KR20220033241A - Conjugated diene-based elastomer and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a conjugated diene-based elastomer and a rubber composition comprising the same. The present invention provides the conjugated diene-based elastomer which comprises: 100 parts by weight of a modified conjugated diene-based polymer; and 10 parts by weight or less of a functional group-containing oligomer having a weight average molecular weight of 50,000 g/mol or less and has an N atom content of 100 ppm or more with respect to the total weight of the elastomer, and the rubber composition comprising the same.

Description

Conjugated diene-based elastomer and rubber composition comprising the same

The present invention relates to a conjugated diene-based elastomer having excellent processability, abrasion resistance and rotation resistance, and a rubber composition comprising the same.

Recently, as interest in energy saving and environmental issues increases, automobile fuel efficiency is required. As a rubber material for tires, it has low rolling resistance, excellent abrasion resistance and tensile properties, and also has adjustment stability typified by wet skid resistance. is being requested

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, tan δ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small tan δ and Goodrich heat generation is preferable.

As one of the methods for realizing this, a method of lowering the exothermicity of the tire by using an inorganic filler such as silica or carbon black in the rubber composition for forming a tire has been proposed, but this is because the inorganic filler in the rubber composition is not easily dispersed. Rather, there is a problem in that the physical properties of the rubber composition, including abrasion resistance, crack resistance, or processability, etc. are generally lowered.

In order to solve this problem, as a method for increasing the dispersibility of inorganic fillers such as silica or carbon black in the rubber composition, the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organic lithium can interact with the inorganic filler. Although a method of modifying with a modifier containing a functional group has been proposed, low heat generation is still improved, but there is a problem in that tensile properties, abrasion resistance, and workability are deteriorated.

JP, WO2013-077018, A1

The present invention has been devised to solve the problems of the prior art, and includes a modified conjugated diene-based polymer and a functional group-containing oligomer having a weight average molecular weight of 50,000 g/mol or less, and 100 parts by weight of the oligomer to the modified conjugated diene-based polymer An object of the present invention is to provide a conjugated diene-based elastomer having excellent filler affinity by including 10 parts by weight or less as a basis.

An object of the present invention is to provide a rubber composition excellent in workability, tensile properties, abrasion resistance and viscoelastic properties in a well-balanced manner, including the conjugated diene-based elastomer.

According to one embodiment of the present invention for solving the above problems, the present invention is a modified conjugated diene-based polymer 100 parts by weight; and 10 parts by weight or less of a functional group-containing oligomer having a weight average molecular weight of 50,000 g/mol or less, and an N atom content of 100 ppm or more based on the total weight of the elastomer.

In addition, the present invention provides a rubber composition comprising the conjugated diene-based elastomer and a filler.

The conjugated diene-based elastomer according to the present invention contains a functional group-containing oligomer having a weight average molecular weight of 50,000 g/mol or less together with the modified conjugated diene-based polymer in a specific content or less, and contains N atoms in a specific content or more with respect to the total weight of the elastomer. It has excellent affinity and has the effect of improving processability, tensile properties, abrasion resistance and viscoelastic properties of a rubber composition containing the same in a balanced way.

Since the rubber composition according to the present invention contains the above-mentioned conjugated diene-based elastomer, the interaction between the rubber component and the filler is excellent, the polymer chain formation occurring between the fillers is suppressed, and the viscosity increase during processing can be suppressed, so that the processability is excellent. In addition, there is an excellent effect in balance between tensile properties, abrasion resistance and viscoelastic properties.

Hereinafter, the present invention will be described in more detail to help the understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Justice

As used herein, the term 'polymer' refers to a polymer compound prepared by polymerizing monomers, whether of the same or different type. The generic term polymer thus encompasses the terms homopolymer and copolymer, which are commonly used to refer to polymers prepared from only one monomer.

As used herein, the term 'oligomer chain' refers to an oligomer chain in which one or more monomers are polymerized so that monomer-derived units are repeatedly connected, and the number of repeats is several to several dozen, which means an oligomer chain with a relatively small molecular weight. there is.

As used herein, the term 'oligomer' may refer to an aggregate of oligomer chains including the oligomer chains.

As used herein, the term 'vinyl content' refers to the mass (or weight) of butadiene contained in positions 1 and 2 in the polymer chain, based on the portion (total amount of polymerized butadiene) of the conjugated diene monomer (butadiene, etc.) in the polymer. ) refers to the percentage.

As used herein, the term 'monovalent hydrocarbon group' refers to a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, and an aryl group. and the minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon may be determined according to the type of each substituent.

As used herein, the term 'divalent hydrocarbon group' refers to a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group including one or more unsaturated bonds, and an arylene group, such as carbon and hydrogen bonded 2 It may mean a valent atomic group, and the minimum number of carbon atoms of the substituent represented by the divalent hydrocarbon may be determined according to the type of each substituent.

As used herein, the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl and isopropyl, sec-butyl, ter It may mean including all branched alkyl groups such as tert-butyl and neopentyl.

As used herein, the term 'alkenyl group' may refer to a monovalent aliphatic unsaturated hydrocarbon including one or two or more double bonds.

As used herein, the term 'alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more triple bonds.

As used herein, the term 'alkylene group' may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

In the present specification, the term 'aryl group' may mean an aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded (polycyclic aromatic hydrocarbon) may be meant to include all of them.

As used herein, the term 'heterocyclic group' refers to a carbon atom in a cycloalkyl group or an aryl group in which one or more hetero atoms are substituted, for example, it may mean including both a heterocycloalkyl group or a heteroaryl group.

