EP2554721A1 - Fibre hygroscopique et son procédé de fabrication - Google Patents

Fibre hygroscopique et son procédé de fabrication Download PDF

Info

Publication number
EP2554721A1
EP2554721A1 EP11762512A EP11762512A EP2554721A1 EP 2554721 A1 EP2554721 A1 EP 2554721A1 EP 11762512 A EP11762512 A EP 11762512A EP 11762512 A EP11762512 A EP 11762512A EP 2554721 A1 EP2554721 A1 EP 2554721A1
Authority
EP
European Patent Office
Prior art keywords
fiber
polyamide
fabric
spinning
hygroscopic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11762512A
Other languages
German (de)
English (en)
Other versions
EP2554721A4 (fr
EP2554721B1 (fr
Inventor
Kenji Itou
Kentaro Takagi
Takahiro Kuribayashi
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.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
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 Toray Industries Inc filed Critical Toray Industries Inc
Publication of EP2554721A1 publication Critical patent/EP2554721A1/fr
Publication of EP2554721A4 publication Critical patent/EP2554721A4/fr
Application granted granted Critical
Publication of EP2554721B1 publication Critical patent/EP2554721B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—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
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41B—SHIRTS; UNDERWEAR; BABY LINEN; HANDKERCHIEFS
    • A41B9/00—Undergarments
    • 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
    • D01D5/04—Dry spinning methods
    • 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
    • D01D5/12—Stretch-spinning methods
    • 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
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • 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
    • Y10T428/2915—Rod, strand, filament or fiber including textile, cloth or fabric

