KR20180038146A - Rubber composition and tire comprising the same - Google Patents

Abstract

The present invention relates to a rubber composition and a tire comprising the rubber composition, wherein the rubber composition is capable of being used even in low temperature environment by having excellent rotation resistance and tensile properties without deteriorating snow performance and wet road surface resistance. The rubber composition of the present invention comprises a base rubber including a first conjugated diene based copolymer and a second conjugated diene based copolymer, wherein the first conjugated diene based copolymer comprises first conjugated diene based monomer-derived repeating units and first aromatic vinyl monomer-derived repeating units, the first conjugated diene based copolymer has a modifier-derived functional group included at one end thereof, the content of the first conjugated diene based monomer-derived repeating units which form a vinyl bond among the first conjugated diene based monomer-derived repeating units is 20 wt% or less with respect to the first conjugated diene based copolymer, the content of the first aromatic vinyl monomer-derived repeating units is more than 0 wt% to not more than 20 wt% with respect to the first conjugated diene based copolymer, the first conjugated diene based copolymer has a glass transition temperature (Tg) of -50°C or less, and the second conjugated diene based copolymer comprises second conjugated diene based monomer-derived repeating units and second aromatic vinyl monomer-derived repeating units.

Description

RUBBER COMPOSITION AND TIRE COMPRISING THE SAME [0001]

The present invention relates to a rubber composition, and more particularly, to a rubber composition which is excellent in rolling resistance and tensile properties without deteriorating snow performance and wet road surface resistance, and which can be used in a low temperature environment.

Recently, as a rubber material for a tire, there has been demanded a conjugated diene polymer having low rolling resistance, excellent abrasion resistance, tensile properties, and adjustment stability represented by wet road surface resistance, in accordance with recent demand for low fuel consumption in automobiles.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As the evaluation index of such vulcanized rubber, repulsive elasticity of 50 DEG C to 80 DEG C, tan delta, Goodrich heat, and the like are used. That is, a rubber material having a large rebound resilience at that temperature or a small tan δ Goodrich heat is preferable.

Natural rubbers, polyisoprene rubbers, polybutadiene rubbers, and the like are known as rubber materials having a small hysteresis loss, but these have a problem that wet road surface resistance is small. Recently, a conjugated diene polymer or copolymer such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) has been produced by emulsion polymerization or solution polymerization and is used as a rubber for a tire . Of these, the greatest advantage of solution polymerization over emulsion polymerization is that vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled and molecular weight and physical properties, etc., can be controlled by coupling, It can be adjusted. Therefore, it is easy to change the structure of the finally prepared SBR or BR, and it is possible to reduce the movement of the chain terminal due to bonding or modification of the chain terminal and increase the bonding force with the filler such as silica or carbon black, It is widely used as a rubber material.

When such a solution-polymerized SBR is used as a rubber material for a tire, by increasing the vinyl content in the SBR, it is possible to increase the glass transition temperature of the rubber to control tire properties such as running resistance and braking force, By properly adjusting it, fuel consumption can be reduced. The solution-polymerized SBR is prepared by using an anionic polymerization initiator, and chain ends of the formed polymer are bonded or denatured by using various modifiers. For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the chain terminal of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, a monofunctional initiator, is bonded using a binder such as a tin compound Respectively.

On the other hand, in the case of tire treads used in winter tires, snow tires, or all seasons (for four seasons) tires, tread compounds, that is, low glass transition temperatures are required for rubber compositions, because they are intended for use in low temperature environments.

In order to impart a low glass transition temperature to the tread compound, the use amount of the solution-polymerized SBR is reduced and a butadiene rubber (BR, glass transition temperature -110 ° C. to -100 ° C.) or a natural rubber (NR, glass transition temperature -75 ° C. To -70 deg. C) is used in some cases. However, the low temperature characteristics for use in a low temperature environment are improved, but mechanical properties such as rotational resistance and static friction performance are deteriorated.

Regarding this issue, EU tire labeling regulations have been implemented since November 2012, and restrictions on tire rolling resistance and wet road surface resistance have intensified. As a result, regulations for winter tires, snow tires and all- There is a continuing need for improvement of physical properties.

US 4397994 A JP 1994-271706 A

Disclosure of Invention Technical Problem [8] The present invention has been conceived to solve the problems of the prior art, and it is an object of the present invention to provide a rubber composition which is excellent in rolling resistance and tensile property without deteriorating snow performance and wet road surface resistance, The purpose.

