EP1330563A1 - Verfahren zum spinnen und aufspulen von polyester-filamenten, durch das spinn-verfahren erhältliche polyester-filamente, strecktexturierung der polyester-filamente sowie durch die strecktexturierung erhältliche bauschige polyester-filamente - Google Patents
Verfahren zum spinnen und aufspulen von polyester-filamenten, durch das spinn-verfahren erhältliche polyester-filamente, strecktexturierung der polyester-filamente sowie durch die strecktexturierung erhältliche bauschige polyester-filamenteInfo
- Publication number
- EP1330563A1 EP1330563A1 EP01992806A EP01992806A EP1330563A1 EP 1330563 A1 EP1330563 A1 EP 1330563A1 EP 01992806 A EP01992806 A EP 01992806A EP 01992806 A EP01992806 A EP 01992806A EP 1330563 A1 EP1330563 A1 EP 1330563A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- filaments
- polyester
- winding
- thread
- ptmt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
Definitions
- the present invention relates to ner drives for spinning and winding up pre-oriented polyester filaments which consist of at least 90% by weight, based on the total weight of the polyester filament, of polybutylene terephthalate (PBT) and / or polytrimethylene terephthalate (PTMT), preferably of PTMT. and the pre-oriented polyester filaments obtainable by the process. Furthermore, the present invention also relates to processes for stretch texturing of the spun and wound polyester filaments and the bulky polyester filaments obtainable by stretch texturing.
- PBT polybutylene terephthalate
- PTMT polytrimethylene terephthalate
- polyester filaments in particular of polyethylene terephthalate (PET) filaments
- PET polyethylene terephthalate
- PET or PTMT filaments age more when stored. Structural hardening occurs, which leads to such a sharp decrease in the shrinkage that recrystallization can be demonstrated.
- PBT or PTMT filaments are only of limited suitability for further processing, they lead to errors in the stretch texturing and to a significant reduction in the tensile strength of the textured yarn. The result is a reduction in the texturing speed or the stretching ratio.
- These differences between PET and PBT or PTMT can be attributed to structure and property differences, such as those described in Chemical Fibers Int., P. 53, vol. 50 (2000) and topic on the 39th Int. Manmade Fiber Congress in Dornbirn from September 13th to 15th. It is assumed that different chain formations are responsible for the property differences.
- WO 99/27168 discloses a polyester fiber which consists of at least 90% by weight of polytrimethylene terephthalate and has a boiling shrinkage of between 5% and 16% and an elongation at break of 20% to 60%.
- the polyester fiber described in WO 99/27168 is produced by spinning and drawing. Spinning take-off speeds of up to 2100 m / min are specified. The process is uneconomical due to the low spinning speed.
- the polyester fibers obtained are, as the key figures indicated, highly crystalline and therefore only of limited suitability for stretch texturing processes.
- European patent EP 0.731.196 B1 claims a process for spinning, drawing and winding a synthetic thread, in which the thread is subjected to a heat treatment after stretching and before winding to reduce the tendency to shrink.
- Usable synthetic fibers also include polytrimethylene terephthalate fibers.
- the heat treatment takes place in that the synthetic thread is guided in close proximity but essentially without contact along an elongated heating surface. The use of heat treatment makes the process more expensive and also provides synthetic threads with high crystallinity, which are only of limited suitability for stretch texturing processes.
- the tensile strength of the polytrimethylene terephthalate fibers is 26.5 cN / tex (texturing speed of 450 m / min) or 29.15 cN / tex (texturing speed of 850 m / min) and the elongation at break is 38.0% (texturing speed of 450 m / min) or 33.5% (texturing speed of 850 m / min).
- FIG. 1 describes the change in the cooking shrinkage for three PTMT-POY coils as a function of the storage time under normal climate conditions.
- the change in POY cooking shrinkage for three coils with different initial values over the storage period under normal climatic conditions was examined. Coils no. 16 and 17 with a high initial value> 40% show a boiling shrinkage above 30%, preferably above 40% after 4 weeks. If, however, the initial value of the cooking shrinkage is less than 40%, the coil 18 shows that, after 4 weeks of storage, it falls below the critical value of 30%.
- NW natural draw ratio
- Cook shrinkage is a measure of the processability and degree of crystallization of the fibers.
- the fibers described in WO 01/04393 have plastics with a higher degree of crystallization, which are much worse to process and can only be processed at a lower stretching ratio and / or lower texturing speed.
- pre-oriented polyester filaments which consist of at least 90% by weight> based on the total weight of the filaments of PBT and / or PTMT
- the pre-oriented polyester filaments should have elongation at break values in the range from 90% to 165%, high uniformity with regard to the filament characteristics and a low degree of crystallization.
- Another object of the present invention was to provide a method for spinning and winding up pre-oriented polyester filaments which can be carried out on an industrial scale and at low cost.
- the method according to the invention should allow the highest possible take-off speeds, preferably greater than 2200 m / min and high thread weights on the bobbin of more than 4 kg.
