EP0517628B1 - Process for the production of polyamide filaments with better productivity - Google Patents
Process for the production of polyamide filaments with better productivity Download PDFInfo
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- EP0517628B1 EP0517628B1 EP92420185A EP92420185A EP0517628B1 EP 0517628 B1 EP0517628 B1 EP 0517628B1 EP 92420185 A EP92420185 A EP 92420185A EP 92420185 A EP92420185 A EP 92420185A EP 0517628 B1 EP0517628 B1 EP 0517628B1
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- Prior art keywords
- spinning
- silica
- polyamide
- speed
- filaments
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- 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
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Definitions
- the present invention relates to a method for obtaining non-stretched polyamide based (PA) filaments with better productivity.
- Polyamide based yarn generally not drawn used for false twist stretch-texturing operation must have orientation and crystallinity properties weak, in order to better orient the macromolecules then to crystallize and thus fix the orientation during the process stretch-texturing without degrading or breaking the filaments during thermal fixing of the wire.
- PA compositions for compression and injection molding having more extensive softening and melting zones, making it possible to maintain a viscous flow and to avoid gels by incorporating PA mineral charges such as SiO 2 with a particle size of 1 to 40 ⁇ m.
- the present invention relates to the preparation of yarns for base of unstretched PA, preoriented, with improved productivity.
- a method according to claim 1 designed to improve the productivity during the spinning of a preoriented polyamide-based yarn, at a speed of at least 4000 m / min, by introduction into the molten polymer before spinning , in an amount of 0.05 to 1%, preferably 0.05 to 0.5% by weight of combustion silica, of particle size between 5 and 15 nm, in the form of a dispersion in a masterbatch of the same PA as that intended to be conformed.
- the mean interparticle distance of the SiO 2 aggregates in the final polymer is between 0.2 and 0.7 ⁇ m, the maximum value between 2 aggregates being ⁇ 3 ⁇ m.
- the filaments are cooled using a gas stream at room temperature then sized and returned to a speed between 4200 and 5800 m / min, the filaments preferably being intertwined before being returned.
- the productivity gain obtained is greater than 10%, more usually more than 15% or even more.
- the present invention also relates to wires according to claim 4.
- They are wires pre-oriented unstretched PA-based, containing 0.05 to 1%, preferably 0.05 to 0.5% by weight of particulate combustion silica between 5 and 15 nm (50 to 150 ⁇ ) evenly distributed in the PA, having a delay in crystallization and orientation.
- polyamide means polyhexamethylene adipamide, or copolyamides containing 85% or more hexamethylene adipamide units and up to 15% of other units obtained by replacing, for example, the starting adipic acid with a other diacid such as terephthalic acid, sebacic acid, and or replacing the two monomers with caprolactam for example.
- the starting polyamides may also contain known additives such as matting agents, stabilization with regard to light, heat and oxidation, additives intended to reduce the accumulation of static charges or modify the suitability for dyeing, etc.
- the polyamide used according to the present invention has a relative viscosity measured on a solution at 8.4% by weight by volume in 90% formic acid between 38 and 52, preferably 40 about.
- combustion silica is understood to mean silicon dioxide obtained by combustion of an organosilicon compound and commercially available under different brands such as the Aerosil 300 type from the Degussa company, or a silicon dioxide treated on the surface of known manner to avoid re-agglomerations.
- Silicas are ultrafine fillers in the form of aggregates consisting of elementary particles with a specific surface of between 100 and 450 m 2 / g, the size of which is between 5 and 15 nm (50 to 150 ⁇ ), more generally of the order of a hundred ⁇ and gathered in linear chains.
- the combustion silica is mixed with PA identical to PA to be conformed in a phase mixing apparatus fondue such as a twin screw extruder or any suitable device, in proportions such as a master mix of 1-10% silica, preferably 2-5% is obtained in the form of granules at 260-280 ° C, preferably about 260-270 ° C.
- the masterbatch granules thus obtained contain very uniformly distributed silica. Distribution in the final polymer is evaluated by the mean interparticle distance of the aggregates.
- the interparticle distance average of the aggregates in the final polymer is between 0.2 and 0.7 ⁇ m, the maximum value between two silica aggregates being ⁇ 3 ⁇ m.
- interparticle distance obviously depends on the rate of introduced silica: the higher the silica, the lower the distance interparticle.
- dispersion of silica in the polyamide depends in part on the type of silica used, certain silicas coated disperses better than uncoated silica.
- silica content is> 1%, this will affect the rheological behavior of the polymer and in particular the spinning risk to be disturbed by broken strands.
- the silica content is less than 0.05%, the distance mean interparticle becomes too high, the silica level introduced is insufficient to modify the structure of the polyamide of so that the desired effect is not obtained.
- Masterbatches are introduced in proportions various depending on the desired silica content, in the polyamide which can be either in the molten state or in the state of granules, before spinning by example using a twin screw mixer extruder heated between 260-270 ° C or any other suitable means.
- the desired level of silica on wire is between 0.05 and 1%, preferably 0.05 and 0.5% by weight.
- the spinning is carried out at the usual temperatures for the polyamide between 280 and 295 ° C, preferably close to 285 ° C and the filaments are cooled under the die by a gas stream of cooling then sized and rewound at speeds between 4200 and 5800 m / min. Cooling conditions may vary by depending on the cooling device used, the precise speed the spinning, the title and the number of filaments, these settings being spring of the skilled person.
- the filaments are intertwined and / or intertwined before rewinding for better subsequent rewinding.
- the method according to the invention surprisingly and unexpected, allows to obtain unstretched, preoriented filaments, with improved productivity greater than 10%, generally greater than 15% or even more, due to a delay in the orientation of the filaments: that is to say that for the same level of orientation of the filaments, the winding speed is greater than 10% or even 15% or more.
- the introduction of 0.05 to 1% preferably 0.05% to 0.5% of combustion silica caused a delay in the reduction of the elongation at break or close to break of the filaments in function of the spinning speed, delay which corresponds to a delay at the orientation of the filaments along the spinning path.
- This delayed orientation provides pre-oriented, unstretched yarn having characteristics identical to those of the wires obtained at at least 10% lower speeds, more generally at least 15%, calculated in relation to the values of their elongation at rupture, or their elongation corresponding to the same stress, close to breaking.
