Adherent rubber composition for steel cord

Abstract: An adherent rubber composition suitable for adhesion to steel cords comprises 0.1-10 parts by weight of an inorganic salt hydrate and 3-8 parts by weight of sulfur based on 100 parts by weight of rubber ingredient comprising not less than 10% by weight of at least one synthetic rubber and the remainder being natural rubber.

Description: This invention relates to an adherent rubber composition for steel cord, and more particularly to an adherent rubber composition suitable for adhesion to brass plated steel cords. Heretofore, steel cords have been used as a reinforcing member in order to improve performances of rubber articles such as automobile tires, conveyor belts and the like. In general, steel cord is subjected to brass plating in order to enhance the reinforcing effect or adhesiveness to rubber. In the adhesion of rubber to brass plated steel cord through vulcanization, it is necessary that an unvulcanized rubber contains a certain amount of water in order to sufficiently ensure adhesiveness just after the vulcanization. In a dry winter season, however, the water content in the unvulcanized rubber lowers and hence the adhesiveness may be deficient. Thus, the adhesiveness just after the vulcanization becomes particularly unstable in the winter season, so that it is desired to stably ensure the adhesiveness between rubber and steel cord even in the winter season. In order to ensure a given water content in the unvulcanized rubber at the dry winter season, there is proposed a method wherein water is merely added to the unvulcanized rubber or water is adsorbed on carbon black or rubber chemicals in the unvulcanized rubber composition. However, this method is not effective because a rotor in a kneader for the rubber composition slips or water is evaporated during the kneading. Furthermore, there is proposed a method of leaving the unvulcanized rubber in a humidity controller to adjust the water content, which has a drawback that a long leaving time is taken for the adjustment of the water content. On the other hand, when the rubber composition for use in the adhesion to steel cord mainly contains natural rubber as a rubber ingredient, the adhesion property to steel cord is excellent, but the thermal aging resistance may become poor. In order to improve the thermal aging resistance, it is suitable to use a synthetic rubber having less carbon-carbon double bond (>C=C<) in its main chain, but there is a problem that the adhesion property is inversely lowered. It is, therefore, an object of the present invention to provide an adherent rubber composition capable of stably providing adhesiveness just after vulcanization irrespective of season to form a rubber-steel cord composite body having excellent adhesiveness or further thermal aging resistance. The present inventors have made various studies in order to achieve the above object and found that in order to simply and reliably raise the water content of the rubber composition, it is effective to use an inorganic salt hydrate as a compound capable of releasing water during kneading or vulcanization together with a synthetic rubber having a low water content, if necessary, in addition to compounding with natural rubber having a high water content, and as a result the invention has been accomplished. According to the invention, there is provided an adherent rubber composition for steel cord comprising 0.1-10 parts by weight of an inorganic salt hydrate and 3-8 parts by weight of sulfur based on 100 parts by weight of rubber ingredient comprised of at least one rubber selected from natural rubber and/or one or more synthetic rubbers, characterized in that the inorganic salt hydrate is selected from NiSO 4· .7H 2 O, COSO 4 .7H 2 O, NaSO 4 .10H 2 O, CaSO 4 .2H 2 O, CuSO 4 .5H 2 O, Al 2 (SO 4 ) 3 .18H 2 O, FeSO 4 .7H 2 O, ZnSO 4 .7H 2 O, MgSO 4 .7H 2 O, Na 2 S.9H 2 O, Na 3 PO 4 .12H 2 O, NaH 2 PO 4 .12H 2 O, Na 2 HPO 4 .12H 2 O, Ni 3 (PO 4 ) 2 .8H 2 O, Mg 3 (PO 4 ) 2 .8H 2 O, Li 3 PO 4 .5H 2 O, Na 4 P 2 O 7 .10H 2 O, Ni 2 P 2 O 7 . 6H 2 O, Mn 4 (P 2 O 7 ) 3 .14H 2 O, CoCO 3 .6H 2 O NiCO 3 .6H 2 O, Na 2 CO 3 .10H 2 O, Nd 2 (CO 3 ) 3 . 8H 2 O, Na 2 SO 3 .7H 2 O, CaCl 2 .6H 2 O, NiCl 2 .6H 2 O, FeCl 3 .6H 2 O, Na 2 SiO 3 .9H 2 O, and Na 2 P 2 O 5 .10H 2 O. In a preferable embodiment of the invention, the rubber ingredient contains at least 50% by weight of natural rubber. In another preferable embodiment of the invention, the synthetic rubber is selected from styrene-butadiene rubber (SBR), butadiene rubber (BR), butyl rubber (IIR), halogenated butyl rubber (halogenated IIR), butyl rubber having paramethylstyrene group therein, isoprene rubber (IR) and ethylene-propylene-diene rubber (EPDM). In still another preferable embodiment of the invention, the amount of the inorganic salt hydrate is 0.2-8 parts by weight, more particularly 0.3-3 parts by weight. In a further preferable embodiment of the invention, the rubber composition further comprises one or more of 2-10 parts by weight of zinc white, 0.3-2 parts by weight of a vulcanization accelerator, 0.25-3 parts by weight of an adhesion promoter, and 30-70 parts by weight of carbon black, respectively based on 100 parts by weight of the