WO1989008554A1 - Bandes textiles avec revetement interne en polymere de silicone - Google Patents

Bandes textiles avec revetement interne en polymere de silicone Download PDF

Info

Publication number
WO1989008554A1
WO1989008554A1 PCT/US1989/001008 US8901008W WO8908554A1 WO 1989008554 A1 WO1989008554 A1 WO 1989008554A1 US 8901008 W US8901008 W US 8901008W WO 8908554 A1 WO8908554 A1 WO 8908554A1
Authority
WO
WIPO (PCT)
Prior art keywords
web
silicone polymer
fabric
impregnant
fibers
Prior art date
Application number
PCT/US1989/001008
Other languages
English (en)
Inventor
James Michael Caldwell
Original Assignee
Sili-Tex, Inc.
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 claimed from US07/319,778 external-priority patent/US5004643A/en
Application filed by Sili-Tex, Inc. filed Critical Sili-Tex, Inc.
Publication of WO1989008554A1 publication Critical patent/WO1989008554A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51456—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties
    • A61F13/51458—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable
    • A61F13/51462—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable being defined by a value or parameter
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/01—Non-adhesive bandages or dressings
    • A61F13/01008—Non-adhesive bandages or dressings characterised by the material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51401—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material
    • A61F13/51405—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material treated or coated, e.g. with moisture repellent agent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/52—Water-repellants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C3/00—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material
    • B05C3/18—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material only one side of the work coming into contact with the liquid or other fluent material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-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
    • D04H1/42—Non-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
    • D04H1/4209—Inorganic fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-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
    • D04H1/42—Non-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
    • D04H1/425—Cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-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
    • D04H1/42—Non-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
    • D04H1/4266—Natural fibres not provided for in group D04H1/425
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B15/00—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
    • D06B15/08—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours by scraping
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/657—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing fluorine
    • 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
    • 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
    • D06N3/04—Artificial 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
    • D06N3/047—Artificial 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 fluoropolymers
    • 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
    • D06N3/12—Artificial 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
    • 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
    • D06N3/12—Artificial 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
    • D06N3/128—Artificial 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 silicon polymers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F2013/00089—Wound bandages
    • A61F2013/00119—Wound bandages elastic
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F2013/00089—Wound bandages
    • A61F2013/00246—Wound bandages in a special way pervious to air or vapours
    • A61F2013/00255—Wound bandages in a special way pervious to air or vapours with pores
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F2013/00361—Plasters
    • A61F2013/00727—Plasters means for wound humidity control
    • A61F2013/00731—Plasters means for wound humidity control with absorbing pads
    • A61F2013/00744—Plasters means for wound humidity control with absorbing pads containing non-woven
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F2013/00361—Plasters
    • A61F2013/00855—Plasters pervious to air or vapours
    • A61F2013/00863—Plasters pervious to air or vapours with pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/02—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface
    • B05C11/04—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface with blades
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention generally concerns porous fibrous webs (especially fabrics) that are modified in their properties by incorporation thereinto an internal layer of silicone polymer. Such webs are prepared by pressurized impregnation methods.
  • U.S. Patent Nos. 3,436,366; 3,639,155; 4,472,470; 4,500,584; and 4,666,765 disclose silicone coated fabrics. Silicone coatings are known to exhibit relative inertness to extreme temperatures of both heat and cold and to be relatively resistant to ozone and ultraviolet light. Also, a silicone coating can selectively exhibit resistance to soiling, strength enhancement, and/or flame retardancy. Fluorochemical treatment of webs is known to impart properties, such as soil resistance, grease resistance, and the like.
  • Prior art fluorochemical and silicone fabric treatment evidently each can protect only that side of the fabric upon which they are disposed. Such treatments characteristically significantly alter the hand, or tactile feel, of the treated side.
  • Prior silicone fabric coatings typically degrade the tactile finish, or hand, of the fabric and give the coated fabric side a rubberized finish which is not appealing for many fabric uses, particularly garments.
  • U.S. Patent No. 4,454,191 describes a waterproof and moisture-conducting fabric coated with a hydrophilic polymer.
  • the polymer is a compressed foam of an acrylic resin modified with polyvinyl chloride or polyurethane and serves as a sort of "sponge" soaking up excess moisture vapor.
  • microporous polymeric coatings have been used in prior art attempts to make a garment breathable, yet waterproof.
  • U.S. Patent No. 2,673,823 teaches impregnating a polymer into the interstices of a fabric and thus fully filling the interstices. This patent provides no control of the saturation of the fabric. It teaches full saturation of the interstices of the fabric.
  • liquid or paste compositions to textiles for purposes of saturation and/or impregnation is typically accomplished by an immersion process.
  • an immersion application of a liquid or paste composition to the web is achieved, for example, by the so-called padding process wherein a fabric material is passed first through a bath and subsequently through squeeze rollers in the process sometimes called single-dip, single-nip padding.
  • the fabric can be passed between squeeze rollers, the bottom one of which carries the liquid or paste composition in a process sometimes called double-dip or double-nip padding.
  • One prior art silicone resin composition is taught by U.S. Patent Nos. 4,472,470 and 4,500,584, and includes a vinyl terminated polysiloxane, typically one having a viscosity of up to about 2,000,000 centipoises at 25°C, and a resinous organosiloxane polymer.
  • the composition further includes a platinum catalyst, and an organohydrogenpolysiloxane crosslinking agent, and is typically liquid.
  • Such composition is curable at temperatures ranging from room temperature to 100°C or higher depending upon such variables as the amount of platinum catalyst present in the composition, and the time and the temperature allowed for curing.
  • Such compositions may additionally include fillers, including finely divided inorganic fillers.
  • Fillers including finely divided inorganic fillers.
  • Silicone resin compositions that are free of any fillers are generally transparent or translucent, whereas silicone resin compositions containing fillers are translucent or opaque depending upon the particular filler employed.
  • Cured silicone resin compositions are variously more resinous, or hard, dependent upon such variables as the ratio of resinous copolymer to vinyl terminated polysiloxane, the viscosity of the polysiloxane, and the like.
  • This invention relates to a flexible porous web which contains an internal coating of a silicone polymer composition.
  • the webs can comprise fibers in the form of monofilaments, yarns, staples, or the like.
  • the web can also be comprised of a matrix having open cells or pores therein.
  • the web may be a fabric which is woven or non- woven with fibers that can be of any desired composition.
  • the web will generally be tensionable, but not too weak or elastomeric to be processed in accordance with the teachings of the present invention.
  • the web fibers are preferably comprised of a synthetic organic polymer; however, fibers comprised of natural fibrous materials can be used.
  • Webs of the present invention contain a curable silicone polymer impregnant that is present as a film, or coating, or layer within a web that envelopes at least a portion of the fibers or cell or pore walls of the web.
  • the interstices or open cells in the region of the internal coating are mostly filled or plugged by impregnant.
  • the outer surfaces of the web are preferably substantially free of impregnant. However, the web remains breathable and is either water resistant or waterproof.
  • the thickness of the film, coating or layer is generally in the range of 0.01 to 50 microns.
  • a web of the present invention for example, a fabric
  • a web of the present invention can be regarded as being a complex structure, but generally the internal layer is discernable under microscopic examination as shown in the accompanying scanning electron microscope photographs that will be discussed hereinafter.
  • Silicone polymer which substantially, completely encapsulates a web's fibers or lines its cell or pore walls and forms an internal layer means, that the silicone polymer is located mostly upon surface portions of the interior of the web.
  • a web of the present invention preserves much, or even substantially all, of its original untreated hand even after an extended period of use while demonstrating excellent abrasion resistance.
  • an untreated web typically loses its original hand and displays reduced abrasion resistance after an extended period of use. This is achieved by the formation of an internal layer that prevents new fiber surfaces from being exposed, thereby minimizing the amount of untreated surfaces that degrade much faster than the treated fibers.
  • a web of this invention can undergo a large number of machine washings with detergent without experiencing appreciable or significant change or deterioration.
  • the silicone polymer composition prolongs the use and service life of a web, usually by at least an order of magnitude, depending on such factors as web type, extent and type of treatment by the teachings of this invention, and the like.
  • agents or additives carried by the silicone polymer composition into a web can be stably fixed in the web with the cured silicone polymer.
  • agents such as ultraviolet light absorbers, dulling agents, reflectivity enhancers, and the like, which modify a web's response to light and radiation are desirably located substantially upon the surfaces of the web's fibers.
