• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    rubber tread tire containing a combination of resin and vegetable oil, especially soybean oil this invention relates to a tire with a rubber tread composition on the circumference consisting of a silica reinforced rubber composition containing polymers at the circumference based on dienes in combination with traction-resistant resin (s) and vegetable oil, especially soybean oil.
    公开号:BR102013028847B1
    申请号:R102013028847
    申请日:2013-11-08
    公开日:2020-04-07
    发明作者:Ramanathan Ahalya；Harry Sandstrom Paul；Rodewald Stephan
    申请人:Goodyear Tire & Rubber；
    IPC主号:
    专利说明:

    “RUBBER AND TIRE COMPOSITION CONTAINING A COMPONENT”
    Field of the invention [001] This invention relates to a tire with a tread composition on the circumference consisting of a rubber composition reinforced with silica, containing diene-based polymers in combination with resin (s) resistant to traction and vegetable oil, especially soybean oil.
    Background of the Invention [002] Pneumatic rubber tires are often used for purposes where traction, (for example, tire tread skid resistance on dry or wet road surfaces) is a significant consideration.
    [003] Therefore, it is necessary that the rubber compositions have good adhesion, or traction, but also offer good rolling resistance for fuel economy and good tread wear, or abrasion resistance, to extend the tire life.
    [004] The use of various traction resins has been suggested to improve the dry and wet traction of such tread compositions, such as, for example, coumarone-indene resins, alkylated hydrocarbon resins, aromatic petroleum resins , dicyclopentadiene resins and styrene-alpha-methylstyrene resins. For example, and among others, see U.S. Patent Nos. 6 525 133, 6 242 523, 6 221 953 and 5 901 766.
    [005] However, such traction resins when used in tire rubber tread compositions also tend to increase tread wear (reduce abrasion resistance) in exchange for performance. It has been found that the use of such resins in tread compositions, which also contain silica as a reinforcing filler and soy oil as a processing aid, provides the desired improvement in traction with
    Petition 870200002393, of 06/01/2020, p. 10/33
    2/21 significantly better resistance to abrasion, which predicts better performance (reduced) to tread wear and, consequently, extended tire life. In one embodiment, it is desirable to use functionalized polymers, namely elastomers containing functional groups reactive with hydroxyl groups contained in the precipitated silica, for this approach, especially a polymerization with a functionalized solution prepared with styrene / butadiene rubber (S-SBR).
    [006] In practice, a choice of resin for a tire tread rubber composition may depend on its softening point to increase the traction of a tire rubber tread at an ideal operating temperature for the tire tread. tire running. For example, a resin with a softening point of approximately 30 ° C would be expected to soften and become significantly hysteretic at a temperature in the tire tread in a range of approximately 20 ° C to approximately 50 ° C and through addition, it helps to provide traction to the tread for a tread in such a temperature range. A resin with a significantly higher softening point might be desirable for a tire tread designed to operate at a significantly higher temperature (for example, at least 100 ° C).
    [007] Consequently, the aim is to assess whether the addition of a combination of triglyceride-based vegetable oils (eg soy oil), instead of petroleum-based oils, together with one or more traction resins could be used in rubber compositions reinforced with silica, containing diene based elastomers, especially functionalized elastomers containing one or more functional groups reactive with hydroxyl groups contained in said precipitated silica (to increase rolling resistance and tread wear performance ), especially for
    Petition 870200002393, of 06/01/2020, p. 11/33
    3/21 tire treads in contact with roads to enhance dry and wet traction, while minimizing changes in rolling resistance and tread wear performance.
    [008] For such an assessment, it is important to recognize that various vegetable oils, including soybean oil, differ significantly from petroleum based oils, especially when such vegetable oils are triglycerides that contain a significant degree of unsaturation and clearly not an oil based of linear or aromatic oil.
    [009] Triglycerides or vegetable oils include, for example, soybean oil, sunflower oil and canola oil which are in the form of esters containing a certain degree of unsaturation.
    [0010] For information purposes and to illustrate the precedent in terms of relative contents of saturated, monounsaturated and polyunsaturated of various vegetable oils, Table A is provided below.
