KR20200134588A - Rubber composition for a tire and a method for manufacturing the same - Google Patents

Abstract

An embodiment of the present invention provides: a rubber composition for a tire which comprises an emulsion-polymerized copolymer including an aromatic vinyl monomer, a conjugated diene-based monomer, and a functional monomer, and silica, and is manufactured in a wet master batch method; and a manufacturing method thereof. According to an aspect of the present invention, it is possible to provide the rubber composition for the tire having excellent dispersibility of a filler.

Description

Rubber composition for tire and its manufacturing method {RUBBER COMPOSITION FOR A TIRE AND A METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a rubber composition for a tire and a method for manufacturing the same, and more particularly, to a rubber composition for a tire manufactured by a wet master batch.

In relation to the general purpose rubber, emulsion styrene-butadiene rubber (ESBR), studies to differentiate products by improving its physical, mechanical and dynamic properties have been continuously conducted. In recent years, technologies for rubber products that further include functional monomers in addition to styrene and butadiene, which are the main raw materials for emulsion polymerization styrene-butadiene rubber, are being developed. In particular, this technology is drawing attention in that it can variously control or improve the physical properties of general-purpose rubber through the introduction of functional monomers.

However, the emulsion-polymerized styrene-butadiene rubber containing a functional monomer has a problem in that the gel is excessively formed during the vulcanization process of making a blended rubber using this. Excessive gel formation may rather act as a factor to reduce the product's intrinsic properties, and further has a disadvantage in that it affects the processability of manufacturing the compounded rubber. Therefore, there is a need for a new polymerization technology or process technology capable of suppressing gel formation occurring in the vulcanization process.

The present invention is to solve the problems of the prior art described above, the object of the present invention is to suppress or prevent the formation of rubber gel that occurs when the rubber composition for tires is compounded using a wet master batch method, and the processability of the compounded rubber and It is to improve physical properties.

One aspect of the present invention is an emulsion-polymerized copolymer including an aromatic vinyl monomer, a conjugated diene-based monomer, and a functional monomer; And silica; containing, and prepared by a wet master batch method, provides a rubber composition for a tire.

In one embodiment, the functional monomer may be a (meth)acrylic monomer.

In one embodiment, the (meth)acrylic monomer may include an epoxy group.

In one embodiment, the content of the (meth)acrylic monomer may be 0.1 to 20% by weight based on the total weight of the monomer.

In one embodiment, the silica may be surface-modified with 0.1 to 20% by weight of an organosilane compound represented by Formula 1 based on the total weight of the silica:

[Formula 1]

(RO) ₃ Si(CH ₂ ) _a -(S) _n -(CH ₂ ) _b Si(OR') ₃

In Formula 1, R and R'are each an alkyl group having 1 to 10 carbon atoms, a and b are each independently an integer of 1 to 5, and n is an integer of 1 to 4.

In one embodiment, the composition may further include oil, additives, sulfur and a vulcanization accelerator.

Another aspect of the present invention is, (a) mixing an emulsion-polymerized copolymer including an aromatic vinyl monomer, a conjugated diene-based monomer and a functional monomer at 30 to 90° C. with a slurry comprising silica and water; And (b) coagulating and drying the product of the step (a); containing, it provides a method for producing a rubber composition for a tire.

In one embodiment, the functional monomer may be a (meth)acrylic monomer.

In one embodiment, the (meth)acrylic monomer may include an epoxy group.

In one embodiment, the silica may be surface-modified with 0.1 to 20% by weight of an organosilane compound represented by Formula 1 based on the total weight of the silica:

[Formula 1]

(RO) ₃ Si(CH ₂ ) _a -(S) _n -(CH ₂ ) _b Si(OR') ₃

In Formula 1, R and R'are each an alkyl group having 1 to 10 carbon atoms, a and b are each independently an integer of 1 to 5, and n is an integer of 1 to 4.

In one embodiment, after step (b), (c) mixing the product of step (b) with oil, additives, sulfur, and a vulcanization accelerator; may further include.

According to one aspect of the present invention, it is possible to provide a rubber composition for a tire having excellent dispersibility of the filler.