Definitions

  • the present invention relates to a highly hygroscopic fiber comprising a polyamide 56 resin.
  • Synthetic fibers each made of a thermoplastic resin, such as a polyamide or a polyester, are widely used for clothing, and for industries since the fibers are excellent in strength, chemical resistant, heat resistant, and other characteristics.
  • polyamide fiber is widely used for innerwear, sportswear, and others while the fiber makes good use of a softness, a high tensile strength, a color developability when dyed, a high heat resistant and other characteristics peculiar to the fiber.
  • Patent Document 1 suggests a method in which after a polyamide fiber is formed, at the stage of post-treating the fiber a moisture absorbent is given to the surface of the fiber.
  • Patent Document 2 suggests a method of using a polyamide resin into which a hydrophilic component, such as polyoxyalkylene glycol, is copolymerized to manufacture a fiber.
  • Patent Document 3 suggests a method of rendering the structure of a fiber a core-in-sheath structure having a core region made of a thermoplastic resin high in hygroscopicity, and a sheath region made of a thermoplastic resin excellent in mechanical properties, thereby forming the fiber with compatibility between hygroscopicity and mechanical properties.
  • Patent Document 4 suggests a method of: melt-spinning a blend composite composed of an alcohol-soluble polyamide, and a fiber-forming thermoplastic resin compatible with the alcohol-soluble polyamide; and then partially dissolving out, from the resultant, the alcohol-soluble polyamide to yield a hygroscopic fiber similar to a natural fiber.
  • Patent Document 1 suggests a method of blending a polyamide with polyvinyl pyrrolidone as a hydrophilic polymer, and then spinning the resultant blend, thereby improving the resultant fiber in hygroscopicity.
  • polyamide fibers are lower in hygroscopicity than natural fibers to cause, for example, a stuffy or sweaty state based on sweating-out from the skin.
  • the polyamide fibers have a problem of being poorer in comfortableness than natural fibers.
  • the method has the following drawbacks: a fabric of the fiber is lowered in washing resistance; and further when the fabric receives the supply of a large amount of a moisture absorbent to gain a high hygroscopicity, the fabric gets slimy in the surface thereof because of moisture absorption to give an unpleasant feeling.
  • the fiber in order to attain a sufficient hygroscopicity, the fiber is required to be made high in copolymerization proportion of comonomer.
  • the requirement causes the fiber to be remarkably damaged in mechanical properties of the yarn, such as the strength and elongation thereof.
  • a fiber satisfying hygroscopicity and mechanical properties simultaneously has not yet been attained.
  • the composite fiber of Patent Document 3 has a drawback that a manufacturing apparatus therefor becomes complex so that costs increase.
  • the fiber also has, for example, the following drawback because of the difference in water absorbing power between the polymers used in the core region and in the sheath region: at the time of subjecting the fiber to treatments with hot water, such as refining and dyeing, the hygroscopic resin in the core region absorbs water to swell largely; thus, the surface of the fiber is cracked so that the polymer in the core region is unfavorably dissolved out.
  • a fiber cannot gain a sufficient hygroscopicity when the quantity of the dissolved-out component is small. Conversely, when the quantity of the dissolved-out component is large, the fiber turns insufficient in physical properties, such as strength. Thus, when clothing thereof is worn, for example, a drawback that the fabric (of the clothing) is whitened or made into fibrils is caused. In short, it is difficult that the fiber satisfies both of hygroscopicity and physical properties.
  • the fiber according to the method of Patent Document 1 is excellent as a hygroscopic fiber, the fiber is insufficient in heat resistance for being subjected to heat forming, because of the addition of polyvinyl pyrrolidone to the base of polyamide 6 as a polyamide, under such a situation that: in recent years, for example, there has been recognized a fashion trend that women who wear T-shirts fitted tightly to their bodies have been increasing; and with the trend, a demand for heat-formed brassieres, which are not easily reflected onto outerwear, has been increasing.
  • polyamide 66 which has a high melting point, as a base
  • the temperature for spinning polyamide 66 is high so that polyvinyl pyrrolidone is thermally deteriorated.
  • this blend material cannot be stably spun.
  • An object of the present invention is to overcome the problems in the prior art, and provide a highly value-added, hygroscopic synthetic fiber, which has a high moisture absorptivity, without damaging the strength, the chemical resistant, the heat resistant nor other characteristics s of polyamide.
  • the object of the invention is also attained by a method for manufacturing a hygroscopic fiber by a direct spin draw method comprising cooling and solidifying a polyamide 56 fiber discharged from a spinneret by cooling wind, depositing a spinning oil onto the fiber, drawing the fiber, and then winding the fiber, wherein the following requirements (1) and (2) are satisfied:
  • the object of the invention is further attained by a fiber structure comprising the fabric.
  • the hygroscopic fiber of the invention preferably has a birefringence ranging from 30 x 10 -3 or more to 40 x 10 -3 or less.
  • the fabric of the invention is preferably a fabric wherein the hygroscopic fiber is used, the fabric comprising a portion shaped by mold process.
  • the fiber structure of the invention is preferably an innerwear.
  • the invention makes it possible to yield a highly value-added, hygroscopic synthetic fiber, which has a high moisture absorptivity, without damaging the strength, the chemical resistant, the heat resistant nor other characteristics of polyamide.
  • Fig. 1 is a schematic view illustrating an example of a process for manufacturing a synthetic fiber according to the invention.
  • the polyamide 56 fiber of the invention is a fiber containing, as main constituting units, 1,5-diaminopentane units and adipic acid units.
  • the polyamide 56 fiber of the invention preferably contains 1, 5-diaminopentane units obtained by use of a biomass since the fiber is very good in environment adaptability.
  • the quantity of 1,5-diaminopentane units obtained by use of a biomass is 50% or more of the quantity of the 1,5-diaminopentane units constituting the polyamide 56.
  • the quantity is more preferably 75% or more thereof, most preferably 100% thereof.
  • the polyamide 56 in the invention is preferably a polymer having a 98%-sulfuric acid relative viscosity ranging from 2.4 or more to 2.6 or less for an effective production of the advantageous effects of the invention.
