DE3001838A1 - METHOD FOR GLUING GLASS FIBERS WITH RUBBER OR RUBBER - Google Patents

Description

DR.-ING. WALTER ABITZ DR. DIETER F. MORP DIPL.-PHYS. M. GRITSCHNEDSR

Patent attorneys

f Abltz, Mori, GriUchneder, Po »tf, 68QlQO, 3OOQ Munich 86 ~~] Munich,

January 18, 1980

PoaSanechriit / Poetal Addroaa Pootfsch Q3OSO0, BOOO MUnchon ββ

PionsennuorstrafJo SS Tolsfon Θβ 32 SS Tologrammo: Cbomindua Munich

Tolsx: CO) 623692

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The General Tire a Rubber Company One General Street, Akron Ohio 44329

Process for gluing glass fibers with rubber or rubber

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The present invention relates to a method for gluing glass fibers with rubber using a Composition of a rubbery vinyl pyridine copolymer, a polybutadiene rubber and a phenolic resin.

It is the object of the present invention to provide a composite material made of a glass fiber reinforcement element glued with rubber, For example, carcass and belt inserts for tires obtained by gluing fiberglass tire cords are available to deliver. Furthermore, the object of the invention is to provide fiberglass reinforcement elements, such as those in the Carcass and belt inserts of tires are used to create that provided with a small amount of an adhesive and can therefore be bonded to the rubber by vulcanization. The invention is also intended to provide a method for bonding glass fiber materials, in particular glass fiber textiles, fibers, cords, yarns and the like with rubber make available in which only a single immersion bath is required. Finally, by the present invention an adhesive immersion bath for glass fibers or glass fiber cords can be created. The following description and the exemplary embodiments serve to explain the objects and advantages according to the invention in more detail.

US Pat. No. 3,300,426 discloses an adhesive dipping bath (solids content 5 to 30%) made of a polybutadiene rubber latex, 94% of the rubber having a cis-1,4 configuration and 6% a trans- 1,4 configuration, and a phenol or a resorcinol-formaldehyde resin, the ratio of resin to rubber latex being 1:10 to 2.5:10. At least one third of the latex is PBD latex, while the remainder can be rubbery vinyl pyridine latex plus other latexes. The aldehyde is used in an amount of 0.5 to 1.5 moles per mole of phenol. It can be seen from Tables I to III, Column 4 of this patent specification that adhesives containing a different PBD latex or an SBR latex are not equivalent to those containing the cis-1,4-PBD-

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Latex included. The adhesive is used in an amount of 1 to 8% by weight to bond rayon, polyester or polyamide cord or fibers to rubber by vulcanization.

US Pat. No. 3,567,671 discloses an aqueous immersion bath for impregnating glass fibers, which consists of a resorcinol-formaldehyde resin, a butadiene-styrene-vinylpyridine terpolymer, a carboxylated butadiene-styrene latex and microcrystalline paraffin wax »

US Pat. No. 3,787,224 discloses an aqueous immersion bath for impregnating glass fibers, which consists of a resorcinol-formaldehyde resin, a butadiene-styrene-vinylpyridine terpolymer, a dicarboxylated styrene-butadiene resin, in which the ratio of styrene to butadiene is 50/50 to 85/15 (high styrene content, resin-like rather than rubber-like), and consists of a microcrystalline wax. It should be noted here that the 3,567,671 carboxylated used in DER US Patent SBR resin latex is a monocarboxylated SBR resin latex.

US Pat. No. 3,844,821 discloses a cord immersion bath made from a vinylpyridine-butadiene-styrene terpolymer latex, an RF resin, a vinyl chloride-vinylidene chloride copolymer, an incompatible microcrystalline wax and an acrylonitrile butadiene. Styrene resin latex in which the BD is as little as 5 to 25 parts by weight per 100 parts by weight of the BD-STY-VCN terpolymer (hence it is a resin). Another immersion bath is also described in which the vinyl chloride-vinylidene chloride copolymer has been replaced by a dicarboxylated butadiene-styrene resin latex.

U.S. Patent 4,060,658 discloses a tire cord irapregnant which is suitable for coating glass cords and which consists of a vinyl pyridine latex, a polybutadiene latex, a wax emulsion and an RF resin. The wax emulsion preferably contains about 75% by weight paraffin wax and 25% by weight micro. crystalline wax. Some of the polybutadiene latex can pass through

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SBR latex (up to 50% by weight in the dried impregnation agent) can be replaced, which consists of a STY-BD copolymer from 25 parts by weight of STY and 35 parts by weight of BD, i.e. a copolymer with a high styrene-butadiene content. Part of the polybutadiene latex can also be replaced by a VCN-BD latex (up to 50% by weight in the dried Impregnation agent) consisting of 65 parts by weight of VCN and 35 parts by weight of BD, i.e. a resin, can be replaced. In one of the claims glass fibers are explained, which the residue from about 1 0 to 60% by weight of the vinyl pyridine terpolymer, 30 to 80 % By weight of the polybutadiene, wax in an amount of 4 to 6 % By weight and R-F resin in an amount of 3 to 4% by weight.

British Patent 1,256,705 discloses a cord dipping bath for rayon or nylon cords, which is made up of a vinylpyridine terpolymer latex, a butadiene-styrene-itaconic acid terpolymer latex and an RF resin (or separately added Resorcinol and formaldehyde) in a molar ratio of phenol to aldehyde of 1: 1 to 1: 3. The ratio of the VP latex to the carboxylated latex is between 80: 0 and 20: 100 (the VP latex has a solids content of 41%, while the carboxylated latex has a solids content of 53%). A comparative experiment was carried out in which the carboxylated latex was replaced by an SBR latex.

According to the invention it has been found that a composition of matter in the form of an aqueous alkaline dispersion of a rubbery vinylpyridine copolymer, a rubbery polybutadiene or a rubbery copolymer of at least about 80% butadiene and a thermally convertible, water-soluble phenol-aldehyde resin in certain amounts, and where the rubber-like polymers have a reduced gel content, are very suitable as treatment, dipping or coating material for bonding glass fiber reinforcement elements with rubber mixtures. To achieve the desired pH value _r to avoid latex coagulation and to stabilize the dispersion (or one or more

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their components before they are mixed) a sufficient amount of alkali, for example aqueous sodium or potassium hydroxide solution, incorporate. The amount of alkali used depends on the pH values the resin and the latex, which can vary from batch to batch. Because the proportion of each component is different The amount of alkali required can also vary, depending on the adhesive on the glass fiber reinforcement element was dried to remove the water and to thermally cure the adhesive application, you can use the adhesive Laminating or calendering the element with a vulcanizable rubber mixture and vulcanizing the composite material obtained, what usually happens in a mold »The result is a laminate with high adhesive strength. The usage the rubbery vinyl pyridine copolymer with low gel content reduces the risk of cracking or breaking, what can be seen on glass cords as belt inserts in tires when they are exposed to low or low temperatures will. The use of polybutadiene rubber or rubbery butadiene copolymers with a low gel content make processing easier. In particular, it reduces that Flaking or rubbing off during processing, handling and drying of the item immersed in the adhesive bath Cords. Peeling or rubbing will reduce the amount of glue left on the cord. This rubbing off or flaking also leads to pollution of the atmosphere in the form of small particles, that is, it occurs with Dust-related problems and there is also a fire hazard when drying in the oven, as the particles are very small and organic in nature.

