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 a repeat unit derived from an aromatic petroleum resin monomer; at least a part of the silane-based compound is grafted onto the petroleum resin; the silane-based compound comprises sulfur (S); and the value according to Formula 1 below is 3% or higher. The tire composition has improved grip, wear, and rolling resistance properties. <Formula 1> W2 / W1 (%) In Formula 1, W1 is the amount of the silane-based compound contained in the petroleum resin composition, and W2 is the amount of the silane-based compound contained in the refined petroleum resin composition.

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 spraying properties and crosslinking properties with polymers.

[0006] Alternatively, a petroleum 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 repeating units derived from an aromatic 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 the value according to Formula 1 below is 3% or more.

[0008] <Equation 1>

[0009] W2 / W1X 100(%)

[0010] Among the above Equation 1

[0011] W1 is the content of the silane compound included in the petroleum resin composition, and

[0012] W2 is the content of silane compounds included in the refined petroleum resin composition.

[0013] Another aspect of the present invention relates to a resin composition for tires comprising a polymer; and the petroleum resin composition.

[0014] The petroleum resin composition according to the present invention comprises a petroleum resin grafted with a silane compound, satisfying a value according to Formula 1 of 3% or more, and wherein the silane compound comprises sulfur (S), so that the resin composition for tires comprising the petroleum resin composition may have excellent silica dispersion characteristics and crosslinking characteristics with the polymer.

[0015] Accordingly, a tire manufactured from the above-mentioned resin composition for tires can simultaneously improve wear characteristics and rolling resistance characteristics while maintaining excellent processability and grip characteristics.

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

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

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

[0019] 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.

[0020] 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 repeating units derived from an aromatic petroleum resin monomer, at least a portion of the silane compound is grafted onto the petroleum resin, and the silane compound comprises sulfur (S), and the value according to Formula 1 below is 3% or more.

[0021] <Equation 1>

[0022] W2x 100 / W1

[0023] Among the above Equation 1

[0024] W1 is the weight of the silane compound contained in the petroleum resin composition, and W2 is the weight of the silane compound contained in the refined petroleum resin composition.

[0025] The petroleum resin composition of the present invention satisfies the range of the value of Formula 1 above, and the silane compound contains sulfur (S), so the resin composition for tires containing the petroleum resin composition may have excellent dispersion of silica and polymer. Accordingly, a tire prepared from the resin composition for tires containing the petroleum resin composition may simultaneously improve wear characteristics and rolling resistance characteristics.

[0026] The above petroleum resin composition may include an unreacted silane compound and a silane compound grafted onto the petroleum resin.

[0027] 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.

[0028] 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.

[0029] 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 to be described later 1 It is measured through H-NMR analysis.

[0030] Conventional petroleum resin compositions could not easily satisfy the range of the value in Formula 1 by simultaneously polymerizing aromatic petroleum resin monomers and silane compounds. On the other hand, since the petroleum resin composition is prepared by polymerizing aromatic petroleum resin monomers to prepare a petroleum resin and then reacting a silane compound with the petroleum resin in the presence of a polymerization initiator, the petroleum resin composition can easily satisfy the range of the value in Formula 1. The polymerization initiator may include a peroxide-based initiator. The polymerization initiator may include benzoyl peroxide.

[0031] Furthermore, conventional petroleum resin compositions simultaneously polymerize aromatic petroleum resin monomers and silane compounds, so the silane compounds are bonded within the main chain of the petroleum resin. In contrast, the petroleum resin composition of the present invention reacts with the petroleum resin polymerized with silane compounds, so the silane compounds can be bonded to the terminal or side chains of the petroleum resin. The silane compounds bonded to the terminal or side chains of the petroleum resin exhibit superior interaction with silica compared to the silane compounds bonded within the main chain, thereby further improving the dispersibility of silica. Accordingly, a tire prepared from a resin composition for tires containing the above petroleum resin composition can simultaneously improve wear characteristics and rolling resistance characteristics.

[0032] According to one embodiment, the petroleum resin composition may have a value according to Formula 1 of 3 to 50%, 3 to 40%, 3 to 30%, 3 to 20%, 5 to 20%, 6 to 20%, 7 to 20%, 8 to 20%, 9 to 20%, 10 to 20%, 12 to 20%, 13 to 20%, or 14 to 20%. When the value according to Formula 1 satisfies the above ranges, the tire manufactured from the resin composition for tires containing the petroleum resin composition may have improved processability, grip characteristics, wear resistance, and rolling resistance characteristics.

