Tread rubber composition having majority amount of renewable inclusion

Abstract

To provide a tire rubber composition which is sustainable, is biologically renewable, is friendly to an environment, and is made of a non-fossil fuel resource.SOLUTION: A rubber composition contains, based on 100 pts.wt. of an elastomer (phr), a blend of at least two rubber elastomers selected from the group consisting of approximately 40 phr to approximately 50 phr of polybutadiene, approximately 35 phr or less of a styrene-butadiene copolymer, and approximately 45 phr or less of natural rubber, a bio-derived resin material, and a bio-derived filler containing silica and a carbon black filler. The carbon black filler is at least partially derived from a bio-based supply material after addition to the rubber composition. The resin and the silica are derived from a renewable material.SELECTED DRAWING: None

Description

Technical Field

[0001]

[0001] The exemplary embodiment relates to a tire rubber composition containing a majority weight percent of renewable inclusions. This embodiment finds particular uses with tread members and is described by specific reference thereto. However, it should be understood that the exemplary embodiment can also be applied to other similar uses.

Background Art

[0002]

[0002] In order to improve sustainability in the tire industry, continuous efforts have been made to develop rubber tire compositions from renewable resources. However, sustainable compositions must exhibit predictable behavior in order for the tire to perform its intended function. Thus, there is a desire for a sustainable rubber composition that compromises little, if at all, on rubber performance.

[0003]

[0003] In rubber tire compounds, the raw materials and additives are each combined with an elastomer to impart specific properties in the resulting tire. Currently, some materials - resins and carbon black are two of them - are derived from fossil (also referred to herein as "hydrocarbon") fuel resources (i.e., petroleum, coal or natural gas). Emissions associated with the production of these petroleum-derived materials can include organics, sulfur compounds, carbon monoxide (CO) and other pollutants. In order to reduce the environmental impact of such emissions, there is a desire to reduce or completely eliminate materials of fossil fuel origin from rubber compounds. However, it is technically difficult to reproduce the performance of conventional materials in tire compounds with just one bio-derived alternative material or in combination with multiple bio-derived alternative materials.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent document 2

Patent Document 3

Patent document 4

Patent document 5

Patent document 6

Patent document 7

Patent document 8

Non-licensed literature

[0005]

Non-licensed literature 1

Non-licensed Document 2

Non-licensed Document 4

Non-licensed Document 5

Non-licensed Document 6

Non-licensed Document 7

[0006]

[0004] In order to address the challenge of providing sustainable, biorenewable, environmentally friendly tire rubber compositions from non-fossil fuel resources, it is desirable to evaluate rubber compositions formed from combinations of materials including resins derived from renewable resources. [Means for solving the problem]

[0007]

[0005] One embodiment of the present disclosure relates to a tire component formed from a rubber composition comprising a majority by weight percentage of renewable material. The rubber composition is based on 100 parts by weight of elastomer (rubber) (phr), A blend of at least two rubber elastomers selected from the group consisting of polybutadiene with a rating of approximately 40 phr to 50 phr, styrene-butadiene copolymer with a rating of approximately 35 phr or less, and natural rubber with a rating of approximately 45 phr or less; Bio-derived resin materials; and Bio-derived fillers containing silica and carbon black fillers This includes, in the intended embodiment, the carbon black filler is at least partially derived from a bio-based supply material before being added to the rubber composition. The resin and silica are also derived from renewable materials. [Modes for carrying out the invention]

[0008]

[0006] The disclosure relates to a rubber composition comprising a majority by weight percent of renewable content. The disclosure further relates to a rubber tire having a tire component comprising a compound. As used herein, the terms "compound rubber", "rubber compound", and "compound" mean a rubber composition containing an elastomer compounded or mixed with appropriate rubber compounding ingredients. The terms "rubber", "elastomer", and "polymer" are used interchangeably unless otherwise indicated. Such terms are considered well-known to those skilled in the art.

[0009] As used herein, unless the context requires otherwise, the terms "comprise", "comprising", "comprises", and variations such as "comprised" are not intended to exclude further additives, components, integers, or steps. As used herein, the phrase "from about" means approximately and can include values within about ±1 of the value described herein.

[0010] As used herein, the terms "bio-based" or "bio-derived" represent materials derived from renewable or sustainable resources or natural resources, and may further include industrial resources, for example, when by-products or waste are captured and reused to reduce or eliminate environmentally harmful emissions. One non-limiting example is the sequestration of carbon dioxide for use as a feedstock.

[0011] As used herein, "renewable" and "sustainable" are used interchangeably and hereinafter also include recycled materials, and "inclusions" and "materials" are used interchangeably.

[0012] Partially, more preferably completely, exclude radiocarbon materials and fossil carbon materials derived from petroleum, coal or natural gas resources. Examples of resources from which bio-based materials can be derived include, but are not limited to, fresh (or from fermentation) biomass materials such as corn and vegetable oils.

[0013]

[0012] An important aspect of the present disclosure is a renewable inclusion having a weight percent content achieved using various combinations of renewable materials. A further aspect of the disclosed rubber composition is that the performance of a cured rubber composition having a majority weight percent of renewable inclusions is comparable to or exceeds the tread performance (wet traction, wear, and rolling resistance) of conventional rubber compositions made from petroleum-derived materials. Rubber polymer

[0013] The disclosed rubber composition includes a mixture of at least two rubbers, and more particularly, a conjugated diene elastomer. In practice, various conjugated diene elastomers can be used in rubber compositions such as polymers and copolymers of at least one of isoprene and 1,3-butadiene, and styrene copolymerized with at least one of isoprene and 1,3-butadiene. Representatives of such conjugated diene elastomers include, for example, cis 1,4-polyisoprene (natural and synthetic), cis 1,4-polybutadiene, styrene / butadiene copolymers, medium vinyl polybutadiene having a vinyl 1,2-content in the range of about 15 to about 90 percent, isoprene / butadiene copolymers, and at least one of styrene / isoprene / butadiene terpolymers.

