KR102058693B1 - Rubber composition and tire produced by the same - Google Patents

Abstract

The present invention relates to a rubber composition having improved fuel economy, a rubber molded article and a tire produced therefrom. Accordingly, the rubber composition may include a silaneamine-based additive to improve the binding property between the filler and the rubber component, and thus, a rubber molded article, such as a tire, manufactured from the rubber composition may have excellent tensile properties as well as rolling resistance properties. It can be improved, and thus fuel efficiency can be excellent.

Description

Rubber composition and tire produced by the same}

The present invention relates to rubber compositions with improved rolling resistance properties, rubber molded articles and tires produced therefrom.

Recently, in accordance with the demand for low fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers with low rolling resistance, excellent wear resistance and tensile properties, and adjustment stability represented by wet skid resistance.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As an evaluation index of the vulcanized rubber, a repulsive elasticity of 50 ° C. to 80 ° C., tan δ, Goodrich heating and the like are used. That is, a rubber material having a high rebound elasticity at the above temperature or a small tan δ or good rich heat generation is preferable.

In general, a method of blending an inorganic filler such as silica or carbon black with a rubbery polymer is used to obtain a rubber material having a low heat generation. However, since the interaction between the rubbery polymer and the inorganic filler is very weak, there is a problem in that, among the inorganic fillers, silica is particularly difficult to disperse in the rubber composition and has a large torque during kneading.

For this problem, a method of increasing the affinity with silica by using a modified polymer for silica containing a silane `coupling agent or a functional group which interacts with silica has been proposed. In one example, a modified conjugated diene-based polymer wherein a modified conjugated diene-based polymer obtained by modifying the polymerization active terminal of the conjugated diene-based polymer obtained by anionic polymerization of a conjugated diene monomer using an organolithium compound as a polymerization initiator contains a functional group that interacts with a filler. Proposed.

However, in the rubber composition using the modified conjugated diene-based polymer produced by the above method, when the reinforcing filler is blended, low heat generation can be ensured, but wear resistance is greatly reduced.

Therefore, there is a need for the development of a rubber composition in which the balance between the tensile properties and the abrasion resistance is improved, along with the improved fuel efficiency characteristics due to the lowering of the exothermicity caused by the reduction of rolling resistance in the tire.

JP 2014-047327 A

The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a rubber composition capable of providing a molded article, such as a tire having excellent rolling resistance characteristics.

Another object of the present invention is to provide a rubber molded article prepared from the rubber composition.

Another object of the present invention is to provide a tire made from the rubber composition.

In order to solve the above problems, the present invention 100 parts by weight of the conjugated diene polymer; And it provides a rubber composition comprising a silane amine-based additive 0.05 parts by weight to 1.0 parts by weight, wherein the silane amine-based additive is any one or more of the compounds represented by the following formula (1) and (2).

[Formula 1]

[Formula 2]

In Chemical Formula 1 or Chemical Formula 2,

R ₁ to R ₆ is independently of each other a hydrogen atom or alkyl having 1 to 24 carbon atoms.

The present invention also provides a rubber molded article prepared from the rubber composition.

In addition, the present invention provides a tire produced from the rubber composition.

The rubber composition according to the present invention may improve the binding property of the filler, such as carbon black and the conjugated diene-based polymer, which is a rubber component, by including a silaneamine-based additive in a specific content, and may improve processability.

In addition, the rubber molded article according to the present invention, for example, the tire is manufactured from the rubber composition, as well as excellent in the tensile properties and can improve the rolling resistance properties, it can be excellent in fuel economy.

Thus, the rubber composition according to the invention and a rubber molded article such as a tire made therefrom can be easily applied to an industry in need thereof, such as the automobile or tire industry.

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

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The present invention provides a rubber composition capable of providing a tire having excellent fuel efficiency.

The rubber composition according to an embodiment of the present invention is 100 parts by weight of the conjugated diene polymer; And 0.05 to 1.0 parts by weight of the silane amine-based additive, characterized in that the silane amine-based additive is any one or more of the compounds represented by the following formula (1) and (2).

[Formula 1]

[Formula 2]

In Chemical Formula 1 or Chemical Formula 2,

R ₁ to R ₆ are each independently a hydrogen atom or alkyl having 1 to 24 carbon atoms.