According to another aspect of the present invention, it is possible to provide a rubber composition for a tire capable of improving the physical properties of a final product by suppressing the formation of rubber gel occurring in the blending process.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

When a range of numerical values is described herein, the value has the precision of significant figures provided according to the standard rules in chemistry for significant figures, unless a specific range thereof is stated otherwise. For example, 10 includes a range of 5.0 to 14.9, and the number 10.0 includes a range of 9.50 to 10.49.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Tire rubber composition

A rubber composition for a tire according to an aspect of the present invention includes an emulsion-polymerized copolymer including an aromatic vinyl monomer, a conjugated diene monomer, and a functional monomer; And silica; and may be prepared by a wet master batch method.

The aromatic vinyl-based monomer may be one of styrene, α-methylstyrene, α-ethylstyrene, paramethylstyrene, vinyltoluene, and a mixture of two or more thereof, but is not limited thereto.

The conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and It may be one of a mixture of two or more of these, but is not limited thereto.

The copolymer may be, for example, a low-temperature emulsion polymerization styrene-butadiene rubber or a high-temperature emulsion polymerization styrene-butadiene rubber. In addition, the copolymer may be coupled or end-modified to improve the interaction with the silica. The copolymer may be emulsion-polymerized including a functional monomer to improve mechanical strength and dynamic properties of the final product.

The functional monomer may be a (meth)acrylic monomer, and the (meth)acrylic monomer may include an epoxy group, but is not limited thereto. The (meth)acrylic monomer may be, for example, glycidyl methacrylate, but is not limited thereto. The content of the (meth)acrylic monomer may be 0.1 to 20% by weight, 2.5 to 17.5% by weight, 5 to 15% by weight, or 7.5 to 12.5% by weight based on the total weight of the monomer, but is not limited thereto. The (meth)acrylic monomer may interact with the silica to improve rolling resistance, abrasion resistance, and mechanical strength of the final product.

The term "masterbatch" used in the present specification is a high concentration of additives dispersed in advance during the manufacture of a rubber composite, and using such a masterbatch method can improve the dispersibility of the additives in the rubber matrix, and thus Accordingly, the physical properties of the rubber composite may be improved.

Masterbatch can be divided into dry masterbatch (DMB) and wet masterbatch (WMB). The dry masterbatch is manufactured by a single process of injecting raw materials into a mixer and then mixing, but when the dry masterbatch method is applied to a high content of silica, dispersibility may be lowered, resulting in a non-uniform silica mixture.

The wet masterbatch is prepared by mixing and agglomeration of raw materials in a slurry, and it can uniformly disperse a high content of silica, thereby improving processability and energy efficiency of the rubber composite.

When a rubber composition is prepared from a copolymer containing a functional monomer using a conventional dry masterbatch method and then a vulcanization process is performed, in addition to the above-described disadvantages, excessive gel is formed, thereby deteriorating the physical properties of the final product. For example, when applied to a tire tread, heat is generated due to excessive gel formation, resulting in a decrease in rolling resistance, expressed as a tanδ value at 60°C, and a decrease in wear resistance and mechanical strength.

On the other hand, the rubber composition for a tire manufactured using a wet master batch method according to an embodiment of the present invention may suppress the above-described gel formation, thereby improving processability and physical properties of the final product. The crosslinking density, which means the amount of gel formation, can be measured by, for example, a Flory-Rhener method or a Mooney-Rivlin method through a swelling method.

The silica may be surface-modified to 0.1 to 20% by weight, 2.5 to 17.5% by weight, 5 to 15% by weight, or 7.5 to 12.5% by weight of an organosilane compound represented by Formula 1 below, based on the total weight of the silica, Not limited to:

[Formula 1]

(RO) ₃ Si(CH ₂ ) _a -(S) _n -(CH ₂ ) _b Si(OR') ₃

In Formula 1, R and R'are each an alkyl group having 1 to 10 carbon atoms, a and b are each independently an integer of 1 to 5, and n is an integer of 1 to 4.

The organosilane compound may be, for example, bis(3-triethoxysilylpropyl)disulfide or bis(3-triethoxysilylpropyl)tetrasulfide, but is not limited thereto.

The rubber composition for a tire may further include oil, additives, sulfur and a vulcanization accelerator. The additive may be, for example, zinc oxide, stearic acid, or a known compound used in the manufacture of a tire tread, such as an antioxidant, but is not limited thereto. In addition, the rubber composition for a tire may further include a known filler such as carbon black, carbon nanotubes, or silica.

