JPS6253004B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention describes the use of rubber to glass fibers using compositions of graft or overpolymers of rubbery vinylpyridine copolymers on polyacrylate seed polymers, preferably with polybutadiene and phenolic resins. Regarding adhesion. One object of the invention is to provide a composite of glass fiber reinforced elements adhesively bonded to a rubber compound;
For example, to provide adhesively bonded glass fiber tire cords to provide carcass plies or belt plies for tire manufacturing. Another object is to provide glass fiber reinforced elements, such as those used in tire belt plies and carcass plies, having a small amount of adhesive so that the adhesive-containing element can later adhere to the rubber during curing. be. A further object is to provide a method for bonding glass fibers, particularly glass fiber fabrics, fibers, cords, yarns, etc., to rubber compounds using a single dip. A further object is to provide a glass fiber or cord adhesive dipping composition. Yet another object is to provide a rubbery overcopolymer or graft copolymer having a vinylpyridine copolymer (shell) on a polyacrylate seed (core) useful in making glass tire cord adhesives. These objects and other objects and advantages of the invention will become apparent to those skilled in the art from the following detailed description and examples. In the present invention, a rubbery graft polymerized or overpolymerized copolymer having a rubbery diene-vinylpyridine copolymer shell on an acrylate polymer seed or core having a Tg not exceeding about -20°C. A composition comprising an aqueous alkaline dispersion, preferably also containing an amount of polybutadiene and a heat-reactive, water-soluble phenolic-aldehyde resin, is used to bond the glass fiber reinforcement element to the rubber compound. It has been found to be extremely useful as a treatment, immersion or coating material. To obtain the desired pH and to provide stabilization to prevent coagulation of the latex, add sufficient alkaline material, such as an aqueous solution of KOH, NaOH or NH ₄ OH, to the dispersion (or to the dispersion before mixing the components of the dispersion). (one or more of the ingredients). This will vary with the pH of the resin and latex, all of which can vary from batch to batch. Since the amount of each compound may vary, the amount of alkaline material required may also vary. After removing the water and drying the adhesive on the glass fiber reinforced element to heat cure or heat set the adhesive on the element, the adhesive-containing element is combined with a curable rubber compound or calendered to form the adhesive. The assembly is usually cured in a mold to provide a laminate that exhibits good adhesion at ambient and elevated temperatures. Glass cords coated with graft copolymers containing adhesive exhibit improved fracture properties at low temperatures. Use of this graft copolymer can reduce fractures that may be experienced in glass cords such as belts in tires during normal operation at cold or low temperatures. The method involves only one dipping step, and by varying the concentration of the dipping solution and the rate at which the cord passes through the dipping fluid to provide the amount needed to produce the required adhesive bond. This method can be modified to provide the desired coverage or solids above. It is thus possible to run the cord through successive immersions of the same or varying amounts of the above substances to obtain the desired coverage, but this is unnecessary as satisfactory results are generally achieved in a single immersion. It is. The glass fiber reinforcement element or cord consists of a plurality of substantially continuous and parallel glass fibers or glass monofilaments. The reinforcing elements or fibers have little or no twist. In other words, it is not intentionally added to the element or fiber. The only losses, if any, in the elements or fibers are during passage through glass fiber processing equipment and during wrapping or winding of the cord to form bobbins or spools.
However, in a continuous process, the element can be advanced directly from the glass processing equipment, soaked in an aqueous adhesive cord dip, dried, and then given about 1.5 twists per inch. The elements are then calendered with a woven rubber ply or skim stock into a woven tire fabric with very small nylon or polyester wefts or elements, which may be monofilaments, but having about 1 thread per inch. The glass fiber reinforced ply stock is then ready for use in tire manufacturing or other applications. Glass compositions useful for making reinforcing elements or fibers for glass tire cords are well known in the art. One type of glass that can be used is the glass known as E-glass, published in “Mechanics of Pneumatic Tires,” Clark, National Bureau of Standards.
Bureau of Standards Monograph) No. 122, U.S. Department of Commerce, November 1971, pp. 241-243, 290
This is what is described on page 291. The number of glass filaments or fibers used in a glass fiber reinforcement element or cord can vary considerably depending on the end use and usage requirements. Similarly, the number of glass fiber strands used to make the glass fiber reinforcement element or cord can vary widely. Generally, the number of filaments in a glass fiber reinforced element or cord for passenger car tires is approximately 500.
to 3000, and the number of strands in the reinforcing element is from 1 to 10, preferably 1 strand.
