EP3350361A1 - Fibre de polyamide présentant une gestion améliorée du confort, procédé pour ladite fibre et article fabriqué à partir de ladite fibre - Google Patents

Fibre de polyamide présentant une gestion améliorée du confort, procédé pour ladite fibre et article fabriqué à partir de ladite fibre

Info

Publication number
EP3350361A1
EP3350361A1 EP15778712.8A EP15778712A EP3350361A1 EP 3350361 A1 EP3350361 A1 EP 3350361A1 EP 15778712 A EP15778712 A EP 15778712A EP 3350361 A1 EP3350361 A1 EP 3350361A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
fiber
lobes
coalescent
article
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15778712.8A
Other languages
German (de)
English (en)
Inventor
Renata REDONDO BONALDI
Pierre Hansu Pak
Fabio Pereira De Lacerda
Nathalia COSTA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Poliamida e Especialidades Ltda
Original Assignee
Rhodia Poliamida e Especialidades Ltda
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Poliamida e Especialidades Ltda filed Critical Rhodia Poliamida e Especialidades Ltda
Publication of EP3350361A1 publication Critical patent/EP3350361A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • 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
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • 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
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • 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
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/02—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist
    • D02G1/0206—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by twisting, fixing the twist and backtwisting, i.e. by imparting false twist by false-twisting
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel

Definitions

  • the present invention relates to a polyamide fiber with improved comfort management properties.
  • the present invention also discloses a method for obtaining such fiber and articles made therefrom.
  • the polyamide fiber is produced from a hygroscopic polyamide in a multilobal cross section profile.
  • the hygroscopic polyamide fiber is produced preferably from polyamide 5.X, X being an integer from 4 to 16.
  • the present invention thus discloses a polyamide fiber and articles made therefrom for sportswear and leisurewear applications, with improved water absorption, wicking and drying properties, wherein the sweat is transported away from the skin and is quickly dried, thereby reducing the wet sensation and chill during activity.
  • the present invention provides freshness and comfort by maintaining a pleasant skin temperature and microclimate.
  • Polyamide fiber is the most suitable fiber for improving comfort among the synthetic fibers available in the market.
  • Polyamide is very soft, smooth and pleasant to the skin.
  • the high flexibility, lightness and abrasion resistance provide a very comfortable sensation, in addition to the well-balanced moisture behavior.
  • Polyamide also has high durability, good physical and chemical properties, easy-care and fast drying properties.
  • Polyamide, also known as nylon is a linear condensation polymer composed of repeated primary bonds of amide group.
  • the amide group -(-CO-NH-)- provides hydrogen bonding between polyamide intermolecular chains.
  • a polyamide fiber is generally produced by melt-spinning extrusion and is available in staple fiber, tow, monofilament, multi-filament, flat or texturized form.
  • polyamide is a promising candidate for sportswear, underwear, leisurewear and other next-to-skin applications.
  • the next-to-skin fabric is normally a soft, skin-friendly fabric composed of hydrophilic and/or porous fibers, and is designed to wick the sweat away from the body, maintaining a pleasant skin microclimate. Sweating is a necessary mechanism for body cooling in response to high levels of body heat production. The skin microclimate quickly becomes humid during sweating. For efficient cooling the evaporated sweat needs to be transported as water vapor through the clothing and air layers adjacent to the skin and/or by convection through openings in the clothing.
  • the next-to-skin fabric controls the microclimate temperature and humidity of the skin. With low metabolic activity the fabric must reduce air movement, as the microclimate is maintained by the still air. With higher metabolic activity, heat and moisture should be transported from the fabric to cool the skin. Moisture control is then performed by absorption, by transportation or by ventilation.
  • Synthetic fibers are durable, easy-care, but are mostly hydrophobic. Using hydrophobic textiles next to skin quickly increases humidity with sweating, hence hydrophobic fabrics need to be engineered to transport water away quickly by capillarity spaces between fibers and yarns. On the other hand, hydrophilic and/or hygroscopic fibers absorb and transport water through the fiber itself and by capillarity, thus facilitating the evaporation.
  • the textile needs to have a reasonable hydrophilicity, high wicking speed and high drying rate in order to be effective in maintaining a pleasant microclimate and comfort. If the hydrophilicity is too high, as in the case of natural fibers, the drying rate may be delayed as water is absorbed and retained inside the fiber for longer periods. A poor wicking may also lead to saturated regions and reduced transport and drying rates. Therefore, an optimal balance should be achieved among hydrophilicity, wicking and fast drying properties.
  • cooling agents are inserted in the polyamide fiber matrix in order to improve the cooling and moisture management properties.
  • Chinese patent applications CN 104178839 and CN 103088459 disclose this method. Disadvantages of this approach include lack of fast drying rate, water absorption and wicking speed. The cooling mechanism may also lead to uncomfortable sensation during active sweating, such as hypothermia due to excessive cooling.
  • Chinese patent application CN103882550 also proposes a cooling polyamide fiber with the use of a cooling agent, such as inorganic metal oxide particles, but adds PVP to the fiber with the intention to improve the water absorption.
  • a cooling agent such as inorganic metal oxide particles
  • PVP adds to the fiber with the intention to improve the water absorption.
  • a drawback of the use of PVP is the fact that the occurrence of pyrrolidone as a by-product tend to causes fiber yellowing, thereby affecting the desired mechanical and chemical properties for textile applications.
  • the fast wicking and drying behavior are not demonstrated and could cause discomfort during excessive sweating and sports activities.
  • US 2015013047 disclosed a cooling polyamide yarn, with the use of cooling inorganic additives, modified cross section and low crimp module.
  • the disclosed cross section is a flat cross section.
  • a disadvantage of this cross section is the fact that a flat fiber profile leads to more skin coverage, lower insulation, less entrapped air and more contact points with the skin what may reduce the skin sensorial wear comfort. It does not offer capillarity and does not increase wicking speed and drying rate, hence not being suitable for high sweating activity.
  • the flat cross section evaluated in the experiments of the present invention has shown poor processing behavior, what suggests that a flat cross section may be more difficult to be processed by melt-spinning.
  • EP 2554721 discloses a hygroscopic polyamide 5.6 fiber; however, without the additional advantage of high wicking speed and drying rate as are offered by the present invention. Hence, patent number EP 2554721 does not offer a solution for comfort management of sportswear textiles, where wicking and higher drying rates are desired. There is still no existing fiber in the market that offers at the same time hydrophilic properties, cooling effect, and wicking.
  • the present invention is a solution for obtaining highly comfortable and refreshing polyamide fibers in order to provide a pleasant feeling for the wearer.
  • the present invention thus provides a polyamide fiber with improved comfort management comprising a hygroscopic polyamide, being an aliphatic biobased polyamide selected from the group consisting of polyamide 5.
  • a hygroscopic polyamide being an aliphatic biobased polyamide selected from the group consisting of polyamide 5.
  • X being an integer from 4 to 16 and mixtures thereof, said fiber having a multilobal cross section characterized by having at least 2 coalescent centers and at least 5 equally dimensioned oblong lobes, each coalescent center connecting at least 3 equally dimensioned oblong lobes according to an angular symmetry between the adjacent equally dimensioned oblong lobes.
  • such a polyamide fiber shows substantially higher hygroscopicity, water drying rate, water spreading rate and water absorption compared to non-hygroscopic polyamide with round cross section. It has been proven that by enhancing the water absorption, wicking and dryings rates, which leads to a better moisture management, comfort is also substantially improved.
  • the present invention also aims at a method for obtaining said polyamide fiber with improved comfort management, wherein the polyamide fiber is obtained by melt-spinning extrusion of a polyamide composition comprising the hygroscopic polyamide, for example by using a new multilobal cross sections spinneret.
