US3793130A - Fiber reinforced elastomers - Google Patents

Fiber reinforced elastomers Download PDF

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US3793130A
US3793130A US3793130DA US3793130A US 3793130 A US3793130 A US 3793130A US 3793130D A US3793130D A US 3793130DA US 3793130 A US3793130 A US 3793130A
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fiber bundle
bundle
elastomer
fibers
retarder
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A Marzocchi
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Owens Corning
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Owens Corning Fiberglas Corp
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Assigned to OWENS-CORNING FIBERGLAS CORPORATION, A CORP. OF DE. reassignment OWENS-CORNING FIBERGLAS CORPORATION, A CORP. OF DE. TERMINATION OF SECURITY AGREEMENT RECORDED NOV. 13, 1986. REEL 4652 FRAMES 351-420 Assignors: WADE, WILLIAM J. (TRUSTEES), WILMINGTON TRUST COMPANY, A DE. BANKING CORPORATION
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    • 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
    • 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
    • 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
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10S156/91—Bonding tire cord and elastomer: improved adhesive system
    • 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
    • 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
    • Y10T428/2973—Particular cross section
    • 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
    • Y10T442/2934—Coating or impregnation contains vinyl polymer or copolymer
    • 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
    • Y10T442/2951—Coating or impregnation contains epoxy polymer or copolymer or polyether
    • 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
    • Y10T442/2959—Coating or impregnation contains aldehyde or ketone condensation product
    • 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 elastomeric products reinforced or otherwise combined with organic or inorganic fibers, and more particularly to a method and composition employed in the treatment of fibers, including glass fibers, metal fibers, and organic fibers such as polyester fibers, nylon fibers and rayon fibers, to enhance the bonding relationship between the fibers and the elastomeric material for more complete utilization of the desirable characteristics of the fibers in their combination with the elastomeric materials.
  • elastomer is meant to include natural rubber in the cured or uncured stage, vulcanized or unvulcanized stage, and synthetic organic elastomeric materials such as butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, chloroprene, isoprene, neoprene, isobutyl rubber and the like elastomeric polymers and copolymers in their cured or uncured stages, and vulcanized or unvulcanized stages.
  • synthetic organic elastomeric materials such as butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, chloroprene, isoprene, neoprene, isobutyl rubber and the like elastomeric polymers and copolymers in their cured or uncured stages, and vulcanized or unvulcanized stages.
  • EPDM rubbers such as those formed by the interpolymerization of ethylene, an alpha-monoolefin having from 3-20 carbon atoms, such as propylene, and a polyene, such as dicyclopentadiene, 1,4-hexadiene and preferably an alkylene or alkylidene norbornene, such as -alkylidene-2- norbornene and the like in which the alkylidene group numbers from 2-12 carbon atoms, and polysulfone rubber.
  • an alpha-monoolefin having from 3-20 carbon atoms such as propylene
  • a polyene such as dicyclopentadiene, 1,4-hexadiene and preferably an alkylene or alkylidene norbornene, such as -alkylidene-2- norbornene and the like in which the alkylidene group numbers from 2-12 carbon atoms, and polysulfone rubber.
  • This invention is addressed to the more complete utilization of the desirable characteristics of inorganic and organic fibers as a reinforcement or as a stabilizing agent in belt manufacture, as cords, strands and fabrics to increase structure, life, wearability, and service characteristics in rubber tires, and as a reinforcement and the like in other elastomeric coated fabrics and molded elastomeric products.
  • FIG. 1 is a cross-sectional view of a fiber reinforced elastomeric product prepared in accordance with the prior art
  • FIG. 2 is a schematic flow diagram of a method for treating impregnated fiber bundles in accordance with one concept of the present invention
  • FIG. 3 is a cross-sectional view of a fiber bundle processed in accordance with the diagram shown in FIG.
  • FIG. 4 is a cross-sectional view of a fiber bundle prepared in accordance with another concept of this invention.
  • FIG. 5 is a cross-setional view of a fiber reinforced elastomeric product formed with a fiber bundle of the type shown in FIGS. 3 or 4 in accordance with this invention.
  • this difficulty in part stems from the completely smooth, rod-like surfaces of the glass fibers and in part from the fact that the glass fiber surfaces are highly hydrophilic in nature, thereby resulting in the formation of a thin, but tenacious film of moisture on the glass fiber surfaces almost immediately after they are formed which serves to destroy any bond, chemical or physical, which would otherwise be established between the glass fiber surfaces and the elastomeric material.