- the values of elongations at break or at a given stress are measured with a known normal dynamoneter commercially under the brand Instron 1122 connected to a calcuter; each value represents the average over 20 measurements.
- Figure 1 shows the offset of the elongation values at the breakage as a function of the spinning speed by loaded wires respectively 0.05 and 0.5% by weight of silica relative to a uncharged control polymer and for speeds greater than 4000 m / min.
- the value of elongations on unstretched polyamide yarn control, spun at speeds below 4000 m / min is also indicated with reference.
- the delay in the orientation of the modified yarns according to the invention is confirmed by the values of the sonic and birefringence module which are measured as follows.
- Sonic module we measure the phase change caused by variations in mechanical wavelength longitudinal of a wire which passes between a frequency transmitting probe 6750 cycles / sec and a receiving probe. Phase changes, for example a simple relationship, directly represent the changes in the speed of sound which are, by well known changes, the image of module changes.
- the sonic or dynamic module is directly proportional to the square of the speed of sound in the sample by the density of matter.
- Birefringence measured on circular strand only.
- the refractive indices are obtained by a method compensation optics (polarized light and Berek compensator) on individual filament kept taut under low tension in dispersion in petroleum jelly oil.
- the present invention therefore makes it possible to produce at speeds of spinning above 4000 m / min of pre-oriented polyamide yarns, not stretched with a delayed orientation corresponding to those of yarn obtained at speeds lower by at least 10%, more usually 15% or even more.
- Such threads having an orientation have the mechanical characteristics of wires obtained at lower speeds which allows their false texturing torsion under good conditions by the texturing stretching processes simultaneous, skewer or friction. They can also be used for all textile transformations such as weaving, hosiery or the manufacture of non-woven tablecloths.
- silica does not alter the mechanical properties of the wires necessary for their use later; moreover, the combustion silica is inexpensive and does not no significant modification of industrial installations required of spinning.
- a 5% silica masterbatch is produced using an extruder fully meshed corotative double screw, known commercially as the Leistreitz LSM 30/34 brand, working at a rotational speed average of 300 rpm and at a temperature varying from 260-270 ° C.
- the combustion silica used is an ultrafine commercial filler of the A 300 type from the Degussa company. It is in the form of aggregates made up of elementary particles with a specific surface of 300 m 2 / g, with an apparent density of 0.05 to 0.06, the particle size being between 5 and 15 nm (50 to 150 ⁇ ).
- the master mixture of 5% silica is then introduced in various proportions, according to the final desired silica content, into the polyamide in the molten state before spinning, by means of a twin-screw kneader extruder heated to an increasing temperature. from 260 to 270 ° C and with a rotation speed of 300 rpm.
- the temperature profile allows the material to melt polyamide before the addition of the filler which is therefore done in the middle molten.
- a vacuum zone is established on part of the extruder in order to ensure the drying of the polyamide.
- the final silica content and the average interparticle distance between aggregates in the final polymer are as follows:
- Polyamide loaded with silica is spun through a plate die maintained at 283 ° C with 2 times 7 round section orifices 0.34 mm in diameter and the hole height is 4 times its diameter. Spinning is carried out at a constant flow rate per orifice of 1.68 g / min.
- the filaments are converged and simultaneously sized and then interlaced by means of a pneumatic nozzle, (air pressure 2 bar) and rewound at different speeds: 4200 - 5000 - 5800 m / min.
- control wire is obtained in an identical manner but lower spinning speeds were achieved for the evaluation of the productivity gain from elongation at break values.
- Examples 1 to 3 The process used in Examples 1 to 3 is reproduced in using combustion silica with the same specific surface area and density, surface treated with octamethylcyclotetrasilaxone in gas phase to avoid re-agglomerations.
- a master mixture is prepared with 5% of treated silica of the as indicated in Examples 1 to 3.
- the masterbatch is introduced in the form of granules at the same time as the polyamide to conform in a twin screw mixer extruder heated to a increasing temperature between 260 and 270 ° C and with a speed of rotation of 300 rpm.
- a vacuum zone ensures the drying of the polymer in the last part of the extruder.
- the final silica content and the average interparticle distance in the final polymer are as follows: Ex. Silica content by weight Average interparticle distance between aggregates Aggregate size 4 0.5% 0.7 ⁇ m 0.1 ⁇ m 5 1% 0.6 ⁇ m 0.1 ⁇ m
- Polyamide loaded with silica is spun through a plate die maintained at 282 ° C comprising twice 10 orifices of round section 0.39 mm in diameter and the height of the orifice is 4 times its diameter.
- the spinning is carried out on a constant basis.
- the filaments are converged and sized simultaneously then interlaced by means of a pneumatic nozzle (air pressure 2.2 bars) and rewound at different speeds: 4800 - 5500 m / min.
- control thread is obtained in an identical manner (but lower spinning speeds were achieved for the evaluation of the productivity gain from elongation values).
- the wire elongation values are collated in the following table: Speed m / min % SiO2 Elongation% Productivity gain % 4800 0 66.6 - 4800 0.5 73.9 17 4800 1 76.1 21.5 5500 0 56.7 - 5500 0.5 64.2 11 5500 1 67.4 15.9
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
La présente invention concerne un procédé permettant d'obtenir des filaments à base de polyamide (PA) non étirés avec une meilleure productivité.The present invention relates to a method for obtaining non-stretched polyamide based (PA) filaments with better productivity.
Elle concerne également les fils modifiés non étirés à base de polyamide convenant pour la texturation par étirage-texturation fausse torsion.It also relates to modified non-stretched yarns based on polyamide suitable for false stretch-texturing texturing torsion.
Les fils à base de polyamide non étirés généralement utilisés pour l'opération d'étirage-texturation par fausse torsion doivent présenter des propriétés d'orientation et de cristallinité faible, de manière à mieux orienter les macromolécules puis à cristalliser et fixer ainsi l'orientation au cours du processus d'étirage-texturation sans dégrader ou casser les filaments lors de la fixation thermique du fil.Polyamide based yarn generally not drawn used for false twist stretch-texturing operation must have orientation and crystallinity properties weak, in order to better orient the macromolecules then to crystallize and thus fix the orientation during the process stretch-texturing without degrading or breaking the filaments during thermal fixing of the wire.
