GD INT NATIONAL APPLICATION PUBL (19) World Intellectual Property > Organization International Burau Z = D UNDER THE PATENT COOPERATION TREATY (PCT) AAO AA (10) International Publication Number WO 2020/016439 Al 23 January 2020 (23.01.2020) WIPO|PCT (1) International Patent Classificatio HAKARO, Kannika; 181/270 Charoenpradit Road, CURL. 7/00 (2006.01) CORK 5/54 (2006.01) Muang Pattani, 94000 (TH), NOORDERMEER, Jacques, CUBK 3704 (2006.01) COBK 3/36 (2006.01 COBK 5/10 (2006.01) CUBK 5/1515 (2006.01) COSL, 900 (2006.01) COBL. 9706 (2006.01) BOC 100 2006.01) (CO8K $18 2006.01) International Application Number: PCT/EP2019/069573 ay ay Intern: nal Filing Date: 19 July 2019 (19.07.2019) ling Language: English (26) Publication Languas English (0) Priority Data: LUIOORSS 20 July 2018 20.07.2018) LU (71) Applicant: APOLLO TYRES GLOBAL R&D B.V. [NLINL]: Colosseum 2, 7521 PT Enschede (NL) (72) Inventors: HAYIC 2172 Yarang Rd, Muang. Pata Chesidi; Jnbangtikor, 94000 (TH), SA my en) W. Mz Millenervog 6, 6118 BV Nicwvstadt (NL). REUVEKAMP, Louis A. B. M.: Staverdenhock 3, 7546 GE Enschede (NL), BLUME, Anke; Trierer Strate 45, 53919 Weilesswist (DB) Agent: MICHALSKI HCTTERMANN & PARTNER PATENTANWALTE MBB: Speditionstrabe 21, 40221 Diisseldort (DE), Designated States wiless otherwise indicated, for every Kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DI, DK, DM, DO, DZ. EC, EE, EG. ES, Fl, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN.IR, 1S, 10, JP. KE, KG, KH, KN, KP. KR, KW, KZ, LA, LC,LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI. NO, NZ, ‘OM, PA, PE, PG, PH, PL, PT, QA, RO,RS, RU, RW, SA. SC. SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM. TN, ‘TR TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW < a a z S Ss s a S a E (G4) Title: RUBBER COMPOSITION FOR TYRES COMPRISING MODIFIED UNSATURATED OILS| 500 ea Without oil faa TAR =e HP03% 3 30 g #003 mero 3" ~B+0.04 mEPO 2 250 E200 2 F so 2 1 0 ° a 1 19, 100 1000 sual) FIG (67) Abstract: A cross-linkable mbber composition comprises: a nibber component selected from the group of styrene-butadiene nbber (SBR), polybutadiene mbber (BR), natural rubber (NR) ora mixture theteo. a filer component, 2 silane coupling agent and a process cil component comprising an unsaturated fatty acid triglyceride where atleast one carbon-carbon double bond inthe molecule tas been subjected to one or mare chemical reactions ("modified unsaturated oi"). The filler component comprises silica, the filler component ‘comprises > 0 phr to = 25 phr of carbon black, as the modified unsaturated ol in the process oil component is used: an epoxide of an unsaturated fatty acid triglyceride, a stoichiomettically complete or partial reaction product of an epoxide of an unsaturated fatty acid triglyceride witha molecule containing a micleophilic group, or a mixture thereof and the process oil component comprises > 0 phr to 25 phr of treated distilled aromatic extract (TDAE), mild extracted solvate (MES) and naphthenic (NAP) ols [Continued on next page}WO 2020/016439 A. MMII MON NH N00 TT A i (84) Designated States fanless otherwise indicated, for every ind of regional protection available): ARIPO (BW, Gli, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TI, ‘TMD, European (AL, AT, BE, BG. CH, CY, CZ, DE, DK. EE, ES, Fl, FR, GB, GR. HR. HU, IE. IS, IT, LT, LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI. SK, SM, ‘TR), OAPI (BF, BI, CF, CG, Cl, CM, GA, GN, GO, GW, KM, ML, MR, NE, SN, TD, TO), Published: = wth international search report grt. 213)WO 2020/016439 PCT/EP2019/069573 The present invention relates toa cross-linkable rubber composition, a cross-linked rubber composition obtained by cross-linking such a rubber composition, a method of preparing a tyre and atyre. 5. Tread rubber is one of the important portions of a pneumatic tyre which contributes enormously to the overall performance of a tyre. A tyre has to perform well in severe weather conditions and it has to exhibit a variety of performances such as wet grip, abrasion resistance and low rolling resistance. In addition, further requirements for all: son and winter tyres are required, such as retaining good, performance on snow and ice. 10 After a ban of distillate aromatic extract (DAE) oil containing polycyclic aromatic hydrocarbons (PAHs) for the production of tyres or parts of tyres after I January 2010 (European Directive 2005/69/EC), the safe process oils such as treated distillate aromatic extract (TDAE), mild extracted solvate (MES) and naphthenic (NAP) oils are the alternatives. However, due to scarceness of the supply of petroleum-based process oils in the near future and a need for more 15 sustainable tyre compositions, natural oils, especially plant or vegetable-based oils, have been considered as alternative process oils for rubber compounds, For rubber-tyre technology, carbon black has been conventionally used as reinforcing filler for a long time. Lately, silica-reinforced tyre tread compounds show improvement of key tyre performance, ie, lower rolling resistance and better wet traction while maintaining the abrasion 20 resistance when compared to the carbon black-filled tyre compounds. A reduction of rolling resistance of about 20% of the silica-filled tyre rubber compared with the use of carbon black can save 3-44 of fuel. For silica-silane technology in the silica-reinforced rubber compounds for low rolling resistance tyre treads, reactions take place between the alkoxy groups in the silane coupling agents and the 25. silanol groups on the sili on, the so-called silanization, and a coupling reaction takes place between the silane moieties with