  • the polymer can gain a sufficient strength when made into a fiber. Additionally, when into a fiber, the polymer can gain an appropriate crystallinity degree and a sufficient hygroscopicity.
  • the pressure for feeding the polymer in a melted state, and the rate of a rise in the pressure with time are appropriate so that an excessive burden is not imposed to the manufacturing facilities and, for example, the period for changing the spinneret is not required to be shortened. Thus, a high manufacturability is kept.
  • the 98%-sulfuric acid relative viscosity referred to herein is a value obtained by dissolving 25 g of the fiber into 25 mL of 98% sulfuric acid and then using an Ostwald viscometer to make the viscosity thereof at 25°C.
  • a second component and a third component may be copolymerized or blended with the main component as far as the object of the invention can be attained.
  • the copolymerizable component(s) that can be contained therein include structural units each derived from an aliphatic carboxylic acid, an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid.
  • the polyamide 56 may contain structural units each derived from an aliphatic diamine such as ethylenediamine or cyclohexanediamine, an alicyclic diamine such as bis-(4-aminocyclohexyl)methane, an aromatic diamine such as xylylenediamine, an amino acid such as 6-amino caproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, or p-aminomethylbenzoic acid, or a lactam such as ⁇ -caprolactam or ⁇ -laurolactam.
  • an aliphatic diamine such as ethylenediamine or cyclohexanediamine
  • an alicyclic diamine such as bis-(4-aminocyclohexyl)methane
  • an aromatic diamine such as xylylenediamine
  • an amino acid such as 6-amino caproic acid, 11-aminoundecanoic acid, 12-
  • One or more out of various additives may be copolymerized into or blended with the polyamide 56 in the invention in a total content of 0.001 to 10% by weight, examples of the additives including a delustering agent, a flame retardant, an antioxidant, an ultraviolet absorbent, an infrared absorbent, a crystal nucleus agent, a fluorescent whitening agent, and an antistatic agent.
  • the shape or form of a cross section of a monofilament of the polyamide 56 fiber of the invention may be, besides a circular shape, various sectional shapes or forms, such as a flat shape, a Y-shape and a T-shape, or a hollow form, a cross-in-square form and a double-cross form.
  • the cross section is preferably a Y-shape, T-shape or double-cross form cross section, or some other cross section in order that when the fiber is made into a fabric, gaps can be generated between adjacent ones of the filaments so that the fabric can express water absorptivity by a capillary phenomenon.
  • the fiber has a higher moisture absorption and desorption parameter ⁇ MR, which shows the moisture absorptivity.
  • the ⁇ MR is an index for a purpose that the fiber can gain comfortableness by a matter that when the clothing is worn, the moisture inside the clothing is emitted to the outside air.
  • the index is a difference between the moisture absorptivity at the temperature and the humidity of the inside of clothing of a person when the person works or exercises at a light or middle level, a typical example thereof being 30°C and 90% RH, and that at the temperature and the humidity of the outside air, a typical example thereof being 20°C and 65% RH.
  • this ⁇ MR as a parameter is used as an index for evaluating a fiber about moisture absorption performance.
  • the fiber As a fiber has a larger ⁇ MR, the fiber is higher in moisture absorption and desorption power, which corresponds to a matter that when a person wears clothing thereof, the person feels more comfortable.
  • polyamide 6, polyamide 66 or some other polyamide fiber has a ⁇ MR of about 1.5 to 2.0.
  • the polyamide fiber of the invention has a ⁇ MR of 3.0% or more to show a high moisture absorption and desorption.
  • a fiber has a ⁇ MR less than 3.0%, the fiber is merely equivalent in moisture absorption and desorption to ordinary polyamide 6 or polyamide 66 species so as to result in a problem that when a person wears clothing thereof, the person does not feel a high comfortableness.
  • the upper limit thereof is not limited. However, even when the ⁇ MR is made considerably large, a large difference is not generated for bodily sensation. Thus, the ⁇ MR is sufficient to be about 20%.
  • the moisture absorption and desorption power of the above-mentioned polyamide fiber largely depends on the crystal structure of the fiber.
  • the moisture absorption of any polyamide fiber is classified into the following two cases: a case where water is coordinated to amide groups of the polyamide to be bonded thereto; and a case where water is taken into amorphous regions where polyamide molecular chains in the fiber are present in a random state.
  • the ⁇ MR, or some other reversible moisture absorption and desorption power depends particularly on the proportion of the amorphous regions in the fiber. Accordingly, in order to improve a polyamide fiber in ⁇ MR, it is important to increase the proportion of amorphous regions therein as far as the fiber is not damaged in spinning operability nor quality.
  • fibers wherein the orientation of molecular chains is enhanced are large in birefringence while fibers wherein the orientation is not enhanced are small therein.
  • the orientation of the molecular chains is an important parameter since the orientation produces a large effect onto the water absorption coefficient of the fiber as will be described in the following: the moisture absorption of a polyamide fiber is classified into two cases, i.e., a case where water is coordinated to amide groups of the polyamide to be bonded thereto, and a case where water is taken into amorphous regions where polyamide molecular chains in the fiber are present in a random state; in particular, the proportion of the amorphous regions in the fiber produces a large effect onto the ⁇ MR value.
  • any polyamide fiber the proportion of its crystal regions is large while that of its amorphous regions, which can hold water, is small.
  • the crystal regions are large in proportion, water on the surface of the fiber cannot reach the vicinity of amide groups inside the polyamide fiber.
  • the orientation of the molecular chains can be represented through the birefringence.
  • the fiber becomes larger in birefringence, the fiber tends to become larger in water absorption coefficient. If the fiber is too large in water absorption coefficient, the fiber excessively absorbs the spinning oil, and water in the air so that the yarn swells. Thus, stable spinning cannot be attained, and further structures of the fiber are varied so that the fiber is deteriorated in quality.
  • the orientation and crystallization of the molecular chains in the fiber are enhanced, so that the fiber tends to be declined in moisture absorptivity.
  • the birefringence is preferably set into the range of 30 x 10 -3 or more to 40 x 10- 3 or less.
  • the birefringence is set into this range, a polyamide 56 fiber having high moisture absorption and desorption is obtained without damaging the spinning operability of the polyamide 56 fiber nor the quality of the yarn.
