EP3150751B1 - Polyamide fibers, fiber structure using same, and clothing - Google Patents
Polyamide fibers, fiber structure using same, and clothing Download PDFInfo
- Publication number
- EP3150751B1 EP3150751B1 EP15798772.8A EP15798772A EP3150751B1 EP 3150751 B1 EP3150751 B1 EP 3150751B1 EP 15798772 A EP15798772 A EP 15798772A EP 3150751 B1 EP3150751 B1 EP 3150751B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- polyamide
- component
- polyamide fiber
- water
- 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.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims description 212
- 239000004952 Polyamide Substances 0.000 title claims description 105
- 229920002647 polyamide Polymers 0.000 title claims description 105
- 238000010521 absorption reaction Methods 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 15
- 229920000728 polyester Polymers 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 229920002292 Nylon 6 Polymers 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 description 44
- 238000011156 evaluation Methods 0.000 description 30
- 238000005259 measurement Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 12
- 238000009987 spinning Methods 0.000 description 12
- 229920002302 Nylon 6,6 Polymers 0.000 description 11
- -1 for example Polymers 0.000 description 10
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 8
- 239000002216 antistatic agent Substances 0.000 description 6
- 238000009940 knitting Methods 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 5
- 229920000299 Nylon 12 Polymers 0.000 description 5
- 229920000572 Nylon 6/12 Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000004745 nonwoven fabric Substances 0.000 description 5
- 238000009991 scouring Methods 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229920000305 Nylon 6,10 Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- PZNPLUBHRSSFHT-RRHRGVEJSA-N 1-hexadecanoyl-2-octadecanoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[C@@H](COP([O-])(=O)OCC[N+](C)(C)C)COC(=O)CCCCCCCCCCCCCCC PZNPLUBHRSSFHT-RRHRGVEJSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- UGDVGCADUVDYET-UHFFFAOYSA-N ethane-1,2-diamine;hexanedioic acid Chemical compound [NH3+]CC[NH3+].[O-]C(=O)CCCCC([O-])=O UGDVGCADUVDYET-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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
- A41B17/00—Selection of special materials for underwear
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/01—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof
- D06M11/05—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with hydrogen, water or heavy water; with hydrides of metals or complexes thereof; with boranes, diboranes, silanes, disilanes, phosphines, diphosphines, stibines, distibines, arsines, or diarsines or complexes thereof with water, e.g. steam; with heavy water
-
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/36—Matrix structure; Spinnerette packs therefor
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/24—Polymers or copolymers of alkenylalcohols or esters thereof; Polymers or copolymers of alkenylethers, acetals or ketones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
Definitions
- the present invention relates to a polyamide fiber for forming, for example, clothing for sports and underwear, and a fiber structure formed using the polyamide fiber.
- Known synthetic fibers for example, polyester fibers, and polyamide fibers such as nylon-6 and nylon-6,6, are used not only for clothing, but also for a wide range of industrial purposes due to their good physical and chemical properties. These fibers are of high industrial value.
- polyester fibers for example, some methods have been proposed for improving the low moisture absorbency and water absorbency, which can be referred to as the main shortcoming of the polyester fibers.
- the proposed methods include, for example, a method in which polyester fibers are post-treated using a hydrophilic post-processing agent, and a method in which polyester fibers are caused to have pores in their surfaces or interiors to obtain moisture absorbency and water absorbency.
- a method in which polyester fibers are post-treated using a hydrophilic post-processing agent and a method in which polyester fibers are caused to have pores in their surfaces or interiors to obtain moisture absorbency and water absorbency.
- the moisture absorbency and water absorbency are insufficiently improved, and the properties provided to the fibers are deteriorated by washing.
- an ethylene-vinyl alcohol-based copolymer which is obtained by saponifying an ethylene-vinyl acetate-based copolymer, is conjugated with another thermoplastic polymer such as polyester, polyamide, or polyolefin, and the resultant conjugated material is formed into fibers, thereby improving dimensional stability (see, for example, Patent Documents 1-3).
- the ethylene-vinyl alcohol-based copolymer according to the above-described known techniques has insufficient resistance to moist heat, which disadvantageously limits its applications.
- nylon fibers used in underwear, socks, and other clothing it is difficult to improve comfort of a fiber structure and clothing containing nylon fibers sufficiently by simply providing the nylon fibers themselves with moisture absorbency. Therefore, there is an increasing demand for moisture-absorbing, and water-absorbing extensible fibers capable of controlling humidity.
- a polyamide fiber of the present invention has a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83.
- the present invention provides a fiber structure which controls humidity highly effectively and provides more comfort than ever.
- a polyamide fiber of the present invention has a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83. If the degree of orientation were lower than 0.7, sufficient colorfast could not be obtained. If the degree of orientation were higher than 0.83, the fiber would reversibly extend and contract in an insufficient manner upon absorbing and releasing water. This would cause the stitches in woven or knitted fabric to open and close insufficiently and make it impossible to obtain a highly comfortable fiber structure.
- a fiber structure such as woven or knitted fabric is produced using the polyamide fibers having a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83.
- the polyamide fibers When absorbing sweat, for example, the polyamide fibers extend to cause the stitches in the woven or knitted fabric to open, thereby releasing humidity inside the clothing. When dried, the polyamide fibers contract to restore the original length and cause the stitches to close, thereby preventing heat from being released outside the clothing.
- the use of the polyamide fibers of the present invention may provide woven or knitted fabric which is highly comfortable and has a so-called self-control function.
- the degree of orientation of the polyamide fiber is beneficially equal to or higher than 0.72, and more beneficially equal to or higher than 0.75. Further, the degree of orientation of the polyamide fiber is equal to or lower than 0.83, more beneficially equal to or lower than 0.8, and still more beneficially lower than 0.80. The degree of orientation of the polyamide fiber is calculated by a measurement method which will be described later with reference to examples.
- the polyamide fiber of the present invention beneficially has a moisture absorption rate equal to or higher than 5% at a temperature of 35°C and a humidity of 95%RH, and a water absorption extension rate equal to or higher than 5% at a temperature of 20°C and a humidity of 65%RH.
- a moisture absorption rate lower than 5% would cause a user to feel stickiness and sweatiness.
- a water absorption extension rate lower than 5% would cause the fiber to reversibly extend and contract in an insufficient manner upon absorbing and releasing, and would prevent stitches in woven or knitted fabric from opening and closing sufficiently. Such moisture absorption rate and water absorption extension rate make it impossible to obtain a highly comfortable fiber structure.
- the use of the polyamide fiber having the above-specified moisture absorption rate and water absorption extension rate may enable the production of a fiber structure such as woven or knitted fabric, which has the self-control function described above and provides more comfort.
- the moisture absorption rate is beneficially equal to or higher than 5% and equal to or lower than 30%, and more beneficially equal to or higher than 8% and equal to or lower than 25%.
- the water absorption extension rate is beneficially equal to or higher than 5%, more beneficially equal to or higher than 7%, still more beneficially equal to or higher than 8%, and particularly beneficially equal to or higher than 10%.
- the water absorption extension rate is beneficially equal to or lower than 30%, more beneficially equal to or lower than 25%, and still more beneficially equal to or lower than 20%.
- the moisture absorption rate and the water absorption extension rate of the polyamide fiber are measured according to a measurement method which will be described later with reference to the examples.
- the polyamide fiber has a crimp extension rate which is beneficially equal to or higher than 1.5% and equal to or lower than 10%, more beneficially equal to or higher than 2% and equal to or lower than 8%, and still more beneficially equal to or higher than 2.5% and equal to or lower than 5.8%.
- a crimp extension rate equal to or higher than 1.5% and equal to or lower than 10% provides silk-like feel and texture, and makes fabric soft and pleasant to the touch.
- polyamide to be used in the present invention examples include: polycaproamide (nylon-6), poly- ⁇ -aminoheptanoic acid (nylon-7), polyundecaneamide (nylon-11), polyethylene diamine adipamide (nylon-2,6), polytetramethylene adipamide (nylon-4,6), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene sebacamide (nylon-2,10), polyhexamethylene dodecamide (nylon-6,12), polyoctamethylene adipamide (nylon-8,6), polydecanomethylene adipamide (nylon-10,6), and polydodecamethylene sebacamide (nylon-10,8).
- polyamide examples include: caprolactam/lauric lactam copolymer (nylon-6/12), caprolactam/ ⁇ -aminononanoic acid copolymer (nylon-6/9), caprolactam/hexamethylene adipate copolymer (nylon-6/6,6), lauric lactam/hexamethylene diamine adipate copolymer (nylon-12/6,6), hexamethylene diamine adipate/hexamethylene diamine sebacate copolymer (nylon-6,6/6,10), ethylenediamine adipate/hexamethylene diamine adipate copolymer (nylon-2,6/6,6), and caprolactam/hexamethylene diamine adipate/hexamethylene diamine sebacate copolymer (nylon-6,6/6,10).