As used herein, the term 'single bond' may mean a single covalent bond itself that does not include a separate atom or molecular group.

The terms 'comprising', 'having' and their derivatives herein are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. . For the avoidance of any doubt, all compositions claimed through use of the term 'comprising', unless stated to the contrary, contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except as not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.

Measurement method and conditions

In the present specification, the 'vinyl content' refers to the vinyl content in each polymer was measured and analyzed using Varian VNMRS 500 MHz NMR, and 1,1,2,2-tetrachloroethane was used as the solvent for NMR measurement. , the solvent peak is calculated as 6.0 ppm, 7.2-6.9 ppm is random styrene, 6.9-6.2 ppm is block styrene, 5.8-5.1 ppm is 1,4-vinyl and 1,2-vinyl, 5.1-4.5 ppm is 1, It is measured by calculating the content of 1,2-vinyl bonds in the entire polymer using the peak of 2-vinyl.

In the present specification, 'weight average molecular weight (Mw)', 'number average molecular weight (Mn)' and 'molecular weight distribution (MWD)' are measured through gel permeation chromatohraph (GPC) analysis, and measured by checking the molecular weight distribution curve. will be. Molecular weight distribution (PDI, MWD, Mw/Mn) is calculated from each of the measured molecular weights. Specifically, the GPC uses a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and when calculating molecular weight, the GPC reference material (Standard material) is PS (polystyrene) The GPC measurement solvent is prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

In the present specification, the 'N atom content' also refers to the N atom content, which may be measured by, for example, an NSX analysis method, and the NSX analysis method is measured using a trace nitrogen quantitative analyzer (NSX-2100H). Exemplarily, when using the trace nitrogen quantitative analyzer, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), Ar at 250 ml/min, O ₂ at 350 ml/min, ozonizer 300 ml/ Set the carrier gas flow rate to min, set the heater to 800°C, and wait for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, a calibration curve in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was prepared using Nitrogen standard (AccuStandard S-22750-01-5 ml), and the area corresponding to each concentration was obtained. Then, draw a straight line using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample is placed on the auto sampler of the analyzer to obtain an area, and the N content is calculated using the area of the sample obtained and the calibration curve. At this time, the sample is a modified conjugated diene-based polymer in which the solvent is removed by putting it in hot water heated with steam and stirring, and the residual monomer, residual modifier, and oil are removed.

The present invention provides a conjugated diene-based elastomer that improves the processability, tensile properties, abrasion resistance and viscoelastic properties of a rubber composition including the improved remarkably improved affinity with the filler by including the functional group-containing oligomer together with the modified conjugated diene-based polymer in a balanced manner provides

The conjugated diene-based elastomer according to an embodiment of the present invention comprises: 100 parts by weight of a modified conjugated diene-based polymer; and 10 parts by weight or less of a functional group-containing oligomer having a weight average molecular weight of 50,000 g/mol or less, and an N atom content of 100 ppm or more based on the total weight of the conjugated diene-based elastomer.

According to an embodiment of the present invention, the modified conjugated diene-based polymer is a homopolymer including a repeating unit derived from a conjugated diene-based monomer or a copolymer including a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer. can

In addition, the modified conjugated diene-based polymer may include a functional group derived from a modifier, whether the homopolymer or copolymer.

Here, the repeating unit derived from the conjugated diene-based monomer may mean a repeating unit formed during polymerization of the conjugated diene-based monomer, and the repeating unit derived from the aromatic vinyl-based monomer may mean a repeating unit formed during polymerization of the aromatic vinyl-based monomer. , The functional group derived from the modifier is derived from a modifier present at at least one end of the active polymer through a reaction or coupling between a modifier and an active polymer prepared by polymerization of a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer It may mean a functional group.

According to an embodiment of the present invention, the conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 It may be at least one selected from the group consisting of -phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom).

The aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1 It may be at least one selected from the group consisting of -vinyl-5-hexylnaphthalene.

In addition, when the modified conjugated diene-based polymer is a copolymer, the modified conjugated diene-based polymer may include an aromatic vinyl monomer-derived repeating unit in an amount of 30% by weight or more, or 30% to 50% by weight, within this range There is an excellent balance between resistance and wet road resistance.

As another example, the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with the repeating unit derived from the conjugated diene-based monomer. The repeating unit derived from the diene-based monomer may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1,2-butadiene. . When the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer contains more than 0% by weight to 1% by weight of a repeating unit derived from the diene-based monomer, more than 0% by weight to 0.1% by weight, It may contain more than 0 wt% to 0.01 wt%, or more than 0 wt% to 0.001 wt%, and has the effect of preventing gel formation within this range.

According to an embodiment of the present invention, the copolymer may be a random copolymer, and in this case, an excellent balance between physical properties is obtained. The random copolymer may mean that repeating units constituting the copolymer are disorderly arranged.

In addition, the modified conjugated diene-based polymer may include a functional group including at least one of an N-containing functional group and Si.

For example, the functional group may be an amino group, an amide group, an imino group, an imidazole group, a pyrimidyl group, a cyclic amino group, or a silyl group substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, and a carbon number A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a heteroalkyl group having 2 to 20 carbon atoms including N, O or S, or N; It may be a heterocyclic group having 2 to 20 carbon atoms including O or S.

In another example, the functional group is an alkylamino group, an allylamino group, an alkylallylamino group, an alkylaminosilyl group, an alkylaminoalkylsilyl group, a trialkoxysilyl group, an alkylalkoxysilyl group, an alkylaminoalkoxysilyl group, a di(alkylsilyl)amino group or a di(alkylamino)silyl group.