    Table A Percentage Percentage Percentage Vegetable oil Saturated Monounsaturated Polyunsaturated
    Soy 16 23 58 Sunflower 10 45 40 Canola (Rapeseed) 7 63 28 Corn 13 28 55 Coconut 87 6 2 Cotton seed 26 18 52 Olive 14 73 11 Palm 49 37 9 Peanut 17 46 32 Safflower 10 45 40
    Petition 870200002393, of 06/01/2020, p. 12/33
    4/21 [0011] Therefore, these vegetable oils, such as, for example, soybean oil, contain a significant content of unsaturation that is not present in petroleum-based rubber processing oils.
    [0012] The challenge of combining such vegetable oils (eg soy oil) with diene-based polymers and tensile and silica resins as the reinforcing filler in an internal rubber mixer (eg Banbury ™ mixer) should face be evaluated with unknown results until the evaluation is undertaken.
    [0013] In describing this invention, the term "combined" rubber compositions and the term "compounds", when used, refer to rubber compositions that have been combined, or mixed, with component ingredients suitable for rubber. The terms "rubber", "polymer" and "elastomer" may be used interchangeably, unless otherwise indicated. The quantities of materials are generally expressed in parts of material per 100 parts of rubber by weight (phr).
    Summary and practice of the invention [0014] According to this invention, there is provided a rubber composition consisting of, based on parts by weight per 100 parts by weight of elastomer (phr):
    (A) at least one diene-based conjugated elastomer, desirably including a diene-conjugated elastomer containing one or more functional groups reactive with hydroxyl groups contained in precipitated silica, and (B) approximately 5 to approximately 60, alternately approximately 10 to approximately 40 phr of at least one vegetable oil based on triglycerides (eg soy oil) and (C) approximately 1 to approximately 30, alternately
    Petition 870200002393, of 06/01/2020, p. 13/33
    5/21 approximately 2 to approximately 20 phr of resin consisting of at least one of coumarone-indene resins, alkylated hydrocarbon resins, aromatic petroleum resins, dicyclopentadiene resins and styrene-alpha-methylstyrene resins, and (D) approximately 30 to approximately 140, alternately from approximately 50 to approximately 120 phr of reinforcing charge consisting of:
    (1) precipitated silica or (2) a combination of rubber reinforcing carbon black and precipitated silica (containing, for example, approximately 20 to approximately 90 weight percent of precipitated silica, alternately approximately 55 to approximately 90 percent by weight of precipitated silica for a reinforcing filler rich in silica) and (E) silica coupling agent reactive with hydroxyl groups (eg silanol groups) in said precipitated silica and another different interactive group with carbon-carbon double bonds from said conjugated elastomers based on diene;
    wherein said rubber composition is free of oil-extended elastomer (elastomer containing petroleum-based oil or vegetable oil, including soybean oil, added during the manufacture of the elastomer).
    [0015] In a first embodiment, said resin is made up of one of said resins.
    [0016] In a second embodiment, said resins are constituted by two of said resins, the same or different, whose individual softening or melting points are spaced apart by at least 20 ° C.
    [0017] In a third embodiment, said resins consist of three of said resins, whose individual softening points are spaced apart by at least 20 ° C.
    Petition 870200002393, of 06/01/2020, p. 14/33
    6/21 [0018] In one aspect, the softening point of said coumarone-indene resin is in a range of approximately 20 to approximately 140 ° C.
    [0019] In another aspect, the softening point of said alkylated hydrocarbon resin is in a range of approximately 40 to approximately 140 ° C.
    Representatives of such alkylated hydrocarbon resins are, for example, and among others, butene copolymers and other alpha-olefin comonomers.
    [0021] In yet another aspect, the softening point of said aromatic petroleum resin is in a range of approximately 40 to approximately 160 ° C.
    [0022] In an additional aspect, the softening point of said dicyclopentadiene resin is in a range of approximately 40 to approximately 140 ° C.
    [0023] In yet another aspect, the softening point of said styrene-alpha-methylstyrene resin is in a range of approximately 65 to approximately 95 ° C.
