Liquid petroleum resin, method for preparing same, and tire tread composition comprising same

Abstract

The present invention relates to a novel liquid petroleum resin, a method for manufacturing same, and a tire tread composition comprising same, wherein the novel liquid petroleum resin can replace existing process oils causing environmental problems while improving rotational resistance, braking properties, and abrasion resistance of a tire tread used for tire manufacturing.

Description

Liquid petroleum resin, method for producing same, and tire tread composition comprising same

[0001] The present invention relates to a new liquid petroleum resin that can replace existing process oils that cause environmental problems while improving the rolling resistance, braking performance, and wear resistance of tire treads used in tire manufacturing, a method for manufacturing the same, and a tire tread composition comprising the same.

[0002] In the manufacture of tire treads, process oil is used to improve compatibility with rubber and dispersibility of silica.

[0003] Initially, DAE (distillate aromatic extract) was used as the process oil, but it had the disadvantage of containing excessive amounts of PAH (polycyclic aromatic hydrocarbon), an environmentally regulated substance. Currently, TDA (treated distillate aromatic extract) oil is used as the main process oil.

[0004] However, TDAE oil, although within the regulatory limits, contains polycyclic aromatic hydrocarbons (PAHs), which are known to be carcinogenic, mutagenic and reproductively toxic and are classified as persistent organic pollutants under the Stockholm Convention.

[0005] Accordingly, there is a trend to regulate the use or content of PAHs in products. For example, the EU has regulated the use of specific PAHs in tire products sold since 2010, and has regulated the content of specific PAHs in extender oils in tire products. The total content of eight types of PAHs, including benzo(a)pyrene, benzo(a)anthracene, benzo(b)phloranthene, benzo(k)phloranthene, benzo(e)pyrene, chrysene, benzo(j)phloracene, and dibenzo(a,h)anthracene, is limited to 10 mg / kg (ppm) or less, thereby restricting the use of extender oils. In addition, the content of PAHs in vulcanized rubber and vulcanized rubber compounds in tire products is limited to less than 0.35%.

[0006] Therefore, considering the environmental problems of TDAE oil, a process oil with a high PAHs content, it is important to find a substitute that can replace it.

[0007] The present invention relates to an environmentally friendly processing oil that can replace TDAE oil, which is used as a process oil (or extender oil) in the manufacture of tire treads. As a result of various studies, the present invention has discovered the optimal composition of a new liquid petroleum resin that can replace TDAE oil while satisfying or improving the properties required for tire treads. In other words, the present invention provides a liquid petroleum resin, a method for producing the same, a tire tread composition using the same, a tire tread processed using the same, and a tire.

[0008] The liquid petroleum resin of the present invention for solving the above problem is a hydrogenated liquid petroleum resin obtained by hydrogenating a DCPD (Dicyclopentadine) polymer, wherein the DCPD polymer is a polymer obtained by polymerizing DCPD (Dicyclopentadine), a C5 compound, and a styrene compound, and the hydrogenated liquid petroleum resin has a weight average molecular weight of 200 to 500 and a viscosity at 40°C of 50 to 1,000 cP.

[0009] As a preferred embodiment of the present invention, the C5 compound in the liquid petroleum resin composition may include at least one selected from 1,3-pentadiene, isoprene, piperylene, cyclopentadiene, cyclopentene, 1-pentene, 2-methyl-2-butene, and n-pentane.

[0010] As a preferred embodiment of the present invention, the polymer is obtained by polymerizing 1 to 10 parts by weight of a C5 compound and 1 to 50 parts by weight of a styrene compound with respect to 100 parts by weight of DCPD.

[0011] As a preferred embodiment of the present invention, the hydrogenated liquid petroleum resin (or hydrogenated petroleum resin) can satisfy an aromatic hydrogenation rate of 50 to 70% according to the following mathematical expression 1.

[0012] [Mathematical Formula 1]

[0013] Aromatic hydrogenation rate (%) = (AB) / A × 100%

[0014] In mathematical expression 1, A and B are 1 It refers to the area ratio of the aromatic compound peak measured by H-NMR, A refers to the area ratio of the aromatic compound peak of the polymer before the hydrogenation reaction, and B refers to the area ratio of the aromatic compound peak of the polymer after the hydrogenation reaction.

[0015] As a preferred embodiment of the present invention, the hydrogenated liquid petroleum resin (or hydrogenated petroleum resin) is 1 When measuring H-NMR, the following equation 1 can be satisfied.

[0016] [Equation 1]

[0017] 0.01 < C / (C+D+E) < 10.0

[0018] In equation 1, C and D represent the hydrogenated liquid petroleum resins. 1This is the area ratio of the peak measured by H-NMR, C is the area ratio of the aromatic compound peak, D is the area ratio of the aliphatic compound peak, and E is the area ratio of the olefin compound peak.

[0019] Another object of the present invention relates to a method for producing a liquid petroleum resin as described above, comprising: a first step of producing a polymer; a second step of hydrogenating the polymer; and a third step of extracting a liquid hydrogenated liquid petroleum resin from the reaction product of the second step hydrogenation reaction.

[0020] As a preferred embodiment of the present invention, the polymer in step 1 includes a polymer obtained by polymerizing DCPD (Dicyclopentadine), a C5 compound, and a styrene compound.

[0021] As a preferred embodiment of the present invention, the two-step hydrogenation reaction is performed by introducing a hydrogenation catalyst into a packed continuous hydrogenation reactor.

[0022] As a preferred embodiment of the present invention, the extraction in the third step is performed by a purification process to select a product having a weight average molecular weight of 200 to 500 and a viscosity at 40°C of 50 to 1,000 cp, thereby obtaining a liquid hydrogenated liquid petroleum resin.

[0023] In addition, the object of the present invention relates to a tire tread composition, wherein the hydrogenated liquid petroleum resin described above includes process oil (or extender oil).

[0024] In a preferred embodiment of the present invention, the process oil may contain only a hydrogenated liquid petroleum resin, or may contain a mixed resin of the hydrogenated liquid petroleum resin and other liquid petroleum resins.

[0025] As a preferred embodiment of the present invention, the other liquid petroleum resin among the mixed resins includes at least one selected from a non-hydrogenated liquid petroleum resin and an aromatic copolymer liquid petroleum resin, and the aromatic copolymer liquid petroleum resin may be a hydrogenated liquid petroleum resin obtained by hydrogenating a polymer obtained by polymerizing DCPD (Dicyclopentadine), a C5 compound, and a styrene compound.

[0026] In a preferred embodiment of the present invention, the tire tread composition of the present invention may include a rubber resin, a filler, an activator, an antioxidant, a vulcanization accelerator, a vulcanizing agent, the process oil, and a petroleum resin. In this case, the petroleum resin in the tire tread composition is a different petroleum resin from the hydrogenated liquid petroleum resin in the process oil.

[0027] As a preferred embodiment of the present invention, the tire tread composition of the present invention may include 35.0 to 50.0 wt% of a filler, 0.5 to 3.5 wt% of an activator, 0.1 to 1.0 wt% of an antioxidant, 0.3 to 3.0 wt% of a vulcanization accelerator, 0.1 to 1.2 wt% of a vulcanizing agent, 1.0 to 10.0 wt% of the process oil, 5.0 to 15.0 wt% of a petroleum resin (a petroleum resin different from the hydrogenated liquid petroleum resin in the process oil), and a rubber resin with the remaining balance of 100 wt%.

