MXPA97010394A - A compound for wire cover containing acid esters aminobenzo - Google Patents

Abstract

The present invention relates to the discovery that when the aminobenzoic acid esters are used in total or partial replacement of conventional cobalt materials, the adhesion properties of rubber-to-wire are maintained.

Description

A COMPOUND FOR WIRE COVER CONTAINING AMINOBENZOIC ACID ESTERS Background of the Invention U.S. Patent 4,513,121 discloses a rubber liner mixture containing organo-cobalt compounds as adhesion promoters. Representative examples of such organocobalt compounds include the cobalt salts of fatty acids, cobalt salts of alicyclic or aliphatic carboxylic acids having from 6 to 30 carbon atoms, cobalt chloride, cobalt naphthenate, cobalt carboxylate and boro-cobalt-organ complexes. The problems associated with the cobalt-organ compounds include their availability properties and strong pro-oxidants that can adversely affect the rubber by accelerating its oxidation.

SUMMARY OF THE INVENTION The present invention relates to a rubber composition suitable particularly as a wire coating mixture containing aminobenzoic acid esters Detailed Description of the Invention A wire coating composition is disclosed comprising: (a) a rubber selected from the group consisting of natural rubber and a mixture of natural rubber and a synthetic rubber derived from a diene monomer, Y (b) from about .1 to about 10 phr of an aminobenzoic acid ester of the formula: wherein R is a radical alkali having from 8 to 24 carbon atoms; (c) from li to 10 phr of a methylene acceptor and (d) from .1 to 10 phr of an ethylene donor The aminobenzoic acid esters for use in the present invention are those of the formula I above. Preferably, R is a radical alkali having from 8 to 24 carbon atoms. Representative examples of these esters include octyl aminobenzoate, nonyl aminobenzoate, decyl aminobenzoate, undecyl aminobenzoate, dodecyl aminobenzoate, tridecyl aminobenzoate, tetradecyl aminobenzoate, pentadecyl aminobenzoate, hexadecyl aminobenzoate, heptadecyl aminobenzoate, aminobenzoate of octadecyl, nonadecyl aminobenzoate and eicosyl aminobenzoate.

Inasmuch as the most common isomeric form of the above esters is, for example, the octadecyl-4-aminobenzoate, it is contemplated herein that 3- and even 2-forms can be used. To facilitate the preparation and cost, the preferred form is the isomeric-4.

The above ester is present in the wire coating composition in a range of about .1 to 10 phr. Preferably, the ester is in an amount ranging from about .5 to 2 phr.

The wire coating compound contains natural rubber. Natural rubber includes several forms, for example, pale crepe and smoked sheet, and balata and gut hanger. The rubber can be only natural rubber or a mixture of natural rubber with synthetic rubber. Synthetic polymers are derived from a diene monomer and include those prepared from a single monomer (homopolymer) or a mixture of two or more copolymerizable monomers (copolymer) when the monomers are combined in the random or block form. The monomers may be substitutable or non-substitutable and may possess one or more double bonds, dienes and conjugated and non-conjugated monoolefins, including cyclic and acyclic monoolefins, especially vinyl and vinylidene monomers. Examples of conjugated dienes are butadene-1,3, isoprene, chloroprene, 2-ethyl-1,3-butadene, 2,3-dimethyl-1,3-butadene and piperylene. Examples of non-conjugated dienes are 1,4-pentaiden, 1,4-hexadiene, 1,5-hexadiene, dicyclopentadiene, 1,5-cyclooctadiene and norbonene "of ethyldiene Examples of acyclic monoolefins are ethylene, propylene, 1-butane , isolutylene, 1-pentene and 1-hexene Examples of cyclic monoolefins are cyclopentane, cyclohexene, cyclopentane, cyclooctane and 4-methyl-cyclooctane Examples of vinyl monomers are styrene?, acrylonitrile, acrylic acids, ethylacrilate, vinyl chloride, butylacrylate, methyl methyl ether, vinyl acetate and vinyl pyridine. Examples of vinylidene monomers are alpha-methylstyrene, ac or methacrylic, methyl methacrylate, itaconic acid, ethyl methacrylate, glycidyl methacrylate and vinyldene chloride. The representative examples of the synthetic polymers used in the practice of this invention are the polychloroprene homopolymers of a 1,3-diene conjugate, such as isoprene and butadiene, and in particular, polysoprenes and polybutanedienes which have essentially all their repeating combined units in a cis-1 structure,; and copolymers of a 1,3-diene conjugate, such as isoprene and butadiene with up to 50 percent by weight of at least one copolymerizable monomer, including ethylenically unsaturated monomers or styrene and acrylonitrile; and butyl rubber, which is a polymerization product of higher proportion than that of amino aminephine and a smaller proportion of a diolefin such as butadiene or isoprene. The rubber can be a polymerized emulsion or a polymerized solution.

