JPH04370126A - Rubber composition - Google Patents

Abstract

PURPOSE:To provide the subject rubber composition having an improved abrasion resistance while keeping its low heat built-up and low impact resilience and suitable for a tire tread of a passenger car, a track and a bus. CONSTITUTION:With 100 pts.wt. rubber component, 35-100 pts.wt. furnace carbon black having 60-160m<2>/g specific surface area measured by nitrogen adsorption and 90-150ml/100g DBP oil absorption, belonging to hard group and showing characteristics represented by the formula (Dp mode diameter is most probable mode diameter in pore size distribution between carbon black particles, measured by differential scanning calorimeter; Dst mode diameter is stokes mode diameter of carbon black, measured by discentrifuge device) is blended.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention provides a rubber composition suitable for use in tire tread members, and more particularly, a rubber composition that exhibits improved wear resistance without impairing low heat generation properties. The present invention relates to a rubber composition. [0002]Recently, as the performance of automobiles increases, demands for high-speed performance, stability performance, and durability performance have increased.
It is an important issue to improve the properties of tire tread members that are involved in these various performances, especially to achieve both wear resistance and low heat generation. In addition, in order to respond to social demands such as resource conservation and energy conservation, the development of fuel-efficient tires is actively underway. It is essential to have these characteristics. [0003] In general, the performance of rubber, such as wear and heat generation, is largely controlled by the properties of the carbon black to be blended, but it is known that these rubber performances have an antinomic relationship. For example, in order to provide the low heat build-up required for fuel-efficient tires, it is effective to incorporate a small amount of carbon black, which has a relatively large particle size, into rubber; A deterioration in characteristics such as braking performance on road surfaces is unavoidable. Additionally, carbon black, which has the characteristics of having the smallest possible particle size and large structure, is effective for tire treads that require a high degree of wear resistance under harsh driving conditions. This increases the heat generation property of the rubber composition, leading to the risk of accelerating phenomena such as destruction of the internal structure due to heat accumulation during running and aging of the constituent materials. [0004] For this reason, in addition to the basic properties of carbon black such as particle size (specific surface area) and structure, other properties were micro-evaluated, and carbon black with specific selective properties was blended into rubber. Many techniques have been proposed to simultaneously improve wear resistance and low heat generation. Among these, the following proposals target N339 class carbon black, which is often used as tire treads for passenger cars and light trucks. (1) Nitrogen adsorption specific surface area (N2SA) is 60m2/g
As described above, carbon black for rubber compounding (Japanese Patent Publication No. 1-53978) has a compressed DBP in a range of 112 ml/100 g or more and a Stokes mode diameter and a Stokes mode distribution of carbon black aggregates of a certain value or more. (2) N2 SA is 60m2/g or more, DBP is 10
8 ml/100 g or more, the true specific gravity per specific surface area is set to a specific range that is significantly lower than that of known carbon blacks, and the coloring power and distribution width per aggregate mode diameter are controlled to above a certain value. Rubber composition containing black (Japanese Patent Application Laid-Open No. 59-14024
Publication No. 1). (3) N2 SA is 65 to 84 m2/g, N2 SA
/iodine adsorption amount (IA) ratio is in the range of 1.10 to 1.35, and the value defined by the formula using compressed DBP, blackness, IA, and aggregate mode diameter as variables is greater than a specific value. Carbon black for rubber compounding with set properties (
JP-A-63-225639). (4) N2 SA is 75-105m2/g, compression D
The BP is in the range of 110 ml/100 g or more, the true specific gravity per certain specific surface area is set to a specific range lower than that of known carbon black, and the distribution width per particle aggregate pore diameter and aggregate mode diameter is set to a certain value or more. carbon black for rubber compounding which has the property of maintaining [0006] Further, the following improvement proposals have been made for N220 and N110 class carbon blacks, which are mainly used in large tire tread members for trucks and buses. (5) A rubber composition containing carbon black having an N2 SA in the range of 100 to 200 m2/g and having a relatively broad aggregate Stokes size distribution with respect to the particle size (Japanese Patent Application Laid-open No. 112638/1983) ). (6) A rubber composition containing carbon black having an N2 SA in the range of 70 to 185 m2/g and an aggregate Stokes diameter distribution having two maximum points in a specific range (Japanese Patent Application Laid-open No. 179941/1983). . (7) N2 SA is in the range of 110 to 155 m2/g, DBP, compressed DBP, blackness, N2
A rubber composition containing carbon black whose value is within a specific range defined by a formula using SA and iodine adsorption as variables (Japanese Unexamined Patent Publication No. 63-297439). However, in recent years, demands for fuel-efficient tires have become increasingly sophisticated, and there is a demand for the development of low heat generation rubber compositions that have superior abrasion resistance while maintaining a high level of rebound. . The present inventor has developed a rubber composition with characteristics that meet this requirement, with a nitrogen adsorption specific surface area (N
2SA) belongs to the hard type region of 60 to 100 m2/g, and the mode diameter (Dp) of the aggregate intergranular pores is D.