[0028] In a preferred embodiment of the present invention, the rubber resin in the tire tread composition of the present invention may include at least one selected from natural rubber, butadiene rubber, nitrile rubber, silicone rubber, isoprene rubber, styrene-butadiene rubber (SBR), isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber, halogenated butyl rubber, halogenated isoprene rubber, halogenated isobutylene copolymer, chloroprene rubber, butyl rubber, and halogenated isobutylene-p-methylstyrene rubber.

[0029] Another object of the present invention relates to a tire tread, which is a processed product processed using the tire tread composition described above, and when measured under the conditions of -80 to 110°C and 10 Hz based on a dynamic mechanical analysis method, it is possible to obtain better braking characteristics (0°C, Tanδ) and rolling resistance characteristics (60°C, Tanδ) than when using conventional tire processing oil (TDAE oil).

[0030] In addition, the tire tread of the present invention can satisfy a relative wear rate of 70% to 95% according to Equation 2 when measured according to the ASTM D 5963 or KS M ISO 4649 method, preferably when measured according to the KS M ISO 4649 method.

[0031] [Formula 2]

[0032] Relative wear rate (%) = (Wear value of the tire tread rubber to be measured / Wear value of the control group) × 100%

[0033] In Equation 2, the control group is one in which TDAE (Treated Distillate Aromatic Extract) is used solely as an extender oil in the manufacture of tire tread rubber, and the control group and the tire tread rubber to be measured have the same composition (ingredients) used in the manufacture of tire tread rubber, except for the extender oil.

[0034] In addition, an object of the present invention is to provide a tire to which the tire tread described above is applied.

[0035] The liquid petroleum resin of the present invention has a very low or no content of PAHs subject to environmental regulations in the resin itself, and when the liquid petroleum resin of the present invention is applied as a process oil (or extender oil) used in the manufacture of tire treads, it has the effect of replacing TDAE oil, which has been used as a conventional process oil, while improving braking and rolling resistance characteristics and wear resistance, which are properties required as tire treads.

[0036] Hereinafter, the present invention will be described in more detail.

[0037] The liquid petroleum resin of the present invention is a hydrogenated (hydrogenated) petroleum resin having no or very low PAHs content, and is a hydrogenated liquid petroleum resin obtained by hydrogenating a DCPD (Dicyclopentadine) polymer.

[0038] The above-mentioned hydrogenated liquid petroleum resin may have a weight average molecular weight of 200 to 500 and a viscosity at 40°C of 50 to 1,000 cp, preferably a weight average molecular weight of 220 to 450 and a viscosity at 40°C of 120 to 800 cp, and more preferably a weight average molecular weight of 230 to 400 and a viscosity at 40°C of 160 to 700 cp.

[0039] And, the liquid petroleum resin (or hydrogenated fiber resin) of the present invention satisfies an aromatic hydrogenation rate of 30.0 to 99.0%, preferably 40.0 to 98.0%, and more preferably 50.0 to 97.0% according to the following mathematical formula 1.

[0040] [Mathematical Formula 1]

[0041] Aromatic hydrogenation rate (%) = (AB) / A×100%

[0042] In mathematical expression 1, A and B are 1 It refers to the area ratio of the aromatic compound peak measured by H-NMR, A refers to the area ratio of the aromatic compound peak of the polymer before the hydrogenation reaction, and B refers to the area ratio of the aromatic compound peak of the polymer after the hydrogenation reaction.

[0043] In addition, the liquid petroleum resin of the present invention 1 When measuring H-NMR, the following equation 1 can be satisfied.

[0044] [Equation 1]

[0045] 0.01 < C / (C+D+E) < 30.0, preferably 0.01 < C / (C+D+E) < 20.0, more preferably 0.01 < C / (C+D+E) < 10.0

[0046] In equation 1, C and D represent the hydrogenated liquid petroleum resins. 1 It is the area ratio of the peak measured by H-NMR, C is the area ratio of the aromatic compound peak, D is the area ratio of the aliphatic compound peak, and E is the area ratio of the olefin compound peak.

[0047] The liquid petroleum resin of the present invention is manufactured by hydrogenating a DCPD polymer, and the DCPD polymer before hydrogenation is a polymer obtained by polymerizing DCPD, a C5 compound, and a styrene compound. More specifically, it is a polymer obtained by polymerizing 1 to 20 parts by weight of a C5 compound and 1 to 70 parts by weight of a styrene compound with respect to 100 parts by weight of DCPD, preferably a polymer obtained by polymerizing 1 to 10 parts by weight of a C5 compound and 1 to 50 parts by weight of a styrene compound with respect to 100 parts by weight of DCPD, and more preferably a polymer obtained by polymerizing 1.0 to 5.0 parts by weight of a C5 compound and 30.0 to 50.0 parts by weight of a styrene compound with respect to 100 parts by weight of DCPD.

[0048] At this time, if the C5 compound is less than 1 part by weight, there may be a problem of low molecular weight, and if the C5 compound is more than 10 parts by weight, there may be a problem of low production yield. In addition, if the styrene compound is less than 1 part by weight or more than 50 parts by weight, there may be a problem of low compatibility with rubber.

[0049] And, the C5 compound may include at least one selected from 1,3-pentadiene, isoprene, piperylene, cyclopentadiene, cyclopentene, 1-pentene, 2-methyl-2-butene, and n-pentane.

[0050] In addition, the styrene-based compound may include a substituted or unsubstituted styrene-based compound, and preferably may include at least one selected from styrene, alpha methyl styrene, para methyl styrene, indene, methyl indene, and vinyl toluene.

[0051] The liquid petroleum resin of the present invention described above can be manufactured by performing the following process.

[0052] A process is performed including: a first step of producing a polymer; a second step of subjecting the polymer to a hydrogenation reaction; and a third step of extracting a liquid hydrogenated petroleum resin from the reaction product of the second step hydrogenation reaction.

[0053] The polymer of step 1 is a polymer produced by polymerizing DCPD (Dicyclopentadine), a C5 compound, and a styrene compound, and the types and amounts of DCPD, C5 compound, and styrene compound used in the production of the polymer are as described above.

[0054] And, the polymerization of the first stage can be carried out through a general polymerization method used in the art, and a preferred example is a process including a first thermal polymerization step 1-1 of carrying out the first polymerization of a petroleum resin under non-catalytic conditions in a continuous stirred tank reactor (CSTR); and a second thermal polymerization step 1-2 of carrying out the second thermal polymerization of the first polymer under non-catalytic conditions in a plug flow reactor (PFR).

[0055] A reactant that does not contain a catalyst or initiator is first thermally polymerized in a continuous stirred tank reactor (CSTR). Thereafter, the first polymer produced therefrom is supplied to a plug flow reactor (PFR) connected to the continuous stirred tank reactor to perform a second thermal polymerization, thereby producing a petroleum resin. By producing the polymerization through step-by-step polymerization in this way, the heat of polymerization reaction can be easily controlled, the monomer conversion rate or polymerization rate is significantly improved, and a petroleum resin having a narrow molecular weight distribution and uniform physical properties can be produced.

