US2994617A - Leather substitute - Google Patents

Leather substitute Download PDF

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Publication number
US2994617A
US2994617A US62037156A US2994617A US 2994617 A US2994617 A US 2994617A US 62037156 A US62037156 A US 62037156A US 2994617 A US2994617 A US 2994617A
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Prior art keywords
fibers
stratum
polyvinyl chloride
binder
parts
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James S Proctor
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US62037156 priority Critical patent/US2994617A/en
Priority to FR1183897D priority patent/FR1183897A/fr
Priority to DEP19593A priority patent/DE1143477B/de
Priority to GB3453757A priority patent/GB824476A/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
    • D06N3/0029—Stretchable fibres; Stretching of fibres during manufacture
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, 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
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0054—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by mechanical perforations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/904—Artificial leather
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10—Methods of surface bonding and/or assembly therefor
    • Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
    • Y10T156/1056—Perforating lamina
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
    • Y10T428/24322—Composite web or sheet
    • Y10T428/24331—Composite web or sheet including nonapertured component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24438—Artificial wood or leather grain surface
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • This invention relates to leather replacement materials, and more particularly to multi-layer, water-vapor permeable, scufi resistant sheet materials comprising a compressed interconnecting pore-containing layer of non- Woven matted fibers bound together with an extensible polymeric binder and adhered thereto a surface layer of a perforated, extensible, scuff-resistant polymeric material.
  • Stage A in the drawing represents a portion of a crosssection in greatly enlarged form of a non-woven mat of fibers 10.
  • Such mats, or bats as they are also called, the formation of which may be considered as the starting point in forming the base layer or stratum of the products of the invention, are readily prepared by known methods for laying down and interlacing fibers, such as the techniques used in wool carding and paper making.
  • the well-known felt making technique is followed by superposing a plurality of single webs or slivers of fibers from a carding machine in parallel or crosslapped piles. Added strength can be imparted to the fiber mats by passing them thru a needle loom. Needle looming tends to orient some of the fibers in a direction generally perpendicular to the surfaces of the mat as illustrated by fibers A in the drawing.
  • fibers can be used in preparing the non-woven mat.
  • suitable fibers are those made of synthetic linear polyamides such as polyhexamethylene adipamide, polyhexamethylene sebacamide, polycaproamide and interpolyamides; and polyesters, and polyesteramides, and mixtures or blends thereof such asdibasic diamide or amino acid polyamides, dibasic dihydroxy acid/polyester; and the intermixed polyester/polyamide products described in U.S. Patents 2,071,250, 2,071,251, 2,071,253, 2,130,948, 2,224,037 and 2,572,833 fall in this category of linear condensation polymers.
  • Fibers which can be used preferably as mixtures with fibers of the polyamide, polyester or polyesteramide types, include cotton, ramie, viscose rayon, acetate rayon, wool, polyacrylonitrile, acrylonitrile copolymers, polyurethanes, polyvinyl acetals and glass.
  • Preferred are the syntheic linear polyamide fibers.
  • the denier and the length of the fibers used in making the mats can be varied widely. Ordinarily, the length will he in the range of from about 0.01 inch up to 8 inches. About 1.5 inches is preferred. The denier will ordinarily be within the range of from 0.5 to denier per filament. About 3 denier is preferred.
  • step 1 in the drawing can be effected in any convenient manner.
  • the mat can be permeated with a solution or suspension of the binder.
  • the binder can be spread on to or distributed thruout the mat in the form of finely divided particles.
  • the binder is of a kind that can be made in sheet or film form, such sheets or films can be laid in contact with the fiber mats.
  • the binder is one that can be made in fiber form, fibers of the binder can be mixed with the fibers used to form the mat during the mat forming step.
  • Still another method involves the use of structural or mat forming fibers that have been coated with the binder material prior to forming the mat.
  • the extensible polymeric binder used can be any of a great variety of soft, elastic, initially thermoplastic (i.e., flows under the conditions of the subsequent hot pressing step), synthetic polymers which may be classified generally as elastomers. Care should be taken, however, to select a polymeric binder that is chemically different from the structural fiber used in making the non-woven mat. A convenient rule is that the binder when softened or melted in the subsequent hot pressing step be incompatible with the structural fibers. Additionally, the binder selected should be relatively fusible with respect to the structural fiber which, in terms of practical commercial op eration, means that the diiferential in the temperature at which the fiber and the binder soften and develop adhesive properties is preferably not substantially less than about 50 F. In other words, the binder should flow at a temperature at least 50 F. below the deformation temperature of the structural fiber.
  • extensible polymeric materials which can be used as binders in making the products of this invention are those classified as elastomers by H. L. Fisher in Industrial and Engineering Chemistry, August 1939,
  • polymers include the various vinylidene hydrocarbon polymers such as butadiene/styrene, polyisobutylene, polyisoprene, both synthetic and natural; the various negatively substituted polymers such as the vinylidene halide including vinyl.