According to one embodiment of the present invention for solving the above problems, the present invention provides a rubber composition comprising a raw rubber comprising a first conjugated diene-based copolymer and a second conjugated diene-based copolymer, wherein the first conjugated diene- And the repeating unit derived from the first conjugated diene monomer and the repeating unit derived from the first aromatic vinyl monomer and having a functional group derived from the modifier at one end thereof, 1-conjugated diene-based monomer is 20% by weight or less based on the first conjugated diene-based copolymer, and the content of the first aromatic vinyl monomer-derived repeating unit is 0% by weight or less based on the first conjugated diene- And a glass transition temperature (Tg) of -50 占 폚 or less, and the second conjugated diene-based copolymer has a second conjugated diene-based monomer-derived repeating unit and a second room Group to provide a rubber composition for the vinyl monomer will be derived from the repeating unit.

The present invention also provides a tire comprising the rubber composition.

When the rubber composition contains the first conjugated diene-based copolymer and the second conjugated diene-based copolymer as the raw rubber to be contained in the rubber composition, the tire containing the rubber composition, without degrading the snow performance and wet road surface resistance, There is an effect of improving the rolling resistance and the tensile characteristics.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the description of the present invention and in the claims should not be construed to be limited to ordinary or dictionary terms and the inventor should appropriately interpret the concept of the term appropriately The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention.

The term " derived unit " and " derived functional group " in the present invention may refer to a component, structure or the substance itself resulting from a substance.

The rubber composition according to the present invention comprises a raw rubber comprising a first conjugated diene-based copolymer and a second conjugated diene-based copolymer, wherein the first conjugated diene-based copolymer contains a first conjugated diene-based monomer- Wherein the content of the repeating unit derived from the first conjugated diene monomer and the content of the repeating unit derived from the first conjugated diene monomer constituting the vinyl bond in the first conjugated diene monomer- 1 conjugated diene-based copolymer, the content of the first aromatic vinyl monomer-derived repeating unit relative to the first conjugated diene-based copolymer is more than 0 wt% and not more than 20 wt%, and the glass transition temperature Tg) is -50 占 폚 or less, and the second conjugated diene-based copolymer contains the second conjugated diene-based monomer-derived repeating unit and the second aromatic vinyl monomer-derived repeating unit .

The repeating unit derived from the first conjugated diene monomer and the repeating unit derived from the second conjugated diene monomer may mean repeating units formed by polymerization of the first conjugated diene monomer and the second conjugated diene monomer, Examples of the conjugated diene monomer and the second conjugated diene monomer include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3 -butyl-1,3-octadiene, isoprene, 1,3-butadiene and 2-halo-1,3-butadiene (wherein halo means a halogen atom), and the first conjugated diene monomer and the second conjugate The diene-based monomers may be the same or different.

The repeating unit derived from the first aromatic vinyl monomer and the repeating unit derived from the second aromatic vinyl monomer may mean repeating units formed by polymerization of the first aromatic vinyl monomer and the second aromatic vinyl monomer, Examples of the second aromatic vinyl monomer include styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- And 1-vinyl-5-hexynaphthalene, and the first aromatic vinyl monomer and the second aromatic vinyl monomer may be the same or different from each other.

The first conjugated diene-based copolymer is a first component of the starting rubber contained in the rubber composition, and has a low glass transition temperature of -50 캜 or less. As described above, the first conjugated diene-based copolymer has a low glass transition temperature, thereby lowering the glass transition temperature of the whole raw rubber to improve the abrasion resistance. At the same time, the copolymer contains a repeating unit derived from an aromatic vinyl monomer in the copolymer , Wet road surface resistance and rotational resistance.

Specifically, in the first conjugated diene-based copolymer, the content of the repeating unit derived from the first conjugated diene-based monomer constituting the vinyl bond in the first conjugated diene-based monomer-derived repeating unit is 20 wt% By weight or less, 5% by weight to 20% by weight, or 10% by weight to 20% by weight. Within this range, there is an effect of excellent tensile characteristics and abrasion resistance. Here, the content of the repeating unit derived from the first conjugated diene-based monomer constituting the vinyl bond may mean the content of the 1,2-added conjugated diene monomer, not 1,4-added.

