BE682956A - - Google Patents

Description

  

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   The present invention relates to coated fabrics. It relates more particularly to coated and partially impregnated fabrics, the coating or coating of which is specially prepared so that the product obtained can be used as a substitute for artificial leather or leather.



   At the present time, there is only a limited number of expensive and difficult to prepare materials which present the feel, in addition to the aesthetic properties of natural leather, grain, hardness, deformability, resistance to abrasion. compression, water vapor permeability, heat transmitting power and other qualities required on the comfort and appearance of footwear, as well as strength, durability and resistance to ambient conditions re- suitable for long use.



   Heretofore, vapor permeable leather substitutes have been prepared by applying polymeric coatings, particularly vinyl polymer coatings, to porous carrier fabrics and mechanically piercing these coatings, to achieve porosity. desired location. The product thus obtained has not been found to be widely acceptable, because the pores thus produced are visible. In addition, these pores tend to enlarge, when the product is subjected to bending during use, ¯on normal, so that the pores end up uniting and the product tears. .

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   In another attempt to spare a substitute or substitute for leather, nonwoven fibrous webs were impregnated with a blend of polymers, then one of the components was extracted to handle? preferential.



  Recently, leather substitutes have been prepared by first coating a fibrous backing with a polyurethane dissolved in a hydroscopic solvent, and then coagulating the polymer on the surface of the backing with the aid of. action of water, either by spraying or by exposure to conditions of high humidity. None of these processes has, however, been entirely satisfactory, either because of the difficulty of manufacture or because the product obtained does not exhibit one or more of the desirable characteristics of natural leather.



   The object of the present invention is an artificial leather having the properties of natural leather, as listed above, of artificial leather obtainable by a simple and convenient process.



   According to the present invention, an artificial leather suitable for use in shoe uppers, gloves, straps or bands, upholstery, clothing and other applications of natural leather is obtained. by partially impregnating and covering a fibrous support with the aid of a cellular elastomer of the polyurethane type, having determined physical properties with regard to its density, elasticity and hardness.



  The new cair replacement product according to the present invention comprises a fibrous and porous support, partially impregnated with a cellular elastomer of the polyurethane type and bearing a coating of cellular elastomer of the polyurethane type.

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 polyurethane type integral with the elastomer which permeates it. In the process according to the invention, a low elasticity polyurethane elastomer is applied to a fabric.
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 su, so as to permeate pariell.?; : 1: 'ealui and to form an integral coating of the przéai.>' .Rj..v, nat'¯cn. The best results are obtained with '.1:. :: determined depth of penetration. Mere adhesion of the elastomer to the surface of the fabric is not sufficient.
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  The novel polyurethane elastomer specially prepared according to the present invention not only possesses determined density, elasticity and hardness, but also good tear and abrasion resistance, high elongation under tension and elongation curve.
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 ment under stress at low hyst.r: .'... All of these properties, especially the last mentioned one, are important in an artificial leather.

   The low hysteresis during strain elongation is particularly important in the manufacture of footwear. When the shoe is put on form, it elongates or stretches and does not return to its original dimensions, when the form is
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 removed, i.e. the shoe takes on a permanent elongation. In addition, - and this is of critical importance for the comfort of the shoe, - the latter takes on a
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 second permanent elongation at co,; r; 5 ':: the period of adaptation of the shoe to the user's foot. It is also necessary that
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 artificial leather transmits the heat and is permeable to water vapor, without being permeable; 1l \ ub.1.8: il / liquid water.



  The polymer used in the context of the present invention is prepared Qn p: 'pa.2.: -: ..: 1 J,) rJ a prc-polymer, by reaction of a pOlyalkylûne ether or ol / alkùne ester diol

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 having a tolJular weight of about 700 to 9000, preferably 700 to 2000, with an organic diisocyanate, using a molar ratio of diisocyanate to diol of 1.5-3.5 / 1 cc so as to form a prepolymer of high molecular weight, wherein the end groups are isocyanate groups.

   The reaction is carried out by keeping the reactants in contact with each other at a temperature of about 60 to 1400 ° C, for about 0.5 to 16 hours, for example 2 to 4 hours.



   Suitable polyalkylene ether diols retort, which are
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 can be used to prepare the prepolymers according to the present invention, mention may be made of polyethylene, polypropylene, polytramt;: y2¯jne, polyhexamethylene, polyoctamethylene, polynonamûthylene and polydicamethylene ether diols, as well as their mixtures. The invention also provides for the use
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 mixed polyalkyl ether diols, such as those prepared from mixtures of propylene oxide and ethylene. Preferred polyalkylene ether diols are polytetramethylene ether diols.
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  Polyalkylene ester diols suitable for use in the context of the present invention are products II. : veticn alkylene diols and dicarboxylic acids.



  Corrre do2 u .¯.:, ', L: s, one can quote, for example, ethyl-? [. Ne glycol l opy10ne glycol, butylene glycol and' ¯ '::: r: << dic. C0n dicarboxylic acids include, between utr1 adipic acid and phthalic acids, such as t.sr p '. ^. Tlic acid.



  The organic diisocyanates can hearth chosen #lZs: i the diisocY, :: i.T1 ", t8S al: .p-: atiç.ies and aromatics, such as for example, the toluene diisocyanates (in particular the

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 mixtures of 2,4 and 2,6-toluene diisocyanate which are
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 found in 1 r: 0 -; '' rt: under the name 1'DI); : 1! '::'. \: J :); '0: 1'f2.è1'> diisocyanate, 4,4'-diisocyana -: '3 da 3,3'-bitolylene , the.-i'.3CCY2.r ::. \ '>: ,, i; * aphé # yléne,:' (0 of ¯i. >> <: anate of 1-chloro - ^, .-. : cny? .. n, '¯;, <¯isocyanate en'],] - dimeth; / 1-1, ± '- diphenyl, di.isoc ,, an; <t <; of 1.1 ,. -tétrā: .tzyiene and, 1,6-hexamathylene .'liisocyanate.



  The prepolymer is then subjected to chain extension using a curing agent which can be selected from polyalkylene ether and ester diols or mixtures thereof, having a molecular weight of from about 90 to about 1300, from preferably 200 '. 400, in the presence of about 0.2
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 to one part weight of expansion or swelling per 500 parts by weight of the total reaction mixture.



  The amount of curing agent used can, in particular, be about 10 to 50% by weight, based on the quantity.
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 weight of pr, s-, a'.ymra. As will be seen later, in detail, If, - <:: ", preferred swelling points are those which are only activated at relatively high temperatures, preferably at temperatures between about 110 and 190 C. The formation of the elastomer according to the present
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 invention takes place, by reacting the prepolymer with the chosen diol: C: 1: -. t; C: C-q1 <1; to a. '' ènpé = arure of about; () J, 1, '0 "C, for about 2 to 25 minutes. It is preferred' 1:; (: 1 curing is carried out at a temperature,: the From 10 to 190 ° C, higher cure times shorter cure times are possible.

   However, low temperature curing cycles, eg 24 hour cycles at room temperature, can also be used. The presence of catalysts and / or agents

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 surfactants help to facilitate the reaction, in accordance with
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 traditional techniques. Polymers and / or other additives can be used to achieve special effects.
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  CO: 71. ': ", () Agsntu de,; onfle - ^^; 1t or ^ .; panston appropriate- 4s, we egg to cite, by Tx4mple, the l: n: t; 7y dinitrosotéréphta-lamido, azo-bis isocv: rronitril4 and water The swelling agent can be absorbed in a molecular sieve, if desired, although such absorption is not essential.



   As catalysts which can be used, there may be mentioned, between
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 others, stannous octoate, lead octoate and triethylenediamine. The catalyst or catalyst is generally: e:; t used a, at;: <ccn.n <^. ¯ "¯c :. from about 0.01 to about 0.3 part by weight, per relative to the weight of the reaction mixture.
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  TeniQ-actives which can be used to aid the reaction and, in particular, to control the size of the pores, are various silicone oils which are commercially available.
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  The product obtained is an elastol, Jre of expanded or cellular polyurethane which can be used directly, for example in cases where gold: would use leather to obtain
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 des <'. i't'.L.' .: ,, ': cox'J.tl.f: 3, without it being: a!.' f¯353irB do the sou- I '. ^. LL. '' Oal: r:. :: fear, pH ',.:> Xi :: nple for wall decoration ..: 3: is coi% pri: 2c between rr: .rc :, J ,, f3 to 1.2 g / cm 3 Its elasticity is between erti-e about 5, and 30 zij, this elasticity being measured by the standard bounce test of a ball or ball. Its hardness is less than 90 on the Shore A durometer.

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  Although the product can be used on its own, it
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 especially suitable for impregnating panic-llement and coating a fabric.



  A p ':' 8fj;: -,) prepolymer can be obtained by mixing a 1% polyalkylene ether. the ':,' ::; G.3us described having a molecular weight of about 1030 30CO, with a diisocyanate, in a soft ratio? of the diisocyanate to the diol of 2-2.1 / 1, at a temperature of about 80 to 125 C, for in-
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 about 0.25 - 2 hours, then e-. 4, -. iairitating the mixture for about 2 - 12 hours at a temperature of about 120 to 125 C. The resulting prepolymer is cured by reaction with a
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 diol, in the presence of an agent <1 <,> on: '1mazt or expansion, exactly as described above, so as to obtain
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 ning an elastomer having the desired physical properties of density, elasticity and hardness.