the rubber molecules. The silanization usually takes place during mixing and it is known that basic conditions or alkalinity havea talytic effect on the condensation reaction, An effective silanization leads to an improved compatibility between the silica surface and the rubber molecule or to enhanced silica-rubber 30 interactions Process oils are generally added into the rubber compounds with high loading of fillers to improve the processability and dispersibility of fillers in the rubber matrix. The petroleum-based distillate extract (DAE) was conventionally used in carbon black-filled tyre compounds. Based onWO 2020/016439 PCT the report of investigation on tyre particles on the road surface by The Swedish National Chemicals Inspectorate (2003), the DAE oil contains polycyclic aromatic hydrocarbons (PAHs) in which some of them are already classifi d as carcinogenic substances. Thereafter, the DAE oil has been banned. for the production of tyres or parts of tyres and shall not be placed on the market from 1 January ate aromatic 5 2010 according to Directive 2005/69/EC. The safe process oils such as treated dis extract (TDAE), mild extracted solvate (MES) and naphthenic (NAP) oils are the alternatives. In anticipation of a s aarceness of the supply of petroleum-based process oils in the near future and a need for more susta able tyre compositions, natural oils especially plant or vegetable-based oils have been con: lered as altern: fe process oils for rubber compounds. 10 However, the plant- or vegetable-oils contain some unsaturated fatty whose double bonds could react with the curing agent and interfere the vulcanization reaction, This can be addressed by modifying the oil structure to reduce the double bond and to increase the compatibility between the oil and rubber as well as filler, One modification methods that is widely used for bio-oils is epoxidation. 15. The publication by A. Wae-chi., A, Rungwichaniwat,, K. Sahakaro, “Chemically modified natural- based safe process oils in carbon black filled-natural rubber/styrene butadiene rubber blends”, RubberCon 2013, Royal Orchid Sheraton, Bangkok, 16-18 December 2013 is concerned with the in carbon black-filled NR/SBR rubber blends, use of such The publication by S, Ieadsang, A. Thitithammawong, C, Nakason, A. Kaesaman “Influence of N- 20 Phenyl-p-Phenylenediamine modified epoxidized palm oil on properties of carbon black filled natural rubber compound and vulcanizate”, Advanced Materials Research, 844, 239-242 (2014) discloses the use of such a modified oil in carbon black-filled NR compounds, The publication by C. Moojea-Te, A. Rungvichaniwat, K. Sahakaro “Influence of processing oil based on modified epoxidized vegetable oil with N-phenyl-p-phenylenediamine (PPD) on extrusion 25 _ process behaviors of natural rubber compounds”, Key Engineering Materials, 659, 423-427 (2015) focuses on the use in carbon black-filled natural rubber compounds with an emphasis on extrusion behaviors, The publication by A. Thitithammawong, C, Nakason, C. Hayichelach “Influence of oxirane ring and phenylenediamine structures in modified palm processing oils on properties of ENR/PP TPV 30 Macromolecular Symposia, 354, 21-27 (2015) relates to blends of polypropylene (PP) anc epoxidized natural rubber (ENR). EP 2 340 946 Al discloses a pneumatic tire comprising at least one component selected from thePCT WO 2020/016439 group consisting of beads, apexes, and sidewall veneers, the at least one component comprising a rubber composition, the rubber composition comprising at least one diene based elastomer, an epoxidized palm oil and less than 1 phr of steai The present invention has the object of providing a cross-linkable rubber composition which may be used as a tread rubber in a tyre where petroleum-based process oils can be used in a lower amount or can be omitted entirely. This object is achieved by a cross-linkable rubber composition according to claim 1, a cross-linked rubber composition according (0 claim 8, a method according to claim 14 and a tyre according to claim 15, Advantageous embodiments are the subject of dependent claims. They may be combined 10 freely unless the context clearly indicates otherwise Accordingly, a cross-linkable rubber composition comprises: a rubber component selected from the group of styrene-butadiene rubber (SBR), polybutadiene rubber (BR), natural rubber (NR) or a mixture thereof; a filler component, 15 asilane coupling agent and a process oil component comprising an unsaturated fatty acid triglyceride where at least one carbon-carbon double bond in the molecule has been subjected to one or more chemical reactions (“modified unsaturated oil”) wherein the filler component comprises silica, 20 the filler component comprises > 0 ph to < 25 (preferably > 0 phr to < 10 phr) of carbon black, as the modified unsaturated oil in the process oil component is used: aan epoxide of an unsaturated fatty acid triglyceride, a stoichiometrically complete or partial reaction product of an epoxide of an unsaturated fatty acid triglyceride with a molecule containing a nucleophilic group, 25 or a mixture thereof and the process oil component comprises > 0 phr to = 25 phr (preferably > 0 phr to < 10 phr) of, treated distilled aromatic extract (TDAE), mild extracted solvate (MES) and naphthenic (NAP)WO 2020/016439 PCT hr” denotes “per hundred parts by weight of rubber”. It has surprisingly been found that the modified unsaturated oils according to the invention permit the substantial or complete substitution of petrochemically-based process oils in silica-filled rubber formulations with little or no carbon black fillers without