Method for producing rubber composition for tire

A method for preparing a rubber composition for a tire according to another aspect of the present invention includes an aromatic vinyl monomer, a conjugated diene monomer, and a functional monomer at 30 to 90°C, 40 to 80°C or 50 to 70°C. Mixing the polymerized copolymer with a slurry comprising silica and water; And (b) coagulating and drying the product of step (a).

The functional monomer may be a (meth)acrylic monomer, and the (meth)acrylic monomer may include an epoxy group.

The types and properties of the aromatic vinyl monomer, conjugated diene monomer, and (meth)acrylic monomer are the same as described above.

The silica may be surface-modified to 0.1 to 20% by weight, 2.5 to 17.5% by weight, 5 to 15% by weight, or 7.5 to 12.5% by weight of an organosilane compound represented by Formula 1 below, based on the total weight of the silica, Not limited to:

[Formula 1]

(RO) ₃ Si(CH ₂ ) _a -(S) _n -(CH ₂ ) _b Si(OR') ₃

In Formula 1, R and R'are each an alkyl group having 1 to 10 carbon atoms, a and b are each independently an integer of 1 to 5, and n is an integer of 1 to 4.

After step (b), (c) mixing the product of step (b) with oil, additives, sulfur, and a vulcanization accelerator; may further include. In addition, in step (c), a known filler such as carbon black, carbon nanotubes, and silica may be further included to control the physical properties of the final product.

In the step (c), for example, 150 to 250 parts by weight of the product of step (b), 25 to 50 parts by weight of the oil, and 1 to 10 parts by weight of additives are mixed at 100 to 200°C according to the mixing order, and then sulfur 1 to 5 parts by weight and 1 to 5 parts by weight of a vulcanization accelerator may be added to perform the vulcanization process, but the present invention is not limited thereto.

Hereinafter, embodiments of the present invention will be described in more detail. However, the following experimental results are only representative of the above examples, and cannot be interpreted as the scope and content of the present invention are reduced or limited by examples. Effects of each of the various embodiments of the present invention not explicitly presented below will be specifically described in the corresponding section.

Manufacturing example

1,600 parts by weight of ion-exchanged water, 260 parts by weight of styrene, 30 parts by weight of glycidyl methacrylate, 10 parts by weight of fatty acid potassium, 20 parts by weight of potassium rosinate, 1.5 parts by weight of potassium chloride Part by weight, 0.4 parts by weight of sodium hydrosulfite, 0.1 parts by weight of ferrosulfate, 0.4 parts by weight of sodium formaldehyde sulfonate, 1 part by weight of n-dodecylmercaptan, and 0.5 parts by weight of ethylenediaminetetraacetic acid were added to the reactor. Replaced with nitrogen. 0.6 parts by weight of methane hydroperoxide was added, and the reactor was replaced with nitrogen again. 710 parts by weight of 1,3-butadiene was added together with nitrogen through the gas line of the reactor. After the conversion rate measured using a moisture analyzer reached 60%, residual butadiene was removed through a vent line, and 1 part by weight of diethylhydroxyamine was added to obtain a copolymer (SBR 1).

Comparative Production Example

1,600 parts by weight of ion-exchanged water, 280 parts by weight of styrene, 10 parts by weight of fatty acid potassium, 20 parts by weight of potassium rosinate, 1.5 parts by weight of potassium chloride, 0.4 parts by weight of sodium hydrosulfite in a 2L stainless steel high pressure reactor under the conditions of 8-10℃ , 0.1 parts by weight of ferrosulfate, 0.4 parts by weight of sodium formaldehyde sulfonate, 1 part by weight of n-dodecylmercaptan and 0.5 parts by weight of ethylenediaminetetraacetic acid were added, and then the reactor was replaced with nitrogen. 0.6 parts by weight of methane hydroperoxide was added, and the reactor was replaced with nitrogen again. 720 parts by weight of 1,3-butadiene was added together with nitrogen through the gas line of the reactor. After the conversion rate measured using a moisture analyzer reached 60%, residual butadiene was removed through a vent line, and 1 part by weight of diethylhydroxyamine was added to obtain a copolymer (SBR 2).