  • FIG. 1 of the drawing depicts a fiber bundle-reinforced elastomeric product prepared in accordance with the concepts of the prior art.
  • a plurality of fiber bundles 10 are molded between layers 12 and 14 of elastomeric material to cure and/or vulcanize the elastomeric material to securely anchor the fiber bundles to the elastomeric material.
  • the interface 16 referred to above is formed between the elastomeric material immediately adjacent to the fiber bundles and the elastomeric material forming the bulk of the continuous phase 12 and 14 in which the fiber bundles are distributed.
  • the overcuring or overvulcanization ofthe elastomeric material immediately adjacent to the fiber bundles is a result of the migration of low molecular weight components from the impregnant in the fiber bundles into the elastomeric material, to thereby trigger accelerators which are conventionally blended with the elastomeric material for activation during cure and/or vulcanization, and/or to thereby serve as accelerators in their own right.
  • the elastomer-elastomer interface referred to above can be substantially minimized or eliminated with the result that the bonding relationship between the fiber bundles is significantly improved by providing the fiber bundles with at least a thin coating of a vulcanization retarder. It has been determined that the vulcanization retarder serves to moderate the rate of vulcanization and/or cure of the elastomeric material immediately adjacent to the fiber bundles with the result that a more uniform rate of vulcanization and/or cure takes place throughout the fiber bundleelastomeric composite.
  • vulcanization retarders use can be made of a variety of materials useful for this purpose.
  • One preferred group of retarders are the N-nitroso amines derived from secondary amines and having a boiling point sufficiently high to minimize their elimination from the bundle during vulcanization and/or cure of the bundleelastomer composite.
  • Such retarders have the formula NO I N wherein R is aryl containing 6 to 14 carbon atoms, and preferably phenyl or naphthyl and R is alkyl containing 2 to 20 carbon atoms (e.g., ethyl, propyl, butyl, isouty tncntxlz et -L cy loa y q taininait lfil atbon atoms (e.g., cyclopentyl, cyclohexyl, etc.) or aryl in fi t 1.4 @5 29 ms-in a diiq ulitalism R can be substituted by one or more substituents including amino, cyano, C to C alkyl, hydroxy, etc.
  • R is aryl containing 6 to 14 carbon atoms, and preferably phenyl or naphthyl and R is alkyl containing 2 to 20 carbon atoms (e.g., ethyl
  • Such retarders include N- nitrosodiphenylamine, N- nitrosoisopropylphenylamine, N-nitrosophenylnaphthylamine, N-nitrosophenylpentylamine, N-
  • retarders which can be used in the practice of this invention are the carboxylic acids and their corresponding anhydrides or acid halides having a boiling point above 200 C to minimize elimination of the acid during cure and/or vulcanization.
  • carboxylic acids and their corresponding anhydrides or acid halides having a boiling point above 200 C to minimize elimination of the acid during cure and/or vulcanization.
  • benzoic acid as well as substituted derivatives thereof in which the substituents are amino, cyano, C to C alkyl, hydroxy groups as well as a number of others.
  • Salicylic acid has been found to be a particularly suitable retarder in accordance with the present invention.
  • preferred acids are aromatic polycarboxylic acids containing 8-20 carbon atoms and 2-6 carboxyl groups as well as their corresponding anhydrides and acid halides.
  • Such acids, anhydrides and acid halides are phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, l,3,S-benzenetricarboxylic acid, 1,2,3,4-benzenetetracarboxylic acid, l,2,3,5-benzenetetracarboxylic acid, benzenehexacarboxylic acid, naphthalic acid, l,2,3,4-naphthalenetetracarboxylic acid, etc.
  • cobalt complexing agents in the practice of this invention, which have been found to serve as vulcanization retarders.
  • Preferred cobalt complexing agents are the cobaltammines, and preferably the cobalthexammines and pentammines. Representative of such complexing agents is cobalt III hexammine chloride.
  • cobalt complexing agent is well known to those skilled in the art and may likewise be used in the practice of the invention.
  • many of the cobalt complexing agents are unstable in aqueous systems, it is generally desirable to avoid the use of such cobalt complexing agents in aqueous medium.