Preferred synthetic rubbers which can be used in the present invention are cis-1,4 polyisoprene, polybutadiene, polychloroprene and the copolymers of isoprene and butadiene, copolymers of acrylonitrile and butadiene, copolymers of acrylonitrile and isoprene, copolymers of styrene and butadiene and mixtures thereof. Since the compounds of the present invention are used as a wire coating composition, the natural rubber is preferably present in an amount ranging from 5 to 95 weight percent of the total rubber present in the coating composition. of wire.

The resins that are formed in-Situ in the wire coating mixtures and involve the reaction of a methylene acceptor and a methylene donor. The term "methylene donor" is intended to mean a compound capable of reacting with a methylene acceptor and generating the resin in-situ. Examples of methylene donors which have a suitable use in the present invention include: hexamethylenetetramine, hexaethoxymethylmelamine, hexametoxymethylmelamine, lauryloxymethylpyridinum chloride, ethoxymethylpyridinium chloride, trioxane hexametoxymethylmelanin, the group of hydroxides that can be esterified or partially esterified, and formaldehyde polymers such as paradormaldehyde. In addition, the methylene donors can be N-substituted oxymethylmelamines of the general formula: R3 R2 wherein X is an alkali having 1 to 8 carbon atoms, R (l), R (2), (3), R (4), and R (5) are individually selected from the group q? e It consists of hydrogen, an alkali that has from 1 to 8 atoms, the -CH2OX group or its condensation products. Methylene-specific donors include hexakis- (methoxymethyl) melamine, N, N ', N "-trimethyl / N, M', N" -t imetylol elamine, hexamethylolmelamine, N-mehylmelamine, N, N'-di * methylolmelamine, N, N'N "-tris (metosimetj 1) melamine and N, N ', N". tributyl-N, N ', N "-trimethylol-melamine The M-methylol derivatives of melamine are prepared by known methods.

The amount of the methylene donor that is present in the rubber mixture may vary. Typically, the amount of the methylene donor that is present will vary from about 0.1 phr to 10. phr. Preferably, the amount of the methylene donor varies from about 2.0 phr to about 5.0 phr.

Examples of methylene acceptors include phenols activated by ring substitution of a phenolic resin of the modified novalak type of cashew nut oil. Representative examples of phenols activated by ring substitution include resorcinol, cresols, butyl-t phenols. isopropyl phenols, ethyl phenols and mixtures thereof. Novalak phenolic resins modified from cashew nut oil are commercially available from Schenectady Chemicals Inc. under the designation SP6700. The modification rate of the oil based on phenolic total resin of the novolak type can vary from 10 to 50 percent. Several processes can be used for the production of phenolic resin of the novolak type modified with cashew nut oil. For example, phenols such as phenol, cresol and resorcinol can react with aldehydes such as formaldeids, paraformaldeido and benzaldeido using acid catalysts. Examples of acid catalysts include oxalic acid, hydrochloric acid, sulfuric acid and toluenesulfonic acid-p. After the reaction of the catalyst, the resin is modified with the oil.