Example

After adding 10% by weight of bis(3-triethoxysilylpropyl)tetrasulfide (TESPT)-treated surface-modified silica to distilled water based on the total weight of silica, 15 at 60°C. By stirring for a minute, a silica slurry was prepared. The copolymer (SBR 1) of Preparation Example was heated to 60° C., mixed with the slurry, and stirred for 30 minutes to prepare a wet masterbatch composition (WMB 1). The composition was coagulated with ₂ % by weight of CaCl ₂ aqueous solution, washed once with distilled water, and dried at 60° C. for 24 hours.

The composition 180 parts by weight, process oil (tetrakis (dimethylamino) ethylene, TDAE) 37.5 parts by weight, zinc oxide 3 parts by weight, stearic acid 2 parts by weight, silica 3.1 parts by weight, TEPST 1.9 parts by weight, N-(1,3- 1 part by weight of dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD) was sequentially added to the hermetic mixer (kneader). 70% of the internal capacity of the mixer was set as an appropriate filling rate, the heat transfer temperature was set to 110℃, the internal mixing temperature was maintained at 145~150℃, the rotor speed of the kneader was set at 25 rpm, and the rubber, filler, and additives were added in order. Then, the mixture was first kneaded for 12 minutes. The discharge temperature of the kneaded material was set to about 155°C.

After secondary kneading the kneaded product for 1 minute in an 8-inch double roll mill with a rotor speed ratio of 1:1.4, 1.5 parts by weight of sulfur, N-cyclohexyl-2-benzotiazolesulfenamide (N-cyclohexyl-2-benzotiazolesulfenamide, CBS) 1.5 parts by weight and 1.5 parts by weight of diphenylguanidine (DPG) were added and mixed for 2 minutes to obtain a rubber compound composition. A tread composite specimen was prepared using the composition.

Comparative Example 1

A silica slurry was prepared by adding 10% by weight of surface-modified silica treated with TESPT based on the total weight of silica into distilled water, followed by stirring at 60°C for 15 minutes. The copolymer (SBR 2) of Comparative Preparation Example was heated to 60° C., mixed with the slurry, and stirred for 30 minutes to prepare a wet master batch composition (WMB 2). The composition was coagulated with ₂ % by weight of CaCl ₂ aqueous solution, washed once with distilled water, and dried at 60° C. for 24 hours.

180 parts by weight of the composition, 37.5 parts by weight of process oil, 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 3.7 parts by weight of silica, 1.85 parts by weight of TEPST, N-(1,3-dimethylbutyl)-N'-phenyl- 1 part by weight of p-phenylenediamine was sequentially added to a closed mixer (kneader). 70% of the internal capacity of the mixer was set as an appropriate filling rate, the heat transfer temperature was set to 110℃, the internal mixing temperature was maintained at 145~150℃, the rotor speed of the kneader was set at 25 rpm, and the rubber, filler, and additives were added in order. Then, the mixture was first kneaded for 12 minutes. The discharge temperature of the kneaded material was set to about 155°C.

After secondary kneading the kneaded product for 1 minute in an 8-inch double roll mill with a rotor speed ratio of 1:1.4, 1.5 parts by weight of sulfur, 1.5 parts by weight of N-cyclohexyl-2-benzothiazolesulfenamide, 1.5 parts by weight of diphenylguanidine Part was added and mixed for 2 minutes to obtain a rubber compound composition. A tread composite specimen was prepared using the composition.

Comparative Example 2

100 parts by weight of the copolymer (SBR 1) of Preparation Example, 37.5 parts by weight of process oil, 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 80 parts by weight of surface-modified silica treated with 10% by weight of TESPT based on the total weight of silica Parts and 1 part by weight of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine were sequentially added to the hermetic mixer (kneader). 70% of the internal capacity of the mixer was set as an appropriate filling rate, the heat transfer temperature was set to 110℃, the internal mixing temperature was maintained at 145~150℃, the rotor speed of the kneader was set at 25 rpm, and the rubber, filler, and additives were added in order. Then, the mixture was first kneaded for 12 minutes. The discharge temperature of the kneaded material was set to about 155°C.

After secondary kneading the kneaded product for 1 minute in an 8-inch double roll mill with a rotor speed ratio of 1:1.4, 1.5 parts by weight of sulfur, 1.5 parts by weight of N-cyclohexyl-2-benzothiazolesulfenamide, 1.5 parts by weight of diphenylguanidine Part was added and mixed for 2 minutes to obtain a rubber compound composition. A tread composite specimen was prepared using the composition.