Furnace carbon black that satisfies the relational expression p≦1.543×Dst mode diameter) -55.0 was used as rubber component 1.
Developed a rubber composition containing 35 to 100 parts by weight to 00 parts by weight (Japanese Patent Application No. 2-340732)
No.). [0008] However, although the rubber composition according to the prior invention is suitable for tire treads of passenger cars and light trucks, it is not suitable for use in large buses and trucks used under more severe conditions. The tire tread installed on the vehicle had some shortcomings in its characteristics. [0009] As a result of continued research to solve the above-mentioned problems, the present invention has developed a system with N2 SA of 60 to 160 m2.
/g, is a carbon black that belongs to the hard type region with a DBP oil absorption of 90 to 150 ml/100 g, and contrary to the prior invention, the mode diameter of aggregate intergranular pores is smaller than that of previously known carbon blacks. The rubber composition, which has been selected and blended with great properties, was developed based on the discovery that it has both rebound resilience (low heat generation) and abrasion resistance, making it suitable for a wide range of tire treads, from passenger cars to trucks and buses. It is something that [0010] Accordingly, an object of the present invention is to provide a rubber composition that exhibits high wear resistance while maintaining low heat generation properties suitable for use in fuel-efficient tire treads for vehicles ranging from passenger cars to trucks and buses. Means for Solving the Problems The rubber composition according to the present invention for achieving the above object has a nitrogen adsorption specific surface area (N
2SA) is 60-160m2/g, DBP oil absorption (D
BP) belongs to the hard type range of 90 to 150 ml/100 g, and carbon black having the following selective properties is blended at a ratio of 35 to 100 parts by weight per 100 parts by weight of the rubber component. Features. Dp mode diameter ≧ 1.543 × (Dst mode diameter) -30.0 However, Dp mode diameter refers to the mode diameter of the maximum frequency in the pore diameter distribution between carbon black particles measured by differential scanning calorimeter (DSC). ,
The Dst mode diameter is the disk centrifuge device (DS
C) refers to the Stokes mode diameter of carbon black aggregate measured by [0012] For each characteristic of the carbon black having the above structure, values obtained by the following measuring method are used. Nitrogen adsorption specific surface area (N2SA); ASTM D303
7-88 “Standard Test Meth
od for Carbon Black-Surfa
ceArea by Nitrogen Absorp
tion” by MethodB.I by this method
The measured value of RB#6 is 76 m2/g. DBP oil absorption (DBP); JIS K6221 (1
982) “Testing method for carbon black for rubber” 6 ・
Items 1 and 2, based on oil absorption method A. IR using this method
The measured value of B#6 is 99.0ml/100g. [0013] Dp mode diameter; JIS K6221
(1982) 5. After drying based on "How to prepare a dry sample", a precisely weighed carbon black sample was mixed with distilled water to obtain a carbon black concentration of 0.250 g/cm3.
