US3305430A - Process for bonding rubber to yarn and the resulting product - Google Patents

Process for bonding rubber to yarn and the resulting product Download PDF

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US3305430A
US3305430A US165002A US16500262A US3305430A US 3305430 A US3305430 A US 3305430A US 165002 A US165002 A US 165002A US 16500262 A US16500262 A US 16500262A US 3305430 A US3305430 A US 3305430A
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rubber
yarn
cord
fabric
diene
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Hennemann Georg
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Akzona Inc
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American Enka Corp
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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
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/487—Aziridinylphosphines; Aziridinylphosphine-oxides or sulfides; Carbonylaziridinyl or carbonylbisaziridinyl compounds; Sulfonylaziridinyl or sulfonylbisaziridinyl compounds
    • 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
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31826—Of natural rubber
    • Y10T428/31833—Next to aldehyde or ketone condensation product or addition polymer from unsaturated monomers
    • 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
    • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric

Definitions

  • the present invention relates to the manufacture of yarn, cord, or fabric from macromolecular polyalkylene terephthalate which adheres satisfactorily to rubber, and to yarn, cord, or fabric thus treated, and to rubber articles reinforced therewith.
  • yarn, cord or fabric is first wetted with water and subsequently treated with a latex dispersion of a copolymer of a vinyl pyridine with a diene in an aqueous solution of a pre-condensation product of resorcinol and formaldehyde. If thus-treated yarn, cord, or fabric of macromolecular polyethylene terephthalate is used as a reinforcement in rubber, the adhesion of said products to rubber is not satisfactory.
  • Textile structure such as yarn, cord, or fabric comprising a macromolecular polyalkylene terepththalate th-us treated adheres satisfactorily to rubber.
  • the improved adhesion provided by the foregoing treatment can be improved further by adding amines to the solutions or emulsions of homoor copolymers of vinyl or/and vinylidene halides.
  • the present invention provides a process for the manufacture of yarn, cord, or fabric of a macromolecular polyalkylene terephthalate, which yarn, cord, or fabric retains substantially the resiliency of the untreated material while adhering well to rubber.
  • the process of the present invention for the manufacture of yarn, cord, or fabric comprising macromolecular po'lyaikylene terephthalate having satisfactory adhesion to rubber while retaining substantially its resiliency, comprises in a first step treating the yarn, cord, or fabric with an aqueous solution of polyethylene imine and thereafter drying the treated material, and in a second step treating the so pre-treated yarn, cord, or fabric in a per se known manner with a latex dispersion of a copolymer of a vinyl pyridine with a diene in an aqueous solution of a pro-condensation product of a phenol with an aldehyde, and finally drying the treated material under ten SlOI1.
  • the class of macromolecular polyalkylene terephthalates includes all polymeric esters containing a large proportion of esters which may be obtained by subjecting glycols of the series HO(CH ),,OH, where n is an integer which may vary from 2 to 10, together with terephthalic acid or a mixture of terephthalic acid and isophthalic acid, to a heat treatment under conditions yielding high-polymeric esters.
  • an ester forming derivative thereof for instance an aliphatic (including a cycloaliphatic) or an aromatic ester or a semi-ester, an acid halide or an ammonium or amine salt can be used.
  • the aliphatic glycol can be replaced with a cyclo aliphatic glycol.
  • yarns include both threads made up of continuous filaments and threads spun from staple fibres.
  • the terms cord and fabric as used herein are intended to refer respectively to tire cord and tire cord fabric.
  • the rubber can be any natural rubber, including guttapercha, balata, compound rubber, modified rubber, for instance hydroxylated rubibers, condensation derivatives of rubber and cyclized rubber.
  • the rubber also can be synthetic rubber, for instance synthetic rubber-like dienepolymers and diene-copolymers, such as neoprenes, butadiene-styrene-interpolymers, butadiene-acrylic acid nitrileinterpolymers, poly-sulphide rubbers and rubber-like copolymers of an alkyl acry'late and a chloralkylvinylether.
  • the treatment according to the present invention comprises in the first step, contacting threads, cords, or fabrics with a solution of polyethylene imine, the threads, cords and fabrics being relaxed or under tension.
  • a solution of polyethylene imine for example yarns or cords may be treated while they are in skein form. Or, with the aid of rollers, they may 'be continuously passed through a bath containing a polyethylene imine solution. If necessary, excess amounts of solution are removed in any suitable manner as by centrifuging or squeezing.
  • the temperature in the first process step is not critical but below .the softening point of the polymer.
  • the treatment is carried out at room temperature.
  • polyethylene imines suitable for use in the method of the present invention is the product commercially available under the trademark, Polymin P, which has a degree of polymerization of the order of about 160 and a composition corresponding to the formula: H N(OH CH NH),,H, where n is about 160.
  • the concentration of the polyethylene imine solution may vary from 0.1 to 3% by weight. Although a concentration below 0.1% by weight is effective to some extent, the effect i reduced considerably at lower concentrations. Preferably, solutions having a concentration higher than 0.5% by weight are used in the method of the present invention. Concentrations higher than 3% by weight yield good results, but from the point of view of economy they are not necessary.