a negative change of the rubber properties, as they relate to tyre treads. Specific properties such as tan delta values at 60 °C (equating to a lower rolling resistance) are even lowered (improved). Without wishing to be bound by theory it is believed that becau ¢ the epoxidized oils contain less double bonds and increased polarity they exhibit a positive effect on the vulcanization and silica-oil compatibility. Moreover, the further modifi tion of epoxidized oil is believed to additionally help 10 _ to promote the silanization reaction or to enhance hydrophobation by the oil adsorption. The cross-linkable rubber composition according to the invention comprises cross-linkable groups in the individual rubber components. They may be cross-linked (cured, vulcanised) by methods known to a skilled person in the rubber technology field. The cross-linkable rubber compositions may be sulfur-vuleanizable and/or peroxide-vulcanizable, Other vulcanization systems may also be 15 used. If desired, additives can be added. Examples of usual additives are stabilizers, antioxidants, lubricants, fillers, dyes, pigments, flame retardants, conductive fibres and reinforcing fibres. The SBR rubber component may contain one type of SBR rubber or several different types. Preferably, at least one type of SBR rubber is wanufactured according to the solution process (SSBR or solution SBR). Likewise, the BR rubber component may contain one type of BR rubber 20 or several different types. It is further understood that in formulations discussed in connection with the present invention the phr amount of all rubber components adds up to 100. The cross-linkable rubber composition also comprises a silane coupling agent. Particularly suitable silane compounds comprise di- and tetrasulphides and mercaptosilanes. In an embodiment of the 25 cross-linkable rubber composition the silane coupling agent is a trialkoxymercaptoalkyl silane, bis|3-(triethoxysily))propyl] tetrasulfide (TESPT), bis (3-triethoxysilylpropyl) disulfide (TESPD). bis(trimethylsilylmethyl) tetrasulfide (TMSMT), 3-mercaptopropyltriethoxy silane, 7- glycidyloxypropyl trimethoxy silane, vinyl tri(2-methoxyethoxy) silane, y-methacryloxypropyl trimethoxy silane, octyltriethoxysilane, aminopropyl_triethoxy silane, 3-octanoyl-thio- 30. propyltriethoxysilane (Nxt), 3-inercaptopropyl-ti(tridecan-I-oxy-13- penta(ethyleneoxide))ethoxysilane (VP Si-363) or a mixture of at least two of the aforementioned components.WO 2020/016439 PCT The modified unsaturated oil according to the invention can be an epoxide of an unsaturated fatty acid triglyceride (also designated as unsaturated fat or unsaturated oil). In the triglyceride, one, two or three fatty acids may contain C=C double bonds for epoxidization. The epoxidization may be complete, i.e. 100% of available C=C double bonds in the fatty acid triglyceride have been 5 converted, of incomplete, ie. the fatty id triglyceride contains epoxy groups and C=C double bonds, The incomplete case is preferred, The modified unsaturated oil may also be further modified in the sense that a molecule containing a nucleophilic group such as an OH group, an NH> group or an SH group reacts with the epoxidized fatty acid triglyceride, This reaction may be stoichiometrically complete, ie. all epoxy groups have 10 undergone the ring-opening addition of the nucleophili species. Alternatively, the reaction may also be stoichiometrically incomplete, meaning that the modified unsaturated oil comprises epoxy groups and the products of the ring-opening addition, Of course, C=C double bonds may also still be present in these modified unsaturated oils. By the epoxidation reaction, the epoxidized oil has a more saturated structure and higher polarity 15 due to a change of double bonds into the epoxide rings which can interact with the silanol groups of the silica surface, For si jica/silane-reinforced rubber compounds in which the reaction between the silanol groups on the silica surface and the alkoxy groups on the silane molecules, i.e. the silanization reaction, is preferably promoted. The presence of amines such as diphenyl guanidines or linear aliphatic amines can act as the silanization booster 20 In particular, to replace the petroleum-based process oil with bio-based oil in silica-reinforced rubber compounds, an amine-modified epoxidized palm oil (m-EPO) may be selected based on the assumption that the amine functionality attached to the oil molecules may act as a silanization and vulcanization booster, and later to enhance hydrophobation of the silica surface due to the adsorption of amine-modified oil after the silanization. The palm oil may be selected as a base 25 material for modification due to its high proportion of saturated fatty acids over the unsaturated ones (43.4/56.6), According to the invention the filler component comprises > 0 phr to = 25 phr, preferably = 0 phr to 10 phr, of carbon black. Furthermore, the process oil component comprises > 0 phr to < 25 phr (preferably 2 0 phr to < 10 30 phr) of treated distillate aromatic extract (TDAE) , mild extracted solvate (MES) and naphthenic (NAP) oils, Particularly preferred are = 0 phr to < 1 phr, more preferred > 0 phr to < 0.1 phr. In essence, it is most preferred that the filler component is free from these oils with the exception of any technically unavoidable impurities as they may arise in a rubber processing facility,WO 2020/016439 PCT In one embodiment the unsaturated fatty acid triglyceride used as starting material for the modified Unsaturated oil is a glyceride of a-linolenic acid, stearidoni acid, eicosapentaenoic acid docosahexaenoic acid, linoleic