SE185444C1

SE185444C1 -

Info

Publication number: SE185444C1
Authority: SE
Publication date: 1963-01-01

Description

Uppfinnare: E A Rodman• Prioritet begdrd irdn den '1 oktober 1.954 (USA) Foreliggande uppfinning avser ett arkformigt material samt ett forfarande for framstallning av ett sadant material. Inventor: E A Rodman • Priority as of October 1, 1954 (USA). The present invention relates to a sheet material and to a process for producing such a material.

Det huvudsakliga andamalet med uppfinningen iir att framstalla ett arkformigt material, som ser ut som fader och aven har dess egenskaper, som liar samma storleksordning pa vattenangpermeabiliteten som det material, som anvandes till ovanlader, och som gOr stort motstand mot forslitning eller avskavning (scuff). Eft annat Ondaml att framstalla porosa, pappersliknande produkter. Andra betydelsefulla avsikter komma att framga av den beskrivning pa uppfinningen, som ges nedan. The main object of the invention is to produce a sheet-like material which looks like a father and also has its properties which are of the same order of magnitude of the water vapor permeability as the material used for superchargers and which have great resistance to abrasion or scuffing. . After another Ondaml to produce porous, paper-like products. Other significant objects will become apparent from the description of the invention given below.

Foreliggande arkformiga material utgores av en icke vavd matta, bestaende av tradar eller fibrer av en linjar tereftalatester sammanfogade medelst den polymera reaktionsprodukt med en molekylvikt av lagst 750, som erhalles vid reaktionen mellan en polyalkyleneterglykol, ett organiskt diisocyanat och en kedjeforlangande forening, innehallande aktiva vateatomer. Forhallandet mellan tradar och bindemedel i produkten ligger fOretradesvis inom intervallerna 1 till 0,3 och 1 till 2,0. Den polymera, linjara tereftalatestern kan vara en ester av tereftalsyra och en glykol med den empiriska formeln HO(C1-12).0H, van i n betecknar ett helt tal frau 2 till 4, t. ex. polyetylentereftalat. Tradarna kan eventuellt ha ett deniertal som är mindre an 1. The present sheet material consists of a non-woven mat, consisting of threads or fibers of a linear terephthalate ester joined by the polymeric reaction product having a molecular weight of at least 750, which is obtained by the reaction between a polyalkylene ether glycol, an organic diisocyanate and an active chain content . The ratio between trader and binder in the product is preferably in the ranges 1 to 0.3 and 1 to 2.0. The polymeric linear terephthalate ester may be an ester of terephthalic acid and a glycol of the empirical formula HO (C1-12) .0H, van i n denotes an integer from 2 to 4, e.g. polyethylene terephthalate. Traders may have a denier number of less than 1.

Foreliggande forfarande kannetecknas darav, att en matta bildas av lost sammanfogade tradar av en polymer, linjar tereftalatester och att den polymera reaktionsprodukten av en polyalkyleneterglykol med molekylvikten lagst 750, ett organiskt diisocyanat och en kedjeforlangande f Orening, innehallande aktiva vateatomer, fordelas I mattan varpa mattan uppvarmes och pressas sa, att tradarna och den polymera reaktionsprodukten hardas till en enhetlig struktur. Tradarna av polymer, linjar tereftalatester utgores lampligen av polyetylentereftalat. Tradarnas deniertal kan vara mindre an 1 per enkeltrad. Lampligen genomf Ores forfarandet sã, ,att mattan av lost sammanfogade fibrer av den polyinera, linjara tereftalatestern genomstickes med nalar och ilarpa uppvarmes, varigenom fibrerna krympa, att den krympta mattan impregneras med en lOsning av den polymera reaktionsprodukten i ett flyktigt, vattenlosligt, organiskt losningsmedel, varpa den impregnerade mattan behandlaS med vatten och darpa uppvarmes sá, att det organiska, losningsmedlet och vattriet fOrangas, samt att den tbrra, impregnerade mattan slutligen ut- sättes for varme och tryck. Atminstone den ena sidan av den torra, impregnerade mattan kan efter varme- och tryckbehandling poleras sa, att utskjutande delar av fibrerna avlagsnas, varefter den polerade sidan foretradesvis kan forses med ett vattengenomslappligt overdrag. Den polymera reaktionsprodukten kan eventuellt fordelas likformigt i hela mattan under bildning av ett laminat, genom att man- separat framstaller en film av den polymera reaktionsprodukten, placerar atminstone ett sadant filinskikt pa minst ett lager av mattan och utsatter de pa varandra liggande skikten for varme och tryck, sá att man erhaller ett enhetligt material. The present process can be characterized in that a mat is formed from loosely joined strands of a polymer, lines of terephthalate ester and that the polymeric reaction product of a polyalkylene ether glycol having a molecular weight of at least 750, an organic diisocyanate and a chain extending compound containing active mats in aqueous atoms heated and pressed so that the threads and the polymeric reaction product harden to a uniform structure. The trades of polymer, lines of terephthalate ester are suitably composed of polyethylene terephthalate. The denier number of trades can be less than 1 per single line. The Ore method is carried out in such a way that the carpet of loosely joined fibers of the polyinear, linear terephthalate ester is pierced with needles and heated, whereby the fibers shrink, that the shrunken carpet is impregnated with a solution of the polymeric reaction product in a volatile, aqueous solvent. , the impregnated carpet is treated with water and the tarpaulin is heated so that the organic, solvent and water are evaporated, and the dry, impregnated carpet is finally exposed to heat and pressure. At least one side of the dry, impregnated mat can be polished after heat and pressure treatment so that protruding parts of the fibers are removed, after which the polished side can preferably be provided with a water-permeable coating. The polymeric reaction product may optionally be uniformly distributed throughout the mat to form a laminate, by separately producing a film of the polymeric reaction product, placing at least one such filin layer on at least one layer of the mat and subjecting the superimposed layers to heat and pressure, so that a uniform material is obtained.