The total number of filaments can be about 2000. In this connection, see Wolf, Rubber Journal, February 1971, pages 26-27, and U.S. Pat. No. 3,433,689. Shortly after the glass fibers are formed, they are coated with very little or negligible weight of substances (such as spraying or dipping and air drying) that act as a protective coating during processing and handling of the glass fibers in the formation of strands or reinforcing elements, and during packaging. ) is usually subjected to sizing treatment. It is believed that the size is not removed during subsequent immersion in the water-based adhesive tire cord dip. Materials used as sizing agents for glass fibers are well known in the art. Silanes are used as sizing agents, especially those having groups capable of chemically or physically bonding or coordinating with at least some portion of the glass surface of the glass fibers and with at least one or more of the components of the aqueous adhesive cord dipping solution for glass fibers. Preferably, silane is used. A very useful sizing agent for use with glass fibers is gamma-aminopropyltriethoxysilane, or similar aminoalkylalkoxysilanes, which, when applied to the glass fibers, hydrolyze and polymerize to form polystyrene. (aminosiloxane) in which a portion of this polymer adheres to the glass and another portion reacts with cord dip fluid components such as phenolic resins, polybutadiene compounds or grafted vinylpyridine copolymer compounds. It contains an amino group (with an active hydrogen atom) that Chromium complexes with functional groups can also be used. Glass fiber sizing compounds are known and several compositions are shown in US Pat. Nos. 3,252,278, 3,287,204, and 3,538,974. Water-soluble thermosetting (heat-reactive) phenolic aldehyde resins are made by reacting aldehydes with phenolic compounds. The preferred aldehyde for use is formaldehyde, although acetaldehyde and furfural can also be used. Other formaldehyde donors such as paraformaldehyde or hexamethylenetetramine can also be used in place of formaldehyde. It is also preferred to start with formalin, which is usually a 37% solution of formaldehyde in water, which is easier to use. Mixtures of aldehydes can be used. The phenolic compound can be phenol itself, resorcinol (preferred), cresols, xylenols, p-tert-butylphenol or p-phenylphenol or mixtures thereof. The reactants are usually reacted in water in the presence of a catalyst. Starting with a thermoplastic resin, a mole or less of aldehyde is reacted with a phenolic compound to form a condensation product, and then when the dip fluid is formulated sufficient aldehyde is added to make the product thermoset, i.e. It is also possible to make a resin that does not melt when heated. Alternatively, a molar excess of aldehyde may be reacted with a phenolic compound to form a condensation product of the thermoset type upon heating. This stuff should be used immediately. However, the alternative reaction is somewhat longer. In either case, the final product after heating is a thermosetting phenol-aldehyde resin. Alkaline substances are generally added before use. Information on the production of water-soluble thermoset phenolic-aldehyde resins can be found in Encyclopedia of Chemical Technology, Kirk-Othmer, Volume 15, 2nd Edition, 1968, Inter. Science Publishers (Jiyoung)
Technology of Adhesives, Delmonte, Reinhold Publishing Co., New York, New York, pp. 176-208.
1947, pp. 22-52; "Formaldehyde" Walker, ACS Monograph Series,
Reinhold Publishing Co., New York, NY, 3rd edition 1964, pp. 304-344; Chemistry of Phenolic Resins, Martin, John Wiley & Sons, New York, 1956.
It will be found in the year. Rubbery graft copolymers or overpolymerized copolymers consist of an acrylate polymer seed or core and a vinylpyridine polymer shell.
In this specification, the graft copolymer refers to a copolymer produced as follows. The copolymer is made by first forming a seed latex of acrylate polymer by polymerizing acrylate monomers to at least 85% conversion, preferably complete, by free radical aqueous emulsion polymerization. Then seed the acrylate polymer with conjugated diene monomer and vinyl pyridine monomer and add water, free radical initiator,
Grafting or overpolymerization of the diene and vinylpyridine onto the seed acrylate polymer to give a graft copolymer, optionally modifiers, emulsifiers or surfactants etc. are added and the polymerization is continued preferably to completion. Produce docopolymer. Grafting seems to be the appropriate term to describe the entire copolymerization method. The acrylate monomer used to form the seed acrylate polymer is a monomer that forms an acrylate polymer having a glass transition temperature (Tg) not exceeding about -20°C. Examples of such monomers are ethyl acrylate, n-propyl acrylate, n-butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate,
These include methoxyethyl acrylate, ethoxyethyl acrylate, methoxypropyl acrylate, and ethoxypropyl acrylate. These monomers thus have the general formula CH ₂ =CH−COOR
, where R is an alkyl group of 2 to 10 carbon atoms or a -R'OR'' group, where R' is 2 to 3
poly(n-butyl acrylate) has a Tg of -55°C and R'' is an alkyl group of 1 to 2 carbon atoms.
-ethylhexyl acrylate) at -77℃
It is noteworthy that it has a Tg of (DSC). Also formula H ₂ C
Acrylate monomers such as n-octyl _methacrylate , n-dodecyl methacrylate, hexadecyl methacrylate and n-octadecyl methacrylate are also suitable Can be used as Poly(n-octyl methacrylate) has a Tg of -20°C and poly(n-octadecyl methacrylate) has a Tg of -100
It has a Tg of °C. Mixtures of these acrylate monomers can be used to make seed polymer latexes. Among these acrylate monomers, it is preferred to use n-butyl acrylate or 2-ethylhexyl acrylate, or mixtures thereof. The diene monomers used to make the graft copolymer shell are conjugated dienes having from 4 to 6 carbon atoms, such as butadiene-1,3, isoprene, 2,3-dimethylbutadiene-1,3, or piperylene. It is. Mixtures of these monomers may also be used. Preference is given to using butadiene-1,3. The vinylpyridine monomers copolymerized with the diene monomer to form the graft copolymer shell have from 7 to 9 carbon atoms and include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl- 5-vinylpyridine, 2,
