KR19990033223A - Carbon Black and Rubber Composition Containing the Same - Google Patents

Abstract

The present invention relates to carbon black and a rubber composition containing the same, a nitrogen adsorption specific surface area (NSA) of 70 to 150 m 2 / g, dibutyl phthalate oil absorption (DBP) of 70 to 140 ㏄ / 100 g, iodine adsorption specific surface area (12NO) is 70 to 160 mg / g, compressed dibutyl phthalate oil absorption (24M4 DBP) is 70 to 130 ㏄ / 100g, and at the same time the tint (TINT) is at least 8.1 or more than the PT value defined by Equation 1 below. Carbon black and rubber composition containing 40 to 150 parts by weight of the carbon black per 100 parts by weight of natural or synthetic rubber, the wear resistance and traction performance that overcomes the inverse correlation of the conventional carbon black characteristics To improve.

Equation 1

PT = (0.60879 * NSA) + (0.000572 * DBP)-(0.25726 * 12NO)-(0.18418 * 24M4DBP)

Description

Carbon black and Rubber composition containing the same

FIELD OF THE INVENTION The present invention relates to Paanes carbon black with new features, and in particular to carbobon black and rubber compositions containing the carbon black, which exhibit excellent properties when applied to rubber.

In general, carbon black is mainly manufactured by the Panes process in which raw material oil injected in a reaction zone is formed by pyrolysis of hot oil generated after complete combustion of fuel oil in a combustion chamber to form carbon black particles having a predetermined size by pyrolysis. .

The type of the carbon black is generally classified according to the size of the particle size and the degree of development of the structure.

Carbon black is optionally used as a black pigment, as a filler or as a reinforcing agent. Especially in the rubber application field, carbon black is well known as a very important property controlling factor such as greatly improving the physical properties of rubber compound when incorporated into rubber as a filler or reinforcing agent.

Among the rubber application fields, the weight is mainly used for various automobile tires. In the tire structure, especially the part which touches the road surface, the tread carbon black is generally made of HAF, ISAF, SAF, etc., depending on the degree of reinforcement. Are distinguished. When this kind of carbon black is mixed with rubber, various characteristics required for tires, such as wear resistance, traction performance expressed on a dry or wet road surface, slip performance, fuel consumption and handling characteristics, and cornering directly related to fuel consumption Characteristics and the like are remarkably improved.

In addition, the rubber used in the tire includes natural rubber and synthetic rubber. The synthetic rubber is mainly composed of SBR and BAL, but depending on the purpose, nitrile rubber, EPM, EPDM, IIR, etc. Used.

In general, carbon black has a higher specific surface area, that is, a smaller particle size improves abrasion resistance, but consequently, deteriorates fuel efficiency. In other words, the smaller the particle size, the higher the exothermicity, which means an increase in hysteresis, which in turn increases fuel consumption due to the correlation with the rolling resistance of the tire. As the particle size is smaller, the wear resistance is improved but the fuel economy is inversely correlated. In addition, when the particle size is smaller than the limit, not only is it difficult to disperse, but also the wear property of the dispersing device is increased accordingly. Accordingly, in order to increase the dispersibility, the mixing is required several times, and the productivity is lowered, and the mixing energy having a high energy must be used.

On the other hand, the smaller the specific surface area of the carbon black, that is, the larger the particle size of the carbon black, the better the workability, but the wear resistance is deteriorated and the fuel efficiency is improved.

The required characteristics of these tires are inversely correlated with each other, so it is very difficult to improve them at the same time, and it is like magic, and is referred to as Magic Triangle in the related industry.

Therefore, the present invention was devised to simultaneously improve the various properties in the above correlation, carbon black by controlling the characteristics of the carbon wear resistance, good fuel efficiency, excellent traction and good processability carbon black The purpose is to provide.

It is another object of the present invention to provide a rubber composition containing the carbon black.

