SE188909C1

SE188909C1 -

Info

Publication number: SE188909C1
Authority: SE
Publication date: 1963-01-01

Description

Uppfinnare: W F Dacey, R A Gregg och N W Hess Prioritet begiird frdn den 12 augusti 1953 och den 7 januart 1954 (USA) Fireliggande uppfinning hanfor sig till ett forbattrat textilmaterial och narmare bestamt till en farbattrad nylontextil belagd med en polyuretanelastomer liksom till ett salt att framstalla sadan belagd textil. Inventors: WF Dacey, RA Gregg and NW Hess Priority Beginned from August 12, 1953 and January 7, 1954 (USA) sadan coated textile.

Ehuru tyg framstallt av nylon (syntetiska tradpolyamider) har ett stort antal fordelaktiga egenskaper till foljd av nylonens stora draghallfasthet och bestandighet mot kemiskt angrepp, har den icke desto mindre varit behaftad med den Overraskande olagenheten att ha relativt clang slitstyrka under vissa fOrhallanden. Trots nylonens overlagsna fysikaliska, egenskaper i manga hanseenden har det paradoxalt nog visat sig i praktiken, att tygovanlader far sportskor och liknande av nylon icke ha samma slitstyrka som den vanliga smartingen, som anvandes for detta andamal. Det har darfOr hittills icke varit m8jligt att utnyttja nylonens draghallfasthet och kemiska bestandighet for framstallning av battre ovanlader. Situationen forbattras icke heller genom belaggning av nylontyget pa nagot kant salt, emedan de tidigare belaggningsforfarandena icke kunna genomforas kommersiellt eller emedan sadant belagt nylontyg icke fyller sin uppgift under de vanliga anvandningsforhallandena for ovanlader. Although fabric made of nylon (synthetic tradpolyamides) has a large number of advantageous properties due to the nylon's high tensile strength and resistance to chemical attack, it has nevertheless been endowed with the surprising inability to have relatively durable durability under certain conditions. Despite the superior physical properties of nylon in many male respects, it has paradoxically been shown in practice that fabric removers made of sports shoes and the like of nylon do not have the same durability as the usual smarting used for this purpose. It has therefore hitherto not been possible to use the tensile strength and chemical resistance of the nylon for the production of better topcoats. The situation is also not improved by coating the nylon fabric on any edge of salt, because the previous coating procedures cannot be carried out commercially or because such coated nylon fabric does not fulfill its task under the usual conditions of use for overloads.

Ett huvudandamal med foreliggande uppfinning Sr darfOr att astadkomma ett belagt nylontyg med forbattrade egenskaper speciellt betraffande notningshallfastheten. Ett annat andamal Or att astadkomma ett effekttivt och ekonomiskt genomforbart salt att belagga nylontyg. Ett ytterligare andamal Sr att astadkornma ett belagt nylontyg, som icke veckas eller brytes Mit och som icke Sr spratt och vidare att astadkomma ett satt att belagga nylontyg, vilket Or speciellt lampat far framstallning av tyg, som kan andas. A principal object of the present invention is to provide a coated nylon fabric with improved properties, especially with respect to the notch durability. Another goal is to provide an efficient and economically feasible salt to coat nylon fabric. A further purpose is to provide a coated nylon fabric which does not crease or break Mit and which does not crack and further to provide a method of coating nylon fabric, which is particularly suitable for the production of breathable fabric.

Dupl. kl. 8 k: 1/08; 8 k: 3; 8 1: 4 Ytterligare ett andamal med uppfinningen bestar i att astadkomma ett glest nylontyg belagt med en polyuretanelastomer, som liar hardats pa nylonen in situ under sadana forhallanden, att man far en limn belaggning, som Sr fri frail ytojamnheter och inre hOdrum samt har tilltalande utseende. Dupl. at 8 k: 1/08; 8 k: 3; 8 1: 4 A further object of the invention is to provide a sparse nylon fabric coated with a polyurethane elastomer which is cured on the nylon in situ under such conditions that a glue coating is obtained which provides free surface surfaces and internal cavities and has an attractive appearance.

Foreliggande uppfinning kannetecknas i huvudsak av att nylontyget belagges med en ohardad, normalt klibbig, flytande mellanprodukt fran en reaktion mellan en polyester och ett diisocyanat innehallantle oreagerade isoeyanalgrupper, samt att mellanprodukten sedan hardas ph nylontyget med en diprimar diamin som hardare, sa att den onwandlas till fast, klibbfritt, hardat tillstand med. nylontyget fast inbaddat. The present invention is mainly characterized in that the nylon fabric is coated with an uncured, normally sticky, liquid intermediate from a reaction between a polyester and a diisocyanate containing some unreacted isoeyanal groups, and that the intermediate product is then cured in the nylon fabric with a diprimar diamine which is hardened. solid, non-stick, hardened condition with. nylon fabric firmly embedded.

Uppfinningen kommer i det foljantle att beskrivas narmare under hanvisning till bifogade ritning. Fig. 1 Or en planvy av en del av ett nylontyg, innan det har behandlats enligt uppfinningen. Fig. 2 Sr en schematisk sidovy av en apparat, som lampar sig far genomforande av sattet enligt uppfinningen. Fig. 3 Sr ett tvarsnitt efter linjen 4-4 i fig. 1 av tyget, sedan det har belagts enligt uppfinningen. The invention will be described in more detail below with reference to the accompanying drawing. Fig. 1 is a plan view of a part of a nylon fabric, before it has been treated according to the invention. Fig. 2 is a schematic side view of an apparatus which illuminates before carrying out the set according to the invention. Fig. 3 is a cross-sectional view taken along line 4-4 of Fig. 1 of the fabric, after it has been coated according to the invention.