  • the drying process following the treatment of the first step can be carried out while the yarn, the cord, or the fabric is under tension.
  • the yarn, the cord, or the fabric also may be subjected to the drying process while relaxed.
  • the yarn can be treated in the second step with the latex dispersion while the yarn, the cord or the fabric is kept under tension.
  • the yarn, the cord, or the fabric can be under substantially no tension during this treatment.
  • the pre-treated yarn, cord, or fabric is contacted with a latex dispersion of copolymers of vinyl pyridines with dienes in aqueous solutions of precondensation products of phenols with aldehydes which latter as such are known in the prior art.
  • Vinyl pyridines are used together with dienes for the preparation of copolymers thereof.
  • Illustrative of the vinyl pyridines are a-vinyl pyridines, fi-vinyl pyridines or -vinyl pyridines, or homologues thereof, for example: 5-ethyl-2-vinyl pyridine, 5-propyl-2-vinyl pyridine, S-butyl-vinyl pyridine, 5- hexyl-vinyl pyridine, S-heptyl-vinyl pyridine, 6-methyl-2- vinyl pyridine, 4,6-dimethyl-2-vinyl pyridine, 2-methyl-4- vinyl pyridine, 2-ethyl-5-vinyl pyridine and 2-methyl-6- vinyl pyridine.
  • dienes which can be used with vinyl pyridines for the preparation of copolymers are: 1,3- butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl 1,3 butadiene, 1,3-dimethyl-l,3-butadiene, 1,3-pentadiene, 2,4- pentadiene, 3-methyl-2,4-pentadiene and 3,4-dimethyl-2,4- pentadiene.
  • the latex dispersions of the second step can contain natural rubber as well as the copolymers of vinyl pyridines with dienes.
  • styrene styrene
  • filling agents vulcanization accelerators and plasticizers.
  • vulcanization accelerators vulcanization accelerators and plasticizers.
  • the phenols employed for the preparation of the dispersions of the second steps are monoor polyhydric phenols.
  • Suitable monohydric phenols are, for instance, phenol, cresols, xylenols, and naphthols.
  • Suitable polyhydric phenols are: resorcinol, catechol, phloroglucinol, orcinol and hydroquinone.
  • the aldehydes used for the preparation of the dispersions of the second step are preferably: paraformaldehyde, acetaldehyde, butyraldehyde, chloral, furfurol and salicylaldehyde.
  • the excess amount of dispersion employed in the second step can be removed in any suitable way, as by centrifuging, or squeezing with rollers.
  • the excess amount is removed by high pressure air jets or scrapers.
  • the yarns, cords, or fabrics treated in the second step are dried, while under tension, at a temperature of at least 100 C. but below the softening temperature of the material.
  • a latex dispersion comprising a dispersion of a copolymer of 2-vinyl pyridine and butadiene in .a solution of the pre-condensation product of resorcinol and formaldehyde.
  • Adhesion can be improved even further using as a latex dispersion a dispersion comprising a copolymer of 2-vinyl pyridine, butadiene and styrene in an aqueous solution of the pre-condensation product of resorcinol and formaldehyde.
  • Natural rubber can be dispersed in the latex dispersion employed in the process of the present invention.
  • the yarn, cord or fabric can be treated under substantially no tension with an approximately 1.5% by weight aqueous solution of polyethylene imine and subsequently be dried, while relaxed, or under no substantial tension at a temperature below C.
  • Example A tire cord comprising polyethylene terephthalate in the form of a skein was immersed for 10 minutes in a 1.5% by weight aqueous solution of Polymin P (polyethylene imine) and subsequently centrifuged.
  • the pretreated tire cord was then wound on a bobbin, from which it was continuously passed by means of rollers through a bath at 23 C.
  • Gen Tac a commercially available latex, which is an aqueous dispersion of a coplymer of a mixture of butadiene, 2-vinyl pyridine and styrene.
  • the mixture contains about 5 to 30% of 2-vinyl pyridine or 10 to 35% of a mixture of 2-vinyl pyridine and styrene), 11 parts by weight of formaldehyde, 19 parts by weight of resorcinol, and 425 parts by weight of water.
  • the tire cord treated in this manner was dried under tension for 20 seconds at 210 C.
  • the tire cord was very resilient and not stiff. After the tire cord had been embedded in GR-S rubber or natural rubber, and cured, adhesion between cord and rubber was very satisfactory.
  • a tire cord subjected to the same treatment, but not to a pre-treatment with polyethylene imine showed poor adhesion to rubber.
  • a tire cord subjected to the same treatment, after pretreatment with polyvinyl chloride instead of polyethylene imine showed good adhesion to rubber, but was very stiff.
  • a process for treating a textile structure selected from the group consisting of yarn, cord, and fabric comprising macromolecular polyalkylene terephthalate which adheres satisfactorily to rubber whilst retaining substantially the resiliency of the untreated textile structure which comprises contacting said textile structure comprising macromolecular polyalkylene terephthalate with an aqueous solution of polymerized ethylene imine, drying the so pretreated structure, contacting the dried, pretreatstructure with latex dispersion comprising a copolymer of a vinyl pyridine with a diene in an aqueous solution of a precondensation product of a phenol 'and an aldehyde, and drying and curing the resultant structure while under tension.
  • a rubber article reinforced with polyethylene terephthalate formed structure said polyethylene terephthalate formed structure having been treated with polyethylene imine and latex dispersion comprising a copolymer of a vinylpyridine with a diene in an aqueous solution of a precondensation product of a phenol and an aldehyde and cured before embedding in the rubber selected from the group consisting of natural rubber, gutta-percha, balata,

