KR101186169B1 - Tire tread rubber composition - Google Patents

Abstract

The present invention relates to a tire tread rubber composition, and more specifically, to a tire tread rubber composition, 50 to 100 parts by weight of silica based on 100 parts by weight of raw material rubber, and a diphenyl disulfur siloxane copolymer as a modified silicone oil. The present invention relates to a tire comprising a tread rubber composition, a rubber made of the rubber composition, and a rubber made of the rubber composition, which may include 1 to 10 parts by weight to improve wear resistance and / or rotation resistance.
According to the present invention, a tire having improved wear resistance and / or rolling resistance can be provided to a consumer, so that consumers can drive safely and economically. Also, a tire manufacturer can supply tires of superior quality to consumers. There is industrial applicability because it can contribute to economic gains.

Description

Tire tread rubber composition

The present invention relates to a tire tread rubber composition, and more specifically, to a tire tread rubber composition, 50 to 100 parts by weight of silica based on 100 parts by weight of raw material rubber, and a diphenyl disulfur siloxane copolymer as a modified silicone oil. The present invention relates to a tire comprising a tread rubber composition, a rubber made of the rubber composition, and a rubber made of the rubber composition, which may include 1 to 10 parts by weight to improve wear resistance and / or rotation resistance.

With the development of the automobile industry and the improvement of the road environment conditions for automobiles, the demand for consumers to drive better vehicles is gradually increasing.

Consumers' demands for vehicles are increasingly moving from the vehicle itself to vehicle driving.

Since the movement of the vehicle depends entirely on the quality of the tire, development of high performance tires is required not only for driving the vehicle under better conditions but also for a tire that is a means for supporting and moving the vehicle. In addition, according to high oil prices and environmental regulations around the world, the development of low-fuel tires and tire rubber compositions through the reduction of tire rolling resistance is being continuously developed.

In recent years, tire manufacturers are increasing the rubber composition to apply silica (silica) as a reinforcing agent to improve the rolling resistance characteristics in addition to the reinforcement in rubber.

However, when silica is applied as an additive for improving the reinforcement of the tire rubber composition, the dispersibility of the silica tends to decrease because the tendency to agglomerate between the silica in the rubber composition is strong. Due to the poor dispersibility of the silica, the viscosity is increased, and if left for a long time, there is a problem in that the stability of the rubber composition decreases due to a change in time such as gelation reaction. Therefore, unlike carbon black, which is one of the additives to improve the reinforcement properties of the conventional tire rubber composition for improving the dispersibility of silica, there is no affinity with the polymer (couple) to improve the bond between the polymer and silica. There is a need for a couplng agent.

Therefore, the inventor of the present invention is a separate process when using a diphenyl disulfur siloxane copolymer as a modified silicone oil in a rubber composition using silica as a reinforcing filler during the study to solve the above problems. The present invention was completed by knowing that it is possible to obtain a tire tread rubber composition which does not need process oil and can improve dispersibility of silica, thereby improving wear resistance and / or rolling resistance. .

Therefore, in the tire rubber composition, the tire tread rubber may include a diphenyl disulfur siloxane copolymer as silica and a modified silicone oil to improve wear resistance and / or rolling resistance. It is to provide a tire comprising a composition, a rubber made of the rubber composition, a rubber made of the rubber composition.

The present invention is to provide a tire tread rubber composition that can improve the wear resistance and / or rolling resistance characteristics.

The present invention is to provide a rubber made of a tire tread rubber composition that can improve the wear resistance and / or rolling resistance properties.

The present invention is to provide a tire comprising a rubber made of a tire tread rubber composition that can improve the wear resistance and / or rolling resistance properties.

The present invention is a tire tread rubber composition, wear resistance characteristics and / or rotational resistance to include 1 to 10 parts by weight of diphenyl disulfur siloxane copolymer as modified silicone oil with respect to 100 parts by weight of raw rubber It is possible to provide a tire tread rubber composition that can improve characteristics.