[0056] Among the existing methods for manufacturing petroleum resins, non-catalytic thermal polymerization methods have limitations in that they usually have a wide molecular weight distribution and thus do not provide consistent physical properties of petroleum resins. However, the present invention, by adopting a process performed in a continuous stirred tank reactor (CSTR) and a plug flow reactor (PFR) as described above, can provide a petroleum resin that can be controlled to have a narrow molecular weight distribution, thereby realizing remarkable effects such as prevention of contamination due to increased migration over long-term use when used as a uniform physical property and an adhesive. The term non-catalyst or non-initiator means that it does not include any metal catalysts, cationic catalysts, anionic catalysts that artificially act as catalysts, or peroxide initiators, azo initiators, or redox catalysts that artificially induce radical polymerization.

[0057] The continuous stirred tank reactor described above is not particularly limited as long as it is used in the art, and can proceed with a polymerization reaction along with continuous input and mixing of the monomer composition. By performing the primary thermal polymerization in the continuous stirred tank reactor described above, the temperature is maintained uniformly during the reaction, thereby reducing the probability of occurrence of local hot spots and enabling a narrow molecular weight distribution.

[0058] The reaction temperature (T1) in the above step 1-1 may be 210°C to 270°C, and preferably 220°C to 270°C. When the reaction is performed at the above reaction temperature, the conversion rate or polymerization rate of the monomer is excellent, and the occurrence of side reactions such as crosslinking reactions can be suppressed, thereby having a low polydispersity index, and uniform physical properties can be realized with a narrow molecular weight distribution. In addition, the reaction pressure in step 1-1 may be 1 bar to 40 bar, preferably 5 bar to 35 bar, and more preferably 10 bar to 30 bar. When performed at the above reaction pressure, the reactivity of the monomer can be increased without causing a safety hazard. In addition, the reaction time in the above step 1-1 may be 10 minutes to 180 minutes, preferably 20 minutes to 150 minutes, and more preferably 30 minutes to 100 minutes. When performed with the above reaction time, side reactions due to mixing of raw materials can be suppressed and a narrow molecular weight distribution can be provided.

[0059] The monomer conversion rate of the monomer composition in the above step 1-1 may be 5% to 70%, preferably 10% to 60%, and more preferably 15% to 50%. When the first thermal polymerization is performed by adjusting the conversion rate, the yield of the polymer in the second thermal polymerization can be significantly increased, and the occurrence of channeling or dead zones can be prevented, thereby improving the polymerization reaction efficiency.

[0060] The above step 1-2 is a process for manufacturing a petroleum resin by supplying the first polymer product that has undergone the first thermal polymerization of step 1-1 to a plug flow reactor and performing a second thermal polymerization without stirring. At this time, the plug flow reactor may be connected to a continuous stirred tank reactor that performed the first thermal polymerization, and the polymer product may be supplied therefrom to perform continuous polymerization.

[0061] If thermal polymerization is performed only in a continuous stirred tank reactor, channeling by fluids containing unreacted substances and products may occur inside the reactor, reducing the polymerization reaction rate and efficiency, and producing a polymer with non-uniform properties. In addition, if thermal polymerization is performed only in the plug flow reactor, polymerization cannot help but occur under high temperature and high pressure reaction conditions, and although the reactor has the advantage of high monomer conversion per reactor volume because it does not have an internal stirring device, insufficient stirring may cause local hot spots and side reactions. Instead of putting the polymer into the plug flow reactor from the beginning and performing thermal polymerization, a second thermal polymerization reaction is performed on the reaction product that has been polymerized to a certain level through the first thermal polymerization in the continuous stirred tank reactor. This suppresses the occurrence of local hot spots due to the reduction of polymerization heat, and can produce a petroleum resin with uniform properties by having a narrow molecular weight distribution. The above plug flow reactor is not particularly limited as long as it is one commonly used in the technical field to which the present invention belongs, and may be connected in series to the continuous stirred tank type reactor, and a continuous polymerization reaction can be performed with continuous input of the primary polymer product that has undergone primary thermal polymerization.

[0062] The reaction temperature (T2) in the above steps 1-2 may be 180°C to 300°C, preferably 180°C to 290°C, and more preferably 180°C to 280°C. More specifically, the reaction temperature (T2) in the above steps 1-2 may be the reaction temperature (T1) ±30°C of the step 1-1, preferably the reaction temperature (T1) ±20°C, and more preferably the reaction temperature (T1) ±10°C. When performed at the above reaction temperature, side reactions can be suppressed and productivity can be increased. In addition, the reaction pressure in the above steps 1-2 may be 1 bar to 40 bar, preferably 5 bar to 35 bar, and more preferably 10 bar to 30 bar. When performed at the above reaction pressure, the occurrence of a dead zone due to the vaporized monomer can be suppressed without causing a safety accident risk. In addition, the reaction time of the above steps 1-2 may be 10 to 360 minutes, preferably 20 to 240 minutes, and more preferably 30 to 140 minutes. More specifically, the reaction time in step b) may be 1 to 4 times, preferably 1 to 3 times, and more preferably 1 to 2 times, the reaction time of step 1-1. When performed with the above reaction time, side reactions can be suppressed, and a petroleum resin with a narrow molecular weight distribution can be produced.

[0063] In addition, the internal volume of the plug flow reactor may be 1 to 3 times the internal volume of the continuous stirred tank type reactor, preferably 1 to 2.5 times, and more preferably 1 to 2 times. When the internal volume of the plug flow reactor has the same size as the internal volume of the continuous stirred tank type reactor, the initial reaction heat can be easily controlled, thereby suppressing the generation of impurities, and the polymerization efficiency can be increased by controlling the reaction temperature while simultaneously implementing uniform physical properties.

[0064] The above plug flow reaction may be performed by connecting one or more static mixers in series, such as a Kenics mixer and a Sulzer mixer. By including such a mixer, a pressure drop within the reactor due to the flow of a highly viscous solution can be prevented.

[0065] A filter may be further included in the connecting section of the continuous stirred tank reactor (CSTR) and the plug flow reactor (PFR). The filter may be made of one or more materials selected from metals, polymers, ceramics, etc., and may have a pore size of 100 nm to 10 μm, preferably 100 nm to 1 μm. There are no particular limitations on the filter as long as it can filter out foreign substances.

[0066] The method for producing a petroleum resin by performing the above steps 1-1 and 1-2 can have a high yield of 50% or more, preferably 60% or more, and more preferably 65% ​​or more, by performing thermal polymerization in two stages under non-catalyst and non-initiator conditions, despite a relatively short reaction time, and can exhibit a narrow molecular weight distribution.

[0067] Next, in the liquid petroleum resin manufacturing method of the present invention, the hydrogenation reaction in the second step is a reaction in which hydrogen is added to an unsaturated double bond to form a single bond, and is a process for manufacturing a hydrogenated petroleum resin in which the double bond disappears through the hydrogenation reaction of the petroleum resin.

