JP5819656B2 - Manufacturing apparatus and manufacturing method of rubber compounding composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an apparatus and a method for producing a rubber compounding composition, and in particular, a rubber compounding composition by kneading the rubber composition with a vulcanizing agent and a vulcanization accelerator added (so-called “B kneading”). The present invention relates to an apparatus and a method for generating a message.

  The rubber kneading process is generally divided into two steps. In other words, additives other than vulcanizing compounding agents such as a vulcanizing agent and a vulcanization accelerator, for example, a so-called A kneading step in which a reinforcing agent such as silica or carbon black is added, and a vulcanizing system in the material after the A kneading step It is said B kneading process which adds a compounding agent.

  The B kneading step is kneaded at a lower temperature than the A kneading step (see, for example, the example of Patent Document 1). This is because the vulcanizing compound is added as an additive in the B kneading step, so that if the material remains at a high temperature, the material temperature increases excessively during kneading, and the rubber composition is not sufficiently kneaded. This is because there is a possibility that the product may be cross-linked. If such a phenomenon occurs, the rubber hardness increases and the moldability deteriorates. Further, when insoluble sulfur is used as a vulcanizing compounding agent, it becomes soluble at a high temperature, and there is a risk of generating bloom that causes poor adhesion.

  When the rubber component is kneaded in the mixer, the temperature in the mixer rises due to heat generated by the viscous flow of rubber. In particular, when the kneading process is performed in a state where the vulcanizing compounding agent is introduced, the crosslinking process is started when the temperature reaches about 120 ° C. For this reason, conventionally, when the temperature reaches the above-mentioned temperature, the outside of the mixer is taken out, and the vulcanizing agent cannot be kneaded for a sufficient period of time, which may cause poor dispersion of the vulcanizing agent. When a rubber compounding composition with poor dispersion of the vulcanizing agent is subjected to a post-process such as molding, for example, a vulcanization accelerator such as a guanidine compound is present as a foreign substance in the product, color unevenness occurs on the product surface, There is a possibility that problems such as the generation of bubbles frequently occur, leading to an increase in the defect rate.

  In the following Patent Document 1, a configuration including a cooling device for lowering the temperature in the mixer at the time of kneading is disclosed.

JP 2007-320184 A

  However, according to the method of Patent Document 1, since a cooling device for lowering the temperature is required, there are problems that the installation space is increased and the production cost is greatly increased. Further, since the temperature in the mixer depends on the performance and function of the cooling device, it cannot always be maintained in a desirable temperature environment.

  The present invention provides a manufacturing apparatus and a manufacturing method of a rubber compounding composition that enables a vulcanizing agent to be dispersed in a rubber composition without causing progress of crosslinking with inexpensive and space-saving equipment. Objective.

In order to achieve the above object, the apparatus for producing a rubber compounding composition according to the present invention comprises:
A slot for feeding materials;
An agitation rotor for agitating the material charged from the charging port in a sealed kneading chamber;
A control unit for automatically controlling the rotation speed of the stirring rotor;
A temperature sensor that detects the temperature in the kneading chamber and outputs information on the detected actual temperature to the control unit;
The control unit is based on the information on the measured temperature and the information on the set target temperature until the set control time elapses in a state where at least the rubber component and the vulcanizing agent exist in the kneading chamber. The rotational speed is automatically controlled by PID control for setting the measured temperature to the target temperature.

  More specifically, the control unit may be configured to automatically control the rotation speed of a motor for rotationally driving the stirring rotor.

In order to achieve the above object, a method for producing a rubber compounding composition according to the present invention comprises:
A method for producing a rubber compounding composition comprising:
A step of mixing at least a rubber component and a vulcanizing agent in a sealed kneading chamber that is equipped with a stirring rotor capable of automatically controlling the rotation speed by the control unit and capable of detecting and outputting the internal temperature;
Setting the control unit for the control time and the target temperature;
PID control for setting the measured temperature to the target temperature by the control unit based on the information about the measured temperature in the kneading chamber and the target temperature until the control time elapses after the completion of the two steps. And agitating the kneading chamber while automatically controlling the rotation speed.

  Here, the target temperature is preferably set to a temperature lower than the lower limit temperature at which the rubber component starts crosslinking.

