JP2694547B2 - Rubber composition for tire tread - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rubber composition for a tire tread, which has stable grip performance over a wide temperature range and is excellent in gripping snow and ice road surfaces.

[Conventional technology]

Conventionally, performances required for automobile tires include safety, economy, riding comfort, and the like. In recent years, in particular, with the development of highway networks, the emergence of tires with further improved cornering characteristics, steering characteristics such as braking performance, and safety during high-speed running of vehicles has been strongly desired. As a measure to improve the tire's dynamic performance, particularly grip performance, it is important to increase the frictional force with the road surface by increasing the hysteresis loss of the tread rubber. That is, the tread surface that is in friction with the road surface is subjected to high-speed deformation due to the fine irregularities of the road surface, and the greater the energy dissipation due to the hysteresis loss that occurs during this cyclic deformation process, the greater the frictional force. Moreover, since the deformation on the friction surface is extremely fast, it is known that according to the Williams-Landel-Ferry temperature-time conversion rule, it depends on the hysteresis loss measured at a temperature lower than the temperature at which the tire is used. ing. In fact, there is a good correlation between tan δ (loss factor), which is a measure of hysteresis loss, and the coefficient of friction of the tire, but in this case tan δ measured at a temperature 30 to 40 ° C lower than the temperature at which the tire is used is involved. doing. Conventionally, in order to increase the hysteresis loss of a rubber composition, a method of compounding a rubber having a high glass transition temperature (Tg) such as a styrene-butadiene copolymer rubber having a high styrene content has been used. This is because the tan δ of rubber has a peak near Tg, so the tan δ peak should be close to the temperature range involved in friction performance (corresponding to 0 ° C. if the tire running temperature is 30 ° C.). Therefore, it is intended to use a high tan δ.

FIG. 3 shows the tan δ temperature dependence of emulsion-polymerized styrene-butadiene copolymer rubbers having different styrene contents. When the styrene content increases, the tan δ peak temperature shifts to the high temperature side, and the tan δ value increases near 0 ° C., which is the skirt of the tan δ peak. But at the same time,
The temperature dependence of tan δ near 0 ° C also becomes large, and therefore the grip performance of the tire also greatly changes depending on the environmental temperature. Furthermore, the elastic modulus also changes rapidly in response to the peak of tan δ. That is, as the temperature decreases, the elastic modulus rapidly increases, so that the rubber cannot follow the unevenness of the road surface. Alternatively, in the case of an icy road surface, the rubber cannot be deformed at all, and there is a problem that maneuverability and braking performance are deteriorated.

On the other hand, when a polymer having a low Tg, as represented by high cis BR, is used, the grip performance at low temperatures improves, but on the other hand, tan δ near 0 ° C decreases, and grip performance becomes insufficient at high temperatures. There is a contradiction of being lost. Therefore, it has been attempted to blend the above-mentioned trade-offs by blending different polymers called SBR / BR or by blending a large amount of small-sized carbon (D.
F. Moore, “The Friction of Pneumatic Tires”, Elasevi
er Scientific Publishing Company: 1975, US Patent N
o.4,748,168, JP-A-62-12932, etc.).

However, such a rubber exhibits intermediate properties of the blended polymer, so that the inherent advantages of the constituent polymer cannot be fully utilized, and there is a drawback in that the grip at a high temperature and the grip at a low temperature are not completely satisfactory. In addition, there is a problem in that a large amount of small-sized carbon is compounded, and there is a problem in workability, and heat generation becomes large.

As a measure against such a trade-off, JP-A-61-
Japanese Patent No. 66733 and Japanese Patent Laid-Open No. 62-62840 disclose a technique of adding a low-temperature plasticizer to these blend polymers, but in this case, although the improvement of the low-temperature grip is certainly confirmed, the rubber at a high temperature is recognized. The elastic modulus is remarkably reduced, and it is not at a satisfactory level to satisfy both the steering stability at high temperature and the grip at low temperature. It is clear that this cause depends on the viscoelastic properties of the polymer. Therefore, in order to control the temperature dependence of viscoelasticity, it has been attempted in recent years to modify SBR and BR produced mainly by using an organolithium initiator.