It can be 4-dimethyl-6-vinylpyridine and 5-ethyl-2-vinylpyridine or a mixture of the above. Among these vinylpyridines, it is preferable to use 2-vinylpyridine. Butadiene-vinylpyridine copolymers are well known, as illustrated by US Pat. On a dry weight basis, the final rubbery graft copolymer of the present invention has from about 8 to 20 weight percent acrylate monomer, from 3 to 20 weight percent vinylpyridine monomer, and from 60 to 89 weight percent diene monomer; Preferably there is about 10 to 15 weight percent acrylate monomer, 7 to 15 weight percent vinylpyridine monomer, and 70 to 83 weight percent diene monomer. Aqueous alkaline latexes of rubbery polybutadiene made by free radical aqueous emulsion polymerization of butadiene-1,3 are known. The polybutadiene should have a glass transition temperature Tg not exceeding about -70°C. Butadiene-vinylpyridine- on a dry weight basis
The weight percent ratio of acrylate graft copolymer to polybutadiene is about 20:80 to 60:40, preferably about 40% acrylate graft copolymer and 60% polybutadiene. The graft copolymer latex and polybutadiene latex are easily blended or mixed together. Optionally seed polymers with acrylates (preferred), shells with very small weights of other copolymerizable monomers, as long as the useful properties and Tg of these polymers for use as glass cord adhesives are not adversely affected. Polymers of butadiene and vinylpyridine, or polybutadiene and butadiene may be copolymerized. Examples of such monomers are styrene, acrylonitrile, vinyl acetate, methyl methacrylate, methyl acrylate, methacrylamide, butadiene-1,3, isoprene, piperylene,
2,3-dimethylbutadiene-1,3, ethylene glycol diacrylate, ethylene glycol dimethacrylate divinylbenzene (preferred), trimethylolpropane trimethacrylate, trimethylolpropane triacrylate,
1,3-butylene glycol diacrylate, triallyl cyanurate, etc., and mixtures thereof. If desired, the polyunsaturated monomer may provide some crosslinking to control the high temperature flow of one or more of the seeds or shells of the dry polymer or copolymer or graft copolymer. Preferably, crosslinking polyunsaturated monomers are used or copolymerized with the core or seed acrylate monomer in an amount of about 0.05 to 1.5 parts by weight per 100 parts by weight of the acrylate monomer. The polymerization of the monomers is carried out by means of a free radical initiator (free radical forming agent or free radical forming catalyst) such as ammonium persulfate, potassium or sodium persulfate, H ₂ O ₂ and a sufficient amount to obtain the desired molecular weight. done in quantity. Other free radical initiators can also be used which decompose or become activated at the temperature used during the polymerization. Examples of other free radical initiators are cumene hydroperoxide, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, bis(p-methoxybenzoyl) peroxide. oxide, t-butyl peroxypivalate, dicumyl peroxide, isopropyl percarbonate, di-sec-butyl peroxydicarbonate, azobisdimethyl-valeronitrile, 2,2'-azobisisobutyronitrile, 2 , 2'-azobis-2-methylbutyronitrile and 2,2'-azobis(methylisobutyrate), and mixtures thereof. Only small amounts of initiator are required to carry out the polymerization. Emulsifiers, surfactants, or dispersants, such as soaps, are used in amounts sufficient to provide an aqueous emulsion of water, monomer, and resultant polymer. Some examples of emulsifiers are potassium laurate, potassium soap of disproportionated rosin, potassium stearate, potassium oleate, sodium lauryl sulfate, sodium dodecyl sulfonate, sodium decyl sulfate, sodium salt of condensed naphthalene sulfonic acid, sodium rosinate, etc. and mixtures thereof. Other well known surfactants can also be used. Chain transfer agents and moderators are well known in the emulsion polymerization of vinyl and diene monomers to form polymers. These are commonly used to control molecular weight and reduce crosslinking. Although many types have been proposed, it is preferred to use alkyl and/or aralkyl mercaptans having from 8 to 18 carbon atoms. Among these, tertiary alkyl mercaptans are particularly preferred. Examples of some mercaptans are n-octyl mercaptan, n-dodecyl mercaptan, t-octyl mercaptan, t-dodecyl mercaptan, p-tridecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, and mixtures thereof. If little or no mercaptan is used and the polymerization is continued to completion, a gel will form and the molecular weight can become very high or even infinite. Although some low molecular weight fractions are also found. If desired, NaOH, KOH, NH ₄ OH, etc. may be added to the polymerization reactor before, during or after the polymerization to adjust the pH. Polymerization can be carried out under acidic conditions and after polymerization the latex can be converted to the alkaline side. The water should be free of harmful substances and should preferably be distilled or ion-exchanged. Sufficient water is used to enable the formation of an emulsion and to allow the ingredients to be properly mixed or agitated during the polymerization to obtain the desired polymerization rate, degree of polymerization, heat exchange, etc. The solids content of the resulting aqueous alkaline latex or dispersion, graft copolymer and/or polybutadiene is thus from about 25 to 60% by weight, and the pH is about
It can vary from 7.0 to 11.5. Stabilizers, antioxidants and chelating agents may be used during the polymerization. The use of polymerization terminators at the end of free radical polymerization is also well known. These are used not only to stop the polymerization in the reactor at the desired conversion, but also to prevent further polymerization, crosslinking, etc. during stripping, work-up, etc. Some examples of polymerization terminators are hydroquinone,
