Process Oil and Rubber composition including the same

Abstract

A process oil and a rubber composition comprising the process oil are provided, the process oil comprising a polymer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group; and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group. The rubber composition has improved compounding processability, and the low-temperature properties may be improved by lowering the viscosity and glass transition temperature of the process oil.

Description

Technology Field

[0001] The present invention relates to a process oil and a rubber composition containing the same. Background Technology

[0002] In the general manufacturing of tires, a green tire is completed from a tire molding composition containing a vulcanizing agent and rubber molecules, and the green tire is placed in a vulcanization mold and vulcanized for a certain period of time while applying heat and pressure to the inner and outer sides of the green tire, thereby cross-linking the vulcanizing agent and rubber molecules contained in the tire molding composition to obtain stable inherent properties of tire rubber.

[0003] During this vulcanization process, a thin, sack-shaped layer of tire rubber is used inside the green tire to determine its appearance. Since tire rubber is used under harsh conditions of high temperature and pressure, it requires properties different from those of other general rubbers. Under these circumstances, the development of tire rubber that offers superior performance and a long lifespan can directly lead to cost reduction; consequently, research and efforts to improve tire rubber have been continuously pursued.

[0004] In addition, various types of additives are used in tire rubber to improve or strengthen the physical properties required for tires. Among these additives, process oil is used to improve the mixing load when mixing rubber with various additives (chemicals). The process oil is used as a softener to reduce the loss of mixing energy required during the compounding of tire rubber composition components, and to improve the dispersion and compatibility between the rubber, chemicals, and fillers, which are the various materials used in the rubber composition.

[0005] Process oils used in rubber compositions for tires are generally viscous oils composed of hydrocarbon compounds, such as aromatic, paraffinic, and naphthenic components. The process oil widely used in the butyl rubber compounding process is a petroleum-based paraffinic oil, and castor oil is mixed in to improve production efficiency and the physical properties of butyl rubber products.

[0006] Meanwhile, it has been consistently pointed out that hydrocarbon compounds commonly used in process oils are petroleum-based oils that can cause problems such as environmental pollution. In particular, with the recent increase in social demand for eco-friendly raw materials related to ESG (Environment Social Governance) and sustainability, as well as the development of products utilizing them, there is a growing need to develop tire process oils using eco-friendly raw materials related to ESG and sustainability. Prior art literature

[0007] Korean Registered Patent No. 10-2138311 The problem to be solved

[0008] The technical problem that the present invention aims to solve is to provide a process oil prepared using eco-friendly materials and a rubber composition containing the same. means of solving the problem

[0010] One aspect of the present invention relates to a process oil comprising a polymer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group.

[0011] Another aspect of the present invention relates to a rubber composition comprising the process oil. Effects of the invention

[0013] The process oil according to the present invention comprises a polymer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group, and the process oil can easily achieve excellent blending processability.

[0014] In addition, the process oil has low viscosity and glass transition temperature, so the low-temperature properties of the rubber composition containing the process oil can be improved. Specific details for implementing the invention

[0016] Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

[0017] Terms and words used in this specification and claims shall not be interpreted as being limited to their ordinary or dictionary meanings, but shall be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0018] The terms used in this invention are used merely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this invention, terms such as "comprising" or "having" are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0019] Specifically, one aspect of the present invention provides a process oil comprising a polymer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group.

[0020] For example, the process oil comprises a polymer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group, thereby easily enabling excellent formulation processability.

[0021] In addition, since the process oil has low viscosity and glass transition temperature, a rubber composition containing the process oil can have excellent low-temperature properties.

[0022] According to one embodiment, the ethylene-based unsaturated monomer containing the ester group is represented by the following chemical formula 1, and the ethylene-based unsaturated monomer containing the carboxyl group can be represented by the following chemical formula 2.

[0023] <Chemical Formula 1>

[0024]

[0025] <Chemical Formula 2>

[0026]

[0027] Among the above chemical formulas 1 and 2,

[0028] R 11 to R 14 and R 21 to R 24 is independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R 15 to R 16 and R 25 are independently alkyl groups having 1 to 20 carbon atoms, a11 and a21 are independently integers from 1 to 20, and a13 and a23 are independently integers from 1 to 50.

[0029] According to one embodiment, among the above chemical formulas 1 and 2, R 11 to R 14 and R 21 to R 24 are independently hydrogen, a methyl group, or an ethyl group, and R 15 to R 16 and R 25 The groups can be independently methyl, ethyl, or propyl groups.

[0030] According to one embodiment, among the above chemical formulas 1 and 2, R 11 to R 14 and R 21 to R 24 are hydrogen, and R 15 to R 16 and R 25 The groups can be independently methyl, ethyl, or propyl groups.

[0031] According to one embodiment, among the above formulas 1 and 2, a11 and a21 may independently be integers from 1 to 15, integers from 1 to 12, integers from 1 to 9, integers from 1 to 6, integers from 1 to 5, or integers from 1 to 3.

[0032] According to one embodiment, among the above formulas 1 and 2, a13 and a23 may independently be integers from 1 to 50, integers from 1 to 45, integers from 1 to 40, integers from 1 to 35, integers from 1 to 30, integers from 1 to 25, integers from 1 to 20, integers from 2 to 50, integers from 4 to 50, integers from 5 to 50, or integers from 5 to 20.

[0033] According to one embodiment, the ratio of the number of moles of a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group to the number of moles of a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group among the polymers may be 1 to 20.

[0034] For example, the ratio of the number of moles of the unit (A) derived from the ethylene-based unsaturated monomer containing the ester group to the number of moles of the unit (B) derived from the ethylene-based unsaturated monomer containing the carboxyl group among the polymers may be 1 to 18, 1 to 16, 1 to 14, 1 to 12, 1 to 10, 1 to 8, 2 to 20, 2 to 10, 3 to 20, 3 to 10, or 3 to 8.