By the way, the environment that a car encounters is various, and even if only the road surface temperature is considered, there is a change of several tens of degrees. In order to stabilize the grip performance over such a wide temperature range, rubber having a relatively high tan δ peak temperature and a small temperature change, that is, a tan δ peak having a broad peak is ideal. Block polymers are known as an attempt to broaden the peak of tan δ. For example,
JP-A-57-102912 and JP-A-57-109817 propose block polymers composed of two types of SBR blocks having different vinyl bond amounts in the styrene and butadiene moieties. Although these block polymers have a broader tan δ peak than conventional polymers, they do not cover the temperature range of tens of degrees as described above, and depending on how the two types of blocks are combined, In some cases, the peak temperature position shifts, and improvement in grip performance cannot be expected. Also, the ice skid resistance is not considered, and it is not at a satisfactory level.

Further, JP-A-54-62248 discloses a technique for improving wet grip performance and reducing rolling resistance by increasing the amount of 1,2-vinyl bond in butadiene. These polymers have a high Tg and inevitably have poor grip performance at low temperatures. The composition of the binary block copolymer is disclosed in JP-A-57-109817 and JP-A-57-108142. These are styrene 20-50% by weight, vinyl 40-75% by weight
With a high Tg SBR block and a styrene content of 10% by weight or less,
It is intended to co-polymerize with an SBR block with a vinyl content of 20 to 50% by weight and a low Tg, which can improve wet grip performance and reduce rolling resistance. JP 57-102912
In the publication, when a styrene content and a vinyl content are 10 to 50% by weight and 20 to 50% by weight and a block of 1 to 30% by weight and 60% by weight or more are used in a binary block copolymer. , They have Tg corresponding to each block when they are not vulcanized because they have different solubility parameters, but they become compatible with each other by the vulcanization process and have a single Tg. It has been shown that the peaks of the temperature curve are very broad. JP
In JP-A 60-192739, when SBR blocks having a styrene content of 10 to 80% by weight and a vinyl content of 30 to 70% by weight are subjected to block copolymerization with butadiene having a vinyl content of 60% by weight or less, the Tg of both is
It is possible to make the peak of tan δ broad by making the difference of 30 ° C or more, widening the distribution range of vinyl bond, and widening the temperature range of the transition region. Therefore, the physical properties of wet skid, ice skid, rolling It says that a high degree of balance between resistance and breakdown characteristics will be achieved. JP 61-55
JP-A No. 60-192739 discloses that the weight-average molecular weight / number-average molecular weight ratio of the block copolymer disclosed in JP-A-60-192739 is 1.8 to 5.0 to further improve the performance balance. However, with these techniques, ta
Although the peak of nδ is broad, at the same time, it is inevitable that the absolute value of tanδ itself will decrease, and even if it is possible to balance wet grip performance, steering stability, ice skid performance, each performance is very high. I'm still dissatisfied with the goal of achieving it at a level. JP 61-23
Japanese Patent No. 1016 also discloses a block polymer composed of three SBR blocks, which has relatively good ice skid resistance performance and wet grip performance well balanced, but still satisfies the required level. I have not caught up with.

[Problems to be solved by the invention]

An object of the present invention is to provide a rubber composition for a tire tread, which has stable grip performance over a wide temperature range and is excellent in gripping snow and ice road surfaces. This composition is suitable for all season type high performance tires.

The present inventors have extensively studied to broaden the peak of tan δ in styrene-butadiene copolymer rubber and further increase the absolute value of tan δ in the temperature range involved in friction, and as a result, contain styrene limited to a specific range. The present inventors have found that a block copolymer composed of a styrene-butadiene copolymer block having an amount and a glass transition temperature and having a narrow Tg transition temperature range can achieve the above object, and thus reached the present invention. The essence of the present invention is to combine an SBR having a high Tg and therefore a high grip performance with an SBR having a low Tg, that is, an excellent snow and ice performance to form a single polymer having only the advantages of both. For that purpose, contrary to the prior art, Tg of the block polymer constituting the binary block copolymer is 60 ° C or more apart, and the transition temperature range is
The finding that the temperature needs to be 12 ° C or lower is the motive of the present invention.