[0014]

[0014] In practice, preferred rubbers or elastomers are polyisoprene (natural or synthetic), polybutadiene, and SBR. In a further embodiment, the rubber elastomer is polyisoprene and polybutadiene. In one embodiment, polybutadiene is present in a majority amount. In a preferred embodiment, polyisoprene is present in a majority amount.

[0015]

[0015] In one embodiment, the rubber composition includes about 30 phr to about 60 phr of polybutadiene, and more preferably includes about 40 phr to about 50 phr of polybutadiene. In one embodiment, the rubber composition includes up to 20 weight percent of polybutadiene.

[0016]

[0016] In practice, cis1,4-polybutadiene elastomers are considered to be cis1,4-polybutadiene rubber prepared with a neodymium catalyst, which can be prepared, for example, by polymerizing 1,3-butadiene monomer in an organic solvent solution in the presence of a catalyst system composed of a neodymium compound. However, such 1,4-polybutadiene can instead be prepared with an organic solution nickel catalyst of cis1,3-butadiene rubber.

[0017]

[0017] Representative neodymium catalysts for preparing cis1,4-polybutadiene include, for example, BUD1223™ from Goodyear Tire & Rubber Company and CB25™ from Lanxess, for example, though not intended to be limiting.

[0018]

[0018] cis1,4-polyisoprene and cis1,4-polyisoprene natural rubber are well known to those familiar with rubber technology. In practice, the second rubber polymer may also contain polyisoprene. In one embodiment, polyisoprene may be present in small amounts. In another embodiment, polyisoprene may be present in majority amounts. In practice, preferred rubbers or elastomers contain some amount of polyisoprene (natural or synthetic). In one embodiment, the rubber composition contains up to about 45 phr of polyisoprene, preferably in the form of natural rubber. In one embodiment, the rubber composition contains at least about 35 phr of polyisoprene, preferably in the form of natural rubber. In a particular embodiment, the rubber composition contains about 35 phr to about 45 phr of polyisoprene in the form of natural rubber. In one embodiment, the rubber composition contains about 10 to about 35 weight percent, more preferably about 15 to about 30 weight percent, of polyisoprene.

[0019]

[0019] In one intended embodiment, at least one rubber polymer comprises styrene-butadiene rubber. Styrene / butadiene copolymers include those prepared by aqueous emulsion polymerization (ESBR) and organic solvent solution polymerization (SSBR). In one embodiment, SBR prepared by solution polymerization (SSBR) is also intended, which typically has a bound styrene content ranging from about 9 to about 36 percent. However, embodiments are intended in which the SSBR has a bound styrene content greater than 30 percent, such as 34%.

[0020]

[0020] The rubber composition may contain up to about 35 phr of styrene-butadiene rubber. In one embodiment, the rubber composition includes ESBR and SSBR. In one embodiment, the rubber composition includes SSBR and excludes ESBR. In embodiments where the blend of rubber polymers includes SSBR, the SSBR may be present in an amount of about 5 phr to about 30 phr, more preferably about 10 to about 25 phr. In certain embodiments, the rubber composition contains up to about 5 weight percent of SSBR.

[0021]

[0021] SSBR can be conveniently prepared, for example, by the catalytic action of organolithium in the presence of an organic hydrocarbon solvent. In one embodiment, the SSBR is not functionalized. In one embodiment, at least one rubber polymer, such as SSBR, can be functionalized.

[0022]

[0022] A typical example of a functionalized elastomer is, (A) Amine functional groups that are reactive with hydroxyl groups on precipitated silica, (B) Siloxy functional groups including chain-terminus siloxy functional groups that are reactive with hydroxyl groups on precipitated silica, (C) A combination of an amine functional group and a siloxy functional group that are reactive with hydroxyl groups on the precipitated silica, (D) A combination of thiol functional groups and siloxy (e.g., ethoxysilane) functional groups that are reactive with hydroxyl groups on precipitated silica. (E) A combination of imine and siloxy functional groups that are reactive with hydroxyl groups on precipitated silica. (F) Hydroxyl functional groups that are reactive with precipitated silica, This is a styrene / butadiene elastomer containing one or more functional groups composed of the following:

[0023]

[0023] As for functionalized elastomers, a representative example of amine-functionalized SBR elastomers is the chain-functionalized SBR elastomer described in U.S. Patent No. 6,936,669.

[0024]

[0024] Representative combinations of amino-siloxy functionalized SBR elastomers having one or more amino-siloxy groups bonded to an elastomer are, for example, the amino-siloxy functionalized SBR elastomers described in HPR355 (trademark) from JSR and U.S. Patent No. 7,981,966.

[0025]

[0025] Typical styrene / butadiene elastomers terminally functionalized with silane sulfide groups are described, for example, in U.S. Patent Nos. 8,217,103 and 8,569,409.

[0026]

[0026] In certain embodiments, the rubber elastomer may be a copolymer of butyl rubber, particularly isobutylene, and a small amount of diene hydrocarbons such as isoprene and halogenated butyl rubber.

[0027]

[0027] In certain embodiments, the elastomer may further include halobutyl rubber, which may include a blend of chlorobutyl rubber, bromobutyl rubber, and mixtures thereof.

[0028]

[0028] Elastomers produced by tin coupling can also be used, for example, styrene / butadiene copolymers, isoprene / butadiene copolymers, styrene / isoprene copolymers, polybutadiene and the aforementioned functionalized styrene / butadiene elastomers, etc., produced by tin-coupled organic solution polymerization. oil

[0029] Desiring a rubber composition to contain fewer or no petroleum-derived materials means that the rubber composition should contain, if any, petroleum-based processing oils to a minimum. For example, it is desirable that the rubber composition be limited to 0 to about 5 phr of petroleum-based processing oils, more preferably less than about 2 phr of rubber petroleum-based processing oils.

