阅读说明：本技术 橡胶组合物 (Rubber composition ) 是由 罗六烈 崔在宣 金鲁马 金镇英 金唯真 全在彣 于 2019-04-10 设计创作，主要内容包括：本发明涉及一种通过控制橡胶组分之间的相容性而具有优异的耐磨性和改善的拉伸性能和粘弹性能的橡胶组合物,以及使用该橡胶组合物制造的轮胎。(The present invention relates to a rubber composition having excellent wear resistance and improved tensile properties and viscoelastic properties by controlling compatibility between rubber components, and a tire manufactured using the same.)

1. A rubber composition comprising:

a first synthetic rubber;

a second synthetic rubber; and

the filler is filled in the inner cavity of the shell,

wherein the difference in solubility parameters between the first synthetic rubber and the second synthetic rubber is greater than 0.6,

the first synthetic rubber is a solution-polymerized conjugated diene rubber having a styrene bond content of 30 wt% or more,

the second synthetic rubber is a lithium-catalyzed modified butadiene-based rubber having at least one terminal bonded with a functional group.

2. The rubber composition of claim 1, wherein the difference in solubility parameter between the first synthetic rubber and the second synthetic rubber is greater than 0.8 and less than or equal to 1.1.

3. The rubber composition according to claim 1, wherein the first synthetic rubber is a solution-polymerized conjugated diene rubber having a styrene bond content of 38% by weight or more and 55% by weight or less.

4. The rubber composition according to claim 1, wherein the first synthetic rubber is a solution-polymerized conjugated diene rubber containing a repeating unit derived from a conjugated diene monomer and a repeating unit derived from an aromatic vinyl monomer.

5. The rubber composition according to claim 1, wherein the first synthetic rubber is a modified conjugated diene-based rubber to which a functional group is bonded at least one end.

6. The rubber composition according to claim 1, wherein the vinyl bond content in the polymer of the second synthetic rubber is 50% by weight or less.

7. The rubber composition according to claim 1, wherein the rubber composition comprises, based on 100 parts by weight of a rubber component comprising the first synthetic rubber and the second synthetic rubber: 30 to 90 parts by weight of the first synthetic rubber; 10 to 70 parts by weight of the second synthetic rubber; and 30 to 200 parts by weight of the filler.

8. The rubber composition of claim 1, wherein the filler is silica or carbon black.

9. The rubber composition of claim 1, wherein the rubber composition comprises a vulcanizing agent.

10. The rubber composition according to claim 1, wherein the rubber composition comprises one or more additives selected from a vulcanization accelerator, a processing oil, and an anti-aging agent.

11. A tire manufactured using the rubber composition described in claim 1.

Technical Field

[ Cross-reference to related applications ]

This application claims benefit based on priority of korean patent application No.10-2018-0056729 filed on 17.5.2018, the entire contents of which are incorporated herein by reference.

Background

Recently, according to the demand for automobiles with low fuel consumption rates, there is a demand for tires with reduced rolling resistance, and with modulated stability as represented by wet skid resistance and excellent wear resistance and tensile properties in terms of safety concerns. Therefore, there is known a method of making low rolling resistance and modulation stability coexist by combining a filler such as silica with a rubber component constituting a tire, specifically, a tread portion of a tire.

For example, in order to reduce the rolling resistance of a tire, there is a method of reducing the hysteresis loss of a vulcanized rubber, and rebound resilience at 50 ℃ to 80 ℃, tan δ, Goodrich heat generation, and the like are used as evaluation indexes of the vulcanized rubber. That is, it is desirable to use a rubber material having high resilience or low tan δ value or Goodrich heat generation at the above-mentioned temperature.

Natural rubber, polyisoprene rubber or polybutadiene rubber is known as a rubber material having low hysteresis loss, but these rubbers have a disadvantage of low wet skid resistance. Therefore, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as "SBR") and butadiene rubber (hereinafter referred to as "BR") are produced by emulsion polymerization or solution polymerization to be used as rubber for tires. Among these polymerization methods, the solution polymerization has the greatest advantage over the emulsion polymerization that the vinyl structure content and styrene content, which determine the physical properties of the rubber, can be arbitrarily adjusted, and the molecular weight and physical properties thereof can be controlled by coupling or modification. Therefore, since the structure of the finally prepared SBR or BR is easily changed and the movement of the chain ends can be reduced and the coupling force with fillers such as silica and carbon black can be increased by coupling or modification of the chain ends, the SBR prepared by solution polymerization is widely used as a rubber material for tires.

