EP0915192A2 - Verfahren zur Herstellung und Regelung von wärmeverbindbaren Kern-Mantel-Polyolefinfasern und daraus hergestellte Vliesstoffe - Google Patents

Verfahren zur Herstellung und Regelung von wärmeverbindbaren Kern-Mantel-Polyolefinfasern und daraus hergestellte Vliesstoffe Download PDF

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Publication number
EP0915192A2
EP0915192A2 EP98660111A EP98660111A EP0915192A2 EP 0915192 A2 EP0915192 A2 EP 0915192A2 EP 98660111 A EP98660111 A EP 98660111A EP 98660111 A EP98660111 A EP 98660111A EP 0915192 A2 EP0915192 A2 EP 0915192A2
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Prior art keywords
nozzle
spinning
polymer
oxidation
filament
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EP98660111A
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English (en)
French (fr)
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EP0915192A3 (de
EP0915192B1 (de
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Simo Mäkipirtti
Erkki Lampila
Heikki Bergholm
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Suominen Nonwovens Ltd
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Jw Suominen Oy
Suominen J W Oy
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/007—Addition polymers
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
    • D04H1/5412—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sheath-core
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43828—Composite fibres sheath-core
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion

Definitions

  • a first object of the present innovation is to both improve and regulate as well as monitor the manufacturing conditions of skin-core type polyolefin fibers so that the product fibers will have improved physical characteristics.
  • a second object of the innovation is to prepare from the said polyolefin fibers nonwoven fabrics with improved strength and softness characteristics.
  • the preparation and regulation method according to the new innovation is based on substantially improving and regulating the polymer molecular chain degradation process following molten state autogenous oxidation of the surface layer of spinning fibers.
  • the method is applied especially to high-capacity meltspinning apparatuses having a short cooling system.
  • the object of the invention is thus a method for regulating the oxidative degradation of the molecular chains in the surfaces areas of molten polymer filaments, which method is applicable in a polyolefin, especially a polypropylene shortspinning system for the production of filaments, according to which the stabilized polymer is extruded and melt spun and the spinning filaments formed are oxidized and quenched, the method being characterized in that
  • the constant c 1 is a function of the position of the oxidation nozzle both with respect the spinning nozzle and the filament bundle, the dimensions and temperature of the oxidizing gas jet, the spinning deformation of the melt filament;
  • the constant c 2 is a function of the position of the quenching gas nozzle, the dimensions, the composition, the temperature of the quenching gas jet;
  • the constant c 3 is a function of the level of oxidative degradation of the filament caused by the quenching gas phase, the nozzle diameter, the spinning temperature, the molecular weight distribution of the polymer matrix, and the level and type of additive addition.
  • the molecular chain degradation occuring during quenching of the molten polymer filament is regulated by regulating the oxygen partial pressure of the quenching gas phase.
  • the thermal molecular chain degradation of the molten polyolefin can be regulated in the extruder by regulating the melt temperature and extrusion delay time, especially so that the polyolefin is extruded in a temperature range of 250 - 290 °C, the delay time of the spinning melt in the extruder and the ducts being 5 - 15 minutes.
  • the molten filament is preferably quenched under conditions, where the volume, velocity and temperature of the quenching gas are in the range of 400 - 1100 Nm 3 /h, 20 - 60 m/s and 25 ⁇ 5 °C, respectively, the amount of polymer supplied being 20 - 40 kg/h per nozzle plate.
  • a gas poor in air and free oxygen such as a combustion gas mixture, is used as the quenching gas, the oxygen partial pressure being in the range of 0.01 - 0.21 bar.
  • the constant c 3 typically has a value ⁇ 5.
  • the number average molecular mass values of the filament polymer is reduced at the most by 30 % and its dispersion values are increased at the most by 40 % from the values prior to nozzle oxidation, by using an oxygen partial pressure velocity in the oxidation gas and at the same time an oxygen partial pressure correspondingly within the range 0.1 - 25 m/s and 40 - 100 % by vol. O 2 and simultaneously preventing, by regulating the velocity of the quenching air, an increase of the maximum values for the filament tension above appr. 30 mN/m 2 .
  • the spinning nozzle is preferably internally heated, for example using an effect of 0.25 kW/kg of weight unit of the nozzle plate to prevent the nozzle from cooling.
