RUBBER COMPOSITION WITH ENHANCED CURING AND ADHESION PROPERTIES, PROCESS FOR ITS PREPARATION, AND ENGINEERED RUBBER PRODUCTS MADE THEREFROM

Abstract

The invention relates to a rubber composition with enhanced curing and adhesion properties, comprising the following ingredients: R1—an elastomer or rubber E which is preferably a diene-based elastomer, R2—a particulate active filler which is preferably carbon black, or silica, or a combination of both, R3—a cobalt free curing or crosslinking or vulcanising system which includes sulphur, an active zinc composition ZnX having a specific surface area of from 10 m.sup.2/g to 100 m.sup.2/g, and accelerators, R4—a novolak composition NC which is a mixture of a novolak resin PA and a urethane-aldehyde resin UA′, and R5—a methylene donor, to a process to cure these rubber compositions, and to a method of use of these rubber compositions in engineered rubber products selected from the group consisting of hoses, pressure hoses, conveyor belts, gaskets, and tyres.

Claims

1.-15. (canceled)

16. A rubber composition with enhanced curing and adhesion properties, comprising the following ingredients: R1 an elastomer or rubber E which is preferably a diene-based elastomer, R2 a particulate active filler which is preferably carbon black, or silica, or a combination of both, R3 a cobalt free curing or crosslinking or vulcanising system which includes sulphur, an active zinc composition ZnX having a specific surface area of from 10 m.sup.2/g to 100 m.sup.2/g, and accelerators, R4 a novolak composition NC which is a mixture of a novolak resin PA and a urethane-aldehyde resin UA′, and R5 a methylene donor.

17. The rubber composition as claimed in claim 16, wherein the active zinc composition ZnX is prepared by treating aqueous solutions of zinc salts with a soluble base or soluble carbonate salts from which a mixture of zinc carbonate or zinc hydroxide is precipitated, followed by a controlled and gentle drying step.

18. The rubber composition as claimed in claim 17, wherein the gentle drying step is via spray drying or contact drying at temperatures of between 150° C. and 400° C.

19. The rubber composition of claim 16, wherein the active zinc composition ZnX has a specific surface area from 10 m.sup.2/g to 100 m.sup.2/g, and an average composition according to the general formula Zn.sub.x O.sub.y (OH).sub.z (CO.sub.3).sub.v, wherein the indexes x, y, z, and v are integer and non-integer numbers in the following ranges: x=1 to 6, y=0 to 5, z=0 to 6, and v=0 to 5, with the requirement that at least one of y, z and v is greater than zero, and wherein the sum 2×x−2×y−z−2×v=0.

20. The rubber composition of claim 16, wherein the specific surface area of the active zinc composition ZnX is from 10 m.sup.2/g to 100 m.sup.2/g.

21. The rubber composition of claim 16, wherein the specific surface area of the active zinc composition ZnX is from 20 m.sup.2/g to 65 m.sup.2/g.

22. The rubber composition of claim 16, wherein the active zinc composition ZnX is in powder form.

23. The rubber composition of claim 16, wherein the active zinc composition ZnX is in the form of a masterbatch in a polymeric matrix, the latter being selected from the class of polyolefins, polyolefin copolymers with dienes, acrylates, esters and anhydrides of olefinically unsaturated acids, copolymerisable acetates of olefinically unsaturated acids, acrylonitrile, and polyesters, phenolic resins and amino resins, synthetic and natural rubber compounds, e.g. polyisoprene (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), ethylene-propylene diene rubber (EPDM), butylrubber (IIR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), all of the preceding rubber types being diene-based elastomers, polyurethane rubbers (polyesterurethane AU), polyetherurethane (EU), alkyl-acrylate copolymer rubber (ACM), hydrogenated acrylonitrile butadiene rubber (HNBR), chlorosulphonated polyethylene (CSM), vinylmethyl silicone rubber (VMQ), and phenylmethyl silicone rubber (PMQ), wherein the mass fraction w(ZnX) of active zinc composition ZnX in the masterbatch is from 5% to 80%, based on the mass of the masterbatch.

24. The rubber composition of claim 16, wherein the elastomer E is selected from the group consisting of the diene-based elastomers natural rubber NR, synthetic polyisoprene IR, butadiene rubber BR, and styrene-butadiene rubber SBR.

25. The rubber composition of claim 16, wherein the particulate filler R2 is selected from the group consisting of carbon black, silica aluminates, and hydrated and anhydrous silica, and from mixtures of these.