The silaneamine-based additive serves to improve the binding property between the filler and the rubber component, specifically, the carbon black and the conjugated diene-based polymer, and is included in the rubber composition in an amount of 0.05 to 1.0 parts by weight based on 100 parts by weight of the conjugated diene-based polymer. It may be. If the silanamine additive is included in an amount of less than 0.05 parts by weight, the effect of improving the binding property between the filler and the high component may be insignificant, and as a result, it may be difficult to expect the effect of improving the fuel efficiency of the molded article, for example, a tire. When included in excess of the weight part, the torque is greatly reduced during processing, and the workability may be reduced, and a blooming phenomenon may occur in the manufactured molded product, and thus, the surface of the molded product may be slippery.

Specifically, in Chemical Formula 1, R ₁ may be alkyl having 1 to 6 carbon atoms, R ₂ may be alkyl having 1 to 20 carbon atoms, and R ₃ may be a hydrogen atom.

In addition, in Formula 2, R ₄ may be alkyl having 1 to 20 carbon atoms, and R ₅ and R ₆ may be independently alkyl having 1 to 6 carbon atoms.

More specifically, the silaneamine-based additive may be a compound represented by the following formula (3).

[Formula 3]

In Chemical Formula 3, TMS is trimethylsilane.

In addition, the conjugated diene polymer may be a lanthanum rare earth element catalyzed conjugated diene polymer.

Here, the lanthanum-based rare earth element catalyzed conjugated diene polymer represents a conjugated diene polymer prepared using a lanthanum series rare earth element catalyst, and the conjugated diene polymer is an organic solvent using a lanthanum series rare earth element catalyst. It may be prepared by polymerizing a conjugated diene monomer in the. In this case, the lanthanum-based rare earth element catalyst may represent a catalyst or catalyst composition including a lanthanum-based rare earth element-containing compound.

The conjugated diene-based polymer may be a butadiene homopolymer such as polybutadiene or a butadiene copolymer such as butadiene-isoprene copolymer.

Specifically, the conjugated diene-based polymer contains 80 to 100% by weight of 1,3-butadiene monomer-derived unit and 20% by weight or less of other butadiene-based monomer-derived unit copolymerizable with 1,3-butadiene. It may be. When the content of the 1,3-butadiene monomer-derived unit in the conjugated diene-based polymer is less than 80% by weight, the content of 1,4-cis bond in the polymer may be lowered. In this case, the 1,3-butadiene monomer may be 1,3-butadiene or derivatives thereof such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene or 2-ethyl-1,3-butadiene. . In addition, the other butadiene monomer copolymerizable with 1,3-butadiene is 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl- 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, and the like, and one or two or more of these compounds may be used.

In addition, the conjugated diene-based polymer may have a narrow molecular weight distribution (Mw / Mn) of 2.5 to 3.5. When the molecular weight distribution of the conjugated diene-based polymer is more than 3.5 or less than 2.5, there is a fear that the tensile properties and viscoelasticity of the rubber composition including the same decrease. Specifically, in consideration of the remarkable properties of the tensile properties and viscoelasticity improvement effect according to the molecular weight distribution control, the molecular weight distribution of the conjugated diene-based polymer may be 3.0 to 3.2.

Here, the molecular weight distribution can be calculated from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). In this case, the number average molecular weight (Mn) is a common average of the individual polymer molecular weights calculated by dividing the molecular weight of n polymer molecules by calculating the sum of these molecular weights and dividing by n, and the weight average molecular weight (Mw) is The molecular weight distribution of the polymer composition is shown. All molecular weight averages may be expressed in grams per mole (g / mol), and the weight average molecular weight and the number average molecular weight may be polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), respectively.

In addition, the conjugated diene-based polymer according to an embodiment of the present invention satisfies the above-described molecular weight distribution conditions, the weight average molecular weight (Mw) is 5 × 10 ⁵ g / mol to 1.2 × 10 ⁶ g / mol, specifically And from 9 × 10 ⁵ g / mol to 1.0 × 10 ⁶ g / mol. In addition, the conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 1.5 × 10 ⁵ g / mol to 3.5 × 10 ⁵ g / mol, specifically 3.0 × 10 ⁵ g / mol to 3.2 × 10 ⁵ g / mol. When the weight average molecular weight (Mw) of the conjugated diene-based polymer is less than 5 × 10 ⁵ g / mol or the number average molecular weight (Mn) is less than 1.5 × 10 ⁵ g / mol, the tensile properties of the rubber composition comprising the same may be reduced There is concern. In addition, when the weight average molecular weight (Mw) exceeds 1.2 × 10 ⁶ g / mol, or the number average molecular weight (Mn) exceeds 3.5 × 10 ⁵ g / mol, the processability of the conjugated diene-based polymer of the rubber composition Workability deteriorates, kneading becomes difficult, and it may be difficult to fully improve the physical properties of the rubber composition.