acid, linolelaidic acid, y-linolenic acid, dihomo-y-linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, accenic acid, paullinic acid, oleic acid, 5 elaidic acid, gondoic acid, erucic acid, nervonic acid, mead acid or a mixture thereof. In another embodiment the unsaturated fatty acid triglyceride used as starting material for the modified unsaturated oil is olive oil, peanut oil, soybean oil, sesame oil, com oil, sunflower oil, canola oil, palm oil or a mixture thereof. In another embodiment the modified unsaturated oil comprises > 1 mol-% to < 10 mol-% of epoxy 10 groups, based on the molar amount of unsaturated fatty acid trigliceride uses as starting material in its synthesis, Preferred are > 2 mol-% to <7 mol-6, more preferred > 3 mol-Y% to < 5 mol-% In another embodiment the modified unsaturated oil is the reaction product of > 0.01 mol to < 0.1 mol of the molecule containing a nucleophilic group per 1000 g of the epoxide of an unsaturated fatty acid triglyceride. Preferred are > 0.02 mol to < 0.08 mol, more preferred > 0.03 mol to < 0.05 15 mol. In another embodiment the molecule contai ing a nucleophilic group is a primary aromatic amine Preferred are amines of the PPD type such as with N-phenyl-p-phenylenediamine. Other types of phenylenediamine, preferably p-phenylenediamine or aliphatic diamines are also suitable, These amines have the additional advantage of providing antioxidant properties. 20 In another embodiment the crosslinkable rubber composition according 10 the invention Natural rubber (NR) © 10 phr to = 100 phr (preferably = 50 phr to = 100 ph) Styrene butadiene rubber (SBR), butadiene =O phr to = 50 phr rubber (BR), isoprene rubber (IR) or a mixture of at least two of the aforementioned rubbers Silica’ 40 phr to = 130 phr (preferably = 50 phr to= 60 phr) Bis[3-(Griethoxysily propyl] tetrasulfide © 1 phr to = 13 phr (preferably = 2 phr to < 10 (TESPT) phr) Epoxidized palm oil, a reaction product of © 5 phr to $20 phr epoxidized palm oil with N-phenyl-p- phenylenedliamine (PPD) or a mixture thereof Carbon black © 0 phr to = 10 phr ‘Treated distilled aromatic extract (TDAE), =O phr to = 10 phr extracted solvate (MES) and naphthenic (NAP) oilsWO 2020/016439 PCT The invention is also directed towards a cross-linked rubber composition which is obtained by cross-linking a rubber composition according to the invention In one embodiment the cross-linked rubber composition has a difference in storage moduli G” at 5 0.56% elongation and 100% elongation of 2 250 kPa, the storage moduli being determined at a temperature of 100 °C and a frequency of 0.5 Hz. The difference in storage moduli at low and high strains, for instance G'(at 0.56%)-G"(at 100%), is called the Payne effect and can be taken as a measure for the level of filler-filler inter: jon within the rubber compounds. The Payne effect can be determined with a rubber process analyzer (RPA) using uncured compounds. Preferably the 10 difference is > 250 kPa to < 350 kPa, more preferred > 260 kPa to < 340 kPa, In another embodiment the cross-linked rubber composition has a tensile strength according to ASTM D412 of > 24 MPa. Preferably the modulus is > 25 MPa to < 30 MPa. Furthermore, the g to this tes modulus at 100% elongation accor ing procedure may be > 1.7 MPa to < 2.0 MPa, the modulus at 200% elongation > 4.5 MPa to < 6.0 MPa and the modulus at 300% elongation may 15 be>9.5 MPa to < 12.0 MPa, In another embodiment the cross-linked rubber composition has an elongation at break according to ASTM D412 of > 480%. Preferably the elongation at break is 520% to < 580%. 2 500% to < 600%, more preferred > In another embodiment the cross-linked rubber composition has a maximum of the tan delta value 20. (determined from DMA measurements according to ISO 4664-I, frequency 10 Hz, 0.1% dynamic strain) at > -80 °C to = -20 °C, preferably > -60 °C to < -50 °C. jon has a tan delta at 0 °C of > 0.1 to < In another embodiment the cross-linked rubber compos 1g to ISO 4664-1, frequency 10 Hz, 0.1% 0.15 (determined from DMA measurements accor dynamic strain) and a tan delta at 60 °C of 2 0.05 to < 0.15 (determined from DMA measurements 25 according to ISO 4664-1, frequency 10 Hz, 1 % dynamic strain), Preferred are tan delta values at 0 °C of 20.11 to < 0.12 and at 60 °C of 20.06 to < 0.08, The present invention also relates to a method of preparing a tyre, comp ing the steps of - providing a tyre assembly comprising @ cross-linkable rubber composition according to the invention; 30. - cross-linking at least the crosslinkable rubber composition according to the invention in the tyre assembly.WO 2020/016439 PCT Another aspect of the invention is a tyre comprising a tyre tread, wherein the tyre tread comprises a cross-linked rubber composi ion according to the invention. ‘The present invention will be further described with reference to the following figures and examples without wishing to be limited by them. 5 FIG.1 shows storage moduli at varying strain of, ica-reinforced rubber tyre compounds with different process oils FIG. 2. shows Payne effects of silica-reinforced rubber tyre compounds with different process oils, FIG.3 shows cure characteristics of s reinforced rubber tyre compounds with different process oils 10 FIG. 4 shows mechanical properties of silica-reinforced rubber tyre compounds with different process oils FIG. 5. shows elongations at break of silica+ inforced rubber tyre compounds with different process oils FIG. 6 shows tan 8 values of silica-reinforced rubber tyre compounds with different process oils as 15 analysed by DMA under temperature sweep FIG. 7 shows tan 3 values at 60°C of silica-reinforced