US3185582A - Process for making and finishing artificial hides or leathers - Google Patents

Process for making and finishing artificial hides or leathers Download PDF

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Publication number
US3185582A
US3185582A US92170A US9217061A US3185582A US 3185582 A US3185582 A US 3185582A US 92170 A US92170 A US 92170A US 9217061 A US9217061 A US 9217061A US 3185582 A US3185582 A US 3185582A
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United States
Prior art keywords
lap
latex
bonded
water
water content
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
US92170A
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English (en)
Inventor
Alegre Antonio Albareda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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
Priority to DENDAT1288061D priority Critical patent/DE1288061B/de
Priority to FR1115866D priority patent/FR1115866A/fr
Priority to FR1115864D priority patent/FR1115864A/fr
Priority to DEA21751A priority patent/DE1204618B/de
Priority to US92170A priority patent/US3185582A/en
Application filed by Individual filed Critical Individual
Priority to FR888990A priority patent/FR81199E/fr
Priority to ES0275317A priority patent/ES275317A1/es
Priority to GB7777/62A priority patent/GB992261A/en
Priority to NL275386A priority patent/NL126058C/xx
Application granted granted Critical
Publication of US3185582A publication Critical patent/US3185582A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00Surface finishing of leather
    • C14C11/003Surface finishing of leather using macromolecular compounds
    • 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
    • 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
    • D06N3/0056Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • 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
    • D06N3/04Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D06N3/04Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/10Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/904Artificial leather