  • the foregoing acidic-type vulcanization retarders are effective in providing a uniform rate of vulcanization and/or cure in a fiber reinforced elastomeric product through reaction with the low molecular weight components in the impregnant to thereby minimize or prevent migration of such components into the continuous phase formed of the elastomeric material.
  • impregnants for use in this invention are the combinations of a basic elastomer latex and a resorcinolaldehyde resin prepared in the presence of primary and secondary alkyl amines in which the alkyl groups contain 1 to 4 carbon atoms.
  • Such impregnants are commercially available under the trademark Lotol of the US. Rubber Co., and the method for their preparation is described in Canadian Pat. No. 435,754.
  • resorcinol is reacted in aqueous medium with a lower aliphatic aldehyde, and preferably formaldehyde in a mole ratio of at least 2.0 moles of aldehyde per mole of resorcinol in the presence of the amine in a mole ratio of at least 1.3 moles of amine per mole of resorcinol to form an aqueous solution of the resorcinol aldehyde resin, which can be added to an alkaline elastomer latex without precipitation of the resin or coagulation of the latex.
  • terpolymer latexes in which the terpolymer is formed of butadiene, styrene and vinyl pyridine in the practice of this invention, either alone or in combination with an elastomer latex.
  • the vinyl pyridine-butadiene-styrene terpolymer is available from the General Tire and Chemical Company under the tradename Gentac or from the Goodyear Tire and Rubber Company under the tradename of Pliolite VP 100, and in which the materials are present in the weight ratio of 15 percent by weight vinyl pyridine, 15 percent by weight Styrene and 70 percent by weight butadiene.
  • impregnant material containing a low molecular weight component reactive with the acidic retarders of this invention.
  • Representative impregnants include ureaaldehyde resins, melamine-aldehyde resins, polyesters, polyamides, polyepoxides, all of which are known to the art.
  • the retarder may be combined with the impregnant in any convenient manner.
  • an impregnated bundle is coated with a thin coating of the retarder.
  • the retarder is preferably formulated into the impregnating composition for the impregnation of a fiber bundle for best results.
  • the amount of the retarder employed is not critical and can be varied within wide limits. It is generally advisable that the retarder, whether present as a coating or as a component of the impregnant, constitutes from 0.1 to 25 percent by weight, and preferably 1 to percent by weight of the impregnant.
  • the concepts of the present invention are applicable to a wide variety of fibers, including metal wire fibers, and fibers formed from organic materials including rayon, polyamides, polyesters, dacron and other systhetic fibers fromed of resinous polymeric material.
  • fibers including metal wire fibers, and fibers formed from organic materials including rayon, polyamides, polyesters, dacron and other systhetic fibers fromed of resinous polymeric material.
  • copending application Ser. No. 87,196 filed Nov. 5, 1970, and nowabandoned the disclosure of which is incorporated herein by reference.
  • the chemical nature of the fibers is not critical to the practice of the invention.
  • EXAMPLE 1 This example illustrates the treatment of a glass fiber bundle impregnated with a resorcinol formaldehyde latex to form a coating of a vulcanization retarder on the surface of the bundle.
  • a strand 18 of glass fibers which have been preferably, although not necessarily, sized in forming is passed over a guide roller 20 for passage downwardly into an impregnating bath 22 containing the following impregnating composition:
  • the bundle is then turned under a pair of rollers 24 to effect a sharp bend in the bundle which operates to open the bundle to facilitate more complete penetration of the aqueous impregnating composition in the bundle of sized glass fibers for complete impregnation of the bundle.
  • the impregnated bundle is then raised from the bath for passage through a roller or die 26 which operates to remove excess impregnating composition from the bundle and to work the impregnating composition into the bundle.
  • the endless bundle is advanced over roller 28 into a drying oven 30, preferably in the form of an air drying oven maintained at a temperature above ambient temperature, and preferably within the range of l50-250 F. to accelerate removal of the aqueous diluent and to set the impregnant in situ in the fiber bundle. Drying will occur in relatively short time, generally ranging from 1-30 minutes depending somewhat on the temperature of drying.
  • the impregnated bundle 32 is coated with a solution of one of the retarders of this invention dissolved in an inert solvent.
  • Application of a coating may be made by passing the impregnated bundle 32 over a roller 34 which is constantly wet with the retarder solution from bath 36.