- a pressing together of the bobbin during storage, in particular a shrinking of the winding body on the winding mandrel and the formation of a saddle with hard edges and a run-in middle part should be prevented as far as possible, so that no run-off problems occur when processing the bobbins.
- the preoriented polyester filaments should be able to be processed in a simple manner in a drawing or drawing texturing process, in particular at high texturing speeds, preferably greater than 450 m / min.
- the filaments obtainable by stretch texturing should have excellent material properties, e.g. B. a high tensile strength of more than 26 cN / tex and a high elongation at break of more than 30% for HE filaments or more than 36% for SET filaments.
- a) the spinning delay is set in the range 70 to 500, b) the filaments pass through a cooling delay zone of 30 mm to 200 mm in length immediately after emerging from the spinneret, c) the filaments are cooled below the solidification temperature, d) the filaments are bundled at a distance between 500 mm and 2500 mm from the underside of the nozzle, e) the thread tension before and between the take-off godets is set between 0.05 cN / dtex to 0.20 cN / dtex, preferably up to 0.15 cN / dtex, f) the thread with a thread tension between 0.025 cN /
- the method according to the invention has a number of further advantages. These include:
- the method according to the invention can be carried out in a simple manner, on an industrial scale and inexpensively.
- the method allows spinning and winding at high take-off speeds of at least 2200 m / min and the production of high thread weights on the bobbin of more than 4 kg.
- polyester filaments can be obtained particularly inexpensively.
- * > The pre-oriented polyester filaments obtainable by the process can thus be processed in a simple manner, on an industrial scale and inexpensively in a drawing or drawing texturing process. The texturing can take place at speeds greater than 450 m / min.
- the filaments obtainable by stretch texturing have a high tear strength of more than 26 cN / tex and a high elongation at break of more than 30% for HE filaments and more than 36% for SET filaments.
- the present invention relates to a method for producing and winding up pre-oriented polyester filaments which consist of at least 90% by weight, based on the total weight of the filament, of polybutylene terephthalate (PBT) and / or polytrimethylene terephthalate (PTMT).
- PBT polybutylene terephthalate
- PTMT polytrimethylene terephthalate
- Polybutylene terephthalate can be obtained by polycondensation of terephthalic acid with equimolar amounts of 1,4-butanediol, polytrimethylene terephthalate by polycondensation of terephthalic acid with equimolar amounts of 1,3-propanediol. Mixtures of the two polyesters are also conceivable. PTMT is preferred according to the invention.
- the polyesters can be both homopolymers and copolymers.
- Particularly suitable copolymers are those which, in addition to recurring PTMT and / or PBT units up to 15 mol% based on all repeating units of the polyester repeating units of conventional comonomers, such as. B. ethylene glycol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, isophthalic acid and / or adipic acid.
- polyester homopolymers are preferred in the context of the present invention.
- the polyesters according to the invention can contain customary amounts of other additives, such as catalysts, stabilizers, antistatic agents, antioxidants, flame retardants, dyes, dye absorption modifiers, light stabilizers, organic phosphites, optical brighteners and matting agents.
- additives such as catalysts, stabilizers, antistatic agents, antioxidants, flame retardants, dyes, dye absorption modifiers, light stabilizers, organic phosphites, optical brighteners and matting agents.
- the polyesters preferably contain 0 to 5% by weight, based on the total weight of the filament, of additives.
- the polyesters can also contain a small proportion, preferably up to 0.5% by weight, based on the total weight of the filament, of branching components.
- the branching components preferred according to the invention include, inter alia, polyfunctional acids, such as trimellitic acid, pyromellitic acid, or tri- to hexavalent alcohols, such as trimethylolpropane, pentaerythritol, dipentaerythritol, glycerol, or corresponding hydroxy acids.
- polyesters which can be used in the context of the invention are preferably thermoplastic and can be spun into filaments and wound up. Those polyesters which have an intrinsic viscosity in the range from 0.70 dl / g to 0.95 dl / g are particularly advantageous.
- a melt or melt mixture of the polyester is produced by means of spinning pumps at a constant speed, the speed being set according to the known formula so that the desired thread titer is obtained, pressed into die packs and extruded through the die holes of the die plate of the pack to form molten filaments.
- the melt can be produced, for example, from polymer chips in an extruder, it being particularly advantageous to dry the chips beforehand to a water content ⁇ 30 ppm, in particular to a water content ⁇ 15 ppm.
- the temperature of the melt which is commonly referred to as the spinning temperature and is measured in front of the spinning pump, depends on the melting point of the polymer or polymer mixture used. It is preferably in the range given by Formula 1:
- T Sp spinning temperature [° C].
- the specified parameters serve to limit the hydrolytic and / or thermal viscosity reduction, which should expediently be as low as possible.
- the homogeneity of the melt has a direct influence on the material properties of the spun filaments.
- a static mixer with at least one element, which is installed after the spinning pump, is therefore preferably used to homogenize the melt.
- the temperature of the nozzle plate which is dependent on the spinning temperature, is regulated by its so-called trace heating.