[0033] According to one embodiment, the silane compound grafted onto the petroleum resin may include a unit represented by the following chemical formula 1.

[0034] <Chemical Formula 1>

[0035]

[0036] Among the above chemical formula 1,

[0037] x1 is an integer from 1 to 5, and

[0038] L1 is a single bond or an alkylene group having 1 to 12 carbon atoms, and

[0039] a1 is an integer from 1 to 5, and

[0040] R1 is an alkyl group having 1 to 12 carbon atoms, and

[0041] * is a bonding site with a neighboring atom.

[0042] 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.

[0043] 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.

[0044] For example, the above silane compound may include (3-mercaptopropyl)triethoxysilane, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-(3-triethoxysilylpropyl)polysulfide, or any combination thereof.

[0045] According to one embodiment, the content of the silane compound may be 20% by weight or less with respect to the total weight of the petroleum resin composition.

[0046] The content of the silane compound may be 15 wt% or less, 10 wt% or less, 7 wt% or less, 0.1 to 20 wt%, 0.2 to 20 wt%, 0.3 to 20 wt%, 0.4 to 20 wt%, 0.5 to 20 wt%, or 0.5 to 10 wt% based on the total weight of the petroleum resin composition. The content of the silane compound includes a silane compound grafted onto the petroleum resin and an unreacted silane compound. The content of the silane compound is 1 It can be measured through H-NMR analysis.

[0047] The above 1 H-NMR analysis is performed by preparing a sample of the above-mentioned petroleum resin composition and measuring the prepared sample of the above-mentioned petroleum resin composition using a Jeol 400MHz NMR (model: JNM-ECZ400SL1) at 23℃ under analysis conditions of a relaxation delay of 4 seconds, 32 scans, an X offset of 5 ppm, an X sweep of 15 ppm, and 32768 acquisition points, and analyzing the measured results using Delta 5.3.1 software.

[0048] The preparation of the above petroleum resin composition sample is carried out by adding 0.1g of the above petroleum resin composition and 0.6ml of deuterated chloroform (Chloroform-d6) to a 4ml vial and stirring; if some undissolved components are present, the undissolved components are filtered using a 0.45㎛ PTFE filter, and then placed into a 5mm NMR tube. The above 1g of deuterated chloroform (Chloroform-d6) is a solvent containing 0.3% of TMS (Tetramethylsilane), which is a reference material.

[0049] For example, the above 1 The content of the silane compound (W1) contained in the petroleum resin composition and the content of the silane compound (W2) contained in the refined petroleum resin composition are measured through H-NMR analysis.

[0050] According to one embodiment, the break-in value of the petroleum resin composition may be 1 Br.cg / g to 10 Br.cg / g. The break-in value of the petroleum resin composition may be 1 Br.cg / g to 8 Br.cg / g, 1 Br.cg / g to 7 Br.cg / g, 1 Br.cg / g to 6 Br.cg / g, 1 Br.cg / g to 5 Br.cg / g, 1 Br.cg / g to 4 Br.cg / g, 2 Br.cg / g to 10 Br.cg / g, or 2 Br.cg / g to 4 Br.cg / g.

[0051] According to one embodiment, the petroleum resin may include repeating units derived from an aromatic petroleum resin monomer. The petroleum resin may be prepared by polymerizing an aromatic petroleum resin monomer and then grafting a silane compound.

[0052] For example, the above petroleum resin may contain only repeating units derived from aromatic petroleum resin monomers.

[0053] According to one embodiment, the aromatic petroleum resin monomer may include styrene or alpha-methyl-styrene (α-Me-Styrene). The aromatic petroleum resin monomer may include styrene and alpha-methyl-styrene (α-Me-Styrene).

[0054] According to one embodiment, the petroleum resin may be a pure monomer resin. The pure monomer resin refers to a petroleum resin comprising repeating units derived from styrene or alpha-methyl-styrene (α-Me-Styrene). The pure monomer resin refers to a petroleum resin prepared by refining a specific monomer (e.g., a styrene-based monomer) from a fraction (e.g., a C9 fraction) and then polymerizing the refined monomer.