rubber tyre compounds with different process oils as analysed by RPA under frequency sweep Methods: Payne effect: The storage shear moduli (G") of rubber compounds without curatives was evaluated 20 by using Rubber Process Analyzer (RPA) (Alpha ‘Technologies, Akron, USA) under the temperature of 100 °C, frequency of 0.5 Hz and varying strains in the range of 0.28-100%. The Payne effect was calculated from different storage shear moduli at low strain (0.56%) and high strain (100%), Cure behaviors: Cure behaviors were tested using RPA at 150 °C, frequency 0.833 Hz. and 2.79% 25 _ strain according to ASTM D5289-95. Mechanical properties: Type 2 dumb-bell test specimens were prepared and then tensile properties were tested with a Zwvick tensile tester Model Z1.0/THIS (Zwick Roell Group, Ulm, Germany) at a crosshead speed of 500) mm/min according to ASTM D412.WO 2020/016439 PCT Dynamic mechanical properties by DMA: Dynamic mechanical properties of silica-reinforced rubber compounds were characterized in tension mode using a 6x4x2 mm’ test specimen, The test was conducted with DMA800) (Perkin Elmer) at a frequency of 10 Hz. and 0.1% strain in a temperature range of -80 to 100 °C. Dynami al property by RPA: The loss tangent of the rubber vuleanizates was determined using RPA at 60 °C and a strain of 3.49% with varying frequencies in the range of 0,05-33 Hz. The rubber compounds were cured prior to the loss tangent measurement in the PRA chamber at 150 °C to their respective optimum cure times. 10 Silica-reinforced rubber tyre compounds were prepared. ‘The rubber compounding formulations are NR (natural rubber; 100 phr), silica (55 phr), TESPT (bis[3-(triethoxysily)propyl] tetrasulfide; 5 phr), ZnO (3 phr), stearic acid (1 phr), TMQ (1,2-dihydro- process oil (8 phr), OCT (octadecylar 4-trimethylquinoline polymer; 1 phr), 1.0 phr), CBS (N-cyclohexyl-2-benzothiazole sulfenamide; 1.5 phr) and sulfur (1.5 phr), In this study, the octadecylamine (OCT) was used as 15 diphenylguanidine (DPG) alternative to give the rubber compounds having less toxie ingredients and becoming a more green product. “Different types of process oils used in this study were treated distilled aromatic extract (TDAE), epoxidized palm oil with 3 mole % epoxide groups (EPO3%), amine-mo with 0,03 mol of amine in 1000 g of EPO3% (0.03 mEPO), and amine-modified epoxidized palm 20 _ oil with 0.04 mol of amine in 1000 g of EPO3% (01.04 mEPO). ied epoxidized palm oil 1) Preparation of epoxidized palm oil (EPO) The epoxidation reaction was cartied out using peracid generated from formic acid and hydrogen peroxide. 150 g of palm oil was added into a three necked flask (250 mL capacity) equipped with a mechanical stirrer, thermometer and reflux condenser at 45 °C. Then, the palm oil was acidified 25 with formic id under continuous stirring. Hydrogen peroxide was subsequently slowly added was 1:2:4. Fast introduction of H2Os should dropwise, The molar ratio of palm oil: HCOOH: be avoided as it causes an excessive development of oxygen due to the decomposition of the peroxide. After reaching the reaction time of 3 hrs, the reaction mixture was taken out from the reactor, thoroughly washed with sodium bicarbonate (5 wt%), distilled water and sodium chloride 30. (5 wt%) to separate the organic layer from the mixture. 2) Preparation of amine-modified EPO The amine-modified EPO was synthesized by reacting the EPO with N-phenyl-p-phenylenediamineWO 2020/016439 -10- PCT (PPD) having zinc chloride (ZnCI,) as catalyst. The weight ratio of EPO: PPD: ZnCl: was fixed at 10:1:0.5, The reaction mit (ure was heated at 100 °C for 3 and 5 hrs, respectively, under continuous stirring. After that, the ZnCls was separated by filtration through a cotton wool. The unreacted PPD in the oils was eliminated by absorbing with silica gel. In this step, the crude modified oil was 5 diluted with a mixture of hexane and diethylacetate (1/1) before passing through the column packed with the silica gel. The solvent was finally eliminated by rotary evaporator. The modified oils were characterized to confirm the presence of the functional groups by means of FTIR and'H NMR. The bio-based oils obt yed were then used for rubber compounding, cated in an internal mixer (Brabender Plasticorder 350s) for 2 min with the 10 mixing conditions of fill factor 0.70, initial mixer temperature setting of 100 °C and rotor speed of 60 rpm, Then, a half of silica and a half of TESPT together with a quarter of octadecylamine were added in the mixing chamber and mixed for 5 min, Subsequently, the remaining of silica and TESPT with a quarter of octadecylamine were incorporated and mixed for 5 mins prior to the addition of ZnO, stearic acid, TMQ and process oil into the rubber compounds. 15. The rubber compound mixed in the internal mixer was discharged at 15 mins. The curing agents, ie. CBS, sulfur and remaining octadecylamine, were finally mixed into the rubber compound on a two-roll mill. Afterwards, the rubbers were cured the rubbers were cured to their respective optimum cure time (ty) by using a compression press at 150 °C and 100 bar Results: 20 FIG. 1 shows a reduction of the storage moduli with increasing strain of different compounds due to a breakdown of filler network and slip of polymer chains on the filler surface under dynamic deformation. A breakdown of filler network diminishes filler-fller interaction, allowing a better dispersion of filler in the rubber matrix, The difference in storage moduli at low and high strains, that is, G’(at 0.56%)-G"(at 100%), the so- an be taken as a measure for the level of filler-filler interaction within the 25 called