- trace heating come, for example, a spinning beam heated with "Diphyl” or additional ones Convection or radiant heater in question.
- the temperature of the nozzle plates is usually at the level of the spinning temperature.
- a temperature increase on the nozzle plate can be achieved through the pressure drop in the nozzle package.
- Known derivations such as, for example, K. Riggert "Advances in the Production of Polyester Tire Cord Yarn” Chemical fibers 21, page 379 (1971), describe a temperature increase of approximately 4 ° C. per 100 bar pressure drop.
- nozzle pressure by using loose filter media, in particular steel sand with an average grain size between 0.10 mm and 1.2 mm, preferably between 0.12 mm and 0.75 mm and / or filter discs made of metal mesh or nonwovens with a fineness of ⁇ 40 ⁇ can be produced.
- loose filter media in particular steel sand with an average grain size between 0.10 mm and 1.2 mm, preferably between 0.12 mm and 0.75 mm and / or filter discs made of metal mesh or nonwovens with a fineness of ⁇ 40 ⁇ can be produced.
- the pressure drop in the nozzle hole contributes to the total pressure.
- the nozzle pressure is preferably set between 80 bar and 450 bar, in particular between 100 bar and 250 bar.
- the spinning draft i Sp ie the quotient of the take-off speed and the spraying speed, is calculated according to US Pat. No. 5,250,245 using Formula 2 with the density of the polymer or the polymer mixture, the nozzle hole diameter and the titer of the single filament:
- the spinning delay is between 70 and 500, preferably between 100 and 250.
- the length-to-diameter ratio of the nozzle hole is preferably chosen between 1.5 and 6, in particular between 1.5 and 4.
- the extruded filaments pass through a cooling delay zone. Directly below the nozzle package, this is designed as a recess zone, in which the filaments emerging from the nozzle holes are protected from the direct action of the cooling gas and are delayed in delay or cooling.
- An active part of the recess is designed as an offset of the nozzle package into the spinning beam, so that the filaments are surrounded by heated walls.
- a passive part is formed by insulation layers and unheated frames. The lengths of the active recess are between 0 and 100 mm, those of the passive part between 20 and 120 mm, with a total length of 30-200 mm, preferably 30-120 mm being maintained.
- a reheater can be installed below the spinning beam.
- this zone with a cylindrical or rectangular cross section then has at least one heating independent of the spinning beam.
- the cooling delay can be achieved with the aid of cylindrical covers.
- the filaments are then cooled to temperatures below their solidification temperature.
- the solidification temperature denotes the temperature at which the melt changes to the solid state.
- it has proven particularly expedient to cool the filaments to a temperature at which they are essentially no longer sticky. It is particularly advantageous to cool the filaments to temperatures below their crystallization temperature, in particular to temperatures below their glass transition temperature.
- Means for cooling the filaments are known to the person skilled in the art from the prior art.
- the use of cooling gases, in particular cooled air, has proven particularly useful according to the invention.
- the cooling air preferably has a temperature of 12 ° C. to 35 ° C., in particular 16 ° C. to 26 ° C.
- the speed of the cooling air is advantageously in the range from 0.20 m / sec to 0.55 m / sec.
- single thread systems can be used which consist of individual cooling tubes with a perforated wall.
- a cooling of each individual filament is achieved by active cooling air supply or also by using the self-suction effect of the filaments.
- the known cross-flow blowing systems can also be used.
- a special embodiment of the cooling and warping area is to supply the filaments emerging from the delay zone in a zone of length in the range from 10 to 175 cm, preferably in a zone of length in the range of 10 to 80 cm, of cooling air.
- the filaments and the air accompanying them are passed together through a reduced-cross-section channel, with control of the cross-sectional taper and the dimensioning in the thread running direction Ratio of the air to the thread speed when pulling from 0.2 to 20: 1, preferably 0.4 to 5: 1, is set.
- the distance of the bundling from the underside of the nozzle which is suitable according to the invention can be determined by methods known to the person skilled in the art for online measurement of the thread speed and / or thread temperature, for example using a laser Doppler anemometer from TSI / D or an infrared camera from Goratec / D Type IRRIS 160. It is 500 to 2500 mm, preferably 500 to 1800 mm. Filaments with a titer ⁇ 3.5 dtex are preferably bundled at a smaller distance ⁇ 1500 mm, thicker filaments preferably at a larger distance.
- the filaments are bundled in an oiling stone, which feeds the desired amount of spin finish evenly to the thread.
- a particularly suitable oil stone is characterized by an inlet part, the thread channel with an oil inlet opening and the outlet part.
- the inlet part is widened in a funnel shape, so that contact through the still dry filaments is avoided.
- the point of impact of the filaments takes place within the thread channel after the inflow of the preparation.
- the width of the thread channel and oil inlet opening is adapted to the thread titer and the number of filaments. Openings and widths in the range from 1.0 mm to 4.0 mm have proven particularly successful.
- the outlet part of the oiler is designed as an equalization section, which preferably has oil reservoirs. Such oilers can be obtained, for example, from Cermatec / D or Goulston / USA.