- nylon-6 and nylon-6,6 are most suitable as the polyamide of the present invention.
- Nylon-6 is still more beneficial because it is unexpansive and versatile, and has high moisture absorbency.
- nylon-6/6,6 and nylon-6/12 are beneficial.
- the composition ratio between the component having a carbon number of 6 and the component having a carbon number of 12 that form the nylon-6/12 is not particularly limited, the component having a carbon number of 12 beneficially constitutes 50 mol% or less, and more beneficially 40 mol% or less.
- the polyamide copolymers may be caused to contain an anti-static agent, a lubricant, an anti-blocking agent, a stabilizer, a dye, or a pigment, for example.
- the polyamide fiber of the present invention may be produced by any method as long as the polyamide fiber has the above-described degree of orientation, moisture absorption rate, and water absorption extension rate.
- a polyamide component (component A) and another soluble component (component B) are formed into a conjugated fiber, and thereafter, the component B is dissolved and removed, thereby suitably producing the polyamide fiber of the present invention.
- the use of such a conjugated fiber enables the control of the structure of the polyamide component, thereby enabling the production of a fiber which is exclusively made of polyamide, has a specific degree of orientation, high moisture absorbency and high water absorption extensibility, and is capable of reversibly extending and contracting upon absorbing and releasing water.
- the other component i.e., the soluble component (component B) plays an important role in the structure control.
- An exemplary polymer which can be used as the component B is a water-soluble thermoplastic polyvinyl alcohol-based polymer. This polyvinyl alcohol-based polymer beneficially has a viscosity average degree of polymerization of 200-500, a degree of saponification of 90-99.99 mol%, and a melting point of 160-230°C.
- the polyvinyl alcohol-based polymer may be a monopolymer or a copolymer
- the polyamide fiber of the present invention can be suitably obtained by removing, by using hot water, the water-soluble thermoplastic polyvinyl alcohol-based polymer from the conjugated fiber including the component B.
- a polyester-based polymer which is soluble in alkali at a high speed is another example which can be used as the component B.
- examples of such an easily alkali-soluble polyester-based polymer include a polylactic acid, and copolymerized polyester formed by copolymerizing 1-5 mol% of 5-sodium sulfoisophthalic acid, 5-30 wt.% of polyalkylene glycol, a conventionally used diol component, and a conventionally used dicarboxylic acid component.
- the polyamide fiber of the present invention may be suitably obtained by the removal of the easily alkali-soluble polyester-based polymer by alkaline treatment.
- the conjugated fiber for producing the polyamide fiber of the present invention has a fiber cross section of which 50% or more is coated with the soluble component (component B). It is more beneficial that the entire cross section is coated with the soluble component (component B). That is to say, the conjugated fiber beneficially has a sheath-core cross section in which the polyamide component forms the core and the component B forms the sheath, or a sea-island cross section in which the polyamide component forms the islands and the component B forms the sea.
- a conjugate ratio (A:B) of the conjugated fiber of the present invention between the polyamide component (A component) and the soluble component (B component) ranges beneficially from 90:10 to 40:60 (weight ratio), and more beneficially from 80:20 to 60:40 (weight ratio).
- the ratio may be adjusted according to fiber shapes. Note that if the component B is used in a small amount, it may become difficult to control the polyamide structure. This may makes it impossible to achieve desired moisture absorbency and water absorption extensibility, resulting in difficulty in humidity control.
- the cross section of the conjugated fiber of the present invention is not particularly limited, provided that the component B is dissolved and removed by hot water treatment or alkali treatment, and cracks are not caused in the component A.
- the cross section may be of a concentric, eccentric, or multi-centric type, for example. Further, the cross section may have, besides the circular shape shown in FIGS. 1 and 2 , a multifoil shape shown in FIG. 3 , or a modified shape such as a triangle or flat shape. Furthermore, as shown in FIG. 4 , the component A may include therein a hollow portion.
- the cross section may have one or multiple hollow portions, without causing any problem.
- the polyamide fiber of the present invention may beneficially have a monofilament size of 0.03-10 dtex, which is not limiting.
- the polyamide fiber of the present invention may be used not only as a long fiber, but also as a short fiber or a short-cut fiber.
- the conjugated fiber of the present invention may be formed by using a known conjugated fiber-spinning machine.
- Setting of fiber formation conditions is important to obtain the fiber of the present invention. It is most suitable to form the fiber by direct spinning and drawing method at a high speed. If the fiber is melt spun at a low or intermediate speed, and subjected to drawing thereafter, the temperature of heat treatment for the drawing is set to a temperature lower than 100°C, and beneficially to 80°C or lower, and the drawing rate is set to a rate lower than 2. If drawing and false twisting are performed at the same time or continuously after the spinning, the temperature of the heat treatment is also set to a temperature lower than 100°C, and beneficially to 80°C or lower, and the drawing rate is limited to a rate lower than 2. If the temperature were set to 100°C or higher, or if the drawing rate were set to 2 or higher, it would be difficult to control the polyamide structure, and desired degree of orientation, moisture absorbency, and water absorption extensibility could not be achieved.
- the polyamide fiber of the present invention may be used to form various types of fiber structures (fiber aggregates).
- the "fiber structure” may be configured as a multifilament thread, a spun yarn, woven or knitted fabric, non-woven fabric, paper, synthetic leather, and wadding which are exclusively made of the polyamide fiber of the present invention.
- the "fiber structure" may be configured as: woven or knitted fabric or non-woven fabric, part of which is made of the polyamide fiber of the present invention; combined woven or knitted fabric additionally containing fibers of a different type such as natural fibers, artificial fibers, synthetic fibers, or semi synthetic fibers; and woven or knitted fabric, cotton-containing non-woven fabric, or fiber layered product in which the polyamide fibers of the present invention are used as a finished yarn such as a blended yarn, a doubling- and-twisted yarn, a confound yarn, or a crimp yarn.
- the weight ratio of the polyamide fiber of the present invention with respect to the entire woven or knitted fabric or non-woven fabric is beneficially 15 wt. % or more, more beneficially 18 wt.% or more, particularly beneficially 23 wt.% or more.
- the fibers of the present invention may be subjected to napping treatment by means of wire raising or any other finishing.
- a fiber structure may be formed using the fiber which contains polyamide alone and from which the component B has been removed.
- the component B may be removed from a fiber structure which has been formed using the conjugated fiber.
- Nylon-6 having a reduced viscosity of 1.80 dL/g (at a concentration of 1g/dL in orthoclorophenol at 30°C) was used as a polyamide component (component A), and a thermoplastic modified polyvinyl alcohol (modified PVA) (product of Kuraray Co., Ltd. having a saponification degree of 98.5, an ethylene content of 8.0 mol%, and a degree of polymerization of 390) was used as a soluble component (component B).
- modified PVA modified polyvinyl alcohol
- component B The components A and B were separately melted in different extruders, and a conjugated fiber having a cross section shown in FIG.
- the degree of orientation of the produced polyamide fiber was measured by using the following measurement device under the following measurement conditions.
- the produced polyamide fiber was wound into a hank, and the hank was treated at no tension and in boiling water for 30 minutes. Thereafter, the hank was air-dried at a temperature of 20°C and a humidity of 65%RH, thereby regulating the humidity. The thread was then subjected to a dry heat treatment for two minutes in an atmosphere at 160°C, at no tension, and in a contactless fashion. Then, the thread was left in an atmosphere at a temperature of 20°C and a humidity of 65%RH for 24 hours. After the lapse of 24 hours, the length of the thread with a load of 0.88 ⁇ 10 -3 cN/dtex applied thereto was measured.
- the thread length in dry state This length is referred to as "the thread length in dry state.” Thereafter, the thread was immersed in softened water having a temperature adjusted to 20°C for one minute. The thread was then raised from the water, sandwiched between two sheets of filter paper which had been air-dried in an atmosphere at a temperature of 20°C and a humidity of 65%RH, and placed on a flat table. A weight of 1.5 g/cm 2 was put and left over the thread for two seconds to remove excessive moisture on the fiber surface. After 10 seconds, the length of the thread was measured with a load of 0.88 ⁇ 10 -3 cN/dtex applied thereto. This length is referred to as "the thread length in water absorption state.” The water absorption extension rate of the polyamide fiber was calculated according to the following expression.