    Representatives of such vegetable triglyceride oils mentioned above are, for example, at least one among soybean, sunflower, canola (rapeseed), corn, coconut, cottonseed, olive, palm, peanut and safflower oils. Generally, at least one among soy, sunflower, canola and corn oils, and especially soy, is desired.
    [0025] In one embodiment, said vegetable oils based on triglycerides are composed of a mixture of natural triglycerides recovered from, for example, soybeans, composed of at least one, usually at least three tri-esters of glycerol of at least one e, normal
    Petition 870200002393, of 06/01/2020, p. 15/33
    7/21 at least three unsaturated fatty acids. Such fatty acids are typically comprised primarily, for example, of at least one of linolenic acid, linoleic acid and oleic acid. For example, such a combination of unsaturated fatty acids can consist of a mixture of:
    [0026] In the case of soybean oil, for example, the percentage distribution shown above, or combination, of the fatty acids for the glycerol triesters, namely triglycerides, is indicated as an average value and may vary slightly depending on type, or the origin of the soybean crop, and may also depend on the conditions of cultivation of a particular soybean crop from which the soybean oil was obtained. There are also significant amounts of other saturated fatty acids typically present, although these do not normally exceed 20 percent of soy oil.
    [0027] In a preferred embodiment, the functionalized elastomer based on diene can be a functionalized elastomer containing, for example, at least one functional group formed by at least one among amine, siloxy, carboxyl and hydroxyl groups, especially hydroxyl groups reactive with hydroxyl groups (eg silonol groups) contained in precipitated silica.
    [0028] In one embodiment, at least one of the aforementioned elastomers
    Petition 870200002393, of 06/01/2020, p. 16/33
    8/21 The diene base can be an elastomer coupled with tin or coupled with silicon, specially coupled with tin (for example, styrene / butadiene elastomer). Such coupled elastomer can, for example, be used to promote a beneficial improvement (reduction) in rolling wear and a beneficial reduction in tire rolling resistance when used in tire tread rubber compositions. Such a tin-coupled styrene-butadiene elastomer can be prepared, for example, by coupling the elastomer with a tin coupling agent at the end or near the end of the polymerization used to synthesize the elastomer. In the coupling process, the live ends of the polymer chains react with the tin coupling agent, thereby coupling the elastomer. For example, up to four chain ends of the living polymer react with tin tetrahalides, such as tin tetrachloride, thereby coupling the polymer chains.
    [0029] The coupling efficiency of the tin coupling agent is dependent on many factors, such as the number of live chain ends available for the coupling and the amount and type of polar modifier, if present, employed in the polymerization. For example, tin coupling agents are generally not as effective in the presence of polar modifiers. However, polar modifiers, such as tetramethyl ethylenediamine, are often used to increase the glass transition temperature of rubber in order to improve properties, such as improved traction characteristics in tire tread compounds. Coupling reactions that are carried out in the presence of polar modifiers typically have coupling efficiency of approximately 50 to 60 percent in batch processes.
    [0030] In cases in which the tin-coupled elastomer will be used
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    9/21 used in rubber compositions that are loaded primarily with carbon black reinforcement, the coupling agent for preparing the elastomer can typically be a tin halide. The tin halide will normally be a tin tetrahalide, such as tin tetrachloride, tin tetrabromide, tin tetrafluoride or tin tetraiodide. However, monoalkyl-tin trihalides can also optionally be used. Polymers coupled with monoalkyl-tin trihalides have a maximum of three arms. This, of course, in contrast to elastomers coupled with tin tetrahalides that have a maximum of four arms. To induce a higher level of branching, tin tetrahalides are usually preferred. Tin tetrachloride is generally the most preferred.
    [0031] In cases in which the coupled elastomer will be used in compounds loaded with high levels of silica, the coupling agent to prepare the elastomer may, if desired, be a silicon halide. The silicon coupling agents that can be used will normally be silicon tetrahalides, such as silicon tetrachloride, silicon tetrabromide, silicon tetrafluoride or silicon tetraiodide. However, monoalkylsilicon trihalides can also optionally be used. Elastomers coupled with silicon trihalides have a maximum of three arms. This, of course, in contrast to elastomers coupled with silicon tetrahalides during production, which have a maximum of four arms. To induce a higher level of branching, if desired, of the elastomer during its production, silicon tetrahalides are usually preferred. In general, silicon tetrachloride is usually the most desirable of the silicon coupling agents for this purpose.