[0035] According to one embodiment, at least one of the ethylene-based unsaturated monomer containing an ester group and the ethylene-based unsaturated monomer containing a carboxyl group may be derived from edible oil.

[0036] For example, the above edible oil may include room temperature liquid fatty oils such as rapeseed oil or salad oil, and room temperature solid fats such as palm oil or hydrogenated oil. For example, the above edible oil may be waste edible oil. Waste edible oil may refer to edible oil remaining after using the above edible oil.

[0037] According to one embodiment, an ethylene-based unsaturated monomer containing an ester group and an ethylene-based unsaturated monomer containing a carboxyl group may each be derived from edible oil.

[0038] For example, if each of the ethylene-based unsaturated monomer containing an ester group and the ethylene-based unsaturated monomer containing a carboxyl group is derived from edible oil, the polymer may be a self-polymer of the edible oil. For example, the self-polymer of the edible oil may refer to a polymer formed by polymerizing the ethylene-based unsaturated monomer containing an ester group and the ethylene-based unsaturated monomer containing a carboxyl group contained in the same edible oil. For example, the self-polymer refers to a polymer formed by polymerizing the ethylene-based unsaturated monomer containing an ester group and / or the ethylene-based unsaturated monomer containing a carboxyl group contained in the edible oil. For example, self-polymerization means that the ethylene-based unsaturated monomers contained in the edible oil are polymerized together.

[0039] According to one embodiment, the polymer may be a dimer. For example, the dimer may be a polymer formed by combining two monomer molecules. For example, the dimer may refer to a polymer formed by combining two molecules of an ethylene-based unsaturated monomer contained in the edible oil. For example, the ethylene-based unsaturated monomer contained in the edible oil may include an ester group or a carboxyl group.

[0040] According to one embodiment, the polymer may comprise two or more of: a dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group; a dimer comprising a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group; and a dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group.

[0041] The polymer may include a dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group; a dimer comprising a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group; and a dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group.

[0042] According to one embodiment, the ratio of the moles of a dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group to the moles of a dimer comprising a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group to the moles of a dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group may be 1 to 35 : 1 to 35 : 50 to 98.

[0043] The number of moles of a dimer containing a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group is the number of moles excluding the dimer containing a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group among the dimers containing a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group.

[0044] The number of moles of a dimer comprising a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group is the number of moles excluding the dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group among the dimers comprising a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group. For example, the number of moles of the dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group among the polymers is 1 to 35 mole%, 1 to 30 mole%, 1 to 25 mole% or less, 2 to 25 mole%, 2.5 to 25 mole%, 3 to 25 mole%, 1 to 23 mole%, 1 to 22 mole%, 1 to 17 mole%, 2.5 to It may be 17 mol% or 3 to 16 mol%.

[0045] For example, the number of moles of a dimer containing a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group among the polymers may be 1 to 35 mole%, 1 to 30 mole%, 1 to 25 mole%, 5 to 30 mole%, 5 to 25 mole%, 7 to 30 mole%, 7 to 25 mole%, 10 to 30 mole%, 12 to 30 mole%, 14 to 30 mole%, 1 to 25 mole%, 1 to 23 mole%, 1 to 20 mole%, 1 to 18 mole%, 6 to 23 mole%, or 7 to 18 mole% with respect to the total number of moles of the polymers.

[0046] For example, the moles of a dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group among the above polymers may be 50 to 98 mole%, 50 to 90 mole%, 50 to 87 mole%, 50 to 85 mole%, 50 to 80 mole%, 55 to 90 mole%, 56 to 90 mole%, 66 to 90 mole%, 67 to 90 mole%, 66 to 79 mole%, or 67 to 78 mole% with respect to the total moles of the polymers. For example, the polymer comprises a dimer comprising two units (A) derived from an ethylene-based unsaturated monomer containing an ester group; a dimer comprising two units (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group; A dimer comprising one unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and one unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group; and two or more of these may be included. For example, the polymer may include a dimer comprising two units (A) derived from an ethylene-based unsaturated monomer containing an ester group; a dimer comprising two units (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group; and a dimer comprising one unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and one unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group.

[0047] According to one embodiment, the ratio of the moles of a dimer comprising two units (A) derived from an ethylene-based unsaturated monomer containing an ester group to the moles of a dimer comprising two units (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group to the moles of a dimer comprising one unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and one unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group, respectively, may be 1 to 35 : 1 to 35 : 50 to 98.

[0048] For example, the moles of a dimer comprising two units (A) derived from an ethylene-based unsaturated monomer containing an ester group among the polymers may be 1 to 35 mole%, 1 to 30 mole%, 1 to 25 mole% or less, 2 to 25 mole%, 2.5 to 25 mole%, 3 to 25 mole%, 1 to 23 mole%, 1 to 22 mole%, 1 to 17 mole%, 2.5 to 17 mole%, or 3 to 16 mole% with respect to the total moles of the polymers.

[0049] For example, the moles of a dimer comprising two units (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group among the polymers may be 1 to 35 mole%, 1 to 30 mole%, 1 to 25 mole%, 5 to 30 mole%, 5 to 25 mole%, 7 to 30 mole%, 7 to 25 mole%, 10 to 30 mole%, 12 to 30 mole%, 14 to 30 mole%, 1 to 25 mole%, 1 to 23 mole%, 1 to 20 mole%, 1 to 18 mole%, 6 to 23 mole%, or 7 to 18 mole% with respect to the total moles of the polymers.