  • Fig. 1 is a graphical plot illustrating the flow of the silicone polymer composition over time upon and in fabrics both pretreated and untreated with water repellent chemicals, such as fluorochemicals;
  • Fig. 2 is a plan view of a prior art silicone polymer treated fabric magnified 150 times;
  • Fig. 3a is a photomicrograph of a fabric of the invention magnified 120 times;
  • FIGs. 4a and 4b illustrate diagrammatically one embodiment of an apparatus suitable for use in the practice of the present invention
  • Fig. 5 is a diagrammatic representation illustrating the process in accordance with the present invention
  • FIG. 7 illustrates diagrammatically another embodiment of an apparatus suitable for use in the practice of the present invention
  • Figs. 8a through 8d are graphs illustrating ways of plotting rheological behavior
  • Fig. 9 is a schematic vector diagram illustrating surface tension forces
  • Figs. 11a through lid show representative velocity profiles
  • Figs. 12a through 12c illustrate diagrammatically another and presently preferred embodiment of apparatus suitable for use in the practice of the present invention.
  • Figs. 13a through 13c are scanning electron microscope photomicrographs of another representative fabric of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • filament refers a fiber of indefinite length.
  • a flexible porous web used as a starting material in this invention is generally and typically, essentially planar or flat and has generally opposed, parallel facing surfaces.
  • Such a web is a three dimensional structure comprised of a plurality of fibers with interstices therebetween or a matrix having open cells or pores therein.
  • the matrix can be comprised of polymeric solids including fibrous and non-fibrous elements.
  • Non-fibrous elements such as particulate fillers, binders, dyes, sizes and the like can be added to fibers in a web.
  • Preferred webs have at least about 85% of their structure comprised of fibrous or fiber materials and are untreated with any sizing agent, coating, or the like.
  • Two principal classes of substrates having open pores or cells may be utilized in the present invention: leathers (including natural leathers, and man-made or synthetic leathers) , and foamed plastic sheets (or films) having open cells.
  • Natural leathers suitable for use in this invention are typically split hides.
  • Synthetic leathers have wide variations in composition (or structure) and properties, but they look like leather in the goods in which they are used.
  • synthetic leathers can be divided into two general categories: coated fabrics and poromerics.
  • Synthetic leathers which are poromerics are manufactured so as to resemble leather closely in breathability and moisture vapor permeability, as well as in workability, machinability, and other properties.
  • the barrier and permeability properties normally are obtained by manufacturing a controlled microporous (open celled) structure.
  • interwoven refers to the forming of a film or layer located within a porous solid in a specified region, such as a planar region extending interiorly through a porous web or substrate in spaced, parallel relationship to a surface thereof.
  • a film or layer envelopes, and/or surrounds, and/or impregnates individual fibers or lines cell or pore walls of the porous web or substrate in the specified region.
  • envelope refers to the partial or complete surrounding, encasement, or enclosing by a discrete layer, film, coating, or the like, of exposed surface portions of at least some individual fiber or lining of a cell or pore wall of a porous web. Such a layer can sometimes be contiguous or integral with other portions of the same enveloping material which becomes deposited on internal areas of a web which are adjacent to such enveloping layer, enveloped fiber, lined cell or pore wall, or the like.
  • curing refers to a change in state, condition, and/or structure in a material, such as a curable silicone polymer composition that is usually, but not necessarily, induced by at least one applied variable, such as time, temperature, radiation, presence and quantity in such material of a curing catalyst or curing accelerator, or the like.
  • a flexible, porous fibrous web is preferably untreated or scoured before being treated in accordance with the present invention.
  • a web is preliminarily treated, preferably saturated, for example, by padding, to substantially uniformly impregnate the web with a fluorochemical.
  • the treating composition comprises a dispersion of fluorochemical in a liquid carrier.
  • the liquid carrier is preferably aqueous and can be driven off with heat after application.
  • the treating composition has a low viscosity, typically comparable to the viscosity of water or less. After such a treatment, it is presently preferred that the resulting treated web exhibits a contact angle with water measured on an outer surface of the treated web that is greater than about 90 degrees.
  • the treated web preferably contains fluorochemical substantially uniformly distributed therethrough. Thus, the fluorochemical is believed to be located primarily on and in the individual fibers, cells or pores with the web interstices or open cells being substantially free of fluorochemical.
  • a presently preferred concentration of fluorochemical in a treatment composition is typically in the range of about 1 to about 10% fluorochemical by weight of the total treating composition weight, and more preferably is about 2.5% of an aqueous treating dispersion.
  • Web weight add-ons of the fluorochemical can vary depending upon such factors as the particular web treated, the silicone polymer impregnant to be utilized in the next step of the treatment process of this invention, the ultimate intended use and properties of the treated web of this invention, and the like.
  • the fluorochemical weight add-on is typically in the range of about 0.01 to about 5% of the weight of the untreated web.
  • the. web is preferably squeezed to remove excess fluorochemical composition after which the web is heated or otherwise dried to evaporate carrier liquid and thereby also accomplish fluorochemical insolubilization or sintering, if permitted or possible with the particular composition used.
  • the fluorochemical treated web is thereafter impregnated under pressure by the procedures taught by this invention, with a predetermined amount of a curable silicone polymer impregnant composition to form a web whose fibers, cells or pores are at least partially enveloped or lined with the curable silicone polymer impregnant, whose web outer surfaces are substantially free of the curable impregnant, whose web interstices or open cells are not completely filled with the curable impregnant and which contains an internal layer of silicone polymer.
  • the curable impregnant composition utilized preferably exhibits a viscosity greater than 1,000 centipoise and less than 2,000,000 centipoise at rest at 25°C at a shear rate of 10 reciprocal seconds.
  • the depth of silicone polymer impregnation into a web can be .controlled by the application procedures herein described to provide a selective placement of the silicone polymer impregnant within the substrate or web. This allows the shear thinning, i.e., viscosity reduction, action to take place throughout the web.
  • the silicone polymer composition is theorized to be caused to flow and distribute itself over fibers, cells or pores in a web under the influence of the processing conditions provided by this invention. This flow and distribution is further theorized to be facilitated and promoted by the presence of a fluorochemical which has been preliminarily impregnated into a web, as taught herein.
  • the amount of fluorochemical or fluorochemical residue in a web is believed to influence the amount, and the locations, where the liquid silicone polymer impregnant will collect and deposit, and produce an internal coating in the web.
  • the silicone polymer film is contiguous, or substantially so, relative to fluorochemical molecules on a fiber surface, and that the layer of silicone polymer on a fiber surface is so thin that any dislodge ent of the fluorochemical may release the fluorochemical into the silicone polymer film thereby allowing the fluoroine to orient with the required cure temperature of the silicone, reactivating the water surface contact angle so that the water repellant properties of an underlying fluorochemical are exertable through the silicone poly er film.
  • silicone polymer film and fluorochemical results in a fiber envelopment or cell or pore wall lining and the formation of an internal layer of silicone polymer in a web when this invention is practiced. After curing, the silicone polymer is permanently fixed material.
  • the curable silicone polymer impregnant is applied in an amount at least sufficient to partially saturate the web and fill some of the interstices or open cells of the web. Then, the web, while tensioned, is passed over and against shearing means or through a compression zone, such as between rollers or against a shear knife. Thus transversely applied shear force and compressive pressure is applied to the web.
  • the combination of tensioning, shearing forces, and web traveling speed is sufficient to cause the curable silicone polymer impregnant to move into the web, out from the interstices or open cells around the web fibers, cells or pores being enveloped, thereby leaving at least some of the interstices and/or open cells unfilled in regions of the web outside of the region occupied by the interior coating, and preferably substantially free of, silicone polymer impregnant.
  • the web is preferably at least slightly distorted by tensioning or stretching, while being somewhat transversely compressed at the location of the impregnation. This distortion is believed to facilitate the entrance of the silicone polymer composition into the web. When the compression and tension are released, the silicone polymer composition is believed to be squeezed or compressed within and through the interstitial spaces, or open cell spaces, of the treated web.
  • Such roller rotates (i) in the same direction as a facing roller and (ii) oppositely to the direction of movement of a continuously moving web traveling past the localized impregnation area achieved between such roller and such moving web.
  • the unidirectional rotation of the two rollers is believed to produce a distorting and stretching force or effect upon the web. This force is believed to promote penetration of the silicone polymer impregnant into the web.
  • This form of impregnant application or coating can be termed "reverse roll coating" for convenience.
  • the reverse coating rollers have generally horizontal axes while the moving web moves generally horizontally.
  • the web is further concurrently both longitudinally tensioned and distorted by being stretched against metering bars, bar knives, and the like which are urged against the web. 5 .
  • Such an initial pressured impregnation step is preferably followed by a series of further pressured web treatment steps believed to accomplish impregnant reintroduction, impregnant distribution, impregnant scraping, and excess impregnant removal and recovery.
  • the collective result of such steps gradually produces a web wherein the silicone polymer impregnant envelopes to a desired extent the fibers or lines the cell or pore walls comprising the web and collects within a desired internal region or zone in the web thereby filling or 5 plugging intersticial spaces, or open cells or pores, of the web in such region, but not filling the internal structure of the treated web with silicone polymer beyond a desired extent.
