Petroleum resin composition and tire composition comprising same

Abstract

The present invention relates to a petroleum resin composition and a tire resin composition comprising same, the petroleum resin composition including a petroleum resin and a silane-based compound, wherein: the petroleum resin comprises at least one of a repeat unit derived from an aromatic petroleum resin monomer and a repeat unit derived from an alicyclic petroleum resin monomer; at least a part of the silane-based compound is grafted onto the petroleum resin; the silane-based compound includes sulfur (S); and the petroleum resin composition has a bromine value of 1-18 Br.cg / g. The tire resin composition has improved grip, wear, and rolling resistance properties.

Description

Petroleum resin composition and tire composition containing the same

[0001] The present invention relates to a petroleum resin composition and a resin composition for tires containing the same.

[0002] In the conventional manufacturing of tires, when the tire resin composition includes a petroleum resin composition, processability and grip characteristics are improved, but silica dispersion characteristics and polymer crosslinking characteristics are degraded, leading to a problem of reduced tire wear and rolling resistance characteristics.

[0003] Accordingly, much research has been conducted to simultaneously improve tire wear and rolling resistance characteristics while maintaining excellent processability and grip properties. In particular, research on introducing silanes into petroleum resins has been actively pursued to improve the dispersion properties of silica and the crosslinking properties of polymers.

[0004] However, even though silane was introduced into the petroleum resin, there was a problem where a large amount of the introduced silane remained as unreacted silane without bonding with the petroleum resin, or where the hydrogenation reaction in the petroleum resin was difficult after the introduction of silane, resulting in a decrease in processability, grip properties, wear performance, and rolling resistance properties.

[0005] The present invention provides a petroleum resin composition with excellent silica dispersion properties and crosslinking properties with a polymer.

[0006] Alternatively, a resin composition for tires comprising the above petroleum resin composition is provided.

[0007] One aspect of the present invention relates to a petroleum resin composition comprising a petroleum resin and a silane compound, wherein the petroleum resin comprises at least one of a repeating unit derived from an aromatic petroleum resin monomer and a repeating unit derived from a cycloaliphatic petroleum resin monomer, and at least a portion of the silane compound is grafted onto the petroleum resin, and the silane compound comprises sulfur (S) and has a bromine value of 1 Br.cg / g to 18 Br.cg / g.

[0008] Another aspect of the present invention relates to a resin composition for tires comprising a polymer; the petroleum resin composition; and silica.

[0009] The petroleum resin composition according to the present invention comprises a petroleum resin grafted with a silane compound containing sulfur (S), and by adjusting the bromine value to 1 Br.cg / g to 18 Br.cg / g, the silica dispersion characteristics and crosslinking characteristics with the polymer of the tire resin composition containing the same can be improved.

[0010] Accordingly, the processability, grip characteristics, wear resistance, and rolling resistance characteristics of a tire manufactured from a resin composition for tires containing the above petroleum resin composition can be improved.

[0011] In addition, the above petroleum resin composition includes a petroleum resin and a silane compound, and the wear resistance and rolling resistance characteristics can be further improved by increasing the proportion of the silane compound graphed on the petroleum resin among the silane compounds.

[0012] Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

[0013] Terms and words used in this specification and claims shall not be interpreted as being limited to their ordinary or dictionary meanings, but shall be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0014] The terms used in this invention are used merely to describe specific embodiments and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this invention, terms such as "comprising" or "having" are intended to indicate the existence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0015] In the present invention, an alkyl group having 1 to 12 carbon atoms is a group having one bonding site formed by removing one hydrogen from a saturated hydrocarbon chain, and includes methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl, etc. An alkylene group having 1 to 12 carbon atoms is a group having two bonding sites formed by removing two hydrogens from a saturated hydrocarbon chain, and includes methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decanyl, etc.

[0016] Specifically, a petroleum resin composition according to one aspect of the present invention comprises a petroleum resin; and a silane compound, wherein the petroleum resin comprises at least one of a repeating unit derived from an aromatic petroleum resin monomer and a repeating unit derived from a cycloaliphatic petroleum resin monomer, at least some of the unsaturated bonds included in the petroleum resin are hydrogenated, at least some of the silane compound is grafted onto the petroleum resin, and the silane compound comprises sulfur (S) and has a bromine value of 1 Br.cg / g to 18 Br.cg / g.

[0017] The above petroleum resin composition comprises a petroleum resin grafted with a silane-based compound containing sulfur (S), and by controlling the bromine value of the petroleum resin composition to a certain range, the silica dispersion characteristics and crosslinking characteristics with the polymer of the tire resin composition containing it are improved. Accordingly, a tire manufactured from a tire resin composition containing the above petroleum resin composition may have excellent processability, grip characteristics, wear resistance, and rolling resistance characteristics.