Termerna »fiber» och »tract>, vilka anvandas i beskrivningen, aro synonyma och beteckna Oval stapelfibrer som andlosa tradar. The terms "fiber" and "tract", which are used in the description, are synonymous and denote Oval staple fibers as breathless threads.

Den aven anvanda termen »fibrer av en polymer linjar tereftalatester* avser fibrer av hogpolymeriserade, linjara estrar till tereftalsyra och en glykol frail serien HO(C1-12)OH, van i n är ett helt tal mellan 2 och 10. Fibrerna av den polymera, linjara tereftalestern kunna framstallas enligt det amerikanska patentet 2 465 319, utfardat den 22 mars 1949 for J. R. Whinfiled et al. I foljande exempel anvandas fibrer av polyetylentereftalat, men man far darmed joke forutsatta, att man vid tillampandet av nppfinningen icke kan anvanda a.ven de hogpolymeriserade estrar, som erhallas vid reaktionen mellan tereftalsyra 2— — och polymetylenglykoler, vilka ha mer an 2 men icke mer an 10 metylengrupper, sasom trimetylenglykol, tetrametylenglykol, pentametylenglykol, heptametylenglykol, oktametylenglykol, nonometylenglykol och dekametylenglykol. Man foredrar glykoler med 2-4 metylengrupper. The term also used "fibers of a polymer linear terephthalate ester" refers to fibers of highly polymerized, linear esters of terephthalic acid and a glycol frail series HO (C1-12) OH, used in an integer between 2 and 10. The fibers of the polymer, The linear terephthal ester can be prepared according to U.S. Patent 2,465,319, issued March 22, 1949 to JR Whinfiled et al. In the following examples, polyethylene terephthalate fibers are used, but it is jokingly assumed that in the application of the invention it is not possible to use even the highly polymerized esters obtained in the reaction between terephthalic acid 2- and polymethylene glycols which have more than 2 but not more than 10 methylene groups, such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, heptamethylene glycol, octamethylene glycol, nonomethylene glycol and decamethylene glycol. Glycols with 2-4 methylene groups are preferred.

De fibrer, vilka ha ett Mgt deniertal [mindre an 1,0 denier per trad (relativ tjocklek)], och vilka anvandas i nagra av fOljande exempel, kunna framstallas medelst Overstrackning (super-stretching) av de polymera, linjara tereftalestrarna enligt satt, som beskrives i den amerikanska patentskriften 2 578 899, utfardad den 18 december 1951 for A. Pace Jr. Det finns icke nagon speciell lagre grans for det antal denier, som fibrerna av det polymera linjara tereftalatet maste ha for att vara anvandbara enligt uppfinningen. Fibrer, vilka ha en diameter av 0,1 mikron (0,00008 denier per trad), aro anvandbara. Tradar med ett hogre deniertal an 1,0 ge ark, vilka ha &lig motstandsformaga mot avskavning i jamforelse med lader. Darf Or erfordras fibrer med lagt deniertal (lagre an 1,0 denier per trad) till de produkter, vilka anvandas sasom laderersattning, och vilka fordra hog motstandsformaga mot avskavning. Det finns icke flagon speciell Ovre grans for det antal denier, som erfordras for fibrer, vilka arivandas for andra andamal, sasom underlag fiir bojliga ytbelaggningar och pappersliknande produkter, vilka joke fordra stor motstandsfOrmaga mot avskavning. Av fibrer, vilka ha ett deniertal av 50-70, framstallas anvandbara, icke vavda tyger. Om man Onskar sarskilt grov flit, kan man anvanda annu grovre tract med ett deniertal av 100-150. Fibrerna kunna vara raka eller krusiga. The fibers, which have a Mgt denier number [less than 1.0 denier per thread (relative thickness)], and which are used in some of the following examples, can be produced by super-stretching the polymeric, linear terephthalate esters according to the method, as described in U.S. Patent 2,578,899, issued December 18, 1951 to A. Pace Jr. There is no particular bearing on the number of denier that the fibers of the polymeric linear terephthalate must have in order to be useful in the present invention. Fibers having a diameter of 0.1 micron (0.00008 denier per thread) are usable. Trades with a higher denier number of 1.0 yield sheets, which are highly resistant to abrasion compared to chargers. Darf Or requires fibers with added denier number (less than 1.0 denier per trad) for the products which are used as charger replacement, and which require high resistance to abrasion. There is no special upper limit for the number of denier required for fibers which are used for other purposes, such as substrates for flexible coatings and paper-like products, which jokes require great resistance to abrasion. From fibers having a denier number of 50-70, usable, nonwoven fabrics are made. If you want a particularly rough diligence, you can use an even coarser tract with a denier number of 100-150. The fibers can be straight or curly.