Sodium sulfide, hydroxyammonium acid sulfate, hydroxylammonium sulfate, sodium diethyldithiocarbamate, diethylhydroxylamine, sodium dimethyldithiocarbamate, potassium dimethyldithiocarbamate, dimethylammonium dimethyldithiocarbamate, hydroxylamine sulfate with sodium hydrosulfite These include things that have been added. The temperature used during the polymerization should be sufficient to effect polymerization by activation of the double bonds of the initiator and monomer. The temperature should not be too high to cause runaway reactions or too low to retard polymerization. Generally the temperature can be from about 2 to 90°C. If lower temperatures are used, it is desirable to add an inert antifreeze material to the polymerization medium. The polymerization is preferably carried out using a stirrer or other agitation means, heating, cooling means, nitrogen, helium,
Means for introducing inert gas such as argon or neon by flash or pump, monomer, water,
Means for charging initiator etc., means for venting (exhaust),
It should be carried out in a closed reactor, such as a pressure reactor, equipped with means for recovering the polymer.
The reactor should be cleaned or flushed between polymerization runs to remove any traces of polymerization terminators, initiators, regulators, residues, etc. that may interfere with subsequent polymerization runs. The polymerization medium should be thoroughly agitated or agitated to ensure adequate mixing, dispersion, contact, etc. All of the polymerization components, except for termination, may be charged to the reactor at once, or at intervals, or incrementally, or sequentially. Also, the components can be added separately or in a mixture. The rubbery polymers are thus prepared in water using known techniques using free radical initiators, chelating agents, modifiers, emulsifiers, surfactants, stabilizers, polymerization terminators, and the like. They may be hot or cold polymerized, and polymerization may or may not be carried out to about 100% conversion. Low gel or gel-free polymers are possible if the polymerization is carried out using appropriate amounts of chain transfer agents or regulators and the conversion is stopped below 100% conversion. Free radical aqueous emulsion polymerization and materials therefor are well known. (1) Whitby et al., "Synthetic Rubber," John Willey & Sons, New York, 1954. (2) Schildknecht, Vinyl and Related Polymers, John Willey & Sons, New York, 1952. (3) Encyclopedia of Polymers
"Science and Technology," Interscience Publishers (a division of John Willey & Sons, Inc.) New York, Volume 2 (1965), Volume 3 (1965), Volume 5.
Volume (1966), Volume 7 (1967) and Volume 9 (1968), and (4) "Materials, Compounding Ingredients, and Machinery for Rubber" ), Bill Comunications, New York, 1977, published by Ruberwald. (5) Bovey et al., Emulsion Polymerization, Interscience Publishers, Inc., New York, 1955. To determine the gel content of a rubbery graft copolymer, take a sample of the particular latex of interest, separate the rubber from water by coagulating the rubber, grind the resulting rubber, and dissolve the rubber in toluene. , the mixture is filtered and the gel content is determined. See Whittby et al., supra. A process for obtaining rubbery polymers such as rubbery vinyl pyridine copolymers, rubbery polybutadiene and rubbery butadiene copolymers with little or no gel by high conversion aqueous free radical emulsion polymerization includes: United States Patent No. 1 entitled "Aqueous Free Radical Emulsion Polymerization" granted on March 20, 1979.
No. 4145494 is fully clarified. The technique of polymerizing or copolymerizing one or more monomers in the presence of a polymer or substrate is known as "grafting technology" and is often referred to as graft polymerization or graft copolymerization. Regarding this, see ``Proceedings of the Third Rubber Technology Congress,'' 1954, published by D.
& Sons, Cambridge (W. Heffer & Sons)
Sons, Ltd.Cambridze) pp. 185-195; “Copolymerization” High Polymers
Polymers), Ham, 323-324,
pp. 335-420 and 573, Interscience Publishers, a division of John Wiley and Sons, New York, 1964; "Block and Graft Polymers" Burlant and Hoffman, Reinhold Publishing Corporation, New York 1960; "Block and Graft Copolymers" Cereza, Butterworth and
Company (Publishers) Co., Ltd.
Butterworth & Co. (Publeshers) Ltd. London 1962; and “Graft Copolymers” Polymer Revues, vol. 16 Butterworth & Co.
Trigia (Polymer Reviews Vol.16, Battaerd
and Tre—gear, ) Interscience Publishers, a division of John Willey and Sons, New York, 1967. The graft copolymer shell may include all graft copolymers, but may also be a mixture of homopolymers, copolymers, and the graft itself. Thus, if the seed or core conversion is not complete, Bd
When loaded with Vp and Vp, the shell may also contain some acrylate homopolymers, Bd homopolymers, Bd-acrylates, Bd-Vp and Bd-Vp-acrylate copolymers, etc., as well as grafts. However, it is generally believed that the Vp (vinyl pyridine) moiety is on the outside of the latex particle where the adhesive effect is obtained, and the acrylate is on the inside. The PH of the latex and the PH of the soaking solution should be on the alkaline side, with the addition of any surfactants and stabilizers and other additives, including freeze-thaw stabilizers.
The pH should be alkaline, compatible, or neutral to avoid improper coagulation of the latex. Water is used to provide the desired dispersion of rubber or latex particles, to provide a solution of the phenolic resin and any other additives, to obtain the desired viscosity, and to provide the necessary penetration on and between the cord fibers. A sufficient amount is used to provide a suitable solids content to obtain solids pick-up. The water content in the cord soaking fluid is generally about 30-50
