Resorcinol-formaldehyde-latex dips

S. Bandyopadhyay, S.L. Agrawal, P. Sajith, N. Mandal, S. Dasgupta, R. Mukhopadhyay, A.S. Deuri, and S.C. Ameta, Research on the application of recycled waste RFL (Resorcinol-Formaldehyde-Latex) dip solid in Styrene Butadiene Rubber based compounds. Progress in Rubber, Plastics and Recycling Technology, 23(1), 21, 2007. 

Examples and data are then prepared to show that the same mechanisms of migration and chemical interaction are operative in various approaches for vulcanization bonding of elastomers to textiles. The systems discussed are the work-horse RFL (resorcinol-formaldehyde- latex) dips, self-bonding elastomers (via two different approaches), and a versatile proprietary bonding agent. 

The most common textile bonding compositions are, of course, the RFL (resorcinol-formaldehyde-latex) dips used to adhere tire carcass rubber to cord reinforcing members. A typical RFL composition calls for a latex terpolymer of styrene-butadiene-vinyl pyridine as well as the resorcinol and hexamethylene tetramine. Some natural rubber latex or regular SBR latex may also be added. The R F resin which forms in situ is able to react chemically with rayon by methylol etherification of the cellulose s hydroxyls. Similar reaction is likely with the amide groups of nylon fibers as shown in Figure 7. 

Resorcinol formaldehyde latex (RFL) cord dips have only a limited application within the general rubber goods industry and for adhesion to be achieved with synthetic fibres it is necessary to use the systems developed by Bayer and Degussa. These systems are based upon a combination of resorcinol, a formaldehyde donor and a hydrated silica filler (commonly called the RFK system). This system is incorporated as dry ingredients into the rubber compound and is activated by the application of heat. 

Cord Resorcinol Formaldehyde Latex (RFL) Dipping/Drying Lines.170... 

SRF. [S nectady] Resorcinol formaldehyde preform resin sol n. bonding agent ukd in rubber compds. to improve adhesion resorcinol donor in re-sordncd-formaldehyde latex dips. 

Dispersions of copolymers of butadiene with acrylic acid or methacrylic acid in aqueous potassium hydroxide have been mentioned in the patent literature" as a dip for adhering rayon tire cord to rubber. The effect is most evident when carboxyl groups are present in the adhesive, the tie cement, and the cover stocks. The adhesive may be applied as latex, aqueous dispersion, or cement. A patent issued to the Dunlop Company Ltd." describes the use of a styrene-butadiene-itaconic acid copolymer with Gen-Tac Latex (GenCorp) in formulating an RFL (resorcinol formaldehyde latex) type adhesive for bonding a natural rubber compound to Nylon 66 and rayon tire cords. Brodnyan" also claims carboxylic adhesives for rayon, nylon, and Dacron cords. In this case, the tire cords were treated with a mixed polymer latex containing resorcinol-formaldehyde condensate, a butadiene-vinyl pyridine copolymer, an SBR copolymer, and a multifunctional copolymer from methyl acrylate, 2-hydroxy propyl methacrylate, and acrylic acid. A different approach was reported by Badenkov" whereby rayon or nylon tire cords were coated with... 

The dip is prepared by dissolving the aminimide and surfactant in water with moderate stirring. The epoxy resin is then added with rapid stirring. The dip is ready for use and stable for 10-14 days. It is applied to the cord in a 1-3 sec dip. This is followed by drying in an oven at about 450 F (depending on cord type and desired properties) for about 45-60 sec. A second cover dip of conventional resorcinol-formaldehyde-latex emulsion is then applied followed by 45 sec drying at 450°F. 

