HUE030332T2 - Lobbanásvédett szintetikus cellulóz szálak - Google Patents

Description

FiPROÖFmi ÜLOS1C MAN-MADE fibers OESCRipTiÖN lia ihventien feiatss to estiuiosib viscose-, moiisPorii^aii^ber vs^Sï isermansoi fiam^retardarîi:vs^ôrélh the fiame-retardant property, by the addition of an oxidiiÉá ^odsneafë ef ed tefrakäs hydioxyatkyi phosphonium sait *iiivammftPia end/or δ nitrogenous compound whicheenistihs one pf more amine groups, produces a spinning mass or spinning soioiisn and the É&r has a stiepgi (ultimate tensile strength): in the dititioned state of more than IB iMlM,

According to BiSFA (The intemationai Bureau for the Standardization of idertmede Fibors), iyoceli fibers are ceilulosic man-made fern, which are spun from an organic solvent without cterivat-sstion of: celiigsp {direct spinning method). This also inelodes tipers that are spun from solutions of cellulose in ionic lipoids.

An overview of the inethods for flame refardanee of oeikflosic textiles and the underlying mechanisms of fismoirotstdansy is provided in the publication: Hoiiocks. A, R.; Kandots, 8. K. Tiarne Retardant Ceiluiosic Textiles'' Spec. Pubi. - Rayai Society of Cbsmisdy, Uoibrne 224,1988, pages 3ÁMB2;, The methods descried differ ip the type of éléments responsible for the flame taistdansy fmlniy : phosphorus In! also nitrogen,: boron and $tfö4;:ü: Ä el Ippiibation l&r göte sh: additive In fiber production for man-made fibers) and the permanence {delrse pf iesistance of the fiame-roferdant properties to washing).

The greater part of pnrmenant iiame-retardant ceiieiosic textiles is: pteduee# by means of die blending of ootfen: fabric with fetro Thydroxymstbyi) phosphonium: derivatives (for example Preban® - blend) mwlfh Nnaeihyfsi diaikyi phospPbno problsnamide (o,g, Pyrovafex CP®}. However, the finished1 textiles have a very hard: feeling.

Among cefiutesie synthetic fibers (memmadb Ibers), a large number of substances: base been proposed for viscose fibers as fiamé retardant additives in fiber produefion. US 3,266,918 diseissas tris(2<3mfomopfppyl) phosphate as s fiarne retardant. Such :a fiber was produced fnduwisiiy 1er some time, bui prôdnettçn was discontinued based onihe toxicity of the fiamé refardsht, A substance class used as a flame retardant is that of substituted pbnsphsaaensS:. Ibsed: on these substances, adtaíné retardant viscose fiber was also produced industrially (Ul 3;466>713K The flame retardant, : however, la liquid, can only be spun with low yield1 irt viscose (about 71 wt-i) end tends to migrate from the riper,: thereby imparting a nemdoslred stickiness id |#f|§§.

Similar compounds have been disclosed in patents but never tested on an industrial scale for viscose übers (BP 1.521,404; US 2,909,446, US 3,983,832; JP SÖÖ46920; DE 2,42|854; || 1:,464,641:: US: 3,266:134): US a 083.833; US 4.040,843; US 4,111,701. US 3,MJ00: ill 3;«;S98; US 3,848,167; US 3,632,628:; US 3,506,087; :y# 3 JBruft?). Ali those substances are lipui mê. bave the same disadvantages as for US 3,466)/13.: in: addition to the asove-rffeniionel ths(2,3-bromopfopyi) phosphate, a number of other phosphates and,phosphonates:: of amides were disetosed ds a fiamé: retardent for viscose (DE 2451.802; DE 2,022(6(58;: US 4,193,806; US 4,242,188; 4P :51-1:3631:4( DE 4.128,638). Őf íhrs: siess of SuhsÄes, only the edmpmsnb 2,2hexybis p,6vdime8iyi-1,8,2-dioxabitcsphoEinanel 2:!:2’-disuificie previously fulled me requirements in farms of effootiyeness freguired sptoning aoidunf according to EU ||£? 16026:2002), quantitative yiejd of the spinning process and haiogen-fim fh addifipn tn {he above-mentrohed phosphores compounds, flame-retardant viscose fibers epnfaihing silicic acid have been disclosed (£P 619 848; BP 1,753,300; EP 1,318,431)- However, these fibers only pass the aforementioned Came test with disproportionate level® of siea amî tee Ibers do not achieve the fitter strengths required for texie ÂÉ8 to fite high content of pigment; hot contributing to the strength.