Under det att deniertalet pa fibern ar en betydelsefull faktor vid tillampandet av uppfinningen har langden icke samma betydelse utan den kan variera frail s. litet som 0,25 mm till 200 mm eller mer. Fiberlangden bestammes i huvudsak av den metod, som anvandes vid tillverkningen av fibermattan. T. ex. anvandas fibrer med langden cirka 13 mm eller kortare, om mat-tan tillverkas medelst teknik kand frail pappersindustrien. Vid mattor framstallda medelst bias-fling med luft och med darfor avsedda anordningar, sasom beskrives i den amerikanska patentskriften 2 451 915, utfardat den 19 oktober 1948 for Fracis M. Buresh, anvandas fibrer, vilka icke aro langre an cirka 38 mm. Mattor av fibrer med langdeu 38 mm och mer framstallas foretTadesvis pa kardningsmaskiner. While the denier number of the fiber is an important factor in the practice of the invention, the length does not have the same significance but can vary from as little as 0.25 mm to 200 mm or more. The fiber length is mainly determined by the method used in the manufacture of the fiber mat. Eg. fibers with a length of approximately 13 mm or less are used, if the mat is manufactured by means of technology known to the paper industry. In carpets made by bias-fling with air and with dedicated devices, as described in U.S. Pat. No. 2,451,915, issued October 19, 1948 to Fracis M. Buresh, fibers not exceeding about 38 mm are used. Carpets of fiber with a length of 38 mm and more are mainly made on carding machines.

Man kan aven anvanda blandningar av polymera, linjara tereftalat-fibrer och liknande fibrer. Vid anyandningen av fiberblandningar skola fibrerna av det polymera, linjara tereftalatet overvaga. Andra fibrer, vilka kunna blandas med fibrerna av det polymera, linjara tereftalatet, innefatta fibrer av nylon, polyakrylnitril, bomull, ull, glas och viskos-rayon. Mixtures of polymeric, linear terephthalate fibers and similar fibers can also be used. When using fiber blends, the fibers of the polymeric, linear terephthalate should monitor. Other fibers which may be blended with the fibers of the polymeric linear terephthalate include fibers of nylon, polyacrylonitrile, cotton, wool, glass and viscose rayon.

Termen »polyalkyleneterglykoh avser polyalkyleneterglykoler med hydroxigrupper i and-stalling, Dessa foreningar harleda sig van ligen fran polymeriseringen av cykliska etrar, sasom alkylenoxider eller dioxolaner, eller fran kondensationen av glykoler. De motsvara ibland formeln HO(R0)H, i vilken R betecknar en alkylenradikal och n ar ett hen tal storre On 1. I de polyetrar, vilka Oro anvandbara vid framstallningen av de polymera elastomererna enligt uppfinningen, Or n betydligt storre, sa att polyalkyleneterglykolema fa en molekylvikt av minst 750. Molekylvikten kan vara sa hog som 10000. Man foredrar de glykoler, som ha molekylvikter av 750 till 3500. Man kan aven anvanda polyglykoler, vilka bildats vid sampolymeriseringen av en blandning av olika alkylenoxider eller glykoler, eller den polyglykol, som harletts fran en cyklisk eter, sasom dioxolan, varvid en produkt med formeln HO(CH20C21-14).H erhalles. Exempel pa anvandbara foreningar, vilka innehalla flera alkylenradikaler, aro de polyetrar, som beskrivas i den amerikanska patentskriften 2 492 955 for Ballard et al, och vilka ha molekylvikter Mom det iinskade omradet. Alkylenradikalerna kunna ha raka kedjor eller forgrenade kedjor, sasorn polypropyleneterglykol, dvs. HO(CH,CH-0).H. The term "polyalkylene ether glycoh" refers to polyalkylene ether glycols having hydroxy groups in their form. These compounds usually derive from the polymerization of cyclic ethers, such as alkylene oxides or dioxolanes, or from the condensation of glycols. They sometimes correspond to the formula HO (R0) H, in which R represents an alkylene radical and n is a number of larger On 1. In the polyethers which are useful in the preparation of the polymeric elastomers according to the invention, Or n is considerably larger, so that the polyalkylene ether glycols have a molecular weight of at least 750. The molecular weight can be as high as 10000. The glycols having molecular weights of 750 to 3500 are preferred. Polyglycols, which are formed in the copolymerization of a mixture of different alkylene oxides or glycols, or the polyglycol, can also be used. , which is derived from a cyclic ether, such as dioxolane, to give a product of the formula HO (CH 2 OC 21-14) .H. Examples of useful compounds which contain several alkylene radicals are the polyethers described in U.S. Pat. No. 2,492,955 to Ballard et al., And which have molecular weights within the reduced range. The alkylene radicals may have straight chains or branched chains, such as polypropylene ether glycol, ie. HO (CH, CH-O) .H.

CH3 Andra specifika exempel pa polyalkyleneterglykoler Oro polyetyleneterglykol, polybutyleneterglykol, 1,2-polydhnetyleneterglykol och polydekametyleneterglykol. CH3 Other specific examples of polyalkylene ether glycols Concrete polyethylene ether glycol, polybutylene ether glycol, 1,2-polydimethylene ether glycol and polydecamethylene ether glycol.