En particulier, il est connu selon la demande de brevet français publiée sous le n° 2 274 710 de préparer des fils PA utilisables directement dans des procédés d'étirage-texturation par fausse torsion, par filage à l'état fondu de polyhexaméthylène adipamide, refroidissement, traitement dans une atmosphère de vapeur d'eau et sous pression pour obtenir les propriétés désirées de fil, et de préférence léger surétirage des fils avant le renvidage. Celui-ci est réalisé à des vitesses généralement comprises entre 2700 et 4000 m/min.In particular, it is known according to the patent application French published under No. 2,274,710 to prepare PA yarns usable directly in stretch-texturing processes by false twist, by melt spinning of polyhexamethylene adipamide, cooling, treatment in a vapor atmosphere of water and under pressure to obtain the desired properties of yarn, and preferably slight overstretching of the threads before rewinding. It is performed at speeds generally between 2700 and 4000 m / min.
Pour augmenter la vitesse de filage sans modifier sensiblement les propriétés de cristallinité et d'orientation des fils POY non étirés, il a également été proposé dans la demande de brevet européen publiée sous le n° 08274 (A) d'introduire dans le PA fondu du polyéthylène ou de polypropylène formant ensuite des mocrofibrilles dans les filaments obtenus.To increase spinning speed without significantly changing the crystallinity and orientation properties of POY yarns not stretched, it has also been proposed in the European patent application published under No. 08274 (A) to introduce into the melted PA of polyethylene or polypropylene then forming microfibrils in the filaments obtained.
Mais l'addition de polymère sous forme de fines particules présente des inconvénients lors d'une réalisation industrielle : en particulier, elle nécessite une technologie très sophistiquée pour l'obtention de mélanges ayant une finesse et une stabilité dans le temps suffisantes pour permettre un filage fiable et sans casses de brins. De fait une telle technique n'est pas utilisable industriellement.But the addition of polymer in the form of fine particles has drawbacks during industrial production: particular, it requires very sophisticated technology to obtaining mixtures with finesse and stability over time sufficient to allow reliable spinning without breakage of strands. Of made such a technique is not usable industrially.
Il est également connu d'améliorer la productivité des fils PA non orientés, aptes à la texturation par fausse-torsion, par introduction dans les chaínes polymériques de 0,01 à 1 mole % d'un agent de branchement tel que la bishexaméthylène triamine, ou l'acide trimésique, ou l'aminométhyl-4 diamino octane-1,8. Mais de tels composés modifient la rhéologie du polymère en augmentant sa viscoélasticité de sorte que le filage de tels copolymères devient très délicat et présente des risques importants de casses de brins.It is also known to improve the productivity of yarns PA not oriented, suitable for texturing by false-twist, by introduction into the polymer chains of 0.01 to 1 mol% of an agent connection such as bishexamethylene triamine, or acid trimesic, or 4-aminomethyl diamino octane-1,8. But such compounds modify the rheology of the polymer by increasing its viscoelasticity by so that the spinning of such copolymers becomes very delicate and presents significant risks of breakage of strands.
Par ailleurs, il est également connu, selon la demande de brevet français publiée sous le n° 1 428 439 de préparer des compositions résineuses de PA contenant de la silice sous forme de particules < 10 µm de conductance spécifique < 5.10-4 mho/cm.Furthermore, it is also known, according to French patent application published under No. 1,428,439, to prepare resinous compositions of PA containing silica in the form of particles <10 μm of specific conductance <5.10 -4 mho / cm .
Mais l'utilisation de telles compositions concerne les applications matières plastiques.But the use of such compositions relates to plastics applications.
Il est également connu selon le brevet français n° 1 169 578 de préparer des compositions de PA pour moulage par compression et injection ayant des zones de ramollissement et de fusion plus étendues, permettant de maintenir un écoulement visqueux et d'éviter les gels en incorporant au PA des charges minérales telles que le SiO2 de dimension de particule 1 à 40 µm.It is also known according to French Patent No. 1,169,578 to prepare PA compositions for compression and injection molding having more extensive softening and melting zones, making it possible to maintain a viscous flow and to avoid gels by incorporating PA mineral charges such as SiO 2 with a particle size of 1 to 40 µm.
Il est aussi connu selon le brevet français n°. 951 371 un procédé de fabrication de (filaments et) fils à base, entre autres, de polyhéxaméthylèneadipamide, dans lequel procédé on incorpore dans le polymère, avant son filage conventionnel à l' état de fusion, une substance inerte en quantité de 0,005 % à 0,05 %, substance inerte qui, même en étant de préférence le dioxyde de titane, néanmoins peut consister aussi en de la silice. Cependant, ce procédé connu est à basse vitesse et les fils obtenus sont étirés.It is also known according to French patent no. 951 371 a process for manufacturing (filaments and) yarns based on, between others, of polyhexamethyleneadipamide, in which process one incorporates into the polymer, before its spinning conventional in the molten state, an inert substance in an amount of 0.005% to 0.05%, an inert substance which, even preferably being titanium dioxide, nevertheless may also consist of silica. However, this known method is at low speed and the wires obtained are drawn.
La présente invention a pour objet la préparation de fils à base de PA non étirés, préorientés, avec une productivité améliorée.The present invention relates to the preparation of yarns for base of unstretched PA, preoriented, with improved productivity.
Plus particulièrement elle concerne un procédé selon la revendication 1, conçu pour améliorer la productivité lors du filage d'un fil préorienté à base de polyamide, à une vitesse d'au moins 4000 m/min, par introduction, dans le polymère fondu avant filage, d'une quantité de 0,05 à 1% de préférence de 0,05 à 0,5 % en poids de silice de combustion, de dimension particulaire comprise entre 5 et 15 nm, sous forme de dispersion dans un mélange maítre du même PA que celui destiné à être conformé. La distance interparticulaire moyenne des agrégats de SiO2 dans le polymère final est comprise entre 0,2 et 0,7 µm, la valeur maximale entre 2 agrégats étant ≤ 3 µm.More particularly, it relates to a method according to claim 1, designed to improve the productivity during the spinning of a preoriented polyamide-based yarn, at a speed of at least 4000 m / min, by introduction into the molten polymer before spinning , in an amount of 0.05 to 1%, preferably 0.05 to 0.5% by weight of combustion silica, of particle size between 5 and 15 nm, in the form of a dispersion in a masterbatch of the same PA as that intended to be conformed. The mean interparticle distance of the SiO 2 aggregates in the final polymer is between 0.2 and 0.7 μm, the maximum value between 2 aggregates being ≤ 3 μm.