In a series of paten! applieafions. possible ways hávf.fceen disclosed AO impart latrmytetafdPt propeftisg also to cetiuioso fibers, yiliteh are produced by" the amino mxide process,, M> 93/12173 disofesp pfec«pimisi<apÄ^' retardants lor siaSile materials, te particular polyurethane team. Claim 18 mentions cellulose spun from a solution in s tertiary amine oxide, butwilhout giving an example of fne actual suitability of the compounds a® feme retardanis 1er caiieioss. WO 84/28962 discloses the addition of a fetrakis hydroxyalkyi phosphonium chlorine (THPC) - urea - formaldehyde pfeccndonsate to die wet fiber before drying'* teafibtet vditeiÄÄ, cohdensäfion, oÄfton 'Ä-:d^^::'$ft8r ?epi^eIn»dħ. te®, condensation reactions at liberlevel hrarngtlcslty atfecl tee fiber properties (embrittlement}. WO S$/öS3Sd disöidsés ipceil fibers being: denied witepesohoric acid and urea and msteteined û 1§Ö "C- for 4S rhinbtes; The of thé: tiers to a large extent, HP 0836634 discloses Hi® incorporation of phosphorus-containing compounds as flame retardants for regenerated cellulose liber, in psfiiôùiat iyocell fibers. 1iWdidscbuiyi^,®5te'tetmhydroxy'1 W-dioxopiioptföfittan is given as an example: Tire method has: the disadvantage Wat;the;teöbrpöration yield of the fiamé retardant is only Söl and therefore problems ahse 111 the closed, cycles of the Iyocell process. U.i/Pat :l,88Mlf and W§ 3Ö07/322SSI disclose clay :(ífiönftiríÜ»ri®öRljfes- :^cferi]6gi): as an aditfori to lpcaii fibers. The fiairté rstardant effect of fh®ge :sdÄes is insufficient for textile producta, the vertical fiame-teaf ^cerding to Eld f|t2 i§025:2bS2 Method B> Edge flaming, must bepsssd, the Korean Paient Application fengkaelaeho Kciigbo 2öŐ0/Ö2fi|t| bind® a phosphorus-containing fiamé retardant to the eeliuiose via a siticonroxygaa groups This bond, however, product i® thus not suitable for washing articles, fiion® of the rrteîhods deartebed for the lyoPOli method has gained industeai importance. this process, tee ciosod cyctes of tho nrtrfhed make particular demand® on tee yleid in teo ificorpéretiôn of g solid or liquid additive in the spinning matte, The solvent recovery is over §9% and thus small amou nis of contemihant® accumulate in tee winning batWwashing water doe to noPgeahiiteilve spinning yield ranching the circuits and causing problems in spinning and in tea workup/punficalten of tee solvent No patent® have so far disclosed flams retarded iyocell fihem made »1 ionic liquids:.

The use of isirskis hydroxysikylpbosphorttum chipiteefTHPC) --ores - pre-condehsatelbr the flame retardant btend: of, in parttcoiar. colon with the procesh stepdfnprsgnstion: of the precondensate * irsatrneht wit ammonia cöhdefÄOh: - Otedaiten: Is known (fer evafete®,Probante- metbodi·

The: use: of condensed products is described in ϋ:Ι2,Μδ,93|, AccOrdinglto the table in column 4 oft# 3,:6415,036, a 11fiPOferea/MH::s polymer displays no flame mterdanpy :fe &amp; viscose fiber,: According: Ac tee teaching: bf the: paterd,: the incorporation of: an amuteniahstraktsteydrovyalkyi phosphorubm chloride: polymer (THPC/Nrifepolymer} with the: spinning quantity required to: pass: the iSameitesip)!}: b^:^^fe.Msiiebêr,1bi^sKb,v#i'.:teifÂtt sfsbtllty |l .OSg/den " about S,? cH/tex}:,

Su^ltetegiy, it has been (bunb test fiamé feMeet eolibhteic viscose-, modal- or iyocell libers with a higher strength, which eontate a: fiÂfite^M'SubsteniëiiteiMam^rôW^Éây^lIlafnediifeab^iW.iâ^poupl^fÂibb^teiiS.^tit^.

The Same fetardant cettulesfö viscose-, modal- er iyocell fiber according; te fee invention contain a fiamé Ärdsnt sdbstehce in tee term of an oxidised cendensate of a tatraki® hydroxyaikyl phosphonium salt with contains one br several ämineigrbbP^iitersdenzedJnteabteeifife^teiöterieÄtei^^^te^-asfie^^^Äetep'igmfiiex,. The ifrogenobs compound issprsferahiybrea or ammonia,

The production of viscose and modal fibers is known î>er se. The addition of functions! additives is carried out her« by means of spin dosage of a genersly aqueous dispersion. ffehietiisrly tee tefevwnf steps: - production of g viscoss ofooiiuiose xanfhugsnate addition of a ntodifeatlon agent r addition si S wt>% to 5ö wb! fessed on cefeiose: of the iSarne-retardtes: substance in tee form of ars aqueous dispersion of the pigment 'Spinhitig of me spinning mass through a spinneret into aspinning Path • stretching the prseipitated ffemente - aiter-treatment via washing, bleaching. finishing: - cutting to staple tiers, and is characterized in that for the production of the fiber: - the pulp used has si R-18 content of 93>S6% « the cellulose contant of die viscose is between 4 and 7% - the alkali ratio is between 07 and 1.5 content of thé visdesefs betwecnli and 411:

- festWeen 1 wt>*l hhli: tet >-%: of a modifying agdnibaselo« cellulose |s: added teihe yippee -. the spinhing gemma: feléé Pf thé viscose lies hetesen 18 end M, p?eterahly between; Id and IS - the spinning viscosity is SO to 120 failing bait seconds • the temperature bi:the spin bate te stesen 34 te • tee following spirt bate concentrations are used H2SÖ4 68-90 g/i f4a2$0410Ί 60 g/t ZnS04 30 61 g/i petfemed at: a speed of between IS und 60 m/mrrt

The fente retardant eefetestb iypseif fier la feteer produced according to the Invention by a direct spinning «tetesd: wherein the direef-seivent tor tee eefetesa is pretefaiy a têrtiâfy émies oxide. N-meteyimsrphoiins oxide (NMteöirfe pertictíiaríy sufebie as the dlreot solvent which isrÂplÿ::iè^:t^-eê«te®M%u ionic liquids séchas are Hnswn, M exarngite fnsht:Í511:12808012108, may fee used

Iteeproductionoflyoceltfee^^ oxide nteteod is earned out in the fofewirtg step; 1:} bfihpg the crushed ; pp tete estest ®th an aqueous femetey I morphojin oxide (NMMÖ) soidsen 1} evsppfaipn pf tee excess smuuntofwsterunder sheaf uni formation ora ffoonfrae spinnittg mass 3) extmsion of the spinning mass through nozzles, stretching in an air gap, preSipttatfon of the cetlufose in so aqueous iMfdQv conteinidg sptehsng bate; washing and drying.

AftemaSfety, the formation of tee spinning mass through direst dissolution of the ceiiuiose in approximately:13% of water containing: NMMO {NMMOfrtenohydfate} in e.g, an extrudes

The additienmf the feme retardaot may be applied as a powder or asdisperslsn In water or aqueous: in step 1

The éfeé lÄfhe term of a:dispersion in flte&amp;fO. wherein tee NMtp has a water cö« tent between; 13 wt.-% and 29 wbl.

Alternatively, the feme îï dardant may be added as a powder in an extruder.

Ils average pSÄÄili Se retarda« should be well under the half fiber diameter, preferably below 10¾ of the fiber :ôwfï»wWt / mm ίο an additional purification step m diluted acid, has ptevod; to be padleuladv satebie fer the ivoceii process A partfcuiahy suitabieihsteed iirpodueing a fiamé retardant age« ter use mceilulosic fibsmconpses tee tetfewing steps: (abreaction .phcKSp^g^ftjm comppund having at least sne nitrogen «ompeund selected from the group urea, urea, pasidine end dicyandiamide. in order to obtain a piper, wherein tbs mbiar ratioeffhe fetrakis hydroxysiyi phespfenium compound te Ose nitrogen compound is in the range of 1: (0,05 to 2.0). preferably in the range of 1 ; (8.5 to 1,5), more profteabiy in fbe range of 1: (0.65 to 1,2). (a1) crossiinking of the polymer obtained in method step (a) with tee aid of ammonia, and (b) oxidation of the phosphorus contained In the crossiinked polymer by adding an oxidizing agent to obtain the tiame retardant.

The first step of fhr> production method (as or steps (af and (a:) servefs} to produce a polymer by reacting the at least one tetrakls bydroxyaikyi phosphonium compbhd having at least one nitrogen compound: selected from the group of ammonia, urea, thiourea, biuret, maiamine, eiytene uma, guanidifse and dicyendigmide. UNt- Ι||$?0Χ$$ρ -Φ '.tefcai^ %dtexya!k$. jpiphonHter pupound are hydroxymethyl, hydroxyothyi, hydroxypropyl or hydroxybutyi.

The el least one leiakis hydmxyalkyliphoapftehium compound Is partieuiady preferably 8 fetrakis hydroxymethyl phosphonium compound, hereinafter ai^ reterredte as xTHA^:hayäng:;tee general formuia (PiCiÄÄT::örslso-ffiixtures^|isuit compounds, wherein X· is an anion and t represents tee significance of Its anion, i may represent m integer of 1: or 2. Spffaie, hydrogen sulfate, phosphate-, mono-or dihydfbgen phoephste. acetate or halogen anions, such as; fiuoride, chlonde and bæmide. are, M example, suitable as aniens Xc

