EP3310948A1 - Polyamide fiber with enhanced dyeing properties, process for obtaining such fiber and polyamide article made therefrom - Google Patents
Polyamide fiber with enhanced dyeing properties, process for obtaining such fiber and polyamide article made therefromInfo
- Publication number
- EP3310948A1 EP3310948A1 EP15733890.6A EP15733890A EP3310948A1 EP 3310948 A1 EP3310948 A1 EP 3310948A1 EP 15733890 A EP15733890 A EP 15733890A EP 3310948 A1 EP3310948 A1 EP 3310948A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyamide
- fiber
- article
- anyone
- melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002647 polyamide Polymers 0.000 title claims abstract description 348
- 239000004952 Polyamide Substances 0.000 title claims abstract description 347
- 239000000835 fiber Substances 0.000 title claims abstract description 125
- 238000004043 dyeing Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000008569 process Effects 0.000 title claims description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 23
- 238000002074 melt spinning Methods 0.000 claims abstract description 22
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 8
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 44
- 239000000980 acid dye Substances 0.000 claims description 20
- 238000009987 spinning Methods 0.000 claims description 20
- 239000008188 pellet Substances 0.000 claims description 17
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 claims description 14
- 229920002292 Nylon 6 Polymers 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 239000004753 textile Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 229920000571 Nylon 11 Polymers 0.000 claims description 5
- 229920000299 Nylon 12 Polymers 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 244000144992 flock Species 0.000 claims description 3
- 238000009940 knitting Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 238000009941 weaving Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 abstract description 7
- 238000009835 boiling Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 25
- 239000004744 fabric Substances 0.000 description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical group 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000000985 reactive dye Substances 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000982 direct dye Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 229960000250 adipic acid Drugs 0.000 description 3
- -1 poly(hexamethylene adipamide) Polymers 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 2
- 239000005700 Putrescine Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- GJBRTCPWCKRSTQ-UHFFFAOYSA-N decanedioic acid Chemical compound OC(=O)CCCCCCCCC(O)=O.OC(=O)CCCCCCCCC(O)=O GJBRTCPWCKRSTQ-UHFFFAOYSA-N 0.000 description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 2
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- WPBWJEYRHXACLR-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O.OC(=O)CCCCCCCC(O)=O WPBWJEYRHXACLR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000004879 dioscorea Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010035 extrusion spinning Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XEUHNWODXVYLFD-UHFFFAOYSA-N heptanedioic acid Chemical compound OC(=O)CCCCCC(O)=O.OC(=O)CCCCCC(O)=O XEUHNWODXVYLFD-UHFFFAOYSA-N 0.000 description 1
- SWFMWXHHVGHUFO-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN.NCCCCCCN SWFMWXHHVGHUFO-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- TWHMVKPVFOOAMY-UHFFFAOYSA-N octanedioic acid Chemical compound OC(=O)CCCCCCC(O)=O.OC(=O)CCCCCCC(O)=O TWHMVKPVFOOAMY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YKEKYBOBVREARV-UHFFFAOYSA-N pentanedioic acid Chemical compound OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O YKEKYBOBVREARV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
Definitions
- the present invention relates to a polyamide fiber with enhanced dyeing properties.
- the polyamide fiber is suitable for low-temperature dyeing and shorter dyeing cycle.
- the present invention also discloses a method for obtaining such a fiber.
- the polyamide fiber is obtained by blending at least a polyamide 5.X, X being an integer from 4 to 16 with an aliphatic polyamide during the melt-spinning extrusion of the polyamide fiber.
- the blended polyamide fiber and articles made therefrom can be dyed at a lower temperature than the usual boiling temperature, and the dyeing time is half of the time of a normal dyeing cycle.
- the dyed polyamide fiber and article also show enhanced fastness to washing and perspiration.
- Polyamide also known as nylon, is a linear condensation polymer composed of repeated primary bonds of amide group.
- a polyamide fiber is generally produced by melt-spinning extrusion and is available in staple fiber, tow, monofilament, multi-filament, flat or texturized form.
- Polyamides are semi-crystalline polymers.