[0029]

[0030] In one embodiment, the rubber composition may contain up to about 20 phr of rubber processing oil. In other embodiments, the rubber composition may contain about 1 phr or more of rubber processing oil. In practice, the composition may contain about 1 to about 20 phr of rubber processing oil, more preferably about 15 to about 20 phr of rubber processing oil. Processing oil can be included in the rubber composition as an extensor oil typically used to stretch the elastomer. Processing oil can also be directly included in the rubber composition by the addition of oil during rubber compounding. Processing oil used in the rubber composition may include both extensor oil present in the elastomer and processing oil added during compounding. Suitable processing oils include a variety of oils known in the art, including aromatic, paraffinic, naphthenic, vegetable triglyceride oils, and low PCA oils such as MES, TDAE, SRAE, and heavy naphthenic oils. Suitable low PCA oils include those with a polycyclic aromatic content of less than 3 weight percent as determined by the IP346 method. The procedure for the IP346 method can be found in *Standard Methods for Analys & Testing of Petroleum and Related Products and British Standard 2000 Parts*, 2003, 62nd edition, published by the Institute of Petroleum, UK.

[0030]

[0031] A suitable vegetable triglyceride oil consists of a combination of saturated and unsaturated esters, where the unsaturated esters consist of a combination of at least one of oleic acid esters, linoleic acid esters, and linolenic acid esters. The saturated esters consist of at least one of, for example, stearic acid esters and palmitic acid esters, but are not intended to be limiting.

[0031]

[0032] In one embodiment, the vegetable triglyceride oil is composed of at least one of soybean oil, sunflower oil, rapeseed oil, and canola oil, and is in the form of an ester containing a certain degree of unsaturation. Other preferred examples of vegetable triglyceride oils include corn, coconut, cottonseed, olive, palm, peanut, and safflower oils. In practice, the oil contains at least one of soybean oil and sunflower oil.

[0032]

[0033] In the case of soybean oil, for example, the above-mentioned composition ratio or combination of fatty acids for glycerol triesters, i.e., triglycerides, is expressed as an average value and may vary somewhat depending mainly on the type and source of the soybean crop, and may also depend on the cultivation conditions of the specific soybean crop from which the soybean oil was obtained. Furthermore, significant amounts of other saturated fatty acids are usually present, but soybean oil does not usually exceed 20 percent.

[0033]

[0034] The intended embodiments include a composition containing about 1 to 10 weight percent of bio-derived rubber processing oil. In one embodiment, the rubber processing oil accounts for about 3 to 8 weight percent of the composition. resin

[0035] An important aspect of this disclosure is the use of bio-derived resin materials, partially, but preferably entirely, instead of petroleum resins. Conventional resins are petroleum-derived. Examples of these resins include hydrocarbon-based resins (AMS, coumarone indene, C5, C9, C5 / C9, DCPD, DCPD / C9, etc.) and any of their modifiers (phenol, C9, hydrogenated, recycled monomer, etc.). On the other hand, one embodiment of the present invention intends to use these types of resins, but a preferred embodiment uses renewable bio-based chemical resins and their modifiers and mixtures instead. Representative resins further include coumarone-based resins, including coumarone-indene resins and mixtures of coumarone resins, naphthenic oils, phenolic resins, and rosin. Other suitable resins include phenol-terpene resins such as phenol-acetylene resins, phenol-formaldehyde resins, alkylphenol-formaldehyde resins, terpene-phenol resins, polyterpene resins, and xylene-formaldehyde resins.

[0034]

[0036] Terpene-phenol resins can be used. Terpene-phenol resins can be obtained by copolymerization of phenol monomers with terpenes such as limonene, pinene, and delta-3-carene. In one embodiment, the resin may be an alpha-pinene resin characterized by a softening point Tg between 60°C and 130°C.

[0035]

[0037] In one embodiment, the resin is derived from rosin and its derivatives. Typical examples include gum rosin, wood rosin, and tall oil rosin. While the amount of rosin component may vary, gum rosin, wood rosin, and tall oil rosin have similar compositions. Such resins can be dimerized, polymerized, or disproportionated. Such resins may also be in the form of esters of rosin acid with polyols such as pentaerythritol or glycol.

[0036]

[0038] In one embodiment, the resin may be partially or completely hydrogenated.

[0039] In one embodiment, an embodiment is envisioned in which another type of resin may also be added to the composition, but the rubber composition comprises at least one resin in a quantity of about 10 to about 80 phr, more preferably a bio-derived resin in a quantity of about 10 to about 80 phr. In one embodiment, the rubber composition comprises a resin of 15 phr or more, more preferably a resin of about 20 phr or more. In one embodiment, the rubber composition comprises a resin of 20 phr or more and 60 phr or less.

[0037]

[0040] The intended embodiments include a composition containing about 10–15 weight percent of bio-resin material. In one embodiment, the resin material accounts for about 12–15 weight percent of the composition. Filler

[0041] The disclosed rubber composition contains a silica filler of 80 to 150 phr. In one embodiment, the composition contains at least 90 phr of silica. In one embodiment, the composition contains 100 phr or more of silica.

[0038]

[0042] In one embodiment, precipitated silica is (A) Precipitated silica derived from inorganic sand (silicon dioxide-based sand), or (B) Precipitated silica derived from rice husks (silicon dioxide containing rice husks) It is composed of.

