EP3091107B1 - Copolymerized aramid dope-dyed yarn and method for preparing same - Google Patents
Copolymerized aramid dope-dyed yarn and method for preparing same Download PDFInfo
- Publication number
- EP3091107B1 EP3091107B1 EP14877413.6A EP14877413A EP3091107B1 EP 3091107 B1 EP3091107 B1 EP 3091107B1 EP 14877413 A EP14877413 A EP 14877413A EP 3091107 B1 EP3091107 B1 EP 3091107B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymerized aramid
- cation
- basic
- basic blue
- filament
- 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
- 239000004760 aramid Substances 0.000 title claims description 128
- 229920003235 aromatic polyamide Polymers 0.000 title claims description 128
- 238000000034 method Methods 0.000 title claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 75
- 238000009987 spinning Methods 0.000 claims description 68
- 229920000642 polymer Polymers 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 44
- 238000004040 coloring Methods 0.000 claims description 35
- 239000003960 organic solvent Substances 0.000 claims description 35
- 150000001768 cations Chemical class 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 29
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 27
- NRZZJDPJVVRJIB-UHFFFAOYSA-N (4-aminophenyl)cyanamide Chemical compound NC1=CC=C(NC#N)C=C1 NRZZJDPJVVRJIB-UHFFFAOYSA-N 0.000 claims description 26
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 claims description 24
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 21
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 19
- 150000004984 aromatic diamines Chemical class 0.000 claims description 12
- ZRVPOURSNDQODC-UHFFFAOYSA-M 4-[(2,4-dimethyl-1,2,4-triazol-4-ium-3-yl)diazenyl]-n,n-dimethylaniline;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(C)C)=CC=C1N=NC1=[N+](C)C=NN1C ZRVPOURSNDQODC-UHFFFAOYSA-M 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 6
- IVFRHOQHKQWEHJ-UHFFFAOYSA-N 1-amino-4-[4-[(dimethylamino)methyl]anilino]anthracene-9,10-dione Chemical compound C1=CC(CN(C)C)=CC=C1NC1=CC=C(N)C2=C1C(=O)C1=CC=CC=C1C2=O IVFRHOQHKQWEHJ-UHFFFAOYSA-N 0.000 claims description 5
- AWHMVXSOQJUERN-UHFFFAOYSA-P CC(O)=O.CC(O)C(O)=O.CCN(CC)CCCNC1=NC(NC2=CC=C3C(=C2)C=C(C(N=NC2=CC=C(C=C2)N=NC2=CC=CC=C2)=C3O)S(O)(=O)=O)=NC(NCCC[NH+](CC)CC)=N1.CCN(CC)CCCNC1=NC(NC2=CC=C3C(=C2)C=C(C(N=NC2=CC=C(C=C2)N=NC2=CC=CC=C2)=C3O)S(O)(=O)=O)=NC(NCCC[NH+](CC)CC)=N1 Chemical compound CC(O)=O.CC(O)C(O)=O.CCN(CC)CCCNC1=NC(NC2=CC=C3C(=C2)C=C(C(N=NC2=CC=C(C=C2)N=NC2=CC=CC=C2)=C3O)S(O)(=O)=O)=NC(NCCC[NH+](CC)CC)=N1.CCN(CC)CCCNC1=NC(NC2=CC=C3C(=C2)C=C(C(N=NC2=CC=C(C=C2)N=NC2=CC=CC=C2)=C3O)S(O)(=O)=O)=NC(NCCC[NH+](CC)CC)=N1 AWHMVXSOQJUERN-UHFFFAOYSA-P 0.000 claims description 5
- VJDDAARZIFHSQY-UHFFFAOYSA-N basic black 2 Chemical compound [Cl-].C=1C2=[N+](C=3C=CC=CC=3)C3=CC(N(CC)CC)=CC=C3N=C2C=CC=1NN=C1C=CC(=O)C=C1 VJDDAARZIFHSQY-UHFFFAOYSA-N 0.000 claims description 5
- SQHOAFZGYFNDQX-UHFFFAOYSA-N ethyl-[7-(ethylamino)-2,8-dimethylphenothiazin-3-ylidene]azanium;chloride Chemical compound [Cl-].S1C2=CC(=[NH+]CC)C(C)=CC2=NC2=C1C=C(NCC)C(C)=C2 SQHOAFZGYFNDQX-UHFFFAOYSA-N 0.000 claims description 5
- ASWFVRBTTRCNAK-UHFFFAOYSA-O trimethyl-[3-[[4-(methylamino)-9,10-dioxoanthracen-1-yl]amino]propyl]azanium Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCC[N+](C)(C)C)=CC=C2NC ASWFVRBTTRCNAK-UHFFFAOYSA-O 0.000 claims description 5
- -1 C.I. Basic Red 32 Chemical compound 0.000 claims description 3
- XJCPMUIIBDVFDM-UHFFFAOYSA-M nile blue A Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4[O+]=C3C=C(N)C2=C1 XJCPMUIIBDVFDM-UHFFFAOYSA-M 0.000 claims 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 80