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Description

3,305,430 Patented Feb. 21, 1967 3,305,430 PRUClEfiS FOR BONDING RUBBER T YARN AND THE RESULTING PRODUCT Georg Hennemann, Velp, Netherlands, assignor, by mesne assignments, to American Enka Corporation, Erika, N.C., a corporation of Delaware No Drawing. Filed Jan. 8, 1962, Ser. No. 165,002
Claims priority, application Netherlands, Jan. 23, 1961, 260,385 3 Claims. (Cl. 161227) The present invention relates to the manufacture of yarn, cord, or fabric from macromolecular polyalkylene terephthalate which adheres satisfactorily to rubber, and to yarn, cord, or fabric thus treated, and to rubber articles reinforced therewith.
Various processes for the improvement of adhesion of textile structures such as yarns, cords or fabrics to rubber have been proposed previously. According to one of these processes, yarn, cord or fabric is first wetted with water and subsequently treated with a latex dispersion of a copolymer of a vinyl pyridine with a diene in an aqueous solution of a pre-condensation product of resorcinol and formaldehyde. If thus-treated yarn, cord, or fabric of macromolecular polyethylene terephthalate is used as a reinforcement in rubber, the adhesion of said products to rubber is not satisfactory.
It has therefore been suggested to first subject textile structures selected from the group consisting of yarns, cords, or fabrics of macromolecular polyalkylene terephthalates to a pre-treatment with a solution or emulsion of a homoorcopolymer of a vinyl or/ and a vinylidene halide, subsequently to dry them, and thereafter to treat them with the aforementioned latex dispersion of a copolymer of a vinyl pyridine with a diene in a solution of a reaction product of a phenol and an aldehyde.
Textile structure such as yarn, cord, or fabric comprising a macromolecular polyalkylene terepththalate th-us treated adheres satisfactorily to rubber.
It was also suggested that the improved adhesion provided by the foregoing treatment can be improved further by adding amines to the solutions or emulsions of homoor copolymers of vinyl or/and vinylidene halides.
This prior art treatment has the disadvantage that it causes the yarn, cords, or fabrics to lose a great deal of their resilience, which renders them very stiff. As a result, they are less suitable to be used for reinforcing rubber articles.
The present invention provides a process for the manufacture of yarn, cord, or fabric of a macromolecular polyalkylene terephthalate, which yarn, cord, or fabric retains substantially the resiliency of the untreated material while adhering well to rubber.
It is one of the principal objects of the present invention to provide yarn, cord, and fabric comprising macromolecular polyalkylene terephtha'late having good adherence to rubber while retaining substantially their initial resiliency. It is another object of the present invention to provide a method of treating yarn, cord, or fabric comprising macromolecular polyalkylene terephthalate to provide articles of the aforementioned classes having satisfactory adherence to rubber while retaining the resiliency of the untreated material. It is a further object of the present invention to provide rubber articles reinforced with yarn, cord, or fabric comprising macromolecular polyalkylene terephthalate in which the yarn, cord or fabric adheres satisfactorily to the rubber while retaining substantially the resiliency of the macromolecular polyalkylene terephthalate.
The process of the present invention, for the manufacture of yarn, cord, or fabric comprising macromolecular po'lyaikylene terephthalate having satisfactory adhesion to rubber while retaining substantially its resiliency, comprises in a first step treating the yarn, cord, or fabric with an aqueous solution of polyethylene imine and thereafter drying the treated material, and in a second step treating the so pre-treated yarn, cord, or fabric in a per se known manner with a latex dispersion of a copolymer of a vinyl pyridine with a diene in an aqueous solution of a pro-condensation product of a phenol with an aldehyde, and finally drying the treated material under ten SlOI1.
As those skilled in the art know, the class of macromolecular polyalkylene terephthalates includes all polymeric esters containing a large proportion of esters which may be obtained by subjecting glycols of the series HO(CH ),,OH, where n is an integer which may vary from 2 to 10, together with terephthalic acid or a mixture of terephthalic acid and isophthalic acid, to a heat treatment under conditions yielding high-polymeric esters. Instead of employing the terephthalic or the isophthalic acid or both, an ester forming derivative thereof, for instance an aliphatic (including a cycloaliphatic) or an aromatic ester or a semi-ester, an acid halide or an ammonium or amine salt can be used. The aliphatic glycol can be replaced with a cyclo aliphatic glycol.