[0039]

[0043] In one embodiment, the precipitated silica is derived from naturally occurring inorganic sand (e.g., SiO2, silicon dioxide, which may contain trace minerals). Inorganic sand is typically treated with a strong base, such as sodium hydroxide, to form an aqueous silicate solution (e.g., sodium silicate). Synthetic precipitated silica is formed therefrom by controlled treatment of the silicate with an acid (e.g., mineral acid and / or an acidifying gas, such as carbon dioxide). An electrolyte (e.g., sodium sulfate) may be present to promote the formation of precipitated silica particles. The recovered precipitated silica is amorphous precipitated silica.

[0040]

[0044] In a preferred embodiment, the precipitated silica is precipitated silica derived from rice husks. Such precipitated silica is derived from rice husks (e.g., incinerated rice husk ash) that contain SiO2, silicon dioxide, and may also contain trace minerals from the soil in which the rice was planted. In a similar manner, rice husks (e.g., rice husk ash) are typically treated with a strong base, such as sodium hydroxide, to form an aqueous silicate solution (e.g., sodium silicate), and synthetic precipitated silica is formed therefrom by controlling the treatment of the silicate with an acid (e.g., mineral acid and / or an acidifying gas, such as carbon dioxide), which may contain an electrolyte (e.g., sodium sulfate) to promote the formation of precipitated silica particles derived from rice husks. The recovered precipitated silica is amorphous precipitated silica. See, for example, U.S. Patent Application No. 2003 / 0096900. In a preferred embodiment, the rubber composition contains 30 to 40 weight percent of rice husk ash silica, more preferably between 34 and 37 weight percent of rice husk ash silica.

[0041]

[0045] Even if the precipitated silica originates from the aforementioned silicon dioxide or rice husks, it may have a BET surface area ranging from, for example, about 40 to about 600, more generally, about 50 to about 300 square meters per gram, as measured using nitrogen gas. The BET method for measuring surface area is described, for example, in the Journal of the American Chemical Society, Vol. 60, and ASTM D3037.

[0042]

[0046] Such precipitated silica may further have a dibutyl phthalate (DBP) absorption value in the range of approximately 100 to 400, more generally, approximately 150 to 300 cc / 100g.

[0043]

[0047] Other embodiments are envisioned in which silica is used in combination with other fillers, such as carbon black.

[0048] In one embodiment, the rubber composition optionally contains about 0 to about 50 phr of carbon black based on 100 parts by weight of elastomer. In one embodiment, the rubber composition contains 20 phr or less of carbon black. In another embodiment, the rubber composition contains 0.1 phr or more of carbon black, and in a particular embodiment, 1 phr or more of carbon black. In one embodiment, the rubber composition contains about 1 to about 15 phr of carbon black. In a preferred embodiment, the carbon black is bio-based carbon black.

[0044]

[0049] The ASTM-D6866 method for determining the "bio-based" content is based on the same concept as radiocarbon dating, but does not use an age equation. This method determines the radiocarbon content in an unknown sample. 14 This relies on determining the ratio of the amount of C) to the amount of the modern reference standard. This ratio is reported as a percentage in the unit "pMC" (percent of modern carbon). If the material analyzed is a mixture of modern radiocarbon and fossil carbon (fossil carbon derived from petroleum, coal, or natural gas resources), the resulting pMC value is directly related to the amount of biomass material present in the sample.

[0045]

[0050] The modern reference standard used in radiocarbon dating is the National Institute of Standards and Technology (NIST-USA) standard, which uses known radiocarbon content equivalent to approximately AD 1950, before excess radiocarbon was introduced into the atmosphere. AD 1950 represents zero years and 100 pMC. Modern (fresh) biomass materials and materials derived from them exhibit a radiocarbon signature of approximately 107.5.

[0046]

[0051] Radiocarbon dating isotopes ( 14 C) has a nuclear half-life of 5730 years. Fossil carbon depends on its source, 14 The carbon content is very close to zero. Assuming that 107.5 pMC represents modern biomass material and 0 pMC represents petroleum (fossil carbon) derivatives, the pMC value measured for a material will reflect the proportion of the two constituent types. Therefore, a material derived 100% from modern vegetable oil should show a radiocarbon signature of around 107.5 pMC. If that substance is diluted with 50% petroleum derivative, it should show a radiocarbon signature of around 54 pMC.

[0047]

[0052] The biomass content results are derived by assigning 100% to 107.5 pMC and 0% to 0 pMC. In this sense, a sample measured at 99 pMC would have a corresponding biomass content of 93%. This value is called the "average biomass result" and assumes that all components in the analyzed material were of modern or fossil origin.

[0048]

[0053] The results provided by the ASTM D6866 method are mean biosystem results and include a 6% absolute range (±3% on either side of the mean biosystem result) to account for variability in the endo-component radiocarbon signature. All materials are presumed to be of modern or fossil origin. This result represents the amount of biosystem components "present" in the material, not the amount of biosystem material "used" in the manufacturing process.

[0049]

[0054] In one embodiment, the tire component is formed from a rubber composition containing a carbon black filler having a modern carbon content of more than 1 percent (1%) as defined by ASTM D6866. The carbon black is produced from a bio-based supply material before being added to the rubber composition. In one embodiment, the carbon black is at least partially derived from a bio-based supply material and, in a preferred embodiment, contains no fossil carbon at all.

[0050]

[0055] In one embodiment, the bio-based feedstock derived from carbon black includes at least one triglyceride vegetable oil, such as soybean oil, sunflower oil, canola oil, rapeseed oil, or a combination thereof. In one embodiment, the bio-based feedstock derived from carbon black includes at least one plant biomass, animal biomass, and municipal waste biomass, or a combination thereof.

[0051]

[0056] In one embodiment, the carbon black has a modern carbon content of at least 1%. In one embodiment, the carbon black has a modern carbon content of at least about 10%, more preferably at least about 25%, and most preferably at least about 50%. In one embodiment, the carbon black has a biomass content of at least about 1 pMC, more preferably at least about 54 pMC. In one embodiment, the carbon black may have a biomass content of at least about 80 pMC.