26. The rubber composition of claim 16, wherein the vulcanising system R3 comprises sulphur together with accelerators selected from the group consisting of thiazoles and sulfenamides and secondary accelerators selected from the group consisting of amine-aldehyde adducts, guanidines, thiurams, thioureas, and dithiocarbamates.

27. The rubber composition of claim 16, wherein the component R4 comprises a mixture of a novolak resin and a urethane-aldehyde resin.

28. The rubber composition of claim 16, wherein the ratio m(ZnX)/m.sub.R1 of the mass m(ZnX) of the active zinc composition ZnX in the rubber composition to the mass m.sub.R1 of the elastomer component R1 is from 0.1 kg/(100 kg) [0.1 phr] to 10 kg/(100 kg) [10 phr].

29. The rubber composition of claim 28, wherein the ratio m(ZnX)/m.sub.R1 of the mass m(ZnX) of the active zinc composition ZnX in the rubber composition to the mass m.sub.R1 of the elastomer component R1 is from 0.4 phr to 8 phr.

30. A process to cure rubber compositions wherein the rubber composition comprises the following ingredients: R1 an elastomer or rubber E, R2 a particulate active filler, R3 a cobalt free curing or crosslinking or vulcanising system which includes sulphur, an active zinc composition ZnX having a specific surface area of from 10 m.sup.2/g to 100 m.sup.2/g, and accelerators, R4 a novolak composition NC which is a mixture of a novolak resin PA and a urethane-aldehyde resin UA′, and R5 a methylene donor.

31. The process of claim 30, wherein R1 is a diene-based elastomer, R2 is carbon black, or silica, or a combination of both.

32. The process of claim 30, wherein the ratio m(ZnX)/m.sub.R1 of the mass m(ZnX) of active zinc composition in the rubber composition to the mass m.sub.R1 of the elastomer component R1 is from 0.1 kg/(100 kg) [0.1 phr] to 10 kg/(100 kg) [10 phr].

33. The process of claim 32, wherein the ratio m(ZnX)/m.sub.R1 of the mass m(ZnX) of active zinc composition in the rubber composition to the mass m.sub.R1 of the elastomer component R1 is from 0.4 phr to 8 phr.

34. A method of use of the rubber composition of claim 16 in the preparation of engineered rubber products.

35. The method of claim 34 wherein the engineered rubber products are selected from the group consisting of hoses, pressure hoses, conveyor belts, gaskets, and tyres.

Description

DETAILED DISCLOSURE OF THE PREFERRED EMBODIMENTS

[0019] The rubber compositions according to the present invention are based on elastomeric materials, or rubbers, and are usually selected from the group consisting of natural rubber (NR) which is mostly produced from the Para rubber tree, Hevea Brasiliensis, and is originally a latex comprising water and a polymer derived from isoprene, together with minor impurities of other organic compounds; and synthetic rubbers, the best known of which are synthetic polyisoprene (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), ethylene-propylene diene rubber (EPDM), butylrubber (IIR), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), all of the preceding rubber types being diene-based elastomers, polyurethane rubbers (polyesterurethane AU), polyetherurethane (EU), alkyl-acrylate copolymer rubber (ACM), hydrogenated acrylonitrile butadiene rubber (HNBR), chlorosulphonated polyethylene (CSM), vinylmethyl silicone rubber (VMQ), and phenylmethyl silicone rubber (PMQ). Mixtures of these different elastomeric materials can also be used. Among these, NR, IR, BR, EPDM, IIR, CR, NBR, and SBR are mostly vulcanised, or cured, with sulphur. For engineered rubber products, particularly for tyres, SBR is mostly used.

[0020] Sulphur if used alone is a slow vulcanising agent and is only used for elastomeric materials having olefinic unsaturation. Vulcanisation accelerators have to be used which need to be tailored to the rubber type and intended end use. Usually, a large number of diverse additives, comprising the so-called “cure package,” are necessary. The combined cure package in a typical rubber composition consists of sulphur together with an assortment of compounds that modify the kinetics of crosslinking and stabilise (protect) the final product. These additives include accelerators for vulcanising, activators for vulcanising like zinc oxide and stearic acid, softeners such as petroleum oil, pine tar, resins, and waxes as processing aids, and for tack improvement, and antidegradants such as waxes, antiozonants, and antioxydants to protect the tyres against heat and against oxydation. The accelerators and activators are catalysts. Retarding agents that inhibit vulcanisation until some optimal time or temperature have been reached are also used. Antidegradants are used to prevent ageing and degradation of the vulcanised product by heat, oxygen, and ozone. All these chemicals and additives are also commonly referred to as “rubber chemicals”.

