CA1096773A - Antimycotically active fibres and filaments - Google Patents
Antimycotically active fibres and filamentsInfo
- Publication number
- CA1096773A CA1096773A CA298,538A CA298538A CA1096773A CA 1096773 A CA1096773 A CA 1096773A CA 298538 A CA298538 A CA 298538A CA 1096773 A CA1096773 A CA 1096773A
- Authority
- CA
- Canada
- Prior art keywords
- radical
- phenyl
- substituted
- polymer
- filaments
- 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.)
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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
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- 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)
Abstract
ABSTRACT OF THE DISCLOSURE
Antimycotic active fibers and filaments of a synthetic polymer which contain as the active ingredient an azole compound of the general formula R1, R2, R3, Az and n being defined in the specification;
and process for their production. The filaments and fibers can be employed for the production if any kind of textile.
Antimycotic active fibers and filaments of a synthetic polymer which contain as the active ingredient an azole compound of the general formula R1, R2, R3, Az and n being defined in the specification;
and process for their production. The filaments and fibers can be employed for the production if any kind of textile.
Description
10~6773 This invention relates to antimycotlcally actlve flbres, filaments and rilament ysrns whlch contaln one or more azole derivatives as actlve constltuents. The lnvention also relates to a process ror produclng flbres and filaments Or this type. Through the presence Or one or more azole derivatives according to the lnventlon ln the flbre or fllament materlal, pathogenic fungl comlng lnto contact with the correspondlng textlles are lnactlvated, thus preventing them from being spread or transrerred to other ob~ects, materials or organlsms.
The antlmycotlc rinlshing Or rlbres and textlle materlals 18 known. In general, the antlmycotloally actlve substance le applled to the surrace Or the rlbre or te~tlle ln a separate process step, the substance belng used ln pure rorm or even ln con~unctlon wlth a surrace-active agent, a blnder or a resln ln order to lmprove dlstributlon and permanence. One dlsadvantage oi thls process is that the antlmycotlcally actlve substance applied to the surrace can readily be removed in washing and cleanln~ processes. In addition, the impurities applied with the antimycotic agent to the polymer surface Orten have adverse errects upon the ieel, appearance and solllng, ageing and wearing behaviour Or the correspondingly rinished te~tlles.
Accordingly, attempts have been made to incorporate the actlve substance ln the ribre substrate it~elr. Unrortunately products such a~ these have not yet been successrully marketed becau~e con~lder~ble dlrrlcultles were obvlously Le ~ 17 846 -2-q~
l~g67~.3 encountered in the production of the rlbres, the activlty Or the product~ ~pun into the ilbres was lnadequate and thelr toxlcological or phy~iologlcal errects upon the human or anlmal body were at lea~t questlonable. Antl-mycotically active additives to polymars which can be ~pun lnto ribres have to be able to klll mlcroorganl~m~ and to prevent thelr growth. ~owever, they must not have any damaging errect upon the ~kin or the body Or warm-blooded anlmal~. In additlon, the compounds used should not adversely airect the dyeabillty oi' the rlbres nor should they accelerate the destructlon Or dye~ and the rlbre~, even ln the presence Or llght. Many baslcally active antlmycotics do not Jati~ry these requirement~ and the require~ents di~cu~sed hereinarter ror the Jub~trate~ Or synthetic ilbreJ or testlles produced thererro~.
Hy contrast, the rilamentJ and ribres accordlng to the lnventlon with the characterlslng reatureJ Or the maln ClalD
have the advantage that they can be process~d wlthout any partlcular technlcal problems lnto rlbres whlch are not dlrrerent in thelr te~tile propertie~ rrom unmodiiied type~.
At the sa~e tlae, they ~how a hltherto uDattainod activity against the ~pr-ading and tranJrer of iungi whlch are pathogenic to hu~ans and aniaals, coupled with complete co patibility with the skin and ~ucosa. Another advantage i~ that the azole derivative~ used in accordance with the lnventlon show high ther~al ~tability. In addition, they are subJtantially insoluble in water ~o that their concentration iJ not reduced Le A 17 846 -3-l~g6773 beyond a tolerable extent by washing, dyeing and finishing process.
Accordingly, the present invention provides antimycotically active fibres and filaments of synthetic polymers which are characterised in that they contain at least 0.01% by weight of an azole derivative corresponding to the general formula:
R2 ..
Rl ~ C - R3 (IH2) Az in which Az represents an optionally substituted imidazole or triazole radical;
_ = 0 or 1;
Rl represents hydrogen, an optionally substituted aliphatic or cyclo-aliphatic radical, or an optionally substituted phenyl or pyridyl radical;
R2 represents an optionally substituted phenyl radical, 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 S-membered heteroaromatic ring, the group of a carboxylic acid derivative B
iO~6773 or the group -Y-R4 where Y is a keto group or a runctional derlvative Or the keto group and R4 18 an optionally substltuted aliphatlc or cycloallphatic radlcal, an optionally substituted aryl or sralkyl radlcal; and R2 and R3, where both radlcals represent an optlonally substituted phenyl radical, are attached ln the o-posltion through -(CH2)~-, where m = 0 to 2, -CH=CH-, o~ygen or sulphur.
Prererred antimycotlcally active rlbres and rllaments are characterlsed ln that they contain an azole derivatlve correspondlng to the general rormula:
Rl _ C - R3 ( ICH2)n Az in whlch Az represents the radlcal N or N\
HC CH HC N
Il 11 ll 11 N CH N - CH
Rl represents hydrogen;
R2 represent~ the radlcsl ~ where Z,~
Z~ = halogen, halogen phenyl or phenyl, and m = 0 to 2; and R3 represents the radlcal -~ C(CH3)3 where Le A 17 846 -5_ B = CO or CH(OH).
Other preferred antimycotically active fibres and rilaments are characterised ln that they contaln an azole derlvatlve correspondlng to the general formula:
Rl C __ R3 (ClH2)n Az ln whlch Azrepresents the radlcal N or N
/ \ / \
HC CH HC N
Il li 11 li N _ CH N - CH
n = O or l;
Rl represents the radlcal ~ ~ O _ where m Zm = halogeD, halogen phenyl or phenyl, and = O to 2;
R represents a phenyl radlcal optlonally substltuted by halogen, halogen phenyl or phenyl, attachment to the phenyl radlcal occurrlng in the o-posltlon through -(CH2)m - where m = O to 2; and R represents an alkyl, alkenyl, alkinyl, alko~y carbonyl or alkyl carbonyl radlcal, or a phenyl radlcal optlonally substltuted by halogen, halogen phenyl or phenyl, or an imldazole or trlazole radlcal optlonally substltuted by halogen or alkyl.
Particularly preferred antlmy¢otlcally actlve flbres Le A 17 846 -6-1~"6~3 and filaments are characterised in that they contaln a~
azole derivative corresponding to the general rormula:
Rl C R3 CH2)n Az in which Az represents the radical N \
BC CH
il 11 N ~ CH
n = O, Rl represents a hydrogen atom, R2 represent~ the radical Cl ~ O-, and R3 represents the radical _E_C(CH3)3.
The azole antimycotic~ uqed in accordance with the invention are already known and are described in the rollowing publication~:
DT-OS NOB. BE-PS NOB. US-PS Nos.
1,911,646 720,801 774,621 3,737,531 1,949,012 741,310 776,212 3,737,548
The antlmycotlc rinlshing Or rlbres and textlle materlals 18 known. In general, the antlmycotloally actlve substance le applled to the surrace Or the rlbre or te~tlle ln a separate process step, the substance belng used ln pure rorm or even ln con~unctlon wlth a surrace-active agent, a blnder or a resln ln order to lmprove dlstributlon and permanence. One dlsadvantage oi thls process is that the antlmycotlcally actlve substance applied to the surrace can readily be removed in washing and cleanln~ processes. In addition, the impurities applied with the antimycotic agent to the polymer surface Orten have adverse errects upon the ieel, appearance and solllng, ageing and wearing behaviour Or the correspondingly rinished te~tlles.
Accordingly, attempts have been made to incorporate the actlve substance ln the ribre substrate it~elr. Unrortunately products such a~ these have not yet been successrully marketed becau~e con~lder~ble dlrrlcultles were obvlously Le ~ 17 846 -2-q~
l~g67~.3 encountered in the production of the rlbres, the activlty Or the product~ ~pun into the ilbres was lnadequate and thelr toxlcological or phy~iologlcal errects upon the human or anlmal body were at lea~t questlonable. Antl-mycotically active additives to polymars which can be ~pun lnto ribres have to be able to klll mlcroorganl~m~ and to prevent thelr growth. ~owever, they must not have any damaging errect upon the ~kin or the body Or warm-blooded anlmal~. In additlon, the compounds used should not adversely airect the dyeabillty oi' the rlbres nor should they accelerate the destructlon Or dye~ and the rlbre~, even ln the presence Or llght. Many baslcally active antlmycotics do not Jati~ry these requirement~ and the require~ents di~cu~sed hereinarter ror the Jub~trate~ Or synthetic ilbreJ or testlles produced thererro~.
Hy contrast, the rilamentJ and ribres accordlng to the lnventlon with the characterlslng reatureJ Or the maln ClalD
have the advantage that they can be process~d wlthout any partlcular technlcal problems lnto rlbres whlch are not dlrrerent in thelr te~tile propertie~ rrom unmodiiied type~.
At the sa~e tlae, they ~how a hltherto uDattainod activity against the ~pr-ading and tranJrer of iungi whlch are pathogenic to hu~ans and aniaals, coupled with complete co patibility with the skin and ~ucosa. Another advantage i~ that the azole derivative~ used in accordance with the lnventlon show high ther~al ~tability. In addition, they are subJtantially insoluble in water ~o that their concentration iJ not reduced Le A 17 846 -3-l~g6773 beyond a tolerable extent by washing, dyeing and finishing process.