- the produced polyamide fiber was knitted into some pieces of cylindrical knitted fabric by a circular knitting machine. Ten arbitrarily chosen testers passed one day with the resultant pieces put on their elbows and knees. The testers made sensory evaluation concerning feeling of stickiness and sweatiness. The results of the sensory evaluation were qualified in terms of points: "No feeling of stickiness or sweatiness and highly comfortable” was qualified as two points, “Comfortable” as one point, and “uncomfortable” as 0 point. The pieces of the knitted fabric were evaluated and classified into the following four levels according to the total sums of points. Table 1 shows the results.
- the polyamide fiber was wound into a small hank having 20 turns by using a sizing reel of which the frame perimeter was 1.125 m.
- the resultant small hank was heat-treated in boiling water at 98°C for five minutes with no load applied to the hank.
- the small hank was then left in a chamber at constant temperature and humidity (at a temperature of 20 ⁇ 2°C and a relative humidity of 65 ⁇ 2%) for 24 hours.
- a load of 2 mg/d was applied to the humidity-regulated fiber, and the hank length L 1 was measured after one minute.
- a load of 0.1 g/d was applied to the small hank, and the hank length L 2 was measured after one minute.
- g/d represents a number of grams per denier.
- Table 1 shows the results of these measurements and evaluation.
- a polyamide fiber was produced in the same manner as in Example 1, except that polyethylene terephthalate (copolymerized PET) having a limiting viscosity number [ ⁇ ] of 0.52 dL/g and copolymerized with 8 wt.% of polyethylene glycol having a molecular weight of 2000 and 5 mol% of 5-sodium sulfoisophthalic acid was used as the component B.
- the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate of this polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 1.
- Example 3 a polyamide fiber of each of these examples was produced in the same manner as in Example 1, except that nylon-6,6 (Example 3) or nylon-6/12 (Example 4) was used as the component A.
- nylon-6,6 Example 3
- nylon-6/12 Example 4
- the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 1.
- Example 5 a polyamide fiber of each of these examples was produced in the same manner as in Example 1, except that the conjugated fiber was caused to have a cross section shown in FIG. 2 (Example 5) or a cross section shown in FIG. 4 (Example 6).
- the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 1.
- a polyamide fiber was produced in the same manner as in Example 1, except that the soluble component (component B) was omitted.
- the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate of this fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 1.
- a conjugated fiber (size: 275 dtex) having a cross section shown in FIG. 1 was injected through a multi-component fiber spinning nozzle, in the same manner as in Example 1. Subsequently, a thread injected from a spinneret was cooled using a horizontal cooling air blower having a length of 1.0 m. Thereafter, water-free spinning oil including, as its components, an anti-static agent and a lubricating agent was applied to the thread. The thread was then taken off using a roller at a speed of 1000 m/min., and drawn continuously without being wound. The thread was drawn until its length became 2.5 times as long as the original length, while being thermo-set at 150°C.
- a conjugated fiber (110 dtex/24 filaments) was produced at a speed of 2500 m/min.
- the produced conjugated fiber was knitted into cylindrical fabric by a circular knitting machine (28 gauge).
- the resultant knitted fabric was subjected to a scouring step using hot water (90°C, 20 minutes) to dissolve and remove the modified PVA.
- the polyamide fiber of this comparative example was produced.
- a polyamide fiber was produced in the same manner as in Example 1, except that nylon-12 was used as the component A.
- the degree of orientation and the water absorption extension rate of this polyamide fiber were measured, and the evaluation of knitted of the fiber was performed through a wear test. Note that the moisture absorption rate and the crimp extension rate were not measured. The results of these measurements and evaluation are shown in Table 1.
- a conjugated fiber (size: 275 dtex) having a cross section shown in FIG. 1 was injected through a multi-component fiber spinning nozzle, in the same manner as in Example 1. Subsequently, a thread injected through a spinneret was cooled using a horizontal cooling air blower having a length of 1.0 m. Thereafter, water-free spinning oil including, as its components, an anti-static agent and a lubricating agent was applied to the thread. The thread was then taken off using a roller at a speed of 2000 m/min., thereby obtaining undrawn thread. The obtained undrawn thread was knitted into cylindrical fabric by a circular knitting machine (28 gauge). The resultant knitted fabric was subjected to a scouring step using hot water (90°C, 20 minutes) to dissolve and remove the modified PVA. In this manner, the polyamide fiber of this comparative example was produced.
- the polyamide fibers of Examples 1,3-6 have a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83. Therefore, these fibers have a water absorption extension rate of 5% or more at a temperature of 20°C and a humidity of 65%RH. This means that these polyamide fibers effectively control humidity, and knitted fabric made of these fibers is highly comfortable when worn.
- the polyamide fibers of Comparative Examples 1-3 have a degree of orientation equal to or higher than 0.83. Therefore, these fibers have a water absorption extension rate lower than 5% at a temperature of 20°C and a humidity of 65%RH. This means that these fibers control humidity less effectively and the knitted fabric made of the fibers of these comparative examples is notably uncomfortable when worn, as compared to the fibers of Examples 1-6.
- nylon-12 used in Comparative Example 3 is highly hydrophobic and has a high crystal orientation among polyamide resin. Consequently, the fiber of Comparative Example 3 has a high degree of orientation as shown in Table 1, which means that the obtained knitted fabric exhibits no water absorption extension rate and is remarkably uncomfortable when worn.
- the polyamide fiber of Comparative Example 4 has a degree of orientation lower than 0.7. Therefore, the water absorption extension rate of this polyamide fiber is excessively high, resulting in that the fabric made of this fiber is remarkably uncomfortable when worn.
- Nylon-6 having a reduced viscosity of 1.80 dL/g (at a concentration of 1g/dL in orthoclorophenol at 30°C) was used as a polyamide component (component A), and a thermoplastic modified polyvinyl alcohol (modified PVA) (product of Kuraray Co., Ltd. having a saponification degree of 98.5, an ethylene content of 8.0 mol%, and a degree of polymerization of 380) was used as the other component, i.e., the soluble component (component B).
- modified PVA modified polyvinyl alcohol
- component B the soluble component
- Example 2 In the same manner as in Example 1, the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate of this polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 2.
- a polyamide fiber of Example 8 (not according to present invention) was produced in the same manner as in Example 7, except that polyethylene terephthalate (copolymerized PET) having a limiting viscosity number [ ⁇ ] of 0.52 dL/g and copolymerized with 8 wt.% of polyethylene glycol having a molecular weight of 2000 and 5 mol% of 5-sodium sulfoisophthalic acid was used as the component B.
- a polyamide fiber of Example 9 was produced in the same manner as in Example 7, except that polylactic acid was used as the soluble component (component B), and a ratio of nylon-6:component B was set to 67:33. The degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate of each polyamide fiber were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 2.
- Example 2 a polyamide fiber of each of these examples was produced in the same manner as in Example 7, except that nylon-6,6 (Example 10) or nylon-6/12 (Example 11) was used as the component A.
- nylon-6,6 Example 10
- nylon-6/12 Example 11
- the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 2.
- a polyamide fiber of each of these examples was produced in the same manner as in Example 7, except that the conjugated fiber was caused to have a cross section shown in FIG. 2 (Example 12) or a cross section shown in FIG. 3 (Example 13).
- the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 2.
- a conjugated fiber (size: 220 dtex) having a cross section shown in FIG. 1 was injected through a multi-component fiber spinning nozzle, in the same or similar manner to Example 7. Subsequently, a thread injected through a spinneret was cooled using a horizontal cooling air blower having a length of 1.0 m. Thereafter, water-free spinning oil including, as its components, an anti-static agent and a lubricating agent was applied to the thread. The thread was then taken off using a roller at a speed of 1000 m/min., and drawn continuously without being wound. The thread was drawn until its length became 2.5 times as long as the original length, while being thermo-set at 150°C.
- a conjugated fiber (110 dtex/24 filaments) was produced at a speed of 2500 m/min.
- the produced conjugated fiber was knitted into cylindrical fabric by a circular knitting machine (28 gauge).
- the resultant knitted fabric was subjected to a scouring step using hot water (90°C, 20 minutes) to dissolve and remove the modified PVA.
- the polyamide fiber of this comparative example was produced.
- a polyamide fiber was produced in the same manner as in Example 7, except that nylon-12 was used as the component A.
- the moisture absorption rate and the water absorption extension rate of this polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test. Note that the degree of orientation and the crimp extension rate were not measured. The results of these measurements and evaluation are shown in Table 2.
- the polyamide fibers of Examples 7-13 have a moisture absorption rate equal to or higher than 5% at a temperature 35°C and a humidity 95%RH, and a water absorption extension rate equal to or higher than 5% at a temperature 20°C and a humidity of 65%RH. This means that these polyamide fibers effectively control humidity, and knitted fabric made of these fibers is highly comfortable when worn.
- the polyamide fibers of Comparative Examples 5 and 6 have a moisture absorption rate lower than 5% at a temperature of 35°C and a humidity of 95%RH, and a water absorption extension rate lower than 5% at a temperature of 20°C and a humidity of 65%RH.