Comparative Example 3

100 parts by weight of the copolymer (SBR 2) of the comparative preparation example, 37.5 parts by weight of process oil, 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 80 parts by weight of silica, and N-(1,3-dimethylbutyl)-N' -Phenyl-p-phenylenediamine 1 part by weight was sequentially added to a closed mixer (kneader). 70% of the internal capacity of the mixer was set as an appropriate filling rate, the heat transfer temperature was set to 110℃, the internal mixing temperature was maintained at 145~150℃, the rotor speed of the kneader was set at 25 rpm, and the rubber, filler, and additives were added in order. Then, the mixture was first kneaded for 12 minutes. The discharge temperature of the kneaded material was set to about 155°C.

After secondary kneading the kneaded product for 1 minute in an 8-inch double roll mill with a rotor speed ratio of 1:1.4, 1.5 parts by weight of sulfur, 1.5 parts by weight of N-cyclohexyl-2-benzothiazolesulfenamide, 1.5 parts by weight of diphenylguanidine Part was added and mixed for 2 minutes to obtain a rubber compound composition. A tread composite specimen was prepared using the composition.

Comparative Example 4

100 parts by weight of the copolymer (SBR 2) of the comparative preparation example, 37.5 parts by weight of process oil, 3 parts by weight of zinc oxide, 2 parts by weight of stearic acid, surface modified silica 80 treated with 10% by weight of TESPT based on the total weight of silica Parts by weight and 1 part by weight of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine were sequentially added to the hermetic mixer (kneader). 70% of the internal capacity of the mixer was set as an appropriate filling rate, the heat transfer temperature was set to 110℃, the internal mixing temperature was maintained at 145~150℃, the rotor speed of the kneader was set at 25 rpm, and the rubber, filler, and additives were added in order. Then, the mixture was first kneaded for 12 minutes. The discharge temperature of the kneaded material was set to about 155°C.

After secondary kneading the kneaded product for 1 minute in an 8-inch double roll mill with a rotor speed ratio of 1:1.4, 1.5 parts by weight of sulfur, 1.5 parts by weight of N-cyclohexyl-2-benzothiazolesulfenamide, 1.5 parts by weight of diphenylguanidine Part was added and mixed for 2 minutes to obtain a rubber compound composition. A tread composite specimen was prepared using the composition.

The composition of the compounded rubber prepared in the above Examples and Comparative Examples is shown in Table 1 below.

- Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Master batch Wet Wet deflation deflation deflation WMB 1 180 0 0 0 0 WMB 2 0 180 0 0 0 SBR 1 0 0 100 0 0 SBR 2 0 0 0 100 100 Process oil 37.5 37.5 37.5 37.5 37.5 Surface modified silica 0 0 80 0 80 Silica 3.1 3.7 0 80 0 Silane (TESPT) 1.9 1.85 0 0 0 Zinc oxide 3 3 3 3 3 Stearic acid 2 2 2 2 2 6PPD One One One One One brimstone 1.5 1.5 1.5 1.5 1.5 CBS 1.5 1.5 1.5 1.5 1.5 DPG 1.5 1.5 1.5 1.5 1.5

(Unit: phr, parts per hundred rubber)

Experimental example

The physical properties of each specimen prepared in the Examples and Comparative Examples were measured and shown in Table 2 below.

-Mooney viscosity (ML ₁₊₄ @100°C): It was measured with a Mooney viscometer (Vluchem IND Co., Korea) according to ASTM D-1646.

-Mechanical properties: A dumbbell-shaped specimen was manufactured according to ASTM D412, and modulus (M _100% ) at 100% elongation using a universal test machine (UTM, KSU-05M-C, KSU Co., Korea). ), modulus at 300% elongation (M _300% ), and elongation were measured. The universal testing machine is a machine capable of measuring mechanical properties by stretching a specimen at a speed of 500 mm/min with a force of 5,000 N.

-DIN wear loss: According to DIN 53516, a cylindrical specimen having a diameter of 16 mm and a thickness of 8 mm was prepared. The mass reduction amount was measured by grinding 40 mg of the specimen at a speed of 40 rpm using a German industrial standard (Deutsche Industrie Normen, DIN) wear tester.