[0018] Conventional petroleum resin compositions containing silane compounds could not control the bromine value of the petroleum resin composition to the above range. However, the petroleum resin composition according to the present invention can easily control the bromine value of the petroleum resin composition to the above range before reacting the silane compound with the petroleum resin. Accordingly, a tire manufactured from a tire resin composition containing the petroleum resin composition may have excellent processability, grip characteristics, wear resistance, and rolling resistance characteristics.

[0019] The above cancellation value may be 1 Br.cg / g to 18 Br.cg / g, 2 Br.cg / g to 18 Br.cg / g, 3 Br.cg / g to 18 Br.cg / g, 4 Br.cg / g to 18 Br.cg / g, 5 Br.cg / g to 18 Br.cg / g, 1 Br.cg / g to 15 Br.cg / g, 1 Br.cg / g to 14 Br.cg / g, 1 Br.cg / g to 13 Br.cg / g, 1 Br.cg / g to 12 Br.cg / g, 1 Br.cg / g to 10 Br.cg / g, or 2 Br.cg / g to 8 Br.cg / g.

[0020] According to one embodiment, at least some of the unsaturated bonds included in the petroleum resin can be hydrogenated.

[0021] In conventional petroleum resin compositions, the activity of the hydrogenation catalyst is hindered by the silane compound, which reduces the lifespan of the hydrogenation catalyst and lowers the hydrogenation efficiency. On the other hand, the petroleum resin according to the present invention performs a hydrogenation reaction before reacting with the silane compound, thereby allowing at least some of the double bonds contained in the petroleum resin to be hydrogenated.

[0022] According to one embodiment, the silane compound can be grafted onto the end or side chain of the petroleum resin. For example, since the silane compound reacts with the polymerized petroleum resin rather than the petroleum resin monomer, it can be grafted onto the end or side chain of the petroleum resin rather than the main chain. The silane compound bonded to the end or side chain of the petroleum resin has superior interaction with silica compared to the silane compound bonded inside the main chain, thereby further improving the dispersibility of silica. Accordingly, a tire prepared from a resin composition for tires containing the petroleum resin composition can simultaneously improve wear characteristics and rolling resistance characteristics.

[0023] According to one embodiment, the silane compound grafted onto the petroleum resin may include a unit represented by the following chemical formula 1.

[0024] <Chemical Formula 1>

[0025]

[0026] Among the above chemical formula 1,

[0027] x1 is an integer from 1 to 5, and

[0028] L1 is a single bond or an alkylene group having 1 to 12 carbon atoms, and

[0029] a1 is an integer from 1 to 5, and

[0030] R1 is an alkyl group having 1 to 12 carbon atoms, and

[0031] * is a bonding site with a neighboring atom.

[0032] For example, in the above formula 1, R1 may be a methyl group, an ethyl group, or a propyl group. x1 may be an integer from 1 to 4. L1 may be a methylene group, an ethylene group, or a propylene group.

[0033] According to one embodiment, the silane compound may include (3-mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methoxydiethoxysilane, bis-(3-triethoxysilylpropyl)disulfide, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-(3-triethoxysilylpropyl)polysulfide, or any combination thereof.

[0034] For example, the above silane compound may include (3-mercaptopropyl)triethoxysilane, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-(3-triethoxysilylpropyl)polysulfide, or any combination thereof.

[0035] According to one embodiment, the content of the silane compound may be 1% by weight or more with respect to the total weight of the petroleum resin composition.

[0036] The content of the above silane compound may be 3 wt% or more, 1 wt% to 50 wt%, 3 wt% to 50 wt%, 3 wt% to 40 wt%, 3 wt% to 30 wt%, 5 wt% to 30 wt%, 6 wt% to 30 wt%, 3 wt% to 20 wt%, 3 wt% to 16 wt%, 3 wt% to 12 wt%, 3 wt% to 10 wt%, or 5 wt% to 16 wt% based on the total weight of the petroleum resin composition. The content of the above silane compound includes a silane compound grafted onto the petroleum resin and an unreacted silane compound. The content of the above silane compound is 1 It can be measured through H-NMR analysis.

[0037] The above 1 H-NMR analysis is performed by preparing a sample containing the above petroleum resin composition, measuring the prepared sample at 23°C using a Jeol 400 MHz NMR (model: JNM-ECZ400SL1) under analysis conditions of a relaxation delay of 4 seconds, 32 scans, an X-axis offset of 5 ppm, an X-axis sweep of 15 ppm, and 32768 acquisition points, and analyzing the measured results using Delta 5.3.1 software. For the preparation of the sample, 0.1 g of the above petroleum resin composition and 0.6 ml of deuterated chloroform (Chloroform-d6) are placed in a 4 ml vial and stirred; if any undissolved components are present, the undissolved components are filtered using a 0.45 µm PTFE filter. Afterward, the sample is prepared by placing it in a 5 mm NMR tube. The above 1g deuterated chloroform (Chloroform-d6) is a solvent containing 0.3% of the reference material TMS (Tetramethylsilane).