[0021] The addition of zinc oxide (ZnO) as an activator for the sulphur vulcanisation of rubbers enhances the vulcanisation efficiency and vulcanisate properties and reduces the vulcanisation time. The curing and physical properties found with the standard quality ZnO (“Red Seal”, mass fraction of ZnO is more than 99.5%, specific surface area ≈4.5 m.sup.2/g) can be retained with a reduced level of an active zinc composition ZnX according to the invention down to 1 phr or 2 phr.

[0022] In rubber compounding, it has become common to specify the amount of each individual added component (additive mixtures, chemical compounds, fillers, reinforcing fibres etc.) by their relative mass (m.sub.C/m.sub.Elastomer)×100, m.sub.C being the mass of an individual added component, and m.sub.Elastomer being the sum of masses of all elastomeric components in the mixture, and use the designation “phr” as a unit.

[0023] Zinc oxide varieties used in rubber compounding are the so-called thermal zinc oxide grades, one of them being the “Red Seal” grade mentioned supra, that are made synthetically by oxydation of vapour of metallic zinc, either by the so-called French or indirect process which starts from (purified) metallic zinc which is vaporised, and then oxydised, or the so-called American or direct process which starts from zinc ores or smelter by-products which are reduced in a carbothermal reduction by heating with a source of carbon such as anthracite to produce zinc vapour, which is then oxidised as in the indirect process. Because of the lower purity of the source material, the final product is also of lower quality in the direct process as compared to the indirect process.

[0024] A process that leads to a material having a higher specific surface area is a wet chemical process where aqueous solutions of zinc salts are treated with a soluble base or soluble carbonate salts from which zinc carbonate or zinc hydroxide is precipitated, followed by separation of the precipitate and a controlled and gentle drying step referred to as “calcination” in the context of this invention. This calcination step is preferably conducted by spray drying or contact drying, and preferably at a temperature of from 150° C. to 400° C. The zinc compositions thus obtained comprise one or more zinc compounds, viz., at least one of oxides, hydroxides, carbonates and basic carbonates of zinc as constituents which have an average composition according to the general formula Zn O.sub.y (OH).sub.z (CO.sub.3).sub.v and are referred to as “active zinc composition ZnX” in the context of this invention, with specific surface areas from 10 m.sup.2/g to 100 m.sup.2/g, preferably from 20 m.sup.2/g to 65 m.sup.2/g. In the active zinc composition ZnX according to the invention, the indexes x, y, z, and v are integer and non-integer numbers in the following ranges: x=1 to 6, y=0 to 5, z′=0 to 6, and v=0 to 5, with the requirement that at least one of y, z and v is greater than zero. It goes without saying that the values for x, y, z, and v have to be chosen in a way that the valences of zinc cations on one side, and those of the anions oxide, hydroxide, and carbonate must be stoichiometrically balanced, i. e. their sum 2× x−2× y−z−2× v must be zero.

[0025] According to the invention, the use of the active zinc composition ZnX together with an adhesion enhancement additive which is a novolak resin composition leads to rubber compounds which do not need the presence of additional cobalt compounds in the rubber compounds during curing, but cure as fast or faster as a cobalt compound-containing rubber compositions and have the same level of adhesion of rubber to the brass-plated steel wire used for reinforcing of rubber compounds for applications in engineered rubber products, including tyres, hoses, gaskets, and conveyor belts, and also does not need the presence of resorcinol alone or in the form of resorcinol-aldehyde resins.

[0026] Cobalt (Co) and its compounds are widely distributed in nature and are part of numerous anthropogenic activities. Although cobalt has a biologically necessary role, e. g., as metal constituent of vitamin B12, excessive exposure has been shown to induce various adverse health effects. See the review of L. Leyssens et al, “Cobalt toxicity in humans-A review of the potential sources and systemic health effects” in Toxicology 2017, Volume 387, 15 Jul. 2017, pages 43 to 56.

[0027] Cobalt is usually used in rubber compounding in the form of its lipophilic salts, such as salts of fatty acids, of naphthenic acids (a mixture of acidic fractions originally present in crude oil, and also formed during refining and oxydation steps, which are mostly cycloaliphatic monocarboxylic acids having cyclopentyl and cyclohexyl structures, and a molar mass of from 120 g/mol to about 700 g/mol), of isooctanoic acid (2-ethylhexanoic acid), or of neodecanoic acid (a highly alpha-branched aliphatic monocarboxylic acid) having a mass fraction of cobalt metal ions of up to (20.5±0.5) %.