As another example, in the first conjugated diene-based copolymer, the content of the repeating unit derived from the first aromatic vinyl monomer in the first conjugated diene-based copolymer is more than 0 wt% to 20 wt%, 5 wt% to 20 wt% , Or 10% by weight to 20% by weight, and the snow resistance is maintained within the above range, but the rolling resistance and the wet surface roughness resistance are excellent.

On the other hand, the first conjugated diene-based copolymer may have a glass transition temperature (Tg) of -50 DEG C or lower, -90 DEG C to -50 DEG C, or -70 DEG C to -80 DEG C, There is an effect of excellent rolling resistance and tensile properties without lowering the resistance.

As another example, the first conjugated diene-based copolymer may have a Mooney viscosity of 10 to 180, 30 to 150, or 70 to 100, and within this range, excellent workability and productivity are obtained.

According to an embodiment of the present invention, the first conjugated diene-based copolymer has a number average molecular weight (Mn) of 10,000 g / mol to 2,000,000 g / mol, 50,000 g / mol to 1,500,000 g / mol, (Mw) of from 10,000 g / mol to 3,000,000 g / mol, from 50,000 g / mol to 2,000,000 g / mol, from 100,000 g / mol to 1,000,000 g / mol, or from 150,000 g / mol to 700,000 g / mol, And may have a molecular weight distribution (MWD) of 1 to 5, 1.2 to 3, or 1.5 to 2.5, and may have a molecular weight distribution within the molecular weight and molecular weight distribution range The balance of physical properties between the respective physical properties is excellent.

On the other hand, the first conjugated diene-based copolymer may contain a modifier-derived functional group at one end. The modifier-derived functional group may be a functional group derived from an anionic one-terminal end of an active polymer polymerized by an anionic polymerization reaction and a denaturation or coupling reaction between the denaturant, and the first conjugated diene- It is possible to improve the affinity with the inorganic filler and improve the tensile properties and the rotation resistance.

According to an embodiment of the present invention, the modifier may be an alkoxysilane-based modifier. When an alkoxysilane-based modifier is used as a modifier according to the present invention, there is an effect of significantly improving the affinity between the first conjugated diene-based copolymer and the silica-based inorganic filler when blended with the silica-based inorganic filler, thereby further improving the mechanical properties .

According to an embodiment of the present invention, the alkoxysilane-based modifier may be a nitrogen atom-containing alkoxysilane-based modifier.

As a specific example, the first conjugated diene-based copolymer containing a modifier-derived functional group at one end may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

또는

일 수 있으며, R⁹, R¹⁰, R¹¹, 및 R¹²는 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.R ₃ , R ₄ , R ₆ and R ₇ may each independently be an alkyl group having 1 to 10 carbon atoms, R ₁ , R ₂ , and R ₅ may each independently be an alkylene group having 1 to 10 carbon atoms, _And a and c may each independently be 0, 1, or 2, and b and d may be the same or different and are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, Each of a + b and c + d may independently be 1, 2, or 3, and A is

or

And R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² may each independently be hydrogen, or an alkyl group having 1 to 10 carbon atoms.

As another example, the first conjugated diene-based copolymer containing a functional group derived from a modifier at one end may be obtained by polymerizing (a) a first conjugated diene monomer and a first aromatic vinyl compound monomer in a hydrocarbon solvent containing an organometallic compound Thereby producing an alkali metal-bonded active polymer; And (b) reacting the active polymer with a compound represented by the following formula (2): < EMI ID = 2.0 >

(2)

In Formula 2,

R ¹ , R ² and R ⁵ may each independently be an alkylene group having 1 to 10 carbon atoms, R ³ , R ⁴ , R ⁶ and R ⁷ each independently may be an alkyl group having 1 to 10 carbon atoms, and R ⁸ May be hydrogen or an alkyl group having 1 to 10 carbon atoms, a and c each independently may be 0, 1, 2 or 3, a + c? 1,

또는

일 수 있으며,A is

or

Lt; / RTI >

R ⁹ , R ¹⁰ , R ^11, and R ¹² may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

According to one embodiment of the present invention, the first conjugated diene-based copolymer may be a random copolymer, and in this case, there is an effect of excellent balance among physical properties. The random copolymer may mean that the repeating units constituting the copolymer are randomly arranged. According to an embodiment of the present invention, the first conjugated diene-based copolymer may be a conjugated diene-based copolymer polymerized by solution polymerization.

