EA003951B1 - Method for the spinning and winding of polyester filaments, polyester filaments obtained by the spinning method, draw texturing of the polyester filaments and bulked polyester filaments obtained by draw texturing - Google Patents

Abstract

1. A process for producing and spooling preoriented polyester filaments comprising at least 90 weight % (relative to the total weight of the polyester filaments) polybutylene terephthalate (PBT) and/or polytrimethylene terephthalate (PTMT), preferably of PTMT, characterized by a) spinning the filaments in a spinning nozzle with a spinning delay in the range of 70 to 500; b) passing the filaments through a cooling delay zone of from 30 mm to 200 mm in length immediately after exiting from the spinning nozzle; c) cooling the filaments to below the PBT or PTMT solidification temperature; d) bundling the filaments into thread at a distance of between 500 mm and 2500 mm from the spinning nozzle; e) setting the thread tension in front of and behind removal galettes to between 0.05 cN/dtex to 0.20 cN/dtex; f) spooling the thread with a thread tension of between 0.025 cN/dtex to 0.15 cN/dtex; g) adjusting the spooling speed to between 2200 m/min. and 3500 m/min. 2. The process according to claim 1, wherein the PBT and/or PTMT are used with a limiting viscosity in the range from 0.7 dl/g to 0.95 dl/g. 3. The process according to claim 1, wherein the temperature in the vicinity of the thread coil is set to <=45 degree C during the spooling. 4. The process according to claim 1, further comprising storing the spooled thread for at least 4 hours at 12 to 35 degree C and at 40 to 85% relative humidity. 5. Preoriented polyester filaments produced according to any of preceding claims characterized in that after 4 weeks of storage under normal conditions in accordance with DIN 53802 the filaments have the following properties: a) an elongation upon tearing of between 90 and 165%; b) a processing shrinkage of at least 30%; c) a normal uster below 1.1%; d) a double refraction between 0.030 and 0.058; e) a density less than 1.35 g/cm<3> f) a coefficient of variation of the maximum tensile strength of <=45%; and g) a coefficient of variation of the elongation upon tearing of <=4.5%. 6. A process for the production of bulky polyester filaments, the process comprising processing the filaments of claim 5 into bulky threads in a stretch texturing machine at a speed of at least 500 m/min. and a stretching ratio of at least 1:1.35. 7. Bulky polyester SET filaments, produced according to claim 6, characterized in that a resistance to tearing is >26 cN/tex and an elongation upon tearing is >36%. 8. Bulky polyester HE filament, produced according to claim 6, characterized in that a resistance to tearing of more than 26 cN/tex and an elongation upon tearing of more than 30%.

Description

The present invention relates to a method of forming and winding pre-oriented polyester monofilaments consisting of at least 90% by weight of the total mass of polyester monofilament from polybutylene terephthalate (PBT) and / or polytrimethylene terephthalate (PTMT), mainly from PTMT, as well as to the obtained in this way pre-oriented polyester monofilaments. Further, the present invention also relates to a method for texturing in a stretching process of molded and wound polyester monofilaments, as well as to the bulk polyester monofilaments obtained by texturing in a stretching process.

The manufacture of continuous polyester monofilaments, in particular polyethylene terephthalate (PET) filaments, is already known in a two-step process. In this case, at the first stage, smooth, pre-oriented monofilaments are formed and wound, which at the second stage are finally stretched and thermofixed or subjected to texturing during the stretching process into bulk monofilaments.

An overview of this is given in the book by R. Roite. ZUSCHISCHSy Rocket (1995), released in Munich by Napkeg-Wegad. It, however, describes only the manufacture of PET fibers, and it does not set out a solid molding technology, but, rather, provides an overview, which describes a variety of signs.

The manufacture of fibers from various formable polymers, including polypropylene, polyamides, polyether, etc., is the subject of the application-Θ8 3819913. However, in the examples only the manufacture of PET fibers is described, as far as can be judged by the temperature at which recycle polymer.

In the manufacture of continuous PTMT or PBT monofilaments, there is a problem that pre-oriented monofilaments, both immediately after molding and winding, and several hours after winding during aging at ambient temperature, have a noticeable tendency to shrinkage, leading to shortening of the thread. Due to this, the package is compressed, so that in the extreme case it is firmly shrinking on the sleeve, and the package can no longer be removed. Further, in the package, a so-called saddle is formed with hard edges and a narrowed middle part. Because of this, the textile parameters of the monofilaments, for example, the unevenness of Uster, become more uneven, and there are problems in rewinding packages. Help here can only limit the weight of packages to less than 4 kg. Similar problems do not arise when processing PETvolokon.

Further, it was found that, in contrast to PET mononiths, pre-oriented PBT or PTMT monofilaments age more strongly during aging. Hardening of the structure occurs, leading to such a strong decrease in shrinkage in boiling water that subsequent crystallization can be detected. Such PBT or PTMT monofilaments are only conditionally suitable for further processing, they lead to defects in texturing during the drawing process and to a noticeable decrease in the breaking strength of a textured multifilament yarn. The result is a decrease in texturing speed or drawing ratio.