[0055] According to one embodiment, the weight average molecular weight (Mw) of the petroleum resin composition may be 1,000 to 2,400 g / mol. The weight average molecular weight (Mw) of the petroleum resin may be 1,100 to 2,400 g / mol, 1,200 to 2,400 g / mol, 1,300 to 2,400 g / mol, 1,000 to 2,000 g / mol, 1,000 to 1,800 g / mol, 1,000 to 1,600 g / mol, or 1,300 to 1,600 g / mol. The weight average molecular weight (Mw) of the petroleum resin composition refers to the weight average molecular weight of the petroleum resin composition containing the petroleum resin and the silane compound.

[0056] 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 80 to 105°C, 80 to 100°C, 80 to 95°C, or 82 to 95°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.

[0057] 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; and the above-described petroleum resin composition.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] The above reinforcing agent may include silica or carbon black.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] Preparation Example 1: Petroleum resin composition

[0072] A mixture of styrene and alpha-methyl styrene dissolved in toluene, a solvent, was prepared in a 1L autoclave. After the reactor was closed, when the reaction temperature reached 30°C, 0.1 mol of BF3 catalyst was added per 1 kg of styrene and alpha-methyl styrene. The reaction was then carried out for 1 hour while maintaining the reaction temperature at 30°C, after which the reaction was terminated. Slaked lime (Ca(OH)2), a neutralizing agent, was added to the polymerization oil after the reaction was completed, and the mixture was neutralized at 60°C for 1 hour. The mixture was then filtered to separate waste lime and residues, and the filtered polymerization oil was obtained.

[0073] 1 L of the obtained polymerization oil was poured into a 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°C with stirring. When the temperature reached 260°C, the concentration time was measured and maintained for 10 minutes. When the concentration was completed, the vacuum was released and the petroleum resin was obtained.

[0074] 10% by weight of (3-mercaptopropyl)triethoxysilane, a silane compound, was added to 90% by weight of the above petroleum resin. Subsequently, 3% by weight of benzoyl peroxide was additionally added, and a silane grafting reaction was performed. After the reaction was completed, the reaction product was distilled at 260°C for 10 minutes under a vacuum of 1 to 10 torr to obtain a petroleum resin composition.

[0075] Preparation Examples 2 to 6

[0076] A petroleum resin composition was obtained in the same manner as in Preparation Example 1, except that the weight of the petroleum resin, the weight of the silane compound, and the weight of the benzoyl peroxide were changed as shown in Table 1 below.

[0077] Comparative Manufacturing Example 1

[0078] A petroleum resin composition was obtained in the same manner as in Preparation Example 1, except that the silane grafting reaction was not performed.

[0079] Comparative Manufacturing Example 2

[0080] A mixture was prepared by dissolving styrene and alpha-methyl styrene in xylene, a solvent, in a 1L autoclave. Then, (3-mercaptopropyltriethoxysilane) was added so that the weight ratio of the petroleum resin monomer to the silane monomer was 90:10, and the mixture was placed in a reactor. A thermal polymerization reaction was then carried out for 1 hour while maintaining the reaction temperature at 200°C to polymerize the aromatic petroleum resin monomer and the silane compound together, and a petroleum resin composition was obtained in the same manner as in Preparation Example 1.

[0081] Comparative Manufacturing Example 3

[0082] A petroleum resin composition was obtained in the same manner as in Preparation Example 1, except that triethoxyvinyl silane was used instead of (3-mercaptopropyltriethoxy silane) during the silane grafting reaction.

[0083] Evaluation Example 1: Evaluation of Physical Properties of Petroleum Resin Composition

[0084] (1) Molecular weight: The weight-average molecular weight (Mw) of the petroleum resin compositions according to Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 3 was measured by polystyrene conversion using gel permeation chromatography (Hewlett-Packard, model HP-1100). 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.

[0085] (2) Softening point: The softening point of the petroleum resin compositions according to Manufacturing Examples 1 to 6 and Comparative Manufacturing Examples 1 to 3 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).

[0086] (3) Reaction value: 0.5 g of petroleum resin compositions according to Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 3 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 measure the reaction value. The reaction value refers to the amount of bromine reacting with double bonds, and the more double bonds the resin has, the greater the amount of bromine reacting, and thus the higher the reaction value.

[0087] (4) Equation 1(W2 / W1 (%))

[0088] 1) w1: For each of the petroleum resin compositions according to Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 3, the content of silane included in the petroleum resin composition 1 It was measured through H-NMR analysis.

[0089] 1For 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.

[0090] 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.

[0091] 2) w2: The petroleum resin compositions according to Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 3 were each purified to remove unreacted silane compounds. For each of the purified petroleum resin compositions, the silane content contained therein 1 It was measured through H-NMR analysis.