  • a silicone polymer composition may be made 0 to substantially completely envelope the fibers or line the cells or pores thereof and fill the interstitial spaces thereof in such internal region.
  • silicone polymer impregnant to 5 a web occurs from a reservoir.
  • This reservoir of silicone impregnant is positioned tightly against the tensioned, moving web (or fabric) .
  • the linearly extending, preferably vertically upwardly moving, web (or fabric) constitutes a wall portion of the 0 reservoir.
  • a bar or shear knife is pressed strongly and transversely against and laterally across the longitudinally tensioned web (or fabric) .
  • a shear blade or flexible scraper knife is also strongly 5 and transversely forced laterally across and against the tensioned web.
  • More than one shear knife, or more than one flexible compressive knife can be successively positioned along the path of web movement.
  • These blade means are believed to reintroduce the silicone impregnant into the ' web, to distribute the silicone polymer, and to promote and complete the envelopment of fibers or lining of the cell or pore walls and fillage of interstices and open cells with silicone polymer, and form an internal coating in a desired region in a web.
  • These scraper knives or shear blades are also believed to force the silicone polymer impregnant further into the three-dimensional structure of the web. Also, these knives, particularly the scraper knives, wipe or scrape excess silicone polymer impregnant off the surface of the web, thereby regulating the amount of silicone polymer impregnated.
  • the transversely applied shear forces applied across and against the web are sufficiently high to achieve temporarily and locally, a lowering of the viscosity of the preferably thixotropic viscous silicone polymer impregnant.
  • the lowered viscosity silicone polymer impregnant is thus enabled to flow into, and upon, the internal three-dimensional structure of the web. Because the silicone polymer composition that is being applied is subject to cure with heat or radiation and time, and because the pressured impregnation is believed to produce localized heat, the shearing conditions used prior to curing are preferably controlled to minimize premature curing.
  • the properties of the silicone polymer impregnant are preferably selected to be such that cure, or excessive cure, does not occur while the web is being treated with silicone polymer during the pressured impregnation.
  • the cure preferably occurs only after the web impregnation procedure has been completed.
  • the cure temperature of the silicone polymer composition is relatively high (preferably above about 250°F) and the heat exposure time is such as is needed to obtain a desired solid resilient elastomeric silicone polymer.
  • the rheology of the silicone polymer impregnant may be altered or controlled. Characteristics of a web are believed to be influenced by rheology, but it is believed that, in general, this invention can be practiced without careful control of rheology while controlling viscosity.
  • the viscosity of the silicone polymer impregnant is preferably lowered by the high pressure (shear) forces exerted during impregnation.
  • a pressure- and/or temperature-induced lowered viscosity should not go down too low, otherwise the impregnant can flow substantially uncontrolled in the web in the manner of a low viscosity liquid that is saturated and impregnated into a web as in prior art web treatments.
  • the web interstices or open cells can become excessively filled therewith, and the impregnant is not, for example, reliably and controllably applied to achieve an envelopment of the structural elements (including fibers) of the web being treated together with internal coating formation.
  • Benzophenones and particularly 2,4- dihydroxybenzophenone, are believed to be a particularly useful class of additives to the starting silicone polymer composition, as hereinbelow described.
  • curing the activity transpiring at a final step in the practice of a method of this invention is generically referred to herein as curing.
  • Conventional curing conditions known to the prior art for curing silicone polymer compositions are generally suitable for use in the practice of this invention.
  • temperatures in the range of about 250°F to about 350°F are used and times in the range of about 30 seconds to about 1 minute can be used, although longer and shorter curing times and temperatures may be used, if desired, when thermal curing is practiced.
  • Radiation curing as with an electron beam or ultraviolet light can also be used.
  • platinum catalysts to accelerate the cure while using lower temperatures and shorter cure times is preferable.
  • the webs are characteristically air permeable or breathable.
  • the fluorochemical impregnation is preferably accomplished by first saturating a web with a liquid composition which incorporates the fluorochemical, and then, thereafter, removing the excess liquid composition and residual carrier fluid by draining, compression, drying, or some combination .thereof from the treated web.
  • a typical fluorochemica-1 of the type used for web treatment can be characterized as a compound having one or more highly fluorinated portions, each portion being a fluoroaliphatic radical or the like, that is (or are) functionally associated with at least one generally non-fluorinated organic portion.
  • organic portion can be part of a polymer, part of a reactive monomer, a moiety with a reactable site adapted to react with a binder, or the like.
  • Such a compound is typically applied to a fabric or other web as a suspension or solution in either aqueous or non-aqueous media. Such application may be conventionally carried out in combination with a non-fluorine or fluorine containing resin or binder material for the purpose of providing improved durability as regards such factors as laundering, dry cleaning, and the like.
  • Fluorochemicals are sometimes known in the art as durable water repellant (DWR) chemicals, although such materials are typically believed to be not particularly durable and to have a tendency to wash out from a fabric treated therewith.
  • fiber enveloped webs of this invention which have been pretreated with a fluorochemical display excellent durability and washability characteristics.
  • fluorochemical pretreatment and silicone polymer fiber envelopment such as provided by the present invention appears to provide synergistic property enhancement because the effects or properties obtained appear to be better than can be obtained than by using either the fluorochemical or the silicone polymer alone for web treatment.
  • Exemplary water repellant fluorochemical compositions include the compositions sold under the name Milease" by ICI Americas Inc. with the type designations F-14N, F-34, F-31X, F-53. Those compositions with the "F” prefix indicate that they contain a fluorochemical as the principal active ingredient. More particularly, Milease" F-14 fluorochemical, for example, is said to contain approximately 18 percent perfluoroacrylate copolymer, 10 percent ethylene glycol (CAS 107-21-1) and 7 percent acetone (CAS 67-64-1) dispersed and dissolved in 65 percent water. Milease” F-31X is said to be a dispersion of a combination of fluorinated resin, acetone, and water.
  • Still another suitable class of water repellant chemicals is the Phobote ' x R chemicals of Ciba/Geigy identified as Phototex R FC104, FC461, FC731, FC208 and FC232 which are each believed to be suitable for use, typically in approximately a 5 percent concentration, in saturating a web for use in the invention.
  • These and many other water repellent fluorochemicals are believed to be capable of creating a surface contact angle with water of greater than about
  • One preferred class of fluorochemical treating compositions useful in the practice of this invention comprises about 1 to about 10 weight percent, more preferably about 5 weight percent of one of the above indicated TEFLON R -type water repellent fluorochemcials in water.
  • Another major group of suitable water repellent fluorochemical compositions useful in the practice of the invention is commercially available under the designation ZEPEL R rain and stain repellent chemicals of E.I. duPont de Nemours & Co. Inc., such as ZEPEL R water repellent chemicals types B, D, K, RN, RC, OR, HT, 6700 and 7040.
  • ZEPEL R water repellent chemicals types B, D, K, RN, RC, OR, HT, 6700 and 7040 Each is believed to be a fluorochemical in polymeric form that is disperible in all proportions at room temperature.
  • the dispersants ZEPEL B, D, K, and RN are believed to be cationic, while the dispersant ZEPEL R RC is
  • Another major group of water repellent fluorochemicals comprises the Scotchgard" water repellent chemicals of 3M Co. , St. Paul, Minnesota.
  • the Scotchgard” fluorochemicals are believed to be aqueously dispersed fluorochemicals in polymeric form.
  • the compositions of two suitable Scotchgard" water repellent fluorochemicals are believed to be disclosed in U.S. Patent Nos. 3,393,186 and 3,356,628, which patents are incorporated herein by reference.
  • the Scotchgard" fluorochemical of U.S. Patent No. 3,356,628 consists of copolymers of perfluoroacrylates and hydroxyalkyl acrylates.
  • copolymers are suitable for use as an oil and water repellent coating on a fibrous or porous surface. They have a carbon to carbon main chain and contain recurring monovalent perfluorocarbon groups having from 4 to 18 carbon atoms each and also having recurring hydroxyl radicals. From 20 to 70 percent of the weight of such copolymer is contributed by fluorine atoms in the perfluorocarbon groups and from 0.05 to 2 percent of the weight of the copolymer is contributed by the hydroxyl radicals. Such copolymer is said to have improved surface adherability properties as compared to the homopolymer of a corresponding fluorocarbon monomer.
  • the Scotchgard" fluorochemical of U.S. Patent No. 3,393,186 consists of perfluoroalkenylacrylates and polymers thereof.
  • An exemplary fluorinated monomer has the formula:
  • R f is a fluorocarbon group having from 3 to 18 carbon atoms
  • R is hydrogen or methyl
  • n is 0-16.
  • the water (or liquid carier) and other volatile components of the composition are removed by conventional techniques to provide a treated web that contains the impregnated fluorochemical throughout the web substrate.
  • a web is substantially completely saturated with an aqueous dispersion of a fluorochemical. Thereafter, the resulting impregnated web is compressed to remove excess portions of said dispersion. Finally, the web is heated to evaporate the carrier liquid. If the fluorochemical is curable, then the heating also accomplishes curing. After the fluorochemical treatment, the fluorochemical is found only on or in the web structural elements or fibers and is substantially completely absent from the web interstices.
  • the fluorochemical concentration in the treating composition is such as to permit a treated fluorochemical containing web, after volatiles of the treating composition are removed, to exhibit a contact angle with water applied to an outer web surface which is greater than about 90°. More preferably, the contact angle provided is greater than about 130°.
  • the web weight add-on provided by the fluorochemical after removal of volatiles is usually relatively minor.
  • the weight add on can vary with such factors as the nature of web treated, the type of silicone impregnant utilized in the next step of the • process, the temperature at which the impregnant is applied, the ultimate use contemplated for a web, and the like.