The carbon black of the present invention for achieving the above object has a nitrogen adsorption specific surface area (NSA) of 70 to 150 m 2 / g, dibutyl phthalate oil absorption (DBP) of 70 to 140 Pa / 100g, iodine adsorption specific surface area ( 12NO) is 70 to 160 mg / g, compressed dibutyl phthalate oil absorption (24M4 DBP) is 70 to 130 ㏄ / 100g, and at the same time the coloring degree (TINT) is at least 8.1 or more than the PT value defined by the following equation (1) It is to be done.

PT = (0.60879 * NSA) + (0.000572 * DBP)-(0.25726 * 12NO)-(0.18418 * 24M4DBP)

The rubber composition for achieving another object of the present invention described above is 100% by weight of natural rubber alone or synthetic rubber alone, or a mixture of these at a certain ratio, or a mixture of two or more different synthetic rubber at a constant ratio When it is negative, the carbon black is characterized in that it is mixed to at least 40 to 150 parts by weight.

The synthetic rubber may be SBR, BAL, Nitrile Rubber, EPM, EPDM, IIR, etc. After-treatment can also be used.

1 is a cross-sectional view of a reactor for producing carbon black according to the present invention.

* Explanation of symbols for the main parts of the drawings *

1 fuel oil introduction nozzle 2 preheating air inlet

3: raw material oil introduction port 4: cooling water introduction port

5: combustion zone 6: reaction zone

7: reaction termination zone

Hereinafter, the present invention will be described in detail.

The carbon black according to the present invention has a nitrogen adsorption specific surface area (NSA) of 70 to 150 m 2 / g, a dibutyl phthalate oil absorption (DBP) of 70 to 140 Pa / 100g, and an iodine adsorption specific surface area (12NO) of 70 to 160 Mg / g, compressed dibutyl phthalate oil absorption (24M4 DBP) is 70 to 130 ㏄ / 100g and at the same time the tint (TINT) is at least 8.1 or more than the PT value defined by the equation (1).

Equation 1

PT = (0.60879 * NSA) + (0.000572 * DBP)-(0.25726 * 12NO)-(0.18418 * 24M4DBP)

In addition, the rubber composition containing the carbon black of the present invention may be 100 parts by weight of natural rubber alone or synthetic rubber alone, or a mixture of these at a constant ratio, or a mixture of two or more different synthetic rubbers at a constant ratio. At this time, the carbon black according to the present invention is incorporated at least 40 to 150 parts by weight. The synthetic rubber used at this time is SBR, BAL, Nitrile Rubber, EPM, EPDM, IIR, etc. The processed thing can also be used.

Carbon black according to the present invention can be prepared through the Paanes method, which is a typical method for producing the same. This will be described with reference to the accompanying drawings.

1 is a cross-sectional view of a reactor used in the Paanes method, the reactor is the overall shape of one cylindrical shape, the inner wall is composed of a high heat-resistant refractory. In the combustion zone 5, a carbon having a particle size of a certain size is formed in the reaction zone 6, which is provided with a raw oil inlet 3 for forming energy necessary for pyrolysis of the raw oil and introducing the raw oil into the reactor. The black formation reaction occurs, and in the reaction termination zone (7), a reaction to terminate the carbon black formation reaction by cooling water occurs. The reactor also has an air preheater to obtain combustion air preheated to a high temperature for complete combustion of the fuel oil at the rear end of the reaction zone, separating the carbon black from the hot heat gas containing the carbon black produced in the reactor. It consists of a collector, a granulator that makes the shape of carbon black into a small spherical shape, and a dryer to remove the water input during the assembly process of the front end, and finally, a packing machine that packs the carbon black of the finished product in a certain unit quantity. It is.

Fuel oil and raw oil used in the production of carbon black of the present invention are the same petroleum-based heavy oils generated in crude oil refining process, the characteristics are shown in Table 1.

Characteristics of Fuel Oil and Raw Oil division Characteristics Carbon content weight ratio (%) 90.2 Hydrogen content weight ratio (%) 7.6 Viscosity, SUS 60F 71.0 Specific gravity, 60F 1.10 Asphaltes content weight ratio (%) 5.4 Sulfur content weight ratio (%) 0.6 BMCI 142.0

In order to evaluate the basic characteristics and rubber mixing characteristics of the carbon black according to the present invention, the following test evaluation method was used.