  According to the present invention, the rotation speed of the stirring rotor is automatically controlled by PID control by the control unit, so that the temperature in the kneading chamber can be kept within a certain range over a certain time. This makes it possible to stir and knead in the kneading chamber for a certain period of time while maintaining the temperature, so that it has better characteristics than the conventional configuration in which the rubber compound is discharged when the temperature reaches a certain temperature or higher. The rubber compounding composition which shows can be manufactured.

  In particular, according to the configuration of the present invention, it is possible to keep the temperature lower than the temperature at which the cross-linking reaction is started without necessarily providing a cooling device. A composition can be produced.

1 is a schematic structural diagram of a kneading apparatus according to the present invention. It is a flowchart which shows the flow of the rubber processing method performed with this apparatus. It is the graph which showed the change of the actual temperature in a kneading chamber and the rotation speed of a motor under PID control from a control part in this device with time.

  FIG. 1 shows a schematic diagram of a manufacturing apparatus according to the present invention (hereinafter referred to as “the present apparatus”). This apparatus 1 shown in FIG. 1 is a closed mixer, a cylinder 2 used for raising and lowering a ram 4, a charging port 3 for charging work material, a kneading chamber 5 for kneading material, and kneaded. A drop door 7 for discharging the rubber is provided. The ram 4 is arranged to adjust the pressure in the kneading chamber 5 by raising and lowering.

  The kneading chamber 5 is provided with a pair of agitation rotors 6 for agitating the material, and the agitation rotors 6 are rotationally driven around a rotary shaft 12 by a motor (not shown). The kneading chamber 5 is provided with a temperature sensor 13 for detecting the temperature in the chamber. The temperature sensor 13 may be installed inside the drop door 7, for example.

  The rotation speed of the motor that rotates the stirring rotor 6 is adjusted based on a control signal from the control unit 11. The controller 11 controls the rotational speed of the motor based on the temperature information in the kneading chamber 5 sent from the temperature sensor 13. The motor may be configured so that the rotation speed can be freely changed by the control unit 11, and is configured by an inverter motor, for example.

  More specifically, the rotational speed of the motor is proportional to the deviation between the measured temperature Tp in the kneading chamber 5 detected by the temperature sensor 13 and the target temperature Ts by the PID calculation processing unit provided inside the control unit 11. PID control based on execution of operations of (P), integration (I), and differentiation (D) is executed. That is, the PID calculation processing unit calculates a control amount in proportion to the difference (deviation e) between the measured temperature Tp in the kneading chamber 5 detected by the temperature sensor 13 and the target temperature Ts (deviation). For each controlled variable obtained by an integral (I) operation for calculating a controlled variable by an integral value obtained by integrating e in the time axis direction, and a differential (D) operation for calculating a controlled variable from the slope of the deviation e, that is, a differential value. The rotational speed of the motor is determined by the total value.

  In FIG. 2, the flow of the rubber processing method performed by this apparatus 1 is illustrated as a flowchart. When a rubber composition, a vulcanizing agent, and a vulcanization accelerator as required are introduced into the apparatus 1 (step S1), based on the values of the target temperature Ts and the control set time tm input in step S2. Then, PID control to the motor is started by the control unit 11 (step S3). That is, the rotational speed of the motor is determined based on the control signal from the control unit 11, and thereby the rotational speed of the stirring rotor 6 (that is, the stirring speed) is determined. Information regarding the target temperature Ts and the control set time tm may be given in advance to the control unit 11 in the stage before step S1.

  In addition, as a rubber composition thrown in in step S1, what was obtained by kneading | mixing compounding agents other than vulcanization type compounding agents, such as a vulcanizing agent and a vulcanization accelerator, with a rubber component (A kneaded rubber) May be used.

  In step S1, the rubber composition, the vulcanizing agent, and the vulcanization accelerator may be independently fed into the apparatus 1, or the vulcanizing agent and the vulcanization accelerator are mixed. The rubber composition before stirring may be charged.

  The control unit 11 performs PID control on the rotational speed of the motor until the elapsed time t from the control start time becomes equal to or longer than the control set time tm (No in step S4). As for the specific control contents, as described above, based on the deviation between the measured temperature Tp and the target temperature Ts in the kneading chamber 5 sent from the temperature sensor 13, the deviation integral value, and the deviation differential value, To change.