The at leasirode nitrogen :::compôund:Whiçh::i^ teirakis hydroxyikyl phosphonium compound in tee method steps: (a) and (a’) gshdriy comprises one cdtepou?te;lwe compounds, three:epmpöun# ór more compounds selected item the gteup of ammonia, prpa, iblppi««, bibret, metanifes, ëtbÿfebô bîfeâ^ guaptbinë änd dicysbdtemide. Aßperdipg ίο à prpfefrpd êfnbôdifepnt of the invention, fite miregen oempound is urea, According to a partfeuiafif preferred embodiment ^tee teveniion, at least bhe hlttegdh: compound::detected fern: the group urea, thiourea,: iuteh: meiamlhe, ethylene urea;.: guanidine and dicyandiamide is reacted te method step (a), arid ernssiinked with ammonia in a:subsequent ntefhpd step (a1), in a preterred embodimeni:according to the invention, tee readier, in method step (a) arifeptipnaliy also in method step (a) is iparformed ln a; solvents The preferred the at least two compounds to be reacted imroethod step (a) or (a’) may vary and is generally from TO w«% i^îffeei:::|pffeferâËiii|éte 40% wt.«%, based on tee. teif mass ofihs reactign mixture used in method step fa) or (a'), which contains at feast the solve«.

The molar ratio of the fetrakis hydrcxyaikylphosphohiyfe compound to the nitrogen compound may vary over wide : ranges and iS: (0.f55 to ^„preferably 1: pb ie l.I), more preferably: i: (0.85 to 1.2). Tfte targetterteritedteaiectlcn of ps meiar rsflo ensifres that the flame teteteantspreteueef acccteihf Invention do not dissolve, prpniy to a small extent, in tee solvents used In the production of ilame-reimda« cellulose fibers.

The reaction in method step (a) or (a() is generally at a temperature if! the range of 4f) tp 120 °C, preferably at a temperature in the period of T te T8 hours, pteferabiy carried out for a period ofl fethobrs.

According te method st# (a) mä adssrdteg: te $ pterai embödshfeht of fee inwntiôîi, the reaction feixtet® which fehfelns IN poiyhrer abireom temperature. Le. st áitefeperaterefn tes range of abôut iS tö 25 “G, preferably a ternparsters sí 20 e0, cools, er is cooled, befere crosslinking fee polymer wife anhnbhialc method step {a‘|.

According to m actyaotepous es®ö|imeht of the invention,, pne or ntore dlspmirsg ágerás er® added to fee potymer after carrying out method step (a) and befere carry»·*} out method step fab, add feus prfer to carrying out fee crosslinking f>y mesas of ammome. Thesa bfepersdnts are preferebiy chosen terfed fpp cellulose (HPCj, sad: potpfhySeue giyeo! (PEG), The dispersing egefe serves te staiiLre thaicornpeantsef the eofepfetion, a# prevente an aggtefesfetion of fee polymers I« -the· töisoaHy. the at less! one dispersing agent ls::added in a coaceatration te: fee rang® of Q.0irwfo% to 3 wt.-%, preferably irr the reage of 0;lwt.--% to 1 wt.-%, based on the react*»·} mixture. t? the produofios of ttse polymer ?S carried oist in two steps, Le. comprising the steps of fa) and fa%.then to method step (e:) ammonia: is added in a molar ratio to tbs tetrakis hydroxy methyl phosphonium compound in 'fee range of (1 to 4.0): 1, preferably in fee range at (12 fe 3.5): 1i p}ere preferably fe fee range of (life 2,0): 1 in this ease and aecgfdfeg to apreferredi embodiment of fee invention, ammonia Is added until the reaction mixture reaches s pH vaine in fee range of 7 to 10. preferebiy in the range of 8 to 9. in this way, the polymer obtained in step (a) Is crosstlnkod by moans of the ammonia m step fa'}, and a precursor of the (lame retardant is obtained:: which is oxidised in the subsequent step, method step (b). The reaction: tfete ia iprscaas feep (al ls gerierely Imfee range of 1 min to 50 min

Tho efedfeioh ih method step fb) may be effected with the help of the usual oxidising agents stteh as hydrogen peroxide, ammorsfem peroxydfeutfafe,: eir (oxygen) and perchloric acid. The (noter ratio between the praeufsor of the flame retardant end the oxidizing agoni Is generally about 1:1 to 1.1.2.

The Same retardant in step fb) is washed with an acid in a subsequent mothod step fc) according to a preferred embodiment, wherein the flame retardants are previously pre-efeaned, for example by filtration by means of conventional methods known to the person skiifed in tho art. The edd used in method step (c) is generally selected from the group HCÍ. tfeSCk l-bPO* and acetic acid. The acid fe generaly diluted:in a seivent in a cenpnfeation: of abouti 1 te 75%, preferably In a concentration of about 1fo 20%, pafecelarly preferably in a concentration of about 1 to 9% selected from the group el water, methanol, ethanol, tifldimsfeyitermamkie (DteF) and; N-meth^morpheilne oxide |ΝΜδ) er a Äure of fesse. The preferred solvent ter fee ditebdn of fee add is wafer. The amount df sold fest is used for washing fcli«»!« obtained In method step (b) may vary over vada ranges. Generaliy, a vefebte fraction of fiamé retardant with a volume fteotfeh of acid is used for washing, wniie, according te s preferred embodiment, a double yeiurno traction Is used fer washing, and, secordteg feafoarticulady 6« fee volume of acid fe used ter washing.