Accordingly, the present invention provides antimycotically active fibres and filaments of synthetic polymers which are characterised in that they contain at least 0.01% by weight of an azole derivative corresponding to the general formula:
R2 ..
Rl ~ C - R3 (IH2) Az in which Az represents an optionally substituted imidazole or triazole radical;
_ = 0 or 1;
Rl represents hydrogen, an optionally substituted aliphatic or cyclo-aliphatic radical, or an optionally substituted phenyl or pyridyl radical;
R2 represents an optionally substituted phenyl radical, 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 S-membered heteroaromatic ring, the group of a carboxylic acid derivative B
iO~6773 or the group -Y-R4 where Y is a keto group or a runctional derlvative Or the keto group and R4 18 an optionally substltuted aliphatlc or cycloallphatic radlcal, an optionally substituted aryl or sralkyl radlcal; and R2 and R3, where both radlcals represent an optlonally substituted phenyl radical, are attached ln the o-posltion through -(CH2)~-, where m = 0 to 2, -CH=CH-, o~ygen or sulphur.
Prererred antimycotlcally active rlbres and rllaments are characterlsed ln that they contain an azole derivatlve correspondlng to the general rormula:
Rl _ C - R3 ( ICH2)n Az in whlch Az represents the radlcal N or N\
HC CH HC N
Il 11 ll 11 N CH N - CH
Rl represents hydrogen;
R2 represent~ the radlcsl ~ where Z,~
Z~ = halogen, halogen phenyl or phenyl, and m = 0 to 2; and R3 represents the radlcal -~ C(CH3)3 where Le A 17 846 -5_ B = CO or CH(OH).
Other preferred antimycotically active fibres and rilaments are characterised ln that they contaln an azole derlvatlve correspondlng to the general formula:
Rl C __ R3 (ClH2)n Az ln whlch Azrepresents the radlcal N or N
/ \ / \
HC CH HC N
Il li 11 li N _ CH N - CH
n = O or l;
Rl represents the radlcal ~ ~ O _ where m Zm = halogeD, halogen phenyl or phenyl, and = O to 2;
R represents a phenyl radlcal optlonally substltuted by halogen, halogen phenyl or phenyl, attachment to the phenyl radlcal occurrlng in the o-posltlon through -(CH2)m - where m = O to 2; and R represents an alkyl, alkenyl, alkinyl, alko~y carbonyl or alkyl carbonyl radlcal, or a phenyl radlcal optlonally substltuted by halogen, halogen phenyl or phenyl, or an imldazole or trlazole radlcal optlonally substltuted by halogen or alkyl.
Particularly preferred antlmy¢otlcally actlve flbres Le A 17 846 -6-1~"6~3 and filaments are characterised in that they contaln a~
azole derivative corresponding to the general rormula:
Rl C R3 CH2)n Az in which Az represents the radical N \
BC CH
il 11 N ~ CH
n = O, Rl represents a hydrogen atom, R2 represent~ the radical Cl ~ O-, and R3 represents the radical _E_C(CH3)3.
The azole antimycotic~ uqed in accordance with the invention are already known and are described in the rollowing publication~:
DT-OS NOB. BE-PS NOB. 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 be~t to use at least 0.01 % by weight, but prererably rroD 0.01 to 5 ~ by weight,based on the total weight of the fibres or filaments of at least one of Le A 17 846 -7-10"6773 the azole derivatives defined ln detall above, The present lnventlon also provides a process for the productlon Or the flbre-rormlng polymers wlth the charncterlslng features of the maln Clalm. This process 18 characterlsed ln that azole derlvatives corresponding to the rormulae Or the maln Clalm are added to and mlxed wlth the poly~ers be~ore splnnlng.
The antlmycotlcally actlve azole derlvatives may be mi~ed in by varlous nethods. The partlcular procedure adopted will be determined by the partlcular polymer to be spun. The problem can be solved most easlly in the case Or fibre~rorming polymers which are spun rrom solvents by the dry spinning or wet spinning process, In the solutlon splnnlng processes, the particular polymer 18 dissolved in a solvent, Fll~ment rormatlon 18 obtalned by evaporatlng the solvent or by coagulsting the polyner in the precipitation bath. Processes such as these are descrlbed in detall, ror e~ample, ln Ullmanns Encyclopadle der technischen Chemie; Verlag Chemle, WeiDheim/Bergstrasse;
4th Edition, Vol, 11; pages 257 et seq, The antlmycotlc agents used in accordance with the invention may be dissolved in the solvent berore the poly er to be spun is introduced into the solvent, However, the products used accordiDg to the invention may also be introduced into the spinnable solutions or the polymer, In this case, it is possible individually to add theD dissolved in a solvent to the spinning solution before spinning or in~ediately be~ore the solution emerges rrom the Le ~ 17 846 -8-splnning ~et. In every csse, provislon must be made to ensure that the addltlve 18 uni~ormly dlstrlbuted ln the spinning solutlon. This can be guaranteed with su~rlclent certalnty by dynamlc and static mi~ers.
The solvent rOr the antimycotic used in accordance with the invention does not have to be ldentlcal wlth the solvent ror the polymer. Thu~, it i~ posslble by sultably ~electing variou~ solv~nt~ to produce a splnnable emulslon when the solvent Or the antlmycotlc 18 not s-luble ln the solutlon Or the poly~er. The solution Or the antlmycotlc is present in this emul~ion in the rorm Or ~lne droplet~
ln the splnnlng ~olution. Arter precipltatlon Or the polymer ln dry or wet spinnlng proceeees, l~land~ with an increased concentration Or antlmycotlc are ror ed ln the rlla~ent. The ~igratablllty Or the actlve substance can be purposerully lnrluenced by measures such as these.
Polymers and correspondlng solvents whlch are proces~ed lnto rlbres and rllaments by solutlon eplnning processes are described in Ullmanns Encyclopadle der technlechen Chemle, Vol. 11; pages 291 et seq.
Accordlngly, the preYent lnventlon also provides a process ror the produotlon Or antimycotlcally actlvo ribres and Silaments Or synthetic spinnable polymere which i~
characterised in that an azole derivative correspondine to the general rormula ln the maln Clalm 18 dlssolved or emul~iried ln a solvent and the polymer, optionally dissolved in the same solvent or a diiferent solvent, is introduced Le A 17 846 -9-1~96773 into thc resulting ~olution or emulsion or the azole derivative i~ dissolved or emulsirled in a spinnable solution of the poly~er, and the resultlng solutlons or emulelons are spun. In the case oi polymers processed lnto rlbres and ril~ents rro~ the melt, the procedure by which the antimycotics are inoorporated has to be modlrled.
Beiore they are proc3ssed lnto rlbres and rllaments ruslble polymers are generally present ln the rorn Or granulate~
rormed by cuttlng polymer wlree or ribbons. It 18 also posslble, however, to spin poly~er po~der~ rrOm the melt.
~he azole derlvatlves u~ed ln accordanoe wlth the lnventlon may be mised with the polyners to bo ~eltsd berore ~plnnlng.
Mising m8y be carried out ln a tumble ~lxer. Slnce the antlmycotlc and polymer are ln danger Or dl~lntegratlng, better and more unlrorm dlstrlbutlon may be obtalned by blnding the antlmyootlc to the granules by mean~ Or a coupllng agent, such a8 ror esample a stearylamlne ethosylated 20 tlmes, ln a low concentratlon. Slnterlng on at elevated temperatures by means Or a rluld mixer also leads to a flr~er bond between the active substance and the polyner surrace.
In one prererred process accordlng to the lnventlon, the antl-ycotlcally active compound is added to the partlcular polymer melt l~edlately berore splnnlng. Slnce the pure actlve substance cannot erfectlvely bc metered lnto the elt, the required azole derivative is dlssolved ln a eubstantlally lnvolatlle ~olvent, mstered lnto the melt by means or a pressure plston or gear meterlng pump and unlrormly Le ~ 17 846 -10-1al~6773 dissolved or distributed ln the ~elt by means of dynamic or statlc mixers. In thls case, too, the state o~
distribution of the antimycotic ln the polymer matrix may largely be influenced by the cholce Or the solvent. Ir, ror e~ample, a solvent whlch 19 soluble ln the polymer IR
selected ror the antimycotic, the solvent and antlmyootlc are dlstrlbuted completely unlrormly in the polymer.
~owever, lf a substance whlch 19 lnsoluble ln the polymer ls selected as the solvent, the solutlon of the antlmycotlc in the polymer 19 present ln the form Or rine droplets which, after splnning and drawlng, change shape into flne rlbrils ln the polymer. Polymers whlch are spun from the melt and the melt spraying technique ltselr are described ln detall ln Ullmanns Encyclopadle der technlschen Chemle; Vol. 11;
pages 291 et seq and pages 264 et seq. In thls connectlon, partloular slgnlflcance ls attached to the modificatlon Or polyamides.
Accordlngly, the present inventlon also provides a process ror the production Or antlmycotically actlve rlbres and rilaments Or synthetic ~plnnable polymers, characterised in that an azole derivative corresponding to the general rormula in the main Claim is added to and mixed wlth a granulated or powder-rorm spinnable polymer, optionally using a coupling agent or the technique of sintering on, and the granulated or powder-rorm polymer is spun by the melt ~pinning process.
A preferred process is one in whlch the azole derlvatlve Le A 17 846 -11-l~q6 773 is bound to the grsnulated or powder-iorm polymer uslng a polyalkylene oxide compound having a molecular welght ot rrom 400 to 20,000 as an adhesion pro~oter.
Stearylamine ethoxylated 20 times, oleyl or stearyl alcohol ethoxylated rrom 20 to 40 times or polyalkylene o~idH
coDpounds modiried by a terminal dimethyl urethane group are particularly suitable ror this purpose.