In addition, the functional group of the modified conjugated diene-based polymer may further include a ketone group, an epoxy group, an ether group, or an ester group in addition to a functional group including at least one of N and Si.

On the other hand, the functional group included in the modified conjugated diene-based polymer is a functional group derived from a modifier, and the modifier is a compound that can provide the above functional group among compounds applied as a modifier for the conjugated diene-based polymer. can be applied

In addition, the modified conjugated diene-based polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 100,000 g/mol to 3,000,000 g/mol, 200,000 g/mol to 2,000,000 g/mol Alternatively, it may be 300,000 g/mol to 1,500,000 g/mol, and within this range, driving resistance and wet road resistance are more balanced and excellent.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 or more and 2.0 or less, specifically 1.5 or more and 2.0 or less, and has excellent tensile properties and viscoelastic properties within this range, and each There is an excellent effect of the balance between the physical properties.

Meanwhile, the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000,000 g/mol, or 100,000 g/mol to 800,000 g/mol.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a 1,2-vinyl bond content of 5 to 30% by weight based on the total weight of the polymer, and in this case, abrasion resistance and rotation resistance may be more excellent. .

On the other hand, the modified conjugated diene-based polymer according to an embodiment of the present invention can be prepared through a conventional batch-type or continuous polymerization method, for example, in a hydrocarbon solvent, in the presence of a polymerization initiator, a conjugated diene-based monomer or conjugated An active polymer may be prepared by batch- or continuous polymerization of a diene-based monomer and an aromatic vinyl-based monomer, and may be prepared by reacting the prepared active polymer with a modifier.

Here, the hydrocarbon solvent is not particularly limited, but may be, for example, at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene, and a polymerization initiator For example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naph tyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium , lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and may be at least one selected from the group consisting of lithium isopropylamide.

In addition, the polymerization may be carried out by including a polar additive, and the polar additive is, for example, tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether. , diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine It may be at least one selected from the group consisting of, preferably triethylamine or tetramethylethylenediamine, and when the polar additive is included, a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer. In this case, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in their reaction rate.

In addition, the functional group-containing oligomer has a weight average molecular weight of 50,000 g/mol or less, specifically 1,000 g/mol or more and 50,000 g/mol or less, 1,000 g/mol or more and 30,000 g/mol or less, or 1,000 g/mol or more and 20,000 g or more. It may be less than /mol. In this case, the filler affinity of the conjugated diene-based elastomer including the same may be more excellent, and as a result, there is an effect of excellent mechanical properties such as tensile properties and viscoelastic properties of the rubber composition including the same.

In addition, the conjugated diene-based elastomer according to an embodiment of the present invention may include the functional group-containing oligomer in an amount of 10 parts by weight or less, or 0.001 parts by weight or more and 4 parts by weight or less, based on 100 parts by weight of the modified conjugated diene-based polymer. In this case, the filler affinity of the conjugated diene-based elastomer may be further improved, and the rolling resistance property of the rubber composition including the conjugated diene-based elastomer may be improved.

Meanwhile, the functional group-containing oligomer may include a functional group-containing oligomer chain including a repeating unit derived from a nitrogen-containing monomer and a unit derived from a modifier, wherein the modifier may be a compound comprising an aminoalkoxysilyl group or an alkoxysilyl group. .

In addition, the functional group-containing oligomer may have a structure in which functional group-containing oligomer chains including a repeating unit derived from a nitrogen-containing monomer are coupled by the modifier-derived unit.

Specifically, the functional group-containing oligomer is prepared by polymerizing a nitrogen-containing monomer in the presence of a polymerization initiator in a hydrocarbon solvent to prepare an active polymer of low molecular weight including a repeating unit derived from the nitrogen-containing monomer, and reacting it with a modifier. , it may have a structure in which one end of the active polymer is bonded to a silyl group in the molecule of the modifier through a substitution reaction between the anionic active site located at one end of the active polymer and the alkoxy group of the modifier.

On the other hand, the oligomer chain may further include a repeating unit derived from a conjugated diene-based monomer. In this case, the functional group-containing oligomer is an active oligomer by polymerizing a nitrogen-containing monomer and a conjugated diene-based monomer in the presence of a polymerization initiator in a hydrocarbon solvent. It may be prepared by reacting it with a denaturant.

At this time, the number of active polymers binding to the silyl group in the molecule of the modifier can be controlled by controlling the ratio of the modifier during the reaction between the active polymer and the modifier. The ratio of the modifier is not particularly limited, but at least two active polymers per molecule of the modifier While binding, the weight average molecular weight of the functional group-containing oligomer may be adjusted to be within the range described above.

On the other hand, the nitrogen-containing monomer may be an aromatic vinyl-based monomer, a monoene-based monomer, a diene-based monomer, a silyl group-containing diene-based monomer or a heterocyclic monomer substituted with a nitrogen atom or a substituent containing a nitrogen atom in the molecule. and the substituent including the nitrogen atom may be an alkylamino group, an allylamino group, an alkylallylamino group, an alkylaminosilyl group, a di(alkylsilyl)amino group, or a di(alkylamino)silyl group.

Specifically, the nitrogen-containing monomer may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

X is N or CH;

R _8a to R _8c are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms, a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms,

R _8d is a single bond, a substituted or unsubstituted C 1 to C 20 alkylene group; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _8e is an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; Or a functional group represented by the following formula (1a),

O is an integer of 0 to 5, at least one of R _8e is a functional group represented by the following formula 1a, and when o is an integer of 2 to 5, a plurality of R _8e may be the same or different from each other,

[Formula 1a]

In Formula 8a,

R _8f is a single bond, a C 1 to C 20 alkylene group unsubstituted or substituted with a substituent; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _8g and R _8h are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; A heterocyclic group having 3 to 20 carbon atoms or a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or R _8g and R _8h are connected to each other and together with N a heterocyclic group having 2 to 10 carbon atoms to form a ring.