  The curing or chain extension reaction of the beta elastomers as the above-described reaction can be carried out in a single step. In the preferred process for preparing an artificial leather, this reaction takes place in two stages.



   In the presently preferred embodiment for the preparation of an artificial leather, a prepolymer prepared from the strip described above is mixed with a compound.
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 curing or r.:t:;'cati,;r. agent, a blowing or expanding agent and other selected ways of addition and mixing! applied on a tear-off paper that
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 can be embossed. The application of the mixture under gold;:, e of a layer can be carried out by any conventional method, for example by spraying, by application by means of a knife, by application by means of rollers, by applica-

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 tion by brush or by casting.

   The thickness of the applied layer can vary within wide limits, depending on the end application envisioned. This thickness is generally between about 0.25 and 0.5 mm.



   The coated or coated paper is heated to a temperature of about 80 to 1800 ° C in a baking oven, for a time of between about 1/2 to 5 minutes. The pre-cure temperature is not high enough to activate the blowing or expanding agent.

   During the
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 pre-dU1'ci5; (, I ", ::. t, the viscosity of the mixture first decreases to, 7% 1 2000 about 1 so that the product 3 'flows or spreads uniformly over the surface of the 'papi3 ", S,;, ::.,}" .3cusit6 then increased to about 100,000 to 600,000- Lc 3uoocrt in selected fabric will try placed on the cured p811met product and the partial impregnation is, :: fc' :. '' '\ 0G.. \ ..,.; .- ;, cl. 3n passing the assembly through 4 intervals? -' successive pinching of rollers, adjusted to give a pre> ;; ion of 300 to .500 g by 2.5 cm da width of the Ci.'t :.

   The! 1. '.' CISSGiîCn .. .3s ;, alQ8 completed, by heating the inset <iJ1J ''. ', 1L1 ,. 'r. oven: l <:: Uj.S: 30r1 a temperature of approximately they: .r, (, C. 3 '' '' - '. zone # emx-4ra #> Jre supuriaure at the tempera- ..,. :,;; ac: ..; ..: -: d-- ':' '\, e: \ ::' do:; onfl-srr.r;:; 1t. or expansion, pen- '.: "" 1- .-.: ',' 1.r: '-,' ::,:; "During this period, the agent of gon- i:; -;: - <i) '-' '- :, '.':. ::::;. "1s :: 'C: 1. "st activated. The gas produced forms, danx 2e.;:,) lY :: l '': 'e 1'on: .e: n" viscous structure microporeusa jui, s ": 8S"' i1: : ":::. lC for heat permeability and vapor for deforrnability.



  By this series of operations, the solid or expanded polyurethane polymer is produced in and on the

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 support in:, i s '.;' ¯,. l.;. release paper is then torn off, so that one -: 1 ur product suitable for use as C '....-'- - ¯:: .. i.l. û¯n¯: :: 1 "2.: -: ..,;,: - \ -. '3 this mode 0 T:' \ t () i. ' preferred the mixture contains the j, r; µ -> <j2j, -> n <Xre is: r.,; -poé.> 4 er, ', re a loose ca- pier and the chosen. fabric. The result is then covered with a second layer of release paper and the '3n5' .. '. wheat is made to pass between pressure rollers,' so as to
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 partially impregnate the fabric. The product obtained is then
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 fully cured at a temperature of about 110-190 ° C for 10-10 minutes.

   The release paper is then removed, so that q i 10 'v: t .: ¯: r the desired product.



  If we -: 5 ,: \ ;,:. -, .. can itself be processed using a;, g <; ni of dta, ::::., co; r; lt: cala will be described later. The supcr '. may be chosen as a layered product formed of neck, s. '. 3.



  ('::;' 1 ;; 1-: ', it has been indicated plus 1, a, at, it is essential that a # e = 1.; Fx e6r impregnation takes place .. so that the product:;:, t,?: \ 1. \ se; a tissue? sr.iellamen * '. impregnates carrying a layer,;. ,, r :: w.re which in 3 colidaria. If the penetration of l 'èls4o0r ians l0 tiss' .-? 3t too strong, the product obtained is ': "4P.,. ....: f' ai il0: nl. '.' 3: '") 2.2': Cr .: .7 leather ': "' v. 1 a: w,,) 1. If the? N '.'" "''. R '. Doe 1'; ', Tz = ;;: Qi">, ". ", too low, 13 ro?" "i .... tees f ..> 1i" = .. ':? "-.'; ::. î: 3.'s.,;. ':.:; qul; e: 3 and, 1 product is: J! ¯ <,:' ''. ,: ;;.: .. lJ>; e c .., r. > <i; n <5t = at'.cn - '"rt, syen:,. she" A S ;; 19 :. ", 1 <.: 3: <' r'ace to 1. '\ 3' ..:.,:, fac is not enough. The penetra- tior .Tpt;: - ..: ..: varies 8: 0r .. 1'- '.. :::::': 1 c .: ..e.¯. selor. so: '. thickness.

   This? 0nnt, in most cases. a p-lri4Lrarion from 2 to 80 ',, s ... ,,; a' :: '¯3 :::': ':',: \; l '::. '\' f.C d '.:. 2.:;;.;u whose thickness is included: 1.' ::. rB approximately 1>, and a7.,) mm.

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  The fabrics which present these thicknesses are those which are best suited for the preparation of artificial leather.



   For the preparation of an artificial leather, the thick- ness of the layer above the surface .¯ ... fabric is also
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 important (!. This thickness ri: u ;. rie ^ between fairly wide limits, 1 - ;, is, in general, about 10 to 50% of the total thickness of 1 f <-W..s. tor & re lie above the surface of the fabric.



   In a product according to the present invention, selected by way of example, a fabric with a thickness of 0.8 mm is
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 impregnated to a depth of 0.35 mm and the elastomer prelastomer above the fabric surface is 0.35 mm.



  In another product, a fabric with a thickness of 0.375 mm is imprinted to: 3 a depth of 0.275 so that the thickness of above the surface of the fabric is 0.03 mm.
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  The proti ,, zil ta,: a: .s, the invention can be treated with one qUJ:; 'CO'1que of ;: commonly used to form the end layers of Nazurùl leather, for in améli - adorn the aspect or prolong the durüb..1.itÓ. Any of the various known leather covers can be used.



  Various coatings based on natural or synthetic resin ¯ 1 particu! .ar based on acrylic resins or substances.: - ':' o:; 1L1w.1 '::;, can & tl' apply, according to current techniques?.! - 1;,.) a :, improve '' : '...' touch this r..lspact. layer of ... ;; a: .w .-, c: ,, tol '.. ".' a layer of c.) ?,).} ', re chloride of;. ¯yvi: .A>; <Maleic anhydride, can be used for an: l.: T :: w The bond between the artificial leather and the finishing layer.

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Although, in general, any natural or artificial fabric, woven or non-woven, can be used.
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 Sé, for the preparation of leather # rtif ± ci 1 In the context of the preaente invention, the fabrics:

   preferred jont; 1, .x which were treated using a - "13:.: lc: o3me :; 'agent and which are then impregnated with uni) ,, ": 3iaa, to force a flexible and strong product.
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 The fibers are often impregnated with poly: nr es or polynesisable substances, in order to improve various properties. For the production of flexible fabrics impregnated with polymers, unsatisfactory products have been obtained because the impregnation has been found to considerably reduce the tear strength of the fabric. The property that is most often adversely affected is resistance to tearing by stitches, needles and slits.

   These unfavorable effects are particularly important, when the treated fabric is to serve as a backing for an artificial leather to be used in the manufacture (the footwear, where the product is to be cut and sewn. Such a fabric allows tears to occur at the place of the cutout or in the holes formed during sewing, so that the finished product behaves very poorly.
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  The present invention relates ".? Fix, 1, ix;,;: it a novel fibrous tissue comprising a body of fibers carried by an en-
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 flexible polymer film or vehicle, ":" a flaxible polymer impregnating at least partially at -nto'janting said body of fibers, the fibrous tissue containing a loosening element interposed between the fibers. bru ::;.:;, r: t; van ,, in said fiber body and the polymer flxtblu. cot ta ar; t: detach-

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 ment being capable ci) substantially reducing the adhesion between the fibers and the flexible polymer, these fibers being free to move relative to the flexible polymer.



   The preferred flexible fabric for use in the context of the present invention is a fabric containing fibers which can move freely relative to neighboring fibers, so that there is no stress concentration at the edges. places of cutouts, stitches or slits. In order to achieve this result, the individual fibers contained in a body or set of fibers are coated with a release agent or agent preventing their adhesion, before the fabric is impregnated with a flexible polymer intended to form an envelope. or matrix for the protected fibers.

   This new fabric can be used not only as a support for the artificial leather prepared within the scope of the present invention, but it can also be used as such in furnishings, clothing and the making of sails. Not only does the treated fabric not lose this tear resistance, due to the superior resistance to stresses among the fibers, but the result is further improved with regard to the very precise qualities which are important in a fabric. artificial leather, namely feel, drape, abrasion resistance, flex resistance and deformation resistance.

