EP0790335B1 - Cut-resistant aramid fibres, yarns containing these fibres and their use - Google Patents
Cut-resistant aramid fibres, yarns containing these fibres and their use Download PDFInfo
- Publication number
- EP0790335B1 EP0790335B1 EP97101675A EP97101675A EP0790335B1 EP 0790335 B1 EP0790335 B1 EP 0790335B1 EP 97101675 A EP97101675 A EP 97101675A EP 97101675 A EP97101675 A EP 97101675A EP 0790335 B1 EP0790335 B1 EP 0790335B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phenylene
- mol
- structural repeat
- formula
- cut
- 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.)
- Expired - Lifetime
Links
- 229920003235 aromatic polyamide Polymers 0.000 title description 16
- 239000000835 fiber Substances 0.000 claims description 68
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 38
- 239000000945 filler Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- -1 methyl- Chemical group 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 claims description 2
- LNWWQYYLZVZXKS-UHFFFAOYSA-N 1-pyrrolidin-1-ylethanone Chemical compound CC(=O)N1CCCC1 LNWWQYYLZVZXKS-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 2
- 229910052914 metal silicate Inorganic materials 0.000 claims description 2
- GXMIHVHJTLPVKL-UHFFFAOYSA-N n,n,2-trimethylpropanamide Chemical compound CC(C)C(=O)N(C)C GXMIHVHJTLPVKL-UHFFFAOYSA-N 0.000 claims description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims 4
- KBRJTGNCPIFGFI-AATRIKPKSA-N (e)-n,n,n',n'-tetramethylbut-2-enediamide Chemical compound CN(C)C(=O)\C=C\C(=O)N(C)C KBRJTGNCPIFGFI-AATRIKPKSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims 1
- 239000004760 aramid Substances 0.000 description 14
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 11
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 6
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 6
- BIEJPBBEABOGMM-UHFFFAOYSA-N 2-[4-(2-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC=C1OC(C=C1)=CC=C1OC1=CC=CC=C1N BIEJPBBEABOGMM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 150000002843 nonmetals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/442—Cut or abrasion resistant yarns or threads
-
- 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
- D01F1/10—Other agents for modifying properties
-
- 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
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
- D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
- Y10T428/2969—Polyamide, polyimide or polyester
Definitions
- the present invention relates to aramid fibers having an improved Have cut resistance.
- fiber-forming polymers are commonly used Solids, such as titanium dioxide or colloidal quartz, added as a matting agent. Also, the addition of other solids, for example, to generate magnetic Properties are known per se. Examples thereof are disclosed in JP-A-55-098,909 or in JP-A-3-130,413. The use of such matting agents in solution-spun aramid fibers is not common practice.
- EP-A-599,231 discloses fibers containing liquid crystalline polymers, which are equipped with Mohs hardness fillers of at least 3. In This document also includes liquid-crystalline aromatic polyamides described as a fiber-forming material.
- Aromatic polyamides are known to be raw materials of high thermal and chemical stability and low flammability. For example, show Fibers and films of such raw materials very good mechanical properties, such as high strength and high initial modulus (Young's modulus) and are for technical applications well suited - for example, to reinforce Plastics or as filter materials.
- filaments or fibers of polyaramids with high strength and high initial modulus can be produced when the amide bonds to the aromatic cores are oriented coaxially or nearly parallel to each other, whereby rigid, rod-shaped polymer molecules are formed.
- a typical one Polyamide of this type is, for example, poly (p-phenylene terephthalamide).
- the present invention relates to cut-resistant fibers comprising a filler having a Mohs hardness of greater than or equal to 3 and as fiber-forming material an aromatic polyamide soluble in polar aprotic organic solvents comprising the recurring structural units of the formulas I, II and optionally IIa -OC-Ar 1 -CO-NH-Ar 2 -NH- -OC-Ar 1 -CO-NH-Ar 3 -NH -OC-Ar 1 -CO-NH-Ar 3a -NH wherein Ar 1 , Ar 2 , Ar 3 and Ar 3a independently represent a divalent mono- or polynuclear aromatic radical whose free valencies are in the para position or in the meta position or in a parallel, coaxial or angled position comparable to these positions to each other, and Accept, Ar 2, Ar 3 and optionally Ar 3a are in each case different meanings within the scope of the given definitions, and the respective underlying the polymer monomer units are selected so that an organic solvent-soluble and preferably iso
- the polymers to be used in the fibers according to the invention are Aramid, which is a significant proportion of para-aromatic monomers and soluble in polar aprotic organic solvents are.
- soluble aromatic polyamide is in the context of this invention to understand aromatic polyamide that at 25 ° C, a solubility in N-methylpyrrolidone of at least 50 g / l.
- the polar aprotic organic solvent contains at least an amide-type solvent, e.g. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-piperidone, N, N'-dimethylethyleneurea, N, N, N ', N'-tetramethylmaleic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N'-dimethylpropionamide, N, N-dimethylisobutylamide, N-methylformamide, N, N'-dimethyl propylene.
- an amide-type solvent e.g. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-piperidone, N, N'-dimethylethyleneurea, N, N, N '
- aromatic polyamides are compounds which are known in polar aprotic organic solvents preferably under the Training isotropic solutions are soluble and the least two, in particular three different recurring ones differing in the diamine units Having structural units according to the above definition.
- Any radicals are bivalent aromatic radicals whose Valence bonds are in para- or comparable coaxial or parallel Position to each other, so it is one or more nuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mononuclear or polynuclear.
- heterocyclic-aromatic radicals in particular, these have one or two oxygen, nitrogen or Sulfur atoms in the aromatic nucleus.
- Polynuclear aromatic radicals may be fused together or via C-C bonds or via -CO-NH- groups be linearly interconnected.
- valence bonds in coaxial or parallel position stand, are directed opposite.
- An example of coaxial, opposite directed bonds are the biphenyl-4,4'-ene bonds.
- An example of parallel, oppositely directed bonds are the naphthalene-1,5 or -2,6-bonds, while the naphthalene-1,8 bonds are rectified in parallel.
- Examples of preferred divalent aromatic radicals their valence bonds in para- or in a comparable coaxial or parallel position to each other are mononuclear aromatic radicals with each other para-free Valencies, in particular 1,4-phenylene or dinuclear fused aromatic Residues with parallel, oppositely directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or binuclear linked via a C-C bond aromatic residues with coaxial, oppositely directed bonds, in particular 4,4'-biphenylene.
- Any radicals are bivalent aromatic radicals whose Valence bonds in meta or in a comparable angled position to each other, so it is one or more polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mononuclear or polynuclear.
- heterocyclic-aromatic radicals in particular, these have one or two oxygen, nitrogen or Sulfur atoms in the aromatic nucleus.
- Polynuclear aromatic radicals may be condensed with one another or linked to one another via C-C bonds or via bridging groups, such as, for example, -O-, -CH 2 -, -S-, -CO- or -SO 2 .
- Examples of preferred divalent aromatic radicals, their valence bonds are in meta or in a comparable angled position to each other are mononuclear aromatic radicals with mutually meta-free valences, in particular 1,3-phenylene or binuclear condensed aromatic radicals with mutually angled bonds, in particular 1,6- and 2,7-naphthylene, or binuclear aromatic residues linked via a C-C bond with mutually angled bonds, in particular 3,4'-biphenylene.
- Lower proportions, for example up to 5 mol% of the monomer units, based to the polymer, may be aliphatic or cycloaliphatic nature, For example, represent alkylene or cycloalkylene units.
- alkylene radicals is branched and in particular straight-chain alkylene to for example, alkylene having two to four carbon atoms, especially ethylene.
- cycloalkylene radicals are radicals having from five to eight To understand carbon atoms, in particular cyclohexylene.
- substituents are alkyl, alkoxy or halogen.
- Alkyl radicals include branched and in particular straight-chain alkyl For example, alkyl having one to six carbon atoms, in particular Methyl.
- Alkoxy radicals include branched and in particular straight-chain alkoxy for example, alkoxy of one to six carbon atoms, especially methoxy.
- radicals halogen it is, for example, to Fluorine, bromine or especially chlorine.
- dicarboxylic acid unit in the aromatic polyamides containing the recurring structural units of the formulas I, II and optionally III sets preferably terephthalic acid units.
- the preferred cut-resistant fibers employ particularly aromatic copolyamides containing the recurring structural units of formulas III and IV or of formulas III and VI or of formulas III, IV and V or of formulas III, IV and VI or of formulas IV, V and VI contain -OC-Ar 1 -CO-NH-Ar 4 -NH- -OC-Ar 1 -CO-NH-Ar 5 -Q-Ar 6 -NH- -OC-Ar 1 -CO-NH-Ar 7 -Y-Ar 8 -NH- in which Ar 1 and Ar 4, independently of one another, represent a divalent mononuclear or polynuclear aromatic radical whose free valences are in the para position or in a parallel or coaxial position comparable to this position, in particular mononuclear or binuclear aromatic radicals, Ar 5 and Ar 6 independently represent a divalent mononuclear or polynuclear aromatic radical whose free valences are in the para position or in a position comparable to this position
- Examples of preferred diamine combinations that have these preferred repeating structural units of the formulas III and IV or of the formulas III and VI or Formulas III, IV and V or Formulas III, IV and VI, are 1,4-phenylenediamine and 3,4'-diaminodiphenyl ether; 1,4-phenylenediamine, 4,4'-diaminodiphenylmethane and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; and 1,4-phenylenediamine, 1,4-bis (aminophenoxy) benzene and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; and 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; and 1,4-phenylenediamine, 3,4'-d
- Aramids derived from such combinations of diamines and preferred according to the present invention are disclosed in part in EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP-A-424,860 described.
- aromatic polyamides to be used according to the invention are per se known.
- the polycondensation and the production of fibers from the invention coaramides to be used is carried out according to methods known per se, such as these e.g. have been described in the above-mentioned writings.
- the meddling of the filler and the production of filler-containing fibers, for example take place according to the method described in EP-A-662,534.
- the aromatic copolyaramides to be used according to the invention must be suitable for the fiber production have sufficient molecular weight.
- a sufficient molecular chain length of the invention to be used Copolyaramide is present, for example, when the viscosity of the at Polycondensation obtained polymer solution of an inherent viscosity of the Polymer of more than 2.5 dl / g, preferably 2.5 to 7.0 dl / g corresponds.
- ⁇ rel means the relative viscosity, c the applied concentration in g / 100 ml.
- the filler used in the fibers of the present invention has all generally a Mohs hardness of greater than or equal to 3, preferably greater than or equal to 5 on.
- fillers can be used any materials, ie semi-metals or preferably metals or non-metals and alloys of these materials, if they have the above-defined hardness.
- Preferably used metals are, for example, aluminum, iron, nickel, stainless steel, copper, zinc, tantalum, titanium, tungsten or mixtures thereof.
- metal alloys with tungsten as Alloy component having a Mohs hardness of 6.5 to 7.5.
- non-metals are, for example, metal oxides, such as alumina; Metal carbides, such as tungsten carbide; Metal nitrides, metal silicates, Metal sulfates, metal phosphates, metal borides or mixtures thereof. Furthermore it is also possible to use ceramic materials.
- the proportion of the filler in the fiber according to the invention is in any case so Choose the cut resistance in comparison with the unmodified fiber is increased, for example by at least more than 8% (measured after the CPP) test. Surprisingly, the remaining mechanical properties the fibers, such as tensile strength or modulus, through the use of the filler only insignificantly impaired. For example, the tensile strength of a filled decreases Fiber with increased cut resistance to about 205 cN / tex, compared to the Tensile strength of about 215 cN / tex of unfilled fiber.
- Typical amounts of filler are in the range of less than 25% by weight. based on the weight of the fiber, preferably in the range of 0.05 to 20 Wt.%.
- the particle shape of the filler used can be arbitrary; for example, spherical or elliptical or irregular.
- the filler will for example, mixed in the form of a powder.
- the filler has an average particle diameter of smaller equal to 20 microns, in particular from 0.05 to 5 microns.
- fibers is in its broadest meaning in the context of this invention to understand; This includes, for example, staple fibers or in particular Filaments of any denier, including monofilaments.
- the fibers according to the invention are distinguished by excellent mechanical properties Properties such as high tensile strength and initial moduli and low Elongation at break, as well as by the above-mentioned increased cut resistance.
- the fibers of the invention preferably have single filament titres of greater equal to 0.6 dtex, in particular from 1 to 20 dtex, on.
- the tensile strength of the fibers of the invention is preferably 150 to 300 cN / tex.
- the initial modulus, based on 100% elongation, of the fibers according to the invention is preferably 20 to 120 N / tex.
- the cross-sectional shape of the fibers according to the invention can be arbitrary, for example triangular, tri- or multilobal or in particular elliptical or round.
- the fibers according to the invention can be used for the production of protective clothing, Use anti-vandal textiles and composites.
- the use of Fibers for these purposes is also an object of the present invention.
- the fibers of the invention are generally in the form of yarns used. These may be secondary spun yarns or preferably to act multifilament yarns. Typical yarn titers are in the range of 50 up to 9000 dtex.
- Yarns containing the fibers of the invention are also an article of the present invention.
- a preferred embodiment relates to blended yarns containing the Fibers and fibers of inorganic materials, such as glass, according to the invention, Boron, carbon, metals or ceramic materials. Such blended yarns are characterized by a further increased cutting resistance.
- a fiber consisting of an aromatic copolyamide derived from terephthaloyl chloride, 50 mole% 3,3'-dimethylbenzidine, 25 mole% p-phenylenediamine and 25 mole% 1,4-bis (4-aminophenoxy) benzene and 0.5 wt% alumina was compared in terms of tensile strength and cut resistance with an unfilled fiber of the same aromatic copolyamide. The following values were determined: Cut resistance (CPP test) Grams per cm 2 [Ounce per squ. yard] tensile strenght CN / tex unfilled fiber 0.33 (96) 212 filled fiber 0.37 (110) 203
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Description
Die vorliegende Erfindung betrifft Aramidfasern, die eine verbesserte Schnittresistenz aufweisen.The present invention relates to aramid fibers having an improved Have cut resistance.
Beim Schmelzspinnen werden faserbildendenden Polymeren üblicherweise Feststoffe, wie Titandioxid oder kolloider Quarz, als Mattierungsmittel beigemischt. Auch der Zusatz anderer Feststoffe, beispielsweise zum Erzeugen magnetischer Eigenschaften ist an sich bekannt. Beispiele dafür sind in der JP-A-55-098,909 oder in der JP-A-3-130,413 zu finden. Der Einsatz derartiger Mattierungsmittel in lösungsgesponnenen Aramidfasern ist bislang nicht üblich.In melt spinning, fiber-forming polymers are commonly used Solids, such as titanium dioxide or colloidal quartz, added as a matting agent. Also, the addition of other solids, for example, to generate magnetic Properties are known per se. Examples thereof are disclosed in JP-A-55-098,909 or in JP-A-3-130,413. The use of such matting agents in solution-spun aramid fibers is not common practice.
Der Zusatz von Metallen bei der Herstellung von Schutzbekleidung ist ebenfalls bereits beschrieben worden. Derartige Produkte werden z.B. in den US-A-2,328,105 oder US-A-5,020,161 offenbart.The addition of metals in the manufacture of protective clothing is also already described. Such products are e.g. in US-A-2,328,105 or US-A-5,020,161.
Schnittresistente Handschuhe wurden ebenfalls bereits beschrieben. Aus den US-A-4,004,295, -4,384,449, -4,470,251 und aus der EP-A-458,343 sind Handschuhe bekannt, die aus hochfesten Fasern bestehen oder die aus Garnen enthaltend Metalldrähte hergestellt worden sind.Cut Resistant Gloves have also been previously described. From US-A-4,004,295, -4,384,449, -4,470,251 and EP-A-458,343 are gloves known, which consist of high-strength fibers or containing from yarns Metal wires have been produced.
Aus der EP-A-599,231 sind Fasern enthaltend flüssigkristalline Polymere bekannt, die mit Füllstoffen einer Härte nach Mohs von wenigstens 3 ausgerüstet sind. In dieser Schrift werden unter anderem auch flüssigkristalline aromatische Polyamide als faserbildendes Material beschrieben.EP-A-599,231 discloses fibers containing liquid crystalline polymers, which are equipped with Mohs hardness fillers of at least 3. In This document also includes liquid-crystalline aromatic polyamides described as a fiber-forming material.
Aromatische Polyamide (Aramide) sind bekanntlich Rohstoffe von hoher thermischer und chemischer Stabilität sowie geringer Brennbarkeit. So zeigen beispielsweise Fasern und Folien aus solchen Rohstoffen sehr gute mechanische Eigenschaften, wie hohe Festigkeit und hohen Anfangsmodul (Elastizitätsmodul) und sind für technische Einsatzgebiete gut geeignet - beispielsweise zur Verstärkung von Kunststoffen oder als Filtermaterialien.Aromatic polyamides (aramids) are known to be raw materials of high thermal and chemical stability and low flammability. For example, show Fibers and films of such raw materials very good mechanical properties, such as high strength and high initial modulus (Young's modulus) and are for technical applications well suited - for example, to reinforce Plastics or as filter materials.
Es ist bekannt, daß Fäden oder Fasern aus Polyaramiden mit hoher Festigkeit und hohem Anfangsmodul hergestellt werden können, wenn die Amidbindungen an den aromatischen Kernen koaxial oder nahezu parallel zueinander orientiert sind, wodurch starre, stäbchenförmige Polymermoleküle entstehen. Ein typisches Polyamid dieser Art ist beispielsweise Poly-(p-phenylenterephthalamid).It is known that filaments or fibers of polyaramids with high strength and high initial modulus can be produced when the amide bonds to the aromatic cores are oriented coaxially or nearly parallel to each other, whereby rigid, rod-shaped polymer molecules are formed. A typical one Polyamide of this type is, for example, poly (p-phenylene terephthalamide).
Neben derartigen aromatischen Polyamiden, die infolge ihrer Unlöslichkeit in polaren organischen Lösungsmitteln schwierig herzustellen und zu verarbeiten sind, wurden Copolyamide entwickelt, welche eine gute Löslichkeit in den bekannten Amid-Lösungsmitteln haben, die sich auch gut verspinnen lassen und deren Filamente sich nach Verstreckung durch hohe Festigkeitswerte und Anfangsmoduli auszeichnen. Beispiele für derartige aromatische Copolyamide finden sich in der DE-PS-2,556,883, in der DE-A-3,007,063, und in den EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 und EP-A-424,860 beschrieben.In addition to such aromatic polyamides, due to their insolubility in polar organic solvents are difficult to prepare and process, Copolyamides were developed, which have a good solubility in the known Have amide solvents that can be well spin and their Filaments stretch after high strength values and initial moduli distinguished. Examples of such aromatic copolyamides can be found in the DE-PS-2,556,883, in DE-A-3,007,063, and in EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP-A-424,860.
Es wurde jetzt gefunden, daß die schon von Haus aus gute Schnittresistenz von Fasern aus derartigen Copolyamiden noch erheblich und über das erwartete Maß hinausgehend verbessert werden kann. Die Schnittresistenz derartiger Fasern, ermittelt nach der sogenannten Cut Protection Performance Test (CCP-Test), liegt üblicherweise mehr als ca. 8 % über derjenigen von Fasern aus unlöslichen Amiden.It has now been found that the already good cut resistance of Fibers from such copolyamides still significantly and beyond the expected level can be improved beyond. The cut resistance of such fibers, determined according to the so-called Cut Protection Performance Test (CCP test), is usually more than about 8% higher than that of insoluble fibers Amides.
Die vorliegende Erfindung betrifft schnittresistente Fasern enthaltend einen Füllstoff
mit einer Härte nach Mohs von größer gleich 3 und als faserbildendes Material ein
in polaren aprotischen organischen Lösungsmitteln lösliches aromatisches Polyamid
enthaltend die wiederkehrenden Struktureinheiten der Formeln I, II und
gegebenenfalls IIa
Ar2, Ar3 und gegebenenfalls Ar3a im Einzelfall jeweils unterschiedliche im Rahmen
der gegebenen Definitionen liegende Bedeutungen annehmen, und wobei die
jeweiligen dem Polymeren zugrundeliegenden Monomerbausteine so ausgewählt
werden, daß sich ein in organischen Lösungsmitteln lösliches und vorzugsweise
isotrope Lösungen bildendes aromatisches Polyamid ergibt.The present invention relates to cut-resistant fibers comprising a filler having a Mohs hardness of greater than or equal to 3 and as fiber-forming material an aromatic polyamide soluble in polar aprotic organic solvents comprising the recurring structural units of the formulas I, II and optionally IIa
Accept, Ar 2, Ar 3 and optionally Ar 3a are in each case different meanings within the scope of the given definitions, and the respective underlying the polymer monomer units are selected so that an organic solvent-soluble and preferably isotropic solutions forming aromatic polyamide is obtained.
Bei den in den erfindungsgemäßen Fasern einzusetzenden Polymeren handelt es sich um Aramide, die zu einem wesentlichen Anteil para-aromatischen Monomeren aufgebaut sind, und die in polaren aprotischen organischen Lösungsmitteln löslich sind.The polymers to be used in the fibers according to the invention are Aramid, which is a significant proportion of para-aromatic monomers and soluble in polar aprotic organic solvents are.
Unter löslichem aromatischen Polyamid ist im Rahmen dieser Erfindung ein aromatisches Polyamid zu verstehen, daß bei 25°C eine Löslichkeit in N-Methylpyrrolidon von mindestens 50 g/l aufweist.Among soluble aromatic polyamide is in the context of this invention to understand aromatic polyamide that at 25 ° C, a solubility in N-methylpyrrolidone of at least 50 g / l.
Vorzugsweise enthält das polare aprotische organische Lösungsmittel zumindest ein Lösungsmittel vom Amidtyp, wie z.B. N-Methyl-2-pyrrolidon, N,N-Dimethylacetamid, Tetramethylharnstoff, N-Methyl-2-piperidon, N,N'-Dimethylethylenharnstoff, N,N,N',N'-Tetramethylmaleinsäureamid, N-Methylcaprolactam, N-Acetylpyrrolidin, N,N-Diethylacetamid, N-Ethyl-2-pyrrolidon, N,N'-Dimethylpropionsäureamid, N,N-Dimethylisobutylamid, N-Methylformamid, N,N'-Dimethylpropylenharnstoff. Für das erfindungsgemäße Verfahren sind die bevorzugten organischen Lösungsmittel N-Methyl-2-pyrrolidon, N,N-Dimethylacetamid und eine Mischung dieser Verbindungen. Preferably, the polar aprotic organic solvent contains at least an amide-type solvent, e.g. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, tetramethylurea, N-methyl-2-piperidone, N, N'-dimethylethyleneurea, N, N, N ', N'-tetramethylmaleic acid amide, N-methylcaprolactam, N-acetylpyrrolidine, N, N-diethylacetamide, N-ethyl-2-pyrrolidone, N, N'-dimethylpropionamide, N, N-dimethylisobutylamide, N-methylformamide, N, N'-dimethyl propylene. For the inventive method are the preferred organic solvent N-methyl-2-pyrrolidone, N, N-dimethylacetamide and a mixture of these compounds.
Bei den erfindungsgemäß einzusetzenden aromatischen Polyamiden (im folgenden auch aromatische Copolyamide genannt) handelt es sich um Verbindungen, die in polaren aprotischen organischen Lösungsmitteln vorzugsweise unter der Ausbildung isotroper Lösungen löslich sind und die mindestens zwei, insbesondere drei verschiedene sich in den Diamineinheiten unterscheidende wiederkehrende Struktureinheiten gemäß der obigen Definition aufweisen.In the invention to be used aromatic polyamides (hereinafter also called aromatic copolyamides) are compounds which are known in polar aprotic organic solvents preferably under the Training isotropic solutions are soluble and the least two, in particular three different recurring ones differing in the diamine units Having structural units according to the above definition.
Bedeuten irgendwelche Reste zweiwertige aromatische Reste, deren Valenzbindungen sich in para- oder in vergleichbarer koaxialer oder paralleler Position zueinander befinden, so handelt es sich dabei um ein- oder mehrkernige aromatische Kohlenwasserstoffreste oder um heterocyclisch-aromatische Reste, die ein- oder mehrkernig sein können. Im Falle von heterocyclisch-aromatischen Resten weisen diese insbesondere ein oder zwei Sauerstoff-, Stickstoff- oder Schwefelatome im aromatischen Kern auf.Any radicals are bivalent aromatic radicals whose Valence bonds are in para- or comparable coaxial or parallel Position to each other, so it is one or more nuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mononuclear or polynuclear. In the case of heterocyclic-aromatic radicals in particular, these have one or two oxygen, nitrogen or Sulfur atoms in the aromatic nucleus.
Mehrkernige aromatische Reste können miteinander kondensiert sein oder über C-C-Bindungen oder über -CO-NH- Gruppen linear miteinander verbunden sein.Polynuclear aromatic radicals may be fused together or via C-C bonds or via -CO-NH- groups be linearly interconnected.
Die Valenzbindungen, die in koaxialer oder parallel zueinander befindlicher Stellung stehen, sind entgegengesetzt gerichtet. Ein Beispiel für koaxiale, entgegengesetzt gerichtete Bindungen sind die Biphenyl-4,4'-en-Bindungen. Ein Beispiel für parallel, entgegegesetzt gerichtete Bindungen sind die Naphthalin-1,5- oder -2,6-Bindungen, während die Naphthalin-1,8-Bindungen parallel gleichgerichtet sind.The valence bonds in coaxial or parallel position stand, are directed opposite. An example of coaxial, opposite directed bonds are the biphenyl-4,4'-ene bonds. An example of parallel, oppositely directed bonds are the naphthalene-1,5 or -2,6-bonds, while the naphthalene-1,8 bonds are rectified in parallel.
Beispiele für bevorzugte zweiwertige aromatische Reste, deren Valenzbindungen sich in para- oder in vergleichbarer koaxialer oder paralleler Position zueinander befinden, sind einkernige aromatische Reste mit zueinander para-ständigen freien Valenzen, insbesondere 1,4-Phenylen oder zweikernige kondensierte aromatische Reste mit parallelen, entgegengesetzt gerichteten Bindungen, insbesondere 1,4-, 1,5- und 2,6-Naphthylen, oder zweikernige über eine C-C Bindung verknüpfte aromatische Reste mit koaxialen, entgegengesetzt gerichteten Bindungen, insbesondere 4,4'-Biphenylen. Examples of preferred divalent aromatic radicals, their valence bonds in para- or in a comparable coaxial or parallel position to each other are mononuclear aromatic radicals with each other para-free Valencies, in particular 1,4-phenylene or dinuclear fused aromatic Residues with parallel, oppositely directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or binuclear linked via a C-C bond aromatic residues with coaxial, oppositely directed bonds, in particular 4,4'-biphenylene.
Bedeuten irgendwelche Reste zweiwertige aromatische Reste, deren Valenzbindungen sich in meta- oder in vergleichbarer gewinkelter Position zueinander befinden, so handelt es sich dabei um ein- oder mehrkernige aromatische Kohlenwasserstoffreste oder um heterocyclisch-aromatische Reste, die ein- oder mehrkernig sein können. Im Falle von heterocyclisch-aromatischen Resten weisen diese insbesondere ein oder zwei Sauerstoff-, Stickstoff- oder Schwefelatome im aromatischen Kern auf.Any radicals are bivalent aromatic radicals whose Valence bonds in meta or in a comparable angled position to each other, so it is one or more polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mononuclear or polynuclear. In the case of heterocyclic-aromatic radicals in particular, these have one or two oxygen, nitrogen or Sulfur atoms in the aromatic nucleus.
Mehrkernige aromatische Reste können miteinander kondensiert sein oder über C-C-Bindungen oder über Brückengruppen, wie z.B. -O-, -CH2-, -S-, -CO- oder -SO2miteinander verbunden sein.Polynuclear aromatic radicals may be condensed with one another or linked to one another via C-C bonds or via bridging groups, such as, for example, -O-, -CH 2 -, -S-, -CO- or -SO 2 .
Beispiele für bevorzugte zweiwertige aromatische Reste, deren Valenzbindungen sich in meta- oder in vergleichbarer gewinkelter Position zueinander befinden, sind einkernige aromatische Reste mit zueinander meta-ständigen freien Valenzen, insbesondere 1,3-Phenylen oder zweikernige kondensierte aromatische Reste mit zueinander gewinkelt gerichteten Bindungen, insbesondere 1,6- und 2,7-Naphthylen, oder zweikernige über eine C-C Bindung verknüpfte aromatische Reste mit zueinander gewinkelt gerichteten Bindungen, insbesondere 3,4'-Biphenylen.Examples of preferred divalent aromatic radicals, their valence bonds are in meta or in a comparable angled position to each other are mononuclear aromatic radicals with mutually meta-free valences, in particular 1,3-phenylene or binuclear condensed aromatic radicals with mutually angled bonds, in particular 1,6- and 2,7-naphthylene, or binuclear aromatic residues linked via a C-C bond with mutually angled bonds, in particular 3,4'-biphenylene.
Geringere Anteile, beispielsweise bis zu 5 Mol % der Monomereinheiten, bezogen auf das Polymere, können aliphatischer oder cycloaliphatischer Natur sein, beispielsweise Alkylen- oder Cycloalkyleneinheiten darstellen.Lower proportions, for example up to 5 mol% of the monomer units, based to the polymer, may be aliphatic or cycloaliphatic nature, For example, represent alkylene or cycloalkylene units.
Unter Alkylenresten ist verzweigtes und insbesondere geradkettiges Alkylen zu verstehen, beispielsweise Alkylen mit zwei bis vier Kohlenstoffatomen, insbesondere Ethylen.Among alkylene radicals is branched and in particular straight-chain alkylene to for example, alkylene having two to four carbon atoms, especially ethylene.
Unter Cycloalkylenresten sind beispielsweise Reste mit fünf bis acht Kohlenstoffatomen zu verstehen, insbesondere Cyclohexylen.Examples of cycloalkylene radicals are radicals having from five to eight To understand carbon atoms, in particular cyclohexylene.
Alle diese aliphatischen, cycloaliphatischen oder aromatischen Reste können mit inerten Gruppen substituiert sein. Darunter sind Substituenten zu verstehen, die die ins Auge gefaßte Anwendung nicht negativ beeinflussen.All of these aliphatic, cycloaliphatic or aromatic radicals can with substituted in inert groups. These are to be understood as meaning substituents which the do not adversely affect the intended application.
Beispiele für solche Substituenten sind Alkyl, Alkoxy oder Halogen.Examples of such substituents are alkyl, alkoxy or halogen.
Unter Alkylresten ist verzweigtes und insbesondere geradkettiges Alkyl zu verstehen, beispielsweise Alkyl mit ein bis sechs Kohlenstoffatomen, insbesondere Methyl.Alkyl radicals include branched and in particular straight-chain alkyl For example, alkyl having one to six carbon atoms, in particular Methyl.
Unter Alkoxyresten ist verzweigtes und insbesondere geradkettiges Alkoxy zu verstehen, beispielsweise Alkoxy mit ein bis sechs Kohlenstoffatomen, insbesondere Methoxy.Alkoxy radicals include branched and in particular straight-chain alkoxy for example, alkoxy of one to six carbon atoms, especially methoxy.
Bedeuten irgendwelche Reste Halogen, so handelt es sich dabei beispielsweise um Fluor, Brom oder insbesondere um Chlor.If any radicals halogen, it is, for example, to Fluorine, bromine or especially chlorine.
Bevorzugt verwendet aromatische Polyamide auf der Basis von unsubstituierten Resten.Preferably used aromatic polyamides based on unsubstituted Residues.
Als Dicarbonsäureeinheit in den aromatischen Polyamiden enthaltend die wiederkehrenden Struktureinheiten der Formeln I, II und gegebenenfalls III setzt man vorzugsweise Terephthalsäureeinheiten ein.As the dicarboxylic acid unit in the aromatic polyamides containing the recurring structural units of the formulas I, II and optionally III sets preferably terephthalic acid units.
In den bevorzugten schnittresistenten Fasern werden besonders aromatische
Copolyamide eingesetzt, die die wiederkehrenden Struktureinheiten der Formeln III
und IV oder der Formeln III und VI oder der Formeln III, IV und V oder der Formeln
III, IV und VI oder der Formeln IV, V und VI enthalten
Ar5 und Ar6 unabhängig voneinander einen zweiwertigen ein- oder mehrkernigen
aromatischen Rest darstellen, dessen freie Valenzen sich in para-Stellung oder in
einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung
zueinander befinden, oder worin Ar6 zusätzlich einen zweiwertigen ein- oder
mehrkernigen aromatischen Rest darstellen kann, dessen freie Valenzen sich in
meta-Stellung oder in einer zu dieser Stellung vergleichbaren gewinkelten Stellung
zueinander befinden,
Q eine direkte C-C-Bindung oder eine Gruppe der Formel -O-, -S-, -SO2-, -O-Phenylen-O-
oder Alkylen ist,
Ar7 und Ar8 eine der für Ar5 und Ar6 definierten Bedeutungen annehmen,
Y eine der für Q definierten Bedeutungen annimmt oder zusätzlich eine Gruppe der
Formel -HN-CO- bedeuten kann, und
X eine Gruppe der Formel -O-, -S- oder insbesondere -NR1- bedeutet, worin R1
Alkyl, Cycloalkyl, Aryl, Aralkyl oder insbesondere Wasserstoff ist.The preferred cut-resistant fibers employ particularly aromatic copolyamides containing the recurring structural units of formulas III and IV or of formulas III and VI or of formulas III, IV and V or of formulas III, IV and VI or of formulas IV, V and VI contain
Ar 5 and Ar 6 independently represent a divalent mononuclear or polynuclear aromatic radical whose free valences are in the para position or in a position comparable to this position parallel or coaxial position to each other, or wherein Ar 6 additionally a divalent mononuclear or polynuclear may represent an aromatic radical whose free valences are in the meta position or in an angular position comparable to this position relative to one another,
Q is a direct CC bond or a group of the formula -O-, -S-, -SO 2 -, -O-phenylene-O- or alkylene,
Ar 7 and Ar 8 assume one of the meanings defined for Ar 5 and Ar 6 ,
Y assumes one of the meanings defined for Q or additionally may denote a group of the formula -HN-CO-, and
X represents a group of the formula -O-, -S- or especially -NR 1 -, wherein R 1 is alkyl, cycloalkyl, aryl, aralkyl or especially hydrogen.
Besonders bevorzugt werden schnittresistente Fasern enthaltend aromatische
Copolyamide mit den wiederkehrenden Struktureinheiten der Formeln III, IV und V,
worin Ar1 1,4-Phenylen ist, Ar4 1,4-Phenylen oder ein zweiwertiger Rest des 4,4'-Diaminobenzanilids
ist, Ar5, Ar6 und Ar7 1,4-Phenylen darstellen, Ar8 1,3-Phenylen
bedeutet, Q -O-1,4-Phenylen-O- ist und Y -O- ist; dabei werden diejenigen
aromatischen Copolyamide besonders bevorzugt eingesetzt, bei denen sich die
Mengenanteile der wiederkehrenden Struktureinheiten der Formeln III, IV und V sich
innerhalb folgender Bereiche, bezogen auf die Gesamtmenge dieser
Struktureinheiten, bewegen:
Ebenfalls besonders bevorzugt werden schnittresistente Fasern enthaltend
aromatische Copolyamide mit den wiederkehrenden Struktureinheiten der Formeln
III, IV und V, worin Ar1 1,4-Phenylen ist, Ar4 1,4-Phenylen oder ein zweiwertiger
Rest des 4,4'-Diaminobenzanilids ist, Ar5 und Ar6 1,4-Phenylen darstellen, Ar7 und
Ar8 methyl-, methoxy- oder chlorsubstituiertens 1,4-Phenylen bedeuten, Q -O-1,4-Phenylen-O-
ist und Y eine direkte C-C-Bindung ist; dabei werden diejenigen
aromatischen Copolyamide besonders bevorzugt eingesetzt, bei denen sich die
Mengenanteile der wiederkehrenden Struktureinheiten der Formeln III, IV und V sich
innerhalb folgender Bereiche, bezogen auf die Gesamtmenge dieser
Struktureinheiten, bewegen:
Ebenfalls besonders bevorzugt werden schnittresistente Fasern enthaltend
aromatische Copolyamide mit den wiederkehrenden Struktureinheiten der Formeln
III, IV und V, worin Ar1 1,4-Phenylen ist, Ar4 1,4-Phenylen oder ein zweiwertiger
Rest des 4,4'-Diaminobenzanilids ist, Ar5 und Ar6 1,4-Phenylen darstellen, Ar7 und
Ar8 methyl-, methoxy- oder chlorsubstituiertens 1,4-Phenylen bedeuten, Q -O- ist
und Y eine direkte C-C-Bindung ist; dabei werden diejenigen aromatischen
Copolyamide besonders bevorzugt eingesetzt, bei denen sich die Mengenanteile
der wiederkehrenden Struktureinheiten der Formeln III, IV und V sich innerhalb
folgender Bereiche, bezogen auf die Gesamtmenge dieser Struktureinheiten,
bewegen:
Ebenfalls besonders bevorzugt werden schnittresistente Fasern enthaltend
aromatische Copolyamide mit den wiederkehrenden Struktureinheiten der Formeln
III und IV, worin Ar1 1,4-Phenylen ist, Ar4 1,4-Phenylen oder ein zweiwertiger Rest
des 4,4'-Diaminobenzanilids ist, Ar5 1,4-Phenylen ist, Ar6 1,3-Phenylen ist und Q -
O- ist; dabei werden diejenigen aromatischen Copolyamide besonders bevorzugt
eingesetzt, bei denen sich die Mengenanteile der wiederkehrenden
Struktureinheiten der Formeln III und IV sich innerhalb folgender Bereiche, bezogen
auf die Gesamtmenge dieser Struktureinheiten, bewegen:
Ebenfalls besonders bevorzugt werden schnittresistente Fasern enthaltend
aromatische Copolyamide mit den wiederkehrenden Struktureinheiten der Formeln
III und VI, worin Ar1 1,4-Phenylen ist, Ar4 1,4-Phenylen oder ein zweiwertiger Rest
des 4,4'-Diaminobenzanilids ist und X -NH- bedeutet; dabei werden diejenigen
aromatischen Copolyamide besonders bevorzugt eingesetzt, bei denen sich die
Mengenanteile der wiederkehrenden Struktureinheiten der Formeln III und VI sich
innerhalb folgender Bereiche, bezogen auf die Gesamtmenge dieser
Struktureinheiten, bewegen:
Ebenfalls besonders bevorzugt werden schnittresistente Fasern enthaltend
aromatische Copolyamide mit den wiederkehrenden Struktureinheiten der Formeln
III, IV und VI, worin Ar1 1,4-Phenylen ist, Ar4 1,4-Phenylen oder ein zweiwertiger
Rest des 4,4'-Diaminobenzanilids ist, Ar5 1,4-Phenylen ist, Ar6 1,4- oder 1,3-Phenylen
ist, Q -O- oder -O-1,4-Phenylen-O- bedeutet und X -NH- ist; dabei werden
diejenigen aromatischen Copolyamide besonders bevorzugt eingesetzt, bei denen
sich die Mengenanteile der wiederkehrenden Struktureinheiten der Formeln III, IV
und VI sich innerhalb folgender Bereiche, bezogen auf die Gesamtmenge dieser
Struktureinheiten, bewegen:
Ebenfalls besonders bevorzugt werden schnittresistente Fasern enthaltend
aromatische Copolyamide mit den wiederkehrenden Struktureinheiten der Formeln
IV, V und VI, worin Ar1 1,4-Phenylen ist, Ar5 1,4-Phenylen ist, Ar6 1,4- oder 1,3-Phenylen
ist, Q -O- oder -O-1,4-Phenylen-O- bedeutet, Ar7 und Ar8 methyl-,
methoxy- oder chlorsubstituiertes 1,4-Phenylen ist, Y eine direkte C-C-Bindung
bedeutet und X -NH- ist; dabei werden diejenigen aromatischen Copolyamide
besonders bevorzugt eingesetzt, bei denen sich die Mengenanteile der
wiederkehrenden Struktureinheiten der Formeln IV, V und VI sich innerhalb
folgender Bereiche, bezogen auf die Gesamtmenge dieser Struktureinheiten,
bewegen:
Beispiele für bevorzugte Diaminkombinationen, die diesen bevorzugten wiederkehrenden Struktureinheiten der Formeln III und IV oder der Formeln III und VI oder der Formeln III, IV und V oder der Formeln III, IV und VI zugrundeliegen, sind 1,4-Phenylendiamin und 3,4'-Diaminodiphenylether; 1,4-Phenylendiamin, 4,4'-Diaminodiphenylmethan und 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin; sowie 1,4-Phenylendiamin, 1,4-Bis-(aminophenoxy)-benzol und 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin; sowie 1,4-Phenylendiamin, 3,4'-Diaminodiphenylether und 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin; sowie 1,4-Phenylendiamin, 3,4'-Diaminodiphenylether und 4,4'-Diaminobenzanilid; sowie 1,4-Phenylendiamin, 1,4-Bis-(aminophenoxy)-benzol und 3,4'-Diaminodiphenylether; sowie 1,4-Phenylendiamin und 5(6)-Amino-2-(para-aminophenyl)-benzimidazol; sowie 1,4-Phenylendiamin, 5(6)-Amino-2-(para-aminophenyl)-benzimidazol und 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin; sowie 1,4-Phenylendiamin, 5(6)-Amino-2-(para-aminophenyl)-benzimidazol und 3,4'-Diaminodiphenylether; sowie 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin, 5(6)-Amino-2-(para-aminophenyl)-benzimidazol und 1,4-Bis-(aminophenoxy)-benzol; sowie 5(6)-Amino-2-(para-aminophenyl)-benzimidazol, 3,3'-Dichlor-, 3,3'-Dimethyl- oder 3,3'-Dimethoxybenzidin und 3,4'-Diaminodiphenylether; sowie 1,4-Phenylendiamin, 5(6)-Amino-2-(para-aminophenyl)-benzimidazol und 1,4-Bis-(aminophenoxy)-benzol.Examples of preferred diamine combinations that have these preferred repeating structural units of the formulas III and IV or of the formulas III and VI or Formulas III, IV and V or Formulas III, IV and VI, are 1,4-phenylenediamine and 3,4'-diaminodiphenyl ether; 1,4-phenylenediamine, 4,4'-diaminodiphenylmethane and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; and 1,4-phenylenediamine, 1,4-bis (aminophenoxy) benzene and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; and 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; and 1,4-phenylenediamine, 3,4'-diaminodiphenyl ether and 4,4'-diaminobenzanilide; and 1,4-phenylenediamine, 1,4-bis (aminophenoxy) benzene and 3,4'-diaminodiphenyl ether; and 1,4-phenylenediamine and 5 (6) -amino-2- (para-aminophenyl) -benzimidazole; and 1,4-phenylenediamine, 5 (6) -amino-2- (para-aminophenyl) -benzimidazole and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine; and 1,4-phenylenediamine, 5 (6) -amino-2- (para-aminophenyl) -benzimidazole and 3,4'-diaminodiphenyl ether; and 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine, 5 (6) -amino-2- (para-aminophenyl) -benzimidazole and 1,4-bis (aminophenoxy) benzene; and 5 (6) -amino-2- (para-aminophenyl) -benzimidazole, 3,3'-dichloro, 3,3'-dimethyl or 3,3'-dimethoxybenzidine and 3,4'-diaminodiphenyl ether; and 1,4-phenylenediamine, 5 (6) -amino-2- (para-aminophenyl) -benzimidazole and 1,4-bis (aminophenoxy) benzene.
Aramide, die sich von solchen Diaminkombinationen ableiten und die sich bevorzugt gemäß der vorliegenden Erfindung einsetzen lassen, sind zum Teil in den EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 und EP-A-424,860 beschrieben.Aramids derived from such combinations of diamines and preferred according to the present invention are disclosed in part in EP-A-199,090, EP-A-364,891, EP-A-364,892, EP-A-364,893 and EP-A-424,860 described.
Die erfindungsgemäß einzusetzenden aromatischen Polyamide sind an sich bekannt.The aromatic polyamides to be used according to the invention are per se known.
Die Polykondensation und die Herstellung von Fasern aus den erfindungsgemäß einzusetzenden Coaramiden erfolgt nach an sich bekannten Verfahren, wie diese z.B. in den oben aufgeführten Schriften beschrieben worden sind. Das Einmischen des Füllstoffes und die Herstellung von füllstoffhaltigen Fasern kann beispielsweise nach dem in der EP-A- 662,534 beschriebenen Verfahren erfolgen.The polycondensation and the production of fibers from the invention coaramides to be used is carried out according to methods known per se, such as these e.g. have been described in the above-mentioned writings. The meddling of the filler and the production of filler-containing fibers, for example take place according to the method described in EP-A-662,534.
Die erfindungsgemäß einzusetzenden aromatischen Copolyaramide müssen ein für die Faserherstellung ausreichendes Molekulargewicht aufweisen. Eine ausreichende Molekül-Kettenlänge der erfindungsgemäß einzusetzenden Copolyaramide liegt beispielsweise vor, wenn die Viskosität der bei der Polykondensation erhaltenen Polymerlösung einer inhärenten Viskosität des Polymers von mehr als 2,5 dl/g, vorzugsweise 2,5 bis 7,0 dl/g, entspricht.The aromatic copolyaramides to be used according to the invention must be suitable for the fiber production have sufficient molecular weight. A sufficient molecular chain length of the invention to be used Copolyaramide is present, for example, when the viscosity of the at Polycondensation obtained polymer solution of an inherent viscosity of the Polymer of more than 2.5 dl / g, preferably 2.5 to 7.0 dl / g corresponds.
Unter inhärenter Viskosität wird der Ausdruck
ηrel bedeutet dabei die relative Viskosität, c die angewandte Konzentration in g/100 ml. η rel means the relative viscosity, c the applied concentration in g / 100 ml.
Sie wird für die Zwecke der vorliegenden Erfindung bestimmt an 0,25 %igen Lösungen von Polymer in N-Methylpyrrolidon bei 25°C.It is determined to be 0.25% for the purposes of the present invention Solutions of polymer in N-methylpyrrolidone at 25 ° C.
Der in den erfindungsgemäßen Fasern zum Einsatz kommende Füllstoff weist ganz allgemein eine Härte nach Mohs von größer gleich 3, vorzugsweise größer gleich 5 auf.The filler used in the fibers of the present invention has all generally a Mohs hardness of greater than or equal to 3, preferably greater than or equal to 5 on.
Als Füllstoffe lassen sich beliebige Materialien einsetzen, also Halbmetalle oder vorzugsweise Metalle oder Nichtmetalle sowie Legierungen dieser Materialien, sofern diese die oben definierte Härte aufweisen.As fillers can be used any materials, ie semi-metals or preferably metals or non-metals and alloys of these materials, if they have the above-defined hardness.
Bevorzugt eingesetzte Metalle sind beispielsweise Aluminium, Eisen, Nickel, rostfreier Stahl, Kupfer, Zink, Tantal, Titan, Wolfram oder Mischungen davon.Preferably used metals are, for example, aluminum, iron, nickel, stainless steel, copper, zinc, tantalum, titanium, tungsten or mixtures thereof.
Besonders bevorzugt werden Metallegierungen mit Wolfram als Legierungsbestandteil, die eine Härte nach Mohs von 6,5 bis 7,5 aufweisen.Particularly preferred are metal alloys with tungsten as Alloy component having a Mohs hardness of 6.5 to 7.5.
Bevorzugt eingesetzte Nichtmetalle sind beispielsweise Metalloxide, wie Aluminiumoxid; Metallcarbide, wie Wolframcarbid; Metallnitride, Metallsilikate, Metallsulfate, Metalphosphate, Metallboride oder Mischungen davon. Des weiteren können auch keramische Materialien eingesetzt werden.Preferably used non-metals are, for example, metal oxides, such as alumina; Metal carbides, such as tungsten carbide; Metal nitrides, metal silicates, Metal sulfates, metal phosphates, metal borides or mixtures thereof. Furthermore It is also possible to use ceramic materials.
Der Anteil des Füllstoffes in der erfindungsgemäßen Faser ist auf jeden Fall so zu wählen, daß die Schnittresistenz im Vergleich mit der unmodifizierten Faser vergrößert ist, beispielsweise um mindestens mehr als 8 % (gemessen nach dem CPP-Test). Überraschenderweise werden die übrigen mechanischen Eigenschaften der Fasern, wie Zugfestigkeit oder Modul, durch den Einsatz des Füllstoffes nur unwesentlich beeinträchtigt. So sinkt beispielsweise die Zugfestigkeit einer gefüllten Faser mit erhöhter Schnittfestigkeit auf etwa 205 cN/tex, verglichen mit der Zugfestigkeit von etwa 215 cN/tex der ungefüllten Faser.The proportion of the filler in the fiber according to the invention is in any case so Choose the cut resistance in comparison with the unmodified fiber is increased, for example by at least more than 8% (measured after the CPP) test. Surprisingly, the remaining mechanical properties the fibers, such as tensile strength or modulus, through the use of the filler only insignificantly impaired. For example, the tensile strength of a filled decreases Fiber with increased cut resistance to about 205 cN / tex, compared to the Tensile strength of about 215 cN / tex of unfilled fiber.
Typische Mengen an Füllstoff bewegen sich im Bereich von weniger als 25 Gew.%, bezogen auf das Gewicht der Faser, vorzugsweise im Bereich von 0,05 bis 20 Gew.%.Typical amounts of filler are in the range of less than 25% by weight. based on the weight of the fiber, preferably in the range of 0.05 to 20 Wt.%.
Die Partikelform des zum Einsatz kommenden Füllstoffes kann beliebig sein; beispielsweise kugel- oder ellipsenförmig oder auch irregulär. Der Füllstoff wird beispielsweise in Form eines Pulvers eingemischt.The particle shape of the filler used can be arbitrary; for example, spherical or elliptical or irregular. The filler will for example, mixed in the form of a powder.
Vorzugsweise weist der Füllstoff einen mittleren Teilchendurchmesser von kleiner gleich 20 µm, insbesondere von 0,05 bis 5 µm auf.Preferably, the filler has an average particle diameter of smaller equal to 20 microns, in particular from 0.05 to 5 microns.
Der Begriff "Fasern" ist im Rahmen dieser Erfindung in seiner breitesten Bedeutung zu verstehen; dazu zählen also zum Beispiel Stapelfasern oder insbesondere Filamente beliebiger Titer, einschließlich von Monofilamenten.The term "fibers" is in its broadest meaning in the context of this invention to understand; This includes, for example, staple fibers or in particular Filaments of any denier, including monofilaments.
Die erfindungsgemäßen Fasern zeichnen sich durch ausgezeichnete mechanische Eigenschaften, wie hohe Reißfestigkeiten und Anfangsmoduli und niedrige Reißdehnungen, sowie durch die oben erwähnte erhöhte Schnittresistenz aus.The fibers according to the invention are distinguished by excellent mechanical properties Properties such as high tensile strength and initial moduli and low Elongation at break, as well as by the above-mentioned increased cut resistance.
Die erfindungsgemäßen Fasern weisen vorzugsweise Einzelfilamenttiter von größer gleich 0,6 dtex, insbesondere von 1 bis 20 dtex, auf.The fibers of the invention preferably have single filament titres of greater equal to 0.6 dtex, in particular from 1 to 20 dtex, on.
Die Zugfestigkeit der erfindungsgemäßen Fasern beträgt vorzugsweise 150 bis 300 cN/tex.The tensile strength of the fibers of the invention is preferably 150 to 300 cN / tex.
Der Anfangsmodul, bezogen auf 100 % Dehnung, der erfindungsgemäßen Fasern beträgt vorzugsweise 20 bis 120 N/tex.The initial modulus, based on 100% elongation, of the fibers according to the invention is preferably 20 to 120 N / tex.
Die Querschnittsform der erfindungsgemäßen Fasern kann beliebig sein, beispielsweise dreieckig, tri- oder multilobal oder insbesondere elliptisch oder rund.The cross-sectional shape of the fibers according to the invention can be arbitrary, for example triangular, tri- or multilobal or in particular elliptical or round.
Die erfindungsgemäßen Fasern lassen sich zur Herstellung von Schutzkleidung, Antivandalismus-Textilien und Verbundwerkstoffen einsetzen. Die Verwendung der Fasern zu diesen Zwecken ist ebenfalls Gegenstand der vorliegenden Erfindung. The fibers according to the invention can be used for the production of protective clothing, Use anti-vandal textiles and composites. The use of Fibers for these purposes is also an object of the present invention.
Die erfindungsgemäßen Fasern werden im allgemeinen in Form von Garnen eingesetzt. Dabei kann es sich um sekundärgesponnene Garne oder vorzugsweise um Multifilamentgarne handeln. Typische Garntiter bewegen sich im Bereich von 50 bis 9000 dtex.The fibers of the invention are generally in the form of yarns used. These may be secondary spun yarns or preferably to act multifilament yarns. Typical yarn titers are in the range of 50 up to 9000 dtex.
Garne enthaltend die erfindungsgemäßen Fasern sind ebenfalls ein Gegenstand der vorliegenden Erfindung.Yarns containing the fibers of the invention are also an article of the present invention.
Einer bevorzugte Ausführungsform betrifft Mischgarne enthaltend die erfindungsgemäßen Fasern und Fasern aus anorganischen Materialien, wie Glas, Bor, Kohlenstoff, Metallen oder keramischen Materialien. Derartige Mischgarne zeichnen sich durch eine nochmals erhöhte Schnittresistenz aus.A preferred embodiment relates to blended yarns containing the Fibers and fibers of inorganic materials, such as glass, according to the invention, Boron, carbon, metals or ceramic materials. Such blended yarns are characterized by a further increased cutting resistance.
Das nachfolgende Beispiel verdeutlicht die Erfindung.The following example illustrates the invention.
Eine Faser bestehend aus einem aromatischen Copolyamid abgeleitet von
Terephthaloylchlorid, 50 Mol.-% 3,3'-Dimethylbenzidin, 25 Mol.-% p-Phenylendiamin
und 25 Mol.-% 1,4-Bis-(4-aminophenoxy)-benzol und aus 0,5 Gew.-%
Aluminiumoxid wurde hinsichtlich der Zugfestigkeit und der Schnittfestigkeit mit
einer ungefüllten Faser aus demselben aromatischen Copolyamid verglichen. Es
wurden folgende Werte ermittelt:
Gramm pro cm2
[ounze per squ. yard]
cN/tex
Grams per cm 2
[Ounce per squ. yard]
CN / tex
Claims (21)
- A cut-resistant fiber comprising a filler having a Mohs hardness of greater/equal 3 and a fiber-forming material comprising an aromatic copolyamid which contains the structural repeat units of the formulae I, II and optionally IIa
- The cut-resistant fiber of claim 1 wherein the aromatic copolyamide contains the structural repeat units of the formulae III and IV or of the formulae III and VI or of the formulae III, IV and V or of the formulae III, IV and VI or of the formulae IV, V and VIwhere Ar1 and Ar4 are each independently of the other a bivalent mono- or polycyclic aromatic radical whose free valences are disposed para or comparably parallel or coaxial to each other, and are in particular monocyclic or bicyclic aromatic radicals,
Ar5 and Ar6 are each independently of the other a bivalent mono- or polycyclic aromatic radical whose free valences are disposed para or comparably parallel or coaxial to each other, or where Ar6 additionally may be a bivalent mono- or polycyclic aromatic radical whose free valences are disposed meta or comparably angled to each other,
Q is a direct C-C bond or a group of the formula -O-, -S-, -SO2-, -O-phenylene-O- or alkylene,
Ar7 and Ar8 each have one of the meanings defined for Ar5 and Ar6,
Y has one of the meanings defined for Q or may additionally be a group of the formula -HN-CO-, and
X is a group of the formula -O-, -S- or in particular -NR1-, where R1 is alkyl, cycloalkyl, aryl, aralkyl or in particular hydrogen. - The cut-resistant fiber of claim 2 wherein aromatic copolyamides contain the structural repeat units of the formulae III, IV and V where Ar1 is 1,4-phenylene, Ar4 is 1,4-phenylene or a bivalent radical of 4,4'-diaminobenzanilide, Ar5, Ar6 and Ar7 are each 1,4-phenylene, Ar8 is 1,3-phenylene, Q is -O-1,4-phenylene-O- and Y is -O-; and the proportions of the structural repeat units of the formulae III, IV and V preferably vary within the following ranges, based on the total amount of these structural units:structural repeat unit of the formula III: 40-60 mol%,structural repeat unit of the formula IV: 1-20 mol%, andstructural repeat unit of the formula V: 15-40 mol%.
- The cut-resistant fiber of claim 2 wherein the aromatic copolyamides contain the structural repeat units of the formulae III, IV and V where Ar1 is 1,4-phenylene, Ar4 is 1,4-phenylene or a bivalent radical of 4,4'-diaminobenzanilide, Ar5 and Ar6 are each 1,4-phenylene, Ar7 and Ar8 are each methyl-, methoxy- or chlorine-substituted 1,4-phenylene, Q is -O-1,4-phenylene-O- and Y is a direct C-C bond; and the proportions of the structural repeat units of the formulae III, IV and V preferably vary within the following ranges, based on the total amount of these structural units:structural repeat unit of the formula III: 10-30 mol%,structural repeat unit of the formula IV: 10-30 mol%, andstructural repeat unit of the formula V: 10-60 mol%.
- The cut-resistant fiber of claim 2 wherein the aromatic copolyamides contain the structural repeat units of the formulae III, IV and V where Ar1 is 1,4-phenylene, Ar4 is 1,4-phenylene or a bivalent radical of 4,4'-diaminobenzanilide, Ar5 and Ar6 are each 1,4-phenylene, Ar7 and Ar8 are each methyl-, methoxy- or chlorine-substituted 1,4-phenylene, Q is -O- and Y is a direct C-C bond; and the proportions of the structural repeat units of the formulae III, IV and V preferably vary within the following ranges, based on the total amount of these structural units:structural repeat unit of formula III: 10-30 mol%,structural repeat unit of formula IV: 10-30 mol%, andstructural repeat unit of formula V: 10-60 mol%.
- The cut-resistant fiber of claim 2 wherein the aromatic copolyamides contain the structural repeat units of the formulae III and IV where Ar1 is 1,4-phenylene, Ar4 is 1,4-phenylene or a bivalent radical of 4,4'-diaminobenzanilide, Ar5 is 1,4-phenylene, Ar6 is 1,3-phenylene and Q is -O-; and the proportions of the structural repeat units of the formulae III and IV preferably vary within the following ranges, based on the total amount of these structural units:structural repeat unit of the formula III: 20-50 mol%, andstructural repeat unit of the formula IV: 40-60 mol%.
- The cut-resistant fiber of claim 2 wherein the aromatic copolyamides contain the structural repeat units of the formulae III and VI where Ar1 is 1,4-phenylene, Ar4 is 1,4-phenylene or a bivalent radical of 4,4'-diaminobenzanilide and X is -NH-; and the proportions of the structural repeat units of the formulae III and VI preferably vary within the following ranges, based on the total amount of these structural units:structural repeat unit of the formula III: 30-70 mol%, andstructural repeat unit of the formula VI: 70-30 mol%.
- The cut-resistant fiber of claim 2 wherein the aromatic copolyamides contain the structural repeat units of the formulae III, IV and VI where Ar1 is 1,4-phenylene, Ar4 is 1,4-phenylene or a bivalent radical of 4,4'-diaminobenzanilide, Ar5 is 1,4-phenylene, Ar6 is 1,4- or 1,3-phenylene, Q is -O- or -O-1,4-phenylene-O-and X is -NH-; and the proportions of the structural repeat units of the formulae III, IV and VI preferably vary within the following ranges, based on the total amount of these structural units:structural repeat unit of formula III: 10-30 mol%,structural repeat unit of the formula IV: 10-40 mol%, andstructural repeat unit of the formula VI: 50-70 mol%.
- The cut-resistant fiber of claim 2 wherein the aromatic copolyamides contain the structural repeat units of the formulae IV, V and VI where Ar1 is 1,4-phenylene, Ar5 is 1,4-phenylene, Ar6 is 1,4-phenylene or 1,3-phenylene, Q is -O- or -O-1,4-phenylene-O-, Ar7 and Ar8 are each methyl-, methoxy- or chlorine-substituted 1,4-phenylene, Y is a direct C-C bond, and X is -NH-; and the proportions of the structural repeat units of the formulae IV, V and VI preferably vary within the following ranges, based on the total amount of these structural units:structural repeat unit of the formula IV: 10-40 mol%,structural repeat unit of the formula V: 30-60 mol%, andstructural repeat unit of the formula VI: 50-70 mol%.
- The cut-resistant fiber of claim 1, wherein the polar aprotic organic solvent comprises at least one solvent of the amide type, for example N-methyl-2-pyrrolidone, N,N-dimethylacetamide, tetra-methylurea, N-methyl-2-piperidone, N,N'-dimethylethyleneurea, N,N,N',N'-tetramethylmaleamide, N-methylcaprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N'-dimethylpropionamide, N,N-dimethylisobutylamide, N-methylformamide, N, N'-dimethylpropyleneurea.
- The cut-resistant fiber of claim 1, wherein the filler is present in the fiber in an amount of 0.05 to 20% by weight.
- The cut-resistant fiber of claim 1, wherein the filler has a Mohs hardness of greater/equal 5.
- The cut-resistant fiber of claim 1, wherein the filler has an average particle diameter of less/equal 20 µm, preferably of 0.05 to 5 µm.
- The cut-resistant fiber of claim 1, wherein the particles of the filler have the shape of an ellipsoid which has an average particle diameter of less/equal 20 µm, preferably of 0.05 to 5 µm.
- The cut-resistant fiber of claim 1, wherein the filler is a metal and/or a metal alloy, preferably aluminum, iron, nickel, stainless steel, copper, zinc, tantalum, titanium, tungsten or a mixture thereof.
- The cut-resistant fiber of claim 1, wherein the filler is a nonmetal, preferably a metal oxide, metal carbide, metal nitride, metal silicate, metal sulfate, metal phosphate, metal boride or a mixture thereof.
- The cut-resistant fiber of claim 1 having a filament linear density of 1 to 20 dtex.
- A yarn comprising the fibers of claim 1.
- The yarn of claim 18, comprising a blend of fibers of claim 1 and fibers composed of inorganic materials.
- The yarn of claim 18, wherein the fibers which are composed of inorganic materials are fibers composed of glass, boron, carbon, metals or ceramic materials.
- The use of the cut-resistant fibers of claim 1 for manufacturing protective clothing, antivandalism textiles and composite materials.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19605511 | 1996-02-15 | ||
| DE19605511A DE19605511A1 (en) | 1996-02-15 | 1996-02-15 | Cut-resistant aramid fibers, yarns containing these aramid fibers and their use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0790335A1 EP0790335A1 (en) | 1997-08-20 |
| EP0790335B1 true EP0790335B1 (en) | 2005-06-15 |
Family
ID=7785416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97101675A Expired - Lifetime EP0790335B1 (en) | 1996-02-15 | 1997-02-04 | Cut-resistant aramid fibres, yarns containing these fibres and their use |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US5738940A (en) |
| EP (1) | EP0790335B1 (en) |
| DE (2) | DE19605511A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6162538A (en) * | 1992-11-24 | 2000-12-19 | Clemson University Research Foundation | Filled cut-resistant fibers |
| US6080474A (en) * | 1997-10-08 | 2000-06-27 | Hoechst Celanese Corporation | Polymeric articles having improved cut-resistance |
| WO1999036606A1 (en) * | 1998-01-20 | 1999-07-22 | Hna Holdings, Inc. | Ballistic-resistant textile articles made from cut-resistant fibers |
| FR2789094B1 (en) * | 1999-02-03 | 2001-05-25 | Speed France | CUTTING WIRE OR FISHING WIRE IN SYNTHETIC MATERIAL |
| DE60013977T2 (en) * | 1999-07-29 | 2005-10-06 | Sumitomo Chemical Co. Ltd. | Heat-resistant sheet-shaped catalyst and process for its preparation |
| JP4831974B2 (en) * | 2005-01-27 | 2011-12-07 | 帝人テクノプロダクツ株式会社 | Protective clothing |
| US9334587B2 (en) * | 2005-02-11 | 2016-05-10 | W. L. Gore & Associates, Inc. | Fluoropolymer fiber composite bundle |
| US20060182962A1 (en) * | 2005-02-11 | 2006-08-17 | Bucher Richard A | Fluoropolymer fiber composite bundle |
| KR100749962B1 (en) * | 2005-07-06 | 2007-08-16 | 주식회사 코오롱 | Aromatic polyamide filament and method of manufacturing the same |
| US7559653B2 (en) * | 2005-12-14 | 2009-07-14 | Eastman Kodak Company | Stereoscopic display apparatus using LCD panel |
| WO2008012925A1 (en) * | 2006-07-26 | 2008-01-31 | Teijin Techno Products Limited | Aromatic polyamide fiber and process for producing the same and protective clothing using said aromatic polyamide fiber |
| CN101611182B (en) * | 2006-12-15 | 2012-08-01 | 帝人高科技产品株式会社 | Heterocyclic ring-containing aromatic polyamide fiber, method for producing the same, fabric comprising the fiber, fiber-reinforced composite material reinforced with the fiber |
| JP7372004B2 (en) | 2017-04-03 | 2023-10-31 | アビエント プロテクティブ マテリアルズ ビー． ブイ． | Filled elongated bodies that are cut resistant |
| US11598027B2 (en) | 2019-12-18 | 2023-03-07 | Patrick Yarn Mills, Inc. | Methods and systems for forming a composite yarn |
| KR102208801B1 (en) * | 2020-12-16 | 2021-01-28 | 김용건 | High tenacity fiber and method for manufacturing glove using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2328105A (en) | 1940-12-28 | 1943-08-31 | Louis J Strobino | X-ray shield |
| DE2556883C2 (en) | 1974-12-27 | 1981-11-26 | Teijin Ltd., Osaka | Aromatic copolyamides and their use for the production of fibers, threads, films and foils |
| US4004295A (en) | 1975-12-30 | 1977-01-25 | Byrnes Sr Robert M | Protective glove constructed of flexible strands of metal wire and fiber yarn |
| US4384449A (en) | 1976-10-05 | 1983-05-24 | Robert M. Byrnes, Sr. | Protective gloves and the like and a yarn with flexible core wrapped with aramid fiber |
| US4470251A (en) | 1978-03-30 | 1984-09-11 | Bettcher Industries, Inc. | Knittable yarn and safety apparel made therewith |
| JPS5598909A (en) | 1979-01-24 | 1980-07-28 | Takeshi Naito | Fiber and sewn product |
| JPS55115428A (en) | 1979-02-26 | 1980-09-05 | Teijin Ltd | Aromatic compolyamide and preparation thereof |
| EP0199090B1 (en) | 1985-03-23 | 1990-10-03 | Hoechst Aktiengesellschaft | Shaped articles of aromatic copolyamides, and process for their manufacture |
| DE3835405A1 (en) | 1988-10-18 | 1990-05-03 | Hoechst Ag | FULLY FLAVORED POLYAMIDES, METHOD FOR THE PRODUCTION THEREOF AND MOLDS MADE THEREOF |
| DE3835441A1 (en) | 1988-10-18 | 1990-04-26 | Hoechst Ag | FULL-AROMATIC POLYAMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEREFORE MOLDED PICTURES |
| DE3835419A1 (en) | 1988-10-18 | 1990-04-19 | Hoechst Ag | FULLY FLAVORED POLYAMIDES, METHOD FOR THE PRODUCTION THEREOF AND MOLDS MADE THEREOF |
| US5020161A (en) | 1989-09-29 | 1991-06-04 | E. I. Dupont De Nemours And Company | Waterproof glove for protective coveralls |
| JPH03130413A (en) | 1989-10-17 | 1991-06-04 | Teijin Ltd | Sheath-core conjugated magnetic fiber and aggregate of magnetic fiber produced by using the same |
| DE3935472A1 (en) | 1989-10-25 | 1991-05-02 | Hoechst Ag | FULLY FLAVORED POLYAMIDES, METHOD FOR THE PRODUCTION THEREOF AND MOLDS MADE THEREOF |
| CA2043062C (en) | 1990-05-25 | 2001-12-11 | Joseph Hummel | Knittable yarn and safety apparel |
| JP3563752B2 (en) | 1992-11-24 | 2004-09-08 | エイチエヌエイ・ホールディングス・インコーポレーテッド | Filled fiber |
| US5276085A (en) * | 1993-04-23 | 1994-01-04 | E. I. Du Pont De Nemours And Company | Aromatic polyamide compositions and fibers |
| DE4400248A1 (en) | 1994-01-06 | 1995-07-13 | Hoechst Ag | A process for the preparation of bulk-colored aromatic polyamide-based shaped bodies, bulk-dyed fibers, and blending for the production of bulk-colored shaped structures |
| DE4401233A1 (en) * | 1994-01-18 | 1995-07-20 | Hoechst Ag | Bundles of staple fibers made from aromatic polyamides with improved dispersibility in viscous matrices, and process for producing fiber-reinforced composites |
| EP0678539A3 (en) * | 1994-04-06 | 1997-01-15 | Hoechst Ag | Aromatic copolyamides, process for their preparation, moulded articles and their manufacture. |
| DE4411755A1 (en) * | 1994-04-06 | 1995-10-12 | Hoechst Ag | Prodn. of fibres and film based on aromatic polyamide |
| CN1089815C (en) * | 1994-05-16 | 2002-08-28 | 赫希斯特人造丝公司 | Filled cut-resistant fiber |
| TW307802B (en) * | 1995-06-07 | 1997-06-11 | Hoechst Celanese Corp | |
| US5597649A (en) * | 1995-11-16 | 1997-01-28 | Hoechst Celanese Corp. | Composite yarns having high cut resistance for severe service |
-
1996
- 1996-02-15 DE DE19605511A patent/DE19605511A1/en not_active Withdrawn
-
1997
- 1997-02-04 EP EP97101675A patent/EP0790335B1/en not_active Expired - Lifetime
- 1997-02-04 DE DE59712341T patent/DE59712341D1/en not_active Expired - Lifetime
- 1997-02-18 US US08/800,530 patent/US5738940A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE59712341D1 (en) | 2005-07-21 |
| EP0790335A1 (en) | 1997-08-20 |
| US5738940A (en) | 1998-04-14 |
| DE19605511A1 (en) | 1997-08-21 |
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