In addition, the nitrogen-containing monomer may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2,

X ₁ -X ₂ is CH ₂ -CH ₂ or CH=CH,

X ₃ -X ₄ is CH ₂ -CH ₂ , CH=N or N=N.

In addition, the nitrogen-containing monomer may be a compound represented by the following formula (3).

[Formula 3]

In Formula 3,

R _11a and R _11b are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; Or a functional group represented by the following formula 4a,

R _11c is an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; vinyl group; Or a functional group represented by the following formula 4a,

At least one of R _11a , R _11b and R _11c is a functional group represented by Formula 3a,

[Formula 3a]

In Formula 3a,

R _11d is a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a single bond; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _11e and R _11f are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

In addition, the nitrogen-containing monomer may be a compound represented by the following formula (4).

[Formula 4]

In Formula 4,

R _12a is a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a single bond; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _12b and R _12c are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

Meanwhile, the functional group-containing oligomer chain may further include a repeating unit derived from a conjugated diene-based monomer.

In addition, the compound including an aminoalkoxysilyl group among the modifiers may be exemplarily a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, R ¹ may be a single bond or an alkylene group having 1 to 10 carbon atoms, R ² and R ³ may each independently be an alkyl group having 1 to 10 carbon atoms, and R ⁴ is hydrogen, an epoxy group, or an alkylene group having 1 to 10 carbon atoms. It may be a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, an allyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, R ²¹ may be a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, and a and m are each independently from 1 to 3 It may be an integer selected from, n may be an integer from 0 to 2, and j may be an integer selected from 1 to 30.

As a specific example, the compound represented by Formula 5 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine(N,N-bis(3-(dimethoxy(methyl)silyl) )propyl)-methyl-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine (N,N-bis(3-(diethoxy(methyl)silyl) )propyl)-methyl-1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine(N,N-bis(3-(trimethoxysilyl)propyl)-methyl- 1-amine), N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine), tri (trimethoxysilyl)amine), tri(3-(trimethoxysilyl)propyl)amine), N,N-bis(3- (diethoxy (methyl) silyl) propyl) -1,1,1-trimethylsilanamine (N, N-bis (3- (diethoxy (methyl) silyl) propyl) -1,1,1-trimethlysilanamine), N- (3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine ( N-(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(trimethoxysilyl)propyl)propan-1-amine), 3-(trimethoxysilyl) )-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl) Propyl)propan-1-amine(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimehtoxysilyl)propyl)-1H-1,2,4- triazol-3-yl)propyl)propan-1-amine), N-allyl-N-(3-(trimethoxysilyl)prop Phil)prop-2-en-1amine (N-allyl-N-(3-(trimethoxysilyl)propyl)prop-2-en-1-amine), N,N-bis(oxiran-2-ylmethyl) )-3-(trimethoxysilyl)propan 1-amine (N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine), 1,1,1-trimethyl-N- (3- (triethoxysilyl) propyl) -N- (trimethylsilyl) silanamine (1,1,1-trimethyl-N- (3- (triethoxysilyl) propyl) -N- (trimethylsilyl) silanamine) and N; N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine) may be one selected from the group consisting of.

As another example, the modifier may include a compound represented by the following formula (6).

[Formula 6]

또는

일 수 있으며, 이 때, R¹³, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.In Formula 6, R ⁵ , R ⁶ and R ⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 10 carbon atoms. may be, R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 1, 2 or 3, b+c≥4, and A is

or

may be, and in this case, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

As a specific example, the compound represented by Formula 6 is N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl Propan-1-amine (N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) and 3-(4 ,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine (3-(4,5-dihydro-1H-imidazol) It may be one selected from the group consisting of -1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

As another example, the modifier may include a compound represented by the following formula (7).

[Formula 7]

In Formula 7, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms including or not including an oxygen atom, and R ¹⁷ to R ²⁰ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. may be a hydrocarbon group, and L ¹ to L ⁴ are each independently a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ may be connected to each other to form a ring having 1 to 5 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, a ring formed may include 1 to 3 at least one hetero atom selected from the group consisting of N, O and S.

As a specific example, the compound represented by Formula 7 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetra Ethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3′-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N ,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)( 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetra Methoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3′-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N ,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) ( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimpropylpropan-1-amine), 3,3'-(1,1,3,3-tetra Ethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3′-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis( N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine )(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3 -tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) (3, 3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxy Cydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)(3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N, N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine) (3 ,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrae Toxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)(3,3′-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N ,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3- Tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine)(3,3′-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N ,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine) ( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetra Propoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N ,N-dimethylmethan-1-amine), 3,3'-(1,1,3, 3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) )bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1 -amine) (3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3 ,3-Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-) diyl)bis(N,N-dipropylmethan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl) ))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine(N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3, 1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl) Bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine(N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3) -diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraprotoxy) Cydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine(N,N'-((1,1, 3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1, 1,3,3-tetramethoxydisiloxane-1,3-diyl) Bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine(N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3 -diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3) -diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane- 1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (N,N'-((1,1,3,3-tetrapropoxydisiloxane-) 1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), 1,3-bis(3-(1H-imidazol-1-yl) propyl) 1,1,3,3-tetramethoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane), 1,3- Bis(3-(1H-imidazol-1-yl)propyl)1,1,3,3-tetraethoxydisiloxane(1,3-bis(3-(1H-imidazol-1-yl)propyl)- 1,1,3,3-tetraethoxydisiloxane), and 1,3-bis(3-(1H-imidazol-1-yl)propyl)1,1,3,3-tetrapropoxydisiloxane (1,3- It may be one selected from the group consisting of bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane).

