Rubber composition, process for producing thereof and use thereof

Abstract: This invention describes a process for producing a rubber composition comprising (i) a total amount of 100 parts by weight of starting rubbers (A) and (B), including 30 to 90 parts by weight of the starting rubber (A) having a glass transition temperature (Tg) of -40 to 10°C and 10 to 40 parts by weight of the starting rubber (B) which is viscoelastically incompatible with the starting rubber (A) and has a Tg of at least 20°C lower than the Tg of the starting rubber (A) and (ii) 60 to 100 parts by weight of a reinforcing agent, wherein the starting rubber (A) and at least 80% by weight of the total weight of the reinforcing agent are mixed in a hermetic type mixer at 130°C to 200°C for at least 10 seconds, then the starting rubber (B) and the remaining reinforcing agent are added and mixed. This invention describes also a rubber composition and the use thereof for a tire tread.

Description: The present invention relates to a process for producing a rubber composition usable for a vehicle tire tread, and to a rubber composition obtainable by such a process. More specifically, it relates to a rubber composition for a vehicle tire tread which has a smaller change in the tanδ of the dynamic viscoelasticities at 0°C and 40°C, while maintaining the breaking strength thereof. A tire having a strong grip on the road surface is required for improving safety when driving a vehicle. The grip of a tire is closely related to the tanδ of the dynamic viscoelasticity. For example, as described in "Jidosha Gijutsu (Automobile Technology)", vol. 43, No. 3, p. 8 (1989), the grip on a wet road surface (i.e., "wet property") is considered to be correlated with the tanδ at about 0°C. However, this is in the case where the temperature of the water is near room temperature. For example, when the water temperature is 60°C, it is correlated with the tanδ at about 40°C. Further, the grip on a dry road surface is considered to be correlated on an average with a tanδ of from 0°C to 60°C. In this way, to get a tire to exhibit a stable grip in the face of ambient changes, it is required that the tanδ of a wide temperature range be high and stable. That is, it is desirable that the temperature gradient of the tanδ be small. In general, when the amount of a reinforcing agent such as carbon black or white carbon is increased, the temperature gradient of the tanδ becomes smaller, but this causes a rise in the viscosity of unvulcanized rubber and leads to problems such as a decline in the workability, a decline in the breaking strength of the vulcanized rubber, and a susceptibility to breakage, and hence is not desirable for a rubber for tire tread use. For the wet property, it is desirable to increase the tanδ at 0°C and reduce the tanδ at 40°C, that is, to increase the temperature gradient of the tanδ expressed by (tanδ at 0°C) ÷ (tanδ at 40°C) . In general, if the amount of a reinforcing agent such as carbon black or white carbon is decreased, the temperature gradient of the tanδ becomes larger, but this causes a decline in the breaking strength, hardness, etc. of the vulcanized rubber, so is not desirable for a rubber for tire tread use. Therefore, many techniques have been reported for improving the wet property at a low roll resistance. For example, Japanese Unexamined Patent Publication (Kokai) No. 61-218404 and Japanese Unexamined Patent Publication (Kokai) No. 4-325535 propose the use of white carbon and a specific carbon black for the reinforcing agent to be added to the rubber composition, Japanese Examined Patent Publication (Kokoku) No. 5-1298 proposes the use of a starting rubber with modified molecular terminals, and Japanese Unexamined Patent Publication (Kokai) No. 4-35654 proposes means for improvement from the aspect of the materials such as the addition of a dinitroso amine compound. Further, Japanese Unexamined Patent Publication (Kokai) No. 6-32941 proposes the means of improvement by tinkering with the mixing method. However, while these techniques give some effect of improvement, further improvement is desired to satisfy the performance requirements of a tire tread. Further, Rubber Chem. Technol., vol. 47, p. 48 (1974), vol. 50, p. 301 (1977), vol. 61, p. 609 (1988), and vol. 66, p. 276 (1993) report that the impact resilience changes depending on the combination of mixture of the master batch prepared by mixing the starting rubber with the carbon black in advance and the other starting rubber. However, these studies do not elucidate at all what is involved in the effect on the temperature gradient of the tanδ. Japanese Unexamined Patent Publication (Kokai) No. 6-200083 proposes the method of vulcanizing a formulation comprised of a starting rubber having a low glass transition temperature (Tg), then adding a high Tg starting rubber, but this has the defect that the viscosity of the rubber composition is increased, so there is a tendency for burning during the processing and, also, there is the limitation that the high Tg starting rubber must form a continuous (matrix) phase, therefore it is necessary to make the high Tg rubber content at least 50% by weight, which is disadvantageous