  • the invention also concerns an apparatus for the regulation of the oxidative degradation of the molecular chains in the molten polymer filament surface areas of polyolefins, especially polypropylene, in a filament production method, comprising a melt spinning device with spinning nozzles, and means, especially a quenching nozzle for quenching the polymer filaments, which apparatus is characterized in that it contains means for oxidizing the polymer filaments, especially an oxidation nozzle, which is separate from the quenching means.
  • the size of the free openings of the quenching and oxidation nozzles are correspondingly (10-20) x 480 mm and (0.5-1.5) x 460 mm, i.e. the relationship between their surface areas is 7 - 42.
  • the invention also concerns the use of the method according to the invention for regulating the temperatures and bonding strengths in a process of thermobonding fibers produced by the said method, especially the melting point and melt quantity of the partial melts formed from the filament surface during thermobonding, as well as the quality characteristics of fabrics made from the fibers.
  • the invention further concerns a method for regulating the thermobonding of skin-core-type fibers made by degrading the molecules in a filament surface layer based on a controlled autogenous oxidation of the molten-state spinning filaments made from polyolefins, especially polypropylene, which method is characterized in that
  • the new regulation method is thus a combination of several partial methods and is based on a large number of measurements and observations.
  • the regulation method is divided into a main part and a side part. One part is directed to the molten state, controlled oxidation of the polymer, and the second part, if necessary, to controlling and changing, prior to spinning oxidation, the polymer molecular weight distribution, i.a. in the radial direction of the nozzle filament, by mixing therewith, prior to the spinning nozzle, a very short-chain homopolymer of the same polymer quality.
  • Characteristic features of the new method are i.a. :
  • a starting polymer which has been stabilized in a known manner, whereby especially peroxide degradation agents, such as phosphite-phosphonite mixtures come into question, typically in an amount of not more than appr. 0.5 %.
  • the draw viscosity: ⁇ , gf ⁇ s/cm 2 is presumed to be a function only of temperature and internal viscosity,
  • the filament density: ⁇ , g/cm 3 and the isobaric specific heat: Cp, cal/g. degree are presumed to be constant.
  • a number of studies / i.a. 2/ relating to fiber filament formation have been presented in the past decades. However, the said equations and their solutions /1/ are associated with fairly abundant experimental reference documentation, which in practice covers the most important spinning phenomena and technical applications.
  • the stationary state solutions to the differential equations /1/-/3/ give the changes in the cross-sectional area of the fiber filament, A(y), and the temperature, T(y) as a function of the distance, y measured from the spinning head under a multitude of spinning conditions.
  • the obtained solutions are then correlated to the properties of the filament thread.
  • the following can be said about the essential results obtained from the solutions to the spinning model equations [IBM 1401] in the melt spinning of polypropylene:
  • the polypropylene filament threads crystallize rapidly in melt spinning, which makes the crystallinity and orientation important.
  • the birefringence, ⁇ n increases rapidly. It can be shown that the birefringence of the thread is directly proportional to the tensile strength at the solidification point, (F/A).
  • melt spinning filament crystallization takes place subject to molecular orientation under non-isothermal conditions.
  • the degree of crystallization ( ⁇ ) can be obtained from the equation at any desired point of time provided the rate temperature dependance and the cooling function of the system are known.
  • the temperature function of the isothermal crystallization rate is an almost symmetrical bell function with respect to the maximum rate value.
  • the maximum value for the crystallization rate is below the polymer solidification temperature for polyolefins.
  • the filament crystallinity is, in addition to the crystallization rate, dependant on the length of time the polymer spends at the temperature range where it has its highest crystallization rate.
  • the hydroperoxides are most often primary main products of polymer oxidation, and they play, as initiators of autogenous oxidation, an important role in the oxidative degradation.
  • the products from the oxidative pyrolysis of polypropylene at the temperature 289°C was determined /5/ IR-spectrofotometrically from the GC-fractions and partly using mass spectrometry.
  • the semiquantitative product yield order was: ethanol, acetone, butanol, methylvinylketone, C 6 -ketone, propylene, methanal, methanol, propanol, 2-methylpropanol, 2-pentanone, C 5 -aldehyde, 3-methyl-3,5-hexadiene.
  • the appearance of the hydrocarbon products ethane, propane, propylene etc.
  • the measurement results correspond to an extrusion temperature of 260°C. Based on the results of the study it can be concluded that as a result of the multiple random degradation of polypropylene carried out under oxidative conditions, the values for the molecular weights and dispersion decrease conventionally and regularly as a function of the melt index.