[0050] For example, the moles of a dimer comprising one unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and one unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group among the polymers may be 50 to 98 moles, 50 to 90 moles, 50 to 87 moles, 50 to 85 moles, 50 to 80 moles, 55 to 90 moles, 56 to 90 moles, 66 to 90 moles, 67 to 90 moles, 66 to 79 moles, or 67 to 78 moles with respect to the total moles of the polymers.

[0051] According to one embodiment, the polymer may include two or more of the compounds represented by the following chemical formulas 3 to 5.

[0052] <Chemical Formula 3>

[0053]

[0054] <Chemical Formula 4>

[0055]

[0056] <Chemical Formula 5>

[0057]

[0058] Among the above chemical formulas 3 to 5,

[0059] L 31 , L 32 , L 41 , L 42 , L 51 and L 52 is a single bond independently of each other; or an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms, and

[0060] R 31 to R 36 , R 41 to R 46 and R 51 to R 56 The groups are independently hydrogen or alkyl groups having 1 to 20 carbon atoms, and

[0061] R37 , R 38 , R 47 , R 48 , R 49 , R 57 , R 58 , R 59a and R 59b are independently alkyl groups having 1 to 20 carbon atoms, and

[0062] a31, a32, a41, a42, a51, and a52 are independent integers from 1 to 50.

[0063] According to one embodiment, among the above chemical formulas 3 to 5, L 31 , L 32 , L 41 , L 42 , L 51 and L 52 The bonds can be independent of each other, single bonds, methylene groups, ethylene groups, or propylene groups.

[0064] According to one embodiment, among the above chemical formulas 3 to 5, R 31 to R 36 , R 41 to R 46 and R 51 to R 56 The groups can be hydrogen, methyl, ethyl, or propyl groups independently of each other.

[0065] According to one embodiment, among the above chemical formulas 3 to 5, R 37 , R 38 , R 47 , R 48 , R 49 , R 57 , R 58 , R 59a and R 59b It can be a methyl group, an ethyl group, a propyl group, or a butyl group.

[0066] According to one embodiment, among the above chemical formulas 3 to 5, a31, a32, a41, a42, a51 and a52 may independently be integers from 1 to 50, integers from 1 to 45, integers from 1 to 40, integers from 1 to 35, integers from 1 to 30, integers from 1 to 25, integers from 1 to 20, integers from 2 to 50, integers from 4 to 50, integers from 5 to 50, or integers from 5 to 20.

[0067] For example, the compound represented by Chemical Formula 3 above may be a compound in which two molecules of an ethylene-based unsaturated monomer containing a carboxyl group are combined. For example, the compound represented by Chemical Formula 4 above may be a compound in which an ethylene-based unsaturated monomer containing a carboxyl group and an ethylene-based unsaturated monomer containing an ester group are combined. For example, the compound represented by Chemical Formula 5 above may be a compound in which two molecules of an ethylene-based unsaturated monomer containing an ester group are combined.

[0068] According to one embodiment, the polymer may include a compound represented by Chemical Formula 3 and a compound represented by Chemical Formula 4. For example, the polymer may include a compound represented by Chemical Formula 3 and a compound represented by Chemical Formula 5. For example, the polymer may include a compound represented by Chemical Formula 4 and a compound represented by Chemical Formula 5. For example, the polymer may include a compound represented by Chemical Formula 3, a compound represented by Chemical Formula 4, and a compound represented by Chemical Formula 5.

[0069] According to one embodiment, the polymer comprises a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5, and the ratio of the moles of the compound represented by Formula 3 to the moles of the compound represented by Formula 4 to the moles of the compound represented by Formula 5 may be 1 to 35: 1 to 35: 50 to 98.

[0070] For example, the moles of the compound represented by Formula 3 among the polymers may be 1 to 35 mole%, 1 to 30 mole%, 1 to 25 mole% or less, 2 to 25 mole%, 2.5 to 25 mole%, 3 to 25 mole%, 1 to 23 mole%, 1 to 22 mole%, 1 to 17 mole%, 2.5 to 17 mole%, or 3 to 16 mole% with respect to the total moles of the polymers.

[0071] For example, the moles of the compound represented by Formula 4 among the polymers may be 1 to 35 mole%, 1 to 30 mole%, 1 to 25 mole%, 5 to 30 mole%, 5 to 25 mole%, 7 to 30 mole%, 7 to 25 mole%, 10 to 30 mole%, 12 to 30 mole%, 14 to 30 mole%, 1 to 25 mole%, 1 to 23 mole%, 1 to 20 mole%, 1 to 18 mole%, 6 to 23 mole%, or 7 to 18 mole% with respect to the total moles of the polymers.

[0072] For example, the moles of the compound represented by Formula 5 among the polymers may be 50 to 98 moles, 50 to 90 moles, 50 to 87 moles, 50 to 85 moles, 50 to 80 moles, 55 to 90 moles, 56 to 90 moles, 66 to 90 moles, 67 to 90 moles, 66 to 79 moles, or 67 to 78 moles with respect to the total moles of the polymers.

[0073] According to one embodiment, the weight average molecular weight (Mw) of the process oil may be 500 to 8,000 g / mol, and the number average molecular weight (Mn) of the process oil may be 100 to 5,000 g / mol.

[0074] For example, the weight average molecular weight (Mw) of the process oil may be 600 to 8,000 g / mol, 800 to 8,000 g / mol, 1,000 to 8,000 g / mol, 500 to 7,000 g / mol, 500 to 6,000 g / mol, 500 to 5,000 g / mol, 500 to 4,000 g / mol, or 1,000 to 4,000 g / mol.