for a low roll resistance. The rubber composition is reduced in the tanδ due to the kneading due to the promotion of the dispersion of the carbon black and the breakdown of the structure. Japanese Unexamined Patent Publication (Kokai) No. 55-104343 discloses a method of adding and mixing carbon black to 40 to 60% by weight of a starting rubber, then adding the remaining starting rubber, but since it is necessary to add a large amount of carbon black to a small amount of a starting rubber, the viscosity of the master batch becomes extremely high and there are problems in workability and also there is a limitation to a blend of BR and NR. As explained above, it was known that the tanδ of vulcanized rubber changes by changing the method of mixing a rubber composition, but in the past the research was mostly concerned with applying that effect to the reduction of the tanδ or the increase of the temperature dependency. No attempt had been made to apply it to the reduction of the temperature dependency of the tanδ. Accordingly, the objects of the present invention are to provide a process for producing a rubber composition for a tire tread which eliminates the problems in the prior art explained above and gives a small temperature dependency of the tanδ without impairing the breaking strength and to provide the rubber compositions obtained by the same. Another object of the present invention is to provide a process for preparing a rubber composition for a tire tread which eliminates the problems in the prior art explained above and gives an excellent wet property and low roll resistance without impairing the breaking strength and to provide rubber compositions obtained by the same. The present invention provides a process for producing a rubber composition as defined in claim 1, a rubber composition obtainable by such a process and the use thereof for a tire tread. The present invention will now be further illustrated with reference to the accompanying drawing of Fig. 1 which is a graph showing the relationship between the temperature of a rubber composition comprising two types of starting rubber in the case of a state of viscoelastic incompatibility and the logarithmic value of the tanδ. The present inventors found that by mixing three groups of the starting rubbers (A'), (B'), and (C') having specific Tgs and compatibilities and a reinforcing agent in a specific order, it is possible to increase the temperature dependence of the tanδ while maintaining the breaking strength. Further, there is the advantage that with this process, the rise in viscosity of the master batch during the mixing is small. Details will be explained below. It is known that when mixing in advance part of the starting rubber and carbon black and then adding the remaining starting rubber, the carbon black tends to be unevenly distributed in the starting rubber and the tanδ changes. The previously cited Rubber Chem. Technol., vol. 61, p. 276 (1993) describes the effects of the method of mixing on the impact resiliences of a large number of blends. This reference does not describe anything regarding the correlation with the Tg of the rubber blends, but the present inventors noted this on their own and found that when the impact resiliences described are converted to tanδ, the tanδ becomes lower when the carbon black was made to be unevenly distributed in the low Tg starting rubber rather than distributing it homogeneously in the high Tg and low Tg starting rubbers. However, there are differences in the magnitude of the effect depending on if part of the carbon black moves between blend phases in the process of mixing and the combination of the starting rubbers. No all-encompassing interpretation could be made of the state of the temperature gradient at 0°C and 40°C. Therefore, the inventors measured and studied the two Tgs and the viscoelastic compatibilities in systems comprising a large number of combinations of starting rubber and, as a result, found that the temperature gradient of tanδ at a certain degree of unevenness of distribution of the carbon black becomes larger the closer the Tg of the high Tg component to -20°C when two types of starting rubbers are viscoelastically incompatible and the two Tgs are separate from each other. Accordingly, the effect is greater when the Tgs of the two types of incompatible starting rubbers are as far apart from each other as possible. The difference must be at least 20°C, preferably at least 35°C. "Viscoelastically incompatible" as spoken of here means that, when measuring the temperature dependency of the viscoelasticity of the vulcanized rubber, the tanδ peaks exhibited by the two starting rubbers are observed to be separate. This is believed to occur when the starting rubbers in the rubber composition are not completely mixed together and are separate in layers or islands of a size of at least several tends of nanometers and are separate in Tg. More specifically, as shown in Fig. 1, it is learned that rubber stocks are viscoelastically incompatible when there are two points which are sharing a tangent on the temperature dependence curve of the tanδ when the measured values of the tanδ are expressed on a logarithmic scale with respect to the