- the fibers of these comparative examples control humidity less effectively and knitted fabric made of the fibers of these comparative examples is notably uncomfortable when worn, as compared to the fibers of Examples 7-13.
- nylon-12 used in Comparative Example 6 is highly hydrophobic and has high crystal orientation among polyamide resin. Consequently, the fiber of Comparative Example 6 has a notably reduced moisture absorption rate, as shown in Table 2, which means that the obtained knitted fabric exhibits no water absorption extension rate and is remarkably uncomfortable when worn.
- the polyamide fiber of the present invention suitably absorbs and releases moisture, and extends and contracts reversibly upon absorbing and releasing water. Therefore, a fiber structure containing the polyamide fiber of the present invention exhibits a self-control function by which the opening degree of stitches in the fiber structure is varied depending on absorption and release of water. Thus, the polyamide fiber of the present invention may enable the production of a highly comfortable fiber structure.
- the polyamide fiber of the present invention is highly suitable for the field of clothing, and exhibits good performance when used in sportswear, underwear, lining, pantyhose, socks, and other types of clothing.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Multicomponent Fibers (AREA)
- Knitting Of Fabric (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
- Woven Fabrics (AREA)
Description
- The present invention relates to a polyamide fiber for forming, for example, clothing for sports and underwear, and a fiber structure formed using the polyamide fiber.
- Known synthetic fibers, for example, polyester fibers, and polyamide fibers such as nylon-6 and nylon-6,6, are used not only for clothing, but also for a wide range of industrial purposes due to their good physical and chemical properties. These fibers are of high industrial value.
- Unfortunately, these synthetic fibers are low in moisture absorbency and water absorbency, which actually limits their applications to clothing which are required to be absorbent of moisture and water, such as underwear, intermediate garment, bed sheets, and towels. In view of this, for polyester fibers, for example, some methods have been proposed for improving the low moisture absorbency and water absorbency, which can be referred to as the main shortcoming of the polyester fibers.
- More specifically, the proposed methods include, for example, a method in which polyester fibers are post-treated using a hydrophilic post-processing agent, and a method in which polyester fibers are caused to have pores in their surfaces or interiors to obtain moisture absorbency and water absorbency. However, according to these methods, the moisture absorbency and water absorbency are insufficiently improved, and the properties provided to the fibers are deteriorated by washing.
- Some methods have been proposed to solve the above problems. According to such methods, an ethylene-vinyl alcohol-based copolymer, which is obtained by saponifying an ethylene-vinyl acetate-based copolymer, is conjugated with another thermoplastic polymer such as polyester, polyamide, or polyolefin, and the resultant conjugated material is formed into fibers, thereby improving dimensional stability (see, for example, Patent Documents 1-3).
- Further documents dealing with similar subject-matter are
US 2011183563 andJP3379142B2 -
- Patent Document 1:
Japanese Examined Utility Model Publication No. S56-005846 - Patent Document 2:
Japanese Examined Utility Model Publication No. S55-001372 - Patent Document 3:
Japanese Examined Utility Model Publication No. H07-084681 - However, the ethylene-vinyl alcohol-based copolymer according to the above-described known techniques has insufficient resistance to moist heat, which disadvantageously limits its applications.
- Meanwhile, regarding nylon fibers used in underwear, socks, and other clothing, it is difficult to improve comfort of a fiber structure and clothing containing nylon fibers sufficiently by simply providing the nylon fibers themselves with moisture absorbency. Therefore, there is an increasing demand for moisture-absorbing, and water-absorbing extensible fibers capable of controlling humidity.
- In view of the foregoing background, it is therefore an object of the present invention to provide a highly moisture-absorbent polyamide fiber which extends and contracts significantly in a reversible manner upon absorbing and releasing water, and from which a highly comfortable fiber structure can be produced. The present invention also aims to provide a fiber structure and clothing which are formed using the polyamide fiber.
- To achieve the object, a polyamide fiber of the present invention has a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83.
- The present invention provides a fiber structure which controls humidity highly effectively and provides more comfort than ever.
-
- [
FIG. 1] FIG. 1 is a photograph of an exemplary cross section of a conjugated fiber for obtaining a fiber of the present invention. - [
FIG. 2] FIG. 2 is a photograph of an exemplary cross section of a conjugated fiber for obtaining a fiber of the present invention. - [
FIG. 3] FIG. 3 is a photograph of an exemplary cross section of a conjugated fiber for obtaining a fiber of the present invention. - [
FIG. 4] FIG. 4 is a photograph of an exemplary cross section of a conjugated fiber for obtaining a fiber of the present invention. - A polyamide fiber of the present invention has a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83. If the degree of orientation were lower than 0.7, sufficient colorfast could not be obtained. If the degree of orientation were higher than 0.83, the fiber would reversibly extend and contract in an insufficient manner upon absorbing and releasing water. This would cause the stitches in woven or knitted fabric to open and close insufficiently and make it impossible to obtain a highly comfortable fiber structure.
- Thus, a fiber structure such as woven or knitted fabric is produced using the polyamide fibers having a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83. When absorbing sweat, for example, the polyamide fibers extend to cause the stitches in the woven or knitted fabric to open, thereby releasing humidity inside the clothing. When dried, the polyamide fibers contract to restore the original length and cause the stitches to close, thereby preventing heat from being released outside the clothing. Thus, the use of the polyamide fibers of the present invention may provide woven or knitted fabric which is highly comfortable and has a so-called self-control function.
- Note that the degree of orientation of the polyamide fiber is beneficially equal to or higher than 0.72, and more beneficially equal to or higher than 0.75. Further, the degree of orientation of the polyamide fiber is equal to or lower than 0.83, more beneficially equal to or lower than 0.8, and still more beneficially lower than 0.80. The degree of orientation of the polyamide fiber is calculated by a measurement method which will be described later with reference to examples.
- The polyamide fiber of the present invention beneficially has a moisture absorption rate equal to or higher than 5% at a temperature of 35°C and a humidity of 95%RH, and a water absorption extension rate equal to or higher than 5% at a temperature of 20°C and a humidity of 65%RH. A moisture absorption rate lower than 5% would cause a user to feel stickiness and sweatiness. A water absorption extension rate lower than 5% would cause the fiber to reversibly extend and contract in an insufficient manner upon absorbing and releasing, and would prevent stitches in woven or knitted fabric from opening and closing sufficiently. Such moisture absorption rate and water absorption extension rate make it impossible to obtain a highly comfortable fiber structure.
- Thus, the use of the polyamide fiber having the above-specified moisture absorption rate and water absorption extension rate may enable the production of a fiber structure such as woven or knitted fabric, which has the self-control function described above and provides more comfort.
- Excessive increases in the moisture absorption rate and the water absorption extension rate tend to reduce wash-fastness, weather resistance, light resistance, and chemical resistance, for example. In view of this, the moisture absorption rate is beneficially equal to or higher than 5% and equal to or lower than 30%, and more beneficially equal to or higher than 8% and equal to or lower than 25%. The water absorption extension rate is beneficially equal to or higher than 5%, more beneficially equal to or higher than 7%, still more beneficially equal to or higher than 8%, and particularly beneficially equal to or higher than 10%. Further, the water absorption extension rate is beneficially equal to or lower than 30%, more beneficially equal to or lower than 25%, and still more beneficially equal to or lower than 20%. The moisture absorption rate and the water absorption extension rate of the polyamide fiber are measured according to a measurement method which will be described later with reference to the examples.
- The polyamide fiber has a crimp extension rate which is beneficially equal to or higher than 1.5% and equal to or lower than 10%, more beneficially equal to or higher than 2% and equal to or lower than 8%, and still more beneficially equal to or higher than 2.5% and equal to or lower than 5.8%. A crimp extension rate equal to or higher than 1.5% and equal to or lower than 10% provides silk-like feel and texture, and makes fabric soft and pleasant to the touch.
- Examples of the polyamide to be used in the present invention include: polycaproamide (nylon-6), poly-ω-aminoheptanoic acid (nylon-7), polyundecaneamide (nylon-11), polyethylene diamine adipamide (nylon-2,6), polytetramethylene adipamide (nylon-4,6), polyhexamethylene adipamide (nylon-6,6), polyhexamethylene sebacamide (nylon-2,10), polyhexamethylene dodecamide (nylon-6,12), polyoctamethylene adipamide (nylon-8,6), polydecanomethylene adipamide (nylon-10,6), and polydodecamethylene sebacamide (nylon-10,8). Examples of the polyamide further include: caprolactam/lauric lactam copolymer (nylon-6/12), caprolactam/ω-aminononanoic acid copolymer (nylon-6/9), caprolactam/hexamethylene adipate copolymer (nylon-6/6,6), lauric lactam/hexamethylene diamine adipate copolymer (nylon-12/6,6), hexamethylene diamine adipate/hexamethylene diamine sebacate copolymer (nylon-6,6/6,10), ethylenediamine adipate/hexamethylene diamine adipate copolymer (nylon-2,6/6,6), and caprolactam/hexamethylene diamine adipate/hexamethylene diamine sebacate copolymer (nylon-6,6/6,10).