As another example, the modifier may include a compound represented by the following formula (8).

[Formula 8]

In Formula 8, R _b2 to R _b4 are each independently an alkylene group having 1 to 10 carbon atoms, R _b5 to R _b8 are each independently an alkyl group having 1 to 10 carbon atoms, and R _b13 and R _b14 are each independently a carbon number an alkylene group of 1 to 10, R _b15 to R _b18 are each independently an alkyl group having 1 to 10 carbon atoms, and m _{1 ,} m ₂ , m ₃ and m ₄ are each independently an integer of 1 to 3.

As another example, the modifier may include a compound represented by the following Chemical Formula 9.

[Formula 9]

In Formula 9, R _e1 and R _e2 are each independently an alkylene group having 1 to 10 carbon atoms, and _Re3 to R _e6 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or -R _e7 SiR _e8 R _e9 R _e10 However, at least one of _Re3 to _Re6 is —R _e7 SiR _e8 Re9 _{Re9 Re10} , wherein _Re7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and _Re8 to _Re10 are independently of each other 1 carbon number an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein at least one of R _e8 to _Re10 is an alkoxy group having 1 to 10 carbon atoms.

As another example, the modifier may include a compound represented by the following Chemical Formula 10.

[Formula 10]

In Formula 10, X is O or S, R _f1 and R _f2 are each independently a single bond, or an alkylene group having 1 to 10 carbon atoms,

R _f3 to R _f8 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms; , p is 0 or an integer of 1, and when p is 0, Rf1 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

As another example, the modifier may include a compound represented by the following Chemical Formula 11.

[Formula 11]

In Formula 11, R _g1 to R _g4 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -R _g5 Si(OR _g6)r (R _g7 ) _3-r , wherein at least one of R _g1 to R _g4 is -R _g5 Si(OR _g6)r (R _g7 ) _3-r , wherein R _g5 is a single bond or an alkylene group having 1 to 10 carbon atoms. and R _g6 and R _g7 are each independently an alkyl group having 1 to 10 carbon atoms, r is 1 to 3, Y is C or N, but when Y is N, R _g4 is not present.

As another example, the modifier may include a compound represented by the following Chemical Formula 12.

[Formula 12]

In Formula 12, R _h1 and R _h2 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R _h3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and A ₃ is -Si (R _h4 R _h5 R _h6 ) or —N[Si(R _h7 R _h8 R _h9 )] ₂ , wherein R _h4 to R _h9 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. am.

As another example, the modifier may include a compound represented by the following Chemical Formula 13.

[Formula 13]

In Formula 13, R _g1 to R _g3 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R _g4 is an alkoxy group having 1 to 10 carbon atoms, and q is an integer from 2 to 100 .

In addition, the present invention provides a rubber composition comprising the conjugated diene-based elastomer and a filler.

The rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the conjugated diene-based elastomer. The filler may be, for example, a silica-based filler or a carbon black-based filler, and specific examples thereof include wet silica (hydrous silicic acid), fumed silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably fracture properties. It may be the wet silica which has the best effect of improving the effect and wet grip.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation may be used together, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide , bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) propyl) tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-Mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl It may be silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in consideration of the reinforcing improvement effect, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, the rubber composition according to an embodiment of the present invention includes a modified conjugated diene-based polymer in which a functional group with high affinity for silica is introduced as a rubber component in the active site, and contains a functional group-containing oligomer, so silane The blending amount of the coupling agent may be reduced than in the usual case, and accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight, based on 100 parts by weight of silica, within this range. There is an effect of preventing gelation of the rubber component while sufficiently exhibiting the effect as a coupling agent in the interior.

In addition, the rubber composition may further include other rubber components in addition to the modified conjugated diene-based polymer, if necessary, wherein the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer in the conjugated diene-based elastomer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber that are modified or refined of the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-) propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene) -co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

The rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, and within this range, the vulcanized rubber composition has a low fuel efficiency while securing the required elasticity modulus and strength. It has an excellent effect.

The rubber composition according to an embodiment of the present invention includes, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, an anti-scorch agent, zinc white, It may further include stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound. Naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.

The antioxidant is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2 ,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, etc., may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, an internal mixer, etc. according to the compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for each member of the tire such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, cheffer, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of

In addition, the present invention provides a tire manufactured using the rubber composition.

The tire may include a tire or a tire tread.

Example

Hereinafter, in order to describe the present invention in detail, examples will be described in detail. However, the embodiment according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiment described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1

1) Manufacture of modified conjugated diene-based polymer

After putting 215 g of styrene, 765 g of 1,3-butadiene, 5000 g of n-hexane and 2,2-di(2-tetrahydrofuryl)propane as a polar additive in a 20 L autoclave reactor, the temperature inside the reactor was increased to 40°C. The temperature was raised. When the internal temperature of the reactor reached 40 °C, 4.3 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. After 20 extra lapses, 20 g of 1,3-butadiene was added, and the end of the polymer chain was capped with butadiene. After 5 minutes, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine) was added as a denaturant for 15 minutes. reacted (denaturant:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in 0.3 wt% in n-hexane was added to prepare a polymer solution containing a modified conjugated diene-based polymer.