  • Typical weight add-ons of fluorochemical are in the range of about 1 to about 10 percent of the original weight of the web. More preferably, such weight add-ons are about 2 to about 4 weight percent of the weight of the starting fabric.
  • Durability of a web that has been treated with a fluorochemical and durability of a web that is subsequently treated with a silicone polymer can sometimes be improved by the conventional process of "sintering".
  • the exact physical and chemical processes that occur during sintering are unknown.
  • the so-called sintering temperature utilized is a function of the fluorochemical composition utilized and such temperature is frequently recommended by fluorochemical manufacturers. Typically, sintering is carried out at a temperature of about 130 to about 160°C for a period of time of about 2 to about 5 minutes. Acid catalysts can be added to give improved durability to laundering and dry cleaning solvents.
  • the fluorochemical is believed to provide more than water or other repellent properties to the resulting treated (impregnated) web, particularly since the curable silicone impregnant is often itself a water repellent. Rather, and without wishing to be bound by theory, it is believed that the fluorochemical in a treated web provides relative lubricity for the treated fibers during the pressure application of the curable silicone polymer impregnant.
  • the silicone polymer impregnant is applied under pressures which can be relatively high, and this impregnant is itself relatively viscous, as is discussed herein.
  • the fibers of the web may move over and against each other to a limited extent, thereby to permit entry of the silicone impregnant into and around the fibers. It is thought that the fluorochemical deposits may facilitate such fiber motion and facilitate envelopment during the pressure impregnation and subsequent shearing processing.
  • the fluorochemical may inhibit deposition of the silicone polymer impregnant at the positions of the fluorochemical deposits which somehow ultimately tends to cause thin enveloping layers of silicone polymer to form on fibers.
  • a piece of fabric for example the Red Kap Milliken poplin polyester cotton blend fabric, is cut into swatches.
  • One swatch is treated with an adjuvant, for example a three percent solution of the durable water-repellent chemical Milease" F-31X.
  • the treated swatch and an untreated swatch are each positioned at a 45° angle to plumb.
  • the fluorochemical pretreated web generally increases the surface contact angle of the silicone polymer while reducing the amount of saturation of the silicone polymer into the fibers themselves.
  • a curable silicone polymer impregnant composition utilized in the practice of this invention preferably has a viscosity that is sufficient to achieve an internal coating of the web. Generally, the viscosity is greater than about 1000 centipoise and less than about 2,000,000 centipoise at a shear rate of 10 reciprocal seconds. It is presently most preferred that such composition have a viscosity in the range of about 5,000 to about 10,000 centipoise at 25°C. Such a composition is believed to contain less than about 1% by weight of volatile material.
  • the silicone polymer is believed to be typically polymeric and to be commonly a mixture of co- curable polymers, oligomers, and/or monomers.
  • A at least one organo-hydrosilane polymer (including copolymers) ;
  • B at least one vinyl substituted polysiloxane (including copolymers) ;
  • Typical silicone hydrides are polymethylhydrosiloxanes which are dimethyl siloxane copolymers.
  • Typical vinyl terminated siloxanes are vinyldimethyl terminated or vinyl substituted polydimethylsiloxanes.
  • Typical catalyst systems include solutions or complexes of chloroplatinic acid in alcohols, ethers, divinylsiloxanes, and cyclic vinyl siloxanes.
  • the polymethylhydrosiloxanes (component A) are used in the form of their dimethyl copolymers because their reactivity is more controllable than that of the homopolymers and*because they result in tougher polymers with a lower cross-link density.
  • component B the reaction with vinyl functional silicones
  • the minimum ratio of hydride (component A) to vinyl (component B) in commercial products is reportedly about 2:1 and may be as high as 6:1.
  • Elastomers produced from such a curing reaction are known to demonstrate toughness, tensile strength, and dimensional stability.
  • Particulate fillers are known to be useful additives for incorporation into liquid silicone polymer compositions. Such fillers apparently not only can extend and reinforce the cured compositions produced therefrom, but also can favorably influence thixotropic behavior in such compositions. Thixotropic behavior is presently preferred in compositions used in the practice of this invention.
  • a terminal silanol (Si-OH) group makes such silanol siloxanes susceptible to reaction in curing, as is believed desirable.
  • component B can be replaced with a so called silanol vinyl terminated polysiloxane while using an organotin compound as a suitable curing catalyst as is disclosed in U.S. Patent No. 4,162,356.
  • an organotin compound as a suitable curing catalyst as is disclosed in U.S. Patent No. 4,162,356.
  • vinyl substituted polysiloxanes it is presently preferred to use vinyl substituted polysiloxanes in component B.
  • a silicone composition useful in this invention can contain curable silicone resin, curable polyurethane, curable fluorosilicone, curable modified polyurethane silicones, curable modified silicone polyurethanes, curable acrylics, polytetrafluoro- ethylene, and the like.
  • curable silicone resin curable polyurethane, curable fluorosilicone, curable modified polyurethane silicones, curable modified silicone polyurethanes, curable acrylics, polytetrafluoro- ethylene, and the like.
  • silicone impregnant composition which is believed to be well suited for use in the impregnation step of the method of the invention is taught in U.S. Patent Nos. 4,472,470 and 4,500,584 and in U.S. Patent No. 4,666,765. The contents of these patents are incorporated herein by reference.
  • Such a composition comprises in combination:
  • a resinous organopolysiloxane copolymer comprising: (i) (R 2 ) 3 siO o 5 units and Si0 2 units, or
  • R a is a monovalent hydrocarbon radical free of aliphatic unsaturation
  • a has a value of from about 1.0 to about 2.1
  • b has a value of from about 0.1 to about 1.0
  • the sum of a and b is from about 2.0 to about 2.7, there being at least two silicon- bonded hydrogen atoms per molecule.
  • such a composition can contain a finely divided inorganic filler (identified herein for convenience as component (v) ) .
  • such a composition can comprise on a parts by weight basis: (a) 100 parts of above component (i) ;
  • one package can comprise components (i) and (ii) which can be formulated together with at least some of component (ii) being dissolved in the component (i) , along with component (iii) and some or all of component (v) (if employed)
  • the second package can comprise component (iv) and optionally a portion of component (v) (if employed) .
  • the quantity of catalyst component (iii) required to produce a desired curable composition is achieved.
  • component (iii) and the component (iv) are not included together in the same package.
  • the distribution of the components between the two packages is preferably such that from about 0.1 to 1 part by weight of the second package is employed per part of the first package.
  • the two packages are merely mixed together in suitable fashion at the point of use.
  • Other suitable silicone polymer compositions are disclosed in the following U.S. patents:
  • U.S. Patent No. 4,032,502 provide compositions containing a linear polydiorganosiloxane having two siloxane bonded vinyl groups per molecule, organosiloxane that is soluble in such linear polydiorganosiloxane and comprised of a mixture of a polyorganosiloxane and a polydiorganosiloxane, platinum- containing catalyst, a platinum catalyst inhibitor, and a reinforcing silica filler whose surface has been treated with an organosilicone compound.
  • U.S. Patent No. 4,250,075 discloses a liquid silicone polymer composition that comprises vinyldiorganosiloxy endblocked polydiorganosiloxane, polyorganohydrogensiloxane, platinum catalyst, platinum catalyst inhibitor, and carbonaceous particles. Such a silicone polymer composition is useful when a web of this invention is being prepared that has electrically conductive properties.
  • U.S. Patent No. 4,427,801 discloses a curable organopolysiloxane of liquid triorganosiloxy endblocked polydiorganosiloxane wherein the triorganosiloxy groups are vinyl dimethylsiloxy or vinylmethylphenylsiloxy, finely divided amorphous silica particles treated with mixed trimethylsiloxy groups and vinyl-containing siloxy groups, organopolysiloxane resin containing vinyl groups, organohydrogensiloxane, and a platinum containing catalyst.
  • U.S. Patent No. 4,500,659 discloses a silicone composition of liquid triorganosiloxy endblocked polydimethylsiloxane wherein the triorganosiloxy units are dimethylvinylsiloxy or methylphenylvinylsiloxy, a reinforcing filler whose surface has been treated with a liquid hydroxyl end-blocked polyorganosiloxane which is fluorine-substituted, a liquid methylhydrogensiloxane, and a platinum-containing catalyst.
  • U.S. Patent No. 4,585,830 disccloses an organosiloxane composition of a triorganosiloxy- endblocked polydiorganosiloxane containing at least two vinyl radicals per molecule, an organohydrogensiloxane containing at least two silicone-bonded hydrogen atoms per molecule, a platinum-containing hydrosilation catalyst, optionally a catalyst inhibitor, a finely divided silica filler, and a silica treating agent which is at least partially immiscible with said polydiorganosiloxane.
  • U.S. Patent No. 4,753,978 discloses an organosiloxane composition of a first diorganovinylsiloxy terminated polydiorganosiloxane exhibiting a specified viscosity and having no ethylenically unsaturated hydrocrabon radicals bonded to non-terminal silicon atoms, a second diorganovinylsiloxy terminated polydiorganosiloxane that is miscible with the first polydiorganosiloxane and contains a vinyl radical, an organohydrogensiloxane, a platinum hydrosilation catalyst, * and a treated reinforcing silica filler.
  • 4,329,274 discloses viscous liquid silicone polymer compositions that are believed to be suitable and which are comprised of vinyl containing diorganopolysiloxane (corresponding to component B) , silicon hydride siloxane (corresponding to component A) and an effective amount of a catalyst which is a halogenated tetrameric platinum complex.
  • Silicone resin compositions shown in Table I below have all been used in the practice of this invention. Such compositions of Table I are believed to involve formulations that are of the type hereinabove characterized. Table I Illustrative Starting Silicone Polymer Compositions
  • Identified components do not represent complete composition of the individual products shown.
  • a polymer composition of a silicone polymer and a benzophenone is impregnated into a porous web as taught herein, protection of an organic web against ultraviolet radiation is improved, and the degradation effects associated with ultraviolet light exposure are inhibited, as may be expected from prior art teachings concerning the behavior of benzophenones.