Uppfinningen grundar sig pa den upptarkten, att sueressiva hehandlingar av nylontyg med en mellanprodukt av reaktion mellan en polyester och ett diisocyanat saint ett hardningsmedel for derma reaktionsprodukt kunna snabbt och effektivt astadkomma ett nylontyg, som Or belagt med gummiartad polyuretan, samt att ett sadant tyg har en helt ovantad slitstyrka under vissa forhallanden. Sadant belagt nylontyg utgOr ett material for ovanlader, vilket vida overtraffar de basta tyger, som tidigare ha anvants for detta andamal. Det kan salunda racka lika lange som skons gummidelar. 2— — Det nylontyg, som anvandes yid genomf5- rande ay uppfinningen, kan yara ay godtycklig typ och utgores lampligen. ay ett vayt tyg. Uppfinningen kan tillampas sarskilt vid framstallning ay .tyg, som kan andas, och for detta andamal foredrar man en gles eller p0- rOsNylontyg vayt ay otyinnade, fler- tra'diga garner foredrages sars.kilt pa grund al; sadana tygers stora bestandighet mot sonderslitning. Detta tyg fir sarskilt lampligt, om det foreligger i form ay en gles yay av linong-typ. The invention is based on the premise that suersive treatments of nylon fabric with an intermediate reaction between a polyester and a diisocyanate and a curing agent for this reaction product can quickly and efficiently produce a nylon fabric coated with rubbery polyurethane, and that such a fabric has a completely unexpected wear resistance under certain conditions. Such a coated nylon fabric constitutes a material for upper loads, which far exceeds the best fabrics that have previously been used for this purpose. It can thus last as long as the shoe's rubber parts. The nylon fabric used in carrying out the invention may be of any type and may be suitably made. ay a vayt fabric. The invention can be particularly applied in the manufacture of breathable fabrics, and for this purpose a sparse or porous nylon fabric is preferred over unwound, multi-strand yarns, especially on the basis of; the great resistance of such fabrics to wear and tear. This fabric is particularly suitable if it is in the form of a sparse yong of the linong type.

Enligt det foredragna utforan.det ay uppfinningen bildas belaggningsmaterialet in situ pa nylontyget genom inyerkan ay en diprimfir diamin pa. en mellanprodukt yid reaktionen mellan en polyester och ett diis.ocyanat. Denna mellanprodukt framstalles forst i flytande form ay en polyester med rak kedja framstalld air en. glykol, exempelvis en blandning air etylen- och propylenglykoler, saint en mat-tad alifatisk dikarbonsyra, exempetvis adipinsyra, under anyandning ay ett ■averskott ay -glykolen: i forhall-ande till syran,- sa. att den bildade polyestern kommer att innehalla alkoholiska hydroxylgrupper yid andarna. Vanligen anyander man en sadan mangd glykol, att man far en polyester med ett hydroxyltal ay 20-120 och lampligen 36-67, samt ett lagt syrayarde, under 2 och lampligen under 1. Polyesterns molekylvikt är lampligen 1700-3000, Denna polyester bringaS att reagera med ett dlisocyanat, exem- pelvis1,5-diisocyanat eller p,p'- difenylmetan-diisocyanat under anyandning av ett avseyart, molart overskott, Yanligen 20-250 % och lampligen 50-100 %, ay diisocyanatet 1 forhallande till den mangd, som fordras for att reagera med alla de alkoholiska hydroxylgrupper, som tillforas med polyester.. Reaktionen genomfores lampligen genom upphettning ay en blandning ay polyester. och diisocyanatet under utestangning ay -yatten _till exempelyis 70-150°C fOr hildning ay ett losligt, ohardat, flytande ma terial, som utgores ay en rak polyuretan med isocyanatgrupper yid andarna. According to the preferred embodiment of the invention, the coating material is formed in situ on the nylon fabric through the inner layer of a diprimphyramine on. an intermediate in the reaction between a polyester and a diisocyanate. This intermediate is first made in liquid form from a straight chain polyester made from air. glycol, for example a mixture of air ethylene and propylene glycols, saint a saturated aliphatic dicarboxylic acid, for example adipic acid, while taking ay a ■ excess ay -glycol: in relation to the acid, - sa. that the polyester formed will contain alcoholic hydroxyl groups in the spirits. Usually such a large amount of glycol is obtained that a polyester having a hydroxyl number ay of 20-120 and probably 36-67, and a layer of acid, below 2 and probably below 1. The molecular weight of the polyester is probably 1700-3000. react with a dlisocyanate, for example 1,5-diisocyanate or p, p'-diphenylmethane diisocyanate to give an avseyart, molar excess, Yanligen 20-250% and lamply 50-100%, ay diisocyanate 1 relative to the amount, which is required to react with all the alcoholic hydroxyl groups which are fed with polyester. The reaction is conveniently carried out by heating a mixture of polyester. and the diisocyanate under exclusion on the surface - for example 70-150 ° C for pouring on a loose, uncured, liquid material, which is formed of a straight polyurethane with isocyanate groups in the spirits.