The method according to the invention contains only one immersion stage and can be varied to achieve the desired solids uptake on the cord by changing the concentration of the immersion bath or the passage speed of the cord through the bath with regard to the necessary to achieve the Adhesive binding required amount of substance varies. You can use the cord through several immersion baths one after the other

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the same or different amounts of the aforementioned materials through it in order to achieve the desired substance uptake, but this is not necessary because it also deals with obtain satisfactory results from a single immersion bath.

The glass fiber reinforcement element or the glass fiber cord contains several, essentially uninterrupted and parallel glass fibers or monofilaments. The reinforcement element or the fibers have little or no twist. More precisely, there is no twisting of the element or the fibers intended; if there is a twist, it was exclusively the one that the reinforcing element or the fibers as they pass through the glass fiber processing system and when the cord is packaged or wound up into a roll or coil by chance. In the case of continuous operation, however, the elements can be taken directly from the glass processing plant come and immersed in the aqueous cord adhesive immersion bath, dried and then with a Twist of about 3.8 turns / cm (about 1.5 turns / in) can be equipped. Then the reinforcement elements woven into a tire fabric that contains about one relatively thin weft yarn or element of nylon or Polyester, which can be a monofilament, has. A rubber layer or a rubber layer is then applied to the fabric "Skimmed" rubber mass (skim stock) calendered. You get one for tire production or for others Purposes of ready-to-use, fiberglass-reinforced cord sheet.

Glasses suitable for producing the fibers for the reinforcement elements or glass fiber cords are known. Among the preferred Glasses belong to the so-called "Ε-glass", which is described in "Mechanics of Pneumatic Tires", Clark, National Bureau of Standards Monograph 122, U.S. Dept. of Commerce, (November 1971), pages 241-243, 290 and 291. However, it can also G, H and K glass can be used. The number of glass filaments or fibers in the glass fiber reinforcement element or cord

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to a considerable extent on the end use and the requirements prevailing during use. The number of fiberglass strands used to make a fiberglass reinforcement member or cord can also vary widely. In general, the number of filaments in the fiberglass reinforcing member or cord for a passenger tire is about 500 to 3,000, while the number of strands in the reinforcing member can be 1 to 10. The number of strands is preferably 1 to 7 and the number of filaments about 2000. A commercially available tire cord known under the designation "G-75" (or "G-75.5 / 0") has 5 strands with 408 glass filaments each on. Another such cord, designated "G-15", contains a single strand of 2040 glass filaments. In this regard, see Wolf, "Rubber Journal" (February 1971), pages 26 and 27, and US Pat. No. 3,433,689.

Shortly after their manufacture, the glass fibers are usually (by spraying or dipping or the like and then * send drying in air) sized with a very small amount of an agent that is used in the processing of the glass fibers on the strands or reinforcing elements as well as during the packaging as a protective cover. During the subsequent immersion the size is presumably not removed in the aqueous adhesive dipping bath. Sizing materials for glass fibers are known. For this purpose, preference is given to using silanes, in particular those with groups which at least have Share the surface of the glass fibers and with at least one or more components of the immersion bath a chemical or physical bond or coordination. A very good sizing agent for the glass fibers are γ aminopropyltriethoxysilane and similar aminoalkylalkoxysilanes. If you put the silanes on the glass fibers, go they through hydrolysis and polymerization into poly- (aminosiloxanes) over, in which part of the polymer is bonded to the glass, while another part is amino groups (with active hydrogen atoms) for implementation with components of the immersion bath

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such as the phenol resin, the polybutadiene compound or the vinyl pyridine copolymer compound. Sizing materials for glass fibers are known and some of them are disclosed in U.S. Patents 3 2F? 278 , 3,287,204 and 3,538,974 .

The water-soluble, thermosetting (heat-converting) phenol-aldehyde resin is made by reacting an aldehyde with a phenolic compound. A molar excess (more than the stoichiometrically necessary amount) of the aldehyde is reacted with the phenol compound. Preferably Formaldehyde is used, but acetaldehyde and furfural can also be used. Preferably from Formalin, usually a 37 percent solution of formaldehyde in water, is assumed because it is easier to handle. as well Mixtures of aldehydes can be used. As a phenolic compound can be phenol, resorcinol, the cresols, the xylenols, p-tert-butylphenol or p-phenylphenol or mixtures of these are used. Preferably, formaldehyde and resorcinol are used as reactants, which in water, usually in the presence of an alkaline catalyst or a previously added alkaline material. More information for the production of water-soluble, thermosetting Phenol-aldehyde resins are described in "Encyclopedia of Chemical Technology", Kirk-Othmer, Volume 15, Second Edition, 1968, Interscience Publishers Division of John Wiley & Sons, Inc., New York, pages 176-208; "Technology of Adhesives," Delmonte, Reinhold Publishing Corp., New York, N.Y., 1947, pages 22-52; "Formaldehyde", Walker, A.C.S. Monograph Series, Reinhold Publishing Corp., New York, N.Y., Third Edition, 1964, pages 304 to 344 and "The Chemistry of Phenolic Resins", Martin, John Wiley & Sons, Inc., New York, 1956.

Rubbery, aqueous, alkaline vinyl pyridine copolymer latices are known from U.S. Patents 2561215, 2 615 and 3,437,122 known. They comprise a copolymer of about 50 to 95% by weight 1,3-butadiene, 5 to 40% by weight of a vinyl pyridine and 0 to 40% by weight of an aromatic vinyl compound

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like styrene. Examples of suitable vinyl pyridines are 2-vinyl pyridine, 4-vinyl pyridine, 2-methyl-5-vinyl pyridine and 5-ethyl-2-vinyl pyridine. Preferably, a latex is a terpolymer of about 60 to 80 percent "usually -% butadiene-1,3, from about 7 to 32 wt .-% of styrene and from about 4 to 22 wt _o -% 2-vinylpyridine is used. Even more preferred is a terpolymer of about 7% by weight 1,3-butadiene, 15% by weight styrene, and 15% by weight 2-vinylpyridine. The rubbery vinylpyridine copolymer should have little or no gel content, the maximum gel content of the rubbery vinylpyridine copolymer should be about 60%, that is, for example, the copolymer should have a gel content of about 0 to 60%.

Rubber-like, aqueous, alkaline polybutadiene latices are known. These latices can be used as such. Or those latices can be used in which the 1,3-butadiene has been copolymerized with one or more copolymerizable, monoethylenically unsaturated monomers having not more than 14 carbon atoms, the monomer not being a vinylpyridine monomer. As monomers may be used a nitrile such as acrylonitrile and methacrylonitrile, an amide such as acrylamide, methacrylamide and Äthacrylamid, an acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate, ethyl hexyl acrylate and octyl acrylate, a alkacrylate such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, Methyläthacrylat, Äthyläthacrylat, Butyläthacrylat, hydroxyethyl methacrylate and octyl ethacrylate, an acid such as acrylic acid, methacrylic acid, xthacrylic acid, maleic acid, maleic anhydride, itaconic acid and citraconic acid, an aromatic compound such as styrene, alpha-methylstyrene, p-tert-butylstyrene, methylviny! toluene and p-vinyltoluene and the like, and mixtures of this. In these rubber-like copolymers of 1,3-butadiene and the or ₆ monoethylenically unsaturated monomers, 1,3-butadiene is used in an amount of at least about 80% by weight and the vinyl monomer in an amount of not more than about 20% by weight .-% used. Examples of such rubber-like polymers are polybutadiene-1,3, butadiene-1,3-styrene copolymers, butadiene-1,3-

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Methacrylic acid copolymers, butadiene-1,3-methyl acrylate copolymers, 1-butadiene, S-acrylonitrile copolymers, 1,3-butadiene-styrene-acrylonitrile copolymers, Butadiene-1,3-acrylamide copolymers and the like, as well as mixtures of these. The rubbery polybutadiene or butadiene copolymers should have no or only a low gel content, the maximum gel content of the rubbery polybutadiene or rubbery butadiene copolymers should be about 70%, that is, for example, a gel content of about 0 to 70%.