As already mentioned, lt i~ posslble by uslng solvent~
during the addition Or the antimycotlcs to polymer solutlons and melts to control the distribution Or the active substance ln the polymers, which in turn enables their migration behaviour to be inrluenced. Ir caprolactam,ror e~ample, 18 selected as solvent, the caprolactam solvent and antimycotlc are present in completely unirorm distribution in the polyamide arter metering into a polycaprolactam melt because both components have dissolved in the melt. Ir, however, an oleyl alcohol etho~ylated 20 times i9 selected as solvent, rine flbrils containlng the etho~ylated oleyl alcohol and, thereln, the antimycotic are formed in the oriented polymer. This ethoxylated oleyl al¢ohol cannot be washed out to any signirlcant e~tent in washing and dyeing proce~ses. By virtue Or its ribrll structure, the antimycotic h~s become labile in the polyamide and can migrate to the surface Or the polymer and develop its requlred efrect there. Some e~amples Or solvents with which the antimycotics can be spun into the particular polymer6 in homogeneous, dis601ved rorm or in ribril ~orm are given in Table 1 below.
Le ~ 17 846 -12-10~6773 ~P~ ~ ,., .
o ~ ~
~ a o o o ` '' o o o ~ ~ ~ ~ .
~ ~ bO 00 R ~ o o o .. ~ .
O ~~ 0 3 0 a ~cJ~ :,.o o~d6b o --~ A ~1 ~ ~ J ~ ,~
o ~ ~ ~ ~ o~ ~1 a ~ e ~ 3 o~ ~ 0~ ~ o3 O C ~ t 0~ b~ 0 u~ ~ ~ t~ o ~ P, ._.
;
.
.0 0 ~ ~0 ~ d a ~ ~
Tt O C~ ~ ~
~ ~ 0 a a O
~ o o 51 4 b b 1~3 ~.
Le A17 846 -13-10~677~
or these solvents, ~hose with a water retention capacity or hydrophillc properties are preferred. Particularly suitable hydrophilicity-increasing solvents ~or the antimycotics are the derivatives Or polyalkylene osides with molecular weights Or from 400 to 20,000, particularly those of poly-ethylene oxide. Their hydrophilising effect is known irom publications in which the relationship between static charging, relative air humidity and the presence oi' poly-alkylene oxides is described ~or textiles (5hemie-fasern/Textilindustrie; May 1972, page~ 397 et seq). The antimycotic activity can also be greatly improved by the presence of small quantitles of water (Dle ~ygiene des Teppichbodens, Manfred Rotter; Gustav Flscher Verlag;
Stuttgart 1975; page 240).
Accordingly, a partlcularly prererred proce~s is one in which the azole derivative 18 added to the prepared splnning solution or to the poly~er melt immediately before spinning using ~solvents~. 20 s Ethoxylated stearylamine, 20 to 40 x ethoxylated oleyl or stearyl alcohol, polyalkylene oxide compounds modified with a terminal dlmethyl urethane grDup, trls-nonyl-phenyl phosphlte and, in the case o~ the polyamides, t-caprolactam are particularly suitable ror this purpose.
The polymers produced ln accordance with the lnvention and the ~ibres obtained from them may be processed without particular difficulty into textlles ln the textile lndu~try.
The flbres may be processed either on their own or in admixture Le A 17 846 -14-l~q6773 with non-antlmicrobially active natural and synthetic fibres.
The following are mentioned as esamples of textiles ror whlch antimycotic activity is particularly de8irable: car-petings, ~tockings, shirts and the like. The testile~ in s que~tion primarily consist of or contaln the fibres produced by the process according to the invention and may come into permanent or even temporary contact with the suriace Or the body. In the presence of antimycotics, the fungi which may possibly be transrerred in the event Or such contact 10 are killed ofi'. Any propagation and tran~fer Or the fungi to other regions Or the skin or other organisms i~ lnterrupted.
The interruption Or this transfer chain is particularly signiricant in the case Or testile floor coverings on which people frequently tread with bare feet, i.e. in the case Or floor coverings in the bedrooms and bathrooms Or hotels and private dwellings.
The following Examples illustrate the invention without limiting it. The percentages are by weight.
,EXAMPl.E 1 200 g Or a 20 s ethosylated stearylamine are added in a tumble miser in the absence oi' moisture to 100 kg of a dried polyamide-6 granulate which contains 0.05 ~ by weight oi' titanium dioside and which has a relative viscosity of 2.7, as measured on a 1 ~ solution in m-cresol at 25C. The misture is tumbled rOr about 2 hours, ai'ter which 200 g of a rinely ground antimycotic correQponding to the formula:
Le A 17 846 -15-Cl- ~ -0-C -C-C(C~3)3 ~C C~
,1 il N CH
are added, rollowed by mi~ing ~or another 3 hours. The granulate is rused and spun ln an extruder.
The screw Or this eYtruder has a length Or 72 cm and a diameter of 3 cm. The extruder barrel i8 heated to 285C.
The screw has a rotatlonal speed Or 90 rpm. The melt shows a pressure Or 80 bars at the output end Or the extruder. It rlows lnto two double gear meterlng pumps which divide the rlow of melt into iour component streams, each having a quantitative rlow oi 40 g Or polya~ide per minute. Each Or these component etreams is iorced through a metal gauze with16000meshes/cm2 and spun through a spinning ~et with 16 bores having n dia~eter Or O.30 ~m. The bundlo Or rilaments issuing irom the iour ~ets is treated with a spin-finlsh arter cooling in the epinning duct and wound up at 8 rate oi 460 metres per minute. The undrawn iilsments have sn individual denier Or 54 dtex. The rilaDents can be processed into spun iibres snd rilament yarn.
a. Production Or spun ribres The iilanente are combined rrom ten bobbins to iorm a tow, drawn in a ratio Or 1:3.4 by means Or drawing rolls and crimped in a sturrer bo~. The crimped tow csn then be cut in such a way that an average staple length Or 150 is obtained.After heat-setting with saturated ~team at 130 C~
Le A 17 846 -16-lOq6773 the ribres have an lndividual denier Or 17 dte~. They are spun by one Or the methods nor~ally used in the te~tllo industry to ~orm a yarn having a yarn count Or 37. A turted carpet with a ribre input weight Or 700 g/m2 i~ produced from this yarn.
b. Production Or textured rll~ent yarn The rilaments are combined rrom two bobbin~ into a tow, drawn in a ratio oi 1:3.4 over godets and crimped with superheated steam ln a teYturing nozzle at a temperature oi' 160C. A~ter cooling in the absence Or tension, the yarn is wound up. It has a total denier Or 2200 dtex. The i'ila ents have an lndividual denier Or 17 dte~. A turted carpet with a ribre input weight Or 700 g/m2 i~ produced rro-the i'ilaments.
The turted carpets are dyed in a winch vat with dye~
having the rollowing constitution:
~ N=N ~ N-N ~ C2~5 (dye I) ~ N = N ~ \/ (dye II) ~\
CF3 ~0 so3 Le A 17 846 -17-10~6773 0 N~
~ S03~ (dy~ III) NH ~ NH-C0-CH3 B ln the presence of 0.5 S of Levegal FTS, an ~nlon-actlve levelllng aid produced by BAYER AG, at a pH-vslue Or from 4 to 5. The carpet 18 backed wlth a coatlng Or Lipolan CT 35, a rubber lateY produced by Chemlsche Werke Huls AG. In order to test the dye finishes for fastness to llght, fibre ~ample~
are dyed. The results are set out ln Table 2 below.
c. Comparlson tests c.l The 20 s ethoYylated stearylamlne above ls applied to the polya~lde-~-granulate in a tu~ble miYer. The splnnlng condltlons are the ~a~e.
c.2 Unmodlfled polyamlde-~-granulate 18 spun under the same condltlons.
ade rn~rK
Le A 17 84~ -18-1~6773 ~oc ~
o ~ , , , ~ "
C~ ~1 O ID P
,~ s ~¦ ~ ~ , ~ a '¢ E~ 6 Le A 17 846 -19-~6773 As in Esample 1, polyamlde-6~ granulate i8 melted in an eYtruder. The melt rlows through a static miser of the type described in German Auslegeschrift No. 2,328,795. The static oiYer has a length or 36 cm and a diameter of 2 cm. Berore entering the miser, 1.60 g/minute Or a 20 % solution heated to 80C Or the antimycotic corresponding to the rormula in Example 1 in caprolactam are added to the melt by means Or a piston pump (LEWA pump; type M~ 1). The rlbres contalnlng 0.2 % oi the antlmycotlc are spun and worked up in the oame way as in Example 1.
Polyamide-6 granulate 1~ melted ln the same wsy as described in E~ample 1. Arter the estruder, the melt rlows through a dynamic miser havlng a dlameter or 6 cm. (~AHMAG:
Inrormation Service No. 11/1975). The additive i9 lntroduced and the rlbres are worked up in the same way as described in Esamples 2 and 1.
Poly~mide-6 granulate is melted in nn e~truder and introduced into a dynamic miYer in the same way as described in Esample 3. Bei'ore entering the mixer, 4.8 g/minute o~
a 10 f solution heated to 80C or tho antimycotlc corresponding to the rormula in Example 1 in 20 x ethoxylated stearyl alcohol, Or which the terminal OH-radical has been reacted to rorm a dimethyl urethane group in accordance with German O~fenlegungsschri~t No. 2,410,861, are addod to the melt. The ribres are spun and worked up in the same way as in Esample 1.
Le A 17 846 ~20-10~6773 Esamination Or the ribres under an optical micro~cope re~eals ribrillsr inclusions Or the additlves in the ribrefi. The ~ibrils have a diameter Or about 2 ~n and an average length o~ more than 100 ~m.