Create a paste and thoroughly disperse it using ultrasound. Within 10 minutes after ultrasonic dispersion, a differential scanning calorimeter (DSC, Me
Start measuring the distribution of aggregate intergranular pores using DSC30 (manufactured by Ttler). In this case, the amount of paste to be collected should be within the range of approximately 3 to 5 mg, and after placing it in an aluminum sample container and sealing it, confirm the mass of the paste and use the DS mentioned above.
Set it in the C device and measure in the next step. ■Quickly cool from room temperature to -80℃. ■From -80℃ to -5℃1
0°C/min. Heat at a speed of ■-5℃ to -0
．． 1°C/min. After heating at a rate of
Maintain at -0.1°C (0.1°C lower than the freezing point of distilled water) for 10 minutes. ■-0.1℃ to -8℃
up to 0.1°C/min. Cool gradually at a rate of and record the compensation energy. Then, from the chart of compensation energy obtained in step ■, each temperature (in 0.1°C increments)
Read the height (y) of the mountain and perform the following (2) and (3).
The pore diameter (Dp) and pore distribution (ΔV/ΔDp) between aggregate particles are obtained from the equation. Dp = (135.34/ΔT)+1.14...
(2) ΔV /ΔDp=K・(ΔT)2/Wa×y
...(3) In the equations (2) and (3), ΔT is the freezing point depression width of distilled water, Wa is the heat of solidification of distilled water, and K is D
This is a factor that takes into account the sensitivity of the SC device and the mass of the sample. These formulas were derived by Brun et al., Thermochimica Acta, 21
(1977) 59-88 “A NEW METHOD”
FOR THE SIMULTANEOUS DETE
RMINATION OF THE SIZE AND
THE SHAPE OF PORES: THE
THERMOPOROMETRY”. In addition, ASTM D-24 St
andard Reference Black C-
The Dp mode diameter of 3(N234) was 77.6 nm. Dst mode diameter: Dry carbon black is mixed with a 20% aqueous ethanol solution containing a small amount of surfactant to create a dispersion liquid with a carbon black concentration of 50 ml/l, and this is sufficiently dispersed with ultrasonic waves to prepare a sample. shall be. Disc centrifuge device [UK Joyes Lob
[manufactured by El Corporation] was set at a rotation speed of 8,000 rpm, 10 ml of spin solution (2% glycerin solution) was added, and 1 ml of buffer solution (ethanol aqueous solution) was injected. Next, 0.5 ml of the carbon black dispersion liquid is added with a syringe to start centrifugal sedimentation, and at the same time, a recorder is activated to optically create a distribution curve of the aggregate Stokes equivalent diameter. The Stokes equivalent diameter of the maximum frequency in the obtained distribution curve is defined as the Dst mode diameter. ASTM D-24 Standard measured using this method
Reference Black C-3 (N234)
The Dst mode diameter of was 80 nm. Among the carbon black characteristic items specified in the present invention, nitrogen adsorption specific surface area (N2SA) is 60 to 16
Particle size range of 0m2/g and DBP oil absorption 90~1
The structure range of 50 ml/100 g belongs to the hard type range of ordinary products, and is a prerequisite for imparting a high degree of abrasion resistance to compounded rubber and maintaining an appropriate low heat generation property. This nitrogen adsorption specific surface area (N2SA) is 60m
If it is less than 2/g, the abrasion resistance will be significantly reduced;
If it exceeds 2/g, the dispersibility in rubber deteriorates, wear resistance does not improve smoothly, and heat generation also increases. Also, D.B.