    [0032] Representative examples of various diene-based elastomers are, for example, at least one of the 1,4-polyisoprene elastomers, cis 1,4
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    10/21 polybutadiene, isoprene / butadiene, styrene / isoprene, styrene / butadiene and styrene / isoprene / butadiene. Additional examples of elastomers that can be used include 3,4-polyisoprene rubber, carboxylated rubber, silicon-coupled and tin-coupled elastomers with star-like branches. Often, the desired rubber or elastomers are 1,4-polybutadiene cis rubber, styrene / butadiene rubber and 1,4-polyisoprene cis rubber.
    [0033] Such precipitated silicas can be, for example, characterized by having a surface area by the BET method, as measured using nitrogen gas, in the range of, for example, approximately 40 to approximately 600 and, more commonly, in a range of approximately 50 to approximately 300 square meters per gram. The BET method of measuring the surface area could be described, for example, in the Journal of the American Chemical Society, Volume 60, as well as in ASTM D3037.
    [0034] Such precipitated silicas can also, for example, be characterized by having a dibutyl phthalate (DBP) absorption value, for example, in a range of approximately 100 to approximately 400 and, more commonly, from 150 to approximately 300 cc / 100 g.
    [0035] Conventional precipitated silica could be expected to have an average final particle size, for example, in the range of 0.01 to 0.05 microns as determined by the electron microscope, although the silica particles may be even smaller, or possibly larger in size.
    [0036] Various commercially available precipitated silicas can be used, such as, only as an example in this specification, among others, silicas from PPG Industries under the trade name Hi-Sil with designations 210, 243, etc .; Rhodia silicas with, for example, the designations Z1165MP and Z165GR, Evonic silicas with, for example, the designations VN2
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    11/21 and VN3 and chemically treated precipitated silicas such as, for example, PPG's Agilon ™ 400.
    [0037] Representative examples of rubber reinforcing carbon blacks are, for example, among others, those with the ASTM designations of N110, N121, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 and N991. Such rubber reinforcing carbon blacks can have iodine absorptions ranging from, for example, 9 to 145 g / kg and DBP numbers ranging from 34 to 150 cc / 100 g.
    [0038] Other fillers can be used in the composition of vulcanizable rubber, including, among others, fillers of particles including ultra high molecular weight polyethylene (UHMWPE); particulate polymer gels such as those described in US Patent Nos. 6,242,534, 6,207,757, 6,136,364, 6,372,857, 5,395,891 or 6,127,488, and plasticized composite starch filler such as that described in US Patent No. 5672 639. One or more other fillers may be used in an amount ranging from about 1 to about 20 phr.
    [0039] It may be desired that the precipitated silica-containing rubber composition contains a silica coupling agent for silica, consisting, for example, of:
    (A) bis (3-trialkoxy-silyl-alkyl) polysulfide containing, on average, a range of approximately 2 to approximately 4 sulfur atoms in its interconnecting bridge, or (B) an organoalkoxyercaptosilane, or (C) the combination of both.
    A representative of such a bis (3-trialoxy-silyl-alkyl) polysulfide consists of bis (3-triethoxy-silyl-propyl) polysulfide.