[0038] The main analysis conditions for all samples were a relaxation delay of 4 seconds, 32 scans, an X offset of 5 ppm, an X sweep of 15 ppm, and 32,768 acquisition points, and measurements were performed at around 23°C. The instrument used for analysis was a Jeol 400 MHz NMR (Model: JNM-ECZ400SL1), and the software used was Delta 5.3.1.

[0039] According to one embodiment, the petroleum resin composition may have a value of 20% or more according to Formula 1 below.

[0040] <Equation 1>

[0041] W2 / W1x 100(%)

[0042] Among the above Equation 1

[0043] W1 is the content of silane compounds contained in the petroleum resin composition, and W2 is the content of silane compounds contained in the refined petroleum resin composition.

[0044] The above-described refined petroleum resin composition is a petroleum resin composition from which unreacted silane compounds have been removed, excluding the silane compounds grafted onto the petroleum resin among the silane compounds included in the petroleum resin composition.

[0045] The purified petroleum resin composition is obtained by completely dissolving 1 g of the petroleum resin composition in 100 mL of toluene, then slowly adding 400 mL of ethanol, and filtering the precipitated material using filter paper (100% cotton linter cellulose, pore size 5 μm) as the ethanol is added. The ethanol dissolves unreacted silane compounds, thereby selectively removing unreacted silane compounds contained in the petroleum resin composition. The purified petroleum resin composition is a petroleum resin composition from which unreacted silane compounds among the silane compounds contained in the petroleum resin composition have been removed.

[0046] W1 above refers to the total amount of unreacted silane compounds and grafted silane compounds. W2 above refers to the total amount of grafted silane compounds.

[0047] Formula 1 above represents the weight ratio of the silane compound grafted onto the petroleum resin among the silane compounds to the total weight of the silane compounds included in the petroleum resin composition. W1 and W2 are as described above. 1 It is measured through H-NMR analysis.

[0048] Formula 1 above represents the ratio of the content of the silane compound grafted onto the petroleum resin among the silane compounds to the total content of the silane compounds included in the petroleum resin composition. W1 and W2 are as described above. 1 It is measured through H-NMR analysis.

[0049] When the value according to Formula 1 of the above petroleum resin composition is 20% or more, the resin composition for tires containing the above petroleum resin composition may have excellent dispersion of polymer and silica. Accordingly, the tire prepared from the above resin composition for tires may have improved wear characteristics and rolling resistance characteristics.

[0050] According to one embodiment, the petroleum resin composition has a value according to Formula 1 of 25% or more, 30% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 20 to 99%, 25 to 99%, 30 to 99%, 40 to 99%, 45 to 99%, 50 to 99%, 55 to 99%, 60 to 99%, 65 to 99%, 70 to 99%, 20 to 98%, 20 to 97%, 20 to 96%, 20 to 95%, 20 to 94%, 20 to 93%, 20 to 92%, 20 to 91%, 20 to 90%, or 70 It can be up to 90%.

[0051] According to one embodiment, the petroleum resin may comprise at least one of a repeating unit derived from an aromatic petroleum resin monomer and a repeating unit derived from a cycloaliphatic petroleum resin monomer. The petroleum resin may be prepared by polymerizing at least one of an aromatic petroleum resin monomer and a cycloaliphatic petroleum resin monomer, and then grafting a silane compound.

[0052] For example, the above petroleum resin may include repeating units derived from aromatic petroleum resin monomers and repeating units derived from alicyclic petroleum resin monomers.

[0053] According to one embodiment, the aromatic petroleum resin monomer comprises a C9 fraction, and the alicyclic petroleum resin monomer may comprise DCPD.

[0054] The above C9 fraction includes at least one of styrene, alpha-methyl-styrene (α-Me-Styrene), vinyl toluene, trans-beta-methyl-styrene (Trans-β-Me-Styrene) and indene, and the content of these may be 50% or more.

[0055] According to one embodiment, the content of the petroleum resin may be 50% to 99% by weight, 60% to 99% by weight, 70% to 99% by weight, 80% to 99% by weight, 84% to 99% by weight, 88% to 99% by weight, 90% to 99% by weight, 50% to 97% by weight, 50% to 96% by weight, 50% to 95% by weight, 50% to 94% by weight, 50% to 93% by weight, or 80% to 95% by weight, based on the total weight of the petroleum resin composition.

[0056] According to one embodiment, the weight average molecular weight (Mw) of the petroleum resin composition may be 750 to 1,500 g / mol. The weight average molecular weight (Mw) of the petroleum resin composition may be 750 to 1,400 g / mol, 750 to 1,300 g / mol, 750 to 1,200 g / mol, 750 to 1,100 g / mol, 750 to 1,050 g / mol, 750 to 1,000 g / mol, 800 to 1,500 g / mol, 850 to 1,500 g / mol, 900 to 1,500 g / mol, 900 to 1,100 g / mol, or 900 to 1,000 g / mol. The weight average molecular weight (Mw) of the above petroleum resin composition refers to the weight average molecular weight of the petroleum resin composition containing the petroleum resin and the silane compound.