- the amide group -(-CO-NH-)- provides hydrogen bonding between polyamide intermolecular chains, providing high strength at elevated temperatures, toughness at low temperatures, wear and abrasion resistance, low friction coefficient and good chemical resistance. These properties have made polyamides among the strongest of all available man-made fibers.
- the dyeing efficiency of polyamide fibers is related to the carboxyl end groups -COOH and especially amine end groups -NH2, which exhibit polar and hydrophilic characteristics.
- the dye diffusion into fibers is related to the amorphous and crystalline balance, molecular orientation, molecular weight, intra-molecular and inter-molecular bonds and available hydroxyls or polar groups.
- the dye color uptake, rate of dyeing, homogeneity and fastness depend on the dyeing process conditions such as temperature, time and pH, and also on the dyeing equipment like exhaust or padding equipment.
- the chemical auxiliaries for instance, leveling agent, surfactant, retarders, fixing and so forth, are also important for an effective dyeing.
- the dye is classified according to its chemical composition, mechanism of reaction, size of molecules and so on.
- the most common types of dyes are reactive dyes, direct dyes, basic dyes, acid dyes, metallic dyes, azo dyes, dispersed dyes and vat dyes.
- Polyamides contain primary amino end-groups that are more suitable for acid dyes, for which the best dye uptake and fastness is obtained.
- the acid dye contains hydrophilic groups of sodium sulfonate radicals (- S0 3 Na) that can be combined with the amino groups (- NH+) of the polyamide fiber by the ionic bonds or electrostatic forces to provide better dyeability and brighter color.
- the rest of the aforementioned dyes are combined with polyamide fiber by hydrogen bonds or Van der Waals forces to provide a lighter color.
- the common temperature and process time for dyeing polyamide is boiling temperature ( ⁇ 100 9 C) and 60 minutes of processing time. This temperature is known as necessary to generate a swollen morphological structure of the fiber, by spacing the molecules and breaking the intermolecular bonds so that the dye can diffuse into the interior of the fiber and form permanent chemical bonds.
- the time of 60 minutes is known to be required for achieving a deep, regular and homogenous color.
- those temperatures and time are energy consuming and not environment friendly.
- the present invention aims to find a solution for obtaining a polyamide article that is dyed with significantly lower temperature and time and that yields a dark, homogenous and durable color; and surprisingly, the inventors have found that a specific polyamide fiber blend has enhanced dyeing capabilities such as low-temperature dyeing of dark and light colors and reduced dyeing time.
- the present invention thus provides a polyamide fiber with enhanced dyeing properties, wherein the polyamide fiber is a blend of at least two different polyamides: a first polyamide and second polyamide,
- the first polyamide being an aliphatic polyamide selected from the group consisting of polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.12, polyamide 6.10, polyamide 11, polyamide 12, polyamide 10.10, polyamide 4.6, polyamide 4.10, polyamide 12.12, polyamide 10.12 and mixtures thereof, and
- the second polyamide being selected between polyamide 5.
- X being an integer from 4 to 16 and mixtures thereof.
- the present invention also aims at a method for obtaining said polyamide fiber with enhanced dyeing properties, wherein the polyamide fiber is obtained by melt-spinning extrusion of at least the first and the second polyamide as defined above and below in the specification.
- the present invention proposes a polyamide article comprising the polyamide fiber with enhanced dyeing properties as defined above and below in the following paragraphs; and a method for obtaining such a polyamide article, wherein the polyamide fiber of the invention is transformed by texturizing, drawing, warping, knitting, weaving, nonwoven processing, garment manufacturing or a combination thereof.
- another object of the present invention is the use of a second polyamide being a polyamide 5.
- X being an integer from 4 to 16 or mixtures thereof in combination with at least a first polyamide being an aliphatic polyamide selected from the group consisting of polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.12, polyamide 6.10, polyamide 11, polyamide 12, polyamide 10.10, polyamide 4.6 polyamide 4.10, polyamide 12.12, polyamide 10.12 and mixtures thereof in order to enhance the dyeing properties of a polyamide fiber made therefrom.
