NL8100369A - PROCESS FOR THE PREPARATION OF A PHENOLIC ALDEHYD RESIN AND A RESIN MATERIAL FOR AN ADHESIVE SYSTEM FOR APPLICATION TO GLASS FIBERS. - Google Patents

Abstract

A method of preparing a thermoplastic, water-soluble, phenolic aldehyde resin involves two steps. Firstly, the phenolic compound and aldehyde are reacted to less than 100 percent completion at an aldehyde to phenolic compound mole ratio of 0.6 to 1.5 and at a pH of 3.5 to 5.5 for 3 to 10 hours at a temperature of 13 to 32 DEG C. Secondly the pH of the reaction is adjusted to above 7.0 to 7.5 and the reaction is continued between the unreacted phenolic compound and aldehyde and resinous mixture to produce a resinous mixture that has a predominant amount of trimer polymer with slight cross-linking and a minor amount of dimer and higher oligomers. The phenolic compound is preferably resorcinol or a mixture of resorcinol and phenol. The resin mixture is processed into an adhesive by combining it with one or more elastomeric latex and various latex additives. The adhesive is aged and has added to it an amine or ammonia to tie up any unreacted aldehyde. Also additional phenolic compound may be added. The adhesive is used to coat filamentary materials in particular glass fibres and the coated filamentary materials are dried to produce reinforcement material for rubber. Uses:- Tyre cords adhesives

Description

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Process for the preparation of a phenolic aldehyde resin and a resin material for an adhesive medium system for application to glass fibers.

The invention relates to a process for the preparation of a phenolic aldehyde resin. More particularly, the invention relates to a process for the preparation of a resorcinol formaldehyde resin for use in an adhesive system for bonding glass fibers to rubber to produce reinforced rubber products.

Filament materials have been widely used as a reinforcing material in rubber for manufacturing reinforced rubber products such as pneumatic belts, force TO transmitting belts, conveyor belts, high pressure tubes and the like. The filament materials used to reinforce the rubher material include naturally occurring or synthetic filaments and may be in the form of individual fibers, groups of fibers, in the form of strands, tape, cord, roving cloth and the like. The naturally occurring fibers include cotton, side ramie, and the synthetic fibers include rayon, nylon, polyester, and glass fibers.

Glass fibers are excellent filament material for reinforced rubber and are better than the natural or synthetic organic filament materials because the glass fibers do not stretch or deform under tension to the same extent as the other filament materials. Unlike other filament materials, certain combinations of glass fibers with sheathing co-act together to provide reinforced rubber materials which have greater strength than the glass and the coating material alone. Although filament materials other than glass 8 1 0 0 36 8 &. , / r. - - - - - 2 fibers, which are subject to considerable stress elongation, are tensile strength limited to the base strength of the fibers, even when properly coated, coated glass fibers have greater strength than the glass alone. For example, the low modulus of elasticity of glass can be utilized to provide reinforced rubber tires with excellent road handling when providing a suitable coating medium for transferring stresses to all fibers in the glass fiber cord so that the load is uniform throughout the material, This phenomenon is illustrated by the observation that a typical uncoated fiber glass cord (G75.5 / 0, filament number 2000, ie 2000 filaments of G fiber with a diameter of about 9.1 µm, 15,120 meters per kg, 5 strands per string) has a tensile strength of about 35 to kO pounds 15 (156 - 178 Newton) ASTM Test G178-52, but after coating with a coating, e.g. res orcinol formaldehyde latex coating, such a cord has a tensile strength of about 50 to about 70 pounds. (220 - 311 Newton).

The aforementioned coated glass fiber cord, GT-75, 5/020 has been found to be particularly useful for the reinforcement of rubber, which is used in power transmission belts and with fiber glass. reinforced tires and the like. In such a coated glass fiber cord, a resorein formaldehyde latex coating is used as the adhesive system to transfer the stresses and to provide adhesion between the glass fibers and the rubber. Typically, the resorcinol formaldehyde or resorcinol phenol aldehyde resin used in the adhesive systems for the bonding of the glass fibers to rubber is prepared according to a method using a basic pH environment, ie around a pH of 8 10. The phenolic aldehyde resin usually has an aldehyde level to phenolic var. bond level, usually resorcinol, from 0.8 - 0.8 to a phenolic compound on a mole basis. Such a resin is characterized by a low degree of polymerization and a minimum molecular weight. A particularly useful phenol aldehyde condensate, which is a resorcinol formaldehyde resin, has a ratio of 8 1 0 0 36 9. * 4-3.6 formaldehyde to 1 resorcinol and is sold under the trade name Penacolite R-2200 resin.

Several methods have been known for preparing phenol aldehyde polymers for adhesive systems. According to U.S. Pat. No. 2,385,372 of 19 ^ 7, a permanently fusible resin is prepared from dihydroxybenzene (resorcinol) and an aldehyde in two steps so that a catalyst is not present during the steps of the reaction. It was believed that with the catalyst present in the early stages of the reaction 10, the resin would be too thick to remove the water that is formed in the reaction. The problem is overcome by using a two-stage reaction in which the dihydroxybenzene (resorcinol) reacts with aldehyde at reflux conditions without a catalyst until most of the reaction is complete. Then either an alkaline or acid catalyst is added and the last increment of aldehyde reacts with the dihydroxybenzene.

A multistage reaction has also been used to prepare a phenolic aldehyde condensate in US patent h.025, wherein a precondensate of formaldehyde, resorcinol and a para-substituted phenol and a precondensate of resorcinol and formaldehyde are used. In a first step, resorcinol and a para-substituted phenol with two active methylene groups are condensed in the presence of an acid catalyst. In a two-stage formaldehyde is condensed with the product of the first stage in an alkaline medium. Then, in the third stage, the second stage product is dissolved in water along with a resorcinol precondensate to form the phenoplastic system, which is a mixture of phenol aldehyde condensates, then combined with an elastomeric latex to form the textile fiber adhesive. .

According to U.S. Patent 3,956,205, a resole is prepared in a two-stage reaction. The first stage of the reaction is run under novolac forming conditions, where an acidic catalyst is used to provide a pK less than 5. In the first stage, 1 moles of phenol react with 0.05 to 0.30 moles of formaldehyde to favor the formation of the dimer polymer and suppress the formation of higher oligomers. In the second stage 5, reaction is carried out in the presence of a basic catalyst, which has a pK greater than 9, with the addition of 1.75 to 3.5 moles of formaldehyde per mole of original phenol for the resole reaction. At the end of the reaction, the catalyst is neutralized by adding acid to lower the pH to between 6 and 8.5 to form the resole resin.

Prior art phenolic aldehyde resins, such as. Penacolite resorcinol formaldehyde resin, and those prepared by the multistage processes discussed above can be improved for use in an adhesive system for coating the glass fibers used to reinforce rubber products. An improvement of the phenolic aldehyde resin is desirable to give the coated glass fibers more flexibility and better resistance to compression fatigue, thereby providing more durable rubber products.

One of many reinforced rubber products that would benefit from the use of coated glass fibers with more flexibility and better resistance to compression breakage are pneumatic tires. A belt with coated glass fibers, which have more flexibility and better resistance to compression fatigue, would improve the wear properties and give higher mileage. Also radial fiberglass tires, alone or in combination with other fiber-material tires, which contain coated fiberglass with greater flexibility and better compression fatigue resistance, will provide higher mileage and improved handling.