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    12/21 [0040] It is readily understood by those skilled in the art that the vulcanizable rubber composition will be combined by methods generally known in the art for rubber composition, such as, for example, mixing several additional elastomers capable of being vulcanised with sulfur with the rubber composition containing said diene-based elastomer and various commonly used additive materials such as, for example, sulfur curing agent and sulfur donors, sulfur curing agents for vulcanization, such as activators and retardants and additives of the processing, resins including resins and plasticizers that promote stickiness, fillers such as reinforcing fillers of rubber, pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozones and peptizing agents. As is known to those skilled in the art, depending on the intended use of the sulfur-cured and sulfur-cured material (rubbers), the additives mentioned above are selected and commonly used in conventional amounts. Representative examples of sulfur donors include elemental sulfur (free sulfur), amine disulfide, polymeric polysulfide and olefinic sulfur adducts. In general, it is desired that the sulfur-curing agent is elemental sulfur. The sulfur-curing agent can be used in an amount ranging, for example, from approximately 0.5 to 8 phr, with a range of 1.5 to 6 phr being often preferred. Typical amounts of tackiness-promoting resins, if used, may comprise, for example, approximately 0.5 to approximately 10 phr, usually approximately 1 to approximately 5 phr. Typical amounts of processing aids comprise approximately 1 to approximately 50 phr. Additional petroleum-based oils for the rubber process, if desired, can be added at very low levels during mixing of the rubber composition, in addition to vegetable triglyceride oil (s), especially soybean oil, as the major processing oil (for example,
    Petition 870200002393, of 06/01/2020, p. 21/33
    13/21 less than 50 percent of the combination of petroleum or vegetable and rubber processing oils). Additional petroleum-based oils or derivatives for rubber processing may include, for example, aromatic, paraffinic, naphthenic and low PCA oils such as MEW, TDAE, and heavy naphthenic oils, although low PCA may be preferred. Typical amounts of antioxidants can comprise, for example, approximately 1 to approximately 5 phr. Representative antioxidants can be, for example, diphenyl-p-phenylenediamine and others, such as, for example, those described in the Vanderbilt Rubber Handbook (1978), pages 344 to 346. Typical amounts of antiozonants can comprise, for example, approximately 1 at 5 phr. Typical amounts of fatty acids, if used, which may include stearic acid, comprise approximately 0.5 to approximately 3 phr. Typical amounts of zinc oxide may comprise, for example, approximately 2 to approximately 5 phr. Typical amounts of waxes comprise approximately 1 to approximately 5 phr. Microcrystalline waxes are often used. Typical amounts of peptizers, when used, can be used, for example, from approximately 0.1 to approximately 1 phr. Typical peptides can be, for example, pentachlorothiophenol and dibenzamidodiphenyl disulfide.
    [0041] Sulfur vulcanization accelerators are used to control the necessary time and / or temperature for vulcanization and to improve the properties of the vulcanized product. In one embodiment, a single accelerator system can be used, that is, a primary accelerator. The primary accelerator (s) can be used in total amounts ranging, for example, from approximately 0.5 to approximately 4, sometimes desirably from approximately 0.8 to approximately 1 , 5 phr. In another modality, combinations of a primary and a secondary accelerator could be used, with the secondary accelerator being used in smaller quantities, such as
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    14/21, for example, from approximately 0.05 to approximately 3 phr, in order to activate and improve the properties of the vulcanized product. A synergistic effect produced by combinations of these accelerators could be expected on the final properties, and they are slightly better than those produced by using any of the accelerators alone. In addition, delayed action accelerators can be used that are not affected by normal processing temperatures, but that produce satisfactory curing at common vulcanization temperatures. Vulcanization retarders could also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thiourea, thiazoles, thiouramas, sulfenamides, dithiocarbamates and xanthates. Often, the primary accelerator is desirably a sulfenamide. If a second accelerator is used, the secondary accelerator is often desirably a guanidine, for example, a diphenylguanidine, dithiocarbamate or thiourama compound.
    [0042] The mixing of the vulcanizable rubber composition can be carried out by methods known to those skilled in the art relating to the rubber mixing technique. For example, ingredients are typically mixed in at least two stages, namely, at least one non-productive stage followed by a productive mixing stage. Final curing agents, including sulfur vulcanizing agents, are typically mixed in the final stage, which is conventionally called the productive mixing stage, in which mixing typically occurs at a temperature, or final temperature, that is lower than (s) mixing temperature (s) of the preceding non-productive mixing stage (s). The terms “non-productive” and productive mixing stages are well known to those skilled in the art regarding the rubber mixing technique. The rubber composition can be subjected to a step
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    15/21 thermomechanical mixture. The thermomechanical mixing step generally comprises working in a mixer or extruder for an appropriate period of time to produce a temperature in the rubber between 140 ° C and 190 ° C. The appropriate duration of thermomechanical work varies depending on the operating conditions and the volume and nature of the components. For example, thermomechanical work can be from 1 to 20 minutes.