[0052]

[0057] Other embodiments are conceived that utilize carbon-dioxide-generated carbon reinforcing fillers. Suitable carbon-dioxide-generated carbon reinforcing fillers are manufactured by methods such as those described in US8,679,444, US10,500,582, and U.S. Patent Application No. 17 / 109,262, the contents of which are each incorporated herein in their entirety and together incorporated herein in full by reference.

[0053]

[0058] Various combinations of carbon black (including conventional petroleum-carbon black, having different particle sizes and / or other properties) can also be used in the disclosed rubber compositions. Representative examples of rubber-reinforced carbon black are listed, for example, in The Vanderbilt Rubber Handbook, 13th edition, 1990, pages 417 and 418, along with their ASTM standards, but are not limited to these. Such rubber-reinforced carbon black may have, for example, iodine absorption in the range of 60 to 240 g / kg and DBP values ​​in the range of 34 to 150 cc / 100 g. Coupling agent

[0059] A typical silica coupler of the aforementioned precipitated silica is, (A) Bis(3-trialkoxysilylalkyl) polysulfide containing an average of about 2 to about 4, or about 2 to about 2.6, or about 3.2 to about 3.8 sulfur atoms in the connecting bridge, or (B) Alkoxyorganic mercaptosilane, (C) combinations of those That is the case.

[0054]

[0060] A representative example of such bis(3-trialkoxysilylalkyl) polysulfides is bis(3-triethoxysilylpropyl) polysulfide.

[0061] As previously discussed, silica is preferably added to the rubber composition in combination with bis(3-triethoxysilylpropyl) polysulfide due to its in-situ reaction within the rubber composition.

[0055]

[0062] In one embodiment, the composition comprises about 1 phr to about 20 phr of coupling agent, more preferably about 8 phr to about 12 phr of coupling agent. Processing aid - Fatty acid derivative

[0063] Another aspect of this disclosure is the addition of bio-derived processing aids to rubber compositions. In preferred embodiments, the processing aid may be a bio-based fatty acid derivative and / or a blend of bio-based fatty acid derivatives. The processing aid may have a softening point (Tg) in the range of about 105°C to about 120°C. Generally, about 0.5 to about 5 phr, more preferably about 1 to about 3 phr of processing aid may be included in the composition. In one intended embodiment, the processing aid can be obtained as ZB49 from Struktol®, etc. In some embodiments, the processing aid may be used to promote coupling between polymer networks, silica fillers, and / or coupling between parts on the polymers.

[0056]

[0064] Those skilled in the art will readily understand that rubber compositions are to be formulated by methods generally known in rubber compounding technology, such as mixing various sulfur-curable constituent rubbers with curing aids such as sulfur donors; activators, accelerators, and retarders; and various commonly used additives such as processing additives, fillers, pigments, fatty acids, zinc oxide, waxes, antioxidants, ozone decomposition inhibitors, and decoction agents. As is well known to those skilled in the art, the above additives are selected and commonly used in conventional amounts depending on the intended use of the sulfur-vulcanizable and sulfur-vulcanized materials (rubber).

[0057]

[0065] Typical examples of sulfur donors include elemental sulfur (free sulfur), amine disulfides, polymeric polysulfides, and sulfur olefin adducts. Elemental sulfur is preferred as the sulfur vulcanizing agent. The sulfur vulcanizing agent can be used in amounts ranging from about 0.5 to 8 phr, but is preferably in the range of about 1 to 6 phr. A typical amount of antioxidant is about 0.5 to 5 phr. Typical antioxidants may include, for example, polymerized trimethyldihydroquinoline, a mixture of aryl-p-phenylenediamine, and others, as disclosed on pages 344-346 of The Vanderbilt Rubber Handbook (1978). In preferred embodiments, the antioxidant is a lignin-based antioxidant. A typical amount of ozone decomposition inhibitor is about 1 to 5 phr. A non-limiting typical ozone decomposition inhibitor is, for example, N-(1,3-dimethylbutyl)-n'-phenyl-p-phenylenediamine. A typical amount of fatty acid, if used, may include, for example, stearic acid, and may contain about 0.5 to about 5 phr. A typical amount of zinc oxide contains about 1 to about 5 phr. In preferred embodiments, the zinc oxide is derived from recycled content. A typical amount of wax contains about 1 to about 5 phr. Often, microcrystalline wax is used, but purified paraffin wax or a combination of both can be used. A typical amount of thiglioside contains about 0.1 to about 1 phr. Typical thigliosides may be, for example, pentachlorothiophenol and dibenzamide diphenyl disulfide.

[0058]

[0066] Accelerators are used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanized product. In one embodiment, a single accelerator system, i.e., a primary accelerator, can be used. The primary accelerator can be used in a total amount ranging from about 0.2 to about 3, preferably about 2 to about 2.5 phr. In another embodiment, a combination of primary and secondary accelerators is used to activate the vulcanized product and to improve its properties, with the secondary accelerator being used in a total amount ranging from about 0.2 to about 3, preferably about 2 to about 2.5 phr. These accelerator combinations are expected to produce a synergistic effect on the final properties, which are somewhat better than those produced using either accelerator alone. Furthermore, retarding accelerators can be used that are not affected by standard processing temperatures but provide satisfactory curing at normal vulcanization temperatures. Vulcanization retarders can also be used. A non-limiting example of a retarder may be N-cyclohexylthiophthalimide (CTP). Suitable types of accelerators that can be used in the present invention include amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, and xanthogenic salts. Preferably, the primary accelerator is a sulfenamide, such as N-cyclohexyl-2-benzothiazole sulfenamide (CBS). If a secondary accelerator is used, suitable secondary accelerators include guanidines (such as diphenylguanidine (DPG)), dithiocarbamates (such as zinc dimethyldithiocarbamate or zinc dibenzyldithiocarbamate), or thiurams compounds.