The present invention can provide a rubber made of a tire tread rubber composition capable of improving the above-mentioned wear resistance and / or rotational resistance characteristics.

The present invention can provide a tire comprising a rubber made of a tire tread rubber composition capable of improving wear resistance and / or rolling resistance.

The present invention is a tire tread rubber composition that can improve the wear resistance and / or rolling resistance properties, the tire tread rubber composition consisting of a rubber and a tire tread rubber composition with improved abrasion resistance and / or rolling resistance properties It can provide a tire with improved wear resistance and / or rolling resistance properties, including.

The present invention represents a tire tread rubber composition capable of improving wear resistance and / or rolling resistance properties.

In the tire tread rubber composition, 50 to 100 parts by weight of silica and 1 to 10 parts by weight of diphenyl disulfur siloxane copolymer as modified silicone oil are included in the tire tread rubber composition. A tire tread rubber composition capable of improving wear characteristics and / or rolling resistance characteristics is shown.

In the above, the raw rubber may be natural rubber.

In the above, the raw rubber may be synthetic rubber.

In the above, the raw rubber may be a mixture of natural rubber and synthetic rubber.

In the above raw material rubber, natural rubber and synthetic rubber may be mixed rubber mixed in a weight ratio of 5 to 95: 5 to 95.

Synthetic rubber is styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, isoprene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, nitrile rubber Hydrogenated nitrile rubber, nitrile butadiene rubber (NBR), modified nitrile butadiene rubber, chlorinated polyethylene rubber, styrene ethylene butylene styrene (SEBS) rubber, ethylene propylene rubber, ethylene propylene diene (EPDM) rubber, hypalon rubber, Chloroprene rubber, ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromomethylstyrene butyl rubber, maleic acid styrene butadiene rubber, carboxylic acid styrene butadiene rubber, epoxy isoprene rubber, ethylene propylene propylene Rubber, carboxylic acid nitrile butadiene rubber, polyurethane rubber One or more selected from the group of EPDM rubber and brominated polyisobutyl isoprene-co-paramethyl styrene (BIMS) may be used.

In the above rubber composition, silica, which is an additive used as a reinforcing filler to improve reinforcement, may be used in an amount of 50 to 100 parts by weight based on 100 parts by weight of the raw material rubber.

When the silica is used less than 50 parts by weight based on 100 parts by weight of the raw material rubber, there is no meaning to use as a reinforcing filler, and when the content is used in excess of 100 parts by weight, the cohesiveness between the silicas increases due to the use of excess silica. There is a fear that the dispersibility of the rubber composition decreases.

Therefore, in the tire tread rubber composition of the present invention, silica may be used in an amount of 50 to 100 parts by weight based on 100 parts by weight of the rubber material.

In the above, the silica may use a BET surface area of 110 ~ 130㎡ / g.

In the silica, the surface of the silica may be a surface-treated silica treated with silanetriol (silanetriol).

The silica surface-treated with the silane triol may be one in which the silane triol is treated with 5 to 50% of the silica weight on the surface of the silica having a BET surface area of 110 to 130 m 2 / g.

As the modified silicone oil, diphenyl disulfur siloxane copolymer may be used in an amount of 1 to 10 parts by weight based on 100 parts by weight of the raw material rubber.

When using a modified silicone oil (Diphenyl disulfur siloxane copolymer) less than 1 part by weight or more than 10 parts by weight based on 100 parts by weight of the raw material rubber, the tendency to agglomerate between silica increases, so that the dispersibility decreases and the physical properties decrease. There is a concern.

Therefore, in the tire tread rubber composition of the present invention, 50 to 100 parts by weight of silica and 1 to 10 parts by weight of modified silicone oil (Diphenyl disulfur siloxane copolymer) may be used with respect to 100 parts by weight of the raw rubber.

As the modified silicone oil, diphenyl disulfur siloxane copolymer of the following structural formula (1) may be used.