Tire Cord. Melamine resins are also used to improve the adhesion of mbber to reinforcing cord in tires. Textile cord is normally coated with a latex dip solution composed of a vinylpyridine—styrene—butadiene latex mbber containing resorcinol—formaldehyde resin.. The dip coat is cured prior to use. The dip coat improves the adhesion of the textile cord to mbber. Further improvement in adhesion is provided by adding resorcinol and hexa(methoxymethyl) melamine [3089-11 -0] (HMMM) to the mbber compound which is in contact with the textile cord. The HMMM resin and resorcinol cross-link during mbber vulcanization and cure to form an interpenetrating polymer within the mbber matrix which strengthens or reinforces the mbber and increases adhesion to the textile cord. Brass-coated steel cord is also widely used in tires for reinforcement. Steel belts and bead wire are common apphcations. Again, HMMM resins and resorcinol [108-46-3] are used in the mbber compound which is in contact with the steel cord to reinforce the mbber and increase the adhesion of the mbber to the steel cord. This use of melamine resins is described in the patent Hterature (49). 

Methacrylatochromic chloride bonding agent, latex dips Hexamehoxymethylmelamine, Resorcinol-formaldehyde resin bonding agent, NBR Chemlok 205... 

Rubber products such as tyres, belts and hose rely on reinforcement by textiles to achieve the required physical properties. To effect reinforcement, textile and rubber must be adequately bonded together, and to promote adhesion, there is a range of treatments to suit most fibre-rubber systems. The adhesion-promoting material (dip) is usually a terpolymer latex of butadiene-styrene-vinyl pyridine (or a blend of SBR and vinyl pyridine), which bonds well to the fibres, together with a resorcinol formaldehyde precondensate, which, on curing, bonds well to mbber a three-dimensional resin network is formed. 

The standard aqueous treatment for textile adhesion is based on resorcinol/formaldehyde resin/latex (RFL) dip systems. A typical formulation for such an adhesive dip is given in Table 9.1. 

An RFL dip consists of an aqueous resorcinol formaldehyde resin liquid with a ruhher latex. The RF resin is used to achieve good adhesion to the organic fiber substrate whether it be rayon, nylon, or polyester. The rubber latex portion can be a natural rubber latex or a styrene butadiene vinylpyridine (terpolymer) latex or even a neoprene latex. This rubber latex is present to achieve good adhesion with the rubber matrix itself. So the RFL allows good adhesion between the rubber and the textile cord reinforcement whether it is used in the manufacture of passenger tires, truck tires, off-the-road tires, power transmission belts, V-belts, timing belts, or various hose products. 

Amino resin adhesives may also be used to improve bonding between other materials. For example, tire cord is normally treated with a rubber latex to improve adhesion to the vulcanized rubber. The latex dip solution may also contain a resorcinol-formaldehyde resin or an amino resin to improve the bonding. Both urea and melamine resins are mentioned in patents, but melamine-formaldehyde is said to be most effective. 

Most of the aramid adhesive systems initially used were based on a first-step dip of either an epoxide or a blocked polyisocyanate and then a second or top coat of RFL. Wenghoefer in his patent disclosed a somewhat different first step dip which consisted of bis(j3-azido-formyl oxyethyl)isophthalate. After drying, the cord thus treated, was then dipped in a phenolic adhesive and cured at 230 C for 60 seconds. A patent issued to Van Gils uses a one-step dip based on vinyl pyridine latex, trimethylol-phenol, resorcinol-formaldehyde resin, and... 

In the demanding application of polyester tension members in raw edge V belts, the polyester cord is pretreated by the supplier with an isocyanate priming coat followed by a resorcinol-formaldehyde/vinyl pyridine latex dip. 

The actual ratios of resorcinol to formaldehyde and of resin to rubber solids may be varied within reasonable limits, the generally accepted optimum ratios being between 1 1.5 and 1 2 for the resorcinol to formaldehyde and between 1 5 and 1 7 for the resin to rubber ratio. Within these limits, it is possible to fine tune the RFL formulation to suit the particular rubber compound with which it is to be used. Generally, however, it is more convenient to use a standard dip formulation for most applications, to avoid excessive complexity, while still maintaining perfectly adequate adhesion levels to a wide range of rubber compounds. For most applications, the preferred latex used is a styrene/ butadiene/vinyl pyridine (VP) terpolymer latex. 

---