WO2015011796A1 - カーボンブラック、カーボンブラックの製造方法およびゴム組成物 - Google Patents
カーボンブラック、カーボンブラックの製造方法およびゴム組成物 Download PDFInfo
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- WO2015011796A1 WO2015011796A1 PCT/JP2013/070020 JP2013070020W WO2015011796A1 WO 2015011796 A1 WO2015011796 A1 WO 2015011796A1 JP 2013070020 W JP2013070020 W JP 2013070020W WO 2015011796 A1 WO2015011796 A1 WO 2015011796A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1836—Heating and cooling the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00203—Coils
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Definitions
- the present invention relates to carbon black, a method for producing carbon black, and a rubber composition.
- Carbon black for rubber reinforcement there are various varieties depending on the characteristics, and these characteristics are the main factors for determining various performances of rubber. Carbon black has been selected that has properties suitable for component applications.
- rubber members that require a high degree of wear resistance such as tire tread parts, have conventionally had high structures such as SAF (N110) and ISAF (N220) that have a small primary particle size and a large specific surface area.
- SAF SAF
- ISAF ISAF
- a rubber obtained from a rubber composition formed by blending these carbon blacks has a technical problem that heat generation characteristics are likely to increase while providing high reinforcement. Had.
- the tread portion of the fuel-efficient tire is required to have a rubber having excellent reinforcement and low heat generation.
- the carbon black compounded to improve the reinforcement and heat generation are improved.
- the particle size and specific surface area are completely different and are in a contradictory relationship, so it is possible to obtain the desired rubber composition by adjusting the particle size and specific surface area of the carbon black to be blended Have difficulty.
- the present invention provides a completely new carbon black that can improve rubber properties such as reinforcement and heat generation properties, and also provides a method for easily producing the carbon black, and further provides reinforcement properties.
- An object of the present invention is to provide a rubber composition capable of improving rubber characteristics such as heat generation characteristics and processability.
- the average particle diameter of primary particles is 15 to 35 nm
- the Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis is 140 to 180 nm.
- the inventors have found that the above problems can be solved by carbon black having a spherical aggregate shape when observed with a transmission electron microscope, and have completed the present invention based on this finding.
- the present invention (1) The average particle diameter of primary particles is 15 to 35 nm, the Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis is 140 to 180 nm, and the shape of the aggregate when observed with a transmission electron microscope is Carbon black, characterized by a spherical shape, (2) The carbon black according to (1), wherein the DBP absorption is 120 to 160 ml / 100 g, and the nitrogen adsorption specific surface area is 70 to 120 m 2 / g, (3) A method for producing carbon black using a fluidized bed reactor, wherein a hydrocarbon gas is supplied into the fluidized bed reactor to generate a gas flow, which is separately introduced into the fluidized bed reactor.
- the raw material carbon black in which the average particle diameter of primary particles is 15 to 35 nm and the Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis is 50 to 115 nm is stirred and flowed by heating with the gas flow.
- a rubber composition is provided.
- ADVANTAGE OF THE INVENTION when it uses as a compounding component of a rubber composition, while improving the reinforcement property of the rubber
- the carbon black of the present invention has an average primary particle diameter of 15 to 35 nm and an aggregate Stokes mode diameter of 140 to 180 nm measured by centrifugal sedimentation analysis.
- the gate has a spherical shape.
- the carbon black of the present invention is composed of primary particles.
- Carbon black usually forms secondary particles having a complex structure in which primary particles, that is, basic particles of spherical carbon aggregate and branch into irregular chains, and the minimum unit of the aggregate structure is an aggregate. It is called.
- the average particle diameter of the primary particles is 15 to 35 nm, preferably 17 to 35 nm, more preferably 17 to 32 nm, and 17 to 30 nm. Is more preferable, 20 to 32 nm is more preferable, 20 to 30 nm is still more preferable, and 20 to 25 nm is even more preferable.
- the average particle diameter of the primary particles constituting the carbon black is 15 to 35 nm, a rubber having a low heat generation and a high resilience can be obtained when the carbon black is blended into a rubber composition. Can be easily obtained. If the average particle diameter of the primary particles is less than 15 nm, the basic particles constituting the carbon black may be too small, and the exothermic property of the rubber obtained when used in the rubber composition may increase. If the particle diameter exceeds 35 nm, the reinforcing performance of the rubber obtained when used in the rubber composition may be lowered.
- the average particle diameter of the said primary particle which comprises carbon black means the average value when the particle diameter of 1000 primary particles is measured using a transmission electron microscope.
- the Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis is 140 to 180 nm, preferably 145 to 180 nm, more preferably 145 to 177 nm, and more preferably 150 to 175 nm. More preferably, it is more preferably 150 to 170 nm.
- the aggregate has a Stokes mode diameter of 140 to 180 nm
- the Stokes mode diameter of the aggregate is less than 140 nm, the exothermic property of the rubber obtained when used in the rubber composition may increase.
- the average particle diameter of the aggregate exceeds 180 nm, the rubber composition In some cases, the reinforcing properties of the rubber obtained when used for the above are lowered.
- the Stokes mode diameter of the aggregate constituting the carbon black is measured by a centrifugal sedimentation method, and specifically means a value calculated by the following method. That is, a carbon black sample dried according to JIS K 6221 (1982) 5 “How to Make a Dry Sample” is mixed with a 20 vol% ethanol aqueous solution containing a small amount of a surfactant to obtain a dispersion having a carbon black concentration of 50 mg / l. It is prepared and sufficiently dispersed with ultrasonic waves to prepare a carbon black dispersion liquid as a measurement sample.
- a centrifugal sedimentation type particle size distribution analyzer (disc centrefuge device manufactured by Joyes Robert, UK) was set at a rotation speed of 8000 rpm, 10 ml of spin solution (2 wt% glycerin aqueous solution, 25 ° C.) was added, and then 1 ml of buffer solution (20 A volume% ethanol aqueous solution (25 ° C.) is injected. Next, 0.5 ml of the above carbon black dispersion at a liquid temperature of 25 ° C. was added with a syringe, and then centrifugal sedimentation was started. At the same time, the recorder was operated, and the horizontal axis was added after the carbon black dispersion was added with a syringe.
- a distribution curve is prepared with the elapsed time (seconds) and the vertical axis representing the absorbance at the measurement point changed with the centrifugal sedimentation of carbon black.
- Each time T (second) is read from this distribution curve and substituted into the following equation (Equation 1) to calculate the Stokes equivalent diameter Dst (nm) corresponding to each time T (second).
- ⁇ is the viscosity of the spin liquid (0.935 cp)
- N is the disk rotation speed (8000 rpm)
- r 1 is the radius of the carbon black dispersion injection point (4.56 cm)
- r 2 is the absorbance measurement point.
- ⁇ CB is carbon black density (g / cm 3)
- the [rho l is the density of the spin fluid (1.00178g / cm 3).
- the Stokes equivalent diameter and the maximum Stokes equivalent diameter in the absorbance distribution curve thus obtained are defined as the Stokes mode diameter (Dst mode diameter (nm)).
- the carbon black of the present invention has a spherical aggregate shape when observed with a transmission electron microscope.
- the aggregate of carbon black is usually one in which primary particles aggregate to form a linear shape (dendritic shape) when observed with a transmission microscope.
- the agglomeration further proceeds to form a spherical aggregate as shown in FIG.
- the aggregate is “spherical” means that a carbon black sample dispersed in chloroform and placed on a carbon reinforced support film was obtained with a transmission electron microscope at a magnification of 5000 times.