- the uniformity of the oil application can be of great importance according to the invention. It can be determined, for example, with a Rossa measuring device according to the method described in chemical fibers / textile industry, 42794, Nov. 1992 on page 896. With such a procedure, values for the standard deviation of the oil application of less than 90 digits, in particular less than 60 digits, are preferably obtained. According to the invention, values for the standard deviation of the oil application of less than 45 digits, in particular of less than 30 digits, are particularly preferred. A value for the standard deviation of 90 digits or 45 digits corresponds to approximately 6.2% or 3.1% of the coefficient of variation.
- nozzles with closed yarn channels have proven to be particularly suitable, since in such systems the thread is prevented from getting caught in the insertion slot even with low thread tension and high air pressure.
- the entangling nozzles are preferably arranged between godets, the exit thread tension being regulated by means of different speeds of the inlet and outlet godets. It should not exceed 0.20 cN / dtex and should primarily have values between 0.05 cN / dtex and 0.15 cN / dtex.
- the air pressure of the entangling air is between 0.5 and 5.5 bar, with winding speeds up to 3500 m / min at a maximum of 3.0 bar.
- Node numbers of at least 10 nm are preferably set. Maximum opening lengths of less than 100 cm and values for the coefficient of variation of the number of nodes below 100% are of particular interest. When using air pressures above 1.0 bar, node numbers> 15 n / m are advantageously achieved, which are characterized by a high degree of uniformity, the coefficient of variation being less than or equal to 70% and the maximum opening length being 50 cm.
- systems of the type LD from Temco / D, the double system from Slack & Parr / USA, or nozzles of the type Polyjet from Heberlein have proven to be particularly suitable.
- the peripheral speed of the first godet unit is referred to as the take-off speed.
- Additional godet systems can be used before the thread in the winder assembly is wound into bobbins (bobbins) on cores.
- Stable, error-free thread packages are a basic prerequisite for error-free thread withdrawal and for error-free further processing. Therefore, a winding tension in the range of 0.025 cN / dtex - 0.15 cN / dtex, preferably in the range of 0.03 cN / dtex - 0.08 cN / dtex, is used in the context of the present method.
- an important parameter of the method according to the invention is the setting of the thread tension before and between the take-off godets.
- this tension essentially consists of the actual orientation tension according to Hamana, the friction tension on the thread guides and the oiler and the thread-air friction tension.
- the thread tension before and between the take-off godets is in the range from 0.05 cN / dtex to 0.20 cN / dtex, preferably between 0.08 cN / dtex and 0.15 cN / dtex.
- a too low tension below 0.05 cN / dtex no longer results in the desired degree of pre-orientation. If the tension exceeds 0.20 cN / dtex, this tension triggers a memory effect when winding and storing the bobbins, which leads to a deterioration of the thread characteristics.
- the tension is regulated by the oiler distance from the nozzle, the friction surfaces and the length of the distance between the oiler and the discharge godet.
- This line length is advantageously not more than 6.0 m, preferably less than 2.0 m, the spinning mill and the take-off machine being arranged by means of a parallel construction in such a way that straight thread running is ensured.
- the conditioning parameters of the thread between the bundling point and the winding are also described by the geometric parameters.
- the rapid relaxation during this time influences the quality of the coil structure.
- the conditioning time defined in this way is preferably chosen between 50 and 200 ms.
- the winding speed of the POY is between 2200 m / min and 3500 m / min.
- a temperature ⁇ 45 ° C., in particular between 12 and 35 ° C., and a relative humidity of 40-85% is set in the vicinity of the thread winding during the implementation of the method according to the invention.
- the POY is preferably stored until further processing at a temperature ⁇ 45 ° C. Furthermore, it is advisable to store the POY coils at least 4 hours at 12 to 35 ° C and a relative humidity of 40-85% before further processing.
- the filament according to the invention has a) an elongation at break between 90 and 165%>, preferably between 90 and 135% b) a boiling shrinkage of at least 30%, preferably> 40%, c) a normal uster below 1 , 1%>, preferably less than 0.9%, d) a birefringence between 0.030 and 0.058, e) a density less than 1.35 g / cm 3 , preferably less than 1.33 g / cm 3 , f) a variation coefficient of the breaking load ⁇ 4.5%, preferably ⁇ 2.5% and g) a coefficient of variation of the elongation at break ⁇ 4.5%, preferably ⁇ 2.5%.
- normal conditions is known to the person skilled in the art and is defined by the DIN 53802 standard. Under “normal conditions” according to DIN 53802, the temperature is 20 + 2 ° C and the relative humidity is 65 ⁇ 2%.
- the cooking shrinkage measured directly after winding, is between 50 and 65% and after 4 weeks of storage under normal conditions is at least 30%, preferably> 40%.
- the cooking shrinkage measured directly after winding, is between 50 and 65% and after 4 weeks of storage under normal conditions is at least 30%, preferably> 40%.