  • the present invention proposes a polyamide article comprising the polyamide fiber with improved comfort management as defined above and below in the following paragraphs; and a method for obtaining such a polyamide article, wherein the polyamide fiber of the invention is transformed by texturizing, drawing, warping, knitting, weaving, nonwoven processing, garment manufacturing or a combination thereof.
  • Another object of the present invention is the use of said polyamide fiber with improved comfort management as defined above and below in the following paragraphs in order to increase the comfort management of polyamide articles made therefrom, notably for textile articles.
  • polyamide fiber in the sense of the present invention is the generic term including the following spun articles: a fiber, a monofilament, a multifilament and a yarn.
  • a "polyamide article” according to the invention is a transformed or treated polyamide fiber and includes staple fibers, any flock or any textile composition made of polyamide fiber, especially fabrics and/or garments.
  • fiber any flock or any textile composition made of polyamide fiber, especially fabrics and/or garments.
  • the present invention provides a polyamide fiber with improved comfort management, comprising a hygroscopic polyamide, being an aliphatic biobased polyamide selected from the group consisting of polyamide 5.
  • a hygroscopic polyamide being an aliphatic biobased polyamide selected from the group consisting of polyamide 5.
  • X being an integer from 4 to 16 and mixtures thereof, said fiber having a multilobal cross section characterized by having at least 2 coalescent centers and at least 5 equally dimensioned oblong lobes, each coalescent center connecting at least 3 equally dimensioned oblong lobes according to an angular symmetry between the adjacent equally dimensioned oblong lobes.
  • the hygroscopic polyamide is an aliphatic polyamide composed of polyamide 5.X, X being an integer from 4 to 16 or mixtures thereof. Polyamide 5.X is made of pentamethylenediamine and an aliphatic dicarboxylic acid(s) as raw materials.
  • dicarboxylic acids is the following: butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid. All those diacids are commercially available.
  • Polyamides 5.X have the advantage of being able to be manufactured from biomass according to ASTM6866.
  • pentamethylenediamine can also be prepared from bio-resources according to ASTM6866, the resulting polyamide can be produced from 40% to 100% of bio-resources.
  • the amino terminal groups (ATG) content of those biobased polyamides is advantageously from 25 to 60 equivalent/ton, and the carboxyl terminal groups (CTG) is advantageously from 45 to 90 equivalent/ton.
  • Those amino/carboxyl end groups contents are measured according to the methodology explained hereinafter in the experimental part.
  • the hygroscopic polyamide is preferably polyamide 5.X, with X being an even integer from 4 to 16, such as polyamide 5.4, polyamide 5.6, polyamide 5.8, polyamide 5.10, polyamide 5.12, polyamide 5.14, polyamide 5.16 and mixtures thereof. Even more preferably X is 6 or 10, and advantageously 6 such as polyamide 5.6 (Nylon 5.6), also called poly(pentamethylene adipamide), which is made by polycondensation reaction of pentamethylenediamine and adipic acid as raw materials.
  • the preferred polyamide 5.6 may have a viscosity index (IVN) in the range of 100 to 200 ml/g, preferably between about 120 and 170.
  • a particularly preferred polyamide 5.6 according to the present invention has an IVN (viscosity index) of from 138 to 142, and ATG (amine terminal groups) from 38 to 42.
  • the hygroscopic behavior of the polyamide 5.6 is at least 4%, as measured according to the methodology explained hereinafter in the experimental part.
  • the hygroscopic feature is due to the odd/even configuration of the diamine (5 carbons) and diacid (6 carbons), what leads to misalignment of intermolecular bonds, resulting is less hydrogen bonds and hence more water-friendly accessible sites within the molecules.
  • the polyamide fiber according to the invention comprises advantageously more than 75% by weight of hygroscopic polyamide, preferably more than 85% by weight and even more preferably more than 95% by weight, based on the total weight of the fiber.
  • the polyamide fiber according to the invention can contains other polymers such as PA 6.6, PA 6.10 and PA 6 and/or additives like plasticizers, antioxidants, stabilizers such as heat or light stabilizers, colorants, pigments, nucleating agents such as talc, matifying agents such as titanium dioxide or zinc sulphide, processing aids, biocides, viscosity modifiers, cooling agents, catalysts, Far Infrared Rays emitting minerals, anti-static additives, functional additives, optical brightening agents, nanocapsules, anti-bacterial, anti-mite, anti-fungi or other conventional additives.
  • additives like plasticizers, antioxidants, stabilizers such as heat or light stabilizers, colorants, pigments, nucleating agents such as talc, matifying agents such as titanium dioxide or zinc sulphide, processing aids, biocides, viscosity modifiers, cooling agents, catalysts, Far Infrared Rays emitting minerals, anti-static additives, functional additives, optical brightening agents,
  • the amount of additives in the fiber represents up to 25 %by weight, more preferably up to 10% by weight.
  • a cooling agent or thermo regulating agent is employed.
  • the cooling agent may comprise any far infrared ceramic powder, inorganic fillers such as inorganic metal oxides (ex: Ti02, Zr02, MgO, Sn02, ZnO, BaO), jade powder, zirconia powder, silica powder, mica, boron nitride, calcium carbonate, barium carbonate, magnesium carbonate, aluminum silicate, alumina, zeolite and talc.
  • thermo regulating agent also comprises phase change materials such as paraffin or endothermic substances such as sugar alcohol like xylitol or erythritol. Cooling or thermo regulating agents provide good thermal conductivity, fast heat conduction through the body to produce cool contact feeling, through slow endothermic and fast heat dissipation characteristics.
  • the polyamide fiber of the present invention has multilobal transversal cross section characterized by having at least 2 coalescent centers and at least 5 equally dimensioned oblong lobes, each coalescent center connecting at least 3 equally dimensioned oblong lobes according to an angular symmetry between the adjacent equally dimensioned oblong lobes.
  • a "lobe" is understood to be the oblong part/section of the fiber cross section that is connected to at least one coalescent center.
  • a "coalescent center” is understood to be the converging point of at least 3 lobes.
  • the multilobal cross section has 2 to 6 coalescent centers, preferably 2 or 3 coalescent centers, each coalescent center connecting symmetrically 3 or 4 equally dimensioned oblong lobes according an angle of 120° or 90° respectively between adjacent lobes, and the best results are obtained when each coalescent center connects symmetrically 3 equally dimensioned oblong lobes according to an angle of 120°between adjacent lobes.
  • FIG. 1 A schematic example of multilobal cross section is illustrated in Figure 1.
  • Figure 1 there are 3 coalescent centers shown by letter a, b represents a lobe and in this particular example there are 7 lobes, and c represents the 120° angle that is reproduced between each adjacent lobe.