The production of the rubbery vinyl pyridine copolymer and the rubbery polybutadiene or rubbery Butadiene copolymers are made using free in water Free radicals - forming catalysts, gelling agents, modifiers, Emulsifiers, surfactants, stabilizers, terminators and the like. You can in be polymerized in the cold or in the heat, and the polymerization can be up to a degree of conversion of 100% or can also be carried out below. Polymers with little or no gel content can be made if the polymerization reactions are carried out in the presence of suitable amounts of chain transfer agents or modifying agents and the reactions are stopped below a degree of conversion of 100%. The free radical aqueous emulsion polymerization is known and described, for example, in:

(1) Whitby et al., "Synthetic Rubber", John Wiley & Sons, Inc., New York, 1954;

(2) Schildknecht, "Vinyl and Related Polymers", John Wiley & Sons, Inc., New York, 1952;

(3) "Encyclopedia of Polymer Science and Technology", Interscience Publishers, a division of John Wiley & Sons, Inc., New York, Volume 2 (1965), Volume 3 (1965), Volume 5 (1966), Volume 7 (1967) and Volume 9 (1968); and

(4) "Materials, Compounding Ingredients and Machinery for Rubber", published by "Rubber World ", Bill Communications Inc., New York, 1977.

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The gel content of the rubbery vinyl pyridine copolymer or the polybutadiene or its copolymer is thereby increased determines that the rubber of a sample of the particular latex used is coagulated, the rubber is freed from water and then grind it and then dissolve it in toluene and finally filter the mixture to determine the gel content. (See reference (1), Whitby et al.)

An aqueous, free radical emulsion polymerization process up to high degrees of conversion for the production of rubbery polymers such as rubbery vinylpyridine copolymers, rubbery polybutadienes and rubbery butadiene copolymers with little or no gel content is the same in German patent application P 28 49 414.6 Applicant discloses the entire disclosure of which is incorporated herein should be"

The weight ratio (dry matter) of the rubbery Vinyl pyridine copolymer to the rubbery polybutadiene (or the rubbery butadiene copolymer) is about 20 to 60 parts by weight of rubbery vinyl pyridine copolymer to about 80 to 40 parts by weight of rubbery polybutadiene or rubbery butadiene copolymer for a total of 100 parts by weight of rubber. The phenol-aldehyde resin (dry substance) is in an amount of from about 3 to 15, preferably from 5 to 10 parts by weight per 100 parts by weight of the total weight made of rubbery vinyl pyridine copolymers and rubbery polybutadiene or rubbery butadiene copolymers used.

The pH of the latices and the immersion bath should be alkaline be. Likewise, the pH of surfactants and stabilizers, including anti-freeze agents, should be used and other additives, be alkaline, or they should be compatible or neutral with one another, so that no undesirable Coagulation of the latices takes place.

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One uses one for the desired dispersion of the rubber or Latex particles and sufficient water for the solution of the phenolic resin and the other additives to achieve the desired To achieve viscosity and the correct solids content, so that the necessary absorption of the plague substances and their penetration can take place between the fibers of the cord. The amount of water in the cord immersion bath can generally be varied within limits within which there is a solids content of about 25 to 50% by weight, preferably of about 30 to 40% by weight. A If the water content is too high, it may be necessary to immerse it again in the immersion bath or to apply excessive heat to remove the water in the drying stage. In contrast Too low a water content can cause uneven penetration or too slow coating speeds to lead.

In addition to the surface-active ones already in the latlces Agents or wetting agents and antioxidants can add surfactants to the immersion bath be added, for example in small amounts of up to 10 parts by weight per 100 parts by weight of rubber (dry substance) . Likewise, antioxidants and other stabilizers can be used in small amounts up to about 5 parts by weight each 100 parts by weight of total rubber (dry substance) are added. A small amount of wax can also be added to the immersion bath (natural or synthetic wax), based on the rubber solids present in the immersion bath, can be added, for example about 2 to 10 parts by weight of wax per 100 parts by weight of rubber (dry matter). A suitable wax is for example a wax emulsion, a mixture of paraffin and microcrystalline waxes in water.

To apply the latex adhesive in a reliable manner to the fiberglass cords to apply, the latter is guided through the adhesive immersion bath and under a slight predetermined tension then in a drying oven, where they are placed under a slight predetermined tension (to prevent the

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hanging without noticeable stretching). After leaving the oven, the cords are fed into a cooling zone, where they are air-cooled before being relaxed. In each case, which are leaving the immersion bath, the adhesive-coated cords in the oven for about 5 to 300 lake at about 93.3 to 315.6 ⁰ C (about 200-600 ⁰ F), preferably about 30 to 90 see at about 204.4 to 26O ⁰ C (about 400-500 ⁰ F), dried. The period of time during which the cord remains in the adhesive immersion bath is about a few seconds or at least long enough to ensure that the cord is wetted and that the cord fibers are at least almost completely impregnated the adhesive-coated fiberglass cords can be made in one or more dipping baths and in one or more ovens for different periods of time and at different temperatures.

The static adhesive strength of the dried (heat-converted or heat-cured) adhesive-coated glass fiber cords on rubber is then determined with the aid of the single cord * - H tensile test. The rubber test specimens are each produced from a vulcanizable rubber composition which contains rubber, reinforcing carbon black and the usual mixing and vulcanization auxiliaries. The cords to be tested are each placed parallel to one another in a multi-strand form of the type described in ASTM test standard D 2138-67 relating to the single-cord H tensile adhesion test. The mold is filled with the unvulcanized rubber composition with the cords each held under a tension of 50 g. The rubber is (about 305 ⁰ F) then vulcanized for 20 minutes at about 151.7 ⁰ C to the elastic state "Each rubber test specimen having a thickness of about 6.35 mm (1/4 in) and has a Cordeinbettung in a Length of about 9.52 mm (3/8 in). After vulcanization, the hot, vulcanized piece of rubber is removed from the mold, cooled down and test specimens cut out for the Η test. Each test specimen consists of a single cord that is wrapped in rubber. Both ends of the

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Test specimens are embedded in the middle of a rubber strip or rubber bed with a length of about 2.5 cm (about 1 in). The test specimens are then kept at room temperature for at least 16 hours. Subsequently one determines the force required to separate the cord from the rubber strength at room temperature or 121 ° C (25O ⁰ F) with the aid of a vehicle equipped with test sample grips Instron tester. The maximum force in kilograms (lbs) required to separate the cords from the rubber is the H bond strength. All the values given in the examples below have been obtained under identical test conditions, and all test samples were prepared and tested in the same way, generally in accordance with ASTM regulation D 2138-67. Glass fiber cords or fabrics which have been coated with the adhesive according to the invention using the one-step or single immersion bath according to the invention can have an applied proportion of the solids of the adhesive immersion bath of about 10 to 40% by weight, preferably from about 15 to 25% by weight (dry substance), based on the weight of the cord or fabric. They are suitable for the production of carcasses, belts, flippers (rubber-coated fabric strips to strengthen the bond between the wire core bead and the tire sidewall) and bead protection strips for radial or belted tires, diagonal tires or diagonal radial tires for cars, trucks, motorcycles and bicycles as well as off-road vehicle tires and Aircraft tires and also for the production of drive belts, V-belts, conveyor belts, hoses, seals or sealing sleeves, tarpaulins and the like.