- preferred yarns of the present invention do not have any changed dyeing depth of the DTY even after a storage time of 2 months. After a storage period of 20 months, the color change is within 95 ⁇ 3% as long as the ambient temperature is not greater than 45 ° C.
- preferred filaments have a natural draw ratio greater than or equal to 15%. This size is particularly preferably in the range from 18 to 65%. The higher the natural stretch ratio, the better the stretchability. With the same elongation, a higher draw ratio is achieved with a high natural draw ratio.
- the natural stretch ratio is defined as the plateau section in percent of the force-strain diagram. This size is known and is determined on the ripper in one operation when determining strength and elongation.
- FIGS. 2 a) and 2 b) schematically show the specified parameter of the natural draw ratio (NW), the natural draw ratio in FIG. 2 b) being zero.
- NW natural draw ratio
- the force against the elongation is plotted in each of the diagrams, schematic diagrams being shown in order to explain the parameter in more detail.
- the natural draw ratio is a measure of the thread orientation and a value NW ⁇ 15% describes the beginning crystallization of the polyester.
- Low NW values are obtained, for example, by thermal treatment of the thread up to winding with temperatures that are at least 8 ° C above the glass transition temperature of the PES.
- the intrinsic viscosity is measured in a capillary viscometer from Ubbelohde at 25 ° C and calculated using a known formula.
- a mixture of phenol / 1,2-dichlorobenzene in a weight ratio of 3: 2 is used as the solvent.
- the concentration of the solution is 0.5 g polyester per 100 ml solution.
- a calorimeter DSC device from Mettler is used to determine the melting point, the crystallization temperature and the glass transition temperature.
- the sample is first heated to 280 ° C and melted and then quenched.
- the DSC measurement takes place in the range from 20 ° C to 280 ° C with a heating rate of 10 K / min.
- the temperature values are determined by the processor.
- the density of filaments is determined in a density gradient column at a temperature of 23 + 0.1 ° C.
- N-Heptane (C 7 H 16 ) and tetrachloraiethan (CC1 4 ) are used as reagents.
- the result of the density measurement can be used to calculate the degree of crystallinity by using the density of the amorphous polyester D a and the density of the crystalline polyester D k .
- the titer is determined in a known manner using a precision weight and a weighing device.
- the pre-tension is expediently 0.05 cN / dtex for pre-oriented filaments (POYs) and 0.2 cN / dtex for textured yarn (DTY).
- the tensile strength and the elongation at break are determined in a Statimat measuring device under the following conditions; the clamping length is 200 mm for POY or 500 mm for DTY, the measuring speed is 2000 mm / min for POY or 1500 mm min for DTY, the preload is 0.05 cN / dtex for POY or 0.2 cN / dtex for DTY.
- the tensile strength is determined by dividing the values for the maximum tear load by the titer, and the elongation at break is evaluated at maximum load.
- strands of filaments are treated without tension in water at 95 ⁇ 1 ° C for 10 ⁇ 1 min.
- the strands are produced using a willow with a pretension of 0.05 cN / dtex for POY or 0.2 cN / dtex for DTY;
- the length measurement of the strands before and after the temperature treatment takes place at 0.2 cN / dtex.
- the cooking shrinkage is calculated in a known manner from the difference in length.
- the birefringence is determined in accordance with the procedure described in DE 19,519,898. Therefore, in this context, reference is made explicitly to the disclosure of DE 19,519,898.
- the crimped kemi values of the textured filaments are measured in accordance with DIN 53840, Part 1 using the Stein / D texture data at a development temperature of 120 ° C.
- the normal Uster values are determined with the Uster tester 4-CX and specified as Uster% values.
- the test time is 2.5 min at a test speed of 100 m / min.
- the POY according to the invention can be further processed in a simple manner, in particular stretch-textured.
- the stretch texturing is preferably carried out at a texturing speed of at least 500 m / min, particularly preferably at a texturing speed of at least 700 m / min.
- the draw ratio is preferably at least 1: 1.35, in particular at least 1: 1.40.
- Stretch texturing on a machine of the high-temperature heater type, such as the AFK from Barmag has proven to be particularly useful.
- the bulky filaments produced in this way have a small number of fluff and, after dyeing under cooking conditions at 95 ° C. with a disperse dye (Terasil navy blue) without a carrier, have excellent color depth and color uniformity.
- Bulky SET filaments produced according to the invention preferably have a tensile strength of more than 26 cN / tex and an elongation at break of more than 36%.
- the tensile strength is preferably more than 26 cN / tex and the elongation at break is more than 30%.
- the bulk and elasticity behavior of the filaments according to the invention is excellent.
- PTMT chips with an intrinsic viscosity of 0.93 dl / g, a melt viscosity of 325 Pa s (measured at 2.4 Hz and 255 ° C), a melting point of 227 ° C, a crystallization temperature of 72 ° C and one Glass transition temperature of 45 ° C were dried at a temperature of 130 ° C in a tumble dryer to a water content of 11 ppm.