  • T M T M O - [2RT M T M O /( ⁇ H M )u] [(lnX)/X] + f(X), where T M O is the melting point of a perfect crystal having a finite molecular mass, ( ⁇ H M )u is the melting enthalpy of the polymer monomer unit and X is the degree of polymerisation.
  • the effect of air on the polymer at the extrusion temperature is thus known, as is also the prevention thereof and both effects, in addition to a "chemical”, also from a kinetic point of view.
  • the adhesion of a polyethylene structure (film) to inks, metals, paper and polymers of different qualities is improved.
  • the polymer is subjected to nitrous oxide containing air (5-20 % N 2 O) at the extrusion temperature range (150-325°C), preferably in the presence of UV-light ( ⁇ ⁇ 3900 ⁇ ) and is quenched.
  • the rapid spinning process for synthetic fibers is improved by including on-line-zone heating in a conventional method.
  • the filament exiting the spinning head is quenched to a temperature above the glass-transition temperature (e.g. a smectic structure for the product phase) and is then fed to a heating zone, where the desired fiber characteristics (crystallinity, orientation, strengths) are produced. Finally the filament is quenched again and wound up.
  • zone length and temperature values are given which correspond to a specific winding speed.
  • the molten surface layer forms a protective layer preventing cracks on the surface of the brittle, high-molecular weight, oriented core layer and simultaneously functions as a lubricant.
  • the spinning speed and capacity of a rapid spinning process for bicomponent fibers in a polyethylene-polypropylene-system are improved above the values for the end components.
  • the polyethylene forms the continuous and the polypropylene the dispersive phase in the matrix.
  • the product fiber has good thermobonding properties.
  • polymer composites having high impact strength are made in the presence of a Ziegler catalyst. These contain polypropylene as the continuous phase and as the discontinous phase a thermoplastic polymer containing 90% polymerized ethylene and the rest other ⁇ -olefins. The mixture is heated in the presence of a free radical in order to decrease the viscosity of the system.
  • conjugate fibers having both a superior thermal adhesion and absorption capacity are made by melt spinning.
  • the fibers contain as one component a crystalline ⁇ -olefin and as another component an ethylene-dialkylaminoalkyl acrylamide copolymer.
  • a crystalline ⁇ -olefin and as another component an ethylene-dialkylaminoalkyl acrylamide copolymer.
  • /16/ spontaneously curly conjugate fibers with high strength characteristics are made.
  • One component in the structure containing at least two components is comprised of polypropylene and 5-50% of a thermosetting plastic (catalyzed from a hydrocarbon containing at least four carbon atoms or a colophonium derivative) and the other of polypropylene and a varying quantity of a thermosetting plastic.
  • multicomponent polymer filaments are made, by mounting a high speed lateral quenching unit close to the lowermost surface of one or more spinning heads having a high nozzle density, in order to prevent the aggregation of pre-fibers and/or of molten filaments.
  • a spinning head suitable for the simultaneous spinning of several different filaments can be used (US 4.406.850, 5.162.074).
  • a shortspinning system is applied to a complicated polymeric multicomponent rapid spinning system.
  • the spinning nozzle apparatus comprises, between the plate containing the filter space and the actual nozzle plate, an insulating space through which the polymer flows, the melt temperature being below the temperature of substantial degradation, through extended feeding tubes to the nozzles in the nozzle plate.
  • the nozzle plate is electrically heated to produce a steep temperature gradient ( ⁇ 60°C) in the polymer (in the feed tube and the capillary) so that the shearing stress is momentarily reduced at the capillary wall, without polymer degradation.
  • polymer powder is screw-compressed against a melting diaphragm, into which an electrical resistance plate is apertured.
  • the screw tube is surrounded by a water cooled mantle, by means of which the temperature of the polymer powder is kept below the lowest melting point of its components.
  • the polymer is conducted to the nozzles immediately after the filter.
  • the polymer remains in a molten state for a short time.
  • the main objective of the method according to the patent US 5.281.378/200592,/18/, is to improve control of the polymer degradation, spinning and quenching stages and to produce a fiber, which is capable of providing a nonwoven product with increased strength, elasticity and uniformity values.
  • a further object of the method is to develop the thermobonding properties of a fiber spun from a polyolefin containing melt.