The amount of the methylene acceptor that is present in the rubber mixture can vary. Typically, the amount of the methylene acceptor that is present will vary from about 0.1 phr to 10 phr. Preferably, the amount of the methylene acceptor ranges from about 2.0 phr to 5.0 phr.

As is known to the experts of the art, in order to cure a rubber mixture, it is necessary to have a sulfur vulcanizing agent. Examples of sulfur vulcanizing agents include elemental sulfur (free sulfur) or a sulfur donor vulcanizing agent, for example, an amino disulfide, polymeric polysulfide or sulfur olefin adducts. Preferably, the sulfur vulcanizing agent is elemental sulfur in the insoluble form. The amount of the sulfur vulcanizing agent will vary depending on the components of the rubber mixture and the particular type of sulfur vulcanizing agent that is used. The sulfur vulcanizing agent is generally present in an amount ranging from about 0.5 to about 8 phr. Preferably, the sulfur vulcanizing agent is present in an amount ranging from about 0.75 phr to about 4.0 phr.

Conventional rubber additives can be incorporated into the rubber mixture in the present invention. Additives that are commonly used in rubber blends include fillers, plasticizers, waxes, process oils, retarders, anti-ozone agents, antioxidants and the like. The total amount of the filler that can be used can vary from about 30 to about phr, with a preferred range from about 45 to about 100 phr. The fillers include clay, calcium carbonate, calcium silicate, titanium dioxide and carbon black. Representative carbon blacks commonly used in rubber blends include N326, N330, N472, N630, N642, N660, N754, N762 and N990. The plasticizers that are used conventionally preferably have amounts ranging * from about 2 to about 50 phr with a range of about 5 to 30 phr. The amount of plasticizers that are used will depend on the softening effect that is desired. * Examples of suitable plasticizers include extracts of aromatic oils, oil softeners, including asphaltenes, pantachlorophenol, saturated and unsaturated hydrocarbons and nitrogen bases, tar coal products, cumarone-indene resins and esters such as dib? Tylphthalate and tricresol phosphate. Common waxes that can be used include paraffin waxes and microcrystalline mixtures. These waxes are used in amounts ranging from approximately 0.5 to 3 phr. Materials used in compounds that function as activator-accelerator include metal oxides such as zinc oxide and magnesium oxide which is used in association with acidic materials such as fatty acid, for example, stearic acid, oleic acid and the like. the amount of metal oxide that is preferred may vary from about 1 to about 8 hpr. The preferred amount of fatty acid that can be used can vary from about 0 phr to about 5.0 phr with a range from about 0 phr to about 2 phr. Accelerators are used to control the time and / or temperature that is required to vulcanize and improve the properties of the vulcanizer. In one embodiment, a single accelerator system may be used; that is, primary accelerator. The primary accelerator (s) can be used in total amounts ranging from about 0.5 to about 4, preferably about 0.8 to about 2.0 phr. In another embodiment, the combinations of a primary and secondary accelerator can be used with the secondary accelerator that is used in a smaller amount, equal to or greater than that of the primary accelerator. It is expected that the combinations of these accelerators produce a synergistic effect on the final properties and that in some way they are better than those produced by the use of any accelerator alone. In addition, delayed action accelerators can be used, which are not affected by normal process temperatures but produce a satisfactory hardening at ordinary vulcanization temperatures. Vulcanization retarders can also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanfates. Preferably, the primary accelerator is a fulfenamide. If a secondary accelerator is used, the secondary accelerator is preferably a compound of guanidine, dithiocarba ate or thiuram.

The rubber compounds of the present invention may also contain a hardening activator. A representative hardening activator is ammonium chloride (Cs-Cio) trialcali of methyl which is commercially available under the brand Adogen® 464 from the Sherex Chemical Company of Dublin, Ohio. The amount of the activator can be used in a range of about 0.05 to 5 phr.