- the chips were melted in a 3E4 extruder from Barmag, so that the temperature of the melt was 255 ° C. It was then fed to the spinning pump through a product line which contained a static mixer from Sulzer, type SMX 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 min, the amount metered into the nozzle pack by the spinning pump was 30.7 g / min.
- An element of a static mixer, type HD-CSE with 10 mm inside diameter from Fluitec was installed after the spinning pump before entering the nozzle package.
- the trace heating of the product line and spinning block, which contained the pump and the nozzle package, were set to 255 ° C.
- the nozzle package contained steel sand with a grain size of 350-500 ⁇ m with a height of 30 mm as well as a 20 ⁇ m fleece and a 40 ⁇ m fabric filter.
- the melt was extruded through a die plate 80 mm in diameter and 34 holes 0.25 mm in diameter and 1.0 mm in length.
- the nozzle pressure was 120 bar.
- the cooling delay zone was 100 mm long, with 30 mm heated wall and 70 mm insulation and unheated frame.
- the melt threads were then cooled in a blow shaft with cross-flow blowing with a blow length of 1500 mm.
- the cooling air had a speed of 0.35 m / sec, a temperature of 18 ° C and a relative humidity of 80%.
- the solidification point of the filaments was 800 mm below the spinneret.
- the threads were provided with spinning preparation and bundled.
- the oiler was designed with a TriboFil surface and had an inlet opening of 1 mm in diameter.
- the amount of preparation applied was 0.40% based on the thread weight.
- the bundled thread was then fed to the winding machine.
- the distance between the oiler and the first discharge godet was 3.2 m.
- the conditioning time is 144 or 168 ms, depending on the speed.
- a pair of godets was wrapped in an S-shaped thread.
- a Temco entangling nozzle was installed between the godets and operated at an air pressure of 1.5 bar.
- the winding speed of the type SW6 winder from Barmag was set in such a way that the winding thread tension was 5 cN.
- the indoor climate was set to 24 ° C at 60% relative humidity, so that a temperature of about 34 ° C was established in the area surrounding the thread winding.
- the take-off speed was either 2940 m / min (example 1) or 2506 m / min (example 2).
- Table 1 shows the further test parameters
- Table 2 the material properties of the pre-oriented filaments (POYs) obtained. With both settings, bobbin weights of 10 kg could be produced and easily removed from the winder dome.
- the PTMT filament spools were stored for four weeks in normal climate in accordance with DIN 53802 and then presented to a stretch texturing machine from Barmag, type FK6-S-900.
- the search parameters of the stretch texturing for the production of so-called SET filaments are shown in Table 3, the material properties of the resulting bulky SET filaments are summarized in Table 4.
- F -CN variation coefficient of F Table 4: Material properties of the stretch-textured filaments
- a cold mode of operation of the 2nd heater i.e. H.
- the manufacturing behavior can be varied by producing so-called HE filaments.
- the crimp then increases to about 47%.
- the teardowns then drop to 33% o.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10054422 | 2000-11-03 | ||
DE10054422 | 2000-11-03 | ||
PCT/EP2001/012683 WO2002036862A1 (de) | 2000-11-03 | 2001-11-02 | Verfahren zum spinnen und aufspulen von polyester-filamenten, durch das spinn-verfahren erhältliche polyester-filamente, strecktexturierung der polyester-filamente sowie durch die strecktexturierung erhältliche bauschige polyester-filamente |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1330563A1 true EP1330563A1 (de) | 2003-07-30 |
EP1330563B1 EP1330563B1 (de) | 2005-03-23 |
Family
ID=7661977
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01992808A Expired - Lifetime EP1330564B1 (de) | 2000-11-03 | 2001-11-02 | Verfahren zum spinnen und aufspulen von polyester-filamenten unter verwendung von spinnadditiven, durch das spinn-verfahren erhältliche polyester-filamente, strecktexturierung der polyester-filamente sowie durch die strecktexturierung erhältliche bauschige polyester-filamente |
EP01992806A Expired - Lifetime EP1330563B1 (de) | 2000-11-03 | 2001-11-02 | Verfahren zum spinnen und aufspulen von polyester-filamenten, durch das spinn-verfahren erhältliche polyester-filamente, strecktexturierung der polyester-filamente sowie durch die strecktexturierung erhältliche bauschige polyester-filamente |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01992808A Expired - Lifetime EP1330564B1 (de) | 2000-11-03 | 2001-11-02 | Verfahren zum spinnen und aufspulen von polyester-filamenten unter verwendung von spinnadditiven, durch das spinn-verfahren erhältliche polyester-filamente, strecktexturierung der polyester-filamente sowie durch die strecktexturierung erhältliche bauschige polyester-filamente |