The object of the invention is to provide a process for the preparation of a thermoplastic phenolic long chain formaldehyde resin with better flexibility and toughness and which consists of a considerable amount of the 8 1 0 0 36 9 ........ ......... fc-5 trimer polymer and for providing this resin material for use in an adhesive system used for coating glass fibers to make the glass fibers more flexible and more resistant to compression fatigue failure.

Summary of the Invention According to the invention, there is provided a thermoplastic phenolic aldehyde resin containing a substantial amount of trimer polymer and containing a small amount of unreacted aldehyde. The method includes a two-stage response. In the first step, a phenolic compound and the aldehyde are reacted in such amounts that the ratio of aldehyde and phenolic compound is in the range of from about 0.6 to about 1.5 and less than 100% by volume. in an acid medium at ambient conditions, generally for a time equivalent to about 3 hours to about 10 hours at a temperature in the range of about 11 ° C to about 32 ° C to prepare a phenolic aldehyde resin mixture with a substantial amount of trimer Polymer and a smaller amount of dimer or higher oligomeric polymers than trimer, together with unreacted phenolic compound and unreacted aldehyde. In the second tran, the pH of the first stage resin mixture is adjusted in a range from above 7 to about J.5 to continue the condensation reaction of the phenolic compound and aldehyde and resin mixture to form the more flexible and tough, thermoplastic water-soluble phenolic aldehyde resin, mainly containing the trimer polymer, and with a small amount of unreacted aldehyde. The resinous mixture obtained is a thermoplastic water-soluble phenolic aldehyde resin, which is excellent for use in an adhesive system, such as HFL systems, for coating glass fibers to give the coated glass fibers better adhesion to rubber for manufacturing reinforced rubber products.

Generally, the phenolic compound and the aldehyde and an acidic or basic catalyst, if used, for controlling the pH in the steps of the process of the invention, may include any phenolic compound, aldehyde, acidic or basic catalyst known for phenolic aldehyde resins. The terra "resin" refers to synthetic resins, which are organics obtained by synthesis from relatively simple chemical compounds by condensation polymerization reactions.

The phenolic aldehyde resin, which is obtained by the precisely controlled two-stage process according to the invention, gives phenolic aldehyde resins, which are flexible and tough, which, when used in an adhesive system for coating glass fibers, make the coated glass fibers more flexible and more resistant to compression fatigue. to make. Due to the pH control in both 15 stages of a two-stage process and because the reagents fed in the first stage do not fully react and because of the relationship of temperature and time conditions in both stages, the trimer polymer is the predominant polymer, which in the two-stage reaction is formed. Other nolymeric forms, such as the dimer and the higher oligomeric polymer forms, are also formed, but in less amount than the trimer. The trimer polymer form can be represented by the formula 1 of the formula sheet wherein R is hydrogen or a hydroxyl group or a mixture thereof, and the trimer may also have one or more on the phenolic rings in it. trimer have pendant methyl groups. The second stage pH control allows for a low degree of cross-linking between the polymer forms and mainly the trimer polymers in the reaction product. of the first stage reaction.

The phenolic aldehyde resin, which has been prepared according to the method described above, is in fact a mixture of polymer forms, in which the trimer chain is the predominant polymer chain and in which there is a small amount of cross-linking between the polymer chains. This phenolic aldehyde resin is an excellent resin for use in an adhesive system for bonding glass fibers to rubber. The resin is first combined with a.

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This is conventional elastomeric latex so that the resin is present in an amount of from about 5 to about 50 parts by weight of the resin per 100 parts by weight of elastomeric latex solids. Other components such as waxes, antioxidants and bond promoters, one of which is example resorcinol, and cross-linking retardants, eg concentrated ammonia, can be added to the adhesive system. Sufficient water is present or added to adjust the total solids content of the adhesive system to about 20 to about 100% solids. This adhesive system is used for coating glass fiber materials, such as individual glass fibers and groups of glass fibers in the form of strands, tape, cord, roving, cloth and the like.

Detailed Description The phenolic aldehyde resin of the invention has, as noted above, a critical composition, that is, predominantly trimer polymers in the blend of polymers which form the phenolic aldehyde resin, and is prepared by a precisely controlled multi-critical process.

In the first step, the reactants are reacted to less than 100% completely in an acidic pH of about 3.5 to 5.5, and in the second step, the resin reaction is continued at a piT in the range of about 7 to about 755 .

It is believed, but the invention is not limited by this assumption, that the critical process and the amounts of the starting material result in the critical composition in the following manner. The phenolic compound has a strong ortho-para-directing effect because of the hydroxyl group, and resorcinol, the predominant phenolic compound, is double activated at the 2, b and 6 position of the ring. When the ratio of the aldehyde and the phenolic compound is about 1, a resin is obtained in an acidic medium which is permanently meltable and soluble. Very little, if any, cross-linking occurs and the resin consists mainly of chains in which the phenolic cores are bonded to the activated sites of the phenolic cores by methylene bridges. In the 81 0 0 36 9 ψ · .., *

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The medium and the 2 and 6 positions of the phenolic nuclei are favored for the condensation reaction. The reaction rate for the formation of the resin is directly proportional to the hydrogen ion concentration. By controlling the acidic pH in the first 5 steps for acid and by controlling the temperature and residence time in the indicated limits, the resin reaction is less than 100% complete. The result is that together with the resin formed in the first stage there is also some unreacted aldehyde and possibly some unreacted phenolic compound. Since the first stage resin formation reaction is less than 100% complete, even when the aldehyde and phenolic compound ratio may be more than 1, even up to about 1.5, the resin formed is still permanently meltable and soluble. The average molecular weight of the resin in the first stage of the reaction is generally less than 1000.

The first stage resin product contains a predominant amount of the trimer polymer, but this is in fact a resinous mixture, which also contains a small amount of diraer polymer and a small amount of higher oligoromer polymers, such as tetramer and pentamer. It is desirable to keep the amount of higher oligomers at a minimum because these higher oligomers are not water-soluble. The resin mixture with a substantial amount of trimer polymer has good flexibility, which is extensible on a substrate coated with the phenolic aldehyde resin of the invention.

The first stage reaction mixture has a pH adjusted in a range from above 7 to about 7.5. Although the rate of resin formation in the presence of basic catalysts is independent of the hydroxyl ion concentration above low catalyst concentrations, the small amount of basic catalyst added to raise the pH above 7 to 7.5 is low enough that the hydroxyl ion concentration has an effect on the reaction rate. The resinous material out. the. first, stage continues, with hotter aging with the unreacted aldehyde and all not. reacted phenolic compound, which is present from the first stage for 8 1 0 0 36 9

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and forming methylol groups which further condense as the second stage resinous material ages to form a slightly cross-linked but still substantially linear thermoplastic phenolic resin with a predominant amount of trimer polymers in the mixture of polymers that make up the phenolic aldehyde resin.

Since a basic pH is used in the second stage only, the formation of the second stage phenolic alcohols is mainly limited to methylol instead of 10 dialol or trial alcohols, and this limiting effect supports the growth of the essentially linear thermoplastic resin from the first stage. The limitation of the methylol phenolic alcohols together with the directing influence of a basic environment for reacting at the 2, U and 6 sites leads to the growth of cross-links in the essentially linear chains in the first stage resinous mixture . The addition of the methylol groups to provide a small amount of cross-linking in the linear chain of the first stage resinous material gives the resinous material a degree of toughness while maintaining the flexibility of the linear chain. The second stage reaction is continued for about 2 to about 10 hours to obtain the resin with good flexibility and a small amount of cross-linking to impart a degree of toughness to the resin. The cross-linking and / or branching 25 is not such that the resin becomes cross-linked and infusible.