[0075] For example, the number average molecular weight (Mn) of the process oil may be 100 to 5,000 g / mol, 200 to 5,000 g / mol, 400 to 5,000 g / mol, 500 to 5,000 g / mol, 100 to 4,500 g / mol, 100 to 4,000 g / mol, 100 to 3,500 g / mol, 100 to 3,000 g / mol, or 500 to 3,000 g / mol.

[0076] According to one embodiment, the kinematic viscosity (cst, 40°C) of the process oil may be 20 cSt to 70 cSt, the glass transition temperature of the process oil may be -90°C to -60°C, the iodine value (gI2 / 100g) of the process oil may be 60 to 120, and the acid value (mgKOH / g) of the process oil may be 0.1 to 10. For example, the kinematic viscosity (cst, 40°C) was measured according to ASTM D 445. For example, the glass transition temperature was measured using a differential scanning calorimeter (DSC). For example, the iodine value (gI2 / 100g) was measured according to ASTM D 5768.

[0077] According to one embodiment, the process oil may be prepared by polymerizing the ethylene-based unsaturated monomer containing the ester group and the ethylene-based unsaturated monomer containing the carboxyl group.

[0078] According to one embodiment, the polymerization may be carried out in the presence of an acid catalyst. For example, the acid catalyst may include an organic acid catalyst, an inorganic acid catalyst, or a Lewis acid catalyst.

[0079] According to one embodiment, the organic acid catalyst may include an alkylsulfonic acid having 1 to 6 carbon atoms, an arylsulfonic acid having 6 to 14 carbon atoms, an alkylarylsulfonic acid having 7 to 20 carbon atoms, or an arylalkylsulfonic acid having 7 to 20 carbon atoms.

[0080] According to one embodiment, the inorganic acid catalyst may include sulfuric acid, hydrochloric acid, nitric acid, boric acid, or phosphoric acid.

[0081] According to one embodiment, the Lewis acid catalyst may include boron chloride (BCl3), aluminum chloride (AlCl3), tin chloride (SnCl4), titanium chloride (TiCl4), vanadium chloride (VCl5), iron chloride (FeCl3), boron fluoride (BF3), etc., and organic aluminum compounds such as chlorodiethyl aluminum (Et2AlCl) and dichloroethyl aluminum (EtAlCl2).

[0082] According to one embodiment, the acid catalyst may include sulfuric acid, hydrochloric acid, nitric acid, boric acid, phosphoric acid, sulfonic acid, or para toluenesulfonic acid.

[0083] According to one embodiment, the content of the catalyst may vary depending on the type of catalyst. For example, if the catalyst is a homogeneous catalyst, the content of the catalyst may be 0.01 to 5 weight%, 0.01 to 3 weight%, 1 to 5 weight%, or 2 to 4 weight% with respect to the total weight of the reactants. For example, if the catalyst is a heterogeneous catalyst, the content of the catalyst may be 5 to 200 weight%, 5 to 100 weight%, 20 to 200 weight%, or 20 to 150 weight% with respect to the total weight of the reactants.

[0084] For example, the polymerization may be carried out at 40°C to 100°C, 45°C to 100°C, 50°C to 100°C, 40°C to 90°C, 40°C to 80°C, 40°C to 70°C, 40°C to 60°C, or 50°C to 60°C.

[0085] For example, the polymerization may be performed for 1 to 10 hours, 2 to 10 hours, 3 to 10 hours, 4 to 10 hours, 5 to 10 hours, 1 to 8 hours, 1 to 6 hours, or 5 to 6 hours.

[0086] For example, the above process oil may be a process oil for tires. The above process oil for tires may be mixed with rubber during tire manufacturing to prepare a rubber composition.

[0087] Another aspect of the present invention provides a rubber composition comprising raw rubber and the process oil described above.

[0088] According to one embodiment, the rubber composition may be a rubber composition for tires. For example, a tire or a tire tread may be prepared from the rubber composition for tires.

[0089] According to one embodiment, the raw rubber may include, for example, at least one of natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, isoprene-styrene rubber, isoprene-butadiene-styrene rubber, isobutylene and ethylene propylene diene rubber (EPDM).

[0090] According to one embodiment, the content of the process oil may be 10 to 50 weight%, 10 to 40 weight%, 10 to 30 weight%, or 15 to 25 weight% with respect to the total weight of the rubber composition.

[0091] According to one embodiment, the rubber composition further comprises a tackifier, and the content of the tackifier may be 1 to 10 weight percent with respect to the total weight of the rubber composition. For example, the rubber composition may include the process oil described above, thereby reducing the content of the tackifier included in the rubber composition.

[0092] For example, the adhesive may comprise rosin or rosin derivatives, e.g., gum rosin, wood rosin, and tall oil rosin, and their hydrogenated and unbalanced forms, as well as various derivatives, e.g., alkyl-phenol compounds, acetylene-phenol compounds, and combinations thereof. For example, the adhesive may comprise alkyl phenols, e.g., condensation products of butyl phenol and acetylene, alkylphenol-acetylene resin adhesives, and colorless transparent gum rosin. For example, the adhesive may comprise alkylphenol resin adhesives.

[0093] According to one embodiment, the rubber composition may further include at least one of a reinforcing filler, a vulcanizing agent, a vulcanization accelerator, a crosslinking activator (e.g., zinc oxide or stearic acid), and a degradation inhibitor such as waxes, in addition to the process oil or the raw rubber. For example, the rubber composition may appropriately incorporate materials commonly used in the rubber industry.

[0094] For example, reinforcing fillers may include carbon black, silica, titanium dioxide, clay, layered silicate, tungsten, talc, or syndiotactic-1,2-polybutadiene (SPB).