- the ratio defined by the minimum length / maximum length is meant to be 0.6 to 1.
- the carbon black of the present invention may include a spherical shape as well as a linear shape (a dendritic shape) as an aggregate.
- a minimum of 1000 aggregates is determined by the above method. When the length / maximum length is measured and the ratio defined by the minimum length / maximum length is 60% to 100%, the carbon black is constituted. Assume that the aggregate is spherical.
- the aggregate usually forms an aggregate having a complex structure in which primary particles are aggregated and branched in an irregular chain shape, and the shape thereof also usually takes an irregular dendritic shape.
- the aggregate constituting the carbon black of the present invention maintains the particle diameter of the primary particles by fusing, polymerizing and aggregating the aggregates of the raw material carbon black having the above dendritic shape. As a whole, it is considered that a spherical structure with an increased Stokes mode diameter is formed, and for this reason, it is considered that processability is improved when rubber is compounded.
- the average particle diameter of primary particles is 15 to 35 nm. Therefore, the resulting rubber can be imparted with low heat build-up, and the Stokes mode diameter of the aggregate which is secondary particles (aggregates obtained by fusing and polymerizing aggregates of the raw material carbon black) is 140 to 180 nm. Therefore, it is considered that when blended with rubber, reinforcing rubber and low heat build-up can be imparted to the resulting rubber.
- the carbon black of the present invention preferably has a DBP absorption of 120 to 160 ml / 100 g, more preferably 125 to 160 ml / 100 g, still more preferably 125 to 155 ml / 100 g, and 130 to 155 ml / 100 g.
- the amount is more preferably 100 g, and even more preferably 130 to 150 ml / 100 g.
- the DBP absorption amount is an index representing the degree of structure development, that is, the degree of complexity of the aggregate structure.
- the DBP absorption is less than 120 ml / 100 g, the dispersibility of the carbon black is deteriorated when blended in the rubber composition, and the reinforcing property of the resulting rubber tends to be lowered.
- the DBP absorption exceeds 160 ml / 100 g, the rubber composition In some cases, the processability of the rubber obtained when blended into the resin is lowered.
- DBP absorption means a value measured by the method defined in JIS K6217-4 “Carbon black for rubber—Basic characteristics—Part 4, Determination of DBP absorption”.
- the carbon black of the present invention preferably has a nitrogen adsorption specific surface area of 70 to 120 m 2 / g, more preferably 75 to 120 m 2 / g, still more preferably 75 to 115 m 2 / g, More preferably, it is 80 to 115 m 2 / g, and still more preferably 80 to 110 m 2 / g.
- the nitrogen adsorption specific surface area is an index for judging the size of the primary particles constituting the carbon black.
- the nitrogen adsorption specific surface area is less than 70 m 2 / g, there may be cases where sufficient reinforcement cannot be imparted to the rubber obtained when blended in the rubber composition, and when it exceeds 120 m 2 / g, the rubber composition The exothermic property of the rubber obtained when blended may increase.
- the specific surface area of nitrogen adsorption is measured by the method specified in JISK6217-2 “Carbon black for rubber—Basic characteristics—Part 2, Determination of specific surface area—Nitrogen adsorption method, single point method”. Means the value to be
- the carbon black of the present invention When used as a compounding component of a rubber composition, it can improve the reinforcing property of the resulting rubber and improve the heat generation characteristics and rebound resilience of the rubber.
- the carbon black of the present invention can be suitably used as a compounding component of a rubber composition for tire treads.
- Examples of the method for producing the carbon black of the present invention include the method for producing the carbon black of the present invention described in detail below.
- the method for producing carbon black of the present invention is a method for producing carbon black using a fluidized bed reactor, wherein a hydrocarbon gas is supplied into the fluidized bed reactor to generate a gas flow, and the fluidized bed Separately introduced into the reactor, raw carbon black having an average primary particle diameter of 15 to 35 nm and an aggregate Stokes mode diameter of 50 to 115 nm measured by centrifugal sedimentation analysis is obtained by the gas flow. It is characterized by stirring and flowing under heating.
- the hydrocarbon gas supplied into the fluidized bed reactor may be one or more selected from aromatic hydrocarbon gases such as benzene, toluene, xylene, naphthalene and anthracene. .
- the primary carbon black has a primary particle diameter of 15 to 35 nm, preferably 17 to 35 nm, more preferably 17 to 32 nm, and more preferably 17 to 30 nm. More preferably, it is more preferably 20 to 32 nm, even more preferably 20 to 30 nm, and still more preferably 20 to 25 nm.
- the raw material carbon black has a Stokes mode diameter of the aggregate measured by a centrifugal sedimentation analysis method of 50 to 115 nm, preferably 55 to 115 nm, preferably 55 to 95 nm. Is more preferably 60 to 95 nm, and still more preferably 60 to 90 nm.
- the raw material carbon black may be appropriately selected from commercially available products having the above particle diameter, and preferably carbon such as FEF (N550) and ISAF (N220). What is necessary is just to select what has the said particle diameter from the hard type
- the primary particle size and aggregate Stokes mode diameter are desired by using raw material carbon black in which the primary particle size and aggregate Stokes mode size are within the above ranges. Carbon black in the range can be produced.
- the average particle diameter of the primary particle which comprises raw material carbon black means the average value when the particle diameter of 1000 primary particles is measured using a transmission electron microscope.
- the Stokes mode diameter of the aggregate constituting the raw material carbon black is measured by a centrifugal sedimentation type particle size distribution meter (UK) by the same method as the measurement method of the Stokes mode diameter of the spherical aggregate described above. This means a value measured by a centrifugal sedimentation method using a disc centrifuge device manufactured by Joyes Robert.
- Examples of the fluidized bed reactor used in the method for producing carbon black of the present invention include those shown in FIG.
- the fluidized bed reactor 1 shown in FIG. 1 has a substantially cylindrical shape, and the furnace axis extends in the vertical direction.
- a fluidized bed reactor 1 shown in FIG. 1 has a gas inlet 21 for supplying hydrocarbon gas from the lower part of the reactor body 2 toward the upper part, and an exhaust port 22 at the upper part of the reactor body 2. It is.
- the fluidized bed reactor 1 includes a heater coil 3 in which a heating wire is spirally wound around the entire outer periphery of the furnace wall of the reactor main body 2, and is provided inside the reactor main body 2.
- the stirring region 4 can be heated.
- a hydrocarbon gas is supplied to a fluidized bed reactor to generate a gas flow.
- the hydrocarbon gas is preferably supplied into the fluidized bed reactor in a preheated state.
- the preheating temperature is preferably 400 to 600 ° C, more preferably 450 to 600 ° C, and further preferably 450 to 550 ° C.
- 480 to 550 ° C is more preferable, and 480 to 520 ° C is even more preferable.
- the hydrocarbon gas is preferably supplied to the fluidized bed reactor so as to be 4.0 to 6.0 Nm 3 / hour, and is preferably supplied to be 4.5 to 6.0 Nm 3 / hour.
- the hydrocarbon gas introduced into the fluidized bed reactor is preferably supplied so that the pressure at the gas inlet is 1.0 to 2.0 MPa, and is 1.1 to 2.0 MPa. It is more preferable to supply, more preferably 1.1 to 1.8 MPa, still more preferably 1.2 to 1.8 MPa, and even more preferably 1.2 to 1.5 MPa. It is still more preferable to supply so that it becomes.