  • the multilobal cross section having at least 2 coalescent centers of 4 lobes that are arranged by 90° angular symmetry means that any adjacent lobes are connected by 90°. For instance, 2 coalescent centers connects 7 lobes, 3 coalescent centers connects 10 lobes, and so forth. For any "M" number of coalescent center, the number of lobes is "(M*3)+l".
  • the lobes are symmetrically angular, which means any adjacent lobes are connected by 90°.
  • the total number of lobes of the cross section can be from 5 (image "A” of figure 3) to 13 (image “F” of figure 3).
  • the best cross section sharpness and processability is achieved with cross section having angle of 120° between adjacent lobes and more specifically, with the cross section containing 2 (image "A” of figure 3) and 3 (image “B” of figure 3) coalescent centers having 5 lobes and 7 lobes respectively.
  • Non-symmetric cross sections such as sample “G” and “H” of figure 3, exhibit poor processability and should be avoided. These cross sections are shown for comparison only, as well as sample “K” of figure 3, which is the conventional circular cross section and does not belong to the present invention. In general, flat cross sections like “G” and “H” of figure 3 are more difficult to be processed.
  • the specific multilobal cross sections of the invention generate special micro and continuous concavities lengthwise the fibers.
  • the capillarity and higher surface area of the fibers of the invention increase the water absorption, spreading and drying rates, thereby improving the moisture management and comfort of the textiles made therefrom.
  • a less compact yarn is obtained, contributing to more air space within the filaments which increases the insulation, capillarity, and thermoregulation of the textiles made therefrom.
  • the higher surface area of the cross sections of the present invention allow the sweat to spread out, what significantly contributes to faster sweat evaporation, so the textile article made therefrom dries quicker and the wearer remains comfortable and dry while exercising. The thermal insulation of the textile article made therefrom is thus maintained, which avoids the post-exercising chilling effect of wet clothes.
  • the handle and softness are also significantly improved because of the lower flexural rigidity generated by the irregular and preferred bending direction of the cross section, as opposite to the resilient behavior of round and trilobal cross section (Y shapes). Similar phenomenon of softness is also observed in the "bean" shape cross section of cotton fiber. For instance, “image "B” of Figure 3 has a preferred bending direction towards the deeper concavity.
  • the polyamide fiber according to the invention has advantageously an overall dtex of about 40 to 300, and a dpf (dtex per filament) of about 0.1 to 5, a tenacity (at break) from 20 to 80 cN/Tex and an elongation (at break) from 20% to 90%.
  • the invention also provides a method for obtaining the polyamide fiber with improved comfort management as described above.
  • the polyamide fiber is obtained by melt-spinning extrusion.
  • the "melt-spinning extrusion” is understood to mean the extrusion process of converting the polyamide into polyamide fibers.
  • the polyamide(s) may be fed to the melt-spinning device in pellet, powder or melt form.
  • the method includes any conventional extrusion spinning means suitable for melt-spinning extrusion of polyamides, these means being well known by a person skilled in the art, such as single-screw extruder, double-screw extruder, bi-component extruder and grid spinning head.
  • the melt-spinning extrusion can be further defined as being LOY (low- oriented yarn), POY (partially oriented yarn), FDY (fully drawn yarn), FOY (fully oriented yarn), LDI (Low denier Industrial) or HDI (High denier Industrial).
  • the melt-spinning extrusion advantageously comprises the following steps: al. Feeding the polyamide composition comprising the hygroscopic polyamide in the form of a melt, pellet or powder into the inlet of a screw extruder,
  • the hygroscopic polyamide is advantageously continuously introduced as a melt, pellet or powder into the inlet of a screw extruder.
  • the polyamide is preferably melted, homogenized and pressurized inside the screw extruder, preferably at a temperature from 260 to 310?C, which is above the melting temperature of the polyamide, and at an extrusion pressure from 30 to 70 bar.
  • the molten polyamide is spun into fibers (or yarns or filaments) preferably at a temperature from 260 to 3102C, spinning pack pressure from 150 to 250 Bar and a spinning pack flow rate from 3 to 8 kg/h, with the use of a spinning screen-pack containing filtering elements and a spinneret.
  • a special spinneret should be used during step a3 to obtain the multilobal cross section having coaiescent centers, equally dimensioned oblong lobes and angular symmetry.
  • a spinneret is a metal plate containing orifices which are used for extruding the polymer into the desired cross section and size.
  • the special spinneret comprises multilobal orifices, each orifice having at least 2 coaiescent centers, at least 5 equally dimensioned oblong lobes and an angular symmetry between adjacent equally dimensioned oblong lobes.
  • the multilobal orifices have preferably 2 to 6 coaiescent centers, each coaiescent center connecting symmetrically 3 or 4 equally dimensioned oblong lobes according an angle of 120° or 90° respectively between adjacent lobes.
  • a "lobe” is understood to be a section, orifice or hole, where the molten polymer passes through during extrusion to form solid filaments upon cooling and which is going to form the oblong part/section of the fiber cross section.
  • a "coalescent center” is understood to be the point of at least 3 lobes where the molten polymer does pass through during extrusion, but that is going to connect the at least 3 lobes after coalescence.
  • coalescent centers and equally dimensioned oblong lobes of the orifices of the spinneret are necessary for obtaining a good polymer distribution in the orifice upon extrusion; whereas, the angular symmetry ensures stability, shape and sharpness of the cross section, enhancing the grooves and capillarity of the fibers.
  • the multilobal cross section having coalescent centers of 3 lobes connected by angles of 120° are illustrated in images "A” to "F” of figure 3.
  • the multilobal cross section having coalescent centers of 4 lobes connected by angles of 90° are illustrated in images "I” and "J” of figure 3.
  • coalescence is well understood by those skilled in the art, it is a process by which two or more separate sections (also called lobes) merge during contact to form a single section. Therefore, the lobes are not connected within each other in the spinneret; instead, the lobe sections are merged upon extrusion to form a single continuous filament. A coalescent center is then the center of separate lobes, especially 3 or 4 lobes, according to the present invention.
  • Each set of lobes from the samples of figure 3 correspond to a single continuous filament upon extrusion, which are joined by the coalescence phenomenon.
  • the total number of orifices (sets of lobes) in the spinneret can be designed to produce yarns from 10 to 200 filaments.
  • the lobes have oblong shape and are of exactly same dimensions.
  • Step a4 is the step of cooling down the fibers (or yarns or filaments) until the solidified form and winding the polyamide fibers into bobbins.
  • a spinning oil can also be added onto the fiber at this step.
  • the winding speed is from 3000 m/min to 6500 m/min.