If solution polymerized SBR is used as a rubber material for tires, since the glass transition temperature of rubber is raised by increasing the vinyl content in SBR, it is possible to control physical properties required for tires such as running resistance and braking force, and also to reduce fuel consumption by appropriately adjusting the glass transition temperature. The solution-polymerized SBR is prepared by using an anionic polymerization initiator, and is used by coupling or modifying chain ends of the polymer thus formed using various modifiers.

In addition, carbon black, silica, or the like is used as a reinforcing filler for a tire tread, and if silica is used as the reinforcing filler, the advantage of improving low hysteresis loss and wet skid resistance is achieved. However, affinity of silica of a hydrophilic surface with a rubber component is low and coagulation between silica is increased as compared with carbon black of a hydrophobic surface, and thus, a separate silane coupling agent is required to improve dispersibility or to couple silica-rubber. Therefore, a method of introducing a functional group having affinity or reactivity with silica to the terminal of a rubber molecule has been carried out, but the effect is insufficient.

Disclosure of Invention

Technical problem

The present invention is designed to solve the above-mentioned problems of the conventional art, and an object is to provide a rubber composition having excellent abrasion resistance and improved tensile properties and viscoelastic properties by controlling compatibility between rubber components.

Further, another object of the present invention is to provide a tire manufactured using the rubber composition.

Technical scheme

In order to solve the above-mentioned task, the present invention provides a rubber composition comprising: a first synthetic rubber; a second synthetic rubber; and a filler, wherein a difference in solubility parameter between the first synthetic rubber and the second synthetic rubber is greater than 0.6, the first synthetic rubber is a solution-polymerized conjugated diene-based rubber having a styrene bond content of 30 wt% or more, and the second synthetic rubber is a lithium-catalyzed modified butadiene-based rubber having at least one terminal bonded with a functional group.

In addition, in the present invention, there is provided a tire manufactured using the rubber composition.

Advantageous effects

The rubber composition according to the present invention comprises heterogeneous rubber components of a first synthetic rubber and a second synthetic rubber, wherein the first synthetic rubber and the second synthetic rubber are selected and contained such that a difference in solubility parameter therebetween is greater than a specific range, in order to control compatibility between rubbers, thereby achieving excellent wear resistance and improved tensile properties and viscoelastic properties. Further, the rubber composition contains a lithium-catalyzed modified butadiene rubber having at least one terminal bonded with a functional group as the second synthetic rubber, and can have better affinity with the filler and further improved dispersibility of the filler in the rubber composition, thereby greatly improving viscoelastic properties.

Drawings

The following drawings attached to the present specification illustrate preferred embodiments of the present invention and together with the detailed description of the invention given below serve to enable the technical concept of the invention to be further understood, and the invention should not be construed as being limited to the contents of the drawings.

FIG. 1 shows graphs of G "(dynamic loss modulus) as a function of temperature for rubber compositions of examples 1 and 2, and comparative examples 1 to 3 according to embodiments of the present invention;

fig. 2 shows TEM images (magnification of 28K (28,000)) of the rubber compositions of example 1, and comparative examples 1 to 3 according to an embodiment of the present invention.

Detailed Description

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

It should be understood that the words or terms used in the specification and claims of this invention should not be construed as meanings defined in commonly used dictionaries. It should also be understood that these words or terms should be interpreted as having meanings consistent with their meanings in the technical idea of the present invention based on the principle that the inventor can appropriately define the meanings of the words or terms to best explain the invention.

The term "solubility parameter (. delta.) as used in the present invention means a characteristic value of a substance, which is a measure of a mixture of substances, and is calculated by the following mathematical formula 1, which is a known calculation formula of solubility parameter (RUBBER CHEMISTRYANDENDTECHNOLOGY: 11.1996, volume 69, phase 5, page 769-780).

[ mathematical formula 1]

δ ═ 17.17+0.0272 (wt% styrene) -0.0069 (wt% vinyl)

The present invention provides a rubber composition having excellent abrasion resistance and improved tensile properties and viscoelastic properties.