These differences between PET and PBT or PTMT are explained by differences in the structure and properties, as they were set forth, for example, in “Syetha1 Ilegk 1n, p. 53, No. 50 (2000), and were the topic at 39.! N (. Sopdgekk, September 13-15, Dornbirn. Thus, it is assumed that different formations of chains are responsible for differences in properties.

The first proposals for solving these problems are described in EDO 99/27168 and EP 0731196 B1. In EDO 99/27168, polyester fiber is disclosed, which consists of polytrimethylene terephthalate at least 90% by weight and has a shrinkage in boiling water of 5-16%, and an elongation of 20-60%. The fabrication of the polyester fiber described in EDO 99/27168 is carried out by molding and pulling. At the same time, the acceptance rates for molding at the most 2100 m / min are indicated. The method is uneconomical due to the low molding speed. In addition, the obtained polyester fibers, as confirmed by these parameters, are highly crystalline and, thus, only conditionally suitable for texturing in the drawing process.

In EP 0731196 B1 claimed method of molding, stretching and winding synthetic yarn, in which the thread after stretching and before winding to reduce the tendency to shrink is subjected to heat treatment. Synthetic yarns used also include polytrimethylene terephthalate fibers. According to EP 0731196 B1, heat treatment is carried out due to the fact that the synthetic thread in close proximity, however, essentially, without touching, is conducted along the elongated heating surface. The use of heat treatment increases the cost of the method and gives, moreover, synthetic threads with high crystallinity, which are only conditionally suitable for texturing in the drawing process.

The article Όγ. H.8. ΒΐΌ \ νπ. N.N. Syiai “Tech! Ippd oh 1kh1be ybatep! The group is registered on the basis of the report, but the synergy of the laboratory is 1, February. 1997, No. 47, pp. 72-74 described texturing in the process of drawing polytrimethylene terephthalate monofilaments at texturing speeds of 450-850 m / min. According to this publication, for polytrimethylene terephthalate monofilaments, a lower texturing speed of 450 m / min is better suited, since in this case fibers with better material properties are obtained. The tensile strength of polytrimethylene terephthalate monofilaments of 26.5 cN / tex (texturing speed 450 m / min) and 29.15 cN / tex (texturing speed 850 m / min), as well as the breaking elongation of 38.0% (texturing speed 450 m / min ) and 33.5% (texturing speed of 850 m / min).

PTMT monofilaments having a shrinkage in boiling water in the range of 340% are described in W \ 01/04393. This value is determined, however, immediately after the manufacture of monofilaments. After exposure for 4 weeks under normal conditions, this value falls below 20%, as confirmed by the attached FIG. one.

FIG. 1 describes the change in shrinkage in boiling water for three packages of pre-oriented PTMT monofilaments depending on the exposure time in normal climatic conditions. At the same time, the change in shrinkage in boiling water of pre-oriented monofilaments for three packages with different initial values was studied depending on the exposure time in normal climatic conditions. Packages No. 16 and 17 with a high baseline value> 40% had shrinkage in boiling water after 4 weeks in excess of 30%, preferably in excess of 40%. If the initial shrinkage value in boiling water is below 40%, then packing 18 shows that the shrinkage value after 4 weeks of exposure falls below the critical value of 30%.

FIG. 2 schematically depicts load-elongation diagrams of pre-oriented PTMT monofilaments. With equal tensile elongation in FIG. 2a) shows a diagram according to the invention with a natural stretch ratio (νν) greater than or equal to 15%, and FIG. 2b) is a diagram with Ννν = 0%.

Boiling water shrinkage is a measure of processability and degree of crystallization of fibers. The fibers described in XVO 01/04393 contain polymers with a high degree of crystallization, which are processed much worse and only with a low draw ratio and / or low texturing speed.

In view of the prior art, the object of the present invention was to create a method for forming and winding pre-oriented polyester monofilaments consisting of at least 90% by weight of the total weight of PBT and / or PTMT monofilaments, which would simply produce and wind pre-oriented polyester monofilament. In particular, pre-oriented polyester monofilaments should have a breaking elongation in the range of 90-165%, high uniformity in terms of monofilament parameters, as well as a small degree of crystallization.

Another objective of the present invention was to create a method of forming and winding pre-oriented polyester monofilaments that could be carried out in large technical volumes and cost-effective. The method according to the invention should ensure the highest possible speed of acceptance, preferably more than 2200 m / min, and high masses of the yarn in the package more than 4 kg.

The object of the present invention was also to improve the durability of the pre-oriented polyester monofilaments obtained by the method according to the invention. They must be resistant to aging also for a long period of time, for example 4 weeks. The compacting of the packages during aging, in particular the solid shrinkage of the package on the sleeve, as well as the formation of a saddle with hard edges and a narrowed middle part, should be prevented as far as possible, so that when unwinding the packages there are no problems.

According to the invention, the pre-oriented polyester monofilaments should be able to be further processed in a simple manner when drawing or texturing during drawing, in particular at high texturing speeds, preferably above 450 m / min. The monofilaments obtained by texturing in the process of extrusion should have excellent material properties, for example, high tensile strength above 26 cN / tex and high tensile elongation above 30% for non-monofilaments and over 36% for 8ET monofilaments.