[0028] Rubber compositions for the preparation of engineered rubber products further comprise fillers that include active or reinforcing fillers such as carbon black or silica, or a combination of both, which active fillers increase hardness, stiffness (modulus), strength, tear resistance, and abrasion resistance.

[0029] The rubber compositions according to the invention therefore have the following essential ingredients: [0030] R1 an elastomer or rubber E which is preferably a diene-based elastomer, [0031] R2 a particulate active filler which is preferably carbon black, or silica, or a combination of both, [0032] R3 a cobalt free curing or crosslinking or vulcanising system which includes sulphur, an active zinc composition ZnX having a specific surface area of from 10 m.sup.2/g to 100 m.sup.2/g, and accelerators, [0033] R4 a reinforcing resin which comprises a novolak resin composition that is preferably resorcinol free, and [0034] R5 a methylene donor.

[0035] The term “cobalt-free” as used in this application means that the ratio 100× m(Co)/m(E) of the mass m(Co) of cobalt to the mass m(E) of elastomers E in the rubber composition is less than 0.001 kg/100 kg (0.001 phr). Preferably, this ratio is below the detection limit. It is particularly preferred to use no cobalt compounds at all in the rubber compositions according to this invention.

[0036] The term “resorcinol-free” as used in this application means that the ratio 100×m(Res)/m(E) of the mass m(Res) of resorcinol present as free compound is less than 0.001 kg/100 kg (0.001 phr), and less than 0.005 kg/100 kg (0.005 phr) for bound resorcinol in resorcinol derived resins. Preferably, this ratio is below the detection limit. It is particularly preferred to use no resorcinol at all, and also no resorcinol derived resins in the rubber compositions according to this invention.

[0037] The elastomer R1 is preferably selected from the diene-based elastomers natural rubber NR, synthetic polyisoprene IR, butadiene rubber BR, and styrene-butadiene rubber SBR. These elastomers are usually cured with sulphur, and accelerators which are described below in more detail.

[0038] The particulate filler R2 can be chosen from a variety of fillers which are usually classified by their (average) particle size, as degradative fillers (from ca. 7 μm to ca. 100 μm, grinded calcium carbonate, mica, talc), dilution fillers (1 μm to 7 μm, mica, talc, clays), semi-reinforcing fillers (100 nm to 1 μm, precipitated calcium carbonate, TiO.sub.2, ZnO, carbon black), and reinforcing fillers (10 nm to 100 nm, carbon black, silica aluminates, hydrated and anhydrous silica). For engineered rubber products, such as hoses, pressure hoses, gaskets, and tyres, particularly tyres, which need elasticity, stiffness, rebound resilience, and low abrasion, semi-reinforcing and reinforcing fillers are preferably used, mainly, carbon black and silica grades. Mixtures of these fillers can also be used.

[0039] The curing or crosslinking or vulcanising system R3 comprises a principal vulcanising agent, such as sulphur, peroxides, or metal oxides for some halogenated rubber types. Sulphur is mainly used for diene-based elastomers, other vulcanising agents therefor are phenolic resins, quinone derivates, and maleimides. Peroxides can also be used for these diene-based rubber types, but they are used particularly for those rubber types where no olefinic unsaturation remains in the polymer, such as silicone rubbers, ethylene-propylene rubbers, acrylate rubbers, and urethane rubbers. As sulphur itself is a slow vulcanising agent, it is generally used together with accelerators which comprise the families of thiazoles and sulfenamides (also referred to as “Primary Accelerators”) which provide good processing safety, a broad vulcanisation plateau, and optimum crosslink density, as well as desired reversion delay, and also basic accelerators such as amine-aldehyde adducts, guanidines, thiurams, thioureas, and dithiocarbamates (also referred to as “Secondary Accelerators”) which are used to activate the Primary Accelerators. The use of Secondary Accelerators increases the speed of vulcanisation substantially, but at the expense of scorch safety. Dosage of the Primary Accelerators is from 0.5≤100×m.sub.PA/m.sub.R1≤1.5 in most rubber compounds (from 0.5 phr to 1.5 phr), where m.sub.R1 is the mass of the elastomer component R1, and m.sub.PA is the mass of Primary Accelerator. The dosages of the Secondary Accelerators are generally in a range of 10%≤m.sub.SA/m.sub.PA≤40%, where m.sub.SA is the mass of Secondary Accelerator.