[0068] The above hydrogenation reaction can be carried out according to a general method known in the art, and preferably, the hydrogenation reaction can be carried out by introducing the polymer into a continuous hydrogenation reactor packed with a hydrogenation catalyst, and the hydrogenation reaction can be carried out at a temperature of 150°C to 300°C under a pressure of 50 bar to 150 bar, but is not limited thereto. When carried out at the above pressure and temperature, destruction of the molecular structure can be prevented.

[0069] In addition, the hydrogenation catalyst is not particularly limited, but any known hydrogenation catalyst may be used, and a preferred example may include at least one selected from Ni, Fe, Cu, Co, Mo, Pd, Rh, Pt, Nb, Au, Rd, and Raney Ni.

[0070] In addition, the hydrogenation catalyst may be included in a molar ratio of 0.001 to 0.500, preferably 0.05 to 0.20, per 1 mol of the polymer to be hydrogenated to improve reactivity, but is not limited thereto.

[0071] And, the above extraction in the third step can be performed by performing a purification process to select a product having a weight average molecular weight of 200 to 500 and a viscosity at 40°C of 50 to 1,000 cp, thereby obtaining a liquid hydrogenated liquid petroleum resin.

[0072] And, the above purification process performs a first degassing process and a second degassing process on a solution containing a reaction product that has undergone a two-step process, thereby obtaining a hydrogenated liquid petroleum resin in the form of an oligomer.

[0073] The solution containing the reaction product that has undergone the two-step process comprises about 28 to 45 wt% of the petroleum resin, about 10 to 30 wt% of the oligomeric hydrogenated liquid petroleum resin and the remainder of the solvent among 100 wt%, preferably about 30 to 40 wt% of the petroleum resin, about 10 to 20 wt% of the oligomeric hydrogenated liquid petroleum resin and the remainder of the solvent among 100 wt%, more preferably about 32 to 38 wt% of the petroleum resin, about 13 to 18 wt% of the oligomeric hydrogenated liquid petroleum resin and the remainder of the solvent among 100 wt%.

[0074] And, the first degassing process is a process for removing the solvent in the solution, and is a process for removing the solvent by evaporating it by performing the degassing process at a temperature of 110°C to 140°C, preferably 120°C to 140°C, and the reaction product from which the solvent has been degassed contains petroleum resin and hydrogenated liquid petroleum resin.

[0075] In addition, the secondary degassing process is a process for separating the hydrocarbon resin and the hydrogenated liquid hydrocarbon resin, which are the reaction product components obtained by performing the primary degassing process, and the degassing process is performed at a temperature of 160°C to 185°C, preferably 165°C to 175°C, to obtain (extract) the hydrogenated liquid hydrocarbon resin.

[0076] The liquid petroleum resin of the present invention described above can be used as a process oil (or extender oil) of a tire tread, completely replacing TDAE oil or used together with TDAE oil.

[0077] The tire tread composition of the present invention, which introduces the above liquid petroleum resin as a process oil, may contain the above liquid petroleum resin alone as a process oil, or may contain a mixed resin in which the above liquid petroleum resin and other liquid petroleum resins are mixed.

[0078] Among the above mixed resins, the other liquid petroleum resin may include at least one selected from a non-hydrogenated liquid petroleum resin and an aromatic copolymer liquid petroleum resin, and the aromatic copolymer liquid petroleum resin may be a hydrogenated C5-based petroleum resin obtained by hydrogenating a polymer obtained by polymerizing DCPD (Dicyclopentadine), a C5-based compound, and a styrene compound.

[0079] As a composition used in the manufacture of the tire tread of the present invention, for example, in a preferred embodiment, the composition of the present invention may include a rubber resin, a filler, an activator, an antioxidant, a vulcanization accelerator, a vulcanizing agent, the process oil, and a petroleum resin. In this case, the petroleum resin refers to a petroleum resin different from the hydrogenated liquid petroleum resin that is a component of the process oil.

[0080] Among the tire tread compositions of the present invention described above, the raw rubber of the rubber resin may include at least one selected from the group consisting of natural rubber, butadiene rubber, nitrile rubber, silicone rubber, isoprene rubber, styrene-butadiene rubber (SBR), isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber, halogenated butyl rubber, halogenated isoprene rubber, halogenated isobutylene copolymer, chloroprene rubber, butyl rubber, and halogenated isobutylene-p-methylstyrene rubber, and preferably at least one selected from styrene-butadiene rubber, natural rubber, and butadiene rubber.

[0081] In addition, the filler serves to improve the mechanical properties of the tire tread, and may include at least one selected from silica and carbon black (C / B).

[0082] In addition, the activator in the composition is used in combination with the vulcanization accelerator to further enhance the acceleration effect, and the activator may include at least one selected from among metal oxides such as zinc oxide and magnesium oxide; metal hydroxides such as calcium hydroxide; metal carbonates such as zinc carbonate and basic zinc carbonate; fatty acids such as stearic acid and oleic acid; aliphatic metal salts such as zinc stearate and magnesium stearate; amines such as n-butylamine and dicyclohexylamine; and organic activators such as ethylene dimethacrylate, diallyl phthalate, N,Nm-phenylenedimaleimide, triallyl isocyanurate, and trimethylolpropane trimethacrylate.

[0083] In addition, the antioxidant in the composition is an additive used to stop the chain reaction in which the tire is automatically oxidized by oxygen.

[0084] As the above antioxidant, one or more selected from among amine-based, phenol-based, quinoline-based, imidazole-based, carbamic acid metal salt, wax, etc. can be appropriately selected and used.

[0085] The above amine antioxidant may be any one selected from the group consisting of N-phenyl-N'-(1,3-dimethyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-diaryl-p-phenylenediamine, N-phenyl-N'-cyclohexyl p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof. The above phenol antioxidant may include at least one selected from the group consisting of phenols such as 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), and 2,6-di-t-butyl-p-cresol.

[0086] In addition, the quinoline-based antioxidant may use 2,2,4-trimethyl-1,2-dihydroquinoline and its derivatives, and specifically may include at least one selected from among 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, and 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline.

[0087] Additionally, wax hydrocarbon can preferably be used as the wax.

[0088] In addition, a sulfur-based vulcanizing agent may be used as the vulcanizing agent in the composition. The sulfur-based vulcanizing agent may be an inorganic vulcanizing agent such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S), or colloidal sulfur. Specifically, the sulfur-based vulcanizing agent may be elemental sulfur or a vulcanizing agent that produces sulfur, for example, amine disulfide, polymeric sulfur, etc.

[0089] In addition, in the composition, the vulcanization accelerator may be at least one selected from among thiuram accelerators such as trimethylthiuram monosulfide, tetramethylthiuram disulfide, and tetraethylthiuram disulfide; thiazole accelerators such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide; sulfenamide accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide and N-oxydiethylene-2-benzothiazolylsulfenamide; aldehyde-amine accelerators such as n-butyraldehyde-aniline condensate and butyraldehyde-monobutylamine condensate; aldehyde-ammonia accelerators such as hexamethylenetetramine; thiourea accelerators such as thiocarbanilide; and guanidine accelerators such as 1,3-diphenylguanidine. When mixing these vulcanization accelerators, one type may be used alone, or two or more types may be used in combination. As a preferred example, 1,3-diphenylguanidine (DPG) and N-cyclohexyl-2-benzothiazylsulfenamide (CBTS) may be mixed and used as vulcanization accelerators.