  • the polyamide fiber of the invention may be manufactured by the following method:
  • FIG. 1 is a schematic view illustrating an example of a process for manufacturing a synthetic fiber according to the invention.
  • a melted polyamide is weighted and fed through a metering pump, and then discharged from a spinneret 2.
  • a cooling device 3 such as a chimney, is used to blow cooling wind onto the resultant to cool the fiber to room temperature.
  • an oiling device 4 a spinning oil is supplied thereto while the filaments of the fiber are collected into a bundle.
  • a first interlacer 5 the collected filaments are interlaced with each other, and the resultant fiber is passed through a take up roller 6 and a draw roller 7. At this time, the fiber is drawn in accordance with the ratio between the peripheral velocity of the take up roller 6 and that of the draw roller 7. Furthermore, by means of the draw roller 7, the yarn is thermally set, and then wound up onto a winder 8.
  • the discharged fiber gives a spinning liner velocity ranging from 14 m/min or more to 30 m/min or less.
  • the spinning liner velocity is a value obtained by dividing the discharged volume per unit time of the polymer from holes in the spinneret, from which the yarn is discharged, by the area of the holes in the spinneret, and is a parameter which controls the degree of the orientation of the yarn-form polymer discharged from the spinneret. If this spinning liner velocity is small, the ratio between the spinning liner velocity and the velocity of the take up roller 6 is large when the yarn is taken up through the take up roller 6. Thus, an excessive draw tension is applied to the filaments which are being taken up, so that the single yarn is broken.
  • the polyamide cannot be stably spun. If the spinning liner velocity is too large, the orientation of the fiber is excessively promoted after the yarn is taken up through the take up roller 6 and then drawn through the draw roller 7. As a result, the fiber unfavorably becomes a fiber small in moisture absorptivity.
  • a condition for the spinning is set to adjust, to 3,900 or more and 4,500 or less, the product of the take up velocity (m/min) of the yarn taken up through the take up roller 6, and the draw ratio, which is a value of the ratio between the peripheral velocity of the take up roller 6 and that of the draw roller 7.
  • This numerical value represents the total draw quantity of the polymer discharged from the spinneret while the polymer is drawn until the spinning liner velocity is turned to the peripheral velocity of the take up roller 6 and further drawn until the peripheral velocity of the take up roller 6 is turned to the peripheral velocity of the draw roller 7. If this value is too small, the fiber is low in orientation degree to become a fiber having an excessively large moisture absorptivity.
  • the fiber excessively absorbs the spinning oil, or water in the air, so that the yarn swells.
  • the polyamide cannot be stably spun. If this value is too large, the fiber is excessively enhanced in orientation degree to become a fiber small in moisture absorptivity.
  • the spinning oil which is given by means of the oiling device 4, is preferably a water-free oil.
  • the water-free oil is given thereto, it is not feared that water is absorbed into the polyamide 56 while the oil is given.
  • the so-called polyamide swelling is not caused, so that the fiber length is not varied in the spinning.
  • the yarn can be stably wound up.
  • the tensile strength is preferably 3.5 cN/dtex or more.
  • the fiber can realize an actual strength for a fabric for clothing, such as innerwear, for which the polyamide fabric is mainly used.
  • the tensile strength is more preferably 4.0 cN/dtex or more.
  • the elongation is preferably 35% or more.
  • the fiber becomes good in processability in higher-order steps such as weaving, knitting, and false-twisting.
  • the total fineness is preferably 100 dtex or less, more preferably 60 dtex or less from the viewpoint of the thickness obtained when the fiber is worked into a fabric.
  • the single filament fineness is preferably 4.0 dtex or less, more preferably 2.0 dtex or less from the viewpoint of the softness attained when the fiber is worked into a fabric.
  • the structure of the hygroscopic fiber yielded in the above-mentioned way is not limited to the above-mentioned structure, and may be a filament or staple.
  • the structure is selected in accordance with an article to which the fiber is applied.
  • the form of the fabric may be selected from textile, knitting, nonwoven fabric, and others in accordance with a purpose thereof, and may be a clothing form.
  • the fiber of the invention is woven or knitted, subsequently worked, and then sewn to be made into various products for clothing, such as innerwear, panty stockings, and tights.
  • the fabric of the invention Since the fabric of the invention has both of heat resistance and water absorptivity, which are not easily compatible with each other in conventional polyamide fibers, the fabric is in particular preferably a fabric containing a region shaped by mold process.
  • the fiber structure of the invention is preferably used as an innerwear molded to create a curved surface of a concave, a convex, a narrow region for, for example, cups of a brassier, panties, or a waist or hip portion of a girdle, or as an innerwear having such a molded portion.
  • the molding is a working of inserting a fabric, such as woven fabric, knitted fabric or nonwoven fabric, into a gap between parts of a mold, and then subjecting the fabric to heat treatment to make the fabric roundish.
  • a fabric such as woven fabric, knitted fabric or nonwoven fabric
  • the surface temperature of the mold is usually from 160 to 230°C, preferably from 170 to 220°C, more preferably from 190 to 200°C.
  • the treatment period is preferably from 0.5 to 3 minutes.
  • a differentialscanning calorimetry (PerkinElmer, DSC-7), is used to measure 10 mg of a sample at a temperature-raising rate of 15°C/minute.
  • a peak showing an extreme value at the endothermic side thereof is determined to be the melt peak thereof.
  • the temperature at which the extreme value is given is defined as the melting point Tm (°C).
  • Tm melting point
  • the temperature at which an extreme value is given at a higher temperature out of the values is used as the melting point.
  • MR 1 W 65 - W 0 / W 0 x 100 %
  • MR 2 W 90 - W 0 / W 0 x 100 %
  • ⁇ MR MR 2 - MR 1
  • a polarization microscope (Nikon, POH) is used to measure each of two monofilaments taken out from a fiber about the retardation and the diameter thereof, using a white light ray as a light source. Thus, the respective birefringences are measured. The average thereof is then calculated.
  • a reel having a length of 1 m per circumference is caused to make ten turns to form five 10-turn reeled threads that are each in a loop form. These are used as samples for weight-measurement.