Caprolactam i8 continuou~ly polymerised into polyamlde-6 The melt is rreed rrom low molecular weight rraction~ in a vacuum stage and then delivered to several ~pinning units.
A component stream or 1350 g/minute enters a statlc miser 120 cm long and 10 cm in diameter, Or the type de~cribed in German Auslegeschrift No. 2,328,795. Berore the ~tatlc miser, 27 g/minute Or a 10 ~ solution heated to 80C ot the antimycotic corresponding to the rormula in Esample 1 in 20 s ethosylated oleyl alcohol are added. The melt i8 distributed to nine spinning stations each comprising a 126-bore ~pinning Jet. The ribres is~uing rrom the spinning ~ets are blown cool with air, prepared and wound up at a rate Or 200 metres per minute. The rilaments are processed in the sa~e way a~ in Esample lb. Fibrils are visible under an optical microscope, as described in Esample 4.
200 g Or a 20 s ethosylated stearyl alcohol arc added in a tumble miser in the absence Or moisture to 100 kg Or a polyethylene terephthalate granulate which contains 0.25 ~
by weight Or titanium dioside and which has a solution viscosity Or o.66 as measured in accordance with DIN 53 728. In the same way as in Esa~ple 1, 200 g Or the antimycotic corre~ponding Le ~ 17 846 -21-~6773 to the ~or~ula ln E~ample l are bound to the sur~ace oi the granulate. Spinnlng 1~ carrled out ln the apparatus dcscrlbed ln E~auple l. The rollowlng te~t para~eters are ~alntalned:
Temperature oi' the ostruder barrel: 295C
Melt pressure: 90 bars Throughput: 11.6 kg/h Take-orr rate: lO00 ~/ lnute Jet~: 4 s 36 bore~;
0.25 Gross d-nler: 484 dtes.
The iila ents are drawn ln a draw-twlstlng ~achlne.
The drawlng rstlo 18 1:4.4. The rllanent yarns havlng a denler oi' llO dtes are testured by the ralse-twl~t Dethod and ~ade up lnto a knitted i'abrlc.
Polyethylene terephthalate 18 ~elted ln the sa~e way as descrlbed ln Esa ple 6. The estruder 18 iollowed by a statlc ~i~er ln the sa~e way as ln Esa~ple 2. Beiore enterln~ the ~lser, 3.86 g/~lnute Or a 15 ~ oolutlon oi the antl~ycotlc correspondlng to the i'or~ula ln Exauple 1, ln trl~-nonyl-phenyl phosphlte, are added to and ~lsed wlth the polyester ~elt. The rllaDents are ~pun and worked up ln the sa~e way as ln Esa ple 6.
No ilbrlllar lncluslon~ are vlslble under an optlcal rlcroscope.
Polyethylene terephthalate 19 ~elted ln the sa~e way Le A 17 846 -22-~q6773 as described ln E~ple 6. ~iter the estruder, the nelt rlows throu~h a dyna~lc miser ln tho same way as ln E~ample 3.
Before entering the miYer, 3.90 g Or a 10 % solution heated to 80C of the antimycotic correspondlng to the i'ormula in E~ample 1 in 20 s etho~ylated stearyl alcohol, which contains a terminal dlmethyl urethane group in accordance with German Ofrenlegung9~chrift No. 2,409,715, are addod to the melt.
The rilaments are spun and worked up in the same way ae described in Esa~ple 6.
Fibrillar inclusions are visiblo in the filaments undor an optical microscope.
100 parts of syndiotactic polyvinyl chloride are dissolved at 140 C in 505 part~ by weight o~ cycloho~anone with uniror addition of 1.5 parts by weight ot an organic tln stabiliser.
0.1 part Or the antimycotic corre~ponding to the i'ornula ln Esample 1 i~ added to this solution. Arter 10 mlnutes, the spinning solution obtained i9 riltered at 135C and pressed by means Or a heated gear pu-p through the ~plnning ~et which is also heated. 38 . 5 g/minute Or solution are delivered through the 300 bore spinning jet with a bore diameter oi' 0.08 mm.
This corresponds to 6 . 35 g o~ PVC .
The precipitation bath consists of a misture of 20 %
of cyclohesanone, 30 ,~ oi isopropanol and 50 % of water.
The precipitation bath has a temperature of 60C. The bundle of filaments is drawn off from the nozzle at 7 metres per minute and intensively washed in water at 60 to 80C.
Le A 17 846 -23-~3~6773 The bundle of rilaments is then drawn ln boiling water in a ratio ot 1:3.5 and drled ln reclrculatlng alr at 120C.
A splnning solutlon i8 prepared by heatlng 280 parts by welght Or polyacrylonltrlle powder and 720 parts by welght of dlmethyl rormamide to 80C. 1.40 parts by welght of the antlmlcroblal compound to be used in accordance with the lnvention, whlch corresponds to the rormula in EYample 1, are added to this splnnlng solutlon. The solutlon ls then stlrred ior 4 hours untll lt has become clear and strlngy.
It is then spun through a 120 bore ~et lnto a heated spinnlng duct and wound up at a speed or 200 metres per mlnute. The fllaments thus obtalned have a spun denler Or 32 dte~. The i'ilaments are drawn in a ratio Or 1:2.2 ln bolling water and continuously dried at 160C. The rilaments are then crimped in known manner by the sturrer bo~ method, cut and ri~ed at 110C in a screen drum steamer. Staple ribres with a denier Or 17 dteY and a staple length Or 100 mm are obtained.
Determination of antimycotic activity Fibres and test carpets antimycotlcally rlnished in accordance with the invention were sub~ected to anti-infection tests in vitro with the test germs Candida albicans and Trichophyton menta~roPhytes. The antimycotic inhibiting effect wa~ tested in three different test nrrangements.
A) Te~t methods Le A 17 846 -24- ~-`
The rollowing observatlons on the antl-lnrectlon errect Or the additlves according to the lnventlon ln rlbres are ba~ed on three test arrangement~:
l) agar dlrrusion test 2) dlrect contamlnatlon test
The antlmycotlcally actlve azole derlvatives may be mi~ed in by varlous nethods. The partlcular procedure adopted will be determined by the partlcular polymer to be spun. The problem can be solved most easlly in the case Or fibre~rorming polymers which are spun rrom solvents by the dry spinning or wet spinning process, In the solutlon splnnlng processes, the particular polymer 18 dissolved in a solvent, Fll~ment rormatlon 18 obtalned by evaporatlng the solvent or by coagulsting the polyner in the precipitation bath. Processes such as these are descrlbed in detall, ror e~ample, ln Ullmanns Encyclopadle der technischen Chemie; Verlag Chemle, WeiDheim/Bergstrasse;
4th Edition, Vol, 11; pages 257 et seq, The antlmycotlc agents used in accordance with the invention may be dissolved in the solvent berore the poly er to be spun is introduced into the solvent, However, the products used accordiDg to the invention may also be introduced into the spinnable solutions or the polymer, In this case, it is possible individually to add theD dissolved in a solvent to the spinning solution before spinning or in~ediately be~ore the solution emerges rrom the Le ~ 17 846 -8-splnning ~et. In every csse, provislon must be made to ensure that the addltlve 18 uni~ormly dlstrlbuted ln the spinning solutlon. This can be guaranteed with su~rlclent certalnty by dynamlc and static mi~ers.
The solvent rOr the antimycotic used in accordance with the invention does not have to be ldentlcal wlth the solvent ror the polymer. Thu~, it i~ posslble by sultably ~electing variou~ solv~nt~ to produce a splnnable emulslon when the solvent Or the antlmycotlc 18 not s-luble ln the solutlon Or the poly~er. The solution Or the antlmycotlc is present in this emul~ion in the rorm Or ~lne droplet~
ln the splnnlng ~olution. Arter precipltatlon Or the polymer ln dry or wet spinnlng proceeees, l~land~ with an increased concentration Or antlmycotlc are ror ed ln the rlla~ent. The ~igratablllty Or the actlve substance can be purposerully lnrluenced by measures such as these.
Polymers and correspondlng solvents whlch are proces~ed lnto rlbres and rllaments by solutlon eplnning processes are described in Ullmanns Encyclopadle der technlechen Chemle, Vol. 11; pages 291 et seq.
Accordlngly, the preYent lnventlon also provides a process ror the produotlon Or antimycotlcally actlvo ribres and Silaments Or synthetic spinnable polymere which i~
characterised in that an azole derivative correspondine to the general rormula ln the maln Clalm 18 dlssolved or emul~iried ln a solvent and the polymer, optionally dissolved in the same solvent or a diiferent solvent, is introduced Le A 17 846 -9-1~96773 into thc resulting ~olution or emulsion or the azole derivative i~ dissolved or emulsirled in a spinnable solution of the poly~er, and the resultlng solutlons or emulelons are spun. In the case oi polymers processed lnto rlbres and ril~ents rro~ the melt, the procedure by which the antimycotics are inoorporated has to be modlrled.
Beiore they are proc3ssed lnto rlbres and rllaments ruslble polymers are generally present ln the rorn Or granulate~
rormed by cuttlng polymer wlree or ribbons. It 18 also posslble, however, to spin poly~er po~der~ rrOm the melt.
~he azole derlvatlves u~ed ln accordanoe wlth the lnventlon may be mised with the polyners to bo ~eltsd berore ~plnnlng.
Mising m8y be carried out ln a tumble ~lxer. Slnce the antlmycotlc and polymer are ln danger Or dl~lntegratlng, better and more unlrorm dlstrlbutlon may be obtalned by blnding the antlmyootlc to the granules by mean~ Or a coupllng agent, such a8 ror esample a stearylamlne ethosylated 20 tlmes, ln a low concentratlon. Slnterlng on at elevated temperatures by means Or a rluld mixer also leads to a flr~er bond between the active substance and the polyner surrace.