If the P oil absorption amount is less than 90 ml/100 g, the wear resistance will be impaired, and if it exceeds 150 ml/100 g, the ice skid property will decrease, leading to a decline in safety performance. The selective characteristic regarding the Dp mode diameter set in the present invention is an index indicating the properties of aggregates in which carbon black is firmly fused and bonded, and is determined by the size of the carbon black aggregate itself ( D
It is characterized in that the size of the aggregate intergranular pores (Dp mode diameter) is relatively large compared to the Dp mode diameter). And Dp mode diameter ≧ 1.543×
(Dst mode diameter) When the requirement of -30.0 is satisfied, it becomes possible to impart suitable low heat build-up and significantly improved abrasion resistance to the compounded rubber. [0017] Carbon black with these characteristics has a combustion chamber having an air supply port in the tangential direction at the furnace head and a combustion burner inserted in the axial direction of the furnace, and several stages coaxially connected to the combustion chamber. By using an oil furnace with a structure that has a narrow diameter reaction zone and a wide diameter reaction zone, combustion conditions such as fuel oil supply amount and air supply amount, feed amount of feedstock oil introduced in multiple stages into the narrow diameter reaction zone, etc. are controlled. can be manufactured. The above-mentioned carbon black is blended into an elastomer such as natural rubber, diene-based synthetic rubber, or a blended rubber obtained by blending diene-based synthetic rubber with natural rubber or isoprene rubber in accordance with a conventional method. The blending ratio of carbon black is 35 to 100 parts by weight per 100 parts by weight of the rubber component, and it is combined with a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a vulcanization aid,
The rubber composition of the present invention is obtained by kneading with necessary components such as a softener and a plasticizer. [Operation] The Dp mode diameter of the aggregate intergranular pores is
It is closely related to the conditions during production, such as the reaction temperature and degree of disturbance of combustion gas in the carbon black production process, and therefore has a large correlation with the structure and specific surface area of the produced carbon black. According to the inventor's study, it has been confirmed that the Dp mode diameter of carbon black currently on the market is within the range of formulas (4) and (5) below. Dp mode diameter = [75.2 x (DBP/N2SA)]
±3.0Dp mode diameter = [1.543 × (Dst mode diameter) -42.8±8.0 For example, ASTM D
-24 Standard Reference Bl
The actual measured Dp mode diameter of ack C-3 (N234) is 77.6 nm, but this value is calculated from the actual measured Dst mode diameter of 80 nm, which is calculated from the above equation (5).
The p mode diameter is within the range of 72.6 to 88.6 nm. [0020] Therefore, the Dp specified in the present invention
The mode diameter is determined in relation to the Dst mode diameter (5
) is located at a higher level than the value calculated from the formula,
It is presumed that this unique property functions effectively to increase the abrasion resistance of the compounded rubber without impairing its low heat build-up properties. This function is different from the function of the invention of Japanese Patent Application No. 2-340732 in which the Dp mode diameter is set to a low level, which improves the heat resistance to a greater extent than the wear resistance. [0021] The above functions are premised on a rubber composition that combines low heat build-up and high abrasion resistance and is suitable for tire treads, in conjunction with the ability to adjust rubber performance through nitrogen adsorption specific surface area and DBP oil absorption. It becomes possible to provide [Example] Examples 1 to 3, Comparative Examples 1 to 3 A combustion chamber (diameter 900 mm, length 10
A first stage narrow-diameter reaction zone (diameter 200 mm, length 600 m) is installed and coaxially connected to the combustion chamber.