- hydrocarbon gas is supplied from the gas inlet 21.
- the hydrocarbon gas may be supplied in a state where the raw material carbon black is previously introduced into the reaction furnace, or after the hydrocarbon gas is supplied into the reaction furnace, You may introduce raw material carbon black from the supply port provided separately.
- raw material carbon black what is marketed as FEF (N550), HAF (N330), etc. can be used suitably.
- the raw material carbon black introduced into the reaction furnace is stirred and fluidized under heating by a gas flow of hydrocarbon gas.
- the heating temperature is preferably 500 to 750 ° C., more preferably 550 to 750 ° C., further preferably 550 to 720 ° C., further preferably 600 to 720 ° C., and still more preferably 600 to 700 ° C.
- the stirring and flowing time is preferably 100 to 300 seconds, more preferably 110 to 300 seconds, further preferably 110 to 280 seconds, still more preferably 120 to 280 seconds, and still more preferably 120 to 250 seconds.
- the stirring region heated by the heater coil 2 after supplying hydrocarbon gas from the gas inlet 21 In 4 the raw material carbon black is stirred and mixed.
- a hydrocarbon gas is supplied into a furnace under heating, and the raw material carbon black is stirred and fluidized by a gas flow of the hydrocarbon gas to bring them into contact with each other, thereby causing thermal decomposition.
- the deposited carbon dioxide gas is deposited on the surface of the aggregate constituting the raw material carbon black, and the agglomeration between the aggregates and the polymerization are promoted by agitation by the gas flow of the hydrocarbon gas. It is considered that carbon black composed of aggregates that are largely agglomerated can be obtained without changing the diameter size.
- the fluidized bed reactor 1 shown in FIG. 1 when the fluidized bed reactor 1 shown in FIG. 1 is used, hydrocarbon gas is supplied from the gas inlet 21 at the bottom of the reactor 1 under the heating condition by the heater coil 3. Then, the raw material carbon black is stirred and fluidized in the stirring region 4 by the gas flow of the hydrocarbon gas to bring them into contact with each other. It is considered that the target carbon black can be obtained by depositing on the gate surface and further promoting fusion and polymerization between the aggregates by stirring with the gas flow of the hydrocarbon gas.
- the reaction can be stopped by stopping the supply of the hydrogen carbonate gas, preferably introducing nitrogen gas, and naturally cooling the generated carbon black.
- the nitrogen gas is preferably supplied into the fluidized bed reactor so as to be 4.0 to 6.0 Nm 3 / hour, and is preferably supplied so as to be 4.5 to 6.0 Nm 3 / hour. More preferably, it is more preferably supplied at 4.5 to 5.5 Nm 3 / hour, still more preferably at 5.0 to 5.5 Nm 3 / hour, more preferably 5.0 to 5 It is even more preferable to supply at 3 Nm 3 / hour.
- the target carbon black can be recovered by separating and collecting the cooled carbon black particles using a separation and collection device such as a cyclone or a bag filter.
- the carbon black that can improve the reinforcing property of the resulting rubber and improve the heat generation characteristics and the resilience can be simplified. Can be manufactured.
- the rubber composition of the present invention is characterized by containing 20 to 100 parts by mass of the carbon black of the present invention or the carbon black obtained by the production method of the present invention with respect to 100 parts by mass of the rubber component.
- the rubber component is at least selected from diene rubbers such as natural rubber, styrene-butadiene rubber, polybutadiene rubber, isoprene rubber, butyl rubber, chloroprene rubber and acrylonitrile-butadiene copolymer rubber.
- diene rubbers such as natural rubber, styrene-butadiene rubber, polybutadiene rubber, isoprene rubber, butyl rubber, chloroprene rubber and acrylonitrile-butadiene copolymer rubber.
- the rubber composition of the present invention contains the carbon black of the present invention or the carbon black obtained by the production method of the present invention, and the details of the carbon black contained in the rubber composition are as described above.
- the rubber composition of the present invention contains the carbon black of the present invention or the carbon black obtained by the production method of the present invention, and the carbon black of the present invention or the carbon black obtained by the production method of the present invention comprises: Since the aggregate constituting the carbon black has a spherical structure with an increased Stokes mode diameter, it is considered that viscosity (viscosity) can be suitably reduced and excellent processability can be imparted to the rubber composition. .
- the carbon black of the present invention or the carbon black obtained by the production method of the present invention which is composed of aggregates having a spherical shape as a whole and having a large Stokes mode diameter, has an average primary particle diameter within a desired range.
- the rubber composition can be imparted with excellent low heat build-up, and the Stokes mode diameter of the spherical aggregate constituting the carbon black is within a desired range, whereby the rubber composition has excellent reinforcing properties, It is thought that low exothermic property can be provided.
- the rubber composition of the present invention contains 20 to 100 parts by mass, preferably 30 to 100 parts by mass of the carbon black of the present invention or the carbon black obtained by the production method of the present invention with respect to 100 parts by mass of the rubber component.
- 30 to 90 parts by mass are included, more preferably 40 to 90 parts by mass, and still more preferably 40 to 80 parts by mass.
- the carbon black content of the present invention or the carbon black obtained by the production method of the present invention is 20 to 100 parts by mass with respect to 100 parts by mass of the rubber component, the processability In addition, it is possible to obtain a rubber excellent in reinforcing property, heat generation property, rebound resilience, and the like.
- examples of components that can be included in addition to the rubber component and carbon black include inorganic reinforcing materials.
- inorganic reinforcing materials include dry silica, wet silica (hydrous silicic acid, precipitated silica), aluminum hydroxide, calcium carbonate, clay, magnesium hydroxide, talc, mica, and a composite of carbon black with these. 1 or more types selected from
- the content of the inorganic reinforcing material is preferably 20 to 150 parts by mass, more preferably 30 to 150 parts by mass, and further preferably 30 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
- the amount is preferably 40 to 100 parts by mass, and more preferably 40 to 80 parts by mass.
- the content of the inorganic reinforcing material is 20 to 150 parts by mass with respect to 100 parts by mass of the rubber component, the increase in viscosity during the production of the rubber composition described later is suppressed and the production efficiency is improved.
- the reinforcing effect of the obtained rubber can be effectively improved and the effect of reducing the heat generation can be efficiently exhibited.
- the rubber composition of the present invention contains silica as an inorganic reinforcing material, it may further contain a silane coupling agent.
- the content of the silane coupling agent is preferably 3 to 20 parts by mass with respect to 100 parts by mass of the inorganic reinforcing material.
- the content ratio of the silane coupling agent is within the above range, the dispersibility of the inorganic reinforcing material in the rubber composition can be improved or the reinforcing property by the inorganic reinforcing material can be sufficiently improved.
- the rubber composition of the present invention may contain necessary components such as commonly used vulcanizing agents, vulcanization accelerators, anti-aging agents, vulcanization aids, softeners, and plasticizers.
- the rubber composition of the present invention comprises a desired amount of the carbon black and, if necessary, an inorganic reinforcing material, a silane coupling agent, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a vulcanizing aid, a softening agent,
- a desired amount of a plasticizer or the like can be obtained by kneading with a rubber component.
- the kneading can be performed using a kneader such as a known mixer or mill.
- the desired rubber can be obtained by appropriately heating and curing the rubber composition of the present invention at 130 to 180 ° C.
- the rubber composition of the present invention can improve the properties of the resulting rubber, such as reinforcement, heat build-up and rebound resilience, and is improved in a good balance between reinforcement and heat build-up. Suitable as a composition.