De diisocyanat, som anyandas vid framstallningen ay den flytande mellanprodukten ay polyester-diisocyanat, kunna representelas ay den generella formeln OCN-R-NCO, dar 11 betecknar -en divalent kolvateradikal, exempelyis i -polymetylen-diisocyanater, shsom- etylendiisocyanat, hexametylendiisocyanat och tetrametylendiisocyanat, alkylendiisocyanater, sasom propylen-1-2-diisocyan.at, en cykloalkyl 1 isocyanater, sasom 1,4-dilsocyanatcyklohexan, liksom aromatiska diisocyanater, sasom m- och p-fenylendiisocyanat, toluendiisocyanat, p,p'-difenyldiis.ocyanat och 1,5-naftalen-dilsocyanat, till yilken grupp Oven hanforas alifatiska-aromatiska-diiso-cyanater, sasom p,p'-difenylmetandiisocyanat och fenyletylendllsocyanat C6H (OCN—CH—CH2—NCO). The diisocyanates which are used in the preparation of the liquid intermediate of polyester diisocyanate can be represented by the general formula OCN-R-NCO, where 11 denotes a divalent hydrocarbon radical, for example in -polymethylene diisocyanates, shsomethylethyl diisocyanate, , alkylene diisocyanates, such as propylene -1-2-diisocyanate, a cycloalkyl 1 isocyanates, such as 1,4-dilsocyanate cyclohexane, as well as aromatic diisocyanates, such as m- and p-phenylene diisocyanate, toluene diisocyanate, p, p'-diphenyl diisocyanate. 5-Naphthalene diisocyanate, to which group Aliphatic-aromatic diisocyanates, such as p, p'-diphenylmethane diisocyanate and phenylethylene diisocyanate C6H (OCN-CH-CH2-NCO) are also present.

Uppfinningen omfattar anhringandet air en --sadan mellanprodukt innehallande ett polyester-diisocyanat med oreagerade isocyanalgrupper ph nylontyget ph lampligt sail, sâsont bestrykidn.g, papensling, doppning eller sprutning, under anyandning ay polyesterdilsocyanatet som shdant eller en losning air detta i ett losningsmedel, som sedan avdriyes. Mellanprodukten forblir yanligen pa nylontyget i flytande och klibbigt tillstand under alltfor lang tid. Under dessa farhallanden skulle tyget naturligtvis icke yam lampligt for ytterligare -behandling och for tillyerkning air anvandbara fOremal med Onskade egenskaper. Om emellertid en diprimar diamin inforliyas i polyesterdiisocyanatmellanproduktert pa tyget, kan eyanatet overforas till klibbfritt tillstand overraskande snabbt, sh att man mycket fort far ett belagt tyg, som Or latt att bearheta vidare. Belaggningen kan, om den lamnas i vila eller om den upphettas, under inverkan ay den diprimara diaminen oyerforas i ett tillstand, dar den kan betraktas som sluthardad, och i yilket belaggningen har formen ay ett polyuretan.gummi, som bar utomordentliga, fysikaliska egenskaper samt i yilket nylonen, Or inbaddad. The invention encompasses the attachment of an intermediate containing a polyester diisocyanate with unreacted isocyanal groups to the nylon fabric, suitable for coating, cardboard coating, dipping or spraying, while using the polyester diisocyanate as a solvent or a solvent in it. then avdriyes. The intermediate product usually remains on the nylon fabric in a liquid and sticky state for too long. Under these conditions, the fabric would, of course, not be suitable for further processing and for applying air-usable objects with desired properties. However, if a diprimaric diamine is incorporated into the polyester diisocyanate intermediate produced on the fabric, the eyanate can be transferred to the tack-free state surprisingly quickly, so that a coated fabric is obtained very quickly, which can be further processed. The coating, if left at rest or heated, under the influence of the diprimaric diamine can be transferred into a state where it can be considered as final cured, and in which the coating has the form of a polyurethane rubber, which had excellent physical properties and i yilket nylon, Or embedded.

De far detta andamal lampliga, diprimara diaminerna kunna representeras ay den all-manna formeln, NH2-A-NH2, i vilken A betecknar en divalent, organisk radikal, dar atomerna yid andarna utgoras air kol och som lampligen Or fri fran grupper, yilka kunna reagera med diisocyanatet, dirs. de bagge primara aminogrupperna utgOra lampligen de enda grupperna i molekylen, vilka reagera med polyesterdiisocyanatets dlisocyanatgrupper far hstadkommande air i'mskad hardning. I de diprimara diaminer, so.m foretradem:is artyandas enligt uppfinningen, Oro de bagge primara aminogrupperna sammankopplade gen.omen divalent kolvateradikal, som kan vara alifatisk, cykloalifatisk eller aromatisk eller nagon kombination ay dessa, sasom i hexametylendiamin, 1,4-diamincyklohexan, m- eller p-fenylendiamin, 4,4'-diaminodifenylmetan, p(13-aminoetyr)-anilin, 4-(/3-aminoety1)-cyklohexylamin och p-(4-aminocyklohexyl)-anilin. Den fOrbindande radikalen mellan de bagge yasentliga, primara aminogrupperna behover icke utgoras ay ett rent kolvate utan kan innehalla andra atomer forutom kol och vate, sasom 1 3,3'-diaminodipropyleter, diamin.odifenyleter och diaminodibutylsulfid. They can be represented by this andamally suitable, diprimaric diamines in the general formula, NH2-A-NH2, in which A represents a divalent, organic radical, in which the atoms yid the spirits are constituted air carbon and which are suitably free from groups, which can react with the diisocyanate, dirs. the minor primary amino groups are suitably the only groups in the molecule which react with the dlisocyanate groups of the polyester diisocyanate to cause curing air. In the diprimaric diamines, such as fortrademic artyandase according to the invention, the minor primary amino groups are linked by a divalent hydrocarbon radical, which may be aliphatic, cycloaliphatic or aromatic or any combination thereof, such as hexamethylenediamine, 1,4-diaminecyclohex , m- or p-phenylenediamine, 4,4'-diaminodiphenylmethane, p (13-aminoethyl) -aniline, 4 - (β-aminoethyl) -cyclohexylamine and p- (4-aminocyclohexyl) -aniline. The linking radical between the minor primary amino groups does not need to be a pure hydrocarbon but may contain other atoms in addition to carbon and hydrogen, such as 3,3'-diaminodipropyl ether, diamine odiphenyl ether and diaminodibutyl sulfide.