%, preferably about 35-40% by weight. Too much moisture will require re-soaking and the use of extra heat to evaporate the moisture during drying. If there is too little water, penetration will be uneven or the rate of coverage will be too slow. In addition to the surfactants or wetting agents and optional antioxidants already present in the latex, additional surfactants and antioxidants can be added in small amounts to the dip solution. Other deterioration inhibitors and waxes can also be added. One example of a useful wax is a wax emulsion, a combination of paraffin and microcrystalline wax in water. On a dry weight basis, the phenol-aldehyde resin is 100% of the rubbery graft copolymer or the above graft copolymer and the above butadiene in the adhesive composition.
It is used in an amount of about 3 to 15 parts by weight, preferably about 4 to 10 parts by weight. In order to reliably apply latex adhesive to fiberglass cord, the cord is held under a small predetermined tension by passing it through an adhesive soaking bath and then into a drying oven where it is removed (with no appreciable elongation). Dry these under a small predetermined tension (to prevent sagging without). When the cord leaves the furnace,
It enters a cooling zone where it is air cooled before tension is released. The adhesive-coated cord leaving the immersion liquid in each case is dried in an oven at about 200-600°C (93.3-315.6°C) for about 300-5 seconds. The cord stays in the adhesive for about 2 to 3 seconds or more.
or sufficient time to effect wetting of the cord and impregnation of at least substantially all of the cord fibers. Soaking the cord and drying or curing the adhesive treated fiberglass cord can be accomplished in one or more dipping tanks and one or more ovens at different times and temperatures. Using a single cord H-tensile H-adhesion test,
Static adhesion to dried (heat cured or cured) adhesive coated glass fiber cords was measured. In each case, the rubber test specimens are made from a vulcanizable rubber composition consisting of rubber, reinforcing carbon black, and conventional compounding and curing ingredients. In each case, the cords to be tested are placed in parallel positions in a multi-strand mold of the type described in the Single Cord H Tensile Adhesion Test designated ASTM D2138-67. Fill the mold with unvulcanized rubber composition and add 50g of cord each.
The rubber is held under tension to harden. Each rubber test specimen was 1/4 inch thick with a 3/8 inch cord embedded layer. After the rubber has cured, the hot cured rubber piece is removed from the mold, allowed to cool, and H test specimens are cut from the piece. Each specimen consists of a single cord encapsulated in rubber, each end of which is embedded in the center of a rubber tab or embedding layer approximately one inch long. The specimens are then aged for at least 16 hours at room temperature. Then use an Instron tester with a specimen grip to measure the force required to separate the cord from the rubber at room temperature or 250
Measured at ℃). The maximum force in pounds required to separate the cord from the rubber is the H-bond strength. All data presented in the examples below are based on the same test conditions and all test specimens were generally manufactured and tested in the same manner in accordance with ASTM designation D2138-72. The flexibility of single yarns impregnated with the adhesive of the invention and dried was determined by the MIT test (as described in TAPPI Standard Method T423m-50 for Folding Durability of Paper). In this case, the sample was flexed at 3 cycles per second through a total arc of 270 degrees until it broke. The number of bends to failure is recorded as a direct measure of the yarn's low temperature durability. The bending temperature can be varied from about -40°C to about +130°C. Two variations of the test are Method A - A single treated yarn is flexed under 500 grams of tension. Method B - 1 single treated thread embedded in rubber
Bending under tension of Kg. The sample is approx.
6″ (15.24 cm) long, 3/16″ (0.48 cm) wide, and 0.030″ (0.076 cm) thick. The coated glass cord or fabric is
Based on the cord weight, the solids content of the adhesive dip on the cord is about 10-40%, preferably about 15-25% by weight
Manufacture of carcass, belts, flippers and tie-furs for radial, bias or belted bias passenger car tires, truck tires, motorcycle tires, off-road tires and aircraft tires, as well as power transmission belts and V-belts. It can be used to manufacture conveyor belts, hoses, gaskets, tarpaulin (waterproof cloth), etc. Glass fiber reinforced elements containing adhesives can be bonded to vulcanizable natural rubber and rubbery butadiene styrene copolymers, or blends thereof, by combining them together and curing, but the above Rubber, nitrile rubber, chloroprene rubber,
By curing or vulcanization in combination with rubbers such as polyisoprene, polybutadiene, acrylic rubbers, isoprene-acrylonitrile rubbers, etc., and one or more of mixtures thereof.
It is clear that thermoset adhesive-containing glass fiber reinforcement elements can be bonded to other vulcanizable rubbery materials. These rubbers may contain sulfur, stearic acid, zinc oxide, magnesium oxide, silica, carbon black, accelerators, antioxidants, anti-aging agents and other hardening agents well known to those skilled in the art for the particular rubber used. It can be mixed with ordinary compounding ingredients including rubber compounding ingredients. The adhesive dip of the present invention may also be used to bond other natural and synthetic fiber cords, yarns, etc. to rubber compounds. The following examples will serve those skilled in the art to illustrate the invention in detail. In these examples, parts are by weight unless otherwise indicated. EXAMPLE The preparation of the latex described below was completed with stirring in a polymerization bottle flushed with nitrogen in a water bath.