- Among these substances, nylon-6 and nylon-6,6 are most suitable as the polyamide of the present invention. Nylon-6 is still more beneficial because it is unexpansive and versatile, and has high moisture absorbency. Among the above copolymers, nylon-6/6,6 and nylon-6/12 are beneficial. Although the composition ratio between the component having a carbon number of 6 and the component having a carbon number of 12 that form the nylon-6/12 is not particularly limited, the component having a carbon number of 12 beneficially constitutes 50 mol% or less, and more beneficially 40 mol% or less.
- The polyamide copolymers may be caused to contain an anti-static agent, a lubricant, an anti-blocking agent, a stabilizer, a dye, or a pigment, for example.
- The polyamide fiber of the present invention may be produced by any method as long as the polyamide fiber has the above-described degree of orientation, moisture absorption rate, and water absorption extension rate. For example, a polyamide component (component A) and another soluble component (component B) are formed into a conjugated fiber, and thereafter, the component B is dissolved and removed, thereby suitably producing the polyamide fiber of the present invention. The use of such a conjugated fiber enables the control of the structure of the polyamide component, thereby enabling the production of a fiber which is exclusively made of polyamide, has a specific degree of orientation, high moisture absorbency and high water absorption extensibility, and is capable of reversibly extending and contracting upon absorbing and releasing water.
- If the polyamide fiber of the present invention is produced from the conjugated fiber as described above, the other component, i.e., the soluble component (component B) plays an important role in the structure control. An exemplary polymer which can be used as the component B is a water-soluble thermoplastic polyvinyl alcohol-based polymer. This polyvinyl alcohol-based polymer beneficially has a viscosity average degree of polymerization of 200-500, a degree of saponification of 90-99.99 mol%, and a melting point of 160-230°C. Although the polyvinyl alcohol-based polymer may be a monopolymer or a copolymer, it is recommended to use a copolymerized polyvinyl alcohol which is 0.1-20 mol% modified by α-olefin having a carbon number of 4 or less such as ethylene or propylene, in order to ensure ease of melt spinning, water solubility, and fiber physical properties. The polyamide fiber of the present invention can be suitably obtained by removing, by using hot water, the water-soluble thermoplastic polyvinyl alcohol-based polymer from the conjugated fiber including the component B.
- A polyester-based polymer which is soluble in alkali at a high speed (easily alkali-soluble polyester-based polymer) is another example which can be used as the component B. Examples of such an easily alkali-soluble polyester-based polymer include a polylactic acid, and copolymerized polyester formed by copolymerizing 1-5 mol% of 5-sodium sulfoisophthalic acid, 5-30 wt.% of polyalkylene glycol, a conventionally used diol component, and a conventionally used dicarboxylic acid component. From a conjugated fiber containing this component B, the polyamide fiber of the present invention may be suitably obtained by the removal of the easily alkali-soluble polyester-based polymer by alkaline treatment.
- It is beneficial that the conjugated fiber for producing the polyamide fiber of the present invention has a fiber cross section of which 50% or more is coated with the soluble component (component B). It is more beneficial that the entire cross section is coated with the soluble component (component B). That is to say, the conjugated fiber beneficially has a sheath-core cross section in which the polyamide component forms the core and the component B forms the sheath, or a sea-island cross section in which the polyamide component forms the islands and the component B forms the sea.
- A conjugate ratio (A:B) of the conjugated fiber of the present invention between the polyamide component (A component) and the soluble component (B component) ranges beneficially from 90:10 to 40:60 (weight ratio), and more beneficially from 80:20 to 60:40 (weight ratio). The ratio may be adjusted according to fiber shapes. Note that if the component B is used in a small amount, it may become difficult to control the polyamide structure. This may makes it impossible to achieve desired moisture absorbency and water absorption extensibility, resulting in difficulty in humidity control.
- The cross section of the conjugated fiber of the present invention is not particularly limited, provided that the component B is dissolved and removed by hot water treatment or alkali treatment, and cracks are not caused in the component A. The cross section may be of a concentric, eccentric, or multi-centric type, for example. Further, the cross section may have, besides the circular shape shown in
FIGS. 1 and 2 , a multifoil shape shown inFIG. 3 , or a modified shape such as a triangle or flat shape. Furthermore, as shown inFIG. 4 , the component A may include therein a hollow portion. The cross section may have one or multiple hollow portions, without causing any problem. - The polyamide fiber of the present invention may beneficially have a monofilament size of 0.03-10 dtex, which is not limiting. The polyamide fiber of the present invention may be used not only as a long fiber, but also as a short fiber or a short-cut fiber.
- Once a combination of a polyamide component (component A) and the other component, i.e., the soluble component (component B), is determined, the conjugated fiber of the present invention may be formed by using a known conjugated fiber-spinning machine.
- Setting of fiber formation conditions is important to obtain the fiber of the present invention. It is most suitable to form the fiber by direct spinning and drawing method at a high speed. If the fiber is melt spun at a low or intermediate speed, and subjected to drawing thereafter, the temperature of heat treatment for the drawing is set to a temperature lower than 100°C, and beneficially to 80°C or lower, and the drawing rate is set to a rate lower than 2. If drawing and false twisting are performed at the same time or continuously after the spinning, the temperature of the heat treatment is also set to a temperature lower than 100°C, and beneficially to 80°C or lower, and the drawing rate is limited to a rate lower than 2. If the temperature were set to 100°C or higher, or if the drawing rate were set to 2 or higher, it would be difficult to control the polyamide structure, and desired degree of orientation, moisture absorbency, and water absorption extensibility could not be achieved.
- The polyamide fiber of the present invention may be used to form various types of fiber structures (fiber aggregates). Here, the "fiber structure" may be configured as a multifilament thread, a spun yarn, woven or knitted fabric, non-woven fabric, paper, synthetic leather, and wadding which are exclusively made of the polyamide fiber of the present invention. Alternatively, the "fiber structure" may be configured as: woven or knitted fabric or non-woven fabric, part of which is made of the polyamide fiber of the present invention; combined woven or knitted fabric additionally containing fibers of a different type such as natural fibers, artificial fibers, synthetic fibers, or semi synthetic fibers; and woven or knitted fabric, cotton-containing non-woven fabric, or fiber layered product in which the polyamide fibers of the present invention are used as a finished yarn such as a blended yarn, a doubling- and-twisted yarn, a confound yarn, or a crimp yarn.
- The weight ratio of the polyamide fiber of the present invention with respect to the entire woven or knitted fabric or non-woven fabric is beneficially 15 wt. % or more, more beneficially 18 wt.% or more, particularly beneficially 23 wt.% or more. After woven or knitted into fabric, or formed into a non-woven fabric, the fibers of the present invention may be subjected to napping treatment by means of wire raising or any other finishing.
- If the polyamide fiber of the present invention is produced via the conjugated fiber described above, a fiber structure may be formed using the fiber which contains polyamide alone and from which the component B has been removed. Alternatively, the component B may be removed from a fiber structure which has been formed using the conjugated fiber.
- The present invention will be described more specifically below with reference to examples.
- Nylon-6 having a reduced viscosity of 1.80 dL/g (at a concentration of 1g/dL in orthoclorophenol at 30°C) was used as a polyamide component (component A), and a thermoplastic modified polyvinyl alcohol (modified PVA) (product of Kuraray Co., Ltd. having a saponification degree of 98.5, an ethylene content of 8.0 mol%, and a degree of polymerization of 390) was used as a soluble component (component B). The components A and B were separately melted in different extruders, and a conjugated fiber having a cross section shown in
FIG. 1 was injected through a multi-component fiber-spinning nozzle with a ratio of nylon-6:modified PVA set at 60:40 (weight ratio). Subsequently, a thread injected through a spinneret was cooled using a horizontal cooling air blower having a length of 1.0 m. Thereafter, water-free spinning oil including, as its components, an anti-static agent and a lubricating agent was applied to the thread. The thread was then wound using a roller at a take-off speed of 3500 m/min. In this manner, a conjugated fiber (111 dtex/24 filaments) was produced. Note that the process steps of fiber production were performed smoothly. The produced conjugated fiber was knitted into cylindrical fabric by a circular knitting machine (28 gauge). The resultant knitted fabric was subjected to a scouring step using hot water (90°C, 20 minutes) to dissolve and remove the modified PVA. In this manner, the polyamide fiber of the present invention was produced. - Next, the degree of orientation of the produced polyamide fiber was measured by using the following measurement device under the following measurement conditions.