    [0043] The vulcanizable rubber composition containing the SSBR extended with triglyceride oil can be incorporated into a variety and rubber components of an article of manufacture such as, for example, a tire. For example, the rubber component for the tire is a tread.
    [0044] The pneumatic tire of the present invention can be a racing tire, passenger transport tire, aircraft tire, agricultural tractor tire, earthmoving tire, off-road truck and the like. Usually, the desirable tire is a passenger or truck tire. The tire can also be a radial or diagonal bend tire, a radial bend tire is usually desired.
    [0045] The vulcanization of the pneumatic tire of the present invention is generally carried out at conventional temperatures in a range, for example, approximately 140 ° C to 200 ° C. Often, it is desired that the vulcanization be carried out at temperatures ranging from approximately 150 ° C to 180 ° C. Any of the usual vulcanization processes can be used, such as press or mold heating, heating with superheated steam or hot air. Such tires can be built, configured, molded and cured by various methods, which are known and will be readily apparent to those skilled in the art.
    [0046] The following examples are presented for the purpose of illustrating and not to limit the present invention. All parts and percentages
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    16/21 are parts by weight, usually parts by weight per 100 parts by weight of rubber (phr) unless otherwise indicated.
    EXAMPLE I [0047] In this example, the effect of using a triglyceride oil, namely soy oil, as a substitute for petroleum-based processing oil, was investigated. For this Example, the rubber compositions evaluated were a 70/30 mixture of styrene / butadiene rubber (S-SBR), prepared from a solution functionalized by polymerization, and rubber with a high content of cis-polybutadiene (PBD) with the addition of a traction resin to improve the traction imparted, especially wet traction, as well as soy oil. Elastomers extended with oil were not used.
    [0048] The rubber samples were prepared by mixing the elastomers with silica as the main reinforcing filler. For such preparation, ingredients, in addition to sulfur curing agents and sulfur accelerator, were mixed in a first stage of non-productive mixing (NP1) in an internal rubber mixer for approximately 4 minutes at a temperature of approximately 160 ° C . The resulting mixture was subsequently mixed in a sequential second stage of non-productive mixture (NP2) in an internal rubber mixer at a temperature of approximately 160 ° C without any additional ingredients added. The rubber composition was subsequently mixed in a productive mixing (P) stage in an internal sulfur-filled rubber mixer for curing, namely sulfur and sulfur curing accelerator (s), for approximately 2 minutes at a temperature approximately 115 ° C. The rubber composition is removed from its internal mixer after each mixing stage and cooled to below 40 ° C between each individual non-productive mixing stage and before the final productive mixing stage.
    [0049] The basic formulation for Sample A of Control rubber and
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    17/21
    Experimental rubber samples are shown in Table 1 below, expressed as parts by weight per 100 parts of rubber (phr) unless otherwise indicated.
    Table 1
    Non-productive mixing stage (NP1) Parts by weight (phr) Styrene / butadiene rubber (S-SBR) 1 70 or 50 1,4-Polybutadiene cis rubber (PBD) 2 30 or 50 Precipitated silica 3 65 Silica coupler 4 5 Carbon Black 5 4 Wax 1.5 Zinc oxide 3.5 Fatty acid 6 2 Process oil, derived from petroleum (naphtha- 12 or 20 nico) 7 Soy oil 8 12 or 20 Traction resin 9 0 or 15 Production mixing stage (P)Sulfur 1.7 Sulfur curing accelerator (s) 10 3.1 Antioxidant 3
    1 Styrene / butadiene rubber, polymerization solution prepared from copolymer functionalized as SLR 4602 by Styron, understood to be a styrene / butadiene elastomer coupled with tin, containing siloxy functional groups at the ends, reactive with precipitated silica hydroxyl groups .