The siliceous pigments can be used in the applications of the rubber compounds of the present invention, including the precipitated and pyrogenic silicon pigments (silica), although precipitated silicas are preferred. The silica pigments which are preferably used in this invention are the precipitated silicas, for example, those obtained by the acidification of the soluble silica, for example, sodium silicate. These silicas can be characterized, for example, by having a BET surface area, as a measure, using nitrogen gas, preferably in the range of about 40 to about 600, and more usually in a range of about 50 to about 300 square meters. per gram. The BET method for measuring surface area is described in the Journal of the American Chemical Society, Volume 60, page 304 (1930). Silica can also be characterized as having a dibutylphthalate absorption value (DBP) in a range of about 100 to about 400, and more usually 150 to about 300. It is expected that the silica will have a final average particle size. , for example, in the range of 0.01 to 0.05 microns as determined by the electron microscope, although the silica particles are even smaller, or possibly larger in size. Several of the silicas that are commercially available may be considered for use in this invention, such as, for example only and without limitation, the silicas commercially available from PPG Industries under the trademark Hi-Sil with designations 210 , 243, etc; the silicas available from Rhone-Poulenc, with, for example, designations of Z1165MP and Z165GR and silicas available from Degussa AG with, for example, designations VN2 and VN3, etc. Generally speaking, the amount of silica can vary from 5 to 120 phr. Since the intention of the use of the present invention is that of a wire coating compound, the sylk will generally vary from about 10 to 30 phr.

A class of composite materials known as surface burn retardants are those that are commonly used. The known retarders are phthalic anhydride, salicyclic acid, sodium acetate and cyclohexyl thiothphthalimide-M. The retarders are generally used in amounts ranging from approximately 0.1 to 0.5 phr.

Conventionally, antioxidants and sometimes anti-ozone agents that will henceforth be referred to as antidegradants, are added to rubber blends. Representative antidegradants include monophenols, bisphenols, thiobisphenols, polyphenols, hydroquinone derivatives, phosphites, thioesters, naphthyl amines, diphenyl-p-phenylenediamines, diphenylamines and other diaryl amino derivatives, para-phenylenediamines, quinolines and mixtures thereof. Specific examples of these antidegradants are disclosed in The Vanderbilt Rubber Handbook (1990), pages 282-286. Antidegradants are generally used in approximate amounts of 0.25 to about 5.0 phr with a preferred range of about 1.0 to about 3.0 phr.

The rubber compound of the present invention is used as a wire covering or a pearl layer for use on a rim. In these instances, the aminobenzoic acid ester can be used as a substitute in whole or in part for the cobalt materials. When it is desired to use the aminobenzoic acid ester as a partial substitute, any of the materials known in the art can be used to promote the adhesion of the rubber to the metal. Thus, suitable cobalt materials which can be used include cobalt salts of fatty acids such as stearic, palmitic, oleic, linoleic and the like; cobalt salts of alicyclic or aliphatic carboxylic acids having from 6 to 30 carbon atoms, such as cobalt neodecanoate; cobalt chloride, cobalt naphrenate; cobalt carboxylate and an orgeno-cobalo-boron complex that is commercially available under the designation of Manobond C from Wyro? gh and Loser, Ine, in Trenton, New Jersey. It is believed that Monobond C has the structure of: 0 Co-O-C 11-R ti O 0 O ll R * • C-0-Co-0-B-O-Co-0-C-Rf wherein R (6) is an alkyl group having 9 1 12 carbon atoms.

The amounts of the organo-cobalt compound that can be employed depends on the specific nature of the selected cobalt material, particularly the amount of cobalt metal present in the compound.

The amount of cobalt material can vary from approximately .2 to 5 phr. Preferably, the amount of the cobalt compound can vary from about .5 to about 2 phr. When the amount of the cobalt material present in the composition of the mixture is used, it should be sufficient to provide about 0.01 percent to about 0.50 percent by weight of the cobalt metal based on the total weight of the blend composition. of rubber with the preferred amounts that are from 0.03 percent to about 0.2 percent by weight of the cobalt metal based on the total weight of the composition of the finishing mixture.