Those skilled in the art know that yarns include both threads made up of continuous filaments and threads spun from staple fibres. The terms cord and fabric as used herein are intended to refer respectively to tire cord and tire cord fabric.
The rubber can be any natural rubber, including guttapercha, balata, compound rubber, modified rubber, for instance hydroxylated rubibers, condensation derivatives of rubber and cyclized rubber. The rubber also can be synthetic rubber, for instance synthetic rubber-like dienepolymers and diene-copolymers, such as neoprenes, butadiene-styrene-interpolymers, butadiene-acrylic acid nitrileinterpolymers, poly-sulphide rubbers and rubber-like copolymers of an alkyl acry'late and a chloralkylvinylether.
The treatment according to the present invention comprises in the first step, contacting threads, cords, or fabrics with a solution of polyethylene imine, the threads, cords and fabrics being relaxed or under tension. For example yarns or cords may be treated while they are in skein form. Or, with the aid of rollers, they may 'be continuously passed through a bath containing a polyethylene imine solution. If necessary, excess amounts of solution are removed in any suitable manner as by centrifuging or squeezing.
The temperature in the first process step is not critical but below .the softening point of the polymer. For economy, the treatment is carried out at room temperature.
Illustrative of the polyethylene imines suitable for use in the method of the present invention is the product commercially available under the trademark, Polymin P, which has a degree of polymerization of the order of about 160 and a composition corresponding to the formula: H N(OH CH NH),,H, where n is about 160.
The concentration of the polyethylene imine solution may vary from 0.1 to 3% by weight. Although a concentration below 0.1% by weight is effective to some extent, the effect i reduced considerably at lower concentrations. Preferably, solutions having a concentration higher than 0.5% by weight are used in the method of the present invention. Concentrations higher than 3% by weight yield good results, but from the point of view of economy they are not necessary.
The drying process following the treatment of the first step can be carried out while the yarn, the cord, or the fabric is under tension. However, the yarn, the cord, or the fabric also may be subjected to the drying process while relaxed.
In the process of the present invention, the yarn can be treated in the second step with the latex dispersion while the yarn, the cord or the fabric is kept under tension. However, the yarn, the cord, or the fabric can be under substantially no tension during this treatment.
As mentioned before, in the second step of the process of the present invention the pre-treated yarn, cord, or fabric is contacted with a latex dispersion of copolymers of vinyl pyridines with dienes in aqueous solutions of precondensation products of phenols with aldehydes which latter as such are known in the prior art.
Vinyl pyridines, known to those skilled in the art, are used together with dienes for the preparation of copolymers thereof. Illustrative of the vinyl pyridines are a-vinyl pyridines, fi-vinyl pyridines or -vinyl pyridines, or homologues thereof, for example: 5-ethyl-2-vinyl pyridine, 5-propyl-2-vinyl pyridine, S-butyl-vinyl pyridine, 5- hexyl-vinyl pyridine, S-heptyl-vinyl pyridine, 6-methyl-2- vinyl pyridine, 4,6-dimethyl-2-vinyl pyridine, 2-methyl-4- vinyl pyridine, 2-ethyl-5-vinyl pyridine and 2-methyl-6- vinyl pyridine.
Illustrative of dienes which can be used with vinyl pyridines for the preparation of copolymers, are: 1,3- butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl 1,3 butadiene, 1,3-dimethyl-l,3-butadiene, 1,3-pentadiene, 2,4- pentadiene, 3-methyl-2,4-pentadiene and 3,4-dimethyl-2,4- pentadiene.
The latex dispersions of the second step can contain natural rubber as well as the copolymers of vinyl pyridines with dienes.
Furthermore, other substances may be added, for example styrene, filling agents, vulcanization accelerators and plasticizers.
The phenols employed for the preparation of the dispersions of the second steps are monoor polyhydric phenols.
However, mixtures thereof can also be used. Suitable monohydric phenols are, for instance, phenol, cresols, xylenols, and naphthols.
Examples of suitable polyhydric phenols are: resorcinol, catechol, phloroglucinol, orcinol and hydroquinone.
The aldehydes used for the preparation of the dispersions of the second step are preferably: paraformaldehyde, acetaldehyde, butyraldehyde, chloral, furfurol and salicylaldehyde.