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 20
- 239000001110 calcium chloride Substances 0.000 description 20
- 229910001628 calcium chloride Inorganic materials 0.000 description 20
- 239000000701 coagulant Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 19
- 239000012299 nitrogen atmosphere Substances 0.000 description 19
- 238000004804 winding Methods 0.000 description 19
- 229920006231 aramid fiber Polymers 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000975 dye Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- SHXOKQKTZJXHHR-UHFFFAOYSA-N n,n-diethyl-5-iminobenzo[a]phenoxazin-9-amine;hydrochloride Chemical compound [Cl-].C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=[NH2+])C2=C1 SHXOKQKTZJXHHR-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- LIKZXCROQGHXTI-UHFFFAOYSA-M acid blue 25 Chemical compound [Na+].C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S([O-])(=O)=O)C=C1NC1=CC=CC=C1 LIKZXCROQGHXTI-UHFFFAOYSA-M 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- CZWHGIACASUWJC-UHFFFAOYSA-L disodium 5-acetamido-3-[(4-dodecylphenyl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].CCCCCCCCCCCCc1ccc(cc1)N=Nc1c(O)c2c(NC(C)=O)cc(cc2cc1S([O-])(=O)=O)S([O-])(=O)=O CZWHGIACASUWJC-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- UZGKAASZIMOAMU-UHFFFAOYSA-N 124177-85-1 Chemical compound NP(=O)=O UZGKAASZIMOAMU-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/04—Pigments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/06—Dyes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
-
- 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/20—Physical properties optical
Definitions
- the present invention relates to a copolymerized aramid dope-dyed yarn and a method for preparing the same, and more particularly, to a method for preparing a copolymerized aramid dope-dyed yarn with excellent color strength and color fastness by mixing a coloring matter having a cation in a polymerization solution when spinning the polymerization solution containing a copolymerized aramid polymer by means of a spinning spinneret without using sulfuric acid.
- Aromatic polyamide commonly referred to as an aramid, includes a para-based aramid having a structure in which benzene rings are linked linearly through an amide group (-CONH) and a meta-based aramid which has a linkage structure different from the para-based aramid.
- the para-based aramid has excellent characteristics such as a high strength, high elasticity and low shrinkage. Since the para-based aramid has a high enough strength so as to be able to lift a two-ton vehicle with a thin cable made thereof having a thickness of about 5 mm, it is widely used for bulletproofing, as well as in a variety of applications in advanced industries of an aerospace field.
- the aramid is carbonized and becomes black at 500°C or more, thus being also spotlighted in fields requiring high heat-resistant properties.
- aramid fiber The preparation method of aramid fiber has been explained well in Korean Patent Registration No. 10-0910537 owned by the present applicant.
- a mixture solution is prepared by dissolving aromatic diamine in a polymerization solvent, then, followed by adding aromatic diacid to the above solution to prepare an aramid polymer.
- the aramid polymer is dissolved in a sulfuric acid solvent to prepare a spin dope, the spin dope is spun, followed by conducting coagulation, washing and drying processes in this order, thereby finally completing an aramid fiber.