Nitrogen adsorption specific surface area (NSA)

It was measured by D3037-81 "Surface area by nitrogen adsorption" of the American Test and Material Standard (ASTM).

Dibutyl Phthalate Oil Absorption Rate (DBP)

It was measured by D2414-82 "Dibutyl phthalate absorption" of the American Test and Material Standard (ASTM).

Iodine adsorption specific surface area (12NO)

It was measured by D1510-92b "Standard test method for carbon black-iodine adsorption number" of the American Test and Material Standard (ASTM).

Compressed dibutyl phthalate oil absorption (24M4 DBP)

Standard test method for carbon black-n-dibutyl phthalate absorption number of compressed sample of D3493-93 "carbon black of the American Test and Material Standard (ASTM) ) ".

Coloring degree (TINT)

It was measured by D3265-80 "TINT strength" of the American Test and Material Standard (ASTM).

Lambbourn Abrasion

Rambon wear is to measure the amount of wear under the same conditions using a rambon wearer to indicate the percentage of an example for comparison. In other words, the higher the value, the better the wear resistance, and the lower the value means the opposite. Test specimens shall be 54 mm in diameter and 12.7 mm thick, vulcanized for 40 minutes at 145 ° C for natural rubber formulations and 50 minutes at 145 ° C for synthetic rubber formulations. Grinding stone is C type, roughness is 80 mesh (# 80), binding degree is K degree. Pressurized load was constant at 12 kg, but slip ratios were varied at 15%, 30% and 50%. Abrasion yarns were flown 10g per minute of specification # 100.

Tensile stress, tensile strength, elongation

It was measured by D412 of the American Test and Material Standard (ASTM). However, the vulcanization condition of the specimen was vulcanized at 145 ° C. for 30 minutes for natural rubber compounding and for 50 minutes for synthetic rubber compounding.

Dispersion

It was measured by method C in D2663-89 "Standard test methods for carbon black-Dispersion in rubber" of the American Test and Material Standard (ASTM).

Fuel efficiency index and attraction index

Viscoelastic group, model 881, manufactured by MTS Co., Ltd. was used, and the fuel efficiency index was expressed as a percentage of the comparative example based on the loss tangent at 60 ° C. It is expressed as a percentage compared to the example. The higher the fuel economy index, the greater the fuel consumption. The larger the index, the better the performance. The test specimens were 2 inches in diameter and 1 inch thick, and were vulcanized at 145 ° C. for 40 minutes for natural rubber blends and 60 minutes for synthetic rubber blends.

When the carbon black according to the present invention is incorporated into rubber, natural rubber blends and synthetic rubber blends used for evaluating their expression characteristics are shown in Tables 2 and 3 below.

Natural rubber compounding ratio Mixing Weight content (PHR) Natural rubber 100 Carbon black 50 Zinc Oxide (ZnO) 5.0 Stearic acid 3.0 Accelerator (MBTS) 0.6 brimstone 2.5

Synthetic rubber compounding ratio Mixing Weight content (PHR) Synthetic rubber 100 Carbon black 50 Zinc Oxide (ZnO) 3.0 Stearic acid 1.0 Accelerator (MBTS) 1.0 brimstone 1.75

Examples and Comparative Examples

Carbon black according to the present invention was prepared in the reactor of FIG. 1 using fuel oil and raw oil having the characteristics mentioned in Table 1 above. As shown in Table 4, three carbon blacks having different nitrogen adsorption specific surface areas, namely, Example 1, Example 2, and Example 3, were obtained under different operating conditions.

Manufacturing Conditions of Carbon Black division Example 1 Example 2 Example 3 Preheated air amount (nm ³ / h) 10200 8700 6100 Air preheating temperature (℃) 650 545 550 Raw material flow rate (㎏ / h) 2533 2394 2450 Fuel flow rate (㎏ / h) 615 528 490

The carbon adsorption specific surface area of carbon black according to Example 1 was 140 m 2 / g. In order to compare the properties, the conventional SAF having similar nitrogen adsorption specific surface area was used as Comparative Example 1, and the basic properties, natural rubber compounding properties, and synthetic rubber compounding of carbon black according to Example 1 and Comparative Example 1 The properties are shown in Table 5.