m), a second stage narrow-diameter reaction zone (diameter 160 mm, length 600 mm) and a subsequent wide-diameter reaction zone (diameter 4
Three types of carbon black were produced by changing the generation conditions using an oil furnace consisting of a 100 mm diameter oil furnace with feedstock oil introduction nozzles installed in each of the first and second narrow-diameter reaction zones. As raw material oil, specific gravity (15/4
°C) 1.073, viscosity (Engler 40/20 °C)
2.10, toluene insoluble content 0.03%, correlation coefficient (B
Aromatic hydrocarbon oil with MCI) 140 and fuel oil with specific gravity (15/4 °C) 0.903 and viscosity (Cst/
50℃) 16.1, residual coal content 5.4%, flash point 96
℃ hydrocarbon oil was used. Table 1 shows carbon black generation conditions, Table 2
Examples of the characteristics of carbon black obtained in
No. Displayed in accordance with. In addition, Comparative Examples 1 to 1 in Table 2
No. 3 is a conventional type of carbon black that has equivalent hard properties but does not meet the selective property requirements of the present invention. [Table 1] [Table 2] Table note: (1) [1.543×(Dst mode diameter) −30.0] Calculated value (same for Table 6). (2) Comparative Example 1: N351, Comparative Example 2: N347, Comparative Example 3: N339 Next, these carbon black samples were blended into styrene-butadiene rubber (SBR) at the blending ratio shown in Table 3. Table 4 shows the results of measuring various rubber properties for each rubber composition obtained by vulcanizing the formulations in Table 3 at a temperature of 145° C. for 50 minutes. The rubber properties were measured as follows. ■Wear amount Using a Lambourne abrasion tester (mechanical slip mechanism),
Measurement was performed under the following conditions. Test piece: Thickness 10mm, outer diameter 44mm Emery wheel: GC type, particle size 80, hardness H-added carborundum powder: particle size 80 mesh, addition amount approximately 9g/mi
n. Relative slip rate between emery wheel surface and test piece: 24%
, 60% Test piece rotation speed: 535 rpm Test load: 4 kg 0029 ■ tan δ (loss coefficient) Visco Elastic Spec manufactured by Iwamoto Seisakusho
It was measured using a trometer under the following conditions. Test piece: 2mm thick, 30mm long, 5mm wide Frequency:
50Hz Dynamic strain rate: 1.2% Temperature: 60°C ■Other properties According to JIS K6301 "Vulcanized Rubber Physical Test Method". [Table 4] From Table 4, the results of the examples show that tan δ (loss coefficient ) and impact resilience were the same, but it was recognized that the wear resistance performance was significantly improved. Examples 4-5, Comparative Examples 4-5 Using the same oil furnace, raw material oil and fuel oil as in Example 1,
Two types of carbon black were produced under the generation conditions shown in Table 5. [Table 5] The properties of the obtained carbon black are as shown in Table 6. Note that Comparative Examples 4 and 5 listed in Table 6 are existing carbon blacks having the same specific surface area. [Table 6] Table note; Comparative example 4: N220, Comparative example 5: N11
0. Next, each carbon black was blended with natural rubber under the blending conditions shown in Table 7. [0037] [0038] The formulation shown in Table 7 was vulcanized at a temperature of 145°C for 40 minutes, and various properties of the obtained rubber composition were measured. The results are shown in Table 8. [Table 8] From Table 8, Examples 4 and 5, which meet the selective property requirements of the present invention, have low heat build-up and high-grade properties that are equal to or higher than those of the comparative example with the same specific surface area level even when compounded with natural rubber. It has abrasion resistance. [0041] As described above, the rubber composition of the present invention is provided with effectively improved abrasion resistance while maintaining suitable low heat generation properties and rebound resilience. The combination of these properties makes it extremely useful for tire treads of all types of vehicles, from passenger cars to trucks and buses, which require high speed, stability, and durability under severe driving conditions.

Claims (1)

[Claims] [Claim 1] Nitrogen adsorption specific surface area (N2SA) is 60
~160m2/g, DBP oil absorption (DBP) is 90
~150ml/100g A rubber composition characterized by being blended with furnace carbon black belonging to the hard type region and having the following selective properties at a ratio of 35 to 100 parts by weight per 100 parts by weight of the rubber component. . Dp mode diameter ≧ 1.543 × (Dst mode diameter) -30.0 However, Dp mode diameter refers to the mode diameter of the maximum frequency in the pore diameter distribution between carbon black particles measured by differential scanning calorimeter (DSC). ,
The Dst mode diameter is the disc centrifuge device (DC
F) refers to the Stokes mode diameter of carbon black measured by