- Measurement device: a two dimensional detector-equipped X-ray diffractometer (product of Bruker AXS K.K., product name; "D8 Discover with GADDS")
- Detector: Two-dimensional PSPC • Hi-STAR
- Measurement conditions: a current of 110 mA ; a voltage of 45 kV; a camera distance of 15 cm; a collimator diameter of 0.5 mm; an exposure time of 1200 sec.; 2θ axis at 22°; ω axis at 0°; and χ axis at 90° (equator line) • 0° (meridian)
- Thereafter, two-dimensional data in the meridian direction obtained in the foregoing manner was converted to an X-ray diffraction intensity curve in an azimuthal direction under the following conditions.
2θ = 9.7°-11.7°, χ = -150°-30°, step width = 0.1° -
- Next, the produced polyamide fiber was maintained in a thermo-hygrostat chamber regulated at 35°C and 90%RH for 24-hour humidity regulation. The moisture absorption rate of the fiber was then calculated based on an absolute dry sample weight and a humidity-regulated sample weight, according to the following expression. The results are shown in Table 1.
- The produced polyamide fiber was wound into a hank, and the hank was treated at no tension and in boiling water for 30 minutes. Thereafter, the hank was air-dried at a temperature of 20°C and a humidity of 65%RH, thereby regulating the humidity. The thread was then subjected to a dry heat treatment for two minutes in an atmosphere at 160°C, at no tension, and in a contactless fashion. Then, the thread was left in an atmosphere at a temperature of 20°C and a humidity of 65%RH for 24 hours. After the lapse of 24 hours, the length of the thread with a load of 0.88 × 10-3 cN/dtex applied thereto was measured. This length is referred to as "the thread length in dry state." Thereafter, the thread was immersed in softened water having a temperature adjusted to 20°C for one minute. The thread was then raised from the water, sandwiched between two sheets of filter paper which had been air-dried in an atmosphere at a temperature of 20°C and a humidity of 65%RH, and placed on a flat table. A weight of 1.5 g/cm2 was put and left over the thread for two seconds to remove excessive moisture on the fiber surface. After 10 seconds, the length of the thread was measured with a load of 0.88 × 10-3 cN/dtex applied thereto. This length is referred to as "the thread length in water absorption state." The water absorption extension rate of the polyamide fiber was calculated according to the following expression. Note that all the measurements were performed in an atmosphere at a temperature of 20°C and a humidity of 65%RH.
- The produced polyamide fiber was knitted into some pieces of cylindrical knitted fabric by a circular knitting machine. Ten arbitrarily chosen testers passed one day with the resultant pieces put on their elbows and knees. The testers made sensory evaluation concerning feeling of stickiness and sweatiness. The results of the sensory evaluation were qualified in terms of points: "No feeling of stickiness or sweatiness and highly comfortable" was qualified as two points, "Comfortable" as one point, and "uncomfortable" as 0 point. The pieces of the knitted fabric were evaluated and classified into the following four levels according to the total sums of points. Table 1 shows the results.
- A: 15 points or more in total
- B: 8-14 points in total
- C: 5-7 points in total
- D: 4 points or less in total
- The polyamide fiber was wound into a small hank having 20 turns by using a sizing reel of which the frame perimeter was 1.125 m. The resultant small hank was heat-treated in boiling water at 98°C for five minutes with no load applied to the hank. The small hank was then left in a chamber at constant temperature and humidity (at a temperature of 20±2°C and a relative humidity of 65±2%) for 24 hours. A load of 2 mg/d was applied to the humidity-regulated fiber, and the hank length L1 was measured after one minute. Next, a load of 0.1 g/d was applied to the small hank, and the hank length L2 was measured after one minute. The crimp extension rate is given by the following expression:
- Here, "g/d" represents a number of grams per denier.
- Table 1 shows the results of these measurements and evaluation.
- A polyamide fiber was produced in the same manner as in Example 1, except that polyethylene terephthalate (copolymerized PET) having a limiting viscosity number [η] of 0.52 dL/g and copolymerized with 8 wt.% of polyethylene glycol having a molecular weight of 2000 and 5 mol% of 5-sodium sulfoisophthalic acid was used as the component B. The degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate of this polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 1.
- As shown in Table 1, a polyamide fiber of each of these examples was produced in the same manner as in Example 1, except that nylon-6,6 (Example 3) or nylon-6/12 (Example 4) was used as the component A. For each fiber, the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 1.
- As shown in Table 1, a polyamide fiber of each of these examples was produced in the same manner as in Example 1, except that the conjugated fiber was caused to have a cross section shown in
FIG. 2 (Example 5) or a cross section shown inFIG. 4 (Example 6). For each fiber, the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 1. - A polyamide fiber was produced in the same manner as in Example 1, except that the soluble component (component B) was omitted. The degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate of this fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 1.
- A conjugated fiber (size: 275 dtex) having a cross section shown in
FIG. 1 was injected through a multi-component fiber spinning nozzle, in the same manner as in Example 1. Subsequently, a thread injected from a spinneret was cooled using a horizontal cooling air blower having a length of 1.0 m. Thereafter, water-free spinning oil including, as its components, an anti-static agent and a lubricating agent was applied to the thread. The thread was then taken off using a roller at a speed of 1000 m/min., and drawn continuously without being wound. The thread was drawn until its length became 2.5 times as long as the original length, while being thermo-set at 150°C. In this manner, a conjugated fiber (110 dtex/24 filaments) was produced at a speed of 2500 m/min. The produced conjugated fiber was knitted into cylindrical fabric by a circular knitting machine (28 gauge). The resultant knitted fabric was subjected to a scouring step using hot water (90°C, 20 minutes) to dissolve and remove the modified PVA. In this manner, the polyamide fiber of this comparative example was produced. - Next, the degree of orientation and the water absorption extension rate of the polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test, in the same manner as in Example 1. Note that the moisture absorption rate and the crimp extension rate were not measured. The results of these measurements and evaluation are shown in Table 1.
- A polyamide fiber was produced in the same manner as in Example 1, except that nylon-12 was used as the component A. The degree of orientation and the water absorption extension rate of this polyamide fiber were measured, and the evaluation of knitted of the fiber was performed through a wear test. Note that the moisture absorption rate and the crimp extension rate were not measured. The results of these measurements and evaluation are shown in Table 1.
- A conjugated fiber (size: 275 dtex) having a cross section shown in
FIG. 1 was injected through a multi-component fiber spinning nozzle, in the same manner as in Example 1. Subsequently, a thread injected through a spinneret was cooled using a horizontal cooling air blower having a length of 1.0 m. Thereafter, water-free spinning oil including, as its components, an anti-static agent and a lubricating agent was applied to the thread. The thread was then taken off using a roller at a speed of 2000 m/min., thereby obtaining undrawn thread. The obtained undrawn thread was knitted into cylindrical fabric by a circular knitting machine (28 gauge). The resultant knitted fabric was subjected to a scouring step using hot water (90°C, 20 minutes) to dissolve and remove the modified PVA. In this manner, the polyamide fiber of this comparative example was produced. - Next, the degree of orientation and the water absorption extension of this polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test in the same manner as in Example 1. Note that the moisture absorption rate and the crimp extension rate were not measured. The results of these measurements and evaluation are shown in Table 1.
- As shown in Table 1, the polyamide fibers of Examples 1,3-6 have a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83. Therefore, these fibers have a water absorption extension rate of 5% or more at a temperature of 20°C and a humidity of 65%RH. This means that these polyamide fibers effectively control humidity, and knitted fabric made of these fibers is highly comfortable when worn.
- On the other hand, the polyamide fibers of Comparative Examples 1-3 have a degree of orientation equal to or higher than 0.83. Therefore, these fibers have a water absorption extension rate lower than 5% at a temperature of 20°C and a humidity of 65%RH. This means that these fibers control humidity less effectively and the knitted fabric made of the fibers of these comparative examples is notably uncomfortable when worn, as compared to the fibers of Examples 1-6. In particular, nylon-12 used in Comparative Example 3 is highly hydrophobic and has a high crystal orientation among polyamide resin. Consequently, the fiber of Comparative Example 3 has a high degree of orientation as shown in Table 1, which means that the obtained knitted fabric exhibits no water absorption extension rate and is remarkably uncomfortable when worn.
- The polyamide fiber of Comparative Example 4 has a degree of orientation lower than 0.7. Therefore, the water absorption extension rate of this polyamide fiber is excessively high, resulting in that the fabric made of this fiber is remarkably uncomfortable when worn.
