2.5 2.6 34.9 34.7 30.6 25.6 22.8 17.0 Tit hilar dtex 3.1 2.6 2.4 2.3 3.0 2.7 86.3 81.4 72.5 58.1 36.5 Ext. Tear% 4 7 7.8 50.8 60 7 61 27 22.1 6.3 2.9 Ext. Tear -CV% 0.35 0.37 0.4 0.37 Res. Tear cN / tex 0.48 0.54 0.57 0.84 5 4.6 3.5 1.8 Load CV% 1 41 1.07 1.78 2.4 40 70 40 Double x 10"3 Shrinkage cooking% Crystallinity% Uster- inert medium?% -Normal u% Tens. Dynafil cN / tex CV-Dynafíl% Prop. -estir.Dynafil% The spinning yarns according to the invention, textured in line as in the example El, with a processing speed of 1,000m / min. The characteristic textile data are presented in table 8 as the average value of the 6 coils of each of the tests. TABLE 8 Results of the line texturing of the E5-E8 tests (positive positive + 0 = positive with conditions; - = negative). As excellent the amount of additive was adjusted to the spinning conditions in the E6 test. Here, he obtained the best properties of textured skein online. Also without any problem was an increase in the texturing speed to 1,000m / min, with a positive processing behavior, where on the other hand the comparison skein according to the state of the art of the El example, with JL. ¿HÉiat ?? i tóíftfeas »uss an increase in the texturing speed from 800 to 1000, had already shown a worsening of the processing behavior (table 6). Also in examples E5, E7 and E8, good on-line texturing results are achieved. The amount of additive in these tests is, however, no longer in the preferred zone. This is manifested in a slight reduction, however not yet critical of the tear strength and the tear extension, especially in the example E8, where the amount of additive deviates strongly from the especially preferred range. EXAMPLE 7 In the metering system and spinning system according to Example 6 and under the same spinning conditions, the same additive polymer as in Example 6 was added to the polyethylene terephthalate chips or chips again with different concentrations. In this case, the spinning speed or pull was constant and adjusted to 4,350m / min. The polymer passage in each spinneret was 55g / min. The nozzle pressure remained in the range of 130 to 145 bar. Table 9 contains the characteristic data of the spun yarns with average value of the 4 coils of each of the tests. "*. 54 TABLE 9 The spinning yarns were textured in line as in the El test with a processing speed of lOOOm / min. The characteristic textile data are presented in Table 10, as the average value of all the 6 coils in each of the tests. In the E10 test, the additive concentration was adjusted particularly well to the spinning speed, so that especially preferred properties of the spun yarn resulted, and secondly also in the in-line texturing, the best skein properties were obtained and the better processing behavior. Also in the Eli and E12 tests, high-quality, textured skeins were produced in line. In the Eli test, the amount of additive that was dosed was no longer in the preferred range. In this way also the tear extension of the spun yarn was outside the preferred zone and compared to the E10 test, a slight reduction of the tear strength and tear extension of the inline textured skein was recognized. This trend continues in the E12 test, where the amount of the additive is also outside the preferred aggregation range. TABLE 10 Online texturing results of the E10-E12 assay (+ positive positive 0 = lavorable with conditions; - = negative). EXAMPLE 8 In the spinning dosing system according to example 6 and under the same spinning conditions, the spinning speed was varied between 3,200m / min and 6,000m / min, here the additive quantity dosed was adjusted in such a way that Tears of the POY skein resulted between 115% and 133%. Table 11 contains the characteristic data of the spun yarns as the average value of all the 6 coils of each of the tests. To compare, the data contained in the test No. El is entered in table 5 once more.

TABLE 11 The spun yarns were textured on line as in Example 5, with a processing speed of lOOOm / min. The characteristic textile data are shown in table 12, as the average value of all the 6 coils of each of the tests. TABLE 12 Results of the test line texturing El, E6, E10, E13, E14. + + positive positive 0 = lavorable with conditions; negative). In all the tests according to this invention, the amount of additive ideally added to the spinning speed was adjusted. Spun yarns with preferred properties were obtained which also provided outstanding texturing results online. Example 9 The spinning system according to example 2 was changed here, so that the number of static mixers used in the mixture of the additive was reduced from 15 to 9, 3, corresponding to residence times of 4426 or 9 seconds. In general, the same spinning conditions were maintained. In the arc testing of the modified polyester that came out of the spinning nozzle, REM investigations were carried out to evaluate the distribution of the additive. The result is presented in Table 13, together with the extent of tear of the resulting skein POY. In insufficient mixing of the additive (MI test) is its effectiveness - recognizable in the reduction of the extension of tears - markedly reduced. The cause for this reduced effectiveness of the additive is the increasing fraction of additive particles with a diameter greater than 10000 nm and the poor distribution in the cross section of the skein, this is visible in REM sockets and in graphic applications of the particle size with regarding the number of particles.

TABLE 13 Influx of the mixer arrangement (nominal width DN15) Example 10 Manufacturing examples for copolymers. l. In a polymerization vessel 101 equipped with stirrer, reflux condenser and thermometer, a mixture of totally scruffy water of 4.750 g and 118 g Degapas (MR) 8105 S was heated to 40 ° C. Under agitation, 4,750 g of water was now added. mixture of 86.2 parts by weight of methyl methacrylate (MMA), 8.8 parts by weight of styrene, 5 parts by weight of cyclohexylmaleiminide, 0.14 parts by weight of 2-ethylhexyl ester of thioglycolic acid, 0.09 parts by weight of t-dodecyl mercaptan, 0.05 parts by weight weight of stearinic acid and 0.25 parts by weight of dilauroyl peroxide. The whole was polymerized for 165 min. at 80 ° C and polymerized 60 min at 90 ° C and then cooled to room temperature. The beads of the polymer were filtered, washed basically with thoroughly disheveled water, and dried in a swirl bed dryer at 80 ° C. 4,710 clear polymerized beads with a viscosity number of 99.6 ccm / g were obtained. 2. In a 51 polymerization vessel equipped with stirrer, reflux condenser and thermometer, a mixture of 2,400 g of totally scruffy water and 46 g of a 6% aqueous solution of a methacrylic acid copolymer was heated at 40 ° C. Under stirring, 2,400 g of a mixture of 90.65 parts by weight of methyl methacrylate (MMA), 8.75 parts by weight of styrene, 0.15 parts by weight of 2-ethylhexyl ester of thioglycolic acid, 0.1 parts by weight of t-dodecyl mercaptan, were added. 0.05 parts by weight stearinic acid and 0.3 parts by weight dilauroyl peroxide. the whole was polymerized 105 minutes at 80 ° C and 30 mm at 90 ° C and then cooled to room temperature. The polymerized beads were filtered, basically washed with thoroughly scruffy water and dried in a swirl bed dryer at 80 ° C. 2283g of clear polymerized beads with a viscosity number 98.5ccm / g were obtained. 3. In a polymerization vessel of 51 equipped with stirrer, reflux condenser and thermometer a mixture of completely scruffy water of 2400g and 46g of a 6% aqueous solution of a methacrylic acid polymer was heated to 40 °. Under stirring, 2,400 g of a mixture of 90,715 parts by weight of methyl methacrylate (MMA), 8.75 parts by weight of styrene, 0.115 parts by weight of 2-ethylhexyl ester of thioglycolic acid, 0.1 part by weight of t-dodecyl mercaptan, were added. 0.07 parts by weight stearinic acid and 0.03 parts by weight dilaurroyl peroxide. The whole was polymerized 150 minutes at 80 ° C and 60 minutes at 90 ° C and then cooled to room temperature. Polymerized beads were filteredBasically, they were washed with completely disheveled water and dried in a swirl bed dryer at 80 ° C. 2299g of clear polymerized beads with a viscosity number of 118.4 were obtained. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (21)

1. CLAIMS Having described the invention as above, the content of the following is claimed as property: 1.- Procedure for the preparation of pre-oriented filaments 5 of the polymer mixtures prepared in the melt, based on polyester, adding an amorphous copolymer thermoplastic with a vitreous transition temperature greater than 100 ° C, by spinning the molten polymer blends at an extraction rate of at least 10 2500 m / min, process characterized in that the ratio of the melt viscosity of the copolymer to the viscosity of the polyester melt is 1: 1 to 10: 1, because the amount added to the polyester of the copolymer is at least 0.05. % and maximum corresponds to an amount M, 15 where M is given by the formula M = [1/1600. V (m / min) -0.8] [% weight].
2. 2. Method according to claim 1, characterized in that, the ratio of the viscosity of the copolymer melt to the viscosity of the mass 20 cast polyester is 1.4; 1 to 8: 1.
3. 3. Method according to claim 1 or 2, characterized in that the ratio of the viscosity of the melt of the copolymer to the viscosity of the melt of the polyester is 1.7: 1 to 6.5: 1.
4. 4. - Procedure according to the claims siSs., "- ~" "" "*» 1, 2 or 3, characterized in that the copolymer contains the following monomer units: A = Acrylic acid, methacrylic acid or CH2 = CR COORA wherein R is an H atom or a group CH3 and R 'is an alkyl radical with 1 to 15 carbon atoms or a cycloalkyl radical with 5 to 12 carbon atoms or an aryl radical with 6 to 14 carbon atoms, B = styrene or styrene substituted with alkyl with 1 to 3 carbon atoms, wherein the copolymer consists of 60 to 98% by weight of A and 2 to 40% by weight of B (total = 100% by weight).
5. 5. Process according to claim 4, characterized in that the copolymer consists of 83 to 98% by weight of A and 2 to 17% by weight of B (total = 100% by weight).
6. 6. Process according to claim 4 or 5, characterized in that the copolymer consists of 90 to 98% by weight of A and 2 to 10% by weight of B (total = 100% by weight).
7. 7. Process according to claim 1, 2 or 3, characterized in that the copolymer contains the following monomer units: C = styrene or styrene substituted with alkyl having 1 to 3 carbon atoms, D = one or more of the monomers of the formula I, II or III wherein R1 t R2 and R3 are each an H atom, or an alkyl radical with 1 to 15 carbon atoms or a cycloalkyl radical with 5 to 12 carbon atoms or an aryl radical with from 6 to 14 carbon atoms, and wherein the copolymer consists of 15 to 95% by weight of C and 2 to 80% by weight of D, the total of C and D being equal to 100%.
8. 8. Process according to claim 7, characterized in that the copolymer consists of 50 to 90% by weight C and 5 to 50% by weight D, the total of C and D being equal to 100%.
9. 9. Process according to claim 7 or 8, characterized in that the copolymer consists of 70 to 85% by weight in C and 15 to 30% by weight D, the total of C and D being equal to 100%.
10. 10. Process according to claims 1, 2 or 3, characterized in that the copolymer contains the following monomer units: E = acrylic acid, methacrylic acid or CH2 = CR-COOR1 wherein R is an H atom or a CH3 group and R1 an alkyl radical having from 1 to 15 carbon atoms or a cycloalkyl radical having from 5 to 22 carbon atoms or an aryl radical having from 6 to 14 carbon atoms, F = styrene or styrene substituted with alkyl having from 1 to 3 carbon atoms, G = one or more monomers of the formula I, II or III wherein R 1 t R 3 and R 3 are each an H atom, or an alkyl radical with 1 to 15 carbon atoms or a cycloalkyl radical with 5 to 12 carbon atoms or an aryl radical with 6 to 14 carbon atoms , H = one or more ethylene-unsaturated monomers copolymerizable with E and / or F and / or G, of the group consisting of a-methylstyrene, vinyl acetate, esters of acrylic acid, esters of methacrylic acid, which are different from E, vinyl chloride, vinylidene chloride, halogen substituted styrenes, vinyl ethers, isopropenyl ethers and dienes, wherein the copolymer consists of 30 to 99% by weight of E, 0 to 50% by weight of F, >0 to 50% by weight of G and 0 to 50% by weight of H, the sum of E, F, G and H being equal to 100%.
11. 11. - Process according to claim 10, characterized in that the copolymer consists of 45 to 97% by weight of E; 0 to 30% by weight of F, 3 to 40% by weight of G and 0 to 30% by weight of H being the sum of E, F, G and H equal to 100%.
12. 12. Process according to claim 10 or 11, characterized in that the copolymer consists of 60 to 94% by weight of E, 0 to 20% by weight of F, 6 to 30% by weight of G and 0 to 20% in weight of H, being the sum of E, F, G and H equal to 100%.
13. 13. Method according to one or more of claims 1 to 12, characterized in that the copolymer contains additives to improve the polymer properties in an amount of > 1% by weight
14. 14. Method according to one or more of claims 1 to 13, characterized in that the preparation of polymer mixtures is carried out after melting the polyester and the copolymer in a static mixer, whose diameter is selected in such a way that the rate of tear is between 16 and 129 s * 1 and the product of the tear rate and the 0.8va power of the dwell time in seconds is greater than 250.
15. 15. Method according to one or more of claims 14, characterized in that the mixture during the mixing process is torn in such a way that the average particle size of the copolymer immediately after the exit of the spinning nozzles is maximum 400 nm, because less than 1% of the copolymer particles contained in the mixture have a particle size > 1 μm and the length / diameter ratio of the copolymer particles is > 2, wherein the copolymer particles after spinning are in the filaments in the form of fibrils and the length / diameter ratio of the fibrils is > 50.
16. 16. Method according to one or more of claims 15, characterized in that the polyester is a thermoplastically manageable polyester, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate or polybutylene terephthalate, and can selectively contain the polyester. up to 15% by weight of a comonomer and / or up to 0.5% by weight of a polyfunctional branching component.
17. 17. Method according to one or more of claims 1 to 16, characterized in that the filaments after spinning are wound and then subjected to a longitudinal texturing, the stretch ratio being between 1: 1.35 and 1: 2.20.
18. 18. Method according to claim 17, characterized in that texturized filaments with a capillary titer greater than 2 dtex are produced at a production speed of at least 750 m / min and textured filaments with a capillary titer less than 2 dtex a a production speed of at least 400 m / min.
19. 19. Preorientated filaments, produced according to a process according to one or more of claims 16, characterized in that they have a breaking stretch of 85 to 180%, a breaking strength of at least 17 cN / tex, a cooking shrinkage of 32 to 69%, a double break of 0.030 to 0.075 as well as a crystallinity of less than 20%.
20. 20. Pre-oriented filaments according to claim 19, characterized in that it has a breaking extension of 109 to I46% m, a breaking strength of at least 22 cN / tex and a normal Uster < 0.7%.
21. 21. Textured filaments, characterized in that they are prepared from the preoriented filaments according to claims 19 and 20 corresponding to the process according to claims 17 and 18.