    2 Cis-polybutadiene rubber like BUD1207 from Goodyear Tire & Rubber Company
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    18/21 3 Silica precipitated as Zeosil Z1165 MP from Rhodia Company 4 Silica coupler as Si266 ™ from Evonic Company, consisting of bis (3-triethoxy-silyl-propyl) polysulfide containing on average approximately 2 to approximately 2.4 atoms of interconnecting sulfur in its polysulfidic bridge 5 Carbon black N550 rubber reinforcing, ASTM identification 6 Consisting primarily of stearic, palmitic and oleic acids 7Petroleum based oil for rubber processing like Naprex 38 from ExxonMobil Company 8 Soy oil like Sterling Oil from Stratas Foods Company
    9 Tensile resin as styrene / alpha-methylstyrene resin as Resin 2336 ™ by Eastman Chemical Company 10 Sulfenamide and diphenylguanidine accelerators [0050] Table 2 below illustrates the curing behavior and various physical properties of rubber compositions based on the recipe basic of Table 1. When cured rubber samples are examined, such as for stress-strain, hot rebound and hardness values, the rubber samples were cured for approximately 14 minutes at a temperature of approximately 160 ° Ç.
    Table 2
    Rubber samples
    Parts (phr)
    ----THE
    S-SBR70
    PBD30
    Petroleum processing oil
    Soybean oil0
    Traction resin0
    Wet traction indication (for
    B Ç D AND F 70 70 50 50 50 30 30 50 50 50 12 0 20 12 0 0 12 0 0 12 15 15 0 15 15
    rolling band surface
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    19/21 shooting) - Lower is better
    Cold rebound value (0 ° C) 24.3 13.4 14.4 36.1 25.7 26.3
    Abrasion resistance (Wear resistance indicator) - Lower is better
    Grosch abrasion rate 1 (mg / km) high accuracy (70 N), 16 ° slip angle, disc speed = 20 km / h, distance
    tance = 500 mRoll resistance indication ^ 487 then (Hi 527sterese) 489 475 492 476 Hot rebound value (100 66 64 63 62 60 58 ° C) (higher is better) Tan delta (100 ° C), 10% tension are, 11 Hz (lower is better) 0.065 0.076 0.082 0.074 0.079 0.08 Shear strength 295 ° (N) (higher is better) 71 84 104 84 98 107
    1 The Grosch abrasion rate was determined on a LAT100 abrasion tester and measured in terms of mg / km of abrasive rubber removed. The rubber sample under test is placed at a slip angle under constant load (Newtons) as it travels a certain distance on a rotating abrasive wheel (wheel from HB Schleifmittel GmbH). A high rigor test was conducted at a load of 70 Newtons, with a sliding angle of 12 degrees and a disk speed of 20 km / h and a sample distance of 25 meters.
    2 Data obtained according to a shear strength test (adhesiveness) to determine the interfacial adhesion between two samples of a rubber composition. Specifically, such interfacial adhesion is determined by pulling and pulling one rubber composition away from the other at right angles to the unbroken test specimen, with the two ends of the rubber compositions being pulled and spaced 180 ° away from each other using an Instron at 95 ° C and reported in Newtons of force.
    [0051] Samples A and B of rubber are Rubber Samples of
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    20/21
    Control containing a mixture of 70 phr of functionalized S-SBR with 30 phr of cis-PBD (for Rubber Sample A) and 50 phr of functionalized S-SBR with 50 phr of cis-PBD (for Rubber Sample D) ).
    [0052] Samples B and E of rubber are Comparative Samples of rubber in which 15 phr of a traction resin has been replaced by 8 phr of petroleum based rubber processing oil, used in Samples A and D of Control rubber .
    [0053] Samples C and F of rubber are Experimental Samples of rubber, similar to Comparative Samples B and E, respectively, except that they contain soybean oil in place of petroleum-based processing oil and also contain 15 phr of petroleum resin. traction.
    [0054] As seen in Table 2, the results clearly show the benefit of soy oil in Experimental Samples C and F rubber, when used as a substitute for petroleum based rubber processing oil, when used in combination with a traction resin, compared to Comparative Samples B and E of rubber. For example, when comparing Comparative Sample B of rubber with Experimental Sample C of rubber and when comparing Comparative Sample E of rubber with Experimental Sample F of rubber, it is possible to see similar results for indicators of tensile strength and bearing with an advantage in resistance to abrasion and shear for Experimental Samples C and F of rubber that contain soy oil instead of petroleum based rubber processing oil.