....... 구조식(1)

....... Structural formula (1)

M is an integer of 20 to 100 in the formula (1); n is an integer of 1 to 5; m / n is from 20 to 100; R1 and R2 are each independently an alkyl group having 1 to 20 carbon atoms.

The tire tread rubber composition of the present invention may contain 5 to 20 parts by weight of the second reinforcing filler in addition to 100 parts by weight of the raw material rubber in addition to the silica mentioned above.

The second reinforcing filler may be carbon black.

In the second reinforcing filler may be used calcium carbonate (calcium carbonate).

In the second reinforcing filler may be used titanium dioxide (titanium dioxide).

In the above second reinforcing filler may be used (clay).

The second reinforcing filler may be used a layered silicate (layered silicate).

In the above second reinforcing filler may be used tungsten (tungsten).

The second reinforcing filler may be used talc (Talc).

The second reinforcing filler may be used syndiotactic-1,2-polybutadiene (SPB).

In the above, the second reinforcing filler may use plate graphite.

The second reinforcing filler is carbon black, calcium carbonate, titanium dioxide, clay, layered silicate, tungsten, and talc. Syndiotactic-1,2-polybutadiene (SPB), two or more kinds of plate graphite in the same weight ratio may be used as a mixed component.

Carbon black iodine adsorption 135-145g / kg, DBP adsorption 125-135ml / 100g can be used in the above.

In the carbon black, iodine adsorption is 140g / kg, DBP adsorption may be used that 130ml / 100g.

In the above, the layered silicate may be used having an interlayer spacing of 0.1 to 10 nm.

In the above-described layered silicate, an aspect ratio (l / d) representing a ratio of the plane width l to the thickness d may be 5 or more.

In the above, the layered silicate may have a flattening ratio of 5 to 100.

The layered silicate may be a natural layered silicate capable of cation exchange reaction and / or anion exchange reaction.

The layered silicate may be a synthetic layered silicate capable of cation exchange and / or anion exchange reaction.

The layered silicate may be an organic layered silicate organically treated with a material having a cationic group and / or a material having an anionic group.

The layered silicates are montmorillonite, saponite, hectorite, hectorite, rectorite, vermiculite, mica, illite, kaolinite, and kaolinite. Any one selected from the group of sodium montmorillonite (Na-MMT) and claisite 15A can be used.

Among the fillers described above, syndiotactic-1,2-polybutadiene (SPB) may have a diameter of 0.01 to 0.1 µm and a specific surface area of 80 to 90 m ² / g.

Among the above fillers, syndiotactic-1,2-polybutadiene (SPB) may have a diameter of 1 to 10 µm and a specific surface area of 100 to 120 m ² / g.

Among the above fillers, plate graphite may have a particle size of 0.1 to 20 µm.

In the above-mentioned fillers, plate graphite may be one having an interlayer spacing of 0.1 to 10 nm.

Among the above fillers, plate graphite may be one having an aspect ratio (l / d) of 5 or more, which represents the ratio of the plane width l to the thickness d.

In the above fillers, plate graphite may have a flattening ratio of 5 to 100.

Among the above fillers, plate graphite may have a particle size of 0.1 to 20 µm, an interlayer spacing of 0.1 to 10 nm, and a flat ratio of 5 to 100.

Among the fillers, the plate graphite may be one obtained from the following steps (a) and (b).

(A) immersing the graphite in a mixed solution of sulfuric acid and nitric acid in a weight ratio of 1: 9-9:

(B) washing and washing the dried graphite at 700-900 ° C. for 1-5 minutes after immersion.

In step (a), the immersion is carried out at 60 to 80 ° C. for 10 to 48 hours, preferably at 70 ° C. for 10 hours, and the -SO 4 ^{2 -} ion of sulfuric acid or -NO ₃ ^- ion of nitric acid is formed between the plate graphite layers. Make sure this is fully inserted.