Payne effect, rubber compounds, as shown in FIG. 2. The Payne effect of the silica-filled rubber compounds is normally used to explain the degree of filler—filler interactions that are mainly caused by hydrogen bonding, leading to formation of the filler network in the rubber matrix, The rubber compounds with EPO3% and 0.03 mEPO show lower Payne effect than the compound with TDAE oil, but the 30. mix with 0.04 mEPO shows higher value, When compared among the compounds with process oils, the use of EPO and 0,03mEPO gives lower, ie. better, Payne effect compared to state-of-the- art TDAE. But too many functional groups that lead to higher polarity have a detrimental effect. In the case of without oil, the compound was subjected to higher shear force during mixing because ofWO 2020/016439 ie PCT higher viscosity and thus resulted in greater breakdown of both filler network and rubber molecules. This highlights the advantages of the invention over TDAE. During curing, the rubber compounds without oil shows shorter scorch time but higher cure time and slower cure rate than the ones with process oils. This means that the presence of process oil in the rubber compounds improves the cure behaviour. The rubber compounds with process oils show similar scorch time and cure time. The compounds with amine-modified EPO show shorter cure time than the mix with EPO presumably due to the presence of alkaline amine in the oil structure that helps to promote the cure reaction, In addition, the rubber compositions comprising of amine- modified (m-EPO) have higher cure reaction rate and higher extent of cure torque increase (Mu- 10M.) compared to the compound with state-of-the-art TDAE. The increase of cure torque indicates crosslink density within the rubber matrix. The inventive use of mEPO is better than without oil and with TDAE as indicated by faster cure rate and higher cure torque increase (indicative for crosslink density). ‘The mechanical properties, i.e. moduli at different strains, tensile strength and elongation at break, 15 are shown in FIG, 4 and FIG 5. The presence of process oils gives a positive effect on the improvement of mechanical properties. The rubber compounds with process oils show higher modulus, tensile strength and elongation at break than the compound without oil. The silica-filled vulcanizates with m-EPO have excellent tensile strength and elongation at break compared to the compound with TDAE due to the improvement in the filler dispersion as well as the crosslink 20. density as indicated by the cure torque difference (FIG. 3) within the rubber matrix. The loss tangent or tan delta values of silica-reinforced rubber compounds with different process oils were tested by using Dynamic Mechanical Analyzer (DMA) and Rubber Process Analyzer (RPA), as shown in FIG. 6 and FIG. 7. The presence of process oils causes a slight shift of the glass transition temperature towards lower value due to the increased mobility of the rubber chains, 25 compared to the compound without oil. In the lab-scale test, the loss tangent values at 0 and 60 °C of rubber vulcanizate are commonly used as indicative for wet grip and rolling resistance, respectively. The results show that the use of all process oil types gives better rolling resistance than the compound without oil with slightly inferior wet grip due to the increased in rubber elasticity, The compos ns comprising m-EPO display similar dynamic mechanical properties to 30 the reference compound with TDAE as determined by DMA. But based on RPA tested over a range of frequencies, the use of m-EPO give lower loss tangent at 60°C compared to TDAE: a potential for lower rolling resistance tyre tread made thereof. In conclusion, tyre compounds comprising EPO and 0.03 mEPO have lower Payne effect than the one with TDAE, The presence of process oils in the rubber compounds shows an improvement onWO 2020/016439 +12 PCT the cure behaviour. The rubber compounds with amine-modified (m-EPO) have higher cure reaction rate and higher extent of cure torque increase (Mu-M), indicative for crosslink density, compared to the compound with state-of-the-art TDAE. The amine moiety grafted on the modified process oil molecule has an acceleration effect on the vulcanization resulting in faster cure time 5 compared to other compounds. The rubber compounds with process oils show better mechanical properties, i.e, modulus, tensile strength and elongation at break, and lower (better) loss tangent at 60°C compared to the rubber compound without oil due to a reduction of filler-filler interaction and an increase of crosslink density. The rubber compound with 0,03 mEPO shows better mechanical and dynamic mechanical properties than the compound with TDAE oil, Based on RPA tested over a 10 range of frequencies, the use of m-EPO give lower tan delta at 60°C compared to TDAE; a potential for lower rolling resistance tyre tread made thereof. The use of amine modified-epoxidized palm oil as a process oil in the silica-reinforced rubber tyre compounds gives better properties when compared to the use of state-of-the-art petroleum-based TDAE oil. The rubber compounds with EPO3% and 0,03 mEPO show lower Payne effect than the 15 compound with TDAE oil, The rubber compounds with modified oils show the enhanced cure properties, i.e. increased cure rate and higher cure torque difference, resulting in good end-use properties especially tan delta at 60 °C which is an indication for tyre rolling resistance. The amine- modified EPO gives overall better properties than EPO and can be a potential alternative for TDAE in order to produce rubber compositions comprising biosource