    [0055] Therefore, it is concluded that this evaluation has successfully demonstrated the advantage of replacing petroleum-based processing oil with a vegetable oil, namely soybean oil, rubber mixture composition of a functionalized SBR solution and with high content of cis-PBD in the presence of
    Petition 870200002393, of 06/01/2020, p. 29/33
    21/21 a traction resin. The results clearly show that it is possible to improve the expected traction for such compounds without giving up other critical properties such as abrasion and shear resistance, while maintaining the similar expected rolling resistance performance.
    [0056] Although certain representative modalities and details have been shown for the purpose of illustrating the invention in question, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention in question.
    权利要求:
    Claims (10)
    [1]
    1. Rubber composition FEATURED for comprising, based on parts by weight, per 100 parts by weight of elastomer (phr):
    (A) at least one diene-based conjugated elastomer, including at least one diene-based conjugated elastomer, which contains one or more functional groups reactive with hydroxyl groups contained in silica, wherein said diene-functionalized elastomer contains at least one functional group comprising at least one of amine, siloxy and carboxyl groups reactive with said hydroxyl groups contained in said silica;
    (B) 5 to 60 phr of at least one of soy oil and canola oil;
    (C) from 1 to 30 phr of styrene-alpha-methylstyrene resin, (D) from 30 to 140 phr of reinforcing charge comprising:
    (1) silica, or (2) a combination of carbon black and silica; and (E) silica coupling agent reactive with hydroxyl groups contained in the silica and another different interactive group with carbonocarbon double bonds of the conjugated diene elastomers;
    wherein said rubber composition is free of oil-extended elastomer and excludes addition of petroleum-based rubber processing oil.
    [2]
    2. Rubber composition according to claim 1, CHARACTERIZED by the fact that reinforcing filler is a combination of reinforcing carbon black and silica precipitated from diene.
    [3]
    3. Rubber composition, according to claim 1, CHARACTERIZED by the fact that the vegetable oil of triglycerides excludes oil based on petroleum.
    [4]
    4. Rubber composition, according to any of the previous claims, CHARACTERIZED by the fact that the rubber composition
    Petition 870200002393, of 06/01/2020, p. 31/33
    2/2 rubber contains 30 to 140 phr of reinforcing charge comprising:
    (A) precipitated silica, or (B) combination of reinforcing carbon black and precipitated silica, and (C) silica coupling agent having a reactive group with hydroxyl groups on said precipitated silica and another different interactive group with double bonds carbon-carbon of said conjugated elastomers based on diene.
    [5]
    5. Rubber composition according to any of the preceding claims, CHARACTERIZED by the fact that the styrene-alpha-methyl styrene resin has a softening point in the range of 65 ° C to 95 ° C.
    [6]
    6. Rubber composition according to any one of the preceding claims, CHARACTERIZED by the fact that at least one of said diene-based elastomers is an elastomer coupled with tin or silicon.
    [7]
    7. Rubber composition according to any one of the preceding claims, CHARACTERIZED by the fact that the rubber composition comprises from 7 to 25 phr of at least one of soy oil and canola oil.
    [8]
    8. Rubber composition according to any one of the preceding claims, CHARACTERIZED by the fact that the rubber composition comprises 10 to 20 phr of the styrene-alpha-methylstyrene resin.
    [9]
    9. Tire containing a component, the component CHARACTERIZED by the fact that it comprises the rubber composition defined in any of the preceding claims.
    [10]
    10. Tire according to claim 9, CHARACTERIZED by the fact that the component is a tread or a tread cover.
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    同族专利:
    公开号 | 公开日
    BR102013028847A2|2014-10-21|
    US20140135437A1|2014-05-15|
    CN103819768A|2014-05-28|
    EP2733170B1|2015-09-23|
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    法律状态:
    2014-10-21| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-03-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-04-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/11/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/677,605|US20140135437A1|2012-11-15|2012-11-15|Tire with rubber tread containing combination of resin and vegetable oil, particularly soybean oil|
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