[0059]

[0067] The mixing of rubber compositions can be achieved by methods known to those skilled in the art of rubber mixing. For example, the components are typically mixed in at least two stages, namely at least one non-productive stage followed by a productive mixing stage. The final curing agent, including a sulfur vulcanizing agent, is typically mixed in a final stage conventionally called the “productive” mixing stage, where the mixing is typically carried out at a temperature lower than the mixing temperature of the preceding non-productive mixing stage, or at an ultimate temperature. The terms “non-productive” and “productive” mixing stages are well known to those skilled in the art of rubber mixing. The rubber composition may also be subjected to a thermomechanical mixing process. This thermomechanical mixing process generally involves mechanical work in a mixer or extruder for a time appropriate to produce a rubber temperature of 140°C to 190°C. The appropriate time for the thermomechanical work varies depending on the operating conditions, as well as the volume and properties of the components. For example, the thermomechanical work may last from 1 to 20 minutes.

[0060]

[0068] The vulcanization of the pneumatic tire of the present invention is generally carried out at a conventional temperature, for example, in the range of about 100°C to 200°C. Preferably, the vulcanization is carried out at a temperature in the range of about 110°C to 180°C. Any conventional vulcanization process may be used, such as heating in a press or mold, or heating with superheated steam or hot air. Such tires can be constructed, shaped, molded and cured by a variety of methods known to those skilled in the art and readily apparent.

[0061]

[0069] This disclosure intends to describe tire components formed by such methods. Similarly, tire components may be incorporated into a tire. Tire components may or may not touch the ground. Tires may or may not be pneumatic. In one embodiment, tire components may be a tread.

[0062]

[0070] The tires of this disclosure may be racing tires, passenger car tires, aircraft tires, agricultural tires, earthmoving machinery tires, off-road tires, truck tires (commercial or passenger), etc. Preferably, the tires are for passenger cars or trucks. The tires may be radial or bias.

[0063]

[0071] The rubber composition itself, depending largely on the selection and level of renewable materials, may be useful as a tire sidewall or other tire component, or in rubber trucks, conveyor belts or other industrial products such as windshield wiper blades, brake diaphragms, washers, seals, gaskets, hoses, conveyor belts, power transmission belts, shoe soles, shoe uppers, and building floor mats or in automotive applications.

[0064]

[0072] The following examples are provided for illustrative purposes only and are not intended to limit the present invention. Unless otherwise specified, all parts are measured in parts by weight. [Examples]

[0065]

[0073] These examples illustrate the effect of the disclosed combinations of renewable ingredients on the performance of the rubber compounds. The rubber compositions were mixed using a multi-step mixing procedure according to the recipes in Tables 1-6.

[0066]

[0074] Control rubber compound samples A, D, F, K, N, and Q were formed from equal amounts of similar components. These control samples were formed using a blend of polybutadiene (BR), emulsion-polymerized styrene-butadiene copolymer (ESBR), solution-polymerized styrene-butadiene copolymer (ESBR), and additives including oil (soybean), carbon black filler, bio-based silane coupling agent, wax, ozone decomposition inhibitor, lignin-based antioxidant, bio-based fatty acid derivative blend, and recycled zinc oxide. The controls were also formed using alpha-methylstyrene resin, which is petroleum-derived. Standard curing techniques were also used. [Examples]

[0067]

[0075] Experimental samples B and C are shown in Table 1. In samples B and C, petroleum resin is replaced with bio-derived resin, more specifically, alpha-pinene resin. Sample C has the same other components and quantities as control A, but with an 8 percent (8%) increase in sulfur and accelerator.

[0068]

[0076] The rubber compound was then cured and tested for various properties, particularly abrasion, wet traction, and rolling resistance.

[0077] The basic formulations, expressed in parts per 100 parts by weight (phr), are shown in Table 1 below. Table 1 further compares the curing properties of control sample A and experimental samples B and C.

[0069] [Table 1-1]

[0070] [Table 1-2]

[0071]

[0078] Table 1 shows that when petroleum-derived resins were replaced with bio-derived resins, there was a slight shift in stiffness between experimental sample B and control A. This change was adjusted between experimental sample C and experimental sample B (both formed using bio-derived resins) by increasing the amounts of sulfur and accelerator. This improved the delta torque value of sample C, thereby better matching that of control A.

[0072]

[0079] In summary, similar performance indicators were observed between experimental samples B and C and control A. It can be concluded that resins made from sustainable resources, instead of petroleum-based resins, do not affect the performance of the compound. [Examples]

[0073]

[0080] Experimental sample E is shown in Table 2. In sample E, conventional petroleum-derived carbon black is replaced with bio-derived carbon black. Sample E contains a larger amount of carbon black than control D, while all other components are present in the same amounts.

[0074]

[0081] The rubber compound was then cured and tested for various properties, particularly abrasion, wet traction, and rolling resistance.

[0082] The basic formulations, expressed as parts per 100 parts by weight (phr), are shown in Table 2 below. Table 2 further compares the curing properties of control sample D and experimental sample E.

[0075] [Table 2]

[0076]

[0083] When petroleum-derived carbon black is replaced with bio-derived carbon black, Table 2 shows an increase in low-strain stiffness between experimental sample E and control D.