  • a high-strength spinning fiber is made by utilizing oxidative chain degradation of the surface of a molten spinning filament as well as a slow quenching stage for the melt filament as applied to polypropylene having a broad molecular weight distribution.
  • the method is applicable for use in a rapid spinning system.
  • the method has the following essential functions: In a first stage of the method, the polypropylene containing melt is extruded under the following conditions:
  • the subexample 1.1 discloses the manufacturing equipment and operation thereof for fibers and fabrics corresponding to the examples of the description of the invention and used for developing the method.
  • the so-called short spinning-method and corresponding apparatuses were used.
  • the spinning and drawing test series were generally performed on pilot scale apparatuses which differed from production scale apparatuses only to the number of spinning units, but not to their size.
  • the pilot apparatuses were better equipped from a measurement technical standpoint as compared to the production apparatuses.
  • the nozzle diameters (mm) and nozzle numbers in the spinning nozzle plates used for the test series were: 0.25 and 0.30/30500, 0.40/22862 and 0.70/12132.
  • n r is the speed of rotation of the polymer pump (min -1 ).
  • the deformational changes of the molten-state spinning filament after the nozzle under varying spinning conditions was photographed with a CCD camera and the information recorded on magnetic tape.
  • the record analysis and measurements were performed using image-analysis methods. Part of the samples used for analyzing details of the invention were made under controlled conditions on a Haake-Rheocord-90-apparatus, which was provided also with a mechanical drawing apparatus with oven.
  • the fiber structure was analyzed using X-ray WAXS- and SAXS-technique (Philips PW 1730/10, PW 1710/00, Kratky-KCSAS), AFM-technique (TME-rasterscope 2000) and electron microscopy (Cambridge 360 and Cameca Camevax Microbeam).
  • the conventional apparatus used in the production of the fiber nonwovens and bonding was according to the Figure 2.
  • the parts of the apparatus are: 1. opener, 2. fine-opener, 3. storage silo, 4. feeder, 5. carding apparatus, 6. bonding rolls and 7. winding apparatus. All the apparatuses shown in the drawing are of production scale.
  • the production and bonding speed of the fiber web on the bonding line were adjustable in the range of 25-100 m/min.
  • the upper roll provided with diamond or round protrusions and the smooth lower roll of the bonding apparatus were temperature and pressure adjustable.
  • the diameter of the bonding roll was of production scale, but its width was only 2.2 m.
  • the relative positions of the quenching, oxidation and spinning nozzles of the melt spinning apparatus used in the pilot tests are shown in the Figure 3.
  • the position of the quenching nozzle was decided based on the best spinning result.
  • the angle between the central plane of the quenching nozzle (1) and the spinning nozzle surface was appr. 24 ⁇ 1°.
  • the distance of the longer center line of the rectangular nozzle opening from the spinning nozzle plane was 42 ⁇ 2 mm and its distance in the direction of the angle of the nozzle from the central plane of the cable bundle (6) was appr. 49 ⁇ 2 mm, the diameter of the spinning nozzle being 0.70 mm.
  • the spinning nozzle diameter was 0.25 mm, the values for the distance were only 0-10 mm shorter than the above mentioned.
  • the size opening of the quenching nozzle was maintained constant in the tests, i.e. 11.2 x 478 mm.
  • the positions of the oxidation nozzle (2) were a, b and c in the test runs ( Figure 3).
  • the directional angles corresponding to the nozzle positions were 7.5 ⁇ 0.5°, 17.5 ⁇ 0.5° and 2 ⁇ 1°, the distances in the nozzle direction were 62 ⁇ 5, 64 ⁇ 5 and 32 ⁇ 5 mm and in the height direction (as measured from the longer center line of the rectangular nozzle opening) 27.5 ⁇ 3, 27.5 ⁇ 3 and 1 ⁇ 2 mm.
  • the size of the nozzle opening of the oxidation nozzle was 0.6 x 460 mm.
  • the subexample 1.2 studies the dynamic deformation during quenching of a molten polymer filament exiting the spinning nozzle in a production scale spinning system.
  • the Table 1 contains the spinning conditions for samples used in one series for measuring the deformation of the molten filament, and the corresponding results calculated from the filament profile are given in the Figure 4.
  • the changes in the filament cross-section and shell surfaces (A(y) and A v (y)), the temperature ( ⁇ (y)) and spinning delay time (T(y)) as a function of the distance (y) calculated from the nozzle in the direction of the filament axis were determined.