[0090] In addition, the petroleum resin in the composition of the present invention is included in a rubber composition for a tire tread to further improve the adhesive performance between rubbers and to improve the mixing, dispersibility, and processability of fillers and other additives, thereby improving the physical properties of the rubber composition, and may include at least one selected from among C5 petroleum resin, C9 petroleum resin, C5 / C9 petroleum resin, PMR (pure monomer resin), coumarone-indene resin, terpene resin, alkylphenol resin, and DCPD resin.

[0091] And, the composition of the present invention may include 35.0 to 50.0 wt% of filler, 0.5 to 3.5 wt% of activator, 0.1 to 1.0 wt% of antioxidant, 0.3 to 3.0 wt% of vulcanization accelerator, 0.1 to 1.2 wt% of vulcanizing agent, 1.0 to 10.0 wt% of the process oil, 5.0 to 30.0 wt% of petroleum resin and the remaining balance of 100 wt% of rubber resin, and preferably 38.0 to 49.5 wt% of filler, 0.7 to 2.2 wt% of activator, 0.3 to 0.8 wt% of antioxidant, 0.5 to 2.0 wt% of vulcanization accelerator, 0.3 to 1.0 wt% of vulcanizing agent, 5.0 to 10.0 wt% of the process oil, and 5.0 to 25.0 wt% of petroleum resin. It may contain the remaining balance of rubber resin among 100 wt% and more preferably 42.0 to 48.5 wt% of filler, 1.0 to 2.2 wt% of activator, 0.4 to 0.8 wt% of antioxidant, 0.5 to 1.5 wt% of vulcanization accelerator, 0.3 to 0.9 wt% of vulcanizing agent, 6.0 to 10.0 wt% of the process oil, 5.0 to 25.0 wt% of petroleum resin and the remaining balance of rubber resin among 100 wt%.

[0092] At this time, if the content of the filler in the composition is less than 35.0 wt%, sufficient wear resistance, durability, and other physical properties of the tire tread may not be secured, and if it is used in excess of 47.0 wt%, there may be a problem that the processability is not good due to excessive use and the braking characteristics of the tire may rather deteriorate.

[0093] In addition, if the content of the activator is less than 0.5 wt%, there may be a problem of lowering the vulcanization efficiency, and if the content of the activator exceeds 3.5 wt%, there may be a problem of excessive increase in the elasticity of the rubber due to excessive vulcanization effect.

[0094] In addition, if the content of the antioxidant is less than 0.1 wt%, the amount used may be too small, resulting in a problem of insufficient antioxidant effect. If the content of the antioxidant exceeds 1.0 wt%, the excessive use may result in a problem of inhibiting vulcanization efficiency.

[0095] In addition, if the content of the vulcanization accelerator is less than 0.3 wt%, there may be a problem that the vulcanization delay effect occurs because the amount used is too small, and if the content of the vulcanization accelerator exceeds 3.0 wt%, there may be a problem that it is difficult to control the vulcanization speed due to excessive use.

[0096] In addition, if the content of the vulcanizing agent is less than 0.1 wt%, the amount used may be too small, which may cause a problem in that the elasticity of the rubber may become too low, and if the content of the vulcanizing agent exceeds 1.2 wt%, which may cause a problem in that the elasticity of the rubber may become too high due to excessive use.

[0097] In addition, if the process oil content is less than 1.0 wt%, the amount used may be too small, which may result in a deterioration in the braking characteristics of the tire tread, and if the process oil content exceeds 10.0 wt%, there may be a problem in which the rolling resistance characteristics deteriorate due to excessive use.

[0098] In addition, the petroleum resin content may be appropriate in the range of 5 to 25 wt% in terms of harmony between processability and viscoelasticity of rubber.

[0099] The tire tread of the present invention is a processed product processed from the composition described above, and when measured under the conditions of a temperature of -80°C to 110°C and a frequency of 10 Hz based on a dynamic mechanical analysis method, the tire tread satisfies a Tanδ value of 95 to 120 at 0°C, preferably satisfies a Tanδ value of 98 to 118 at 0°C, and more preferably satisfies a Tanδ value of 100 to 118 at 0°C, thereby having very high braking characteristics.

[0100] In addition, the tire tread of the present invention can satisfy a Tanδ value of 100 to 115 at 60°C, preferably a Tanδ value of 104 to 115 at 60°C, and more preferably a Tanδ value of 105 to 114 at 60°C, thereby having very high rolling resistance characteristics.

[0101] In addition, the tire tread of the present invention can satisfy a relative wear rate of 70% to 95% according to Equation 2, preferably 77% to 94%, and more preferably 80% to 93%, when measured according to the KS M ISO 4649 method.

[0102] [Formula 2]

[0103] Relative wear rate (%) = (Wear value of the tire tread rubber to be measured / Wear value of the control group) × 100%

[0104] In Equation 2, the control group is one in which TDAE (Treated Distillate Aromatic Extract) is used solely as an extender oil in the manufacture of tire tread rubber, and the control group and the tire tread rubber to be measured have the same composition (ingredients) used in the manufacture of tire tread rubber, except for the extender oil.

[0105] By using the tire tread of the present invention having high braking performance, rolling characteristics, and wear resistance, it is possible to manufacture a tire that is both environmentally friendly and has excellent marketability.

[0106]

[0107] Hereinafter, the present invention will be described in more detail through examples, but the following examples do not limit the scope of the present invention, and should be interpreted as helping to understand the present invention.

[0108] [Example]

[0109] Example 1: Preparation of liquid hydrogenated petroleum resin (liquid petroleum resin)

[0110] (1) Manufacturing of DCPD polymer (liquid petroleum resin)

[0111] A monomer composition was prepared by mixing 693 g of dicyclopentadiene, 7 g of piperylene, and 300 g of styrene with 1,000 g of xylene as a solvent. Next, the monomer composition was continuously supplied to a continuous stirred tank reactor (CSTR) with an internal volume of 0.416 L, and polymerization was performed with stirring for 42 minutes under conditions of a temperature of 265°C and a pressure of 25 bar to prepare a primary polymer.

[0112] The manufactured primary polymer was continuously supplied to a plug flow reactor (PFR) with an internal volume of 0.590 L connected to the continuous stirred tank type reactor, and polymerization was performed for 63 minutes under the conditions of a temperature of 277°C and a pressure of 25 bar. The reaction product, after the polymerization reaction was completed, was depressurized at 130°C for 15 minutes to remove the solvent, and then the temperature was raised to 170°C and depressurized for 30 minutes to recover the volatilized liquid petroleum resin.

[0113] (2) Manufacturing of hydrogenated liquid petroleum resin

[0114] A monomer composition was prepared by mixing 693 g of dicyclopentadiene, 7 g of piperylene, and 300 g of styrene with 1,000 g of xylene as a solvent. Next, the monomer composition was continuously supplied to a continuous stirred tank reactor (CSTR) with an internal volume of 0.416 L, and reacted with stirring for 42 minutes under conditions of a temperature of 265°C and a pressure of 25 bar to prepare a primary polymer.