  • halide polymers e.g., polyvinylidene chloride, polyvinyl chloride and polyvinyl fluoride; derivatives of such polymers as halogenated vinyl and vinylidene polymers, e.g., chlorinated polyethylene, and chlorinated polyvinyl chloride; the various vinylidene polymers wherein one or both of the indicated free valences of the 2-carbon of the vinylidene group are bonded to carboxyl groups, or groups hydrolyzable to carboxyl groups, either directly to the acyl carbon thereof (e.g. polymethyl acrylate) or to the oxy oxygen thereof (e.g., polyvinyl acetate); vinylidene carboxylic acids and their derivatives such as acrylic acid, acrylonitrile, and methacrylatnide.
  • halide polymers e.g., polyvinylidene chloride, polyvinyl chloride and polyvinyl fluoride
  • derivatives of such polymers as halogenated vinyl and
  • various copolymers of such vinylidene monomers including specifically the various monoene and diene copolymers of this class such as 2,3-dichlorobutadiene-1,3/2-chlorobutadiene-l,3 copolymers; the various.
  • monoenelvinylidene copolymers such as the commercially important vinyl and vinylidene chloride copolymers, e.g.,.vinyl chloride/ vinyl acetate, vinyl chloride/vinylidene chloride, and vinyl chloride/vinyl acetate/acrylonitrile copolymers; the various vinylidene hydrocarbon negatively substituted vinylidene copolymers, e.g., ethylene/vinyl acetate and, the hydrolyzed products therefrom; ethylene/vinyl chloride, and butadiene/acrylonitrile copolymers.
  • the commercially important vinyl and vinylidene chloride copolymers e.g.,.vinyl chloride/ vinyl acetate, vinyl chloride/vinylidene chloride, and vinyl chloride/vinyl acetate/acrylonitrile copolymers
  • the various vinylidene hydrocarbon negatively substituted vinylidene copolymers e.g., ethylene/vinyl
  • polyesters containing terephthalic acid or derivatives thereof as essential components are also useful as binder polymers. These include polyethylene terephthalate and copolyesters made from ethylene glycol, terephthalic acid and sebacic acid of the general type described and claimed in United States Patents Nos. 2,623,031 and 2,623,033 in the name of M. D. Snyder.
  • Polyamides useful as a binder polymer include N-methoxymethyl polyhexamethylene adipamide and other similar polymers disclosed and claimed in the United States Patent No. 2,430,860.
  • binder polymers are the polyvinyl acetals, such as polyvinyl butyral, polyvinyl laural, etc.
  • Still other elastomeric polymers which can be employed as binders in the present invention are the polyurethanes which are essentially reaction products of (1) an organic polyisocyanate or polyisothiocyanate with (2) a compound obtainable by reacting (a) one or more polyhydric alcohols with (b) one or more polycarboxylic acids (either in the presence or absence of one or more monocarboxylic acids).
  • Specified products of this type are described and claimed in United States Patent No. 2,333,639 to R. E. Christ and W. E. Hanford.
  • plasticizers for the binder polymers in the binder composition. This is particularly. important in the'case of the vinylidene resins. Plasticizers provide high pliability and desirable drape in products that might otherwise be too stiff. This is particularly true of the higher molecular weight, negatively substituted vinylidene polymers and copolymers, such as the vinyl chloride/vinylidene chloride and vinyl chloride/vinyl acetate copolymers.
  • plasticizers include the monoor dicarboxylic acid/ alcohol or/polyolesters such as glycol dibenzoate, dioctyl sebacate, dioctyl phthalate, and polypropylene sebacate; or the polyesters 'of the lower polyalkllene oxides such as methoxypolyethylene glycol octoate.
  • the weight ratio of binder polymer to structural fibers in the base layer is in general between 30:70 and 70:30, and more preferably, the binder amounts to from 40 to 60% by weight of the base layer.
  • Products made containing too low a quantity of binder polymer feel more like felt than leather and those containing too much binder are ordinarily stiff or brittle and hence undesirable.
  • the resulting composite is then hot-pressed, that is, it is heated under pressure, and then cooled to form a compacted unitary base structure in which the mat of fibers is substantially embedded in and the fibers thereof are bound by the binder polymer.
  • step 2 The hot-pressing and cooling operation is represented by step 2 in the drawing and the resulting structure is suitable v 4 represented by stage B which shows the fibers 10 that constitute the non-woven mate embedded in and bound by the binder 11.
  • the temperature used can be varied as desired keeping in mind the requirement that it must be high enough to cause the binder polymer to flow but not so high as to fuse or transpose the structural fibers of the non-woven mat appreciably.
  • This requirement also makes apparent the need, as indicated heretofore, in selecting the structural fiber and the binder to be used, to choose a fiber that is, with respect to the binder, relatively non-fusible, which in terms of. practical commercial operations means that the differential in the temperature at which the fiber and the binder soften and develop adhesive properties is preferably. not substantially less than about 50 F. With most combinations of fiber and binder a temperature in the range 200 C. are preferred.