[0040] Useful Primary Accelerators are the thiazoles MBT (2-mercaptobenzothiazole), MBTS (2-2′-dithiobis[benzothiazole]), and ZMBT (zinc-2-mercaptobenzothiazole), and the sulfen-amides CBS (N-cyclohexyl-2-benzothiazole sulfenamide), TBBS (N-tert-butyl-2-benzothiazole sulfenamide), MBS (2-[4-morpholinothio]-benzothiazole) and DCBS (N,N′-dicyclo-hexyl-2-benzothiazole sulfenamide). Useful Secondary Accelerators are the aldehyde-amine adducts hexamethylene tetramine (HMT), heptaldehyde-aniline adduct (BA), the guanidines diphenyl guanidine (DPG), N, N′-diorthotolyl guanidine (DOTG), the thioureas ethylene thiourea (ETU), di-pentamethylene thiourea (DPTU), dibutylthiourea (DBTU), the thiurams tetramethylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), dipenta-methylenethiuram tetrasulfide (DPTT), and tetrabenzylthiuram disulfide (TBzTD), the dithiocarbamates zinc dimethyldithiocarbamate (ZDMC), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), zinc dibenzyldithiocarbamate (ZDBC), and the xanthate zinc-isopropylxanthate (ZIX).

[0041] Zinc oxide is typically used together with sulphur as vulcanising agent in the crosslinking system R3, and the efficiency of zinc in combination with accelerators is often enhanced by the presence of lipophilic acids such as stearic acid.

[0042] According to the invention, the so-called active zinc composition ZnX is used as a mandatory constituent of R3 which is preferably made in a wet process, and which has a specific surface area of at least 10 m.sup.2/g. The ratio m(ZnX)/m.sub.R1 of the mass m(ZnX) of the active zinc composition ZnX in the rubber composition to the mass m.sub.R1 of the elastomer component R1 is preferably from 0.1 kg/(100 kg) [0.1 phr] to 10 kg/(100 kg) [10 phr], preferably from 0.2 phr to 9 phr, and particularly preferred, from 0.4 phr to 8 phr.

[0043] The reinforcing and adhesion-enhancing resin component R4 serves to increase certain mechanical properties of the rubber compound, particularly tensile strength, hardness, and abrasion resistance which are important for engineered rubber goods and tyres and the adhesion to the reinforcing cord. This component comprises a novolak composition NC, together with a methylene donor R5 which is preferably selected from the group consisting of hexamethylene tetramine, and hexamethoxymethyl melamine.

[0044] According to the invention, a novolak composition NC which is a mixture of a novolak resin PA and a urethane-aldehyde resin UA′ is used together with a methylene donor, which mixture of a novolak resin PA and a urethane-aldehyde resin UA′ is also referred to as a reinforcing resin or adhesion-enhancing resin, and with special preference, a novolak composition NC wherein the novolak resin PA has been synthesised in the presence of a preformed urethane-aldehyde resin UA′ as disclosed in EP 2432810 B1. These mixtures act as reinforcing resins, together with a methylene donor, and also as adhesion enhancers to both fibre cord and metal wire cord in a cord-reinforced rubber product.

[0045] The novolak resin PA is preferably based on a phenol P which is an aromatic compound having at least one hydroxyl group bound to an aromatic nucleus, and has at least one reactive hydrogen atom in ortho- or para-position to the phenolic hydroxyl group, the aromatic compound being mononuclear, or polynuclear, i. e. having more than one aromatic nucleus annealed or bound by a direct bond or a divalent group. Examples are phenol itself, alkylphenols such as o-, m-, or p-cresol, 2,4-xylenol, 2,6-xylenol, ethylphenols, and also longer chain alkyl phenols such as 4-tert-butylphenol, 4-isooctylphenol, 4-nonyl phenol, 4-octadecyl-o-cresol, or cardanol (a mixture of C.sub.15-alk(en)ylphenols made by decarboxylation of anacardic acid which is obtained from cashew nutshell liquid, of general formula C.sub.21H.sub.36-nO, where n is mostly 0, 2, 4, or 6), and also divalent hydroxyaromatics such as resorcinol and bisphenol A. Mixtures of these phenols P can also be used. Preferred is phenol itself, and mixtures of phenol with cresols and other alkylphenols having one phenolic hydroxyl group. These phenols P are reacted with aldehydes A, preferably formaldehyde or compounds that liberate formaldehyde under heating, in the presence of acidic catalysts, to form a novolak resin PA.