  • the change in the shell area of the spinning filament, A v (y), is opposite to that of the A(y)- and ⁇ (y)-changes.
  • the spinning model /1/ simulates a long-spinning system, whereas the object of comparison is a shortspinning system.
  • an increase in the nozzle opening size results in a strong retardation of the cooling effect and of the thinning of the filament, wherefore, during melt deformation, the difference especially in the shell surfaces increases to be substantially bigger than the difference between the nozzle capacities (in the samples the production capacities are of equal, but the nozzle capacities of different magnitude). In this case also the overall delay time of filament deformation increases substantially.
  • An increase in the nozzle opening size thus affects very advantageously oxygen transport and a favourable implementation of the oxidative degradation in the filament.
  • the diffusional oxygen transport through the molten filament surface formed in spinning and subject to deformation as a function of time will be briefly studied.
  • the Table 2 and the Figure 4 show the surface-areas of the filaments as a function of time, temperature and distance from the nozzle.
  • the filaments used for comparison correspond to the nozzle diameter values 0.70 mm (no. 319) and 0.30 mm (no. 14).
  • the sample 0.30 mm (no. 18) is included in the comparison for establishing the effect of oxygen.
  • N x A v x ⁇ (cm 2 ⁇ s) which is proportional to the level of oxygen transport
  • the following values are obtained at the said distances: N x A v x ⁇ /no: 3.426/319 - 0.327/14 - 0.742/18 and (115 °C) 30.69/319 - 0.436/14 - 1.615/18.
  • the difference between the oxygen diffusion constants corresponding to the spinning and solidification temperatures is approximately 1.5-2 decades.
  • the results of the subexample 1.2 clearly show that the oxidation nozzle has to be placed in the immediate vicinity of the spinning nozzle surface.
  • the oxygen partial pressure in the oxidative gaseous phase should be as a high as possible.
  • the subexample 1.3 concerns the implementation of an autogenous oxidation-degradation process of a molten-state spinning filament surface and a corresponding regulation method by means of pilot test series.
  • the quenching distance of the filament after the nozzle is only 25 mm, that is very short compared to the 250-1500 mm of the longspinning system. Due to the very low processing space, the oxidation and quenching nozzles for the filament are separated from each other in the method according to the invention.
  • oxidation is carried out as a targeted oxidation using a very narrow nozzle gap (0.60 x 460 mm) and sufficently high velocity, so that the oxidation gas phase, if necessary, is able to penetrate the tail part of the quenching gas stream into the filament space.
  • the method of blowing is based on the poor mixability of the gases under the said conditions /22/.
  • the position of the oxidation nozzle with respect to the filament bundles and the spinning nozzle surface has to be adjusted carefully (Figure 3) for the oxidation to be successful.
  • oxygen enriched air is used in the oxidation and in the adjustment thereof, if necessary.
  • An increase in the oxygen level in the blowing air affects the steepness of the radial oxygen concentration gradient in the filament /21/, and simultaneously the level and site of molecular chain degradation.
  • By decreasing the oxygen deficiency in the filament surface and outside it is possible to affect the quality and quantity of evaporating oxygen compounds.
  • difficult spinning conditions small nozzle diameter, production of fine filaments, etc.
  • the performance of the regulation system according to the invention was tested with respect to the operation of the quenching and oxidation nozzles.
  • the temperatures of the extruder heating zones and the spinning spinneret were: 255-265-265-280-290-290 °C and 295 °C.
  • the spinning melt temperature was 286 °C.
  • the sample numbers 7-16 of the Table 2 correspond to the position b of the oxidation nozzle and the sample numbers 21-25 correspond to the position a.
  • the flow velocities of the oxidation jet do not exceed those of the quenching jet, and consequently the regulation equation changes from the former to be according to that of the equation /17/.
  • the slightly negative factor for the oxygen flow indicates the cooling effect of the oxygen in the system.
  • the oxidation nozzle was moved to the position c (Fig. 3) and it could be used either 1- or 2-sidedly (series no. 325 and no. 326).
  • the oxidation nozzle operating in the near vicinity of the spinning nozzle surface, cools the same small electrical resistances have been mounted in the spinning nozzles to increase the surface temperature of the spinning nozzles to correspond to the spinning temperature and at the same time to eliminate polymer surface growth.