In the method and composition of the invention, the structure of the phenolic compound is an important factor in the characteristics of the flexibility and toughness of the resin and the resin coated substrates. The rate of resinization depends on the nature and degree of the substitution of the phenolic compound. With the phenolic compound, which reacts with the aldehyde at the ortho and para positions with one or more hydroxyl groups on the ring, there must be at least two open places, ortho or para, relative to a hydroxyl group. The phenolic compounds, which which may be used in the method and composition of the invention include 81 0 0 36 9 5 'k-10-resorcinol, as well as resorcinol mixed with small amounts of phenol, cresol and mixtures of the isomers thereof, xylenol or mixtures of the isomers thereof , a mixture of homologs of phenol and dihydric phenols, such as phloroglucinol, orcinol, cresorcinol and m-xylorcinol. It is preferred to use resorcinol as the phenolic compounds and alternatively a mixture of resorcinol and phenol.

The aldehyde which can be used in the process and composition of the invention is an aldehyde which acts as a methylene donor and is soluble in the reaction medium. Aldehydes which can be used include: formaldehyde commonly used as a 37% aqueous solution referred to as formalin, various polymers of formaldehyde such as paraformaldehyde, hexamethylene-tetramine, acetaldehyde and furfural, and mixtures thereof. It is preferred to use formaldehyde in the form of formalin.

In the following description, the phenolic compound will be referred to as "resorcinol", the preferred phenolic compound, and the aldehyde will be referred to as "formaldehyde", the preferred aldehyde. It should be noted, however, that any of the aforementioned phenolic compounds or aldehydes can be used as described, instead of or in combination with the resorcinol and the formaldehyde.

The amounts of resorcinol and formaldehyde used are those which give a molar ratio of formaldehyde and resorcinol in the range of from about 0.6 to about 1.5 and preferably from about 0.8 to about 1., 5 ..

An example of the ratio is 1 mole formaldehyde: 1.5 moles resorcinol to obtain a mole ratio of formaldehyde to resorcinol of about 0.65.

When too small an amount of resorcinol or too much formaldehyde is used, an infusible cross-linked resin will be formed instead of a fusible, thermoplastic mainly trimer resin with very little cross-linking, which is flexible and tough. When too much resorcinol and too little formaldehyde are used, the resin formed will not be as flexible as possible, because the number of trimer polymers in the polymer mixture will not be very large.

In the first stage of the invention, the type 5 acid catalyst which can be used includes: sulfuric acid, oxalic acid, hydrogen chloride, sulfamic acid, benzenesulfonic acid, toluenesulfonic acid or trifluoroacetic acid. The concentration of the acid catalyst can be in the range of from about 0.001 to 0.002 mole equivalents per mole of resorcinol, but the acidic pH of the first step reaction can be any acidic pi with a sufficient amount of added catalyst to obtain the desired pH. Preferably, the pH of the first stage reaction is the acidic pH obtained by combining the resorcinol and formaldehyde in the form of formalin before the reaction. Most preferably, this pH, which is obtained by combining the reagents, found autocatalysis in the pH range of about 3.5 to 5.5. An acidic pH above 5.5, which is obtained by autocatalysis, can be used by adding a small amount of basic catalyst. When the pH above 20 is about 5.5, resorcinolic alcohols such as methanol can be formed and cross-linking can occur.

The first stage reaction can be performed by adding the resorcinol and formaldehyde to a reaction vessel. Preferably, resorcinol and formaldehyde, as formalin, are added to a reaction vessel in the appropriate amounts to give the desired molar ratio.

When a monohydric phenol, such as phenol, is present in any amount, the reaction conditions must be enhanced because monohydric phenols react more slowly than resorcinol and polyhydric phenols. Generally, in the first stage, the resin reaction is conducted under ambient temperature conditions for the resin reaction between resorcinol and formaldehyde in the range of about 13 to about 32 ° C, when the residence time for the resin reaction in the first stage is in the range of about Is 3 hours to about 1H hours, where the temperature and time are reversed. An equivalent residence time and temperature can be used to obtain the same reaction rate as obtained using the aforementioned conditions, that is, when the temperature is increased, the.

5 residence time becomes shorter. When the temperature is raised above 32 ° C, the residence time is shortened to less than 3 hours, and when the temperature is lowered below 11 ° C, the residence time must be extended to above 10 hours.

At the end of the first stage reaction, a resinous or polymer mixture is formed containing a major amount of trimer and lesser dimers and higher oligomers of the resorcinol, along with some unreacted formaldehyde and some unreacted resorcinol,

The greatest amount of trimer is at least about 10% of the converted materials in the polymer blend.

The hard mixture. of the first stage is subjected to a second stage by adjusting the pfi of the resin mixture in the range above 7 to about 7.5. This adjustment is made by adding a basic catalyst to the resin mixture. Suitable basic catalysts are: sodium hydroxide, potassium hydroxide and other alkali metal hydroxides as well as alkali metal carbonates and alkaline earth metal hydroxides.

These can be used as solids, but are preferably used in aqueous solution. The basic catalyst concentration is generally about 3% per mole of resin, and preferably about 0.01 to about 0.06 mole, of catalyst, per mole of resin.

After the pH of the resin mixture is adjusted to the correct pH, the resin reaction is continued so that the unreacted formaldehyde reacts with the resin and the unreacted resorcinol. The reaction is conducted at ambient conditions, which are generally a temperature in the range from about 13 to about 32 ° C, when the residence time is in the range from about 2 to about 10 hours. When the temperature is raised or lowered above or below this range, the residence time is reversed "81 0 0 36 9 •" - - <· 4 -13- and therefore any temperature and residence time can be used, which has an equivalent reaction rate to which allows for the aforementioned conditions of temperature and time.

When the pH is above about 7.5 s, too many methylol groups will form and the resin can be crosslinked to an excessive degree. When the pH is less than about 7, the acid type resin reaction of the first stage will proceed and the linear tripolymer chain and smaller amount of other polymer forms will not get too small amount of cross-linking for a tough flexible resin.

The above-described two-stage process can be performed in a batch type reaction in a vessel or in a semi-continuous type or continuous type reaction in a single stage vessel or in single vessel vessel, in which the reagents and products pass from one vessel to the next flow. The reaction vessels used in the two-stage process are all reaction vessels which are known to be suitable for resin-forming reactions.

Preferably, the reaction vessels or containers are those which are used at ambient conditions, but which are jacketed for heating and cooling, when ambient temperatures are too low during winter or too high during summer in industrial production plants.