- the aramid fiber is prepared according to the above-described processes, an aramid polymer in a solid state is prepared and again dissolved in a sulfuric acid solvent to prepare a spin dope, followed by spinning the same. Therefore, a manufacturing process becomes complicated, is harmful for a human body, and may cause a problem such as a decrease in durability due to corrosion of an apparatus.
- Korean Patent Registration No. 10-171994 discloses a method for fabricating an aramid fiber directly using a copolymerized aramid polymerization solution as a spin dope, thus not requiring a sulfuric acid solvent.
- a copolymerized aramid fiber is manufactured by adding terephthaloyl dichloride to an organic solvent in which para-phenylenediamine and cyano-para-phenylenediamine are dissolved, and reacting the same to prepare a polymerization solution containing a copolymerized aramid polymer, then, spinning and coagulating the polymerization solution.
- the conventional art entails a problem that the prepared copolymerized aramid fiber has deteriorated dyeing property due to high crystalline property although having an advantage of not using the sulfuric acid solvent.
- Korean Patent Registration No. 10-067338 discloses a method for fabricating a copolymerized aramid fiber that includes adding polyvinyl pyrrolidone as a non-crystalline polymer to a polymerization solution when the copolymerized aramid fiber is manufactured by adding terephthaloyl dichloride to an organic solvent in which paraphenylenediamine and cyano-para-phenylenediamine are dissolved, and reacting the same to polymerize the polymerization solution containing a copolymerized aramid polymer, then, spinning and coagulating the same.
- this method involves problems of deteriorating solubility and dyeing fastness of the polymerization solution although improving dyeing property of the manufactured copolymerized aramid fiber.
- a fabrication method of a copolymerized aramid dope-dyed yarn including addition of a specific coloring matter which may not be bonded to a cyano group (-CN) of the copolymerized aramid through a hydrogen bond, that is, a coloring matter which does not contain a cation, when a copolymerized aramid fiber is prepared by adding terephthaloyl dichloride to an organic solvent in which para-phenylenediamine and cyano-para-phenylenediamine are dissolved, and reacting the same to polymerize a polymerization solution containing a copolymerized aramid polymer, then, spinning and coagulating the polymerization solution.
- a specific coloring matter which may not be bonded to a cyano group (-CN) of the copolymerized aramid through a hydrogen bond
- a coloring matter which does not contain a cation when a copolymerized aramid fiber is prepared by adding terephthalo
- this method entails some problems such as a decrease in a polymerization degree of the copolymerized aramid polymer, a reduction in solubility of the polymerization solution, and a deterioration in a color fastness of the manufactured dope-dyed yarn.
- EP 2 559 792 A1 is directed to a meta-type wholly aromatic polyamide fiber containing an UV absorber with a water solubility of less than 0.04 mg/l and has a degree of dye exhaustion of 90% or more in the form of a dyed fiber.
- US 2012/0041100 A1 relates to a molecular miscible blend solution of aromatic polyamide which is composed of a homogeneous mixture of a highly crystalline para-aromatic polyamide polymer and a non-crystalline polymer.
- An object of the present invention is to provide a copolymerized aramid dope-dyed yarn with excellent color strength and color fastness, and a method for preparing the same while preventing a decrease in a polymerization degree of copolymerized aramid and a reduction in solubility of a polymerization solution.
- the present invention provides a method for preparing a copolymerized aramid yarn, including adding a coloring matter having cations in an amount of 0.1 to 5% by weight ('wt.%') to a weight of a copolymerized aramid polymer in a polymerization process of a polymerization solution containing the copolymerized aramid polymer, when the copolymerized aramid yarn is prepared by adding terephthaloyl dichloride to an organic solvent in which an aromatic diamine having a cyano group is dissolved, reacting the same to polymerize the polymerization solution containing the copolymerized aramid polymer, then, spinning and coagulating the polymerization solution.
- the present invention due to the addition of the coloring matter to the polymerization solution, it is possible to efficiently prevent a decrease in a polymerization degree of the copolymerized aramid polymer or a reduction in solubility of the polymerization solution.