The rubber composition according to one embodiment of the present invention is characterized by comprising: a first synthetic rubber; a second synthetic rubber; and a filler, wherein a difference in solubility parameter between the first synthetic rubber and the second synthetic rubber is greater than 0.6, the first synthetic rubber is a solution-polymerized conjugated diene-based rubber having a styrene bond content of 30 wt% or more, and the second synthetic rubber is a lithium-catalyzed modified butadiene-based rubber having at least one terminal bonded with a functional group.

In addition, the rubber composition may include, based on 100 parts by weight of the rubber component including the first synthetic rubber and the second synthetic rubber: 30 to 90 parts by weight of the first synthetic rubber; 10 to 70 parts by weight of the second synthetic rubber; and 30 to 200 parts by weight of the filler.

In addition, the difference in solubility parameters between the first synthetic rubber and the second synthetic rubber may be greater than 0.6 and less than or equal to 1.1, specifically, greater than 0.8 and less than or equal to 1.1, more specifically, greater than 0.82 and less than or equal to 1.07 or from 0.90 or more to 1.05 or less. If the difference in solubility parameter between the first synthetic rubber and the second synthetic rubber is within the above range, the compatibility between the rubber components can be controlled and the physical properties of the first synthetic rubber and the second synthetic rubber can be simultaneously exhibited without deteriorating the respective physical properties, and therefore, the tensile properties and viscoelastic properties of the rubber composition comprising the synthetic rubbers can become excellent.

Specifically, if the solubility parameter difference is 0.6 or less, phase separation between the first synthetic rubber and the second synthetic rubber may be suppressed, and wet skid resistance (braking performance) may be reduced. Meanwhile, if the solubility parameter difference is greater than 0.6, a desired effect may be achieved, but for a better effect, the solubility parameter difference may be greater than 0.6 and less than or equal to 1.1. If the difference in solubility parameter is greater than 1.1, phase separation between the first synthetic rubber and the second synthetic rubber may excessively occur, and conversely, a decrease in abrasion resistance (or tear property) may occur.

The rubber composition according to one embodiment of the present invention comprises heterogeneous rubber components of the first synthetic rubber and the second synthetic rubber, and the first synthetic rubber and the second synthetic rubber are selected such that solubility parameters therebetween are different within a specific range, and therefore, compatibility between the rubber components can be controlled and respective physical properties of the first synthetic rubber and the second synthetic rubber can be simultaneously exhibited. As a result, the wear resistance can be excellent and the tensile property and viscoelastic property can be improved.

In addition, since the rubber composition according to one embodiment of the present invention includes a lithium-catalyzed modified butadiene rubber having at least one terminal bonded with a functional group as the second synthetic rubber, the affinity with the filler may become more excellent, and therefore, the viscoelastic properties may be further improved.

Hereinafter, each component included in the rubber composition according to the embodiment of the present invention will be specifically described.

First synthetic rubber

In one embodiment of the present invention, the first synthetic rubber may be a solution-polymerized conjugated diene-based rubber having a styrene bond content of 30% by weight or more.

Specifically, the first synthetic rubber may be a solution-polymerized conjugated diene rubber of a high styrene series having a styrene bond content of 30 wt% or more and 55 wt% or less, and more specifically, the styrene bond content of the first synthetic rubber may be 38 wt% or more and 55 wt% or less, or 38 wt% or more and 45 wt% or less. If the first synthetic rubber has the above styrene content, excellent rolling resistance, wet skid resistance and low consumption rate effects can be achieved.

Further, the first synthetic rubber may be a solution-polymerized conjugated diene-based rubber comprising a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer, and in this case, the solution-polymerized conjugated diene-based rubber may comprise 60 to 80% by weight of the repeating unit derived from the conjugated diene-based monomer and 20 to 40% by weight of the repeating unit derived from the aromatic vinyl-based monomer.

Further, in one embodiment of the present invention, the solution-polymerized conjugated diene-based rubber may contain an extender oil, and in this case, the solution-polymerized conjugated diene-based rubber may contain an extender oil in an amount of more than 0% by weight and 37.5% by weight or less.