The resorcinol formaldehyde condensate resin mixture of the invention is directly combined with an aqueous elastomeric latex to form an adhesive system for bonding fibrous materials to rubber. The elastomeric latices usable in the adhesive system are the conventional latices used for the preparation of elastomeric adhesive systems. Suitable elastomeric latices are the synthetic rubber latices, such as vinyl pyridine-styrene-butadiene terpolymer latices, which are sold under the trade name GEIf-TAC, Goodrite or Pyratex. Polybutadiene dispersions, styrene-butadiene latices, regenerated rubber dispersions, butyl rubber dispersions and ethylene propylene-butadiene terpolymer rubber dispersions can also be used. Also other 8 1 0 0 36 9 * 's I1 "" 14 latexes that can be used include natural rubber latex, which may be the raw rubber latex or rubber latex containing added material or treated to change the nature of the rubber, for example, by degradation or by oxidation, or by both It may, for example, contain any desired accelerators, vulcanizers, stabilizers, dispersants and any other substance such as those commonly used in the rubber industry. the rubber used is an artificial dispersion of a known synthetic rubber, it may also contain additional substances such as rubber accelerators, vulcanizers, stabilizers, dispersants, etc. The type or type of rubber dispersion or elastomeric latex, which The degree to which the fibrous material is bonded, in particular the glass fibers, depends to a great extent on the type or type of rubber, where the fiber is to be bound. elastomeric latices and dispersions reported include any combination of the above for the purposes of the invention.

The adhesive system can be prepared in any manner known to the person skilled in the art. The resin to elastomer latex ratio of the adhesive system should range between about 5 and about 50 parts by weight of the resin per 100 parts by weight elastomer. latex solids. The resorcinol formaldehyde resin-elastomeric latex mixture may also contain additives such as a wax to protect the elastomer in the coating material from attack by ultraviolet light; zinc oxide, magnesium oxide, lead monoxide or red lead can be included in the bonding system to promote cross-linking or curing of the elastomeric latex and improving the material's resistance to aging, heat and light; antioxidants for protecting the materials from oxygen degradation; treated diatomaceous earth or chemical diatomaceous earths and other ingredients known to those skilled in the art may be added to the bonding system to impart various properties thereto.

The aqueous adhesion system of the invention must have an 8100369-15 pH, between above 7 to about 10. Any pi adjustment may be made by adding an aqueous alkaline solution, such as sodium hydroxide, or ammonium hydroxide to achieve the desired pH . Also, the alkaline solution such as sodium hydroxide or ammonium hydroxide can be added to bind reacted or unreacted formaldehyde and thereby increase the pH of the bonding system. However, if the added material is a vinyl pyridine latex (PH 10.2), no further pH adjustment may be necessary. The adhesion system thus prepared is ready for direct use or, due to its stability, can be stored for a week before it is used for coating filament materials, in particular glass fibers. The bonding system can be applied to the surface of fibrous materials, especially glass fibers, by any conventional method such as dipping, spraying or spreading.

The filament material for which the adhesion system according to the invention can be used comprises reinforcing materials such as natural and synthetic organic fibers such as cellulose fibers and nylon fibers, polyester fibers and glass fibers.

In particular, the filament material are glass fibers. Generally, in the glass fiber cord forming method according to the invention, the glass fiber is formed on a fiber-forming sleeve, applied with an aqueous sizing agent, which is a conventional sizing agent for glass fibers, collected into a strand and wound on a molding gasket. This process is described in more detail in U.S. Pat. Nos. 3,537,517, 3,559,585 and 3,887-389. The moldings are then dried and rack mounted, wound and coated with the adhesive system coating material of the invention, and the coated strands are dried.

Preferred embodiment

In the preferred embodiment of the invention, resorcinol and formaldehyde in the form of formalin are reacted in a two-step reaction to less than 100% complete, first by starting with a molar ratio of formaldehyde 8100369. . * =? ". -TS- and resorcinol in a range from about 0.8 to about 1.5 and secondly by controlling the reaction conditions.

The reaction conditions of the first stage with the mixture of formaldehyde and resorcinol in the preferred molar ratio include a pi in the range of 3.5 to about 5.5. Therefore, in the first stage of the preferred embodiment, an acid catalyst is not required for obtaining a pH in the range of 3.5 to 5.5 in the reaction between resorcinol and formaldehyde, which is in the form of formalin. In another embodiment with other reagents, "when the pH of the first stage reaction is not in the range of less than 5.5 and greater than 3.5 due to the presence of the reagents alone, an acid catalyst must be used. The first stage reaction between resorcinol and formaldehyde is carried out at ambient conditions of temperature, preferably around 20 ° C to around 32 ° G, for a time of 3 to about 10 hours, preferably about 3 to about 4 hours. The first stage resin product comprises a major 20% amount of trimeric polymer of resorcinol formaldehyde with small amounts of dimer and higher oligomers of resorcinol and formaldehyde together with. unreacted formaldehyde and a smaller amount of unreacted resorcinol.

The reaction conditions of this reaction mixture are adjusted in the second stage. The pH of this resin mixture is adjusted in a range from above 7 to about 7.5 by adding about 0.01 to about 0.06 mole aqueous solution of potash um hydroxide per mole of resin, after which the reaction of the resorcinol formaldehyde resin, unreacted resorcinol and unreacted formaldehyde is continued in the second stage, it sets a pH above about 7 to about 7.5 at a temperature, which is preferably in a range from about 20 ° C to about 32 ° C and for a time in a range from about 2.5 hours to about 10 hours, preferably about 5 hours The second stage resin product is a flexible tough resorcinol -formaldehyde condensate resin mixture, which is "thermoplastic and 8 1 0 0 36 9 -17- - -" * "-" · 5r- ^ is a mixture of polymer forms with a major amount of trimer polymer, which contains a small amount of cross-linking and which also has a of the 20+ unreacted formaldehyde may have an incomplete reaction. The unreacted formaldehyde is available for reaction with the resorcinol formaldehyde condensate mixture when it is combined with an elastomeric latex to form an adhesive system.

In the preferred embodiment, the preferred resorcinol formaldehyde resin formed by the above-described process is combined with a polybutadiene latex such as LPM 6290 available from Goodyear and a vinyl pyridine styrene butadiene terpolymer latex available from Goodyear under the trade name LVP 5622. The amounts of the two latices are in the range of from about 70 to about 90 parts per 100 parts of rubber, most preferably 70 parts of the 6290 and an amount in the range of from about 10 to about 30 parts per 100 parts of rubber, most preferably 30 parts of the 5. 22 terpolymer.

The ratio of resorcinol formaldehyde condensate resin mixture and rubber latex should vary between about 5 and about 50 parts of resin per 100 parts of rubber latex solid, that is, the amount of rubber on a dry basis of the latex. The rubber includes the aforementioned rubbers such as polybutadiene, SBH, vinyl pyridine and the like. Less than about 5 parts of resin will give insufficient adhesion, while more than about 50 parts of resin per 100 parts of latex is economically undesirable. Also added to the resin latex bonding system is a phenolic type antioxidant such as Bostex 29b available from Akron Dispersion or Akron, Ohio. The amount of the antioxidant added is usually in the range of about 1 part per 100 parts of dry rubber to improve coating flexibility over a wide temperature range. Also added is an aliphatic wax, such as Mobilcer Q, available from Mobile Company, which is added in an amount in the range of about 5 parts per 100 parts rubber. Also another oxidant such as

Paracure A09 antioxidant added in an amount of about 8 1 0 0 36 9> * ». . About 0.5 parts per 100 parts of rubber After the bonding system coating material is prepared, it is allowed to age at ambient temperatures for at least about 10 hours. This aging allows the unreacted formaldehyde of the resorcinol formaldehyde condensate resin mixture to react further with the condensate resin in the presence of the elastomeric latexes. This forms a little cross-linked, long-chain thermoplastic condensate resin associated with the latices. After the aging period, a small amount of a nitrogen-containing base, such as ammonia or low to medium boiling amine compounds, ie diethanolamine, but preferably a small amount of concentrated ammonia (28% solution) is added to bind any unreacted formaldehyde so that no further resin cross-linking takes place. The amount added is usually less than 1 part per 100 parts of rubber. The ammonia additive stabilizes the adhesive system coating material and extends its shelf life.