  The value of the target temperature Ts is preferably set lower by a minute temperature than the lower limit temperature at which the rubber component starts crosslinking. This is because the control unit 11 is configured to perform PID control, but it is assumed that the target temperature Ts may be temporarily exceeded in the control process. That is, it is preferable to set the value of the target temperature Ts so that the actually measured temperature Tp in the kneading chamber 5 is temporarily allowed to slightly exceed the target temperature Ts in the control process.

  When the control time t becomes equal to or greater than the control set time tm (Yes in step S4), the control unit 11 finishes the PID control to the motor and discharges the rubber composition from the drop door 7 (step S5). ).

  Here, the control set time tm is set to be longer than the time tc required to sufficiently disperse the vulcanizing agent in the rubber composition.

  FIG. 3 is a graph showing changes over time in the measured temperature Tp in the kneading chamber 5 and the rotational speed of the motor under PID control from the control unit 11 in the present apparatus 1. Note that (b) is an enlarged view of a region A portion in (a).

  According to FIG. 3, it can be seen that the measured temperature Tp in the kneading chamber 5 can be maintained at a value substantially equal to the target temperature Ts over a long period of time by changing (increasing or decreasing) the rotational speed of the motor in small increments. Therefore, by maintaining this temperature longer than the time ti, the vulcanizing agent can be sufficiently dispersed in the rubber composition in the kneading chamber 5. In the example of FIG. 3, PID control was performed with the target temperature Ts set at 95 ° C., and the measured temperature Tp could be maintained at 92 ° C. to 98 ° C.

  In the flowchart of FIG. 2, the PID control by the control unit 11 is always executed after the rubber composition and the vulcanized compound are added. In practice, however, the user determines whether to perform the PID control. The configuration can be selected according to

  Moreover, as a rubber component which comprises the rubber composition thrown in, it is good also as what contains the terminal modified diene type rubber | gum whose number average molecular weights before modification are 150,000 to 400,000. The type of diene rubber to be terminally modified is not particularly limited, but butadiene rubber (BR. For example, high cis BR having 90% or more of cis-1,4 bond, syndiotactic-1,2-polybutadiene (SPB). Containing BR), styrene butadiene rubber (SBR), natural rubber (NR), isoprene rubber (IR), styrene isoprene copolymer rubber, butadiene isoprene copolymer rubber, and the like, more preferably BR and SBR. More preferably, it is SBR.

  As this terminal-modified diene rubber, diene rubber whose polymer terminal is modified with various modifiers can be used, and various known modification methods can be used. Specifically, as the modifier, tin compound, aminobenzophenone compound, isocyanate compound, diglycidylamine compound, cyclic imine compound, halogenated alkoxysilane compound, glycidoxypropylmethoxysilane compound, neodymium compound, alkoxysilane compound, amine Examples thereof include a combination of a compound and an alkoxysilane compound.

  In addition, when an A-kneaded rubber obtained by adding a predetermined additive to the rubber component and kneading is adopted as the rubber composition to be added, the additives include carbon black, silica, silane coupling agent, zinc oxide, stearin Acids, anti-aging agents, softening agents such as waxes and oils can be employed as necessary.

  The vulcanizing agent to be added may be normal sulfur for rubber, and for example, powdered sulfur, precipitated sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used. In order to ensure good rubber strength of the vulcanizable rubber and further improve heat resistance and durability, the sulfur content is 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, it is 0.1-1.0 mass part.

  As the vulcanization accelerator, sulfenamide vulcanization accelerator, thiuram vulcanization accelerator, thiazole vulcanization accelerator, thiourea vulcanization accelerator, guanidine vulcanization, which are usually used for rubber vulcanization. Vulcanization accelerators such as accelerators and dithiocarbamate vulcanization accelerators can be used alone or in admixture.

  By using this apparatus, the temperature in the kneading chamber 5 can be maintained for a certain period of time, so that a good rubber compounding composition can be produced. Specific effects are described in more detail in the following examples.