- Example 1 Production of Carbon Black 1 Carbon black was produced using a fluidized bed reactor 1 shown in FIG. 1 having a substantially cylindrical shape in which the furnace axis extends in the vertical direction.
- the fluidized bed reactor 1 shown in FIG. 1 has a casing made of SUS304 and an inner wall made of mullite, and the reactor main body 2 constituting the fluidized bed reactor 1 is carbonized from the lower part toward the upper part.
- a gas inlet 21 inner diameter: 50 mm
- an exhaust port 22 inner diameter: 30 mm
- the fluidized bed reactor 1 includes a heater coil 3 in which a heating wire is spirally wound around the entire outer periphery of the furnace wall of the reactor main body 2, and a stirring region 4 inside the reactor main body 2. It has a structure capable of heating (inner diameter 100 mm, height 200 mm).
- a SUS filter 5 (mesh interval 0.2 mm) was installed at the connecting portion between the reactor main body 2 and the gas inlet 21.
- Raw carbon black 1 (average particle diameter of primary particles is 24 nm, Stokes mode diameter of aggregate measured by centrifugal sedimentation analysis method is 67 nm, DBP absorption is 45 ml / 100 g, After the introduction of 100 g of nitrogen adsorption specific surface area of 80 m 2 / g), the stirring region 4 is heated to 700 ° C. by the heater coil 3 and then preheated to 500 ° C. from the gas inlet 21 (city Gas 13A: specific gravity 0.638, CH 4 89.6%, calorific value 45 MJ / m 3 ) is supplied at 5 Nm 3 / h and the pressure at the gas inlet is 1.3 MPa.
- Table 1 shows the average particle diameter of primary particles of the obtained carbon black 1, the Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis, the DBP absorption amount, and the nitrogen adsorption specific surface area.
- FIG. 2 shows an electron micrograph of the aggregate when the obtained carbon black 1 is observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.).
- FIG. 3 shows an electron micrograph of an aggregate of the raw material carbon black 1 used in this example.
- the aggregate (FIG. 3) of the raw material carbon black 1 having a dendritic shape is aggregated and polymerized to have a spherical shape (FIG. 2). It can be seen that is generated.
- Example 2 Production of carbon black 2 Carbon black 2 was produced by the same treatment as in Example 1 except that the stirring and flow time with hydrocarbon gas in Example 1 was changed from 2 minutes to 4 minutes. .
- the obtained carbon black 2 was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.), the aggregate of the raw material carbon black 1 aggregated and polymerized to produce a spherical aggregate. I was able to confirm that.
- Table 1 shows the average particle diameter of primary particles of the obtained carbon black 2, the Stokes mode diameter of the aggregate measured by the centrifugal sedimentation analysis method, the DBP absorption amount, and the nitrogen adsorption specific surface area.
- Example 1 (Comparative Example 1) In Example 1, instead of raw material carbon black 1, raw material carbon black 2 (average particle diameter of primary particles is 24 nm, Stokes mode diameter of aggregate measured by centrifugal sedimentation analysis method is 67 nm, DBP absorption is 45 ml / 100 g and a nitrogen adsorption specific surface area of 90 m 2 / g) were employed, and a comparative carbon black 1 was used as it was without performing a reaction using a fluidized reaction bed furnace. When the comparative carbon black 1 was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.), it was confirmed that the aggregate had a dendritic shape.
- JEM-2000FX transmission electron microscope
- Example 2 In Example 1, instead of raw material carbon black 1, raw material carbon black 3 having a dendritic shape (average particle diameter of primary particles is 39 nm, Stokes mode diameter of aggregate measured by centrifugal sedimentation analysis method is 177 nm, DBP absorption The amount was 168 ml / 100 g and the nitrogen adsorption specific surface area was 52 m 2 / g), and the carbon black 2 was used as it was without performing the reaction using a fluidized reaction bed furnace. When the comparative carbon black 2 was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.), it was confirmed that the aggregate had a dendritic shape.
- JEM-2000FX transmission electron microscope
- Example 3 Production of carbon black 3
- the raw material carbon black 4 (average particle diameter of primary particles is 24 nm, the Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis) 79 nm, DBP absorption is 82 ml / 100 g, nitrogen adsorption specific surface area is 90 m 2 / g, and the aggregate has a dendritic shape when observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.)
- the carbon black 3 was obtained by treating in the same manner as in Example 1 except that it was used.
- Example 3 (Comparative Example 3)
- raw material carbon black 5 (average particle diameter of primary particles was 38 nm, Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis was 117 nm, DBP absorption was 65 ml / 100 g and a nitrogen adsorption specific surface area of 50 m 2 / g) were employed, and the carbon black 3 was used as it was without performing a reaction using a fluidized reaction bed furnace.
- the comparative carbon black 3 was observed with a transmission electron microscope (JEM-2000FX manufactured by JEOL Ltd.), it was confirmed that the aggregate had a dendritic shape.
- Example 4 In Example 1, instead of raw material carbon black 1, raw material carbon black 6 (average particle diameter of primary particles was 39 nm, Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis method was 189 nm, DBP absorption was 160 ml / 100 g and a nitrogen adsorption specific surface area of 52 m 2 / g) were employed, and a comparative carbon black 4 was used as it was without performing a reaction using a fluidized reaction bed furnace. When the comparative carbon black 4 was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.), it was confirmed that the aggregate had a dendritic shape.
- JEM-2000FX transmission electron microscope
- Example 4 Production of carbon black 4
- the raw material carbon black 7 (average particle diameter of primary particles is 21 nm, the Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis) Is 115 nm, DBP absorption is 123 ml / 100 g, nitrogen adsorption specific surface area is 113 m 2 / g, and the aggregate has a dendritic shape when observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.) Carbon black 4 was obtained in the same manner as in Example 1.
- Example 5 (Comparative Example 5) In Example 1, instead of raw material carbon black 1, raw material carbon black 8 (average particle diameter of primary particles was 58 nm, Stokes mode diameter of the aggregate measured by centrifugal sedimentation analysis method was 140 nm, DBP absorption was 95 ml / 100 g and a nitrogen adsorption specific surface area of 40 m 2 / g) were employed, and the carbon black 5 was used as it was without performing a reaction using a fluidized reaction bed furnace. When the comparative carbon black 5 was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.), it was confirmed that the aggregate had a dendritic shape.
- JEM-2000FX transmission electron microscope
- Example 6 (Comparative Example 6) In Example 1, instead of raw material carbon black 1, raw material carbon black 9 (average particle diameter of primary particles is 14 nm, Stokes mode diameter of aggregate measured by centrifugal sedimentation analysis method is 160 nm, DBP absorption is 133 ml / 100 g and a nitrogen adsorption specific surface area of 195 m 2 / g) were employed, and a comparative carbon black 6 was used as it was without performing a reaction using a fluidized reaction bed furnace. When the comparative carbon black 6 was observed with a transmission electron microscope (JEM-2000FX, manufactured by JEOL Ltd.), it was confirmed that the aggregate had a dendritic shape.
- JEM-2000FX transmission electron microscope
- Example 5 Production Example of Rubber Composition Carbon black 1 obtained in Example 1 was used as the carbon black, and styrene butadiene rubber (Nippon Zeon Co., Ltd.), which is a rubber component, with respect to 70 parts by mass of the carbon black.