  • a solution of N- nitrosodiphenylamine dissolved in acetone although it will be understood that any of a variety of suitable inert solvents can be used.
  • bundle 10 is formed of a plurality of individual glass fibers 40 having optional size coating 42 on the surfaces thereof.
  • the impregnant 44 which completely penetrates the bundle serves to separate the glass fibers each from the other and to form a unitary bundle structure.
  • the N-nitrosodiphenylamine forms a thin coating 46 on the dried and impregnated bundle and is thus available to moderate the cure and/or vulcanization when the bundle is combined with elastomeric materials in the manufacture of glass fiber-reinforced elastomeric products.
  • Example 2 The procedure of Example 1 is repeated using a plurality of steel fibers which have been previously coated with zinc to reduce corrosion.
  • Introduction of the impregnant composition is made in an amount to impregnate with dry solids of l-25 percent by weight of the fiber system, and preferably -15 percent by weight.
  • an elastomer compatible material such as the RFL employed in this example, be present in the impregnant composition in an amount sufficient to provide a composition having a solids content within the range of 10-50 percent by weight.
  • Example 3 The procedure of Example 1 is again repeated using as the fibrous material, polyester fibers. Again, the impregnant composition is applied to the bundle in an amount to provide dry solids constituting from 10-25 percent by weight of the fibersystem.
  • Example 4 The procedure of Example I is again repeated using a plurality of sized glass fibers and the following impregnant composition:
  • EXAMPLE 5 This example illustrates the use of a vulcanization retarder in accordance with the present invention which has been formulated in the impregnant composition.
  • a resorcinol formaldehyde latex of the type described above is formulated with an N- nitrosodiphenylamine vulcanization retarder in accordance with the following example:
  • Natural rubber latex-resorcinol formaldehyde resin (38% solids-Lotol 5440" N-nitrosodiphenylamine 3% Water 72%
  • the foregoing impregnant composition containing the vulcanization retarder is then applied to a bundle of sized glass fibers in accordance with the method described in FIG. 2 of the drawing, except that the subsetrated by the following examples.
  • the foregoing impregnant composition can be used in the treatment of fibers of the type described above in accordance with the method described in Example EXAMPLE ll Melamine formaldehyde resin (63% 30% solids) N-nitrosophenylnaphthylamine 4% Water 66% EXAMPLE 13
  • the impregnant used in this example is a polyepoxide formed of the condensation reaction product of bisphenol A and epichlorohydrin (Epon 728) marketed by Dow Chemical.
  • an anchoring agent in the form of an organo silicon compound which serves to more securely anchor the fibers, and particularly glass fibers, to elastomeric materials when bundles of impregnated fibers are combined with elastomeric materials in the manufacture of fiber reinforced elastomeric products.
  • an anchoring agent in the form of an organo silicon compound which serves to more securely anchor the fibers, and particularly glass fibers, to elastomeric materials when bundles of impregnated fibers are combined with elastomeric materials in the manufacture of fiber reinforced elastomeric products.
  • the concepts of the present invention substantially minimize the problem of migration of these anchoring agents since the organo silicon compounds are reactive with the vulcanization retarders when the retarders are activated by heat during cure and/or vulcanization of an impregnated bundle in which the impregnant includes an anchoring agent to thereby prevent or minimize migration of the organo silicon compounds into the elastomeric continuous phase of the fiber reinforced elastomeric product.
  • suitable anchoring agents which can be used in the practice of this invention are the organo silicons, their hydrolysis products and polymerization products (polysiloxane) of an organo silane having the formula:
  • Z is a readily hydrolyzable group such as alkoxy having 1-4 carbon atoms (e.g., methoxy, ethoxy, propoxy, etc.) or halogen, such as chlorine, n is an integer from 1 to 3, and R is hydrogen or an organic group in which at least one R group is an alkyl group having 1-10 carbon atoms, such as methyl, ethyl, propyl, etc.; alkenyl having 1-10 carbon atoms, such as vinyl, allyl, etc.; cycloalkyl having 4-8 carbon atoms, such as cyclopentyl, cyclohexyl, etc.; aryl having 6-10 carbon atoms, such as phenyl, naphthyl, benzyl, etc.; alkoxy alkyl, such as methyloxyethyl, etc.; alkenylcarbonyloxyalkyl, such as carbonylpropylmethoxy, etc.; as well as the amino, epoxy,
  • silanes are ethyltrichlorosilane, propyltrimethoxy silane, vinyl trichlorosilane, allyl triethoxy silane, cyclohexylethyltrimethoxy silane, phenyl 10 trichloro silane, phenyl dimethoxy silane, methacryloxypgopyltrimethoxy silane, gammaaminopropyltriethoxy silane, beta-aminovinyldiethoxy silane, N-(gamma-triethoxysilylpropyl)propylamine, gamma-aminoallyltriethoxy silane, paraaminophenyltriethoxy silane, N-(beta-aminoethyl ⁇ gamma-aminopropyltrimethoxy silane, gammachloropropyltrichloro silane, glycidoxy propyltrimethoxy silane, gly
  • the organo silanes are generally present in the impregnant composition in an amount within the range of 0.1 to 5 percent by weight.