  • silicone polymer compositions such as used in this invention contain a benzophenone, the resulting composition is believed to display improved viscosity characteristics, particularly thixotropic characteristics, and also curing acceleration, when such a composition is subjected to high shear forces.
  • a presently preferred benzophenone additive useful in the present invention is 2,4- dihydroxygenzophenone.
  • compositions useful in the present invention a control of compositional rheology, and t particularly of complex viscosity, is accomplishable, if desired, by the selective addition of diluent and additives.
  • These polymer compositions characteristically exhibit performance curves indicating substantially level and constant loss modulus, storage modulus, and complex viscosity over extended temperature ranges.
  • the graphic plots of loss modulus, storage modulus, and complex viscosity versus temperature all are believed to characteristically exhibit a sharp knee that shows the moduli to increase in value rapidly at cure temperatures.
  • compositions of this invention are controllably curable into polymeric materials which are preferably not sticky or tacky, and which have desirable elastomeric, flexural, and resiliency characteristics.
  • a silicone polymer composition which incorporates a benzophenone, one preferably admixes the benzophenone with the silicone polymer composition at the time of use.
  • the benzophenone component can be regarded as, or identified herein for convenience as, component (vi).
  • a composition of this invention preferably contains from about 0.3 to about 10 parts of such component (vi) , although larger and smaller amounts can be used, if desired, without departing from the spirit and scope of the invention.
  • R 1 and R 2 are each selected from the group consisting of hydroxyl, lower alkoxy, and hydrogen, and n and m are each an integer of 1 or 2
  • substituted benzophenones of formula (3) include
  • R 3 is a lower alkyl radical.
  • An example of a substituted benzophenone of formula (4) is: 2-ethylhexyl-2-cyano-3,3- diphenylacrylate (available from BASF under the trademark "Uvinul N-539”) .
  • the contact angle exhibited by a silicone impregnant composition of this invention varies with the particular web which is to be saturated therewith. However, the contact angle of water is generally lower for the non-impregnated side than the impregnated side. e combination of the processed web, the silicone polymer and the fluorochemical generally produces higher water contact angles than webs treated only with fluorochemicals.
  • the performance of an impregnant composition may be determined by the nature of a previously applied saturant such as a fluorochemical.
  • the apparatus employed in the present invention functions first to apply and preferably concurrently impregnate a silicone polymer composition into a web under pressure. Such silicone polymer composition is then reintroduced, distributed, and metered in a controlled manner in the web with the aid of transversely applied shearing force and compressive force such that the impregnated composition becomes distributed in the web so that an internal layer of silicone is formed while the fibers are at least partially enveloped while the interstices or open cells are substantially completely filled with the silicone polymer composition in the region of the internal coating.
  • Metered Film Thickness .05 mil thick Contiguous film on top roller non-contiguous delivery quantity film to 10 mil controlling thicker on roller film presence and allows more impregnant to dam at either second or third stage
  • Adjustment Parameters to Adjustment Adjustment of Web Angle of bar knife Bar knife faces Angle effects shear forward to meet forces on impregnate web coming to and determines bar; bar knife distortion or vertical to web, bar agitation as it faces away or relates to causing racked back from flow of impregnate; web run direc ⁇ can determine tion reintroduction of impregnate by dammed quantity of impregnate
  • Edge Shape Knife very Sharpness of knife sharp affects shear forces. The sharper and thinner the edge, the greater the shear forces at the contact edge
  • the amount of shear force applied by a shear knife 101 or 102 transversely against a web 74 is a function of many variables with probably the most important or principal variables being the fluorochemical pretreatment, the silicone polymer viscosity and the longitudinal -web tension (assuming a fixed spatial position for idler rolls 105, 106 and 107 and shear knives 101 and 102 during operation) .
  • a suitable and preferred level of applied shear force and web tensioning has been achieved to produce a product having enveloped fibers and an internal silicone coating
  • Idler roll 105 also functions as a compensator roll for mechanically adjusting and controlling web tension after coating apparatus 81 and before knife processing begins. Also, conveniently and preferably the web tension is sensed electronically, and then roll 105 is automatically raised or lowered to achieve web tensioning adjustments so as to maintain a preset tension in web 74. After passing over roll 107, the web 74 is passed over the circumferential surface of a conventional padder roll 111.
  • the tenter frame 118 adjusted by the operator so that, as the web passes therethrough, the web can be straightened or shaped either longitudinally or laterally, as desirable or considered necessary for an individual web. If desired, the tenter frame 118 can be automatically operated to apply tensioning forces to a web in accordance with a predetermined program, or the like.
  • the tenter frame 118 also provides the start of a new zone of limited longitudinal and transverse tensioning which extends forwardly along the web pathway from tenter frame 118 through oven 119 to a tension compensator, here shown as utilizing three tension rolls 121, 122 and 123 which are part of a conventional mechanical tension compensator subassembly which is similar in structure and function to the compensator subassembly incorporating the previously described tension rolls 94, 95 and 96.
  • the tensioning longitudinally of web 74 as it passes through oven 119 is employed to control the web 74 as it passes through oven 119 as regards web dimensional limits. This tensioning is chosen to be at a level which does not introduce significant distortion into the web, yet web sagging is avoided, as from thermal expansion and elongation. Rollers (not shown) can be used in the oven 119 to avoid sagging and to maintain uniform heat exposure.
  • the rolls 121, 122 and 123 also serve to provide a cooling pathway for the web 74 as it emerges from the oven 119 before it passes over guide roller 124 and into take-up roll 77.
  • Figs. 12b and 12c two alternate variations or modes are seen. In such views, similar components are similarly numbered but with the addition of single prime marks thereto in the case of Fig. 12b and double prime marks thereto in the case of Fig. 12c.
  • Fig. 12b a further stage of web pressurization is introduced after the flex knife 112' and before the tenter frame 118'.
  • a presently preferred web which is both fluorochemical and silicone resin treated and which is breathable, water resistant and rewashable is characterized as being a longitudinally tensionable porous flexible fibrous web having opposed, substantially parallel surfaces that are comprised of associated fibers with interstices between the fibers or is a matrix having cells or pores therein.
  • the web is substantially uniformly impregnated with a fluorochemical and thereafter impregnated with a silicone polymer composition, to form a web having an internal layer within the web wherein the outer surfaces of the web are substantially full of silicone polymer and the web is breathable and water resistant or waterproof. At least a portion of the fibers or cell walls are enveloped. At least one surface thereof is characterized by having a visual appearance which is substantially the same as the visual appearance of one surface of the starting porous web.
  • the polymer is preferably selected from the group consisting of polyamides, polyesters, regenerated cellulose, cellulose acetate, and mixtures thereof.
  • Preferred webs of this invention are more specifically characterized by having a water drop contact angle in the range of about 90° to about 160°; a rewash capability of at -least about 3; a breathability of at least about 35% of untreated substrate web; and a water repellency rating of at least about 80 prior to washing.
  • a presently preferred process for making a fluorochemical and silicone resin treated web having breathability, water resistance and rewashability which is adapted for continuous operation comprises the successive steps of: impregnating the web with a fluorochemical, longitudinally tensioning the fluorochemical impregnated web while sequentially first applying to one surface thereof a curable silicone polymer composition and concurrently applying a transversely exerted localized ' compressive force against said surface, and moving over said surface of the web substantially rigid shearing means which exerts transversely an applied, localized shear force against said surface and wipes away exposed portions of silicone polymer composition on said surface, thereby forming an internal layer of silicone polymer while enveloping at least some of the fibers or passageways through the matrix; and curing the silicone polymer composition in the web.
  • a relationship is established between the respective surface tensions of the impregnant and the web, creating a specific contact angle.
  • the impregnant responds to a water repellent fluorochemical pretreatment of the substrate so as to permit enhanced flow characteristics of the impregnant into the web.
  • the boundary or edge of the impregnant is moved, preferably repeatedly, in response to applied suitable forces into the interior region of a porous web so as to cause thin films of the impregnant to develop on the fiber surfaces.
  • the word "thixotropy” refers herein to liquid flow behavior in which the viscosity of a liquid is reduced by shear agitation or stirring. It is theorized to be caused by the breakdown of some loosely knit structure in the starting liquid that is built up during a period of rest (storage) and that is torn down during a period of suitable applied stress.
  • Stage 4 can be considered to be the first stage internal matrix dispersing and reintroduction with metering, and also recovery and recycle of excess impregnant.
  • the shear forces cause a temporary lowering of impregnant viscosity, causing it to flow upon and into the three- dimensional structure of the web.
  • the initial visco- elastic character of the impregnant is typically theorized to be recovered almost immediately after shear forces are removed.
  • Stage 5 can be considered to be a second stage internal matrix dispersing and reintroduction with metering and also recovery and recycling of excess impregnant.
  • the variations in the viscosity of the impregnant are equivalent to stage 4.
  • the viscosity of the impregnant is again lowered causing it to flow within the web. Because of the application of repeated shear force induced reductions in viscosity, the thixotropic behavior of an impregnant may not undergo complete recovery, following each application of shear force and the viscosity of the impregnant may not revert to its pre-impregnation values.
  • the silicone polymer composition impregnant is believed to have the capacity to form enveloping internal coating in a predetermined region wherein the interstices or open cells are substantially completely filled within the three- dimensional matrix constituting a web during the time intervals that the impregnant is caused to flow under pressure in and about matrix components. In between these times, the ' impregnant may recover substantially all of its initial high viscosity, although perhaps slightly less so with each repeated application of shearing pressure or force.
