Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
  • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
  • B29C70/06—Fibrous reinforcements only
  • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
  • B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
  • B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
  • B60C9/0028—Reinforcements comprising mineral fibres, e.g. glass or carbon fibres
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
  • C03C25/27—Rubber latex
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
  • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
  • B29K2105/128—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles in the form of a mat
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/273—Coating or impregnation provides wear or abrasion resistance
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2926—Coated or impregnated inorganic fiber fabric
  • Y10T442/2992—Coated or impregnated glass fiber fabric

Definitions

• This invention relates to a new and improved treatment for glass fibers and fabrics formed thereof and it relates more particularly to glass fibers characterized by increased abrasion resistance and to a method for producing same;
• glass fibers Because of their high strength and flexibility coupled with their relative inertness, glass fibers have become widely adopted as an important component in structural materials, reinforced plastics, coated fabrics, or in their more available forms as strands, yarns, cords and textile fabrics and the like. In each of these uses where glass fibers are not directly combined with resinous material, as in reinforced plastics or coated fabrics,it has been found necessary to supplythe fibers with a protective coating, otherwise they would be subject to destruction by mutual abrasion or by abrasion with other surfaces and form of yarns, strands or fabrics, abrasion resistance and the method for securing same become controlling factors in the life and in the use of the glass fiber products.
• Another object is to produce and to provide a method for producing glass fibers and fabrics providedwith a protective coating which imparts exceptionally high abrasion resistance informing and in the final product while at-the same time improving the hand, softness, smoothness and draping qualities of the fabric.
• a further object is'to produce and to provide a method for producing glass'fibers coated with acomposition to inrprove abrasion resistance and which is improved in many respects by Washing or otherwise handling the fabric in the manner for which it was intended.
• a still further object isto provide'a method for improving the softness, feel and wrinkleproofnes'sof a fabiic'which has been coated in the manner herein described to improve its abrasion resistance:
• the abrasion resistance of glass fibers and fabrics formed therefrom can be markedly increased 7 over anything which has heretofore been achieved by treating the fibers from which all previous coatings have preferably been removed with a composition containing a butadiene-acrylonitrile copolymer in combination with polytetrafiuor'oethylene resin dispersed
• the materials should be present in the fibrous structure in amounts ranging from O.1 to 5 percent by weight polytetrafluoroethylene and 0.2 to 25 percent by weight butadiene-acrylonitrile copolymer.
• the two components which make up the treating composition are of substantially dissimilar character but they cooperate in a manner to introduce the desired improved abrasion resistance without impairing the softness, silkiness and good draping qualities which have heretofore characterized fabrics treated in accordance with the cited Waggoner et al. applications, previously referred to for relaxation and weave setting of the glass fibers of the fabric.
• the butadieneacryloiiitrile copolymer functions as a film former upon drying to coat the fibers substantially completely throughout their lengths.
• the polytetrafluoroethylene is selected to be incapable of fusion at the temperatures of tre'atment'for' drying or for forming the butadiene-acrylonitr' e copolymer into a film and therefore remains in particle form dispersed throughout the butadiene-acrylonitr'ile copolymer in the treating composition and in the film which' is formed upon the glass fiber surfaces ofi'd'rying, When applied to the glass fiber surfaces, as a size in forming, the dispersed particles of polytetrafluoroethylene appear to act asball bearing surfaces and facilitate relative movement between fibers without abrasion.
• the twistingefficiency of fibers in strand and yarn formation sized in accordance with this invention is markedly increased and in most instances practically doubled.
• the discrete particles of polytetrafluoroethylene appear to be anchored into the continuous film of the butadiene-acrylonitrile copolymer but the exposed portions of the particles continue to act as bearing surfaces and lubricants to improve the draping qualities, softness and hand of the fibers and fabric formed-thereof.
• the particles of polytetrafluoroethylene function in addition positively to increase the toughness and the abrasion resistance of the composite coating;
• the treatingcomposition is preferably applied with the particles of polytetrafluoroethylene dispersed in a latex of the butadiene-acrylonitrile copolymer.
• concentration of solids within the ratio prescribed depends upon the form of the fibers being treated and the amount thereof which it is desired to have deposited on the glass fiber surfaces.
• the improvement in abrasion'res'istance and inmany other characteristics of glass fibers by'applicationof the butadiene acrylonitrile copolymer and polytetrafiuoroethylene'in particle form is not limited to textile'fabrics' of glass fibers. Marked increase in abrasion resistance and improved efficiency'in fiber handling alsoresult when the individual filaments of glass fibers are treated in forming or when strands, yarns, or other bundles of glass fibers are treated after forming but preferably after the size previously applied'has' beenremoved from the'surfa'ces thereof-as by washing orheat cleaning.