In one prererred process accordlng to the lnventlon, the antl-ycotlcally active compound is added to the partlcular polymer melt l~edlately berore splnnlng. Slnce the pure actlve substance cannot erfectlvely bc metered lnto the elt, the required azole derivative is dlssolved ln a eubstantlally lnvolatlle ~olvent, mstered lnto the melt by means or a pressure plston or gear meterlng pump and unlrormly Le ~ 17 846 -10-1al~6773 dissolved or distributed ln the ~elt by means of dynamic or statlc mixers. In thls case, too, the state o~
distribution of the antimycotic ln the polymer matrix may largely be influenced by the cholce Or the solvent. Ir, ror e~ample, a solvent whlch 19 soluble ln the polymer IR
selected ror the antimycotic, the solvent and antlmyootlc are dlstrlbuted completely unlrormly in the polymer.
~owever, lf a substance whlch 19 lnsoluble ln the polymer ls selected as the solvent, the solutlon of the antlmycotlc in the polymer 19 present ln the form Or rine droplets which, after splnning and drawlng, change shape into flne rlbrils ln the polymer. Polymers whlch are spun from the melt and the melt spraying technique ltselr are described ln detall ln Ullmanns Encyclopadle der technlschen Chemle; Vol. 11;
pages 291 et seq and pages 264 et seq. In thls connectlon, partloular slgnlflcance ls attached to the modificatlon Or polyamides.
Accordlngly, the present inventlon also provides a process ror the production Or antlmycotically actlve rlbres and rilaments Or synthetic ~plnnable polymers, characterised in that an azole derivative corresponding to the general rormula in the main Claim is added to and mixed wlth a granulated or powder-rorm spinnable polymer, optionally using a coupling agent or the technique of sintering on, and the granulated or powder-rorm polymer is spun by the melt ~pinning process.
A preferred process is one in whlch the azole derlvatlve Le A 17 846 -11-l~q6 773 is bound to the grsnulated or powder-iorm polymer uslng a polyalkylene oxide compound having a molecular welght ot rrom 400 to 20,000 as an adhesion pro~oter.
Stearylamine ethoxylated 20 times, oleyl or stearyl alcohol ethoxylated rrom 20 to 40 times or polyalkylene o~idH
coDpounds modiried by a terminal dimethyl urethane group are particularly suitable ror this purpose.
As already mentioned, lt i~ posslble by uslng solvent~
during the addition Or the antimycotlcs to polymer solutlons and melts to control the distribution Or the active substance ln the polymers, which in turn enables their migration behaviour to be inrluenced. Ir caprolactam,ror e~ample, 18 selected as solvent, the caprolactam solvent and antimycotlc are present in completely unirorm distribution in the polyamide arter metering into a polycaprolactam melt because both components have dissolved in the melt. Ir, however, an oleyl alcohol etho~ylated 20 times i9 selected as solvent, rine flbrils containlng the etho~ylated oleyl alcohol and, thereln, the antimycotic are formed in the oriented polymer. This ethoxylated oleyl al¢ohol cannot be washed out to any signirlcant e~tent in washing and dyeing proce~ses. By virtue Or its ribrll structure, the antimycotic h~s become labile in the polyamide and can migrate to the surface Or the polymer and develop its requlred efrect there. Some e~amples Or solvents with which the antimycotics can be spun into the particular polymer6 in homogeneous, dis601ved rorm or in ribril ~orm are given in Table 1 below.
Le ~ 17 846 -12-10~6773 ~P~ ~ ,., .
o ~ ~
~ a o o o ` '' o o o ~ ~ ~ ~ .
~ ~ bO 00 R ~ o o o .. ~ .
O ~~ 0 3 0 a ~cJ~ :,.o o~d6b o --~ A ~1 ~ ~ J ~ ,~
o ~ ~ ~ ~ o~ ~1 a ~ e ~ 3 o~ ~ 0~ ~ o3 O C ~ t 0~ b~ 0 u~ ~ ~ t~ o ~ P, ._.
;
.
.0 0 ~ ~0 ~ d a ~ ~
Tt O C~ ~ ~
~ ~ 0 a a O
~ o o 51 4 b b 1~3 ~.
Le A17 846 -13-10~677~
or these solvents, ~hose with a water retention capacity or hydrophillc properties are preferred. Particularly suitable hydrophilicity-increasing solvents ~or the antimycotics are the derivatives Or polyalkylene osides with molecular weights Or from 400 to 20,000, particularly those of poly-ethylene oxide. Their hydrophilising effect is known irom publications in which the relationship between static charging, relative air humidity and the presence oi' poly-alkylene oxides is described ~or textiles (5hemie-fasern/Textilindustrie; May 1972, page~ 397 et seq). The antimycotic activity can also be greatly improved by the presence of small quantitles of water (Dle ~ygiene des Teppichbodens, Manfred Rotter; Gustav Flscher Verlag;
Stuttgart 1975; page 240).
Accordingly, a partlcularly prererred proce~s is one in which the azole derivative 18 added to the prepared splnning solution or to the poly~er melt immediately before spinning using ~solvents~. 20 s Ethoxylated stearylamine, 20 to 40 x ethoxylated oleyl or stearyl alcohol, polyalkylene oxide compounds modified with a terminal dlmethyl urethane grDup, trls-nonyl-phenyl phosphlte and, in the case o~ the polyamides, t-caprolactam are particularly suitable ror this purpose.
The polymers produced ln accordance with the lnvention and the ~ibres obtained from them may be processed without particular difficulty into textlles ln the textile lndu~try.
The flbres may be processed either on their own or in admixture Le A 17 846 -14-l~q6773 with non-antlmicrobially active natural and synthetic fibres.
The following are mentioned as esamples of textiles ror whlch antimycotic activity is particularly de8irable: car-petings, ~tockings, shirts and the like. The testile~ in s que~tion primarily consist of or contaln the fibres produced by the process according to the invention and may come into permanent or even temporary contact with the suriace Or the body. In the presence of antimycotics, the fungi which may possibly be transrerred in the event Or such contact 10 are killed ofi'. Any propagation and tran~fer Or the fungi to other regions Or the skin or other organisms i~ lnterrupted.
The interruption Or this transfer chain is particularly signiricant in the case Or testile floor coverings on which people frequently tread with bare feet, i.e. in the case Or floor coverings in the bedrooms and bathrooms Or hotels and private dwellings.
The following Examples illustrate the invention without limiting it. The percentages are by weight.
,EXAMPl.E 1 200 g Or a 20 s ethosylated stearylamine are added in a tumble miser in the absence oi' moisture to 100 kg of a dried polyamide-6 granulate which contains 0.05 ~ by weight oi' titanium dioside and which has a relative viscosity of 2.7, as measured on a 1 ~ solution in m-cresol at 25C. The misture is tumbled rOr about 2 hours, ai'ter which 200 g of a rinely ground antimycotic correQponding to the formula:
Le A 17 846 -15-Cl- ~ -0-C -C-C(C~3)3 ~C C~
,1 il N CH
are added, rollowed by mi~ing ~or another 3 hours. The granulate is rused and spun ln an extruder.
The screw Or this eYtruder has a length Or 72 cm and a diameter of 3 cm. The extruder barrel i8 heated to 285C.
The screw has a rotatlonal speed Or 90 rpm. The melt shows a pressure Or 80 bars at the output end Or the extruder. It rlows lnto two double gear meterlng pumps which divide the rlow of melt into iour component streams, each having a quantitative rlow oi 40 g Or polya~ide per minute. Each Or these component etreams is iorced through a metal gauze with16000meshes/cm2 and spun through a spinning ~et with 16 bores having n dia~eter Or O.30 ~m. The bundlo Or rilaments issuing irom the iour ~ets is treated with a spin-finlsh arter cooling in the epinning duct and wound up at 8 rate oi 460 metres per minute. The undrawn iilsments have sn individual denier Or 54 dtex. The rilaDents can be processed into spun iibres snd rilament yarn.
a. Production Or spun ribres The iilanente are combined rrom ten bobbins to iorm a tow, drawn in a ratio Or 1:3.4 by means Or drawing rolls and crimped in a sturrer bo~. The crimped tow csn then be cut in such a way that an average staple length Or 150 is obtained.After heat-setting with saturated ~team at 130 C~
Le A 17 846 -16-lOq6773 the ribres have an lndividual denier Or 17 dte~. They are spun by one Or the methods nor~ally used in the te~tllo industry to ~orm a yarn having a yarn count Or 37. A turted carpet with a ribre input weight Or 700 g/m2 i~ produced from this yarn.
b. Production Or textured rll~ent yarn The rilaments are combined rrom two bobbin~ into a tow, drawn in a ratio oi 1:3.4 over godets and crimped with superheated steam ln a teYturing nozzle at a temperature oi' 160C. A~ter cooling in the absence Or tension, the yarn is wound up. It has a total denier Or 2200 dtex. The i'ila ents have an lndividual denier Or 17 dte~. A turted carpet with a ribre input weight Or 700 g/m2 i~ produced rro-the i'ilaments.
