GB1600103A - Antimycotically active fibres and filaments - Google Patents
Antimycotically active fibres and filaments Download PDFInfo
- Publication number
- GB1600103A GB1600103A GB8975/78A GB897578A GB1600103A GB 1600103 A GB1600103 A GB 1600103A GB 8975/78 A GB8975/78 A GB 8975/78A GB 897578 A GB897578 A GB 897578A GB 1600103 A GB1600103 A GB 1600103A
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- Prior art keywords
- radical
- test
- filaments
- optionally substituted
- polymer
- Prior art date
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- Expired
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- 229920000642 polymer Polymers 0.000 claims description 59
- 238000012360 testing method Methods 0.000 claims description 58
- 230000001857 anti-mycotic effect Effects 0.000 claims description 42
- 239000002543 antimycotic Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 34
- 150000007980 azole derivatives Chemical class 0.000 claims description 30
- 238000009987 spinning Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 25
- 239000000155 melt Substances 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 14
- 239000004753 textile Substances 0.000 claims description 14
- 238000012546 transfer Methods 0.000 claims description 14
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229920002292 Nylon 6 Polymers 0.000 claims description 10
- 238000011109 contamination Methods 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 238000002768 Kirby-Bauer method Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 230000002401 inhibitory effect Effects 0.000 claims description 8
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 8
- 241000222122 Candida albicans Species 0.000 claims description 7
- 241001045770 Trichophyton mentagrophytes Species 0.000 claims description 7
- 229940095731 candida albicans Drugs 0.000 claims description 7
- SUDHEDJJFGYYPL-UHFFFAOYSA-N ethyl n,n-dimethylcarbamate Chemical group CCOC(=O)N(C)C SUDHEDJJFGYYPL-UHFFFAOYSA-N 0.000 claims description 7
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 6
- 244000052616 bacterial pathogen Species 0.000 claims description 6
- 125000000468 ketone group Chemical group 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005864 Sulphur Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000005764 inhibitory process Effects 0.000 claims description 4
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229920001059 synthetic polymer Polymers 0.000 claims description 4
- 206010061217 Infestation Diseases 0.000 claims description 3
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 208000015181 infectious disease Diseases 0.000 claims description 3
- 238000002074 melt spinning Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 description 18
- 239000000975 dye Substances 0.000 description 13
- -1 triazole radical Chemical class 0.000 description 13
- 239000008187 granular material Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000013543 active substance Substances 0.000 description 9
- 230000003068 static effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 241000233866 Fungi Species 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000002924 anti-infective effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229940055577 oleyl alcohol Drugs 0.000 description 4
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006887 Ullmann reaction Methods 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BLXLSQIOCCHAHJ-UHFFFAOYSA-N [2,3,4-tri(nonyl)phenyl] dihydrogen phosphite Chemical group CCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCC)=C1CCCCCCCCC BLXLSQIOCCHAHJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 101000654316 Centruroides limpidus Beta-toxin Cll2 Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 244000053095 fungal pathogen Species 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 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
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
(54) ANTIMYCOTICALLY ACTIVE FIBRES AND FILAMENTS
(71) We, BAYER AKTIENGESELLSCHAFT, a body corporate organised under the laws of the Federal Republic of Germany, of 509 Leverkusen,
Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to antimycotically active fibres, filaments and filament yarns which contain one or more azole derivatives as active constituents. The invention also relates to a process for producing fibres and filaments of this type.
Through the presence of one or more azole derivatives according to the invention in the fibre or filament material, pathogenic fungi coming into contact with the corresponding textiles are inactivated, thus preventing them from being spread or transferred to other objects, materials or organisms.
The antimycotic finishing of fibres and textile materials is known. In general, the antimycotically active substance is applied to the surface of the fibre or textile in a separate process step, the substance being used in pure form or even in conjunction with a surface-active agent, a binder or a resin in order to improve distribution and permanence. One disadvantage of this process is that the antimycotically active substance applied to the surface can readily be removed in washing and cleaning processes. In addition, the impurities applied with the antimycotic agent to the polymer surface often have adverse effects upon the feel, appearance and soiling, ageing and wearing behaviour of the correspondingly finished textiles. Accordingly, attempts have been made to incorporate the active substance in the fibre substrate itself.Unfortunately products such as these have not yet been successfully marketed because considerable difficulties were obviously encountered in the production of the fibres, the activity of the products spun into the fibres was inadequate and their toxicological or physiological effects upon the human or animal body were at least questionable. Anti-mycotically active additives to polymers which can be spun into fibres have to be able to kill microorganisms and to prevent their growth. However, they must not have any damaging effect upon the skin or the body of warm-blooded animals. In addition, the compounds used should not adversely affect the dyeability of the fibres nor should they accelerate the destruction of dyes and the fibres, even in the presence of light.Many basically active antimycotics do not satisfy these requirements and the requirements discussed hereinafer for the substrates of synthetic fibres or textiles produced therefrom.
By contrast, the filaments and fibres according to the invention with the characterising features of the main Claim have the advantage that they can be processed without any particular technical problems into fibres which are not different in their textile properties from unmodified types. At the same time, they show a hitherto unattained activity against the spreading and transfer of fungi which are pathogenic to humans and animals, coupled with complete compatibility with the skin and mucosa. Another advantage is that the azole derivatives used in accordance with the invention show high thermal stability. In addition, they are substantially insoluble in water so that their concentration is not reduced beyond a tolerable extent by washing, dyeing and finishing processes.