Characteristics according to Example 1 and Comparative Example 1 division Example 1 Comparative Example 1 Basic Characteristics of Carbon Black NSA (㎡ / g) 140 143 DBP (㏄ / 100g) 113 113 12NO (mg / g) 145 145 24M4 DBP (㏄ / 100g) 98 98 TINT (%) 133 124 PT 123.3 125.1 TINT-PT 9.7 -1.1 Natural rubber compounding characteristics Tensile Strength (PSI) 4111 4200 300% tensile stress (PSI) 2424 2210 % Elongation 515 520 Slip Rate 15% Abrasion 111 100 Slip Rate 30% Abrasion 107 100 50% slip rate 108 100 Dispersion (%) 92 90 Fuel economy index 101 100 Traction Index 115 100 Synthetic Rubber Compounds Tensile Strength (PSI) 4535 4520 300% tensile stress (PSI) 2934 2790 % Elongation 488 490 Slip Rate 15% Abrasion 108 100 Slip Rate 30% Abrasion 109 100 50% slip rate 113 100 % Dispersion 92 89 Fuel economy index 99 100 Traction Index 117 100

As can be seen from Table 5, the carbon black of Example 1 according to the present invention is the carbon black of Comparative Example 1, wherein the difference between the coloration and the PT value defined by Equation 1 is a conventional carbon black. It is a very large number that cannot be achieved. That is, the conventional carbon black showed a negative value (-1.1).

In addition, the carbon black of the present invention according to Example 1, it can be seen that the tensile stress is higher in the natural rubber compounding and synthetic rubber compounding compared to the conventional carbon black of Comparative Example 1, the case of the conventional carbon black In Example 1, which is the carbon black of the present invention, the fuel efficiency is compared with that of Comparative Example 1, whereas the other property is deteriorated due to mutual correlation between wear resistance, fuel efficiency, and traction performance. It is similar, but wear resistance and traction are greatly improved.

The carbon adsorption specific surface area of the carbon black obtained in Example 2 was 121 m 2 / g. For comparison of characteristics, conventional ISAF having a similar nitrogen adsorption specific surface area was used as Comparative Example 2. Table 6 shows the basic properties, natural rubber compounding properties and synthetic rubber compounding properties of the carbon black according to Example 2 and Comparative Example 2.

Characteristics of Example 2 and Comparative Example 2 division Example 2 Comparative Example 2 Basic Characteristics of Carbon Black NSA (㎡ / g) 121 119 DBP (㏄ / 100g) 114 114 12NO (mg / g) 115 121 24M4 DBP (㏄ / 100g) 90 100 TINT (%) 130 115 PT 120.9 116.3 TINT-PT 9.1 -1.3 Natural rubber compounding characteristics Tensile Strength (PSI) 4345 4091 300% tensile stress (PSI) 2489 2319 % Elongation 484 484 Slip Rate 15% Abrasion 113 100 Slip Rate 30% Abrasion 115 100 50% slip rate 113 100 Dispersion (%) 95 95 Fuel economy index 101 100 Traction Index 111 100 Synthetic Rubber Compounds Tensile Strength (PSI) 4826 4901 300% tensile stress (PSI) 2998 2893 % Elongation 430 442 Slip Rate 15% Abrasion 112 100 Slip Rate 30% Abrasion 112 100 50% slip rate 114 100 % Dispersion 95 93 Fuel economy index 101 100 Traction Index 127 100

As can be seen from Table 6, the carbon black according to Example 2 has a color value and a PT value defined by Equation 1 above is very large value which cannot be achieved by the conventional carbon black according to Comparative Example 2. It was. That is, the conventional carbon black showed a negative value (-1.3).