The turted carpets are dyed in a winch vat with dye~
having the rollowing constitution:
~ N=N ~ N-N ~ C2~5 (dye I) ~ N = N ~ \/ (dye II) ~\
CF3 ~0 so3 Le A 17 846 -17-10~6773 0 N~
~ S03~ (dy~ III) NH ~ NH-C0-CH3 B ln the presence of 0.5 S of Levegal FTS, an ~nlon-actlve levelllng aid produced by BAYER AG, at a pH-vslue Or from 4 to 5. The carpet 18 backed wlth a coatlng Or Lipolan CT 35, a rubber lateY produced by Chemlsche Werke Huls AG. In order to test the dye finishes for fastness to llght, fibre ~ample~
are dyed. The results are set out ln Table 2 below.
c. Comparlson tests c.l The 20 s ethoYylated stearylamlne above ls applied to the polya~lde-~-granulate in a tu~ble miYer. The splnnlng condltlons are the ~a~e.
c.2 Unmodlfled polyamlde-~-granulate 18 spun under the same condltlons.
ade rn~rK
Le A 17 84~ -18-1~6773 ~oc ~
o ~ , , , ~ "
C~ ~1 O ID P
,~ s ~¦ ~ ~ , ~ a '¢ E~ 6 Le A 17 846 -19-~6773 As in Esample 1, polyamlde-6~ granulate i8 melted in an eYtruder. The melt rlows through a static miser of the type described in German Auslegeschrift No. 2,328,795. The static oiYer has a length or 36 cm and a diameter of 2 cm. Berore entering the miser, 1.60 g/minute Or a 20 % solution heated to 80C Or the antimycotic corresponding to the rormula in Example 1 in caprolactam are added to the melt by means Or a piston pump (LEWA pump; type M~ 1). The rlbres contalnlng 0.2 % oi the antlmycotlc are spun and worked up in the oame way as in Example 1.
Polyamide-6 granulate 1~ melted ln the same wsy as described in E~ample 1. Arter the estruder, the melt rlows through a dynamic miser havlng a dlameter or 6 cm. (~AHMAG:
Inrormation Service No. 11/1975). The additive i9 lntroduced and the rlbres are worked up in the same way as described in Esamples 2 and 1.
Poly~mide-6 granulate is melted in nn e~truder and introduced into a dynamic miYer in the same way as described in Esample 3. Bei'ore entering the mixer, 4.8 g/minute o~
a 10 f solution heated to 80C or tho antimycotlc corresponding to the rormula in Example 1 in 20 x ethoxylated stearyl alcohol, Or which the terminal OH-radical has been reacted to rorm a dimethyl urethane group in accordance with German O~fenlegungsschri~t No. 2,410,861, are addod to the melt. The ribres are spun and worked up in the same way as in Esample 1.
Le A 17 846 ~20-10~6773 Esamination Or the ribres under an optical micro~cope re~eals ribrillsr inclusions Or the additlves in the ribrefi. The ~ibrils have a diameter Or about 2 ~n and an average length o~ more than 100 ~m.
Caprolactam i8 continuou~ly polymerised into polyamlde-6 The melt is rreed rrom low molecular weight rraction~ in a vacuum stage and then delivered to several ~pinning units.
A component stream or 1350 g/minute enters a statlc miser 120 cm long and 10 cm in diameter, Or the type de~cribed in German Auslegeschrift No. 2,328,795. Berore the ~tatlc miser, 27 g/minute Or a 10 ~ solution heated to 80C ot the antimycotic corresponding to the rormula in Esample 1 in 20 s ethosylated oleyl alcohol are added. The melt i8 distributed to nine spinning stations each comprising a 126-bore ~pinning Jet. The ribres is~uing rrom the spinning ~ets are blown cool with air, prepared and wound up at a rate Or 200 metres per minute. The rilaments are processed in the sa~e way a~ in Esample lb. Fibrils are visible under an optical microscope, as described in Esample 4.
200 g Or a 20 s ethosylated stearyl alcohol arc added in a tumble miser in the absence Or moisture to 100 kg Or a polyethylene terephthalate granulate which contains 0.25 ~
by weight Or titanium dioside and which has a solution viscosity Or o.66 as measured in accordance with DIN 53 728. In the same way as in Esa~ple 1, 200 g Or the antimycotic corre~ponding Le ~ 17 846 -21-~6773 to the ~or~ula ln E~ample l are bound to the sur~ace oi the granulate. Spinnlng 1~ carrled out ln the apparatus dcscrlbed ln E~auple l. The rollowlng te~t para~eters are ~alntalned:
Temperature oi' the ostruder barrel: 295C
Melt pressure: 90 bars Throughput: 11.6 kg/h Take-orr rate: lO00 ~/ lnute Jet~: 4 s 36 bore~;
0.25 Gross d-nler: 484 dtes.
The iila ents are drawn ln a draw-twlstlng ~achlne.
The drawlng rstlo 18 1:4.4. The rllanent yarns havlng a denler oi' llO dtes are testured by the ralse-twl~t Dethod and ~ade up lnto a knitted i'abrlc.
Polyethylene terephthalate 18 ~elted ln the sa~e way as descrlbed ln Esa ple 6. The estruder 18 iollowed by a statlc ~i~er ln the sa~e way as ln Esa~ple 2. Beiore enterln~ the ~lser, 3.86 g/~lnute Or a 15 ~ oolutlon oi the antl~ycotlc correspondlng to the i'or~ula ln Exauple 1, ln trl~-nonyl-phenyl phosphlte, are added to and ~lsed wlth the polyester ~elt. The rllaDents are ~pun and worked up ln the sa~e way as ln Esa ple 6.
No ilbrlllar lncluslon~ are vlslble under an optlcal rlcroscope.
Polyethylene terephthalate 19 ~elted ln the sa~e way Le A 17 846 -22-~q6773 as described ln E~ple 6. ~iter the estruder, the nelt rlows throu~h a dyna~lc miser ln tho same way as ln E~ample 3.
Before entering the miYer, 3.90 g Or a 10 % solution heated to 80C of the antimycotic correspondlng to the i'ormula in E~ample 1 in 20 s etho~ylated stearyl alcohol, which contains a terminal dlmethyl urethane group in accordance with German Ofrenlegung9~chrift No. 2,409,715, are addod to the melt.
The rilaments are spun and worked up in the same way ae described in Esa~ple 6.
Fibrillar inclusions are visiblo in the filaments undor an optical microscope.
100 parts of syndiotactic polyvinyl chloride are dissolved at 140 C in 505 part~ by weight o~ cycloho~anone with uniror addition of 1.5 parts by weight ot an organic tln stabiliser.
0.1 part Or the antimycotic corre~ponding to the i'ornula ln Esample 1 i~ added to this solution. Arter 10 mlnutes, the spinning solution obtained i9 riltered at 135C and pressed by means Or a heated gear pu-p through the ~plnning ~et which is also heated. 38 . 5 g/minute Or solution are delivered through the 300 bore spinning jet with a bore diameter oi' 0.08 mm.
This corresponds to 6 . 35 g o~ PVC .
The precipitation bath consists of a misture of 20 %
of cyclohesanone, 30 ,~ oi isopropanol and 50 % of water.
The precipitation bath has a temperature of 60C. The bundle of filaments is drawn off from the nozzle at 7 metres per minute and intensively washed in water at 60 to 80C.
Le A 17 846 -23-~3~6773 The bundle of rilaments is then drawn ln boiling water in a ratio ot 1:3.5 and drled ln reclrculatlng alr at 120C.
A splnning solutlon i8 prepared by heatlng 280 parts by welght Or polyacrylonltrlle powder and 720 parts by welght of dlmethyl rormamide to 80C. 1.40 parts by welght of the antlmlcroblal compound to be used in accordance with the lnvention, whlch corresponds to the rormula in EYample 1, are added to this splnnlng solutlon. The solutlon ls then stlrred ior 4 hours untll lt has become clear and strlngy.
It is then spun through a 120 bore ~et lnto a heated spinnlng duct and wound up at a speed or 200 metres per mlnute. The fllaments thus obtalned have a spun denler Or 32 dte~. The i'ilaments are drawn in a ratio Or 1:2.2 ln bolling water and continuously dried at 160C. The rilaments are then crimped in known manner by the sturrer bo~ method, cut and ri~ed at 110C in a screen drum steamer. Staple ribres with a denier Or 17 dteY and a staple length Or 100 mm are obtained.
Determination of antimycotic activity Fibres and test carpets antimycotlcally rlnished in accordance with the invention were sub~ected to anti-infection tests in vitro with the test germs Candida albicans and Trichophyton menta~roPhytes. The antimycotic inhibiting effect wa~ tested in three different test nrrangements.
A) Te~t methods Le A 17 846 -24- ~-`
The rollowing observatlons on the antl-lnrectlon errect Or the additlves according to the lnventlon ln rlbres are ba~ed on three test arrangement~:
l) agar dlrrusion test 2) dlrect contamlnatlon test
3) lndlrect contamlnatlon-transrer test.
l) agar dl~iuslon test This test method provldes sn lnslght lnto the release Or actlve substance ln mol~t medlum as a precondltlon ror a contamlnation-lnhlbltlng or reduclng errect.
Quantities Or l g Or the antlmycotically rlnlshed, rirst undyed and then dyed rlbres and pleces Or sample carpet wlth an edge length Or 2 x 2 cm were lntroduced lnto Petri dlshes contalnlng Nervlna agar (composltlon: 60 g Or Nervina malt, 5 g Or NaCl, 5 g Or peptone, 5 g o~ glycerol wlth 1 1 Or water) ln such a way that they were completely covered by the nutrlent substrate. The surrace Or the Petrl dlshes thu~ prepared were then homogeneously lnoculated wlth germ suspenslons ot TrlchoPhyton mentagroPhYtes (1 ml Or suspenslon containlng approxlmately 3.105 germs per plate) and Candlda alblcans (l ml Or suspenslon contalning approslmately 1.106 germs per plate). Arter lncubation ror 72 and 48 hours at 28C, the lnhibition zones to be eYpected rrom an active antimycotic rinish Or the material were measured out.