[Means for solving the problem]

The present invention comprises 15 to 25% by weight of bound styrene, has a glass transition temperature of −80 ° C. to −60 ° C., and a transition temperature range of 12 ° C. or less, and a bound styrene. Contains 20 to 50% by weight and has a glass transition temperature of -20 ° C.
It is composed of a styrene-butadiene copolymer block (B) having a transition temperature range of 12 ° C or less at a temperature of + 15 ° C, and a difference in glass transition temperature between the block (A) and the block (B).
60 ℃ or more, the total copolymer styrene as a whole copolymer
20-35% by weight, vinyl bond content of all butadiene parts is 20-45
% By weight, 90 to 50 parts by weight of a styrene-butadiene block copolymer rubber having a weight average molecular weight of 20 × 10 ⁴ or more, and a total of 100 parts by weight of rubber containing natural rubber or isoprene rubber as the balance, and nitrogen. 80 to 130 parts by weight of carbon black having a specific surface area of 100 m ² / g or more, a viscosity specific gravity constant of 0.90 to
A rubber composition for a tire tread is characterized in that 20 to 90 parts by weight of a 0.98 petroleum-based softening agent is blended and a shear storage elastic modulus at −30 ° C. is 500 MPa or less.

 Hereinafter, this means will be described in detail.

(1) Rubber content.

90-50 parts by weight of styrene-butadiene block copolymer rubber and the balance of natural rubber or isoprene rubber (IR) (10-
50 parts by weight).

The styrene-butadiene block copolymer rubber contains bound styrene in an amount of 15 to 25% by weight and has a Tg of -80 to -60 ° C.
A styrene-butadiene copolymer block (A) having a transition temperature range of 12 ° C. or less, and 20 to 50% by weight of bound styrene,
It comprises a styrene-butadiene copolymer block (B) having a Tg of -20 ° C to + 15 ° C and a transition temperature range of 12 ° C or less, and the difference in glass transition temperature between the block (A) and the block (B) is 60. ℃ or more, 20-35% by weight of total bound styrene and 20% by weight of vinyl bond in the total butadiene part of the copolymer as a whole.
~ 45% by weight, and the weight average molecular weight is 20 x 10 ⁴ or more.

Tg of one block (A) is -80 ℃ to -60 ℃,
It is essential that the Tg of the other block (B) is −20 ° C. to + 15 ° C., and the difference must be 60 ° C. or more. That is, when the difference in Tg between the blocks is less than 60 ° C., the styrene-butadiene copolymers forming the blocks are compatible with each other, and the tan δ peak does not broaden sufficiently. Furthermore, the transition temperature range must be 12 ° C or less. If the transition temperature range is 12 ° C or more even if the Tg is 60 ° C or more apart, the two are partially compatible but the obtained tan δ-temperature curve has an intermediate property between them. Is not preferable.

In JP-A-60-192739 and 61-55135, the tan δ-temperature curve is broad because the Tg difference of each block of the binary block copolymer is 30 ° C. or more and the transition temperature width is wide. It has been pointed out that Such a block copolymer has two Tg points when it is not vulcanized, but since both are compatible and integrated by vulcanization, they have a single broad peak. According to the above view, if Tg is united, the advantages of each block as a single substance cannot be utilized, and as a result, the physical properties become the same as those of the blended polymer. In other words, although it is improved in terms of physical property balance as compared with the conventional SBR / BR polymer blend, it does not show outstanding physical properties. Therefore, on the contrary, in order to retain the properties of the binary block polymer even after the copolymerization, it was thought that it would be possible to make the block polymers incompatible with each other, and the polymer constitution for that was examined. Under such conditions, it was possible to obtain an improved binary block polymer that retains the unique properties of each constituent polymer alone.