[Table] The polymerization temperature was 50°C. Latex was converted to alkaline side.

【table】

[Table] Polymerization temperature is 50℃. Alkaline latex as made.

[Table] The polymerization temperature was 60°C. Alkaline latex as made.

[Table] The polymerization temperature was 50°C. Alkaline latex as made.

[Table] The polymerization temperature was 60°C. Alkaline latex as made.

[Table] The polymerization temperature was 50°C. Freshly made alkaline latex. Example Preparation of adhesive dip solution for cord treatment Resorcinol roof olumaldehyde (RF)
Add the resin to the desired latex and the latex solids.
An aqueous cord adhesive dip was prepared by mixing 7.5 dry parts of RF resin per 100 parts by weight for a total solids content of 40%. 7.5 parts of dry RF resin is 6.82 parts dry of neutralized PENACOLITE R-2170 (RF
Resin) + 0.68 consists of formaldehyde in the dry part. An example is shown below.

[Front] Glass thread [Owens-Corning Fiberglass Corporation (Owens-Corning
A 1/0 ECH15 sized glass thread (from Fiberglass Corporation) was impregnated into a cord soak solution and passed through a heated oven to impregnate and coat the cord. Inlet temperature is 163℃ and outlet temperature is 219℃
The transit time was 45 seconds at °C. The desired soaking liquid coverage was about 20% by weight on the cord. The formulation for the rubber compound used for the measurement of H-adhesion of glass threads to rubber is shown below. The rubber compound containing the dried adhesive coated glass threads was cured at 152°C for 20 minutes. Rubber compound Component Weight part Smoked sheet (natural rubber) 50 SBR-1502 50 ENDOR 0.15 HAF carbon black 35 Zinc oxide 3 Stearic acid 1 PICCO 100 2 Styrenated phenol (antioxidant) 1 ASTM103 oil ( Plasticizer) 7 Diphenylguanidine 0.15 NOBS #1 (vulcanization accelerator) 0.9 Sulfur 2.6 Examples The tables below were each made using three different methods.
Overall of Bd/VP/BA and Bd/VP/St is 70/15/15
The H-adhesion of dried, adhesive-coated glass threads cured in rubber using the composition of the present invention is compared. a) graph latex, b) formulation, c)
terpolymer

TABLE: The blend with polystyrene, which showed poor adhesion, produced yarns that were extremely brittle at ambient temperatures, while the other two styrene-containing yarns were flexible. All three threads containing BA were flexible. Latexes made with polystyrene species showed the highest adhesion than styrene terpolymers. The yarn containing a styrene terpolymer is considered a control yarn since this terpolymer mimics the normal VP latex used in tire cord adhesives. The three yarns containing BA give equivalent results and are considered to be as good as the yarn containing the styrene terpolymer. Examples The table below shows the totality of Bd/VP/BA and Bd/VP/St made using three different methods as described above.
This is to compare the flexibility of glass threads using a composition of 70/15/15. The yarn contained only dry adhesive dip. They were not embedded in the rubber compound (method A).

Table: Latexes made with poly(BA) seeds exhibit the best flexibility at all three temperatures. Latexes made with polystyrene seeds are -30°C lower than latexes made from terpolymers containing styrene.
It showed much better flexibility in the poly(BA) seeds, but not as good as latexes made from poly(BA) seeds. The poor flexibility at -30°C and 25°C is due to the brittle yarn made by the polystyrene compound. EXAMPLE The table below shows the softness and H-
Indicates adhesion. Blends of these latexes with 60 parts poly(Bd) latex were made. These latexes and latex blends are then
Compared to Bd/VP/St control. Two 60/40 blends of polyBd/graft copolymer latex containing poly(BA) species are 70/40
It exhibits much better flexibility at -30°C than formulations using 15/15Bd/VP/St latex. The 70/15/15Bd/VP/St terpolymer latex alone exhibits poor low temperature flexibility. 80/10/
The 10 graft composition showed slightly lower adhesion than the 70/15/15 graft composition.