[0095] According to one embodiment, the content of the reinforcing filler may be 10 to 90 parts by weight, 30 to 90 parts by weight, or 50 to 90 parts by weight per 100 parts by weight of raw rubber.

[0096] For example, the above vulcanizing agent may include sulfur. For example, the content of the above vulcanizing agent may preferably be used in an amount of 1 to 5 parts by weight per 100 parts by weight of raw rubber.

[0097] For example, the vulcanization accelerator may include at least one of a sulfenamide-based vulcanization accelerator (e.g., CBS (2-Benzothlazolesulfenamide, N-cyclohexyl)), a thiuram-based vulcanization accelerator, a thiazole-based vulcanization accelerator, and a guanidine-based vulcanization accelerator (e.g., DPG (Diphenylguanidine)). The content of the vulcanization accelerator may be 0.1 to 7 parts by weight or 0.5 to 5 parts by weight per 100 parts by weight of raw rubber.

[0098] For example, the crosslinking agent may include zinc oxide or stearic acid. For example, the content of the crosslinking agent may be 1 to 10 parts by weight or 2 to 7 parts by weight per 100 parts by weight of the raw rubber.

[0100] The present invention will be described in more detail below through examples. These examples are intended solely to explain the present invention more specifically, and it will be obvious to those skilled in the art that the scope of the present invention is not limited by these examples.

[0102] Preparation Example 1: Preparation of process oil

[0103] 100g of toluene was added to a 1L glass kettle equipped with a reflux device, and a monomer containing a methyl ester group extracted from waste cooking oil and a monomer containing a carboxyl group extracted from waste cooking oil were added in a molar ratio of 6:1. 1.25ml of BF3-phenoate was added as a catalyst, and the mixture was stirred at 40°C. After a self-polymerization reaction at 60°C for 6 hours, the temperature was raised to 80°C. Subsequently, 200g of water was added, and the mixture was stirred for 20 minutes while maintaining the temperature at 80°C. Afterward, stirring was stopped, and the mixture was allowed to wait until phase separation occurred. Once phase separation occurred, the lower layer (water) was removed, leaving only the upper layer (toluene and reactants). The temperature was then raised to 180°C to remove the toluene, and the pressure was reduced to completely remove any remaining volatile substances. Finally, the mixture was cooled to 40°C to prepare the process oil.

[0104] The number of moles of compound (a) containing carboxyl groups at both ends included in the above process oil : the number of moles of compound (b) containing a carboxyl group at one end and an ester group at the other end : the number of moles of compound (c) containing ester groups at both ends = 1 : 2 : 11.

[0105] The ratio of the number of moles of compound (A) containing ester groups at both ends included in the above process oil to the number of moles of compound (B) containing an ester group at one end and a carboxyl group at the other end and the number of moles of compound (C) containing carboxyl groups at both ends was measured through structural analysis using HNMR.

[0107] Preparation Example 2

[0108] 50g of toluene, a solvent, was added, and the polymerization reaction was carried out at 50°C for 6 hours. A process oil was prepared in the same manner as in Preparation Example 1, except that the molar ratio of the monomer containing a methyl ester group extracted from waste cooking oil and the monomer containing a carboxyl group extracted from waste cooking oil was 7.5:1.

[0109] The number of moles of compound (a) containing carboxyl groups at both ends included in the above process oil : the number of moles of compound (b) containing a carboxyl group at one end and an ester group at the other end : the number of moles of compound (c) containing ester groups at both ends = 1 : 6 : 27.

[0111] Preparation Example 3

[0112] Process oil was prepared in the same manner as in Preparation Example 1, except that 200g of toluene, a solvent, was added and the molar ratio of a monomer containing a methyl ester group extracted from waste cooking oil and a monomer containing a carboxyl group extracted from waste cooking oil was 3:1.

[0113] The number of moles of compound (a) containing carboxyl groups at both ends included in the above process oil : the number of moles of compound (b) containing a carboxyl group at one end and an ester group at the other end : the number of moles of compound (c) containing ester groups at both ends = 1 : 1 : 4.

[0115] Preparation Example 4

[0116] Process oil was prepared in the same manner as in Preparation Example 1, except that 200g of toluene, a solvent, was added and the molar ratio of a monomer containing a methyl ester group extracted from waste cooking oil and a monomer containing a carboxyl group extracted from waste cooking oil was 2:1.

[0117] The number of moles of compound (a) containing carboxyl groups at both ends included in the above process oil : the number of moles of compound (b) containing a carboxyl group at one end and an ester group at the other end : the number of moles of compound (c) containing ester groups at both ends = 2 : 2 : 5.

[0119] Preparation Example 5

[0120] Process oil was prepared in the same manner as in Preparation Example 1, except that 200g of toluene, a solvent, was added and the molar ratio of a monomer containing a methyl ester group extracted from waste cooking oil and a monomer containing a carboxyl group extracted from waste cooking oil was 9:1.

[0121] The number of moles of compound (a) containing carboxyl groups at both ends included in the above process oil : the number of moles of compound (b) containing a carboxyl group at one end and an ester group at the other end : the number of moles of compound (c) containing ester groups at both ends = 1 : 1 : 13.

[0123] Ester:Carboxylic Compound with a carboxyl end (a): Compound with a carboxyl + ester (b): Compound with a ester end (c) Preparation Example 1 6:1 1:2:11 Preparation Example 2 7.5:1 1:6:27 Preparation Example 3 3:1 1:1:4 Preparation Example 4 2:1 2:2:5 Preparation Example 5 9:1 1:1:13

[0125] Evaluation Example 1: Evaluation of Physical Properties of Process Oil

[0126] The kinematic viscosity (cst, 40°C) of the process oil according to Preparation Examples 1 to 5 was measured according to ASTM D445, the iodine value (gI2 / 100g) according to ASTM D5768, the glass transition temperature (°C) using a differential scanning calorimeter (DSC), and the acid value (mgKOH / g) according to ASTM D 664, and are listed in Table 2 below.

