CH280195A - Process for the production of artificial leather. - Google Patents

Process for the production of artificial leather.

Info

Publication number
CH280195A
CH280195A CH280195DA CH280195A CH 280195 A CH280195 A CH 280195A CH 280195D A CH280195D A CH 280195DA CH 280195 A CH280195 A CH 280195A
Authority
CH
Switzerland
Prior art keywords
process according
solutions
artificial leather
pressed
fibers
Prior art date
Application number
Other languages
French (fr)
Inventor
Podnik Svit Narodni
Original Assignee
Svit Np
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Svit Np filed Critical Svit Np
Publication of CH280195A publication Critical patent/CH280195A/en

Links

Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D04H1/645Impregnation followed by a solidification process
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59Polyamides; Polyimides
    • D06M15/595Derivatives obtained by substitution of a hydrogen atom of the carboxamide radical
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/125Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Description

  

  Procédé pour la fabrication de cuir artificiel.    On connaît des procédés pour la fabrica  tion de cuir artificiel où l'on utilise comme  matière première des fibres de polyamide ou  d'autres fibres ou, le cas échéant, une masse  amorphe, obtenue par précipitation de solu  tions de polyamides. Pour conférer aux  fibres     polyamidiques    l'aptitude<B>à</B> se lier entre  elles,<B>il</B> faut traiter leur surface par des  agents corrosifs, par exemple par l'acide  chlorhydrique. Ce traitement cependant doit  être effectué avec de grandes précautions,  surtout quand il s'agit des fibres minces, pour  ne pas altérer leur structure.  



  Le procédé de fabrication de cuir artificiel  selon l'invention est caractérisé en ce que des  masses fibreuses, constituées au moins en  partie de fibres     polvamidiques,    sont impré  gnées avec des solutions de polymères linéaires  contenant de l'azote (par exemple<B>de</B>     poay.-          uréthanes    ou de polyamides et de préférence  <B>(le</B> polyamides modifiées par la     formaldéhyde     et le méthanol) et pressées.  



  L'invention permet d'obtenir un cuir arti  ficiel -de grande valeur, présentant une per  méabilité, une flexibilité, une solidité et une  durabilité élevées. L'imprégnation de la masse  fibreuse, sous forme par exemple (le nappe  ou de feutre, tendu ou non tendu, peut  s'effectuer par immersion, par projection ou  par enduction. Les solutions de polyamides  ou de polyuréthanes peuvent contenir<B>des</B>  additions appropriées, telles que des     pigiuents,     des matières colorantes, des charges, des ra-    mollissants,     etc.    Après l'imprégnation, la  nappe ou<B>le</B> feutre est de préférence séché, au:  moins partiellement, puis pressé dans une  presse ou entre des cylindres.

   L'opération  petit être répétée plusieurs     f        ois    jusqu'à ce  qu'on obtienne une porosité et une épaisseur  convenable pour le cuir artificiel. En proje  tant une couche plus épaisse de la solution de  polyamide sur une face, on petit former la  fleur du cuir. Le cuir artificiel peut être  traité<B>à</B> l'aide des machines d'apprêt habi  tuelles pour former une fleur, un dessin, une  gravure,     etc.   <B>Il</B> va sans dire qu'ensuite le cuir  peut être verni     oucoloré,    pour autant que des  libres colorées n'ont pas été -utilisées comme  matière première.  



  Lorsqu'on utilise des polyamides modifiées  par la     formaldéhyde    et le méthanol, celles-ci,  après un certain temps, perdent leur     sGlubi-          lité,    leurs autres qualités restant cependant  inchangées. Le présent procédé a cet     avait-          tage    qu'on peut travailler avec des solutions  -froides sans que l'uniformité du produit en  soit réduite.

   Pour augmenter     F-aniformité    dit  cuir obtenu, on peut le soumettre<B>à</B> un nou  veau pressage, de préférence<B>à</B> l'état     huinide.     Comme matière première de base on peut,  donc utiliser des fibres de polyamides seules  ou en mélange avec des fibres     naturelleq    ou  d'autres fibres artificielles.  



  Il va sans dire que la nappe ou le feutre  peut être préparé de manière variée; le cas  échéant, on peut utiliser un tissu au Heu      dune nappe. De même, on peut combiner la  nappe avec un tissu léger, lequel, après l'im  prégnation par une solution de polyamides et  après le pressage,     sunit   <B>à</B> perfection avec la  nappe ou avec le feutre.     Dans,ce    cas,<B>le</B> tissu  forme, de préférence, la base de la fleur du  cuir.  