  • the pressure used in the hot-pressing step can be varied widely to give the degree of compacting required. Ordinarily, the pressure applied will be between 50 psi. and 1500 psi, the higher pressures, of course, giving a more dense, tougher structure. For most uses it is preferable to prepare a compacted base stratum having a thickness from about 10 to 70 mils.
  • the hot-pressing step is ordinarily of short duration, in the order of 3 to 20 minutes depending upon the nature of the fiber and binder composition used, the temperature, and pressure, but other times can be used as may be desired with varied combinations of ingredients and processing conditions.
  • the hot-pressing step can be carried out using conventional apparatus.
  • the material to be processed can be passed between heated calender rolls under pressure or pressed between heated plates.
  • a surface coating of an extensible, abrasion resistant, polymeric material is then applied to at least one surface of the base stratum.
  • This surface coating operation is represented by step 3 in the drawing and the resulting coated structure is represented by stage C which shows a compacted mat of fibers 11 bound by binder 10 and coated on one surface with a coating 12.
  • any of the wide variety of extensible abrasion resistant polymeric materials that are compatible with the binder polymer can be used to provide the surface coating.
  • 11- lustrative of such materials are polyvinyl chloride, chlorosulfonated polyethylene such as described in McQueen US. Patent 2,212,786, polyurethanes such as described in Rodman US. 2,723,935, neoprene (polychlorobutadiene), polyacrylic esters (for example, isobutyl acrylate), N-methoxypolyadipamides, butadiene/acrylonitrile copolymers, polyvinyl chloride/ methyl methacrylate copolymers, and the like.
  • the same polymeric material perhaps with slight modifications such as added plasticizers, coloring agents, etc., is used in the surface layer as in the base stratum.
  • the most preferred of such polymeric materials is polyvinyl chloride.
  • the surface coating can be applied by any of the methods known in the art for applying coatings to sheet-like materials.
  • the coating material can be applied as a preformed film or a powder followed by heating, or
  • a surface layer or stratum having a total thickness of from about 1 to 20 mils and more preferably from about 1.5 to 5 mils.
  • the resulting composite is preferably heated under moderate pressure to remove any volatile solvents present, to level or to emboss the coating surface if desirable, and to improve adhesion of the surface coating polymer to the base stratum.
  • color can be imparted to the sheet material of this invention, if desired, by incorporating dyes or pigments into the surface coating composition, or in the binder for the fibers, or alternatively by dyeing the structural fibers prior to forming the nonwoven mat of fibers.
  • concentration of pigments is preferably kept below 5 to by weight of the total sheet in order to minimize the adverse effect on the physical properties of the sheet, particularly the tensile strength, the tear strength, and abrasion resistance of the sheet.
  • the sheet material of stage C, the surface coated bound fiber mat, is then treated to make it permeable to water vapor. This is done by perforating the surface coating to form channels that connect with interconnecting pores that are formed in the base stratum.
  • the interconnecting pores can be formed first according to any of the techniques described hereinafter and the surface coat subsequently perforated to form channels connecting therewith.
  • the surface coat is first perforated and the product so obtained is subsequently treated to form interconnecting pores in the base stratum.
  • the next step in preparing the sheet materials of this invention is to perforate the surface stratum (or strata, if both surfaces of the base stratum have been coated) as represented by step 4 in the drawing to obtain the product represented by stage D in which the surface layer 12 contains many perforations 13 in which the perforations extend completely thru the surface stratum 12 and part way into the base stratum.
  • the step of perforating the surface stratum can be carried out in conventional apparatus designed for making fine perforations in sheet materials and is preferably carried out using what is commonly known as a needle punching apparatus.
  • the punching apparatus is preferably adjusted so that the punches or needles will not extend more than about half way into the base stratum, and still more preferably, so that they will penetrate not more than about one-third the thickness of the base stratum.
  • the punches or needles can be adjusted so that they all penetrate to the same depth or, as illustrated in stage D in the drawing, they can be adjusted to provide varied degrees of penetration.
  • the number of punches or perforations made in the surface layer can vary widely, as desired, from about 300 to 30,000 or more per square inch depending largely upon the diameter of the perforations made, the degree of water vapor permeability desired, and the surface ap pearance sought. In the preferred products of the invention,.the perforations will be. in the range of from about 10,000 to.20,000 per square inch.
  • Needle diameter means the diameter of the needle measured at the top surface ofthe surface stratum at the time the needle has reached itsmaximum penetration. Thus if the tip of the needle is to be inserted 0.01 inch into the material being perforated, then the needle diameter is measured at apoint 0.01 inch from the tip.
  • sheet material of stage D is then treated to form interconnecting pores in the base stratum.
  • the binder polymer used is more extensible or stretchable than the structural fiber polymer is. to: stretch the sheet material as indicated by step 5 in the. drawing to obtain the product sheet material represented by stage E.
  • the stretching is ordinarily carried out by stretching the stage-D sheet material from 10 to 50% in one or more directions. This causes a substantial portion of the fibers in the base stratum to break away from the binder polymer. The result is that a network of channels or pores 14 are formed more or less contiguous with the fibers along a major portion of a substantial number of the fibers. Since the fibers in the base stratum are tightly compacted, there results an interconnecting of a substantial number of the channels or pores that are contiguous with adjacent or substantially touching or intersecting fibers. Porosity and water-vapor permeability is thereby imparted to the base stratum. Simril U.S. Patent 2,757,100 describes such a method in detail.