  • Stage 7 can be considered to be occurring with regard to the exertion of control of curing.
  • at least a partial curing (including cross-linking and/or polymerizing) , is obtained by relatively low temperatures applied for relatively short times, for example, temperatures under about 350°F applied for under about 3 minutes, when, for example, light cotton, nylon or like fabrics are being impregnated.
  • the term "surface tension" can be considered to have reference to a single factor consisting of such variables as intermolecular, or secondary, bonding forces, such as permanent dipole forces, induced forces, dispersion or nonpolar van der Waals forces, and • hydrogen bonding forces.
  • the strong primary bonding forces at an interface due to a chemical reaction are theorized to be excluded from surface tension effects; however, it is noted that even a small degree of chemical reactivity can have a tremendous influence on wetting effects and behavior affected by.surface tension.
  • Surface tension is believed to induce wetting effects which can influence the behavior of a silicone polymer composition impregnant relative to the formation of a fiber enveloped layer therewith in a fibrous porous web.
  • spreading is theorized to be a wetting effect. Retraction occurs for contact angles over 90° or over planar surfaces for any contact angle. However, spontaneous spreading for contact angles less than 90°, especially for small contact angles, may be induced by surface roughness.
  • Fig. 10 is a graph relating the contact angle over a smooth solid surface as a function of ⁇ and i that apply respectively, to adhesion (i cos ⁇ +1) , penetration (i cos ⁇ ) , and spreading (i cos ⁇ -1) . Regions of adhesion versus abhesion, penetration versus repellency, and spreading versus retraction are shown by shaded areas.
  • Fig. 10 illustrates what is theorized to be the relationship of a silicone polyer composition impregnant to silicone polymer composition solids in a treated web as regards such factors as adhesion, penetration, spreading, and retraction.
  • wetting is used to designate such processes as adhesion, penetration, spreading, and cohesion. If wetting transpires as a spontaneous process, then adhesion and penetration are assured when the solid surface tension exceeds the liquid surface tension. Surface roughness promotes these spontaneous wetting actions. On the other hand, no such generalizations can be made when the solid surface tension is less than the liquid surface tension. Surface tension is measured as by S.T.L. units for liquid and by S.T.S. units for solids; both units are dyns/centimeter. When S.T.S. is less than S.T.L. , then wetting is less ubiquitous and prediction of wetting behavior is more difficult.
  • Ratio listed is that recommended by the manufacturer.
  • Syl-off ® (registered trademark of Dow Corning) is a cross-linker.
  • Sylox ® 2 (registered trademark of W.R. Grace & Co.) is a synthetic amorphous silica.
  • Hydral ® 710 (registered trademark of Alcoa) is a hydrated aluminum oxide.
  • Silopren ® LSR Z/3042 registered trademark of
  • Flattening Agent OK412 ® (registered trademark of Degussa Corp.) is a wax coated silicon dioxide.
  • Nalco ® 1SJ-612 Colloidal Silica (registered trademark of Nalco Chemical Company) is an aqueous solution of silica and alumina.
  • Nalco ® 1S -614 Colloidal Alumina (registered trademark of Nalco Chemical Company) is an aqueous colloidal alumina dispersion.
  • Zonyl ® UR (registered trademark of duPont) is an anionic fluorosurfactant.
  • Zonyl ® FSN-100 (registered trademark of duPont) is a nonionic fluorosurfactant.
  • DLX-6000 ® (registered trademark of duPont) is a polytetrafluoroethylene micropowder.
  • TE-3608 ® (registered trademark of duPont) is a polytetrafluoroethylene micropowder.
  • Example 20 Internally Coated. Fiber Encapsulated, Interstice Filled Fabric Preparation A complete, stepwise, application of the inventive method in the production of an encapsulated- fiber fabric was as follows.
  • the selected base fabric was TACTEL ® (gold color) #612071 available from ICI Americas, Inc. through their agent, Arthur Kahn, Inc. This fabric was 100% woven nylon. If desired, this and other fabrics may be calendered to modify surface texture.
  • the fabric was weighed and measured. Its initial weight is 3.1 ounces per square yard. Its thickness equals 9 mils.
  • the fabric was next washed with detergent, rinsed thoroughly, and hung to air dry.
  • the fabric was soaked in water, wrung dry, and weighed. The water retained was equal to 0.8 g water/g fabric.
  • the fabric was then treated with a water repellant fluorochemical, a 2% solution by weight of Zepel ® 7040. In order to do so the fabric must be soaked in a 2.5% solution of Zepel ® water-repellant chemical in distilled water. This was because
  • the treated fabric was then run through a wringer and air dried.
  • the fabric was heated in an oven for 1 minute at 350°F. This heating sinters the water repellant fluorochemical.
  • the fabric with its fluorochemical residue is then run as in the preferred production embodiment, Figure 7, in a vertical configuration and is described below.
  • the fabric is run from a roll that incorporates significant braking or clutching to initiate the tension required for controlled material alignment and coating during application.
  • the fabric web travels through a series of idler rolls ending at the application trough. As it passes the application trough, it picks up a thin coating of silicone impregnant and then moves under a shear blade that is parallel- to the floor.
  • the silicone impregnant is applied at 1.0 oz/sq. yd. and continues under a flex blade that is also parallel to the floor.
  • Multiple process stages of running the fabric with applied impregnant under the blades are preferably made. The multiple process stages are important, and are normally necessary.
  • the impregnant is Mobay 2530
  • ⁇ A/B in a 1:1 ratio can be considered to be a visco- elastic liquid that flows only under the shear forces resulting from the pressured impregnation.
  • the impregnant is believed to return very substantially to its original viscous condition almost immediately upon release of the pressure.
  • the impregnant was believed to flow a short distance within the matrix of the fabric during the short time that it was, because of pressure shearing forces, of lowered viscosity. Therefore, a number of "flows" may be usefully generated in a number of passes in order to properly distribute the impregnant in its preferred position substantially encapsulating the surfaces of the fabric's fibers.
  • the impregnated fabric was run through a line oven, of approximately 10 yards in length, at 4-6 yards per minute, and was cured at 325- 350°F. It then passes through a series of idler rollers and is rolled up on a take-up roll, completing the tension zone.
  • the resultant fabric has a non-tacky thin film of silicone that was internally coated to form a fiber encapsulated, interstice-filled fabric.
  • Exa ple 21 Evaluation of Fiber Encapsulated Fabric Properties The test results of the original versus the produced fiber encapsulated fabric of Example 20 were as follows:
  • Amount Impregnated 1.4 oz/yd 2 * Environmental chamber at 104°F and 74% humidity.
  • the spray test was conducted in accordance with AATCC 22-1974. It measures water repellency of a fabric sample on a scale of 0-100, with a reading of 100 designating a completely water repellent fabric.
  • the rain test was conducted in accordance with AATCC 35-1985. It measures resistance of a fabric sample to penetration of water under static pressure from a shower head of 3 feet/5 minutes. A fabric is stormproof when less than 1.0 gram of water is absorbed by a standardized blotter used in the test.
  • Abrasion resistance is measured by mounting a fabric sample on a Taber Abraser Model 174 and measuring the number of cycles before the fabric begins tearing apart.
  • Test results are expressed in pounds per square inch at which water beads penetrate the fabric.
  • the moisture vapor transmission (MVTR) test was conducted in accordance with ASTM E96-B. The test measures the amount of moisture vapor passing through a fabric sample in a controlled environment during a 24 hour period. The obtained MVTR figure is expressed in grams of water/square meter of surface/24 hour day.. The environmental chamber was held at 104°F and 47% humidity.
  • the moisture vapor transmission (MVTR) test was conducted in ' accordance with ASTM E96-B.
  • the te ⁇ t measures the amount of moisture vapor passing through a fabric sample in a controlled environment during a 24 hour period.
  • the obatined MVTR figure is expressed in grams of water/square meter of surface/24 hour day.
  • the environmental chamber was held at 104°F and 47% humidity.
  • This test involves placing both a fabric sample and a standard blotter sample on top of a water container which contains 700 ml of tap water.
  • the fabric sample and the blotter sample are each then subjected to a continuous pressure of 87 lbs. distributed evenly over 100 square inches of surface area for a period of 30 minutes. After this time, a visual inspection of the fabric is made for any water penetration, and the paper blotter is weighed to detect water gain or penetration.
  • Total weight applied to fabric 87 lbs. Pressure evenly distributed over surface area of 100 sq. in.
  • the 87 lb. weight was distributed evenly over the 100-square-inch area.
  • the rain test results obtained demonstrate the clear superiority of the fiber enveloped fabric of the present invention as compared to the original untreated fabric.
  • the data in the Table below shows that fiber enveloped fabrics pass this test by allowing virtually no water to pass therethrough. This result is comparable to the results obtained with higher cost so-called breathable waterproof fabrics currently commercially available in the market. In contrast, the original, untreated fabrics fail to pass this test because they demonstrate complete saturation.
  • the fiber enveloped fabric samples retain excellent "hand" after the test.
  • ASTM test The purpose and scope of this ASTM test is to evaluate resistance of a fiber enveloped fabric to water under simulated storm conditions.
  • the test specifies that a test fabric is stormproof if less than one gram of water is absorbed by blotter paper with a shower head pressure of 3 feet exerted for 5 minutes.
  • This test method is applicable to any textile fabric, whether or not it has a water repellent finish. It measures the resistance of a fabric to the penetration of water by impact, and thus can be.used to predict the probable rain penetration resistance of a fabric.
  • the results obtained with this method of test depend on the water repellency of the fibers and yarris in the fabric tested, and on the construction of the fabric.
  • the apparatus and materials employed in each test were a modified rain tester, blotter paper, water at 80°F ⁇ 2°F, a laboratory balance, 8" x 8" fabric specimens which had been pre-conditioned in an atmosphere of 65% ( ⁇ 2%) relative humidity and 70°F (+2°F) for four hours before testing, and tape.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Biomedical Technology (AREA)
  • Vascular Medicine (AREA)
  • Dermatology (AREA)
  • Hematology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)