The: feme retardant obtained |imefeodstep :te) m# tte sebsequenity washed with an sold asdssebbed above arte then washed one or several times with a soiverfe wherein single to double the volume of soivent relative to the volume of fee feme retardant, is used for Washing. Preferably a solvent selected from the group of water, methanol, ethanol, N.id-dimefeylformamtea (DM?). M mefeyifebfphoiine oxide (Htetete), or a mixture thereof is used. with water is preferred.

The feme retardant can then he pbs#ueni!y separated by means of conventional separation methods such as ilraiion, drying of feesolyent used, Generally thb: restedai: solvent copfeht thereof amounts to 0 to 4fevte;% preferably 0 fe l3 wt~%, patecuteriy preferably δ to 10 wi.-%. fö fibers to fiber: mafeflaís, fer example, ΐβί^'^^^δ^ΡΤ.νΙΡί^ί it iS: advantageous

If the tee r^aráapí is ffpunä in ä Si!, sand,giess bead orquarfe gHt:=eíái. foë ëxamp^.wsim^o tea range oí 0.5 tó

Jpmi preferably 1 pm, The: grinding may besarsedoti? by means öl wet grinding or drygrirteing.

Production Example 1:

Production of a product wittr a molar ratio of urea tó tetmkls nydroxyrnafevltohosoonfom suffafe (THPS; of 1 tó 0.?? 68.2 kg wafer, 10 § kg of «rsa ana 59.5 kg THPS {75%} are initially introduced and tóén heated fer a period ef 3 dourest IS teM-G white stirring, The reaction mixture is subsequently cooled to a temperature below 30 *C. sod 2.1 kg DufaiânïM:Ti |44 (PW> 251): and 30 kg of ammoiga |25%} is introddeed. The pH value is adjusted with ammonia to a vaiue o? about 6 and the reaction mixture is bfeyfed to react for 1 min. Thereafter. 2l3:t^^y|rqp||^sÄ:i^bft (301) are Intoaduead. The sold obtafeed (feme refardant) Is :^p^|^itä$|;:i^^toft'öM0 "G via a dram iliisr, then washed witeefeiume equifetont amount dt Wafer, This resulted in a wife pmddefwito a sifes content of 35 wtol, t^Sdaetton fxampfe 2:

Production of a product with a molar ratio urea to THPS of 1 to 0,77 63 kg water, 10-3 kg o? urea and 59,5 kgTHPf (25%) am Initially Introduced and then stirred for a period of 5 hours at a temperature efMfe M NS. The reaction mixture to then pooled to a température below 30 ®C, end then Q.S kg Hpstapurw SAS and 30 kg# ammönia (25¾¾ are added. The pH value of toe reactipb mixture is adjusted wife ammonia to a value of &amp; and reacted tor 1 min. Then, 21 3 kg of hydrogen peroxide solution (303¾) are introduced. The soiid obtained (lame retafofeitlfe separated at a temperáimé of 40 5G via a drum isitor, washed with a votome egulvaitott amount of water, then wife a vdiumetoduivsieht amount of 3% HO and then witetet iaesf one volume equivalent amount of: water. This resulted in a white product vdth a smids content of 35 wt,-%,

The thus prepared oxidized condensate of a tetrakis hydroxyaikyi phosphonium satt with a hfetogenous compound is patlicuiariy salable as a flame retardent in a ceiluiosic molded body.

Urea or ammonia is preferably used as the nitrogenous compound.

The tetrakis hydroxyslkyi phosphonium compound ín pmföf^5fy a fâtrâNïô tayctroxyoo^thvi phosphonlurnsait.

The proportion of fee: feme: retardant In fee form of a viscose nr lyoeoll fiber in fee eeilolosic man,made fiber, may hefeelweenS: wfe % and SO wt-%, preferably between 10 wh-l and 30 wt.-%. particularly preferably between 15 wtol and 25 wt.-%, based on the Tiber, Thewffectosdneufiicienf In to# case of fee small a propeidcivoffheTlame^retardant, wnle fee^fdfethäft^pjpilöi&amp;ltoe later deteriorate excessively af higher than fee rncommenderi limit amounts. These proportions sliow a lame-retardant celulosic mäh-feade fear to be dhtoined;. wbicfi is characterized in that fee sfrerigtbin the conditioned state is from: iSwH/fex:toi:53 eiN/tax, tin addition. the iiame-refardant celiuiosic man-made fiber may stilt contain additional additives, such as dyes or bactericides.