Definitions

  • the present invention relates to a process for making and finishing artificial hides or leathers.
  • the main object of this invention is to produce a material having characteristics similar to natural leather.
  • Porosity is a distinctive feature of natural leather and is the feature of natural leather which makes same preferred over plastic materials for many uses. I have found that by bonding and coating natural or synthetic fibers with a natural or synthetic latex, in the hereinafter described manner, useful materials can be attained, the characteristics or" feel and porosity of which are practically the same as those of natural leather.
  • textile fibers such as cotton, rayon, nylon, acetated fibers, etc., and their waste or combinations of same, are formed into Webs, e.g., in a carding engine, and by laying the Webs one over the other a lap is made of the desired thickness.
  • This lap may also be prepared in a machine commonly called a Curlator.
  • the lap of the desired thickness is dipped into a latex bath which is characterized by the ability to coagulate at atemperature in the range of from about 60 to about 80 C. and is of approximately the following composition:
  • the latex-impregnated lap obtained from the immersion in the latex bath then is heated to a temperature in the range of from about 60 to about 80 C. for a time period requisite to effect the coagulation of the latex and to bond the fibers of the lap together.
  • Any suitable means can be employed to effect the coagulation-efiecting heating of the lap.
  • the lateximpregnated lap is passed continuously through an oven, the inside temperature of whichis maintained at about 200 to 300 C., at a rate which allows the latex-impregnated lap to be heated to the aforementioned latexcoagulation conditions.
  • Coagulation can also be obtained by means of dielectric heating, hot contact, or infrared rays, etc. The object of the invention is not affected by the means for heating the impregnated lap.
  • a latex bath having substantially the above-characteristics is employed in order to achieve a final leather-like product of uniform properties.
  • Latices which coagulate much below 60 C., e.g., at about 40 C., are difficult to utilize in that premature coagulation in the latex bath preliminary to 3,185,582 Patented May 25, 1965 the impregnation of the lap is a problem.
  • latices which coagulate at much above 80 C. e.g., at about 95 C.
  • the increased tendency of water in the latex-impregnated lap to evaporate sets up convection currents in the latex solids dispersion which causes rubber particles therein to tend to migrate to the surface of the impregnated lap and coagulate there.
  • This migration deprives the fibers located within the interior of the lap of intended bonding material, whereby an inferior product which is likely to delaminate is obtained.
  • the impregnated lap loses part of its water by evaporation, but it still contains an appreciable proportion of that initially present, e.g., about 100 to about 300% by weight, based on the dry weight of the bonded lap, and the resultant water-containing bonded lap is squeezed through rolls or by press, neither the rolls nor the press being heated, to reduce the water content of the bonded lap, after which operation the material of reduced water content is dried at a temperature not above 120 C.
  • the material after squeezing and before drying, shall contain an amount of water of from to 50% of the total weight of such material so that, upon the evaporation of the water in the drying step, the spaces occupied by the water in said bonded material of reduced water content are superseded by air cells which, in the resultant dry artificial leather product, impart to it the characteristic of porosity.
  • the porous, bonded material when it is dry it is coated by means of aerographing, brushing, calender spreading or analogous methods, the coating, or paint, being prepared with casein containing plasticizers such as sulphoricina-ted oil, glycerine, dibutyl phthalate, etc., pigments to impart the desired color such as synthetic iron oxides, loading or filling materials to provide appropriate feel, such as titanium dioxide, lithopone, barium chloride, barium sulphate,
  • Coating materials prepared with the foregoing elements lack bonding power and resistance in order to avoid premature aging; and their abrasive resistance also usually has to be increased. All of these necessary properties are obtained by adding to the said coating materials aqueous dispersions of resins such as acrylonitrilebutadiene copolymers, butadiene-styrene copolymers, polyvinyl chloride, polymethyl-methacrylate, other poly- 1 meric derivatives of the acrylates, mixtures of said resins,
  • resins such as acrylonitrilebutadiene copolymers, butadiene-styrene copolymers, polyvinyl chloride, polymethyl-methacrylate, other poly- 1 meric derivatives of the acrylates, mixtures of said resins,
  • composition An example of a coating mixture, or paint, employed in the present invention may be prepared according to the following composition:
  • Pigments for example, synthetic iron oxides,
  • Dibutyl phthalate 20 to 35 After applying one coat of the paint on the porous artificial leather, another coat is applied, or two or three as circumstances require, in the latter instances with a paint similar to that described above but free of Wetting agent and characterized by a substantial or total reduction in glycerine or dibutyl phthalate content. As the coats are applied they are dried. When these coats are dry a lustre coat is applied which may be as follows:
  • Casein Parts by weight (dry) Casein (dissolved in water, 15 100 Resin (any one or a combination of those given above) 50 Plasticizer (sulphoricinated oil, for example) 25 to 60 Approximately 2% of formaldehyde or other antiferment is added to all these compositions to avoid posterior decomposition of the casein.
  • the lustre coating is dry, the resulting coated material is treated again with a 15% to 20% formaldehyde solution and thereafter dried at room temperature or in a drying chamber with hot air at 50 to 80 C. After such drying, the material is ironed at 70 to 80 C. for 5 to 30 seconds at a pressure of approximately from about 25 to about 50 kgs./cm
  • a coating e.g., based primarily on plasticized polyvinyl chloride free of casein, is applied to the porous, dry bonded lap prepared by the aforementioned impregnating, coagulating, squeezing and drying steps to provide an excellent leatherlike product.
  • polyvinyl chloride coating layer is the following:
  • the latex contained in the agglomerating mixture present in the impregnated fiber lap is coagulated by means of heat, and then the material is squeezed, eliminating water contained in the coagulated mass in a proportion which may represent from one to three times the weight of the artificial leather in dry condition.
  • the material After squeezing, the material must still contain from 20 to 50% of its weight in water.
  • the pressure exerted by the press or squeezing cylinders for squeezing the material after coagulation has to be adjusted so as to leave in the material a water content varying from 20 to 50% of the Weight of the material, according to the end uses for which the artificial leather is intended.
  • the material is dried, and once the drying is totally completed the material is suitable for receiving a coating of a weight ranging from 70 to 300 grams per square meter, approximately, and
  • the ultimate use of the artifical leather of the present invention does not necessarily require that it be porous, over the first PVC coating which is perfectly anchored on the agglomerated fibers to provide a material possessing the precisely desired degree of porosity, other coating layers may be applied, thus increasing the thickness thereof as desired.
  • a method for producing a substitute leather from a lap of fibers comprising impregnating said lap with a latex selected from the group consisting of natural latex, synthetic latex, and mixtures thereof, heating the resultant latex-impregnated lap at a temperature in the range of from about 60 to about C.
  • a method for producing a substitute leather from a lap of fibers consisting of impregnating said lap with a latex, heating the impregnated lap at a temperature in the range of from about 60 to about 80 C. for a time period sutiicient to coagulate the latex and bind the fibers of the lap together and to produce a bonded lap containing water in an amount appreciably above 50% by weight of said latex-impregnated lap, squeezing said water-containing bonded lap to reduce the water content thereof to a level in the range of from about 20 to about 50% by weight based on the dry weight of the lap, drying the resulting bonded lap of reduced water content at a temperature of about C.
  • said latex is selected from the group consisting of natural latex, synthetic latex, and mixtures thereof.
  • a method for producing a substitute leather from a lap of fibers consisting of impregnating said lap with a latex selected from the group consisting of natural latex, synthetic latex, and mixtures thereof,
  • resultingporous, dry lap with a plurality of coats including a first coat, intermediate coats, and a final coat,,of a resinous dispersion mixture comprising casein, a polymer selected from the group consisting of butadiene-styrene, butadiene-acrylonitrile, polyvinyl chloride, methylmethacrylate, and mixtures thereof, and pigments, fillers, and at least one plasticizer heating the coated lap after each coating to a temperature sufiicient to dry thecoating material and thereby provide a producthaving substantially the porosity of a similarly coated natural leather.
  • a resinous dispersion mixture comprising casein, a polymer selected from the group consisting of butadiene-styrene, butadiene-acrylonitrile, polyvinyl chloride, methylmethacrylate, and mixtures thereof, and pigments, fillers, and at least one plasticizer heating the coated lap after each coating to a temperature sufiicient to dry theco
  • a method for producinga substitute leather from a lap of fibers consisting of impregnating said lap with latex, heating the impregnated lap at a temperature in the range of about 60 to about 80 C. for a time period suflicient to coagulate the latex and bind the fibersof the lap together and, to produce a bonded lap containing Water in an amount appreciably above 50% by weight of said latex-impregnated lap, squeezing said water-containing bonded lap to reduce the water content" thereof toa level in the range of about 20 to about 50% by Weight based on the dry lap, drying the resulting bonded lap-of reduced water content at a temperature of about 120 coating material is deposited on said lap in a total amount C.
  • said latex is selected from the group consisting of natural latex, synthetic latex and mixtures thereof.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
US92170A 1953-12-17 1961-02-28 Process for making and finishing artificial hides or leathers Expired - Lifetime US3185582A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
DENDAT1288061D DE1288061B (de) 1961-02-28
DEA21751A DE1204618B (de) 1953-12-17 1954-12-16 Verfahren zum Behandeln der Oberflaeche von Kunstledern
FR1115866D FR1115866A (fr) 1953-12-17 1954-12-16 Procédé pour la finition de peaux ou cuirs artificiels fabriqués essentiellement avec des fibres naturelles ou synthétiques agglomérées par un latex naturel ou synthétique
FR1115864D FR1115864A (fr) 1953-12-17 1954-12-16 Procédé pour obtenir le durcissement des peaux ou cuirs artificiels
US92170A US3185582A (en) 1953-12-17 1961-02-28 Process for making and finishing artificial hides or leathers
FR888990A FR81199E (fr) 1961-02-28 1962-02-23 Procédé pour la finition de peaux ou cuirs artificiels fabriqués essentiellement avec des fibres naturelles ou synthétiques agglomérées par un latex naturel ou synthétique
ES0275317A ES275317A1 (es) 1961-02-28 1962-02-28 Procedimiento para la fabricaciën y acabado de cueros o pieles artificiales
GB7777/62A GB992261A (en) 1961-02-28 1962-02-28 A process for making and finishing artificial hides or leathers
NL275386A NL126058C (de) 1961-02-28 1962-02-28