Tg of block (B) with high temperature side Tg is from -20 ℃ to +15
Must be ° C. When the temperature is lower than -20 ° C, tan δ in the temperature range that is involved in grip performance cannot be increased, and when it is higher than + 15 ° C, the heat buildup deteriorates and the tire durability is adversely affected. Along with giving it, the snow and ice road grip deteriorates irretrievably. As for the amount of styrene and the amount of 1,2-vinyl for obtaining such Tg, the styrene content of the block (B) is preferably 20% by weight or more, and when the styrene content is less than 20% by weight, the required Tg
However, if the styrene content is more than 50% by weight, a styrene block is likely to be formed, which is not preferable in terms of abrasion resistance and breaking properties. The amount of vinyl is limited due to the relationship between Tg and the amount of styrene, but a desirable range is approximately 40 to 75% by weight.

Further, the Tg of the block (A) needs to be -80 ° C to -60 ° C. If it is higher than −60 ° C., the elastic modulus at low temperature becomes high at low temperature and the snow-ice road surface grip performance deteriorates. On the other hand, in order to obtain a copolymer block having a Tg lower than −80 ° C., the styrene content must be 15% by weight or less, and in that case the breaking property is deteriorated, which is a practical problem. . When the styrene content is more than 25% by weight, a copolymer having the required Tg cannot be obtained. Vinyl content is determined by Tg,
Approximately 10 to 20% by weight. Furthermore, block (A)
When the difference between the Tg of the block and the Tg of the block (B) is less than 60 ° C., the two are compatible with each other and have one broad tan δ-temperature curve. The temperature dependence of such a compatible copolymer viscoelasticity is, for example, suitable for low rolling resistance tires, but as the tread rubber physical properties for all season high performance tires which is the object of the present invention, It is necessary that the tan δ-temperature curve is not only broad, but also trapezoidal and that the absolute value of tan δ itself is large (“About the temperature dependence of hysteresis friction”: Japan Rubber Association magazine '88. October issue). To do so, block (A) and block (B)
Is important to be incompatible or semi-compatible, and such a trapezoidal tan δ-temperature curve cannot be obtained unless the Tg temperature difference is 60 ° C. or more.

The transition temperature range of both blocks (A) and (B) must be 12 ° C or less. If it is higher than 12 ℃, the difference in Tg
Even if the temperature is above 60 ° C, the blocks are partially compatible with each other, and the tan δ-temperature curve is not desirable for an all-season high-performance tire. The weight average molecular weight needs to be 20 × 10 ⁴ or more, preferably 100 × 10 ⁴ or less for processing and breaking physical properties.

The purpose of the binary copolymer block found in conventionally published patent publications is to achieve both low rolling resistance and wet friction,
This is different from the all-season high-performance tire targeted by the present invention. Therefore, the desirable temperature dependence of viscoelasticity is also different, and as a result, the styrene-vinyl composition of each block, the bonding method, etc. must be significantly different from those of the conventional patents.

Therefore, the present invention is different from the conventional invention in the following points, and it can be said that the obtained polymer is sufficiently novel.

1. The amount of styrene and vinyl contained in blocks (A) and (B) are different.

2. The difference in Tg between blocks (A) and (B) is 60 ° C or more.

3. Tg transition temperature range of blocks (A) and (B) is 12 each
Must be below ℃.

In the present invention, it is more preferable that the higher the molecular weight component, the more the block (A) is contained. This is because when the ratio of each block is constant regardless of the molecular weight, when the molecular chain of the high Tg block freezes at low temperature, the motion of the molecular chain of the low Tg side block is inhibited, This is because it becomes difficult to reduce the elastic modulus at that time. Furthermore, when the temperature becomes higher and the molecular chains of the high Tg side block begin to move, this time the temperature dependence of the overall mobility increases sharply, so tan δ decreases sharply, and the curve is broad. Because it is hard to be.
At the same time, it is desirable to apply a technique known as a technique for modifying a copolymer, such as terminal modification or coupling, as long as it does not adversely affect the temperature dependence of viscoelasticity, which is the goal of the present invention. Is.

As a method for producing such a block copolymer, for example, the amount of styrene and the amount of 1,3-butadiene of each of block (A) and block (B) are adjusted to a predetermined ratio, and ether or the like is used in a hydrocarbon solvent. Polymerization temperature, ratio and charging amount of styrene and butadiene in the presence of a lithium-based polymerization initiator, using the polar compound of
Copolymerization may be performed while controlling the polymerization initiator and the like. This method may be a batch system or a continuous polymerization system.

Blending a natural rubber or IR with the styrene-butadiene block copolymer rubber is important from a practical viewpoint. This is because automobile tires have many opportunities not only to run on paved roads but also on rough roads and irregular roads.In such cases, blending natural rubber prevents tread damage due to sudden external forces such as chipping and cutting. This is because it can be reduced. For this purpose, a blending amount of 10 parts by weight or more is required. On the other hand, if the content of natural rubber or IR is too large, the essential properties of the styrene-butadiene block copolymer rubber will be diminished, and the grip performance will decrease. It is necessary to control the amount.

(2) Carbon black.

It has a nitrogen specific surface area of 100 m ² / g or more. Specifically, for example, ISAF, SAF and the like. If the nitrogen specific surface area is less than 100 m ² / g, the grip performance will be poor and the abrasion resistance will be insufficient.

(3) Petroleum-based softener.

The viscosity specific gravity is 0.90 to 0.98. Other than this, the grip performance cannot be exhibited with paraffin oil having a viscosity specific gravity constant of less than 0.90, and conversely, when it exceeds 0.98, there is no sufficient softening effect during mixing. Examples of the petroleum-based softening agent include aromatic process oils and highly aromatic process oils.

(4) The rubber composition of the present invention contains 80 to 130 parts by weight of the carbon black and 20 to 90 parts by weight of the petroleum-based softening agent based on 100 parts by weight of the rubber component.

In order to be put to practical use as a tread for automobile tires, it must have sufficient performance in terms of wear resistance and steering stability. In order to enhance the steering stability to the extent suitable for high-performance tires, it is necessary to blend 80 parts by weight or more of small particle size carbon black having a nitrogen specific surface area of 100 m ² / g or more. However, if it exceeds 130 parts by weight, the wear resistance and the heat generation property are remarkably inferior, and therefore the amount must be made less than that. Also, as other characteristics of the tire,
Although it has riding comfort, noise, braking performance, etc., it is necessary to blend a developing oil (petroleum-based softening agent) in order to improve these properties and also for processability during tire production.
If the viscosity specific gravity constant of the developing oil is less than 0.90, no improvement in braking performance is observed, and 0.90 to 0.98 aromatic developing oil is preferable. It is necessary to adjust the tread rubber elastic modulus by appropriately increasing or decreasing the blending amount of the developing oil according to the blending amount of carbon black. However, if the amount is less than 20 parts by weight, the compounded rubber does not show elongation, resulting in poor chipping and cutting properties, and also difficult processability, which is not preferable. On the other hand, if the amount exceeds 90 parts by weight, the strength decreases and the abrasion resistance becomes extremely poor, so that it is difficult to put into practical use.

The rubber composition of the present invention is obtained as described above, but it is necessary that the shear storage elastic modulus at −30 ° C. is 500 MPa or less. Generally, a rubber-like substance is in a glass state at a temperature of Tg or lower, its elastic modulus is 100 times or more that at room temperature, and it is fragile and breaks with a slight strain. The temperature at this time is called a low temperature embrittlement temperature and is known as an index of the low temperature performance of the rubber material. However, as in the case of the rubber composition of the present invention, when the elastic modulus changes slowly,
The brittleness temperature cannot be estimated simply from Tg. First
The figure is a plot of the low temperature embrittlement temperature and the shear storage elastic modulus (G ′) at that temperature for various rubber compositions. From this, it can be seen that the G'value at the brittle temperature of all samples exceeds 500 MPa. Therefore, 500M
If it is Pa or less, it can be said that the embrittlement temperature is not exceeded. The shear storage elastic modulus at −30 ° C. is because tires are not usually used at a temperature lower than −30 ° C. The shear modulus is measured with a strain of 0.5% and a frequency of 20 Hz using a dynamic torsion tester.

 Examples and comparative examples are shown below.

(Examples, Comparative Examples)

Binary block copolymers A to G having the structures shown in Table 1 were produced. Furthermore, emulsion polymerization for comparison with these copolymers
SBR was vulcanized with the composition shown in Table 2. The numbers in the table are parts by weight unless otherwise specified. The vulcanization conditions were 160 ° C. × 20 minutes, and a 2 mm thick rubber sheet was obtained. The physical properties of this sheet were measured. In addition, this measurement was performed by the following method. The vinyl bond content of the butadiene portion was determined by the Morello method, and the styrene content was determined by the Hampton method using an infrared spectrometer.
Tg and transition temperature range are THERMAL ANALYZER manufactured by DuPont
Was measured at a heating rate of 10 ° C./min, and determined by the extrapolation start temperature and the method shown in FIG. 2, respectively. FIG. 2 shows a DSC curve, and the vertical axis shows the heat flow near the glass transition point. The weight average molecular weight M _W is GP
It is shown in terms of polystyrene by C. The tensile strength T _B and the elongation at break E _B were according to JIS K6301. The shear modulus G '(-30 ° C) at -30 ° C and tan δ at 0 ° C are
Using a dynamic viscoelasticity measuring device manufactured by HEOMETRICS, frequency 20H
z, shear strain was measured at 0.5%.

Comparative Examples 5 and 6 are examples of blends of emulsion polymerized SBR and natural rubber, but the compound of Comparative Example 5 has good low temperature performance.
The tan δ (0 ° C) is low and the wet performance is poor. On the contrary, in Comparative Example 6, tan δ is high, but low temperature performance is not possible. Also,
Comparative Examples 2, 3, and 4 are block (A) and block (B).
This is an example of using a styrene-butadiene copolymer rubber having a Tg temperature difference of 60 ° C. or less. Both blocks are compatible with each other and show a broad tan δ-temperature curve with a single peak. Good, but poor wet performance. In comparison with these, Examples 1 to 3 are well balanced in both performances.

〔The invention's effect〕

As described above, the rubber composition of the present invention has a stable grip performance over a wide temperature range and is excellent in gripping a snow / ice road surface, as compared with the rubber composition of the prior art. It can be suitably used for a tire tread portion, especially for an all season type high performance tire tread portion.

[Brief description of the drawings]

Fig. 1 is a diagram showing the relationship between the low temperature embrittlement temperature and the shear modulus of a rubber compound, Fig. 2 is an explanatory diagram showing the transition temperature range near the glass transition point of the DSC curve, and Fig. 3 is an emulsion polymerization that differs only in the styrene content. It is an tan delta-temperature curve of SBR, and is an explanatory view showing that a thing with a high styrene content has a high peak temperature.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 9/06 C08L 9/06 // (C08L 53/02 7:00) (C08L 53/02 9:00) (C08L 9/06 7:00) (C08L 9/06 9:00)

Claims (1)

(57) [Claims] 1. A styrene-butadiene copolymer block (A) having a glass transition temperature of -80 ° C. to -60 ° C. and a transition temperature range of 12 ° C. or less, containing 15 to 25% by weight of bound styrene, and bound styrene. Containing 20 to 50% by weight and having a glass transition temperature of -20 ° C.
It is composed of a styrene-butadiene copolymer block (B) having a transition temperature range of 12 ° C or less at a temperature of + 15 ° C, and a difference in glass transition temperature between the block (A) and the block (B).
60 ℃ or more, the total copolymer styrene as a whole copolymer
20-35% by weight, vinyl bond content of all butadiene parts is 20-45
% By weight, 90 to 50 parts by weight of a styrene-butadiene block copolymer rubber having a weight average molecular weight of 20 × 10 ⁴ or more, and a total of 100 parts by weight of rubber containing natural rubber or isoprene rubber as the balance, and nitrogen. 80 to 130 parts by weight of carbon black having a specific surface area of 100 m ² / g or more, a viscosity specific gravity constant of 0.90 to
20 to 90 parts by weight of 0.98 petroleum-based softening agent is compounded, and the shear storage elastic modulus at −30 ° C. is 500 MPa or less, a rubber composition for a tire tread.