  • the extruder can be equipped with a metering system for introducing polymers and optionally additives such as masterbatches into the main polymer, at step al and/or a2 and/or a3. Additional additives can be introduced during the method of the invention or may be present in the hygroscopic polyamide polymer.
  • the additives listed above. These additives are generally added in the polymer or at step al and/or a4 of the melt-spinning extrusion, in an amount of 0,001% to 10% by weight of the polyamide fiber.
  • a cooling agent or thermo regulating agent is introduced also at step al, separately from the hygroscopic polyamide, with the use of a dosing apparatus such as gravimetric or volumetric feeding pump.
  • the cooling or thermo regulating agent may be in the form of powder, liquid or solid masterbatch.
  • the cooling or thermo regulating agent is advantageously introduced in an amount of 0.5% to 20.0%, preferably 1.0 to 5.0% by weight of the total weight of the polyamide fiber.
  • the polyamide fiber obtained from the first embodiment is then texturized to produce textured yarns with higher elasticity, volume and softness.
  • This process comprises any technology known by those skilled in the art such as false-twist texturizing, false-twist - fixed texturizing and air-jet texturizing. Most preferably false-twist texturing.
  • the method can include the following steps:
  • the fiber is removed from the package and passes to the delivery rolls.
  • the fiber passes through a heater, then to a cold zone.
  • the fiber passes through a spindle containing rotating discs (friction aggregates)
  • the fiber is wound into bobins.
  • step bl the fiber is advantageously placed in a creel and is unwound from the bobbins to the delivery roll.
  • Step b2 preferably involves passing the fiber inside a heater, with temperature from 120°C to 400°C, in order to assist the mechanical action of stretching and twisting the fibers by softening (making more malleable). The fiber is then cooled.
  • Step b3 is where the twist, volume, crimp and texture are generated in the fiber.
  • the amount of twist is changed by altering the speed of the discs, discs arrangement and the D/Y relationship.
  • the D/Y ratio changes the ratio of speeds between the friction discs and the linear speed of the fiber. This ratio is preferably from 1.0 to 2.8.
  • the disc arrangement is advantageously from 1/2/1 to 1/8/1, being guide disc/work disc/guide disc.
  • step b4 intermingling points and coning oil are applied to the fiber in order to provide lubrication and to improve physical and aesthetic features, in the case of the intermingling.
  • the interlaces per meter are preferably at least 30 per meter.
  • Step b5. is the winding process, where the fiber is wound into bobbins; the winding speed can vary from 150 m/min to 1500 m/min.
  • the drawing ratio is given to the fiber by altering the speed ratio of step bl and step b5, and is an important parameter of the process for achieving the desired linear density.
  • the drawing ratio is advantageously from 1.10 to 4.00.
  • Yarns of more than 1 ply is possible, such as from 1 to 8 plies.
  • the polyamide fiber according to the invention can then be transformed into a polyamide article, notably a textile fabric and/or garment.
  • a polyamide article according to the invention is preferably a fiber, a multifilament yarn, a flock, a woven, a knitted or non-woven fabric or a textile article made from the polyamide fiber of the invention (defined above) or obtained from the process according to the invention.
  • the textile article may be any textile article known in the art including, but not limited to woven fabric, knitted fabric, nonwoven fabric, ropes, cords, sewing thread, and so forth. In the case of clothing, the best results are achieved on fabric with mass per unit area of less than 200 g/m 2 , most preferably less than 150 g/m 2 .
  • the methods for transforming the polyamide fiber into a polyamide article like a textile fabric or garment are well known by the skilled person in the art. Indeed, the polyamide fiber can be transformed into a polyamide article by texturizing, drawing, warping, knitting, weaving, nonwoven processing, garment manufacturing or a combination thereof. These articles are subsequently used in a large number of applications, in particular in hosiery, underwear, sportswear, outerwear and leisurewear.
  • a novel polyamide 5.6 fiber with intrinsic hygroscopicity and capillarity effect is disclosed in the present invention.
  • the polyamide articles exhibit higher rate of water absorption, wicking and drying, when compared to non-hygroscopic polyamides with round cross sections.
  • the synergy among hygroscopicity, capillarity and higher surface area of the cross section speeds up the water drying rate so that the wearer feel dry and comfortable even after intense sweating.
  • the current method is simple and makes use of conventional and well-kwon extrusion machinery.
  • the cross section profile of the present invention improves handle and softness of the fiber because of the lower flexural rigidity due to the irregular and preferred bending direction, as opposite to the resilient behavior of round and triloba! cross section. Similar phenomenon is observed in the "bean" shape cross section of cotton fiber.
  • Wear comfort is a complex phenomenon but in general it can be divided into four different main aspects: a) Thermophysiological wear comfort influences a person ' s thermoregulation, it comprises heat and moisture transport processes through the clothing. Key notions include thermal insulation, breathability and moisture management; b) Skin sensorial wear comfort characterizes the mechanical sensations that a textile causes at direct contact with the skin, pleasant perceptions include smoothness and softness, whereas unpleasant would be scratchy, too stiff, or clings to sweat-wetted skin; c) Ergonomic wear comfort deals with the fit of the clothing and the freedom of movement it allows. It is mainly dependent on the garment ' s pattern and the elasticity of the materials; d) Psychological wear comfort is affected by fashion, personal preferences, ideology etc.
  • Thermophysiological comfort is based on the principle of energy conservation. All the energy produced within the body by metabolism, has to be dissipated in exactly the same amount from the body, by the respiratory heat loss (breathing), the dry heatflux comprising radiation, conduction, convection, and the evaporative heatflow caused by sweating. If more energy is produced than dissipated, the body suffers from hyperthermia. And too high a heat loss leads to hypothermia.
  • Chemical finishing includes mainly hydrophilic topic treatments and is intended to increase the hydrophilic behavior of hydrophobic textiles.
  • the drawback of chemical finishing is the fact that it is a non-durable treatment and may last a few home-washing cycles only, whereas fibers with intrinsic moisture management properties last the entire life time of the textile article.
  • the use of filament yarns leads to too smooth and flat textile surfaces directly at the skin. This structure shows too many contact points with the skin, and the fabric is perceived as too smooth and clinging to sweat-wetted skin.
  • Flat filament yarns provide poor skin sensorial perception, whereas spun yarns or textured yarns provide better skin sensation. Textured yarns provide less contact points with the skin and higher insulation, softness and pleasant touch.
  • Protruding fiber ends are generated, as well as a more 3D structure, in spun yarns and textured yarns, which act as spacers between skin and textile. Yarn cross section with grooves, pores and capillarity channels along the filament are also important to increase the wicking speed and surface area, what leads to wicking and faster drying rate.