- the copolymerized aramid polymer having a cyano group (-CN) and the coloring matter having a cation are bonded through a hydrogen bond in the polymerization process of the polymerization solution containing the copolymerized aramid polymer, and the coloring matter having a cation is bonded with the cyano group (-CN) located on a main chain of the copolymerized aramid polymer through an ionic bond, and can show behavior together with the main chain during formation of a liquid crystal, thereby improving color strength, color fastness to light and color fastness to washing of the copolymerized aramid dope-dyed yarn.
- an inorganic salt is dissolved in an organic solvent, followed by adding aromatic diamine having a cyano group (CN-) thereto.
- the aromatic diamine having a cyano group may include a solution of paraphenylenediamine and cyano-para-phenylenediamine dissolved in a molar ratio of 1:9 to 9:1, or a solution of cyano-para-phenylenediamine alone.
- the organic solvent may include, for example, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), hexamethyl phosphoamide (HMPA), N,N,N',N'-tetramethylurea (TMU), N,N-dimethylformamide (DMF), or a mixture thereof.
- NMP N-methyl-2-pyrrolidone
- DMAc N,N-dimethylacetamide
- HMPA hexamethyl phosphoamide
- TNU N,N,N',N'-tetramethylurea
- DMF N,N-dimethylformamide
- the inorganic salt is added to increase a polymerization degree of the aromatic polyamide, and may include, for example, alkaline metal halide salts or alkali-earth metal halide salts such as CaCl 2 , LiCl, NaCl, KCl, LiBr and KBr, which are added alone or in combination of two or more thereof.
- alkaline metal halide salts or alkali-earth metal halide salts such as CaCl 2 , LiCl, NaCl, KCl, LiBr and KBr, which are added alone or in combination of two or more thereof.
- the inorganic salt is added in an amount of 2 to 5 wt.% to a weight of the organic solvent.
- terephthaloyl dichloride is added in the same molar amount as that of the aromatic diamine having a cyano group to the organic solvent containing aromatic diamine having a cyano group added and dissolved therein.
- the coloring matter having a cation is added to the organic solvent to prepare a polymerization solution containing a copolymerized aramid polymer.
- the coloring matter having a cation has the following representative structures, but it is not limited thereto.
- the coloring matter having a cation is added in an amount of 0.1 to 5 wt. % to a weight of the copolymerized aramid polymer. If the added amount is less than 0.1 wt.%, a color strength is weak, and if it exceeds 5 wt.%, physical properties of a fiber may be deteriorated.
- the cyano group (-CN) has strong electronegativity to thus exhibit a repulsive force from an anionic sulfone group of the coloring matter having an anion.
- the coloring matter having an anion could not be deposited on a polymer but be discharged along with the solvent, hence expressing a color in not a coloring level but a pollution level and having a considerably deterioration in the color strength, color fastness to light and color fastness to washing of the copolymerized aramid dope-dyed yarn.
- coloring matter having an anion examples are as follows.
- the copolymerized aramid dope-dyed yarn of the present invention may include any one of the above coloring matter having a cation alone or in combination of two or more thereof.
- the coloring matter having a cation may be a pigment having a cation, a dye having a cation, or a mixture of the pigment having a cation and the dye having a cation.
- the copolymerized aramid dope-dyed yarn manufactured by the method according to the present invention may include the coloring matter having a cation to thus have an excellent color strength of at least 50 and excellent color fastness to light and color fastness to washing of grade 4 to grade 5. Further, the copolymerized aramid polymer does not show a decrease in a polymerization degree, thus having a high strength of 28 to 35 g/d.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- Color strength and color fastness to light and washing of the manufactured copolymerized aramid dope-dyed yarn were evaluated, and results thereof are shown in Table 1.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid fiber.
- a basic dye prepared by adding 0.2 g of the above dyeing dye (C.I. Basic Red 22) in 100 ml of distilled water and 1.2 ml of glacial acetic acid, and dyed at 100°C for 1 hour, followed by washing and drying the same.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid fiber.
- a basic dye prepared by adding 0.2 g of the above dyeing dye (C.I. Basic Red 22) in 100 ml of distilled water and 1.2 ml of glacial acetic acid, and dyed at 100°C for 1 hour, followed by washing and drying the same.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- NMP N-methyl-2-pyrrolidone
- the multi-filament was washed and the washed multi-filament was dried and drawn by a dry roller set up at a temperature of 150°C.