temperature axis. The present inventors measured the viscoelasticities at 0°C and 40°C and measured the unevenness of distribution of the carbon black obtained by the method of assaying the starting rubber stock composition in the bound rubber (carbon gel) of the unvulcanized rubber described in Rubber Chem. Technol., vol. 61, p. 609 (1988) and studied the relationship between the two in detail. As a result, they learned that, when looking at the effect of improvement of the temperature gradient of the tanδ expressed by (change in temperature gradient of tanδ) ÷ (change in unevenness of distribution of carbon black), with a Tg of the rubber stock of the high Tg component of less than -40°C, even if the carbon black is made to be distributed unevenly, there is almost no improvement in the temperature gradient of the tanδ, while when over -40°C, it gradually becomes smaller, when over -30°C it sharply becomes smaller, and when near - 10°C, becomes the best, but when over that once again becomes smaller. The reason why the effect of improvement of the temperature gradient of the tanδ becomes the best when the Tg of the rubber stock of the high Tg component is near -20°C is not clear, but it is believed that since in general the maximum point of the tanδ curve is at the side 10 to 20°C higher than the Tg of the starting rubber, when the maximum point of the tanδ is near the measurement point, that is, 0°C, the effect of improvement becomes greatest. When trying to improve the temperature dependency of the tanδ by causing uneven distribution of the carbon black, however, there are various problems in terms of industrial usage, as explained below, when just mechanically selecting two types of starting rubbers with different Tgs, mixing the low Tg starting rubber and the carbon black in the initial mixing process in advance, then adding the high Tg starting rubber in a later process, so this is not enough to obtain a rubber composition suited for a tire tread. One problem is that even when adding and mixing additional starting rubber to a master batch obtained by mixing a starting rubber and reinforcing agent in advance, the latter starting rubber will not disperse well. Since starting rubbers inherently are hard to mix with each other, they are viscoelastically incompatible, but since one of the starting rubbers is bonded with the filler and forms a partially three-dimensional structure, mixing becomes even harder. Therefore, even if steps such as increasing the mixing time are taken, the breaking strength and wear resistance of the vulcanized rubber drop. Accordingly, the present inventors discovered the possibility of avoiding this problem by mixing in advance into the starting rubber of the master batch a small amount of a starting rubber easy to mix with the starting rubber to be additionally added and not impairing the shape of the peak of the tanδ. However, it is probably a matter of experience what kind of starting rubber to select to enable both improvement of the temperature dependency of the tanδ and dispersion of the starting rubber (A'). It is possible to research the compatibility of two kinds of polymers using theoretical formulas to some extent, as for example described in Macromolecule, vol. 24, p. 4839 (1991), but this is insufficient. Further, it is extremely difficult to predict whether the viscoelastic incompatibilities can be held using three groups of starting rubbers (A'), (B'), and (C') as in the present invention. The present inventors mixed large numbers of starting rubbers with different Tgs and measured their viscoelasticities so as to study when those combinations were viscoelastically compatible and, as a result, found that if the starting rubber charged in the initial mixing process is the starting rubbers (B') and (C') and the starting rubber charged in the additional mixing process is the starting rubber (A'), selection from among the following four combinations is preferable for achieving the object of the present invention: 1) Starting rubber (A'): emulsion polymerized SBR having a styrene content of 30 to 50% by weight, preferably 35 to 45% by weight, and/or solution polymerized SBR having a 1,2-bond butadiene content in the butadiene component of not more than 70% by weight, preferably 10 to 70% by weight, and a styrene content of the value shown by the following formula (1') Styrene content > 40 - (1,2-bond butadiene content) ÷ 3 Starting rubber (B'): NR and/or IR Starting rubber (C'): emulsion polymerized SBR having a styrene content of not more than 50% by weight, preferably 35 to 45% by weight, and/or a solution polymerized SBR having a 1,2-bond butadiene content of not more than 70% by weight, preferably 10 to 70% by weight, and a styrene content of at least 15% by weight, preferably 20 to 40% by weight 2) Starting rubber (A'): BR having a 1,2-bond butadiene content of at least 65% by weight, preferably 65 to 85% by weight, and/or a solution polymerized SBR having a 1,2-bond butadiene content of at least 70% by weight, preferably 70 to 85% by weight, and a styrene content of not more than 30% by weight, preferably 5 to 20% by weight Starting rubber (B'): emulsion polymerized SBR having a styrene content of not more