Table: Examples A number of additional species-based latexes were made and evaluated in glass tire cord adhesives. Latex variables included seed type, amount of crosslinker in the seed preparation, and amount of mercaptan used during the final grafting step. in the case indicated
A seed latex was prepared in a manner similar to that in the examples above, except for the addition of DVB (divinylbenzene). The final graph latex,
Prepared in a manner similar to item 5 in the above example except that 0.4 parts of potassium carbonate was added to increase the rate of polymerization of VP. In each case Bd/VP/EHA or
The Bd (2-ethylhexyl acrylate or n-butyl acrylate) graft latex composition was 70/15/15 overall. These latexes were compared to a Bd/VP/St terpolymer control in a formulation with 60 parts of poly(Bd) latex. The sample for destructive testing is a composite material that mimics the cross section of a tire, consisting of two polyester plies (a layer of polyester cord that has already been calendered with rubber), two glass belts, and a rubber layer. had a thickness of approximately 1 cm. The glass belt was first made by twisting a 3/0 cord (1.5 times per inch) with dip-treated glass threads (same as in the above example) to form a belt with 16 threads per inch to a thickness of 25 mils. It was made by wrapping a cord around a drum around a rubber sheet. The polyester rubber layer, glass rubber layer and top rubber layer were cured together. 2″×
A 7″ (5.1cm x 17.8cm) specimen was placed at ambient temperature (20−25
The specimens were subjected to oscillation at 2 cycles per second of 0.7'' (1.78 cm) compression and 0.2'' (0.51 cm) tension for a total of 30,000 cycles. The rubber was then buffed so that the top glass belt could be tested for fracture. The formulation for the rubber compound used to determine the failure of this glass during this test is shown below. The rubber composite was cured at 149°C for 45 minutes. The rubber compound used for the H-adhesion test was the same as described in the examples above. Rubber compound components for glass breaking Parts by weight Natural rubber 46.50 PEPTON 76 (slow plucking) 0.13 SBR-1551 38.50 Cis-polybutadiene 15.00 FEF-Carbon Black 45.00 Hi-Sil 210 15.00 Agelite Super AGERITE SUPERFLEX 2.67 Aromatic oil 5.00 Zinc oxide 3.00 Stearic acid 1.50 COHEDUR RL 4.70 TBBS 1.20 CRYSTEX 3.00 Series A The table below shows that the seed polymer was from 2-ethylhexyl acrylate. Figure 2 shows the fracture properties and H-adhesion of adhesive coated glass cords using the graft copolymer latex of the present invention. Except for one case (in the graft copolymer, with the highest DBV in the seed and the lowest mercaptan), failure was low and not significantly affected by changes in DVB and mercaptan. In general, seed latexes provide significantly lower fracture than conventional Bd/VP/St terpolymer latexes. Series B The table below shows the fracture properties and H-adhesion of glass cords coated with adhesives using the graft copolymer latex of the present invention in which the seed polymer was from n-butyl acrylate (BA). show. In all cases using this type of polymer, failure is low and the amount of DVB in the seed and the amount of mercaptan in the graft copolymer formulation have little effect on failure. In all cases, the seed-based latices give significantly lower failure than conventional Bd/VP/St terpolymer latexes. The breakability of glass cords containing latexes based on the seeds of the invention was very favorable compared to that of conventional cords. Six manufactured control samples tested at ambient temperature (20-25°C) for several months showed an average failure of 8.7.

【table】

TABLE The poly(Bd) used in the formulation was the same emulsified polybutadiene as in the previous example.

【table】

TABLE The poly(Bd) used in the formulation was the same emulsion polymerized polybutadiene used in the previous examples. Note: SIPEX UB - Sodium larium ursulfate from American Alcolac. DRESINATE 214 - A disproportionated rosin potash soap from Hercules, Inc. SULFOLE 120 - t-dodecyl mercaptan from Phillips Petroleum's rubber chemicals division. TAMOL N - Rohm and Haas Company's sodium salt of condensed naphthalene sulfonic acid. SBR-1502 - Low temperature non-fouling aqueous emulsifying free radical polymerized copolymer of butadiene-1,3 and styrene (23.5% target bound styrene)52
Nominal Muny viscosity ML1+4 (212〓). ENDOR - activated zinc salt of pentachlorothiophenol, Dupont's fast peptizer for improved processability. PICCO - Resin viscosity additive from Harcules' processing chemicals division. NOBS #1 - American Cyanamide Company's 90% N-oxydiethylenebenzothiazyl-2-sulfenamide and 10%
2,2'-Di-benzothiazyl disulfide. PENACOLITE R-2170 - Aqueous solution, solids, resin of resorcinol formaldehyde resin or condensation product made with excess resorcinol (requiring formaldehyde to convert it to an infusible resin) %75±
2; PH of 0.5-2.0, viscosity at 23℃ (Burdskfield) 35-85 pois, specific gravity of 1.23-1.26 (23
°/23°C), Copper Perth Company, Incoporate Company. PEPTON 76 - An activated dithiobisbenzanilide on an inert carrier from American Cyanamide Company. SBR-1551 - Non-fouling low temperature aqueous free radical emulsion copolymer of butadiene-1,3 and styrene (23.5% target bound styrene)52
Nominal Muny viscosity ML1+4 (212〓). Cis-polybutadiene - 92-93% cis solution polymerized with stereospecificity, nominal Munie viscosity ML1+4 at 100°C of 45-47. Hi-Sil210--PPG Industries' precipitated hydrated amorphous silica. Agerite Superflex
Superflex) - Al, Tay, Vanderbilt (RT
Vanderbilt) diphenylamine-acetone reaction product. Cohedur RL - A mixture of resorcinol and Cohedur A, the hexa- or pentamethyl ether of hexamethylolmelamine, with a small amount of dibutyl phthalate plasticizer for viscosity control. From Naftone, Inc. TBBS - American Cyanamide Company's N-tertiarybutylbenzothiazole-2-sulfenamide. CRYSTEX - Insoluble sulfur with 20% oil from Stauffer Chemical. BA-n-butyl acrylate Bd-butadiene-1,3 VP-2-vinylpyridine St-styrene EHA-2-ethylhexyl acrylate DVB-divinylbenzene (commercial DVB is approx.
55% pure, parts by weight in working examples are based on 100% DVB (commercial products are adjusted for purity)