[0084] In summary, it was shown that bio-derived carbon black does not significantly affect the properties of the compound. Therefore, it can be concluded that bio-derived carbon black can be used as a coloring agent without significantly affecting the performance of the compound. [Examples]

[0077]

[0085] Experimental samples (G-J) are shown in Table 3. Samples (G-J) reduce SSBR and replace ESBR with natural rubber. Sample G uses a conventional petroleum-derived resin with a modified rubber blend. Samples H-J replace the petroleum-derived resin with a bio-derived resin material. Samples I and J use more bio-derived resin material than sample H. Sample J further increases the amount of silica filler compared to samples F-I. The amounts of all other components remained the same, and the curing was fine-tuned between samples H, I, and J.

[0078]

[0086] The rubber compound was then cured and tested for various properties, particularly abrasion, wet traction, and rolling resistance.

[0087] The basic formulations, expressed as parts per 100 parts by weight (phr), are shown in Table 3 below. Table 3 further compares the curing properties of control sample F and experimental samples G to J.

[0079] [Table 3-1]

[0080] [Table 3-2]

[0081]

[0088] In Example 3, the rubber polymer blend was adjusted to shift the polymer's Tg to a lower value. Experimental samples G-J were tested to evaluate the effect of increasing the levels of bio-derived resin and / or silica on the predicted performance.

[0082]

[0089] Switching to natural rubber resulted in an increase in low-strain stiffness for sample H. Shifting the polymer's Tg to a lower value negatively impacted the wet index, but showed improved wear, snow, and rolling resistance indices.

[0083]

[0090] Doubling the amount of bio-derived resin in Sample I showed a significant improvement in the wetness index, but at the expense of rolling resistance. Increasing the plasticizer level was directionally beneficial to the snow index. Overall, it reduced the stiffness of the compound.

[0084]

[0091] By adding more silica in combination with other modifications, sample J showed that its rigidity was restored. The snow index was also found to be equivalent to that of control F.

[0092] It is concluded that by increasing the amount of bio-derived resin materials and silica in the tire, performance characteristics can be controlled, and the percentage of renewable / sustainable content can be adjusted. Such polymer compositions can be incorporated into tire treads. [Examples]

[0085]

[0093] Experimental sample L, shown in Table 4, is a modified version of sample J (which increased the amount of bio-derived resin material used) by further replacing petroleum-derived carbon black with the same amount of bio-derived carbon black. In sample M, the unfunctionalized SSBR of control K and sample L is replaced with functionalized SSBR. The soybean oil level was also adjusted to maintain the plasticizer level of the oil-expanded SSBR of samples K and L.

[0086]

[0094] The curing process was fine-tuned between samples H, I, and J, while keeping the amounts of all other components the same. All other components and amounts in sample L were the same as in sample J, but sample J contained more bio-derived resin and a larger amount of silica filler than the petroleum resin in control K. The curing process was also fine-tuned for sample K.

[0087]

[0095] The rubber compound was then cured and tested for various properties, particularly abrasion, wet traction, and rolling resistance.

[0096] The basic formulations, expressed as parts per 100 parts by weight (phr), are shown in Table 4 below. Table 4 further compares the curing properties of control sample K and experimental samples L and M.

[0088] [Table 4-1]

[0089] [Table 4-2]

[0090]

[0097] In Example 2, replacing petroleum-derived carbon black with bio-derived carbon black showed no effect on the compound's properties. Here, a combination of bio-derived carbon black and bio-derived resin material was tested using high-content silica and functionalized SBR. It was found that using functionalized SBR instead of unfunctionalized SBR improved rolling resistance. Other performance indicators were only slightly affected. Therefore, it can be concluded that functionalized polymers can be used in tire tread rubber compositions containing numerous other bio-derived materials. [Examples]

[0091]

[0098] Experimental sample O has the same formulation as sample M described above. In sample P, the other components and quantities are the same, but the polymer ratio of sample O is adjusted. This change increased the percentage of renewable material (containers) in the composition.

[0092]

[0099] The rubber compound was then cured and tested for various properties, particularly abrasion, wet traction, and rolling resistance. [000100] The basic formulations, expressed in parts per 100 parts by weight (phr), are shown in Table 5 below. Table 5 further compares the curing properties of control sample N and experimental samples O and P.

[0093] [Table 5-1]

[0094] [Table 5-2]

[0095] [000101] Prior to this example, sample M showed the most favorable performance results. In Example 5, the mixing ratio of the three polymers was adjusted and compared with sample M. As a result of this adjustment, the polymer Tg shifted from -80.0°C to -82.6°C (FOX calculation).

[0096] [000102] It was found that increasing the natural rubber content of experimental sample P increased the stiffness and true tensile strength of the compound. Sample P showed improvements in the wet index, wear index, and snow index compared to control N, while also including a substantial percentage increase in the renewable material content. Furthermore, the rolling resistance index was improved to the same level as or better than control N and sample O. [Examples]

[0097] [000103] Experimental sample R has the same formulation as sample P described above. In sample S, ESBR was replaced with a large amount of natural rubber. All other components and their amounts remained the same. This change further increased the percentage of renewable materials (containers) in the composition.

[0098] [000104]The rubber compound was then cured and tested for various properties, particularly abrasion, wet traction, and rolling resistance. [000105] The basic formulations, expressed in parts per 100 parts by weight (phr), are shown in Table 6 below. Table 6 further compares the curing properties of control sample Q and experimental samples R and S.

[0099] [Table 6-1]

[0100] [Table 6-2]

[0101] [000106] To further test increasing the percentage of renewable content in the tread, SBR was removed and replaced with additional natural rubber. Furthermore, in this example, natural rubber accounted for a majority of the rubber polymer in the blend, with a substantial increase. As a result, the polymer's Tg shifted from -82.6°C to -72.3°C (FOX calculation).

[0102] [000107] As a result of polymer adjustment, the rigidity of the compound was slightly reduced. [000108] By increasing the natural rubber level, the percentage of renewable content in the rubber composition was increased from 47% by weight (control Q) to 88% by weight (experimental sample S). Sample S showed improved wet and snow indicators compared to control Q, and furthermore, sample S showed comparable rolling resistance.