Accordingly, the conjugated diene-based polymer according to an embodiment of the present invention simultaneously satisfies the weight average molecular weight (Mw) and the number average molecular weight conditions together with the above molecular weight distribution so that the tensile properties, viscoelasticity and processability of the rubber composition comprising the same. Balance can be improved well.

In addition, the conjugated diene-based polymer according to an embodiment of the present invention may have a Mooney viscosity (MV) of 100 to 50, specifically 60 to 70. When it has the Mooney viscosity of the above-mentioned range, it can exhibit more excellent workability.

Here, the Mooney viscosity can be measured using a Mooney viscometer, for example, Rotor Speed 2 ± 0.02 rpm, Large Rotor at 100 ℃ in Alpha MV2000. At this time, the sample used can be measured by leaving the plate at the room temperature (23 ℃ ± 3) for more than 30 minutes, taking 27 ± 3 g and filling the inside of the die cavity (Platen).

In addition, the lanthanum-based rare earth element-containing catalyst may include a lanthanum-based rare earth element-containing compound, an alkylating agent, and a halogen compound.

The lanthanum-based rare earth element-containing compound may be a compound including any one or two or more elements of the rare earth elements of atomic numbers 57 to 71 of the periodic table such as neodymium, praseodymium, cerium, lanthanum or gadolinium, and specifically, includes neodymium It may be a compound.

In addition, the lanthanum-based rare earth element-containing compound may be a salt soluble in a hydrocarbon solvent such as carboxylate, alkoxide, β-diketone complex, phosphate or phosphite of lanthanum-based rare earth element, and specifically, may be neodymium-containing carboxylate. . Here, the hydrocarbon solvent is a saturated aliphatic hydrocarbon having 4 to 10 carbon atoms such as butane, pentane, hexane, heptane; Saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane; Monoolefins such as 1-butene and 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene; Or halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, and chlorotoluene.

More specifically, the lanthanum-based rare earth element compound may be a neodymium compound of Formula 4 below.

[Formula 4]

In Chemical Formula 4,

R _a to R _c are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.

Specifically, in Formula 4, R _a may be a linear or branched alkyl group having 6 to 12 carbon atoms, and R _b and R _c may be independently a linear or branched alkyl group having 2 to 8 carbon atoms.

More specifically, the neodymium compound is Nd (neodecanoate) ₃ , Nd (2-ethylhexanoate) ₃ , Nd (2,2-diethyl decanoate) ₃ , Nd (2,2- Dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd (2-ethyl-2-propyl decanoate) ₃ , Nd (2-ethyl-2-butyl decanoate) ₃ , Nd (2-ethyl-2-hexyl decanoate) ₃ , Nd (2-propyl -2-butyl decanoate) ₃ , Nd (2-propyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl Decanoate) ₃ , Nd (2-hexyl-2-octyl decanoate) ₃ , Nd (2-t-butyl decanoate) ₃ , Nd (2,2-diethyl octanoate) ₃ , Nd ( 2,2-dipropyl octanoate) ₃ , Nd (2,2-dibutyl octanoate) ₃ , Nd (2,2-dihexyl octanoate) ₃ , Nd (2-ethyl-2-propyl octa Noate) ₃ , Nd (2-ethyl-2-hexyl octanoe Ite) ₃ , Nd (2,2-diethyl nonanoate) ₃ , Nd (2,2-dipropyl nonanoate) ₃ , Nd (2,2-dibutyl nonanoate) ₃ , Nd (2, 2-dihexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ can be one or more selected from the group consisting of. .

 As such, the neodymium compound of Formula 4 includes a carboxylate ligand containing an alkyl group having various lengths of 2 or more carbon atoms at the α position, thereby inducing steric changes around the neodymium center metal to block entanglement between compounds. As a result, oligomerization can be suppressed. In addition, the neodymium compound may have a high solubility in a polymerization solvent and a decrease in the ratio of neodymium located in a central portion having difficulty in converting to a catalytically active species may result in a high conversion rate to the catalytically active species.

In addition, the solubility of the lanthanum-based rare earth element-containing compound may be about 4 g or more per 6 g of nonpolar solvent at room temperature (25 ° C.). In the present invention, the solubility of the neodymium compound may mean the degree of clear dissolution without turbidity.