- polyamide fiber in the sense of the present invention is the generic term including the following spun articles: a fiber, a monofilament, a multifilament and a yarn.
- a "polyamide article” according to the invention is a transformed or treated polyamide fiber and includes staple fibers, any flock or any textile composition made of polyamide fiber, especially fabrics and/or garments.
- fiber fiber, “yarn” and “filament” can be used indifferently without changing the meaning of the invention.
- the present invention provides a polyamide fiber blend with enhanced dyeing capabilities, such as faster and low-temperature dyeing of dark and light colors.
- the polyamide fiber with enhanced dyeing properties according to the invention is a blend of at least two different polyamides: a first polyamide and second polyamide.
- the first polyamide is an aliphatic polyamide composed of AB and/or AABB type, selected from the group consisting of polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.12, polyamide 6.10, polyamide 11, polyamide 12, polyamide 10.10, polyamide 4.6, polyamide 4.10, polyamide 12.12, polyamide 10.12 and mixtures thereof.
- polyamide 6 or polyamide 6.6 and mixtures thereof are preferably selected from the group consisting of polyamide 6 or polyamide 6.6 and mixtures thereof; and even more preferably poly(hexamethylene adipamide) (polyamide 6.6 or Nylon 6.6).
- polyamide 6.6 or Nylon 6.6 are well known in the art and can be obtained by polycondensation of a mixture of diacids and diamines monomers or a salt thereof, which are commercially available.
- the diamines and diacids of polyamide AABB type belong to the group of tetramethylenediamine (1,4-diaminobutane or putrescine), hexamethylenediamine (1,6- hexanediamine), dodecamethylenediamine (1,12- diaminododecane), hexanedioic acid (adipic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid.
- the monomers of the polyamide AB type belong to the group of caprolactam, 11-am ' inoundecanoamide, dodecanolactam or laurolactam.
- poly(hexamethylene adipamide) polyamide 6.6
- the main monomers are hexamethylenediamine and adipic acid.
- these monomers can comprise up to 25 mol% of other diamine or diacid monomers or even amino acid or lactam monomers.
- the amino acid is aminocaproic acid and the lactam is caprolactam.
- the preferred first polyamides may have a viscosity index (IVN) in the range of 100 to 200 ml/g, preferably between about 120 and 170. This IVN is measured according to the standard ISO 307, which is explained hereinafter in the experimental part.
- IVN viscosity index
- the amino terminal groups (ATG) content of those polyamides is advantageously from 25 to 60 equivalent/ton, and the carboxyl terminal groups (CTG) is advantageously from 45 to 90 equivalent/ton.
- Those amino/carboxyl end groups contents are measured according to the methodology explained hereinafter in the experimental part.
- the opacity of this first polyamide can be brilliant, semi-dull, full-dull and mixtures thereof.
- the opacity is related to the amount of titanium dioxide present in the polymer, which is relevant for dyeability, lustre and processability issues. For instance, brilliant has lower amount of titanium dioxide, whereas full-dull has higher amount of titanium dioxide.
- a particularly preferred first polyamide according to the present invention is a polyamide 6.6 containing from 1 to 5% of caprolactam.
- This polyamide has advantageously a IVN (viscosity index) from 128 to 132, and ATG (amine terminal groups) from 40 to 45 and is a full-dull polymer.
- the second polyamide is a polyamide 5.X, X being an integer from 4 to 16 and mixtures thereof. More preferably, the second polyamide is an odd/even polyamide such as polyamide 5.4, 5.6, 5.8, 5.10, 5.12, 5.14. In a preferred embodiment, the second polyamide of the polyamide fiber according to the invention is polyamide 5.6 or polyamide 5.10. The best results in terms of dyeing properties are obtained when the second polyamide is polyamide 5.6.
- Polyamide 5.X is made of pentamethylenediamine and an aliphatic dicarboxylic acid(s) as raw materials.
- dicarboxylic acids is the following: butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid.
- Polyamides 5.6 and 5.10 have the. advantage of being able to be manufactured from biomass according to ASTM6866.