Après filage, les filaments sont refroidis au moyen d'un courant gazeux à température ambiante puis ensimés et renvidés à une vitesse comprise entre 4200 et 5800 m/min, les filaments étant de préférence entrelacés avant d'être renvidés.After spinning, the filaments are cooled using a gas stream at room temperature then sized and returned to a speed between 4200 and 5800 m / min, the filaments preferably being intertwined before being returned.
Le gain de productivité obtenu est supérieur à 10 %, plus généralement supérieur à 15 % ou même plus.The productivity gain obtained is greater than 10%, more usually more than 15% or even more.
La présente invention concerne également des fils selon la revendication 4. Il s'agit de fils préorientés non étirés à base de PA, contenant 0,05 à 1 %, de préférence 0,05 à 0,5 % en poids de silice de combustion de dimension particulaire comprise entre 5 et 15 nm (50 à 150 Å) répartie régulièrement dans le PA, présentant un retard à la cristallisation et à l'orientation.The present invention also relates to wires according to claim 4. They are wires pre-oriented unstretched PA-based, containing 0.05 to 1%, preferably 0.05 to 0.5% by weight of particulate combustion silica between 5 and 15 nm (50 to 150 Å) evenly distributed in the PA, having a delay in crystallization and orientation.
Dans la description, on entend par polyamide le polyhexaméthylène adipamide, ou des copolyamides contenant au moins 85 % d'unités hexaméthylène adipamide et jusqu'à 15 % d'autres unités obtenues en remplaçant par exemple l'acide adipique de départ par un autre diacide tel que l'acide téréphtalique, sébacique, et ou en remplaçant les deux monomères par du caprolactame par exemple.In the description, polyamide means polyhexamethylene adipamide, or copolyamides containing 85% or more hexamethylene adipamide units and up to 15% of other units obtained by replacing, for example, the starting adipic acid with a other diacid such as terephthalic acid, sebacic acid, and or replacing the two monomers with caprolactam for example.
Les polyamides de départ peuvent également contenir des additifs connus tels que des agents matifiants, des agents de stabilisation vis-à-vis de la lumière, de la chaleur et de l'oxydation, des additifs destinés à réduire l'accumulation des charges statiques ou modifier l'aptitude à la teinture, etc...The starting polyamides may also contain known additives such as matting agents, stabilization with regard to light, heat and oxidation, additives intended to reduce the accumulation of static charges or modify the suitability for dyeing, etc.
Le polyamide utilisé selon la présente invention présente une viscosité relative mesurée sur une solution à 8,4 % en poids par volume dans l'acide formique à 90 % comprise entre 38 et 52, de préférence 40 environ.The polyamide used according to the present invention has a relative viscosity measured on a solution at 8.4% by weight by volume in 90% formic acid between 38 and 52, preferably 40 about.
Sous l'expression silice de combustion, on entend le dioxyde de silicium obtenu par combustion d'un composé organosilicié et accessible dans le commerce sous différentes marques tels que le type Aérosil 300 de la Société Degussa, ou un dioxyde de silicium traité en surface de manière connue pour éviter les réagglomérations. Les silices sont des charges ultrafines se présentant sous forme d'agrégats constitués de particules élémentaires de surface spécifique comprise entre 100 et 450 m2/g, dont la taille est comprise entre 5 et 15 nm (50 à 150 Å), plus généralement de l'ordre de la centaine d'Å et rassemblés en chaínes linéaires.The expression combustion silica is understood to mean silicon dioxide obtained by combustion of an organosilicon compound and commercially available under different brands such as the Aerosil 300 type from the Degussa company, or a silicon dioxide treated on the surface of known manner to avoid re-agglomerations. Silicas are ultrafine fillers in the form of aggregates consisting of elementary particles with a specific surface of between 100 and 450 m 2 / g, the size of which is between 5 and 15 nm (50 to 150 Å), more generally of the order of a hundred Å and gathered in linear chains.
Selon l'invention la silice de combustion est mélangée à du PA identique au PA à conformer dans un appareil de mélangeage en phase fondue tel que une extrudeuse double vis ou tout dispositif approprié, dans des proportions telles qu'un mélange maítre à 1-10 % de silice, de préférence 2-5 % est obtenu sous forme de granulés à 260-280°C, de préférence environ 260-270°C.According to the invention the combustion silica is mixed with PA identical to PA to be conformed in a phase mixing apparatus fondue such as a twin screw extruder or any suitable device, in proportions such as a master mix of 1-10% silica, preferably 2-5% is obtained in the form of granules at 260-280 ° C, preferably about 260-270 ° C.
Les granulés de mélange-maítre ainsi obtenus contiennent de la silice très uniformément répartie. La répartition dans le polymère final est évaluée par la distance moyenne interparticulaire des agrégats.The masterbatch granules thus obtained contain very uniformly distributed silica. Distribution in the final polymer is evaluated by the mean interparticle distance of the aggregates.
En effet, selon l'invention, la distance interparticulaire moyenne des agrégats dans le polymère final est comprise entre 0,2 et 0,7 µm, la valeur maximale entre deux agrégats de silice étant ≦ 3 µm. Cette évaluation est faite à partir de photographies réalisées en microscopie électronique, les photographies étant ensuite traitées en analyse d'image afin de connaítre le nombre de particules et de calculer la distance interparticulaire de chaque agrégat.According to the invention, the interparticle distance average of the aggregates in the final polymer is between 0.2 and 0.7 µm, the maximum value between two silica aggregates being ≦ 3 µm. This assessment is made from photographs taken in electron microscopy, the photographs then being processed in image analysis in order to know the number of particles and calculate the interparticle distance of each aggregate.