[0127] Weight-average molecular weight and number-average molecular weight were measured using GPC (Gel permeation chromatograph).

[0129] [Kinematic Viscosity Measurement]

[0130] The kinematic viscosity (cst, 40°C) of the above process oil was measured using a viscometer (Cannon-Fenske Routine Viscometer). The process oils according to Preparation Examples 1 to 5 were each injected into the viscometer so that they filled about half of the lower spherical space of the viscometer. After storing each viscometer in a constant temperature water bath at 40°C for at least 30 minutes, the measurement sample was raised to a certain height of the viscometer using a syringe, and the viscosity was calculated by measuring the travel time for the measurement sample to descend to that certain height. The kinematic viscosity (cst, 40°C) of the above process oil was calculated by multiplying the viscosity constant of the above process oil by the travel time.

[0132] [Acid Value Measurement]

[0133] Process oils according to Preparation Examples 1 to 5 were injected into a 100 ml Erlenmeyer flask. 30 ml of toluene, a neutral solvent, was added to each flask and stirred to dissolve the process oils. 4 to 6 drops of PP (Phenolpthalein) indicator were added to each flask. Titration of the sample containing the process oils was started with 0.1 N alcoholic KOH. Titration continued until the sample containing the process oils changed color and remained at that level for at least 10 seconds (endpoint).

[0134] The acid value was calculated according to Formula 1 below.

[0135] Equation 1:

[0136] V is the titration amount of 0.1N alcoholic KOH,

[0137] F is the 0.1N alcoholic KOA correction factor.

[0139] [Iodine Value Measurement]

[0140] 0.2 g of the process oil according to Preparation Examples 1 to 5 was weighed into each 250 ml Erlenmeyer flask. 10 ml of cyclohexane was added to each flask and stirred to dissolve the process oil according to Preparation Examples 1 to 5. 25 ml of WIJS solution was added, and the mixture was placed in a dark place at 20 to 30°C. It was left in a dark place for 30 minutes if the iodine value was less than 100, and for 1 hour if it was 100 or higher. After standing, 20 ml of KI (10 wt%) solution and 100 ml of distilled water were added to completely dissolve the mixture. 4 to 6 drops of 1% starch solution were added dropwise as an indicator. The mixture was titrated with 0.1 N Na2S2O3 solution until it became colorless. A blank test was performed using the same method.

[0141] The iodine value was calculated from Equation 2 below.

[0142] Equation 2:

[0143] A is the consumption of 0.1 N Na2S2O3 solution (ml) in the blank test,

[0144] B is the consumption of 0.1 N Na2S2O3 solution (ml) in the actual test,

[0145] F is the correction factor (1) of the 0.1 N Na2S2O3 solution.

[0146] The WIJS solution is a solution (1L) prepared by adding non-acetic acid to 7.9g of iodine trichloride (ICl3) and 8.7g of iodine and stirring.

[0148] Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Kinematic viscosity (cst, 40℃) 39 65 25 24 80 Iodine value (gI2 / 100g) 98 70 115 51 118 Tg (°C) -80 -65 -85 -86 -63 Acid value (mgKOH / g) 6.5 9.5 4.5 4.4 9.5 Weight-average molecular weight (g / mol) 1,854 1,950 1,750 1,720 1,980 Number average molecular weight (g / mol) 1,080 1,200 1,050 1,010 1,220 Presence or absence of crystallinity (25℃) radish radish radish you radish

[0150] Example 1: Preparation of a rubber composition

[0151] A rubber composition was prepared by mixing 100g of styrene butadiene rubber (SBR), 80g of silica, 8g of silane, 35g of the above-mentioned process oil, 1.5g of sulfur as a vulcanizing agent, 2g of CBS (2-Benzothlazolesulfenamide, N-cyclohexyl) and 2g of DPG (Diphenylguanidine) as vulcanization accelerators, and 3g of zinc oxide and 2g of stearic acid as crosslinking accelerators.

[0153] Examples 2 to 5

[0154] A rubber composition was prepared in the same manner as in Example 1, except that the type of process oil was corrected as shown in Table 3 below.

[0156] Comparative Examples 1 to 3

[0157] A rubber composition was prepared in the same manner as in Example 1, except that the type of process oil and the content of the adhesive added were corrected as shown in Table 3 below.

[0158] SBR(g) Process oil type Content Example 1 100 Preparation Example 1 35 Example 2 100 Preparation Example 2 35 Example 3 100 Preparation Example 3 35 Example 4 100 Preparation Example 4 35 Example 5 100 Preparation Example 5 35 Comparative Example 1 100 TDAE 35 Comparative Example 2 100 RAE 35 Comparative Example 3 100 waste cooking oil 35

[0159] TDAE: Treated Distillate Aromatic Extract (Petroleum-based Aromatic Oil)

[0160] RAE: Residual Aromatic Extract

[0162] Evaluation Example 2. Evaluation of physical properties of a rubber composition

[0163] The Mooney viscosity (100°C), T05 (125°C), T35 (125°C), rheometer (160°C), mechanical properties, hardness, and dynamic properties of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3 were measured and listed in Tables 4 and 5 below.

[0164] [Moonie Viscosity (100℃)]

[0165] Mooney viscosity is used to evaluate the processability of rubber, and the flow resistance of a rubber sample was measured while a rotor rotated at a speed of 2 rpm at a measurement temperature (100℃). Mooney viscosity was defined as 100 when the torque applied to the rotor was 84.67 kg·f·cm, and the Mooney viscosity of each rubber composition for tires according to Examples 1 to 5 and Comparative Examples 1 to 3 was calculated from the torque applied while the rotor rotated at a speed of 2 rpm. The displacement amount from 0 to 100 M is 2.54 mm.