- pentamethylenediamine can also be prepared from bio-resources according to ASTM6866, the resulting polyamide can be at least 45% bio- sourced and up to 100% from bio-resources.
- Polyamide 5.6 is also known as poly(pentamethylene adipamide), which consists of pentamethylenediamine and adipic acid as raw materials.
- the preferred polyamide 5.6 may have a viscosity index (IVN) in the range of 100 to 200 ml/g, preferably between about 120 and 170. This IVN is measured according to the standard ISO 307, which is explained hereinafter in the experimental part.
- the amino terminal groups (ATG) content is advantageously from 25 to 60 equivalent/ton, and the carboxylic terminal groups (CTG) content is preferably from 45 to 90 equivalent/ton.
- Those amino/carboxyl end groups contents are measured according to the methodology explained hereinafter in the experimental part.
- the opacity of this second polyamide can be brilliant, semi-dull, full-dull and mixtures thereof, as explained above for the first polyamide.
- a particularly preferred polyamide 5.6 according to the present invention has a IVN (viscosity index) of from 138 to 142, and ATG (amine terminal groups) from 38 to 42 and is a brilliant polymer, that is, the polyamide contains no titanium dioxide.
- a polyamide fiber according to the invention is particularly advantageous when the second polyamide is present in an amount of about 1.0% to 40.0%, preferably about 5.0 to 20.0% by weight of the total weight of the polyamide fiber. The best mode is when the second polyamide, in particular polyamide 5.6, is present in an amount of 5% to 10% by weight of the total weight of the polyamide fiber.
- the polyamide fiber according to the invention has advantageously an overall dtex of about 40 to 300, and a dpf (dtex per filament) of about 1 to 5.
- the tenacity (elongation at break) is from 30 to 80 cN/dtex.
- the elongation at break is from 20% to 90%.
- the invention also provides a method for obtaining the polyamide fiber as described above.
- the method involves forming the polyamide fiber blend by melt-spinning extrusion, with at least the first and second polyamides described above.
- melt-spinning is understood to mean the extrusion process of converting the polyamide in a melt form into polyamide fibers.
- the polyamide(s) may be fed to the melt-spinning device in pellet, powder or melt form.
- the method includes any conventional extrusion spinning means suitable for melt-spinning extrusion of polyamide, these means being well known by a person skilled in the art, such as single-screw extruder, double-screw extruder, bi-component extruder and grid spinning head.
- the melt-spinning extrusion is further defined as being LOY (low-oriented yarn), POY (partially oriented yarn), FDY (fully drawn yarn), FOY (fully oriented yarn), LDI (Low denier Industrial) or HDI (High denier Industrial).
- the melt spinning extrusion comprises the following steps:
- the second polyamide is continuously introduced during step al as a pellet or powder, preferably with the use of a dosing apparatus.
- the second polyamide is preferably continuously introduced during step al of the single-screw extruder. It can be added as a polyamide pellet or powder, by means of a dosing apparatus like a dosing pump or a gravimetric feeding apparatus, preferably a gravimetric feeding apparatus.
- the second polyamide is melt-mixed with the first polyamide, before the formation of the fiber.
- the second polyamide can be optionally dried before being introduced in step al.
- the second polyamide is continuously introduced as a pellet by means of a gravimetric feeding apparatus and the quantity added is 5% by weight of the total weight of the polyamide fiber.
- the second polyamide is continuously introduced as a pellet by means of a gravimetric feeding apparatus and the quantity added is 10% by weight of the total weight of the polyamide fiber.
- melt-spinning extrusion comprises the following steps:
- a'l Feeding a blend of at least the first and the second polyamides as a melt, pellet or powder into the inlet of a screw extruder or grid spinning head,
- the blend of at least the first and the second polyamides is obtained by a step aO previous to step a'l, and comprising a polymerization of diacids and diamines monomers corresponding to at least the first and the second polyamides or salts thereof.