When necessary or desirable, the excess amount of dispersion employed in the second step can be removed in any suitable way, as by centrifuging, or squeezing with rollers.
Preferably, however, the excess amount is removed by high pressure air jets or scrapers.
The yarns, cords, or fabrics treated in the second step are dried, while under tension, at a temperature of at least 100 C. but below the softening temperature of the material.
According to the invention, good results are obtained using a latex dispersion comprising a dispersion of a copolymer of 2-vinyl pyridine and butadiene in .a solution of the pre-condensation product of resorcinol and formaldehyde.
Adhesion can be improved even further using as a latex dispersion a dispersion comprising a copolymer of 2-vinyl pyridine, butadiene and styrene in an aqueous solution of the pre-condensation product of resorcinol and formaldehyde.
Natural rubber can be dispersed in the latex dispersion employed in the process of the present invention.
In treating yarn, cord, or cord fabric of polyethylene terephthalate such as those available under the trade names Terylene, Dacron or Terlenka in the first step of the process of the present invention, the yarn, cord or fabric can be treated under substantially no tension with an approximately 1.5% by weight aqueous solution of polyethylene imine and subsequently be dried, while relaxed, or under no substantial tension at a temperature below C.
In order that those skilled in the art may have a better understanding of the present invention, the following illustrative example is provided.
Example A tire cord comprising polyethylene terephthalate in the form of a skein was immersed for 10 minutes in a 1.5% by weight aqueous solution of Polymin P (polyethylene imine) and subsequently centrifuged. The pretreated tire cord was then wound on a bobbin, from which it was continuously passed by means of rollers through a bath at 23 C. prepared from 438 parts by weight of Gen Tac (a commercially available latex, which is an aqueous dispersion of a coplymer of a mixture of butadiene, 2-vinyl pyridine and styrene. The mixture contains about 5 to 30% of 2-vinyl pyridine or 10 to 35% of a mixture of 2-vinyl pyridine and styrene), 11 parts by weight of formaldehyde, 19 parts by weight of resorcinol, and 425 parts by weight of water.
The tire cord treated in this manner was dried under tension for 20 seconds at 210 C. The tire cord was very resilient and not stiff. After the tire cord had been embedded in GR-S rubber or natural rubber, and cured, adhesion between cord and rubber was very satisfactory.
A tire cord subjected to the same treatment, but not to a pre-treatment with polyethylene imine showed poor adhesion to rubber.
A tire cord subjected to the same treatment, after pretreatment with polyvinyl chloride instead of polyethylene imine showed good adhesion to rubber, but was very stiff.
What is claimed is:
1. A process for treating a textile structure selected from the group consisting of yarn, cord, and fabric comprising macromolecular polyalkylene terephthalate which adheres satisfactorily to rubber whilst retaining substantially the resiliency of the untreated textile structure which comprises contacting said textile structure comprising macromolecular polyalkylene terephthalate with an aqueous solution of polymerized ethylene imine, drying the so pretreated structure, contacting the dried, pretreatstructure with latex dispersion comprising a copolymer of a vinyl pyridine with a diene in an aqueous solution of a precondensation product of a phenol 'and an aldehyde, and drying and curing the resultant structure while under tension.
2. The process according to claim 1, wherein 'an approximately 0.l% to about 3% by Weight solution of polymerized ethylene imine is used.
3. A rubber article reinforced with polyethylene terephthalate formed structure, said polyethylene terephthalate formed structure having been treated with polyethylene imine and latex dispersion comprising a copolymer of a vinylpyridine with a diene in an aqueous solution of a precondensation product of a phenol and an aldehyde and cured before embedding in the rubber selected from the group consisting of natural rubber, gutta-percha, balata,
5 compound rubber, modified rubber, condensation derivatives of rubber and cyclized rubber, synthetic rubber-like diene-polymers, diene-copolymers, butdiene-styrene-interpolymers, butadiene-acrylic acid nitrile-interpolymers, polysulphide rubbers, and rubber-like copolyrners of an alkylacrylate and a chloroalkylvinylether of said rubber article.
References Cited by the Examiner UNITED STATES PATENTS 2,272,489 2/1942 Ulrich. 2,691,614 10/1954 Wilson.
Harver 260-29.2 Rosser.
Danielson 161241 Hammermesh 161-191 Blurnberg 161191 X Watkins et a1. 161-227 X EARL M. BERGERT, Primary Examiner. 10 JACOB STEINBERG, Examiner.
E. G. WHITBY, C. B. COSBY, Assistant Examiners.