[0092] 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.

[0093] Petroleum Resin Silane Compound Benzoyl Peroxide (wt%) Molecular Weight (Mw) Softening Point (°C) Breakdown Value (Br.cg / g) Formula 1 (W2*100 / W1) (%) Type Weight Type Weight Preparation Example 1 PMR903-MercaptophthophilTriethoxysilane 103 1,380 85 318.2 Preparation Example 2 PMR953-MercaptophthophilTriethoxysilane 52 1,330 84 410.3 Preparation Example 3 PMR933-MercaptophthophilTriethoxysilane 73 1,370 85 317.8 Preparation Example 4 PMR903-MercaptophthophilTriethoxysilane 102 1,350 83 413.9 Preparation Example 5 PMR953-MercaptophthophilTriethoxy Silane 511,3108348.7 Preparation Example 6 PMR903-Mercaptophthophiltriethoxysilane 1011,32082412.3 Comparative Preparation Example 1 PMR100---1,1008550 Comparative Preparation Example 2 PMR903-Mercaptophthophiltriethoxysilane 1031,1308052.3 Comparative Preparation Example 3 PMR90-Triethoxyvinylsilane 1031,32085315.9

[0094] Referring to Table 1 above, the example in which a silane grafting reaction was performed after petroleum resin polymerization satisfied the value of Formula 1 of the petroleum resin composition at 3% or more, whereas Comparative Example 2, in which a silane compound was added together with the petroleum resin polymerization, had a value of Formula 1 of less than 3%, which fell outside the above range.

[0095] Examples 1 to 6 and Comparative Examples 1 to 3

[0096] To 10 parts by weight of the petroleum resin compositions according to Manufacturing Examples 1 to 6 and Comparative Manufacturing Examples 1 to 3, 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, and a first 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 first compounding product and processed in a Banbury mixer to finally produce the tire resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 3, which contain the petroleum resin compositions according to Manufacturing Examples 1 to 6 and Comparative Manufacturing Examples 1 to 3.

[0097] 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.

[0098] Evaluation Example 2: Evaluation of Physical Properties of Rubber Specimens

[0099] (1) Processability evaluation: Scotch time

[0100] Scotch time was measured for rubber specimens according to Examples 1 to 6 and Comparative Examples 1 to 3 according to ASTM D 5289-95 (2001).

[0101] (2) Evaluation of grip characteristics and rotational resistance: Tan δ@0℃ and Tan δ@60℃

[0102] For the rubber specimens according to Examples 1 to 6 and Comparative Examples 1 to 3 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).

[0103] (3) Abrasion evaluation

[0104] The wear rate according to ASTM D2228 was measured for the rubber specimens according to Examples 1 to 6 and Comparative Examples 1 to 3 above.

[0105] Scorch Time (%) Tan δ @ 0℃ (%) Tan δ @ 60℃ (%) Wear Rate (%) Example 1 9 29 9 10 5 110 Example 2 9 5 10 0 10 4 10 7 Example 3 9 3 10 2 10 5 10 6 Example 4 9 3 9 8 10 2 10 5 Example 5 9 3 9 8 10 3 10 5 Example 6 9 19 7 10 1 10 4 Comparative Example 1 10 0 10 0 10 0 Comparative Example 2 9 0 9 5 9 8 10 2 Comparative Example 3 9 19 9 9 7 9 8

[0106] As shown in Table 2 above, the example using a petroleum resin composition in which the value according to Formula 1 is 3% or more and the silane compound contains sulfur (S) showed improved wear characteristics while maintaining excellent processability, grip characteristics, and rolling resistance characteristics compared to the rubber specimen according to the comparative example using a silane compound that does not contain sulfur (S) or has a value according to Formula 1 outside the above range.

[0107] 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 repeating units derived from aromatic 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 value of 3% 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, 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 20% by weight or less based on the total weight of the above petroleum resin composition. In paragraph 1, A petroleum resin composition having a bromine value of 1 Br.cg / g to 10 Br.cg / g. In paragraph 1, The above aromatic petroleum resin monomer comprises styrene or alpha-methyl-styrene (α-Me-Styrene), a petroleum resin composition. In paragraph 1, The above aromatic petroleum resin monomer is a petroleum resin composition comprising styrene and alpha-methyl-styrene (α-Me-Styrene). In paragraph 1, A petroleum resin composition having a weight average molecular weight (Mw) of 1,000 to 2,400 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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