These and other, implicitly named tasks, which, however, may well be derived or disclosed from the interrelations discussed in the preamble, are solved by means of the molding method and winding with all the features of claim 1 of the claims. Expedient modifications of the method according to the invention are placed under protection in subordinate clauses of the dependent claims. The pre-oriented polyester monofilament obtained by the molding method was characterized in an independent clause on the product. Texturing in the process of drawing a pre-oriented polyester monofilament is stated in item 6, whereas items 7 and 8 per product refer to the texturing obtained in the process of drawing out bulk monofilaments.

Due to the fact that, in the method of manufacturing and winding, pre-oriented polyester monofilaments consisting of at least 90% by weight of the total mass of polyester monofilament from polybutylene terephthalate (PBT) and / or polytrimethylene terephthalate (PTMT), mainly from PTMT,

a) complete stretching in the molding process is set in the range of 70-500;

b) monofilament immediately after leaving the die passes through a cooling zone and a delay of 30–200 mm;

c) the monofilament is cooled below the solidification temperature;

g) monofilament unite at a distance of 500-2500 mm from the bottom side of the die;

e) the tension of the thread before and between the receiving discs is set from 0.05 to 0.20 cN / dtex, preferably up to 0.15 cN / dtex;

e) the thread is wound with a tension of 0.0250.15 cN / dtex;

g) winding speed is set at 22003500 m / min, it is possible to get predictable polyester monofilaments in a quite predictable way, which, even after exposure to normal conditions for 4 weeks, retain excellent material properties. There was no noticeable deterioration in the uniformity values of the yarn due to aging or shrinkage of the molded yarn on the package.

At the same time, the method according to the invention has several additional advantages. These include, among others, the following:

the method according to the invention is easy to implement, in large technical volumes and cost-effective. In particular, the method provides molding and winding at high acceptance speeds of at least 2,200 m / min, and obtaining a large mass of yarn in the package in excess of 4 kg;

thanks to the method according to the invention, spinning additives can be dispensed with. Due to this, polyester monofilaments can be obtained particularly cost-effectively;

The pre-oriented polyester monofilaments obtained by the method according to the invention can be simple in large technical volumes and profitably subjected to further processing in the process of drawing or, respectively, texturing in the process of drawing. At the same time texturing can occur at speeds above 450 m / min;

due to the high uniformity of pre-oriented polyester monofilaments obtained by the method according to the invention, it is possible in a simple manner to establish a good winding structure that ensures uniform and almost free from defects coloring and further processing of pre-oriented polyester monofilaments;

The monofilaments obtained by texturing in the process of extrusion have a high tensile strength above 26 cN / tex and a high tensile elongation above 30% for HE monofilaments and over 36% for 8ET monofilaments.

The present invention relates to a method for manufacturing and winding pre-oriented polyester monofilaments consisting of at least 90% by weight of the total weight of polybutylene terephthalate (PBT) and / or polytrimethylene terephthalate (PTMT) yarn. Polybutylene terephthalate (PBT) and / or polytrimethylene terephthalate (PTMT) are known to the specialist. Polybutylene terephthalate (PBT) can be obtained by polycondensation of terephthalic acid with equimolar amounts of 1,4-butanediol, and polytrimethylene terephthalate by means of polycondensation of terephthalic acid with equimolar amounts of 1,3-propanediol. Mixtures of both polyesters are also possible. According to the invention, PTMT is preferred.

Polyesters can be both homo and copolymers. As copolymers are considered, in particular, such that in addition to repeating PTMT- and / or PBTblocks contain up to 15 mol% with respect to all repeating blocks of polyesters, repeating blocks of conventional comonomers, for example ethylene glycol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, isophthalic acid and / or adipic acid. In the context of the present invention, however, polyester homopolymers are preferred.

The polyesters according to the invention may contain the usual amounts of additional additives as impurities, such as catalysts, stabilizers, antistatic agents, antioxidants, flame retardants, dyes, dye susceptibility codifiers, light stabilizers, organic phosphites, optical brighteners and matting agents. Mostly polyesters contain 0-5 wt.% Additives from the total mass of monofilament.

In addition, polyesters can also contain a small proportion of branching components, preferably up to 0.5% by weight of the total weight of the monofilament. The preferred branching components of the invention include, among others, polyfunctional acids, such as trimellitic acid, pyromellitic acid, alcohols from three to hexavalent, such as trimethylopropane, pentaerythritol, dipentaerythritol, glycerin, or the corresponding hydroxy acids.

The polyesters used in the sense of the invention advantageously have thermoplastic molding and can be molded and wound in monofilament. It is particularly preferred such polyesters, which have a viscosity limit in the range of 0.70-0.95 dl / g.

In the method according to the invention, the melt or mixture of melts of polyester by means of spinning pumps at a constant rotation frequency, the rotational speed is set by the known formula so that the desired thread titer is obtained, pressed through the spin pack and extruded into viscous monofilaments through the holes of the plate die.

The melt can be made, for example, in a polymer crumb extruder, and the preliminary drying of the crumb to a moisture content of <30 ppm, in particular <15 ppm, is particularly favorable.