- the drawn multi-filament was subjected to heat treatment and winding at 250°C, thereby fabricating a copolymerized aramid dope-dyed yarn.
- the color strength was determined by measuring the color according to KS K 0205. More particularly, the aramid fiber was densely wound around a small card with a dimension of 7.5 cm width and 6.5 cm length, then, a color of the aramid fiber was measured on a D65 light source at 10 degree of viewing angle using a spectrophotometer (Konica-Minolta CM-3600d). Herein, the measured value is an average value calculated from three values measured at different locations.
- Color fastness to light was measured according to 206KS K 0700, and a color change was determined based on a measurement of color change grades using a spectrophotometer KS K ISO 105-A05.
- Color fastness to washing was measured according to KS K ISO 105-C06, and a color change of a fabric material after testing was determined based on the measurement of color change grades using a spectrophotometer KS K ISO 105-A05.
- copolymerized aramid dope-dyed yarn according to the present invention may be usefully employed as a raw material for protective gloves or protective clothing.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyamides (AREA)
- Artificial Filaments (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20130166398 | 2013-12-30 | ||
| PCT/KR2014/012809 WO2015102297A1 (ko) | 2013-12-30 | 2014-12-24 | 공중합 아라미드 원착사 및 그의 제조방법 |
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| Publication Number | Publication Date |
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| EP3091107A1 EP3091107A1 (en) | 2016-11-09 |
| EP3091107A4 EP3091107A4 (en) | 2017-08-09 |
| EP3091107B1 true EP3091107B1 (en) | 2019-02-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP14877413.6A Active EP3091107B1 (en) | 2013-12-30 | 2014-12-24 | Copolymerized aramid dope-dyed yarn and method for preparing same |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20180195207A1 (ko) |
| EP (1) | EP3091107B1 (ko) |
| JP (1) | JP6185184B2 (ko) |
| KR (1) | KR102070137B1 (ko) |
| CN (1) | CN105899717B (ko) |
| BR (1) | BR112016015170B1 (ko) |
| WO (1) | WO2015102297A1 (ko) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108841199A (zh) * | 2018-05-31 | 2018-11-20 | 韩学民 | 一种酞菁蓝系列染料碱性蓝140的生产工艺 |
| CN109183179A (zh) * | 2018-09-19 | 2019-01-11 | 超美斯新材料（淮安）有限公司 | 一种间位芳纶有色纤维的制备方法 |
| CN109594177A (zh) * | 2019-02-22 | 2019-04-09 | 江苏工匠服饰科技有限公司 | 一种阻燃面料及其制备方法 |
| JP7342068B2 (ja) * | 2020-06-30 | 2023-09-11 | 住友化学株式会社 | 組成物 |
| CN112281244A (zh) * | 2020-11-23 | 2021-01-29 | 蓝星（成都）新材料有限公司 | 一种原液染色芳纶1414纤维的制备方法 |
| CN115821417A (zh) * | 2021-09-17 | 2023-03-21 | 中国石油化工股份有限公司 | 共聚自着色芳纶的制备方法及共聚自着色芳纶纤维 |
| CN116988184A (zh) * | 2023-07-21 | 2023-11-03 | 江苏新视界先进功能纤维创新中心有限公司 | 一种高分子着色方法、纺丝色浆、纺丝液及着色纤维 |
| CN117004018B (zh) * | 2023-08-22 | 2024-08-09 | 江苏新视界先进功能纤维创新中心有限公司 | 一种高分子着色方法、纺丝液及着色纤维 |
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| US4066396A (en) * | 1974-08-10 | 1978-01-03 | Bayer Aktiengesellschaft | Dyeing dry-spun aromatic polyamides |