than 35% by weight, preferably 20 to 30% by weight, and/or solution polymerized SBR having a 1,2-bond butadiene content of not more than 40% by weight, preferably 5 to 20% by weight, and a styrene content of the value shown by the following formula (2') Styrene content < 40 - (1,2-bond butadiene content) ÷ 3 Starting rubber (C'): BR having a 1,2-bond butadiene content of at least 65%, preferably 65 to 85% by weight, solution polymerized SBR having a 1,2-bond butadiene content of at least 70% by weight, preferably 10 to 70% by weight, and a styrene content of not more than 30% by weight, preferably 5 to 20% by weight, and/or NR, and/or IR 3) Starting rubber (A'): BR having a 1,2-bond butadiene content of at least 65% by weight, preferably 64 to 85% by weight, emulsion polymerized SBR having a styrene content of 30 to 50% by weight, preferably 35 to 45% by weight, solution polymerized SBR having a 1,2-bond butadiene content of at least 70% by weight, preferably 70 to 85% by weight, and a styrene content of not more than 30% by weight, preferably 5 to 20% by weight, and/or solution polymerized SBR having a 1,2-bond butadiene content of not more than 70% by weight, preferably 10 to 70% by weight, and a styrene content of the value shown by the following formula (1') Styrene content > 40 - (1,2-bond butadiene content) ÷ 3 Starting rubber (B'): BR having a cis-1,4 bond butadiene content of at least 95% by weight, preferably 97 to 99% by weight, and/or a BR having a 1,2-bond butadiene content of 10 to 50% by weight, preferably 12 to 20% by weight Starting rubber (C'): BR having a 1,2-bond butadiene content of at least 65% by weight, preferably 65 to 85% by weight, emulsion polymerized SBR having a styrene content of not more than 50% by weight, preferably 35 to 45% by weight, solution polymerized SBR having a 1,2-bond butadiene content of at least 70% by weight, preferably 70 to 85% by weight, and a styrene content of not more than 30%, preferably 10 to 20% by weight, and/or solution polymerized SBR having a 1,2-bond butadiene content of not more than 70% by weight, preferably 10 to 70% by weight, and a styrene content of the value shown by the following formula (1'). Styrene content > 40 - (1,2-bond butadiene content) ÷ 3 4) Starting rubber (A'): BR having a 1,2-bond butadiene content of at least 65% by weight, preferably 65 to 85% by weight Starting rubber (B'): BR having a cis-1,4 bond butadiene content of at least 95% by weight, preferably 97 to 99% by weight, and/or BR having a 1,2-bond butadiene content of 10 to 50% by weight, preferably 12 to 20% by weight Starting rubber (C'): BR having a 1,2-bond butadiene content of at least 65% by weight, preferably 65 to 85% by weight, and/or NR, and/or IR. In all of these four preferable combinations, the following is essential: That is, the starting rubber (A') must have a Tg of -40°C to -15°C and be present in an amount of 10 to 40 parts by weight, preferably 15 to 30 parts by weight. When the Tg is less than -40°C, there is little effect of improvement of the temperature gradient of the tanδ, while when over -15°C, the rubber hardness near 0°C becomes higher and the rubber is not practical for a tire tread. When the amount of formulation is less than 10 parts by weight, there is a poor effect of improvement of the temperature gradient of the tanδ, while when over 40 parts by weight, the viscosity of the master batch becomes higher and the workability is poor. The starting rubber (B') must be viscoelastically incompatible with the starting rubber (A'), have a Tg at least 20°C, preferably 35 to 60°C, lower than the Tg of the starting rubber (A'), and be present in an amount of 30 to 85 parts by weight, preferably 50 to 75 parts by weight. When compatible with the starting rubber (A'), there is no uneven distribution of the reinforcing agent, while when the temperature difference of the Tg is smaller than 20°C, no effect of improvement of the temperature dependency of the tanδ can be expected. When less than 30 parts by weight, the workability becomes poor, while when over 85 parts by weight, the effect of improvement of the temperature dependency becomes poor. The starting rubber (C') must be viscoelastically compatible with the starting rubber (A'), be incompatible with the starting rubber (B'), have a Tg the same or less than the Tg of the starting rubber (A'), and be present in an amount of 5 to 30 parts by weight, preferably 5 to 10 parts by weight. When not compatible with the starting rubber (A') and incompatible with the starting rubber (B'), the dispersion of the rubber of the starting rubber (A') falls, while when the Tg is higher than the starting rubber (A') or the amount of formulation is less than 5 parts by weight, the dispersion of the rubber stock (A) falls. When over 30 parts by weight, the effect of improvement of the temperature gradient of the tanδ is reduced. Another problem in the case of premixing a low Tg starting rubber and carbon black and then mixing the high Tg starting rubber stock is that sometimes the carbon black partially moves to the high Tg component, that is, the starting rubber (A'), added later during the mixing, so there is insufficient unevenness of distribution. The