Den inangfald organiska diisocyanater, vilka kunna anvandas vid framstallningen av de polymera elastomererna, som anvandas enligt uppfinningen, omfatta aromatiska, alifatiska och eykloalifatiska diisoeyanater och blandningar darav. Typiska foreningar omfatta 2,4-tolylendiisocyanat, m-fenylendiisocyanat, 4-klor-1,3-fenylendlisocyanat, 4,4'-bifenylendiisocyanat, 1,5-naftylendiisocyanat, 1,4-tetrametendiisocyanat, 1,6- hexametendiisocyanat, 1,10-dekametendiisocyanat, 1,4-cyklohexendiisocyanat, 4,4'-metylenbis-(cyklohexylisocyanat) och 1,5-tetrahydronaftylendiisocyanat. Arylendiisocyanaterna (de i vilka var och en av de tva isocyanatgrupperna Or direkt bunden vid en aromatisk ring) reagera allmanhet snabbare med polyalkyleneterglykolerna an alkylendiisocyanatema och foredragas darfor. FOreningar, sasom 2,4-tolylendiisoeyanat, i vilken de tva isocyanatgrupperna ha olika reaktionsformaga, Oro sarskilt lampliga. Diisocyanaterna kunna innehalla andra sub stituenter, men man foredrar vanligtvis de, som ej ha andra reaktionsbenagna grupper On de tva isocyanatgrupperna. Vid aromatiska foreningar kunna isocyanatgrupperna, vara bundna antingen till samma eller till olika ringar. Man kan anvanda dimerer till de monomera diisocyanaterna och di(isocyanatary1)-karbamiderna, sasom di-(3-isocyanat-4-metylfeny1)-karbamid. The amounts of organic diisocyanates which can be used in the preparation of the polymeric elastomers used according to the invention include aromatic, aliphatic and cycloaliphatic diisocyanates and mixtures thereof. Typical compounds include 2,4-tolylene diisocyanate, m-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethene diisocyanate, 1, 10-Decamethene diisocyanate, 1,4-cyclohexene diisocyanate, 4,4'-methylenebis- (cyclohexyl isocyanate) and 1,5-tetrahydronaphthylene diisocyanate. The arylene diisocyanates (those in which each of the two isocyanate groups Or is directly attached to an aromatic ring) generally react more rapidly with the polyalkylene ether glycols than the alkylene diisocyanates and are therefore preferred. Compounds, such as 2,4-tolylene diisoyanate, in which the two isocyanate groups have different reactive forms, are particularly suitable. The diisocyanates may contain other substituents, but those which do not have other reaction-prone groups are usually preferred over the two isocyanate groups. In the case of aromatic compounds, the isocyanate groups may be attached either to the same or to different rings. Dimers can be used for the monomeric diisocyanates and the di (isocyanataryl) ureas, such as di- (3-isocyanate-4-methylphenyl) urea.

Polytetrametyleneterglykol Or den glykol, som man enligt uppfinningen lampligen later reagera med 2,4-tolylendiisocyanat. Polytetramethylene ether glycol Or the glycol which according to the invention is suitably reacted with 2,4-tolylene diisocyanate.

. Den hoga styrkan och smidigheten pa det, arkformiga material, som framstallts enligt upp-_ — —3 finningen, beror i stor utstrackning pa affiniteten mellan fibrerna av polymert, linjart tereftalat och det polymera, elastomera bindemedlet. Nar graden av adhesion mellan fibrerna och bindemedlet är for stor, kunna fibrerna brytas en At &igen, om de utsattas for pakanning, vilket ger en lag rivstyrka. Om graden av adhesion mellan fibrer och bindemedel Or for lag, gar den hoga slitstyrkan ferlorad. Graden av adhesion mellan fibrerna av polymert, linjart tereftalat och polymert, elastomert bindemedel skall enligt uppfinningen vara sadan, att produkterna bliva bojliga och fa bade hog riv- och slitstyrka. . The high strength and flexibility of the sheet material produced according to the invention depends to a large extent on the affinity between the fibers of polymeric, linear terephthalate and the polymeric elastomeric binder. When the degree of adhesion between the fibers and the binder is too great, the fibers can break an At & again, if they are subjected to packing, which gives a low tear strength. If the degree of adhesion between fibers and binder Or for law, the high wear resistance is lost. According to the invention, the degree of adhesion between the fibers of polymeric, linear terephthalate and polymeric, elastomeric binder must be such that the products become flexible and have both high tear and wear resistance.

Mattorna av fibrer av polymert, linjart tereftalat kunna framstallas medelst teknik kand fran en mangd omraden, sasom papperstillverkning eller kardning, eller ()Asa kan man avsatta dem fran en luftstrom eller i flagon lamplig anordning f Or framstallning av en bana. The mats of polymeric, linear terephthalate fibers can be made by techniques known in a variety of fields, such as papermaking or carding, or () Asa can be deposited from an air stream or in a flangable device for making a web.

Mattorna av polymert, linjart tereftalat kunna bringas i kontakt med det polymera, elastomera diisocyanatbindemedlet pa en mangd olika satt, t. ex. genom att man impregnerar mattan med en losning eller dispersion av bindemedlet eller genom en enkel blandning, varvid bindemedlet I partikular form bringas i kontakt med fibrerna. Om bindemedlet tillsattes som en dispersion eller som torra partiklar, erfordras varme och tryck for astadkommande av bindemedlets sammansmaltning. I forvag bildade filmer av det polymera, elastomera diisocyanatbindemedlet kunna Oven bringas i kontakt med mattorna av fibrer av polymert, linjart tereftalat. The mats of polymeric, linear terephthalate can be brought into contact with the polymeric, elastomeric diisocyanate binder in a variety of ways, e.g. by impregnating the mat with a solution or dispersion of the binder or by a simple mixing, the binder being brought into contact with the fibers in particulate form. If the binder was added as a dispersion or as dry particles, heat and pressure are required to effect the binder fusion. Formed films of the polymeric elastomeric diisocyanate binder can also be brought into contact with the mats of polymeric, linear terephthalate fibers.

Forhallandet fiber till bindemedel i foljande exempel variera mellan 1,0 och 0,5 och mellan 1,0 och 1,6. Under det att detta representerar den lampligaste sammansattningen, kunna anvandbam produkter framstallas, da forhallandet fiber till bindemedel ligger mellan 1,0 och 0,3 och mellan 1,0 och 2,0. The ratio of fiber to binder in the following examples varies between 1.0 and 0.5 and between 1.0 and 1.6. While this represents the most suitable composition, use products can be produced, as the ratio of fiber to binder is between 1.0 and 0.3 and between 1.0 and 2.0.