  • Air is also an important characteristic for clothes. Air is welcome not only for lightness but also for temperature regulation. A layer of air between garment and skin helps to reduce temperature variations. By reducing the contact points between the skin and garment, air circulates freely and lets the body breath.
  • Moisture management properties are normally assessed by water absorption, vertical wicking, horizontal wicking, air permeability, water vapour transmission, thermal resistance and drying rate.
  • AATCC 195 from "American Association of Chemists and Colorists" can be used for measuring liquid moisture management properties of textiles. Water absorbance can be assessed by AATCC 79. Vertical wicking of textiles is normally evaluated by AATCC 197, whereas horizontal wicking can be measured by AATCC 198.
  • AATCC 199 and AATCC 200 can be used to measure the drying time of textiles at different conditions, using a gravimetric moisture analyzer. Apart from the methods above, thermo-physiological and sensorial tests are also available for assessing comfort, such as using a heated hot plate (ASTM F 1868; ISO 5085-1, 1989; ISO
  • a series of polyamide articles including comparative polyamide articles and control polyamide articles are formed and evaluated for process ability, water wicking rate, water absorption rate, water drying rate, hygroscopicity, mechanical properties, IVN (viscosity index), ATG (terminal amino groups) and CTG (carboxylic terminal groups). Table 1 summarizes the samples.
  • the amino end group (ATG) content was determined by a potentiometric titration method. The quantity of 2 grams of polyamide is added to about 70 ml of phenol 90%wt. The mixture is kept under agitation and temperature of 409C until complete dissolution of the polyamide. The solution is then titrated by 0.1N HCI at about 25?C The result is reported as equivalent/ton (eq/ton). In the case of analyzing fibers and articles, any residue or spin-finish must be previously removed.
  • Solution viscosity The determination of the solution viscosity (IVN) is performed according to ISO 307.
  • the polyamide is dissolved in formic acid 90%wt at 252C at a concentration of 0.005g/ml, and its flow time is measured. The result is reported as ml/g.
  • Carboxylic terminal group content CCG
  • the carboxylic terminal group (CTG) content was determined by a titration method. The quantity of 4 grams of polyamide is added to about 80 ml of benzyl alcohol. The mixture is kept under agitation and temperature of 200?C until complete dissolution of the polyamide. The solution is then titrated by 0.1N of potassium hydroxide in ethylene glycol. The result is reported as equivalent/ton (eq/ton). In the case of analyzing fibers and articles, any residue or spin-finish must be previously removed.
  • AATCC 195 Liquid moisture management of textiles (evaluation of horizontal water wicking speed and water absorption time)
  • the liquid moisture management properties are evaluated by placing a fabric specimen between two horizontal (upper and lower) electrical sensors.
  • a predetermined amount of test solution that aids the measurement of electrical conductivity changes are dropped onto the center of the upward-facing test specimen surface.
  • the test solution is free to move in three directions: radial spreading on the top surface, movement through the specimen from top surface to the bottom surface, and radial spreading on the bottom surface of the specimen.
  • changes in electrical resistance of specimen are measured and recorded.
  • a moisture management tester (MMT) is used with this method.
  • the results of water absorption (seconds) and water spreading speed (mm/second) are given by this method.
  • the rate (distance per unit of time) liquid travels along and/or through a vertical fabric specimen is visually observed, manually timed and recorded at specified intervals. This test method considers the influence of gravity when assessing wicking.
  • Polyamide 6.6 pellet was used for the samples.
  • the polyamide 6.6 pellet was produced from the polymerization of a nylon salt containing mainly hexamethylenediamine and adipic acid.
  • the IVN viscosity index
  • ATG amine terminal groups
  • a polyamide 5.6 fiber was produced by melt-spinning extrusion from polyamide 5.6 pellets, using a spinneret containing multilobal cross section for examples 2 and 3, or a spinneret containing round orifices for examples 1 and 6.
  • the polyamide 5.6 pellet is a commercially available polyamide from Cathay Biotech under the trademark Terryl ® .
  • the IVN is from 138 to 142, ATG from 38 to 42, and CTG from 65 to 75 measured according to the methodology disclosed herein.
  • step al the polyamide composition was fed into the inlet of the screw extruder in the form of dried pellets.
  • step a2 the polyamide was melted, homogenized and pressurized inside the screw extruder at a temperature of around 2902C and at an extrusion pressure of around 50 bars.
  • step a3 the molten polyamide blend was spun into multi-filament yarn at a spinning pack pressure of around 200 bars and at a spinning pack flow rate of around 5 kg/h.
  • Step a4 the polyamide fiber blend was solidified and wound into bobbins at around 4200 m/min.
  • PA 6,6 - examples 4, 5 and 7 A polyamide 6.6 fiber was produced by melt-spinning extrusion from polyamide 6.6 pellets and with the same process as described in example 1, 2, 3 and 6 above, using a spinneret containing multilobal cross section orifices for example 5, or a spinneret containing round orifices for examples 4 and 7.
  • the polyamide 6.6 pellet was produced from the polymerization of a nylon salt containing mainly hexamethylenediamine and adipic acid.
  • the IVN viscosity index
  • ATG amine terminal groups
  • a polyamide 6.10 fiber was produced by melt-spinning extrusion from polyamide 6.10 pellets and with the same process as described in example 1, 2, 3, and 6 above, using a spinneret containing round orifices.
  • the polyamide 6.10 pellet is a commercially available polyamide from Solvay Group under the trademark STABAMID ® .
  • the IVN is from 102 to 118, ATG from 49 to 57 measured according to the methodology disclosed herein.
  • the multi-filament yarns (samples 1, 2, 4, 5, 6 and 7), obtained above, are further texturized into linear density of Ix80f68 dtex (examples 1.1, 2.1, 4.1, 5.1, 6.1 and 7.1).
  • the multi-filament yarns (samples 1 and 4), obtained above, are further texturized into linear density of 2x80f68 dtex (examples 1.2 and 4.2).
  • Invention 2 PA 5.6 100f64 7 lobes FLAT 74.40 28.50
  • the modified multilobal cross section played a significant role in this improvement, by comparing sample 1 (control) and sample 2 (invention), it was found that the water drying rate increased 9%, the water absorption 40% and the water wicking speed 24%.
  • the result of polyamide 6.10 (sample 8) was also given as comparison; very poor results were obtained due to the very low hydrophilicity.
  • TEXTURED YARNS Table 5
  • Textured yarns possess more crimp, texture, volume, elongation and twist; hence they provide more softness, comfort, thermal insulation and are more pleasant to the skin.
  • the current method is simple and makes use of conventional and well-kwon extrusion machinery.
  • the cross section profile of the present invention also improves the handle and softness of the fiber because of the characteristics of the novel multilobal cross sections disclosed.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Woven Fabrics (AREA)