- the polymerization at step aO generally comprises the following steps: 1- concentration of the nylon salt by evaporation of water, in which the nylon salt is a combination of diacids and diamines monomers corresponding to at least the first and the second polyamides or salts thereof; 2- polymerization, under pressure, of the concentrated nylon salt; 3- Reduction in pressure of the polymerization medium in order to remove the residual water by evaporation; 4- Optional maintenance of the polymer temperature, at atmospheric pressure or under reduced pressure, in order to obtain the desired degree of polymerization; 5- Recovery of the polyamide as a melt or transformation of the molten polyamide into pellets.
- the melt-spinning extrusion comprises the following steps:
- the second polyamide is preferably continuously introduced as a polyamide melt during step a3 of the screw extruder, preferably a single-screw extruder. It is added, by means of an additional screw extruder, preferably a single-screw extruder. According to this embodiment, the second polyamide is blended with the first polyamide upon leaving the spinning pack spinneret, at the formation of the fiber, thereby forming a bi-component fiber.
- the second polyamide is advantageously introduced in an amount of 1.0% to 40.0%, preferably 5.0 to 20.0% by weight of the total weight of the polyamide fiber.
- the term "polyamide” also means “polyamide blend", as at least both the first and second polyamide are present.
- the polyamide (or polyamide blend) is melted, homogenized and pressurized inside the screw extruder, preferably at a temperature from 280 to 310 9 C, which is above the melting temperature of the first and second polyamides, and at a extrusion pressure from 30 to 70 bar.
- the molten polyamide (or polyamide blend) is spun into fibers (or yams or filaments) preferably at a temperature from 260 to 310 e C, spinning pack pressure from 150 to 250 and a spinning pack flow rate from 3 to 8 kg/h, with the use of a spinning screen-pack containing filtering elements and a spinneret.
- Step a4 is the step of cooling down the fibers (or yarns or filaments) until the solidified form and winding the polyamide fibers into bobbins.
- a spinning oil can also be added onto the fiber at this step.
- the extruder can be equipped with a metering system and/or additional single-screw extruder for introducing polymers and optionally additives such as masterbatches into the main polymer, at step al and/or a3 and/or a4.
- Additives can be introduced during the method of the invention or may be present in the first and second polyamide pellet.
- the additives are selected from: antioxidants, stabilizers such as heat or light stabilizers, colorants, pigments, nucleating agents such as talc, matifying agents such as titanium dioxide or zinc sulphide, processing aids, biocides, viscosity modifiers, catalysts, Far Infrared Rays emitting minerals, biodegradable "converting" additives, anti-static additives, functional additives, optical brightening agents, nanocapsules, anti-bacterial, anti-mite, anti-fungi or other conventional additives.
- These additives are generally added in the polymer or at step al and/or a4 of the melt-spinning extrusion, in an amount of 0,001% to 10% by weight of the polyamide article.
- the resulting polyamide fiber obtained according to the first, second and third embodiment described above can be dyed.
- the enhanced dyeing properties are generally obtained with dyes consisting of reactive dyes, direct dyes, acid dyes and metallic dyes, preferably with reactive dyes or acid dyes. These dyes combine with polyamide fiber by chemical reactions and will therefore benefit from a faster and lower temperature of dyeing, where the molecular structure is capable of forming chemical bonds.
- acid dyes are advantageously used due to their high compatibility with polyamide amine end-groups.
- the dyeing is performed at a temperature from 40 9 C to 80 e C, preferably at 60 ⁇ C ⁇ 5 ⁇ C.
- the dyeing is preferably performed with a dyeing cycle from 20 to 40 minutes, preferably from 30 minutes ⁇ 5 minutes.
- the polyamide fiber according to the invention can then be transformed into a polyamide article, notably a textile fabric and/or garment.
- a polyamide article according to the invention is preferably a fiber, a staple fiber, a flock, a woven, a knitted or non-woven fabric or a textile article made from the polyamide fiber of the invention (defined above) or obtained from the process according to the invention.
- the textile article may be any textile article known in the art including, but not limited to woven fabric, knitted fabric, nonwoven fabric, ropes, cords, sewing thread, and so forth.
- the polyamide article is preferably dyed, notably with acid dyes.