Claims (1)

[Scope of Claims] 1. On a dry weight basis: (1) having a glass transition temperature not exceeding about -20°C;
a polymeric species of acrylate monomer, optionally copolymerized with the acrylate monomer and may additionally contain a very small weight of crosslinked polyunsaturated monomer, and (2) vinylpyridine of 7 to 9 carbon atoms. a shell of a copolymer of a monomer and a conjugated diene monomer having 4 to 6 carbon atoms, comprising an alkaline latex with a solids content of about 25 to 60% by weight of a rubbery graft copolymer of The total amount of the monomers forming the copolymer is approximately 8 to 20% by weight of the acrylate monomer, 3 to 20% by weight of the vinylpyridine monomer, and 60 to 89% by weight of the conjugated diene monomer.
% by weight of a composition for adhesion between glass fiber reinforced elements and rubber compounds. 2. The composition of claim 1 having a solids content of about 30-50% by weight. 3 The solids content is approximately 35 to 45% by weight, and the total amount of monomers forming the graft copolymer in the graft copolymer is approximately 10 to 45% by weight of acrylate monomers.
15% by weight, 7 to 15% by weight of vinyl pyridine monomer, 70 to 83% by weight of conjugated diene monomer, and about 0.05 to 1.5 parts by weight of crosslinked polyunsaturated monomer, which may be optionally added, based on 100 parts by weight of acrylate monomer.
A composition according to claim 2 used in an amount of parts by weight. 4 The acrylate monomer is selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof, the vinylpyridine monomer is 2-vinylpyridine, the conjugated diene is butadiene-1,3, and the polyunsaturated 4. A composition according to claim 3, wherein the monomer is divinylbenzene. 5 mixed with the graft copolymer and additionally about -
Contains rubbery polybutadiene with a Tg not exceeding 70°C, and the weight percent ratio of the graft copolymer to the polybutadiene on a dry basis is approximately 20:80-60:
40 and the total amount of said polymer is 100 parts by weight. 6 additionally contains, in admixture with the graft copolymer, a rubbery polybutadiene having a Tg not exceeding about -70°C, and on a dry basis the weight percent ratio of graft copolymer to polybutadiene is about 20:80.
60:40 and the total amount of polymer is 100 parts by weight. 7 additionally contains, in admixture with the graft copolymer, a rubbery polybutadiene having a Tg of not more than about -70°C, such that on a dry basis the weight percent of the graft copolymer is about 40 and the weight percent of the polybutadiene is about 60. The composition according to claim 5, wherein the total amount of said polymers is 100 parts by weight. 8 Based on dry weight: (1) have a glass transition temperature not exceeding about -20°C;
a polymeric species of acrylate monomer, optionally copolymerized with the acrylate monomer, which may additionally contain a very small weight of crosslinked polyunsaturated monomer, and (2) vinylpyridine of 7 to 9 carbon atoms. 100 parts by weight of a rubbery graft copolymer consisting of a copolymer shell of a monomer and a conjugated diene monomer having 4 to 6 carbon atoms, and 3 parts by weight of a water-soluble thermosetting phenolic aldehyde resin.
~15 parts by weight of an alkaline aqueous dispersion having a solids content of approximately 30-50% by weight, provided that the total amount of the monomers forming the graft copolymer in the graft copolymer is such that the acrylate monomer is 8-20% by weight of the vinyl pyridine monomer and 60-89% by weight of the conjugated diene monomer. 9 The solids content is approximately 35 to 45% by weight, and the total amount of monomers forming the graft copolymer in the graft copolymer is approximately 10 to 45% by weight of acrylate monomers.
15% by weight, 7 to 15% by weight of vinyl pyridine monomer, 70 to 83% by weight of conjugated diene monomer, and about 0.05 to 1.5 parts by weight of crosslinked polyunsaturated monomer, which may be optionally added, based on 100 parts by weight of acrylate monomer.
9. The composition of claim 8, wherein the phenol-aldehyde resin is used in an amount of about 4 to 10 parts by weight. 10 The acrylate monomer is selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof, the vinylpyridine monomer is 2-vinylpyridine, the conjugated diene is butadiene-1,3, and the polyunsaturated 10. The composition of claim 9, wherein the monomer is divinylbenzene and the phenol-formaldehyde resin is a resorcinol-formaldehyde resin. 11 additionally contains a rubbery polybutadiene having a Tg not exceeding about −70° C. mixed with the graft copolymer and the above-described resin, wherein the weight percent ratio of the graft copolymer to the polybutadiene on a dry basis is about 20 10. The composition according to claim 9, wherein the ratio is 80 to 60:40, and the total amount of the polymer is 100 parts by weight. 12 additionally contains, in admixture with the graft copolymer and the resin, a rubbery polybutadiene having a Tg of not more than about -70°C, the weight percent of the graft copolymer relative to the polybutadiene on a dry basis;
The ratio is about 20:80 to 60:40, and the total amount of polymer is
11. A composition according to claim 10 in an amount of 100 parts by weight. 13 additionally contains, in admixture with the graft copolymer and the resin, a rubbery polybutadiene having a Tg of not more than about -70°C; 60 and the total amount of said polymer is 100 parts by weight.