2) Preparation of functional group-containing oligomers

In a 2 L autoclave reactor, 20 g of N,N-dimethyl-1-(4-vinylphenyl)methanamine, 100 g of 1,3-butadiene, n - After putting 500 g of hexane and 2,2-di(2-tetrahydrofuryl)propane as a polar additive, the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 40 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine) was added as a denaturant and reacted for 15 minutes (denaturant :act.Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution containing an antioxidant IR1520 (BASF) dissolved in 0.3 wt% in n-hexane was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 2

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

In a 2 L autoclave reactor, 20 g of N,N-dimethyl-1-(4-vinylphenyl)methanamine, 100 g of 1,3-butadiene, n - After putting 500 g of hexane and 2,2-di(2-tetrahydrofuryl)propane as a polar additive, the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 20 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. N,N-diethyl-3-(trimethoxysilyl)propan-1-amine was added as a modifier and reacted for 15 minutes (modifier:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution containing an antioxidant IR1520 (BASF) dissolved in 0.3 wt% in n-hexane was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 3

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

In a 2 L autoclave reactor, 20 g of 2-vinylpyridine, 100 g of 1,3-butadiene, 500 g of n-hexane and 2,2-di(2-tetrahydrofuryl)propane as a polar additive were added. Afterwards, the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 20 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. Denaturant N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine (N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan -1-amine) and reacted for 15 minutes (denaturant:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 4

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

In a 2 L autoclave reactor, 1-vinyl-1H-1,2,3-triazole (1-vinyl-1H-1,2,3-triazole) 20 g, 1,3-butadiene 100 g, n-hexane 500 g and 2,2-di(2-tetrahydrofuryl)propane as a polar additive, and then the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 20 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N- (3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) was added and reacted for 15 minutes (denaturant: act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution containing an antioxidant IR1520 (BASF) dissolved in 0.3 wt% in n-hexane was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 5

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

20 g, 1, N,N,N',N',1-pentamethyl-1-vinylsilanediamine (N,N,N',N',1-pentamethyl-1-vinylsilanediamine) in a 2 L autoclave reactor 100 g of 3-butadiene, 500 g of n-hexane, and 2,2-di(2-tetrahydrofuryl)propane as a polar additive were added, and then the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 20 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. N,N'-(Cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine)( N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) was added and reacted for 15 minutes ( Denaturant: act. Li = 0.7:1 molar ratio) After stopping the polymerization reaction using ethanol, 5 ml of a solution in which an antioxidant IR1520 (BASF) is dissolved in 0.3 wt% in n-hexane is added to the functional group-containing oligomer An oligomer solution containing

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 6

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

In a 2 L autoclave reactor, 20 g of N,N-dimethyl-1-(4-vinylphenyl)methanamine, 100 g of 1,3-butadiene, 500 g of n-hexane and 2,2-di(2- After 0.89 g of tetrahydrofuryl) propane was added, the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 20 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. 3,3,7,7-tetramethoxy-5,5-bis((trimethoxysilyl)methyl)-2,8-dioxa-3,7-disilanonan (3,3,7, 7-tetramethoxy-5,5-bis((trimethoxysilyl)methyl)-2,8-dioxa-3,7-disilanonane) was added and reacted for 15 minutes (denaturant: act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Example 7

1) Preparation of modified conjugated diene-based polymer

A polymer solution containing a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

2) Preparation of functional group-containing oligomers

An oligomer solution including a functional group-containing oligomer was prepared in the same manner as in Example 1.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 4.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Comparative Example 1

In a 20 L autoclave reactor, 215 g of styrene, 765 g of 1,3-butadiene, 5000 g of n-hexane, and 2,2-di(2-tetrahydrofuryl)propane as a polar additive were put in, and then the temperature inside the reactor was increased to 40°C. The temperature was raised. When the internal temperature of the reactor reached 40 °C, 4.3 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. After 20 extra lapses, 20 g of 1,3-butadiene was added, and the end of the polymer chain was capped with butadiene. After 5 minutes, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine as a modifier was added and reacted for 15 minutes (modifier:act. Li=0.7:1 molar ratio). was added and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene-based polymer.

Comparative Example 2

1) Preparation of first modified conjugated diene-based polymer

A modified conjugated diene-based polymer solution prepared in the same manner as in 1) of Example 1 was prepared, and this was used as the first modified conjugated diene-based polymer solution.

2) Preparation of the second modified conjugated diene-based polymer

In a 2 L autoclave reactor, 20 g of styrene, 100 g of 1,3-butadiene, 500 g of n-hexane and 2,2-di(2-tetrahydrofuryl)propane as a polar additive were put in, and then the temperature inside the reactor was increased to 40°C. adjusted. When the internal temperature of the reactor reached 40 °C, 4 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. As a denaturant, tetraethyl orthosilicate was added and reacted for 15 minutes (denaturant:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which an antioxidant IR1520 (BASF Corporation) was dissolved in 0.3 wt% of n-hexane was added to the second modified conjugated diene containing the second modified conjugated diene-based polymer. A polymer solution was prepared.

3) Preparation of conjugated diene-based elastomer

A mixed polymer is obtained by mixing the first modified conjugated diene-based polymer solution prepared in 1) with the second modified conjugated diene-based polymer solution prepared in 2) above, and the obtained polymer is placed in hot water heated with steam and stirred to obtain a solvent. It was removed to prepare a conjugated diene-based elastomer. At this time, the second modified conjugated diene-based polymer solution is mixed so that the solid content of the second modified conjugated diene-based polymer in the solution is 1.0 parts by weight based on 100 parts by weight of the solid content of the first modified conjugated diene-based polymer in the first modified conjugated diene-based polymer solution. did

Comparative Example 3

1) Preparation of first modified conjugated diene-based polymer

A modified conjugated diene-based polymer solution prepared in the same manner as in 1) of Example 1 was prepared, and this was used as the first modified conjugated diene-based polymer solution.