Further, the vinyl content of the solution-polymerized conjugated diene-based rubber may be 10% by weight or more, 10% by weight to 40% by weight, or 20% by weight to 40% by weight, in which range the glass transition temperature may be controlled within a suitable range, and rolling resistance, wet skid resistance and low fuel consumption rate may be excellent. Here, the vinyl content may refer to the amount of 1, 2-added, not 1, 4-added, conjugated diene-based monomer with respect to 100% by weight of the conjugated diene-based rubber composed of the monomer having a vinyl group and the aromatic vinyl-based monomer.

Further, the first synthetic rubber according to an embodiment of the present invention may be a modified conjugated diene-based rubber to at least one terminal of which a functional group is bonded, and in this case, the functional group may be any one or more selected from the group consisting of an amine group and an aminoalkoxysilane group. Specifically, the first synthetic rubber according to an embodiment of the present invention may be a solution-polymerized modified conjugated diene-based rubber having a functional group bonded to one end or both ends. In the case where the first synthetic rubber is a solution-polymerized modified conjugated diene-based rubber having a functional group bonded to one end, one or more of an amine group and an aminoalkoxysilane group may be bonded to one end, and in the case where the first synthetic rubber is a solution-polymerized modified conjugated diene-based rubber having functional groups bonded to both ends, an amine group or an aminoalkoxysilane group is bonded to both ends, or an amine group is bonded to one end and an aminoalkoxysilane group is bonded to the other end.

Further, the first synthetic rubber can have a number average molecular weight (Mn) of 20,000 to 800,000g/mol, 100,000 to 550,000g/mol, or 150,000 to 500,000g/mol, and a weight average molecular weight (Mw) of 40,000 to 2,000,000g/mol, 150,000 to 900,000g/mol, or 200,000 to 800,000 g/mol. Within these ranges, rolling resistance and wet skid resistance are excellent. In another embodiment, the solution-polymerized conjugated diene-based rubber may have a molecular weight distribution (Mw/Mn) of 1.0 to 4.0, 1.1 to 3.5, or 1.3 to 3.0, within which the balance between physical properties is excellent.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene-equivalent molecular weights analyzed by Gel Permeation Chromatography (GPC), respectively, and the molecular weight distribution (Mw/Mn) is also referred to as polydispersity and calculated as a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

In another embodiment, the first synthetic rubber may have a mooney viscosity at 100 ℃ of 40 to 120, or 50 to 100, within which range processability and productivity are excellent. In this case, the first synthetic rubber may not contain extender oil.

Here, the Mooney viscosity is measured by using a Mooney viscometer, for example, using a large spindle MV2000E (ALPHA technologies Co.), at a rotation speed of 2. + -. 0.02rpm, at a temperature of 100 ℃ and 140 ℃. Specifically, the polymer was left at room temperature (23. + -. 3 ℃ C.) for 30 minutes or more, 27. + -.3 g of the polymer was collected and put into a cavity, and then the platen was operated and measured while applying a torque.

The term "repeating unit from …" as used herein may refer to a component or structure from a substance or the substance itself. For example, the repeating unit derived from the conjugated diene-based monomer may refer to a repeating unit formed from the conjugated diene-based monomer during polymerization, and the repeating unit derived from the aromatic vinyl-based monomer may refer to a repeating unit formed from the aromatic vinyl-based monomer during polymerization.

Meanwhile, the first synthetic rubber according to one embodiment of the present invention may be prepared by polymerizing an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing an organometallic compound to prepare an active polymer combined with an organometallic, and then reacting the active polymer thus prepared with a modifier, or by polymerizing an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing a modification initiator to prepare an active polymer combined with a functional group derived from the modification initiator and an organometallic, and then reacting the active polymer thus prepared with a modifier.

The hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

The conjugated diene-based monomer is not particularly limited, but may be, for example, 1, 3-butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene, 2, 3-dimethyl-1, 3-butadiene, 2-ethyl-1, 3-butadiene, 2-methyl-1, 3-pentadiene, 3-methyl-1, 3-pentadiene, 4-methyl-1, 3-pentadiene or 2, 4-hexadiene, and may be specifically 1, 3-butadiene.

The aromatic vinyl monomer is not particularly limited, but may be, for example, styrene, α -methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, 1-vinyl-5-hexylnaphthalene and the like, and may be particularly styrene.