  • impregnant compositions formulated to include such silanes may be illustrated by the following examples.
  • EXAMPLE 14 Natural rubber latex-resorcinol 25% formaldehyde resin (38% solids-Lotol 5440") Gamma-aminopropyltriethoxy silane 1% N-nitrosodiphenylamine 6% Water 68% EXAMPLE 15 Vinyl pyridine-butadlene-styrene 30% terpolymer(4l% solids-Gentac”) 3,4-epoxycyclohexylethyl-trimethoxy 1.5% silane Phthalic anhydride 6.0% Tetramethyl ammonium hydroxide 4.0% Water 58.5%
  • an anchoring agent When formulating an anchoring agent into the impregnant compositions in accordance with the concepts of the invention, it is frequently desirable to adjust the pH of the resulting impregnant composition to insure the stability of the system and prevent precipitation of the silane from the solution. For this purpose, it is frequently desirable to formulate the impregnant composition to include a quaternary ammonium hydroxide to adjust the pH to the alkaline side.
  • compositions can be applied to any of the fiber systems of the types described above whereby the vulcanization retarder containing in the impregnant composition serves to moderate the rate of vulcanization when the impregnated bundle is combined with elastomeric material in the manufacture of fiber reinforced elastomeric products.
  • the use of such anchoring agent is particularly desirable in the case of glass fiberreinforced elastomeric products since it is believed that the anchoring agents of the type described serve to intertie the impregnated bundle with the elastomeric material with which the bundle is combined.
  • the elastomeric material with which the fiber bundle is combined will constitute a continuous phase, and it is believed that the tie-in between the impregnated bundles of fibers and the elastomeric material forming the continuous phase will occur primarily during cure or vulcanization of the elastomeric material during fabrication of the fiber reinforced elastomeric product.
  • the bundles are admixed with the elastomeric material or otherwise laid down in the desired arrangement.
  • the combination of the impregnated bundle and the elastomeric material or system is achieved in a conventional manner by molding or curing under heat and compression of the elastomeric material admixed with conventional accelerators, v'ulcanizing agents and/or other conventional processing aids in combination with the impregnated bundle whereby the bundle becomes securely integrated with the elastomeric material in the resultant product without the formation of the undesired elastomer-elastomer interface described above which serves to weaken the overall bond otherwise established between the impregnated fiber bundle and the elastomeric material when it is combined.
  • the glass fiber bundles are thus integrated in the elastomeric material 11 forming the continuous phase without the formation of the elastomer-elastomer interface since the vulcanization retarders of this invention serve to moderate the rate of vulcanization of the elastomeric material immediately adjacent to the fiber bundles 10.
  • the concepts of the present invention are applicable to strands formed of a plurality of individual glass fiber filaments, and to'cords formed of a plurality of strands which have been assembled or twisted together. Strands forming such cords may have a twist, a reverse twist or no twist at all in accordance with well known technology in the manufacture of glass fibers. In addition, the concepts of the invention are also applicable I to woven and non-woven fabrics formed from cords of the type described above.
  • a glass fiber bundle formed of a plurality of glass fibers and an impregnant in the bundle, said impregnant containing an alkaline polymeric elastomer compatible material and containing an acidic vulcanization retarder capable of reaction with low molecular weight components of the elastomer compatible material, said retarder being an N-nitroso amine.
  • a fiber bundle as defined in claim I wherein the amine has the formula wherein R is aryl and substituted derivatives thereof and R is selected from the group consisting of alkyl, cycloalkyl, aryl and substituted derivatives thereof.