Country Status (17)
Country | Link |
---|---|
EP (2) | EP1330564B1 (de) |
JP (2) | JP2004513249A (de) |
KR (2) | KR20030043790A (de) |
CN (2) | CN1210449C (de) |
AT (2) | ATE291114T1 (de) |
AU (2) | AU2002215998A1 (de) |
BR (2) | BR0113515A (de) |
CA (2) | CA2405495A1 (de) |
DE (4) | DE10151893A1 (de) |
EA (2) | EA003951B1 (de) |
EG (2) | EG23364A (de) |
ES (2) | ES2236349T3 (de) |
HK (1) | HK1054577B (de) |
MX (2) | MXPA03001318A (de) |
MY (1) | MY136398A (de) |
TW (2) | TW587108B (de) |
WO (2) | WO2002036864A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3910038B2 (ja) * | 2001-10-18 | 2007-04-25 | 旭化成せんい株式会社 | 前配向糸パッケージとその製造方法 |
JP3862996B2 (ja) * | 2001-10-31 | 2006-12-27 | 帝人ファイバー株式会社 | ポリトリメチレンテレフタレートフィラメント糸およびその製造方法 |
WO2003069034A1 (en) * | 2002-02-12 | 2003-08-21 | Zimmer Ag | A process for the production and for the winding of polyester multi-filament yarns as well as the polyester multi-filament yarns obtainable by said method and a device for the winding of one or more multi-filament yarns |
DE10213921B4 (de) * | 2002-03-28 | 2006-10-12 | Röhm Gmbh | Verfahren zum Spinnen und Aufspulen von Polyester-Multifilament-Garnen unter Verwendung von Spinnadditiven sowie durch das Spinn-Verfahren erhältliche Polyester-Multifilament-Garne |
TW200741049A (en) * | 2005-12-27 | 2007-11-01 | Shell Int Research | Polyester yarn and process for producing |
CN113481624B (zh) * | 2021-06-24 | 2023-04-28 | 杭州惠丰化纤有限公司 | 一种涤纶丝及其生产工艺 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975488A (en) * | 1972-10-24 | 1976-08-17 | Fiber Industries, Inc. | Process for preparing poly(tetramethylene terephthalate) yarn |
JP2001512793A (ja) * | 1997-08-05 | 2001-08-28 | ルルギ ツィマー アクチエンゲゼルシャフト | ポリマー混合物をフィラメントに加工する方法 |
JPH11172526A (ja) * | 1997-11-26 | 1999-06-29 | Asahi Chem Ind Co Ltd | 低熱応力ポリエステル繊維及びその紡糸方法 |
JP3249097B2 (ja) * | 1999-07-12 | 2002-01-21 | 旭化成株式会社 | 仮撚加工に適したポリエステル繊維及び製造方法 |
TW522179B (en) * | 1999-07-12 | 2003-03-01 | Asahi Chemical Ind | Polyester yarn and producing method thereof |
US6287688B1 (en) * | 2000-03-03 | 2001-09-11 | E. I. Du Pont De Nemours And Company | Partially oriented poly(trimethylene terephthalate) yarn |
-
2001
- 2001-10-24 DE DE10151893A patent/DE10151893A1/de not_active Withdrawn
- 2001-10-24 DE DE2001151875 patent/DE10151875A1/de not_active Withdrawn
- 2001-10-26 TW TW090126495A patent/TW587108B/zh not_active IP Right Cessation
- 2001-10-26 TW TW090126494A patent/TW589420B/zh not_active IP Right Cessation
- 2001-11-02 EA EA200201194A patent/EA003951B1/ru not_active IP Right Cessation
- 2001-11-02 EA EA200201196A patent/EA003882B1/ru not_active IP Right Cessation
- 2001-11-02 CA CA002405495A patent/CA2405495A1/en not_active Abandoned
- 2001-11-02 MX MXPA03001318A patent/MXPA03001318A/es active IP Right Grant
- 2001-11-02 JP JP2002539599A patent/JP2004513249A/ja active Pending
- 2001-11-02 KR KR1020027014789A patent/KR20030043790A/ko active IP Right Grant
- 2001-11-02 DE DE50105643T patent/DE50105643D1/de not_active Expired - Fee Related
- 2001-11-02 BR BR0113515-5A patent/BR0113515A/pt not_active Application Discontinuation
- 2001-11-02 ES ES01992806T patent/ES2236349T3/es not_active Expired - Lifetime
- 2001-11-02 JP JP2002539597A patent/JP2004532356A/ja not_active Ceased
- 2001-11-02 WO PCT/EP2001/012684 patent/WO2002036864A1/de active IP Right Grant
- 2001-11-02 KR KR1020027015434A patent/KR100783124B1/ko not_active IP Right Cessation
- 2001-11-02 MX MXPA03001319A patent/MXPA03001319A/es unknown
- 2001-11-02 AU AU2002215998A patent/AU2002215998A1/en not_active Abandoned
- 2001-11-02 AT AT01992808T patent/ATE291114T1/de not_active IP Right Cessation
- 2001-11-02 CN CNB018102972A patent/CN1210449C/zh not_active Expired - Fee Related
- 2001-11-02 AT AT01992806T patent/ATE291651T1/de not_active IP Right Cessation
- 2001-11-02 BR BR0113527-9A patent/BR0113527A/pt not_active Application Discontinuation
- 2001-11-02 MY MYPI20015063A patent/MY136398A/en unknown
- 2001-11-02 CN CNB018102964A patent/CN1210448C/zh not_active Expired - Fee Related
- 2001-11-02 WO PCT/EP2001/012683 patent/WO2002036862A1/de active IP Right Grant
- 2001-11-02 EP EP01992808A patent/EP1330564B1/de not_active Expired - Lifetime
- 2001-11-02 AU AU2002224824A patent/AU2002224824A1/en not_active Abandoned
- 2001-11-02 ES ES01992808T patent/ES2237616T3/es not_active Expired - Lifetime
- 2001-11-02 DE DE50105726T patent/DE50105726D1/de not_active Expired - Fee Related
- 2001-11-02 CA CA002405885A patent/CA2405885A1/en not_active Abandoned
- 2001-11-02 EP EP01992806A patent/EP1330563B1/de not_active Expired - Lifetime
- 2001-11-03 EG EG20011166A patent/EG23364A/xx active
- 2001-11-03 EG EG20011165A patent/EG23028A/xx active
-
2003