Abstract

Un procédé amélioré permet de traiter une bande poreuse (en particulier du tissu) pour produire une nouvelle bande ayant un revêtement interne en polymère de silicone. Dans le procédé, on applique par pression un revêtement d'un polymère de silicone liquide polymérisable de départ sur une surface de la bande, puis la bande est soumise à des forces de cisaillement localisées suffisamment grandes pour déplacer la composition de polymère de silicone dans des parties intérieures de la bande et pour distribuer la compositon de polymère de silicone uniformément dans cette région plane. L'excès de polymère de silicone est enlevé de la surface de la bande. Ensuite, la bande obtenue est chauffée ou irradiée pour polymériser le polymère de silicone. De préférence, une bande est imprégnée au préalable avec un produit fluorochimique. Des bandes produites par ce procédé sont respirables, imperméables ou très hydrofuges et flexibles.
PCT/US1989/001008 1988-03-14 1989-03-13 Bandes textiles avec revetement interne en polymere de silicone WO1989008554A1 (fr)

Applications Claiming Priority (14)

Application Number Priority Date Filing Date Title
US16764388A 1988-03-14 1988-03-14
US16779788A 1988-03-14 1988-03-14
US16763088A 1988-03-14 1988-03-14
US16786988A 1988-03-14 1988-03-14
US167,797 1988-03-14
US167,643 1988-03-14
US167,630 1988-03-14
US167,869 1988-03-14
US31977689A 1989-03-10 1989-03-10
US31977789A 1989-03-10 1989-03-10
US319,776 1989-03-10
US319,777 1989-03-10
US319,778 1989-03-10
US07/319,778 US5004643A (en) 1988-03-14 1989-03-10 Silicone polymer-internally coated webs

Publications (1)

Publication Number Publication Date
WO1989008554A1 true WO1989008554A1 (fr) 1989-09-21

Family

ID=27569110

Family Applications (3)

Application Number Title Priority Date Filing Date
PCT/US1989/001006 WO1989008553A1 (fr) 1988-03-14 1989-03-13 Bandes fibreuses avec encapsulation de polymere de silicone
PCT/US1989/001008 WO1989008554A1 (fr) 1988-03-14 1989-03-13 Bandes textiles avec revetement interne en polymere de silicone
PCT/US1989/001009 WO1989008555A1 (fr) 1988-03-14 1989-03-13 Substrats avec polymere de silicone encapsule

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/US1989/001006 WO1989008553A1 (fr) 1988-03-14 1989-03-13 Bandes fibreuses avec encapsulation de polymere de silicone

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US1989/001009 WO1989008555A1 (fr) 1988-03-14 1989-03-13 Substrats avec polymere de silicone encapsule

Country Status (3)

Country Link
KR (1) KR970002936B1 (fr)
AU (3) AU3346089A (fr)
WO (3) WO1989008553A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112545A (en) * 1990-02-14 1992-05-12 Airfoil Textron Inc. Composite preforms and articles and methods for their manufacture
EP0507760A1 (fr) * 1991-04-03 1992-10-07 Jeffrey L. Taylor Textiles barrières médicaux et méthode de fabrication
US5698303A (en) * 1988-03-14 1997-12-16 Nextec Applications, Inc. Controlling the porosity and permeation of a web
US5846604A (en) * 1988-03-14 1998-12-08 Nextec Applications, Inc. Controlling the porosity and permeation of a web
US5856245A (en) * 1988-03-14 1999-01-05 Nextec Applications, Inc. Articles of barrier webs
EP0893530A1 (fr) * 1997-07-24 1999-01-27 Polymer Group, Inc. Etoffe non-tissée perméable à la vapeur et imperméable aux liquides et méthode
US5874164A (en) * 1988-03-14 1999-02-23 Nextec Applications, Inc. Barrier webs having bioactive surfaces
US5876792A (en) * 1988-03-14 1999-03-02 Nextec Applications, Inc. Methods and apparatus for controlled placement of a polymer composition into a web
US5912116A (en) * 1988-03-14 1999-06-15 Nextec Applications, Inc. Methods of measuring analytes with barrier webs
US5954902A (en) * 1988-03-14 1999-09-21 Nextec Applications, Inc. Controlling the porosity and permeation of a web
US5958137A (en) * 1989-03-10 1999-09-28 Nextec Applications, Inc. Apparatus of feedback control for the placement of a polymer composition into a web
US6040251A (en) * 1988-03-14 2000-03-21 Nextec Applications Inc. Garments of barrier webs
US6071602A (en) * 1995-06-07 2000-06-06 Nextec Applications, Inc. Controlling the porosity and permeation of a web
US6083602A (en) * 1988-03-14 2000-07-04 Nextec Applications, Inc. Incontinent garments
US6312523B1 (en) 1988-03-14 2001-11-06 Nextec Applications, Inc. Apparatus of feedback control for the placement of a polymer composition into a web
US6342280B1 (en) 1998-06-23 2002-01-29 Nextec Applications, Inc. Products of and methods for improving adhesion between substrate and polymer layers
US6416613B1 (en) 1998-06-23 2002-07-09 Nextec Applications, Inc. Products of and method for improving adhesion between substrate and polymer layers