On the other hand, the second conjugated diene-based copolymer according to the present invention is a second component constituting the raw rubber contained in the rubber composition, and is not particularly limited as long as it is a conjugated diene-based copolymer that can be used in a low- But may be a conjugated diene-based copolymer containing a second conjugated diene-based monomer-derived repeating unit and a second aromatic vinyl monomer-containing repeating unit.

However, as a preferred example for achieving the object of the present invention, the second conjugated diene-based copolymer preferably contains the content of the second conjugated diene-based monomer-derived repeating unit constituting the vinyl bond in the second conjugated diene-based monomer- May be 30% by weight or less, 5 to 30% by weight, or 20 to 30% by weight based on the second conjugated diene-based copolymer, and the content of the second aromatic vinyl monomer- 30 to 60% by weight, 30 to 50% by weight, or 35 to 45% by weight based on the total weight of the resin composition. Within this range, there is an effect of excellent rolling resistance and tensile properties without deteriorating the snow performance and wet road surface resistance.

As another example, the second conjugated diene-based copolymer may have a glass transition temperature (Tg) of -40 ° C to -10 ° C, -40 ° C to -20 ° C, or -35 ° C to -25 ° C, , There is an effect of excellent rolling resistance and tensile properties without deterioration of snow performance and wet road surface resistance when mixed with the first conjugated diene-based copolymer.

According to one embodiment of the present invention, the second conjugated diene-based copolymer may have a Mooney viscosity of 10 to 180, 30 to 150, or 70 to 100, and within this range, the second conjugated diene-based copolymer has excellent processability and productivity.

The second conjugated diene-based copolymer may be one in which one end is modified with a modifying agent. In this case, similarly to the first conjugated diene-based copolymer, the affinity with the inorganic filler is improved and the mechanical properties are improved .

According to one embodiment of the present invention, the second conjugated diene-based copolymer may be a random copolymer, and in this case, there is an excellent balance between physical properties. According to an embodiment of the present invention, the second conjugated diene-based copolymer may be a conjugated diene-based copolymer polymerized by solution polymerization.

In addition to the first conjugated diene-based copolymer and the second conjugated diene-based copolymer, the starting rubber contained in the rubber composition according to the present invention may contain at least one rubber component selected from the group consisting of natural rubber and synthetic rubber And may further comprise a third component.

As a specific example, the raw material rubber may include 10 to 90 parts by weight, or 30 to 80 parts by weight, of the first conjugated diene-based copolymer, based on 100 parts by weight of the raw material rubber. 10 to 90 parts by weight, or 20 to 70 parts by weight of the second conjugated diene-based copolymer; And 0 to 80 parts by weight, or 0 to 50 parts by weight of at least one rubber component selected from the group consisting of natural rubber and synthetic rubber. Within this range, excellent mechanical properties are obtained, The balance has an excellent effect. As another example, the raw material rubber may contain, based on 100 parts by weight of the raw material rubber, 30 to 50 parts by weight of the first conjugated diene-based copolymer; 20 to 30 parts by weight of a second conjugated diene-based copolymer; And 30 to 40 parts by weight of at least one rubber component selected from the group consisting of natural rubber and synthetic rubber.

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

For example, the rubber composition may include 0.1 to 200 parts by weight, or 10 to 120 parts by weight of an inorganic filler based on 100 parts by weight of the raw rubber of the present invention. The inorganic filler may be, for example, a silica-based filler. Specific examples thereof include wet silica (hydrated silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, The wet grip can be a wet silica with the most compatible effect. Further, the rubber composition may further include a carbon black filler as required.

As another example, when the silica is used as the inorganic filler, a silane coupling agent may be used together with the silane coupling agent for improving the reinforcing property and the low exothermic property. For example, the silane coupling agent may be bis (3-triethoxysilylpropyl) (3-triethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) Mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, , 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetra Sulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-t- Methoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-triethoxysilylpropyl methacrylate monosulfide, (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropyl Benzothiazolyl tetrasulfide, etc., and any one or a mixture of two or more thereof may be used. Preferably, it may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazetetrasulfide, considering the effect of improving the reinforcing property.

Further, since the first conjugated diene-based copolymer in which the functional group having high affinity with silica is introduced into the active site as the rubber component according to the embodiment of the present invention, the amount of the silane coupling agent to be added is The silane coupling agent can be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica, and within this range, The effect of preventing the gelation of the rubber component is sufficiently exhibited.