Accordingly, the present invention provides antimycotically active fibres and filaments of synthetic polymers which are characterised in that they contain an azole derivative corresponding to the general formula:
in which
Az represents an optionally substituted imidazole or triazole radical;
n=Oor 1;
R1 represents hydrogen, an optionally substituted aliphatic or cycloaliphatic radical, or an optionally substituted phenyl, which may be attached via an oxygen atom, or pyridyl radical;
R2 represents an optionally substituted phenyl radical, which may be attached via a single bond or via hCH2)mwhere m = 1 or 2, the group -X-R4 where X is oxygen or sulphur and R4 is an optionally substituted aliphatic or cycloaliphatic radical, or an optionally substituted aryl or aralkyl radical;;
R3 represents an optionally substituted phenyl radical, an optionally substituted aliphatic or cycloaliphatic radical, an optionally substituted 5membered hetero-aromatic ring, a group derived from a carboxylic acid group (for example, an ester group or an amide group), or the group -Y-R4 where Y is a keto group or a functional derivative of the keto group and R4 is an optionally substituted aliphatic or cycloaliphatic radical, an optionally substituted aryl or aralkyl radical; or
R2 and R3, where both radicals represent an optionally substituted phenyl radical, are attached to each other in the o-positions through a single bond, hCH2)m, where m = 1 or 2, H=CH-, oxygen or sulphur.
Preferred antimycotically active fibres and filaments are characterised in that they contain an azole derivative corresponding to the general formula:
in which
Az represents the radical
R' represents hydrogen;
R2 represents the radical
where
Zm = halogen, halogen phenyl or phenyl, and
m - O to 2; and
R3 represents the radical -B- C(CH,)3 where
B = CO or CH(OH).
Other preferred antimycotically active fibres and filaments are characterised in that they contain an azole derivative corresponding to the general formula
in which
Az represents the radical
n=Oor 1; R1 represents the radical
where
Zm = halogen, halogen phenyl or phenyl, and m=Oto2; R2 represents a phenyl radical optionally substituted by halogen, halogen phenyl or phenyl, the attachment of the rest of the molecule to the phenyl radical occurring in the o-position through a single bond or Cll2)m where m = 1 or 2; and
R3 represents an alkyl, alkenyl, alkynyl, alkoxy carbonyl or alkyl carbonyl radical, or a phenyl radical optionally substituted by halogen, halogen phenyl or phenyl, or an imidazole or triazole radical optionally substituted by halogen or alkyl.
Particularly preferred antimycotically active fibres and filaments are characterised in that they contain an azole derivative corresponding to the general formula:
in which
Az represents the radical
n=O,
R' represents a hydrogen atom,
R2 represents the radical
and
R3 represents the radical
The azole antimycotics used in accordance with the invention are already known and are described in the following publications:
DT-OS Nos. BE-PS Nos. US-PS Nos.
1,911,646 720,801 774,621 3,737,531
1,949,012 741,310 776,212 3,737,548
2,140,865 750,724 787,973 3,711,487
2,324,424 762,463 797,100 3,732,242
2,333,355 764,700 800,914
2,347,057 765,585 804,092
2,350,121 770,662 805,209
2,350,124 771,584 805,210
2,358,592 772,402
It is best to use at least 0.0lVn by weight, but preferably from 0.01 to 5% by weight, based on the total weight of the fibres or filaments of at least one of the azole derivatives defined in detail above.
The present invention also provides a process for the production of the fibreforming polymers with the characterising features of the main Claim. This process is characterised in that azole derivatives corresponding to the formulae of the main
Claim are added to and mixed with the polymers before spinning.
The antimycotically active azole derivatives may be mixed in by various methods. The particular procedure adopted will be determined by the particular polymer to be spun. The problem can be solved most easily in the case of fibreforming polymers which are spun from solvents by the dry spinning or wet spinning process.
In the solution spinning processes, the particular polymer is dissolved in a solvent. Filament formation is obtained by evaporating the solvent or by coagulating the polymer in the precipitation bath. Processes such as these are described in detail, for example, in Ullmanns Encyclopadie der technischen
Chemie; Verlag Chemie, Weinheim/Bergstrasse; 4th Edition, Vol. 11; pages 257 et seq. The antimycotic agents used in accordance with the invention may be dissolved in the solvent before the polymer to be spun is introduced into the solvent. However, the products used according to the invention may also be introduced into the spinnable solutions of the polymer. In this case, it is possible individually to add them dissolved in a solvent to the spinning solution before spinning or immediately before the solution emerges from the spinning jet. In every case, provision must be made to ensure that the additive is uniformly distributed in the spinning solution. This can be guaranteed with sufficient certainty by dynamic and static mixers.
The solvent for the antimycotic used in accordance with the invention does- not have to be identical with the solvent for the polymer. Thus, it is possible by suitably selecting various solvents to produce a spinnable emulsion when the solvent of the antimycotic is not soluble in the solution of the polymer. The solution of the antimycotic is present in this emulsion in the form of fine droplets in the spinning solution. After precipitation of the polymer in dry or wet spinning processes, islands with an increased concentration of antimycotic are formed in the filament. The migratability of the active substance can be purposefully influenced by measures such as these.
Polymers and corresponding solvents which are processed into fibres and filaments by solution spinning processes are described in Ullmanns Encyclopadie der technischen Chemie, Vol. 11; pages 291 et seq.