La distance interparticulaire dépend évidemment du taux de silice introduite : plus celui-ci est élevé plus faible sera la distance interparticulaire. Par ailleurs la dispersion de silice dans le polyamide dépend en partie du type de silice utilisée, certaines silices enrobées se dispersant mieux que les silices non enrobées.The interparticle distance obviously depends on the rate of introduced silica: the higher the silica, the lower the distance interparticle. Furthermore, the dispersion of silica in the polyamide depends in part on the type of silica used, certain silicas coated disperses better than uncoated silica.
Si le taux de silice est > 1 %, cela aura une incidence sur le comportement rhéologique du polymère et en particulier le filage risque d'être perturbé par des casses de brins.If the silica content is> 1%, this will affect the rheological behavior of the polymer and in particular the spinning risk to be disturbed by broken strands.
Si le taux de silice est inférieur à 0,05 %, la distance interparticulaire moyenne devient trop élevée, le taux de silice introduit est insuffisant pour modifier la structure du polyamide de sorte que l'effet recherché n'est pas obtenu.If the silica content is less than 0.05%, the distance mean interparticle becomes too high, the silica level introduced is insufficient to modify the structure of the polyamide of so that the desired effect is not obtained.
Les mélanges maítres sont introduits dans des proportions diverses selon le taux de silice désiré, dans le polyamide qui peut être soit à l'état fondu, soit à l'état de granulés, avant le filage par exemple au moyen d'une extrudeuse malaxeuse double vis chauffée entre 260-270°C ou tout autre moyen approprié.Masterbatches are introduced in proportions various depending on the desired silica content, in the polyamide which can be either in the molten state or in the state of granules, before spinning by example using a twin screw mixer extruder heated between 260-270 ° C or any other suitable means.
Selon l'invention le taux de silice désiré sur fil, est compris entre 0,05 et 1 %, de préférence 0,05 et 0,5 % en poids.According to the invention the desired level of silica on wire is between 0.05 and 1%, preferably 0.05 and 0.5% by weight.
Le filage est réalisé aux températures habituelles pour le polyamide entre 280 et 295°C, de préférence voisine de 285°C et les filaments sont refroidis sous la filière par un courant gazeux de refroidissement puis ensimés et renvidés à des vitesses comprises entre 4200 et 5800 m/min. Les conditions de refroidissement peuvent varier en fonction du dispositif de refroidissement utilisé, de la vitesse précise du filage, du titre et du nombre de filaments, ces réglages étant du ressort de l'homme de métier.The spinning is carried out at the usual temperatures for the polyamide between 280 and 295 ° C, preferably close to 285 ° C and the filaments are cooled under the die by a gas stream of cooling then sized and rewound at speeds between 4200 and 5800 m / min. Cooling conditions may vary by depending on the cooling device used, the precise speed the spinning, the title and the number of filaments, these settings being spring of the skilled person.
De préférence, les filaments sont entrelacés et/ou entremêlés avant le renvidage pour une meilleure dévidabilité ultérieure.Preferably, the filaments are intertwined and / or intertwined before rewinding for better subsequent rewinding.
Le procédé selon l'invention, de manière surprenante et inattendue, permet d'obtenir des filaments non étirés, préorientés, avec une productivité améliorée supérieure à 10 %, généralement supérieure à 15 % ou même plus, due à un retard à l'orientation des filaments : c'est-à-dire que pour un même niveau d'orientation des filaments, la vitesse de renvidage est supérieure à 10 % ou même 15 % et plus.The method according to the invention, surprisingly and unexpected, allows to obtain unstretched, preoriented filaments, with improved productivity greater than 10%, generally greater than 15% or even more, due to a delay in the orientation of the filaments: that is to say that for the same level of orientation of the filaments, the winding speed is greater than 10% or even 15% or more.
Les études scientifiques montrent que lors de l'obtention directe des fils PA non étirés depuis des vitesses très basses (500 à 1000 m/min) jusqu'à au moins plus de 6000 m/min, on observe d'abord une forte orientation des zones cristallines et amorphes, puis une orientation plus faible, l'orientation étant développée essentiellement par la contrainte de filage qui est surtout fonction de la vitesse d'appel et du titre des filaments. L'état d'orientation du matériau, en particulier l'orientation de la phase amorphe, l'organisation des phases cristallines et amorphes, l'interface entre les phases cristallines et amorphes, pour un polyamide donné, est nettement mis en évidence par l'allongement à la rupture des fils issus de ce matériau. Celui-ci, en effet, diminue de manière importante depuis des vitesses de filage allant de 1000 m à 4000 m/min, puis de manière nettement plus faible de 4000 à 6000 m/min et au delà. De ce fait il est difficile d'obtenir des fils polyamides préorientés non étirés, apte aux procédés d'étirage-texturation utilisés à ce jour à des vitesses supérieures à 4000 m/min.Scientific studies show that when obtaining direct PA wires not drawn from very low speeds (500 to 1000 m / min) up to at least more than 6000 m / min, we first observe a strong orientation of crystalline and amorphous areas, then a weaker orientation, the orientation being developed essentially by the spinning constraint which is mainly a function of the speed and title of filaments. The orientation state of the material, in particularly the orientation of the amorphous phase, the organization of the phases crystalline and amorphous, the interface between the crystalline phases and amorphous, for a given polyamide, is clearly highlighted by the elongation at break of the wires from this material. This one, in effect, decreases significantly from spinning speeds from 1000 m to 4000 m / min, then significantly lower by 4000 to 6000 m / min and beyond. This makes it difficult to obtain non-stretched pre-oriented polyamide yarns, suitable for stretch-texturing processes used to date at speeds greater than 4000 m / min.
Selon la présente invention, il a été trouvé, de manière surprenante, que l'introduction de 0,05 à 1 % de préférence 0,05 % à 0,5 %, de silice de combustion provoquait un retard à la diminution de l'allongement à la rupture ou proche de la rupture des filaments en fonction de la vitesse de filage, retard qui correspond à un retard à l'orientation des filaments le long du chemin de filage. Cette orientation retardée permet d'obtenir des fils préorientés, non étirés possédant des caractéristiques identiques à celles des fils obtenus à des vitesses inférieures d'au moins 10 %, plus généralement au moins 15 %, calculées par rapport aux valeurs de leur allongement à la rupture, ou leur allongement correspondant à même contrainte, proche de la rupture.According to the present invention, it has been found, so surprisingly, that the introduction of 0.05 to 1% preferably 0.05% to 0.5% of combustion silica caused a delay in the reduction of the elongation at break or close to break of the filaments in function of the spinning speed, delay which corresponds to a delay at the orientation of the filaments along the spinning path. This delayed orientation provides pre-oriented, unstretched yarn having characteristics identical to those of the wires obtained at at least 10% lower speeds, more generally at least 15%, calculated in relation to the values of their elongation at rupture, or their elongation corresponding to the same stress, close to breaking.