[0057] According to one embodiment, the softening point of the petroleum resin composition may be 80 to 110°C. The softening point of the petroleum resin may be 85 to 110°C, 90 to 110°C, 80 to 105°C, 80 to 100°C, or 90 to 100°C. The softening point of the petroleum resin composition refers to the softening point of a petroleum resin composition containing petroleum resin and a silane compound.

[0058] According to one embodiment, a resin composition for a tire comprising the above-described petroleum resin composition is provided. The resin composition for a tire comprises a polymer; the above-described petroleum resin composition; and silica.

[0059] The above petroleum resin composition is added to a resin composition for tires to improve processability and grip characteristics, as well as to improve the dispersion characteristics of silica and the crosslinking characteristics of the polymer, thereby simultaneously improving the wear and rolling resistance characteristics of the tire manufactured therefrom.

[0060]

[0061] According to one embodiment, the content of the petroleum resin composition included in the resin composition for the tire may be 1 to 20 parts by weight, 5 to 15 parts by weight, or 7 to 12 parts by weight per 100 parts by weight of the polymer.

[0062] According to one embodiment, the polymer may comprise at least one of natural rubber (NR), 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, butyl halogenated rubber, isoprene halogenated rubber, isobutylene copolymer, chloroprene rubber, butyl rubber, and isobutylene-p-methylstyrene halogenated rubber. The polymer may comprise butadiene rubber.

[0063] According to one embodiment, the resin composition for a tire may further include at least one of a reinforcing agent, a silane coupling agent, a vulcanizing agent, and a vulcanization accelerator.

[0064] The above reinforcing agent may include silica or carbon black.

[0065] The silica above may be a reinforcing agent for rubber and may include at least one of dry-process white carbon, wet-process white carbon, synthetic silicate-based white carbon, colloidal silica, and precipitated silica. The content of the silica may be 50 to 100 parts by weight or 70 to 90 parts by weight per 100 parts by weight of the polymer.

[0066] The carbon black may include at least one of Farness black, acetylene black, thermal black, channel black, and graphite as a reinforcing agent for improving wear resistance, improving rolling resistance characteristics, and preventing UV degradation. The content of the carbon black may be 50 to 100 parts by weight or 70 to 90 parts by weight per 100 parts by weight of the polymer.

[0067] The above reinforcing agent may further include at least one of mineral powders such as clay and talc, carbonates such as magnesium carbonate and calcium carbonate, and alumina hydrates such as aluminum hydroxide.

[0068] The above silane coupling agents are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)silane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis(3-(triethoxysilyl)propyl)disulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-Mercaptopropyltriethoxysilane, 2-Mercaptoethyltrimethoxysilane, 2-Mercaptoethyltriethoxysilane, 3-Trimethoxysilylpropyl-N,N-Dimethylthiocarbamoyltetrasulfide, 3-Triethoxysilylpropyl-N,N-Dimethylthiocarbamoyltetrasulfide, 2-Triethoxysilylethyl-N,N-Dimethylthiocarbamoyltetrasulfide, 3-Trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-Triethoxysilylpropylbenzolyltetrasulfide, 3-Triethoxysilylpropylmethacrylate monosulfide, 3-Trimethoxysilylpropylmethacrylate monosulfide, Bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-Mercaptopropyldimethoxymethylsilane, It may include at least one of dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide and dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. The content of the silane coupling agent may be 1 to 15 parts by weight, 2 to 10 parts by weight, or 3 to 8 parts by weight per 100 parts by weight of the polymer.

[0069] The above vulcanizing agent may include at least one of a sulfur vulcanizing agent such as sulfur, morpholine disulfide, alkylphenol disulfide, etc., and an organic peroxide vulcanizing agent such as cyclohexanone peroxide, methylacetoacetate peroxide, tert-butylperoxyisobutylate, tert-butylperoxybenzoate, benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, ditert-butyl peroxide, 1,3-bis(tert-butylperoxyisopropyl)benzene. The content of the above vulcanizing agent may be 0.1 to 10 parts by weight or 0.5 to 5 parts by weight per 100 parts by weight of the polymer.

[0070] The above vulcanization accelerator may include metal oxides such as zinc oxide (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 at least one of ethylene dimethacrylate, diallyl phthalate, N,Nm-phenylenedimaleimide, trialyl isocyanurate, and trimethylolpropane trimethacrylate. The content of the above vulcanization accelerator may be 0.1 to 10 parts by weight per 100 parts by weight of the polymer.

[0071] The above resin composition for tires may further include an additive comprising at least one of an anti-aging agent, a vulcanization retardant, a release agent, a process oil, and a plasticizer. The content of the additive may be 0.1 to 10 parts by weight per 100 parts by weight of the polymer.

[0072] The present invention will be described in more detail below through examples. These examples are intended solely to explain the present invention more specifically, and it will be obvious to those skilled in the art that the scope of the present invention is not limited by these examples.