Accordingly, the present invention also provides a process for the production of antimycotically active fibres and filaments of synthetic spinnable polymers which are characterised in that an azole derivative corresponding to the general formula in the main Claim is dissolved or emulsified in a solvent and the polymer, optionally dissolved in the same solvent or a different solvent, is introduced into the resulting solution or emulsion or the azole derivative is dissolved or emulsified in a spinnable solution of the polymer, and the resulting solutions or emulsions are spun. In the case of polymers processed into fibres and filaments from the melt. the procedure by which the antimycotics are incorporated has to be modified.
Before they are processed into fibres and filaments fusible polymers are generally present in the form of granulates formed by cutting polymer wires or ribbons. It is also possible, however, to spin polymer powders from the melt. The azole derivatives used in accordance with the invention may be mixed with the polymers to be melted before spinning. Mixing may be carried out in a tumble mixer. Since the antimycotic and polymer are in danger of disintegrating, better and more uniform distribution may be obtained by binding the antimycotic to the granules by means of a coupling agent, such as for example a stearylamine ethoxyiated 20 times, in a low concentration. Sintering on at elevated temperatures by means of a fluid mixer also leads to a firmer bond between the active substance and the polymer surface.In one preferred process according to the invention, the antimycotically active compound is added to the particular polymer melt immediately before spinning. Since the pure active substance cannot effectively be metered into the melt, the required azole derivative is dissolved in a substantially involatile solvent, metered into the melt by means of a pressure piston or gear metering pump and uniformly dissolved or distributed in the melt by means of dynamic or static mixers. In this case, too, the state of distribution of the antimycotic in the polymer matrix may largely be influenced by the choice of the solvent. If, for example, a solvent which is soluble in the polymer is selected for the antimycotic, the solvent and antimycotic are distributed completely uniformly in the polymer.However, if a substance which is insoluble in the polymer is selected as the solvent, the solution of the antimycotic in the polymer is present in the form of fine droplets which, after spinning and drawing, change shape into fine fibrils in the polymer. Polymers which are spun from the melt and the melt spraying technique itself are described in detail in Ullmanns Encyclopadie der technischen
Chemie; Vol. Il; pages 291 et seq and pages 264 et seq. In this connection, particular significance is attached to the modification of poiyamides.
Accordingly, the present invention also provides a process for the production of antimycotically active fibres and filaments of synthetic spinnable polymers, characterised in that an azole derivative corresponding to the general formula in the main Claim is added to and mixed with a granulated or powder-form spinnable polymer, optionally using a coupling agent or the technique of sintering on, and the granulated or powder-form polymer is spun by the melt spinning process.
A preferred process is one in which the azole derivatives is bound to the granulated or powder-form polymer using a polyalkylene oxide compound having a molecular weight of from 400 to 20,000 as an adhesion promoter.
Stearylamine ethoxylated 20 times, oleyl or stearyl alcohol ethoxylated from 20 to 40 times or polyalkylene oxide compounds modified by a terminal dimethyl urethane group are particularly suitable for this purpose.
As already mentioned, it is possible by using solvents during the addition of the antimycotics to polymer solutions and melts to control the distribution of the active substance in the polymers, which in turn enables their migration behaviour to be influenced. If caprolactam, for example. is selected as solvent, the caprolactam solvent and antimycotic are present in completely uniform d1stribution in the polyamide after metering into a polycaprolactam melt because both components have dissolved in the melt. If, however, an oleyl alcohol ethoxylated 20 times is selected as solvent, fine fibrils containing the ethoxylated aleyl alcohol and, therein, the antimycotic are formed in the oriented polymer. This ehtoxylated oleyl alcohol cannot be washed out to any singificant extent in washing and dyeing processes.By virtue of its fibril structure, the antimycotic has become labile in the polyamide and can migrate to the surface of the polymer and develop its required effect there. Some examples of solvents with which the antimycotics can be spun into the particular polymers in homogeneous, dissolved form or in fibril form are given in Table 1 below.
TABLE 1
Solvent for Solvent for Distribution of the Polymer Polymer Antimycotic antimycotic in the polymet Polyacrylonitrile dimethyl formamide dimethyl formamide homogeneous Polycaprolactam - caprolactam homogeneous Polycaprolactam - 20 x ethoxylated fibrillar oleyl alcohol Polyethlene terephthalate - tris-nonyl-phenyl homopeneous phosphite Poylethylene terephthalate - 40 x ethoxylated fibrillar stearyl alcohol with a terminal dime thyl urethane group Of these solvents, those with a water retention capacity or hydrophilic properties are preferred. Particularly suitable hydrophilicity-increasing solvents for the antimycotics are the derivatives of polyalkylene oxides with molecular weights of from 400 to 20,000, particularly those of polyethylene oxide. Their hydrophilising effect is known from publications in which the relationship between static charging, relative air humidity and the presence of polyalkylene oxides is described for textiles (Chemie-fasern/Textilindustrie; May 1972, pages 397 et seq).
The antimycotic activity can also be greatly improved by the presence of small quantities of water (Die Hygiene des Teppichbodens, Manfred Rotter; Gustav
Fischer Verlag: Stuttgart 1975; page 240).
Accordingly, a particularly preferred process is one in which the azole derivative is added to the prepared spinning solution or to the polymer melt immediately before spinning using "solvents". 20 x Ethoxylated strearylamine, 20 to 40 x ethoxylated oleyl or stearyl alcohol, polyalkylene oxide compounds modified with a terminal dimethyl urethane group, tris-nonyl-phenyl phosphite and, in the case of the polyamides, E-caprolactam are particularly suitable for this purpose.