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES21276153 1953-12-17
US92170A US3185582A (en) 1953-12-17 1961-02-28 Process for making and finishing artificial hides or leathers

Publications (1)

Publication Number Publication Date
US3185582A true US3185582A (en) 1965-05-25

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US92170A Expired - Lifetime US3185582A (en) 1953-12-17 1961-02-28 Process for making and finishing artificial hides or leathers

Country Status (6)

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US (1) US3185582A (de)
DE (2) DE1204618B (de)
ES (1) ES275317A1 (de)
FR (3) FR1115864A (de)
GB (1) GB992261A (de)
NL (1) NL126058C (de)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356517A (en) * 1963-12-17 1967-12-05 Scott Paper Co Heat coagulatable paper coating composition
US3376158A (en) * 1966-03-16 1968-04-02 Du Pont Process for producing microporous polymeric structures by freeze-coagulation of latices
US3483016A (en) * 1966-08-02 1969-12-09 United Shoe Machinery Corp Treatment of collagen fiber sheet
US3494781A (en) * 1966-12-20 1970-02-10 Shell Oil Co Process for producing a leather substitute
US3519459A (en) * 1964-09-23 1970-07-07 Ciba Ltd Process for producing finely porous coatings
US3524792A (en) * 1966-11-07 1970-08-18 Robert T Dawes Elastically-stretchable,leather-like material and method of making the same
US3620797A (en) * 1969-01-14 1971-11-16 Dhj Ind Inc Impregnation of a nonwoven fabric
US3874913A (en) * 1972-05-12 1975-04-01 Peter Frederick Lofts Method for making a nonwoven fabric
US3920868A (en) * 1971-10-22 1975-11-18 Hoechst Ag Process for the manufacture of a chemically bonded non-woven fiber material in sheet form
US3958057A (en) * 1974-06-28 1976-05-18 Kuraray Co., Ltd. Leather-like sheet material having excellent pearl-like tint and process for preparation thereof
US20050044647A1 (en) * 2002-09-20 2005-03-03 Colgate-Palmolive Company Oral care implement
US7836539B2 (en) 2002-08-09 2010-11-23 Colgate-Palmolive Company Oral care implement
US7841041B2 (en) 2002-08-09 2010-11-30 Colgate-Palmolive Company Oral care implement
US7845042B2 (en) 2002-08-09 2010-12-07 Colgate-Palmolive Company Oral care implement
US8091170B2 (en) 2002-08-09 2012-01-10 Colgate-Palmolive Company Oral care implement
US8151397B2 (en) 2002-08-09 2012-04-10 Colgate-Palmolive Company Oral care implement having flexibly supported cleaning elements extending in opposite directions
US8281448B2 (en) 2005-10-24 2012-10-09 Colgate-Palmolive Company Oral care implement having one or more moving sections
US8393042B2 (en) 2002-08-09 2013-03-12 Colgate-Palmolive Company Oral care implement
US8806695B2 (en) 2002-08-09 2014-08-19 Colgate-Palmolive Company Oral care implement having flexibly supported cleaning elements extending in opposite directions
US8876221B2 (en) 2002-08-09 2014-11-04 Colgate-Palmolive Company Oral care implement
US8990996B2 (en) 2002-08-09 2015-03-31 Colgate-Palmolive Company Toothbrush