I exemplen anvandes dimetylformamid sasom losningsmedel for dispergering av det elastomera bindemedlet vid framstallning av impregneringsmedlet. De sammansatta icke hardade elastomererna kunna Visas i andra lesningsmedel. Verkan av losningsmedlet synes emellertid vara helt specifik och andrar sig frail den ena elastomeren till den andra. Den icke hardade reaktionsprodukt, som erhalles fran en polytetrametyleneterglykol, 2,4-tolylendiisocyanat och vatten, bildar en dispergerad, flytande gel eller losning vid koncentrationer pa 5-10 viktprocent i dimetylformamid, tetrahydrofuran, metyletylketon, toluen, nitrobensen, o-diklorbensen, tetrakloretan, kloroform, tiof en, en 50/50 blandning av tetrahydrofuran och metyletylketon, en 50/50 blandning av tetrahydrofuran och bensen, pyridin, cyklohexanon on dietyletern till etylenglykol. In the examples, dimethylformamide was used as the solvent for dispersing the elastomeric binder in the preparation of the impregnating agent. The composite non-cured elastomers can be displayed in other readings. However, the action of the solvent appears to be quite specific and varies from one elastomer to the other. The uncured reaction product obtained from a polytetramethylene ether glycol, 2,4-tolylene diisocyanate and water forms a dispersed liquid gel or solution at concentrations of 5-10% by weight in dimethylformamide, tetrahydrofuran, methyl ethyl ketone, toluene, nitrobenzene, o-dichlorobenzene, o-dichlorobenzene , chloroform, thiophene, a 50/50 mixture of tetrahydrofuran and methyl ethyl ketone, a 50/50 mixture of tetrahydrofuran and benzene, pyridine, cyclohexanone and the diethyl ether to ethylene glycol.

De polymera reaktionsprodukterna kunna Oven ha bildat bryggor med andra foreningar, sasom toluendiisocyanatkarbamid. The polymeric reaction products may also have formed bridges with other compounds, such as toluene diisocyanate urea.

Man kan forlana det arkformiga materialet enuppfinningen viss farg genom att blanda fangamnen eller pigment i det polymera bindemedlet, genom att farga mattan eller genom att anvanda i forvag fargade eller pigmenterade fibrer. Foretradesvis fargas fibermattan. The sheet-like material of the invention can be given a certain color by mixing the traps or pigments in the polymeric binder, by dyeing the carpet or by using pre-dyed or pigmented fibers. Preferably, the fiber mat is dyed.

Foljande specifika exempel askadliggera uppfinningen narmare utan att begransa densamma. Overallt i beskrivning, exempel och patentansprak ha delar och procenttal uttryckts som viktdelar och viktprocent. The following specific examples further illustrate the invention without limiting it. Throughout the description, examples and patent claims, parts and percentages have been expressed as parts by weight and percentages by weight.

Bestamningen av laderpermeabilitetsvardena (LPV) utfores, sa att man fyller en kristallisationsskal, vars diameter Or 75 mm, med kalciumklorid, med en kornstorlek av hogst 1,4 mm. Man tacker darpa skalen med eft membran .av det material, som skall provas, och staller den tackta skalen i en atmosfar med hog fuktighet (23° C och 90 % relativ fuktighet). Alltsammans vages sedan med jamna mellanrum, och jamviktshastigheten pa sorptionen beraknas som g vatten per 100 m2 yta och timme, vilket Or laderpermeabilitetsvardet. Detta Or en modifiering av ett prov, som utvecklats av Bureau of Standards, Kanogy & Vickers, J. Res. Nat. Bur. of Std. 44, 347-62, 1950 (April). The determination of the charger permeability values (LPV) is performed, so that a crystallization shell, the diameter of Or 75 mm, is filled with calcium chloride, with a grain size of at most 1.4 mm. Dip the shells with a membrane of the material to be tested and place the shelled shell in an atmosphere of high humidity (23 ° C and 90% relative humidity). Everything is then weighed at regular intervals, and the equilibrium velocity of the sorption is calculated as g water per 100 m2 surface area and hour, which Or the charge permeability value. This is a modification of a sample, developed by the Bureau of Standards, Kanogy & Vickers, J. Res. Nat Bur. of Std. 44, 347-62, 1950 (April).

Exempel 1. En pores, lest bunden matta av 32 mm langa stapelfibrer som tillverkats av polyetylentereftalat, och som ha ett deniertal av 0,1 och med ytvikten 339 g/m2 bildades pa en karda. Mattan doppades i en 5-procentig losning av en elastomer av polytetrametyleneterglykol/toluendiisocyanat i dimetylformamid. Mattan pressades for avlagsnande av overskottet losning och utsattes darpa for farskanga, for att polymeren skulle koagulera jamnt i hela mattan, innan den torkades vid 121° C. Vid torkningen blevo fibrerna tatare packade, och det erhallna materialet var ett fibrost laderliknande ark, i vilket bindemedlet i huvudsak var jainnt fordelat. Example 1. A pore, lightly bonded mat of 32 mm long staple fibers made of polyethylene terephthalate, having a denier number of 0.1 and having a basis weight of 339 g / m 2 was formed on a card. The mat was dipped in a 5% solution of a polytetramethylene ether glycol / toluene diisocyanate elastomer in dimethylformamide. The mat was pressed to remove the excess solution and subjected to a barbed wire, so that the polymer would coagulate evenly throughout the mat, before being dried at 121 ° C. During drying, the fibers became tighter packed, and the resulting material was a fibrous charger-like sheet in which the binder was essentially jainnt distributed.