- Nipol NS116R 20 parts by mass of polybutadiene rubber (manufactured by JSR Corporation, JSR BR01), 2 parts by mass of stearic acid, 30 parts by mass of oil (Tudalen 65 by Starry Oil Co., Ltd.), and zinc 3 parts by weight of Hana was kneaded for 4 minutes with a closed mixer (MIXTRON BB-2 manufactured by Kobe Steel), and the resulting kneaded product was vulcanized with accelerator (Kawaguchi Chemical Co., Ltd. CZ)
- a rubber composition having a composition shown in Table 4 was obtained by kneading 2 parts by mass and 2 parts by mass of sulfur with an open roll.
- Mooney viscosity (M)> The Mooney viscosity of the rubber composition (stickiness when the rubber composition was heated at 100 ° C. for 5 minutes) was measured using a Mooney viscometer (AM-3 manufactured by Toyo Seiki Seisakusho Co., Ltd.). The results are shown in Table 5. As described in Tables 5 to 7, the Mooney viscosity is expressed by Mooney unit M. The smaller this value, the easier the rubber flows when molding, and the higher the workability.
- the rubber composition was vulcanized in a 15 cm ⁇ 15 cm ⁇ 0.2 cm mold under a temperature condition of 160 ° C. for 20 minutes to form a vulcanized rubber.
- loss factor (tan ⁇ ) and tensile strength were measured by the following methods. The results are shown in Table 5.
- ⁇ Tensile stress> The tensile stress (MPa) was measured on the test piece; JIS3, tension
- Example 6 Production Example of Rubber Composition
- the carbon black obtained in Example 2 was used instead of the carbon black 1 obtained in Example 1, and the same procedure as in Example 5 was performed.
- a vulcanized rubber was formed from the rubber composition in the same manner as in Example 5, and the loss factor of the vulcanized rubber obtained in the same manner as in Example 5 was obtained. (tan ⁇ ) and tensile strength (300% strain) were measured. The results are shown in Table 5.
- each measurement value obtained in Example 5 is shown as a relative percentage (%) when taken as 100%, and each measurement is shown in parentheses. Value (actual value) shall be indicated.
- Mooney viscosity, tensile strength (300% strain) or loss factor (tan ⁇ ) is improved by 5% or more, it can be considered that each physical property is improved.
- Example 7 Comparative Example 9 to Comparative Example 10
- Example 7 Production Example of Rubber Composition Whether to use carbon black 3 obtained in Example 3 as the carbon black (Example 7) or obtained in Comparative Example 3 and Comparative Example 4
- Each rubber composition was prepared in the same manner as in Example 5 except that the obtained carbon black 3 and carbon black 4 were used (Comparative Example 9 and Comparative Example 10), and the Mooney viscosity was measured.
- Vulcanized rubber was prepared from each rubber composition in the same manner as described above, and the loss factor (tan ⁇ ) and tensile strength (300% strain) of the vulcanized rubber obtained in the same manner as in Example 5 were measured. The results are shown in Table 6.
- Example 8 Comparative Examples 11 to 12
- Example 7 (Production Example of Rubber Composition) Except for using carbon black 4 obtained in Example 4 as a carbon black (Example 8), or using Comparative Carbon Black 5 and Comparative Carbon Black 6 obtained in Comparative Example 5 and Comparative Example 6, respectively.
- Each rubber composition was prepared in the same manner as in Example 5 and the Mooney viscosity was measured.
- a vulcanized rubber was prepared from each rubber composition in the same manner as in Example 5, and obtained in the same manner as in Example 5.
- the loss factor (tan ⁇ ) and tensile strength (300% strain) of the vulcanized rubber were measured. The results are shown in Table 7.
- Example 7 in order to facilitate understanding, the relative ratio when the Mooney viscosity, tensile strength (300% strain), or loss factor (tan ⁇ ) obtained in Example 8 is 100% is shown. Each measured value is shown in parentheses. In Table 7, when the Mooney viscosity, tensile strength (300% strain), or loss factor (tan ⁇ ) is improved by 5% or more, it can be considered that each physical property has been improved.
- the rubber compositions obtained in Example 5 and Example 6 have a lower Mooney viscosity and improved processability compared to the rubber compositions obtained in Comparative Example 7 and Comparative Example 8, and loss factor ( It can be seen that a rubber having improved tan ⁇ ) and a high tensile strength can be obtained.
- the rubber composition obtained in Example 7 is also compared with the rubber compositions obtained in Comparative Example 9 and Comparative Example 10. , The Mooney viscosity is low, the processability is improved, the loss factor (tan ⁇ ) is improved, and a rubber having a high tensile strength is obtained.
- the rubber composition obtained in Example 8 is Compared to the rubber compositions obtained in Comparative Examples 11 and 12, it can be seen that a rubber having a low Mooney viscosity, improved processability, improved loss factor (tan ⁇ ), and high tensile strength can be obtained. For this reason, it can be seen that the rubber compositions obtained in Examples 5 to 8 have excellent processability, excellent reinforcement, and low exothermic properties.
- the present invention when used as a compounding component of a rubber composition, it is possible to provide a carbon black capable of improving the processability and reinforcement of the resulting rubber and improving the heat generation characteristics of the obtained rubber. Can do. Moreover, according to this invention, the method of manufacturing the said carbon black simply can be provided. Furthermore, according to the present invention, it is possible to provide a rubber composition having improved rubber properties such as reinforcement, heat generation, and processability.