component towards better 20 sustainabilityWO 2020/016439 213+ PCT Patent claims 1. A cross-linkable rubber composition, the cross-linkable rubber composition comprising: a rubber component selected from the group of styrene-butadiene rubber (SBR), polybutadiene rubber (BR), natural rubber (NR) or a mixture thereof; 5 a filler component, a silane coupling agent and fa process oil component comprising an unsaturated fatty acid triglyceride where at least one carbon-carbon double bond in the molecule has been subjected to one or more chemical reactions (“modified unsaturated oil”); 10 characterised in that the filler component comprises silica, the filler component comprises > 0 phr to < 25 phr of carbon blac as the modified unsaturated oil in the process oil component is used: an epoxide of an unsaturated fatty acid triglyceride, 15 a stoichiometrically complete or partial reaction product of an epoxide of an unsaturated fatty acid triglyceride with a molecule containing a nucleophilic group, or a mixture thereof and the process oil component comprises > 0 phr to < 25 phr of treated distilled aromatic extract (TDAE), mild extracted solvate (MES) and naphthenic (NAP) oils, 20. wherein the unit “phr” denotes “per hundred parts by weight of rubber”. 2. The rubber composition according to claim 1, wherein the unsaturated fatty acid triglyceride used as starting material for the modified unsaturated oil is a glyceride of a-tinolenic acid, stearidonic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, linolelaidie acid, y- linolenic acid, dihomo--linolenic acid, arachidonic acid, docosatetraenoic acid, palmitoleic acid, 25 accenic acid, paullinic acid, oleic acid, elaidic acid, gondoic acid, erucie acid, nervonic acid, mead acid or a mixture thereof, 3. The rubber composition according to claim 1 or 2, wherein the unsaturated fatty acid triglycerideWO 2020/016439 “14 PCT used as starting material for the modified unsaturated oil is olive oil, peanut oil, soybean oil, corn oil, sunflower oii canola oil, palm oil or a mixture thereof 4. The rubber composition according to one of claims 1 to 3, wherein the modified unsaturated oil comprises > 1 mol-% to < 10 mol-% of epoxy groups, based on the molar amount of unsaturated fatty acid trigliceride uses as starting material in its synthesis. 5. The rubber composition according to one of claims 1 to 4, wherein the modified unsaturated oil is the reaction product of > 0.01 mol to < 0.1 mol of th molecule containing a nucleophilic group per 1000 g of the epoxide of an unsaturated fatty acid triglyceride. 6. The rubber composition according to one of claims 1 to 5, wherein the molecule containing a 10 nucleophilic group is a primary aromatic amine. 7. The rubber composition according to one of claims 1 to 6 comprising: 8) = 10 ph to < 100 phr of natural rubber (NR), b) = 0 phr to < 50 phr of styrene butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR) or a mixture of at least two of the aforementioned rubbers, Is ©) > 40 phr to < 130 phr of silica 4) = I phr to < 12 phe of bisl3-(triethoxysilyl)propyl] tetrasulfide (TESPT), €) = 5 phir to < 20 phr of epoxidized palm oil, a reaction product of epoxidized palm vil with N-phenyl-p-phenylenediamine (PPD) or a mixture thereof, 9 0 phe to < 10 phr of carbon black, 20 g) > 0 phr to < 10 phr of treated distilled aromatic extract (TDAE), mild extracted solvate (MES) and naphthenic (NAP) oils. 8. A cross-linked rubber composition, characterised in that it is obtained by cross-linking a rubber composition according to one of claims 1 t0 7. 9. The cross-linked rubber composition according to claim 8 with a difference in storage moduli G” 25 at 0.56% elongation and 100% elongation of > 250 kPa, the storage moduli being determined at a temperature of 100 °C and a frequency of 0.5 Hz. 10. The cross-linked rubber composition according to claim 8 or 9 with a tensile strength according to ASTM D412 of > 24 MPa.WO 2020/016439 2 15- PCT 11. The cross-linked rubber composi break according to ASTM D412 of > 480%, on according to one of claims 8 to 10 with an elongation at 12, The cross-linked rubber composition according to one of claims 8 to 11 with a maximum of the tan delta value ( -80 °C 10 <-20 °C. 13, The cross-linked rubber composition according to one of claims 8 to 11 with a tan delta at 0 °C of = 0.1 to < 0.15 (determined from DMA measurements according to ISO 4664-1, frequency 10 Hz, 0.1% dynamic strain) and a tan delta at 60 °C of > = 0.05 to < 0.15 (determined from DMA ‘measurements according to ISO 4664-1, frequency 10 Hz, 1 % dynamic strain), 1014. A method of preparing a tyre, comprising the steps of: = providing a tyre assembly comprising a cross-linkable rubber composition according to one of claims 1 t07; Tt 7 in - cross-linking at least the cross-linkable rubber composition according to one of elain the tyre assembly, 15.15. A tyre comprising a tyre tread, characterised in that the tyre tread comprises a cross-linked rubber composition according to one of claims 8 to 13.WO 2020/016439 = PCT/EP2019/069573 © Without oil —#-TDAE = EP03% —é- 0.03 mEPO 8-0.04 mEPO Storage modulus (KPa) strate (%) oe 1000 FIG. 1 Without oil TDAE — EPO3% 0.03 mEPO 0.04 mEPO Type of process oil FIG. 2WO 2020/016439 -24- PCT/EP2019/069573 22 o> Without oil +» TDAE Torque (dN.m) — = -FPO3% — 0.03 mEPO — 0.04 mEPO ‘Time (min) FIG 3 ae) Bu Stress (MPa) a Without oil TDAE —— EPO3% — 0.03 mEPO_ 0.04 mEPO. Type of process oil FIG 4 ‘SUBSTITUTE SHEET (RULE 26)WO 2020/016439 <3 PCT/EP2019/069573 8886382838 s8ssss8 Elongation at break (%) Ss s ° Without oil TDAE — EPO3% 0.03 mEPO 0.04 mEPO Type of process oil FIG. 5 7 Without oil seseeeee TDAE — - -FPO 3% Tané — —0.03 mEPO — 0.04 mEPO #30) 260) 740) 2 20) 10h 20) 40) 60) = 80) = 100 Temperature (°C) FIG 6WO 2020/016439 Puan PCT/EP2019/069573 0,3 eee, go s a ° 3 Without oil on “= TDAE —#-EPO3% -2-0.03 mEPO 20.04 mEPO 0 0,01 O,1 1 10 100 Frequency (Hz) FIG 7 ‘SUBSTITUTE SHEET (RULE 26)INTERNATIONAL SEARCH REPORT Teterational aplication No PCT/EP2019/069573 TNE CORI "CoBKs 04 = coBk3/36 —«COBKS/10 ——-—COBKS/1515 ceBKS/54 —-«cOBL9/00 -—»«COBL9/06.