  • a fiber bundle as defined in claim 1 wherein the elastomer compatible material is a mixture of an elastomer latex with an amine-modified resorcinol aldehyde resin.
  • a fiber bundle as defined in claim 1 wherein the elastomer compatible material is a butadiene-styrenevinyl pyridine terpolymer.
  • a fiber bundle as defined in claim 1 wherein the elastomer compatible material is selected from the group consisting of urea-aldehyde resins, melaminealdehyde resins, polyesters, polyamides and polyepoxides.
  • a glass fiber-reinforced elastomeric product in which an elastomeric material constitutes a continuous phase in which bundles of glass fibers are distributed, the improvement in the bonding relationship between the glass fibers and the elastomeric material comprising an impregnated glass fiber bundle in which the impregnant is an alkaline, polymeric elastomer compatible material and contains an acidic vulcanization retarder capable of reaction with low molecular weight components of the elastomer compatible material in response to heat during cure or vulcanization, said retarder being an N-nitroso amine.
  • a product as defined in claim 13 wherein the amine has the formula wherein R, is aryl and substituted derivatives thereof and R is selected from the group consisting of alkyl, cycloalkyl, aryl and substituted derivatives thereof.
  • elastomer compatible material is a mixture of an elastomer latex with an amine-modified resorcinol aldehyde resin.
  • elastomer compatible material is a butadiene-styrenevinyl pyridine terpolymer.
  • elastomer compatible material is selected from the group consisting of urea-aldehyde resins, melaminealdehyde resins, polyesters, polyamides and polyepoxides.
  • the method for the manufacture of glass fiberreinforced elastomeric products in which a bundle of impregnated fibers is combined with an elastomeric material and the resulting combination is molded under heat and pressure to integrate the glass fiber bundle in the elastomeric material, the improvement comprising providing at least a coating of an acid vulcanization retarder on a bundle impregnated with an alkaline, polymeric elastomer compatible material and molding the bundle with an elastomeric material under heat and pressure whereby a uniform rate of vulcanization or cure is achieved throughout the reinforced elastomeric product, said retarder being an N-nitroso amine.
  • a method as defined in claim 25 wherein the elastomer compatible material is a butadiene-styrene-vinyl pyridine terpolymer.
  • a method as defined in claim 25 wherein the clastomer compatible material is selected from the group consisting of urea-aldehyde resins, melamine-aldehyde resins, polyesters, polyamides and polyepoxides.
  • the improvement in the bonding relationship between the glass fiber bundle and the elastomeric material comprising an impregnated glass fiber bundle in which the impregnant is an alkaline blend of a resorcinolaldehyde resin and an elastomer and contains an acidic vulcanization retarder in the form of an N-nitroso amine having the formula cycloalkyl, aryl and substituted derivatives thereof.

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  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4123287A (en) * 1975-07-24 1978-10-31 Pilkington Brothers Limited Glass fibres for reinforcement of cement products
US4216856A (en) * 1975-04-25 1980-08-12 Dunlop Limited Reinforcement for elastomeric articles
US4467064A (en) * 1980-11-11 1984-08-21 Unitika Ltd. Method of manufacturing polyester fibers with good adhesion to rubber
US4923517A (en) * 1987-09-17 1990-05-08 Exxon Research And Engineering Company Glass fiber reinforced cement compositions
US5079066A (en) * 1988-05-25 1992-01-07 Minnesota Mining And Manufacturing Company Tape having improved tear strength
US5145544A (en) * 1989-08-01 1992-09-08 Minnesota Mining And Manufacturing Company Method for preparing tape having improved tear strength