Claims (1)

  1. 3. A RUBBER ARTICLE REINFORCED WITH POLYETHYLENE TEREPHTHALATE FORMED STRUCTURE, SAID POLYETHYLENE TEREPHTHALATE FORMED STRUCTURE HAVING BEEN TREATED WITH POLYETHYLENE IMINE AND LATEX DISPERSION COMPRISING A COPOLYMER OF A VINYLPYRIDINE WITH A DIENE IN AN AQUEOUS SOLUTION OF A PRECONDENSATION PRODUCT OF A PHENOL AND AN ALDEHYDE AND CURED BEFORE EMBEDDING IN THE RUBBER SELECTED FROM THE GROUP CONSISTING OF NATURAL RUBBER, GUTTA-PERCHA, BALATA, COMPOUND RUBBER, MODIFIED RUBBER, CONDENSATION DERIVATIVES OF RUBBER AND CYCLIZED RUBBER, SYNTHETIC RUBBER-LIKE DIENE-POLYMERS, DIENE-COPOLYMERS, BUTADIENE-STYRENE-INTERPOLYMERS, BUTADIENE-ACRYLIC ACID NITRILE-INTERPOLYMERS, POLYSULPHIDE RUBBERS, AND RUBBER-LIKE COPOLYMERS OF AN ALKYLACRYLATE AND A CHLOROALKYLVINYLETHER OF SAID RUBBER ARTICLE.
US165002A 1961-01-23 1962-01-08 Process for bonding rubber to yarn and the resulting product Expired - Lifetime US3305430A (en)

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BE (1) BE612198A (en)
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NL (2) NL103985C (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3449200A (en) * 1965-10-05 1969-06-10 Gen Tire & Rubber Co Product and method of producing composite polyester textile rubber products
US3547729A (en) * 1967-10-27 1970-12-15 Firestone Tire & Rubber Co Method of adhering rubber to a fabric employing a novel adhesive composition
US3716396A (en) * 1970-04-21 1973-02-13 K Shirano Process for producing polyesters of improved rubber adhesion and product
US3853657A (en) * 1972-02-14 1974-12-10 Monsanto Co Bonding of poly(ethylene terephthalate) induced by low-temperature plasmas
US4283455A (en) * 1979-11-19 1981-08-11 Burlington Industries, Inc. Production of cover fabrics for V belts which function as wear indicators due to different layer characteristics
US10611929B2 (en) 2014-12-19 2020-04-07 Basf Se Composite article