The polymers produced in accordance with the invention and the fibres obtained from them may be processed without particular difficulty into textiles in the textile industry. The fibres may be processed either on their own or in admixture with non-antimicrobially active natural and synthetic fibres. The following are mentioned as examples of textiles for which antimycotic activity is particularly desirable: carpetings, stockings, shirts and the like. The textiles in question primarily consist of or contain the fibres produced by the process according to the invention and may come into permanent or even temporary contact with the surface of the body. In the presence of antimycotics, the fungi which may possibly be transferred in the event of such contact are killed off. Any propagation and transfer of the fungi to other regions of the skin or other organisms is interrupted.The interruption of this transfer chain is particularly significant in the case of textile floor coverings on which people frequently tread with bare feet, i.e. in the case of floor coverings in the bedrooms and bathrooms of hotels and private dwellings.
The following Examples illustrate the invention without limiting it. The percentages are by weight.
Example 1.
200 g of a 20 x ethoxylated stearylamine are added in a tumble mixer in the absence of moisture to 100 kg of a dried polyamide-6 granulate which contains 0.05% by weight of titanium dioxide and which has a relative viscosity of 2.7, as measured on a 1% solution in m-cresol at 250C. The mixture is tumbled for about 2 hours, after which 200 g of a finely ground antimycotic corresponding to the formula:
are added, followed by mixing for another 3 hours. The granulate is fused and spun in an extruder.
The screw of this extruder has a length of 72 cm and a diameter of 3 cm. The extruder barrel is heated to 285 C. The screw has a rotational speed of 90 rpm. The melt shows a pressure of 80 bars at the output end of the extruder. It flows into two double gear metering pumps which divide the flow of melt into four component streams, each having a quantitative flow of 40 g of polyamide per minute. Each of these component streams is forced through a metal gauze with 16000 meshes/cm2 and spun through a spinning jet with 16 bores having a diameter of 0.30 mm. The bundle of filaments issuing from the four jets is treated with a spin-finish after cooling in the spinning duct and wound up at a rate of 460 metres per minute. The undrawn filaments have an individual denier of 54 dtex. The filaments can be processed into spun fibres and filament yarn.
a. Production of spun fibres
The filaments are combined from ten bobbins to form a tow, drawn in a ratio of 1:3.4 by means of drawing rolls and crimped in a stuffer box. The crimped tow can then be cut in such a way that an average staple length of 150 mm is obtained.
After heat-setting with saturated steam at 1300 C, the fibres have an individual denier of 17 dtex. They are spun by one of the methods normally used in the textile industry to form a yarn having a yarn count of 37. A tufted carpet with a fibre input weight of 700 g/m2 is produced from this yarn.
b. Production of textured filament yarn.
The filaments are combined from two bobbins into a tow, drawn in a ratio of 1:3.4 over godets and crimped with superheated steam in a textured nozzle at a temperature of 1600C. After cooling in the absence of tension, the yarn is wound up. It has a total denier of 2200 dtex. The filaments have an individual denier of 17 dtex. A tufted carpet with a fibre input weight of 700 g/m2 is produced from the filaments.
The tufted carpets are dyed in a winch vat with dyes having the following constitution:
(dye I) (dye II) (dye III)
in the presence of 0.5% of Levegal FTS, an anion-active levelling aid produced by
BAYER AG, at a pH-value of from 4 to 5. The carpet is backed with a coating of
Lipolan CT 35, a rubber latex produced by Chemische Werke Huls AG. In order to test the dye finishes for fastness to light, fibre samples are dyed. The results are set out in Table 2 below.
c. Comparison tests c.l The 20 x ethoxylated stearylamine above is applied to the polyamide-6
granulate in a tumble mixer. The spinning conditions are the same.
c.2 Unmodified polyamide-6-granulate is spun under the same conditions. TABLE 2
Assessment of the light stability of dye finishes
0.5% of dye I 0.2% of dye II 0.021% of dye II Sample 0.2% of dye II 0.05% of dye III 0.032% of dye III Comparison 6 6-7 6-7 0.1% A* 6-7 6 6-7 0.2% A* 6 6-7 5-6 0.3% A* 6 6 6 A*: 0.1% and 0.3% of the antimycotic A were spun into fibres.
The light stability values were determined in accordance with DIN 54004 in a Xeno tester 450 manufactured by the Original Hanau Company.
Example 2.
As in Example 1, polyamide-6 granulate is melted in an extruder. The melt flows through a static mixer of the type described in German Auslegeschrift No.
2,328,795. The static mixer has a length of 36 cm and a diameter of 2 cm. Before entering the mixer, 1.60 g/minute of a 20% solution heated to 80 C of the antimycotic corresponding to the formula in Example 1 in caprolactam are added to the melt by means of a piston pump (LEWA pump; type Mk 1). The fibres containing 0.2% of the antimycotic are spun and worked up in the same way as in
Example 1.
Example 3.
Polyamide-6 granulate is melted in the same way as described in Example 1.
After the extruder, the melt flows through a bynamic mixer having a diameter of 6 cm. (BARMAG: Information Service No. 11/1975). The antimycotic is introduced and the fibres are worked up in the same way as described in Examples 2 and 1.
Example 4.