The vulcanizable sulfur rubber compounds harden at a temperature ranging from about 125 ° C to 180 ° C. Preferably, the temperature varies from about 135 ° C to 160 ° C.

The mixture of the rubber compounds can be carried out by methods known to those skilled in the art of mixing rubber. For example, ingredients that are typically mixed in at least two stages, mainly at least one non-productive stage followed by a productive mixing step. The polymerizing end-agents for resins are typically mixed in the final stage which is conventionally called a "productive" mixing stage in which the mixture typically occurs at a final temperature or temperature, which is lower than the temperature (s) of mix that of the previous nonproductive mixing stage (s). The aminobenzoic acid ester and the cobalt compound, if used, are mixed in one or more non-productive mixing stages. Sulfur and accelerator (s) are generally mixed in the stage of productive mixing. The terms of the "non-productive" and "productive" stages are well known to those skilled in the rubber mixing art.

The rubber composition of this invention is directed to the coating of wires or bead layer composites. For example, they can be used in wire coatings on hoses, belts and particularly on rims. These tire rims can be made, shaped, molded and hardened by various methods that are known and will be readily apparent to those skilled in the art. It can be seen that the rim can be a passenger tire, plane tire, truck and the like.

The present invention can be better understood by reference to the following examples in which the parts and percentages are by weight, unless otherwise indicated.

Example 1 Preparation of Octadecyl-4-Amnobenzoate A 1 liter round bottom flask was prepared with a reflux condenser, Dean Stark trap and thermal mantle and charged with 54 g (0.20 mol) of 1-octadecanol, 33 g (0.20 mol) ethyl 4-aminobenzoate, g of p-tol? enosulfuric acid and 500 ml of mixed cilenes. The flask was rinsed with nitrogen and sealed under a nitrogen balloon. The reaction system was heated to reflux with a temperature of about 140 ° C and allowed to reflux for about 1/2 hour before 25 ml of aliquot of xylene-ethanol mixtures were separated through the Dean-Stark trap. Every 5-10 minutes, another 25 ml of aliquot from the cilene-ethanol mixture was removed until a total of 400 ml had been removed from the reaction mixture and the vessel attained a temperature of 150 ° C. The remaining volatiles were separated under 29 inches under Hg vacuum at 70 ° C in a vacuum oven to give 95 g of a cream-colored wax material that melts at 60-70 ° C with an infrared spectrum showing the amino ester -aromatic with a long chain aliphatic tail. • Example 2 Each rubber mix was prepared in two non-productive Banbury mixing processes, a Banbury productive mixing process. The non-productive steps for both examples, other than the ingredients that were named in the Table, contain synthetic polyisoprene, natural rubber, resorcinol, cobalt compound (if used), octadecyl-4-aminobenzoate (if used) and amounts Conventional oil processor, stearic acid, zinc oxide, carbon black, antidegradant and silica. The hexametoximelamine together with the conventional amounts of accelerators, antidegradants, zinc oxide and sulfur, were added during the productive stage. Table I below shows the levels of rubber, composed of cobalt, resorcinol, hexametoximelamine and octadexyl-4-aminobenzoate that were used. All parts and percentages are given by weight, unless otherwise specified.

TABLE 1 Sample Control Control Synthetic polyisoprene1 25 25 25 25 Natural rubber 75 75 75 Cobalt naphthenate 1.0 0.50 0.50 0.5 Octadecyl-4-Aminobenzoate 0 50 1.0 Resorcinol 4 Hexametoximelamine 3 1 Polymerized polyisoprene solution commercially available from The G Company, under the description of the trademark of Natsyn® 200.