Elastomeren av polytetrametyleneterglykol/toluendiisocyanat framstalldes, genom att man under 3 timmar blandade 1 mol polytetrametyleneterglykol med molekylvikten 3230 och 2,1 mol 2,4-tolylendlisocyanat i en Werner-Pleiderer blandningsapparat vid 70-80° C. Darpa tillsattes 5,11 mol vatten och blandandet fortsattes under 33 minuter, varvid temperaturen steg till ungefar 135° C. Vid slutet av denna lid forelag reaktionsmassan i form av gummiliknande stycken. Den avlagsnades ur blandningsapparaten och lades i en valskvarn for gummi, och i denna tillsattes 0,74 delar piperidin for varje 100 delar polymer. Nar den blandats omsorgsfullt, togs den stabilserade elastomeren ur kvarnen i arkform. The polytetramethylene ether glycol / toluene diisocyanate elastomer was prepared by mixing for 1 hour 1 mole of polytetramethylene ether glycol having a molecular weight of 3230 and 2.1 moles of 2,4-tolylene diisocyanate in a Werner-Pleiderer mixer at 70-80 ° C. and mixing was continued for 33 minutes, the temperature rising to about 135 ° C. At the end of this time, the reaction mass was in the form of rubber-like pieces. It was removed from the mixer and placed in a rubber roller mill, to which 0.74 parts of piperidine was added for every 100 parts of polymer. When mixed thoroughly, the stabilized elastomer was removed from the mill in sheet form.

FOrhallandet fiber till bindemedel var 1 till 0,8 och den torkade produkten hade ett LPV-varde av 5000. Det fanns icke nagra synbara brister i materialet efter 10000000 bojningar i Schiltknechts bOj ningsapparat. The ratio of fiber to binder was 1 to 0.8 and the dried product had an LPV value of 5,000. There were no apparent defects in the material after 10,000,000 bends in Schiltknecht's bending apparatus.

Exempel 2. 38 mm langa fibrer av polyetylentereftalat med deniertalet 0,1 matades till en karda, dar det kontinuerligt bildades en pores matta med ytvikten 271 g/m2. Mattan viktes kontinuerligt till en dubbelvikt matta med ytvikten 542 g/m2. Den dubbelvikta mattan passerade kontinuerligt en nalvavstol fer aft erhalla okad styrka. Fran 4— — ualvdvstolen passerade mattan kontinuerligt en till 149' C uppydrmd zon, for att man skulle erhalla en krympning av mattans yta med cirka -procent. Mattan passerade sedan kontinuer- ligtoch impregnerades grundligt med en procentig losning i dimetylformamid av elastomeren, polytetrametyleneterglykol/toluendisisocyanat, som framstallts pa i det foljande beskrivet sdtt. Den impregnerade mattan doppades sedan "kontinuerligt i vatten av rumstemperatur, vilket gjorde, att elastomeren koagulerade i hela mattan. Den impregnerade mattan torkades sedan kontinuerligt, genom aft den lick passera genom en till 93° C uppvarmd zon, sa att vattnet och dimetylformamiden avdunstade. Vid impregnerings- och det ddrpa foljande torkningssteget .packades och hardades mattan, utan att man behovde anvanda flagon som heist behandling -under tryck for att bilda det Ldderliknande ark-. .formiga materialet. Det terra impregnerade la.- derliknande arkformiga materialet polerades ddrpa kontinuerligt pa ena sidan med en 240 J smdrgeldukskldcid vals, for erhallande av en glatt yta. Arket med den glatta ytan besprutades clarpa. pa den polerade sidan (cirka 34 g besprutningsvdtska per m2) med foljande blandning: viktdelar 50-procentig vattenhaltig latex av ett sam- polymerisat av butadien och akrylnitril60,6 36-procentig vattenlosning av ett fenol/f or- maldehydharts 30,3 7,5-procentig vattenlosning av natrium- polyakrylat 9,1 100,0 Del besprutade arket torkades kontinuerligt, genom att det lick passera genom en uppvarmd zon, och under det att det var varmt, praglades det genom aft pressas mellan kalla pressplattor, varav den ena var av stal och hade ett ldderliknande monster ingraverat i sin yta. Example 2. 38 mm long polyethylene terephthalate fibers with a denier number of 0.1 were fed to a carda, where a pore mat with a basis weight of 271 g / m 2 was continuously formed. The carpet is continuously folded into a double-weight carpet with a basis weight of 542 g / m2. The double-folded mat continuously passed a nalvav chair to obtain increased strength. From the 4- - ualvdvstolen, the carpet continuously passed a zone heated to 149 ° C, in order to obtain a shrinkage of the surface of the carpet by about -percent. The mat then passed continuously and was thoroughly impregnated with a percent solution in dimethylformamide of the elastomer, polytetramethylene ether glycol / toluene disisocyanate, prepared in the manner described below. The impregnated mat was then dipped "continuously" in room temperature water, causing the elastomer to coagulate throughout the mat. The impregnated mat was then dried continuously, passing through the lick through a zone heated to 93 ° C, so that the water and dimethylformamide evaporated. During the impregnation and dripping subsequent drying step, the carpet was packed and hardened, without the need to use flakes as a hot treatment-under pressure to form the Leather-like sheet -... The terra impregnated leather-like sheet-like material was dripped polished continuously. on one side with a 240 J slurry cloth roller, to obtain a smooth surface, the sheet with the smooth surface was sprayed clear, on the polished side (about 34 g spray liquid per m2) with the following mixture: parts by weight of 50% aqueous latex of a polymer of butadiene and acrylonitrile60.6 36% aqueous solution of a phenol / formaldehyde resin 30.3 7.5% aqueous solution of sodium polyacrylate 9.1 100.0 Part of the sprayed sheet was dried continuously, passing the leak through a heated zone, and while it was hot, it was pragmatic by pressing between cold press plates, one of which was of stole and had a leather-like monster engraved on its surface.