[0115] The manufactured primary polymer was continuously supplied to a plug flow reactor (PFR) with an internal volume of 0.590 L connected to the continuous stirred tank type reactor, and a polymerization reaction was performed for 63 minutes under conditions of a temperature of 277°C and a pressure of 25 bar.

[0116] The product after the polymerization reaction was depressurized at 130°C for 15 minutes to remove the solvent, and then the temperature was raised to 170°C and the pressure was reduced for 30 minutes to recover the volatilized liquid petroleum resin.

[0117] Then, the liquid petroleum resin was introduced into a continuous hydrogenation reactor packed with a hydrogenation catalyst to perform a hydrogenation reaction. At this time, with respect to the total weight of the liquid petroleum resin, 0.5 wt% of the palladium catalyst and 4 NL / min of hydrogen were supplied, and the hydrogenation reaction was performed three times under the conditions of a temperature of 220°C and a pressure of 100 bar, thereby obtaining a solution containing a reaction product in which the hydrogenation reaction was completed. At this time, the solution contains about 35.3 wt% of the petroleum resin, about 15.5 wt% of the hydrogenated liquid petroleum resin as an oligomer, and the remainder of the solvent among 100 wt%.

[0118] Next, the solution containing the reaction product in which the hydrogenation reaction was completed was purified as follows, and the solution was subjected to a first degassing at 130°C to remove the solvent, and then the reaction product from which the solvent had been removed was subjected to a second degassing at 170°C to produce a hydrogenated liquid petroleum resin separated from the petroleum resin.

[0119]

[0120] Comparative Example 1: Preparation of hydrogenated liquid petroleum resin

[0121] (1) Manufacturing of DCPD polymer (liquid petroleum resin)

[0122] A monomer composition was prepared by mixing 693 g of dicyclopentadiene and 7 g of piperylene in 700 g of xylene solvent. The monomer composition was continuously supplied to a continuous stirred tank reactor (CSTR) with an internal volume of 0.416 L, and reacted with stirring for 32 minutes under conditions of a temperature of 265°C and a pressure of 25 bar to prepare a primary polymer.

[0123] The manufactured primary polymer was continuously supplied to a plug flow reactor (PFR) with an internal volume of 0.590 L connected to the continuous stirred tank type reactor, and polymerized for 43 minutes under the conditions of a temperature of 277°C and a pressure of 25 bar. The reaction product, after the polymerization reaction was completed, was depressurized at 130°C for 15 minutes to remove the solvent, and then the temperature was raised to 170°C and depressurized for 30 minutes to recover the volatilized liquid petroleum resin.

[0124] (2) Manufacturing of hydrogenated liquid petroleum resin

[0125] A monomer composition was prepared by mixing 693 g of dicyclopentadiene and 7 g of piperylene in 700 g of xylene solvent. The monomer composition was continuously supplied to a continuous stirred tank reactor (CSTR) with an internal volume of 0.416 L, and reacted with stirring for 32 minutes under conditions of a temperature of 265°C and a pressure of 25 bar to prepare a primary polymer.

[0126] The manufactured primary polymer was continuously supplied to a plug flow reactor (PFR) with an internal volume of 0.590 L connected to the continuous stirred tank type reactor, and polymerized for 43 minutes under the conditions of a temperature of 277°C and a pressure of 25 bar. The reaction product, after the polymerization reaction was completed, was depressurized at 130°C for 15 minutes to remove the solvent, and then the temperature was raised to 170°C and depressurized for 30 minutes to recover the volatilized liquid petroleum resin.

[0127] Then, the liquid petroleum resin was supplied to a continuous hydrogenation reactor packed with a hydrogenation catalyst to perform a hydrogenation reaction. At this time, the hydrogenation reaction was performed twice under the conditions of a temperature of 260°C and a pressure of 100 bar using 0.5 wt% of the palladium catalyst and 4 NL / min of hydrogen based on the total weight of the liquid petroleum resin.

[0128] Next, the first and second degassing were performed in the same manner as in Example 1 to obtain a hydrogenated liquid petroleum resin as an oligomer.

[0129]

[0130] Experimental Example 1: Measurement of the properties of liquid petroleum resin and hydrogenated liquid petroleum resin.

[0131] The weight average molecular weight, viscosity (cp) and the hydrogenated liquid petroleum resin (DCPD polymer) synthesized in Example 1 and Comparative Example 1, respectively 1 The H-NMR peak area ratio was measured, and the results are shown in Table 1 below.

[0132] In Table 1 below, the aromatic hydrogenation rate (%) is calculated based on the following mathematical formula 1. 1 The H-NMR peak area ratio was calculated using the following equation 1.

[0133] [Mathematical Formula 1]

[0134] Aromatic hydrogenation rate (%) = (AB) / A×100%

[0135] In mathematical expression 1, A and B are 1It refers to the area ratio of the aromatic compound peak measured by H-NMR, A refers to the area ratio of the aromatic compound peak of the polymer before the hydrogenation reaction, and B refers to the area ratio of the aromatic compound peak of the polymer after the hydrogenation reaction.

[0136] [Formula 1]

[0137] C / (C+D+E)

[0138] In Equation 1, C and D represent hydrogenated liquid petroleum resin (liquid petroleum resin). 1 This is the area ratio of the peak measured by H-NMR, C is the area ratio of the aromatic compound peak, D is the area of ​​the aliphatic compound peak, and E is the area ratio of the olefin compound peak.

[0139] Classification Example 1 Comparative Example 1 Liquid petroleum resin Hydrogenated liquid petroleum resin Liquid petroleum resin Hydrogenated liquid petroleum resin Hydrogenation reaction ×○×○ Weight average molecular weight 220 243 194 203 Viscosity 25℃, cp 657 128 30 40℃, cp 170 192 55 67 NMR peak area Aromatic 10.3 3.9 20.9 40.08 Olefin 11.6 9 0.15 14.0 3 0.09 Aliphatic 78.0 19 5.9 3 85.0 4 9 9.82 Aromatic Hydrogenation rate -61.94% -33.12% 1 H-NMR peak area ratio [= C / (C+D+E)] 10.3 3.9 2 0.9 4 0.08

[0140]

[0141] Manufacturing Example 1: Manufacturing of tire tread

[0142] After preparing rubber resin, filler, activator, antioxidant, vulcanization accelerator, vulcanizing agent, process oil, and petroleum resin respectively, they were added in the same composition ratio shown in Table 2 below and then compounded in a Brabender mixer to prepare a rubber composition for tire tread.

[0143] As the above rubber resin, styrene-butadiene rubber (SBR, 5251H from Kumho Petrochemical) and neodymium butadiene rubber (NdBR, NdBR40 from Kumho Petrochemical) were used.

[0144] As fillers, silica (Ultrasil VN3 GR from EVONIK), carbon black (N220 from OEC), and bis(3-(triethoxysilyl)propyl)tetrasulfide (TESPT, Si-69 from EVONIK) were prepared.

[0145] As an antioxidant, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) was used.