2) Direct contamination test The direct contamlnation test was carried out with pieces Or sample carpet having an edge length Or 2 x 2 cm by Le A 17 84~ -25-10~6773 l~pregnating the pleces or carpet wlth a germ suspenslon Or Trichophyton ~entagrophytes and Csndlda albicans ln nutrient solution (compositlon: Yee 1) and then introduclng the~ into moist chambers, rollowed by lncubntlon ror 144 hours at 28C. ~n er~ectlve antl-ycotlc rlnlsh Or the carpet oaterial should prevent a macroecoplcally vlsible inrestation of the pieces o~ oarpet impregnated with the nutrient substrate.
3) Indirect-contaminatlon-transrer test Thls test ay be regarded as a rinal reallstic test ror assessing the anti-lnrectlon eirect of an anti-mycotlc iibre rinish.
Pleces Or sample carpet wlth an edge length or 2 ~ 2 cn ware moistened with 0.2 ml Or a germ suspension Or Trlcho-Dhyton menta~roPhytes and Candida albicans (germ count:
5.104 TrlchoPhyton menta~rophytes, 2.105 Candlda alblcans) in physlologlcal NaCl-solutlon and then slowly dried at room tempersture in empty Petri dlshes. The germs applled remalned on the carpet material ln llvlng ror~. Ir, arter this drylng time o~ 5 days, a transrer Or each plece Or carpet 18 ~ade onto rre~h culture dl~hes contalnlng Nervlna agar, sub-cultures or the prevlously applled rungl are rormed at the transrer polnt ln the ca~e Or unrlnished or lnerrectually rinished carpet materlal.
Both the sub-cultivatability and also the number oi colonies rormed are a direct measure Or the anti-inrectlon errect or the finish. The prevention Or the sub-cultivatabillty Le A 17 846 -26-10~6773 at the transfer polnt ls de~irable ln thls test. It i8 lndlcatlve o~ a funglcidal erreot Or the lncorporated actlve substance on the contamlnatine i'ungl durlng and arter the drying time.
B) Results 1) ~8ar diffu~ioll test~
a) With ~ibreu Table 3 shows the result Or the agar dlrruslon tests with fibres. The letters a, b, c and d alongslde the numbers have the rollo~ing meanings:
a) orlglnal rlbre b) unrised, dyed c) heat-8et with saturated steam at 130 C
d) heat-sot with 8aturatod 8team and dyod.
Slnce agar diriusion tests wlth rlbre~ cannot be quantitstively evaluated exactly, a partlally quantitatlve assese~ent was oade, the symbols used havlng the followlng meanlng:
neg = no lnhlbltlng errect + = ~llght lnhlbltlng errect, lnadequate ror protection agalnst inrection ++ = adequate lnhlbiting efi'ect on germ growth +++ = good efrect ++++ = very good errect, inhibitlon zones 7 40 mm.
Le A 1~ 846 -27-~0~6773 Table 3 Agar diffusion tests with antimycotically finished fibres Fibres produced in Inhibiting effect against accordance with Trich. ment. Cand. alb.
Example No.:
1 a neg. neg.
b neg. neg.
c.l 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 +++ ++
b +++ +++
c ++++ +++
d +++ ++
b ~++ +++
c ++++ +++
d +++ ++
l) agar dl~iuslon test This test method provldes sn lnslght lnto the release Or actlve substance ln mol~t medlum as a precondltlon ror a contamlnation-lnhlbltlng or reduclng errect.
Quantities Or l g Or the antlmycotically rlnlshed, rirst undyed and then dyed rlbres and pleces Or sample carpet wlth an edge length Or 2 x 2 cm were lntroduced lnto Petri dlshes contalnlng Nervlna agar (composltlon: 60 g Or Nervina malt, 5 g Or NaCl, 5 g Or peptone, 5 g o~ glycerol wlth 1 1 Or water) ln such a way that they were completely covered by the nutrlent substrate. The surrace Or the Petrl dlshes thu~ prepared were then homogeneously lnoculated wlth germ suspenslons ot TrlchoPhyton mentagroPhYtes (1 ml Or suspenslon containlng approxlmately 3.105 germs per plate) and Candlda alblcans (l ml Or suspenslon contalning approslmately 1.106 germs per plate). Arter lncubation ror 72 and 48 hours at 28C, the lnhibition zones to be eYpected rrom an active antimycotic rinish Or the material were measured out.
2) Direct contamination test The direct contamlnation test was carried out with pieces Or sample carpet having an edge length Or 2 x 2 cm by Le A 17 84~ -25-10~6773 l~pregnating the pleces or carpet wlth a germ suspenslon Or Trichophyton ~entagrophytes and Csndlda albicans ln nutrient solution (compositlon: Yee 1) and then introduclng the~ into moist chambers, rollowed by lncubntlon ror 144 hours at 28C. ~n er~ectlve antl-ycotlc rlnlsh Or the carpet oaterial should prevent a macroecoplcally vlsible inrestation of the pieces o~ oarpet impregnated with the nutrient substrate.
3) Indirect-contaminatlon-transrer test Thls test ay be regarded as a rinal reallstic test ror assessing the anti-lnrectlon eirect of an anti-mycotlc iibre rinish.
Pleces Or sample carpet wlth an edge length or 2 ~ 2 cn ware moistened with 0.2 ml Or a germ suspension Or Trlcho-Dhyton menta~roPhytes and Candida albicans (germ count:
5.104 TrlchoPhyton menta~rophytes, 2.105 Candlda alblcans) in physlologlcal NaCl-solutlon and then slowly dried at room tempersture in empty Petri dlshes. The germs applled remalned on the carpet material ln llvlng ror~. Ir, arter this drylng time o~ 5 days, a transrer Or each plece Or carpet 18 ~ade onto rre~h culture dl~hes contalnlng Nervlna agar, sub-cultures or the prevlously applled rungl are rormed at the transrer polnt ln the ca~e Or unrlnished or lnerrectually rinished carpet materlal.
Both the sub-cultivatability and also the number oi colonies rormed are a direct measure Or the anti-inrectlon errect or the finish. The prevention Or the sub-cultivatabillty Le A 17 846 -26-10~6773 at the transfer polnt ls de~irable ln thls test. It i8 lndlcatlve o~ a funglcidal erreot Or the lncorporated actlve substance on the contamlnatine i'ungl durlng and arter the drying time.
B) Results 1) ~8ar diffu~ioll test~
a) With ~ibreu Table 3 shows the result Or the agar dlrruslon tests with fibres. The letters a, b, c and d alongslde the numbers have the rollo~ing meanings:
a) orlglnal rlbre b) unrised, dyed c) heat-8et with saturated steam at 130 C
d) heat-sot with 8aturatod 8team and dyod.
Slnce agar diriusion tests wlth rlbre~ cannot be quantitstively evaluated exactly, a partlally quantitatlve assese~ent was oade, the symbols used havlng the followlng meanlng:
neg = no lnhlbltlng errect + = ~llght lnhlbltlng errect, lnadequate ror protection agalnst inrection ++ = adequate lnhlbiting efi'ect on germ growth +++ = good efrect ++++ = very good errect, inhibitlon zones 7 40 mm.
Le A 1~ 846 -27-~0~6773 Table 3 Agar diffusion tests with antimycotically finished fibres Fibres produced in Inhibiting effect against accordance with Trich. ment. Cand. alb.
Example No.:
1 a neg. neg.
b neg. neg.
c.l 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 +++ ++
b +++ +++
c ++++ +++
d +++ ++
b ~++ +++
c ++++ +++
d +++ ++
4 a ++++ ++++
b ++++ +++
c ++++ ++++
d ++++ ++++
a ++++ +++
b ++++ +++
c ++++ ++++
d +++ ++
6 a ++++ +++
b +++ +++
7 a ++++ +++
b +++ +++
8 ++++ ++++
++++ +++
9 a +++ +++
b +++ +++
a ++++ ++++
+++ +++
b) With pieces Or test carpet:
The outcome o~ the rlbre tests as reported sbove prompted the testing Or some te~t carpet3 by comparison wlth an unrinlshed test batch by the agar dlriuslon te~t.
Fig. l shows the result Or a carpet test wlth ~lbres produced in Esample 4. The lnhlbltlon halo around the antimycotic-contalnlng sa~ple, ln whlch no lnrestation by Trichophyton menta~rophytes 1~ ~islble, can clearly be seen. Comparable equally satisractory results were obtained with Candida albicans as test organism. The untreated control batch produced no inhlbltlng errect on elther Or the two test germs (cr. Flg. 2).
2) Direct contaminatlon test Direct contamination tests were carried out with the test carpets according to E~mple 4. Flgures 3 and 4 show the result ~or the test germ TrlchoDhYton mentagro~hytes in the control batch and ln the two test batches.
3) Indlrect contamlnatlon trans~er te~t Table 4 below shows the results obtalned with carpets Or rlbres accordlng to Example 4. The test sa~ples ln questlon were both undyed and dyed. Dl~ruslon tests and transi!er tests are shown together because oi' their casual a~soclatlon.
Table 4 ¦Test carpet Dlrrusion test Tranærer test Cand. alb. Trlch. ment. Cand. alb. Trich.
Undyed ++++ ¦ ++++ ment. , ... .. _ .
dyed ++++ +++
Le A 17 846 -29-10~67~'3 Accordlng to these results, the test carpets are Sully acti~e and may be regarded as proteoted agalnst iniection.
Le ~ 17 846
b ++++ +++
c ++++ ++++
d ++++ ++++
a ++++ +++
b ++++ +++
c ++++ ++++
d +++ ++
6 a ++++ +++
b +++ +++
7 a ++++ +++
b +++ +++
8 ++++ ++++
++++ +++
9 a +++ +++
b +++ +++
a ++++ ++++
+++ +++
b) With pieces Or test carpet:
The outcome o~ the rlbre tests as reported sbove prompted the testing Or some te~t carpet3 by comparison wlth an unrinlshed test batch by the agar dlriuslon te~t.