[0103] [000109] It is concluded that a tread tire rubber composition formed from a combination of different renewable materials to have a majority percentage of renewable content can meet or improve upon the performance of a tire formed from a conventional rubber composition.

[0104] [000110] Modifications of the present invention are possible in light of the description provided herein. Certain representative embodiments and details are given to illustrate the present invention, but 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. Accordingly, it should be understood that any modifications that can be made in the specific embodiments described herein fall within the full intended scope of the invention as defined by the appended claims below.

[0105] [Modes of the Invention] [1] A tire component formed from a rubber composition comprising more than half by weight of renewable material, wherein the rubber composition is based on 100 parts by weight of elastomer (phr), A blend of at least two rubber elastomers selected from the group consisting of polybutadiene with a rating of approximately 40 phr to 50 phr, styrene-butadiene copolymer with a rating of 35 phr or less, and natural rubber with a rating of 45 phr or less; Bio-derived resin materials; and Bio-derived fillers containing silica and carbon black fillers This includes, where the carbon black filler comprises silica and carbon black filler that are at least partially derived from a bio-based supply material before being added to the rubber composition. Tire components. [2] The tire component according to claim 1, wherein the rubber composition comprises more than approximately 75% renewable material. [3] The tire component according to claim 1, wherein the rubber composition comprises more than approximately 85% renewable material. [4] The tire component described in 1, wherein the resin is a terpene resin. [5] The tire component according to claim 1, wherein the resin is alpha-pinene resin. [6] The tire component according to claim 1, wherein petroleum-derived resins, oils, and filler materials are removed from the composition. [7] The rubber composition according to claim 1, wherein the blend of rubber elastomers optionally comprises emulsion polymerized styrene-butadiene copolymer (ESBR) of 35 phr or less. [8] The rubber composition according to claim 1, wherein emulsion polymerized styrene-butadiene copolymer (ESBR) is removed from the rubber elastomer blend. [9] The rubber composition according to 1, wherein the blend of rubber elastomers comprises a solution polymerized styrene-butadiene copolymer (SSBR) of about 5 to about 30 phr.

[10] The rubber composition according to 9, wherein SSBR is oil-distributed.

[11] The rubber composition according to 9, wherein SSBR is functionalized.

[12] The rubber composition according to 9, wherein the SSBR is not functionalized.

[13] The rubber composition according to 9, wherein the blend of rubber elastomers comprises about 5 to about 15 phr of functionalized SSBR.

[14] The rubber composition according to 1, wherein the blend of rubber elastomers contains natural rubber in an amount of approximately 35 phr to approximately 45 phr.

[15] The rubber composition according to 14, wherein ESBR is further removed from the rubber elastomer blend.

[16] Silica of approximately 80 phr to 150 phr, and Approximately 1-15 phr of carbon black The rubber composition according to claim 1, further comprising:

[17] The rubber composition according to 1, wherein the silica is derived from rice husk ash.

[18] The rubber composition according to 1, further characterized by a resin of approximately 10 phr to approximately 50 phr.

[19] The tire component according to 1, wherein carbon black is produced from a supply material from which fossil carbon has been removed before being added to the rubber composition.

Claims

1. 1. A tire component formed from a rubber composition characterized by a majority amount, by weight percent, of renewable materials, said rubber composition comprising, based on 100 parts by weight of elastomer (phr): a blend of at least two rubber elastomers selected from the group consisting of 40 phr to 50 phr polybutadiene, not more than 35 phr styrene-butadiene copolymer, and not more than 45 phr natural rubber; Bio-based resin materials; and Bio-based fillers, including silica and carbon black fillers wherein the carbon black filler is at least partially derived from a bio-based feedstock prior to addition to the rubber composition. Tire components.

2. 10. The tire component of claim 1, wherein the rubber composition comprises greater than 75% renewable materials.

3. 10. The tire component of claim 1, wherein the rubber composition comprises greater than 85% renewable materials.

4. 2. The tire component of claim 1, wherein the resin is a terpene resin.

5. 2. The tire component of claim 1, wherein the resin is an alpha-pinene resin.

6. 10. The tire component of claim 1, wherein the composition is free of petroleum-derived resins, oils, and filler materials.

7. 10. The rubber composition of claim 1, wherein the rubber elastomer blend optionally includes up to 35 phr of emulsion polymerized styrene butadiene copolymer (ESBR).

8. 10. The rubber composition of claim 1, wherein emulsion polymerized styrene butadiene copolymer (ESBR) is excluded from the rubber elastomer blend.

9. 10. The rubber composition of claim 1, wherein the rubber elastomer blend comprises 5 to 30 phr of solution polymerized styrene butadiene copolymer (SSBR).

10. The rubber composition according to claim 9, wherein the SSBR is oil-extended.

11. The rubber composition of claim 9, wherein the SSBR is functionalized.

12. The rubber composition of claim 9, wherein the SSBR is unfunctionalized.

13. 10. The rubber composition of claim 9, wherein the rubber elastomer blend comprises 5 to 15 phr of the functionalized SSBR.

14. 2. The rubber composition of claim 1, wherein the rubber elastomer blend comprises 35 phr to 45 phr of natural rubber.

15. 15. The rubber composition of claim 14, further characterized in that the blend of rubber elastomers further excludes ESBR.

16. 80 phr to 150 phr of silica, and 1 to 15 phr of carbon black The rubber composition of claim 1 further characterized by:

17. The rubber composition according to claim 1, wherein the silica is derived from rice husk ash.

18. The rubber composition of claim 1 further characterized by 10 phr to 50 phr of resin.

19. 10. The tire component of claim 1, wherein the carbon black is produced from a feedstock that has been stripped of fossil carbon prior to addition to the rubber composition.