[0166] [T05(125℃)]

[0167] For each of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3 above, the elapsed time was measured from the time the vulcanization reaction started after reaching the lowest Mooney viscosity (Vm) at 125°C until the lowest Mooney viscosity (Vm) increased by 5M (12.7mm).

[0168] [T35(125℃)]

[0169] For each of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3, after reaching the lowest Mooney viscosity (Vm) at 125°C, the elapsed time (t1) was measured until the vulcanization reaction started and the viscosity increased by 35M (88.9mm) from the lowest Mooney viscosity (Vm), and then T35 (125°C) was measured from the time obtained by subtracting the elapsed time (t2) until the viscosity increased by 5M (12.7mm) from the lowest Mooney viscosity (Vm) from the elapsed time (t1).

[0170] [Rheometer Measurement (160℃)]

[0171] A rheometer is used to evaluate the optimal vulcanization conditions (temperature, time) of rubber. At 165°C, a shear force is applied to the rubber composition for tires according to Examples 1 to 5 and Comparative Examples 1 to 3 as the lower die vibrates at an angle of ±1°, and the vulcanization reaction of the rubber composition for tires according to Examples 1 to 5 and Comparative Examples 1 to 3 proceeds. A torque (lbf·in) is measured by a sensor connected to the upper die according to the degree of progress of the vulcanization reaction.

[0172] ① Rheometer (160℃) Toq.(min) and Toq.(max): The minimum torque value (Toq.(min)) and the maximum torque value (Toq.(max)) were measured from the Rheometer Curve measured by the sensor. As Toq.(min) decreased, the Mooney viscosity tended to be lower, and as Toq.(max) increased, the hardness and modulus tended to be higher.

[0173] ② Rheometer (160℃) T 90 (optimal vulcanization time): The time was measured at 90% of the maximum torque value.

[0174] [Evaluation of Mechanical Properties]

[0175] To evaluate the mechanical properties after vulcanization of the rubber compositions for tires according to Examples 1 to 5 and Comparative Examples 1 to 3, Stress (force per unit area) and Strain (deformation per unit length) were measured using a Load Cell that converts physical quantities such as Force or Load into electrical signals.

[0176] ① Tensile strength: Maximum stress per unit area (kg / cm²) at which the vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3 fracture when pulled. 2 ) was measured.

[0177] ② Elongation: The vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3 were pulled at a constant speed, and the length at break was measured by comparing it to the initial length.

[0178] ③ 100% Elastic Modulus and 300% Elastic Modulus: Stress (kg / cm²) for a specific elongation (100%, 300%) obtained by pulling vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3 above 2 ) was measured.

[0179] [hardness]

[0180] The hardness of the vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3 was measured. The hardness was measured using a Shore A type durometer. The scale of the durometer was divided from 0 (very flexible) to 100 (hard), and a load was applied to the rubber specimen in the form of a static load and a spring.

[0181] [Dynamic Characteristics]

[0182] To evaluate the viscoelastic behavior of the vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3, a vibrating force or deformation was applied to each of the rubber specimens, and the Tanδ value and Tg value according to temperature change were measured from the modulus and energy loss (damping).

[0183] ① Tanδ(0℃): The Tanδ value at 0℃ is a measure of Wet Grip performance.

[0184] ② Tanδ(25℃): The Tanδ value at 25℃ is a measure of Dry Grip performance.

[0185] ③ Tanδ(60℃): The Tanδ value at 60℃ is a measure of cloud resistance.

[0186] ④ Tg(°C): This is the temperature at which the Tanδ value is maximum. The Tg of the vulcanized rubber specimens according to Examples 1 to 5 and Comparative Examples 1 to 3 is measured using a DMA Q800 (TA) in Multi-Frequency-Strain mode under the following conditions.

[0187] - Preload force: 0.01N

[0188] - Poisson's ratio: 0.44

[0189] - Clamp type: Tension film

[0190] - Frequency: 11Hz

[0191] - Measurement temperature range: -50℃ (maintain for 5 min) to 75℃,

[0192] - Heating rate: 3℃ / min

[0193] Example 1 Example 2 Example 3 Example 4 Example 5 Mooney viscosity (100℃) 72 73 70 68 78 T05 (125℃) 23 19 23 22 25 T35 (125℃) 35.8 29.8 34 33 30 Rheometer (160℃) Toq. (max) 29.2 33.1 27.6 25.4 32 Rheometer (160℃) Toq. (min) 7.1 7.5 6.5 6.4 7.4 Rheometer (160℃) T90 9.1 8.2 8.8 8.8 8.3 hardness 73 75 72 70 75 100% elastic modulus (kg / cm²) 2 ) 45 53 43 42 53 300% elastic modulus (kg / cm²) 2 ) 145 165 139 134 164 Tensile strength (kg / cm²) 2 ) 200 210 190 185 212 Growth Rate (%) 405 380 420 450 375 Tg(℃) -27 -23 -30 -30 -23 Tanδ(0℃) 0.2605 0.2913 0.2280 0.2240 0.2915 Tanδ(25℃) 0.1717 0.1775 0.1622 0.1620 0.1782 Tanδ(60℃) 0.1333 0.1404 0.1252 0.1250 0.1408