Fig. l shows the result Or a carpet test wlth ~lbres produced in Esample 4. The lnhlbltlon halo around the antimycotic-contalnlng sa~ple, ln whlch no lnrestation by Trichophyton menta~rophytes 1~ ~islble, can clearly be seen. Comparable equally satisractory results were obtained with Candida albicans as test organism. The untreated control batch produced no inhlbltlng errect on elther Or the two test germs (cr. Flg. 2).
2) Direct contaminatlon test Direct contamination tests were carried out with the test carpets according to E~mple 4. Flgures 3 and 4 show the result ~or the test germ TrlchoDhYton mentagro~hytes in the control batch and ln the two test batches.
3) Indlrect contamlnatlon trans~er te~t Table 4 below shows the results obtalned with carpets Or rlbres accordlng to Example 4. The test sa~ples ln questlon were both undyed and dyed. Dl~ruslon tests and transi!er tests are shown together because oi' their casual a~soclatlon.
Table 4 ¦Test carpet Dlrrusion test Tranærer test Cand. alb. Trlch. ment. Cand. alb. Trich.
Undyed ++++ ¦ ++++ ment. , ... .. _ .
dyed ++++ +++
Le A 17 846 -29-10~67~'3 Accordlng to these results, the test carpets are Sully acti~e and may be regarded as proteoted agalnst iniection.
Le ~ 17 846
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Antimycotically active fibres and filaments of a synthetic polymer, said fibres and filaments containing at least 0.01% by weight of an azole derivative corresponding to the general formula:
(I) in which Az represents an imidazole radical, a triazole radical, a substituted imidazole radical or a substituted triazole radical n = 0 or 1;
R1 represents hydrogen, an aliphatic, a substituted aliphatic a cycloaliphatic, a substituted cyclo aliphatic, a phenyl, a substituted phenyl or a pyridyl radical;
R2 represents a phenyl or a substituted phenyl radical, or the group -X-R4 where X is oxygen or sulphur and R4 is an aliphatic, a substituted aliphatic, a substituted cycloaliphatic, an aryl, a substituted aryl, an aralkyl, or a substituted aralkyl radical;
R3 represents a phenyl, a substituted phenyl, an aliphatic, a substituted aliphatic, a cycloaliphatic or a substituted cycloaliphatic radical, a 5-membered heteroaromatic, a substituted 5-membered hetero-aromatic ring, the group of a carboxylic acid derivative or the group -Y-R4, where Y is a keto group or a functional derivative of the keto group and R4 is an aliphatic, a substituted aliphatic, a cycloaliphatic, a substituted cycloaliphatic aryl, a substituted aryl, an aralkyl or a substituted aralkyl radical; and R2 and R3, where both radicals represent a phenyl or a substituted phenyl radical, are attached in the o-position through -(CH2)m- where m = 0 to 2, -CH=CH-, oxygen or sulphur.
(I) in which Az represents an imidazole radical, a triazole radical, a substituted imidazole radical or a substituted triazole radical n = 0 or 1;
R1 represents hydrogen, an aliphatic, a substituted aliphatic a cycloaliphatic, a substituted cyclo aliphatic, a phenyl, a substituted phenyl or a pyridyl radical;
R2 represents a phenyl or a substituted phenyl radical, or the group -X-R4 where X is oxygen or sulphur and R4 is an aliphatic, a substituted aliphatic, a substituted cycloaliphatic, an aryl, a substituted aryl, an aralkyl, or a substituted aralkyl radical;
R3 represents a phenyl, a substituted phenyl, an aliphatic, a substituted aliphatic, a cycloaliphatic or a substituted cycloaliphatic radical, a 5-membered heteroaromatic, a substituted 5-membered hetero-aromatic ring, the group of a carboxylic acid derivative or the group -Y-R4, where Y is a keto group or a functional derivative of the keto group and R4 is an aliphatic, a substituted aliphatic, a cycloaliphatic, a substituted cycloaliphatic aryl, a substituted aryl, an aralkyl or a substituted aralkyl radical; and R2 and R3, where both radicals represent a phenyl or a substituted phenyl radical, are attached in the o-position through -(CH2)m- where m = 0 to 2, -CH=CH-, oxygen or sulphur.
2. Antimycotically active fibres and filaments as claimed in Claim 1, which contain an azole derivative corresponding to the general formula:
(I) in which Az represents the radical or R1 represents hydrogen;
R2 represents the radical where Zm 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).
(I) in which Az represents the radical or R1 represents hydrogen;
R2 represents the radical where Zm 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 and filaments as claimed in Claim 1, which contain an azole derivative corresponding to the general formula:
(I) in which Az represents the radical or n = represents an integer which is 0 or 1;
R1 represents the radical where Zm = represents halogen, halogen phenyl or phenyl and m = represents an integer from 0 to 2;
R2 represents a phenyl radical or a phenyl radical substituted by halogen, halogen phenyl or phenyl, attachment to the phenyl radical occurring in the o-position through -(CH3)m- where m = 0 to 2; and R3 represents an alkyl, alkenyl, alkinyl, alkoxy carbonyl or alkyl carbonyl radical, a phenyl radical, a phenyl radical substituted by halogen, halogen phenyl or phenyl, or an imidazole or triazole radical or an imidazole or triazole radical by halogen or alkyl.
(I) in which Az represents the radical or n = represents an integer which is 0 or 1;
R1 represents the radical where Zm = represents halogen, halogen phenyl or phenyl and m = represents an integer from 0 to 2;
R2 represents a phenyl radical or a phenyl radical substituted by halogen, halogen phenyl or phenyl, attachment to the phenyl radical occurring in the o-position through -(CH3)m- where m = 0 to 2; and R3 represents an alkyl, alkenyl, alkinyl, alkoxy carbonyl or alkyl carbonyl radical, a phenyl radical, a phenyl radical substituted by halogen, halogen phenyl or phenyl, or an imidazole or triazole radical or an imidazole or triazole radical by halogen or alkyl.
4. Antimycotically active fibres and filaments as claimed in Claim 1, which contain an azole derivative corresponding to the general formula:
(I) in which Az represents the radical n = represents 0 R1 represents a hydrogen atom, R2 corresponds to the radical , and R3 represents the radical -?-C(CH3)3.
(I) in which Az represents the radical n = represents 0 R1 represents a hydrogen atom, R2 corresponds to the radical , and R3 represents the radical -?-C(CH3)3.
5. Antimycotically active fibres and filaments as claimed in Claim 1, wherein the synthetic polymer is a spinnable polyamide, polyacrylonitrile, polyvinyl chloride, polyolefin, polyurethane, polycarbonate or a spinnable polyester.
6. A process for the production of antimycotically active fibres and filaments of a synthetic spinnable polymer, wherein an azole derivative corresponding to the general formula (I) in Claim 1 is dissolved or dis-persed in a solvent, and the polymer as such or dissolved in the same sol-vent, or in a different solvent, is introduced into the resulting solution or emulsion, or the azole derivative is dissolved or dispersed in a spinn-able solution of the polymer, and the solution or emulsion thus obtained is spun.
7. A process for the production of antimycotically active fibres and filaments of a synthetic spinnable polymer, wherein an azole derivative cor-responding to the general formula (I) in Claim 1 is dissolved in a solvent and the resulting solution is added to a spinnable solution of a polymer immediately before a solution spinning process.
8. A process for the production of antimycotically active fibres and filaments of a synthetic spinnable polymer, wherein an azole derivative corresponding to the general formula (I) in Claim 1 is added to and mixed with a granulated or powder-form spinnable polymer, either per se or using a coupling agent or the technique of sintering on, and the granulated or powder-form polymer is spun by the melt spinning process.
9. A process as claimed in Claim 8, 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.
10. A process as claimed in Claim 9, wherein a 20 times ethoxylated stearylamine, a 20 to 40 times ethoxylated oleyl or stearyl alcohol or a polyalkylene oxide compound modified with a terminal dimethyl urethane group is used as the adhesion promoter.
11. 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 (I) 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.
12. A process as claimed in Claim 11, wherein the azole derivative is dissolved or emulsified in .epsilon.-caprolactam, the solution or emulsion is added to a poly-.epsilon.-caprolactam melt and the resulting melt is spun.
13. A process as claimed in Claim 11, wherein the azole derivative is dissolved in 20 to 40 times ethoxylated oleyl or stearyl alcohol or in 20 times 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.
14. A textile article comprising antimycotically active fibres and fil-aments as claimed in Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2710496.7 | 1977-03-10 | ||
| DE19772710496 DE2710496A1 (en) | 1977-03-10 | 1977-03-10 | ANTIMYCOTIC FIBERS AND FABRICS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1096773A true CA1096773A (en) | 1981-03-03 |
Family
ID=6003296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA298,538A Expired CA1096773A (en) | 1977-03-10 | 1978-03-08 | 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 AT AT166878A patent/AT358708B/en not_active IP Right Cessation
- 1978-03-08 JP JP2554078A patent/JPS53139895A/en active Pending
- 1978-03-09 ES ES467696A patent/ES467696A1/en not_active Expired
- 1978-03-09 NL NL7802600A patent/NL7802600A/en not_active Application Discontinuation
- 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 |
|---|---|
| ES467696A1 (en) | 1978-10-16 |
| JPS53139895A (en) | 1978-12-06 |
| FR2383250A1 (en) | 1978-10-06 |
| BE864759A (en) | 1978-09-11 |
| DE2710496A1 (en) | 1978-09-14 |
| FR2383250B1 (en) | 1982-10-22 |
| NL7802600A (en) | 1978-09-12 |
| IT7820980A0 (en) | 1978-03-07 |
| GB1600103A (en) | 1981-10-14 |
| AT358708B (en) | 1980-09-25 |
| ATA166878A (en) | 1980-02-15 |
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