  • contiguous refers to channels or pores ad jacent to portions of fibers throughout the structure.
  • the channels are not necessarily completely annular.
  • the channel may spiral around part of the length of the fiber or may take the form of a hairline crack substantially parallel to or immediately adjacent to the fiber.
  • 'Ihey are formed by breaking away fibers from the binder, and this breaking away occurs especially at points where fibers cross or otherwise contact each other. In general such pores, channels, or cracks form a capillary network in the base stratum.
  • Another method for forming the interconnecting pores in the base stratum is first to soak the stage D sheet material in a liquid at a temperature above the softening temperature of the binder and below the softening temperature of the fibers to swell the fibers and deform the binder in the direction of swelling of the fibers.
  • the sheet material is then cooled to set the binder while the fibers remain in swelled condition.
  • the liquid is then removed from the swelled fibers whereupon the fibers shrink away from the binder to form channels or pores more or less contiguous with the fibers, much the same as is obtained by the stretching method.
  • Water is the liquid preferably used for swelling the fibers, although other liqudis can be used so long as they can be readily removed from the fibers and the surfaces of the treated materials. The liquid is most conveniently removed from the treated material by evaporation.
  • the interconnecting pores in the base stratum can be obtained by first forming the non-woven mat of a mixture of structural fibers with from 40 to 70% by volume of soluble fibers such as those made from polyvinyl alcohol, cellulose acetate, sodium alginate, or carboxymethyl cellulose, and then subsequently treating the sheet material with a liquid which is a solvent for the soluble fibers and a non-solvent for the structural fibers to dissolve the soluble fibers.
  • soluble fibers such as those made from polyvinyl alcohol, cellulose acetate, sodium alginate, or carboxymethyl cellulose
  • the sheet material of this invention is suitable for those uses in which leather is commonly used, for example, upholstery, luggage, handbags, gloves, boots, and shoe uppers, because of its high flex life, tensile strength, extensibility, and especially because of its scuff resistance.
  • the breathability, or permeability to water vapor and air, coupled with the scuif resistant properties make the sheet material of the invention especially suitable for making shoe uppers.
  • Example 1 Dyed staple fibers of polyhexamethylene adipamide (nylon) 1.5 inches long and 3 denier per filament, are
  • Polyvinyl chloride (Geon 121, a B. F. Goodrich Co. product) 55.5 Dioctyl phthalate 20.9 Dioctyl azelate 20.9 Stearic acid 0.5
  • the sprayed slivers are then superposed in a cross grain fashion to build up a pile of about 50 slivers having a weight of about 26 ozs./yd.
  • the structure is placed between a smooth steel plate and a perforated sheet of cellophane on a paper board pad and placed in a press for 12 minutes at 185 C. and 1200 p.s.i. to form a compacted fiber/binder sheet as a base structure.
  • the base structure After cooling under pressure the base structure is coated on one surface by spraying in three stages with a modified 3.37% solution of polyvinyl chloride (Geon 1211) in a 3/1/1 mixture of methyl ethyl ketone, methyl isobutyl ketone and acetone.
  • a modified 3.37% solution of polyvinyl chloride (Geon 1211) in a 3/1/1 mixture of methyl ethyl ketone, methyl isobutyl ketone and acetone.
  • the first spray solution contains 37.5 parts of dioctyl phthalate, 37.5 parts of dioctyl azelate, 40 parts of burnt sienna pigment and 4 parts of a vinyl stabilizer (Barca 10) per 100 parts of the polyvinyl resin;
  • the second spray solution contains 33 parts of plasticizer polypropylene sebacate (ParapleX G-25, a Rhom and Haas Co.
  • the third spray solution contains 33 parts of polymethyl methacrylate, 1.4 parts of stearic acid and 6.6 parts of a silica flatting agent (Santocel silica aerogel, a Monsanto Chemical Company product) to 100 parts of the polyvinyl resin.
  • a total topcoat or surface stratum thickness of about 4 mils is applied.
  • the coated sheet material is dried and then pressed at 150 C. and 800 p.s.i. for 5 minutes and cooled under pressure.
  • the surface coating is needle-punched with 10,000 holes per sq. in. to a depth of about 5 to 7 mils.
  • the structure is then stretched 25% in two directions, 90 to each other, to form interconnecting pores in the base stratum connecting with the perforations in the surface stratum.
  • the product of this example is about 40 mils thick.
  • the leather replacement material of thie example is suitable for making shoe uppers, gloves, upholstery, and the like. It is scuff resistant and has breathability. A numerical measure of the breathability of the product was obtained by measuring its water vapor permeability to obtain a so-called leather permeability value, or LPV, according to the test described by Kanagy and Vickers in Journal of American Leather Chemists Association, 45, 211-242 (April 19, 1950).