effect of improvement of the temperature gradient of the tanδ at this time is reduced. The reason is sometimes that there is insufficient bonding between the carbon black and the molecules of the rubber stock in the initial mixing process and sometimes that the later added starting rubber has a higher affinity with the carbon black. As confirmed by the amount of the bound rubber produced, the bonds between the carbon black and the starting rubber molecules become stronger due to the heat of the mixing, so it is preferable to mix them at a high temperature. To bring out the effect of the present invention, the mixing is performed at 130°C to 200°C, preferably 150°C to 190°C. If the mixing temperature is less than 130°C, the bonding is insufficient, while when over 200°C, there is deterioration due to the heat, so the strength of the vulcanized rubber drops remarkably. By mixing by a hermetic type mixer, the temperature rises along with the mixing time and therefore the mixing temperature is not constant, but when a predetermined temperature is reached, the bonding between the starting rubber stock and the carbon black is completed in a short time of about 10 seconds. That is, as the initial mixing process, it is sufficient to hold the starting rubber (B') and the starting rubber (C') and reinforcing agent in the hermetic type mixer at the necessary temperature range for as little as 10 seconds. Then the starting rubber (A') and remaining reinforcing agent may be mixed by additionally charging them in the mixer after the initial mixing process or alternatively may be mixed in a hermetic mixer or open roll using a master batch obtained by discharging and cooling the initial mixture from the mixer. The affinity of the starting rubber with the reinforcing agent differs depending on the type of the starting rubber. For example, NR, IR, and BR have a higher affinity with a reinforcing agent than SBR due to the large number of double bonds in the molecules. The most effective is the introduction of a functional group called "terminal modification". "Terminal modification", as for example described in Japanese Unexamined Patent Publication (Kokai) No. 64-60604, is an operation for causing a reaction of the alkali metal or alkali earth metal of the synthesis terminals of the starting rubber molecules with a compound having a -CO-N < or -CS-N < bond such as N-methyl-2-pyrrolidone. The effect is greater the higher the rate of modification of the synthesis terminals. Use is usually made of a starting rubber with a rate of modification of at least 20%. The terminal modified starting rubber is believed to bond on a priority basis at the surface of the carbon black. Accordingly, when the affinity of the starting rubber (B') with the reinforcing agent is high, there is little fear of the reinforcing agent moving to the starting rubber (A') additionally added, but in the converse case, unless the temperature of the initial mixing process is raised to ensure sufficient achievement of a bound rubber, the effect of the present invention sometimes will not be sufficiently exhibited. In this way, the present invention becomes more effective by the use of a terminal modified rubber as the starting rubber (B'). The reinforcing agent is generally carbon black, but even when white carbon, a similar selection of starting rubbers and method of mixing as with carbon black may be used. In the case of white carbon (silica), however, generally joint use is made of a silane coupling agent. Such a formulation, however, requires that the white carbon be mixed together at the initial mixing process for improvement of the dispersion and wear resistance. The amount of the reinforcing agent is preferably 30 to 60 parts by weight. When the amount is less than 30 parts by weight, the temperature dependency of the tanδ becomes poorer, while conversely when over 60 parts by weight, the tanδ at 40°C becomes greater even with the process of the present invention and the roll resistance becomes poor. Further, when mixing the starting rubbers (B') and (C'), it is necessary to mix at least 80% of the total amount of the reinforcing agent. The larger the amount of the remaining reinforcing agent mixed in with the starting rubber (A'), the less the effect of improvement of the temperature gradient of the tanδ. The rubber composition of the present invention may have further blended into it in addition to the starting rubbers (A'), (B'), and (C') and the reinforcing agent, various types of additives which are generally mixed into rubber compositions for tires such as sulfur, a vulcanization accelerator, antioxidant, filler, softening agent, or plasticizer. The amounts and methods of mixture of these additives are not particularly limited and may be made the general amounts and methods. The present invention will be further explained in detail by the following Examples. Examples II-1 to II-16 1) Starting materials The following commercially available products were used in the following Examples. (1) Solution polymerized BR: Nippon Zeon Nipole BR1220, Tg = -102°C, cis-1,4 bond content = 98% (2) Solution polymerized BR: Asahi Chemical Industries Diene NF 35R, Tg = -90°C, 1,2-bond content = 13% (3) Natural