[0073] Preparation Example 1: Petroleum resin composition

[0074] A mixture was prepared in a 1L autoclave by dissolving 54 parts by weight of dicyclopentadiene (DCPD, Kolon Industries, Ltd., purity 80.21%) in xylene, a solvent, and to this, C9 　 46 parts by weight of oil (styrene 20 wt%, indene 18 wt%, vinyltoluene 16 wt%, alpha-methylstyrene 5 wt%) was added, and after connecting the reactor, the reaction temperature was maintained at 270 ℃ and the thermal polymerization reaction was carried out for 2 hours, after which the reaction was terminated.

[0075] After the reaction was completed, the obtained product was placed into a 1 L glass 4-neck kettle and a vacuum was applied at room temperature. The vacuum level was maintained at 1 to 10 torr, and once the vacuum was applied, the temperature was raised to 250 ℃ with stirring. Upon reaching 250 ℃, the concentration time was measured and maintained for 10 minutes. Once the concentration was complete, the vacuum was released, and petroleum resin was obtained.

[0076] 1.5 times the amount of hydrogenation solvent was added to the obtained petroleum resin to completely dissolve it, and then it was placed into a 1L autoclave.

[0077] 0.2 mol of palladium catalyst was added here, and after closing the reactor, a partial hydrogenation reaction was performed for 90 minutes at a hydrogen pressure of 80 bar and a temperature of 275 ℃ to produce a partially hydrogenated petroleum resin.

[0078] 20% by weight of (3-mercaptopropyl)triethoxysilane was added as a mercaptosilane to 80% by weight of the prepared petroleum resin. Subsequently, 3% by weight of benzoyl peroxide was additionally added, and a silane grafting reaction was performed at 70°C for 1 hour to produce the petroleum resin. After the reaction was completed, the reaction product was distilled at 250°C for 10 minutes under a vacuum of 1 to 10 torr to prepare the petroleum resin composition.

[0079] Preparation Examples 2 to 10

[0080] A petroleum resin composition was prepared in the same manner as in Preparation Example 1, except that the type and weight of the petroleum resin, whether the petroleum resin was hydrogenated, the type and weight of the silane compound, and the weight of the benzoyl peroxide were changed as shown in Table 1 below.

[0081] Comparative Manufacturing Example 1

[0082] A petroleum resin composition was prepared in the same manner as in Preparation Example 1, except that the silane grafting reaction was not performed.

[0083] Comparative Manufacturing Example 2

[0084] A mixture was prepared by dissolving 49 parts by weight of dicyclopentadiene (DCPD, Kolon Industries Co., Ltd., purity 80.21%) in xylene, a solvent, in a 1L autoclave, and to this, C9 　 41 parts by weight of oil (styrene 20 wt%, indene 18 wt%, vinyltoluene 16 wt%, alpha-methylstyrene 5 wt%) were added. After connecting the reactor, the reaction temperature was maintained at 270 ℃ and the thermal polymerization reaction was carried out for 2 hours. After the hydrogenation reaction, vacuum degassing was performed, and 10 wt% of (3-mercaptopropyltriethoxysilane) was added as a mercapto silane to 90 wt% of the petroleum resin produced. A petroleum resin composition was prepared in the same manner as in Preparation Example 1, except that the reaction was not performed by adding benzoyl peroxide.

[0085] Comparative Manufacturing Example 3

[0086] A petroleum resin composition was prepared in the same manner as in Preparation Example 1, except that a hydrogenation reaction was not performed.

[0087] Comparative Manufacturing Example 4

[0088] A petroleum resin composition was prepared in the same manner as in Preparation Example 1, except that only dicyclopentadiene (DCPD, Kolon Industries Co., Ltd.) was used as the monomer during the preparation of the petroleum resin and no hydrogenation reaction was performed.

[0089] Comparative Manufacturing Example 5

[0090] A petroleum resin composition was prepared in the same manner as in Preparation Example 1, except that triethoxyvinyl silane was used instead of (3-mercaptopropyltriethoxy silane), which is a mercapto silane, during the silane grafting reaction.

[0091] Comparative Manufacturing Example 6

[0092] A petroleum resin composition was prepared in the same manner as in Preparation Example 1, except that only dicyclopentadiene (DCPD, Kolon Industries Co., Ltd.) was used as the monomer during the preparation of the petroleum resin, no hydrogenation reaction was performed, and triethoxyvinyl silane was used instead of (3-mercaptopropyltriethoxy silane), which is a mercapto silane, during the silane grafting reaction.

[0093] Comparative Manufacturing Example 7

[0094] 0.09 mol / kg of AlCl3 catalyst dissolved in xylene was added to 100 parts by weight of C5 fraction (containing 15 wt% isoprene, 15 wt% piperylene, 5 wt% cycloolefin, 5 wt% diolefin, 5 wt% pentene, and 5 wt% cyclopentene) in a 1L autoclave, and after closing the reactor, the reaction temperature was maintained at 60℃ and catalytic polymerization was carried out for 2 hours, after which the reaction was terminated. After the polymerization was terminated, water was added to neutralize the reaction, and after oil-water separation at 60℃ for 2 hours, only the fraction was collected to obtain the polymerized oil.