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Abstract
Description
。
(1)一次粒子の平均粒子径が15~35nmで、遠心沈降分析法により測定されるアグリゲートのストークスモード径が140~180nmであり、透過型電子顕微鏡で観察したときのアグリゲートの形状が球形状であることを特徴とするカーボンブラック、
(2)DBP吸収量が120~160ml/100g、窒素吸着比表面積が70~120m2/gである上記(1)に記載のカーボンブラック、
(3)流動床反応炉を用いてカーボンブラックを製造する方法であって、前記流動床反応炉内に炭化水素ガスを供給してガス流を生じさせ、前記流動床反応炉内に別途導入した、一次粒子の平均粒子径が15~35nmであり、遠心沈降分析法により測定されるアグリゲートのストークスモード径が50~115nmである原料カーボンブラックを、前記ガス流によって加熱下に攪拌、流動することを特徴とする上記(1)に記載のカーボンブラックの製造方法、
および
(4)ゴム成分100質量部に対し、上記(1)もしくは(2)に記載のカーボンブラックまたは(3)に記載の方法で得られたカーボンブラックを20~100質量部含むことを特徴とするゴム組成物を提供するものである。
また、本発明によれば、上記カーボンブラックを簡便に製造する方法を提供することができる。
さらに、本発明によれば、補強性、発熱性、加工性等のゴム特性が向上したゴム組成物を提供することができる。
本発明のカーボンブラックは、一次粒子の平均粒子径が15~35nmで、遠心沈降分析法により測定されるアグリゲートのストークスモード径が140~180nmであり、透過型電子顕微鏡で観察したときのアグリゲートの形状が球形状であることを特徴とするものである。
カーボンブラックは、通常、一次粒子、すなわち球状カーボンの基本粒子が凝集して不規則な鎖状に枝分かれした複雑な構造を有する二次粒子を形成しており、この凝集構造の最小単位はアグリゲートと称されている。
アグリゲートのストークスモード径が140nmを下回ると、ゴム組成物に使用したときに得られるゴムの発熱性が増大する場合があり、一方、アグリゲートの平均粒子径が180nmを超えると、ゴム組成物に使用したときに得られるゴムの補強性が低下する場合がある。
すなわち、JIS K 6221(1982)5「乾燥試料の作り方」に基づいて乾燥したカーボンブラック試料を少量の界面活性剤を含む20容量%エタノール水溶液と混合してカーボンブラック濃度50mg/lの分散液を作製し、これを超音波で十分に分散させて測定試料であるカーボンブラック分散液を調製する。
遠心沈降式粒度分布計(英国Joyes Lobel社製ディスクセントリフュージュ装置)を8000rpmの回転数に設定し、スピン液(2重量%グリセリン水溶液、25℃)を10ml加えたのち、1mlのバッファー液(20容量%エタノール水溶液、25℃)を注入する。
次いで、液温25℃の上記カーボンブラック分散液0.5mlを注射器で加えた後、遠心沈降を開始し、同時に記録計を作動させて、横軸をカーボンブラック分散液を注射器で加えてからの経過時間(秒)、縦軸をカーボンブラックの遠心沈降に伴い変化した測定点での吸光度とする分布曲線を作成する。この分布曲線より各時間T(秒)を読み取り、次式(数1)に代入して各時間T(秒)に対応するストークス相当径Dst(nm)を算出する。
このようにして得られたストークス相当径と吸光度の分布曲線における最大頻度のストークス相当径をストークスモード径(Dstモード径(nm))とする。
カーボンブラックのアグリゲートは、通常、図3に示すように、透過型顕微鏡で観察したときに、一次粒子が凝集して線形状(樹枝形状)を成すものであるが、本発明のカーボンブラックにおいては、さらに凝集が進行して、図4に示すように球形状のアグリゲートを成している。
なお、本発明のカーボンブラックは、アグリゲートとして球形状のものを含むとともに線形状(樹枝形状)のものを含む場合もあるが、本出願書類においては、上記方法で1000個のアグリゲートの最小長さと最大長さを測定したときに、最小長さ/最大長さで規定される比が0.6~1であるものが60%~100%存在する場合には、当該カーボンブラックを構成するアグリゲートは球形状であると表現するものとする。
そして、この全体として球形状を有しストークスモード径の大きなアグリゲートによって構成される本発明のカーボンブラックをゴム組成物に配合した場合には、一次粒子の平均粒子径が15~35nmであることから、得られるゴムに低発熱性を付与することができ、二次粒子であるアグリゲート(原料カーボンブラックのアグリゲート同士が融着、重合してなる凝集物)のストークスモード径が140~180nmであることにより、ゴムに配合した際に、得られるゴムに補強性、低発熱性を付与することができると考えられる。
本発明のカーボンブラックの製造方法は、流動床反応炉を用いてカーボンブラックを製造する方法であって、前記流動床反応炉内に炭化水素ガスを供給してガス流を生じさせ、前記流動床反応炉内に別途導入した、一次粒子の平均粒子径が15~35nmであり、遠心沈降分析法により測定されるアグリゲートのストークスモード径が50~115nmである原料カーボンブラックを、前記ガス流によって加熱下に攪拌、流動することを特徴とするものである。
また、本発明のカーボンブラックの製造方法において、原料カーボンブラックは、遠心沈降分析法により測定されるアグリゲートのストークスモード径が50~115nmであり、55~115nmであることが好ましく、55~95nmであることがより好ましく、60~95nmであることがさらに好ましく、60~90nmであることが一層好ましい。
また、本出願書類において、原料カーボンブラックを構成するアグリゲートのストークスモード径は、上述した球形状を有するアグリゲートのストークスモード径の測定方法と同様の方法によって、遠心沈降式粒度分布計(英国Joyes Lobel社製 ディスクセントリフュージュ装置)を用い、遠心沈降法により測定される値を意味する。
図1に示す流動床反応炉1は、反応炉本体2の下部から上部方向に向かって炭化水素ガスを供給するガス導入口21を有するとともに、反応炉本体2の上部に排気口22を有するものである。また、図1に示すように、流動床反応炉1は、反応炉本体2の炉壁外周全体に電熱線を螺旋状に巻き付けたヒーターコイル3を有し、反応炉本体2の内部に設けられた攪拌領域4を加熱し得る構造を有している。
炭化水素ガスは、予熱した状態で流動床反応炉内に供給することが好ましく、この場合、予熱温度は400~600℃が好ましく、450~600℃がより好ましく、450~550℃がさらに好ましく、480~550℃が一層好ましく、480~520℃がより一層好ましい。
また、炭化水素ガスは、流動床反応炉中に4.0~6.0Nm3/時となるように供給することが好ましく、4.5~6.0Nm3/時となるように供給することがより好ましく、4.5~5.5Nm3/時となるように供給することがさらに好ましく、5.0~5.5Nm3/時となるように供給することが一層好ましく、5.0~5.3Nm3/時となるように供給することがより一層好ましい。
加えて、流動床反応炉中に導入する炭化水素ガスは、ガス導入口の圧力が1.0~2.0MPaとなるように供給することが好ましく、1.1~2.0MPaとなるように供給することがより好ましく、1.1~1.8MPaとなるように供給することがさらに好ましく、1.2~1.8MPaとなるように供給することが一層好ましく、1.2~1.5MPaとなるように供給することがより一層好ましい。
上記加熱温度は、500~750℃が好ましく、550~750℃がより好ましく、550~720℃がさらに好ましく、600~720℃が一層好ましく、600~700℃がより一層好ましい。
また、攪拌、流動時間は、100~300秒間が好ましく、110~300秒間がより好ましく、110~280秒間がさらに好ましく、120~280秒間が一層好ましく、120~250秒間がより一層好ましい。
上記窒素ガスは、流動床反応炉中に、4.0~6.0Nm3/時となるように供給することが好ましく、4.5~6.0Nm3/時となるように供給することがより好ましく、4.5~5.5Nm3/時となるように供給することがさらに好ましく、5.0~5.5Nm3/時となるように供給することが一層好ましく、5.0~5.3Nm3/時となるように供給することがより一層好ましい。
本発明のゴム組成物は、ゴム成分100質量部に対し、本発明のカーボンブラックまたは本発明の製造方法で得られたカーボンブラックを20~100質量部含むことを特徴とするものである。
本発明のゴム組成物は、本発明のカーボンブラックまたは本発明の製造方法で得られたカーボンブラックを含むものであり、本発明のカーボンブラックまたは本発明の製造方法で得られたカーボンブラックは、カーボンブラックを構成するアグリゲートが、ストークスモード径が増大した球形状の構造を成すために、粘性(粘度)を好適に低減して、ゴム組成物に優れた加工性を付与し得ると考えられる。