In addition, the alkylating agent may serve as a cocatalyst as an organometallic compound capable of transferring a hydrocarbyl group to another metal. The alkylating agent may be used without particular limitation as long as it is generally used as an alkylating agent in the preparation of the diene-based polymer. For example, the alkylating agent is soluble in a nonpolar solvent, such as an organoaluminum compound, an organic magnesium compound, or an organolithium compound, and the like. It may be an organometallic compound containing a bond.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and tripentylaluminum, Alkyl aluminum, such as trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; 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 Lide, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl- n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum Hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride or benzyl-n-octylaluminum hydrogen Dihydrocarbyl aluminum hydride; Hydrocarbyl aluminum such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, or n-octylaluminum dihydride Dihydride and the like. In addition, examples of the organic magnesium compound include alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or dibenzyl magnesium, and the like. In addition, examples of the organolithium compound include alkyllithium compounds such as n-butyllithium and the like.

As the alkylating agent, any one or a mixture of two or more of the above-described organoaluminum compounds, organo magnesium compounds, and organolithium compounds may be used, and more specifically, diisobutylaluminum hydride, which may serve as a molecular weight regulator in a polymerization reaction. (DIBAH) can be used.

In addition, the alkylating agent may be used in 1 to 100 mole ratio, specifically 3 to 20 mole ratio with respect to 1 mole of the lanthanum-based rare earth element-containing compound.

In addition, the halogen compound may be used without particular limitation as long as it is used as a halogenating agent in the preparation of the conjugated diene-based polymer, for example, the halogen compound may be used in the aluminum halide compound or the aluminum halogen compound in the form of boron, silicon, tin or titanium. It may be an inorganic halogen compound substituted with an organic halogen compound such as a t-alkylhalogen compound (alkyl having 4 to 20 carbon atoms).

Specifically, the inorganic halogen compound is dimethylaluminum chloride, diethylaluminum chloride (DEAC), dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride , Methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, Methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium broma De, benzyl magnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-t-butyltin dichloride, di-t-butyltin dibromide, dibutyltin dichloride, dibutyl Tin dibromide, tributyltin chloride or tributyltin bromide and the like.

In addition, the organohalogen compounds include t-butyl chloride, t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, triphenylmethyl chloride, Triphenylmethylbromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, Methyl chloroformate, methyl bromoformate, etc. are mentioned.

As the halogen compound, any one or a mixture of two or more of the inorganic halogen compound and the organic halogen compound may be used, and the halogen compound may be 1 mol to 20 mol, specifically 1 mol based on 1 mol of the lanthanum-based rare earth element-containing compound. Can be used in 1 mol to 5 mol, more specifically in 2 mol to 3 mol.

The lanthanum-based rare earth element-containing catalyst may further include a diene monomer. In this case, the diene monomer is premixed with other components of the catalyst as one component of the catalyst and used in the form of a preforming catalyst, thereby improving the activity of the catalyst as well as stabilizing the conjugated diene polymer produced. Can be.

The diene monomer is not particularly limited, but 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 the like, these Any one or two or more of them may be used in combination. In this case, the diene monomer may be used in an amount within a total amount of the monomer used in the conjugated diene-based polymer production, specifically, 1 mol to 100 molar ratio with respect to one lanthanum-based rare earth element-containing compound More specifically, it may be used in 10 to 50 molar ratio, even more specifically 20 to 40 molar ratio.

The lanthanum-based rare earth element-containing catalyst may be prepared by sequentially adding and mixing a lanthanum-based rare earth element-containing compound, an alkylating agent, a halogen compound and optionally a diene monomer in an organic solvent. In this case, the organic solvent may be a nonpolar solvent that is not reactive with the components constituting the catalyst. Specifically, the organic solvent may be an aliphatic hydrocarbon solvent such as pentane, hexane, isopentane, heptane, octane, isooctane, etc .; Cycloaliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like; Or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene, or the like, and one or a mixture of two or more thereof may be used.

On the other hand, the conjugated diene-based polymer may be prepared by introducing a monomer in the presence of the lanthanum-based rare earth element-containing catalyst in the organic solvent, for example, by polymerizing the monomer forming the conjugated diene-based polymer. In this case, the monomer constituting the conjugated diene-based polymer may be a 1,3-butadiene-based monomer, or a 1,3-butadiene-based monomer and a butadiene-based monomer copolymerizable therewith, the specific monomer may be as described above.