US5173141A (en) * 1988-05-25 1992-12-22 Minnesota Mining And Manufacturing Company Preparing tape having improved tear strength
US5240983A (en) * 1989-07-17 1993-08-31 Chisso Corporation Process for producing polyolefin thermoplastic elastomer composition
US5260111A (en) * 1991-08-08 1993-11-09 Bridgestone Corporation Thermoplastic films for heat seaming roof sheeting and method for covering roofs
WO2000023505A1 (en) * 1998-10-15 2000-04-27 N.V.Bekaert S.A. Coated metal reinforcement element and coating methods
US6220304B1 (en) * 1998-07-30 2001-04-24 Toyoda Gosei Co., Ltd. Brake hose
US6537341B2 (en) * 2000-05-30 2003-03-25 Daimlerchrysler Ag Process for recycling fiber composite materials
US20090087657A1 (en) * 2005-12-13 2009-04-02 Ocv Intelletual Capital Llc. Glass fiber for reinforcing rubber products and method for producing it
CN101384648B (zh) * 2006-02-16 2012-01-18 Ngf欧洲公司 通过挤出或模塑形成橡胶制品的方法、涂层胶乳和增强帘线

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5228580A (en) * 1975-08-29 1977-03-03 Honny Chem Ind Co Ltd Method for adhering metals with rubbers
GB2042010B (en) * 1979-02-02 1983-01-26 Ppg Industries Inc Method for preparing composite strands of resin carbon and glass and product formed from said strands

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1844943A (en) * 1928-10-27 1932-02-16 Naugatuck Chem Co Treatment of rubber
US2100085A (en) * 1932-01-05 1937-11-23 Us Rubber Co Production of vulcanized rubber
US2577843A (en) * 1943-03-08 1951-12-11 Dayton Rubber Company Method of manufacturing wire cord
US2773795A (en) * 1953-01-05 1956-12-11 Phillips Petroleum Co Rubber-fabric laminates and method of making same
US2953549A (en) * 1957-02-01 1960-09-20 Exxon Research Engineering Co Preparation and recovery of modified rubbery copolymers
US2974062A (en) * 1956-02-14 1961-03-07 Owens Corning Fiberglass Corp Epoxy-glass fiber systems and method for improving the bonding relation therebetween
US3258388A (en) * 1962-08-31 1966-06-28 Lord Corp Adhesive composition for bonding rubber to metal
US3271182A (en) * 1958-11-26 1966-09-06 Chausson Usines Sa Process for producing sheets of reinforced polyester resin
US3367793A (en) * 1964-01-15 1968-02-06 Burlington Industries Inc Coated glass textile and process of making same
US3384613A (en) * 1964-08-20 1968-05-21 Goodyear Tire & Rubber Retardation of scorch in rubber compounds containing dicumyl peroxide as the vulcanizing agent
US3410749A (en) * 1964-11-12 1968-11-12 Uniroyal Inc Adhesion of polyester cords to elastomers
US3419463A (en) * 1965-11-12 1968-12-31 Celanese Corp Adhesion of polyester to rubber
US3432332A (en) * 1965-01-21 1969-03-11 Owens Corning Fiberglass Corp Method for the impregnation of fibrous glass
US3437610A (en) * 1965-12-27 1969-04-08 Koppers Co Inc Resorcinol-aldehyde resin and polyester tire cord adhesive made therefrom
US3591357A (en) * 1969-08-13 1971-07-06 Owens Corning Fiberglass Corp Method for treating and impregnating glass fiber bundles for reinforcement of elastomeric materials
US3677809A (en) * 1968-11-28 1972-07-18 Henkel & Cie Gmbh Process for the coating of filament bodies with an adhesive for metal and rubber

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1414295A (fr) * 1963-11-13 1965-10-15 Dunlop Rubber Co Perfectionnements au collage de matières textiles à des caoutchoucs

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1844943A (en) * 1928-10-27 1932-02-16 Naugatuck Chem Co Treatment of rubber
US2100085A (en) * 1932-01-05 1937-11-23 Us Rubber Co Production of vulcanized rubber
US2577843A (en) * 1943-03-08 1951-12-11 Dayton Rubber Company Method of manufacturing wire cord
US2773795A (en) * 1953-01-05 1956-12-11 Phillips Petroleum Co Rubber-fabric laminates and method of making same
US2974062A (en) * 1956-02-14 1961-03-07 Owens Corning Fiberglass Corp Epoxy-glass fiber systems and method for improving the bonding relation therebetween
US2953549A (en) * 1957-02-01 1960-09-20 Exxon Research Engineering Co Preparation and recovery of modified rubbery copolymers