While the adhesive-containing fiberglass reinforcement element with a vulcanizable mixture of natural rubber, rubber-like cis-polybutadiene and rubber-like butadiene-styrene copolymers or a mixture of natural rubber and SBR rubber bonded by joint hardening or vulcanization It goes without saying that one can use the glass fiber reinforcing member containing the thermoset adhesive also stick with other vulcanizable rubber materials

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- for this purpose, the reinforcement element is hardened or vulcanized in combination with the rubber, for example with one or more of the aforementioned rubber types, as well as with nitrile rubbers, chloroprene rubbers, polyisoprene, Polybutadienes, vinyl pyridine rubbers, acrylic rubbers, Isoprene-acrylonitrile rubbers and the like, as well as mixtures of these rubbers. You can use the rubbers the usual mixture additives, such as sulfur, stearic acid, zinc oxide, magnesium oxide, silicon dioxide, carbon black, accelerators, Antioxidants, anti-degradation agents and other known rubber additives, depending on the type of rubber used, incorporate. The adhesive dipping bath according to the invention can also be used for gluing cords, yarns and the like Rayon, nylon or polyester used with rubber compounds will.

The following examples serve to illustrate the invention. Parts and percentages relate to the weight, unless otherwise stated.

example

Glass fiber tire cords (sized H-filament glass cords, Owens-Corning Fiberglas Corp.) are passed through an aqueous, alkaline immersion bath, which contains a water-soluble, thermosetting phenolic resins a rubbery vinyl pyridine terpolymer latex and either a rubbery polybutadiene latex or a "rubbery polybutadiene methacrylic acid latex contains. All of these rubbers (latices) were emulsified using 3.25 parts by weight (Dry matter) "Dresinate" 214 (potassium resin soap, a pale, aqueous, paste-like emulsifier from Hercules, Inc., Process Chem. Div :) per 100 parts by weight of the or of the monomer, with the exception of Experiment 31, in which 4.2 parts by weight of "Dresinate" 214 were used. The cords were then passed through a drying oven around the same to dry and harden the coating from the immersion bath. During the drying stage, the abrasion or flaking

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tern observed. The tensile strength of some cords was examined. Other cords were blended, placed in a mold, and vulcanized with carcass compositions and treated with respect to them Η adhesive strength investigated according to the above-mentioned ASTM test. Other cords were worked into tire fabric and used as belt inserts in passenger car tires (radial tires, Polyester carcasses, two glass belt inserts size HR 78) and according to the ARA Cold Gristmill test to determine cracks or break points in glass belt exnlagen examined.

The compositions of the cord dips used and the method for their preparation are shown in Table I below specified:

Table I.

A. Ingredients (dry weights, excluding water) ;

1. VP - 40 parts

2nd Bd or BMAA - 60 parts

3. RF resin - 7.7 parts (5.81 parts resorcinol and 1.75 parts formaldehyde)

4. # 1500 wax - 6 parts

5. Additional wetting agent - variable

6. Antioxidant - variable

7. Water - to make 35% solids.

B. Resin production (dry weights, excluding water):

1. Resorcinol - 5.82 parts
Formaldehyde - 1.75 parts
Water - 5.96 parts

2. The whole is allowed to stand for 4 hours at 26.7 ° C (80 ⁰ F).

3. The following are added:
Water - 1.2 parts

KOH - 0.15 parts (dry weight)

4. The whole is allowed to stand for 4 hours at 26.7 ° C (80 ⁰ F).

C. Preparation of the immersion bath:
VP-Late
mixes.

1. VP latex and Bd latex and H "0 are combined with one another

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2. The resin solution is added to this mixture

(after aging)
-3. Then the wetting agent, the antioxidant and the # 1500 wax are added in that order.

The immersion bath conditions and the results obtained with them are summarized below in Table II =

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The General Tire
Rubber Company &
I. 58 58 + 58 0 29-3 3001838
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No. Table II 60 113 + 113 I3.4 latex
Particle size 1 (Part A) 53 40 4o 58.5 702A ⁰ ( size) Viscosity gel content
Latex ML-4% 58 58 29.3 3100A ° (up to 1300 & 2900) 2 VP 38 . 57 20th 937A ° (.gr.) BD 113 113 73 I8OOA ⁰ (wide-size l800) 3 VP 38 • 57 20th 702A ° (size) BD 58 58 29.3 100OA ⁰ (wide 700 & I3OO) 4th VP + 38 77.8 799A ⁰ (size) ': BD 113 113 73 lOOOA ⁰ fcreit. 700 & 13OO) 5 VP + 38 77.8 702A ⁰ (.'Gr.) BD 58 29.3 100OA ⁰ (size) 6th VP 27.2 799A ° (size) BD 73 100OA ⁰ (size) 7th VP 27.2 702A ° (size) BD 29.3 3IOOA ⁰ 8th VP . 60.5 799A ⁰ (size) BD 73 3IOOA ⁰ 9 VP 60.5 702A ⁰ (size) BD 29.3 3IOOA ⁰ (up to 1300 & 29OO) 10 VP 20th . 799A ° (. _Gr J BD 73 3100A ⁰ (bii3oo & 2900) 11 VP 20th 702AO (size -) BD 29.3 100OA ⁰ (wide 700 & I3OO) 12th VP 77.8 799A ⁰ (size) BD 73 100OA ⁰ (wide 700 & I3OO) 13th VP 77.8 702A ⁰ (size). BD 29.3 100OA ⁰ (size ') 14th VP 27.2 799A ° (Gr) BD. 73 100OA ⁰ (size) 15th VP 27.2 • 7O2A ⁰ (size) BD - 25 - 3IOOA ⁰ 16 VP 30035/0629 799A ⁰ (size) BD BATH ORIGINAL 3IOOA ⁰ VP BD