©—«BGOCI/00 ©—«COBKS/18 ADD. Acsording to Itematonal Patent Cassfeaton (PC) or tobothnatonaelatitoaon and IPC ‘imum documentation seared (lassfcaon system folowed by danaioaion a7 Ban) CesL COBK BEOC Dosurrenaton searched Sher an ranrum docurentaion othe Hert Wal auahGasumnlsSre waded ithe hails Seana Testor database coneuTed dung he Wlematonal earch (name oT dala base ard, where pasioabe search Te ed) Ep0-Internal, WPI Data {DOCUMENTS CONSIDERED TO BE RELEVANT Catgon7 | Ctaton ot docureet, wth heaton, where eppepta, of te eon peeagen etvanta clam, x EP 2 792 689 Al (LANXESS DEUTSCHLAND GMBH 1-3,7,8, [DE]; LANXESS ELASTONEROS DO BRASIL S A 11,14,15 [BR]) 22 October 2014 (2014-10-22) Y paragraphs [0025], [0028] - [0034], 1-3,7,8, [0046], [0070], [0074] - [0078], 11,14,15 A [e086], [0089], [0110] - [0113], [0119] 4-6,9, - [0123]; tables 1,3 10,12)13, page 14 - page 15; examples 3,63 tables x EP 1 072 442 Al (SR CORP [JP]) 1-3,8,11 31 January 2001 (2001-01-31) example Y; table 2 claims 1-8; example 5; table 3 X] Ferherdoourents ar inte inthe sontnuation of Box ©. XK] S00 patent amy annex ‘esis ontegories fe! “men 7 later dosument published ater the inkamatona fing date ox pristy “%"eeoumert dating te goer etch a whch not conse ‘Repo or teary underiing be mvenson “© eq gpision orient pubiabedonoraerteittons!_ gag part eeeen he eine nverton cama “Le document whi may throw doubts on priory sai) orwhion ep when ie cosument taken peat esson (es speaied) reane Being obvious toa parson “P dgeumentpubahed pr to the stem! ng date bt ater han ‘he peony date Samed "8 document member ofthe eame patent amy ‘Date of te satel conploton ofthe lamatonal aoaoh ‘Date of maling of he wieranal seek Topo 29 August 2019 23/09/2019 European Patent flo, PB. 818 Patt 2 I aae0 ev Rjere Tai (ata) 480, Flr) ae0a086 Barker, Stephan Fa POTTSAaIO exons hon) Roa DH page 1 of 3INTERNATIONAL SEARCH REPORT Teterational aplication No PCT/EP2019/069573 ‘iContinvaiony DOCUMENTS CONSIDERED TO BE RELEVANT Ccatepo07" Cation of dosument, wth indation, where aporopiate, fhe relevant paseages| Relevant lain No, x EP 3 251 872 Al (GOODYEAR TIRE & RUBBER [us]) 6 December 2017 (2017-12-06) Page 7, paragraph 1-3 - page 9; example £13; tables 1,3 DATABASE WPI Week 200935 Thomson Scientific, London, GB; ‘AN 2009-J69177 XP002789729, -& JP 2009 114257 A (TOYO RUBBER IND CO LTD) 28 May 2009 (2009-05-28) abstract DATABASE WPI Week 201224 Thomson Scientific, London, GB; AN 2011-k48847 XP002789730, -& KR 2011 0072260 A (HANKOOK TIRE MFG CO LTD) 29 June 2011 (2011-06-29) abstract DATABASE WPI Week 201444 Thomson Scientific, London, GB; AN 2014-33068 xP002789731, -& JP 2014 118455 A (SUMITOMO RUBBER IND LTD) 30 June 2014 (2014-06-30) abstract DATABASE WPI Week 201451 Thomson Scientific, London, GB; AN 2014-N61832 XP002789732, ~& JP 2014 133843 A (SUMITOMO RUBBER IND LTD) 24 July 2014 (2014-07-24) abstract DATABASE WPI Week 201010 Thomson Scientific, London, GB; AN 2009-R37553, xP002789733, -& KR 2009 0116171 A (KUMHO TIRE CO INC) 11 November 2009 (2009-11-11) abstract 1-3 1-3,7,8, 14,15 4-6,9-13 1-3,7,8, 14,15 4-6,9-13 1-3,7,8, 14,15 4-6,9-13 1-3,7,8, 14,15 1-3,7,8, 14,15 4-6,9-13 Fam POTTSH210 foninaan Sacer Seah TB page 2 of 3INTERNATIONAL SEARCH REPORT Teterational aplication No PCT/EP2019/069573 ‘iContinvaiony DOCUMENTS CONSIDERED TO BE RELEVANT ‘category | ciation of dooument, ith ndeation, where appropriate, of the reevantpassages Relevant claim No, y SUPAPORN IEADSANG ET AL: "Influence of 1-3,7,8, N-pheny!-p-phenylenediamine Modified 11,14,18 Epoxidized Palm O11 on Properties of Carbon Black Filled Natural Rubber Compound and vulcanizate", ADVANCED MATERIALS RESEARCH, vol. 844, 15 November 2013 (2013-11-15), pages 239-242, xP002789734, Switzerland ISSN: 1662-8985, DOI: doi: 10.4028/www. scientific.net/AMR.844.239 page 239 - page 242 A SABRINA SOLOI ET AL: "Novel Palm Oi 1-15 Based polyols with Amide functionality", INTERNATIONAL JOURNAL OF SCIENCES: BASIC AND APPLIED RESEARCH (1JSBAR) , vol. 37, no. 1, 15 January 2018 (2018-01-15), pages 74-86, xP002789735, ISSN: 2307-4531 cited in the application pages 74-76,82; figure 1 to 6; table 1 Fam POTTSH210 foninaan Sacer Seah TB page 3 of 3INTERNATIONAL SEARCH REPORT Teterational aplication No Information on patent family members PCT/£P2619/069573 Patent dooument Publestion Patent ami Publeation citedin search report date members) ‘ste EP 2792689 Al 22-10-2014 CN 105121476 A 02-12-2015 EP 2792689 AL 22-10-2014 ep 2986647 Al 24-02-2016 ES 2640791 13 06-11-2017 HK 1221967 AL 16-06-2017 HU 034887 12 28-03-2018 op 6389240 B2 12-09-2018 JP 2016515661 A 30-05-2016 KR 20160012135 A 02-02-2016 PL 2986647 13 30-03-2018 RU 2015149122 A 24-05-2017 SG 11201508408P A 27-11-2015 TW 201509967 A 16-03-2015, US 2016068659 AL 10-03-2016 WO 2014170356 AL 23-10-2014 ZA 26-10-2016 EP 1072442 EP 3251872 oP 2009114257 KR 20110072260 A OP 2014118455 A OP 2014133843 kR 20090116171 A 31-01-2001 06-12-2017 28-05-2009 29-06-2011 30-06-2014 24-07-2014 11-11-2009 201508478 B 60018649 T2 1072442 AL 2238227 13 6518350 B1 "3251872 Al 2017214566 A 2017349733 AL 04-05-2006 31-01-2001 01-09-2005 11-02-2003 06-12-2017 07-12-2017 07-12-2017