  • this test for determining LPV involves covering a small dish or cup, such as a crystallizing dish, filled with 12 mesh calcium chloride with the product to be tested and then suspending the container in an inverted position in an atmosphere of 90% relative humidity and a temperature of 23 C.
  • the increase in weight of the calcium chloride provides a measure of the moisture vapor permeability of the substance under test.
  • the LPV is expressed in terms of grams of Water per 100 square meters of substance under test per hour. It has been determined from prior experience that an LPV of over 1500 grams of water per 100 square meters per hour is necessary for comfort in shoe uppers.
  • the product of the present example has an-LPV of 2000.
  • Example 2 Viscose rayon staple, 1.5" long 3 denier per filament pre-sized with 3.0% dry weight of a silicone oil (DC1107), and a crimped polyadipamide (nylon) staple, 1.5 long, 3 denier per filament, pre-sized with 1% by dry weight of an alkyl aryl polyether alcohol (Triton X- l00) are carded together on a conventional combination garnetting and cross-lapping machine to form a uniform non-woven sliver containing 60 parts of nylon and 40 parts of rayon fiber and weighing about 2.5 oz. per square yard. The sliver is then sprayed with an organosol binder of the following composition to a dry weight pick-up of and dried 2 hours at 240 F.
  • an organosol binder of the following composition to a dry weight pick-up of and dried 2 hours at 240 F.
  • the dried sprayed sliver is then cross lapped to form six plies and pressed between cellophane sheets for 12 minutes at 185 C. and 1200 p.s.i. followed by cooling under pressure.
  • one side of the resulting compacted base stratum is coated by spraying on in three stages a modified 3.37% solution of polyvinyl chloride in a 3/1/1 mixture of methyl ethyl ketone, methyl isobutyl ketone and acetone.
  • the sheet material is then repressed for 5 minutes at C. and 800 p.s.i. and cooled under pressure.
  • the second coat (depth coat), applied at 0.8 oz./ sq. yd., contains as modifiers for each 100 parts of the polyvinyl chloride, 33 parts of a polyester plasticizer (P-araplex G-25) and 1.5 parts of stearic acid.
  • the final (gloss) coat, applied at 0.14 oz./sq. yd., contains as modifiers for each 100 parts of the polyvinyl chloride, 33 parts of polymethyl methacrylate (Lucite 41 acrylic resin, E. I. du Pont de Nemours & Co.), 7 parts of a flatting agent (Santocel) and 1 part of stearic acid.
  • a decorative surface pattern is obtained in an embossing operation by heating for 5 minutes at 150 C. and 800 p.s.i., and then cooling under pressure.
  • the coated surface of the sheet is then perforated to provide 10,000 holes per sq. in. to a depth of 5-7 mils and then the sheet is stretched 25 in each of two directions, 90 to each other, to provide interconnecting pores in the substrate connecting with the perforated top layer.
  • the product has a thickness of about 50 mils and an LPV of 2500.
  • Example 3 Staple fibers of polyhexamethylene adipamide (nylon), 1.5 inches long and 3 denier filament, are carded to form a web or mat using a conventional wool carding method.
  • the web is sprayed with a solution consisting of the following.
  • the four-ply structure is placed betweensheets of cellophane and pressed for minutes at 175 C. and 500 pounds/ square inch to form a compactedfiber-binder'non-woven mat as a base stratum.
  • This base stratum contains about 50% of the polyvinyl chloride binder.
  • the polyvinyl chloride solution-tabulated above is then sprayed on the surface of the base stratum to provide a surface layer or stratum having a thickness of 1.7 mils.
  • the coated structure is then pressed for 5 minutes at 140 C. and 500 pounds/square inch using an embossing plate to impart a graining effect to the surface.
  • the resulting structure is stretched'40% in two directions at right angles to'each other to make the base stratum permeable.
  • the top layer isthen needle punched to provide 450 perforations per square inch.
  • the perforations are about 3 to 5 mils in diameter atthe surface and about 9 mils deep.
  • the total thickness of the sheet material is about 25 mils and the thickness of the surface layer is 1.7 mils; therefore, the perforations extend into the base stratum about 7 mils or about 30% of the thickness of the base stratum.
  • the leather replacement product of this example is suitable for making shoe uppers. It has an LVP of'3300.
  • the product of this example hasoutstanding scuff resistance.
  • a numerical measure of scuff resistance is obtained using an eccentric wheel scuff test.
  • the test instrument used in this test consists of two wheels. One is a non rotatable wheel, 6 inches in diameter and 1' inch wide. The second wheel is a 4 inch diameter, 1 inch thick felt disk mounted so as to rotate about anofl-center axis. The smaller wheel is so arranged that at itsmaximum displacement it abrades strongly against the larger non-rotatable wheel.
  • the sample to be tested is placed on the periphery of the non-rotatable wheel. A single rotation of the off-center wheel is referred to as a scuff.
  • the product of this example shows no fuzzing after being subjected to one thousand scufis.