rubber ingredient. In a still further preferable embodiment of the invention, the styrene-butadiene rubber is a solution-polymerized styrene-butadiene rubber having a vinyl content of 35-85% by weight and a bound styrene content of not more than 30% by weight, and the butadiene rubber has a vinyl content of 1-85% by weight. The invention will be described in detail below. The inorganic salt hydrate used in the invention is selected from NiSO· 4 ·7H 2 O, CoSO 4 ·7H 2 O, NaSO 4 ·10H 2 O, CaSO 4 ·2H 2 O, CuSO 4 ·5H 2 O, Al 2 (SO 4 ) 3 ·18H 2 O, FeSO 4 ·7H 2 O, ZnSO 4 ·7H 2 O, MgSO 4 ·7H 2 O, Na 2 S·9H 2 O, Na 3 PO 4 ·12H 2 O, NaH 2 PO 4 ·12H 2 O, Na 2 HPO 4 ·12H 2 O, Ni 3 (PO 4 ) 2 ·8H 2 O, Mg 3 (PO 4 ) 2 ·8H 2 O, Li 3 PO 4 ·5H 2 O, Na 4 P 2 O 7 ·10H 2 O, Ni 2 P 2 O 7 ·6H 2 O, Mn 4 (P 2 O 7 ) 3 ·14H 2 O, CoCO 3 ·6H 2 O, NiCO 3 ·6H 2 O, Na 2 CO 3 ·10H 2 O, Nd 2 (CO 3 ) 3 ·8H 2 O, Na 2 SO 3 ·7H 2 O, CaCl 2 ·6H 2 O, NiCl 2 ·6H 2 O, FeCl 3 ·6H 2 O, Na 2 SiO 3 ·9H 2 O and Na 2 P 2 O 5 .10H 2 O For example, when the rubber composition contains Na 2 P 2 O 5 ·10H 2 O as the inorganic salt hydrate, H 2 O is released from the inorganic salt hydrate during the vulcanization after the rubber composition is applied onto brass plated steel cords, and hence zinc is diffused from the surface of the brass plated layer into rubber by the released water to facilitate the reaction between copper in the brass plated layer and sulfur in the rubber composition, whereby the formation of cuprous sulfide is promoted at an early time to stabilize the adhesiveness after the vulcanization. The inorganic salt hydrate is compounded in an amount of 0.1-10 parts by weight based on 100 parts by weight of the rubber ingredient. When the amount of the inorganic salt hydrate is less than 0.1 part by weight, the effect of improving the adhesion property is not obtained, while when it exceeds 10 parts by weight, the water content in the rubber composition becomes too high and the adhesion property and fracture properties are undesirably degraded. The amount of the inorganic salt hydrate is preferably 0.2-8 parts by weight, more particularly 0.3-3 parts by weight for obtaining good and stable adhesiveness. In the rubber composition according to the invention, the rubber ingredient preferably contains at least 50% by weight of natural rubber. As the synthetic rubber, use may be made of SBR, BR, IIR, halogenated IIR, IIR having paramethylstyrene group therein (specifically copolymer of isobutyrene and p-halogenated methylstyrene or the like), IR and EPDM. When the amount of natural rubber is less than 50% by weight, the adhesiveness to steel cord and the fracture properties of rubber may be undesirably degraded. Moreover, when the rubber ingredient is a blend of natural rubber and at least one synthetic rubber, if the amount of the synthetic rubber is less than 10% by weight, the thermal aging resistance is undesirably degraded together with the degradation of adhesiveness and fracture properties. Among the synthetic rubbers, it is preferable to use at least one rubber selected from a solution-polymerized SBR having a vinyl content of 35-85% by weight and a bound styrene content of not more than 30% by weight, and a butadiene rubber having a vinyl content of 1-85% by weight. In the solution-polymerized SBR, when the vinyl content is less than 35% by weight, the thermal aging resistance can not be improved, while when it exceeds 85% by weight, the fracture properties are degraded, and when the bound styrene content exceeds 30% by weight, the adhesion lowers. In the butadiene rubber, when the vinyl content is outside the above range, the merit of improving the thermal aging resistance is lost and also the fracture properties are degraded. Furthermore, sulfur is compounded in an amount of 3-8 parts by weight based on 100 parts by weight of the rubber ingredient. When the amount of sulfur is less than 3 parts by weight, it is difficult to ensure the original adhesiveness between brass and sulfur after the vulcanization, while when it exceeds 8 parts by weight, the thermal aging resistance and heat-resistant adhesion are undesirably lowered. Moreover, the rubber composition according to the invention may be compounded with proper amounts of additives usually used in the rubber industry. For example, zinc white is suitably compounded in an amount of 2-10 parts by weight based on 100 parts by weight of the rubber ingredient. When the amount of zinc white is less than 2 parts by weight, sufficient modulus of elasticity is not obtained, while when it exceeds 10 parts by weight, the adhesion lowers. Further, a vulcanization accelerator is suitably compounded in an amount of 0.3-2 parts by weight. When the amount of the vulcanization accelerator is less than 0.3 part by weight, sufficient modulus of elasticity is not obtained, while when it exceeds 2 parts by weight, the adhesion lowers. Further, an adhesion promoter is suitably compounded in an amount of 0.25-3 parts by weight. When the amount of the adhesion promoter is less than 0.25 part by weight, the addition effect is not developed, while when it exceeds 3 parts by weight, the resistance to thermal aging lowers. Also, carbon black is suitably compounded in an amount of 