The hardening properties were determined using a Monsato oscillating disc rheometer which was operated at a temperature of 150 ° C and at 100 cycles per minute. A description of the oscillating disk rheometers can be found in the Vanderbilt Rubber Handbook edited by Robert 0. Ohm (Norwalk, Conn., R.T. Vanderbilt Companyu, Inc., 1990), pages 554-557. The use of this hardening meter and reading of standardized values of the curve are specified in ASTM D-2084. A typical hardening curve that is obtained on an oscillating disc rheometer is shown on page 555 of the 1990 edition of the Vanderbilt Rubber Handbook. In this oscillating disc rheometer, the composite rubber samples are subject to a shared action of constant amplitude oscillation. The is measured. torque of the oscillating disk embedded in the mixture that is being tested and which is required for oscillation of the rotor at a vulcanization temperature. The values obtained using this hardening test are very significant, since the changes in the rubber or in the compound recipe are detected very quickly. It is obvious that it is usually advantageous to have a fast hardening ratio. the following Table II reports the hardening properties that were determined from the hardening curves that were obtained for the rubber mixtures that were prepared. These properties include a minimum of torque. (Min. Of torsion), a maximum torsion moment (Max. Torsion), minutes of 25 percent increase in torsion (t25) and minutes of 90 percent of the. increase in torsion (t90). The Strebler adhesion test was done to determine the interfacial adhesion between the rubber formulas that were prepared. The interfacial adhesion was determined by stretching one compound from another towards a right angle towards a non-ripped test specimen with the two right ends being stretched apart at 180 ° angles with each other using an Instron machine. The contact area was determined from the placement of a Mylar® sheet between the compounds during hardening. A window in the Mylar® allowed the materials to make contact with one another during the test.

The standard wire adhesion tests (S AT) were conducted by imbibing a single brass-plated cord in the respective rubber compositions. The rubber articles were then hardened at 150 ° C for 28 minutes. The steel cord in these rubber compositions was then subjected to drafting tests, in accordance with ASTM Standard D2229-73. The results of these stretching tests (SWAT) are given below and expressed in Newtons. The adhesion tests were also conducted on the rubber articles after hardening and then subjected to cure examples of (1) 5 days in water at 90 ° C, (2) 10 days in water at 90 ° C and (3) ) 10 days at 90 ° relative humidity at 75 ° C. 2ó TABLE II i-, 3 emplo Control Control Cobalt Naphthenate (phr) 1.0 0.5 .50 50 Ester of Example 0 .50 1.0 .50 Hardener rheometer at 10 150 ° C Min. Torque 7.1 7. 8.0 8.2 7.8 Max. Torsion 61.7 58.9 62.1 61.4 63.2 61.9 T25 (min) 6.3 6.3 6.0 5.9 5.9 5.9 T90 (min) 16.7 17.3 16.6 16.4 16, 16.3 fifteen Table II icontinuación Control Control Example Hardener properties 300% yield (Mpa) 13.9 12.8 13.9 13.5 14.1 13.5 Tension brake @ (Mpa) 18.4 18.9 18.8 18.8 18.7 18.0 Lengthening brake @ (%) 4 ¡3300 460 430 450 422 440 10 Bounce @ RT 40.8 41.7 42.3 42.1 42.1 42 Bounce @ 100 ° C 56.2 56.6 57.6 57.7 57.3 57.5 Hardening @ RT 80.0 77.8 80.6 79.0 80 78.1 Hardening @ 100 ° C 76 73.8 76.3 75.5 75.8 74.4 Adhesion Strebeler 15 @ 95 ° C to own 44 77 42 47 46 43 Table II (continued) Example Control Control Fatigue Monsato a Falla 500 652 604 '03 54. ' 500 (cycles) S AT (Newtons) (stretch test results) 10 original 615 621 652 622 652 625 Aging (75 ° C 10 days at 90 ° RH) 720 700 730 711 740 730 Aging (90 ° C 5 days' in water) 652 600 650 600 636 630 15 Aging (90 ° C 10 days in water) 420 431 430 431 451 416 Table II shows that the total or partial substitution of. cobalt with the long chain ester of 4 aminobenzoic acids maintains the state of hardening of the rubber, the properties of tension-pressure, rebound and hardening and Strebler adhesion of the rubber to itself in the cobalt of 1.0 phr. Fatigue-to-failure cycles are also maintained or exceeded with cobalt substitution.