The modification initiator may be a compound prepared by reacting an organometallic compound with a compound containing an amine group.

The organometallic compound may be, for example, one or more selected from methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyl lithium, 4-tolyllithium, cyclohexyllithium, 3, 5-di-n-heptylcyclohexylithium, 4-cyclopentyllithium, naphthylsodium, naphthylpotassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

The amine group-containing compound may be, for example, a compound represented by formula 1 below.

[ formula 1]

In the formula 1, the first and second groups,

R₁to R₃Each independently is hydrogen; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; 2 to 30 carbon atomsAlkynyl of (a); heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, R₄Is a single bond; an alkylene group of 1 to 20 carbon atoms which is substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, R₅Is an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following formula 1a or formula 1b, n is an integer of 1 to 5, and R₅At least one of the groups is a functional group represented by the following formula 1a or formula 1b, and in the case where n is an integer of 2 to 5, a plurality of R₅The groups may be the same or different,

[ formula 1a ]

In formula 1a, R₆Is an alkylene group of 1 to 20 carbon atoms which may be substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, R₇And R₈Each independently an alkylene group of 1 to 20 carbon atoms substituted or unsubstituted with an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, R₉Is hydrogen; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; 1 to 30 carbonsA heteroalkyl group of atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, X is N, O or S atom, R is O or S when X is₉In the absence of the presence of the agent,

[ formula 1b ]

In the case of the formula 1b,

R₁₀is an alkylene group of 1 to 20 carbon atoms which may be substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms,

R₁₁and R₁₂Each independently an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms.

In addition, the modifier may be, for example, a compound represented by formula 2 or formula 3 below, or a combination thereof. That is, the compound represented by formula 2 or the compound represented by formula 3 may be used as the modifier, or the compound represented by formula 2 and the compound represented by formula 3 may be used simultaneously.

[ formula 2]

In formula 2, A₁And A₂Each independently an alkylene group of 1 to 20 carbon atoms, R₂₅To R₂₈Each independently an alkyl group of 1 to 20 carbon atoms, L₁And L₂、L₃And L₄Are linked to each other to form a ring of 1 to 5 carbon atoms, respectively, wherein L is linked to each other₁And L₂、L₃And L₄The ring formed contains one to three heteroatoms selected from N, O and S.

[ formula 3]

In formula 3, R₃₁To R₃₃Each independently an alkylene group of 1 to 10 carbon atoms, R₃₄To R₃₇Each independently an alkyl group of 1 to 10 carbon atoms, R₃₈Is hydrogen or alkyl of 1 to 10 carbon atoms, a and b are each independently integers of 0 to 3, where a + b ≧ 1, A is

Wherein R is₃₉To R₄₂Each independently hydrogen or alkyl of 1 to 10 carbon atoms.

Second synthetic rubber

In one embodiment of the present invention, the second synthetic rubber may be a lithium-catalyzed modified butadiene-based rubber having at least one terminal bonded with a functional group as described above.

Specifically, the lithium-catalyzed modified butadiene-based rubber may have a vinyl bond content of 50 wt% or less, and more specifically, the vinyl content in the polymer may be 45 wt% or less. Here, the vinyl bond is measured by fourier transform infrared spectroscopy.

In addition, the lithium-catalyzed butadiene-based rubber may have a number average molecular weight (Mn) of 20,000 to 800,000g/mol, 100,000 to 550,000g/mol, or 150,000 to 500,000g/mol, and a weight average molecular weight (Mw) of 40,000 to 2,000,000g/mol, 150,000 to 900,000g/mol, or 200,000 to 800,000g/mol, and within these ranges, the balance between physical properties may be excellent.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by the methods described above.

Meanwhile, the lithium-polymerized modified butadiene-based rubber according to one embodiment of the present invention may be prepared by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a lithium-containing compound to prepare an active polymer, and then reacting the thus-prepared active polymer with a modifier. The lithium-catalyzed modified butadiene-based rubber thus prepared can easily incorporate a functional group derived from the modifier, has a narrow molecular weight distribution, and thus has an excellent fuel consumption rate.