そして、この全体として球形状を有しストークスモード径の大きなアグリゲートによって構成される本発明のカーボンブラックまたは本発明の製造方法で得られたカーボンブラックは、一次粒子の平均粒子径が所望範囲にあることからゴム組成物に優れた低発熱性を付与することができ、カーボンブラックを構成する球形状のアグリゲートのストークスモード径が所望範囲にあることにより、ゴム組成物に優れた補強性、低発熱性を付与し得ると考えられる。
無機補強材としては、例えば、乾式法シリカ、湿式法シリカ(含水ケイ酸、沈降シリカ)、水酸化アルミニウム、炭酸カルシウム、クレー、水酸化マグネシウム、タルク、マイカおよびこれ等とカーボンブラックの複合物などから選ばれる1種以上を挙げることができる。
本発明のゴム組成物において、無機補強材の含有割合が、ゴム成分100質量部に対して20~150質量部であると、後述するゴム組成物製造時における粘度上昇を抑制し製造効率を向上させることができ、得られるゴムの補強性向上効果や発熱性低減効果を効率的に発揮することができる。
図1に示す、炉軸が垂直方向に伸びる概略円筒形状を有する流動床反応炉1を用いてカーボンブラックを作製した。
図1に示す流動床反応炉1は、筐体がSUS304、内壁がムライトにより構成されるものであって、流動床反応炉1を構成する反応炉本体2は、下部から上部方向に向かって炭化水素ガスを供給するガス導入口21(内径50mm)を有するとともに、反応炉本体2の上部に排気口22(内径30mm)を有するものである。また、図1に示すように、流動床反応炉1は、反応炉本体2の炉壁外周全体に電熱線を螺旋状に巻き付けたヒーターコイル3を有し、反応炉本体2内部の攪拌領域4(内径100mm、高さ200mm)を加熱し得る構造を有している。
また、反応炉本体2とガス導入口21との連結部には、SUS製フィルタ5(メッシュ間隔0.2mm)を設置した。
得られたカーボンブラック1の一次粒子の平均粒子径、遠心沈降分析法により測定されるアグリゲートのストークスモード径、DBP吸収量、窒素吸着比表面積を表1に示す。
図2と図3とを対比することにより、本実施例においては、樹枝形状を有する原料カーボンブラック1のアグリゲート(図3)が、凝集、重合して球形状を有するアグリゲート(図2)を生成していることが分かる。
実施例1において、炭化水素ガスによる攪拌、流動時間を2分間から4分間に変更した以外は、実施例1と同様に処理してカーボンブラック2を作製した。
得られたカーボンブラック2を透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したところ、原料カーボンブラック1のアグリゲートが凝集、重合して球形状を有するアグリゲートを生成していることを確認することができた。
得られたカーボンブラック2の一次粒子の平均粒子径、遠心沈降分析法により測定されるアグリゲートのストークスモード径、DBP吸収量、窒素吸着比表面積を表1に示す。
実施例1において、原料カーボンブラック1に代えて、原料カーボンブラック2(一次粒子の平均粒子径が24nm、遠心沈降分析法により測定されるアグリゲートのストークスモード径が67nm、DBP吸収量が45ml/100g、窒素吸着比表面積が90m2/gであるもの)を採用し、流動反応床炉を用いた反応を行わずにそのまま比較カーボンブラック1とした。
比較カーボンブラック1は、透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したときにアグリゲートが樹枝形状を有することを確認することができた。
実施例1において、原料カーボンブラック1に代えて、樹枝形状を有する原料カーボンブラック3(一次粒子の平均粒子径が39nm、遠心沈降分析法により測定されるアグリゲートのストークスモード径が177nm、DBP吸収量が168ml/100g、窒素吸着比表面積が52m2/gであるもの)を採用し、流動反応床炉を用いた反応を行わずにそのまま比較カーボンブラック2とした。
比較カーボンブラック2は、透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したときにアグリゲートが樹枝形状を有することを確認することができた。
実施例1において、原料カーボンブラック1に代えて原料カーボンブラック4(一次粒子の平均粒子径が24nm、遠心沈降分析法により測定されるアグリゲートのストークスモード径79nm、DBP吸収量が82ml/100g、窒素吸着比表面積が90m2/gであり、透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したときに、アグリゲートが樹枝形状を有することを確認し得るもの)を用いた以外は、実施例1と同様に処理してカーボンブラック3を得た。
得られたカーボンブラック3を透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したところ、原料カーボンブラック4のアグリゲートが凝集、重合して球形状を有するアグリゲートを生成していることを確認することができた。
得られたカーボンブラック3の一次粒子の平均粒子径、遠心沈降分析法により測定されるアグリゲートのストークスモード径、DBP吸収量、窒素吸着比表面積を表2に示す。
実施例1において、原料カーボンブラック1に代えて、原料カーボンブラック5(一次粒子の平均粒子径が38nm、遠心沈降分析法により測定されるアグリゲートのストークスモード径が117nm、DBP吸収量が65ml/100g、窒素吸着比表面積が50m2/gであるもの)を採用し、流動反応床炉を用いた反応を行わずにそのまま比較カーボンブラック3とした。
比較カーボンブラック3は、透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したときにアグリゲートが樹枝形状を有することを確認することができた。
実施例1において、原料カーボンブラック1に代えて、原料カーボンブラック6(一次粒子の平均粒子径が39nm、遠心沈降分析法により測定されるアグリゲートのストークスモード径が189nm、DBP吸収量が160ml/100g、窒素吸着比表面積が52m2/gであるもの)を採用し、流動反応床炉を用いた反応を行わずにそのまま比較カーボンブラック4とした。
比較カーボンブラック4は、透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したときにアグリゲートが樹枝形状を有することを確認することができた。
実施例1において、原料カーボンブラック1に代えて原料カーボンブラック7(一次粒子の平均粒子径が21nm、遠心沈降分析法により測定されるアグリゲートのストークスモード径が115nm、DBP吸収量が123ml/100g、窒素吸着比表面積が113m2/gであり、透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したときに、アグリゲートが樹枝形状を有することを確認し得るもの)を用い、実施例1と同様に処理してカーボンブラック4を得た。
得られたカーボンブラック4を透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したところ、原料カーボンブラック7のアグリゲートが凝集、重合して球形状を有するアグリゲートを生成していることを確認することができた。
得られたカーボンブラック4の一次粒子の平均粒子径、遠心沈降分析法により測定されるアグリゲートのストークスモード径、DBP吸収量、窒素吸着比表面積を表3に示す。
実施例1において、原料カーボンブラック1に代えて、原料カーボンブラック8(一次粒子の平均粒子径が58nm、遠心沈降分析法により測定されるアグリゲートのストークスモード径が140nm、DBP吸収量が95ml/100g、窒素吸着比表面積が40m2/gであるもの)を採用し、流動反応床炉を用いた反応を行わずにそのまま比較カーボンブラック5とした。
比較カーボンブラック5は、透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したときにアグリゲートが樹枝形状を有することを確認することができた。
実施例1において、原料カーボンブラック1に代えて、原料カーボンブラック9(一次粒子の平均粒子径が14nm、遠心沈降分析法により測定されるアグリゲートのストークスモード径が160nm、DBP吸収量が133ml/100g、窒素吸着比表面積が195m2/gであるもの)を採用し、流動反応床炉を用いた反応を行わずにそのまま比較カーボンブラック6とした。
比較カーボンブラック6は、透過型電子顕微鏡(日本電子株式会社製JEM-2000FX)で観察したときにアグリゲートが樹枝形状を有することを確認することができた。
カーボンブラックとして、実施例1で得られたカーボンブラック1を用い、このカーボンブラック70質量部に対し、ゴム成分であるスチレンブタジエンゴム(日本ゼオン(株)製、Nipol NS116R)80質量部およびポリブタジエンゴム(JSR(株)製、JSR BR01)20質量部と、ステアリン酸2質量部と、オイル(スターリーオイル(株)製