  • 10-turn reeled threads in a loop form are formed, and then ends of each of the reeled threads are tied with each other.
  • the reeled threads in each of which the knot is not untied are prepared, the number of which is five.
  • the reeled threads are used as samples for sample-length-measurement. First, the samples, the total number of which is 10, are allowed to stand still in an environment of 25°C and 55% relative humidity for 48 hours in the state that no load is applied thereto. In this way, the reeled threads are conditioned.
  • the respective weights of the loop-form reeled threads for weight-measurement are measured, and the average A (g) thereof is calculated.
  • the respective reeled thread lengths of the loop-form samples for sample-length-measurement are measured in the same environment.
  • the loop-form reeled threads for sample-length-measurement are each hung onto a hook.
  • a load corresponding to 0.05 cN/dtex is applied to the loop-form reeled thread, and the reeled thread length thereof is measured.
  • the length 20 times the reeled thread length is equal to the sample length.
  • the average B (m) of the five sample lengths is calculated.
  • the value A is divided by the value B, and then the resultant value is multiplied by 10, 000. In this way, the total fineness is determined.
  • the monofilament fineness is determined by dividing the total fineness by the number of the filaments.
  • a stretchable fabric is fixed between two fixing tools in the state of being relaxed without being loosened, the tools each having a thickness of 2 cm, and being each hollowed to have a diameter of 15 mm.
  • a semispherical, hot iron ball having a diameter of 10 cm and a surface heated to 200°C is pushed against the fabric to dent the fabric into a depth of 10 cm. Immediately after 60 seconds, the hot iron ball is pulled out. About the surface form of the bump-shaped region, before and after the working, the external appearance is evaluated in accordance with the following criterion:
  • the surface is rough so that the shaped fabric is unsuitable for a commercial product.
  • the yarn of each of Example 1, and Comparative Examples 1, 5 and 7 is to be used to make evaluations as follows: the yarn is knitted into knitted fabrics, and the fabrics are each sewn to be fitted to a body. In this way, T-shirt samples are produced. Inside a room of 25°C and 65% relative humidity, five examinees each wear one of the T-shirts. In this state, the examinee goes for a jog at 12 km/hour for 5 minutes. Thereafter, the examinee makes a comparative evaluation of the T-shirts about the feeling of stickiness when the examinee sweats, on the basis of his/her own sense, in accordance with the following evaluating criterion:
  • the examinee has no stickiness feeling, and also has a good touch feeling.
  • Good The examinee has no stickiness feeling.
  • Fair The examinee has a bearable stickiness feeling.
  • Bad The examinee has a stickiness feeling to be displeased therefor.
  • the five examinees each make a comparative evaluation of the fabrics about the comfortableness thereof, which is related to the fabric-softness felt when the examinee wears T-shirts, on the basis of his/her own sense, in accordance with the following evaluating criterion:
  • the T-shirt is soft to be comfortable.
  • Bad The T-shirt is hard in touch, and is stiff.
  • a polymer is evaluated about spinning stability on the basis of the following: the number of times of yarn breakage caused when the yarn from the polymer is wound, over 1 hour, by a quantity corresponding to two packages per winder under spinning conditions that will be described later.
  • a batch-type polymerizing can having an internal volume of 80 L, and equipped with a stirrer having a double-helical ribbon vane and further with a heat medium jacket: the aqueous solution; 86.4 g of 1,5-diaminopentane; and 28.2 g of a slurry wherein titanium dioxide was dispersed in ion exchange water to give a concentration of 20%.
  • the inside of the polymerizing can was sufficiently purged with nitrogen, and then the can was started to be heated to 260°C while the inside was stirred. From a time when the pressure in the can reached to 0.2 MPa (gauge pressure), the concentration of the slurry was started.
  • the open degree of the pressure discharge valve was adjusted to keep the internal pressure of the polymerizing can constant.
  • the pressure discharge valve was closed and then the heating temperature was changed to 285°C.
  • the pressure in the can was kept. Over 50 minutes from a time when the inside temperature reached to 255°C, the pressure was gradually decreased to the atmospheric pressure. Thereafter, nitrogen gas was caused to flow at 5 L/minute to be blown into the can for 15 minutes. Thereafter, a nitrogen pressure of 0.4 MPa (gauge pressure) was applied to the inside of the can to jet out the polymer into a water bath.
  • the polymer was pelletized with a strand cutter.
  • the resultant polyamide 56 resin had a sulfuric acid relative viscosity of 2.54, and a terminated amino group quantity of 2.77 x 10 -5 mol/g.
  • the Tm thereof was 254°C.
  • a batch-type polymerizing can having an internal volume of 80 L, and equipped with a stirrer having a double-helical ribbon vane and further with a heat medium jacket: an aqueous solution wherein 30.0 kg of hexamethylenediammonium adipate (manufactured by Rhodia) was dissolved in 30.0 kg of ion exchange water; 140.4 g of adipic acid (manufactured by CaHC Co., Ltd.); and 28.5 g of a slurry wherein titanium dioxide was dispersed in ion exchange water to give a concentration of 20%.
  • the inside of the polymerizing can was sufficiently purged with nitrogen, and then the can was started to be heated to 260°C while the inside was stirred. From a time when the pressure in the can reached to 0.2 MPa (gauge pressure), the concentration of the slurry was started. The open degree of the pressure discharge valve was adjusted to keep the internal pressure of the polymerizing can constant. When the distillated water volume reached to 24.7 kg, the pressure discharge valve was closed and then the heating temperature was changed to 295°C. After the pressure in the can reached to 1.7 MPa (gauge pressure), the pressure in the can was kept. Over 50 minutes from a time when the inside temperature reached to 255°C, the pressure was gradually decreased to the atmospheric pressure.
  • ⁇ -Caprolactam containing 1 wt% of water was continuously supplied at a rate of 30 kg/hour into a first polymerizing reactor having a volume of 0.2m 3 and equipped with a thermostat.
  • the heating temperature was set to 270°C to polymerize the monomer.
  • a polymerization intermediate From a lower region of the first polymerizing reactor, a polymerization intermediate, the amount of which corresponded to the supplied amount, was discharged, and then supplied to a second polymerizing reactor having a volume of 0.08 m 3 and equipped with a condenser and a thermostat.