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| JPS6016964B2 (ja) * | 1976-08-11 | 1985-04-30 | ユニチカ株式会社 | 塩基性染料親和性を有する芳香族ポリアミドの製造法 |
| US4705527A (en) * | 1986-05-14 | 1987-11-10 | Burlington Industries, Inc. | Process for the printing of shaped articles derived from aramid fibers |
| JPH01111014A (ja) * | 1987-10-21 | 1989-04-27 | Asahi Chem Ind Co Ltd | 染料含有ポリーパラフェニレンテレフタルアミド系繊維及びその製造法 |
| JPH01139814A (ja) * | 1987-11-27 | 1989-06-01 | Kuraray Co Ltd | 原着された全芳香族ポリアミド繊維とその製造法 |
| JP3696273B2 (ja) * | 1993-11-26 | 2005-09-14 | 帝人テクノプロダクツ株式会社 | 染色されたパラ系芳香族ポリアミド繊維の製造方法 |
| JP3450075B2 (ja) * | 1995-01-19 | 2003-09-22 | 帝人株式会社 | 吸湿寸法安定性アラミド繊維の製造方法 |
| KR0171994B1 (ko) | 1995-07-13 | 1999-03-30 | 구광시 | 방향족 폴리아미드, 광학적 이방성 도우프와 성형물, 및 이들의 제조방법 |
| JP2001336025A (ja) * | 2000-05-26 | 2001-12-07 | Du Pont Toray Co Ltd | 全芳香族ポリアミド繊維、染色された全芳香族ポリアミドおよびその製造方法 |
| CN1311128C (zh) * | 2002-02-13 | 2007-04-18 | 美国Basf公司 | 阳离子型染色纤维和含有该纤维的物品 |
| CN100422401C (zh) * | 2006-04-13 | 2008-10-01 | 烟台氨纶股份有限公司 | 原液着色间位芳纶短纤维及其制备方法 |
| US7528217B2 (en) * | 2006-10-06 | 2009-05-05 | E.I. Du Pont De Nemours And Company | Polymers and fibers formed therefrom |
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| KR100910537B1 (ko) | 2008-05-27 | 2009-07-31 | 주식회사 코오롱 | 아라미드 섬유의 제조방법 |
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| JP4804590B1 (ja) * | 2010-04-14 | 2011-11-02 | 帝人テクノプロダクツ株式会社 | メタ型全芳香族ポリアミド繊維 |
| WO2012055685A1 (en) * | 2010-10-28 | 2012-05-03 | Teijin Aramid B.V. | Spun-dyed aramid fibers |
| KR20120077714A (ko) * | 2010-12-31 | 2012-07-10 | 금오공과대학교 산학협력단 | 염색성이 향상된 메타 아라미드 성형물 및 이의 제조방법 |
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2014
- 2014-12-23 KR KR1020140187039A patent/KR102070137B1/ko active IP Right Grant
- 2014-12-24 WO PCT/KR2014/012809 patent/WO2015102297A1/ko active Application Filing
- 2014-12-24 EP EP14877413.6A patent/EP3091107B1/en active Active
- 2014-12-24 CN CN201480071976.6A patent/CN105899717B/zh active Active
- 2014-12-24 US US15/106,359 patent/US20180195207A1/en not_active Abandoned
- 2014-12-24 BR BR112016015170-4A patent/BR112016015170B1/pt active IP Right Grant
- 2014-12-24 JP JP2016544566A patent/JP6185184B2/ja active Active
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|---|---|---|---|---|
| US4066396A (en) * | 1974-08-10 | 1978-01-03 | Bayer Aktiengesellschaft | Dyeing dry-spun aromatic polyamides |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017504731A (ja) | 2017-02-09 |
| CN105899717B (zh) | 2018-01-19 |
| BR112016015170B1 (pt) | 2022-01-18 |
| KR102070137B1 (ko) | 2020-01-28 |
| KR20150079425A (ko) | 2015-07-08 |
| EP3091107A1 (en) | 2016-11-09 |
| US20180195207A1 (en) | 2018-07-12 |
| WO2015102297A1 (ko) | 2015-07-09 |
| EP3091107A4 (en) | 2017-08-09 |
| JP6185184B2 (ja) | 2017-08-23 |
| BR112016015170A2 (ko) | 2017-08-08 |
| CN105899717A (zh) | 2016-08-24 |
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