[0046] The urethane-aldehyde resin UA′ is usually based on aliphatic urethanes U such as ethylurethane, butylurethane, and hexylurethane, preferably butylurethane and hexylurethane, and aliphatic aldehydes A′ having from one to four carbon atoms which are formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde, preferably formaldehyde.

[0047] The mass fraction w(UA′) of urethane resins in the mixture of UA′ and PA, or in the product PAUA′ obtained by preparing a novolak resin from a phenol P and an aldehyde A as defined hereinbefore, in the presence of a preformed urethane-aldehyde resin UA′, which is the ratio of the mass m(UA′) of the urethane-aldehyde resin and the sum m(PA)+m(UA′) of the mass m(PA) of the novolak and the mass m(UA′) of the urethane aldehyde resin

w(UA′)=m(UA′)/[m(PA)+m(UA′)]

is preferably between 0.05 kg/kg and 0.5 kg/kg, or between 5% and 50%.

[0048] It has been found in the experiments underlying this invention that the use of a novolak composition NC which is a urethane-aldehyde resin-modified novolak resin PAUA′, or a mixture of a novolak resin PA and a urethane-aldehyde resin UA′, as component in the rubber compounding process, together with the active zinc composition ZnX having a specific surface area of at least 10 m.sup.2/g makes it possible to reduce the amount of cobalt compounds needed to obtain sufficient adhesion of a rubber composition made with this mixture to steel wire and brass-plated steel wire, to a ratio (100×m(Co))/m(E) of the mass m(Co) of cobalt to the mass m(E) of elastomers E in the rubber composition to a value of less than 0.001 kg/100 kg (0.001 phr), or to completely eliminate the addition of cobalt salts. It has even been found in the experiments that addition of cobalt salts (particularly cobalt stearate) to rubber compositions which comprise the same mass fractions of a urethane-aldehyde resin-modified novolak resin PAUA′ (or a mixture of a novolak resin PA and a urethane-aldehyde resin UA′) and the active zinc composition ZnX reduces the values obtained for the maximum S′.sub.max of elastic stress S′ and of rate of increase in elastic stress ΔS′/Δt, determined here as the ratio of difference ΔS' in elastic stress between 20% and 80% of the maximum value S′.sub.max, and the time interval Δt needed to increase the elastic stress from 20% of the maximum value S′.sub.max to 80% of the maximum value S′.sub.max, during vulcanisation as monitored in a moving die rheometer.

[0049] The ratio w.sub.ra=m(UA′,PA)/m(R1) of the mass m(UA′,PA) of the mixture of UA′ and PA which is the sum m(PA)+m(UA′) to the mass m(R1) of the elastomer or rubber R1 present in the rubber composition, or the ratio w.sub.rb=m(PAUA′)/m(R1) of the mass m(PAUA′) of product PAUA′ obtained by preparing a novolak resin from a phenol P and an aldehyde A as defined hereinbefore, to the mass m(R1) of the elastomer or rubber R1 present in the rubber composition is preferably: [0050] 0.005 kg/kg≤w.sub.ra≤0.050 kg/kg, or 0.5 kg/(100 kg)≤w.sub.ra≤5.0 kg/(100 kg), and 0.005 kg/kg≤w.sub.rb 0.050 kg/kg, or 0.5 kg/(100 kg)≤w.sub.rb≤5.0 kg/(100 kg).

[0051] In a preferred embodiment, the limits of these intervals can be from 1 kg/(100 kg) to 4 kg/(100 kg), and particularly preferred, from 1.5 kg/(100 kg) to 3.5 kg/(100 kg).

[0052] It is also possible by using the novolak composition NC according to the invention to reduce the amount of resorcinol in the rubber composition, expressed as the ratio (100×m(Res))/m(E) of the mass m(Res) of resorcinol present as free compound or in the form of a resorcinol-aldehyde resin to the mass m(E) of elastomers E in the rubber composition to a value of less than 0.001 kg/100 kg (0.001 phr) for free resorcinol, and to less that 0.005 kg/100 kg (0.005 phr) for bound resorcinol in resorcinol derived resins. It is particularly preferred to use no resorcinol at all, and also no resorcinol derived resins.