  • the temperature for heating the second polymerizing reactor was set to 250°C, and the intermediate was continuously polymerized under a normal pressure, and then the discharge of a polycapramide, which was a polymerization reaction product, was started. From a time when ⁇ -caprolactam having a volume 1.5 times the volume of the first polymerizing reactor was supplied, the polymer was pelletized to yield a polycapramide spinning material.
  • the resultant polycapramide spinning material was treated with hot water of 95°C for 16 hours to remove low molecular weight components therefrom.
  • the resultant polyamide 6 resin had a sulfuric acid relative viscosity of 2.60, and a terminated amino group quantity of 5.10 x 10 -5 mol/g.
  • the direct spin draw machine illustrated in Fig. 1 was used to perform melt spinning, drawing and thermal treatment continuously to yield a polyamide 56 fiber.
  • the polyamide 56 resin yielded in Production Example 1 was conditioned to have water content of 0.11%, and then charged into a spinning machine.
  • the resin was melted at 290°C and passed through a polymer pipe to be introduced into the spinneret 2
  • the polymer was weighed in the metering pump 1, discharged therefrom, introduced into the spinneret 2, the temperature of which was set to 290°C, and then spun out from the spinneret 2, which had 24 round holes each having a discharge hole diameter of 0.25 mm and a hole length of 0.5 mm.
  • the rotation number of the metering pump 1 was selected to adjust the total fineness of the polyamide 56 fiber to be obtained to 78 dtex, and the discharged amount thereof was set to 31.2 g/min.
  • the yarn was cooled and solidified in the cooling device 3, and a water-free oil was supplied thereto through the oiling device 4. Thereafter, the filaments of the yarn were interlaced with each other through the first interlacer 5, and then wound under conditions that the peripheral velocity of the take up roller 6, which was a first roll, was 2,066 m/min, that of the draw roller 7, which was a second roller, was 4,123 m/min, and the winding rate was 4,000 m/min. In this way, a cheese package was yielded.
  • a polyamide 56 fiber composed of 24 filaments each having a fineness of 78 dtex was yielded in the same way as in Example 1 except that the discharged amount of the metering pump 1 was changed to 34.1 g/min, the peripheral velocity of the first roll to 4,250 m/min, the peripheral velocity of the second roll to 4,463 m/min, and the winding rate to 4,400 m/min. Physical properties of the resultant fiber are shown in Table 1. The resultant fiber was knitted into a tricot knitted fabric. This was molded and then the resultant was evaluated. The result of the evaluation is shown in Table 1.
  • a polyamide 56 fiber composed of 68 filaments each having a fineness of 78 dtex was yielded in the same way as in Example 1 except that the spinneret was changed to a spinneret having 68 round holes each having a discharge hole diameter of 0.20 mm and a hole length of 0.4 mm, and the discharged amount of the metering pump 1 was changed to 30.42 g/min, the peripheral velocity of the first roll to 3,600 m/min, the peripheral velocity of the second roll to 3, 960 m/min, and the winding rate to 3, 900 m/min.
  • Physical properties of the resultant fiber are shown in Table 1.
  • the resultant fiber was knitted into a tricot knitted fabric. This was molded and then the resultant was evaluated. The result of the evaluation is shown in Table 1.
  • a polyamide 56 fiber composed of 13 filaments each having a fineness of 78 dtex was yielded in the same way as in Example 1 except that the discharged amount of the metering pump 1 was changed to 30.9 g/min, and the spinneret was changed to a spinneret having 13 round holes each having a diameter of 0.30 mm and a hole length of 0.6 mm, , the peripheral velocity of the first roll to 1,500 m/min, the peripheral velocity of the second roll to 4, 440 m/min, and the winding rate to 4, 050 m/min.
  • Physical properties of the resultant fiber are shown in Table 1.
  • the resultant fiber was knitted into a tricot knitted fabric. This was molded and then the resultant was evaluated. The result of the evaluation is shown in Table 1.
  • a polyamide 56 fiber composed of 24 filaments each having a fineness of 78 dtex was yielded in the same way as in Example 1 except that the discharged amount of the metering pump 1 was changed to 35.1 g/min, the peripheral velocity of the first roll to 4,400 m/min, the peripheral velocity of the second roll to 4,600 m/min, and the winding rate to 4,550 m/min. Physical properties of the resultant fiber are shown in Table 1.
  • Melt spinning was performed in the same way as in Example 1 except that the discharged amount of the metering pump 1 was changed to 28.9 g/min, the peripheral velocity of the first roll to 2,000 m/min, the peripheral velocity of the second roll to 3,730 m/min, and the winding rate to 3,700 m/min. However, thread breakage was frequently caused in the spinning. Thus, stable spinning was not succeeded.
  • Example 2 Melt spinning was performed in the same way as in Example 1 except that the spinneret was changed to a spinneret having 24 round holes each having a diameter of 0.40 mm and a hole length of 0.8 mm. However, thread breakage was frequently caused in the spinning. Thus, stable spinning was not succeeded.
  • a polyamide 66 fiber was yielded in the same way as in Example 1 except that instead of the polyamide 56 resin, the polyamide 66 resin produced in Production Example 2 was used. Physical properties of the resultant fiber are shown in Table 1. The resultant fiber was knitted into a tricot knitted fabric. This was molded and then the resultant was evaluated. The result of the evaluation is shown in Table 1.
  • a polyamide 6 fiber was yielded in the same way as in Example 1 except that instead of the polyamide 56 resin, a mixed resin was used which was obtained by blending polyvinyl pyrrolidone with the polyamide 6 resin produced in Production Example 3 to give a content of 5% by weight, and further the melting temperature and the spinneret temperature were each set to 260°C. Physical properties of the resultant fiber are shown in Table 1. The resultant fiber was knitted into a tricot knitted fabric. This was molded and then the resultant was evaluated. The result of the evaluation is shown in Table 1.
  • the invention makes it possible to yield a highly value-added, hygroscopic synthetic fiber, which has a high moisture absorptivity, without damaging the strength, the chemical resistant, the heat resistant nor other characteristics of polyamide.
  • the hygroscopic synthetic fiber of the invention is suitable for being used for clothing, in particular, innerwear, sportswear, and others.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Knitting Of Fabric (AREA)
  • Woven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
EP20110762512 2010-03-31 2011-03-09 Fibre hygroscopique et son procédé de fabrication Active EP2554721B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010080643 2010-03-31
PCT/JP2011/055454 WO2011122272A1 (fr) 2010-03-31 2011-03-09 Fibre hygroscopique et son procédé de fabrication