The rubber composition according to an embodiment of the present invention may be sulfur-crosslinkable and may further include a vulcanizing agent (vulcanizing agent). Examples of the vulcanizing agent include inorganic vulcanizing agents such as sulfur powder, insoluble sulfur, precipitated sulfur, and colloidal sulfur, and organic vulcanizing agents such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD) And may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. Within this range, the required modulus of elasticity of the vulcanized rubber composition and / It has an effect of securing strength and excellent low fuel consumption.

The rubber composition according to an embodiment of the present invention may contain various additives commonly used in the rubber industry, specifically vulcanization accelerators (vulcanization accelerators), process oils, plasticizers, antioxidants, scorch inhibitors, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

Examples of the vulcanization accelerator (vulcanization accelerator) include a thiazole series such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide) and CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Compound, or a guanidine compound such as DPG (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 may be a paraffinic, naphthenic, or aromatic compound, which acts as a softening agent in the rubber composition. Considering the aromatic process oil, hysteresis loss, and low temperature characteristics in consideration of tensile strength and abrasion resistance Naphthenic or paraffinic process oils may be used. The process oil may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. Within this range, the process oil has an effect of preventing the tensile strength and the low heat build-up (low fuel consumption) of the vulcanized rubber from being lowered.

Examples of the antioxidant include N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- , 2,4-trimethyl-1,2-dihydroquinoline, or high-temperature condensates of diphenylamine and acetone, and may be used in an amount of 0.1 part by weight 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 kneading the rubber composition using a kneader such as Banbury mixer, roll, internal mixer or the like by the compounding formulation, This excellent rubber composition can be obtained.

Accordingly, the rubber composition can be applied to various members such as tire tread, under-tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, pancake fur, or bead coated rubber, vibration proof rubber, belt conveyor, And can be particularly useful for the production of tire treads usable in a low temperature environment.

In addition, the present invention provides a tire comprising the rubber composition. The tire may be made using the rubber composition. Further, the tire may be one comprising a tire or a tire tread.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example

Examples 1 to 3 and Comparative Example 1

The rubber compositions according to Examples and Comparative Examples were prepared according to the contents (parts by weight) shown in Table 1 below. The raw materials in Table 1 are each parts by weight based on 100 parts by weight of raw rubber.

Specifically, the following rubber compositions were kneaded through a first stage kneading and a second stage kneading. In the first stage kneading, a raw rubber, a filler, an organic silane coupling agent, a process oil (softening agent), a zincifying agent and stearic acid were kneaded using a Banbury mixer equipped with a temperature control device. At this time, the temperature of the kneader was controlled at 150 占 폚, and a primary blend was obtained at an outlet temperature of 150 占 폚 to 180 占 폚. In the second-stage kneading, the above-mentioned first blend was cooled to room temperature, and then a primary blend, a vulcanizing agent (sulfur) and a vulcanization accelerator were added to the kneader, followed by mixing at a temperature of 110 DEG C or lower to obtain a second blend. Thereafter, the rubber composition was prepared by curing at 160 DEG C for 20 minutes.

division Rubber composition Example 1 Example 2 Example 3 Comparative Example 1 First stage kneading Raw rubber SSBR 1 ¹⁾ 80 30 50 - SSBR 2 ²⁾ 20 30 20 30 NR ³⁾ - - 30 30 BR ⁴⁾ - 40 - 40 Silica 90 90 90 90 Coupling agent 7.2 7.2 7.2 7.2 Process oil (softener) 42.49 38.73 42.49 38.74 Zincizing agent (zinc oxide) 3 3 3 3 Stearic acid One One One One Second stage kneading Vulcanizing agent (sulfur) 1.5 1.5 1.5 1.5 Vulcanization accelerator 1 ⁵⁾ 1.5 1.5 1.5 1.5 Vulcanization accelerator 2 ⁶⁾ 2 2 2 2

1) SSBR 1: Polymerized by solution polymerization and having a number average molecular weight (Mn) of 336,000 g / mol, a weight average molecular weight (Mw) of 661,000 g / mol, a molecular weight distribution (MWD) of 1.97, a styrene content of 18% A styrene-butadiene rubber modified with a nitrogen atom-containing alkoxysilane-based modifier having a content of 12.9% by weight, a Mooney viscosity of 85, and a glass transition temperature of -76 캜.