Elastomeren av polymetyleneterglykol/toluendiisocyanat, som anvants i detta exempel, framstalldes pa filljande satt: 3 mol polymetyleneterglykol med mole,kylvikten 920 och innehallande 0,02 mol vatten blandades 3 timmar vid 100° C med 2,02 mol 2,4-tolylendiisocyanat. En polyuretan med hydroxylgrupper i andstallningarna och med en molekylvikt pa 3110 bildades. 311 delar av denna polyuretan och 0,57 delar vatten Manclades 10 minuter vid 30-35° C i en WernerPfleiderer blandningsapparat, varpa. tillsattes delar 2,4-tolylendiisocyanat och massan blandades under 2,5 timmar vid 70-75° C. 12,6 delar vatten sattes till den viskiisa reaktionsmassan, och blandandet fortsattes 30 minuter, under det att temperaturen steg fran 70° till 100° C. Den gummiliknande polymeren togs frau blandningsapparaten och lades i en valskvarn for gummi, ddr 0,7 delar piperidin tillsattes per 100 delar polymer for okning av stabiliseringen. Efter det att stabiliseringsmedlet inblandats omsorgsfullt, uttogs elastomeren i arkform ur kvarnen. The polymethylene ether glycol / toluene diisocyanate elastomer used in this example was prepared as follows: 3 moles of polymethylene ether glycol with mole, cooling weight 920 and containing 0.02 moles of water were mixed for 3 hours at 100 ° C with 2.02 moles of 2,4-tolylene diisocyanate. A polyurethane having hydroxyl groups in the spirits and having a molecular weight of 3110 was formed. 311 parts of this polyurethane and 0.57 parts of water Manclades for 10 minutes at 30-35 ° C in a WernerPfleiderer mixer, warp. parts of 2,4-tolylene diisocyanate were added and the mass was mixed for 2.5 hours at 70-75 ° C. 12.6 parts of water were added to the viscous reaction mass, and the mixing was continued for 30 minutes, while the temperature rose from 70 ° to 100 ° C. The rubber-like polymer was removed from the mixer and placed in a rubber roller mill, where 0.7 parts of piperidine was added per 100 parts of polymer to increase the stabilization. After the stabilizer was thoroughly mixed, the elastomer was removed in sheet form from the mill.

Ldderersattningsprodukten i detta exempel hade samma utseende, kansel och beskaffenhet som sadant lader, som anvandes som ovanldder till skor. Forhallandet fiber till bindemedel var 1 till 0,5. De fysikaliska egenskaperna voro: Ytvikt 378 g/m2 Laderpermeabilitetsvarde 3000 Draghallfasthet —1" remsa (i genom- snitt) 39 kg Rivstyrka (ASTM, D624-48, Die C) 39 kg/cm (Jdmforligt med ldder, som anvandes vid skotillverkningen) Skor vars ovanlader gjorts av produkten i detta exempel, visa tillfredsstallande egenskaper med avseende pa fuktighetsgenomgang. The leather replacement product in this example had the same appearance, chancel and nature as such lader, which was used as an overlay for shoes. The ratio of fiber to binder was 1 to 0.5. The physical properties were: Surface weight 378 g / m2 Charger permeability value 3000 Tensile strength —1 "strip (average) 39 kg Tear strength (ASTM, D624-48, Die C) 39 kg / cm (Compatible with leather, used in shoe manufacturing) Shoes whose uppers are made of the product in this example, show satisfactory properties with respect to moisture penetration.

Exempel 3. Av 16 mm langa stapelfibrer av polyetylentereftalat med deniertalet 3 per enkeltrad bildades ett vattenhaltigt ark, (waterleaf), genom att man gjorde en uppslamning av fibrerna i vatten och darpa medelst gangse teknik vid papperstillverkningen tillverkade ark med ytvikten 68 g/m2. Del vattenhaltiga arket torkades .och impregnerades darpa, genom att det doppades i en 10-procentig losning i koltetraklorid av en elastomer polymer, som framstallts pa foljande satt: 3 mol polytetrametyleneterglykol och 2 mol ,2,4-tolylendiisocyanat lick reagera for att bilda en polyuretan, -vilken i sin tur bringades att reagera med 0,32 mol vatten och 2,3 mol 2,4-tolylendiisocyanat. Overskottet losning fick rinna av arket och sedan lick de flyktiga bestandsdelarna av impregneringsblandningen avdunsta ndstan fullstandigt. Polymeren bringades att koagulera, genom att provet doppades i en 5-procentig losning av dimetylpiperazin i metanol, foljt av en grundlig tvattning med vatten. Vid torkningen av impregneringsmedlet koncentrerades den elasomera polymeren vid fibrernas skarningspunkter och darvid erholls en pords struktur. Example 3. From 16 mm long staple fibers of polyethylene terephthalate with the denier number 3 per single row, an aqueous sheet, (waterleaf) was formed, by making a slurry of the fibers in water and dripping by conventional techniques in papermaking sheets with a basis weight of 68 g / m2. A portion of the aqueous sheet was dried and impregnated by dipping it in a 10% solution in carbon tetrachloride of an elastomeric polymer prepared as follows: 3 moles of polytetramethylene ether glycol and 2 moles of 2,4-tolylene diisocyanate were reacted to form a polyurethane, which in turn was reacted with 0.32 moles of water and 2.3 moles of 2,4-tolylene diisocyanate. The excess solution was allowed to drain from the sheet and then the volatile constituents of the impregnation mixture were licked off completely. The polymer was caused to coagulate by dipping the sample in a 5% solution of dimethylpiperazine in methanol, followed by a thorough washing with water. In the drying of the impregnating agent, the elasomeric polymer was concentrated at the points of intersection of the fibers, thereby obtaining a pore structure.