[0053] It has further been found that there is no adverse effect on the steel cord adhesion of the formulations according to the present invention which are free from cobalt or have a ratio of the mass of cobalt to the mass of elastomers in the rubber composition of less than 0.001 kg/100 kg (0.001 phr).

EXAMPLES

[0054] The following examples are intended to illustrate the invention without limiting the scope thereof.

Example 1 Base Rubber Mixture

[0055] A base rubber mixture was prepared in a kneader at 140° C. from the following constituents: 5 kg of natural rubber (SMR rubber grade CV50 having a mass fraction of ashes of below 0.50%, a plasticity retention index of at least 60% after ageing at 140° C. for thirty minutes, and a Mooney Viscosity ML 1+4 at 100° C. of 50±5); 2.75 kg of carbon black N326 grade (having a specific iodine adsorption of (82±5) g/kg, measured according to ASTM D1510, a specific oil absorption of (72±5) cm.sup.3/(100 g), measured according to ASTM D2414, and a pour density of (440±30) kg/m.sup.3); 0.1 kg of stearic acid in pellet form (Palmera B 1805 from Avokal GmbH, iodine number max. 5 g/hg), and 0.75 kg of precipitated silica (®Ultrasil VN3, Evonik Resource Efficiency GmbH, having a specific surface of 180 m.sup.2/g measured according to ISO 9277, and mass fractions of iron, copper and manganese in the product as follows: w(Fe)≤400 mg/kg, w(Cu)≤6 mg/kg, and w(Mn)≤6 mg/kg).

Example 2 Rubber Compositions

[0056] The following further materials (mass in g) were added to separate portions of this base rubber mixture, each of these portions containing exactly 1 kg of natural rubber, during kneading in the sequence of the rows in Table 1:

TABLE-US-00001 TABLE 1 Additions to the base rubber mixture (mass of added substance in g) Rubber compound added materials R01 R02 R03 R04 R05 ZnO Red Seal.sup.1 60 60 60 ZnX.sup.2 60 60 TMQ.sup.3 10 10 10 10 10 Process Oil.sup.4 40 40 40 40 40 Co stearate.sup.5 7.5 7.5 7.5 Resorcinol.sup.6 30 Novolak.sup.7 25 25 25 25 HMMM.sup.8 38.5 41.5 41.5 41.5 41.5 Sulfur.sup.9 60 60 60 60 60 DCBS.sup.10 6 6 6 6 6 TBBS.sup.11 9 9 9 9 9 .sup.1standard zinc oxide made by the French Process, specific surface area 6.5 m.sup.2/g, Numinor Chemical Industries Ltd. .sup.2active zinc composition ZnX made by the wet process, specific surface area 45 m.sup.2/g. .sup.3polymerised 2,2,4-Trimethyl-1,1-dihydroquinoline, CAS# 26780-96-1, Western Reserve Chemical .sup.4light coloured naphthenic process oil, wax-free (Sunthene 450, Sunoco Europe) .sup.5Ecos ® 9.3 cobalt stearate, mass fraction of Co metal is 9.3%, Umicore Cobalt & Specialty Materials .sup.6Resorcinol, industrial grade .sup.7prepared in accordance with Example 1 from EP 2 253 649 A1 .sup.8Hexamethoxymethylmelamine, on a carrier of precipitated silica, mass fraction of HMMM is 65% (Cyrez ® 964 powder concentrate, Allnex USA Inc.) .sup.9Crystex ™ HD OT 20, sulphur powder with a particle size of less than 30 μm, with a mass fraction of 20% of oil (hydrotreated heavy naphthenic petroleum distillate, CAS # 64742-52-5) .sup.10N,N-Dicyclohexyl -2- benzothiazolesulfenamide; CAS# 4979-32-2 .sup.11N-tert-butyl-benzothiazole sulfonamide; CAS# 95-31-8

Example 3 Vulcanisation and Properties

[0057] From the unvulcanised rubber compositions prepared in Example 2, samples in the form of cylindrical slabs with a volume of 4.5 cm.sup.3 were cut with a sample cutter, and these were tested in a moving die rheometer at a temperature of 155° C., with a fixed frequency of 1.67 Hz.