Om den diprimara diaminen Or vatskeformig yid normal temperatur eller anbringningstemperatur, kan den anbringas pa. tyget genom utbredning, papensling, doppning eller sprutning eller p0 nagot lampligt salt ur en — —3 losning, sarskilt om diaminen icke är flytande. Diaminen kan anbringas ph tyget antingen fore anbringartdet av polyesterdiisoeyanatet eller efter detta eller aven bade fore och efter anbringandet av polyesterdiisocyanatet. Det kan aven i vissa fall vara lampligt att pafOra polyesterdilsocyanatet mer an en gang antingen i fOljd eller omvdxlande med beldggning med diaminen. Det ena materialet, exempelvis polyesterdiisoeyanatet, kan pafOras genom elt forfarande, sasom doppning, medan det andra materialet, sasom diaminen, kan paforas genom nagot annat forfarande, sa.sorn sprutning. Da materialen ph-films genom sprutning anvander man lampligen utspadda losningar, exempelvis 10-procentiga riiknat pa volymen, dvs. 10 volymdelar mellanprodukt i 90 volymdelar i nagot inert, organiskt losningsmedel, sa att man far losningar med lag viskositet. Vid tilldmpning av andra forfaranden anvander man dock ldmpligen mera koncentrerade lOsningar, exempelvis 50-procentiga raknat pa volymen, dvs. 50 volymdelar mellanprodukt i 50 volymdelar losningsmedel. Tygets bagge sidor kunna besprutas eller behandlas en enda gang eller ocksa kan den ena eller bdgge sidorna behandlas upprepade ganger, sa att man far omvaxlande skikt av polyesterdiisocyanat och diprimardiamin med Onskad tjocklek. In tjockare diisocyanatskiktet Or desto Idmpligare är det att anbringa diaminen bade fore och efter diisocyanatet, sh att man far en mera jamn och likforrnig hardning genom hela diisocyanatskiktet genom att diaminen diffunderar in i skiktet frau bagge sidor. If the diprimar diamine is liquid at normal temperature or application temperature, it can be applied to. the fabric by spreading, papeling, dipping or spraying or some suitable salt from a solution, especially if the diamine is not liquid. The diamine can be applied to the fabric either before the application of the polyester diisocyanate or after it or also both before and after the application of the polyester diisocyanate. It may also in some cases be appropriate to apply the polyester diisocyanate more than once, either sequentially or alternately with a coating with diamine. One material, for example the polyester diisocyanate, can be impregnated by any method, such as dipping, while the other material, such as diamine, can be impregnated by any other process, such as spraying. Since the materials are ph-film by spraying, appropriate diluted solutions are used, for example 10% based on the volume, ie. 10 parts by volume of intermediate product in 90 parts by volume in a slightly inert, organic solvent, so that solutions with low viscosity are obtained. When applying other methods, however, one usually uses more concentrated solutions, for example 50% by volume, ie. 50 parts by volume of intermediate in 50 parts by volume of solvent. The ram sides of the fabric can be sprayed or treated once or both or both sides can be treated repeatedly, so as to obtain alternating layers of polyester diisocyanate and diprimardiamine of desired thickness. Thicker diisocyanate layer Or it is even more convenient to apply the diamine both before and after the diisocyanate, so that a more even and uniform hardening is obtained throughout the diisocyanate layer by the diamine diffusing into the layer frau ramge sides.

Det for diisoeyanatet och diaminen anvanda losningsmedlet är pa intet salt kritiskt titan kan utgoras av varje inert, flyktig, oraanisk vdtska, i vilken dessa airmen Oro losliga. Det finnes ett stort antal vanliga orga_- niska losningsmedel som latt losa dessa dmnen, varfOr det icke bereder nagon svhrighet att valja ett lampligt lOsningsmedel. Bland sadana kunna namnas kolvdten, sasom bensen, halogenerade fOreningar, sasom metylenklorid, och ketoner, sasom aceton. Sarskilt for diisoeyanatet anvander man losningsmedel, som avdrivas langsammare, exempelvis med en kokpunkt Over 54°C. Losningsmedlet far dock icke ha alltfOr hog kokpunkt, exempelvis Over 110°C, emedan det eljest icke kan drivas av latt vid uppvdrmningen for hardningen. The solvent used for the diisoyanate and diamine is in no salt critical titanium can be constituted by any inert, volatile, orange liquid in which these substances are soluble. There are a large number of common organic solvents which have these substances resolved, for which reason it does not present any difficulty in choosing a suitable solvent. Among these may be mentioned the piston, such as benzene, halogenated compounds, such as methylene chloride, and ketones, such as acetone. Separately for the diisoeyanate, solvents are used, which are evaporated more slowly, for example with a boiling point above 54 ° C. However, the solvent must not have too high a boiling point, for example above 110 ° C, because otherwise it cannot be driven off easily during heating for curing.