Selon l'invention, les valeurs d'allongements à la rupture ou à une contrainte donnée sont mesurées avec un dynamonètre normal connu dans le commerce sous la marque Instron 1122 relié à un calcuteur ; chaque valeur représente la moyenne sur 20 mesures.According to the invention, the values of elongations at break or at a given stress are measured with a known normal dynamoneter commercially under the brand Instron 1122 connected to a calcuter; each value represents the average over 20 measurements.
Allongement à une contrainte de référence : lc - lo / lo × 100
lc = longueur correspondant à la contrainte de référence ou de rupture,
lo = longueur initiale.Elongation at a reference stress: lc - lo / lo × 100
lc = length corresponding to the reference or rupture stress,
lo = initial length.
La figure 1 montre le décalage des valeurs d'allongement à la rupture en fonction de la vitesse de filage par des fils chargés respectivement de 0,05 et 0,5 % en poids de silice par rapport à un polymère témoin non chargé et pour des vitesses supérieures à 4000 m/min. La valeur des allongements sur fils polyamide non étirés témoin, filés à des vitesses inférieures à 4000 m/min est également indiquée en référence.Figure 1 shows the offset of the elongation values at the breakage as a function of the spinning speed by loaded wires respectively 0.05 and 0.5% by weight of silica relative to a uncharged control polymer and for speeds greater than 4000 m / min. The value of elongations on unstretched polyamide yarn control, spun at speeds below 4000 m / min is also indicated with reference.
Le retard à l'orientation des fils modifiés selon l'invention est confirmé par les valeurs du module sonique et de biréfringence qui sont mesurées de la manière suivante.The delay in the orientation of the modified yarns according to the invention is confirmed by the values of the sonic and birefringence module which are measured as follows.
Module sonique = on effectue la mesure du changement de phase électrique causé par les variations de longueur d'onde mécanique longitudinale d'un fil qui défile entre une sonde émetrice de fréquence 6750 cycles/sec et une sonde réceptrice. Les changements de phase, par une relation simple, représentent directement les changements de la vitesse du son qui sont, par des changements bien connus, l'image des changements de module. Le module sonique ou dynamique est directement proportionnel au carré de la vitesse du son dans l'échantillon par la densité de la matière. Sonic module = we measure the phase change caused by variations in mechanical wavelength longitudinal of a wire which passes between a frequency transmitting probe 6750 cycles / sec and a receiving probe. Phase changes, for example a simple relationship, directly represent the changes in the speed of sound which are, by well known changes, the image of module changes. The sonic or dynamic module is directly proportional to the square of the speed of sound in the sample by the density of matter.
Biréfringence = mesurée sur brin circulaire seulement.Birefringence = measured on circular strand only.
La biréfringence d'un filament témoigne de l'orientation
macromoléculaire de sa matière. Elle est égale à la différence des
indices de réfraction dans les directions parallèles et perpendiculaire
à l'axe du filament :
Les indices de réfractions sont obtenus par une méthode optique de compensation (lumière polarisée et compensateur de Berek) sur filament individuel maintenu tendu sous faible tension en dispersion dans de l'huile de vaseline.The refractive indices are obtained by a method compensation optics (polarized light and Berek compensator) on individual filament kept taut under low tension in dispersion in petroleum jelly oil.
La présente invention permet donc de produire à des vitesses de filage supérieures à 4000 m/min des fils polyamides préorientés, non étirés présentant une orientation retardée correspondant à celles de fils obtenus à des vitesses inférieures d'au moins 10 %, plus généralement 15 % ou même plus. De tels fils ayant une orientation retardée présentent les caractéristiques mécaniques de fils obtenus à des plus basses vitesses ce qui permet leur texturation par fausse torsion dans de bonnes conditions par les procédés d'étirage texturation simultané, brochette ou friction. Ils peuvent également être utilisés pour toutes les transformations textiles telles que tissage, bonneterie ou la fabrication de nappes non-tissées.The present invention therefore makes it possible to produce at speeds of spinning above 4000 m / min of pre-oriented polyamide yarns, not stretched with a delayed orientation corresponding to those of yarn obtained at speeds lower by at least 10%, more usually 15% or even more. Such threads having an orientation have the mechanical characteristics of wires obtained at lower speeds which allows their false texturing torsion under good conditions by the texturing stretching processes simultaneous, skewer or friction. They can also be used for all textile transformations such as weaving, hosiery or the manufacture of non-woven tablecloths.
Par ailleurs l'introduction de silice n'altère pas les propriétés mécaniques des fils nécessaires pour leur utilisation ultérieure ; de plus la silice de combustion est peu onéreuse et ne nécessite pas de modification importante des installations industrielles de filage.Furthermore, the introduction of silica does not alter the mechanical properties of the wires necessary for their use later; moreover, the combustion silica is inexpensive and does not no significant modification of industrial installations required of spinning.
Les exemples qui suivent sont donnés à titre indicatif mais non limitatif pour illustrer l'invention.The examples which follow are given as an indication but nonlimiting to illustrate the invention.
On réalise un mélange maítre à 5 % de silice au moyen d'une extrudeuse double vis corotative totalement engrenée, connue dans le commerce sous la marque Leistreitz LSM 30/34, travaillant à une vitesse de rotation moyenne de 300 t/min et à une température variant de 260-270°C. A 5% silica masterbatch is produced using an extruder fully meshed corotative double screw, known commercially as the Leistreitz LSM 30/34 brand, working at a rotational speed average of 300 rpm and at a temperature varying from 260-270 ° C.