• a composition removes excess composition containing considerably lower concentrations of butadiene-acrylonitrile copolymer and polytetrafiuoroethyene may be used, such for example as compositions containing 15 percent by weight solids within the ratio previously set forth.
• the solids may range through the span of 1 percent by weight up to 25 percent by weight, depending upon the use to be made of the treated fibers.
• application When applied in forming, application may be made by means of a wiping pad or roll applicator as the individual filaments are gathered together and formed into strands.
• application When treatment is to be made of strands or yarns of twisted or intertwisted fibers, as in the manufacture of tire cord or textile treads, application may be made by passing the strand, yarn, or cord through a bath of the treating composition and then through a die which followed by passage through a drying oven for removal of the diluent by volatilization and setting of the butadiene-acrylonitrile copolymer into a continuous film in which the unfused particles of polytetrafiuoroethylene become embedded.
• the composition When applied onto an already formed fabric, as for example upon following the heat treating step described in the applications previously referred to in the Waggoner et al. processes, the composition may be padded or otherwise applied by conventional means onto the fabric followed by drying at a temperature within the range of 250-400 F. or higherso long as the temperature is not sufficient to cause fusion of the particles ofpolytetrafluoroethylene.
• the components may be formulated into a cationic dispersion for application onto the glass fibers whereby the positively charged particles orient with the negative groups that predominate in ordinary glass, it has been found possible and it is preferred to formulate the ingredients into an anionic dispersion whereby the particles become negatively charged for orientation with positive groups having different sites in the surfaces of the glass fibers to provide a new and improved anchorage which is especially desirable in fibers and fabrics formed of lead glass and the like.
• Example 1 In the preparation of a 50 gallon batch of treating composition, 8 pounds of an anionic suspensoid containing 50 percent by weight polytetrafluoroethylene in finely divided form is incorporated with stirring into about 25 gallons of water. 80 pounds of an anionic latex containing 40 percent by weight butadiene-acrylonitrile copolymer is introduced with agitation and then the mix is diluted with water up to 50 gallons. The composition contains about 1 percent by weight polytetrafluoroethylene and about 7 percent by weight butadiene-acrylonitrile copolymer.
• the composition is padded onto a glass fiber fabric after it leaves the oven used in carrying out the heat treating step of the cited Waggoner et a1.
• processes wherein the glass fibers in fabric form are heated at a temperature ranging from 1050 to 50 below the fusion temperature of the glass composition of which the fibers are formed for at least a few seconds at the higher temperature to a few minutes at the lower temperature whereupon the size originally applied to the glass fiber surfaces is burned off at an early stage of the heat treating process and the glass fibers are relaxed and weave set in their fabric form, and then the heat treated fabric is cured at a temperature of about 300 F.
• a composition containing about 1 percent by weight stearato chromic chloride is padded onto the fabric which is again dried at a temperature of about 300 F.
• Example 2 An anionic dispersion containing 1.5 percent by weight polytetrafluoroethylene in finely divided form and 3.5 percent butadiene-acrylonitrile is wiped as a size onto a plurality of glass fiber filaments as they are attenuated from continuous strands of molten glass and gathered together into strands. The formed strands are wound upon drums and later a number of such strands may be twisted or intertwisted into a cord or into yarns for fabric formation.
• the twisting efficiency is greatly increased to almost double the values previously secured with other treating compositions.
• the fibrous structure may be treated with the stearato chromic chloride and then dried at a temperature ranging from 250350 F.
• a composition of the type described by this example is particularly well adapted for use with glass fibers formed of a melt of lead glass in which more than 50 percent of the melt is formed of lead oxide.
• butadiene-acrylonitrile copolymer instead of butadiene-acrylonitrile copolymer, other film forming materials capable of dispersion in aqueous medium and providing an adherent base upon drying may be used in corresponding proportions and amount with polytetrafluoroethylene. Excellent results, for example, have been secured with the combination of polytetrafluoroethylene and a polyacrylate of the type butyl methacrylate or a polyacrylate emulsion sold commercially under the trade name Hycar PA by the B. F. Goodrich Chemical Company. Use may also be made of a latex formed of butadiene-acrylonitrile coplymer compounded with 50-75 percent by weight styrene and marketed under the trade name X-512.
• adherent bases for anchorage of the particles of polytetrafluoroethylene may also be secured by compounding with rubber-like material including buna-S or natural resins, starchy gelatins, proteins, gums and the like.