Diaminen inverkar sh snabbt pa diisocyanatet pa nylontyget, redan vid rumstemperatur, att tyget efter nagra minuter och ibland redan en minut after paforandet är tillrdekligt klibbfritt for att kunna beroras eller utan att skadas kunna ledas Over en rulle. The diamine has such a rapid effect on the diisocyanate on the nylon fabric, already at room temperature, that the fabric after a few minutes and sometimes even a minute after the application is sufficiently non-stick to be able to be touched or without damage can be passed over a roll.

Reaktionen mellan diaminen och diisocyanatet paskyndas genom varnming, och det belagda tyget kan uppyarmas till c:a 38— 93°C under en tid av c:a 0,5-30 min, varefter beldggningen är tillrackligt hardad fOr att tyget stall kunna rullas upp ph sig sjalvt till en mile utan att skadas. Efter ytterligare 0,5-2 h vid en skim temperatur har beldggningen pa tyget uppnatt en avsevard hardningsgrad och dr tillrackligt fast for att kunna hanteras frill, sa att tyget exempelvis kan klippas, sys och stampas for att Overforas till ovanlader far skor. PA della stadium gem belaggningen fortfarande en mjuk och plastisk kansel och har icke Anna uppnatt den modul, som den kan uppna. till slut. Efter flera dygns aldring vid runistemperatur okas belaggningens modul langsamt. The reaction between the diamine and the diisocyanate is accelerated by heating, and the coated fabric can be heated to about 38-93 ° C for a period of about 0.5-30 minutes, after which the coating is sufficiently hardened for the fabric stall to be rolled up. ph itself to a mile without being harmed. After a further 0.5-2 hours at a shimmering temperature, the coating on the fabric has reached a considerable degree of hardening and is sufficiently firm to be able to be handled freely, so that the fabric can, for example, be cut, sewn and stamped to be transferred to unloaded shoes. PA della stage gem coating is still a soft and plastic pulpit and has not Anna achieved the module that it can achieve. at last. After several days of aging at runic temperature, the modulus of the coating increases slowly.

Upplinningen lampar sig sarskilt for framstallning av porost tyg, som kan andas, ehuru man Avon kan tillverka tall, belagt tyg under anvandning av Ware vavt tyg och pafOrande av en beldggning, som sluter till porerna fullstandigl. Sadant tatt, belagt tyg kan anvandas for framstallning av vattentat fotbekladnad, ponchos, hilt, mobeltyger och liknande. The upholstery is particularly suitable for the production of breathable porous fabric, although Avon can manufacture pine, coated fabric using Ware woven fabric and the application of a coating which closes the pores completely. As such, coated fabric can be used to make waterproof footwear, ponchos, hilt, furniture fabrics and the like.

Foljande exempel belyser uppfinningen ytterligare. The following examples further illustrate the invention.

Exempel 1. Enligt delta exempel anvandes en apparat enligt fig. 2, i vilken nylontyg frail en rulle 11 ledes genom ett had sammansalt av en 5-procentig vattenfri losning av 4,4'-diaminodifenylmetan i aceton. Nylontyget bestar, sasom visas i fig. 1, av kontinuer- otvinnat, flertradigt garn 13 i form av en ales• linonavav Acetonen drives av och n lAmnar kvar en avsattning av 4,4'-diaminodifenylmetan pA nylonfibrerna. Det med denna forening belagda tyget ledes sedan genom ett bad 14 bestaende av en 50-procentig, vattenfri lOsning av en polyesterdiisoeyanatmellanprodukt I aceton. Denna mellanprodukt har framstallts av en polyester astadkommen genom upphettning av foljande blandning till 220-230°C: Propylenglykol 11 mol Etylenglykol4,25 mol Adipinsyra 11,25 mol Polypropylenglykolen resulterar i en alkyd med lfigre smaltpunkt och lagre viskositet. Under bildningen av polyestern avdrives oreagerad glykol genom vakuumdestillering och dennas grad bestammer polyesterns molekylvikt, beraknad ur syratalet och hydroxylialet. Den i delta exempel anvanda polyestern har en molekylvikt av c:a 1800, ett hydroxyltal av c:a 60 och ett syratal av mindre an 1. Derma alkyd blandas vid 85°C med ett overskott av p,p'-difenylmetandiisocyanat i proportionerna 80 delar polyester ph 20 delar dilsocyanat. En reaktion intruder mellan alkydens hydroxylgrupper och isoeyanatgrupperna till hildning av en polyuretanmellanprodukt, vilken kanneteeknas av narvaron av oreagerade isocyanatgrupper. Denna mel- 4— — lanprodukt är flytande och loslig i de vanliga organiska losningsmedlen, sasom aceton. Example 1. According to the following example, an apparatus according to Fig. 2 was used, in which nylon fabric from a roll 11 is passed through a salt aggregate of a 5% anhydrous solution of 4,4'-diaminodiphenylmethane in acetone. The nylon fabric, as shown in Fig. 1, consists of continuous unwound, multi-strand yarn 13 in the form of an ales • linonavav The acetone is driven by and n leaves a deposit of 4,4'-diaminodiphenylmethane on the nylon fibers. The fabric coated with this compound is then passed through a bath 14 consisting of a 50% anhydrous solution of a polyester diisoyanate intermediate in acetone. This intermediate has been prepared from a polyester obtained by heating the following mixture to 220-230 ° C: Propylene glycol 11 mol Ethylene glycol 4.25 mol Adipic acid 11.25 mol Polypropylene glycol results in an alkyd with a lower melting point and lower viscosity. During the formation of the polyester, unreacted glycol is evaporated by vacuum distillation and its degree determines the molecular weight of the polyester, calculated from the acid number and the hydroxylial. The polyester used in this example has a molecular weight of about 1800, a hydroxyl number of about 60 and an acid number of less than 1. This alkyd is mixed at 85 ° C with an excess of p, p'-diphenylmethane diisocyanate in the proportions 80 parts polyester ph 20 parts dilsocyanate. A reaction occurs between the hydroxyl groups of the alkyd and the isoeyanate groups to form a polyurethane intermediate, which may be characterized by the presence of unreacted isocyanate groups. This intermediate is liquid and soluble in the usual organic solvents, such as acetone.