  • Example 4* A non-woven mat of polyhexamethylene adipamide fibers is made by cross lapping 4 carded webs of such fibers.
  • the non-woven mat is sprayed with a solution consisting of the following:
  • the sprayed mats are dried and pressed at about 180 C. and 750 pounds/ square inch for 5 minutes and allowed to cool under said pressure.
  • the resulting polyvinyl chloride bound non-woven fiber mat contains 45% polyvinyl chloride.
  • the compacted polyvinyl chloride bound non-woven mat is then coated on one surface by spraying in three stages with a modified 5% solution of polyvinyl chloride in a 75/25 mixture of methyl ethyl ketone and methyl isobutyl ketone.
  • the first spray solution (the color coat) contains 37.5 parts of dioctyl sebacate, 40 parts of pigment, 4 parts of a stabilizer and 1 palt of lubricant;
  • the second spray solution (the depth coat) contains '33 parts of a high molecular weight polypropylene sebacate and one part of lubricant;
  • the third spray solution (the gloss coat) contains 33.3 parts of polymethyl methacrylate, 1.4 parts of lubricant and 6.6 parts of a flatting agent.
  • the surface coated structure is then pressed at 140 C. under a pressure of 500 pounds/ square inch for 2 minutes and cooled under pressure. Ihestructure'is then stretched 25% in two directionsto 'form pores in the base-st'ratum.
  • the surface coating is needle-punched between 25 00 and 5000 times per square inch using needles giving perforations of 3 to 5 mils in diameter at the surface of the mate'- rial. The perforations so obtained pass completely thru the 4-mil thick surface coat and into the base stratum.
  • the total thickness of the product of this example is 30 mils.
  • the product of. this example has an LPV of 2690 and is suitable for use in making shoe uppers, gloves, upholstery, and the like.
  • Example 5 Four carded polyhex-amethylene adipamide webs are sprayed with a solution consisting of the following ingredients:
  • the sprayed webs are cross-lapped and then consolidated by pressing for 5 minutes at 175 C. and 500 pounds/square inch.
  • the compacted bound non-woven base stratum structure obtained contains 45% polyvinyl chloride.
  • Three coats areappliedto the coated structure and the composite is pressed at 110 C. and 700 pounds/ square inch.
  • Eachof these three additional coats contains parts of polyvinyl chloride, 1500 parts of methyl ethyl ketone, 500 parts of methyl isobutyl ketone, and one or more modifying agents.
  • The-first of these coats contains as the modifying agents 50 parts of dioctyl phthalate, 50 parts of dioctyl sebacate, 4 parts of stabilizer, 5 parts of pigment, 4 parts of dye, and0.l part of" anti-foaming agent; in the second (the depth coat)'themodifying agents were 15 parts of dioctyl sebacate, 35 parts of a highmolecular weight polyester plasticizer' Paraplex G 25 and" 4 parts of lubricating agent' stearic acid; andthe modifier inthe third coat (a final gloss coat) was 7 parts of the flatting agent Santoeel and 33 parts of polymethyl methacrylate. The total surface coating after final pressing was 3' mils thick.
  • the surface coated structure is then stretched 25% in each of two directions to form pores in the base stratum.
  • the surface is then needle punched to provide 500 perforations per square inch.
  • the perforations are about 5 mils in diameter at the surface and from about 3 to 5 mils deep.
  • the product sheet is 40 mils thick.
  • the product of this example has an LPV of 1990. It is send resistant and has flex-strength and other properties making it suitable for use in shoe uppers.
  • Example 0' Six carded slivers of a Triton presized Dacron polyester 1 /2" staple fiber are alternately stacked with an equal weight of .0025 thick calendered vinyl films having the following composition:
  • Vinyl chloride/vinyl acetate resin (VYNW-5 Bake- The stack is then placed in a press between smooth Polyacrylonitrile fibers (Orlon acrylic fiber) of l denier per filament and 2 /2" long are carded on conventional equipment to give crosslapped sliver weighing 2.2 oz./sq. yd. and then sized with 4.0% by dry weight of a silicone oil (DC1107) from a methyl ethyl ketone solution. The slivers are then layered alternately with an equal weight of a binder of the following composition in thin films to a total of 25 oz./sq. yd.:
  • Polyvinyl butyral resin 70 Urea-formaldehyde resin (RC718) 10 Burnt sienna 10 Dibutyl Cellosolve sebacate 10 This sheet isneedle punched, stretched 20% in two directions and abraded on the unfinished side. A soft pliable leather-like sheet of 42 mils thickness and LPV of l300 results. V
  • a process for making a-water vapor-permeable, scufl-resistant, flexible sheet material suitable for use as a leather replacement whichcomprises bringing together a non-woven mat of polyhexamethylene adipamide fibers and a polyvinyl chloride plastisol ina polyvinyl chloride: fiber weight ratio of from about 30:70 to 70:30, forming -a compacted base stratum in which the said mat of fibers is substantially embedded in and the fibers thereof are bonded by the polyvinyl chloride by heating the resulting mixture at 150- C.-200 C.