The oolluiosie man-medé: fiber wccoiziing:: to fee iaventi^ÉWfe :to# fequirsiteats according to E.N ISO 14116 (formerly ifi 533) classification limited Seme 8pt®ad:lífoex:3teatha fin# pefouct(textile fabric), when tested ácoordtog feiTi IS0 15025: 28Q2:tesfepd B · Edge laming

In the test method according to EN ISO 15025:2002, a defined feme from a speoied burner to directed lor 10 a at fee sorte (Method A) or the bottom pefeod 8) of verficstiy oriented textile samples.

The spreading of the fedte anddbe afterglow. as weit as fee formation of particto separabod end bufeirig release of particles must be determined.

The requimmeuia ot EN IS014115 for fee "iimifed feme index 3* are as follows: -the flame must not reach tee upper edge of any specimen, -no specimen should give off burning particles - te alterstow must no! spread Iron; the charred pah to (he undamaged part of the specimen - the etterbum time must be less than two seconds eceefing írta Invention, which may be further processed into s textile fabric. Tbsdnvsntete:fiber: may sise Pa esed for the production ofnenwovens.

Tis texffe il cr nonwoven fahre made írom the über of the invention faiblis ills rssMlförheirlis öt BN |Í30 i 41 il β ciessiffcatlee fjásri fested according to EN IS015026^2 Method: 8: - Edge ferning, 'comprising the inventive flame-retardant caiiuiosic man-mads liber may: be mixed wir fibers ei ρείΰίδί ίΰϊ· #dibetiç:çrigie;. The fibers of natural or syfifostie origin may even be: inherently: item© retardant or biênhed to he Üsrne rötoftí 8ht> K^rhSässöf this in et uh é (flame retarded} polyester,: medserylic, pare- and mela-poiyaramide, polyafoideinfids (Kermei®). $Ä'.»tpfe|}' ne^.· :||^S!!d|m.ida^5te iPEIIceoiyimide#^^, polyamides, {feme retarded}: polyamides, fismemeiardsnt seryilo fibefe, melamine fibers, psiypbsoyiene sulfide;{RRS}, poiyteiraliserpetnyieoo (PTPE), fiberglass, coffee, silk, carbon fibers, oxidized; ihennat| Stabilised polyeefyiöHifois (PANO^) add atecirieally condyofes übers, as well as mixtures of tees« übers Para· and meta-poiyaramide and/or poiyimide fibers are perticeiady susfabte for blending with the inventive flame-retardant ceiluiosic man-made fibers.

The fotendedteseoifoe liber or fiber mixtures according te fbe invention eorfelning the inventive über are protective Nothing of. any kind stféb, ea fTeügbíer uniforms. protective clothing : against contact with molten, mete!, oodeeae# and eoifetm peris in foe mltery sphere, textile surfaces in public areas such «ttÄi Ä:'Ä#*e^5 iexie surfaces in irgbsporfâjüpfo such as aircraft seals, made of textile material or aihonwoven flame retardant outer oe^ïM^ÂÉ^^reBkÂkef). s.§. ten mattresses.

Exemple i; from a book pulp frit * W$%% a vfortese «ömpslfe 8,0¾ ceimfoste6,S% NaOH was pteduced using 4Ö%: SS2. A modifying agent (2% .dimethyiamins and 1 % feiyefoytene glycol12000, based on ceiiuiose}, as well as 22% based on eeiiuiose of foe fame ráfsrcient according to Production Example 1, was in 60% NMMO to foe viscose with a spin gamma value of 62 and a visêosiiy of 120 tailing bail seconds, g/i sufitee acid. 120 grtsbdiem sulphate and 60 g/i zinc sulphate at a topéfatüte of 38 *0 was spun wit; a 60 pm noxzte In a spinning beth of foe composition, stretched to 12Q% In a secondary bath (water at 95 :,C). and withdrawn at 42 m/mfo. The post-treatment (hot dilutee H2SÖ4(waterfoesüifurixaÜdhÄedbieaeh/wat8Psoffsning/ was earned eat by known methods

The;dried fibers wore In turn prooessM into a yem Mm 3δ by means of a eireuiarikniiiing maehirte at a stocking knit grernmegaei 208 g/m2. The stocking knit was subiacted fo fos vortical feme test according to EH ÍSO 15025:2002 Method 8 - Edge iteming. The rosuiis pi foe flame test are shewn In fsbte l and foe über data are shewn irrTahie 1 below. Táblát:

Examine 2; 22% based on eeiluioseof foe flame retardant according lo Production Example 1 in foe form of a 12% dispersion in 60% NMMG are added to foe slurry (puip/aqueous NÎ4MO mixture) and the wafer evaporated to produce a fiber-free ginning solution of foe composition of 12% ceiiuiose/77% NMMO/i1% water, k suifetefoigh alpha pulp was used as foa pulp,:

The spinning: mass was spun to 2.2 dtex fibers by fte-knowftwebày spinning process at a spinning:température of11ö"*C by moans of s 100 \m nozzle in 3 spinning bath containing 25% NMMO û a. temperálóé of 20 *C. Tile washed ent ctHeö fibers were processed ÍS a slocking knit as in Exempie 1 and subjected is tine verfissi flame test according to UN iSO 1SÔ2S: 2002 Method B -löge flaming. The results- of the fiamé lesi are shown in Tsbie Sand the fiber data are shown in Table 2 below.

Exampie 3:

The procedure was carried out as in Example 2, bat a flame retardant was used according to Production Example 2. The results of the flame lest: a;«: shewn in. Table 3 and the fiber data are shown in Table 2 below.

Table 2

Tables

Claims (8)

1. wmmmiMmt ί2!ΝΤΕτβ©δΐίΐϋΐ.ΦζΜΐΑΐί SZABADALMI iGêNYPONTOK i< ybhansstglbo celleiöz viszkóz-, modsijo-, ÿâgy lyoeeNZÄ, ptéiyak iobhpsstgàtSè állap? tâitsSmszhak, tsfegfe Aidroxiäil-föSÄdiüdi sébô!, ammóniákkal, és/vagy nitrogénîartaírnö yegyülétieí, âm«iÿ egy, vagy íöbb amin esöpDítot tadaimaz, aasl jeiiamesvP, hogy a szâ!joIHapsfean life mint lloN/ tex szíitóságú. % AZ: 1. igénypont szerintii íobdanásigáíle szál, sasai jeiismezva, hogy a díSfögéniaríálmd iíspesoiahkarbamid, ammóniák; tiókarbamid, bíuret, melamin, etilénkarhamid, pániéin és ditóöndíamsd csopodbOi van kiválasztva.
2. 3. Az I vagy 2. igènÿportt szerinti iííbíáánásígátió ssàî. azzal jsiiemszve, hogy a laykSsa'hidiaxiikiiaoSafcoiuih Sö előnyösen teirskisz-hidfoximsíii-foszfoniuín só.
3. 4, Az eiôzd ÈIÉSiâS^pô szák azzal jeiiamszvá, hogy a szMrdság :i| óN/íék# cNttóX: közötti ártok, A, Az síöző igénypontok egyike szerinti lohbanástgátiS SZÍ, szzaí jsttomozvo, péídáui színpígmaateketi vagy ykioOzjqokat, C Síjárás az 1 .4: ígénpoatok szerinti iohfesoástgiitoít ^szkóz, lelve modai-szaSak előállásához egy tonôôiiâibôl a köveikezö lépéseket összeíogiaíva: « viszkózt állítunk eio coikiiOZ'Xarílogenáíböi - módosító közeg hozzáadása során, - höxzáádyok I :söly%4ö súly %-öb tób&amp;anásigÉiö állag bsiiiííözára vonatkoztatva. a pigmentek vizes bíszjtórziöjáfsak; alakiéban, - főniük a fonóoidaloí egy íonótovókan keresztül egy tonóíutólöhe, - nyúlok a kíosapötíiézáiszövgdékske?, - utänKeseyök mösä^afi iëhéritfêsssl, festêsëtêfikltèssiei, - szètozaipk szliaÉáy azzal J ollomozvé, hogy a szál előáll kásához <az 8Íkih!azöttaeíitanyagl3'S8% R-1ttarta!smrnai rorsdOikozSk, - a viszkóz ceiluiöztaríaima 4 és ?% közötti, - az aikáiiyiszony 0,7 és 1,S között van, - a szenkéneg adalék 36 süiy%-42 súlyí, cellulózra vonatkoztatva, - hozzáadjuk a viszkózhoz agy módosító adalék 1 söíyto és 5 sáíy% közötti mennyiségei, a eeliytózra vönaíközíatva, - a viszkóz fonás! gamma értéke 5048 közötti, előnyösen 55-58jkőzölt van, - a fonás! viszkozitás 50-110 esögolyös viszkozitás értokó: - a tónófürdó hőmérséklete:34-48°C, - következő fonőíürdő koncsrrtrációkat ajkaimazunk: H2SG4 68-00 g/l, Na2$04 §0-160 <3/k:|nS04 3045 φ - a végső lecsspoíást a fonóííirdoböi 1540 m/porc közóiti sebességgel haljuk ylgrs,