Slutprodukten hade foljande fysikaliska egenskaper: Fiber/bindemedel — viktforhallande ..1: 1,6 Sprdngstyrka (kg/em2) 7,2 Elmendorf rivstyrka (g) 554 Tjocklek (mm) 0,64 Produkten var bojlig och hade samma karaktar i utseende och yta som laskpapper. Den var utomordentligt ldmpad sasom forstyvningsmedel i gangkldder, t. ex. kavajer. Den var dvenldmplig vid tillverkningen av underkjolar, vilka dro avsedda aft »fora ut» ytterkladerna. The final product had the following physical properties: Fiber / binder - weight ratio ..1: 1.6 Burst strength (kg / em2) 7.2 Elmendorf tear strength (g) 554 Thickness (mm) 0.64 The product was flexible and had the same character in appearance and surface as tissue paper. It was extraordinarily softened as a stiffener in gait colds, e.g. jackets. It was suitable for the manufacture of petticoats, which pulled intended to "liner out" the outer garments.

En fardel med uppfinningen dr, att man erhaller ett arkformigt material, som har stor fiirmaga att motsta avskavning samtidigt som det bar hog vattenangpermeabilitet, hog drag- och rivhallfasthet och ett tillfredsstallande bojningsvarde. A disadvantage of the invention is that a sheet-like material is obtained which has a large capacity to resist abrasion while having high water vapor permeability, high tensile and tear resistance and a satisfactory bending value.

Pro dukten enligt uppfinningen dr anvandbar sasom laderersattning i handvdskor, jackor, skarp, ovanlader till skor, skyddsbeklddnad, resvdskor, mdbler, bokbinderiarbeten m. m. — —The product according to the invention is usable as a charger replacement in hand-held shoes, jackets, sharp, over-loaded for shoes, protective clothing, travel shoes, furniture, bookbinding work, etc. - -

Claims

Patent claim:

Sheet-shaped material, characterized in that it consists of a non-woven mat, consisting of threads or fibers of a linear terephthalate ester joined together by means of the polymeric reaction product having a molecular weight of at least 750, is obtained in the reaction between a polyalkylene ether glycol, an organic diisocyanate and a chain-extending compound containing active hydrogen atoms.

Product according to patent claim 1, characterized in that the ratio trades to binder Egger Mom ranges 1 to 0.3 and 1 to 2.0.

Product according to claim 1 or 2, characterized in that the polymeric linear terephthalate ester is an ester of terephthalic acid and a glycol of the empirical formula HO (CH2) .0H, in which n is an integer between 2 and 4.

4. A product according to claim 3, characterized in that the polymeric linear terephthalate ester consists of polyethylene terephthalate.

5. A product according to any one of claims 1-4, characterized in that the polyalkylene ether glycol has a molecular weight of 750-10000.

Product according to claim 5, Urinary characterized in that the polyalkylene ether glycol has a molecular weight of 750-3500.

7. A product according to any one of claims 1-6, characterized in that the binder consists of the reaction product of 1 mole of polytetramethylene ether glycol, 2.1 moles of 2,4-tolylene lysocyanate and 5.11 moles of water.

8. A product according to any one of claims 1-7, characterized in that the polymeric reaction product is crosslinked with toluene diisocyanate urea.

9. A product according to any one of the patent laws 1-8, characterized by the fact that essentially all trades have a denier number less than 1.

10. A process for producing nonwoven sheet material according to any one of claims 1 to 9, characterized in that a mat is formed by loosely joined strands of a polymer, linear terephthalate ester and that the polymeric reaction product of a polyalkylene ether glycol having a molecular weight of at least 750, an organic diisocyanate and a chain-extending compound, containing active hydrogen atoms, are distributed in the carpet, the carpet is warmed and pressed, so that the threads and the polymeric reaction product harden into a uniform structure.

11. A process according to claim 10, characterized in that the threads of the polymeric linear terephthalate ester consist of polyethylene terephthalate.

12. A method according to claim 10 or 11, characterized in that the threads of part: polymeric, linear terephthalate have a denier number less On 1 per single row.

13. A process according to any one of claims 10-12, characterized in that the polymeric reaction product consists of the reaction product of 1 mole of polytetramethylene ether glycol, 2.1 moles of 2,4-tolylene diisocyanate and 5.11 moles of water.

14. A method according to claim 10, 11, 12 or 13, characterized in that the mat of loosely joined fibers of the polymeric linear terephthalate ester is pierced with needles and darpa is heated, whereby the fibers shrink, that the crimped mat is impregnated with a solution of the polymeric reaction product in a volatile, water-soluble organic solvent, whereupon the impregnated mat is treated with water and the darpa is heated so that the organic solvent and water evaporate, and that the dry impregnated mat is finally exposed to heat and pressure.

15. A method according to claim 14, characterized in that at least one side of the dry, impregnated mat is polished after the heat and pressure treatment, so that protruding parts of the fibers are removed, and that the polished side of the mat is provided with a water-permeable coating.

16. A method according to claim 10, 11, 12 or 13, characterized in that the polymeric reaction product is uniformly distributed throughout the mat to form a laminate by separately producing a film of the polymeric reaction product, placing at least one such filin layer on at least one layer of the carpet, () eh that you expose the superimposed layers to heat and pressure, so that you get a uniform material. Request publications: U.S. Patent. 2,676,128, 2,692,873.