Here, the conjugated diene monomer may be 1, 3-butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene, 2, 3-dimethyl-1, 3-butadiene, 2-ethyl-1, 3-butadiene, 2-methyl-1, 3-pentadiene, 3-methyl-1, 3-pentadiene, 4-methyl-1, 3-pentadiene or 2, 4-hexadiene, specifically, 1, 3-butadiene.

The catalyst composition may include a lithium-containing compound; an alkylating agent; and a halogen compound.

The lithium-containing compound is a compound which is activated by an alkylating agent to form a catalytically active substance, for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyl lithium, 4-methylphenyllithium, cyclohexyllithium, 3, 5-di-n-heptylcyclohexylium, 4-cyclopentyllithium, lithium alkoxide or lithium amide.

The alkylating agent is capable of transferring a hydrocarbyl group to another metal and acts as a cocatalyst. For example, the alkylating agent may be one or more selected from the group consisting of an organoaluminum compound, an organomagnesium compound, and an organolithium compound.

Specifically, the organoaluminum compound may include: alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, and trioctylaluminum; dialkylaluminum hydrides, such as diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolyl-isobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, Benzyl isobutyl aluminum hydride and benzyl-n-octyl aluminum hydride; hydrocarbyl aluminum dihydrides such as ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride, n-octyl aluminum dihydride, and the like. The organomagnesium compound may include alkylmagnesium compounds such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, and dibenzylmagnesium, and the organolithium compound may include alkyllithium compounds such as n-butyllithium.

Further, the organoaluminum compound may be aluminoxane such as Methyl Aluminoxane (MAO), Modified Methyl Aluminoxane (MMAO), ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, n-pentyl aluminoxane, neopentyl aluminoxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenyl aluminoxane or 2, 6-dimethylphenyl aluminoxane.

Examples of the halide are not particularly limited, but the halide may be a diatomic halogen, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometallic halide, and any one of them or a mixture of two or more of them may be used. Among them, the halide may be any one selected from organic halides, metal halides and organometallic halides, or a mixture of two or more of them, in view of the effect of improving catalytic activity and subsequent reactivity.

The diatomic halogen may include fluorine, chlorine, bromine or iodine.

In addition, the interhalogen compound may include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride, iodine trifluoride, and the like.

Additionally, the hydrogen halide may include hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide.

In addition, the organic halide may include t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chlorodiphenylmethane, bromodiphenylmethane, trityl chloride, trityl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also referred to as "iodoform"), tetraiodomethane, 1-iodopropane, 2-iodopropane, 1, 3-diiodopropane, t-butyl iodide, 2-dimethyl-1-iodopropane (also referred to as "neopentyl iodide"), allyl iodide, iodobenzene, benzyl iodide, Benzhydryl iodide, trityl iodide, benzylidene iodide (also referred to as "benzylidene iodide"), trimethylsilyliodide, triethylsilyliodide, triphenylsilyliodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, methyl iodoformate, and the like.

In addition, the non-metal halide may include phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl)₄) Silicon tetrabromide, arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodooxyphosphate, selenium tetraiodide, and the like.

In addition, the metal halide may include tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum tribromide, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc diiodide, germanium tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

In addition, the organic metal halide may include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, sesquimethylaluminum chloride, sesquiethylaluminum chloride (EASC), sesquiisobutylaluminum chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-t-butyltin dichloride, di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin bromide, Methyl magnesium iodide, dimethyl aluminum iodide, diethyl aluminum iodide, di-n-butyl aluminum iodide, diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methyl aluminum diiodide, ethyl aluminum diiodide, n-butyl aluminum diiodide, isobutyl aluminum diiodide, sesquimethyl aluminum iodide, sesquiethyl aluminum iodide, sesquiisobutyl aluminum iodide, ethyl magnesium iodide, n-butyl magnesium iodide, isobutyl magnesium iodide, phenyl magnesium iodide, benzyl magnesium iodide, trimethyl tin iodide, triethyl tin iodide, tri-n-butyl tin iodide, di-n-butyl tin diiodide, di-t-butyl tin diiodide, and the like.

The modifier may be, for example, the compound represented by formula 2 or formula 3 described above, and one or a mixture of two or more species may be used. That is, the modifier may be formula 2, formula 3, or a combination thereof.

Filler material

In one embodiment of the present invention, the filler may be mixed with the rubber component to function to improve the physical properties of the rubber composition, and may be specifically silica.