- Nylon-6 having a reduced viscosity of 1.80 dL/g (at a concentration of 1g/dL in orthoclorophenol at 30°C) was used as a polyamide component (component A), and a thermoplastic modified polyvinyl alcohol (modified PVA) (product of Kuraray Co., Ltd. having a saponification degree of 98.5, an ethylene content of 8.0 mol%, and a degree of polymerization of 380) was used as the other component, i.e., the soluble component (component B). The components A and B were separately melted in different extruders, and a conjugated fiber having a cross section shown in
FIG. 1 was injected through a multi-component fiber-spinning nozzle with a ratio of nylon-6: modified PVA set to 70:30 (weight ratio). Subsequently, a thread injected through a spinneret was cooled using a horizontal cooling air blower having a length of 1.0 m. Thereafter, water-free spinning oil including, as its components, an anti-static agent and a lubricating agent was applied to the thread. The thread was then wound using a roller at a take-off speed of 3500 m/min. In this manner, a conjugated fiber (111 dtex/24 filaments) was produced. Note that the process steps of fiber production were performed smoothly. The produced conjugated fiber was knitted into cylindrical fabric by a circular knitting machine (28 gauge). The resultant knitted fabric was subjected to a scouring step using hot water (90°C, 20 minutes) to dissolve and remove the modified PVA. - In the same manner as in Example 1, the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate of this polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 2.
- A polyamide fiber of Example 8 (not according to present invention) was produced in the same manner as in Example 7, except that polyethylene terephthalate (copolymerized PET) having a limiting viscosity number [η] of 0.52 dL/g and copolymerized with 8 wt.% of polyethylene glycol having a molecular weight of 2000 and 5 mol% of 5-sodium sulfoisophthalic acid was used as the component B. A polyamide fiber of Example 9 was produced in the same manner as in Example 7, except that polylactic acid was used as the soluble component (component B), and a ratio of nylon-6:component B was set to 67:33. The degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate of each polyamide fiber were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 2.
- As shown in Table 2, a polyamide fiber of each of these examples was produced in the same manner as in Example 7, except that nylon-6,6 (Example 10) or nylon-6/12 (Example 11) was used as the component A. For each fiber, the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 2.
- As shown in Table 2, a polyamide fiber of each of these examples was produced in the same manner as in Example 7, except that the conjugated fiber was caused to have a cross section shown in
FIG. 2 (Example 12) or a cross section shown inFIG. 3 (Example 13). For each fiber, the degree of orientation, the moisture absorption rate, the water absorption extension rate, and the crimp extension rate were measured, and the evaluation of knitted fabric of each fiber was performed through a wear test. The results of these measurements and evaluation are shown in Table 2. - A conjugated fiber (size: 220 dtex) having a cross section shown in
FIG. 1 was injected through a multi-component fiber spinning nozzle, in the same or similar manner to Example 7. Subsequently, a thread injected through a spinneret was cooled using a horizontal cooling air blower having a length of 1.0 m. Thereafter, water-free spinning oil including, as its components, an anti-static agent and a lubricating agent was applied to the thread. The thread was then taken off using a roller at a speed of 1000 m/min., and drawn continuously without being wound. The thread was drawn until its length became 2.5 times as long as the original length, while being thermo-set at 150°C. In this manner, a conjugated fiber (110 dtex/24 filaments) was produced at a speed of 2500 m/min. The produced conjugated fiber was knitted into cylindrical fabric by a circular knitting machine (28 gauge). The resultant knitted fabric was subjected to a scouring step using hot water (90°C, 20 minutes) to dissolve and remove the modified PVA. In this manner, the polyamide fiber of this comparative example was produced. - Next, the moisture absorption rate and the water absorption extension rate of this polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test, in the same or similar manner to Example 7. Note that the degree of orientation and the crimp extension rate were not measured. The results of these measurements and evaluation are shown in Table 2.
- A polyamide fiber was produced in the same manner as in Example 7, except that nylon-12 was used as the component A. The moisture absorption rate and the water absorption extension rate of this polyamide fiber were measured, and the evaluation of knitted fabric of the fiber was performed through a wear test. Note that the degree of orientation and the crimp extension rate were not measured. The results of these measurements and evaluation are shown in Table 2.
- As shown in Table 2, the polyamide fibers of Examples 7-13 have a moisture absorption rate equal to or higher than 5% at a temperature 35°C and a humidity 95%RH, and a water absorption extension rate equal to or higher than 5% at a temperature 20°C and a humidity of 65%RH. This means that these polyamide fibers effectively control humidity, and knitted fabric made of these fibers is highly comfortable when worn.
- On the other hand, the polyamide fibers of Comparative Examples 5 and 6 have a moisture absorption rate lower than 5% at a temperature of 35°C and a humidity of 95%RH, and a water absorption extension rate lower than 5% at a temperature of 20°C and a humidity of 65%RH. This means that the fibers of these comparative examples control humidity less effectively and knitted fabric made of the fibers of these comparative examples is notably uncomfortable when worn, as compared to the fibers of Examples 7-13. In particular, nylon-12 used in Comparative Example 6 is highly hydrophobic and has high crystal orientation among polyamide resin. Consequently, the fiber of Comparative Example 6 has a notably reduced moisture absorption rate, as shown in Table 2, which means that the obtained knitted fabric exhibits no water absorption extension rate and is remarkably uncomfortable when worn.
- The polyamide fiber of the present invention suitably absorbs and releases moisture, and extends and contracts reversibly upon absorbing and releasing water. Therefore, a fiber structure containing the polyamide fiber of the present invention exhibits a self-control function by which the opening degree of stitches in the fiber structure is varied depending on absorption and release of water. Thus, the polyamide fiber of the present invention may enable the production of a highly comfortable fiber structure. The polyamide fiber of the present invention is highly suitable for the field of clothing, and exhibits good performance when used in sportswear, underwear, lining, pantyhose, socks, and other types of clothing.
-
- 1
- Polyamide Component (Component A) in Conjugated fiber
- 2
- Soluble Component (Component B) in Conjugated fiber
- 3
- Hollow Portion in Conjugated fiber
Claims (9)
- A polyamide fiber having a degree of orientation equal to or higher than 0.7 and equal to or lower than 0.83, wherein
the degree of orientation is calculated according to the method described in the description. - The polyamide fiber of claim 1, having a moisture absorption rate equal to or higher than 5% at a temperature of 35°C and a humidity of 95%RH, and a water absorption extension rate equal to or higher than 5% at a temperature of 20°C and a humidity of 65%RH, wherein
the moisture absorption rate of the fiber is calculated by maintaining the polyamide fiber in a thermo-hygrostat chamber regulated at 35°C and 90%RH for 24-hour humidity regulation and by calculating the moisture absorption rate of the fiber according to the following expression:Moisture absorption rate (%) = (humidity-regulated sample weight - absolute dry sample weight) x 100 / absolute dry sample weightand whereinthe water absorption extension rate is measured according to the method described in the description. - The polyamide fiber of claim 1 or 2, obtained by removing, from a conjugated fiber containing a water-soluble thermoplastic polyvinyl alcohol-based polymer and polyamide, the water-soluble thermoplastic polyvinyl alcohol-based polymer by using hot water.
- The polyamide fiber of claim 1 or 2, obtained by removing, from a conjugated fiber containing an easily alkali-soluble polyester-based polymer and polyamide, the easily alkali-soluble polyester-based polymer by alkali treatment.
- The polyamide fiber of claim 3 or 4, wherein
the polyamide is nylon-6. - The polyamide fiber of any one of claims 1-5, wherein
the polyamide fiber extends and contracts reversibly upon absorbing and releasing water. - A fiber structure, at least part of which is made of the polyamide fiber of any one of claims 1-6.
- Clothing made of the fiber structure of claim 7.