  On peut choisir des fibres de même titre  ou un mélange de fibres de titre différent.  De même, la longueur des fibres peut être  adaptée<B>à</B> la fin désirée,  Comme solvant pour les polyamides     niodi-          fiées,    les alcools aliphatiques inférieurs ou  leurs mélanges sont les plus convenables. Le  pressage ou le     calandrage    de la nappe, impré  gnée par la solution de polyamides, peut être  effectué, le     #cas    échéant, encore avant le     sé-          ,cha.ge    complet, et ceci au -cas où l'on utilise,  par exemple, des fibres plus épaisses dont  l'élasticité empêche de les presser<B>à</B> l'épaisseur  désirée.  



  En modifiant le processus de fabrication,  on peut obtenir des produits possédant des  qualités différentes, surtout quant<B>à</B> la per  méabilité     pourdes    gaz     etdes    vapeurs.    <I>Exemple<B>1:</B></I>  On utilise 40 parties de libres coupées de  viscose, obtenues par filature<B>à</B> sec, d'un titre  moyen de<B>15</B>     den.,    et<B>60</B> parties de libres cou  pées, formées de déchets de libres de     e-capro-          lactame    polymérisé, de titre varié, et on en  prépare sur le     loup-briseur    une nappe d'une  épaisseur voisine de 4     em    sur laquelle ensuite  on projette, des deux côtés,

   une solution d'une  partie de polyamide modifiée par la     form-          aldéhyde    et le méthanol dans<B>6</B> parties     d'étha-          nol    et contenant une matière colorante conve  nable. La bande de la masse fibreuse est con  duite<B>à</B> travers une chambre<B>à</B> sécher par  dessus une série de cylindres rotatifs, alterna  tivement d'en haut vers le bas et d'en bas vers  le haut et ensuite entre les cylindres froids de  trois calandres, placées l'une<B>à</B> la suite<B>de</B>  l'autre. L'un des cylindres de la dernière ca  landre porte un dessin en relief pour former  la fleur du cuir artificiel. Le produit possède  une bonne perméabilité aux gaz et aux va-    peurs et en même temps une solidité considé  rable.  



  Le côté envers peut être saupoudré, le cas  échéant, après la projection     d#une    couche ulté  rieure de la solution de polyamide, de courtes  fibres fines, le tout étant ensuite pressé de  nouveau.    Exemple     2:     On a préparé de la même manière qu'à  l'exemple<B>1</B> une nappe en utilisant<B>100</B> parties  de déchets des libres de     e.-caprolactame    poly  mérisé.

   Après l'imprégnation par 2 parties de  la même polyamide, modifiée par la     form-          aldéhyde    et le méthanol, dans<B>11</B> parties       d'éthanol    et contenant de l'ocre comme<B>pig-</B>  ment, la masse fibreuse a été séchée, pressée  entre deux cylindres, munie d'une couche ulté  rieure de la même solution, projetée sur l'un  des côtés et, après un nouveau séchage, pres  sée encore une fois entre des cylindres dont       l'un,porte        undessin    pour former la. fleur. Le  cuir artificiel obtenu est caractérisé par une  solidité et une résistance<B>à</B> l'eau et<B>à</B> diverses  matières chimiques, supérieure<B>à</B> celle du pro  duit de l'exemple<B>1.</B>  



  Le cuir artificiel, obtenu conformément<B>à,</B>  l'invention, résiste d'ordinaire<B>à</B> l'eau, même  <B>à</B> chaud, aux huiles, aux matières grasses,<B>à</B> la  benzine,<B>à</B> d'autres solvants et aux ingrédients  chimiques courants, excepté aux acides forts  et aux lessives alcalines concentrés.



  Process for the production of artificial leather. Processes are known for the manufacture of artificial leather in which polyamide fibers or other fibers or, where appropriate, an amorphous mass, obtained by precipitation of polyamide solutions are used as raw material. In order to give polyamide fibers the ability <B> to </B> bond with each other, <B> it </B> must be treated on their surface with corrosive agents, for example with hydrochloric acid. This treatment, however, must be carried out with great care, especially when it comes to thin fibers, so as not to alter their structure.



  The process for manufacturing artificial leather according to the invention is characterized in that the fibrous masses, consisting at least in part of polvamide fibers, are impregnated with solutions of linear polymers containing nitrogen (for example <B> of </B> poay.- urethanes or polyamides and preferably <B> (the </B> polyamides modified by formaldehyde and methanol) and pressed.