For example, the silica may be wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate or colloidal silica. Preferably, the silica may be wet silica, which has the most remarkable improvement effect of the breaking property and the compatible effect of wet grip.

Meanwhile, the rubber composition according to one embodiment of the present invention may further include other rubber components as needed in addition to the above rubber components, and in this case, the content of the other rubber components may be 90% by weight or less based on the total weight of the rubber composition.

The other rubber component may be, for example, natural rubber or synthetic rubber, and may specifically be Natural Rubber (NR) including cis-1, 4-polyisoprene; modified natural rubber obtained by modifying or purifying conventional natural rubber, such as Epoxidized Natural Rubber (ENR), deproteinized natural rubber (DPNR) and hydrogenated natural rubber; synthetic rubbers, for example, styrene-butadiene copolymers (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, chloroprene rubber, poly (ethylene-co-propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and halogenated butyl rubber, and any one or a mixture of two or more of them may be used.

Further, the rubber composition according to one embodiment of the present invention may be sulfur-crosslinkable and thus may further contain a vulcanizing agent.

The vulcanizing agent may specifically be sulfur powder, and may be contained in an amount of 0.1 parts by weight to 10 parts by weight, based on 100 parts by weight of the rubber component. The amount used in the above range can ensure the elasticity and strength required for the vulcanized rubber composition, and at the same time, can realize an excellent low fuel consumption rate.

In addition, if silica is used as a filler, a silane coupling agent may be used together in the rubber composition according to one embodiment of the present invention for improving the reinforcing and low heat release properties. Specific examples of the silane coupling agent may include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, n-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and any one or a mixture of two or more of them may be used. Preferably, in view of the property-enhancing improvement effect, bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide may be used.

The rubber composition according to one embodiment of the present invention may further contain various additives used in the conventional rubber industry, in particular, a vulcanization accelerator, a processing oil, a plasticizer, an age resistor, an anti-scorching agent, zinc white, stearic acid, a thermosetting resin or a thermoplastic resin, in addition to the above components.

The vulcanization accelerator may include, for example, thiazole compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl Disulfide (DM) and N-cyclohexyl-2-benzothiazylsulfenamide (CZ), or guanidine compounds such as Diphenylguanidine (DPG), and may be contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The processing oil acts as a softener in the rubber composition and may include, for example, paraffins, naphthenes, or aromatics. An aromatic processing oil may be used in consideration of tensile strength and abrasion resistance, and a naphthenic or paraffinic processing oil may be used in consideration of hysteresis loss and low-temperature properties. The content of the processing oil may be 100 parts by weight or less based on 100 parts by weight of the rubber component. Within the above range, the deterioration of the tensile strength and low heat release performance (low fuel consumption rate) of the vulcanized rubber can be prevented.

The age resister may include, 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 condensate of diphenylamine and acetone at a high temperature, and is contained 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 one embodiment of the present invention can be obtained by mixing according to the mixing formulation using a mixing device such as a banbury mixer, a roll and an internal mixer. By the vulcanization process after the molding process, a rubber composition having low heat release properties and good abrasion resistance can be obtained.

Thus, the rubber composition can be used for manufacturing various members of a tire, such as a tire tread, a tread base, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer and a bead coating rubber, or for manufacturing rubber products in various industries, such as a vibration damping rubber, a conveyor belt and a hose.

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

The tire may be a tire or a tire tread.

Hereinafter, the present invention will be described in more detail with reference to embodiments. However, these embodiments are for illustrating the present invention, and the scope of the present invention is not limited thereto.

In examples and comparative examples, parts by weight of components other than the rubber component are expressed based on 100 parts by weight of the rubber component used in each of the examples and comparative examples. Here, the rubber component means only natural rubber obtained by excluding oil from styrene-butadiene rubber and butadiene rubber used in examples and comparative examples, respectively.

In addition, the same substances were used as other components except for the rubber component in examples and comparative examples. The coupling agent is bis (3-triethoxysilylpropyl) tetrasulfide (TESPT), the process oil is a TDAE oil, and the vulcanization accelerator is N-cyclohexyl-2-benzothiazylsulfenamide (CZ) or Diphenylguanidine (DPG).