[0058] The following characteristic values were calculated from the data obtained:

TABLE-US-00002 S′.sub.max maximum value of the elastic stress as measured in the moving die rheometer S′ (20%) S′.sub.max × 0.2 S′ (80%) S′.sub.max × 0.8 t (20%) the time when S′ reaches the value of S′.sub.max × 0.2 during the rise of the stress t (80%) the time when S′ reaches the value of S′.sub.max × 0.8 during the rise of the stress S′ (80%) − S′ (20%)/ steepness of slope, calculated from the [t (80%) − t (20%)] differences of the values supra, as a measure of the rate of increase of the elastic modulus during vulcanisation

[0059] The steps have been chosen to account for the scorch or induction period at the beginning of the vulcanisation process, and to account for reversion or marching. The results for these characteristic values are shown in Table 2.

TABLE-US-00003 TABLE 2 Vulcanisation Behaviour of Rubber Compositions R01 to R05 Rubber Compound Unit R01 R02 R03 R04 R05 S′.sub.max dN .Math. m 38.8 32.6 52.1 46.8 45.3 S′ (20%) dN .Math. m 7.8 6.5 10.4 9.4 9.1 S′ (80%) dN .Math. m 31.0 26.1 41.6 37.5 36.2 t (20%) min 1.4 1.8 1.6 1.5 1.3 t (80%) min 8.3 9.0 8.7 7.8 7.3 S′ (80%) − S′ (20%)/ dN .Math. m/ 3.3 2.7 4.4 4.5 4.5 [t (80%) − t (20%)] min Shore D hardness 31.3 27.8 34.5 33.9 33 Stress at 100% elongation MPa 6 5.15 8.11 7.37 7.69 Stress at 200% elongation MPa 11.09 9.31 Break* 12.74 13.53 POF (TAWI) N 290 375 365 380 270 POF: Pull out force measured on steel cord which was coated with a Cu—Zn—Co ternary alloy TAWI: steel cord coated with a Cu—Zn—Co ternary alloy Break: sample broken at an elongation of 150%

[0060] It can be seen from this table that both vulcanisation speed (rate of increase of the elastic modulus during vulcanisation) and maximum elastic stress S′ when using the system of the invention (Rubber Compositions R04 and R05; active zinc composition ZnX made by the wet process, in combination with a modified novolak resin) are markedly increased over a comparative system according the conventional technology (Rubber Composition R01; comprising resorcinol, a formaldehyde source, and cobalt stearate as accelerators for sulfur vulcanisation).

[0061] While fast vulcanisation has also been found when combining a standard zinc oxide (Red Seal ZnO made by the French process, having lower specific surface area than the active Zinc composition ZnX) with a urethane-aldehyde resin modified novolak resin in rubber composition R03, where an added cobalt salt (cobalt stearate) was also present, with even a higher maximum elastic stress S′, drastically lower performance in both vulcanisation speed and maximum elastic stress S′ was found without addition of cobalt stearate in the comparison composition R02. There is no such influence seen when comparing the results for rubber compositions R04 (without cobalt stearate) and R05 (with added cobalt stearate), when using the combination of active zinc composition ZnX made by the wet process and modified novolak resin, according to the invention. The addition of cobalt salt leads to a small drop in the maximum elastic stress S′ in R05 as compared to R04. The vulcanisation speed remains at a high level.

[0062] Shore hardness tests reveal that the level reached with a resorcinol/cobalt salt reference system (R01) is maintained when using standard zinc oxide in combination with a special adhesion enhancement novolak system and a cobalt salt (R03), and also when using the active zinc composition ZnX in combination with a special adhesion enhancement novolak system according to the invention (R04), the combination of standard zinc oxide and a special adhesion enhancement novolak system (R02) has lower hardness. Addition of a cobalt salt to the system according to the invention (R05) leads to a slight reduction of the Shore hardness. Thus, a cobalt free formulation is preferable. Comparison of stress values at a given elongation of 100% shows the level of the resorcinol/cobalt salt reference system (R01) is improved by the system according to the invention (R04). Addition of cobalt salt to the latter system gives a further improvement (R05), but at the expense of having a cobalt salt containing system. Using conventional zinc oxide (R02, R03) leads to stress values lower (R02) and higher (R03) than those of the reference (R01). However, upon measurement of elastic stress at an elongation of 150%, the samples of R03 broke.

[0063] The measurement of the pull-out force (according to ASTM D 2229-02) reveals that the best results on ternary alloy-coated steel wire are obtained with the system according to the invention (R04), and that addition of cobalt salt to the system according to the invention decreases the pull-out force (R05). A similar effect of added cobalt salt, but on lower level, has been seen when using a standard zinc oxide grade in combination with a special adhesion enhancement and reinforcing novolak system (R02, R03).