Sedan den impregnerade vaven har kornmit upp ur polyester-diisocyanatbadet, ledes den mellan urkramningsrullar 15, varefter losningsmedlet far avdunsta. Tyget ledes darefter forbi ett munstycke 16, genom vilket luft biases ut med hag hastighet for avlagsnande av material, s'om kan ha avsatts i tygets oppna maskor, sä att man far ett porost tyg, som kan andas. Tyget ledes sedan genom ett andra bad 17 av 4,4'-diaminodifenylmetan liknande det forsta badet, och darefter under forutbestamd tid och i fritt hangande tillstand utan kontakt med nagra ytor, medan belaggningen barjar hardas. Under denna tid .diffunderar den diamin, som är avsatt pa tygets yta under belaggningen av mellanprodukten liksom den diamin, sum är avsatt pa dermas yta„ snab'bt in i mellanprodukten och inverkar pa derma, sa att belaggningen blir tillrackligt klibbfri morn en minut fOr att passera Over rullen 18 till en horisontell hardningsugn 19 utan att skadas. Tyget har en hastighet av c:a 1,8 mimin genom impregneringsbaden. After the impregnated fabric has grained mite out of the polyester diisocyanate bath, it is passed between crimping rollers 15, after which the release agent is allowed to evaporate. The fabric is then passed past a nozzle 16, through which air is biased out at a high speed for depositing material, which may have been deposited in the open meshes of the fabric, so that a porous fabric is obtained, which can be breathable. The fabric is then passed through a second bath 17 of 4,4'-diaminodiphenylmethane similar to the first bath, and then for a predetermined time and in a free-hanging state without contact with any surfaces, while the coating starts to harden. During this time, the diamine deposited on the surface of the fabric during the coating of the intermediate product diffuses as well as the diamine deposited on the surface thereof "rapidly into the intermediate product and acts on it so that the coating becomes sufficiently tack-free until one minute before to pass Over the roller 18 to a horizontal curing oven 19 without being damaged. The fabric has a speed of about 1.8 minutes through the impregnation bath.

Det pa detta satt impregnerade tyget be-hover 3 min far att passera genom ugnen, som ãr varmd till 82°C. Vid uttradet ur ugnen ar materialet tillrackligt hardat for att kunna Tunas upp till en rulle 20. F8r ytterligare hardning placeras rullen i ugn upph-ettad till 93°C under ytterligare 2 h. Efter denna tid har belaggningen en nagot mjuk, plastisk kansel och Or tillrackligt hardad for att tyget skall kunna underkastas den vanliga bearbetningen vid framstallning av oven-loner far skor. The impregnated fabric in this way needs 3 minutes to pass through the oven, which is heated to 82 ° C. When exiting the oven, the material is sufficiently hardened to be able to be thinned up to a roll 20. For further hardening, the roll is placed in an oven heated to 93 ° C for a further 2 hours. After this time, the coating has a somewhat soft, plastic pulpit and Or sufficiently hardened so that the fabric can be subjected to the usual processing in the production of furnaces.

Efter aldring ett dygn vid rumstemperatur har det med polyuretangummi belagda garnet en brotthallfasthet av 168 kp/cm2 och derma akar langsamt vid ytterligare aldring till 217 kp/cm2 efter fern dygn. After aging for one day at room temperature, the yarn coated with polyurethane rubber has a breaking strength of 168 kp / cm2 and this slows slowly upon further aging to 217 kp / cm2 after four days.

Det fardiga tyget utmarker sig, s:asom framgar av fig. 3, for att nylongarnet är mngix-et oeh fast inneslutet i ett starkt, bojligt holje 21 av hardad polyuretanelastomer, som binder samman tradarna vid korsningsstallena, sa att tyget stabiliseras samt nylontradarna hindras fran att gnugga och nOta mot varandra, cla tyget bojes eller vikes. The finished fabric stands out, as shown in Fig. 3, because the nylon yarn is mixed and firmly enclosed in a strong, flexible housing 21 of hardened polyurethane elastomer, which binds the threads together at the crossing stalls, so that the fabric is stabilized and the nylon threads are prevented. from rubbing and nOta against each other, cla the fabric is bent or folded.