La silice de combustion utilisée est une charge ultrafine du commerce de type A 300 de la Société Degussa. Elle se présente sous forme d'agrégats constitués de particules élémentaires de surface spécifique 300 m2/g, de densité apparente 0,05 à 0,06, la taille des particules étant comprise entre 5 et 15 nm (50 à 150 Å). Le mélange maítre à 5 % de silice est ensuite introduit dans des proportions diverses, selon le taux final de silice désiré, dans le polyamide à l'état fondu avant le filage, au moyen d'une extrudeuse malaxeuse double vis chauffée à une température croissante de 260 à 270°C et avec une vitesse de rotation de 300 tours/min.The combustion silica used is an ultrafine commercial filler of the A 300 type from the Degussa company. It is in the form of aggregates made up of elementary particles with a specific surface of 300 m 2 / g, with an apparent density of 0.05 to 0.06, the particle size being between 5 and 15 nm (50 to 150 Å). The master mixture of 5% silica is then introduced in various proportions, according to the final desired silica content, into the polyamide in the molten state before spinning, by means of a twin-screw kneader extruder heated to an increasing temperature. from 260 to 270 ° C and with a rotation speed of 300 rpm.
Le profil de température permet la fusion de la matière polyamide avant l'adjonction de la charge qui se fait donc en milieu fondu. Une zone de vide est instaurée sur une partie de l'extrudeuse afin d'assurer le séchage du polyamide.The temperature profile allows the material to melt polyamide before the addition of the filler which is therefore done in the middle molten. A vacuum zone is established on part of the extruder in order to ensure the drying of the polyamide.
Le taux de silice final et la distance interparticulaire moyenne entre agrégats dans le polymère final sont les suivants : The final silica content and the average interparticle distance between aggregates in the final polymer are as follows:
Le polyamide chargé de silice est filé au travers d'une plaque filière maintenue à 283°C comportant 2 fois 7 orifices de section ronde de 0,34 mm de diamètre est dont la hauteur de l'orifice est égale à 4 fois son diamètre. Le filage est effectué à débit constant par orifice de 1,68 g/min. Les filaments sont refroidis par un courant d'air transversal à température ambiante en présence d'humidité (HR = 60 %), envoyé à une vitesse de 50 m/min. Les filaments sont convergés et ensimés simultanément puis entrelacés au moyen d'une buse pneumatique, (pression d'air 2 bars) et renvidés à différentes vitesses : 4200 - 5000 - 5800 m/min. Polyamide loaded with silica is spun through a plate die maintained at 283 ° C with 2 times 7 round section orifices 0.34 mm in diameter and the hole height is 4 times its diameter. Spinning is carried out at a constant flow rate per orifice of 1.68 g / min. The filaments are cooled by a stream of air transverse at room temperature in the presence of humidity (RH = 60%), sent at a speed of 50 m / min. The filaments are converged and simultaneously sized and then interlaced by means of a pneumatic nozzle, (air pressure 2 bar) and rewound at different speeds: 4200 - 5000 - 5800 m / min.
Le fil témoin est obtenu de manière identique mais des vitesses de filage plus basses ont été réalisées pour l'évaluation du gain de productivité à partir des valeurs d'allongement à la rupture.The control wire is obtained in an identical manner but lower spinning speeds were achieved for the evaluation of the productivity gain from elongation at break values.
Les caractéristiques des fils sont rassemblés dans le tableau suivant : The characteristics of the wires are gathered in the following table:
D'après les valeurs ci-dessus on remarque que les meilleurs gains de productivité sont obtenus avec les plus fortes charges en silice. De tels fils sont destinés à la texturation sur les machines de fausse torsion habituelles.From the above values we notice that the best productivity gains are obtained with the highest loads in silica. Such threads are intended for texturing on the machines of usual false twist.
On reproduit le procédé utilisé dans les exemples 1 à 3 en utilisant une silice de combustion de mêmes surface spécifique et densité, traitée en surface par de l'octaméthylcyclotétrasilaxone en phase gazeuse pour éviter les réagglomérations.The process used in Examples 1 to 3 is reproduced in using combustion silica with the same specific surface area and density, surface treated with octamethylcyclotetrasilaxone in gas phase to avoid re-agglomerations.
On prépare un mélange maítre à 5 % de silice traitée de la manière indiquée dans les exemples 1 à 3. Le mélange maítre est introduit sous forme de granulés en même temps que le polyamide à conformer dans une extrudeuse malaxeuse à double vis chauffée à une température croissante entre 260 et 270°C et avec une vitesse de rotation de 300 tours/min. Une zone de vide assure le séchage du polymère dans la dernière partie de l'extrudeuse.A master mixture is prepared with 5% of treated silica of the as indicated in Examples 1 to 3. The masterbatch is introduced in the form of granules at the same time as the polyamide to conform in a twin screw mixer extruder heated to a increasing temperature between 260 and 270 ° C and with a speed of rotation of 300 rpm. A vacuum zone ensures the drying of the polymer in the last part of the extruder.
Le taux de silice final et la distance interparticulaire
moyenne dans le polymère final sont les suivants :
Le polyamide chargé de silice est filé au travers d'une plaque filière maintenue à 282°C comportant 2 fois 10 orifices de section ronde de 0,39 mm de diamètre et dont la hauteur de l'orifice est égale à 4 fois son diamètre. Le filage est effectué à titre constant. Les filaments sont refroidis par un courant d'air transversal à température ambiante en présence d'humidité (HR = 60 %), envoyé à une vitesse de 48 m/min. Les filaments sont convergés et ensimés simultanément puis entrelacés au moyen d'une buse pneumatique (pression d'air 2,2 bars) et renvidés à différentes vitesses : 4800 - 5500 m/min.Polyamide loaded with silica is spun through a plate die maintained at 282 ° C comprising twice 10 orifices of round section 0.39 mm in diameter and the height of the orifice is 4 times its diameter. The spinning is carried out on a constant basis. The filaments are cooled by a transverse air stream at temperature ambient in the presence of humidity (RH = 60%), sent at a speed of 48 m / min. The filaments are converged and sized simultaneously then interlaced by means of a pneumatic nozzle (air pressure 2.2 bars) and rewound at different speeds: 4800 - 5500 m / min.
Le fil témoin est obtenu de manière identique (mais des vitesses de filage plus basses ont été réalisées pour l'évaluation du gain de productivité à partir des valeurs d'allongement).The control thread is obtained in an identical manner (but lower spinning speeds were achieved for the evaluation of the productivity gain from elongation values).