In addition, it has been found that the bonding properties of the bonding system can be improved by adding about 1 part resorcinol per 100 parts rubber after adding the ammonia solution. The added resorcinol increases the adhesion level of the adhesive system by increasing the resin content and increases the polarity of the adhesive system coating material resulting in better wettability and impregnation.

Generally, the method of forming glass fiber bundles coated with the adhesive coating material of the invention is to contact a continuous bundle, for example, strand pre-sized (1), with the coating material. according to the invention and drying the coating in the bundle and then curing the coating present in and around the bundle before. forming a coated cord suitable for rubber reinforcement. It in . Contact may be effected by rolling or by a bath and dyeing device. A particularly advantageous method for forming the glass fiber bundles according to the invention is based on the method described in U.S. Pat. No. 3,619,252. In particular, this invention can be applied to glass fibers, filament bundles, with full filament-5 sheathing and with a relatively high coating weight ratio, i.e., about 15% to 0% by weight of glass.

Preferably, the glass fiber strands are coated in the following manner. A number of glass fiber strands, which have been pre-sized, are combined in parallel and passed through a guide in tangential contact over motor-driven rollers. The rollers are partially dipped in the adhesive system coating material of the present invention and these rollers receive the coating material when rotated. The coating, which is incorporated, is contacted with the glass fiber strand, and coats and impregnates the combined strand bundle. Removing the string in the combined strand bundle opens the spaces between the fibers and. between the strands, thereby increasing the impregnation of the coating in the bundle. Epically, the coating material solids from the aqueous uptake will be about 20 - 10%, depending on the total amount of coating material solids, which are included in the glass fiber cord. A low solids level will form a cord with a low added coating based on the weight of the glass and will provide a higher solids content on a coated glass fiber cord with a large amount of coating solids based on the weight of the glass . The added coating weight is about 15 to about 10%, based on the weight of the glass fibers, preferably about 20 to about 30%, to provide a coated glass fiber bundle or cord useful for reinforcing the elastomer matrices.

After contacting the glass fiber bundle with the coating material of the invention for a sufficient time to fully impregnate the bundle with water and solids-containing immersion, the bundle is passed through a dielectric heater or drying oven. The drying oven has been designed 81 0 0 36 9 3 Μ -: -20- ζο and is operated to quickly remove water from the interior of the bundle as well as from the surface of the bundle without appreciably migrating the solids from the interior to the surface of the beam and without excessive blistering.

The dried glass bundle is then subjected to heating for partial curing of the rubber adhesive coating through the bundle. It is preferred to partially cure the coating while completing the curing of the coating of the glass fibers when it is prayed in the rubber matrix to be reinforced during the curing of the rubber in the final article.

A second method of manufacturing the glass fiber bundles of the invention is based on the method described in U.S. Pat. No. 3,718.

As for the rubber to which the coated stained glass cord will adhere, the invention includes any natural rubber stick or any synthetic rubber stick, such as polymerized isopresin or polymerized butadiene or polymerized halogen-substituted butadiene, such as a halogen-2-butadiene-1, 3 polymer, for example chloro-2-butadiene-1,3 polymer and other types.

The invention is illustrated in the following examples, in which parts are parts by weight unless otherwise stated.

Example I

The thermoplastic resorcinol formaldehyde resin of the invention is prepared by first adding about 70 to 75% of the total water at about 22 to 25 ° C to a premix tank. Resorcinol in an amount of 26 kg is added to the water in the pre-mixing tank and stirred until completely dissolved. Then 27.8 kg of formaldehyde .....

added to the pre-mixing tank, which contains the water and the resorcinol. * The resorcinol and formaldehyde are reacted in the aqueous solution at a. temperature of 25.6 - 2β, T ° C at a ''35 pH of 5.0 + 0.5 for b hours. An aqueous solution of potassium hydroxide was prepared by adding 0.82 kg of 81% potassium hydroxide to 10.39 kg of water and mixing it until the potassium hydroxide is dissolved. At the end of the hours, the aqueous solution of potassium hydroxide was slowly added to the premix tank containing the reacted resorcinol and formaldehyde. After the addition, the temperature was kept at 2k-27 ° C at a pH of 7.5 and the reaction was continued for 5 hours. The resorcinol-formaldehyde resin product after 5 hours is the thermoplastic water-soluble resin of the invention with a predominant amount of trimer polymers which are slightly cross-linked and a smaller amount of non-cross-linked trimer polymers and dimer polymers and oligomers, which may or may not be may be cross-linked, in the polymer mixture, which forms the resin and also contains a small amount of unreacted formaldehyde.

Example II

3.79 liters of deionized water of 3,3 3.3 ° C were added to a tank and 8.71 kg of resorcinol were added to the water in the tank and stirred until dissolved.

9.25 kg of formaldehyde were added to this aqueous resorcinol mixture and the temperature was adjusted to 20-27 ° C at a pH of 5.0 + 0.5. This temperature was maintained for h hours. In the meantime, a solution of potassium hydroxide was prepared by mixing 0.27 kg of potassium hydroxide and 3.3 kg of deionized water. At the end of the hour, the aqueous solution of potassium hydroxide was slowly added to the resorcinol formaldehyde reaction mixture in the tank. After the addition of the aqueous potassium hydroxide solution, the temperature was maintained at 2k-2 ° C at a pH of 7.5 for 5 hours. After 5 hours, the resoreinol formaldehyde resin product was the thermoplastic water-soluble resorcinol formaldehyde resin of the invention.

Example III

Twelve gallons of deionized water at ^ 3.3 ° C were added to a tank and the water and tank were added 9Λ kg of resorcinol and stirred until everything was dissolved. 8100369-22-51 aqueous solution of resorcinol was added 10.3 kg of formaldehyde The aqueous solution of formaldehyde and resorcinol was reacted at a temperature of 26 - 2 ° C and a pH of 5 * 0 + 0 * 5 for 1+ hours. in between, an aqueous solution of potassium hydroxide was prepared by dissolving 0.27 kg of potassium hydroxide in 2 gallons of deionized water After 1+ hours, the aqueous solution of potassium hydroxide was slowly added to the resorcinol formaldehyde reaction mixture After the addition of the aqueous potassium hydroxide, the temperature was The reaction mixture was held at 2k-27 ° C and the reaction pH was continued for 5 hours, after which the resorcinol formaldehyde product followed the thermoplastic water-soluble resorcinol formaldehyde resin s the invention.

Example IV

Preparation of the bonding system with the thermoplastic water-soluble resorcinol formaldehyde resin with. long chain.