The temperature of the melt, which is commonly referred to as the molding temperature and is measured before the spinning pump, depends on the melting point of the polymer used or the polymer mixture used. It lies mainly in the range specified in formula 1.

Formula 1:

Tt + 15 ° С <Т ₃ р <Tt + 45 ° С where T _t is the melting point of polyester [° С] T _8p is the molding temperature [° С] should be as small as possible. In the framework of the present invention, it is desirable to reduce the viscosity by less than 0.12 dl / g, in particular less than 0.08 dl / g.

The homogeneity of the melt has a direct impact on the material properties of molded monofilaments. Therefore, for the homogenization of the melt, a fixed mixer is preferably advantageously used with at least one element mounted behind the spinning pump.

Dependent on the temperature of the molding temperature plate spinnere regulate through its so-called concomitant heating. As an accompanying heating, we consider, for example, a spinning beam heated by diphil or additional convection or radiation heaters. Typically, the temperature of the plate dies lies at the level of the molding temperature.

The temperature rise of the plate dies can be achieved by reducing the pressure in the spin pack. Well-known works, for example, K. Rszddep "Rogysptse η bet NegieeMipd νοη Rokeyeg-Kebspkogdagp. Syepiegakhet 21, p. 379 (1971), describes a temperature rise of about 4 ° C per 100 bar of pressure drop.

Further, the pressure in the die can be controlled through the use of bulk filter media, in particular steel sand with an average grain size of 0.10-1.2 mm, preferably 0.12-0.75 mm, and / or filter circles, which can be made from metal fabrics or canvas with fineness <40 microns.

In addition, the pressure drop in the die hole affects the total pressure. The pressure in the die is set mainly 80450 bar, in particular 100-250 bar.

Full stretching during the molding process is 1 _8p , i.e. the quotient of dividing the rate of acceptance by the rate of extrusion is calculated according to i8 5250245 using formula 2 for the density of the polymer or polymer mixture, the diameter of the die hole and the titre of a single monofilament.

Formula 2:

1 _8р = 2.25-10 ⁵ - (0-p) GO ² (cm) / brG (den), where δ is the melt density [g / cm ³ ]; for PTMT = 1.12 g / cm ³ ;

Ό - diameter of the die hole [cm]; brG - the title of a single monofilament [den].

In the framework of the present invention, the total stretching during the molding process is 70-500, preferably 100-250.

The ratio of the length to the diameter of the orifice of the spinneret is preferably chosen between 1.5-6, in particular 1.5-4.

Extruded monofilaments pass through the cooling delay zone. Directly under the spinneret set, it is made in the form of an elastic reduction zone in which the monofilaments emerging from the nozzles of the spinnerettes protect against direct exposure to the cooling gas and retard their drawing out or cooling. The active part of the elastic recovery is made in the form of displacement of the spunbond set inside the spinning beam, so that the monofilaments are surrounded by heated walls. The passive part is formed by insulating layers and unheated frames. The length of the active part is 0-100 mm, and the passive part is 20-120 mm, and the total length of 30-200 mm, mainly 30-120 mm, is observed.

As an alternative to active elastic recovery, a preheater can be placed under the spinning beam. Unlike active elastic recovery, this zone of cylindrical or rectangular section is then heated independently of the spinning beam.

In radial concentric filaments covering porous cooling systems, cooling delay can be achieved with cylinder-shaped caps.

Then the monofilament is cooled to temperatures below the temperature of their solidification. According to the invention, the solidification temperature means the temperature at which the melt goes into a solid state of aggregation.

In the framework of the present invention, it has proved particularly expedient to cool the threads to a temperature at which they generally cease to be sticky. Especially preferred is the cooling of monofilaments to temperatures below their crystallization temperature, in particular to temperatures below their glass transition temperature.

Funds for cooling monofilament specialist known from the prior art. According to the invention, the use of cooling gases, in particular cooled air, has especially proven itself. The cooling air has a temperature of preferably 12-35 ° C, in particular 16-26 ° C. The speed of the cooling air is preferably in the range of 0.20-0.55 m / s.

For cooling monofilaments, for example, single thread systems consisting of single perforated wall cooling tubes can be used. Due to the active supply of cooling air or also by using the self-suction effect of monofilaments, each single monofilament is cooled. As an alternative to single pipes, well-known cross flow systems can also be used.

A special implementation of the cooling and delay zones consists in supplying cooling air to monofilaments leaving the delay zone on a length of 10-175 cm, mainly on a length of 1080 cm. For monofilaments with a titer with winding <1.5 dtex each monofilament is particularly suitable for the length of the section in the range of 10-40 cm, and for monofilaments with a titer of 1.5-9.0 dtex of each monofilament - the length of the section in the range of 20-80 cm. Following this, the monofilament and the accompanying cooling air is directed through a reduced section of the channel, and at the expense of cont Proportion reduction calculation sections and sizes in the direction of the monofilament running set ratio of the air velocity and the thread at acceptance 0.2-20: 1, preferably 0.4-5: 1.