The tire tread rubber composition of the present invention may further include a dispersing aid for improving the dispersibility of silica and / or the second reinforcing filler.

The dispersing aid may be used 0.1 to 7 parts by weight based on 100 parts by weight of the raw material rubber.

The dispersing aid may be a mixture of hydrocarbon, zinc (Zn soap) and filler (filler) is mixed.

The dispersing aid is hydrocarbon; Zinc 솝; And at least one filler selected from the group consisting of glass fiber, silica, wood powder and chalk. A mixture of 1 to 8: 1 to 8: 1 to 8 by weight ratio may be used.

In the silica dispersion assistant, the hydrocarbon may be a C1-C20 chain hydrocarbon and / or a C6-C18 hydrocarbon.

According to the present invention, various additives such as reinforcing fillers, anti-aging agents, activators, vulcanizing agents, and vulcanization accelerators, which are used in conventional tire tread rubber compositions, in addition to the above-mentioned raw rubber, silica, and modified silicone oil are appropriately selected as necessary. It can be used as a content. However, these are general components used in conventional tire tread rubber compositions and are not essential constituents of the present invention, and thus detailed descriptions thereof will be omitted.

In the tire tread rubber composition of the present invention, the tire tread rubber composition is applied under various conditions such as various components and contents. In order to achieve the object of the present invention, it is understood that the rubber composition for tires under the above-mentioned conditions is preferable. Could.

On the other hand, the present invention includes a rubber produced by the above-mentioned tire tread rubber composition.

The present invention includes a tire containing a rubber produced by the above-mentioned tire tread rubber composition.

The present invention includes a tire containing as a tread the rubber produced by the above-mentioned tire tread rubber composition.

The tire represents any one selected from a tire for an automobile, a tire for a bus, a tire for a truck, an tire for an aircraft, and a tire for a motorcycle.

Hereinafter, the content of the present invention will be described in more detail by Examples, Comparative Examples and Test Examples. However, these are only presented to make the contents of the present invention easier to understand, and the scope of the present invention is not limited thereto.

≪ Example 1 >

80 parts by weight of silica and 100 parts by weight of a raw material rubber consisting of 70 parts by weight of styrene butadiene rubber (SBR) and 40 parts by weight of butadiene rubber (BR), and a diphenyl disulfur siloxane copolymer of the following formula (1) as a modified silicone oil (Diphenyl) 10 parts by weight of disulfur siloxane copolymer, 3 parts by weight of zinc oxide (ZnO), 2 parts by weight of stearic acid, anti-aging agent (2,2,4-trimethly-1,2-dihydroquinoline, RD, Kumho Monsanto, Korea) 1 part by weight, Wax 2 parts by weight, Anti-aging agent (N- (1,3-Dimethylbutyl) -N'-phenyl-p-phenylene diamine, Kumanox-13, Kumho Petrochemical, South Korea) 1.5 parts by weight Banbury mixer Into a mixture at 150 ° C. for 30 minutes and then released to obtain a rubber compound.

To the rubber compound thus obtained, 1.5 parts by weight of sulfur, a vulcanization accelerator (Nt-butylbenzothiazole sulfenamide, NS) and 1.2 parts by weight of vulcanization accelerator (DPG) were added and vulcanized at 160 ° C. for 20 minutes to prepare a rubber specimen. .

....... 구조식(1)

....... Structural formula (1)

In Structural Formula (1), m is 20, n is 1, m / n is 20, and R1 and R2 are methyl groups, respectively.

≪ Comparative Example 1 &

80 parts by weight of silica, silane coupling agent (bis- (3-triethoxisilyl) -propyl-tetrasulfide, TESPT, SI 69 parts by weight, 7 parts by weight of paraffin oil, 3 parts by weight of zinc oxide (ZnO), 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent (RD), 2 parts by weight of wax, anti-aging agent (Kumanox-13) 1.5 parts by weight were placed in a Banbury mixer, blended at 150 ° C. for 30 minutes, and then discharged to obtain a rubber compound.