30-70 parts by weight. When the amount of carbon black is less than 30 parts by weight, sufficient modulus of elasticity is not obtained, while when it exceeds 70 parts by weight, the fracture properties are degraded. Moreover, other additives may be compounded, if necessary. In the brass plating of the steel cord, it is preferable that the Cu content is not more than 75% by weight, more particularly 55-70% by weight in order to obtain a good and stable adhesion between steel cord and rubber. The following examples are given in illustration of the invention and are not intended as limitations thereof. Examples 1-12, Comparative Examples 1-5 Various rubber compositions are prepared in a conventional manner according to a compounding recipe shown in Table 1, and then the water content in unvulcanized rubber, the adhesiveness, and the thermal aging resistance of rubber after vulcanization are measured by the following methods to obtain results as shown in Table 1. On the other hand, natural rubber, synthetic rubber, carbon black, ZnO, antioxidant and sulfur are dried under vacuum before the compounding and then compounded with the inorganic salt hydrate according to the compounding recipe of Table 1 to prepare a rubber composition. The properties of the rubber composition are measured in the same manner to obtain results as shown in Table 1. (1) Measurement of water content The amount of water discharged when 1.0 g of the unvulcanized rubber is heated to 200°C is measured by Karl Fischer titration method. (2) Measurement of adhesiveness Brass plated steel cords (1x5 twisting structure, filament diameter: 0.25 mm, Cu:Zn in brass plating = 63:37) are arranged side by side at an interval of 12.5 mm and embedded in the rubber composition for coating to form a test sample. This sample is cured at 160°C for 20 minutes and then the steel cord is pulled out from the cured sample according to ASTM D-2229 to measure a pulling force for the evaluation of the adhesiveness. The adhesiveness is represented by an index on the basis that Comparative Example 1 is 100. The larger the index value, the better the adhesiveness. (3) Measurement of thermal aging resistance The rubber composition is vulcanized at 160°C for 20 minutes to form a vulcanized sample, which is aged at 100°C for 48 hours. Then, the aged sample is subjected to a tensile test according to JIS K-6301 to measure an elongation at breakage. The thermal aging resistance is represented by an index on the basis that the elongation value of Comparative Example 1 is 100. The larger the index value, the better the thermal aging resistance. As seen from Table 1, even when the starting materials are used at dry state, the lowering of water content in the unvulcanized rubber is controlled by incorporating the inorganic salt hydrate according to the invention into the rubber composition, whereby stable adhesiveness can be obtained while avoiding lowering of the adhesiveness. Examples 13 - 19, Comparative Examples 6-9 Various rubber compositions are prepared in a conventional manner according to a compounding recipe shown in Table 2, and then the adhesiveness and thermal aging resistance are measured by the same methods as in Example 1 to obtain results as shown in Table 2. The adhesiveness is represented by an index on the basis that Comparative Example 6 is 100. The larger the index value, the better the adhesiveness. The thermal aging resistance is represented by an index on the basis that the elongation value of Comparative Example 6 is 100. The larger the index value, the better the thermal aging resistance. As seen from Table 2, Comparative Example 7 is a case of mixing high-vinyl content polybutadiene with natural rubber, in which the thermal aging resistance is improved but the adhesion property is degraded as compared with the case of using only natural rubber. Comparative Example 8 is a case of mixing natural rubber with solution-polymerized SBR as a synthetic rubber. In this case, the thermal aging resistance is improved but the adhesion property is degraded as compared with the case of using only natural rubber. When Example 13 is compared with Comparative Example 7, the adhesion property is improved without degrading the thermal aging resistance owing to the presence of 1 part by weight of the inorganic salt hydrate. It is apparent from Tables 1 and 2 that the amount of the inorganic salt hydrate added is required to be within the range defined in the invention. As mentioned above, according to the invention, the water content in unvulcanized rubber can be raised by adding the inorganic salt hydrate to the rubber composition, whereby control of the water content becomes easy even in the dry winter season or a drying area and hence there can be developed an effect of obtaining stable adhesiveness to steel cords. Furthermore, the thermal aging resistance can be improved by using natural rubber together with particular synthetic rubber as the rubber ingredient. Therefore, when the steel cord-rubber composite treated with the rubber composition according to the invention is applied to a tire structural member, there can be obtained an effect of controlling the occurrence of separation failure at cord end or improving poor adhesiveness.