653 hg of nolybutadiene latex, Goodyear 6290 and 90 kg of vinyl pyridene and polybutadiene latex, Goodyear 5c22 were added to a mixing tank. To this mixture of latices 20 was added 503.5 liters of deionized. water and at the same time 9.8 hg of antioxidant, Boxtex 29b. To an individual mixing ank were added kC gallons of deionized water and H, 9 kg of the antioxidant Paracure Λ-09. To this mixture were added k, 9 kg of wax, Mobilcer Q and the solution was mixed for 10 minutes and then added to the mixture of polybutadiene and vinyl pyridine latices in the main mixing tank. After the resorcinol formaldehyde resin formed according to Example I was aged for 9 hours, it was slowly added to the mixing tank containing the mixture of polybutadiene and vinyl pyridine latices and an antioxidant. After the resorcinol formaldehyde resin was added, the mixture was aged for 10 hours. Care must be taken to ensure that the resorcinol formaldehyde resin has a pH of 7.5 or higher to avoid coagulation of the latices. When the pH of the resin is not 7.5 or higher, it can be adjusted by adding potassium hydroxide to the resin before it is added. the polybutadiene and vinyl pyridine latices. Then, a mixture of aqueous ammonium hydroxide is prepared by dissolving 3.3 kg of ammonium hydroxide in 3 liters of deionized water and after the resin latex mixture has aged, the aqueous ammonium hydroxide 5 is added to the resin latex mixture in the main tank. The mixture is then stirred for a time to form the adhesive system coating material with a percentage solids of 27 + 0.5, a pH of 8.5 + 0.3 and an immersion life of 50 hours. The adhesive system coating material 10 can be used to bond the glass fibers to rubber matrices.

Example V

Preparation of the adhesive system coating material using thermoplastic water-soluble long chain resorcinol-15 formaldehyde resin.

1.5 kg of polybutadiene latex were added to a mixing tank. Goodyear 237 ^ and 181 kg of a styrene-hutadiene-vinyl pyridine latex, Goodyear 5622. In addition, 132 liters of deionized water were added along with 3.6 kg of antioxidant, Bostex 29k. To a separate tank were added 37.9 liters of deionized water along with 1.8 kg of antioxidant Paracure A-Q9 and 18 kg of a wax, --iobilcer Q, which was mixed for 19 minutes and then added to the main mixing tank, which mixture of latices. After the long chain thermoplastic water-soluble resorcinol-formaldehyde prepared in Example III was aged for 9 hours, it was slowly added to the main mixing tank, which contained a mixture of latexes, antioxidant and wax. After the resorcinol formaldehyde resin was added, the mixture was aged for 10 hours. An aqueous solution of ammonium hydroxide was prepared by adding 0.18 kg of ammonium hydroxide to 15 liters of deionized water. This aqueous ammonium hydroxide solution was added very slowly to the resin latex mixture and stirred for about 10 minutes. Then, an aqueous resorcinol solution was prepared by adding 1.8 kg of resorcinol * to 15 liters of deionized water, which was mixed until the 81 00 36 9 V * "V" -2b-resorcinol was completely dissolved. The aqueous resorcinol solution was then very slowly added to the main mixing tank containing a resin latex mixture within about 15 minutes.

The mixture was then stirred for 25 minutes and then stirred automatically for 1 minute every half hour to form an adhesive system coating material with a percentage solids of 27 + 0.5, a pH of 8.5 + 0.3 and an immersion life of 50 hours. The resorcinol solution was added to the resin latex material to improve the bonding properties of the bonding system. The added resorcinol increases the adhesion level of the adhesion system by increasing the resin content and increases the plurality of the dip for better wettability and impregnation.

Example VI

Preparation of a long-chain thermoplastic water-soluble resorcinol coral hyde resin with bonding system.

91 liters of deionized water at 1 + 3.4 ° C were added to a pre-mixing tank. To the water in the reaction vessel were added 3.5 kg of resorcinol, which was stirred until completely dissolved. 25.8 kg of formaldehyde were added to the aqueous solution of resorcinol. The resorcinol and formaldehyde were allowed to react in the aqueous solution at a temperature of 26-27 ° C at a pH of 5.0 + 0.5 for hours. An aqueous potassium hydroxide solution was prepared by dissolving 0.73 kg of potassium hydroxide in 18 kg of deionized water.

After hours of reaction time of the resorcinol and formaldehyde under acidic conditions, the aqueous solution of potassium hydroxide was slowly added to the reaction mixture. After the addition, the pH was about 7.5 and the reaction was continued. temperature of 26 - 27 ° C for. 5 hours. Afterwards.

the resorcinol formaldehyde resin formed was the thermoplastic water-soluble long chain resorcinol formaldehyde resin of the invention.

To a main mixing tank were added kg of a styrene-butadiene latex, Firestone SF.66U2 and 181, kg of a carboxy polybutadiene latex, GenFlow 8020 and 720 pounds of a 8 1 0 0 36 9 * 25-polybutadiene styrene latex, Firestone S-2J2 To this main mixing tank were also added 530 liters of deionized water along with 7.26 kg of antioxidant, Bostex 29b. Then 75 * 5 liters of deionized water and 8 pounds of an antioxidant, Paracure A were added to a separate mixing tank. -09 along with 36.3 kg of wax, Mobilcer Q, which were mixed for 10 minutes and then added to the main mixing tank containing the mixture of latices After the resulting long chain thermoplastic water-soluble resorcinol formaldehyde resin was aged for 9 hours , it was slowly added to the main mixing tank, which contained the mixture of latices.After the resin was added to the mixture, it was aged for 6 hours and the mixture slowly became 127 kg of neoprene latex, Neoprene 735-A, added. An aqueous solution of ammonium hydroxide was prepared by dissolving 2.2 kg of ammonium hydroxide in 23 liters of deionized water. This aqueous solution of ammonium hydroxide was added to the resin latex mixture after the mixture had aged about 30 minutes after neoprene addition. The addition was very slow and after the addition the mixture was aged for 15 minutes and after 1 hour placed on an agitator for 1 minute every half hour for automatic stirring to form a bonding system coating material with a solid content of 28.0 + _ 0.5, a pH of 8.5 + 0.3 and an immersion life of 60 hours.

Example VII

Coating glass fibers with the adhesive system coating material containing the long-chain thermoplastic water-soluble resorcinol formaldehyde resin.

Glass fibers, which were formed on a fiber-forming sleeve, sized with an aqueous sizing material, collected into strands and wound on a molding wrapper, which is then dried and mounted on a spool register, were unwound and coated with the adhesive system coating material of the invention. Fiberglass strands, such as G-75.5 / 0 or 35 G-75/10/0 or G-75.15 / 0, which typically have a diameter -6 -6 from 9.8 x 10 to 9.1 x 10 m and a filament number of 2000 xn 81 0 0 36 9 '-26- a cord which is made of 5 strands each with UOO filaments are coated with the suture coating material of the invention. Also K fibers, such as K-15 strand with typically 100 filaments therein and each filament having a diameter of about 13.3 ^ + 0.63 microns, using 1-3 strands per cord, can also be coated with the suture coating material according to the invention. When G cord is to be used in diagonal bands, the cord should be constructed up to 5 strands and when the cord should be. 10 are used in radial tires, there must be 10 - 15 strands per cord. The 10-15 strands of cord allow for higher packing of the cord per unit area, giving greater strength to the tire carcass. This strength is necessary to obtain the desired properties in radial tires. G fibers were sized with a chemical sizing agent containing mainly polypropylene emulsion with 25% by weight polypropylene and 6% by weight emulsifying agent and also smaller amounts of rolyvinyl alcohol, and amideimidazolene and methyl acryloxypropyltrimethoxysilane.

This sizing material was applied to the fibers during the molding and the strand formed therefrom was dried and / or cured by the method described in U.S. Pat. No. 3,655,353. '

Suture coating material prepared in Examples 25 IV and V were used to coat the glass fiber cord. The glass fiber cord was prepared by coating 15 of the sized strands with the coating material of Example IV and Example V. This cord was incorporated into a rubber mass and also used to reinforce the layers of pneumatic tires *.