Av detta exempel framgar att man enligt uppfinningen erhaller en gummiartad polyuretanbelaggning bildad in situ p0 ett nylontyg genom ett fOrfarande, som lampar sig ftir kontinuerlig och snabb produktion. Eftersom polyesterdiisocyartatet anbringas pa nylontyget i form av en mellanprodukt och i flytande form, kan detta im.pregneras 1011 och jamnt utan 114ton mera vidlyftig anlaggning. Da polyesterdiisocyanatet pa tyget utsattes for inverkan av en diprimar diamin, Overfores mellanprodukten snabbt frail sitt flytande och klibbiga tillstand till ett relativt styvt och klibbfritt tillstand, i -vilket tyget kan hanteras utan att skadas. Det bildade polyuretangummit bildar en enhet med nylonen, sO att tyget kan utharda de svara pafrestningar under anvandningen, som upptrada i tygovanlader. From this example it appears that according to the invention a rubbery polyurethane coating formed in situ on a nylon fabric is obtained by a process which is suitable for continuous and rapid production. Since the polyester diisocyartate is applied to the nylon fabric in the form of an intermediate and in liquid form, it can be impregnated 1011 and evenly without 114 tons of more extensive application. As the polyester diisocyanate on the fabric is subjected to the action of a diprimaric diamine, the intermediate is rapidly transferred from its liquid and tacky state to a relatively rigid and tack-free state, in which the fabric can be handled without being damaged. The polyurethane rubber formed forms a unit with the nylon, so that the fabric can withstand the black stresses during use, which occurred in fabric blanks.

For paxisande av det enligt foreliggande med polyuretanbelagda tygets overlagsna egenskaper framstalldes tennisskor med ovanlader av detta tyg. Dessa skor begagnades av en gymnastiktrupp under langre tid och visade sig darvid vara slitstarkare On skor framstallda av det hittills }Asia materialet, namligen smarting. Delta resultat var synnerligen overraskande med hansyn till, att nylontyg vanligen Or myeket samre an smarting. Gymnastiktruppen fOrklarade Oven, att dessa nya tygskor voro bekvamare pa gru-nd av tygets starre gleshet, sa att luftvaxlingen: omkring foten underlattades och foten kandes svalare. To appease the superior properties of the present polyurethane-coated fabric, tennis shoes with tops of this fabric were made. These shoes were used by a gymnastics team for a long time and turned out to be more durable On shoes made from the hitherto} Asian material, namely smarting. Delta results were particularly surprising in view of the fact that nylon fabrics are usually much smoother than smarting. The gymnastics team also explained that these new cloth shoes were more comfortable due to the rigid sparsity of the fabric, so that the air exchange: around the foot was made easier and the foot felt cooler.

Det ma framhallas, att derma gleshet med afaljande genomslapplighet for luften icke kan uppnas med- obelagt nylontyg eller annat tyg, emedan glesvavt tyg Or for obestandigt till formen for att kunna anvandas i praktiken i ovanlader for skor. Aven i lignontyg glida fyllnadsfibrerna latt mot varandra i det obelagda tyget. It must be pointed out that this sparseness with decreasing permeability to the air cannot be achieved with uncoated nylon fabric or other fabric, because sparse fabric is too unstable in shape to be used in practice in tops for shoes. Even in lignone fabrics, the filler fibers slide easily against each other in the uncoated fabric.

Det ma Oven framhallas, att de genom fOreliggande uppfinning uppnadda resultaten icke kunna uppnas i praktiken genom belaggfling av nylontyget mad andra material. Om tyget salunda belagges med vanligt gummi, uppnas icke dessa resultat, emedan tyg-et icke Or lika stabilt och slitstarkt som det polyuretanbelagda tyget enligt foreliggande uppfinning. Om tyget belagges med ett vinylharts eller nagon annan plast eller en blandning av gummi och konstharts fa de framstallda tygerna icke samma egenskaper som de polyuretanbelagda nylontygerna enlist foreligganrde uppfinning. En sarskild olagenhet med sadana andra belagda tyger Or deras laga. hallfasthet mot bristning genom. veekbildning. Dessa material bilda veek p0. vissa be-- stamda stallen, dal- de bojas starkt, och dessa. veck bilda- en forsvagning, sO. att tyget kommer att vikas pa nytt upprepade ganger pa. samma stalle, sa att det snarl hrister pa denna punkt. Delta Or ett valkant forhallande vid vanliga tyger och ger sig till kanna genom. att sadana material som ovanlader vanligen notas ut forst vid stallena for stOrsta bojning- stallet .for dar notningen Or stOrst, sasom man skulle kunna antaga till en borjan. Detpolyuretanbelagda tyget enligt uppfinningen bildar i motsats till andra tyger icke latt veek, dar det utsattes for starkare bajning, varfor n:agra stallen med snabb forslitningicke Midas. Delta torde vara den fornamsta anledningen till att tyget enligt uppfinningen Or slitstarkare On andra tyger. It should also be pointed out that the results obtained by the present invention can not be obtained in practice by coating the nylon fabric with other materials. If the fabric is thus coated with ordinary rubber, these results are not obtained, because the fabric is not as stable and durable as the polyurethane coated fabric of the present invention. If the fabric is coated with a vinyl resin or any other plastic or a mixture of rubber and synthetic resin, the fabrics produced do not have the same properties as the polyurethane coated nylon fabrics of the present invention. A special inconvenience with such other coated fabrics Or their law. resistance to rupture through. veekbildning. These materials form veek p0. some stabled stables, fell heavily buoyed, and these. folds form a weakening, sO. that the fabric will be folded again repeatedly on. same place, so that it soon shakes at this point. Delta Or a choice edge that adheres to ordinary fabrics and goes to the jug through. that such materials as overloads are usually taken out first at the stables for the largest bending stall, because where the stowage is the largest, as one might assume at the beginning. The polyurethane-coated fabric according to the invention, in contrast to other fabrics, does not form easily soften, where it is subjected to stronger bending, for which reason the stables with fast-wearing non-Midas. Delta is probably the main reason why the fabric according to the invention is more durable than other fabrics.