Publications (3)

Publication Number Publication Date
EP2554721A1 true EP2554721A1 (fr) 2013-02-06
EP2554721A4 EP2554721A4 (fr) 2013-12-25
EP2554721B1 EP2554721B1 (fr) 2015-01-21

Family

ID=44711997

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20110762512 Active EP2554721B1 (fr) 2010-03-31 2011-03-09 Fibre hygroscopique et son procédé de fabrication

Country Status (6)

Country Link
US (1) US20130280513A1 (fr)
EP (1) EP2554721B1 (fr)
JP (1) JP5741434B2 (fr)
KR (1) KR101550960B1 (fr)
CN (1) CN102834556B (fr)
WO (1) WO2011122272A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016108078A1 (fr) 2015-09-14 2016-07-07 Rhodia Poliamida E Especialidades Ltda Fibre de polyamide présentant une gestion améliorée du confort, procédé pour ladite fibre et article fabriqué à partir de ladite fibre
WO2016079724A3 (fr) * 2016-04-04 2017-10-19 Rhodia Poliamida E Especialidades S.A. Fibre polyamide biodégradable, procédé d'obtention d'une telle fibre et article en polyamide fabriqué à partir de celle-ci

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110117833B (zh) * 2013-10-28 2021-12-07 上海凯赛生物技术股份有限公司 尼龙纤维及其制备方法
TWI519687B (zh) * 2014-12-19 2016-02-01 展頌股份有限公司 消光聚醯胺５６纖維及其製造方法
KR102465144B1 (ko) * 2015-05-22 2022-11-10 도레이 카부시키가이샤 흡습성 심초 복합사 및 그 제조 방법
CN104894665A (zh) * 2015-06-19 2015-09-09 南通安恒化纤有限公司 泰纶短纤维及其制备方法
CN108505133B (zh) * 2017-02-24 2022-02-08 上海凯赛生物技术股份有限公司 一种聚酰胺5x纤维及其制备方法
US10784785B2 (en) * 2017-12-21 2020-09-22 Texas Instruments Incorporated Monitoring SMPS power switch voltage via switch drain source capacitance
CN111630216B (zh) * 2018-01-25 2022-11-18 东丽株式会社 聚酰胺复丝及使用其的花边针织物
CN110055602B (zh) * 2019-05-22 2021-05-04 江苏太极实业新材料有限公司 聚酰胺56高强力工业丝及其制备方法
CN112501702B (zh) * 2020-11-27 2022-09-06 军事科学院系统工程研究院军需工程技术研究所 一种功能性聚酰胺56长丝及其制备方法
CN112626626B (zh) * 2020-12-02 2022-07-15 军事科学院系统工程研究院军需工程技术研究所 一种聚酰胺56长丝一步连续成型与柔性变形制备工艺及设备

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004036034A (ja) * 2002-07-03 2004-02-05 Toray Ind Inc ポリアミド系繊維製品およびその製造方法
JP2004270109A (ja) * 2003-03-12 2004-09-30 Toray Ind Inc 超多孔性合成繊維を用いた繊維製品
JP2006132041A (ja) * 2004-11-08 2006-05-25 Toyobo Co Ltd ストッキング
JP2006233380A (ja) * 2005-02-25 2006-09-07 Toray Ind Inc ポリアミドマルチフィラメント糸、その製造方法、インナー用編成物
JP2006265787A (ja) * 2005-03-25 2006-10-05 Toray Ind Inc 吸湿性繊維
JP2009068132A (ja) * 2007-09-12 2009-04-02 Toray Ind Inc 繊維、ゴム補強コード、ならびに補強ゴム
WO2009119302A1 (fr) * 2008-03-26 2009-10-01 東レ株式会社 Filament de polyamide 56 et structure de fibre et tissu de base de coussin de sécurité gonflable comprenant chacun celui-ci

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60246818A (ja) 1984-05-21 1985-12-06 Teijin Ltd 複合合成繊維
JPH03213519A (ja) 1990-01-16 1991-09-18 Kuraray Co Ltd 複合繊維
JPH05209316A (ja) 1992-01-30 1993-08-20 Toray Ind Inc 吸湿性に優れた芯鞘型複合繊維
JP3121150B2 (ja) * 1992-06-18 2000-12-25 旭化成工業株式会社 インクリボン用ポリアミド繊維
JP3716517B2 (ja) 1995-11-06 2005-11-16 東レ株式会社 高吸湿性ポリアミド繊維及びその製造方法
TW371679B (en) * 1996-02-21 1999-10-11 Toray Industries Method for producing coarse and fine polyesteramide staple
JPH11172505A (ja) * 1997-12-10 1999-06-29 Triumph International Japan Ltd 二層構造を有するモールド加工衣料品及びその製造方法
TW507028B (en) * 1999-02-12 2002-10-21 Asahi Chemical Ind A moisture-absorbable synthetic fiber with an improved moisture-release property
US6899836B2 (en) * 2002-05-24 2005-05-31 Invista North America S.A R.L. Process of making polyamide filaments
JP2006144163A (ja) * 2004-11-18 2006-06-08 Mitsubishi Chemicals Corp ポリアミドフィラメント
CN100497768C (zh) * 2005-09-16 2009-06-10 华南理工大学 一种吸湿改性剂及其制备方法与在锦纶纤维中的应用
JP4935695B2 (ja) * 2008-01-30 2012-05-23 東レ株式会社 ポリアミド５６からなる捲縮糸、およびそれを含んでなるカーペット
JP5549244B2 (ja) * 2010-01-29 2014-07-16 東レ株式会社 吸湿性ポリアミド５６短繊維
JP5454191B2 (ja) * 2010-02-09 2014-03-26 東レ株式会社 捲縮糸および繊維構造体