2) SSBR 2: Buna VSL 24382-HM manufactured by Lanxess

3) NR: natural rubber

4) BR: Polybutadiene

5) Vulcanization accelerator 1: CZ (N-cyclohexyl-2-benzothiazylsulfenamide)

6) Vulcanization accelerator 2: DPG (diphenylguanidine)

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the SSBR 1 were measured by GPC (Gel Permeation Chromatography) analysis. The molecular weight distribution (MWD, Mw / Mn) . Specifically, the GPC was a combination of two columns of PLgel Olexis (Polymer Laboratories) columns and a column of PLgel mixed-C (Polymer Laboratories). All of the new columns were of mixed bed type, The GPC reference material (polystyrene) was used for molecular weight calculation.

The styrene content and the vinyl content in butadiene of the SSBR 1 were measured by NMR.

The Mooney viscosity (MV, (ML1 + 4, @ 100 ° C) MU) of the SSBR 1 was measured using MV-2000 (ALPHA Technologies) at 100 ° C. using Rotor Speed 2 ± 0.02 rpm, Large Rotorfmf The samples were allowed to stand at room temperature (23 ± 3 ℃) for more than 30 minutes, 27 ± 3 g were collected, filled in the die cavity, and platen was operated for 4 minutes after 1 minute preheating.

Experimental Example

The Mooney viscosity (ML1 + 4, @ 125 ° C), hardness, tensile, abrasion resistance and viscoelastic properties of the rubber composition prepared in Examples and Comparative Examples and the tires made therefrom were measured The results are shown in Table 2 below.

(1) Mooney viscosity (ML1 + 4, @ 125 ° C)

During the preparation of the rubber composition, the Mooney viscosity of the primary blend was determined according to ASTM D1646. The Mooney viscosity is a value indicating the viscosity of the unvulcanized rubber. The lower the numerical value, the better the workability of the unvulcanized rubber.

(2) Hardness

The hardness of the rubber composition was measured according to DIN 53505. The hardness indicates the adjustment stability, and the higher the hardness, the better the adjustment stability.

(3) Tensile properties

The tensile strength, modulus and elongation were measured at a tensile rate of 50 cm / min at room temperature using an Instron Universal Test Machine 4204 tensile tester according to the tensile test method of ASTM 412. The 300% modulus, tensile strength and elongation, indicate that the higher the value, the better the tensile properties. The elongation percentage means elongation at break, and the strain value until the test piece is broken in the tensile tester is expressed in%.

(4) Wear resistance

The wear resistance of the rubber composition was measured by using a DIN abrasion tester to move the rubber specimen in a direction perpendicular to the rotation direction of the drum by applying a load of 10 N to a rotary drum attached with a safety walk, Was compared with the wear amount of a standard sample and indexed. The rotational speed of the drum is 40 rpm, and the total travel distance of the specimen at the completion of the test is 40 m.

(5) Viscoelastic properties

E ', E "and tan δ were measured by varying the strain at a frequency of 10 Hz and at each measurement temperature (-70 ° C to 70 ° C) in a TENSION mode using a dynamic mechanical analyzer (GABO DMTS). The payne effect is expressed as the difference between the minimum value and the maximum value at 0.07% to 40% of the strain. The higher the temperature of 0 ° C tan δ, the better the wet road surface resistance. The lower the tan δ of 60 ° C, the lower the hysteresis loss and the better the rolling resistance. Further, it is possible to confirm the snow performance of the tire from the E 'value near -30 to -20 out of the E' values obtained at this time.

division Example 1 Example 2 Example 3 Comparative Example 1 Mooney viscosity (@ 125 ℃) 91 80 66 78 Hardness (Shore A) 65 64 65 64 300% modulus (kgfcm ² ) 128 90 110 78 Elongation (%) 415 499 420 483 Wear resistance (index) 106 105 99 100 -30 < 0 > C E '(Mpa) 76.19 57.80 87.78 68.48 0 C tan δ 0.334 0.370 0.342 0.370 60 캜 tan δ 0.148 0.182 0.166 0.219

As shown in Table 2, it was confirmed that Examples 1 to 3 produced according to the present invention had excellent rolling resistance and tensile properties without deteriorating snow performance and wet road surface resistance. Particularly, in the case of Example 1, it was confirmed that wear resistance and snow performance, as well as tensile properties, rotation resistance, wear resistance and snow performance were remarkably improved while maintaining wet road surface resistance at the same level without adding natural rubber and polybutadiene in the raw rubber.