To the rubber compound thus obtained, 1.5 parts by weight of sulfur, 1.2 parts by weight of vulcanization accelerator (NS) and 1 part by weight of vulcanization accelerator (DPG) were added and vulcanized at 160 ° C. for 20 minutes to prepare a rubber specimen.

Comparative Example 2

A rubber specimen was prepared in the same manner as in Comparative Example 1 except that 5 parts by weight of a silane coupling agent (bis- (3-triethoxisilyl) -propyl-tetrasulfide, TESPT, SI-69) and 5 parts by weight of paraffin oil were used. .

Comparative Example and Example Composition of Rubber Specimen (Unit: Weight part) Drug name Comparative Example 1 Comparative Example 2 Example 1 Styrene Butadiene Rubber (SBR) 70 70 70 Butadiene rubber (BR) 30 30 30 Carbon black 10 10 10 Silica 80 80 80 Modified silicone oil - - 10 Silane coupling agent 3 5 - Paraffin oil 7 5 - Zinc Oxide (ZnO) 3 3 3 Stearic acid 2 2 2 Antioxidant (RD) One One One Wax 2 2 2 Antioxidant (Kumanox-13) 1.5 1.5 1.5 Sulfur 1.5 1.5 1.5 Vulcanization accelerator (NS) 1.2 1.2 1.2 Vulcanization accelerator (DPG) One One One

<Test Example>

For each rubber prepared in Comparative Example 1, Comparative 2 and Example 1, the viscosity (100 ℃), scotch time (t5), hardness (Shore-A), 300% modulus, tensile strength according to ASTM-related regulations Physical properties such as elongation, wear resistance (DIN wear), heat resistance, and dynamic viscoelasticity (tanδ (70 ° C.)) were measured and the results are shown in Table 2 below.

Comparative Examples and Examples Physical Properties of Rubber Item Comparative Example 1 Comparative Example 2 Example Pattern viscosity (100 ℃) 79.9 73.0 68.2 Scorch time (t5) 33.6 31.7 34 Shore A 70 69 69 300% modulus (kg / cm ² ) 153 160 168 Tensile strength (kg / Cm2) 158 170 179 Elongation (%) 309 335 348 DIN wear (g) 0.109 0.94 0.86 Heat resistance performance (℃) 18.5 17.0 15.9 tanδ (70 ° C) 0.106 0.094 0.082

* Wear resistance (DIN wear): It shows the amount of rubber wear, the lower the value, the better the wear resistance characteristics.

* Heat generation performance: Lower value means better heat generation performance.

* Dynamic viscoelasticity (tanδ): Measured by changing the temperature at 11 Hz, 1.25% strain (Rheovibron test) using the rheovibron test (test) shows the value. In this case, the smaller the value of tanδ (70 ° C), the better the rotational resistance on the road surface.

The rubber specimens prepared in Example 1 of the present invention to which modified silicone oil (Diphenyl disulfur siloxane copolymer) was applied as in the results of Table 2 had higher mechanical strengths than those of the rubber specimens prepared in Comparative Examples 1 and 2, and increased dispersibility. It was found that the wear resistance, the heat generation performance and the rotational resistance characteristics are excellent.

<Example 2>

A rubber was manufactured in the same manner as in Example 1, except that 1 part by weight of a diphenyl disulfur siloxane copolymer of Structural Formula (1) was used as the modified silicone oil.

<Example 3>

A rubber was manufactured in the same manner as in Example 1, except that 5 parts by weight of a diphenyl disulfur siloxane copolymer of Structural Formula (1) was used as the modified silicone oil.

<Example 4>

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of carbon black was further added as a second reinforcing filler in addition to silica.

In the carbon black, iodine adsorption is 140g / kg, DBP adsorption may be used that 130ml / 100g.

<Example 5>

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of calcium carbonate was further added as a second reinforcing filler.

<Example 6>

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of titanium dioxide was further added as a second reinforcing filler as well as silica.