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004036034A (ja) * 2002-07-03 2004-02-05 Toray Ind Inc ポリアミド系繊維製品およびその製造方法
JP2004270109A (ja) * 2003-03-12 2004-09-30 Toray Ind Inc 超多孔性合成繊維を用いた繊維製品
JP2006132041A (ja) * 2004-11-08 2006-05-25 Toyobo Co Ltd ストッキング
JP2006233380A (ja) * 2005-02-25 2006-09-07 Toray Ind Inc ポリアミドマルチフィラメント糸、その製造方法、インナー用編成物
JP2006265787A (ja) * 2005-03-25 2006-10-05 Toray Ind Inc 吸湿性繊維
JP2009068132A (ja) * 2007-09-12 2009-04-02 Toray Ind Inc 繊維、ゴム補強コード、ならびに補強ゴム
WO2009119302A1 (fr) * 2008-03-26 2009-10-01 東レ株式会社 Filament de polyamide 56 et structure de fibre et tissu de base de coussin de sécurité gonflable comprenant chacun celui-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2011122272A1 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016108078A1 (fr) 2015-09-14 2016-07-07 Rhodia Poliamida E Especialidades Ltda Fibre de polyamide présentant une gestion améliorée du confort, procédé pour ladite fibre et article fabriqué à partir de ladite fibre
WO2016079724A3 (fr) * 2016-04-04 2017-10-19 Rhodia Poliamida E Especialidades S.A. Fibre polyamide biodégradable, procédé d'obtention d'une telle fibre et article en polyamide fabriqué à partir de celle-ci
IL261843A (en) * 2016-04-04 2018-10-31 Rhodia Poliamida E Espec S A A biodegradable polyamide fiber, a process for obtaining such a fiber and a polyamide item made from it
EP3440243B1 (fr) 2016-04-04 2022-06-22 Rhodia Poliamida e Especialidades S.A. Fibre polyamide biodégradable, procédé d'obtention d'une telle fibre et article en polyamide fabriqué à partir de celle-ci
IL261843B2 (en) * 2016-04-04 2024-07-01 Rhodia Poliamida E Espec S A A biodegradable polyamide fiber, a process for obtaining such a fiber and a polyamide item made from it

Also Published As

Publication number Publication date
WO2011122272A1 (fr) 2011-10-06
CN102834556A (zh) 2012-12-19
JPWO2011122272A1 (ja) 2013-07-08
CN102834556B (zh) 2016-01-20
JP5741434B2 (ja) 2015-07-01
US20130280513A1 (en) 2013-10-24
KR20130040793A (ko) 2013-04-24
KR101550960B1 (ko) 2015-09-07
EP2554721A4 (fr) 2013-12-25
EP2554721B1 (fr) 2015-01-21

Similar Documents

Publication Publication Date Title
EP2554721B1 (fr) Fibre hygroscopique et son procédé de fabrication
JP6973079B2 (ja) 吸湿性に優れた海島型複合繊維、仮撚糸および繊維構造体
JP6687035B2 (ja) ポリアミドマルチフィラメントおよびそれを用いたレース編物、ストッキング
US3418199A (en) Crimpable bicomponent nylon filament
KR101918049B1 (ko) 폴리아미드 섬유 및 그 제조 방법
JP2014156685A (ja) ポリ（トリメチレンテレフタラート）の微細デニール糸
EP3299500B1 (fr) Fil conjugué âme-gaine hygroscopique et procédé de production de celui-ci
KR101543113B1 (ko) 신축성이 우수한 폴리에스테르 복합섬유, 그 제조방법 및 이를 이용한 복합가공사
JP6939102B2 (ja) 吸湿性に優れた芯鞘型複合繊維、仮撚糸および繊維構造体
KR102575877B1 (ko) 흡습성, 주름방지성이 우수한 심초 복합 단면섬유
WO2024195613A1 (fr) Multifilament de polyamide, et tissu tissé et tricoté
CN110462119B (zh) 吸放湿性优异的聚酰胺纤维
JP2000136453A (ja) ナイロン異収縮混繊糸およびその製造方法
JP2013036147A (ja) ポリアミド捲縮糸およびカーペット

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120824

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

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20131121

RIC1 Information provided on ipc code assigned before grant

Ipc: D01F 6/60 20060101AFI20131115BHEP

Ipc: D01D 5/12 20060101ALI20131115BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140814

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): 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

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011013369

Country of ref document: DE

Effective date: 20150312

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 709253

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150315

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20150121

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 709253

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150121

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150421

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150421

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150422

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150521

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011013369

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150309

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20151022

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150309

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110309

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150521

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150121

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230515

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240130

Year of fee payment: 14

Ref country code: GB

Payment date: 20240201

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20240212

Year of fee payment: 14

Ref country code: FR

Payment date: 20240213

Year of fee payment: 14