  • the regulation system for oxidation corresponds essentially to the result of the test series no. 309, but the quenching oxidation is still very low (Fig. 5.).
  • MFI 1.914 x v o2 - 0.7363 v i + 62.645
  • the basic factors affecting the level of quenching oxidation and degradation are the temperature, nozzle size and corresponding spinning deformation, feed capacity, oxygen content of the quenching gas, molecular weight distribution, etc.
  • the short-chain polymer would act as a softener in the mixture, especially during extrusion.
  • a degradation rate increase in the system caused by non-random molecular chain end initiation could be taken advantage of.
  • the temperature of the spinning melt could be lowered, whereby the level of thermal degradation in the extrusion would decrease and a properly surface degraded fiber would be obtained without a substantial decrease in the mechanical properties of the product fiber.
  • molten-state filament oxidation is performed on a mixture of two propylene polymers of highly differing chain length.
  • the spinning mixture contained 5 and 10 % by weight polymer with a melt index of 400 (no. 032) mixed with a polymer (no. 031) having a melt index of 4.4.
  • the former mixture is represented by the sample numbers 5-10 and the latter by the sample numbers 1-3 (see also Fig. 5 and the subexample 1.4).
  • the regulation equation for spinning oxidation one obtains as a function of the oxygen flow partial pressure velocity (without recognizing the quenching rate) 5 % no.
  • the subexample 1.4 studies the changes in the polymer molecular distribution and the melt indices occuring in the molten state peripheral oxidation of the filaments of the test series of the subexample 1.3.
  • the obtained result can be compared to the extrusion results obtained both under a protective gas and air atmosphere.
  • the degradation results obtained in the test series 309 in an extruder correspond to conventional multiple extrusion results in the presence of air, i.a. from the MWD-MFI-measurements of H. Hinsken et al /7/.
  • the slope of the functions ln M w , ln M n and ln (M w /M n ) / ln MFI simulating the measurement results are approximately the same in both series.
  • the level of chemical degradation caused by the quenching air after the extruder is dependent on the spinning conditions (subexample 1.3). Under the spinning conditions used in the area of study this level is low as compared to the thermal and mechanical degradation.
  • the use of an oxidation nozzle (side nozzle) in correspondence with the novel method results in substantial changes in the slopes of the ln M/ln MFI functions simulating the degradation effects, as compared to the above mentioned functions obtainable from the measurement values of Hinsken /7/.
  • the ln Mw- values of the samples in the series no. 309 decrease less and the ln Mn-values more steeply as a function of the oxidation degree than the afore mentioned measurement values.
  • the broadening of the polymer molecular weight distribution as a results of the oxidation is not conventional. It can, however, be shown with MWD-balance calculations that in non-random degradation, which degradation following surface oxidation also is, the dispersion of the overall distribution in the filament increases with increased oxidation (the dispersion values of the parts simultaneously decreasing in the radial direction of the filament). It can be mentioned that a similar increase in the dispersion values has been found in solid-state surface degradation (S. Girois et al. /10/, J. E. Brown et al. /9/).
  • the Figure 6 represents a differential molecular weight graph corresponding to the distributions given in the above Table. It shows that the distributions are shifted under the effect of oxidation toward low molecular weights. Based on the distribution graph, it is not, however, possible to evaluate the Mn- and Mw/Mn-changes during oxidation as especially the effect of the Mn-changes on the total distribution is low.
  • the Figure 7 shows an AFM-image of a cross-section of an etched (CrO 3 + H 2 SO 4 ) filament sample. From the image it can be seen that a radial surface layer of the fiber has dissolved, which also shows the weaken-ing of the structure as a result of the oxidation of the filament surface layer and the change in the molecular weight distribution.
  • the Figure 8 shows a BSE-image of cross-section of an oxidized filament sample. From the image the lighter diffusion area (impoverished zone) of the surface layer caused by the oxidation as compared to the inner structure of the filament can be seen. The surface layers of the sample were not able to resist the bombardment from the electron gun sufficiently to carry out a line analysis (apparatuses: SEM, 360 Cambridge and EPMA, Cameca-camevax microbeam).
  • the subexample 1.5 studies thermobonding of staple fibers from molten-state, peripherally oxidized polypropylene filaments made according to the invention.
  • thermobonding of a nonwoven fiber web from synthetic fibers are disclosed in detail in the patent application FI 961252/18.03.96 (EP 97660030.4/14.03.97).