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7809025A (en) * 1978-09-04 1980-03-06 Akzo Nv A PROCESS FOR IMPROVING THE ADHESION OF POLYVINYL CHLORIDE TO A FABRIC, KNITTLE, FLEEC OR OTHER PRODUCTS OF MACROMOLECULAR POLYMETHYLENE PERHALATE MADE FROM THREADS, YARNS OR FIBERS.
US5128054A (en) * 1991-01-02 1992-07-07 Bridgestone/Firestone, Inc. Adhesive-active polyester yarn
US7669626B1 (en) * 2008-11-07 2010-03-02 The Goodyear Tire & Rubber Company Tire with component containing polyketone short fiber and polyethyleneimine

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2272489A (en) * 1935-08-07 1942-02-10 Gen Aniline & Film Corp Nitrogenous condensation products and a process of producing same
US2691614A (en) * 1953-09-03 1954-10-12 Goodrich Co B F Adhesive composition and article containing said adhesive and methods for making thesame
US2699431A (en) * 1951-06-19 1955-01-11 Harvel Res Corp Compositions containing a rubber and an acetone formaldehyde resin
US2828237A (en) * 1955-09-08 1958-03-25 American Viscose Corp Sealing polyethylene to other organic resins
US3018207A (en) * 1960-07-01 1962-01-23 Us Rubber Co Adhering textile materials to rubber
US3077427A (en) * 1960-09-08 1963-02-12 Interchem Corp New vinyl latex adhesives and laminates made therefrom
US3156606A (en) * 1960-04-04 1964-11-10 Interchem Corp Rubber composition and article of manufacture containing said composition
US3182041A (en) * 1960-05-13 1965-05-04 Minnesota Mining & Mfg Polyester and method of making same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2272489A (en) * 1935-08-07 1942-02-10 Gen Aniline & Film Corp Nitrogenous condensation products and a process of producing same
US2699431A (en) * 1951-06-19 1955-01-11 Harvel Res Corp Compositions containing a rubber and an acetone formaldehyde resin
US2691614A (en) * 1953-09-03 1954-10-12 Goodrich Co B F Adhesive composition and article containing said adhesive and methods for making thesame
US2828237A (en) * 1955-09-08 1958-03-25 American Viscose Corp Sealing polyethylene to other organic resins
US3156606A (en) * 1960-04-04 1964-11-10 Interchem Corp Rubber composition and article of manufacture containing said composition
US3182041A (en) * 1960-05-13 1965-05-04 Minnesota Mining & Mfg Polyester and method of making same
US3018207A (en) * 1960-07-01 1962-01-23 Us Rubber Co Adhering textile materials to rubber
US3077427A (en) * 1960-09-08 1963-02-12 Interchem Corp New vinyl latex adhesives and laminates made therefrom

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3449200A (en) * 1965-10-05 1969-06-10 Gen Tire & Rubber Co Product and method of producing composite polyester textile rubber products
US3547729A (en) * 1967-10-27 1970-12-15 Firestone Tire & Rubber Co Method of adhering rubber to a fabric employing a novel adhesive composition
US3716396A (en) * 1970-04-21 1973-02-13 K Shirano Process for producing polyesters of improved rubber adhesion and product
US3853657A (en) * 1972-02-14 1974-12-10 Monsanto Co Bonding of poly(ethylene terephthalate) induced by low-temperature plasmas
US4283455A (en) * 1979-11-19 1981-08-11 Burlington Industries, Inc. Production of cover fabrics for V belts which function as wear indicators due to different layer characteristics
US10611929B2 (en) 2014-12-19 2020-04-07 Basf Se Composite article

Also Published As

Publication number Publication date
BE612198A (en) 1962-05-02
DE1444109A1 (en) 1968-10-24
ES273413A1 (en) 1962-03-01
NL103985C (en) 1900-01-01
GB962174A (en) 1964-07-01
NL260385A (en) 1900-01-01

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