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1290115B (de) * 1963-01-10 1969-03-06 Pfeiffer Richard Verfahren zur Herstellung von farbigen Vlieskunstledern
DE2621195C2 (de) * 1976-05-13 1982-10-14 Giulini Chemie Gmbh, 6700 Ludwigshafen Versteifungsmaterialien für Schuhe und Schuhteile
NL8600359A (nl) * 1986-02-13 1987-09-01 Polysar Financial Services Sa Latex, werkwijze voor de vervaardiging van een geconsolideerd vlies en geconsolideerde vliezen vervaardigd met de werkwijze.
CN110747297A (zh) * 2017-12-22 2020-02-04 海宁文硕科技咨询有限公司 改进型沙发革的制作方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1905749A (en) * 1929-09-17 1933-04-25 Brown Co Manufacture of artificial leather
US2064360A (en) * 1934-07-25 1936-12-15 Brown Co Manufacture of smooth-faced webs of interfelted fiber
US2191654A (en) * 1938-08-10 1940-02-27 Du Pont Leather finish
US2446806A (en) * 1941-06-12 1948-08-10 Bernard Andre Production of substitute leather
US2686764A (en) * 1951-11-09 1954-08-17 Du Pont Leather-finishing compositions containing caprolactam and a resinous polymer
US2696447A (en) * 1952-05-13 1954-12-07 Armstrong Cork Co Felt base floor covering
US2731358A (en) * 1952-11-10 1956-01-17 Armstrong Cork Co Plastic floor coverings and method for producing same
US2742377A (en) * 1952-05-13 1956-04-17 Armstrong Cork Co Flexible floor covering and method of making the same
CA607607A (en) * 1960-10-25 C. Wetterau Paul Decorative surface coverings
US3039913A (en) * 1959-05-04 1962-06-19 Little Inc A Reinforced resin sheet

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB535402A (en) * 1939-10-28 1941-04-08 Arthur Friedmann Improvements in or relating to artificial leather

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA607607A (en) * 1960-10-25 C. Wetterau Paul Decorative surface coverings
US1905749A (en) * 1929-09-17 1933-04-25 Brown Co Manufacture of artificial leather
US2064360A (en) * 1934-07-25 1936-12-15 Brown Co Manufacture of smooth-faced webs of interfelted fiber
US2191654A (en) * 1938-08-10 1940-02-27 Du Pont Leather finish
US2446806A (en) * 1941-06-12 1948-08-10 Bernard Andre Production of substitute leather
US2686764A (en) * 1951-11-09 1954-08-17 Du Pont Leather-finishing compositions containing caprolactam and a resinous polymer
US2696447A (en) * 1952-05-13 1954-12-07 Armstrong Cork Co Felt base floor covering
US2742377A (en) * 1952-05-13 1956-04-17 Armstrong Cork Co Flexible floor covering and method of making the same
US2731358A (en) * 1952-11-10 1956-01-17 Armstrong Cork Co Plastic floor coverings and method for producing same
US3039913A (en) * 1959-05-04 1962-06-19 Little Inc A Reinforced resin sheet