Ehurn- det icke Or avsikten att -begranstt — — uppfinningen till flagon viss arbetshypotes, -verkar det troligt, att de nya tygernas overlagsna egenskaper hero pa den fysikaliska och kemiska affiniteten mellan nylonen och den in situ bildade polyureta.nbelaggningen, sa att de bagge materialert upptrada som en-het i stallet fOr som tva olika material, vilket synes vara fallet, cla nylonen helagges med andra material. Da nylon, som är belagd med andra material, vikes starkt kan man i allmanhet iakttaga, att tyget vitnar langs vikningslinjen, vilket anger att strukturert ãr inhomogen, medan vid nylon belagd med polyuretan bildad in situ denna verkan icke har observerats, vilket antyder, att nylonen och polyuretanen upptrada som en homogen enhet, da den utsattes for starka bojningsspanningar. Denna ovanligt fasta f5rening mellan belaggningen och nylonen beror uppenbarligen pa det forhallandet, att den hardade polyuretanen har bildats in situ pa nylonen genom separat paforing av polyesterdiisocyanatmellanprodukten i flytande, nor-malt klibbigt, ohardat tillstand med efterfi5Ijande behandling med en diprimar diamin for overforing av mellanprodukten fraa det ohardade, klibbiga tillstandet till fast, klibbfritt, hardat tillstand sasom har beskrivits detalj ovan. If the intention is not to limit the invention to a certain working hypothesis, it seems probable that the superior properties of the new fabrics depend on the physical and chemical affinity between the nylon and the in situ formed polyurethane coating, so that they material appeared as a unit in the stable for as two different materials, which seems to be the case, the cla nylon is sanitized with other materials. Since nylon coated with other materials is strongly folded, it can generally be observed that the fabric whitens along the fold line, indicating that structured is inhomogeneous, whereas in nylon coated with polyurethane formed in situ this effect has not been observed, suggesting that the nylon and polyurethane acted as a homogeneous unit, as it was subjected to strong bending stresses. This unusually solid association between the coating and the nylon is obviously due to the fact that the cured polyurethane is formed in situ on the nylon by separate application of the polyester diisocyanate intermediate in the liquid, normally tacky, uncured state following subsequent treatment with a diprimar diamine for transfer. from the uncured, tacky state to the solid, tack-free, cured state as described in detail above.

Claims

Patent claim:

Salt to coat nylon fabric with a polyurethane elastomer cured in situ on the fabric, characterized in that the nylon fabric is coated with an uncured, normally tacky, liquid intermediate from a reaction between a polyester and a diisocyanate containing unreacted isocyanate groups, and that the intermediate product is then cured on with a diprimar diamine as harder, so that it is converted to a solid, non-stick, hardened state with the nylon fabric firmly embedded.

2. Set according to claim 1, characterized in that the hardening is effected by heating the coated nylon fabric.

3. Set according to patent claim 2, Urinated in that the nylon fabric allows the heating to hang frill without contact with other objects, until the intermediate product has Over-continued to a solid, non-stick condition.

4. According to any one of claims 1-3, it may be characterized in that a sparse nylon fabric is coated and an air jet is blown through the fabric after the intermediate product and the diprimary diamine are blown to remove these materials from the meshes of the fabric.

5. A set according to any one of claims 1-4, characterized in that the diprimaric diamine is used in the form of a rim and that the release agent is driven by the release before the heating of the nylon fabric.

Salt according to claim 2, characterized in that the nylon fabric is coated with an intermediate product consisting of the reaction product of (1) a polyester having a hydroxyl number of 20-120 and an acid number below 2, and (2) a 20-250% molar excess of a diisocyanate.

7. Set according to any one of claims 1-6, characterized in that the diprimaric diamine is applied to the nylon fabric in the form of a solution both in the filter and after the application of the intermediate product, and that the solvent is driven off after both the first and the second application of the diprimaric diamines.

8. A kit according to claim 1, characterized in that the reaction product is the product of a reaction between (1) a glycoladipic acid polyester having a hydroxyl number of 36-67, an acid number below 1 and one. molecular weight of 1700-3000, and (2) a 50-100% molar excess of an aromatic diisoeyanate.

A salt according to any one of claims 1-8, characterized in that the amino groups of the diprimaric diamine are bonded to the duck carbon atoms of a double hydrocarbon radical.

10. A kit according to claim 1, characterized in that separate solutions of (A) are applied to the nylon fabric of a normally sticky, liquid intermediate from a reaction between (1) an ethylene and propylene glycol adipic acid polyester having a hydroxyl number of 36-67, an acid number below 1 and a molecular weight of 1700-3000, with (2) a 50-100% molar excess of p, p'-diphenylmethane diisocyanate, the intermediate containing unreacted isocyanate groups, and (B) p, p'-diaminodiphenylmethane, to evaporate the solvent from the nylon fabric thus treated and to participate thereafter is heated for Transfer of the intermediate product on the fabric to non-stick, hardened condition, with the nylon fabric firmly embedded. Request Publications: United Kingdom Patent 690,706, 700,609.