US3271182A (en) * 1958-11-26 1966-09-06 Chausson Usines Sa Process for producing sheets of reinforced polyester resin
US3258388A (en) * 1962-08-31 1966-06-28 Lord Corp Adhesive composition for bonding rubber to metal
US3367793A (en) * 1964-01-15 1968-02-06 Burlington Industries Inc Coated glass textile and process of making same
US3384613A (en) * 1964-08-20 1968-05-21 Goodyear Tire & Rubber Retardation of scorch in rubber compounds containing dicumyl peroxide as the vulcanizing agent
US3410749A (en) * 1964-11-12 1968-11-12 Uniroyal Inc Adhesion of polyester cords to elastomers
US3432332A (en) * 1965-01-21 1969-03-11 Owens Corning Fiberglass Corp Method for the impregnation of fibrous glass
US3419463A (en) * 1965-11-12 1968-12-31 Celanese Corp Adhesion of polyester to rubber
US3437610A (en) * 1965-12-27 1969-04-08 Koppers Co Inc Resorcinol-aldehyde resin and polyester tire cord adhesive made therefrom
US3677809A (en) * 1968-11-28 1972-07-18 Henkel & Cie Gmbh Process for the coating of filament bodies with an adhesive for metal and rubber
US3591357A (en) * 1969-08-13 1971-07-06 Owens Corning Fiberglass Corp Method for treating and impregnating glass fiber bundles for reinforcement of elastomeric materials

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4216856A (en) * 1975-04-25 1980-08-12 Dunlop Limited Reinforcement for elastomeric articles
US4123287A (en) * 1975-07-24 1978-10-31 Pilkington Brothers Limited Glass fibres for reinforcement of cement products
US4467064A (en) * 1980-11-11 1984-08-21 Unitika Ltd. Method of manufacturing polyester fibers with good adhesion to rubber
US4923517A (en) * 1987-09-17 1990-05-08 Exxon Research And Engineering Company Glass fiber reinforced cement compositions
US5079066A (en) * 1988-05-25 1992-01-07 Minnesota Mining And Manufacturing Company Tape having improved tear strength
US5173141A (en) * 1988-05-25 1992-12-22 Minnesota Mining And Manufacturing Company Preparing tape having improved tear strength
US5240983A (en) * 1989-07-17 1993-08-31 Chisso Corporation Process for producing polyolefin thermoplastic elastomer composition
US5145544A (en) * 1989-08-01 1992-09-08 Minnesota Mining And Manufacturing Company Method for preparing tape having improved tear strength
US5260111A (en) * 1991-08-08 1993-11-09 Bridgestone Corporation Thermoplastic films for heat seaming roof sheeting and method for covering roofs
US5486249A (en) * 1991-08-08 1996-01-23 Bridgestone Corporation Thermoplastic films for heat seaming roof sheeting and method for covering roofs
US6220304B1 (en) * 1998-07-30 2001-04-24 Toyoda Gosei Co., Ltd. Brake hose
WO2000023505A1 (en) * 1998-10-15 2000-04-27 N.V.Bekaert S.A. Coated metal reinforcement element and coating methods
WO2000023504A1 (en) * 1998-10-15 2000-04-27 Continental Aktiengesellschaft Composite of a vulcanizable rubber composition and cured rubber product
US6821632B2 (en) 1998-10-15 2004-11-23 Continental Aktiengesellschaft Composite of a vulcanizable rubber composition and cured rubber product
US6830826B2 (en) 1998-10-15 2004-12-14 N.V. Bekaert S.A. Coated metal reinforcement element and coating materials
US6537341B2 (en) * 2000-05-30 2003-03-25 Daimlerchrysler Ag Process for recycling fiber composite materials
US20090087657A1 (en) * 2005-12-13 2009-04-02 Ocv Intelletual Capital Llc. Glass fiber for reinforcing rubber products and method for producing it
US7814741B2 (en) * 2005-12-13 2010-10-19 Ocv Intellectual Capital, Llc Glass fiber for reinforcing rubber products and method for producing it
CN101384648B (zh) * 2006-02-16 2012-01-18 Ngf欧洲公司 通过挤出或模塑形成橡胶制品的方法、涂层胶乳和增强帘线

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NL7203020A (enrdf_load_html_response) 1972-09-12
GB1393104A (en) 1975-05-07
FR2128732A1 (enrdf_load_html_response) 1972-10-20
CA983369A (en) 1976-02-10
BR7201290D0 (pt) 1973-06-14
BE780371A (fr) 1972-07-03
FR2128732B1 (enrdf_load_html_response) 1976-08-06
DE2209082A1 (de) 1972-09-14

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