After cooling the filaments to temperatures below the solidification temperature, they are combined into one thread. The distance from the unification point to the bottom side of the dies can be determined according to the invention by means of real-time measurement of the speed and / or temperature of the thread, for example, using a TSI (Germany) laser Doppler anemometer or Goratech (Germany) infrared camera of type ной8 160. It is 5002500 mm, mainly 500-1800 mm. In this case, monofilaments with a titer of <3.5 dtex are combined mainly with a smaller distance <1500 mm, and thicker ones - mainly with a larger distance.

In the framework of the present invention, it is expedient that advantageously all surfaces that come into contact with the molded monofilaments are made of materials with a particularly low friction coefficient. Thus, the formation of bulges can be largely avoided, and higher quality monofilaments are obtained. Especially suitable for this purpose were the surface with the specification "Tribophil" company "Keramtek" (Germany).

The combination of monofilaments takes place in a sizing device, which feeds the right amount of spinning preparation to the thread. A particularly suitable sizing device is distinguished by an inlet part, a channel for the thread with an inlet for the sizing agent and an outlet part. The entrance part is funnel-shaped, which prevents the contact with still dry monofilaments. Contact monofilament occurs in the channel for the thread after the influx of the preparation. The channel for the thread and the inlet for the sizing are matched in width with the titer of the thread and the number of filaments. Especially proven holes and widths in the range of 1.0-4.0 mm. The output part of the sizing device is made in the form of an alignment section, containing mainly sizing tanks. Such sizing devices can be purchased from Keramtek (Germany) or Goulston (USA).

According to the invention, the uniformity of application of the lubricant can be of great importance. It can be determined, for example, using the Ross measuring device using the method described in SyateeGack / TechSchbitbite, 42./94, November 1992, p. 896. Mostly with this approach, the values of standard deviation of application of a lubricant less than 90 digits, in particular, less than 60 digits. According to the invention, the values of the standard deviation of the application of a sizing agent less than 45 digits, in particular less than 30 digits, are particularly preferred. At the same time, one standard deviation value of 90 and 45 digits corresponds approximately to a variation rate of 6.2% and 3.1%, respectively.

In the framework of the present invention, it has become particularly preferable to make pipelines and pumps self-ejecting in order to avoid the formation of gas bubbles, since they can lead to significant fluctuations in the application of a lubricant.

According to the invention, it is especially preferred to prevent tangling before winding the yarn. At the same time, dies with closed channels turned out to be particularly suitable, since in such systems weaves of the thread in the slotted slot are prevented even with low thread tension and high air pressure. To prevent tangling of filaments, the spinnerets are preferably placed between the disks, and the output tension of the thread is controlled by different speeds of the input and output disks. It should not exceed 0.20 cN / dtex and preferably have values of 0.05-0.15 cN / dtex. The air pressure to prevent tangling of the thread is 0.5-5.5 bar, and at winding speeds up to 3500 m / min - a maximum of 3.0 bar.

It is preferable to set the number of nodes to be at least 10 η / m. Of particular interest are the maximum hole lengths of less than 100 cm and the values of the coefficient of change in the number of nodes below 100%. When using air pressures above 1.0 bar, the number of knots> 15 η / m, characterized by high uniformity, is preferred, with a change rate of less than or equal to 70%, and a maximum length of holes is 50 cm. In practice, PL systems "Temko" (Germany), a double system of the company "Slack & Parr" (USA) or dies of the type "Polydzhet" by the company Heberlein.

The peripheral speed of the first disk unit is called the speed of acceptance. Other disk systems may be used before the thread in the winding unit is wound on sleeves in packages.

Stable, defect-free packings of yarns are the main prerequisite for defect-free acceptance of the yarn and further processing as flawless as possible. Therefore, in the framework of the present method, the tension of the thread is used when winding in the range of 0.025-0.15 cN / dtex, preferably in the range of 0.03-0.08 cN / dtex.

An important parameter of the method according to the invention is the establishment of the thread tension in front of the receiving discs and between them. As is well known, this tension is composed mainly of its own orientation tension according to Napap, the frictional tension on the yarn feeders and in the sizing device, as well as the filament-air frictional tension. In the framework of the present invention, the tension of the thread before the receiving disks and between them lies in the range of 0.05-0.20 cN / dtex, preferably in the range of 0.080.15 cN / dtex.

Too low a tension of less than 0.05 cN / dtex does not give the desired degree of pre-orientation. If the tension exceeds 0.20 cN / dtex, then this tension during winding and holding of the packages causes a memory effect, which leads to a deterioration of the parameters of the thread.

According to the invention, the tension is controlled by the distance of the sizing device to the die, the friction surfaces and the length of the segment between the sizing device and the receiving disk. The length of this segment is preferably not more than 6.0 m, preferably less than 2.0 m, and the forming and receiving machines due to the parallel structure are arranged to provide a straight course of the thread.

At the expense of the geometrical parameters also describe the conditioning time of the thread between the point of unification and winding. Rapid relaxation during this time affects the quality of the package structure. The predominantly determined conditioning time is 50–200 ms.

The winding speed of the pre-oriented thread is according to the invention 2200-3500 m / min.

The preferred method in the implementation of the method around the package set temperature <45 ° C, in particular 12-35 ° C, and a relative humidity of 40-85%. The aging packages pre-oriented thread until further processing is carried out preferably at a temperature <45 ° C. Further, it is advisable to withstand packages of pre-oriented yarn before further processing for at least 4 hours at 12-35 ° C and a relative humidity of 40-85%.

Monofilament according to the invention has after 4 weeks of exposure in normal conditions

a) tensile elongation of 90-165%, preferably 90-135%;

b) shrinkage in boiling water of at least 30%, preferably> 40%;

c) normal unevenness according to Uster is less than 1.1%, preferably less than 0.9%;

d) double refraction 0,030-0,058;

e) a density of less than 1.35 g / cm ³ , preferably less than 1.33 g / cm ³ ;

e) breaking load variation coefficient <4.5%, preferably <2.5%;

g) the rate of change of tensile elongation <4.5%, preferably <2.5%.

In this case, the concept of “normal conditions” is known to a specialist and is defined by the standard ΌΙΝ 53802. In “normal conditions”, according to ΌΙΝ 53802, the temperature is 20 ± 2 ° С, and the relative humidity is 65 ± 2%.

In the framework of the present invention, in addition, a particular advantage is that the shrinkage in boiling water, measured directly after winding, is 50-65%, and after 4 weeks of aging in normal conditions - at least 30%, preferably> 40 % In an unexpected way, it turned out that the pre-oriented yarn packages that were made are perfectly processed further.

It should be noted that in practice, normal climatic conditions in the manufacture, holding or transporting a pre-oriented thread may not always be met. A lowcrystalline yarn often has the problem of changing the shape of the package of a pre-oriented yarn, stretching speed and / or texturing speed has to be reduced, and with further processing more and more gaps appear. Threads that follow the above specifications of shrinkage in boiling water are less likely to have similar problems compared to conventional threads.

In addition, it turns out that the preferred yarns according to the invention, even after holding for 2 months, have no change in the depth of dyeing of the textured yarns. After exposure for 20 months, the color change is within 95 ± 3%, as long as the ambient temperature does not exceed 45 ° C.

Further, preferred monofilaments have a natural draw ratio of greater than or equal to 15%. Particularly preferably, this value lies in the range of 18-65%. The higher the natural draw ratio, the better the stretchability. With equal elongation at a high natural stretch ratio, a higher stretch ratio is achieved.

The natural stretch ratio is defined as a flat segment in percent in the load-elongation diagram. This value is known, and it is determined on a discontinuous device in one operation in determining strength and elongation.

FIG. 2a and 2b schematically depict the indicated parameters of the natural extraction ratio (Ννν), with the natural extraction ratio in FIG. 2b is zero. The diagrams are applied force depending on the elongation, and schematic diagrams are depicted for a more detailed explanation of the parameters.

It is assumed that the natural stretch ratio is a measure of the orientation of the thread, and the value NVV <15% describes the beginning crystallization of the polyester. Low values of Ννν are obtained, for example, by heat treating the yarn up to winding with temperatures lying above the glass transition temperature of the polyester.

Methods for determining the specified material parameters are well known to the skilled person. They can be gleaned from the literature. Although most of the parameters can be defined in different ways, the following methods for determining monofilament parameters turned out to be expedient in the framework of the present invention.

Own viscosity is measured in the capillary viscometer of the company “Ubbelode” at 25 ° C and is calculated by the known formula. A mixture of phenol and 1,2-dichlorobenzene in a mass ratio of 3: 2 is used as a solvent. The concentration of the solution is 0.5 g of polyester per 100 ml of solution.

To determine the melting point, crystallization temperature, and glass transition temperature, a Mettler calorimeter is used for differential scanning calorimetry. In this case, the sample is first heated to 280 ° C and melted, and then cooled rapidly. Measurement using differential scanning calorimetry is carried out in the range of 20,280 ° C with a heating rate of 10 K / min. The temperature is determined by the processor.

The determination of the density of monofilaments is carried out in a gradient tube at a temperature of 23 ± 0.1 ° C. As reagent used pheptan (C ₇ H ₁₆ ) and carbon tetrachloride (CC1 ₄ ). The result of the density measurement can be used to calculate the degree of crystallinity due to the fact that the basis is the density B, amorphous polyester and density B _{to the} crystalline polyester. The corresponding calculation is known from the literature, for example, for PTMT, it is true that B _a = 1.295 g / cm ³ and B _c = 1.429 g / cm ³ .

The titer is determined in a known manner using a precision reel and weighing device. In this case, pre-tensioning is advisable for pre-oriented monofilaments of 0.05 cN / dtex, and for a textured yarn - 0.2 cN / dtex.

Tensile strength and tensile elongation are determined using the Statimat measuring device under the following conditions: the clip length is 200 mm for the pre-oriented thread and 500 mm for the textured thread, the measurement speed is 2000 mm / min for the pre-oriented thread and 1500 mm / min for textured yarn, the pre-tension is 0.05 cN / dtex for the pre-oriented yarn and 0.2 cN / dtex for the textured yarn. By dividing the values of the maximum breaking load by the titer, the breaking strength is determined, and the breaking elongation is estimated at maximum load.

To determine shrinkage in boiling water, monofilament harnesses without tension are treated in water at 95 ± 1 ° С for 10 ± 1 min. The harnesses are made with a reel with a pre-tension of 0.05 cN / dtex for a pre-oriented yarn and 0.2 cN / dtex for a textured yarn, and the length of the harnesses is measured before and after the temperature treatment at 0.2 cN / dtex. From the difference in length in a known manner, shrinkage in boiling water is calculated.

The definition of double refraction is carried out by the method described in BU 19519898. Therefore, in this connection, the content disclosed in BU 19519898 should be explicitly referred to.

The crimp parameters of textured monofilaments are measured at βΙΝ 53840, part 1, using a “Texturmat” instrument from Stein (Germany) at a spin temperature of 120 ° C.

The normal irregularity values according to Uster are determined using a 4-CX tester and are indicated in%. At the same time, with a test speed of 100 m / min, the test time is 2.5 minutes.

Pre-oriented monofilament according to the invention can be simply subjected to further processing, in particular texturing in the drawing process. In the framework of the present invention, texturing in the drawing process takes place preferably at a texturing speed of at least 500 m / min, particularly preferably at least 700 m / min. The multiplicity of extraction is mainly at least 1: 1.35, in particular at least 1: 1.40. At the same time, texturing in the process of drawing on a high-temperature heating type machine, for example, the LEK machine from Barmag, turned out to be particularly expedient.

Bulk monofilaments made in this way have a small number of bulges and, after dyeing in boiling water at 95 ° C with a dispersion dye (dark blue Terrasil) without a carrier, have an excellent depth and uniformity of color.

The bulk 8ET monofilaments made according to the invention have predominantly tensile strength in excess of 26 cN / tex, and the tensile elongation is over 36%. For bulk non-monofilaments, obtained without the use of temperature in the second heater, the tensile strength is over 26 cN / tex, and the tensile strength is over 30%.

The bulk and elasticity of the monofilaments according to the invention are excellent.

Below the invention is explained in more detail by examples, not limited to them.

Examples 1 and 2.

Molding and winding

PTMT-crumb with intrinsic viscosity of 0.93 dl / g, melt viscosity 325 Pa-s (measured at 2.4 Hz and 225 ° C), melting point 227 ° C, crystallization temperature 72 ° C and glass transition temperature 45 ° C were dried at a temperature of 130 ° C in a "drunk barrel" dryer to a moisture content of 11 ppm. The crumb was melted in a 3E4 extruder manufactured by Barmag, so that the melt temperature was 225 ° C. The melt was then fed to a spinning pump through a product line, which contained a fixed mixer of the Sulzer company of type 8МХ with 15 elements and an inner diameter of 15 mm. The amount of melt transported was 63 g / min with a residence time of 6 minutes, the amount supplied by the spinning pump to the spinneret set was 30.7 g / min. After the spinning pump, before entering the die set, one element of static mixers of the type NI-C8E from the company Fluitec was installed with an internal diameter of 10 mm. The accompanying heating of the product pipeline and the spinning unit containing the pump and the die set was set to a temperature of 255 ° C. The die set contained steel sand with a grain size of 350–500 microns, a height of 30 mm, and a nonwoven 20 micron filter and a woven 40 micron filter as filter media. The melt was extruded through a plate die plate with a diameter of 80 mm with 34 holes with a diameter of 0.25 mm and a length of 1.0 mm.

The die pressure was 120 bar.

The cooling delay zone had a length of 100 mm, with 30 mm on the heated wall, and 70 mm on the insulation and the unheated frame. The melt filaments were then cooled in a blower shaft with a transverse blower with a length of 1500 mm. The cooling air had a speed of 0.35 m / s, a temperature of 18 ° C and a relative humidity of 80%. The solidification point of the monofilaments lay at a distance of 800 mm under the spinneret.

Using a sizing device at a distance of 1050 mm from the spinneretter, the threads were supplied with a spinning preparation and combined. The sizing device was made with the surface "Tribophil" and had a supply hole with a diameter of 1 mm. The amount of preparation applied was 0.40% relative to the weight of the yarn.

The combined thread was then supplied to the coiler. The distance between the sizing device and the first receiving disk was 3.2 m. The conditioning time was 144 and 168 ms, depending on the speed. A pair of discs twisted 8 thread. A Temko nozzle was installed between the discs to prevent tangling of the threads, which was operated with an air pressure of 1.5 bar. In accordance with the set speed, the winding speed of the winding type 8 \ Y6 of the firm “Barmag” was set so that the thread tension during winding was 5 cN. The climate in the room was set at 24 ° C with a relative humidity of 60%, so that around 34 ° C the temperature around the nitrile was established.

In the framework of these experiments, the acceptance rate was either 2,940 m / min (example 1) or 2506 m / min (example 2). In tab. 1 shows the other parameters of the experiments, and table. 2 - material properties of the obtained, pre-oriented monofilaments. Using the parameters listed in both tables, we were able to make packages with a mass of 10 kg and easily remove them from the winder mandrel.

Table 1

Experiment Parameters

Experiment Parameters Example 1 Example 2 Acceptance rate, m / min 2940 2506 Winding speed, m / min 2926 2500 Full stretch during molding 178 152 Thread tension: Before disks ¹ , SN 14 ten Between discs ¹ max., CH eleven 7.5 Before disks ² , СН / dtex 0.13 0.08 Between disks ² max., CH / dtex 0.10 0.06 Thread tension during winding ¹ , cN 5.0 5.0 Thread tension during winding ² , cN / dtex 0.048 0.041

¹ : absolute value ² : relative to titer

table 2

Material properties of pre-oriented PTMT monofilaments ¹

Material properties Example 1 Example 2 Titer, dtex 105 123 Tensile strength, SN / Tex 23.4 20.7 Explosive elongation,% 98 127 Normal unevenness by Uster,% 0.9 0.76 Shrinkage in boiling water,% 46 33 Double refraction 10 ³ , Δη 52 43 Density, g / cm ³ 1,320 1,318 SU-breaking load,% 2.2 1.9 SU-rupture elongation,% 2.2 1.9

SU: change coefficient ¹ : measured after 4 weeks of exposure in normal conditions

Texturing while pulling

PTMT monofilament packs were kept for 4 weeks under normal climatic conditions, according to 80 53802, and then installed on a texturing machine in the process of drawing by Barmag, type PK6-8. The parameters of the experiments when texturing in the process of extrusion for the manufacture of so-called 8ET monofilaments are given in table. 3, and the material properties of the obtained bulk 8ET monofilaments - in Table. four.

Texturing defects were recorded using the Barmag instrument, ΝΠΈΝΝΠΈΝδ, with the following set limit values: РР / ЛР = 3,0 сН, иМ / ЬМ = 6.0 сН.

Table 3 The parameters of the experiments when texturing in the process of extrusion

Experiment Parameters Example 1 Example 2 Speed, m / min 700 700 The draw ratio 1: 1.48 1: 1.65 Ώ / Υ ratio 2.1 2.1 Heater temperature 1 ° C 155 155 Heater temperature 2 ° C 160 160 Defect texturing, η / 10 km 0 0 Thread tension G ¹ , before the unit, CH 20 20 G ² , after the unit, CH nineteen 18 G ² -SU,% 1.2 1,3

G ² -SU: coefficient of change G ²

Table 4

Material properties of monofilaments, subjected to texturing in the process of extrusion

Material properties Example 1 Example 2 Titer, dtex 78 82 Tensile strength, SN / Tex 27.7 29.0 Explosive elongation,% 39.4 39.9 Visual assessment of color uniform uniform Resistance to tortuosity,% 85 87 Degree of tortuosity,% 24.5 25

Due to the cold mode of the 2nd heater, i.e. due to the manufacture of so-called NOT monofilaments, the volume can be varied. The degree of tortuosity then increases to about 47%. The values of breaking elongation then fall to 33%.

Claims (8)

CLAIM 1. A method of manufacturing and winding pre-oriented polyester monofilaments consisting of at least 90 wt.% Of the total weight of polyester monofilament of polybutylene terephthalate (PBT) and / or polytrimethylene terephthalate (PTMT), preferably PTMT, characterized in that a) full stretching during molding is set in the range of 70-500; b) the monofilament immediately after leaving the die passes through a cooling delay zone 30–200 mm long; c) monofilament is cooled below the solidification temperature; d) monofilaments are combined at a distance of 500-2500 mm from the bottom of the die; d) the thread tension in front of the receiving discs and between them is set from 0.05 to 0.20 cN / dtex; f) the thread is wound with a tension of 0.0250.15 cN / dtex; g) the winding speed is set at 22003500 m / min. 2. The method according to claim 1, characterized in that they use PBT and / or PTMT with a limit number of viscosity in the range of 0.7-0.95 dl / g 3. The method according to claim 1 or 2, characterized in that when winding in the environment of the package set the temperature <45 ° C. 4. The method according to one of the preceding paragraphs, characterized in that the packages of pre-oriented monofilament are kept before further processing for at least 4 hours at 12-35 ° C and a relative humidity of 40-85%. 5. Pre-oriented polyester monofilament obtained by the method according to one of the preceding paragraphs, characterized in that after 4 weeks of exposure under normal conditions according to ΌΙΝ 53802 it has a) a tensile elongation of 90-165%; b) shrinkage in boiling water of at least 30%; c) the normal roughness according to Uster is less than 1.1%; d) double refraction 0.030-0.058; d) a density of less than 1.35 g / cm ³ , preferably less than 1.33 g / cm; f) breaking load change factor <4.5%; g) the coefficient of change in tensile elongation <4.5%. 6. A method of manufacturing bulk polyester monofilaments by processing the monofilament according to claim 5 in a texturing machine during drawing at a speed of at least 500 m / min and a draw ratio of at least 1: 1.35 into a bulk thread. 7. Bulk polyester 8ET monofilaments obtained by the method according to claim 6 and characterized in that their tensile strength is more than 26 cN / dtex and the tensile elongation is more than 36%. 8. Bulk polyester HE monofilaments obtained by the method according to claim 6 and characterized in that their tensile strength is more than 26 cN / tex and the tensile elongation is more than 30%.