Pour des raisons d'homogénéité des différents essais, les valeurs d'allongement ont été mesurés pour une contrainte de 45,6 cN/tex, identique pour tous les essais.For reasons of homogeneity of the different tests, the elongation values were measured for a stress of 45.6 cN / tex, identical for all tests.
Les valeurs d'allongement des fils sont rassemblées dans le
tableau suivant :
Claims (5)
- Process for manufacturing a polyamide-based undrawn preoriented yarn at a speed of at least 4000 m/min, characterized in that, before the spinning, a quantity of 0.05 to 1 % by weight of pyrogenic silica of particle size of between 5 and 15 nm is introduced into the molten polymer in the form of dispersion in a masterbatch of the same polyamide as that intended to be processed, the filaments after spinning being then cooled by means of a gas stream at room temperature and then sized and wound at a speed of between 4200 and 5800 m/min.
- Process according to Claim 1, characterized in that the gain in output efficiency is at least 10 % based on the measurement of the elongation.
- Process according to Claim 1, characterized in that the gain in output efficiency is at least 15 % based on the measurement of the elongation.
- Undrawn preoriented polyamide yarns obtained by the process according to Claim 1, characterized in that they contain from 0.05 to 1 % by weight of pyrogenic silica of particle size of between 5 and 15 nm and that they exhibit a delay in the orientation.
- Yarns according to Claim 4, characterized in that the mean interparticular distance between the silica aggregates is between 0.2 and 0.7 µm, the maximum value between 2 silica aggregates being ≤ 3 µm.
Applications Claiming Priority (2)
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FR9107190A FR2677376B1 (en) | 1991-06-07 | 1991-06-07 | PROCESS FOR OBTAINING POLYAMIDE YARNS WITH BETTER PRODUCTIVITY. |
FR9107190 | 1991-06-07 |
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FR2677376B1 (en) * | 1991-06-07 | 1994-04-01 | Rhone Poulenc Fibres | PROCESS FOR OBTAINING POLYAMIDE YARNS WITH BETTER PRODUCTIVITY. |
CA2134095C (en) * | 1993-02-23 | 2004-01-27 | Ryoji Okano | High-strength polyamide fiber |
CN1055706C (en) * | 1996-06-05 | 2000-08-23 | 中国科学院化学研究所 | Polyamide and clay nm composite and its prepn. |
CN1082058C (en) * | 1997-03-25 | 2002-04-03 | 北京天龙水处理技术公司 | Co-polymer of sulfonate, the prepn. method and use thereof |
EP1666648A4 (en) * | 2003-09-16 | 2007-10-03 | Teijin Ltd | Wholly aromatic polyamide fiber and process for producing the same |
CN1300251C (en) * | 2004-03-25 | 2007-02-14 | 中国科学院化学研究所 | Polyimide film and its prepn process and use |
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US2385890A (en) * | 1943-03-31 | 1945-10-02 | Du Pont | Spinning process |
DE1047986B (en) * | 1952-10-21 | 1958-12-31 | Degussa | Process for the production of synthetic fiber materials |
US2885308A (en) * | 1955-05-18 | 1959-05-05 | Monsanto Chemicals | Spinnable textile fibers treated with colloidal silica |
US2818173A (en) * | 1955-07-26 | 1957-12-31 | Nat Poultry Equipment Company | Automatic egg scale |
BE553172A (en) * | 1955-12-05 | |||
US3405211A (en) * | 1964-03-16 | 1968-10-08 | Du Pont | Method for producing quality yarn from gel-containing polyamide |
DE1225382B (en) * | 1964-12-23 | 1966-09-22 | Bayer Ag | Process for the production of finely crystalline and morphologically uniform molded parts from polyamides |
CH106968D (en) * | 1965-01-21 | 1900-01-01 | ||
US3652329A (en) * | 1970-01-27 | 1972-03-28 | Nalco Chemical Co | Method of treating textiles |
US3771307A (en) * | 1971-08-24 | 1973-11-13 | Du Pont | Drawing and bulking polyester yarns |
JPS4847550A (en) * | 1971-10-19 | 1973-07-06 | ||
US4096226A (en) * | 1972-01-03 | 1978-06-20 | Basf Aktiengesellschaft | Integrated spin-draw-texturizing process for manufacture of texturized polyamide filaments |
AR204352A1 (en) * | 1974-04-03 | 1975-12-22 | Du Pont | POLYHEXAMETHYLENADIPAMIDE THREAD WITHOUT STRETCHING VAPORIZED AND PROCEDURE FOR OBTAINING IT |
PH15509A (en) * | 1974-05-10 | 1983-02-03 | Du Pont | Improvements in an relating to synthetic polyesters |
JPS53111A (en) * | 1976-06-23 | 1978-01-05 | Nippon Hamondo Kk | Unit for setting tempo of automatic rhythm playing device |
JPS53111121A (en) * | 1977-03-08 | 1978-09-28 | Toyobo Co Ltd | Production of polyamide fiber |
DE3115759A1 (en) * | 1981-04-18 | 1982-11-04 | Hoechst Ag, 6000 Frankfurt | "METHOD FOR THE PRODUCTION OF TEXTURED PROFILE YARN AND THE YARNS OBTAINED THEREFOR" |
DE3271192D1 (en) * | 1981-11-23 | 1986-06-19 | Ici Plc | Process of melt spinning of a blend of a fibre-forming polymer and an immiscible polymer and melt spun fibres produced by such process |
JPS60126337A (en) * | 1983-12-07 | 1985-07-05 | 東レ株式会社 | Production of highly extensible processed yarn |
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1991
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FR2677376A1 (en) | 1992-12-11 |
BR9202261A (en) | 1993-02-02 |
FR2677376B1 (en) | 1994-04-01 |
JP2535121B2 (en) | 1996-09-18 |
JPH05263314A (en) | 1993-10-12 |
CA2070608A1 (en) | 1992-12-08 |
DK0517628T3 (en) | 1998-10-19 |
DE69224935T2 (en) | 1998-09-24 |
DE69224935D1 (en) | 1998-05-07 |
ATE164639T1 (en) | 1998-04-15 |
ES2113932T3 (en) | 1998-05-16 |
CA2070608C (en) | 1996-04-30 |
EP0517628A1 (en) | 1992-12-09 |
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