GT-1510

latex Table II (Ports.) + + 89 Gel content 73 ί. r. .- ■ · I "- 1""T] (Rr-.) VP (Part A) 50-70 53 % 6θο5 fci I3OO & 29ΟΟ) BD viscosity - 89 44.4 latex (Gr.) attempt VP ML-4 89 53 58.5 Particle size (wide-size I8OO) No. BD 113 45 89 44.4 799A ° (C-r.) 17th VP 57 60 53 58.5 310OA ⁰ (wide-size I8OO) BD 89 50-70 44.4 8l0A ° ( ^{& r} 0 18th VP 53 38 · 58.5 l800A ° (wide-size 18ΟΟ) BD 89 Mt ma Av, 65 8IOA ⁰ 19th VP 53 15th I8OOA ⁰ BMAA 89 92.7 8l0A ° (Gr.) 20th VP 53 58.5 Ί8ΟΟΑ ⁰ (wide-size I8OO) BD 50-70 44.4 - (Gr.) '21 VP - 9.4 8OOA ⁰ (.bi-size 800- kl * BD 190 62 OA ⁰ 1900) 22nd 53 44.4 I8OOA ⁰ VP 89 93-6 810A ° fjre 500 & 2200) . 23 BD 21 . Av. 65 I8OOA ⁰ VP 15 · BMAA 89 44.4 8IOA ⁰ (Gr-) 24 VP 41.5 I8OOA ⁰ (bi-800 & 1700) BD 13.4 - (Gx.) 25th VP 91.3 8OOA ⁰ (bi_i000 & 28ΟΟ) BD 44.4 8IOÄ ⁰ (Gr.) 26th VP 50.5 1200A ⁰ (wide-GrJ I8OO) BD 44.4 937AO (Gr.) 27 VP 58.5 3100A ⁰ (wide-size I800) BD 44.4 810A ⁰ (Gr.) 28 VP 58.5 1800A ⁰ (wide-size I8OO) BD Av. 65 810A ⁰ 29 VP 20th 1800A ⁰ (wide-700 & I300) BD - 81OA ⁰ 30th ABC - 26 - 1800A ⁰ 035/0629 700A ° 31 100OA ⁰ - 32

GT-1510

Table II (cont.) - (Part B)

To the immersion bath too Anti Wing. L. Remarks Abrasion attempt seated benet oxidans rate No. medication (Parts) Wing. L. (Parts) sticky 2 1 3.0 B-5 0 considerable 2 .75 "Kickout" 4th originally runs 3 2 KFA 1.5 Wing. L. not really - originally runs 4th 2 KPA 0 Wing. L. not really - Wing. L. Blistering 9 5 __ 0 Blistering. 10 6th —— 1-5 Blistering 7th 7th __ 0 Blistering 8th 8th __ 1.5 Wing. L. - β 9 - 1.5 Wing. L. "Gubbers" 10 —— 0 Blistering 9 Wing. L. sticky 2 11 3.0 B-5 0 - 6th 12th 3.0 B-5 1.5 Wing. L. - 8th 13th 3.0 B-5 1.5 Wing. L. sticky 8th 14th 3.0 B-5 0 Wing. L. <sticky 8th 15th 3.0 B-5 1.5 sticky. 5 16 3-0 B-5 0 Wing. L. - 8th 17th 3.0 B-5 1.5 - 4th 18th 1.5 B-5. .75 Wing. L. little 19th 1.5 B-5 .75 "Kickout" 2 - 5 20th 1.5 B-5 .75 Wing. L. SEF 4th 21 no encore 0 Wing. L. Shear 22nd • 75 (sheared out) "Kickout" 5 Bad abrasion - 23 2 KFA .75 Bad abrasion; 24 - .75 Breaks / tears in the cord; Blistering Adj. 10 SRF - 25th no encore 0

BATH ORIGINAL

GT-15 TO

Table II (cont.) (Part B)

For the immersion bath to-

Try set Benetoxidans medication __ (Parts) Wing. L. Restrictions Abrasion No. (Parts) - Wing. L. rate 5.0 B-5 .75 26th 1.5 B-5 .75 Wing. L. _ _ S. 27 1.5 B-5 "Gubbers" ..75 Wing. L. Blistering 9 28 4.2 Dresinate 21 4 0 - 6th 29 3.0 - S. 30th considerable Ir 0 "Kickout" 7th 31 during the polymerization __ 2 0.4 KPA to the immersion bath j added

030035/0629

1838

P 30 01 838.3 £ 0
The General Tire &
Rubber Company - 8th au · » MIT-F16
bility ^M! Table II C) (37.8) (Cont.) (26.0) February 26, 1980
GT-1510 27.9 D.P.Ü. 49Ο ^Χ (Part sxi- H-Haft-
firmness (33.1) (18.6) attempt
No. 9 18.1 17.1 (4o.4). _f (27.5) 23.4 1 391 ² 15.0 (33-4) (MC-MH)
(NC-NH) (24.2) train
strength 10 20.3 18.3 (40.5) 11.8 (29.8y (61.5) 26.2 2 227 ³ 15.1 (28.4) 8.4 (22.0) 11 19.6 18.4 (38.0) 12.5 (29-5) (51.6) 26.9 3 186 ³ 12.9 (30.6) 11.0 (21.2) 12th 19.5 17.2 (36.9) 13.5 (24.0) (57.8) 25.9 4th 463 ¹ 13.9 (31.7) 10.0 (19.9) 13th 19.4 16.7 (36.Ο) 13.4 (22.7) (59.3) 28.0 5 285 ¹ 14.4 (30.4) 9.6 (21.1) 14th 18.6 16.3 (40.3) 10.9 (27.9) (57.0) 24.3 6th 298 ⁵ 13.8 (31-5) 9.0 (Π2.2) 15th 18.5 18.3 (37.9) 10.3 (27.0) (61.8) 29.6 7th 361 ¹ 14.3 (34.3) 9.6 (22.0) 16 18.8 17.2 (40.8) 12.7 (27.9) (53.5) 26.2 319 ¹ 15.6 (35.3) 10.1 (22.5) 19.7 18.5 (39.3) 12.2 (27.3) (65-3) 24.8 432 ¹ 16.0 (33.5) 10.0 (21.3) 20.1 17.8 (35.1) 12.7 (25.5) (57.7) 26.6 575 ¹ 15.2 (30.5) 10.2 (20.0) 17.8 . 15.9 (37.6) 12.4 (23.0); (54.7) 27.8 464 ¹ 13.8 (31.3) ' 9.7 (21.1) V 18.5 17.0 (34.8) 11.6 (21.6): (58.7) 29.9 687 ¹ 14.2 (25.3) 9.1 (17.2) 19.7 15.8 64.1) 10.4 (22.5) '(61.3) 28.1 490 ¹ 11.5 e4.0) 9.6 (16.2) 18.6 15.5 (36.5) 9.8 (25-4) (66.0) 24.4 365 ¹ 10.9 (29.3) 7.8 (19-3) 18.2 16.5 (38.3) 10.2 (25.7) (62.0) 27.8 508 ¹ 12.3 (30.4) 7.3 (20.2) 17.8 17.4 _ 11, p (53-9) 13.8 630035/0629 8.8 - 29 11/7 (61.3) BATH ORIGINAL 9.2