rubber: TSR20, Tg = -73°C (4) Solution polymerized SBR: Asahi Chemical Industries Tufden 1000R, Tg = -72°C, styrene content = 18%, 1,2-bond content = 9% (5) Terminal modified solution polymerized SBR: Nippon Zeon Nipole NS114, Tg = -47°C, styrene content = 23%, 1,2-bond content = 37% (6) Solution polymerized SBR: Nippon Elastomer Sorprene 303, Tg = -33°C, styrene content = 47%, 1,2-bond content = 29% (7) Emulsion polymerized SBR: Nippon Zeon Nipole 9520, Tg = -32°C, styrene content = 38%, 1,2-bond content = 14%, oil extended product with 37.5 parts by weight of aromatic process oil added based upon 100 parts by weight of rubber stock (8) Terminal modified solution polymerized SBR: Nippon Zeon Nipole NS116, Tg = -30°C, styrene content = 21%, 1,2-bond content = 67% (9) Solution polymerized BR: Nippon Zeon Nipole BR1240, Tg = -30°C, 1,2-bond content = 70% (10) Carbon black, HAF (11) Zinc white no. 3 (12) Industrial stearic acid (13) N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (14) Microcrystalline wax (15) Aromatic process oil (16) 5% oil treated powdered sulfur (17) Diphenylguanidine (18) N-cyclohexyl-2-benzothiazylsulfenamide Note that the parts of the materials in Tables II-1 to II-5 are expressed as parts by weight. 2) Preparation of Rubber Composition The initial mixing process (first process) comprises mixing the starting rubber (B'), the starting rubber (C'), carbon black, zinc white, stearic acid, an antioxidant, wax, and process oil in a 1.8 liter hermetic type mixer for 3 to 5 minutes. The materials are charged into the hermetic type mixer at room temperature. When a predetermined temperature is reached due to the heat of the mixing, the result is discharged and kneaded by an 8 inch open roll to form a sheet-like master batch. The discharge temperature was controlled to 110°C only in Comparative Example II-5 and to 165°C in the other Examples. The additional mixing process (second process) comprises charging the master batch and the starting rubber (A') into a 1.8 liter hermetic type mixer, mixing them for 2 minutes, then discharging the result, adding sulfur and a vulcanization accelerator, and kneading using an 8 inch open roll to obtain a rubber composition. The discharge temperature was 115°C to 125°C. Note that when not using the starting rubber (A'), just the master batch is mixed again in the hermetic type mixer and kneaded by an open roll with the sulfur and vulcanization accelerator to make the rubber composition. 3) Measurement of Physical Properties of Vulcanized Rubber The rubber composition obtained was vulcanized in a 15 × 15 × 0.2 cm mold at 160°C for 20 minutes to prepare a rubber sheet. The breaking strength was measured based on JIS K6251 using a dumbbell shaped no. 3 piece. The value was expressed by MPa. The tanδ at 0°C and 40°C were measured using booklet shaped samples at 20 Hz and an elongation deformation mode of 10±2%. Table II-1 shows the results of use of (3) NR, (5) terminal modified solution polymerized SBR, and (8) terminal modified solution polymerized SBR for the starting rubbers. The (5) terminal modified solution polymerized SBR and (8) terminal modified solution polymerized SBR are compatible, while the (3) NR is incompatible with these two SBR. In Example II-4 (Example of Invention) and Example II-5 (Comparative Example), the starting rubber (A') corresponds to the (8) terminal modified solution polymerized SBR, the starting rubber (B) corresponds to the (3) NR, and the starting rubber (C) corresponds to the (5) terminal modified solution polymerized SBR. The temperature gradient of the tanδ of Example II-1 (Standard Example) where all of the starting rubbers (A'), (B'), and (C') were charged in the first process was 2.57, while in Example II-2 (Standard Example) where the NR was charged in the second process, the temperature gradient was somewhat improved to 2.66 due to the dispersion of the carbon black. Further, Example II-3 (Comparative Example) where the NR and carbon black were mixed in the first process, then two types of SBR were added in the second process was greatly improved in the temperature gradient to 3.00, but had the defect of a reduced breaking strength. On the other hand, Example II-4 (Example of Invention) of the present invention where 10 parts by weight of (4) solution polymerized SBR was mixed together with the (3) NR in the first process showed a recovery of the breaking strength while maintaining a large temperature gradient of the tanδ and exhibited rubber properties desirable for a tire tread. Further, when the temperature of the first process was dropped from 165°C to 110°C with the same formulation as in Example II-4 (Example of Invention), the temperature gradient became lower as seen in Example II-5 (Comparative Example). Table II-2 shows Examples of use of the (4) solution polymerized SBR and (9) solution polymerized BR. The (4) solution polymerized SBR and (9) solution polymerized BR are incompatible. In Example II-7 (Example of Invention), the starting rubber (A') corresponds to the (9) solution polymerized BR, the starting rubber (B') corresponds to the (4) solution polymerized SBR, and the starting rubber (C') corresponds to the (9) solution polymerized BR. The