- The clothing of claim 8, wherein
the clothing is configured as one selected from the group consisting of underwear, sportswear, lining, pantyhose, and socks.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014108167 | 2014-05-26 | ||
JP2014175654 | 2014-08-29 | ||
PCT/JP2015/002575 WO2015182088A1 (en) | 2014-05-26 | 2015-05-21 | Polyamide fibers, fiber structure using same, and clothing |
Publications (3)
Publication Number | Publication Date |
---|---|
EP3150751A1 EP3150751A1 (en) | 2017-04-05 |
EP3150751A4 EP3150751A4 (en) | 2017-05-24 |
EP3150751B1 true EP3150751B1 (en) | 2021-09-08 |
Family
ID=54698443
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15798772.8A Active EP3150751B1 (en) | 2014-05-26 | 2015-05-21 | Polyamide fibers, fiber structure using same, and clothing |
Country Status (6)
Country | Link |
---|---|
US (1) | US20170191190A1 (en) |
EP (1) | EP3150751B1 (en) |
JP (2) | JPWO2015182088A1 (en) |
CN (1) | CN106574404B (en) |
TW (1) | TWI695098B (en) |
WO (1) | WO2015182088A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018051788A1 (en) * | 2016-09-14 | 2018-03-22 | 株式会社クレハ | Vinylidene fluoride resin fibers and sheet-like structure |
JP7050424B2 (en) * | 2017-04-24 | 2022-04-08 | Kbセーレン株式会社 | Method for manufacturing composite fiber, fabric and fiber structure |
TWI687562B (en) * | 2018-03-23 | 2020-03-11 | 新光合成纖維股份有限公司 | Conjugate fiber with moisture-absorbed elongation effect |
EP3922123B1 (en) * | 2019-03-05 | 2023-11-01 | ASICS Corporation | Anti-slip member for article of equipment or sport gear, article of equipment, and article of sport gear |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5214132B2 (en) * | 1972-11-22 | 1977-04-19 | ||
JPS5766116A (en) * | 1980-10-08 | 1982-04-22 | Asahi Chem Ind Co Ltd | High-flexibility, high-elongation polyamide fiber |
JP3379142B2 (en) * | 1993-05-19 | 2003-02-17 | 東レ株式会社 | Nylon 66 rubber reinforcement cord |
JP3510731B2 (en) * | 1996-04-12 | 2004-03-29 | ユニチカ株式会社 | Microporous hollow polyamide fiber and method for producing the same |
DE69917194T2 (en) * | 1998-12-16 | 2005-05-04 | KURARAY CO., LTD, Kurashiki | Thermoplastic polyvinyl alcohol fibers and process for their preparation |
JP3784742B2 (en) * | 2002-03-29 | 2006-06-14 | 株式会社クラレ | Highly hygroscopic and water absorbent polyvinyl alcohol copolymer composite fiber |
JP4325616B2 (en) * | 2002-08-05 | 2009-09-02 | 東レ株式会社 | Nanoporous fiber |
CN101003681A (en) * | 2002-08-05 | 2007-07-25 | 东丽株式会社 | Porous fiber |
CN100363541C (en) * | 2002-10-23 | 2008-01-23 | 东丽株式会社 | Nanofiber aggregate, polymer alloy fiber, hybrid fiber, fibrous structures, and processes for production of them |
TWI311594B (en) * | 2002-10-23 | 2009-07-01 | Toray Industries | Nanofiber aggregate, liquid dispersion, process for producing hybrid fiber, fiber structure and process for producing the same |
CN100523326C (en) * | 2004-09-03 | 2009-08-05 | 帝人纤维株式会社 | Composite fiber |
CN101313091A (en) * | 2005-10-19 | 2008-11-26 | 东丽株式会社 | Crimped yarn, method for manufacture thereof, and fiber structure |
JP2007303019A (en) * | 2006-05-10 | 2007-11-22 | Toray Ind Inc | Nano-fiber woven or knitted fabric and method for producing the same |
CN101074503A (en) * | 2006-05-16 | 2007-11-21 | 东丽纤维研究所(中国)有限公司 | Polymer-alloy fibre and its production |
JP2007332479A (en) * | 2006-06-13 | 2007-12-27 | Unitica Fibers Ltd | Mixture-spun fiber |
JP2010229582A (en) * | 2009-03-26 | 2010-10-14 | Teijin Techno Products Ltd | Method for producing para-type wholly aromatic copolyamide fiber |
US20130209743A1 (en) * | 2010-10-12 | 2013-08-15 | Asahi Kasei Fibers Corporation | Multilayered knitted fabric technical field |
CN102877188A (en) * | 2011-07-15 | 2013-01-16 | 东丽纤维研究所(中国)有限公司 | Hygroscopic polyamide fiber textile and production method thereof |
CN103422190B (en) * | 2012-05-15 | 2016-05-25 | 东丽纤维研究所(中国)有限公司 | A kind of Splittable conjugate fiber and the Superfine Fibre Fabric making thereof |
-
2015
- 2015-05-21 US US15/314,051 patent/US20170191190A1/en not_active Abandoned
- 2015-05-21 CN CN201580028308.XA patent/CN106574404B/en active Active
- 2015-05-21 WO PCT/JP2015/002575 patent/WO2015182088A1/en active Application Filing
- 2015-05-21 JP JP2016523131A patent/JPWO2015182088A1/en active Pending
- 2015-05-21 EP EP15798772.8A patent/EP3150751B1/en active Active
- 2015-05-25 TW TW104116603A patent/TWI695098B/en active
-
2019
- 2019-11-05 JP JP2019200710A patent/JP6793238B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JPWO2015182088A1 (en) | 2017-06-08 |
EP3150751A4 (en) | 2017-05-24 |
CN106574404A (en) | 2017-04-19 |
TWI695098B (en) | 2020-06-01 |
WO2015182088A1 (en) | 2015-12-03 |
US20170191190A1 (en) | 2017-07-06 |
TW201608070A (en) | 2016-03-01 |
JP6793238B2 (en) | 2020-12-02 |
CN106574404B (en) | 2021-01-15 |
EP3150751A1 (en) | 2017-04-05 |
JP2020037763A (en) | 2020-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4571566B2 (en) | Method for producing fabric capable of adsorbing odor | |
JP6545368B2 (en) | Yarns and fabrics and textiles | |
EP3150751B1 (en) | Polyamide fibers, fiber structure using same, and clothing | |
JP2009275296A (en) | Circular knitted fabric having excellent shape stability and adhesion and textile product | |
JP2011226026A (en) | Fabric for clothing | |
JP2009024272A (en) | Knitted fabric and fibrous product excellent in cool feeling | |
WO2016190384A1 (en) | Fabric | |
JP6101231B2 (en) | Knitted fabric for clothing | |
JP2010275649A (en) | Fiber structure and textile product | |
JP2008520846A (en) | Multifilament with excellent antibacterial and sweat absorption | |
JP5216970B2 (en) | Polyester knitted fabric, production method thereof and textile product | |
JP2018178335A (en) | Socks and manufacturing method thereof | |
JP2011117099A (en) | Circular knit and clothes | |
JP5662007B2 (en) | Standing fabric and standing fabric product | |
JP2013049929A (en) | Knitted fabric for clothing material comfortably used in sweating | |
JP2010216036A (en) | Underwear | |
JP2003064558A (en) | Comfortable knitted fabric | |
JP2003096648A (en) | Comfortable shirt fabric | |
JP2007247080A (en) | Warp knitted fabric for sportswear and method for producing the same | |
JP2011195969A (en) | Supporter | |
JP2019065435A (en) | Yarn, fabric and textile product | |
WO2005005699A1 (en) | Fabric having temperature control function | |
JP2008274478A (en) | Moisture-sensitive latently crimping conjugate fiber | |
JP2005163225A (en) | Knitted fabric and fiber product improved in air permeability when wetted | |
JP5260192B2 (en) | Textile structures and textile products |
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: 20161208 |
|
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 |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 20170425 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: D03D 15/00 20060101ALI20170419BHEP Ipc: A41B 17/00 20060101ALI20170419BHEP Ipc: D01F 8/12 20060101ALI20170419BHEP Ipc: D01F 8/14 20060101ALI20170419BHEP Ipc: D01F 6/60 20060101AFI20170419BHEP Ipc: D06M 11/05 20060101ALI20170419BHEP Ipc: D06M 11/00 20060101ALI20170419BHEP |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20210412 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: MURATE, YASUNORI Inventor name: OHGA, DAISUKE Inventor name: IKEDA, TAKAYUKI Inventor name: KAWAKADO, SHINYA Inventor name: NAKATSUKA, HITOSHI |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
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: AT Ref legal event code: REF Ref document number: 1428676 Country of ref document: AT Kind code of ref document: T Effective date: 20210915 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: 602015073137 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20210908 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20210908 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: 20210908 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: 20210908 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: 20210908 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: 20210908 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: 20211208 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: 20210908 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: 20211208 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1428676 Country of ref document: AT Kind code of ref document: T Effective date: 20210908 |
|
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: 20210908 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: 20211209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20210908 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20220108 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: 20210908 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: 20210908 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: 20210908 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: 20220110 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: 20210908 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: 20210908 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: 20210908 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: 20210908 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: 20210908 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015073137 Country of ref document: DE |
|
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 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20210908 |
|
26N | No opposition filed |
Effective date: 20220609 |
|
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: 20210908 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20220531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20210908 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220521 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220531 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 9 |
|
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: 20220521 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20220531 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230529 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230331 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20150521 |
|
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: 20210908 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: 20210908 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240308 Year of fee payment: 10 |
|
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: 20210908 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240402 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20240411 Year of fee payment: 10 |
|
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: 20210908 |