- the enhanced dyeing properties are generally obtained with dyes consisting of reactive dyes, direct dyes, acid dyes and metallic dyes. These dyes combine with polyamide fiber by chemical reactions and will therefore benefit from a faster and lower temperature of dying, where the molecular structure is capable of forming chemical bonds. Most preferably, reactive dyes and acid dyes. In a preferred embodiment of the present invention, acid dyes are advantageously used due to their high compatibility with polyamide amine end-groups.
- the methods for transforming the polyamide fiber into a polyamide article like a textile fabric or garment are well known by the skilled person in the art. Indeed, the polyamide fiber can be transformed into a polyamide article by texturizing, drawing, warping, knitting, weaving, nonwoven processing, garment manufacturing or a combination thereof.
- the method for obtaining a polyamide article can further comprises a dyeing step.
- the enhanced dyeing properties are generally obtained with dyes consisting of reactive dyes, direct dyes, acid dyes and metallic dyes. These dyes combine with polyamide fiber by chemical reactions and will therefore benefit from a faster and lower temperature of dying, where the molecular structure is capable of forming chemical bonds. Most preferably, reactive dyes and acid dyes are chosen for the dyeing step. In a preferred embodiment of the present invention, acid dyes are advantageously used due to their high compatibility with polyamide amine end-groups.
- the dyeing is performed at a temperature from 409C to 80 Q C, preferably at 60 9 C ⁇ 5 9 C.
- the dyeing is performed with a dyeing cycle from 20 to 40 minutes, preferably from 30 minutes ⁇ 5 minutes.
- the advantages of the polyamide fibers and articles made therefrom according to the invention are that they have enhanced dyeing capabilities such as low-temperature dyeing of dark and light colors and reduced dyeing time.
- the dyeing is therefore, uniform, dark and durable colors are possible to be achieved at a more efficient and environmentally friendly process.
- Other details or advantages of the invention will become more clearly apparent in the light of the examples given below.
- a series of polyamide articles (Examples 1 to 12), including comparative polyamide articles (Example 1 to 9 and 12) are formed and evaluated for washing fastness, alkaline and acid perspiration fastness, CIE Lab color intensity "L”, IVN (viscosity index) and ATG (terminal amino groups).
- the amino end group (ATG) content was determined by a potentiometric titration method. The quantity of 2 grams of polyamide is added to about 70 ml of phenol 90%wt. The mixture is kept under agitation and temperature of 40 9 C until complete dissolution of the polyamide. The solution is then titrated by 0.1N HCI at about 25 e C. The result is reported as equivalent/ton (eq/ton). In the case of analyzing fibers and articles, any residue or spin- finish must be previously removed.
- IVN solution viscosity
- the sample is washed at 40 9 C for 30 minutes, using conventional detergent (4g/l). It is then rinsed 3 times in separate portions of 100 ml of water.
- the sample is assessed according to a grey scale in relation to change of color (ISO 105 - A02) and staining of the adjacent fabrics (ISO 105 - A03). The grade varies from 0 to 5, being 0 "low” and 5 "high".
- Acid and alkaline perspirations were assessed.
- the samples were placed in contact with the standard adjacent fabrics (for color transfer) and immersed in simulated alkaline and acid solution (pH 8.0 and 5.5 respectively), drained and placed between two plates under a specific pressure, temperature and time (37 ⁇ 2 9 C, 4 hours, pressure of 5 kg) in a testing device (perspirometer).
- the change in color of the samples and staining of the adjacent fabric is assessed with the Grey scales for color change (ISO 105 - A02) and staining (ISO 105 - A03). The grade varies from 0 to 5, being 0 "low” and 5 "high".
- the polyamide article color intensity "L” was measured by the standardized method CIE L*a*b* (standard CIE 15:2004 of the "Commission Internationale de I'eclairage”). In this method, the polyamide article is assessed using a spectrophotometer or a colorimeter, and the L* a* and b* coordinates are obtained from the equipment.
- the luminosity coordinate "L” varies from 0 to 100, being 0 "black” and 100 “white”.
- the measurement uses the illuminant type D65, and 10 9 for the observation angle. The lower is this parameter, the darker is the color.