[0095] The obtained polymerization oil was placed into a 1 L glass 4-neck kettle and a vacuum was applied at room temperature. The vacuum level was maintained at 1 to 10 torr, and once the vacuum was applied, the temperature was raised to 260 ℃ with stirring. When 260 ℃ was reached, the concentration time was measured and maintained for 10 minutes. When concentration was completed, the vacuum was released to obtain a petroleum resin composition.

[0096] Comparative Manufacturing Example 8

[0097] A mixture was prepared by dissolving 100 parts by weight of C9 fraction (styrene 20 wt%, indene 18 wt%, vinyltoluene 16 wt%, alpha-methylstyrene 5 wt%) in 100 parts by weight of xylene, a solvent, in a 1 L autoclave. After connecting the reactor, when the reaction temperature reached 90 ℃, 0.1 mol of BF3 catalyst / C9 fraction (kg) was added. The reaction was then carried out for 2 hours while maintaining the reaction temperature at 90 ℃, after which the reaction was terminated. Slaked lime (Ca(OH)2), a neutralizing agent, was added to the polymerized oil after the reaction was completed, and the mixture was neutralized at 60 ℃ for 1 hour. The mixture was then filtered to separate waste lime and residues, and the filtered polymerized oil was obtained.

[0098] The obtained product was placed into a 1 L glass 4-neck kettle and a vacuum was applied at room temperature. The vacuum level was maintained at 1 to 10 torr, and once the vacuum was applied, the temperature was raised to 260 ℃ with stirring. When 260 ℃ was reached, the concentration time was started and maintained for 10 minutes. When concentration was completed, the vacuum was released to obtain a petroleum resin composition.

[0099] Comparative Manufacturing Example 9

[0100] A mixture was prepared by dissolving 100 parts by weight of dicyclopentadiene (DCPD, Kolon Industries Co., Ltd., purity 80.21%) in 100 parts by weight of xylene, a solvent, in a 1L autoclave, and after connecting the reactor, the reaction was carried out for 2 hours at a temperature of 270 ℃ for thermal polymerization, and then the reaction was terminated.

[0101] After the reaction was completed, the obtained product was placed into a 1 L glass 4-neck kettle and vacuum was applied at room temperature. The vacuum level was maintained at 1 to 10 torr, and once vacuum was applied, the temperature was raised to 260 ℃ with stirring. Upon reaching 260 ℃, the concentration time was measured and maintained for 10 minutes. Once concentration was complete, the vacuum was released to obtain a petroleum resin composition.

[0102] Evaluation Example 1: Evaluation of Physical Properties of Petroleum Resin Composition

[0103] (1) Molecular weight: The weight-average molecular weight (Mw) was measured by polystyrene conversion using gel permeation chromatography (Hewlett-Packard, model HP-1100) for the petroleum resin compositions according to Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 9. The polymer to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm, and 100 µl was injected into the GPC. Tetrahydrofuran was used as the mobile phase of the GPC and introduced at a flow rate of 1.0 mL / min, and the analysis was performed at 30°C. Three Agilent PIgel columns (1000+500+100 Å) were connected in series. An RI detector (Hewlett-Packard, HP-1047A) was used as the detector and measurements were taken at 30°C.

[0104] (2) Softening point: The softening point of the petroleum resin compositions according to Manufacturing Examples 1 to 10 and Comparative Manufacturing Examples 1 to 9 was measured using the Ring and ball softening method (ASTM E 28). The resin was melted and poured into a ring-shaped mold, placed in a beaker containing glycerin, and then a flame was placed over the ring containing the resin and the temperature was increased at a rate of 5°C per minute to measure the temperature at which the resin melted and the ball fell (softening point).

[0105] (3) Reaction value: 0.5 g of petroleum resin compositions according to Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 9 were each dissolved in 40 ml of cyclohexane, 50 ml of acetic acid was added, and a standard mixed solution of potassium bromide and potassium bromate was titrated to cause an addition reaction with the liberated bromine. After sufficient reaction, 5 ml of potassium iodide solution was added to replace the excess bromine with iodine, and the iodine was back-titrated with a standard sodium thiosulfate solution to be measured. The reaction value refers to the amount of bromine that reacts with double bonds, and the more double bonds the resin has, the greater the amount of bromine that reacts, and thus the higher the reaction value.

[0106] (4) Equation 1(W2 / W1 (%))

[0107] 1) w1: For each of the petroleum resin compositions according to Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 9, the content of silane included in the petroleum resin composition 1 It was measured through H-NMR analysis.