2) Preparation of functional group-containing oligomers

In a 2L autoclave reactor, 20 g of N,N-dimethyl-1-(4-vinylphenyl)methanamine, 100 g of 1,3-butadiene, 500 g of n-hexane and 2,2-di(2-tetra) as a polar additive After adding hydrofuryl) propane, the temperature inside the reactor was adjusted to 40°C. When the internal temperature of the reactor reached 40 °C, 2 mmol of n-butyllithium was added to proceed with an adiabatic temperature rise reaction. N,N-diethyl-3-(trimethoxysilyl)propan-1-amine was added as a modifier and reacted for 15 minutes (modifier:act. Li=0.7:1 molar ratio). Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution containing an antioxidant IR1520 (BASF) dissolved in 0.3 wt% in n-hexane was added to prepare an oligomer solution containing a functional group-containing oligomer.

3) Preparation of conjugated diene-based elastomer

The modified conjugated diene-based polymer solution prepared in 1) is mixed with the oligomer solution prepared in 2) to obtain a mixed polymer, and the obtained polymer is placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based elastomer did At this time, the oligomer solution was mixed so that the functional group-containing oligomer solids in the oligomer solution were 1.0 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solids in the modified conjugated diene-based polymer solution.

Comparative Example 4

A conjugated diene-based elastomer was prepared in the same manner as in Example 1, except that the functional group-containing oligomer solution was used in a proportion such that the functional group-containing oligomer solid content was 15 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer solid content.

Experimental Example 1

The physical properties of each of the conjugated diene-based elastomers prepared in Examples 1 to 7 and Comparative Examples 1 to 4 (meaning a modified conjugated diene-based polymer in Comparative Example 1) were comparatively analyzed, and the results are shown in Table 1 below.

1) Weight average molecular weight (Mw, g/mol)

The weight average molecular weight of each functional group-containing oligomer and the second modified conjugated diene-based polymer was measured through gel permeation chromatohraph (GPC) analysis. The GPC is a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and when calculating molecular weight, the GPC standard material (Standard material) is PS (polystyrene). The GPC measurement solvent was prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

2) N content

The N content in each conjugated diene-based elastomer was measured through the NSX analysis method. For NSX analysis, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) using a trace nitrogen quantitative analyzer (NSX-2100H), Ar 250 ml/min, O ₂ 350 ml/min, ozonizer 300 Set the carrier gas flow rate to ml/min, set the heater to 800°C, wait for about 3 hours to stabilize the analyzer, and after stabilizing the analyzer, use Nitrogen standard (AccuStandard S-22750-01-5 ml) A calibration curve was drawn in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and after obtaining the area corresponding to each concentration, a straight line was drawn using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample was placed on the auto sampler of the analyzer to obtain an area, and the N content was calculated using the area of the obtained sample and the calibration curve.

As shown in Table 1, the conjugated diene-based elastomers of Examples 1 to 7 contained 100 ppm or more of N atoms and, together with the modified conjugated diene-based polymer, a functional group-containing oligomer having a weight average molecular weight of 50,000 g/mol or less. was confirmed to be included.

Example 8

100 parts by weight of the conjugated diene-based elastomer prepared in Example 1, 70 parts by weight of silica, 11.2 parts by weight of an organosilane coupling agent (X50S, Evonik), 37.5 parts by weight of TDAE oil, 3 parts by weight of a zincating agent (ZnO) parts, 2 parts by weight of stearic acid, 2 parts by weight of an antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), 2 parts by weight of an antioxidant (6PPD ((dimethylbutyl)-N-phenyl) -Phenylenediamine) 2 parts by weight and wax (Microcrystaline Wax) 1 part by weight were kneaded.At this time, the initial temperature was controlled to 70° C., and after the mixing was completed, a primary formulation was obtained at a discharge temperature of 145° C. to 155° C. , After cooling the first formulation to room temperature, 1.5 parts by weight of sulfur powder, 1.75 parts by weight of a rubber accelerator (DPG (diphenylguanidine)) and a vulcanization accelerator (CZ (N-cythlohexyl-2-benzothiazylsulfenamide) )) was added and 2 parts by weight was added and mixed at a temperature of 100° C. or less to obtain a secondary formulation, followed by a curing process at 160° C. for 20 minutes to prepare a rubber specimen.

Examples 9 to 14

In Example 8, the first formulation in the same manner except that 100 parts by weight of the conjugated diene-based elastomer prepared in Examples 2 to 7 was used instead of 100 parts by weight of the conjugated diene-based elastomer prepared in Example 1 And to obtain a secondary formulation, finally a rubber specimen was prepared.

Comparative Examples 5 to 8

In Example 8, instead of 100 parts by weight of the conjugated diene-based elastomer prepared in Example 1, 100 parts by weight of each of the modified conjugated diene-based polymer of Comparative Example 1 and each of the conjugated diene-based elastomers of Comparative Examples 2 to 4 was used. Except that, the first and second formulations were obtained in the same manner, and finally, a rubber specimen was prepared.

Experimental Example 2

In order to compare and analyze the physical properties of the rubber compositions prepared in Examples and Comparative Examples, tensile properties, viscoelastic properties, abrasion resistance and processability properties were measured, and the results are shown in Table 2 below.