[0146] As a vulcanization accelerator, 1,3-diphenylguanidine (DPG) and N-cyclohexyl-2-benzothiazylsulfenamide (CBTS) were mixed and used in a weight ratio of 1:0.7.

[0147] As activators, ZnO and stearic acid were used.

[0148] Sulfur was used as a vulcanizing agent.

[0149] As a process oil, the hydrogenated liquid petroleum resin prepared in (2) of Example 1 was used.

[0150] As a petroleum resin, a petroleum resin containing DCPD copolymer, brand name HT-100, was used.

[0151]

[0152] Comparative Manufacturing Example 1

[0153] A tire tread was manufactured using the same method as Manufacturing Example 1, but as shown in Table 2 below, TDAE (Treated Distillate Aromatic Extract) oil was used as a process oil instead of the hydrogenated liquid petroleum resin manufactured in Example 1, and Comparative Manufacturing Example 1 was performed.

[0154]

[0155] Comparative manufacturing examples 2 to 4

[0156] A tire tread was manufactured using the same method as Manufacturing Example 1, but as shown in Table 2 below, as process oils, the non-hydrogenated DCPD-based liquid petroleum shoe manufactured in Comparative Example 1, the hydrogenated DCPD-based liquid petroleum shoe manufactured in Comparative Example 1 by hydrogenating it, and the non-hydrogenated DCPD-based liquid petroleum shoe manufactured in Example 1 were used to perform Comparative Manufacturing Examples 2 to 4, respectively.

[0157] Classification (weight %) Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Comparative Manufacturing Example 3 Comparative Manufacturing Example 4 Manufacturing Example 1 Rubber Resin SBR 27.40 27.40 27.40 27.40 27.40 NdBR 9.209 209 209 209 209 209 20 Filler Silica 36.30 36.30 36.30 36.30 36.30 TESPT 3.68 3.68 3.68 3.68 3.68 Carbon Black 1.84 1.84 1.84 1.84 1.84 Activator ZnO 1.10 1.10 1.10 1.10 1.10 Stearic Acid 0.730.730.730.730.73 Antioxidant 6PPD 0.560.560.560.560.56 Vulcanization accelerator DPG 0.710.710.710.710.710.71 SBTS 0.470.470.470.470.47 Sulfur 0.530.530.530.53 Process oil TDAE oil 6.44 ----Liquid petroleum resin 1-6.44---Liquid petroleum resin 2--6.44--Liquid petroleum resin 3---6.44 -Liquid petroleum resin 4----6.44 Petroleum resin HT-100 (DCPD copolymerized petroleum resin) 11.0411.0411.0411.0411.04Total 100100100100100* Liquid petroleum resin 1: Non-hydrogenated DCPD-based liquid petroleum resin manufactured in (1) of Comparative Example 1* Liquid petroleum resin 2: Hydrogenated DCPD-based liquid petroleum resin manufactured in (2) of Comparative Example 1* Liquid petroleum resin 3: Non-hydrogenated DCPD-based liquid petroleum resin manufactured in (1) of Example 1* Liquid petroleum resin 4: Hydrogenated DCPD-based liquid petroleum resin manufactured in (2) of Example 1

[0158]

[0159] Manufacturing Examples 2 to 5 and Comparative Manufacturing Examples 5 to 8

[0160] A tire tread was manufactured using the same method as Manufacturing Example 1, but as shown in Tables 3 and 4 below, the hydrogenated liquid petroleum resin manufactured in Example 1 and TDAE (Treated Distillate Aromatic Extract) oil were used together as process oils, and Manufacturing Examples 2 to 5 and Comparative Manufacturing Examples 5 to 8 were performed, respectively.

[0161] Classification (weight%) Manufacturing example 2 Manufacturing example 3 Manufacturing example 4 Manufacturing example 5 Rubber resin SBR 27.40 27.40 26.94 26.51 Nd BR 9.13 9.13 8.98 8.84 Filler Silica 36.5 336.5 335.9 335.35 Si-coupling 3.6 5 3.65 3.58 3.54 C / B 1.8 31.8 31.8 1.77 Activator ZnO 1.10 1.10 1.08 1.06 Stearic Acid 0.73 0.73 0.72 0.71 Antioxidant 6 PPD 0.55 0.55 0.54 0.53 Vulcanization accelerator DPG 0.71 0.71 0.70 0.67 SBTS 0.500.500.48 0.47 Vulcanizing agent Sulfur 0.53 0.53 0.52 0.51 Process oil TDAE oil 6.39 6.39 6.30 6.20 Liquid petroleum resin 4 2.74 5.48 1.65 3.24 Petroleum resin HT-100 (DCPD copolymerized petroleum resin) 8.2 15.47 10.78 10.60 Total 100 100 100 100 * Liquid petroleum resin 4: Hydrogenated DCPD-based liquid petroleum resin manufactured in (2) of Example 1

[0162] Classification (weight%)Comparative Manufacturing Example 5Comparative Manufacturing Example 6Comparative Manufacturing Example 7Comparative Manufacturing Example 8Rubber ResinSBR27.427.426.9426.51NdBR9.139.138.988.84FillerSilica36.5336.5335.9335.35Si-coupling3.653.653.583.54C / B1.831.831.801.77ActivatorZnO1.11.11.081.06Stearic Acid 0.73 0.73 0.72 0.71 Antioxidant 6 PPD 0.55 0.55 0.54 0.53 Vulcanization accelerator DPG 0.71 0.71 0.70 0.67 SBTS 0.50 50 48 0.47 Vulcanizing agent Sulfur 0.53 0.53 0.52 0.51 Process oil TDAE oil 6.39 6.39 6.30 6.20 Liquid petroleum resin 2 2.74 5.48 1.65 3.24 Petroleum resin HT-100 (DCPD copolymerized petroleum resin) 8.2 15.47 10.78 10.6 Total 100 100 100 100 * Liquid petroleum resin 2: Hydrogenated DCPD-based liquid petroleum resin manufactured in (2) of Comparative Example 1

[0163]

[0164] Experimental Example 2: Measurement of tire tread properties

[0165] The braking characteristics, rolling resistance, and wear resistance of the tire treads manufactured in the above Manufacturing Examples 1 to 5 and Comparative Manufacturing Examples 1 to 8 were measured, and the results are shown in Table 4 below.

[0166] (1) Method for measuring braking characteristics and rolling resistance

[0167] For the rubber specimens manufactured above, the loss factor (Tan δ) related to wet grip and rolling resistance was measured at a temperature range of -80°C to 110°C and 10 Hz using dynamic mechanical analysis (Model: TA-DMA Q800). At this time, the relative loss factor values ​​of each example and comparative example were calculated based on the result value of Comparative Manufacturing Example 1 as the standard (100), and the results were expressed.

[0168] At 0℃, the Tanδ value is related to wet road braking power, and a higher value means better braking power. At 60℃, the Tanδ value is related to rolling resistance characteristics, and a lower value means lower rolling resistance and better fuel efficiency performance. However, Fig. 2 takes the inverse of the Tanδ value at 60℃ to improve visibility, and in Fig. 2, a higher value is judged to mean lower rolling resistance.