[0108] 1 For H-NMR analysis, samples were prepared by adding 0.1g of the petroleum resin composition and 0.6ml of Chloroform-d6 to each 4ml vial and stirring. Chloroform-d6 is a solvent containing 0.3% of TMS (Tetramethylsilane), which is a reference substance. For samples containing some undissolved components, analysis was performed after filtering using a 0.45µm PTFE filter, and the dissolved samples were transferred to a 5mm NMR tube.

[0109] The main analysis conditions for all samples were a relaxation delay of 4 seconds, 32 scans, an X offset of 5 ppm, an X sweep of 15 ppm, and 32,768 acquisition points, and measurements were performed at around 23°C. The instrument used for analysis was a Jeol 400 MHz NMR (Model: JNM-ECZ400SL1), and the software used was Delta 5.3.1.

[0110] 2) w2: The petroleum resin compositions according to Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 9 were each purified to remove unreacted silane compounds. For each of the purified petroleum resin compositions, the content of the silane contained therein 1 It was measured through H-NMR analysis.

[0111] The above-described refined petroleum resin composition was prepared by completely dissolving 1 g of the above-described petroleum resin composition in 100 mL of toluene, then slowly adding 400 mL of ethanol, and filtering the precipitated material using filter paper (100% cotton linter cellulose, pore size 5 μm) as the ethanol was added.

[0112] Petroleum Resin Hydrogenation Status Silane Compound Benzoyl Peroxide (wt%) Molecular Weight (Mw) Softening Point (°C) Breakdown Amount (Br.cg / g) Formula 1 (W2 / W1)% Type Weight Type Weight Preparation Example 1 DCPD & C980O3-MercaptophthophilTriethoxysilane 2031,04095679.3 Preparation Example 2 DCPD & C990O3-MercaptophthophilTriethoxysilane 10398098973.8 Preparation Example 3 DCPD & C990O3-MercaptophthophilTriethoxysilane 104970100795 Preparation Example 4 DCPD & C993O3-MercaptophthophilTriethoxysilane 7396099592 Preparation Example 5 DCPD & C980O3-MercaptophthophilTriethoxy Silane 2021,03094869.2 Preparation Example 6 DCPD& C990O3-MercaptophthophilTriethoxysilane 101950951229.8 Preparation Example 7 DCPD& C990O3-MercaptophthophilTriethoxysilane 102970961047.5 Preparation Example 8 DCPD& C980O3-MercaptophthophilTriethoxysilane 2011,01092960 Preparation Example 9 DCPD80O3-MercaptophthophilTriethoxysilane 203730981178.5 Preparation Example 10 C980X3-MercaptophthophilTriethoxysilane 1031,200981859.4 Comparative Preparation Example 1 DCPD& C9100O---68010030 Comparative Preparation Example 2 DCPD& C990O3-MercaptophthophilTriethoxysilane 20-70090205.2 Comparison Preparation Example 3 DCPD& C980X3-MercaptophthophilTriethoxysilane 2031,001 95 55 75.6 Comparison Preparation Example 4 DCPD80X3-MercaptophthophilTriethoxysilane 20-820997090 Comparison Preparation Example 5 DCPD& C980O-Triethoxyvinylsilane 20399098 7 77.8 Comparison Preparation Example 6 DCPD80X-Triethoxyvinylsilane 20-7501007095 Comparison Preparation Example 7 C5100X---2,400100420 Comparison Preparation Example 8 C9100X---1,20098200 Comparison Preparation Example 9DCPD100X---710100840

[0113] Referring to Table 1 above, Preparation Example 1, in which a hydrogenation reaction was performed before the silane grafting reaction, satisfied the cancellation value of the prepared petroleum resin composition of 1 to 18 Br.cg / g, whereas Comparative Preparation Example 2, in which a hydrogenation reaction was performed but benzoyl peroxide was not added during the grafting reaction, and Comparative Preparation Examples 3 to 4 and 6 to 9, in which a hydrogenation reaction was not performed, had cancellation values ​​outside the range of 1 to 18 Br.cg / g.

[0114] Examples 1 to 10 and Comparative Examples 1 to 9

[0115] To 10 parts by weight of the petroleum resin compositions according to Manufacturing Examples 1 to 10 and Comparative Manufacturing Examples 1 to 9, 100 parts by weight of rubber mixed with styrene-butadiene rubber (product name: SSBR-5130, Kumho Petrochemical) and butadiene rubber (product name: BR-01, Kumho Petrochemical) in a ratio of 8:2, 80 parts by weight of silica, 6.4 parts by weight of a silane coupling agent, 3 parts by weight of zinc oxide, and 2 parts by weight of stearic acid were added to each, and a primary compounding operation was performed in a Banbury mixer. For the final rubber composition, 1.5 parts by weight of sulfur and 1 part by weight of a rubber vulcanization accelerator were added to the primary compounding product and processed in a Banbury mixer to finally produce the tire resin compositions according to Examples 1 to 10 and Comparative Examples 1 to 9 containing the petroleum resin composition.