The organic solvent used to prepare the conjugated diene-based polymer may be as described above, the amount of the organic solvent is not particularly limited, but for example, the concentration of the monomer in the organic solvent is 3% to 80% by weight It may be used in an amount of%.

In addition, the polymerization may be carried out by radical polymerization, and may be, for example, bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization. Specifically, it may be solution polymerization, and the polymerization may be performed by any of batch and continuous methods.

On the other hand, reaction terminators such as polyoxyethylene glycol phosphate during the polymerization; Or additives such as antioxidants such as 2,6-di-t-butylparacresol. In addition, additives such as chelating agents, dispersing agents, pH adjusting agents, deoxygenating agents or oxygen trapping agents may be further used as desired so that solution polymerization may be easily performed.

In addition, the polymerization may be carried out by polymerizing at a temperature of 20 ℃ to 200 ℃, specifically 20 ℃ to 100 ℃ 15 minutes to 3 hours, specifically 30 minutes to 2 hours. In this case, when the temperature exceeds 200 ° C. during the polymerization reaction, it may be difficult to sufficiently control the polymerization reaction, and the cis-1,4 bond content in the resulting conjugated diene-based polymer may be lowered. In addition, when the temperature is lower than 20 ℃ in the polymerization reaction may decrease the polymerization reaction rate and efficiency.

In addition, in order not to deactivate the lanthanum-based rare earth element-containing catalyst and the polymer formed during the polymerization, it may be to prevent the incorporation of compounds having deactivation effects such as oxygen, water, and carbon dioxide into the polymerization reaction system.

The rubber composition may further include 1 part by weight to 900 parts by weight of the rubber component based on 100 parts by weight of the conjugated diene polymer.

The herb rubber component may be natural rubber or synthetic rubber, and specifically, the rubber component may 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 obtained by modifying or refining 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, butyl rubber, halogenated butyl rubber and the like, and may be any one or a mixture of two or more thereof. .

The rubber composition may further include 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the conjugated diene polymer.

The filler may be a silica-based filler, a carbon black filler or a combination thereof.

In the case where the filler is a silica-based filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.

Specific examples of the silane coupling agent 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 tetrasul Feed, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate Monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

In addition, the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus may further include a vulcanizing agent.

The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the conjugated diene polymer. When included in the content range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain a low fuel consumption.

In addition, the rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white , Stearic acid, thermosetting resin, or thermoplastic resin may be further included.

The said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the conjugated diene polymer.

In addition, the process oil acts as a softener in the rubber composition, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance. And naphthenic or paraffinic process oils may be used when considering low temperature properties. The process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the conjugated diene-based polymer, when included in the content, it is possible to prevent the degradation of tensile strength, low heat generation (low fuel efficiency) of the vulcanized rubber. .

In addition, as the anti-aging agent, specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6- Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone. The anti-aging agent may be used in an amount of 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the conjugated diene polymer.

The rubber composition according to an embodiment of the present invention may be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the above formulation, and also has a rolling resistance characteristic and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.

In addition, the present invention provides a rubber molded article and a tire manufactured from the rubber composition.

The rubber molded article according to an embodiment of the present invention may include various industrial rubber products such as dustproof rubber, a belt conveyor, a hose, and the tire is a tire tread, an under tread, a side wall, a carcass coated rubber, a belt. It may include each member of the tire such as coated rubber, bead filler, pancreaper, or bead coated rubber.

The rubber molded article and the tire according to the exemplary embodiment of the present invention may be manufactured from the rubber composition, thereby improving rolling resistance and excellent rolling characteristics.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following Examples and Experimental Examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

Example

60 parts by weight of carbon black (N330), 15 parts by weight of tetrakis (dimethylamino) ethylene (TDAE), 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, and 100 parts by weight of conjugated diene polymer (GND60, LG Chemical) A rubber composition was prepared by mixing 0.2 parts by weight of N-octadecyltrimethylsilaneamine.

To the rubber composition 180.2 parts by weight, 1.5 parts by weight of sulfur powder and 0.9 parts by weight of N-t-butyl-2-benzothiazyl sulfonamide (TBBS) were added and mixed to prepare a rubber vulcanized mixture. At this time, the rubber vulcanized mixture was prepared according to ASTM D3189 using Farrel banbury mixer BR1600. The rubber vulcanized mixture was vulcanized at 160 ° C. (t90 × 1.3) minutes in accordance with ASTM D412 C tyepe to prepare a vulcanized rubber composition.