Tudalen65)30質量部と、亜鉛華3質量部とを、密閉型ミキサー(神戸製鋼(株)製MIXTRON BB-2)で4分間混練した後、得られた混練物に対し、加硫促進剤(川口化学工業(株)製アクセルCZ)2質量部と、硫黄2質量部とをオープンロールで混練することにより、表4に示す組成を有するゴム組成物を得た。
上記ゴム組成物のムーニー粘度(ゴム組成物を100℃で5分間加熱したとき粘り気)を、ムーニー粘度計((株)東洋精機製作所製AM-3)を用いて測定した。結果を表5に示す。
表5~表7に記載しているように、ムーニー粘度は、ムーニー単位Mにより表記され、この値が小さければ小さいほど成形する際にゴムが流れやすく加工性が高いことを意味する。
得られた加硫ゴムを用い、以下に示す方法により、損失係数(tanδ) 、引張強度を測定した。結果を表5に示す。
得られた加硫ゴムから切り出した下記サイズを有する試験片を用い、粘弾性スペクトロメータ((株)上島製作所製VR-7110)により、下記の条件で損失係数(tanδ)を測定した。なお、60℃tanδは、値が小さいほど発熱性が低いことを示している。
試験片サイズ:厚さ2mm、長さ35mm、幅5mm
周波数:50Hz
動的歪率:1.2%
測定温度:60℃
(株)東洋精機製作所製ストログラフARを用い、試験片;JIS3号、引張速度500±25mm/分の条件で引張応力(MPa)を測定した。
カーボンブラックとして、実施例1で得られたカーボンブラック1に代えて実施例2で得られたカーボンブラックを用いた以外は、実施例5と同様にしてゴム組成物を作製してムーニー粘度を測定した後、実施例5と同様にして上記ゴム組成物から加硫ゴムを形成して、実施例5と同様にして得られた加硫ゴムの損失係数(tanδ)および引張強度(300%歪み)を測定した。結果を表5に示す。
カーボンブラックとして、実施例1で得られたカーボンブラック1に代えて比較例1で得られた比較カーボンブラック1を用いるか(比較例7)、実施例1で得られたカーボンブラック1に代えて比較例2で得られた比較カーボンブラック2を用いた(比較例8)以外は、実施例5と同様にしてゴム組成物を作製してムーニー粘度を測定した後、実施例5と同様にして上記ゴム組成物から加硫ゴムを形成し、実施例5と同様にして得られた加硫ゴムの損失係数(tanδ)および引張応力(300%歪み)をそれぞれ測定した。結果を表5に示す。
カーボンブラックとして実施例3で得られたカーボンブラック3を用いるか(実施例7)、比較例3および比較例4で得られたカーボンブラック3およびカーボンブラック4をそれぞれ用いた(比較例9および比較例10)以外は、実施例5と同様にして各ゴム組成物を作製してムーニー粘度を測定した後、実施例5と同様にして各ゴム組成物から加硫ゴムを作製し、実施例5と同様にして得られた加硫ゴムの損失係数(tanδ)および引張強度(300%歪み)を測定した。結果を表6に示す。
なお、表6においては、理解を容易にするために、実施例7で得られたムーニー粘度、引張強度(300%歪み)または損失係数(tanδ)の値を100%としたときの相対割合をそれぞれ示すとともに、各実測値を括弧内に示す。表6において、ムーニー粘度、引張強度(300%歪み)、または損失係数(tanδ)が5%以上改善されている場合には、それぞれ各物性が改良されたとみなすことができる。
カーボンブラックとして、実施例4で得られたカーボンブラック4を用いるか(実施例8)、比較例5および比較例6で得られた比較カーボンブラック5および比較カーボンブラック6をそれぞれ用いた以外は、実施例5と同様にして各ゴム組成物を作製してムーニー粘度を測定した後、実施例5と同様にして各ゴム組成物から加硫ゴムを作製し、実施例5と同様にして得られた加硫ゴムの損失係数(tanδ)および引張強度(300%歪み)を測定した。結果を表7に示す。
なお、表7においては、理解を容易にするために、実施例8で得られたムーニー粘度、引張強度(300%歪み)、または損失係数(tanδ)の値を100%としたときの相対割合を示すとともに、各実測値を括弧内に示す。表7において、ムーニー粘度、引張強度(300%歪み)、または損失係数(tanδ)が5%以上改善されている場合には、それぞれ各物性が改良されたとみなすことができる。
また、本発明によれば、上記カーボンブラックを簡便に製造する方法を提供することができる。
さらに、本発明によれば、補強性、発熱性、加工性等のゴム特性が向上したゴム組成物を提供することができる。
2 反応炉本体
21 ガス導入口
22 排気口
3 ヒーターコイル
4 攪拌領域
5 フィルタ
Claims (4)
- 一次粒子の平均粒子径が15~35nmで、遠心沈降分析法により測定されるアグリゲートのストークスモード径が140~180nmであり、透過型電子顕微鏡で観察したときのアグリゲートの形状が球形状であることを特徴とするカーボンブラック。
- DBP吸収量が120~160ml/100g、窒素吸着比表面積が70~120m2/gである請求項1に記載のカーボンブラック。
- 流動床反応炉を用いてカーボンブラックを製造する方法であって、前記流動床反応炉内に炭化水素ガスを供給してガス流を生じさせ、前記流動床反応炉内に別途導入した、一次粒子の平均粒子径が15~35nmであり、遠心沈降分析法により測定されるアグリゲートのストークスモード径が50~115nmである原料カーボンブラックを、前記ガス流によって加熱下に攪拌、流動することを特徴とする請求項1に記載のカーボンブラックの製造方法。
- ゴム成分100質量部に対し、請求項1もしくは請求項2に記載のカーボンブラックまたは請求項3に記載の方法で得られたカーボンブラックを20~100質量部含むことを特徴とするゴム組成物。
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JP2015528058A JPWO2015011796A1 (ja) | 2013-07-24 | 2013-07-24 | カーボンブラック、カーボンブラックの製造方法およびゴム組成物 |
KR1020157035131A KR20160034850A (ko) | 2013-07-24 | 2013-07-24 | 카본 블랙, 카본 블랙의 제조 방법 및 고무 조성물 |
CN201380078405.0A CN105392849B (zh) | 2013-07-24 | 2013-07-24 | 炭黑、炭黑的制造方法和橡胶组合物 |
EP13890013.9A EP3026086A4 (en) | 2013-07-24 | 2013-07-24 | Carbon black, method for producing carbon black, and rubber composition |
PCT/JP2013/070020 WO2015011796A1 (ja) | 2013-07-24 | 2013-07-24 | カーボンブラック、カーボンブラックの製造方法およびゴム組成物 |
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JP2017075242A (ja) * | 2015-10-15 | 2017-04-20 | 横浜ゴム株式会社 | タイヤベルトクッション用ゴム組成物 |
WO2024116833A1 (ja) * | 2022-11-30 | 2024-06-06 | 株式会社ブリヂストン | リサイクルカーボンブラック、ゴム組成物及びタイヤ |
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- 2013-07-24 KR KR1020157035131A patent/KR20160034850A/ko not_active Application Discontinuation
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WO2024116833A1 (ja) * | 2022-11-30 | 2024-06-06 | 株式会社ブリヂストン | リサイクルカーボンブラック、ゴム組成物及びタイヤ |
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US20160177102A1 (en) | 2016-06-23 |
EP3026086A4 (en) | 2017-03-29 |
CN105392849A (zh) | 2016-03-09 |
EP3026086A1 (en) | 2016-06-01 |
US9914835B2 (en) | 2018-03-13 |
KR20160034850A (ko) | 2016-03-30 |
JPWO2015011796A1 (ja) | 2017-03-02 |
CN105392849B (zh) | 2017-11-10 |
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