GT-1510

- 24 D. P. U. M.I.T, -FIe Table II C) XX- H-detention- (35.4) (Ports'.) J D. train 28.0 19-3 mobility ^ ³ * (Part ^ strength (31.0) D. attempt 25th 552 ² 1 6 .- 1 (38.0), (MC-M (24.9) 28.9 No. 19.3 14.1 (26.5) (SSC-NI (19.6) 17th 26th 17.2 (37ο2) 11.3 (28.4) strength 29.2 20.4 12.0 (31.2) 8.9 (.18.6) (61.8) 18th 27 4O5 ² 16.9 (37.5) 12.9 (26.8) 26.8 18.6 14.2 (23ο1) 8.4 (19.2) (63.7) 19th 28 477 ² 17.0 (35.6) 12.2 (22.5) 27.4 20.7 10.5 (28 \ 0) (17.3) (64.4) 20th 29 - 16.1 (36.4) ro, 2 (22.5) 26.7 19.2 12.7 (33.2) 7.8 (18.0) (59.0) 21 30th 279 ³ 16.5 (40.3) 10.2 (27.9) 21.5 18.2 15.1 62.2) (22.0) (60.3) 22nd 31 350 18.3 (42.3) 12.7 (28.3) 26.3 20.0 14.6 62.8) 10.0 (23-3) (58.8) 23 32 164 ³ 19.2 (32 .δ) 12.8 (25.7) 27.1 20.0 14.9 ' (22.6) 10.6 (20.0) (47.5) 14.9 68.5) 11.7 (18.8) 26.2 19.4 10.3 (33-2) 9.1 (12.9) (58.0) 270 ³ 17.5 (40.8) 8.5 (28.2) 30.9 18.0 15.1 C33.3) 5.9 (22.1) (59-7) 336 ² 18.5 67.2} 12/8 (27.9) 24.9 19.5 . 15.1 £ 9.6) 10.0 (25.1) (57.8) 332 ³ 16.9 67.5) 12.7 (26.0) 25.6 19.4 13.4 61.8) 11.4 (18.3) (68.2) 363 ³ 17.0 (38.5) 11.8 (27.7) 24.3 20.3 14.4 (33.5) 8.3 (20.5) (54.8) 254 ³ 17.5 (40.3) 12.6 (25.1) 26.9 18.8 15.2 (36.3) 9.3 (20 »8) © 6.5) 353 ¹ 18.3 (35.8) 11.4 (27.4) 29.7 18.7 16.5 £ 9.0) 9.4 (23.5) (53-5) 491 ¹ 16.2 / 0629 12.4 (24.7) 13.2 - 10.7 (17.5) (59-3) S30Q35 11.2 - 30 7.9 (65.4)

GT-1510

attempt tires % ν 'y \ · "^{':? :: _:} -""■*;"."'""J --rr i 77 9 j ■ No. No. (Cont.) V ^ z: .'- '' ■■ - * 1 Β-59 Table II Β-6θ (Part D) ERA 2 Β-83 • ARA Average of fractions 46 ί Β-84 No. of fractions or cracks 3 Β-2 or cracks 24.5 '. ! 38 y Β-3 -24 i
i . '■' ί 4th Β-8 25th -. 6.5 I. 93-5 "; Β-5 7th 5 B-IO 131 69-5 B-Il 6th Β-14 247 91.0 B-15 ⁶ I. ■ 7 Β-19 80 45 130.0 j. . Β-17 182 8th Β-22 277 112.0; Β-23 218 9 Β-28 25th Β-26 66 10 Β-30 3 ⁶ ! Β-31 11 Β-36 Β-34. 58 f 12th Β-39 I. B- 38 23 75! 13th Β-42 50! Β-43 .40 39 y 14th Β-45 76; I. Β-46 57. 15th Β-49 93 Β-51 3 ' 16 Β-54 76 ' Β-56 97 17th Β-63 57; Β-64 69 \ 24 37 39 27 y i6o 30th 109 50 132 44 216 90 134 030 035/0 62 - 31 -

GT-151 • 19th 0 rm * m Table II .. -. - 300 1838 ERA j 100.0 α 37.0; ί 173-5 (Part D) . -,., .... Average cL fractions 20th ERA (Cont.) or cracks i4.o 49-5,: tires Number the breaks 97.5 169.5 25.5 21 No. or cracks 57ο5 attempt B-65 -87 '. 79.5 32.5 No. 22nd B-66 108 18th B-69 100.0 31.5 23 B-71 B- 75 35 "■: 231.0! / 24 B-76 124 \ 25th B-79 82 \ 154.0 B- 80 118 \ 26th B-87 102 B-88 27 B-91 36O B-92 84 28 B-93 224. B-97 136 * 29 B-98 64 B-103 14th 30th B-104 115 B-105 31 B-107 B-IO9 32 . B-IlO BUS B-114 B- 115 224 ' B- II6 28 B-121 B-122 37 A-6 23 i A-7 4o 39 35; 45! 54 34 " ^8l ! 138; 209 23 28

030035/0829

GT-1510

SH -j: ■;: _ ■:

Notes on the example above:

VP - rubber-like terpolymer made from about 70 parts by weight 1,3-butadiene, about 15 parts by weight styrene and about 15 parts by weight of 2-vinylpyridine, produced by a free radical, aqueous alkaline emulsion polymerization.

BD - polybutadiene, produced by free radical, aqueous, alkaline emulsion polymerization.

BMAA - rubbery copolymer made from about 99 parts by weight of 1,3-butadiene and 1 part by weight of methacrylic acid by free radical, aqueous emulsion copolymerization and subsequent alkalization.

ABC - commercially available immersed glass cord material, immersion bath composition on the cord is not known.

ML-4 - Mooney Viscosity at 100 ⁰ C (212 ° F)

+ - too tough or too break-proof for the measurement - means "none" or "not determined"

Av.- Average

A ° - angstrjphone units (0.1 nm)

Size - larger

bi - bimodal

kl, - smaller

wide - width distribution as indicated

B-5 - "Polystep" B-5, Sodium Lauryl Sulphate Emulsifier, Stefan Chem. Co. This wetting agent appears to perform to no increase in glass cord cracks or breaks, but it seems to reduce the Η-bond strength.

KFA - potassium fatty acid soap. This wetting agent appears to increase cracking or breakage in the Glass cord material.

Wing. L - "Wingstay" L, butylated reaction product of p-cresol and dicyclopentadiene, Goodyear Chemical. This Antioxidant does not seem to have any effect on cracking or breaking of the glass cord material.

"Kickout" - shear particles in the immersion bath as a result of the cord passing through the immersion bath.

- 33 -

030035/062 9

GT-1510

Blistering - blistering in the dip coating on the Cord after drying «,

"Gubbers" - soft bubbles »

SRF - The resin used in the dip was different from the one mentioned above. It was developed by Schenectady Chem. Co. obtained using excess resorcinol with respect to formaldehyde. Subsequently, a sufficient Amount of furfural and alkali added to a molar excess of aldehyde and eventually a thermosetting one To obtain phenolic resin.

Wear rate - 1 = best result, 10 = worst result. Abrasion or flaking of the immersion bath material from the Cord during the drying stage.

D.P.U. - Immersion bath material absorption, weight percent drier Immersion bath on the cord.

WITH. - Massachusetts Institute of Technology bending machine. Bend takes place via a 270 ° bend. Test is carried out at room temperature.

Age - the superscript indicates the relative age between diving and testing the cord, which is the shortest Period of time.

H Bond Strength - as stated above in kilograms (lbs).

C - The cord tensile test takes place in the cold (at room temperature, about 25 ⁰ C) -.

H - The cord tensile test was carried out at 121.1 ⁰ C (250 ⁰ F).

M is the rubber compound or compound used for a first series of H bond strength tests

Part of parts by weight

Natural rubber 46.50

Polybutadiene rubber, cis configuration, 15.00 obtained by solution polymerization
(The General Tire & Rubber Co.)
SBR 1778 52.90

(Mixture 38.50 cold SBR rubber
and 14.40 naphthene oil)

- 34 -

030035/0629

GT-1510

U :

M (cont.)

Component parts by weight

finely pressed furnace soot 66.00

Tackifying Resin 2.50

Naphthenic oil 12.00

Zinc oxide 3.80

Stearic acid 1.50

Styrenated Phenol 1.20

"Altax", benzothiazyl disulfide 1.10 (R.T. Vanderbilt Co.)