  • the constant terms for the fabric tensile strength and elongation equations which quite accurately simulate the obtained test results, are indicated in the Table 4.
  • the logarithmic graphs of the equations corresponding to the tensile strength values of the test fabrics are presented in the Figure 9.
  • the fibers corresponding to the numbers 1-7 and 12 in the Table and the Figure are prepared by oxidizing to various degrees of degradation and processing the same starting polymer.
  • the fabrics corresponding to numbers 8, 9, 10 and 11 are for comparison.
  • the fiber no. 11 is a conventional productional fiber made by shortspinning.
  • the tensile strength and elongation ( ⁇ II , ⁇ II ) bonding equations at high bonding temperature of nonwovens from the fibers seem to join and form an envelope of maximum strengths (Fig. 9.: no. 00 and equations no. 1-7, 12).
  • the joining of the equations is not precise for the strength values in the direction perpendicular to the carding direction ( ⁇ ⁇ , ⁇ ⁇ ) which could be due to the wider spread of the measurement values than in the former case.
  • the envelope curve clearly shows that the fabric strength values increase when the bonding temperature decreases, the degradation degree of the fiber surface layer increasing.
  • the improvement in bonding can be derived from an increase in the surface melt quantity of the fiber, the easier relaxation of the draw orientation at decreasing chain length (whereby the orientation derived shrinkage, which is detrimental to bonding, decreases), improvement in the melt-solid-contact, etc. It can also be concluded that the use of a solid-state mechanical drawing process after spinning for increasing fiber strength requires a precise heat treatment also for surface degraded fibers.
  • ⁇ II / ⁇ II [MFI/(MFI) O ] -0.794 x 3.235 x 10 6 x exp[-12390/RT]
  • the elongation and tensile strength ratios it can be concluded from the test results that in the said test series the elongation ratio, ⁇ ⁇ / ⁇ II decreases slightly and correspondingly the tensile strength ratio, ⁇ ⁇ / ⁇ II remains constant or increases slightly when the MFI-values increase.
  • the subexample 1.6 studies the performance of some product fibers peripherally oxidized in a method according to the invention when subjected to oxidizing evaporation and loop bonding.
  • the aim is to recognize possible kinetic differences in fibers oxidized as molten filaments, as a result i.a. of changes in the molecular weight.
  • the Table 5 contains constants for the reaction rate equations for the oxidizing evaporation of some peripherally oxidized fibers (and starting polymer) under isothermal evaporation. According to the Table, the activation energy for the overall process is constant (within limits of accuracy of measurement) both in polymer and fiber evaporation.
  • the molecular weights of the polymers being compared (0-0 and 0-1) differed from each other considerably and were (before oxidation): Mw-Mn-D: 254000-49700-5.1 and 193399-34930-5.53.
  • the polymers 0-0 and 0-1 have activation energy values of equal magnitude for the oxidative evaporation (within the limits of accuracy of measurement).
  • the effect of gas phases containing nitrogen and carbon dioxide on 'oxygen-free' evaporation of polypropylene will be studied by means of dynamic thermogravimetric measurement series.
  • the test series also shows the effect of the bound oxygen contained in the combustion gases from fossile fuels in the oxygen-free evaporation in the filament quenching stage.
  • the results from the dynamic measurements are not accurate but a comparison of the results indicates in a qualitative manner the direction of the reactions. In the comparison, the results have been extrapolated with respect to the temperature.
  • the Table 5 includes results from loop bonding tests (i.a. FI-application no. 961252/180396: p. 29, line 20 - p. 30, line 9; EPO no. 079922) at high (index 2) and low (index 1) temperature for some peripherally oxidized fibers.