The banana properties of these coated fiber glass cords were investigated at the adhesive level of the adhesive system in various rubber compositions. The results of these tests are reported below. The successful binding of rubber to tire cord is measured according to various tests, one of which is a strip adhesion. Strip adhesion for rubber coated 8 1 0 0 36 9 * r: -27- glass cord is determined by the following method. A cylindrical drum is wrapped with a 10.2 x 26.7 x 0.1 cm strip of rubber mass. The rubber mass covered the entire surface of the cylindrical drum. The coated glass fiber yarn 5 is wound cylindrically around the rubber mass on the drum, thereby obtaining a continuous layer of yarn over the rubber mass. The wound rubber mass was removed from the cylinder and cut into a 7.6 x 25, ¾ cm sample. A strip of the 7.6 x 25, ¾ cm rubber is placed in a 7.6 x 25, ¾ cm mold and the rubber strip with the coated strand on it is placed in the mold with the strand side away from the first rubber strip. A number of 27.62 x 2.5¾ cm strips of Holland cloth were placed on opposite ends of the strand side of the rubber strip. Another 75 7.62 x 25 ¾ cm rubber strip is placed on the Holland cloth and finally a 7.62 x 25 ¾ cm coated strand rubber strip is placed thereon on the latter rubber strip with the strand side in contact with the latter rubber strip.

The mold is closed and the rubber cord laminate is cured at 740 Pascal for 30 minutes at 9 ° C. The rubber cold laminate is removed from the mold and simply allowed to cool overnight.

The laminate is cut to 1 x 2.5 cm strips and heated at 121 ° C for 30 minutes, after which the Holland cloth is removed from the laminate. After setting an Instron test device to a length of 1.27 to 1.9 cm and calibrating the unit at a crosshead speed of 5.1 cm per minute, the top layer of the heated rubber and the exposed cord are placed in the top jaw and the top jaw of the heated rubber is placed in the bottom jaw of the test device.

The Instron test device is left to operate until a 5.1 cm separation is obtained and the load is noted. The top layer is inserted in the top claw and the cord in the bottom claw with a length of 1.27 to 1.9 cm. The Instron-35 device is operated until a separation of 5.1 is obtained and the load is noted. The test is repeated 81 0 0 36 9-28.

for the opposite end of the sample and for other samples in the example. The results of the test are averaged for adhesion of the cord to the rubber.

The "In-rubber tensile strength" is determined by hardening the cord in one. rubber matrix and the glass fiber cord reinforced matrix tests in an Instron device with 17.8 - 19 cm and a crosshead speed of 5.1 cm per minute, The claws are separated and the force required to break the sample , will be noted.

The results of the test methods described above are shown in Table A.

Table A -

Cord Strip adhesion in various In-rubber- rubber masses Tensile strength _ 1b 1 2 3

Mass A Mass B Mass C

1b / value- 1b / 'value- 1b / value * * ring_ ring

Covering 21 / 1.3 hl / c., 5 / 3V * », 8 200

material of example IV

Covered with ΜΛ, Τ ^ 5 / 5.0. A / 5.0 210

material of example V.

Coated with 36 / U, 8 ^ 9 / 5.0 1 * 7/5, ° 229 material corresponding to example V in which the Goodyear latices have been replaced by Firestone latices (SR 661 + 2 and SR 272) ^ Ratings 1-5: 1 is adhesive failure, and 5 is cohesive failure.

1. Rubber mass of McCreary Tire & Rubber Co.

2. Rubber mass of B.F. Goodrich Co. .

3. Rubber mass of Firestone Tire & Rubber Co.

Tests were also carried out on the glass fiber cord, coated with the adhesive system coating material of the invention, when the cord was bonded to rubber and used in air teeth. One such test is the Gristmill test, which measures the compression fatigue resistance of the cord. Most of the tension is applied to the outer shoulder of the hand, where cord breakage is most likely to occur. Cord breaks in each tire layer were totaled and set for breaks / meters of layer length for uniformity.

The average Gristmill test includes the following: a) inflation of tires up to 2k psi at 75 ° E, 10 b) mounting a tire on the right front seat of a standard vehicle, which is pre-loaded to 100 $ T and RA load at 2h psi. At this point the handshake is noted and no settings are made, c) the vehicle is propelled at 15 miles per hour 15 for 800 laps in a counterclockwise direction. At the end of the test, temperature and pressure were noted, d) the tested inflated tire was examined by X-rays to determine the condition of the cord.

The cold Gristmill test includes: 2 o 20 a) inflating tires up to 1.69 kg / cm at 21 C, cooling the tires during k hours to -k0 ° C, after which a tire is removed from the cold box and applied in the right front seat of the car. They were allowed to warm to -32 ° C before starting the test. Tire pressure at this point 25 was noted and no adjustments were made, c) the car was driven at a rate of 8.05 kg / h for 10 laps in a counterclockwise direction. This is a cold cycle. The temperature and pressure of the tire at this point were noted. The tape was put back in the cold box at -U0 ° C for 4 hours, d) the tape was put back in the cold box at -k0 ° C for ^ hours, e) steps b, c and d were repeated for the indicated number of cycles, 35 f) the tested inflated tire was examined by X-rays to determine any cord breakage. The test conditions for both ambient and cold included a 24.4 meter diameter circle in which 100 rounds were run at 8.05 kg / h in a counterclockwise direction. The hands were inflated to 1.69 kg / cm. The load is a T & HA 5 load for 24 psi and the fixed mounting location is the front.

Table B gives the results of the Gristmill test on the fiberglass yarn, rubber mass prayer using the adhesive system of Examples IV, V and VI and a commercial glass radial tire.

Table B

Radial tire cord behavior Gr1stmill test

Cord lined with: Gristmill environment Cold Gristmill test 1,600 rounds: 7 cycles: fractures / meter 15 __ fractions / meter * _____

Suture system 3 0

example IV

Suture system _ - 5 3

example V.

Adhesion system 1.5 100

Example VI

Commercial 10 4 cord B / M. is the average number of fractures per meter of tire layer.

. In table C Indoor cold wheel test: 5 ° slip angle includes cooling the tire to -29 ° C, mounting the tire on a loaded wheel and running for 1 hour. This is a cycle; .. This step is then repeated to a total of 4 cycles. The tape is stripped and the layers are assessed. A rating of 7 is not a cord failure and a rating of 1 is excessive cord breaking.

8 1 0 0 36 9 -31-

Table C

Radial tire cord behavior Indoor cold-wheel test: 5 ° slip angle

• A

Cord covered with: Tire rating mg ___ Number of sides Top layer Bottom layer ^ Hecbtsysteem ^ h, 5 6.8

example IV

Adhesive system ^ 5.5 6.9

example V.

Commercial 1+ 5.5 6.5 cord 10 * Tire rating: 1 to J: 1 is severe cord breakage and 7 is not cord breakage.