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4973510A (en) * 1987-09-02 1990-11-27 Teijin Limited Coated sheet material and process for producing same
US5869172A (en) * 1988-03-14 1999-02-09 Nextec Applications, Inc. Internally-coated porous webs with controlled positioning of modifiers therein
GB2276336B (en) * 1990-11-13 1995-07-19 Aaron Sherman Foamed products
GB9024596D0 (en) * 1990-11-13 1991-01-02 Sherman Aaron Foamed products
JP3354220B2 (ja) * 1993-07-09 2002-12-09 日清紡績株式会社 メラミン系樹脂発泡体
FR2715411B1 (fr) * 1994-01-24 1996-04-26 Celta Matériau compact résistant à l'eau et repulpable, à base de matériaux cellulosiques broyés, et son procédé de fabrication.
AU3633100A (en) * 1999-02-22 2000-09-04 Milliken & Company Silicone coated fluid shield fabric
EP1143062B1 (fr) * 2000-03-10 2002-11-13 W.L. GORE & ASSOCIATES GmbH Vêtement nettoyable résistant aux salissures
PL2034088T3 (pl) * 2007-09-10 2013-04-30 Gore W L & Ass Gmbh Tkanina i laminat tkaniny
ES2319065B1 (es) * 2007-10-16 2010-02-11 Comersan, S.A. Procedimiento para la obtencion de un tejido con aspecto de piel curtida o cuero, tejido obtenido a partir de el y su uso.
CN107033596A (zh) * 2010-11-25 2017-08-11 史密夫及内修公开有限公司 组合物i – ii及其产品和用途
WO2014049390A1 (fr) * 2012-09-25 2014-04-03 Mas Research And Innovation (Private) Limited Ensemble textile pourvu d'un revêtement élastomère perméable à l'air et à la vapeur d'eau
US9883702B2 (en) 2015-10-07 2018-02-06 Mast Industries (Far East) Limited Portion of bra and bra having zones of varying elastic moduli
WO2018061691A1 (fr) * 2016-09-27 2018-04-05 富士フイルム株式会社 Procédé de production d'un film

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051296A (en) * 1977-03-14 1977-09-27 International Harvester Company Silicone rubber mold
JPS57149559A (en) * 1981-03-04 1982-09-16 Unitika Ltd Water repellent and water resistant process
US4500584A (en) * 1983-07-07 1985-02-19 General Electric Company Transparent membrane structures

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2117432A (en) * 1935-02-07 1938-05-17 Us Rubber Co Process and apparatus for impregnating fibrous sheet material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051296A (en) * 1977-03-14 1977-09-27 International Harvester Company Silicone rubber mold
JPS57149559A (en) * 1981-03-04 1982-09-16 Unitika Ltd Water repellent and water resistant process
US4500584A (en) * 1983-07-07 1985-02-19 General Electric Company Transparent membrane structures

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5912116A (en) * 1988-03-14 1999-06-15 Nextec Applications, Inc. Methods of measuring analytes with barrier webs
US5876792A (en) * 1988-03-14 1999-03-02 Nextec Applications, Inc. Methods and apparatus for controlled placement of a polymer composition into a web
US6129978A (en) * 1988-03-14 2000-10-10 Nextec Applications, Inc. Porous webs having a polymer composition controllably placed therein
US5846604A (en) * 1988-03-14 1998-12-08 Nextec Applications, Inc. Controlling the porosity and permeation of a web
US5856245A (en) * 1988-03-14 1999-01-05 Nextec Applications, Inc. Articles of barrier webs
US6083602A (en) * 1988-03-14 2000-07-04 Nextec Applications, Inc. Incontinent garments
US5874164A (en) * 1988-03-14 1999-02-23 Nextec Applications, Inc. Barrier webs having bioactive surfaces
US6312523B1 (en) 1988-03-14 2001-11-06 Nextec Applications, Inc. Apparatus of feedback control for the placement of a polymer composition into a web
US5698303A (en) * 1988-03-14 1997-12-16 Nextec Applications, Inc. Controlling the porosity and permeation of a web
US5954902A (en) * 1988-03-14 1999-09-21 Nextec Applications, Inc. Controlling the porosity and permeation of a web
US6040251A (en) * 1988-03-14 2000-03-21 Nextec Applications Inc. Garments of barrier webs
US5958137A (en) * 1989-03-10 1999-09-28 Nextec Applications, Inc. Apparatus of feedback control for the placement of a polymer composition into a web
US6289841B1 (en) 1989-03-10 2001-09-18 Nextec Applications, Inc. Method and apparatus for controlled placement of a polymer composition into a web
US5112545A (en) * 1990-02-14 1992-05-12 Airfoil Textron Inc. Composite preforms and articles and methods for their manufacture
EP0507760A1 (fr) * 1991-04-03 1992-10-07 Jeffrey L. Taylor Textiles barrières médicaux et méthode de fabrication
US6071602A (en) * 1995-06-07 2000-06-06 Nextec Applications, Inc. Controlling the porosity and permeation of a web
EP0893530A1 (fr) * 1997-07-24 1999-01-27 Polymer Group, Inc. Etoffe non-tissée perméable à la vapeur et imperméable aux liquides et méthode
US6342280B1 (en) 1998-06-23 2002-01-29 Nextec Applications, Inc. Products of and methods for improving adhesion between substrate and polymer layers
US6416613B1 (en) 1998-06-23 2002-07-09 Nextec Applications, Inc. Products of and method for improving adhesion between substrate and polymer layers

Also Published As

Publication number Publication date
AU3440689A (en) 1989-10-05
AU689799B2 (en) 1998-04-09
KR970002936B1 (ko) 1997-03-13
AU3346089A (en) 1989-10-05
AU7592594A (en) 1995-05-04
WO1989008555A1 (fr) 1989-09-21
WO1989008553A1 (fr) 1989-09-21
KR900700284A (ko) 1990-08-13
AU3436889A (en) 1989-10-05

Similar Documents

Publication Publication Date Title
US5004643A (en) Silicone polymer-internally coated webs
US5209965A (en) Internally coated webs
US6129978A (en) Porous webs having a polymer composition controllably placed therein
WO1989008554A1 (fr) Bandes textiles avec revetement interne en polymere de silicone
EP0826082B1 (fr) Bandes a revetement interne poreux et a modificateurs positionnes de maniere modulable dans la bande
EP0832318B1 (fr) Procede d'obtention de la permeabilite et de la porosite desirees pour un voile de fibres
US5958137A (en) Apparatus of feedback control for the placement of a polymer composition into a web
US5874164A (en) Barrier webs having bioactive surfaces
US6083602A (en) Incontinent garments
US6040251A (en) Garments of barrier webs
US5856245A (en) Articles of barrier webs
US5912116A (en) Methods of measuring analytes with barrier webs
WO1996036761A9 (fr) Procede d'obtention de la permeabilite et de la porosite desirees pour un voile de fibres
US5698303A (en) Controlling the porosity and permeation of a web
US6312523B1 (en) Apparatus of feedback control for the placement of a polymer composition into a web
US6071602A (en) Controlling the porosity and permeation of a web
US5935637A (en) Method of feedback control for the placement of a polymer composition into a web
CA1338232C (fr) Tissu de polymere de silicone avec revetement interne
US20020088396A1 (en) Apparatus of feedback control for the placement of a polymer composition into a web
CA2221168C (fr) Bandes a revetement interne poreux et a modificateurs positionnes de maniere modulable dans la bande
CA1340808C (fr) Substrats encapsules a base de polymere de silicone
US5954902A (en) Controlling the porosity and permeation of a web

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU DK FI JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE