JPH07118445A - Tire tread rubber composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of providing studless tires, excellent in gripping properties on frozen road surfaces and good in accelerating and braking performances by adding a silane coupling agent to a specific rubber component. CONSTITUTION:This composition is obtained by blending (B) 2-15 pts.wt. silane coupling agent with (A) 100 pts.wt. rubber component in which liquid polyisoprene having carboxyl group or liquid polybutadiene having carboxyl group or both account for 3-40wt.% of the rubber component. Furthermore, components other than (C) a vulcanizing agent, (D) an antioxidant and (E) zinc oxide are preferably basically kneaded at 130-170 deg.C and the components (C), (D) and (E) are then preferably added to carry out the finish kneading.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tire tread rubber composition, and more particularly to a tire tread rubber composition having improved grip performance on a frozen road surface.

[0002]

2. Description of the Related Art Prohibition of spiked tires has been legalized to prevent dust pollution by spiked tires, and studless tires have been used in place of spiked tires in cold regions. As a result of improvements, studless tires have been developed and are now in use that have grip properties close to those of spiked tires.

As factors that control the friction between the tread rubber and the road surface, which influence the grip of a studless tire, Hysteresis loss friction 2. Adhesive friction 3. There is excavation friction, but on roads with a very small friction coefficient such as frozen roads, friction due to hysteresis loss is very small, and adhesive friction and excavation friction show a large proportion.

The surface morphology of the tread pattern and tread rubber is important for increasing the excavation frictional force. Spike tires have a large digging-up frictional force, but even in studless tires, in order to increase the digging-up frictional force, the use of foamed rubber and the incorporation of organic fibers have been devised to increase the unevenness of the tread surface, which is effective. The unevenness of the tread surface also has the effect of eliminating the water film generated between the tread surface and the frozen road surface and increasing the adhesive friction force. However, since this indirectly increases the adhesive friction force by increasing the actual contact area, there is a limit in increasing the actual contact area, and there is also a limit in increasing the adhesive friction force.

Since the rubber substance itself has an influence in order to increase the adhesive frictional force, it is an effective method to increase the contact area with the road surface by softening the rubber substance, for example. For this reason, it has been attempted to reduce the amount of filler, use butadiene rubber or isoprene rubber that is hard to cure even at low temperatures, or add a softener, but from the viewpoint of handling stability and wear resistance. Therefore, it could not be made extremely soft, and it was an insufficient measure.

As described above, the current studless tires have insufficient improvement in gripping property and exhibit a performance comparable to that of spiked tires in terms of snow performance, but on frozen roads, road conditions and temperature In some cases, the grip performance is inferior to that of spiked tires due to such conditions, and improvements are required.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a tread for a studless tire capable of exhibiting excellent grip even on a frozen road surface. To provide a rubber composition.

[0008]

DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventors in order to achieve the above object, liquid polyisoprene and polybutadiene having a carboxyl group are contained in an amount of 3 to 40% (% by weight; hereinafter the same) of a rubber component. The present invention was completed by discovering that a rubber composition containing a silane coupling agent acts to improve the adhesive frictional force and is very effective.

That is, in the present invention, liquid polyisoprene having a carboxyl group and / or liquid polybutadiene having a carboxyl group occupies 3 to 40% of the rubber component, and 100 parts (part by weight; hereinafter the same) of the rubber component silane. The present invention relates to a tire tread rubber composition containing 2 to 15 parts of a coupling agent.

[0010]

Functions and Examples In the present invention, it is considered that the liquid rubber having a hydrophilic carboxyl group has the function of increasing the adhesive frictional force on a frozen road surface by increasing the affinity with ice, while the liquid rubber The deterioration of physical properties can be compensated by using a silane coupling agent to enhance the reinforcing property.

As the rubber component in the present invention, natural rubber, isoprene rubber, butadiene rubber or the like, which has a small increase in hardness at low temperature, is preferably used in order to increase the actual contact area of the frozen road surface on ice and increase the adhesive frictional force. .
These rubbers can be used alone or in any combination.

The rubber component in the present invention contains liquid polyisoprene or polybutadiene having a carboxyl group, alone or in combination.

Both the liquid polyisoprene and the liquid polybutadiene can be used, but the liquid polyisoprene is more effective in improving the adhesive friction.

The liquid polyisoprene having a carboxyl group has 2 to 10 carboxyl groups per molecule.
It is preferable to have one and have a number average molecular weight of about 10,000 to 60,000 from the viewpoint of tire performance and workability. As a commercial product, Kuraprene LIR410 manufactured by Kuraray Co., Ltd.
(Having about 10 carboxyl groups per molecule and a number average molecular weight of 25,000), LIR403 (having about 3 carboxyl groups per molecule and a number average molecular weight of 25,000) and the like.

As the liquid polybutadiene having a carboxyl group, those having carboxyl groups at both ends and having an average molecular weight of about 1,000 to 5,000 are preferable from the viewpoint of tire performance and workability, and commercially available products include Nippon Soda ( Co., Ltd. Nisso PBC (number average molecular weight 15
00), BF Goodrich Chemical Company (BF
Hycar CTB (having a number average molecular weight of 4000) manufactured by Goodrich Chemical Co.) and the like can be mentioned.

The liquid polyisoprene and polybutadiene having a carboxyl group account for 3 to 40%, preferably 5 to 25% of the rubber component in total. If it is less than 3%, no improvement in grip on frozen road surface can be seen,
If it is more than 40%, the breaking property of rubber is deteriorated, and the wear resistance,
Cut resistance tends to decrease.

The silane coupling agent to be added to the rubber composition of the present invention is represented by the formula (I):

[0018]

[Chemical 1]

Or formula (II):

[0020]

[Chemical 2]

(Where n is an integer of 1 to 4 and m and k are 1 to
An integer of 6, X is a mercapto group, an amino group, an epoxy group,
Those which represent a vinyl group or a halogen atom) are particularly preferable in the reinforcing property of rubber. Included in the formula (I) are bis (3-triethoxysilylpropyl) tetrasulfene, bis (3-trimethoxysilylpropyl) monosulfene, and the like, and included in the formula (II) are γ-chloropropyl. Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane and the like. In addition, vinyltrichlorosilane, vinyltris (2
-Methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane and the like can also be used.

The silane coupling agent is a rubber component 10.
2 to 15 parts, preferably 3 to 8 parts are blended with 0 part. If it is less than 2 parts, the reinforcing effect of the rubber is hardly obtained, and if it is more than 15 parts, the unreacted silane coupling agent tends to be deposited on the rubber surface, and on the contrary, the adhesive friction force tends to be lowered.

In the rubber composition of the present invention, organic fibers may be mixed in order to enhance the drainage effect and the scratching effect, and foamed rubber may be used as the rubber component.

In the tire tread rubber composition of the present invention, if necessary, a compounding agent usually used for compounding tire rubbers, such as an antioxidant, a softening agent, zinc white, stearic acid, a vulcanization accelerator, and a vulcanization agent. Agents, sulfur and the like can be appropriately mixed.

The tire tread rubber composition of the present invention can be produced by a usual method using a rubber component, carbon black, a silane coupling agent and the above-mentioned usual compounding agents.

However, zinc oxide reacts with the carboxyl groups of liquid polyisoprene or liquid polybutadiene to prevent the reaction between liquid polyisoprene or polybutadiene and the silane coupling agent, and also the alkaline substance such as an antioxidant is silane. Since it prevents the reaction of the coupling agent, when the base is kneaded, that is, when the components other than the vulcanizing agent are kneaded, neither the antioxidant nor zinc oxide is added. Is preferably added. An anti-aging agent having low reactivity may be added at the time of kneading the base. It is more preferable to add it at the time of kneading the base from the viewpoint of dispersion. Base kneading is 130-170
C., preferably 140 to 160.degree. 130
If it is lower than 70 ° C, the reaction of the silane coupling agent tends not to be sufficiently performed, and if it is higher than 170 ° C, deterioration of rubber molecules tends to occur.

The tire tread rubber composition of the present invention can be applied to treads such as studless tires for passenger cars, studless tires for trucks and studless tires for buses.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Experimental Example 1-1 A vulcanizing agent (sulfur, accelerators), an antiaging agent and a zinc white other than the vulcanizing agent (sulfur, accelerators) were base-kneaded at 150 ° C ± 5 ° C and 100 ° C ± A tread rubber composition was prepared by adding a vulcanizing agent, an antioxidant and zinc white at 5 ° C and finish kneading.

Natural rubber 65 parts Butadiene rubber 30 parts Liquid polyisoprene ⁽¹⁾ 5 parts Carbon black ⁽²⁾ 50 parts Process oil ⁽³⁾ 5 parts Silane coupling agent ⁽⁴⁾ 3 parts Stearic acid 2 parts Zinc white 4 parts Anti-aging agent ⁽⁵⁾ 1 part Sulfur 1.5 parts Vulcanization accelerator ⁽⁶⁾ 0.5 parts As liquid polyisoprene (1), Kuraprene LIR410 manufactured by Kuraray Co., Ltd., carbon black (2)
Is N220 manufactured by Showa Cabot Co., Ltd., process oil (3) is Diana Process PS32 manufactured by Idemitsu Kosan Co., Ltd., and silane coupling agent (4) is Si69 (bis (3-triethoxy) manufactured by Degussa. Silylpropyl) tetrasulfene), as the anti-aging agent (5), Nocrac 6C (N-phenyl-N '-(1,3 dimethylbutyl) -P-phenylenediamine) manufactured by Ouchi Shinko Kagaku Co., Ltd. As the sulfur accelerator (6), Nocceller NS (N-tert-butyl-) manufactured by Ouchi Shinko Chemical Co., Ltd.
2 benzothiazyl sulfenamide) was used.

Experimental Examples 1-2 to 1-10 A rubber composition was prepared in the same manner as in Experimental Example 1-1, except that the compounding ratios of natural rubber, butadiene rubber, liquid polyisoprene, liquid polybutadiene and silane coupling agent were changed as shown in Table 1. Was prepared. As liquid polybutadiene, BF
Hycar CTB manufactured by Goodrich Chemical Co. was used.

[0032]

[Table 1]

Example 2 Experimental Example 2-1 Using the tread rubber composition of Experimental Example 1-1, 165R1
No. 3 studless tire was produced. The internal pressure of this tire is set to 2 kgf / cm ² and the domestic production is 1500 ccFF A.
It was mounted on a BS (anti-lock braking system) vehicle, and the acceleration time and braking stop distance on an iced road were measured under the following conditions.

Measurement place: Sumitomo Rubber Industries, Ltd. Nayoro test course ice board road Temperature: -3 ° C Ice temperature: -2 ° C [acceleration time] Measure the time required to accelerate from a stopped state and run for 50m did. The results are shown in Table 2 as an index with the measurement time of Experimental Example 2-8 using a normal tread rubber composition being 100. The smaller the index, the more preferable.

[Braking stop distance] The distance required to stop at the time of running at 30 km / h was measured. The results are shown in Table 2 as an index, with the distance in Experimental Example 2-8 using a normal tread rubber composition being 100. The smaller the index, the more preferable.

Experimental Example 2-2 Experimental Example 2-using the tread rubber composition of Experimental Example 1-2
The same tire as 1 was produced. The acceleration time and the braking stop distance were measured using these tires in the same manner as in Experimental Example 2-1. The results are shown in Table 2.

Experimental Example 2-3 Experimental Example 2-3-1 Experimental Example 2-using the tread rubber composition of Experimental Example 1-3
The same tire as 1 was produced. The acceleration time and the braking stop distance were measured using these tires in the same manner as in Experimental Example 2-1. The results are shown in Table 2.

Experimental Example 2-3-2 The tread rubber composition of Experimental Example 1-3 was mixed with 1 base kneading.
A tire was prepared in the same manner as in Experimental Example 1-1 except that the test was conducted at 20 ° C., and a tire was prepared in the same manner as in Experimental Example 2-1 and the same test was conducted. The results are shown in Table 2.

Experimental Example 2-3-3 Experimental Example 1-except that the tread rubber composition of Experimental Example 1-3 was added with an antioxidant and zinc white during base kneading.
A tire was prepared in the same manner as in Experimental Example 2-1, and the acceleration time and the braking stop distance were measured in the same manner.
The results are shown in Table 2.

Experimental Examples 2-4 to 2-10 Experimental Examples 1-4, 1-5, 1-6, 1-7, 1-8, 1-
Experimental Example 2-using the tread rubber composition of 9, 1-10
The same tire as 1 was produced. The acceleration time and the braking stop distance were measured using these tires in the same manner as in Experimental Example 2-1. The results are shown in Table 2.

[0041]

[Table 2]

In Example 2, the tread rubber composition of the present invention (Experimental example numbers 1-1, 1-2, 1-3, 1-4,
Experimental Examples 2-1 and 2-using 1-5, 1-6, 1-7)
2, 2-3-1, 2-3-2, 2-3-3, 2-4, 2
Excellent results were obtained at -5, 2-6, and 2-7. In Experimental Examples 2-8, excellent results were not obtained because the tread rubber composition did not contain liquid polyisoprene or liquid polybutadiene and a silane coupling agent. In Experimental Example 2-9, since the silane coupling agent was not included, the acceleration time was long. In Experimental Example 2-10, the tread rubber composition containing an excessively large amount of the silane coupling agent was used, so that the acceleration time and the braking stop distance became long.

[0043]

By using the tire tread rubber composition of the present invention, it is possible to obtain a studless tire having excellent grip performance on a frozen road surface and having good acceleration performance, braking performance and the like.

Claims (2)

[Claims] 1. A liquid polyisoprene having a carboxyl group and / or a liquid polybutadiene having a carboxyl group accounts for 3 to 40% by weight of a rubber component, and 2 to 15 parts by weight of a silane coupling agent to 100 parts by weight of the rubber component.
A tire tread rubber composition containing parts by weight. 2. A component other than a vulcanizing agent, an antioxidant and a zinc oxide is kneaded as a base at 130 to 170 ° C., and then a vulcanizing agent, an antioxidant and a zinc oxide are added and a final kneading is carried out. The obtained tire treggo rubber composition according to claim 1.