1) 300% modulus

Each test piece was prepared according to the test method of ASTM D6746, and the tensile stress (300% modulus) at the time of 300% elongation of the test piece was measured. Specifically, the tensile properties were measured at room temperature at a speed of 50 cm/min using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester.

2) Viscoelastic properties

For the viscoelastic properties, the tan δ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60°C to 60°C) in Film Tension mode using a dynamic mechanical analyzer (GABO). At this time, the lower the high temperature 60 ℃ tan δ value, the less the hysteresis loss and the better the rotation resistance (fuel efficiency). .

3) Wear resistance

For each rubber specimen, a DIN wear test was performed according to ASTM D5963, and based on the measured value of Comparative Example 5, DIN loss index (loss volume index): ARIA (Abration resistance index, Method A) The higher the number, the better.

4) Machinability characteristics

1) Mooney viscosity (MV, (ML1+4, @100℃ MU)) of the primary compound obtained during the manufacture of 1) rubber specimen was measured and the processability characteristics of each polymer were comparatively analyzed. Although the characteristics are excellent, in Table 2 below, since the measured values of Comparative Example 5 were indexed on the basis of 100, the higher the value, the better.

Specifically, using MV-2000 (ALPHA Technologies) at 100°C, using a Rotor Speed of 2±0.02 rpm, and a Large Rotor, each primary formulation was left at room temperature (23±3°C) for at least 30 minutes and then 27 ±3 g was collected, filled inside the die cavity, and the platen was operated for 4 minutes.

As shown in Table 2, in Examples 8 to 14, compared to Comparative Examples 5 to 8, the tensile properties, viscoelastic properties, abrasion resistance and workability properties were improved in a balanced way.

Specifically, Examples 8 to 14 have a 300% modulus of about 8% to 13%, and a rotation resistance (tan δ at 60°C) of 12% to 20%, and The abrasion resistance exhibited a significantly increased effect of 15% to 20%, and compared to Comparative Example 6, the 300% modulus was about 21% to 26%, and the rotational resistance (tan δ at 60℃) ) was about 18% to 26%, and abrasion resistance showed a remarkably improved effect of about 3% to 7%. Here, Comparative Examples 5 and 6 do not include the functional group-containing oligomer presented in the present invention, and in particular, Comparative Example 6 includes two modified conjugated diene-based polymers other than the functional group-containing oligomer presented in the present invention. will do

In addition, Examples 8 to 14 show improved rotational resistance compared to Comparative Example 7, while 300% modulus is about 8% to 13%, which shows a greatly improved effect, and in particular, processability characteristics are about 10% to 17%, and abrasion resistance showed a significantly improved effect of about 10% to 14%. On the other hand, compared to Comparative Example 8, the 300% modulus showed a reduced effect, but the low running resistance was improved, and at the same time, the workability characteristics were improved by about 13% to 20%, and the abrasion resistance by about 35% to 41%. It was confirmed that Examples 8 to 14 had excellent effects in a well-balanced manner in the measured tensile properties, viscoelastic properties, abrasion resistance and workability properties compared to Comparative Example 8. Here, Comparative Example 7 includes a functional group-containing oligomer, but includes a functional group-containing oligomer having a weight average molecular weight exceeding 50,000 g/mol as presented in the present invention, and Comparative Example 8 presents a functional group-containing oligomer in the present invention It is to include in excess of the content.

The results of Tables 1 and 2 show that the conjugated diene-based elastomer according to the present invention contains a functional group-containing oligomer having a weight average molecular weight of 50,000 g/mol or less together with the modified conjugated diene-based polymer in a specific content or less, and in the total weight of the elastomer By containing N atoms in a specific content or more, it means that the filler affinity is excellent and there is an effect of improving the processability, tensile properties, abrasion resistance and viscoelastic properties of a rubber composition containing the same in a balanced way.

Claims (11)

100 parts by weight of a modified conjugated diene-based polymer; and
It contains 10 parts by weight or less of a functional group-containing oligomer having a weight average molecular weight of 50,000 g/mol or less,
A conjugated diene-based elastomer having an N atom content of 100 ppm or more based on the total weight of the conjugated diene-based elastomer.
According to claim 1,
The functional group-containing oligomer is a conjugated diene-based elastomer having a weight average molecular weight of 1,000 g/mol or more and 30,000 g/mol or less.
According to claim 1,
Conjugated diene-based elastomer comprising 0.001 parts by weight or more and 4 parts by weight or less of the functional group-containing oligomer.
According to claim 1,
The functional group-containing oligomer includes a functional group-containing oligomer chain including a repeating unit derived from a nitrogen-containing monomer and a unit derived from a modifier,
The modifier is a conjugated diene-based elastomer that is a compound containing an aminoalkoxysilyl group or an alkoxysilyl group.
5. The method of claim 4,
The functional group-containing oligomer is a conjugated diene-based elastomer in which the functional group-containing oligomer chains are coupled by a denaturant-derived unit.
5. The method of claim 4,
The functional group-containing oligomer chain is a conjugated diene-based elastomer further comprising a repeating unit derived from a conjugated diene-based monomer.
According to claim 1,
The modified conjugated diene-based polymer is a homopolymer comprising a repeating unit derived from a conjugated diene-based monomer or a copolymer comprising a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer.
According to claim 1,
The modified conjugated diene-based polymer is a conjugated diene-based elastomer comprising a functional group including at least one of N and Si.
A rubber composition comprising the conjugated diene-based elastomer of claim 1 and a filler.
10. The method of claim 9,
The filler is a silica-based filler or a carbon black-based filler in a rubber composition.
10. The method of claim 9,
A rubber composition comprising 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the conjugated diene-based elastomer.