  The invention provides a high value artificial leather exhibiting high permeability, flexibility, strength and durability. The impregnation of the fibrous mass, for example in the form (the sheet or of felt, stretched or not stretched, can be carried out by immersion, by spraying or by coating. The polyamide or polyurethane solutions can contain <B> of </B> suitable additions, such as pigments, coloring matters, fillers, softeners, etc. After impregnation, the web or <B> </B> felt is preferably dried, at: less partially, then pressed in a press or between rolls.

   The operation may be repeated several times until a porosity and thickness suitable for the artificial leather is obtained. By spraying a thicker layer of the polyamide solution on one side, the grain of the leather is formed. Artificial leather can be processed <B> with </B> using conventional finishing machines to form a flower, design, engraving, etc. <B> It </B> goes without saying that the leather can then be varnished or colored, provided that colored fibers have not been used as a raw material.



  When polyamides modified with formaldehyde and methanol are used, these, after a certain time, lose their glubility, their other qualities, however, remaining unchanged. The present process has the advantage that it is possible to work with cold solutions without reducing the uniformity of the product.

   To increase the so-called leather uniformity obtained, it can be subjected <B> to </B> a new pressing, preferably <B> in </B> the wet state. As basic raw material, it is therefore possible to use polyamide fibers alone or as a mixture with natural fibers or other artificial fibers.



  It goes without saying that the tablecloth or the felt can be prepared in a variety of ways; where appropriate, a fabric can be used instead of a tablecloth. Likewise, the web can be combined with a light fabric which, after impregnation with a polyamide solution and after pressing, is perfectly matched with the web or with the felt. In this case, <B> the </B> fabric preferably forms the base of the grain of the leather.



  One can choose fibers of the same titer or a mixture of fibers of different titer. Likewise, the length of the fibers can be tailored to the desired end. As the solvent for the niodified polyamides, lower aliphatic alcohols or mixtures thereof are most suitable. The pressing or calendering of the web, impregnated with the polyamide solution, can be carried out, if necessary, even before the complete drying, and this in the case where one uses, for example , thicker fibers whose elasticity prevents them from being pressed <B> to </B> the desired thickness.



  By modifying the manufacturing process, products with different qualities can be obtained, especially in the <B> to </B> permeability for gases and vapors. <I>Example<B>1:</B> </I> 40 parts of viscose cut loose pieces are used, obtained by spinning <B> at </B> dry, with an average count of <B> 15 </B> den., And <B> 60 </B> parts of free cut, formed from waste of free of polymerized e-caprolactam, of varying strength, and a sheet is prepared on the wolf-breaker with a thickness close to 4 em onto which we then project, on both sides,

   a solution of one part polyamide modified with formaldehyde and methanol in <B> 6 </B> parts of ethanol and containing a suitable coloring matter. The web of fibrous mass is led <B> through </B> through a <B> </B> drying chamber over a series of rotating cylinders, alternately from top to bottom and from top to bottom. bottom to top and then between the cold rolls of three calenders, placed one <B> to </B> following <B> of </B> the other. One of the cylinders of the last chalk bears a design in relief to form the flower of the artificial leather. The product has good permeability to gases and vapors and at the same time considerable strength.



  The reverse side can be sprinkled, if desired, after spraying a further layer of the polyamide solution, with short fine fibers, the whole then being pressed again. Example 2: A web was prepared in the same manner as in Example <B> 1 </B> using <B> 100 </B> parts of waste fibers of poly merized e.-caprolactam.

   After impregnation with 2 parts of the same polyamide, modified by formaldehyde and methanol, in <B> 11 </B> parts of ethanol and containing ocher as <B> pig - </ B > ment, the fibrous mass was dried, pressed between two rolls, provided with a subsequent layer of the same solution, projected onto one of the sides and, after further drying, pressed again between rolls of which one, carries a drawing to form the. flower. The artificial leather obtained is characterized by a strength and a resistance <B> to </B> water and <B> to </B> various chemical materials, superior <B> to </B> that of the product of example <B> 1. </B>



  Artificial leather, obtained in accordance with <B> the </B> invention, is usually resistant <B> to </B> water, even <B> to </B> hot, oils, fats, <B> to </B> benzine, <B> to </B> other solvents and common chemical ingredients, except strong acids and concentrated alkaline lyes.