Abstract

La présente invention concerne une fibre de polyamide présentant des propriétés améliorées de gestion du confort. La présente invention concerne également un procédé pour obtenir ladite fibre et des articles fabriqués à partir de cette dernière. La fibre de polyamide est produite à partir d'un polyamide hygroscopique dans un profil de section transversale multilobée. La fibre de polyamide hygroscopique est produite de préférence à partir de polyamide 5.X, X étant un nombre entier de 4 à 16. Plus préférablement, la fibre est produite à partir de polyamide 5.6, qui est un polyamide biosourcé obtenu à partir de pentaméthylènediamine et qui est dérivé de matières premières renouvelables à base de sucre. La présente invention concerne ainsi une fibre polyamide et des articles fabriqués à partir de celle-ci pour des applications de vêtements de sport et de vêtements de loisir, présentant une meilleure absorption d'eau et des propriétés de pénétration capillaire et de séchage améliorées, la sueur étant transportée à l'écart de la peau et rapidement séchée, ce qui permet de réduire la sensation d'humidité et de froid lors d'une activité. La présente invention apporte fraîcheur et confort par conservation d'une température et d'un microclimat agréables pour la peau.
EP15778712.8A 2015-09-14 2015-09-14 Fibre de polyamide présentant une gestion améliorée du confort, procédé pour ladite fibre et article fabriqué à partir de ladite fibre Withdrawn EP3350361A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2015/001609 WO2016108078A1 (fr) 2015-09-14 2015-09-14 Fibre de polyamide présentant une gestion améliorée du confort, procédé pour ladite fibre et article fabriqué à partir de ladite fibre

Publications (1)

Publication Number Publication Date
EP3350361A1 true EP3350361A1 (fr) 2018-07-25

Family

ID=54292829

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15778712.8A Withdrawn EP3350361A1 (fr) 2015-09-14 2015-09-14 Fibre de polyamide présentant une gestion améliorée du confort, procédé pour ladite fibre et article fabriqué à partir de ladite fibre

Country Status (7)

Country Link
US (1) US20180251913A1 (fr)
EP (1) EP3350361A1 (fr)
JP (1) JP6714077B2 (fr)
KR (1) KR102471874B1 (fr)
CN (1) CN108026665A (fr)
IL (1) IL257404A (fr)
WO (1) WO2016108078A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170145596A1 (en) * 2015-10-27 2017-05-25 Tosha Hays Systems and articles of manufacture employing long-term cooling material in woven and non-woven fabrics and processes to generate the long-term cooling material and articles of manufacture
CN110219085A (zh) * 2019-06-24 2019-09-10 吴江京奕特种纤维有限公司 用于提高织物吸湿透湿性能的纺纱方法及织物
CN113430668B (zh) * 2021-06-28 2023-04-11 安踏（中国）有限公司 冰感速干纤维及其制备方法、冰感速干面料及其制备方法
CN118434818A (zh) * 2021-12-22 2024-08-02 诺斯特罗莫有限公司 成核剂
CN114703578A (zh) * 2022-02-17 2022-07-05 长乐力恒锦纶科技有限公司 一种全消光锦纶6热感纤维全拉伸丝生产工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB985295A (en) * 1960-04-22 1965-03-03 Celanese Corp Hollow artificial filaments and spinnerets for their production
US5922830A (en) * 1996-03-29 1999-07-13 Toray Industries, Inc. Highly hygroscopic polyamide fiber, and production and application thereof
JP2000220029A (ja) * 1999-01-28 2000-08-08 Unitika Ltd ポリエステル異形断面糸及び混繊糸
US6753082B1 (en) * 2003-02-26 2004-06-22 Honeywell International Inc. Absorbent fibers
US20130280513A1 (en) * 2010-03-31 2013-10-24 Toray Industries, Inc. Hygroscopic fiber, and manufacturing method for same