Polyamide-6 granulate is melted in an extruder and introduced into a dynamic mixer in the same way as described in Example 3. Before entering the mixer, 4.8 g/minute of a 10% solution heated to 80"C of the antimycotic corresponding to the formula in Example 1 in 20 x ethoxylated stearyl alcohol, of which the terminal
OH-radical has been reacted to form a dimethyl urethane group in accordance with
German Offenlegungsschrift No. 2,410,861, are added to the melt. The fibres are spun and worked up in the same way as in Example 1. Examination of the fibres under an optical microscope reveals fibrillar inclusions of the additives in the fibres. The fibrils have a diameter of about 2 ,am and an average length of more than 100 pom.
Example 5.
Caprolactam is continuously polymerised into polyamide-6. The melt is freed from low molecular weight fractions in a vacuum stage and then delivered to several spmning units. A component stream of 1350 g/minute enters a static mixer 120 cm long and 10 cm in diameter, of the type described in German Auslegeschrift
No. 2,328,795. Before the static mixer, 27 g/minute of a 10% solution heated to 80"C of the antimycotic corresponding to the formula in Example I in 20 x ethoxylated oleyl alcohol are added. The melt is distributed to nine spinning stations each comprising a 126-bore spinning jet. The fibres issuing from the spinning jets are blown cool with air, prepared and wound up at a rate of 200 metres per minute.The filaments are processed in the same way as in Example ib. Fibrils are visible under an optical microscope, as described in Example 4.
Example 6.
200 g of a 20 x ethoxylated stearyl alcohol are added in a tumble mixer in the absence of moisture to 100 kg of a polyethylene terephthalate granulate which contains 0.25% by weight of titanium dioxide and which has a solution viscosity of 0.66 as measured in accordance with DIN 53 728. In the same way as in Example I, 200 g of the antimycotic corresponding to the formula in Example 1 are bound to the surface of the granulate. Spinning is carried out in the apparatus described in
Example 1. The following test parameters are maintained:
Temperature of the extruder barrel: 295"C Melt pressure: 90 bars
Throughput: 11.6 kg/h
Take-off rate: 1000 m/minute
Jets: 4 x 36 bores; 0.25 mm
Gross denier 484 dtex.
The filaments are drawn in a draw-twisting machine. The drawing ratio is 1:4.4.
The filament yarns having a denier of 110 dtex are textured by the false-twist method and made up into a knitted fabric.
Example 7.
Polyethylene terephthalate is melted in the same way as described in Example 6. The extruder is followed by a static mixer in the same way as in Example 2.
Before entering the mixer, 3.86 g/minute of a 15% solution of the antimycotic corresponding to the formula in Example 1, in tris-nonyl-phenyl phosphite, are added to and mixed with the polyester melt. The filaments are spun and worked up in the same way as in Example 6.
No fibrillar inclusions are visible under an optical microscope.
Example 8.
Polyethylene terephthalate is melted in the same way as described m Example 6. After the extruder the melt flows through a dynamic mixer in the same way as in
Example 3. Before Ç ntering the mixer, 3.90 g of a 10% solution heated to 80CC of the antlmycotic cc,responding to the formula in Example 1 in 20 x ethoxylated stearyl alcohol. which contains a terminal dimethyl urethane group in accordance with German Offenlegungsschrift No. 2,409,715, are added to the melt. The filaments are spun and worked up in the same way as described in Example 6.
Fibrillar inclusions are visible in the filaments under an optical microscope.
Example 9.
100 parts of syndiotactic polyvinyl chloride are dissolved at 1400C in 505 parts by weight of cyclohexanone with uniform addition of 1.5 parts by weight of an organic tin stabiliser. 0.1 part of the antimycotic corresponding to the formula in
Example 1 is added to this solution. After 10 minutes, the spinning solution obtained is filtered at 1350C and pressed by means of a heated gear pump through the spinning jet which is also heated. 38.5 g/minute of solution are delivered through the 300 bore spinning jet with a bore diameter of 0.08 mm. This corresponds to 6.35 g of PVC.
The precipitation bath consists of a mixture of 20% of cyclohexanone, 30% of isopropanol and 50 zO of water, The precipitation bath has a temperature of 60"C.
The bundle of filaments is drawn off from the nozzle at 7 metres per minute and intensively washed in water at 60 to 800 C. The bundle of filaments is then drawn in boiling water in a ratio of 1:3.5 and dried in recirculating air at 1200C.
Example 10.
A spinning solution is prepared by heating 280 parts by weight of polyacrylonitrile powder and 720 parts by weight of dimethyl formamide to 800 C.
1.40 parts by weight of the antimicrobial compound to be used in accordance with the invention, which corresponds to the formula in Example 1, are added to this spinning solution. The solution is then stirred for 4 hours until it has become clear and stringy. It is then spun through a 120 bore jet mto a heated spinning duct and wound up at a speed of 200 metres per minute The filaments thus obtained have a spun denier of 32 dtex. The filaments are drawn in a ratio of 1.2.2 in boiling water and continuously dried at 1600C. The filaments are then crimped in known manner by the stuffer box method cut and fixed at 110"C in a screen drum steamer. Staple fibres with a denier of 17 dtex and a staple length of 100 mm are obtained.
Determination of antimycotic activity
Fibres and test carpets antimycotically finished in accordance with the invention were subjected to anti-infection tests in vitro with the test germs Candida albicans and Trichophyton mentagrophytes. The antimycotic inhibiting effect was tested in three different test arrangements.
A) Test methods
The following observations on the anti-infection effect of the additives according to the invention in fibres are based on three test arrangements: I ) agar diffusion test 2) direct contamination test 3) indirect contamination-transfer test.