  • a water vapor-permeable, scuff-resistant, flexible leather replacement sheet material comprising a base stratum having a surface stratum adhered to at least one surface thereof, said base stratum being a compressed layer'having a network of interconnecting pores and comprising as essential constituents a mat of non-woven synthetic linear polyamide fibers substantially embedded in and the fibers thereof bound together with a vinylidene polymer, the vinylidene polymerzfiber weight ratio being from 30:70 to :30, and said surface stratum comprising a vinylidene polymer film having from 300-30,000 perforations of l10 mils diameter per sq. in. connecting with pores in said base stratum.
  • a water vapor-permeable, scufi resistant, flexible leather replacement sheet material comprising a base stratum having a surface stratum adhered to one surface thereof, said base stratum being a compressed layer having a network of interconnecting pores and comprising .as essential constituents a mat of non-woven polyhexamethylene adipamide fibers substantially embedded in and the fibers thereof bound together withpolyvinyl chloride, the polyvinyl chloridezadipamide fiber weight ratio being from 30:70 to 70:30, and said surface stratum comprising a polyvinyl chloride film having from 300-30,000 perforationsof 1-10 mils diameter therein connecting with pores in said basestratum.
US62037156 1956-11-05 1956-11-05 Leather substitute Expired - Lifetime US2994617A (en)

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Application Number Priority Date Filing Date Title
US62037156 US2994617A (en) 1956-11-05 1956-11-05 Leather substitute
FR1183897D FR1183897A (fr) 1956-11-05 1957-10-04 Procédé de fabrication d'un produit de remplacement du cuir
DEP19593A DE1143477B (de) 1956-11-05 1957-11-04 Wasserdampfdurchlaessiges, scheuerfestes, biegsames Kunstleder
GB3453757A GB824476A (en) 1956-11-05 1957-11-05 Improvements in or relating to the production of leather replacement materials

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Cited By (20)

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US3232819A (en) * 1960-05-23 1966-02-01 Kendall & Co Breathable structures
US3245854A (en) * 1961-03-23 1966-04-12 West Point Mfg Co Process of manufacturing nonwoven fabrics
US3255061A (en) * 1962-04-20 1966-06-07 Us Rubber Co Process for making synthetic leather-like material
US3258511A (en) * 1961-12-22 1966-06-28 Mobay Chemical Corp Process for the manufacture of upholstery
US3293095A (en) * 1962-10-10 1966-12-20 Formica Corp Method of producing oil absorptive laminates
US3413179A (en) * 1966-12-28 1968-11-26 Dunlop Rubber Co Flexible sheet material and method for making same
US3451885A (en) * 1962-07-09 1969-06-24 Union Carbide Corp Needled composite web and method of making the same
US3511747A (en) * 1963-03-01 1970-05-12 British Nylon Spinners Ltd Bonded textile materials
US3619316A (en) * 1967-11-15 1971-11-09 Nippon Cloth Industry Co Ltd Process of making porous, bonded fibrous web
US3627567A (en) * 1968-07-27 1971-12-14 Kanegafuchi Spinning Co Ltd Leatherlike material and process of making same
US3657034A (en) * 1968-09-20 1972-04-18 Kurashiki Rayon Co Method of producing sheet materials similar to leather
US3880966A (en) * 1971-09-23 1975-04-29 Celanese Corp Corona treated microporous film
US4009315A (en) * 1966-07-05 1977-02-22 Tenneco Chemicals, Inc. Chemical compositions and process
US4438167A (en) 1979-10-15 1984-03-20 Biax Fiberfilm Corporation Novel porous fabric
US4534994A (en) * 1983-05-03 1985-08-13 Gerhard Feld Process for making fine perforations in plastic sheeting and/or plastic or rubber coated sheet materials
US20070082176A1 (en) * 2003-11-15 2007-04-12 Basf Aktiengesellschaft Substrate provided with a dressing
EP2386399A1 (de) * 2010-04-23 2011-11-16 Albert Ehni GmbH Verfahren zum Einbringen von Löchern in eine wasserdichte Beschichtung
US20140363625A1 (en) * 2013-06-11 2014-12-11 Chen-Cheng Huang Breathable and waterproof composite fabric
US10391736B2 (en) 2013-06-11 2019-08-27 Chen-Cheng Huang Breathable and waterproof composite fabric and a method of making the same
US20210268765A1 (en) * 2005-07-15 2021-09-02 Aspen Aerogels, Inc. Inherently secured aerogel composites

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NZ225978A (en) * 1987-09-11 1990-07-26 Reemay Inc Microporous composite barrier fabric for use in building structures
WO1989010997A1 (en) * 1988-05-03 1989-11-16 Ivan Thomas Fucik Perspiration-absorbing materials

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US2647065A (en) * 1950-05-18 1953-07-28 William M Scholl Apparatus for and method of making adhesive tape