- the polyamide 5.6 pellet is a commercially available polyamide from Cathay Biotech under the trademark Terryl ® . It is a brilliant polyamide containing no titanium dioxide.
- the IVN viscosity index
- ATG amine terminal groups
- a polyamide fiber was obtained during melt-spinning extrusion of the above polyamide 5.6 BR (Brilliant).
- the multi-filament polyamide fiber obtained was further texturized into linear density of
- Comparative Example 4 - 50 9 C - 30 minutes The quantity used was 3.5%wt of a black acid dye, and l%wt of a leveling agent.
- the pH of the solution was adjusted to 3 - 4 with ammonium sulfate and acetic acid.
- the bath relation was 1:30, meaning 1 part of fabric per 30 parts of water. Comparative Examples 5 to 8 - 100% Polyamide 6.6 BR
- the polyamide 6.6 pellet was produced at Rhodia Poliamida e Especialidades Ltda. It is a brilliant polyamide (no titanium dioxide) produced from the polymerization of a nylon salt containing mainly hexamethylenediamine and adipic acid.
- the IVN viscosity index
- ATG amine terminal groups
- a polyamide fiber was obtained during melt-spinning extrusion of the above polyamide 6.6 BR (Brilliant).
- the multi-filament polyamide fiber obtained was further texturized into linear density of 2x80f68 dtex and knitted into fabric.
- the tenacity obtained was 31.5 cN/tex and elongation was 28.8%.
- the knitted fabric was dyed in exhausting equipment at:
- the quantity used was 3.5%wt of a black acid dye, and l%wt of a leveling agent.
- the pH of the solution was adjusted to 3 - 4 with ammonium sulfate and acetic acid.
- the bath relation was 1:30, meaning 1 part of fabric per 30 parts of water.
- the full-dull polymer contains higher amount of titanium dioxide and therefore results in lighter shades than brilliant polymers, using the same amount of dye.
- Examples 1 to 8 are comparable within itself and are important for setting the optimum dyeing temperature and time for the invention.
- examples 9 to 12 are comparable within itself and show the advantages obtained by the present invention in terms of color uptake and fastness.
- Examples of the invention 10 and 11 - Polyamide blend A polyamide fiber blend was obtained during melt-spinning extrusion.
- the first polyamide was the polyamide 6.6 FD (full-dull).
- This polyamide is prepared similarly to comparative examples 5 to 8 and it is full-dull (containing about 1.5% of Titanium dioxide).
- the second polyamide was the polyamide 5.6 (brilliant) as described above for comparative examples 1 to 4.
- the second polyamide was continuously introduced during step al of the single-screw extruder as a polyamide pellet by means of a gravimetric feeding apparatus.
- the polyamide blend was melted, homogenized and pressurized inside the screw extruder at a temperature of around 290 9 C and at an extrusion pressure of around 50 bar.
- the molten polyamide blend was spun into multi-filament yarn at a spinning pack pressure of around 200 bar and at a spinning pack flow rate of around 5 kg/h.
- the polyamide fiber blend was solidified and wound into bobins at 4200 m/min.
- the polyamide 5.6 was continuously added at step al as 5% weight of the total polyamide blend.
- the polyamide 5.6 was continuously added at step al as 10% weight of the total polyamide blend.
- the multi-filament polyamide blends obtained were further texturized into linear density of 2x80f68 dtex and knitted into fabric.
- the knitted fabric was dyed in exhausting equipment at 60 Q C temperature for 30 minutes.
- the quantity used was 3.5%wt of a black acid dye, and l%wt of a leveling agent.
- the pH of the solution was adjusted to 3 - 4 with ammonium sulfate and acetic acid.
- the bath relation was 1:30, meaning 1 part of fabric per 30 parts of water. Comparative Example 9 - 100% Polyamide 6.6 FD
- a polyamide fiber was obtained during melt-spinning extrusion.
- the polyamide was the polyamide 6.6 FD (full-dull) as prepared/described above for examples 10 and 11.
- the multi-filament polyamide fiber obtained was further texturized into linear density of 2x80f68 dtex and knitted into fabric.