The original and aging adhesion of SWAT (stretch test results) of the wire coating compounds containing a partial or total substitution of the cobalt material with the long chain ester of 4 aminobenzoic acids were those that were maintained in a more important for controls after aging.

Claims (10)

REIVINDIC? CIONE. '

1. A coating compound for wire that is «characterized because: (a)? n rubber is selected from rail group < | i? < = > consists of natural rubber and mixtures of natural and synthetic rubber that is derived from diene monomer; (b) from about .1 to about 10 phr of an aminobenzoic acid ester of the formula: wherein R is? n alkyl radical q? e has from 8 to 24 carbon atoms; (• -) d ^ - .1 i 10 phr of d < - '-? i) of.; d < = > .1 l .t 10 phl of a d 'ti i] ^

2. The compound < ie la rei vrndi sentence 1? ^ T ^ '- ?? i '"< i, because rubber is a rubber: that of a dog, and, rubber, rubber, cis-1, 4-polysophenone, polybutadiene, copol ritiere. d < - 'i - r' - > and butadiene, • - • -? l i U I? "yr i Ion if ri I (J bul l ie u, copolymers of styrene, butadiene ei ^ o ^ -n, < -n \? 1 LÜIZU • > Stylist and b? -idi no and mirlas of it? .

3. The "ompute e Ja rei vi ni ^ lt; 1i '; - • < MI J l < III because the rubber comprises a mixture of synthetic rubber and synthetic rubber and eg Caucasian, natural P-n-pt i J p>, -ent in an amount ranging from 5 to '1'- pot op-ntr. <t total weight of the juc o is nt in the '- ni | node.

4. The compound of Id i ^ claimi-aci on J n < -, -; • - • < • n -? < i -u because the methylene donor is selected i a pit t? ¡- > The group consisting of 1-on-1 (-type, hexaetoxymethyl, amine amine, x-methoxymethyl, and even tiie, 1) auryloxymethylpiine, and hexametoxymethylmethyl of trioxan. torma J d < -: ••• i do, he; -, i s- (methoxim.et.il) melamine, N, N ', N "~ t rlniet.ll / IJ, II", !! " - t ri eti lomela i na, hexameth 1 lolmelamine, N-ol i. ioltieo i: ni, M, '-dimethylolmelami na, N, N', H "- f: ri s (ta :).": Imet 1 i ..) -d-mo :. i and N, M'N ", -tribyl-N, N ', N" -trimethylol-melamin.

5. The compound of claim 1 which is • _-._? r .e X = a. i :: a because the methylene acceptor is selected by the group consisting of phenols activated by ring substitution and phenol resins of the ti or nova! al-: modified acei is made of a nutmeg.

6. The compound of claim 5 characterized in that the activated phenol is selected from the group consisting of resorcinol, cresols, t-butyl phenols, isopropyl phenols, ukyl phenols and mixtures thereof.

7. The rubber compound of the rei indicates ion 1 which characterized in that the compound additionally with ti.ene 5 phr of a cobalt compound.

8. The rubber compound according to claim 7, characterized in that the cobalt oo or cobalt is selected from the group consisting of cobalt salts of fatty acids, cobalt salts of aliphatic or alicyclic carboxylic acids having from 6 to 30 carbon atoms, cobalt chloride, cobalt naphthenate, cobalt carboxylate and organocobalt-boron complexes.

9. A pneumatic tire which has a wire coating which is characterized by the compound of claim 1.

10. A pneumatic tire having a pearl cover that is characterized by the compound of claim 1.