temperature gradient of the tanδ of the Example II-6 (Standard Example) is 1.73, while the temperature gradient of Example II-7 (Example of Invention) where 10 parts by weight of the (9) solution polymerized BR was added in the first process and 30 parts by weight was added in the second process was an improved 1.91. Ex. No. II-6 II-7 1st process (4) SBR 30 50 (9) BR 30 10 (10) carbon black 50 50 (11) zinc oxide 3 3 (12) stearic acid 1 1 (13) antioxidant 1 1 (14) wax 1 1 (15) oil 5 5 2nd process (4) SBR 20 - (9) BR 20 40 (16) sulfur 1.8 1.8 (18) vulcanization accelerator 1 1 Physical properties of vulcanized rubber Breaking strength (MPa) 17.2 17.4 tanδ 0°C (A) 0.319 0.321 tanδ 40°C (B) 0.184 0.168 Temperature gradient (A/B) 1.73 1.91 Table II-3 shows Examples of use of the (3) NR and (8) terminal modified solution polymerized SBR for the starting rubbers. The (3) NR and (8) terminal modified solution polymerized SBR are incompatible. In Example II-10 (Example of Invention), the starting rubber (A') corresponds to the (8) terminal modified solution polymerized SBR, the starting rubber (B') corresponds to the (3) NR, and the starting rubber (C') corresponds to the (8) terminal modified solution polymerized SBR. Since the percent compositions of the starting rubbers are made the same in the first process and the second process, the temperature gradient of the tanδ of Example II-8 (Comparative Example) where 21 parts by weight of (3) NR and 9 parts by weight of (8) terminal modified solution polymerized SBR are additionally charged in the second process was 3.35. On the other hand, the temperature gradient of Example II-9 (Comparative Example) where the same 30 parts by weight, but of a high Tg (8) terminal modified solution polymerized SBR was additionally charged in the second process was an improved 3.74, but the breaking strength fell. From this, it is easily learned that charging the starting rubbers divided into processes is not important and that the additional charging of the incompatible high Tg starting rubber in the second process improves the temperature gradient. Example II-10 (Example of Invention) aims at reduction of the breaking strength while maintaining the effect of improvement of the temperature gradient. By adding 5 parts by weight of (8) terminal modified solution polymerized SBR in the first process, the dispersion of the starting rubber added in the second process is improved and the breaking strength is improved over Example II-9 (Comparative Example). Further, the temperature gradient was 3.62 - higher than Example II-8 (Standard Example). Ex. No. II-8 II-9 II-10 1st process (3) NR 49 70 70 (8) SBR 21 5 (10) carbon black 40 40 40 (11) zinc oxide 3 3 3 (12) stearic acid 2 2 2 (13) antioxidant 2 2 2 (14) wax 1 1 1 (15) oil 5 5 5 2nd process (3) NR 21 - - (8) SBR 9 30 25 (16) sulfur 2.1 2.1 2.1 (17) vulcanization accelerator 0.5 0.5 0.5 (18) vulcanization accelerator 0.5 0.5 0.5 Physical properties of vulcanized rubber Breaking strength (MPa) 26.7 23.8 24.9 tanδ 0°C (A) 0.379 2 0.377 tanδ 40°C (B) 0.113 0.101 0.103 Temperature gradient (A/B) 3.35 3.74 3.62 Table II-4 shows examples of use of the (1) solution polymerized BR and (6) solution polymerized SBR for the starting rubbers. The (1) solution polymerized BR and (6) solution polymerized SBR are incompatible. In Example II-12 (Example of Invention), the starting rubber (A') corresponds to the (6) solution polymerized SBR, the starting rubber (B') corresponds to the (1) solution polymerized BR, and the starting rubber (C) corresponds to the (6) solution polymerized SBR. It is learned that in Example II-12 (Example of Invention) of the present invention, the temperature dependency of the tanδ is larger compared with Example II-11 (Comparative Example) where 25 parts by weight of the low Tg (1) solution polymerized BR is additionally charged in the second process. Ex. No. II-11 II-12 1st process (1) BR 45 70 (6) SBR 30 5 (10) carbon black 40 40 (11) zinc oxide 3 3 (12) stearic acid 2 2 (13) antioxidant 2 2 (14) wax 1 1 (15) oil 5 5 2nd process (1) BR 25 - (6) SBR - 25 (16) sulfur 2.1 2.1 (17) vulcanization accelerator 0.5 0.5 (18) vulcanization accelerator 0.5 0.5 Physical properties of vulcanized rubber Breaking strength (MPa) 19.2 19.1 tanδ 0°C (A) 0.343 0.338 tanδ 40°C (B) 0.138 0.134 Temperature gradient (A/B) 1.92 2.1 Table II-5 confirms the present invention by other starting rubbers. Compared with Example II-13 (Standard Example) where the incompatible (2) solution polymerized BR and (7) emulsion polymerized SBR are combined, Example II-14 (Example of Invention) was improved in the temperature gradient. Further, compared with Example II-15 (Standard Example) where the incompatible (2) solution polymerized BR and (9) solution polymerized BR are combined, Example II-16 (Example of Invention) was improved in temperature gradient. As clear from the results of Tables II-1 to II-5, the rubber compositions of the process of production of the present invention feature a large tanδ at 0°C and a low tanδ at 40°C while maintaining the breaking strength. By using them for a tire tread, durability during driving, a strong grip on a wet road surface, and a low roll resistance are obtained.