[0194] Comparative Example 1 Comparative Example 2 Comparative Example 3 Mooney viscosity (100℃) 80 81 78 T5 (125℃) 26 23 22 T35 (125℃) 38.3 34.8 39 Rheometer (160℃) Toq. (max) 39.2 35.6 25.8 Rheometer (160℃) Toq. (min) 8.8 7.9 6.1 Rheometer (160℃) T90 10.5 10.2 10.3 hardness 77 76 67 100% elastic modulus (kg / cm²) 2 ) 60 54 28 300% elastic modulus (kg / cm²) 2 ) 183 166 78 Tensile strength (kg / cm²) 2 ) 177 211 172 Growth Rate (%) 299 370 588 Tg(℃) -20 -18.6 -36 Tanδ(0℃) 0.3514 0.3683 0.2308 Tanδ(25℃) 0.2057 0.2158 0.1622 Tanδ(60℃) 0.1497 0.1459 0.1252

[0195] Referring to the above examples and comparative examples, Examples 1 to 5 have lower Mooney viscosity compared to Comparative Examples 1 to 3, which improves the processability of the mixture. In addition, Examples 1 to 5 have lower glass transition temperatures compared to Comparative Examples 1 to 2, which exhibits excellent low-temperature characteristics and can be more easily applied to winter tires.

[0196] In addition, Examples 1 to 5, which polymerized monomers extracted from waste cooking oil, showed improved mechanical properties such as hardness, 100% elastic modulus, 300% elastic modulus, tensile strength, and elongation compared to Comparative Example 3, which used waste cooking oil as is.

[0198] The aforementioned embodiments and comparative examples are examples for explaining the present invention, and the present invention is not limited thereto. Since a person skilled in the art to which the present invention pertains can implement the present invention by making various modifications therefrom, the technical scope of protection of the present invention should be determined by the appended claims.

Claims

Claim 1 Process oil comprising a polymer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group, wherein the polymer comprises a compound represented by the following chemical formula 3, a compound represented by the following chemical formula 4, and a compound represented by the following chemical formula 5: <Chemical Formula 3> <Chemical Formula 4> <Chemical Formula 5> Among the above chemical formulas 3 to 5, L 31 , L 32 , L 41 , L 42 , L 51 and L 52 is a single bond independently of each other; or an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms; and R 31 to R 36 , R 41 to R 46 and R 51 to R 56 ☐ are independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R 37 , R 38 , R 47 , R 48 , R 49 , R 57 , R 58 , R 59a and R 59b are independently alkyl groups having 1 to 20 carbon atoms, and a31, a32, a41, a42, a51 and a52 are independently integers from 1 to 50. Claim 2 In claim 1, the process oil, wherein the ethylene-based unsaturated monomer containing the ester group is represented by the following Chemical Formula 1, and the ethylene-based unsaturated monomer containing the carboxyl group is represented by the following Chemical Formula 2: <Chemical Formula 1> <Chemical Formula 2> Among the above chemical formulas 1 and 2, R 11 to R 14 and R 21 to R 24 is independently hydrogen or an alkyl group having 1 to 20 carbon atoms, and R 15 to R 16 and R 25 is independently an alkyl group having 1 to 20 carbon atoms, a11 and a21 are independently integers from 1 to 20, and a13 and a23 are independently integers from 1 to 50. Claim 3 In paragraph 2, among the above chemical formulas 1 and 2, R 11 to R 14 and R 21 to R 24 are independently hydrogen, a methyl group, or an ethyl group, and R 15 to R 16 and R 25 Process oils that are independently methyl, ethyl, or propyl groups. Claim 4 A process oil according to paragraph 2, wherein the ratio of the number of moles of a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group to the number of moles of a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group among the polymers is 1 to 20. Claim 5 In claim 1, at least one of the ethylene-based unsaturated monomer containing an ester group and the ethylene-based unsaturated monomer containing a carboxyl group is a process oil derived from edible oil. Claim 6 In claim 1, the polymer comprises a dimer comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group, a dimer comprising a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group, and a process oil comprising a unit (A) derived from an ethylene-based unsaturated monomer containing an ester group and a unit (B) derived from an ethylene-based unsaturated monomer containing a carboxyl group. Claim 7 delete Claim 8 delete Claim 9 A process oil according to claim 1, wherein the moles of the compound represented by Chemical Formula 3 are 1 to 35 mol% with respect to the total moles of the polymer, the moles of the compound represented by Chemical Formula 4 are 1 to 35 mol% with respect to the total moles of the polymer, and the moles of the compound represented by Chemical Formula 5 are 50 to 98 mol% with respect to the total moles of the polymer. Claim 10 A process oil according to claim 1, wherein the weight average molecular weight (Mw) of the process oil is 500 to 8,000 g / mol and the number average molecular weight (Mn) of the process oil is 100 to 5,000 g / mol. Claim 11 A process oil according to claim 1, wherein the kinematic viscosity (cst, 40°C) of the process oil is 20 cSt to 70 cSt, the glass transition temperature of the process oil is -90°C to -60°C, the iodine value (gI2 / 100g) of the process oil is 60 to 120, and the acid value (mgKOH / g) of the process oil is 0.1 to 10. Claim 12 In paragraph 1, the process oil is a process oil for tires. Claim 13 A rubber composition comprising: raw rubber; and process oil according to any one of claims 1 to 6 and claims 9 to 12. Claim 14 In paragraph 13, the above raw rubber comprises butyl rubber, natural rubber, styrene-butadiene rubber, or butadiene rubber, forming a rubber composition. Claim 15 A rubber composition according to claim 13, wherein the content of the process oil is 10 to 50 weight percent with respect to the total weight of the rubber composition. Claim 16 A rubber composition according to claim 13, further comprising at least one of a reinforcing filler, a vulcanizing agent, a vulcanization accelerator, a crosslinking activator, and an anti-deterioration agent.

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