Claims: An adherent rubber composition for steel cord comprising 0.1-10 parts by weight of an inorganic salt hydrate and 3-8 parts by weight of sulfur based on 100 parts by weight of rubber ingredient comprised of at least one rubber selected from natural rubber and/or one or more synthetic rubbers, characterized in that the inorganic salt hydrate is selected from NiSO 4· .7H 2 O, CoSO 4 .7H 2 O, NaSO 4 .10H 2 O, CaSO 4 .2H 2 O, CuSO 4 .5H 2 O, Al 2 (SO 4 ) 3 .18H 2 O, FeSO 4 .7H 2 O, ZnSO 4 .7H 2 O, MgSO 4 .7H 2 O, Na 2 S.9H 2 O, Na 3 PO 4 .12H 2 O, NaH 2 PO 4 .12H 2 O, Na 2 HPO 4 .12H 2 O, Ni 3 (PO 4 ) 2 .8H 2 O, Mg 3 (PO 4 ) 2 .8H 2 O, Li 3 PO 4 .5H 2 O, Na 4 P 2 O 7 .10H 2 O, Ni 2 P 2 O 7 .6H 2 O, Mn 4 (P 2 O 7 ) 3 .14H 2 O, CoCO 3 .6H 2 O, NiCO 3 .6H 2 O, Na 2 CO 3 .10H 2 O, Nd 2 (CO 3 ) 3 .8H 2 O, Na 2 SO 3 .7H 2 O, CaCl 2 .6H 2 O, NiCl 2 .6H 2 O, FeCl 3 .6H 2 O, Na 2 SiO 3 .9H 2 O, and Na 2 P 2 O 5 .10H 2 O. A rubber composition as claimed in claim 1, characterized in that the rubber ingredient contains at least 50% by weight of natural rubber. A rubber composition as claimed in claim 1 or 2, characterized in that the synthetic rubber is selected from styrene-butadiene rubber, butadiene rubber, butyl rubber, halogenated butyl rubber, butyl rubber having paramethylstyrene group therein, isoprene rubber, and ethylene-propylene-diene rubber. A rubber composition as claimed in claim 3, characterized in that the styrene-butadiene rubber is a solution-polymerized styrene-butadiene rubber having a vinyl content of 35-85% by weight and a bound styrene content of not more than 30% by weight, and the butadiene rubber has a vinyl content of 1-85% by weight. A rubber composition as claimed in any of claims 1 to 4, characterized by further comprising one or more of 2-10 parts by weight of zinc white, 0.3-2 parts by weight of a vulcanization accelerator, 0.25-3 parts by weight of an adhesion promoter, and 30-70 parts by weight of carbon black, respectively based on 100 parts by weight of the rubber ingredient. A rubber composition as claimed in any of claims 1 to 5, characterized in that the amount of the inorganic salt hydrate is 0.2-8 parts by weight. A rubber composition as claimed in claim 6, characterized in that the amount of the inorganic salt hydrate is 0.3-3 parts by weight. A rubber composition as claimed in any of claims 1 to 7, characterized in that said rubber ingredient comprises not less than 10% by weight of at least one synthetic rubber and the remainder being natural rubber.

Inventors: FUJIKI KANJI, NAKANE SHINSUKE, FUJIKI, KANJI, NAKANE, SHINSUKE
Applicants: BRIDGESTONE CORP, BRIDGESTONE CORPORATION
Application year: 1996
Main classification: C08K3
IPC codes: C08K3, C08J5