4. 7, Eljárás az ?,-8. igénypontok agytko szerinti lobba násvadehjfeö#száíaknak a Ionéi eljárás szerinti előállításához, azzal Jellemezve, Hogy a lónooidát exiry siója előtt rmzááedank agy tobbanisiptió áiiagöt, és a íehbanásígáííó állag a eellníös-szálbsn I sóly%-S0 súíyl. előnyösen 10 súiy%-30 súiy%. különösen oiSnyósen 15 súiy%45 sáiy% értéket ér el δ, Eljárás az %$, igénypontok sgyike szerint! íobPanásvédett szálak aiöáítitlséte;, s! jellemezva, hogy aiü&amp;banástgáti állagot s fenéitdöhőz történő hozzáadás «lőtt, itieíve# diszperzió előállítása előtt savval, éá yégSS' vizzei mossuk. 8. :Eonai. amely az 1:,-8, igénypontok egyike szedni; lobesnásvédétí sziákat Malimz,
5. 10. Az l-f. jgênypiîok egyike szánni; iofcbanásvádeti szál alkalmazása textil léílplakzi,: tllstva oera szövőit kialakítás előállításához. ÍL M 1,-10; igénypontok egyike mi®ä. fettÉmazó t&amp;dii íaiíjíetalakpt, illetve nem szívéit kláSákilas, azzai jellemezve, hogy 4 taxid felüíetaiakzat, síiéivé nem szövőit kiaiakitás az EN ISO 15025:2002 8 - akarás szerinti vizsgálatnál tepsiíl az EN: IS014118 osztályozás Jmítád flam© spread index tf szannti: követelményeket. 12: Ag 1:-1 1. jgényponlok egyike szerifiit laöb^vásyédeit; sziálai lärtätmaxö :fonál> tszöt féilötátekzat, liléivé narb szövött kíáláAitás, azzal feiiemezve. hegy a lobbanásvédett szál iériaészétes, vagy :szinte5kos Sildéi: szliakkajkkeverakban iii rendelkezésre. 13. A 12. Igénypont: szeriríiiifehai. textil felüíetaiakzat. illetve nem szövött kialakítás, azzal jellemezve, hogy s keverék olyan száiakattartairsta^áfhéiyekmasykmharens jobhanás^atiök,:VagylöOÓá?PtgÉSéan vasinak kiaiakttva,
6. 14. A ÍZ, vagy 1:2, igénypont szerint tőnal, :ték® feíütetaíakzst, illetve nem1 szövött: kialakítás·, azzal j&amp;íiemózv«? begy a löbbaoásváíM szál: keverékben pöilészterrei, ímodakrillai, pará',IS: fbeía-ararniíídsl, polarnídimldd©!, löbfoánásvédöU gyapjöváí; poiibanziniidazoílák poiirriídőéi, poilamlÄk iébbanisvédatf âkrlszâiakkai, mislarmnszálskkeí, pöiiMiíénsgúlílsöaí, polite irafluoretlíénnel, üvegszálakkal. gyapottal., selyemmel. karhonszàlakkaî; oxidált hösfabiiizált poiiaknirtithiszáiakka! és villamoson vezető szálakkal, valamint ezeknek a szálaknak a keverékeivel van seien.
7. 15, Az Í.-12. igénypehtök sgyiha száiinf tobhsnásvádeti száiét tartatmazö textil Möietaiákzat; lelve nem szövött kiaiakitás, azzal jellemezve, hogy aiMbâr#yé#0.sz#:kàv«Â8n:iÂ?i:.vsi^-p^fôiii!Riie,lfeM poilimid szálakkal ven leien.
8. 16, Oxidált köndefizáíum sikaífTiazása tesmlzdifdröxlaiklkfoszlönidm yëgyüietbôl, aítmgénmfmimö vegyüieitek mint bbbanásvédő eszközzéí, egy az előző igénypontok egyike szerinti szátban. azzal jellemezve, hogy a tetrakisz-hidroxiaikil-iosxfónium vegyöiet moláris viszonya á nitrogénvegyülethez 1:(3,06-2,8). élőhpi;gá:1'(ö5<-i,5í, különösen előnyösen 1.(8,85-1,2) értékű. 17. A 13. tgenypnt; szerinti aikategls. ZM^saí jellemeay's, bogy a nltre|ántartaimű vsoyietet karbsmkf ammóniák, tíokarfeamid, hímet, méíamin.étilénkáíbamld, guanidines dtoiándíamiij cseprsiböi yäiaszÄk kl. 1§, A16. s Olirogentartaimu vëgyûlet karhamid: vagy ammóniák. 18, S 18,-16, igénypontok szeriti alkalmazás, ázzál jellemezve. hogy a IteÄ'Wdröxiilä^szförtium: $ό: hldroÄii csöpöf^áí íífdroxlmsöl, íÜ^^j-vágftfe&amp;tÉui csoportból választottuk ki. 28. A 15.-1 i. igénypontok szerinti: alkalmazás, azzal jellemezve, hogy a vegyülni íelfkSsg- hldroximeáí-feszlörslam ső.