[0169] (2) Wear resistance measurement method

[0170] Wear resistance was measured using the KS M ISO 4649 method, and the wear rate was calculated using Equation 2 below. The lower the wear rate, the better the wear resistance.

[0171] [Formula 2]

[0172] Wear rate (%) = (wear rate of tire tread to be measured) / (wear rate of tire tread as control group) × 100%

[0173] Classification Process Oil Tank Characteristics Rotational Resistance Wear Resistance Tanδ@ Value at 0℃ Tanδ@ Value at 60℃ Wear Rate (%) Manufacturing Example 1 Single Type 10310983 Comparative Manufacturing Example 1 (Control) 100 100 100 Comparative Manufacturing Example 28972233 Comparative Manufacturing Example 39110862 Comparative Manufacturing Example 48574165 Classification Process Oil Tank Characteristics Rotational Resistance Wear Resistance Tanδ@ Value at 0℃ Tanδ@ Value at 60℃ Wear Rate (%) Manufacturing Example 2 Mixed Type 8811282 Manufacturing Example 37712480 Manufacturing Example 410610586 Manufacturing Example 511010791 Comparative Manufacturing Example 59111187 Comparative Manufacturing Example 66611788Comparative manufacturing example 71039785Comparative manufacturing example 810210792

[0174] Looking at the property measurement results in Table 5 above, when comparing Manufacturing Example 1 and Comparative Manufacturing Examples 1 to 4, which used only TDAE oil as process oil and either the non-hydrogenated or hydrogenated liquid petroleum resin of Comparative Example 1 or Example 1, the tire tread manufactured using the hydrogenated liquid petroleum resin of Example 1 showed the best overall property results in braking characteristics, rolling resistance, and wear resistance.

[0175] In addition, when looking at Manufacturing Examples 2 to 5 and Comparative Manufacturing Examples 5 to 8 in which either the non-hydrogenated or hydrogenated liquid petroleum resin of Comparative Example 1 or Example 1 was mixed with TDAE oil, Manufacturing Examples 2 to 5 showed relatively superior results in terms of wear rate and rotational resistance.

[0176] Through the above examples and experimental examples, it was confirmed that the liquid petroleum resin of the present invention can replace TDAE oil, which has been used as a process oil in the manufacture of tire treads, and can manufacture tire treads with excellent braking characteristics, rolling resistance, and wear resistance.

Claims

1. It is a hydrogenated liquid petroleum resin produced by hydrogenating a DCPD (Dicyclopentadine) polymer. The above DCPD polymer is a polymer obtained by polymerizing DCPD (Dicyclopentadine), a C5 compound, and a styrene compound. A liquid petroleum resin characterized by a weight average molecular weight of 200 to 500 and a viscosity at 40°C of 50 to 1,000 cP.

2. In the first paragraph, the C5 compound is A liquid petroleum resin characterized by comprising at least one selected from 1,3-pentadiene, isoprene, piperylene, cyclopentadiene, cyclopentene, 1-pentene, 2-methyl-2-butene, and n-pentane.

3. In the first paragraph, the DCPD polymer, A liquid petroleum resin characterized by polymerizing 1 to 10 parts by weight of a C5 compound and 1 to 50 parts by weight of a styrene compound with respect to 100 parts by weight of DCPD.

4. In paragraph 1, the hydrogenated liquid petroleum resin is A liquid petroleum resin characterized in that it satisfies an aromatic hydrogenation rate of 50.0 to 97.0% according to the following mathematical formula 1; [Mathematical Formula 1] Aromatic hydrogenation rate (%) = (AB) / A×100% In mathematical expression 1, A and B are 1 It refers to the area ratio of the aromatic compound peak measured by H-NMR, A refers to the area ratio of the aromatic compound peak of the polymer before the hydrogenation reaction, and B refers to the area ratio of the aromatic compound peak of the polymer after the hydrogenation reaction.

5. In paragraph 1, the hydrogenated liquid petroleum resin 1 A liquid petroleum resin characterized in that it satisfies the following equation 1 when measured by H-NMR; [Equation 1] 0.01 < C / (C+D+E) < 10.0 In equation 1, C and D represent the hydrogenated liquid petroleum resins. 1 It is the area ratio of the peak measured by H-NMR, C is the area ratio of the aromatic compound peak, D is the area ratio of the aliphatic compound peak, and E is the area ratio of the olefin compound peak.

6. Step 1: Synthesizing a polymer by polymerizing DCPD (Dicyclopentadine), C5 compounds, and styrene compounds; Step 2: hydrogenation reaction of the above polymer; Step 3: Extracting liquid hydrogenated petroleum resin from the reaction product of the step 2 hydrogenation reaction; A method for producing a liquid petroleum resin, characterized in that the hydrogenated liquid petroleum resin obtained in step 3 has a weight average molecular weight of 200 to 500 and a viscosity at 40°C of 50 to 1,000 cP.

7. A tire tread composition characterized in that it comprises a liquid petroleum resin selected from any one of claims 1 to 5 as a process oil.

8. In paragraph 7, the process oil is The above hydrogenated liquid petroleum resin; or a mixed resin of the above hydrogenated liquid petroleum resin and other liquid petroleum resins; Among the mixed resins, the above other liquid petroleum resins include at least one selected from among non-hydrogenated liquid petroleum resins and aromatic copolymerized liquid petroleum resins. A tire tread composition characterized in that the aromatic copolymer liquid petroleum resin among the mixed resins is a hydrogenated liquid petroleum resin obtained by hydrogenating a polymer obtained by polymerizing DCPD (Dicyclopentadine), a C5 compound, and a styrene compound.

9. A tire tread composition according to claim 8, characterized in that it comprises a rubber resin, a filler, an activator, an antioxidant, a vulcanization accelerator, a vulcanizing agent, the process oil, and a petroleum resin.

10. In the 9th paragraph, it comprises 35.0 to 50.0 wt% of filler, 0.5 to 3.5 wt% of activator, 0.1 to 1.0 wt% of antioxidant, 0.3 to 3.0 wt% of vulcanization accelerator, 0.1 to 1.2 wt% of vulcanizing agent, 1.0 to 10.0 wt% of the process oil, 5.0 to 15.0 wt% of petroleum resin and the remaining balance of 100 wt% of rubber resin, A tire tread composition characterized in that the rubber resin comprises at least one selected from natural rubber, butadiene rubber, nitrile rubber, silicone rubber, isoprene rubber, styrene-butadiene rubber (SBR), isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber, halogenated butyl rubber, halogenated isoprene rubber, halogenated isobutylene copolymer, chloroprene rubber, butyl rubber, and halogenated isobutylene-p-methylstyrene rubber.

11. A tire tread characterized in that, when measured according to the KS M ISO 4649 method in Article 10, the relative wear rate according to Equation 2 satisfies 70 to 95%; [Formula 2] Relative wear rate (%) = (Wear value of the tire tread rubber to be measured / Wear value of the control group) × 100% In Equation 2, the control group is one in which TDAE (Treated Distillate Aromatic Extract) is used solely as an extender oil in the manufacture of tire tread rubber, and the control group and the tire tread rubber to be measured have the same composition (ingredients) used in the manufacture of tire tread rubber, except for the extender oil.

12. A tire including the tire tread of clause 11.