 

Claims (1)

<B>REVENDICATION:</B> Procédé de fabrication de cuir artificiel,<B>à</B> Faide de polyamides, caractérisé en ce que des masses fibreuses, constituées au moins en par tie de fibres polyamidiquies, sont imprégnées avec des solutions de polymères linéaires con tenant de l'azote et pressées. SOUS-REVENDICATIONS: <B>1.</B> Procédé selon la revendication, caracté risé en ee que l'on utilise des solutions (le polyamides modifiées par la formaldéhyde et le méthanol. 2. Procédé selon la revendication, caracté risé en ce que les masses fibreuses sont, après imprégnation, d'abord séchées, puis pressées. <B> CLAIM: </B> Process for manufacturing artificial leather, <B> with </B> using polyamides, characterized in that the fibrous masses, at least in part made up of polyamide fibers, are impregnated with linear polymer solutions containing nitrogen and pressed. SUB-CLAIMS: <B> 1. </B> Process according to claim, characterized in that one uses solutions (polyamides modified with formaldehyde and methanol. 2. Process according to claim, characterized in what the fibrous masses are, after impregnation, first dried, then pressed. <B>3.</B> Procédé selon la revendication, caracté risé en ce que les masses fibreuses sont, après imprégnation, soumises<B>à</B> un séchage partiel, puis pressées. 4. Procédé selon la revendication, earacté- risé en ce qu#une masse de fibres indépen dantes est combinée avec un tissu, celui-ci formant la base de la fleur du cuir artificiel. <B>5.</B> Procédé selon la revendication, caracté risé cri ce que le produit, après le pressage, est revêtu d'une couche additionnelle de la solution d'un polymère susdit et en ce qu'on imprime un dessin sur le revêtement obtenu, pour former la fleur du cuir artificiel. <B> 3. </B> Process according to claim, characterized in that the fibrous masses are, after impregnation, subjected <B> to </B> partial drying, then pressed. 4. A method according to claim, characterized in that a mass of independent fibers is combined with a fabric, the latter forming the base of the grain of the artificial leather. <B> 5. </B> Process according to claim, characterized in that the product, after pressing, is coated with an additional layer of the solution of a said polymer and in that a drawing is printed on the coating obtained, to form the grain of the artificial leather. <B>6.</B> Procédé selon la revendication, caracté risé en ce qu'on forme une couche addition- helle d'une solution d'un polymère susdit sur une des faces du cuir artificiel, après quoi cette couche encore collante est saupoudrée de courtes fibres fines et le tout est pressé encore une fois. <B>7.</B> Procédé selon la revendication, caracté risé en ce qu'on -utilise des solutions desdits polymères<B>à</B> la température normale. <B>8.</B> Procédé selon la revendication, caracté risé en ce qu'on utilise des solutions desdits polymères contenant des matières colorantes. <B>9.</B> Procédé selon la revendication, caracté risé en ce qu'on -utilise des solutions desdits polymères contenant des pigments. <B> 6. </B> Process according to claim, characterized in that an additional layer of a solution of a said polymer is formed on one side of the artificial leather, after which this still tacky layer is sprinkled with short fine fibers and the whole is pressed again. <B> 7. </B> Process according to claim, characterized in that solutions of said polymers are used <B> at </B> normal temperature. <B> 8. </B> Process according to claim, characterized in that solutions of said polymers containing coloring matter are used. <B> 9. </B> Process according to claim, characterized in that solutions of said polymers containing pigments are used. <B>10.</B> Procédé selon la revendication, carac térisé en ce qu'on utilise des solutions desdits polymères contenant des ramollissants. <B>11.</B> Procédé selon la revendication, carac térisé en ce qu'on utilise des solutions desdits polymères contenant des charges. <B> 10. </B> Process according to claim, characterized in that solutions of said polymers containing softeners are used. <B> 11. </B> Process according to claim, characterized in that solutions of said polymers containing fillers are used.
CH280195D 1947-06-10 1948-06-02 Process for the production of artificial leather. CH280195A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CS280195X 1947-06-10

Publications (1)

Publication Number Publication Date
CH280195A true CH280195A (en) 1952-01-15

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Family Applications (1)

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CH280195D CH280195A (en) 1947-06-10 1948-06-02 Process for the production of artificial leather.

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Country Link
CH (1) CH280195A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1068660B (en) * 1954-10-01 1959-11-12
DE1098909B (en) * 1954-12-29 1961-02-09 Goodrich Co B F Process for the production of a leather-like laminate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1068660B (en) * 1954-10-01 1959-11-12
DE1098909B (en) * 1954-12-29 1961-02-09 Goodrich Co B F Process for the production of a leather-like laminate

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