"Thionex", thiuram monosulfide (du Pont) 0.10

"Crystex" (2/40 insoluble sulfur and 3.00 0.60 petroleum oil, Stauffer Chemical)

N represents that for a second series of H bond strength tests rubber compound or compound used:

Component parts by weight

Natural rubber 50.0

Peptizer x 0.15

Butadiene-styrene rubber, SBR-1502 50.0

Highly abrasion-resistant furnace soot 35.0

ZnO 3.0

Stearic acid 1.0

Processing resin 2.0

Styrenated Phenol 1.0

Naphthenic ■ oil, does not stain or 7.0 does not stain

Diphenylguanidine 0.15

"Nobs" # 1, 90% N-oxydiethylene-2-0.9 benzothxazylsulfenamide and 10% benzothiazyl disulf id (American Cyanamid Co.)

Sulfur 2.60

Tensile Strength - Tensile strength in kilograms (lbs) right now breaking or tearing dipped and heat-dried cord at room temperature in air.

O3OO ~ 3! P / O629

# 1500 wax - wax emulsion, combination of paraffin and microcrystalline waxes with an anionic emulsifying agent (General Latex).

ÄRA - ARA-Test (Automotive Research Association Cold Gristmill- ' Test) carried out as follows:

^{1. The mounted tires are cooled to -4O 0} C (-4O ⁰ P) for 3 hours at a pressure of 1.63 at (24 psi ambient).

2. The tire is then mounted on the right front side of the carriage and the carriage is disengaged when the tire temperature -31.7 ⁰ C (-25 F ⁰⁾ is.

3. The car then runs counterclockwise for 10 laps around an orbit with a diameter of 25.9 m (85 ft.) with a lap lasting 11 seconds and the load on the tire is 748.4 kg (1650 lbs) (Pressure = 1.63 at = 24 psi ambient). The test tire is the one on the right with respect to the center of the circular path outer front tire.

4. The tire is cooled down again for a further 3 hours and then the cycle described under 3 is repeated.

5. After 6 cycles (60 laps), the tire, inflated to 2.4 at (40 psi), is assisted through the rim examined by X-rays. The tire is removed and placed on a special rim with plastic windows mounted to allow X-ray examinations.

6. The X-rays passing through the entire liner are recorded and each fracture or crack is counted.

- 36 -

030035/0629

GT-1510

The invention also relates to a glass fiber reinforcement element with a content of about 10 to 40% by weight (dry substance), based on the weight of the element, a thermoset adhesive composition for bonding the element to a Rubber compound

a) a rubbery vinyl pyridine copolymer with a gel content of about 0 to 60%,

b) at least one rubber-like polymer selected from the group consisting of polybutadiene-1,3 and Copolymers of at least about 80% by weight 1,3-butadiene and no more than about 20% by weight of at least one copolymerizable, monoethylenically unsaturated Monomers having no more than 14 carbon atoms, but this monomer is not a vinyl pyridine monomer and the rubbery polymer has a gel content of about 0 to 70%, and where the ratio from a) to b) is about 20 to 80 to 60 to 40 parts by weight, and

c) a water-soluble, thermosetting phenol-aldehyde resin in an amount of about 3-15 parts by weight per 100 parts by weight of a) + b).

The rubbery vinylpyridine "copolymer (a) is preferably a terpolymer composed of about 60-80% by weight of 1,3-butadiene, about 7-32% by weight styrene and about 4-22% by weight 2-vinylpyridine, wherein the phenol-aldehyde resin (c) in an amount of about 5-10 parts by weight per 100 parts by weight (a) + (b) the phenol-aldehyde resin is used (c) a resorcinol-formaldehyde resin is, the composition of matter additionally about 2-10 parts by weight wax per 100 parts by weight (a) + (b) and the reinforcement element contains about 15-25% by weight of the adhesive composition.

In a particularly preferred embodiment, (a) is a Rubber-like terpolymer composed of about 70% by weight 1,3-butydiene, 15% by weight styrene and 15% by weight 2-vinylpyridine.

- 37 -

030035/0629

GT-1510:

The composition of matter can additionally contain up to about 10% by weight of a surface-active agent per 100 parts by weight of (a) + (b) and additionally up to about 5% by weight of one Contain antioxidant per 100 parts by weight (a) + (ß).

In a preferred embodiment, the component (b) is Polybutadiene or a copolymer of about 99 parts by weight of 1,3-butadiene and 1 part by weight of methacrylic acid »

In summary, the present invention relates to a aqueous alkaline dispersion of a rubbery vinylpyridine copolymer, a rubbery polybutadiene or a rubbery copolymer of at least 80% butadiene and the remainder of a monoethylenically unsaturated one Monomers and a water-soluble, thermally reactive phenolic resin in certain amounts, the rubber-like Polymers have a reduced gel content, this dispersion being a suitable adhesive for bonding Glass fiber reinforcement elements or cords with rubber compounds or masses. After the fiberglass cord has been immersed in a one-step adhesive dipping bath, the coated cord is heated for drying and for heat curing or heat conversion of the adhesive on the cord. Afterward the adhesive-containing fiberglass cord is combined with a vulcanizable rubber composition or laminated (calendered), and then to form a composite material in which the fiberglass cord through the adhesive is glued to the rubber, vulcanized.

- 38 -

Claims (1)