- the knitted fabric was dyed in exhausting equipment at 60 9 C temperature for 30 minutes.
- the quantity used was 3.5%wt of a black acid dye, and l%wt of a leveling agent.
- the pH of the solution was adjusted to 3 - 4 with ammonium sulfate and acetic acid.
- the bath relation was 1:30, meaning 1 part of fabric per 30 parts of water.
- the polyamide was the polyamide 6, FD (full-dull). This texturized polyamide yarn was obtained from the company Antex Ltda as a bobbin.
- the multi-filament polyamide fiber was knitted into fabric.
- the knitted fabric was dyed in exhausting equipment at 60 9 C temperature for 30 minutes.
- the quantity used was 3.5%wt of a black acid dye, and l%wt of a leveling agent.
- the pH of the solution is adjusted to 3 - 4 with ammonium sulfate and acetic acid.
- the bath relation was 1:30, meaning 1 part of fabric per 30 parts of water.
- a posterior fixation step was performed, using 3%wt of a fixation agent for 30 minutes at 80 e C.
- Example 9 Each of the examples (Examples 9 to 12) is evaluated for washing fastness, alkaline and acid perspiration fastness, CIE Lab color intensity "I”, IVN (viscosity index) and ATG (terminal amino groups). The results are shown in the table 2 below.
- polyamide 5.6 and polyamide 6.6 fiber blends low-temperature dyeing properties and shorter dyeing cycle are possible with polyamide 5.6 and polyamide 6.6 fiber blends.
- the resulting color fastness of polyamide blended articles (ex. 10 and 11) is also superior in relation to polyamide 5.6 articles alone (ex. 1 and 3).
- the dyeing property of the polyamide fiber blend is better than the conventional polyamide 6 (ex. 12).
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Abstract
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CN109957854A (en) * | 2017-12-14 | 2019-07-02 | 凯赛(乌苏)生物材料有限公司 | A kind of polyamide blended fiber and its preparation method and application |
JP7173014B2 (en) * | 2018-04-25 | 2022-11-16 | 東レ株式会社 | Polyamide fiber, woven and knitted fabric, and method for producing polyamide fiber |
CN110904535A (en) * | 2018-09-18 | 2020-03-24 | 凯赛(乌苏)生物材料有限公司 | Polyamide monofilament and preparation method and application thereof |
CN111519276A (en) * | 2019-02-02 | 2020-08-11 | 上海凯赛生物技术股份有限公司 | High-shrinkage polyamide fiber and preparation method and application thereof |
CN112680826A (en) * | 2019-10-18 | 2021-04-20 | 上海凯赛生物技术股份有限公司 | Polyamide sea-island fiber and preparation method and application thereof |
KR102267621B1 (en) * | 2019-12-30 | 2021-06-21 | 다이텍연구원 | Dyeing Method of nylon 4,6 fiber |
CN111171312B (en) * | 2020-01-21 | 2022-08-02 | 军事科学院***工程研究院军需工程技术研究所 | Copolyamide 56/66 polymer and preparation method and application thereof |
CN113123013B (en) * | 2021-04-16 | 2022-05-20 | 旷达汽车饰件***有限公司 | Preparation method of automotive interior microfiber fabric |
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US4295329A (en) * | 1980-06-10 | 1981-10-20 | E. I. Du Pont De Nemours And Company | Cobulked continuous filament heather yarn method and product |
JP4595668B2 (en) * | 2004-05-21 | 2010-12-08 | 三菱化学株式会社 | Polyamide resin |
JP5282371B2 (en) | 2006-05-16 | 2013-09-04 | 三菱化学株式会社 | Copolymer polyamide resin |
US8158730B2 (en) * | 2006-05-16 | 2012-04-17 | Mitsubishi Chemical Corporation | Polyamide resin |
JP4935695B2 (en) * | 2008-01-30 | 2012-05-23 | 東レ株式会社 | Crimp yarn made of polyamide 56 and carpet comprising the same |
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TWI519687B (en) * | 2014-12-19 | 2016-02-01 | 展頌股份有限公司 | Dull polyamide 56 fiber and method for manufacturing the same |
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