   These properties are complementary to those of the novel polyurethane elastomer according to the present invention, in order to make it possible to obtain a markedly improved artificial leather.



   The new fabric which can be used in the context of the present invention is prepared by a process which consists in

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 treating this fabric with a release agent which prevents the adhesion of the flexible polymeric material to the fibers, and then impregnating the protected material with a flexible polymer or a composition capable of forming such a polymer. This composition may, if necessary, require curing.



   The term "fabric" as used herein refers to both woven and nonwoven or felt materials. These materials can contain any natural or synthetic fibers. such as cotton, wool, silk, ramie, linen, mercerized cotton, reconstituted cellulose, nylon, polyesters, acrylic fibers, arre, asbestos or their mixtures.



   When the fabric is not woven, it can be obtained by any of the usual methods. Thus, it can be held by a rando-weber or fourdrinier machine, or by a cardae machine. The nonwoven fabric can further be bonded, if desired, by treatment in a needle loom, by treatment with polymer binders, by wet bonding, by thermoplastic bonding or by thermoplastic bonding. spray or powder bonding.



   The release agent should be of a type such as to substantially reduce the adhesion between the flexible impregnating polymer and the fiber, when interposed therebetween in the product. Furthermore, it is preferable that the release agent is insoluble in the flexible polymer.



   A suitable test to determine whether a substance constitutes a satisfactory release agent is to spread the proposed release agent on a metal, paper.

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 pier, a plastic material or a surface of another material.



   It is particularly advantageous to apply the attached release agent to a support surface to which the flexible polymer to serve as the impregnating agent adheres notoriously well. After spreading on the support, the proposed release agent is dried or cured, if necessary, after which the whole is covered with a film or droplets of the product to form the proposed flexible polymer, or / which is then cured otherwise to the flexible polymer form it would have in the finished fabric. The ease with which the proposed polymeric impregnating agent can be removed from the surface is noted. If this removal is impossible or very difficult, the proposed secondment officer is not satisfactory.

   If the polymer is easy to remove, the release agent is suitable for use, within the scope of the present invention, in conjunction with this polymer.



   Although the test described above will allow the value of a proposed release agent to be assessed, these agents must mainly adhere to the fibers, without making them so rigid as to destroy their flexibility, while they must have little or no adhesion to the impregnating agent.

   Examples of suitable release agents which may be mentioned include triglycerides, such as stearin and other vegetable and animal fats and oils, fluorinated hydrocarbons, such as dispersions of
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 polytetra: 4orethylene; heavy petroleum hydroc6.rbur (; jt,) such as oils and waxes; natural and synthetic waxes, such as carnauba, oiticica, candellila, montane waxes, modified polyethylenes and
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 silicones, such as polymers of dimethyliloxane and

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 diethylsiloxane; metallic soaps, such as sodium oleate and zinc stearate, as well as polyolefins, such as emulsified polyethylene and amorphous polypropylene.



   Treatment of the body or bundle of fibers with the release agent to ensure impregnation can be accomplished by any known convenient method.



  Impregnation can be done by soaking or by coating followed by application of suction to the opposite side of the fabric. The coating can be done by padding, by spraying, by casting or by coating by means of rollers.



  The release agent can be applied to the fibers in any suitable form. For example, it can be deposited from a melt, solution, emulsion, latex, dispersion, gel or sol.



  The amount of release agent used can, for example, the release agent used can, for example, be known. If necessary, impregnation can be followed by drying or hardening.



   Impregnation with the flexible polymer can be done in the same way and it can be applied as a solution, latex, gel, sol or other. suitable composition. It can also be dried in the same way, to remove the liquid vehicle.



  In the case where the impregnating agent consists of a partially formed polymer, the polymerization can be completed by an appropriate treatment, for example by heating or by the use of a catalyst, such as a free radical initiator. . The treatment chosen, in the event that any treatment is necessary, depends on the nature of the flexible polymer to be formed.

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 The flexible pç, lyTI1.re serving as an impregnating agent can be chosen from the various known polymers such as,
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 for example ,, lon polrurethane? prepared from polyesters or polyethers; vinyl polymers prepared, for example, from vinyl chloride, vinyl acetate, vinylidene chloride;

     the acrylic polymers obtained; for example, from acrylic or methacrylic esters, polyolefins; and silicones. The amount of flexible polymer used can, for example, be about 50-400% by weight, based on the weight of the fabric.



   In the finished impregnated fabrics prepared as described above, the fibers are in a flexible polymer sheath or matrix. These fibers have a certain freedom of movement, so as to resist a concentration of tearing stresses, since these fibers are protected by a release agent. The shell or matrix is obtained by impregnating, at least partially, the fabric with a flexible polymer, for example in an amount of about 10 to 100 of the total thickness of the fabric, after the treatment with the aid of the secondment agent. The flexible polymer surrounds the fibers and forms a
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 vehicle or a 'r.vlooae for these.



   It is essential that the impregnating polymers are flexible, so that the final fabric itself is flexible and pliable. Thus, rigid polymers, such as chermodified resins of the phenol-foraldehyde type, resins
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 h,. ^. cï-: o:: .1 d: nyda, melamine-fo1 "1Oaldehyde resins, 1 un.J, -forl! aldehyde resins and rigid epoxy resins, ne C: iv :: ': 1: wnc not.

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   The release agent or impregnation agent may contain other auxiliary materials, such as fillers or plasticizers.



   The free permeated '? obtained as described above exhibits, as can be seen, a tear resistance which is significantly better than that of fabrics treated only with impregnating agents and not treated with impregnating agents. prior, with the help of detachment agents. In addition, it has been found that in many cases the tear strength is also improved, compared to that of the original untreated fabric.



   The fabrics so prepared can be combined with the plyureshene cleaving elastomer of the present invention to form excellent artificial leather. They can be treated with the aid of a release agent of the class mentioned above and then be combined with the polyurethane zlastomer. In another variation, the hardening agent, which partially covers and permeates the fabric may be bonded to another fabric which may or may not have been treated in the same way and the partially impregnated and coated laminate product can then be bonded. be combined with the new elastomer according to the invention.

   As has already been pointed out, it is not essential that the fabric has undergone any pre-treatment, before being combined with the cellular elastomer, to form an artificial leather.



   The following examples are given purely by way of illustration and should not be considered as limiting the scope of the invention, as numerous modifications can be made thereto without departing from the scope of the invention. Unless otherwise indicated, all parts and percentages

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   tages.which are referred to in this specification are parts and percentages by weight. Examples 1 to 5 illus-
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 trent r .bl '' Lpo'lrwiv.lJ7, s of fabric x.Tir: 13 and nr0 of detaching agent. Examples 6 to 10 illustrate the preparation of a cellular polyurethane elastomer. Finally, Examples 11 to 13 illustrate the preparation of an artificial leather.



     EXAMPLE 1.



   A felt formed from 100% natural wool fibers 0.16 cm thick and weighing 474.6 g / m is treated with a solution of a release agent consisting of a polymer of curable silicone having the following composition:
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<tb> Ingredients <SEP> Parts
<tb>
 
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 SS-4C01 (polymer of si '.. hardened iconGdble 100 General ± 1 <> crric Company) Toluene 500 SS-w012c (ca: .J. Y "'; ') ir' .. n?;,; - .; :; sat, on do silicone Ctr.::ü! ^ 1criG Company) 10
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 The felt ev-. :? .- t'.re he helped him +,; 0 the solution of the stain agent and the excess of this nccnt is removed by cxpri; aabe between rollers. k fire.r'3 is. sch4 and cured at 1200 C for 10 minutes in a circulating air oven.

   The ut.w absorbed about 10 0 0id5 of agent from d. -: ce. \ (1 t t,: J \) r rJ.pf '() r.: ,, "J back weight f' ... 't'; 5.



  L? feutra: r ,; . by: tarYs :; dt! tacn03tnent and un: C'3: lt: i: v.t7 n <n rdl4¯. -, F; S;. = 1; ,, <- "- ', groin are 1mpr-",: born'3, by trc1i.:a:;e in a (:::'. U1.::.1'H. <: an: enaxt a C0701y. ^. 11 ^ 0 of acrylate do f.hY: '1) and. of a. :: 'ylat.c of ethylo, this copolymer containing the following ingredients:
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 Tn.'T \! C! .T ': 1 ": SP, ir;, 1 <Ts E :: - LJlsior. Àe CO" ,,': ': n'J = - (: .C; de - ..GO! 100 Po'4.y ('. H,) xy) nony' .plit-riol. (aicnt iensio-active) 2
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<tb> Polyacrylic <SEP> <SEP> partially, <SEP> retified <SEP> 57
<tb>
 
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 (er thickness: ulsion) (30 leaked from solid)

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 After soaking, the excess of im8cnation agent is removed using squeezable rollers and the product is heated in a circulating air oven at a temperature of 110 C for 1 hour.

   Each fabric sample absorbed 80% polymer, relative to the par: 3 of the fabric.



   The samples are tested, making a notch in them and trying to tear them by hand. The tissue treated with the release agent could only be torn with great difficulty. The fabric: untreated but impregnated was easily torn.



   EXAMPLE II
A needle-punched, cross-layered, non-woven polyester fabric 0.89 mm thick and 271.2 g / m weight was saturated with a wax solution.
 EMI19.2
 Brulin Perma - Z4old 1-2; in xylene. After passing the fabric through the solution, the excess liquid is removed by means of the rollers. The fabric 0; t then 36cr.a in an oven at 110 ° C for 30 minutes.

   The fabric absorbed about 355 release agent, per WTr ...) tV '' ':) 0: i :: l "1.LJJNa A carboxylated styrene-butadiene latex containing Lo9% dA solid material is mixed. to an aqueous dispersion 1> 6G of 1 zinc oxide, d- '' anirr; obtain uno OnCpi'li .: ilt OT1,;>: <; y. <tp 1o% zinc C 1 T.: r: 2 (i-i5, i treated with the idea of 3.'arer, t detachment and a: c;: ariti ',. lc :, on -; uity of the polyester fabric are: m: rein'. '.. ^. 1' \: W: ¯ ^.,: .- 3p3ion. By soaking and experi.; Ay dP .L'x <: "'3., ..;,'; '-" .: X tissues were then treated for '7: r.inut :. to i (.'r, ..; 315 An3 7a'UX cases, x of impregnation material have, st'.1 ab ::: ;; r : J's. By raoaort to the weight of the fabric.

 <Desc / Clms Page number 20>

 



   Both fabrics were then subjected to the ASTM D 751 trapezoidal tear test along with a sample of the unwoven, unwoven polyester. The initial tissue tear test gave a value of 23.1 kg. The latex impregnated material had a value of 15.8 kg and the material treated with both the release agent and the material.
 EMI20.1
 of imoregnation had a value of 36.2 kg.
EXAMPLE III A 70% nylon and 30% acetate fabric of a
 EMI20.2
 weight of 113.65, Um, which we have pra: ab, rr, t pulvëriu '-'aide an adhesive consisting of a copolymer, iie of the butadiene-acryloniti type <ilp, p3t impregnated with l 'help from an agent.;, nd: tachA; ncnt at j5;. amorphous polypropylene (P.'4, m <>;

  ,, Pn 3, Cù0) in hexane. When the tissue is saturated with the solution, the excess
 EMI20.3
 is removed by stripping between d (= '3 rolls and the fabric is dried for 40 minutes at 105 ° C. in an oven. The fabric is found to have absorbed about 30% polypropylene, based on the weight of the fabric.



   An impregnation solution is then prepared using the following ingredients:
 EMI20.4
 ::: '1 (l :(; i. "! T5 Partis' rpolyrr3rP é;,; ylbne glycol-adipic acid TJI x 100? OlY" 8tr ct'y? .R, e glycol-adipic acid (? , ', ..;:, (, -, 0) 40 .., 4' Tôthjrlén = -bis (2 chlor --- * nilLne) 4.0 Ethyl acetate <(urethane grade) 100
 EMI20.5
 As described in Example VII, the tissue treated with the release agent and the tissue not treated with the release agent are

 <Desc / Clms Page number 21>

 impregnated with the aid of this solution and expressed in order to eliminate any excess of impregnation liquor. The impregnated fabrics are dried. = For 40 minutes at 105 ° C. in a
 EMI21.1
 circulatliin .'r.

   G: -, cntate that -i5-: are absorbed about 30i; d matil <r., '.moré3naticr -ar -erp .., rr to their weight.



   The tear strengths of the two fabrics are then determined by the ASTM D-751 method. The tear strength of the fabric not treated with the release agent is 3.6 kg, while the tear resistance of the fabric treated with the release agent is 5.8 kg .



   EXAMPLE IV
 EMI21.2
 A non-warm felt of crimped cellulose acetate, perforated with three-dp three-gauge guns and weighing 152.5 g / m 2 is saturated with the aid of a 25 i solution of Glyerol tristearate in hexyl acetate, then squeezed out to remove excess solution and dried in a circulating air oven at 180 ° C for 10 minutes.



  The fabric absorbed about 20% rauport release agent to the weight of the fibers.



   A vinyl plastisol is prepared by dispersing the following ingredients by vigorous stirring:
 EMI21.3
 In; 0t0 Pdrtips Resinp dp chloride dp polyviny: quality di5peslon, dp 0ds ^ elevated olecular. 1 (0 g
 EMI21.4
 
<tb> Dioctyl <SEP> <SEP> <SEP> <SEP> 70 <SEP> g
<tb>
<tb> Oil <SEP> d <SEP> soybean <SEP> epoxidized <SEP> 5 <SEP> g
<tb>
<tb> Stabilizer <SEP> to <SEP> base <SEP> of <SEP> barium-cadmium-zinc <SEP> 2 <SEP> g
<tb>
 
Fabric treated as described above and untreated fabric are impregnated with plastisol,

 <Desc / Clms Page number 22>

 applying with a knife, a layer of this plastisol on the fabric and applying a vacuum to the uncoated face of the fabric, so that the olastisol penetrates into the tiasu and impregnates it.

   The two tissue samples are then heated for 5 minutes at 195 ° C. The two edges are then notched and it is found that the tissue not treated with a release agent tears easily, while the tissue treated with a release agent. The detachment can only be torn with difficulty at the point of the notch.



   EXAMPLE V
A shrunken, non-woven, needle-loom perforated dacron felt, 271.2 g / m weight and 1.27 mm thick, is dipped in a solution consisting of a dispersion of Brulin-1-27 wax in an aliphatic hydrocarbon as a solvent. The excess liquid is removed by squeezing into the hens and the tissue is dried in an oven.



   The fabric treated with the release agent is then soaked in a solution of an unreacted polyester urethane polymer. The excess polymer solution is removed by squeezing and the fabric is dried and heat treated in an oven. The absorption of release agent is 88.14 g / mel and the absorption of polymer is 322.03 g / mel. Similar fabric is treated only in the polymer solution.



   The tear resistance of the release agent-treated felt is excellent, while the polymer-coated felt is easily torn by hand.

 <Desc / Clms Page number 23>

 
 EMI23.1
 'SXt.PL VI
 EMI23.2
 A polyester is prepared using a mixture of polyols
 EMI23.3
 consisting of 85% diethylene glycol and dipropylene glycol by weight, by reaction with adipic acid.



  The iolecular weight is about 2.0 OC0, the hydroxyl number is 54-56, and the acid number is less than 1.5 C. The polyester is dehydrated to a water content of È; 2 µ1
 EMI23.4
 to the maximum.
 EMI23.5
 



  One mole of the aforementioned cd! Yester is reacted with 3 moles of diphenylmethane diisocyanate (1.IDI) in which about 80% by weight consists of the remaining 4, w'-diisocyanate Pt lA by other isobars, in thenual one pt / or the other of the isocyanate groups are in position 3, without two groups of isocyanate SA being found on the ^: rA: benzéniaup ring. The reaction is carried out by adding the .'01, which has been <5 spn31bl-mt>, <r free of di; r, er and trirere, with poly- ": 1t" ':: "r. ' , "'; j heating the r: -. o: l33P. : Day bring the trmnérarcre to 125 -,) 0QC. Gatti> tPoerature is' .'1: 7: t''CCUa probing 1 i j neurea.



  The oréxolymôre thus formed cor, tinr.t j i ,,, rouo> s isocyanate termi-
 EMI23.6
 free rates,
 EMI23.7
 This repolymer is incorporated into :: ". P. Composition of; n. ') 3t (') rrrf of expanded urethane, d. ' : r, 3 ;; i ..) rr to obtain the iuilant product:
 EMI23.8
 nr ^, - r? in: lt9 P.ir = 1, = s: rv ^ olyr, re 1 <j0 Triothylolroon 1,0 Trisopi'jpanolamtne 1, 0 1, ..- butan ", diol 1,0? olyethylane glycol (1 '.: 4,600) 5, O solution & 10 /. d'nrobisdiisobutyrcnlzr <, 2e in dp ltacatone 1, ..



  Oil> di thy15Llican (ic0 c = r. ,,: t ": c.s1 1.0 T ± tanatP dA tútrauutyle 0.2

 <Desc / Clms Page number 24>

 
 EMI24.1
 The recited L05 ir.r4dins are mixed well and applied as a 4P coat, by any convenient method, to the surface 15ir. The hardening can be done in dmux phases, then either for 1 to 2 minutes at 80 -100 C then for 8 to 12 minutes
 EMI24.2
 at 1; C-? .G C. The product obtained is an expanded urethane elastomer suitable for use in the manufacture of artificial leather.



   EXAMPLE VII
A polyester is prepared from ethylene glycol,
 EMI24.3
 of 1,), propanAdiol and adipic acid. 1,3, prooanediol represents from 15 to 25% of the total diol content by weight.



  Polyester with substantially linear terminal hydroxyl groups has the following characteristics:
 EMI24.4
 
<tb> Hydroxyl index <SEP> <SEP> 56 <SEP> (54-57)
<tb>
<tb>
<tb> Acid <SEP> index <SEP> minus <SEP> of <SEP> 1.5
<tb>
<tb>
<tb>
<tb>
<tb> Molecular <SEP> weight <SEP> 2.000 <SEP> (approximately)
<tb>
 
 EMI24.5
 Inerva-le fusion 1.0-15C * C (approx)
 EMI24.6
 
<tb> Content <SEP> Pn <SEP> water <SEP> less <SEP> of <SEP> 0, U5 <SEP>% <SEP> in <SEP> weight
<tb>
 One mole of this polyester is reacted with 1.85
 EMI24.7
 ffiolp dn 2, q "t <Jluéne dit50cyanate at a tProraturA of about 12 ± nendan; / 2 to 2 hours so as to form a C07 1 + =! r0O5 isocyanate prepolymer having? a3 roagi ..

   This prepoly- 7,>) X'o. ; t, 3.u ^ ;, is at a ripening at 1 sG. 16coC for 2 to 4 days 5. ± ct; m maturation reduces the ela3ticity of the cured product to the desired level.



    1bzz -; r3: '; - :: s of the aforementioned 3rénolymer, we add.%, 0 <µra "2 + n'3 c'u:" ".'" Say:; C: 1'sl.on containing 4Ù, at rar.7.p & polyester: 5: tc: i;,. : .., 0; r3 "'1" ""'. d .... 4,4 '-m.! thlnbis (2-chloro-aniline), 0, iO; rs: mw "acé" :. ferric acetonate. These constituents are vigorously added and added to 0.20 gram

 <Desc / Clms Page number 25>

 
 EMI25.1
 of azobisditsobutyronitrile disoriented in 1.0 gram of silicone oil cools. resistant to hydrolysis (copolymer of dirr.thyl: Joly ,,, 1.l) x; l: P and a polyoxyalkylene ether, 1500-2000 centigokg. t, <: 1 çuP the one sold under the name Union Carbide L-5.C, or Central ± 1 ctric SF-1CÓ6). These ingredients are yesterday; .:. llang4s one avoiding 1 '?; prLsonxem;>, t of air.



  Li- aforementioned mixture PS deposited, the aid of a device
 EMI25.2
 rollers or other device on a surface treated with
 EMI25.3
 1aidA of a detachment agent, such as one of the surfaces mpntionnép3 plus? high. LP hardening takes place in two stages, i.e. 5 minutes at; c3C C Pt pr.; 1i.J, nt 10-15 minutes at 150 C.



  It sP egg do too!? R! : n single stage by heating for 10-15 minutes at 150- <bll '1 <o R- The product' .'i '.. al> a density of about' 70.96 g / z, 1, a resistance - at break of about 70-140 kg / c: r, z, a value of rPbondir.7 -.tnt de bill; ' about 25 and a Shore A hardness
 EMI25.4
 about 75.
 EMI25.5
 



  Xr ::: ':? LS Vil! At a mea: r of 0.3 mole of pclypromylene glycol (ooids, nol. :: culalrP 1.000) made of = '0.10 mole of polypropylene; 7.ycai (molecular weight 2.000), 1.0 mole is added of 2,4-TDI "la" a, ^ -, T '; l: Llrf' du:, 41anze is orté 14ù "t in 1." '3ace of' C to,; "1.:; -. iiU "'5 ...."! Melaxqo 3t -a: ntnu to iuc- "5Q ± during ur! ft-jl fm - hur.3. The radu: at a prep.J1.J1J1> Ere containing j3 ::: -:) \. \ -, J isocyanate L "tn, 3U: free, l'n:" '):' Y '... l : ". 5 :: a.; 1 elas- or2, 9-.

   JYc: rC starting from this, Ti: l9ngP using the i!: "': ¯. 1, ..: i i ..3 n
 EMI25.6
 in <r4'4iPStâ Pirt 1-3 Frolv ô 3r'3 ..: r <? i-.deaJ, a3 1 (., C ftuile 1- castor (ca3i .: u: ^ t '; e) 1+, ,,, ': Eft ..' 1 / 1-? R '-; ^ c.' ^ LO; 'jl. ^. I..i:' l

 <Desc / Clms Page number 26>

 
 EMI26.1
 5 10 15 20 25
 EMI26.2
 Irédtr.t5 Pa; ti-s i, ', 2.2, -tétrûcloro-i, 2-èifluor / than (Frnon 112) D, j DiffiÓthylsilicn oil (50 to 100 c - =, ii; tock s) 0.8 Di (i-, ethyihe ;; yl) az> in = Jibutvlainoethal 0.4
 EMI26.3
 The in; rd: .P ^, s #Jnt bi..r. di.3: 1, 'r55 "' t. aliqué3, using an Í05lti: of application 1.> layer roller or knife, on a suitable fim upright surface, to
 EMI26.4
 
 EMI26.5
 force a layer of desired thickness. The material is hardened
 EMI26.6
 
 EMI26.7
 in two phases, either for 1-3 minutes & 70-? o C, then for 10- 'minutes at 15C-1S0 C.

   The product 3p present; form
 EMI26.8
 
 EMI26.9
 expanded low elastomer urethan elastomer. The rigidity is of the order of that which is suitable for an artificial leather.
 EMI26.10
 sky.
 EMI26.11
 .: \ -: '".: -' L.: ;; r:,: A rr.ol '1p ry (ttram0thyln ethf-r) C1ycol anhydrous from an' Ooid.'3 ') lécu11Lrp:'. Rvirc ; 65 \ ..-- ÎCU Pst mlse en r <act; cn
 EMI26.12
 
 EMI26.13
 with 0 ': J1' de, -t, I.u '' .. dUsoçy; .1: 1atp. during F'nVlr On heu rp i, tJ5. iC. for:, 7r '^, r un èi7, èrp. .rrGU1'3 hydroxyl ter-: nr ... 1UX. ; ". 1:; u ...: 1tiJ t3 *: lede vl .. '..' ::.; Sr Ti'3 '' ', # n ri? Act" .on with 2,0: T / ) l "'.5' i <:, - Tji. at about 6:) - C a:": art. h f'ures..w <3 'Wo: y ;;. brr is 5 () \. J, 5 à un "zatù; àtlar,.:.:;. (' teTpdratLre de Gù-11? é '1 y '^ ...:.': t about 2 hours,: J.'71 ';, a we left it:, "' 1 ':' 0 d! .. ':" ".s1U' i. l ":. (: - :: ',:". 1t u: "e -1:; ,,] <.l ::"'.

   The prepolbnnè; * rofro di; .it, \ '.r.> Nu,;% nt; <:, i'? Ü: '? 3 0 :: d,. <,,, inra,; t ;, to lu texoàrature 'wv 7 yv. '1 .., J.,. 1 ,,; .A "...., l.iE. 'Or,, -,'. F. Thus a pr ± poly- .-. ' ; - u ¯.'r .j4û?:, - ...: J '.. -, ..'. 1 1, ':::' '', J ^ t un mxcà3 w T3I.



  ...;, .. -....... Js "" o: rll.rf 'J' '. \'. '' '' '' '' '; ....:. 11 .. .. '1, 3 ......), f .... L1 t'1 r13 esz forxé ai d "c-?? Ro! .Y * r" i:'. Rdi --- nt3 nexta: 1 "3Àf" ôTilJi) J # .ùr "'Z È" ±. At "1 ± TidÀ.lGÉ3 # UiVàQt3 ..." '. \ ...,., ..... v 'M' ..... 1 e., "\ .. v., \, 0 .."

 <Desc / Clms Page number 27>

 
 EMI27.1
 
<tb> Ingredients <SEP> Parts
<tb>
<tb> prepolymer <SEP> 100
<tb>
 
 EMI27.2
 Polyppylene glycol (P.V. about 20) 21
 EMI27.3
 
<tb> Tetraethylene <SEP> glycol <SEP> 7
<tb>
<tb> Oil <SEP> from <SEP> dimethyl <SEP> silicone <SEP> (50 <SEP> centistokes)
<tb>
 
 EMI27.4
 tl, Ql-dixetinylamino-2-propanol 2
The ingredients are mixed thoroughly and left in the renos at a temperature of 25-35 C until the viscosity is about 3,000 poise.

   They are then mixed at about 1,000 revolutions per minute using a high speed stirrer, until a pearly reflection appears in the mass.



  The mass of viscous unreacted polymer contains many small air bubbles due to the air being trapped therein.
 EMI27.5
 



  The mixture is applied in one layer, using a knife device, on a surface of 'tac: le- x; ast, 4,1 .xaniére to form a layer having a desired purity; ": 5itaPllr., ent n about 0.125 at C, 75, mm). The surface of the cut may be coated paper (such as the depleted product" aubberlesse C2 "manufactured by SD ',; 'arren 0 0.), a fluorinated hydrocarbon or a metal coated with a release agent.
 EMI27.6
 egg 3trA hardened nar trait, '> ":" pnt! .2: 11inut :; : b5 C, then stretching 5 ^ i. ^, uts u 150 C.; .. 0 hardened3: ", K,": 1t î> f> \ lt., c-r; ant. 3'ottnir, mar d3 treatments including the cycles atur e-tmnc: aturc vjnt from zult hours at 21 C to 4nvLron) minutes; .i stC t ;.

   L'8 JSL '..:. ". Vre - = xpar! Sô fciibtA..T,! I1¯ clasticuf 3bl' '? Nu a J danaity of approximately a, E, ùc #", una réa13tanc> rupture f '+ n <; ir; n> 5-? û k; @c, 0.8! 1:,;. i. a ": 'iâ5i3t) n'": 3: - \ JUf; ' about 5lr k; ycm ", ur. alia: l emant il. rupture: nv: -, 2 '..- C' while 1u.il:" ". 's':'.) 5 solubi": : -: =: ..:. t1: t?: '"l ..:" ... J.3ai ae r.'. ". ': â;.:;,;,'? i1t 1" ball \ t: Ii1 (D .. 56 iUiiki <9: \: 1? G7 'U: 1' value 1a 5 - ,. ù (y Shore hardness n is ^, .. ro; i.

 <Desc / Clms Page number 28>

 



   EXAMPLE X
Epsilon caprolactam containing 10 to 20% of a mixture of isomers of mono methyl epsilon caprolactam is polymerized with ethylene glycol, so as to form a polyester with terminal hydroxyl groups having the following characteristics:
 EMI28.1
 
<tb> Molecular <SEP> weight <SEP> 530-535
<tb> of
<tb> Hydroxyl index <SEP> 210-215
<tb>
<tb> Acid <SEP> index <SEP> minus <SEP> of <SEP> 1
<tb>
<tb> <SEP> content in <SEP> water <SEP> minus <SEP> d, <SEP> 0.1 <SEP>%
<tb> in <SEP> weight
<tb>
 
Or. Reacts one mole of this polyester with 1.9 moles of a commercial mixture of isomers of toluene ditsocyanate containing 80 of?, 4-isomer and 20% of 2,6-isomer.



  Reaction 3 is carried out by slowly adding the polyester to the TDI. with constant stirring at a rate such that the temperature of the reaction mixture does not exceed 90 C. When the reaction is complete, as evidenced by the evolution of heat,
 EMI28.2
 The reaction mixture is kept at 90-10C C for 2 hours, after which it is allowed to cool to room temperature and left for at least 12 hours before use. A substantially linear prepolymer with terminal isocyanate groups is obtained which contains about 9% free isocyanate grids by weight.

   A low elasticity foamed elastomer is prepared using this prepolymer, by
 EMI28.3
 using:!. P5 following ingredients:
 EMI28.4
 
<tb> Ingredients <SEP> Part
<tb>
<tb> prepolymer <SEP> '<SEP> 100
<tb>
<tb> 1.4 <SEP> butanediol <SEP> 1.4
<tb>
<tb> Polyethylene <SEP> glycol, <SEP> P.M. <SEP> 400 <SEP> 4,5
<tb>
<tb> Polypropylene <SEP> glycol, <SEP> P. <SEP> M. <SEP> 425 <SEP> 6.5
<tb>
 
 EMI28.5
 Trirrethylolpropane 1, 2

 <Desc / Clms Page number 29>

 
The trimthylolpropane is melted and dissolved in the mixture of other. polyols and all polyols are
 EMI29.1
 mixed is mixed with the prepolymer at about 5CoC.

   Care is taken to avoid i! Er'.pri50nnf'mfo ',,:;' air in the. ..- ;. <. to which is then added a 10-fold solution of di-ethyl- 'N, Ndinitro5o terophthalamide in 6yl ethyl acetone (1.0 part), as well as a copolymer of c; 1rthylpolY5loxane and d Polyethylene ether, 1,500-2,000 centistokes (0.5 part).



   The ingredients are well dispersed using a high shear mixer. Finally 1 the following catalysts are added and quickly incorporated into the
 EMI29.2
 system, Telanging .'--. ient:
 EMI29.3
 
<tb> Catalysts <SEP> Will depart
<tb>
 
 EMI29.4
 N, K-diJthylaminoethanol 0.6 Di (n-butyl), i7e 0.1 -methyl di0thanolaminp. 0.2
 EMI29.5
 The mixture is decayed 3o'Js in the form of a layer, with the help of a knife or roller device, on an acoronriate detachment surface, aDrè3 which it is hardened in two phases, i.e. for 1, 5 to 2 minutes at 100 C, then for
 EMI29.6
 . -4 minutes at 50-170 C or in one phase, i.e. for 3-6 minutes - 5 at 5G -. '6C C.

   The product obtained has a density of r.:,e È, 6; -t 0.96 g / cmÎu1P low elasticity and rigidity and strength which make it suitable for sus uses.; Pnt. ^ n Ps.



   EXAMPLE XI
A woven monofilament nylon fabric, washed, thermally fixed, 30 denier, high tenacity,
 EMI29.7
 with a thickness of e, cij75 cm, with a weight of 28.1.> 7 glm2 and having 112 x 112 threads, is saturated with a

 <Desc / Clms Page number 30>

 detachment with the following composition:
 EMI30.1
 
<tb> Ingredients <SEP> Parts
<tb>
<tb> Wax <SEP> of <SEP> Carnauba <SEP> 100
<tb>
<tb> Beeswax <SEP> <SEP> 50
<tb>
<tb> Wax <SEP> of <SEP> Candellila <SEP> 50
<tb>
<tb> Benzene <SEP> 600
<tb>
 
The excess solution is removed by squeezing between rollers and the fabric is then dried at 90 ° C. for 45 minutes. The fabric absorbs 30% solution, based on its weight.
 EMI30.2
 



  Two moles of anhydrous polytdtramethylene ether glycol having a molecular weight of about 1000 are reacted with one mole of 2,4-toluene diisocyanate (TDI), for about 2 hours, at a temperature of 80 - 90 ° C. , to form a product with terminal hydroxyl groups. To one mole of this dimer, 4.0 moles of TDI are added, and react.
 EMI30.3
 mixing at a tem, -rat; v., ra of 70-80 C for 2-4 hours, to force a pr-polY: '' '1-' to r.oupe6 isocyanate terminals containing an 'X,': 3 of T8 :::.

   An impregnation solution containing the following ingredients is prepared:
 EMI30.4
 
<tb> Ingredients <SEP> Parts
<tb>
<tb> Polymer <SEP> 100
<tb>
 
 EMI30.5
 Pyrogenic silica (submicroscopic) 5 ethylsilicone oil (viscosity 50 centistokas) 1 Polypropylene glycol (P4 25) 42 octoat <Lw. , them O, l,
 EMI30.6
 
<tb> Expansion <SEP> agent <SEP> dispersion <SEP> 0.20
<tb>
 The disportion of blowing agent is a mixture of N, N'-
 EMI30.7
 dimethyl-N, N'-dinltrosot6rphthalamide, mineral oil and tri (2-ethylhuxyl) phosphate.

 <Desc / Clms Page number 31>

 



   This impregnation solution is applied, using a knife device with an interval of 0.25 mm, in the form of a layer, on paper which has previously been covered with a layer. of cured silicone coating, the latter layer being a release layer. The fabric which has been treated with the release agent is gently applied to the wet impregnating solution layer. A second paper coated with a layer of release agent is placed over the fabric.



  The assembly is then brought between two pressure rollers, so as to distribute the impregnation solution, after which it is subjected to a heat treatment at 1500 ° C. for 15 minutes. The fabric was found to have absorbed 400% impregnation solution, based on the weight of the fibers.



   The product obtained is suitable for use as. artificial leather.



   EXAMPLE 12.



   A nonwoven, bleached, boiled, carded, cross-layered cotton fabric, treated with caustic material, 0.1625 cm thick and weighing of 128.8 g / ml, is treated with the aid of a release agent consisting of a wax, as described in the preceding examples.



   A thermoplastic polyurethane is prepared by heating 1000 g of the polyester of Example 7 to a temperature of 1350 C, then placing it in a container maintained at a constant temperature of 110 C, under an atmosphere of dry nitrogen. . To this polyester is added 400 g of 4,4'-diphenylmethane diisocyanate, after which the reaction is allowed to continue for 30 minutes and 3000 g of dimethylforma-.

 <Desc / Clms Page number 32>

 mide are added. 120 g of 1,4-butanediol and 10 g of stannous octoate are added to the solution obtained. The mixture is further allowed to react for 1 hour, after which 50 g of submicroscopic pyrogenic silica is added and the solution is allowed to cool. Its viscosity increases sharply.

   The cotton fabric treated with the release agent is then impregnated, by applying a layer of the urethane solution prepared above, in an amount sufficient to impregnate half the thickness of the fabric. , while the opposite surface thereof is subjected to a moderate vacuum, to penetrate the solution into the tissue. The partially impregnated fabric is heated to 300 C in an oven. A product suitable for use as an artificial leather is obtained.



   EXAMPLE 13.



   A composition containing the following ingredients is applied, as a layer, to a release paper, using a knife device with an interval of 0.625 mm:
 EMI32.1
 
<tb> Ingredients <SEP> Parts
<tb>
<tb> Pre-polymer <SEP> of <SEP> example <SEP> 11 <SEP> 100
<tb>
<tb> Silica <SEP> pyrogenic <SEP> submicroscopic <SEP> 6
<tb>
<tb> Material <SEP> of addition <SEP> serving <SEP> to <SEP> adjust <SEP> the <SEP> size <SEP> 1
<tb> of <SEP> pores
<tb>
 (Copolymer of dimethylpolysiloxane and a polyalkylene ether with a viscosity of 1500 to 2000 centipoise)
 EMI32.2
 
<tb> Propylene <SEP> glycol <SEP> 415-435 <SEP> MW <SEP> 40
<tb>
<tb> <SEP> expansion <SEP> agent <SEP> example <SEP> 11 <SEP> 0.6
<tb>
<tb> Dispersion <SEP> of <SEP> pigment <SEP> black <SEP> 0.5
<tb>
<tb> Diethylaminoethanol <SEP> 1,

  0
<tb>
 

 <Desc / Clms Page number 33>

 
A Vaposan fabric, namely a fabric of polypropylene and nylon in the form of fibers deposited at random and not woven, @ fabric being perforated with needles
 EMI33.1
 et impréç-11.,: \ 'une 4mul.'j ".:" 1 "' acrylic ver, ri,). by the company Chicoppee Hulls, Inc, New York, NYUSA, es ;; deposited on the wet layer and the whole is bitter to pass through the clamping interval of 4 successive pairs of rollers, each of these rollers being adjusted to apply a pressure of 300-500 g per 2.5 cm of fabric width The pressed assembly is then heated at 150-180 ° C for 15-20 minutes in an oven.

   After this heat treatment, the release paper is torn off from the coated surface, so that the finished artificial quirk is obtained.



   CLAIMS
1.- New skin replacement product comprising a fibrous and porous support, partially impregnated with an impregnating agent based on an expanded or cellular polyurethane elastomer and carrying a layer of expanded polyurethane elastomer or cell forming one body with the impregnation material.



   2. - Leather replacement product according to claim 1, characterized in that the fibrous support has a thickness of 0.5 to 2.5 mm and the impregnation material based on expanded polyurethane penetrates into the fibrous support. over 2 to 80% of the thickness thereof.

** ATTENTION ** end of DESC field can contain start of CLMS **.

 

Claims (1)