US2673171A (en) * 1951-03-02 1954-03-23 Bellavoine Leon Method of making a composite sole leather and product
GB730221A (en) * 1951-11-19 1955-05-18 Hans Eberle Dr Improvements in or relating to artificial leather
US2715588A (en) * 1952-12-16 1955-08-16 Du Pont Leatherlike products and preparation of same
US2757100A (en) * 1952-11-04 1956-07-31 Du Pont Process for forming permeable sheet material
US2772995A (en) * 1954-05-07 1956-12-04 Du Pont Leather replacement compositions and process
US2787572A (en) * 1952-10-24 1957-04-02 Malloran Corp Method of making a resin-treated elastomer mat

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DE884489C (de) * 1944-04-18 1953-07-27 Basf Ag Verfahren zur Herstellung von Kunstleder
FR1006368A (fr) * 1949-01-08 1952-04-22 Procédé de fabrication et de conformation de nappes de matières fibreuses, tissusou produits analogues, imprégnés ou collés
DE824632C (de) * 1950-01-20 1951-12-13 Dr Hans Eberle Verfahren zur Herstellung von poroesem Kunstleder
DE870989C (de) * 1950-01-20 1953-03-19 Hans Dr Eberle Verfahren zur Herstellung von geschmeidigem, luftdurchlaessigem Kunstleder

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US2051888A (en) * 1930-11-22 1936-08-25 Raybestos Manhattan Inc Friction material and process of manufacturing same
US2647065A (en) * 1950-05-18 1953-07-28 William M Scholl Apparatus for and method of making adhesive tape
US2673171A (en) * 1951-03-02 1954-03-23 Bellavoine Leon Method of making a composite sole leather and product
GB730221A (en) * 1951-11-19 1955-05-18 Hans Eberle Dr Improvements in or relating to artificial leather
US2787572A (en) * 1952-10-24 1957-04-02 Malloran Corp Method of making a resin-treated elastomer mat
US2757100A (en) * 1952-11-04 1956-07-31 Du Pont Process for forming permeable sheet material
US2715588A (en) * 1952-12-16 1955-08-16 Du Pont Leatherlike products and preparation of same
US2772995A (en) * 1954-05-07 1956-12-04 Du Pont Leather replacement compositions and process

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3232819A (en) * 1960-05-23 1966-02-01 Kendall & Co Breathable structures
US3245854A (en) * 1961-03-23 1966-04-12 West Point Mfg Co Process of manufacturing nonwoven fabrics
US3258511A (en) * 1961-12-22 1966-06-28 Mobay Chemical Corp Process for the manufacture of upholstery
US3255061A (en) * 1962-04-20 1966-06-07 Us Rubber Co Process for making synthetic leather-like material
US3451885A (en) * 1962-07-09 1969-06-24 Union Carbide Corp Needled composite web and method of making the same
US3293095A (en) * 1962-10-10 1966-12-20 Formica Corp Method of producing oil absorptive laminates
US3511747A (en) * 1963-03-01 1970-05-12 British Nylon Spinners Ltd Bonded textile materials
US4009315A (en) * 1966-07-05 1977-02-22 Tenneco Chemicals, Inc. Chemical compositions and process
US3413179A (en) * 1966-12-28 1968-11-26 Dunlop Rubber Co Flexible sheet material and method for making same
US3619316A (en) * 1967-11-15 1971-11-09 Nippon Cloth Industry Co Ltd Process of making porous, bonded fibrous web
US3627567A (en) * 1968-07-27 1971-12-14 Kanegafuchi Spinning Co Ltd Leatherlike material and process of making same
US3657034A (en) * 1968-09-20 1972-04-18 Kurashiki Rayon Co Method of producing sheet materials similar to leather
US3880966A (en) * 1971-09-23 1975-04-29 Celanese Corp Corona treated microporous film
US4438167A (en) 1979-10-15 1984-03-20 Biax Fiberfilm Corporation Novel porous fabric
US4534994A (en) * 1983-05-03 1985-08-13 Gerhard Feld Process for making fine perforations in plastic sheeting and/or plastic or rubber coated sheet materials
US20070082176A1 (en) * 2003-11-15 2007-04-12 Basf Aktiengesellschaft Substrate provided with a dressing
US8211529B2 (en) * 2003-11-15 2012-07-03 Basf Aktiengesellschaft Substrate provided with a dressing
US20210268765A1 (en) * 2005-07-15 2021-09-02 Aspen Aerogels, Inc. Inherently secured aerogel composites
EP2386399A1 (de) * 2010-04-23 2011-11-16 Albert Ehni GmbH Verfahren zum Einbringen von Löchern in eine wasserdichte Beschichtung
US20140363625A1 (en) * 2013-06-11 2014-12-11 Chen-Cheng Huang Breathable and waterproof composite fabric
US9713914B2 (en) * 2013-06-11 2017-07-25 Chen-Cheng Huang Breathable and waterproof composite fabric
US10391736B2 (en) 2013-06-11 2019-08-27 Chen-Cheng Huang Breathable and waterproof composite fabric and a method of making the same

Also Published As

Publication number Publication date
FR1183897A (fr) 1959-07-15
DE1143477B (de) 1963-02-14
GB824476A (en) 1959-12-02

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