Comparative example

A rubber composition and a vulcanized rubber composition were prepared in the same manner as in the above example, except that no silaneamine additive was used.

Experimental Example

The Mooney viscosity, tensile property, and viscoelasticity of each rubber composition and the vulcanized rubber composition prepared in Examples and Comparative Examples were measured. The results are shown in Table 1 below.

1) Mooney viscosity

Mooney Viscosity (MV, (ML1 + 4, @ 100) (MU): Alpha MV2000 was used to measure Rotor Speed 2 ± 0.02rpm, Large Rotor at 100 ℃, and the sample used was room temperature (23 ℃ ±). After leaving for 30 minutes or longer in 3), 27 ± 3 g was taken, filled into a die cavity, and measured by operating a platen, and the Mooney viscosity was measured for each of the raw polymer (each conjugated diene-based polymer) and the rubber composition.

2) tensile properties

The tensile strength (tensile strength, kg · f / cm 2), 300% modulus (300% modulus, kg · f / cm 2), elongation (elongation,%) is tensile in accordance with ASTM D412 by using the respective vulcanized rubber compositions Strength, modulus at 300% elongation and elongation at break at break were measured.

3) viscoelastic

Using each vulcanized rubber composition, the viscoelastic modulus (tan δ) at 60 was measured at a frequency of 10 Hz and a strain of 3%.

division Example Comparative example Mooney viscosity
(ML1 + 4, @ 100 ° C) (MU) polymer 66.5 66.5 Rubber composition 100 86.5 Vulcanizing Composition 86 80.1 Tensile Properties
(@ 23 ℃) 300% modulus (kgf / cm ² ) 101 95 300% modulus index 99 93 Tensile strength (kgf / cm ² ) 194 196 Tensile strength index 95 96 Elongation (%) 490 525 Elongation index 96 103 Viscoelastic tan δ @ 60 ℃ (index) 0.145 (110) 0.165 (96)

As shown in Table 1, the vulcanized rubber composition of the embodiment according to an embodiment of the present invention shows a reduction in tan δ at 60 ° C. while showing similar or somewhat improved tensile properties compared to the vulcanized rubber composition of the comparative example. Confirmed. This is a result indicating that the rubber composition according to the present invention may have excellent rolling resistance characteristics, and also indicates that fuel efficiency characteristics can be improved.

Claims (14)

100 parts by weight of the conjugated diene polymer; And 0.05 to 1.0 parts by weight of silanamine additives,
Rubber composition wherein the silanamine-based additive is any one or more of the compounds represented by the following formula (1) and (2):
[Formula 1]

[Formula 2]

In Chemical Formula 1,
R ₁ is alkyl having 1 to 6 carbon atoms,
R ₂ is alkyl having 1 to 20 carbon atoms,
R ₃ is a hydrogen atom,
In Chemical Formula 2,
R ₄ is alkyl having 1 to 20 carbon atoms,
R ₅ and R ₆ independently of each other are alkyl having 1 to 6 carbons.
delete delete The method according to claim 1,
The silanamine-based additive is a rubber composition that is a compound represented by the formula (3):
[Formula 3]

In Chemical Formula 3,
TMS is trimethylsilane.
The method according to claim 1,
The conjugated diene-based polymer is a lanthanum-based rare earth element catalyzed conjugated diene-based polymer.
The method according to claim 5,
The lanthanum-based rare earth element catalyst is a rubber composition comprising a lanthanum-based element-containing compound, an alkylating agent and a halogen compound.
The method according to claim 5,
The lanthanum-based rare earth element compound is a rubber composition comprising a neodymium compound of formula (4):
[Formula 4]

In Chemical Formula 4,
R _a to R _c are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.
The method according to claim 7,
In Formula 4, R _a is a linear or branched alkyl group having 6 to 12 carbon atoms,
R _b and R _c are each independently a linear or branched alkyl group having 2 to 8 carbon atoms.
The method according to claim 1,
The rubber composition further comprises 1 part by weight to 900 parts by weight of the rubber component with respect to 100 parts by weight of the conjugated diene-based polymer.
The method according to claim 1,
The rubber composition further comprises 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the conjugated diene polymer.
The method according to claim 10,
The filler is a silica-based filler, a carbon black filler or a combination thereof.
The method according to claim 1,
The rubber composition is sulfur crosslinkable.
Rubber molded article made from the rubber composition of claim 1
A tire made from the rubber composition of claim 1.