[0116] Next, the above-mentioned resin compositions for tires were each injected into an open mill to produce a compound sheet. Test rubber specimens were prepared by vulcanizing at 160°C for 20 minutes.

[0117] Evaluation Example 2: Evaluation of Physical Properties of Rubber Specimens

[0118] (1) Processability evaluation: Scotch time

[0119] Scotch time was measured for rubber specimens according to Examples 1 to 10 and Comparative Examples 1 to 9 according to ASTM D 5289-95 (2001).

[0120] (2) Evaluation of grip characteristics and rotational resistance: Tan δ@0℃ and Tan δ@60℃

[0121] For the rubber specimens according to Examples 1 to 10 and Comparative Examples 1 to 9 above, the loss factor related to grip force (Tan δ@0℃) and the loss factor related to rotational resistance (Tan δ@60℃) at 11Hz were measured using Dynamic Mechanical Analysis (Model: TA-DMA Q800).

[0122] (3) Abrasion evaluation

[0123] The wear rate according to ASTM D2228 was measured for the rubber specimens according to Examples 1 to 10 and Comparative Examples 1 to 9 above.

[0124] Scorch Time (%) Tan δ @ 0℃ (%) Tan δ @ 60℃ (%) Wear Rate (%) Example 1 85 100 104 116 Example 2 9 197 100 115 Example 3 9 110 6 105 111 Example 4 95 105 109 110 Example 5 88 105 101 109 Example 6 90 105 98 105 Example 7 90 95 103 104 Example 8 85 99 100 104 Example 9 84 92 105 111 Example 1 082 105 95 110 Comparative Example 1 100 100 100 100 Comparative Example 2 80 95 97 101 Comparative Example 3 8 1100 96 100 Comparative Example 4859384104 Comparative Example 582999897 Comparative Example 680918488 Comparative Example 795979395 Comparative Example 8971029294 Comparative Example 987908085

[0125] As shown in Table 2 above, the rubber specimen according to the example using a petroleum resin composition that includes a petroleum resin grafted with a silane compound containing sulfur (S) or one that satisfies the range of characteristic cancellation, maintained excellent processability, grip characteristics, and rolling resistance characteristics compared to the rubber specimen according to the comparative example, while also improving wear characteristics.

[0126] The aforementioned embodiments and comparative examples are examples for explaining the present invention, and the present invention is not limited thereto. Since a person skilled in the art to which the present invention pertains can implement the present invention by making various modifications therefrom, the technical scope of protection of the present invention should be determined by the appended claims.

Claims

petroleum resin; and It includes silane compounds, The above petroleum resin comprises at least one of repeating units derived from aromatic petroleum resin monomers and repeating units derived from alicyclic petroleum resin monomers, and At least some of the above silane compounds are grafted onto the petroleum resin, and The above silane compound contains sulfur (S), and A petroleum resin composition having a bromine value of 1 Br.cg / g to 18 Br.cg / g. In paragraph 1, A petroleum resin composition in which at least some of the unsaturated bonds included in the above petroleum resin are hydrogenated. In paragraph 1, A petroleum resin composition comprising a unit represented by the following chemical formula 1, wherein the silane compound grafted onto the above petroleum resin: <Chemical Formula 1> Among the above chemical formula 1, x1 is an integer from 1 to 5, and L1 is a single bond or an alkylene group having 1 to 12 carbon atoms, and a1 is an integer from 1 to 5, and R1 is an alkyl group having 1 to 12 carbon atoms, and * is a bonding site with a neighboring atom. In paragraph 1, A petroleum resin composition comprising the above silane compound (3-mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-mercaptopropyl)methoxydiethoxysilane, bis-(3-triethoxysilylpropyl)disulfide, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-(3-triethoxysilylpropyl)polysulfide, or any combination thereof. In paragraph 1, A petroleum resin composition in which the content of the above silane compound is 1% to 50% by weight based on the total weight of the petroleum resin composition. In paragraph 1, The above petroleum resin composition is a petroleum resin composition having a value of 20% or more according to Formula 1 below: <Equation 1> W2 / W1X 100(%) Among the above Equation 1 W1 is the content of the silane compound included in the petroleum resin composition, and W2 is the content of silane compounds included in the refined petroleum resin composition. In paragraph 1, The above petroleum resin is a petroleum resin composition comprising repeating units derived from aromatic petroleum resin monomers and repeating units derived from alicyclic petroleum resin monomers. In paragraph 1, The above aromatic petroleum resin monomer includes a C9 fraction, and The above-mentioned cycloaliphatic petroleum resin monomer is a petroleum resin composition comprising DCPD (dicyclopentadiene). In paragraph 1, A petroleum resin composition having a content of 50 to 99 weight percent based on the total weight of the petroleum resin composition. In paragraph 1, A petroleum resin composition having a weight average molecular weight (Mw) of 750 to 1,500 g / mol. In paragraph 1, A petroleum resin composition having a softening point of 80 to 110°C. Polymer; and A resin composition for tires comprising a petroleum resin composition according to claim 1.

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