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61160410A (ja) * 1985-01-08 1986-07-21 Teijin Ltd 異型断面繊維
JPS63159511A (ja) * 1986-12-17 1988-07-02 Teijin Ltd 異形断面糸およびその紡糸口金
GB2208277B (en) * 1987-07-30 1991-11-13 Courtaulds Plc Cellulosic fibre
JPH01201513A (ja) * 1988-02-03 1989-08-14 Teijin Ltd 異形断面繊維
JPH05206640A (ja) 1992-01-27 1993-08-13 Nitto Denko Corp 分離回路の接続方法
JP4399699B2 (ja) * 2001-10-31 2010-01-20 東洋紡績株式会社 仮撚加工糸
US6841247B2 (en) * 2002-08-16 2005-01-11 Honeywell International Inc. Fibers having improved dullness and products containing the same
KR100667623B1 (ko) * 2003-11-06 2007-01-11 주식회사 코오롱 흡한 속건성 폴리아미드 섬유 및 그의 제조방법
KR100829475B1 (ko) * 2004-11-19 2008-05-16 주식회사 코오롱 항균성과 흡한속건성이 우수한 멀티필라멘트
JP4983518B2 (ja) * 2007-09-28 2012-07-25 東レ株式会社 仮撚用ポリアミド繊維および仮撚用ポリアミド繊維の製造方法
PL2256237T3 (pl) 2008-03-26 2013-08-30 Toray Industries Włókno ciągłe poliamidu 56, oraz struktura włóknista i tkanina bazowa poduszki powietrznej, które obie je zawierają
JP5762085B2 (ja) 2011-03-31 2015-08-12 ユニチカトレーディング株式会社 吸放湿性ポリアミド仮撚捲縮糸およびその製造方法、該仮撚捲縮糸を用いた織編物
IL218082A0 (en) 2012-02-13 2012-03-29 Nilit Ltd Cooling polyamide yarn
CN103882550B (zh) 2012-12-24 2017-05-24 东丽纤维研究所（中国）有限公司 一种冷感聚酰胺纤维
CN103088459B (zh) 2013-02-07 2014-11-05 浙江蓝天海纺织服饰科技有限公司 锦纶基降温纤维、纱线
CN104178839A (zh) 2013-05-23 2014-12-03 东丽纤维研究所（中国）有限公司 一种聚酰胺纤维

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB985295A (en) * 1960-04-22 1965-03-03 Celanese Corp Hollow artificial filaments and spinnerets for their production
US5922830A (en) * 1996-03-29 1999-07-13 Toray Industries, Inc. Highly hygroscopic polyamide fiber, and production and application thereof
JP2000220029A (ja) * 1999-01-28 2000-08-08 Unitika Ltd ポリエステル異形断面糸及び混繊糸
US6753082B1 (en) * 2003-02-26 2004-06-22 Honeywell International Inc. Absorbent fibers
US20130280513A1 (en) * 2010-03-31 2013-10-24 Toray Industries, Inc. Hygroscopic fiber, and manufacturing method for same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2016108078A1 *

Also Published As

Publication number Publication date
KR102471874B1 (ko) 2022-11-30
JP2018527479A (ja) 2018-09-20
WO2016108078A1 (fr) 2016-07-07
CN108026665A (zh) 2018-05-11
US20180251913A1 (en) 2018-09-06
KR20180045023A (ko) 2018-05-03
IL257404A (en) 2018-04-30
JP6714077B2 (ja) 2020-06-24

Similar Documents

Publication Publication Date Title
US20180251913A1 (en) Polyamide fiber with improved comfort management, process thereof and article made therefrom
JP5741434B2 (ja) 吸湿性繊維およびその製造方法
JP5701767B2 (ja) 温度調節性ならびに耐切断性を有する糸および布
US20190233983A1 (en) Fiber-filled material and fiber product obtained by using same
EP3235932B1 (fr) Fil composite à structure âme/gaine absorbant l'humidité
EP2815011B1 (fr) Fil de polyamide refroidissant
JP2016204784A (ja) 吸湿性、接触冷感に優れたポリアミド系芯鞘複合繊維およびそれを用いた布帛
JP2020105682A (ja) 芯鞘複合繊維
CN113186622A (zh) 一种负离子抗菌保暖纤维及其制备方法
WO2023153459A1 (fr) Fibres frisées
JP5549244B2 (ja) 吸湿性ポリアミド５６短繊維
TWI532893B (zh) 假撚用聚醯胺混纖複合紗
JP2004292982A (ja) ポリアミド繊維を用いて得られるインナーウェア
KR20180079288A (ko) 흡습성, 주름방지성이 우수한 심초 복합 단면섬유
US20190382924A1 (en) Nylon based materials, filaments, and fabrics and associated methods
JP6600969B2 (ja) 吸放湿性能に優れた芯鞘複合断面繊維
JP2019157296A (ja) 嵩高構造糸、中綿、及びそれを用いた繊維詰め物体および繊維製品
JP2015078459A (ja) 織編物
JP2018104839A (ja) 収縮特性に優れた仮撚用ポリアミドマルチフィラメント
JP2004060129A (ja) 高吸放湿ポリアミド繊維およびその製造方法
JP2006132041A (ja) ストッキング
JP2005015969A (ja) ナノポーラスファイバー複合織編物
JP2005048308A (ja) ポリアミド編物およびそれよりなる繊維製品
JP2016194170A (ja) 芯鞘型複合繊維
JP2006077353A (ja) 芯鞘複合フィラメント糸、それを用いた布帛、中空繊維布帛、及びその製造方法。

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180416

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20200417

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Free format text: PREVIOUS MAIN CLASS: D01D0004020000

Ipc: D01F0006600000

RIC1 Information provided on ipc code assigned before grant

Ipc: D01F 6/60 20060101AFI20210331BHEP

Ipc: D01D 4/02 20060101ALI20210331BHEP

Ipc: D01D 5/253 20060101ALI20210331BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20240403