- 2003-09-19 HK HK03106721.0A patent/HK1054577B/zh unknown
Non-Patent Citations (1)
Title |
---|
See references of WO0236862A1 * |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE60108603T3 (de) | Verfahren zur herstellung von polytrimethylenterephthalat-stapelfasern und polytrimethylenterephthalat-stapelfasern, -garne und -flächengebilde | |
DE2747803C2 (de) | ||
DE69617315T2 (de) | Verfahren zur Herstellung von Polypropylenterephthalatgarnen | |
DE69925035T2 (de) | Polytrimethylenterephthalatfasern | |
DE69911525T2 (de) | Polyester-filamentgarn | |
DE3125254C2 (de) | ||
DE60110361T2 (de) | Polytrimethylenterephthalat-stapelfasern mit tetrakanalquerschnitt | |
EP1208252B1 (de) | Polytrimethylenterephthalat-stapelfasern und verfahren zu ihrer herstellung | |
EP1356143B1 (de) | Verfahren zum spinnen und aufspulen von pet-filamenten | |
DE60035128T2 (de) | Baum zum weben und schlichtverfahren | |
EP1330563B1 (de) | Verfahren zum spinnen und aufspulen von polyester-filamenten, durch das spinn-verfahren erhältliche polyester-filamente, strecktexturierung der polyester-filamente sowie durch die strecktexturierung erhältliche bauschige polyester-filamente | |
DE2241718B2 (de) | Verfahren zur herstellung von texturiertem polyestergarn | |
DE10213921B4 (de) | Verfahren zum Spinnen und Aufspulen von Polyester-Multifilament-Garnen unter Verwendung von Spinnadditiven sowie durch das Spinn-Verfahren erhältliche Polyester-Multifilament-Garne | |
EP0630995B1 (de) | Multifilament-Garn aus Polyäthylennaphthalat und Verfahren zu seiner Herstellung | |
DE60121760T2 (de) | Vororientierte garnspule | |
DE69323808T2 (de) | Verfahren für das Hochdruckspinnen von Polyester-Industriegarn | |
DE2461198A1 (de) | Verfahren zum herstellen von polyesterfasern | |
EP0287604B2 (de) | Verfahren zur herstellung eines glatten polyesterfadens und polyesterfaden hergestellt nach dem verfahren | |
DE2211843A1 (de) | Verwendung unverstreckter polyaethylenterephthalatfaeden | |
DE10392272T5 (de) | Verfahren zur Herstellung und zum Aufspulen von Polyester-Multifilament-Fäden, Polyester-Multifilament-Fäden erhältlich durch das Verfahren und Vorrichtung zum Aufspulen eines oder mehrerer Multifilament-Fäden | |
DE3508955A1 (de) | Verfahren zum schnellspinnstrecken synthetischer garne | |
DE3036683A1 (de) | Verfahren und vorrichtung zum schmelzspinnen von synthetischen polymeren | |
DE60314880T2 (de) | Verfahren zur herstellung von stabilen polytrimethylenterephthalat-spulen | |
DE10338821B4 (de) | Verfahren zur Herstellung von feinen Fasern | |
DE2530618A1 (de) | Verfahren und vorrichtung zur herstellung eines aus synthetischem, thermoplastischem, polymeren material bestehenden vielfaedigen garns |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20021010 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050323 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050323 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050323 Ref country code: GB Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050323 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
REF | Corresponds to: |
Ref document number: 50105726 Country of ref document: DE Date of ref document: 20050428 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050623 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050623 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2236349 Country of ref document: ES Kind code of ref document: T3 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050907 |
|
GBV | Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed] |
Effective date: 20050323 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051102 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051130 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051130 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051130 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051130 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051130 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20051227 |
|
EN | Fr: translation not filed | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
BERE | Be: lapsed |
Owner name: ZIMMER A.G. Effective date: 20051130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20050623 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20071123 Year of fee payment: 7 Ref country code: ES Payment date: 20071129 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20071123 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20071101 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050323 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081102 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090603 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20081103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100928 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081102 |