In addition, the carbon black of the present invention according to Example 2, it can be seen that the tensile stress is higher than that of Comparative Example 2 which is a conventional carbon black in natural rubber compounding and synthetic rubber compounding. And the traction can be seen to be greatly improved. In addition, the carbon black of Example 2 according to the present invention exhibited a very high tension index in the case of the synthetic rubber formulation.

The carbon adsorption specific surface area of the carbon black obtained in Example 3 was 83 m 2 / g. For comparison of the properties, conventional HAF having a similar nitrogen adsorption specific surface area was set as Comparative Example 3. Table 7 shows the basic properties, natural rubber compounding properties and synthetic rubber compounding properties of the carbon black according to Example 3 and Comparative Example 3.

Characteristics of Example 3 and Comparative Example 3 division Example 3 Comparative Example 3 Basic Characteristics of Carbon Black NSA (㎡ / g) 83 83 DBP (㏄ / 100g) 100 102 12NO (mg / g) 75 82 24M4 DBP (㏄ / 100g) 85 88 TINT (%) 120 103 PT 109.0 106.6 TINT-PT 11.0 -3.6 Natural rubber compounding characteristics Tensile Strength (PSI) 4120 3920 300% tensile stress (PSI) 2514 2402 % Elongation 477 475 Slip Rate 15% Abrasion 107 100 Slip Rate 30% Abrasion 110 100 50% slip rate 111 100 Dispersion (%) 98 98 Fuel economy index 100 100 Traction Index 107 100 Synthetic Rubber Compounds Tensile Strength (PSI) 4352 4330 300% tensile stress (PSI) 3054 2942 % Elongation 427 432 Slip Rate 15% Abrasion 107 100 Slip Rate 30% Abrasion 105 100 50% slip rate 109 100 % Dispersion 97 96 Fuel economy index 103 100 Traction Index 112 100

As can be seen from Table 7, the carbon black according to Example 3 has a very different coloration and a PT value defined by Equation 1, which cannot be achieved by the conventional carbon black according to Comparative Example 3. It was a great value. That is, the conventional carbon black showed a negative value (-3.6).

In addition, the carbon black according to the present invention, it can be seen that the tensile stress is high compared to Comparative Example 3 which is a conventional carbon black in natural rubber blends and synthetic rubber blends, but similar in fuel efficiency, but the wear resistance and the tension is It can be seen that greatly improved.

In addition, in the conventional case, when the wear resistance was improved, the nitrogen adsorption specific surface area was generally high, but inevitably worsed in dispersion, but the carbon black according to Examples 1, 2, and 3 of the present invention was Comparative Example 1, Compared with 2 and 3, the abrasion resistance was greatly improved without sacrificing dispersion degree by the similar nitrogen adsorption specific surface area.

As described above, unlike the conventional carbon black, the present invention has a high wear resistance, good fuel efficiency, and excellent traction, in which there is no inverse correlation such that one property deteriorates when one property is improved. In addition, carbon black with good processability can be provided.

Claims (4)

Nitrogen adsorption specific surface area (NSA) of 70 to 150 m 2 / g, dibutyl phthalate oil absorption (DBP) of 70 to 140 Pa / 100g, iodine adsorption specific surface area (12NO) of 70 to 160 mg / g, compressed dibutyl phthalate oil absorption (24M4 DBP) is 70 to 130 ㏄ / 100g, and at the same time the coloring degree (TINT) is at least 8.1 than the PT value defined by the following equation (1) Carbon black. Equation 1 PT = (0.60879 * NSA) + (0.000572 * DBP)-(0.25726 * 12NO)-(0.18418 * 24M4DBP) Rubber composition comprising 40 to 150 parts by weight of carbon black according to claim 1 per 100 parts by weight of any one selected from the group consisting of natural rubber and synthetic rubber. The method of claim 2, wherein the synthetic rubber is any one selected from the group consisting of SBR (SBR), BAL (BR), nitrile rubber, EPM, EPDM, EPII (IIR) Rubber composition, including. The rubber composition according to claim 3, wherein the rubber composition comprises pretreatment or posttreatment of the synthetic rubber.