3.- Leather replacement product according to claim 1, characterized in that the expanded polyurethane elastomer has a density of 0.48 to 1.2 g / cm3, a resilience or elasticity of between about 5% and 30%, when measured by the ball rebound test, as well as a hardness less than 90 by the ShoreA durometer. <Desc / Clms Page number 34> 4.- Leather replacement product according to claim 1, characterized in that the expanded polyurethane elastomer is prepared by the process consisting of: (i) reacting at least one compound selected from among polyalkylene ether diols and polyalkylene ester diols having a molecular weight of between about 700 and 9000 with an organic diisocyanate in a molar ratio of about 1.5 - 3.5 moles of diisocyanate per mole of diol, so as to form a pre -polymer; and (ii) extending the chain of this pre-polyalkylene ether diols and the EMI34.1 : 'mother using' at least mpo ê Cl'lOlSl pl # / l .l.èf {pOly-alkylene ester diols having a molecular weight of between about 90 and 1300, in the presence of about 0.2 -1 part by weight of a blowing agent per 500 parts by weight of the total reaction mixture. 5. - Leather replacement product according to claim 4, characterized in that the blowing agent or EMI34.2 swelling is c Ol: 3 from dimethyl dini troDoter6phthalate, azobis (isobutyronitnl) and water. 6.- Leather replacement product according to claim zip characterized in that the expanded polyurethane elastomer is prepared by the process consisting of: (i) reacting a polyalkylene ether diol having a molecular weight of d. 'about 1000 to about 3000, with ur. diisocyanate EMI34.3 ? '. "' ca: '1iqu <.' ... 1 <.. 11S the -olary ratio of 2-2% of diisocyanate per concentration of diol, so as to form a prepolymer ei <; 1). extend the chain of this pr4-polyalkylene ester with at least the ur, c: c: .po: 1é chosen from polyalkylene ether diols et7polyalkylene ester diols having a molecular weight of between about 90 and 1300, in the presence of ' about 0.2-1 part by weight of a blowing agent per 500 parts by weight of the total reaction mixture. <Desc / Clms Page number 35> 7. - Leather replacement product according to claim 6, characterized in that the swelling or expanding agent is chosen from dimethyl dinitrosoterephthalate, azo-bis (isobutyronitrile) and water. 8.- Leather replacement product, characterized in that it comprises a porous and fibrous support, having a thickness of 0.5 to 2.5 mm and partially impregnated with an expanded polyurethane elastomer penetrating into the fibrous support up to 'to 2 to 80% of the thickness thereof and bearing a layer of expanded polyurethane elastomer integral with the elastomer impregnating the support, this layer having a thickness equal to about 10 to 50% of the thickness. total thickness of the material impregnating the support and of this layer, the expanded polyurethane elastomer having a density of about 0.48 to 1.2 g / cm3, a resilience or elasticity of between 5% and 30% , when measured by the ball bounce test, and a hardness less than about 90 on the Shore A durometer. 9.- Leather replacement product according to claim 8, characterized in that the expanded polyurethane elastomer is prepared by the process consisting of: (i) reacting at least one compound selected from polyalkylene ether. diols and polyalkylene ester diols having a molecular weight of between about 700 and 9000, with an organic diisocyanate in the molar ratio of about 1.5-3.5 moles of diisocyanate per mole of diol, so as to form a prepolymer; and (ii) extending the chain of the prepolymer with at least one compound selected from polyalkylene ether diols and polyalkylene ester diols having a molecular weight between 90 and 1300, in the presence of about 0.2-1 part <Desc / Clms Page number 36> by weight of a blowing agent per 500 parts by weight of the total reaction mixture. 10. - Leather replacement product, characterized in that it comprises a fibrous and porous tissue support, comprising a body of fibers carried by a flexible polymer envelope, this flexible polymer at least partially impregnating the body of fibers and surrounding it, the fibrous tissue containing a release agent interposed between the fibers in this body of fibers and said flexible polymer, this release agent being capable of substantially reducing the adhesion between the fibers and the flexible polymer , these fibers having a certain freedom of movement with respect to the flexible polymer, the support of the fibrous and porous fabric being partially impregnated with an expanded polyurethane elastomer and carrying a layer of expanded polyurethane elastomer integral with that which impregnates the support. 11.- Leather replacement product according to claim 10, characterized in that the expanded polyurethane elastomer has a density of about 0.48 to 1.2 g / cm3, a resilience or elasticity of between about 5% and 30%, measured by the ball rebound test and a hardness less than 90 by the Shore A durometer. 12. - Leather replacement product according to claim 10, characterized in that the aforementioned detaching agent is insoluble in the flexible polymer. 13. - Leather replacement product according to claim 10, characterized in that the flexible polymer impregnates the fibrous body over 10 to 100% of the total thickness thereof. <Desc / Clms Page number 37> 14. - Leather replacement product according to claim 10, characterized in that the expanded polyurethane elastomer is prepared by the process consisting of: (i) 'reacting at least one compound selected from polyalkyls. an ether diols and / polyalkylene ester diols having a molecular weight of between about 700 and 9000, with an organic diisocyanate in the molar ratio of about 1.5-3.5 moles of diisocyanate per mole of diol, so as to forming a prepolymer; and (ii) extending the chain of the prepolymer with at least n compound selected from polyalkylene ether diols and polyalkylene ester diols having a molecular weight between 90 and 1300, in the presence of about 0.2-1 part by weight of a blowing agent per 500 parts by weight of the total reaction mixture. 15. - Leather replacement product, characterized in that it comprises a support of fibrous and porous fabric having a thickness of 0.5 to 2.5 mm, this support of fibrous fabric comprising a body of fibers carried by a shell or matrix of flexible polymer, this flexible polymer permeating and surrounding the body of fibers over 10 to 100% of the total thickness thereof, this fibrous fabric containing a release agent soluble in the polymer flexible and interposed between the fibers of this fiber body and the flexible polymer, this release agent adhering to the fibers without making them rigid and being capable of reducing the adhesion between these fibers and the flexible polymer, the fibers being free to move relative to the flexible polymer, the fibrous and porous fabric being partially impregnated with an expanded polyurethane elastomer which penetrates into this fabric over 2 to 80% of the thickness thereof and carrying a layer <Desc / Clms Page number 38> of expanded polyurethane elastomer integral with the elastomer impregnating the fabric, this layer having a thickness of about 10 to 50% of the total thickness of the material impregnating the fabric and of the layer carried by that here, this expanded polyurethane elastomer having a density of about 0.48 to 1.2 g / cm3, a resilience or elasticity of between about 5% and 30%, measured by the rebound test of balls and a hardness less than 90 on the Shore A durometer. 16.- Leather replacement product according to claim 15, characterized in that the expanded polyurethane elastomer is prepared by the process consisting of: (i) reacting at least one compound selected from polyalkylene ether diols and polyalkylene ester diols having a molecular weight of between about 700 and 9000, with an organic diisocyanate in the molar ratio of about 1.5-3.5 moles of diisocyanade per mole of diol, so as to form a pre -polymer; and (ii) extending the chain of the prepolymer with at least a compound selected from polyalkylene ether diols and polyalkylene ester diols having a molecular weight between 90 and 1300, in the presence of about 0.2 - 1 part in weight of a blowing agent per 500 parts by weight of the total reaction mixture. 17. - New fibrous fabric, characterized in that it comprises a body of fibers carried by a shell of flexible polymer, this flexible polymer at least partially impregnating the body with flourishes and surrounding the latter, the fibrous tissue containing a release agent interposed between the fibers in this fiber body and said flexible polymer, this release agent being capable of reducing <Desc / Clms Page number 39> substantially the adhesion between the fibers and the flexible polymer, these fibers being free to move vis-à-vis the aforementioned flexible polymer 18. A fibrous tissue according to claim 17, characterized in that the release agent is insoluble in the flexible polymer. 19. - A fibrous fabric according to claim 17, characterized in that the flexible polymer impregnates the fibrous body over 10 to 100% of the total thickness thereof. 20. A fibrous fabric according to claim 17, characterized in that the flexible polymer almost entirely permeates said fibrous body. 21. A fibrous fabric according to claim 17, charac- terized in that the flexible polymer is chosen from polyurethanes, vinyl polymers, acrylic polymers, polyolefins and flexible silicones. 22. Fibrous tissue according to claim 17, characterized in that the release agent is chosen from triglycerides, fluorinated hydrocarbons, heavy petroleum hydrocarbons, natural and synthetic waxes, silicones, soaps. metals and polyolefins. 23.- New expanded polyurethane elastomer having a density of about 0.48 to 1.2 g / cm3, a resilience or elasticity of between about 5% and 30, measured by the ball rebound test and a lower hardness at 90 to the Shore A durometer. 24.- A novel expanded polyurethane elastomer prepared by the process consisting of: (i) reacting at least one compound selected from polyalkylene ether diols and polyalkylene ester diola having a molecular weight between about 700 and 9000, with an organic diisocyanate in <Desc / Clms Page number 40> molar ratio of about 1.5 - 3.5 moles of diisocyanate per mole of diol, so as to form a prepolymer; and (ii) extending the chain of the prepolymer with at least one compound selected from polyalkylene ether diols and polyalkylene ester diols having a molecular weight of between 90 and 1300, in the presence of about 0.2-1. part by weight of a blowing agent per 500 parts by weight of the total reaction mixture. 25.- Expanded polyurethane prepared by the process, comprising: (i) reacting a compound selected polyalkylene ether diol having a molecular weight of between about 1000 and 3000, with an organic diiscyanate in the molar ratio of enviror 2 - 2.1 moles of diisocyanate per mole of diol, so as to form a prepolymer; and (ii) extending the chain of the prepolymer with at least one compound selected from, polyalkylene ether diols and polyalkylene ester diols having a molecular weight between 90 and 1300, in the presence of about 0.2 - 1 part by weight of a blowing agent per 500 parts by weight of the total reaction mixture. 26.- Process for the preparation of expanded polyurethane elastomers, characterized in that it consists in: (i) reacting at least one compound chosen from polyalkylene ether diols and polyalkylene ester diols having a molecular weight between about 700 and 9000, with an organic diisocyanate in the molar ratio of about 1.5 - 3.5 moles of diisocyanace per mole of diol, by contact of this diol with this diisocyanate at a temperature of about 60 at 125 C for about 0.5 - 16 hours to form a prepolymer; and (ii) extending the chain of the prepolymer <Desc / Clms Page number 41> polyalkylene ether diols and with at least one compound selected from polyalkylene ester diols having a molecular weight of between approximately 90 and 1300; in the presence of about 0.2 - 1 part by weight of a swelling agent per 500 parts by weight of the total reaction mixture, the chain extension reaction being carried out at a temperature of about 80 to 1900 C pandalt about 2 - 25 minutes. 27. A process according to claim 26, characterized in that the chain extension reaction is carried out by first incompletely curing the reaction mixture by heating at a temperature of about 80 to 1800 C and below the activation temperature of the blowing agent, for about 0.5 to 5 minutes, folds by heating the incompletely cured reaction mixture to a temperature of about 110 to 1900 C and above. the activation temperature of said blowing agent for about 4 to 20 minutes. 28.- Process for the preparation of expanded polyurethane elastomers, characterized in that it consists in: (i) reacting a polyalkylene ether diol having a molecular weight of about 1000 to 3000 with a diiscoyanate / in the molar ratio of 2 - 2.1 moles of diisocyanate per -noie of d: ol, by contact of this diol with this diisocyanate at a '? temperature of about 60 - 125 C for about 0.25 - 2 hours ; (ii) maintaining the mixture thus formed at a temperature of about 120 - 125 ° C for about 2 - 12 hours; and (! il) a.long the chain of the prepolymer with at least one compound selected from polyalkylene ether diols and polyalkylene ester diols having a molecular weight between about 90 and 1300, in the presence of about 0.2 - 1 part by weight of a swelling agent per 500 parts of total reaction mixture <Desc / Clms Page number 42> the chain extension reaction being carried out at a temperature of about 80 to 190 ° C for about 2 to 25 minutes. 29. A process according to claim 28, characterized in that the chain extension reaction is carried out by first incompletely curing the reaction mixture by heating to a temperature of about 80 to 180 ° C and below the activation temperature of the blowing agent, for about 0.5 to 5 minutes, then heating the incompletely cured reaction mixture to a temperature of about 110 to 190 C and above activation temperature of said blowing agent for about 4 to 20 minutes. 30. - Process for preparing a fibrous fabric, characterized in that a body of fibers is treated with the aid of a release agent and the body of fibers thus treated is then impregnated with the aid of a flexible polymer, the release agent being capable of substantially reducing the adhesion between the? fibers and flexible polymer. 31. A method according to claim 30, characterized in that the release agent is insoluble in the flexible polymer. 32. The method of claim 30, characterized in that the fiber body is impregnated over 10 to 100% of its total thickness with the flexible polymer. 33.- Process for the preparation of an artificial leather, characterized in that a fibrous and porous support is partially impregnated with the aid of a polyurethane elastomer prepared by the process consisting in reacting at least one compound chosen from polyalkylene ethr diols and polyalkylene ester diols having a molecular weight of <Desc / Clms Page number 43> between about 700 and 9000 with an organic diisocyanate in the molar ratio of about 1.5 - 3.5 moles of diisocyanate per mole of diol, so as to form a prepolymer, and to extend the chain of the prepolymer with at least a compound chosen from polyalkylene ether diols and polyalkylene ester diols having a molecular weight of between approximately 90 and 1300, in the presence of about 0.2 - 1 part by weight of a blowing agent per 500 parts by weight of the total reaction mixture, the chain extension reaction being carried out at a temperature of about 80 - 190 C for about 2 - 25 minutes and at least part of the chain extension reaction being carried out after impregnation of the fibrous and porous support with the polyurethane elastomer, so as to form an artificial leather comprising a support of porous fabric partially impregnated with an expanded polyurethane elastomer. 34. A process according to claim 33, characterized in that the chain extension reaction is carried out by first incompletely curing the aforementioned reaction mixture, before impregnating the fibrous and porous support, by heating at a temperature of about 80-180 ° C and below the activation temperature of said blowing agent for about 0.5-5 minutes, then heating the incompletely cured reaction mixture, after impregnation of the tissue, at a temperature of about 110 to 190 C and above the agent activation, swelling or expansion temperature for about 4 to 20 minutes. 35.- Process for the preparation of an artificial leather, characterized in that a support made of fibrous and porous fabric is partially impregnated, comprising a body of fibers se <Desc / Clms Page number 44> being in a flexible polymer envelope at least partially impregnating and surrounding this body of fibers, the fibrous fabric containing a release agent interposed between the fibers of said body of fibers and the flexible polymer, this release agent being capable of significantly reduce the adhesion between the fibers and the flexible polymer, the fibers being free to move relative to the flexible polymer, the fibrous fabric being impregnated with a polyurethane elastomer prepared by the process of reacting at least one compound selected from polyalkylene ether diols and polyalkylene ester diols having a molecular weight of between about 700 and 9000, with an organic diisocyanate in the molar ratio of about 1.5 - 3.5 moles of diisocyanate per mole of diol, so as to form a prepolymer and to extend the chain of the prepolymer with at least one compound selected from among polyalkylene ether diols and polyalkylene ester diols having a molecular weight of between about 90 and 1300, in the presence of about 0.2 - 1 part by weight of a blowing agent per 500 parts by weight of the total reaction mixture, the chain extension reaction being carried out at a temperature of about 80 to 1900 C for about 2 to 25 minutes and at least part of this chain extension reaction taking place after impregnation of the fibrous and porous support by the polyurethane elastomer, so as to form an artificial leather comprising a support of fibrous fabric partially impregnated with an expanded polyurethane elastomer. 36. The method of claim 35, characterized in that the chain extension reaction is carried out by first incompletely curing the reaction mixture. <Desc / Clms Page number 45> tional by heating at a temperature of about 80 to 1800 C and below the activation temperature of the expelling agent, for about 0.5 to 5 minutes, then heating the incompletely cured reaction mixture. at a temperature of about 110 to 1900 C and above the activation temperature of said blowing agent for about 4 to 20 minutes.