Claims Substance composition in the form of an aqueous alkaline Dispersion with a solids content of about 25-50 Wt .-% off a) a rubbery vinyl pyridine copolymer with a gel content of about 0 to 60%, b) at least one rubber-like polymer selected from the group consisting of polybutadiene-1,3 and Copolymers of at least about 80 weight percent 1,3-butadiene and no more than about 20% by weight of at least one copolymerizable, monoethylenically unsaturated monomers having not more than 14 carbon atoms, wherein this monomer is not a vinyl pyridine monomer, and the rubbery polymer has a gel content of about 0 to 70%, and wherein the ratio of (a) to (b) is about 20:80 to 60:40 parts by weight (Dry matter) is, and c) a water-soluble, thermosetting phenol-aldehyde resin in an amount of about 3 to 15 parts by weight (dry substance) per 100 parts by weight of (a) + (b) (Dry matter). GT-1510 Λ '-''-"- ^: ' - ■ ' 2. A composition of matter according to claim 1, characterized in that the rubbery vinylpyridine copolymer (a) is a terpolymer of about 60 to 80% by weight of 1,3-butadiene, about 7 to 32% by weight of styrene and about 4 to 22% by weight % By weight of 2-vinylpyridine is _f the phenol-aldehyde resin (c) is used in an amount of about 5 to 10 parts by weight (dry substance) per 100 parts by weight (a) + (b) (dry substance), the phenol-aldehyde Resin (c) is a resorcinol-formaldehyde resin, the adhesive composition additionally contains about 2 to 10 parts by weight of wax (dry substance) per 100 parts by weight of (a) + (b) (dry substance), and the solids content about 30 to 40 parts by weight. -% amounts to. 3. A composition of matter according to claim 2, characterized in that (a) is a rubber-like terpolymer composed of about 70% by weight of 1,3-butadiene, 15% by weight of styrene and 15% by weight of 2-vinylpyridine. 4. The composition of matter according to claim 3, characterized in that that (b) is polybutadiene. 5. The composition of matter according to claim 4, characterized in that that the adhesive composition additionally contains up to about 10 parts by weight of a surface-active agent (dry substance) contains per 100 parts by weight of (a) + (b) (dry matter). 6. A composition of matter according to claim 4, characterized in that that the adhesive composition additionally contains up to about 5 parts by weight of an antioxidant (dry substance) per 100 parts by weight (a) + (b) (dry matter) contains. 7. The composition of matter according to claim 5, characterized in that that (b) is a copolymer of about 99 parts by weight of 1,3-butadiene and 1 part by weight of methacrylic acid. 030035/0629 GT-1510 Method for gluing a fiberglass reinforcement element to a rubber mixture, thereby g e k e η η ζ e i without t having to use the reinforcing element with a composition of matter in the form of a aqueous alkaline dispersion with a solids content from about 25 to 50% by weight a) a rubbery vinyl pyridine copolymer with a gel content of about 0 to 60% " b) at least one rubbery polymer selected from the group consisting of polybutadiene-1,3 and copolymers of at least about 80% by weight of butadiene-1,3 and no more than about 20 weight percent of at least one copolymerizable monoethylenically unsaturated one Monomers having no more than 14 carbon atoms, but this monomer is not a vinyl pyridine monomer and the rubbery polymer has a gel content of about 0-70%, and where the ratio from a) to b) is about 20 to 80 to 60 to 40 parts by weight (dry matter), and c) a water-soluble, thermosetting phenol-aldehyde resin in an amount of about 3 to 15 parts by weight (dry substance), based on 100 parts by weight of a) + b) (dry substance) _t treated, the treated reinforcing element for a sufficient time Temperature heated to remove substantially all of the water from the composition of matter, and the reinforcement element with a thermoset adhesive in an amount of about 10 to 40 wt .-% (dry substance), based on the weight of the reinforcement element, the dried , the reinforcing element containing the thermoset adhesive combined with an unvulcanized, vulcanizable rubber mixture and this vulcanized = - 3 0300 35/0 62 9 9. The method according to claim 1, characterized in that the reinforcing element with a composition of matter in the form of an aqueous alkaline dispersion with a solids content of about 30-40% a) a rubbery vinyl pyridine copolymer with a gel content of about 0 - 60%, b) at least one rubber-like polymer selected from the group consisting of polybutadiene-1,3 and Copolymers of at least about 80 weight percent 1,3-butadiene and no more than about 20% by weight of at least one copolymerizable, monoethylenically unsaturated monomers with no more than 14 carbon atoms, however, this monomer is not a vinyl pyridine monomer and the rubbery polymer has a gel content from about 0 to 70%, and wherein the ratio of a) to b) is about 20:80 to 60:40 parts by weight (Dry matter) is, and c) a water-soluble, thermosetting phenol-aldehyde resin in an amount of about 3 to 15 parts by weight (dry substance) per 100 parts by weight of a) + b) dry substance, treated, the treated reinforcing element for about 5-300 seconds to about 93.3-315 ° C (200-600 ⁰ F) heated to all of the water from the composition to be removed, and the reinforcing member with a thermally cured adhesive in an amount of about 15-25 wt .-% (dry substance) is substantially based on the weight of the reinforcing element, combining the dried reinforcing element containing the thermoset adhesive with an unvulcanized, vulcanizable rubber mixture and vulcanizing it. - 4 030035/0629 GT-1510 10. The method according to claim 9 ", characterized in that the rubbery vinylpyridine copolymer (a) is a terpolymer of about 60-80% by weight of 1,3-butadiene, about 7-32% by weight styrene and about 4-22% by weight 2-vinylpyridine is the phenol-aldehyde resin (c) in an amount of about 5-10 parts by weight (dry substance) per 100 parts by weight (a) + (b) (dry substance) is used, the phenol-aldehyde resin (c) being a resorcinol-formaldehyde resin, and wherein the composition of matter additionally comprises about 2-10 Parts by weight of wax (dry matter) per 100 parts by weight (a) + (b) (dry matter) contains, 11. The method according to claim 10, characterized in that (a) a rubbery terpolymer of about 70% by weight 1,3-butadiene, 15% by weight styrene and 15% by weight 2-vinylpyridine is. 12. The method according to claim 11, characterized in that (b) is polybutadiene. 13. The method according to claim 12, characterized in that the composition of matter additionally up to about 10 parts by weight of a surface active agent (dry matter) per 100 parts by weight of (a) + (b) (dry matter). 14. The method according to claim 12, characterized in that the substance composition additionally up to about 5 parts by weight of an antioxidant (dry substance) per Contains 100 parts by weight of (a) H- (b) (dry matter). 15. The method according to claim 11, characterized in that (b) a copolymer of about 99 parts by weight 1,3-butadiene and about 1 part by weight is methacrylic acid. 16. The method according to claim 10, characterized in that the treated reinforcing member is heated for about 30 to 90 seconds at 204.4 to 26O ⁰ C (about 400 to 500 ⁰ P). 17, composite material made of one embedded in vulcanized rubber Glass fiber reinforcement element, where the reinforcement element is about 10 to 40% by weight (dry substance), based on the weight of the element, a thermoset Adhesive composition contains from a) a rubbery vinyl pyridine copolymer with a gel content of about 0 to 60%, b) at least one rubber-like polymer selected from the group consisting of polybutadiene-1,3 and Copolymers of at least about 80 weight percent 1,3-butadiene and no more than about 20% by weight of at least one copolymerizable, monoethylenically unsaturated Monomers having no more than 14 carbon atoms, where this monomer is not a vinyl pyridine monomer and the rubbery polymer has a gel content of about 0-70% by weight, and wherein the ratio of (a) to (b) is about 20:80 to 60:40 parts by weight is, and c) a water-soluble, thermosetting phenol-aldehyde resin in an amount of about 3-15 parts by weight per 100 parts by weight (a) + (b), the adhesive composition the reinforcement element connects to the rubber. 030035/0629 GT-1510 18. Composite material according to claim 17, characterized in that that the rubbery vinylpyridine copolymer (a) is a terpolymer of about 60 to 80% by weight of 1,3-butadiene, about 7 to 32 weight percent styrene and about 4 to 22 weight percent 2-vinyl pyridine is the phenol-aldehyde resin (c) in an amount of about 5 to 10 parts by weight per 100 parts by weight (a) + (b) is used, the phenol-aldehyde resin (c) a resorcinol-formaldehyde resin is, the adhesive composition is additional about 2 to 10 parts by weight wax per 100 parts by weight (a) + (b) and the reinforcing element about 15 to 25% by weight the adhesive composition contains » 19. Composite material according to claim 18, characterized in that that (a) a rubber-like terpolymer of about 70 wt .-% 1,3-butadiene, 15% by weight styrene and 15% by weight 2-vinylpyridine is. 20. Composite material according to claim 19, characterized in that that (b) is polybutadiene. 21. Composite material according to claim 20, characterized in that the adhesive composition additionally up to about 10 parts by weight of a surfactant per Contains 100 parts by weight (a) + (b). GT-1510 22. Composite material according to claim 20, characterized in that that the adhesive composition additionally includes up to about 5 parts by weight of an antioxidant per 100 parts by weight Contains (a) + (b). 23. Composite material according to claim 19, characterized in that that (b) a copolymer of about 99 parts by weight of 1,3-butadiene and 1 part by weight is methacrylic acid. 030035/0629