• Example 3 An aqueous emulsion of 10 percent Hycar PA containing about 50 percent polyacrylate and about 8 percent of a 50 percent dispersion of polytetrafluoroethylene in finely divided form is padded onto a glass fiber fabric just after it emerges from the heat treating oven of the Waggoner et a1. processes previously referred to. The fabric is then heated at 300 F. and coated with a 2 percent solution of stearato chromic chloride followed by curing at about 300 F. v
• a textile fabric treated in accordance with this example exhibits vast improvement in abrasionresistance compared with a similar fabric treated in the usual manner with Hycar PA followed by the stearato chromic chloride.
• the improvement is illustrated by the following results secured in the two types of treatment with a fabric designated as 138:
• Example 4 In the manufacture of tire cord, intertwisted yarns of glass fibers, after heat'cleaning, are passed through a bath in the form of a dispersion containing 15 percent by Weight butadiene-acrylonitrile copolymer and 3 percent by weight polytetrafiuoroethylene in particle form.
• the cord is passed up through a die located over the bath f remove excess of the composition and from the die, the cord is threaded through a baking oven maintained at a temperature between 300 and 350 F. to drive off the diluent and cure the film forming material.
• the treated cord may be passed through a bath containing a small percentage (0.5 to 2.0 percent by weight) of a chromic chloride having an unsaturated acido group coordinated with the trivalent nuclear chromium atom, such for example as methacrylato chromic chloride, followed by heat treatment at about complex.
• a chromic chloride having an unsaturated acido group coordinated with the trivalent nuclear chromium atom such for example as methacrylato chromic chloride
• suitable organic dyes may be added to the butadiene-acrylonitrile copolymer or other film forming material of the type heretofore described and polytetrafiuoroethylene treating composition or else such dyes may be applied afterwards in the usual manner for coloring fabrics since the fibers having the butadiene-acrylonitrile copolymer and polytetrafluoroethylene, with or without the chrome complex, appear to be highly receptive to such coloring agents and provide sufiicient anchorage therefor to retain the color substantially permanently.
• Suitable dyes for use in coloring fibers include the direct dyes of the type Methylene Blue, Fast Red A, or the mordant dyes of the type Alizarin Yellow A, Cerulein A, or the substantive dyes of the type Congo Red, or the azo dyes of the type Primulin, Aniline Yellow, Naphtol Blue Black B, Diamine Blue 23, Congo Blue, or the basic dyes represented by Rhodamine B, thiofiavine and aurarnine dyes or pigments of the type Hansa Yellow G, Toluidine Toner, or Copper phthalocyanine.
• Representative inorganic pigments include Lamp Black, Malachite Green, Iron Blue, Cadmium Yellow and the like.
• the copolymer or the like may 300 F. to cure the percent by weight of the properly be dispersed in combination with the particles of polytetrafluoroethylene.
• Glass fibers the surfaces of which are coated with a composition containing polytetrafluoroethylene in finely divided form dispersed in a polymeric thermoplastic resinous film forming material and present in amounts ranging from 0.1-5 percent by weight of the polytetrafiuoroethylene and 0.2-25 percent by weight of the thermoplastic film forming resin.
• Glass fibers the surfaces of which are coated'with polytetrafiuoroethylene in finely divided form dispersed in a polymeric thermoplastic resinous film forming material present in amounts ranging from 0.1-5 percent by weight of the polytetrafluoroethylene and 0.225 percent by weight of the thermoplastic film forming resin and a Werner complex compound in which the acido group coordinated with the trivalent nuclear chromium atom contains more than 10 carbon atoms coating the polytetrafluoroethylene coated glass fibers.
• Glass fibers the surfaces of which are coated With the combination of a butadiene-acrylonitrile copolymer and polytetrafluoroethylene dispersed therein in finely divided form present in amounts ranging from 0.l-5 polytetrafluoroethylene and 0.2-25 percent by weight of the butadiene-acrylonitrile copolymer and a treating material on the surfaces of the coated fibers comprising a Werner complex compound in which the acido group coordinated with the trivalent nuclear chromium atom contains more than .10 carbon atoms.
• aqueous composition containing 1-25 percent by weight of a film forming polymeric thermoplastic resinous material and .polytetrafiuoroethylene in particle form dispersed there With and present in the ratio of 0.1 to parts by weight polytetrafiuoroethylene to 0.2 to 25 parts by weight of the film forming material, and heating the treated fibrous structure to a temperature Within the range of 300-350 F. to reduce the film forming material to a continuous film without fusion of the particles of'polytetrafiuoroethylene.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Textile Engineering (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• General Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Medicinal Chemistry (AREA)
• Composite Materials (AREA)
• Manufacturing & Machinery (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Laminated Bodies (AREA)

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Cited By (15)

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Citations (8)

• 0
  • BE BE516978D patent/BE516978A/xx unknown
• 1952
  • 1952-01-24 US US26814752 patent/US2754223A/en not_active Expired - Lifetime
• 1953
  • 1953-01-14 FR FR1073528D patent/FR1073528A/fr not_active Expired
  • 1953-01-15 CH CH332751D patent/CH332751A/de unknown
  • 1953-01-16 GB GB138853A patent/GB759356A/en not_active Expired
  • 1953-01-20 DE DEO2763A patent/DE1004133B/de active Pending

Patent Citations (8)

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