1) agar diffusion test
This test method provides an insight into the release of active substance in moist medium as a precondition for a contamination-inhibiting or reducing effect.
Quantities of 1 g of the antimycotically finished, first undyed and then dyed fibres and pieces of sample carpet with an edge length of 2 x 2 cm were introduced into Petri dishes containing Nervina agar (composition: 60 g of Nervina malt, 5 g of NaCI, 5 g of peptone, 5 g of glycerol with 11 of water) in such a way that they were completely covered by the nutrient substrate. The surface of the Petri dishes thus prepared were then homogeneously inoculated with germ suspensions of
Trichophyton mentagrophytes (1 ml of suspension containing approximately 3.105 germs per plate) and Candida albicans (1 ml of suspension containing approximately 1.106 germs per plate). After incubation for 72 and 48 hours at 280C, the inhibition zones to be expected from an active antimycotic finish of the material were measured out.
2) Direct contamination test
The direct contamination test was carried out with pieces of sample carpet having an edge length of 2 x 2 cm by impregnating the pieces of carpet with a germ suspension of Trichophyton mentagrophytes and Candida albicans in nutrient solution (composition: see 1) and then introducing them into moist chambers, followed by incubation for 144 hours at 280C. An effective antimycotic finish of the carpet material should prevent a macroscopically visible infestation of the pieces of carpet impregnated with the nutrient substrate.
3) Indirect-contamination-transfer test
This test may be regarded as a final realistic test for assessing the anti-infection effect of an anti-mycotic fibre finish.
Pieces of sample carpet with an edge length of 2 x 2 cm were moistened with 0.2 ml of a germ suspension of Trichophyton mentagrophytes and Candida albicans (germ count: 5.104 Trichophyton mentagrophytes, 2.105 Candida albicans) in physiological NaC1-solution and then slowly dried at room temperature in empty
Petri dishes. The germs applied remained on the carpet material in living form. If, after this drying time of 5 days, a transfer of each piece of carpet is made onto fresh culture dishes containing Nervina agar, sub-cultures of the previously applied fungi are formed at the transfer point in the case of unfinished or ineffectually finished carpet material.
Both the sub-cultivatability and also the number of colonies formed are a direct measure of the anti-infection effect of the finish. The prevention of the subcultivatability at the transfer point is desirable in this test. It is indicative of a fungicidal effect of the incorporated active substance on the contaminating fungi during and after the drying time.
B) Results 1) Agar diffusion tests a) With fibres
Table 3 shows the result of the agar diffusion tests with fibres. The letters a, b, c and d alongside the numbers have the following meanings:
a) original fibre
b) unfixed, dyed
c) heat-setwith saturatedsteamat 130 C d) heat-set with saturated steam and dyed.
Since agar diffusion tests with fibres cannot be quantitatively evaluated exactly, a partially quantitative assessment was made, the symbols used having the following meaning:
neg = no inhibiting effect
+ = slight inhibiting effect, inadequate for protection against infection
++ = adequate inhibiting effect on germ growth
+++ = good effect
++++ = very good effect, inhibition zones > 40 mm.
TABLE 3
Agar diffusion tests with antimycotically finished fibres
Fibres produced in Inhibiting effect against accondance with Example No.: Trich. ment. Cand. alb.
1 a neg. neg.
b neg. neg.
c.1 c neg. neg.
d neg. neg.
1 a neg. neg.
b neg. neg.
c.2 c neg. neg.
d neg. neg.
1 a ++++ +++ b ++++ ++ c ++++ ++++ d +++ ++ 2 a +++ +++ b ++ ++ c ++++ +++ b +++ ++ 3 a +++ +++ b ++ +++ c ++++ +++ d +++ ++ 4 a ++++ ++++ b ++++ +++ c ++++ ++++ d ++++ ++++ 5 a ++++ +++ b ++++ +++ c ++++ ++++ d +++ ++ 6 a ++++ +++ b +++ +++ 7 a ++++ +++ b +++ +++ 8 ++++ ++++ ++++ +++ 9 a +++ +++ b +++ +++ 10 a ++++ ++++ b ++ +++ b) With pieces of test carpet:
The outcome of the fibre tests as reported above prompted the testing of some test carpets by comparison with an unfinished test batch by the agar diffusion test.
Fig. 1 shows the result of a carpet test with fibres produced in Example 4. The inhibition halo around the antimycotic-containing sample, in which no infestation by Trichophyton mentagrophytes is visible, can clearly be seen. Comparable equally satisfactory results were obtained with Candida albicans as test organism. The untreated control batch produced no inhibiting effect on either of the two test germs (c,f. Fig. 2).
2) Direct contamination test
Direct contamination tests were carried out with the test carpets according to
Example 4. Figures 3 and 4 show the result for the test germ Trichophvton mentagrophytes in the control batch and in the two test batches.
3) Indirect contamination transfer test
Table 4 below shows the results obtained with carpets of fibres according to
Example 4. The test samples in question were both undyed and dyed. Diffusion tests and transfer tests are shown together because of their casual association.
TABLE 4
Diffusion test Transfer test Test carpet Cand. alb. Trich. ment. Cand. alb. Trich. ment.
Undyed Z ++++ ++++ +++ dyed +tt+ According to these results, the test carpets are fully active and may be regarded-as protected against infection.
WHAT WE CLAIM IS:
1. Antimycotically active fibres or filaments of a synthetic polymer, the fibres or filaments containing an azole derivative corresponding to the general formula:
in which
Az represents an optionally substituted imidazole or triazole radical;
n=0 or 1;
R1 represents hydrogen, an optionally substituted aliphatic or cycloaliphatic radical, or an optionally substituted phenyl, which may be attached via an oxygen atom, or pyridyl radical; R2 represents an optionally substituted phenyl radical, which may be attached via a single bond or via CH2)rn where m = 1 or 2, or the group -X-R4 where
X is oxygen or sulphur and R4 is an optionally substituted aliphatic or cycloaliphatic radical, or an optionally substituted aryl or aralkyl radical; ;
R3 represents an optionally substituted phenyl radical, an optionally substituted aliphatic or cycloaliphatic radical, an optionally substituted 5membered hetero-aromatic ring, a group derived from a carboxylic acid group or the group -Y-R4 where Y is a keto group or a functional derivative of the keto group and R4 is an optionally substituted aliphatic or eycloaliphatic radical, or an optionally substituted aryl or aralkyl radical; or
R2 and R3, where both radicals represent an optionally substituted phenyl
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (17)
- **WARNING** start of CLMS field may overlap end of DESC **.b) With pieces of test carpet: The outcome of the fibre tests as reported above prompted the testing of some test carpets by comparison with an unfinished test batch by the agar diffusion test.Fig. 1 shows the result of a carpet test with fibres produced in Example 4. The inhibition halo around the antimycotic-containing sample, in which no infestation by Trichophyton mentagrophytes is visible, can clearly be seen. Comparable equally satisfactory results were obtained with Candida albicans as test organism. The untreated control batch produced no inhibiting effect on either of the two test germs (c,f. Fig. 2).2) Direct contamination test Direct contamination tests were carried out with the test carpets according to Example 4. Figures 3 and 4 show the result for the test germ Trichophvton mentagrophytes in the control batch and in the two test batches.3) Indirect contamination transfer test Table 4 below shows the results obtained with carpets of fibres according to Example 4. The test samples in question were both undyed and dyed. Diffusion tests and transfer tests are shown together because of their casual association.TABLE 4Diffusion test Transfer test Test carpet Cand. alb. Trich. ment. Cand. alb. Trich. ment.Undyed Z ++++ ++++ +++ dyed +tt+ According to these results, the test carpets are fully active and may be regarded-as protected against infection.WHAT WE CLAIM IS: 1. Antimycotically active fibres or filaments of a synthetic polymer, the fibres or filaments containing an azole derivative corresponding to the general formula:in which Az represents an optionally substituted imidazole or triazole radical; n=0 or 1; R1 represents hydrogen, an optionally substituted aliphatic or cycloaliphatic radical, or an optionally substituted phenyl, which may be attached via an oxygen atom, or pyridyl radical; R2 represents an optionally substituted phenyl radical, which may be attached via a single bond or via CH2)rn where m = 1 or 2, or the group -X-R4 where X is oxygen or sulphur and R4 is an optionally substituted aliphatic or cycloaliphatic radical, or an optionally substituted aryl or aralkyl radical;; R3 represents an optionally substituted phenyl radical, an optionally substituted aliphatic or cycloaliphatic radical, an optionally substituted 5membered hetero-aromatic ring, a group derived from a carboxylic acid group or the group -Y-R4 where Y is a keto group or a functional derivative of the keto group and R4 is an optionally substituted aliphatic or eycloaliphatic radical, or an optionally substituted aryl or aralkyl radical; or R2 and R3, where both radicals represent an optionally substituted phenylradical, are attached to each other in the 0-positions through a single bond, -(CH2)m-, where m=1 or 2, -CH=CH-, oxygen or sulphur.
- 2. Antimvcotically active fibres or filaments as claimed in Claim 1. which contain an azole derivative corresponding to the general formula:in which Az represents the radicalR' represents hydrogen; R2 represents the radicalwhere Zm represents halogen, halogen phenyl or phenyl, and m=0 to 2; and R3 represents the radical-B-C(CH3)3 where B = CO or CH(OH).
- 3. Antimycotically active fibres or filaments as claimed in Claim 1, which contain an azole derivative corresponding to the general formula:in which Az represents the radicaln =0 or I; R1 represents the radicalwhere Zm = halogen, halogen phenyl or phenyl, and m=0to2 R2 represents a phenyl radical optionally substituted by halogen, halogen phenyl or phenyl, the attachment of the rest of the molecule to the phenyl radical occurring in the o-position through a single bond or CH2)rn where m = 1 or 2; and R3 represents an alkyl, alkenyl, alkynyl, alkoxy carbonyl or alkyl carbonyl radical, or a phenyl radical optionally substituted by halogen, halogen phenyl or phenyl. or an imidazole or triazole radical optionally substituted by halogen or alkyl.
- 4. Antimycotically active fibres or filaments as claimed in Claim 1, which contain an azole derivative corresponding to the general formula:in which Az represents the radicaln=0, R' represents a hydrogen atom, R2 corresponds to the radicaland R3 represents the radical
- 5. Antimycotically active fibres or filaments as claimed in any one of Claims I to 4, wherein the synthetic polymer is a spinnable polyamide, polyacrylonitrile, polyvinyl chloride, polyolefin, polyurethane, polycarbonate or a spinnable polyester.
- 6. Antimycotically active fibres or filaments as claimed in Claim 1, substantially as hereinbefore described with reference to any of the Examples.