-Using a Dynamic Mechanical Thermal Analysis (DMTA, EPLEXOR 500N, GABO, Germany), the dynamic viscoelastic properties (tanδ) and glass transition temperature (T _g ) of each specimen at a strain 30 ㎛ and a frequency of 10 Hz ) Was measured. The measurement was performed by increasing the temperature at a rate of 3°C/min in a temperature range of -80°C to 70°C in a tension mode.

- Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Raw Mooney viscosity 124 93 124 93 93 Compound Mooney viscosity 124 109 119 103 105 M _100% (kgf/cm ² ) 18.8 21.4 20.6 20.2 20.5 M _300% (kgf/cm ² ) 115.3 89.6 94.0 85.1 84.0 Elongation (%) 632.5 580.7 547.6 582.6 618 DIN wear loss (mg) 94 133 116 132 138 Crosslinking density (10 ^-4 mol/g) 0.88 0.86 0.94 0.88 0.87 T _g (℃) -33.6 -32.3 -29.7 -32.1 -31.3 tanδ℃ 0.231 0.226 0.239 0.241 0.238 tanδ60℃ 0.098 0.135 0.152 0.135 0.130

Referring to Table 2, the specimens of the examples prepared by the wet masterbatch method have excellent dispersibility of the filler and excellent interaction between the rubber and the filler, thereby improving wear resistance, mechanical strength, and rolling resistance. In addition, it can be seen that the amount of gel formation was reduced because the crosslinking density was lower than that of the dry masterbatch method.

On the other hand, the specimen of Comparative Example 2 prepared by the dry masterbatch method included the copolymer (SBR 1) of Preparation Example, but an excessive amount of gel was formed, and the rolling resistance, abrasion resistance, and tensile strength were poor compared to the examples.

In addition, the specimens of Examples including the copolymer of Preparation Example (SBR 1) were superior in various properties compared to Comparative Examples 1, 3 and 4 including the copolymer of Comparative Preparation Example (SBR 2).

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and the concept of equivalents thereof should be construed as being included in the scope of the present invention.

Claims (11)

Emulsion-polymerized copolymer including an aromatic vinyl monomer, a conjugated diene-based monomer, and a functional monomer; And
Containing silica;
A rubber composition for tires manufactured by a wet masterbatch method. The method of claim 1,
The functional monomer is a (meth)acrylic monomer, a rubber composition for a tire. The method of claim 2,
The (meth)acrylic monomer includes an epoxy group, rubber composition for a tire. The method of claim 2,
The content of the (meth)acrylic monomer is 0.1 to 20% by weight based on the total weight of the monomer, rubber composition for a tire. The method of claim 1,
The silica is a rubber composition for a tire surface-modified with 0.1 to 20% by weight of an organosilane compound represented by the following Formula 1 based on the total weight of the silica:
[Formula 1]
(RO) ₃ Si(CH ₂ ) _a -(S) _n -(CH ₂ ) _b Si(OR') ₃
In Formula 1,
R and R'are each an alkyl group having 1 to 10 carbon atoms,
a and b are each independently an integer of 1-5,
n is an integer of 1-4. The method of claim 1,
The composition further comprises oil, additives, sulfur and a vulcanization accelerator, a rubber composition for a tire. (a) mixing an emulsion-polymerized copolymer including an aromatic vinyl monomer, a conjugated diene-based monomer, and a functional monomer at 30 to 90° C. with a slurry containing silica and water; And
(b) coagulating and drying the product of step (a); including, a method for producing a rubber composition for a tire. The method of claim 7,
The functional monomer is a (meth)acrylic monomer, a method for producing a rubber composition for a tire. The method of claim 8,
The (meth)acrylic monomer comprises an epoxy group, a method for producing a rubber composition for a tire. The method of claim 7,
The silica is surface-modified with 1 to 20% by weight of an organosilane compound represented by the following Formula 1 based on the total weight of the silica, a method for preparing a rubber composition for a tire:
[Formula 1]
(RO) ₃ Si(CH ₂ ) _a -(S) _n -(CH ₂ ) _b Si(OR') ₃
In Formula 1,
R and R'are each an alkyl group having 1 to 10 carbon atoms,
a and b are each independently an integer of 1-5,
n is an integer of 1-4. The method of claim 7,
After step (b),
(c) mixing the product of step (b) with oil, additives, sulfur and a vulcanization accelerator; further comprising, a method for producing a rubber composition for a tire.