Claims: A process for producing a rubber composition comprising (i) a total amount of 100 parts by weight of starting rubbers (A'), (B'), and (C'), including 10 to 40 parts by weight of the starting rubber (A'), 30 to 85 parts by weight of the starting rubber (B') and 5 to 30 parts by weight of the starting rubber (C'), and (ii) 30 to 60 parts by weight of a reinforcing agent, comprising the steps of; mixing the starting rubbers (B') and (C') and at least 80% by weight of the total weight of the reinforcing agent in a hermetic type mixer at 150°C to 200°C for at least 10 seconds; and then adding thereto the starting rubber (A') and the remaining reinforcing agent, followed by mixing together,the starting rubber (A') having a glass transition temperature (Tg) of -40 to -15°C and being at least one rubber selected from the group consisting of (a) emulsion polymerized styrene-butadiene copolymers (SBR) having a styrene content of 30 to 50% by weight, (b) solution polymerized SBR having a 1,2-bond butadiene content in the butadiene component of not more than 70% by weight and a styrene content of the value shown by the following formula (1'): Styrene content > 40 - (1.2-bond butadiene content) ÷ 3 (c) polybutadiene rubbers (BR) having a 1,2-bond butadiene content of at least 65% by weight, and (d) solution polymerized SBR having a 1,2-bond butadiene content of at least 70% by weight and a styrene content of not more than 30% by weight, the starting rubber (B') being viscoelastically incompatible with the starting rubber (A'), having a Tg of at least 20°C lower than the Tg of the starting rubber (A'), and being at least one rubber selected from the group consisting of (a) natural rubbers (NR), (b) polyisoprene rubbers (IR), (c) emulsion polymerized SBR having a styrene content of not more than 35% by weight, (d) solution polymerized SBR having a 1.2-bond butadiene content of not more than 40% by weight and a styrene content having the value shown by the following formula (2'): Styrene content < 40 - (1.2-bond butadiene content) ÷ 3 (e) BR having a cis-1,4 bond butadiene content of at least 95% by weight and (f) BR having a 1.2-bond butadiene content of 10 to 50% by weight; and the starting rubber (C') being viscoelastically compatible with the starting rubber (A'), incompatible with the starting rubber (B'), having a Tg equal to or less than the Tg of the starting rubber (A'), and being at least one rubber selected from the group consisting of (a) emulsion polymerized SBR having a styrene content of not more than 50% by weight, (b) a solution polymerized SBR having a 1.2-bond butadiene content of not more than 70% by weight and a styrene content of at least 15% by weight, (c) BR having a 1.2-bond butadiene content of at least 65%, (d) solution polymerized SBR having a 1.2-bond butadiene content of at least 70% by weight and a styrene content of not more than 30% by weight, (e) NR, (f) IR, and (g) solution polymerized SBR having a 1.2-bond butadiene content of not more than 70% by weight and a styrene content of the value shown by the following formula (1'): Styrene content > 40 - (1.2-bond butadiene content) ÷ 3 A rubber composition obtainable by the process according to claim 1. A rubber composition as claimed in claim 2 wherein at least one rubber selected from the group consisting of solution polymerized rubbers obtainable by reacting at least 29% by weight of the alkali metal or alkali earth metal of the synthesis terminals in the rubber molecules with a terminal modifying compound having a -CO-N< or -CS-N< bond in its molecule is used for at least part of the starting rubber (B'). Use of a rubber composition as defined in claim 2 or 3 for a tire tread.

Inventors: KAIDOU HIROYUKI, KAWAZURA TETSUJI, KAIDOU, HIROYUKI, KAWAZURA, TETSUJI, Kaidou, Hiroyuki c/o the Yokohama Rubber Co., Ltd., Kawazura, Tetsuji c/o the Yokohama Rubber Co., Ltd
Applicants: YOKOHAMA RUBBER CO LTD, THE YOKOHAMA RUBBER CO., LTD.
Application year: 1995
Main classification: C08L21
IPC codes: B60C1, C08J3, C08L21