  • thermobonding of peripherally oxidized fibers where the change in tensile strength as a function of temperature is small, but on the other hand the increase in elongation (%) and energy to break (mN x mm) is considerable. This is due to the better wettability and spreadability of the bonding melt along the solid surfaces of the fiber body.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Multicomponent Fibers (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Medical Uses (AREA)
EP98660111A 1997-11-07 1998-10-30 Verfahren zur Herstellung und Regelung von wärmeverbindbaren Kern-Mantel-Polyolefinfasern und daraus hergestellte Vliesstoffe Expired - Lifetime EP0915192B1 (de)

Applications Claiming Priority (2)

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FI974169 1997-11-07
FI974169A FI106046B (fi) 1997-11-07 1997-11-07 Polymeerien sulatilaista kehruuhapetusta soveltaen tuotettavien skin-core-tyyppisten, termosidottavien polyolefiinikuitujen valmistus- ja säätömenetelmä sekä tähän liittyvä nonwoven-kankaiden lujuusominaisuuksien säätömenetelmä

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004020722A2 (en) * 2002-08-28 2004-03-11 Corovin Gmbh Spunbonded nonwoven made of endless fibers
WO2013023985A3 (de) * 2011-08-12 2013-06-20 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Verfahren zur herstellung von oberflächenmodifizierten polyolefinfilamentgarnen, die danach erhältlichen polyolefinfilamentgarne sowie deren verwendung
CN115103935A (zh) * 2020-02-24 2022-09-23 兰精股份公司 用于制造纺粘型无纺织物的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0445536A2 (de) * 1990-02-05 1991-09-11 Hercules Incorporated Heiss-verschweissbare Faser mit hoher Festigkeit
EP0552013A2 (de) * 1992-01-13 1993-07-21 Hercules Incorporated Wärmeverbindbare Fasern für wiederstandsfähige Vliesstoffe
EP0630996A2 (de) * 1993-06-24 1994-12-28 Hercules Incorporated Kern-Mantel-Faser mit hoher thermischer Haftfestigkeit in einem Schmelzspinnsystem
EP0719879A2 (de) * 1994-12-19 1996-07-03 Hercules Incorporated Verfahren zur Herstellung von Fasern für hochfeste Vliesstoffen und daraus hergestellte Fasern und Vliesstoffe
EP0799922A1 (de) * 1996-03-18 1997-10-08 J.W. Suominen Oy Verfahren zur Regelung der thermischen Vliesverfestigung für Kunstfasern
WO1997037065A1 (en) * 1996-03-29 1997-10-09 Hercules Incorporated Polypropylene fibers and items made therefrom

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0445536A2 (de) * 1990-02-05 1991-09-11 Hercules Incorporated Heiss-verschweissbare Faser mit hoher Festigkeit
EP0552013A2 (de) * 1992-01-13 1993-07-21 Hercules Incorporated Wärmeverbindbare Fasern für wiederstandsfähige Vliesstoffe
EP0630996A2 (de) * 1993-06-24 1994-12-28 Hercules Incorporated Kern-Mantel-Faser mit hoher thermischer Haftfestigkeit in einem Schmelzspinnsystem
EP0719879A2 (de) * 1994-12-19 1996-07-03 Hercules Incorporated Verfahren zur Herstellung von Fasern für hochfeste Vliesstoffen und daraus hergestellte Fasern und Vliesstoffe
EP0799922A1 (de) * 1996-03-18 1997-10-08 J.W. Suominen Oy Verfahren zur Regelung der thermischen Vliesverfestigung für Kunstfasern
WO1997037065A1 (en) * 1996-03-29 1997-10-09 Hercules Incorporated Polypropylene fibers and items made therefrom

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004020722A2 (en) * 2002-08-28 2004-03-11 Corovin Gmbh Spunbonded nonwoven made of endless fibers
WO2004020722A3 (en) * 2002-08-28 2004-05-13 Corovin Gmbh Spunbonded nonwoven made of endless fibers
US7326663B2 (en) 2002-08-28 2008-02-05 Fiberweb Corovin Gmbh Spunbonded nonwoven made of endless fibers
WO2013023985A3 (de) * 2011-08-12 2013-06-20 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Verfahren zur herstellung von oberflächenmodifizierten polyolefinfilamentgarnen, die danach erhältlichen polyolefinfilamentgarne sowie deren verwendung
CN115103935A (zh) * 2020-02-24 2022-09-23 兰精股份公司 用于制造纺粘型无纺织物的方法
CN115103935B (zh) * 2020-02-24 2024-05-28 兰精股份公司 用于制造纺粘型无纺织物的方法

Also Published As

Publication number Publication date
FI974169A0 (fi) 1997-11-07
DE69815993T2 (de) 2004-05-19
EP0915192A3 (de) 1999-10-13
EP0915192B1 (de) 2003-07-02
FI106046B (fi) 2000-11-15
DE69815993D1 (de) 2003-08-07
FI974169A (fi) 1999-05-08
ATE244327T1 (de) 2003-07-15

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