- 7. A process for the production of antimycotically active fibres or filaments of a synthetic spinnable polymer, wherein an azole derivative corresponding to the general formula in Claim 1 is dissolved or dispersed in a solvent, and the polymer, optionally dissolved in the same solvent or in a different solvent, is introduced into the resulting solution or emulsion, or the azole derivative is dissolved or dispersed in a spinnable solution of the polymer, and the solution or emulsion thus obtained is spun.
- 8. A process for the production of antimycotically active fibres or filaments of a synthetic spinnable polymer, wherein an azole derivative corresponding to the general formula in Claim I is dissolved in a solvent and the resulting solution is added to a spinnable solution of a polymer immediately before a solution spinning process.
- 9. A process for the production of antimycotically active fibres or filaments of a synthetic spinnable polymer, wherein an azole derivative corresponding jto the general formula in Claim 1 is added to and mixed with a granulated or powder-form spinnable polymer, optionally using a coupling agent or the technique of-sintering on, and the granulated or powder-form polymer is spun by the melt spinning process.
- 10. A process as claimed in Claim 9, wherein the azole derivative is bound to the granulated or powder-form polymer using a polyalkylene oxide compound having a molecular weight of from 400 to 20,000 as an adhesion promoter.
- I I. A process as claimed in Claim 10, wherein a 20 x ethoxylated stearylamine, a 20 to 40 x ethoxylated oleyl or stearyl alcohol or a polyalkylene oxide compound modified with a terminal dimethyl urethane group is used as the adhesion promoter.
- 12. A process for the production of antimycotically active fibres or filaments or a synthetic spinnable polymer, wherein an azole derivative corresponding to the general formula in Claim 1 is dissolved in a substantially involatile solvent, which is soluble or insoluble in the molten polymer, the solution is added by means of a pump to the melt of the polymer, and the melt thus obtained is spun by the melt spinning process.
- 13. A process as claimed in Claim 12, wherein the azole derivative is dissolved or emulsified in E-caprolactam, the solution or emulsion is added to a poly-- caprolactam melt and the resulting melt is spun.
- 14. A process as claimed in Claim 12, wherein the azole derivative is dissolved in 20 to 40 x ethoxylated oleyl or stearyl alcohol or in 20 x ethoxylated stearylamine or in a polyalkylene oxide compound terminally modified with a dimethyl urethane group, the solution or emulsion is added to a spinnable polymer melt, and the resulting melt is spun.
- 15. A process for the production of antimycotically active fibres or filaments of a synthetic spinnable polymer, substantially as hereinbefore described with reference to any of the Examples.
- 16. Antimycotically active fibres or filaments produced by a process as claimed in any one of Claims 7 to 15.
- 17. A textile article comprising antimycotically active fibres or filaments as claimed in any one of Claims 1 to 6 and 16.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772710496 DE2710496A1 (en) | 1977-03-10 | 1977-03-10 | ANTIMYCOTIC FIBERS AND FABRICS |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1600103A true GB1600103A (en) | 1981-10-14 |
Family
ID=6003296
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8975/78A Expired GB1600103A (en) | 1977-03-10 | 1978-03-07 | Antimycotically active fibres and filaments |
Country Status (10)
Country | Link |
---|---|
JP (1) | JPS53139895A (en) |
AT (1) | AT358708B (en) |
BE (1) | BE864759A (en) |
CA (1) | CA1096773A (en) |
DE (1) | DE2710496A1 (en) |
ES (1) | ES467696A1 (en) |
FR (1) | FR2383250A1 (en) |
GB (1) | GB1600103A (en) |
IT (1) | IT7820980A0 (en) |
NL (1) | NL7802600A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3429665A1 (en) * | 1984-08-11 | 1986-02-20 | Bayer Ag, 5090 Leverkusen | WASHABLE, ANTIMICROBIALLY EFFECTIVE FIBERS AND THREADS AND THEIR PRODUCTION |
GB9212403D0 (en) * | 1992-06-11 | 1992-07-22 | Courtaulds Plc | Fibres and filaments |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5319345B2 (en) * | 1974-05-17 | 1978-06-20 |
-
1977
- 1977-03-10 DE DE19772710496 patent/DE2710496A1/en not_active Withdrawn
-
1978
- 1978-03-07 IT IT7820980A patent/IT7820980A0/en unknown
- 1978-03-07 GB GB8975/78A patent/GB1600103A/en not_active Expired
- 1978-03-08 CA CA298,538A patent/CA1096773A/en not_active Expired
- 1978-03-08 JP JP2554078A patent/JPS53139895A/en active Pending
- 1978-03-08 AT AT166878A patent/AT358708B/en not_active IP Right Cessation
- 1978-03-09 NL NL7802600A patent/NL7802600A/en not_active Application Discontinuation
- 1978-03-09 ES ES467696A patent/ES467696A1/en not_active Expired
- 1978-03-10 FR FR7807055A patent/FR2383250A1/en active Granted
- 1978-03-10 BE BE185818A patent/BE864759A/en unknown
Also Published As
Publication number | Publication date |
---|---|
IT7820980A0 (en) | 1978-03-07 |
FR2383250A1 (en) | 1978-10-06 |
FR2383250B1 (en) | 1982-10-22 |
NL7802600A (en) | 1978-09-12 |
BE864759A (en) | 1978-09-11 |
ATA166878A (en) | 1980-02-15 |
ES467696A1 (en) | 1978-10-16 |
AT358708B (en) | 1980-09-25 |
JPS53139895A (en) | 1978-12-06 |
CA1096773A (en) | 1981-03-03 |
DE2710496A1 (en) | 1978-09-14 |
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