81 0 0 36 9

Claims (21)

1. Improved flexible and tough phenolic aldehyde resin, characterized in that it contains a thermoplastic water-soluble phenolic aldehyde resin which is a mixture of 5 polymers with a major amount of trimer polymer and only a minor amount of dimer and higher oligomers formed with low cross-linking by: a) reacting to less than 100% completely of a phenolic compound with an aldehyde in an amount of aldehyde to phenolic compound in molar ratios in a range from about 0.8 to about 1.5 at a pH in a range from about 3.5 to about 5.5 to limit the formation of phenolic alcohol for a time equivalent to a time in the range from about 3 hours to about 10 hours at a temperature in the range from about 13 to about 32 ° C to form a polymeric resin mixture containing a major amount of Primer and a minor amount of dimer and higher oligomeric polymers containing, together with unreacted phenolic compound and aldehyde 20 in the polymer mixture, b) continuing the resin reaction at a pH maintained above 7 to about 7.5 at a temperature in the range of 13 to 32 ° C, the residence time being in the range of 0.75 to 10 hours, making the thermoplastic, 25 µm. water-soluble phenolic aldehyde resin mixture is formed with improved flexibility and toughness, since it mainly contains trimer polymers and has little cross-linking. 2. Material according to claim 1, characterized in that the phenolic compound is resorcinol or a mixture of resorcinol and phenol. Material according to claim 1, characterized in that the aldehyde is formaldehyde. The material according to claim 3, characterized in that the formaldehyde is in the form of formalin. The material according to claim, characterized in that the slightly cross-linked, thermoplastic, water-soluble 81 0 0 36 9 tr last -33-phenolic aldehyde resin mixture contains up to 20% unreacted aldehyde. 6. The material according to claim 1, characterized in that an acidic catalyst is used to obtain a pH from about 3.5 to about 5.5. T. Adhesive coating material with the phenolic aldehyde resin mixture of claim 1 or 5 and one or more elastomeric latexes, wherein the resin mixture is present in an amount between about 5 and about 15 parts of resin per 100 parts of 10 elastomeric latex solids. Material according to claim 7, characterized in that the mixture of elastomeric latexes is about 70 to about 90 parts per 100 parts of rubber of polybutadiene and about 10 to about 30 parts per 100 parts of rubber of the vinyl-15 pyridene styrene butadiene terpolymer. . Material according to claim 7, characterized in that there are contained 25 parts by weight of wax. 10. Material according to claim 7 or 8, characterized in that it contains around Idl per 100 parts of resorcinol resin. Material according to claim 7 or 8, characterized in that it contains 0.1 to 1 parts by weight of diatomaceous earth treated with calcium or magnesium. 12. Filament tape cord containing a dried residue of the material of claim 7 or 8. Filament cord according to claim 12, characterized in that it contains from about 15 to about 50 weight percent of the dried residue of the material, based on the weight of the filament material. Filament fiber cord of claim 12, characterized in that the filament material therein are glass fiber strands. Filament fiber cord according to claim 13, characterized in that the filament material are glass fiber strands. 16. Adhesive coating material for coating 35 filament materials, which can be used in reinforcing rubbery materials prepared by reacting: 81 00 36 9 '-3k-% ra) to less than 100% completely of a phenolic compound and an aldehyde in an amount phenolic compound to aldehyde to phenolic compound in the range of molar ratios in the range of from about 0.8 to about 1.5 and a pH in the range from about 3.5 to about 5> 5 to limit the formation of resorcinol alcohols for a time equivalent to the time in the range of about 3 hours to about 10 hours, at a temperature in the range of about 13 to about 32 ° C to form a resin mixture containing mainly trimer polymer and smaller amounts of dimer polymer and higher oligomeric polymer together with unreacted phenolic compound and unreacted aldehyde, and b) continuing reaction of the phenolic compound 15 and aldehyde and reaction mixture at a pH held in the range of about 7 to about 7.5 at a temperature in the range of about 13 ° C to about 3 ° C, the residence time being in the range from about 0.75 to about 10 hours, to form the flexible but tough resin mixture with a predominant amount of trimer polymer and smaller amounts of dimer and higher oligomer polymers and with low cross-linking, and less than 20% unreacted aldehyde C, of the resin blend of step (b) with one or more elastomeric latexes, the resin blend 25. is present in an amount in the range of from about 5 to about 15 parts per 100 parts of latex solids, c) aging the combination of step (c) for at least about 10 hours at ambient conditions to remove some of the reacting unreacted aldehyde with the resin, d) adding to the aged combination of step (d) a small amount of nitrogen-containing base selected from ammonia and amines to bind all reacted formaldehyde. r. The adhesive coating material of claim 16, characterized in that the One or more elastomeric latices have about 70 to 81 0 0 36 9 -35- 90 parts of a polybutadiene polymer and about T0 to 30 parts per 100 parts of rubber of a vinyl pyridine styrene butadiene terpolymer. Adhesive coating material according to claim 16 or 17, 5, characterized in that the additional phenolic compound is added after the addition of the nitrogen-containing base compound. Adhesive coating material according to claim 16 or 17, characterized in that the phenolic compound is resorcinol or a mixture of resorcinol and phenol. Adhesive coating material according to claim 16 or 17, characterized in that the aldehyde is formaldehyde in an aqueous solution. Adhesive coating material according to claim 16 or 17, 15, characterized in that it contains up to 25 parts by weight of wax. Adhesive coating material according to claim 16 or 17, characterized in that it contains 0.1 to 1 part by weight of calcium or magnesium-treated diatomaceous earth. Adhesive coating material according to claim 16 or 17, 20, characterized in that it contains one or more compounds from the group containing antioxidants, accelerators, culcanizing agents, stabilizers, dispersants and curing agents. 2k, Filament tape with the dried residue of the material of claim 16 or 17 on it. A process for the preparation of a filament tape cord, coated with a suture coating to provide better flexibility and toughness in the coated cord, which can be used for reinforcing rubber, characterized by: a) reacting to less than 100 $ complete of a phenolic compound and an aldehyde in an amount of phenolic compound to aldehyde to phenolic compound in the range of mole ratios in the range of 0.8 to about 1.5 at a pH in the range of about 3.5 to about 5 »5 to limit the formation of resorcinol 35 alcohols for a time equivalent to the time in the range of from about 3 hours to about 10 hours, at an 8 1 0 0 36 9 J - # r. ^ - -36- temperature in the range from about 13 ° C to about 32 ° C to form a resin mixture, which mainly contains trimer polymer and smaller amounts of dimer polymer and higher oligomer polymer, together with unreacted phenolic compound and not reacted aldehyde, and b) continuing the reaction of the phenolic compound and aldehyde and reaction mixture at a pH maintained in the range from above 7 to about 7.5 at a temperature in the range from about 13 ° C to about 32 ° C, 10 with the residence time in the range of from about 0.75 to about 10 hours, to form the flexible but tough resin mixture 1 with a predominant amount of trimer polymer and less amount of dimer and higher oligomeric polymer and with low cross-linking , and with less than 20% unreacted aldehyde O, combining the resin mixture of step (b) with one or more elastomeric latices, the resin mixture being present in an amount, in the range of about 5 to about 15 parts per 100 parts, of latex solids,. c.) aging the combination of step (c) for at least about 10 hours at ambient conditions to react some of the unreacted aldehyde with a resin, d) adding to the aged combination of tran (d) from a minor amount of a nitrogen-containing base selected from ammonia and amines to bind unreacted formaldehyde, e) coating the filament material selected from fiberglass skein or skeins, finished fiberglass skeins, polyester fibers, polyaride fibers and cellylose acetate fibers, and f) drying of the coated filament material to release formaldehyde for further cross-linking the phenolic aldehyde resin and curing the polymeric materials. 26. Filament cord obtained by the process according to claim 25. t 81 0 0 36 9 OH OH OH - fS-CHi-S-CH2-kiA.R ^ R p β 81 0 0 36 9 PPG Industries, Ine. , Pittsburgh, Pennsylvania, USA, America