In comparison with Comparative Example 1, in the case of Example 2 in which the same amount of SSBR 1 satisfying the characteristics of the first conjugated diene copolymer according to the present invention was added to the raw rubber instead of natural rubber, the wet road surface resistance was equivalent Rotation resistance and abrasion resistance were improved, while Example 3 in which SSBR 1 was added instead of polybutadiene in the raw rubber improved tensile properties and rotational resistance, and significantly improved snow performance and workability And it was confirmed that it was improved.

From the above results, it was confirmed that the rolling resistance and the tensile properties were remarkably improved without deteriorating the snow performance and the wet road surface resistance of the tire including the rubber composition of the present invention.

Claims (14)

A first conjugated diene-based copolymer and a second conjugated diene-based copolymer,
Wherein the first conjugated diene-based copolymer comprises a first conjugated diene-based monomer-derived repeating unit and a first aromatic vinyl monomer-containing repeating unit, the first conjugated diene-based copolymer comprising a functional group derived from a denaturant at one end, Wherein the content of the first conjugated diene monomer-derived repeating unit constituting the vinyl bond in the unit is 20% by weight or less based on the first conjugated diene-based copolymer, and the content of the first aromatic vinyl monomer- Is not less than 0% by weight and not more than 20% by weight based on the copolymer, and has a glass transition temperature (Tg)
Wherein the second conjugated diene-based copolymer comprises a repeating unit derived from a second conjugated diene-based monomer and a repeating unit derived from a second aromatic vinyl monomer. The method according to claim 1,
The content of the first conjugated dienic monomer-derived repeating unit constituting the vinyl bond in the first conjugated diene-based monomer repeating unit is 5 to 20% by weight based on the first conjugated diene-based copolymer, And the content of the first aromatic vinyl monomer-derived repeating unit is 5 wt% to 20 wt% with respect to the first conjugated diene-based copolymer, and the glass transition temperature (Tg) is -90 ° C to -50 ° C / RTI > The method according to claim 1,
Wherein the first conjugated diene-based copolymer has a Mooney viscosity of 10 to 180. The method according to claim 1,
The first conjugated diene-based copolymer has a number average molecular weight (Mn) of 10,000 g / mol to 2,000,000 g / mol, a weight average molecular weight (Mw) of 10,000 g / mol to 3,000,000 g / mol, Is from 1 to 5. The method according to claim 1,
Wherein the modifier is an alkoxysilane-based modifier. The method according to claim 1,
Wherein the first conjugated diene-based copolymer is represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
R a _1, R _2, and R ₅ are each independently an alkylene group having 1 to _{10, R 3, R 4,} R 6 and R ₇ are independently an alkyl group having 1 to 10, R ₈ is hydrogen or A and c are each independently 0, 1 or 2, b and d are each independently 1, 2 or 3, and R < 3 > is an alkyl group having 1 to 10 carbon atoms, a + b and c + d are each independently 1, 2, or 3, and A is

or

And R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. The method according to claim 1,
The content of the second conjugated diene monomer-derived repeating unit constituting the vinyl bond in the second conjugated diene-based monomer repeating unit is 30% by weight or less based on the second conjugated diene-based copolymer , And the content of the second aromatic vinyl monomer-derived repeating unit is 30 to 60% by weight based on the second conjugated diene-based copolymer. The method according to claim 1,
And the second conjugated diene-based copolymer has a glass transition temperature (Tg) of -40 캜 to -10 캜. The method according to claim 1,
Wherein the second conjugated diene-based copolymer has a Mooney viscosity of from 10 to 180. The method according to claim 1,
Wherein the raw material rubber further comprises at least one rubber component selected from the group consisting of natural rubber and synthetic rubber. The method according to claim 1,
Based on 100 parts by weight of the raw material rubber, 30 parts by weight to 80 parts by weight of the first conjugated diene-based copolymer; 20 to 70 parts by weight of a second conjugated diene-based copolymer; And 0 to 50 parts by weight of at least one rubber component selected from the group consisting of natural rubber and synthetic rubber. The method according to claim 1,
Wherein the rubber composition comprises 0.1 to 200 parts by weight of an inorganic filler based on 100 parts by weight of the raw rubber. 13. The method of claim 12,
Wherein the inorganic filler is at least one selected from the group consisting of wet silica, dry silica, calcium silicate, aluminum silicate and colloidal silica. A tire comprising the rubber composition according to any one of claims 1 to 13.