&Lt; Example 7 >

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of clay was further added as a second reinforcing filler in addition to silica.

&Lt; Example 8 >

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of layered silicate was further added as a second reinforcing filler.

In the above-described layered silicate, hectorite having an aspect ratio (l / d) of 20 ± 1 indicating an interlayer spacing of 5 ± 1 nm and a plane width (l) to thickness (d) was used.

&Lt; Example 9 >

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of tungsten was further added as a second reinforcing filler as well as silica.

&Lt; Example 10 >

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of talc was further added as a second reinforcing filler as well as silica.

<Example 11>

The same method as in Example 1 except that 10 parts by weight of syndiotactic-1,2-polybutadiene (SPB) is further added as a second reinforcing filler. Rubber was prepared.

In the above syndiotactic-1,2-polybutadiene (SPB) was used a diameter of 0.05 ± 0.01 ㎛ 1, a specific surface area of 85 ± 1 m ² / g.

&Lt; Example 12 >

The same method as in Example 1 except that 10 parts by weight of syndiotactic-1,2-polybutadiene (SPB) is further added as a second reinforcing filler. Rubber was prepared.

Syndiotactic-1,2-polybutadiene (SPB) was used as a diameter of 5 ± 1㎛, specific surface area of 110 ± 2m ² / g.

&Lt; Example 13 >

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of plate graphite was further added as a second reinforcing filler as well as silica.

In the above-described plate graphite, graphite was added to a mixed solution of sulfuric acid and nitric acid in a weight ratio of 1: 1, soaked at 70 ° C for 10 hours, washed with water, and dried graphite was heated at 800 ° C for 3 minutes.

&Lt; Example 14 >

A rubber was manufactured in the same manner as in Example 1, except that 10 parts by weight of carbon black and 4.5 parts by weight of a dispersing aid were further added as a second reinforcing filler.

In the carbon black, iodine adsorption is 140g / kg, DBP adsorption may be used that 130ml / 100g.

The dispersing aid may be a mixture of hydrocarbon, zinc (Zn soap) and filler (filler) is mixed.

The dispersing aid is a hydrocarbon having 10 carbon atoms; Zinc 솝; And a filler of glass fiber (glass fiber); was used a mixture mixed in a weight ratio of 1: 1: 1.

&Lt; Example 15 >

Except for using 5 parts by weight of diphenyl disulfur siloxane copolymer of formula (2) instead of 10 parts by weight of diphenyl disulfur siloxane copolymer of formula (1) Rubber was prepared in the same manner as in Example 1.

....... 구조식(1)

....... Structural formula (1)

In Structural Formula (1), m is 30, n is 1, m / n is 30, R1 is an ethyl group, and R2 is a methyl group.

As described above, it is described with reference to preferred embodiments, comparative examples and test examples of the present invention, but those skilled in the art without departing from the spirit and scope of the invention described in the claims below It will be understood that various modifications and variations can be made in the present invention.

According to the present invention, a tire having improved wear resistance and / or rolling resistance can be provided to a consumer, so that consumers can drive safely and economically. There is industrial applicability because it can contribute to economic gains.

Claims (4)

In a tire tread rubber composition,
A tire tread rubber composition comprising 50 to 100 parts by weight of silica and 1 to 10 parts by weight of diphenyl disulfur siloxane copolymer as a modified silicone oil based on 100 parts by weight of raw rubber. The method of claim 1,
Diphenyl disulfur siloxane copolymer (Diphenyl disulfur siloxane copolymer) is a tire tread rubber composition, characterized in that represented by the following structural formula (1).

....... Structural formula (1)
M is an integer of 20 to 100 in the formula (1); n is an integer of 1 to 5; m / n is from 20 to 100; R1 and R2 are each independently an alkyl group having 1 to 20 carbon atoms. A rubber comprising the rubber composition of claim 1. A tire comprising a rubber comprising the rubber composition of claim 1.