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356517A (en) * 1963-12-17 1967-12-05 Scott Paper Co Heat coagulatable paper coating composition
US3519459A (en) * 1964-09-23 1970-07-07 Ciba Ltd Process for producing finely porous coatings
US3376158A (en) * 1966-03-16 1968-04-02 Du Pont Process for producing microporous polymeric structures by freeze-coagulation of latices
US3483016A (en) * 1966-08-02 1969-12-09 United Shoe Machinery Corp Treatment of collagen fiber sheet
US3524792A (en) * 1966-11-07 1970-08-18 Robert T Dawes Elastically-stretchable,leather-like material and method of making the same
US3494781A (en) * 1966-12-20 1970-02-10 Shell Oil Co Process for producing a leather substitute
US3620797A (en) * 1969-01-14 1971-11-16 Dhj Ind Inc Impregnation of a nonwoven fabric
US3920868A (en) * 1971-10-22 1975-11-18 Hoechst Ag Process for the manufacture of a chemically bonded non-woven fiber material in sheet form
US3874913A (en) * 1972-05-12 1975-04-01 Peter Frederick Lofts Method for making a nonwoven fabric
US3958057A (en) * 1974-06-28 1976-05-18 Kuraray Co., Ltd. Leather-like sheet material having excellent pearl-like tint and process for preparation thereof
US7845042B2 (en) 2002-08-09 2010-12-07 Colgate-Palmolive Company Oral care implement
US8990996B2 (en) 2002-08-09 2015-03-31 Colgate-Palmolive Company Toothbrush
US10512323B2 (en) 2002-08-09 2019-12-24 Colgate-Palmolive Company Oral care implement
US9603441B2 (en) 2002-08-09 2017-03-28 Colgate-Palmolive Company Toothbrush
US7836539B2 (en) 2002-08-09 2010-11-23 Colgate-Palmolive Company Oral care implement
US7841041B2 (en) 2002-08-09 2010-11-30 Colgate-Palmolive Company Oral care implement
US9545148B2 (en) 2002-08-09 2017-01-17 Colgate-Palmolive Company Oral care implement
US7975346B2 (en) 2002-08-09 2011-07-12 Colgate-Palmolive Company Oral care implement
US8091170B2 (en) 2002-08-09 2012-01-10 Colgate-Palmolive Company Oral care implement
US8151397B2 (en) 2002-08-09 2012-04-10 Colgate-Palmolive Company Oral care implement having flexibly supported cleaning elements extending in opposite directions
US9167888B2 (en) 2002-08-09 2015-10-27 Colgate-Palmolive Company Oral care implement having flexibly supported cleaning elements extending in opposite directions
US8393042B2 (en) 2002-08-09 2013-03-12 Colgate-Palmolive Company Oral care implement
US8561247B2 (en) 2002-08-09 2013-10-22 Colgate-Palmolive Company Oral care implement
US8876221B2 (en) 2002-08-09 2014-11-04 Colgate-Palmolive Company Oral care implement
US8800093B2 (en) 2002-08-09 2014-08-12 Colgate-Palmolive Company Oral care implement
US8806695B2 (en) 2002-08-09 2014-08-19 Colgate-Palmolive Company Oral care implement having flexibly supported cleaning elements extending in opposite directions
US8839481B2 (en) 2002-08-09 2014-09-23 Colgate-Palmolive Company Oral care implement
US7047591B2 (en) 2002-09-20 2006-05-23 Colgate-Palmolive Company Oral care implement
US20050044647A1 (en) * 2002-09-20 2005-03-03 Colgate-Palmolive Company Oral care implement
US7458125B2 (en) 2002-09-20 2008-12-02 Colgate-Palmolive Company Oral care implement
US20070119010A1 (en) * 2002-09-20 2007-05-31 Hohlbein Douglas J Oral care implement
US8857919B2 (en) 2005-10-24 2014-10-14 Colgate-Palmolive Company Oral care implement having one or more moving sections
US8578546B2 (en) 2005-10-24 2013-11-12 Colgate-Palmolive Company Oral care implement having one or more moving pieces
US8281448B2 (en) 2005-10-24 2012-10-09 Colgate-Palmolive Company Oral care implement having one or more moving sections
US9271564B2 (en) 2005-10-24 2016-03-01 Colgate-Palmolive Company Oral care implement having one or more moving sections

Also Published As

Publication number Publication date
NL126058C (de) 1968-10-15
FR1115864A (fr) 1956-04-30
DE1204618B (de) 1965-11-11
FR1115866A (fr) 1956-04-30
ES275317A1 (es) 1962-07-16
FR81199E (fr) 1963-08-09
GB992261A (en) 1965-05-19
DE1288061B (de) 1969-01-30

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