  Table 1 below shows the results of the case of kneading under PID control by the present apparatus 1 as Example 1, and the case of kneading without performing PID control as Comparative Examples 1-2.

  In Comparative Example 1, kneading was performed without performing PID control, and the kneading process was terminated when the temperature in the kneading chamber 5 showed 110 ° C. The kneading time at this time was 60 seconds.

  In Comparative Example 2, kneading was performed without performing PID control, and the kneading process was terminated when the temperature in the kneading chamber 5 showed 125 ° C. The kneading time at this time was 120 seconds.

  In Example 1, kneading was performed while maintaining the temperature in the kneading chamber 5 at 110 ° C. by PID control by the apparatus 1, and kneading was terminated when 120 seconds, which is the same kneading time as in Comparative Example 2, had elapsed.

  In addition, the value regarding the vulcanization | cure speed | rate and scorch time shown in Table 1 is shown by the relative value when the value in the comparative example 1 is made into the reference | standard (100). Further, in each of the examples and comparative examples, the kneading process was performed in a state where a vulcanizing agent and a vulcanization accelerator were mixed in the A-kneaded rubber obtained by kneading the following materials.

(A kneaded rubber material)
Modified styrene butadiene rubber (modified SBR): HPR340 (modified S-SBR, amount of bonded styrene: 10% by mass, modified with amine and alkoxyl silane) manufactured by JSR Corporation.
・ Untreated silica: Tosoh Silica Industry Co., Ltd. “Nipseal AQ”
Silane coupling agent: bis- (3-triethoxysilylpropyl) disulfide, “Si-75” manufactured by Degussa
Protected mercaptosilane: (C _n H _{2n + 1} O) ₃ Si—C _m H _2m —S—CO—C _k H _{2k + 1} (n = 2, m = 3, k = 7) Momentive Performance Materials "NXT"
・ Oil: Japan Energy Co., Ltd. “Process X-140”

(Vulcanizing agent)
・ "5% oil-treated sulfur" manufactured by Hosoi Chemical Co., Ltd. (vulcanization accelerator)
・ N-cyclohexyl lu 2-benzothiazolylsulfenamide ("Noxeller CZ-G (CZ)", manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

  Note that the lower limit temperature at which the rubber component starts to be crosslinked is approximately 120 ° C. when the above materials are employed. That is, the vulcanizing agent and the vulcanization accelerator can be added while preventing the cross-linking reaction of the rubber component from occurring by carrying out the stirring treatment while maintaining a temperature range below about 120 ° C., more preferably a temperature range of 1110 ° C. or less. It becomes possible to disperse sufficiently. As described above, in Example 1, the stirring process is performed while maintaining the inside of the kneading chamber 5 at 110 ° C., which is within the above temperature range, by the PID control of the apparatus 1.

  In addition, about each item, a value was measured by the method shown below, and it obtained by calculating | requiring the relative value with respect to the comparative example 1. FIG.

(Vulcanization speed)
It performs 60 minutes of vulcanization test at 160 ° C. using a rheometer for rubber composition taken out from the mixer, the maximum value _{M H} and the minimum value _{M L} of the torque _{(M H} -M L) to 50% The time from the start of measurement until the time was measured. It is suggested that the smaller this value is, the shorter the time for reaching the vulcanized state is and the better the dispersed state of the vulcanizing agent.

(Scorch time)
About the rubber compounding composition taken out from the mixer, the scorch time (Sco (t5)) at 125 ° C. was measured according to JIS-K 6300-1. It is suggested that vulcanization of the rubber compounding composition at the time of taking out from the mixer is not progressing, so that this value is large.

  Comparative Example 2 shows a significantly lower scorch time than Comparative Example 1. This is because in Comparative Example 2, the temperature in the kneading chamber 5 at the time of take-out is higher than that in Comparative Example 1, so that the vulcanization proceeds more during the kneading process in Comparative Example 2. Suggests that. Moreover, about the vulcanization | cure speed | velocity, the direction of the comparative example 2 has shown the larger value than the comparative example 1, and it is suggested that the dispersion effect of a vulcanizing agent is falling with the temperature rise.

  When Example 1 is compared with Comparative Example 1, Example 1 has a smaller vulcanization rate value. Unlike Comparative Example 1 in which stirring is terminated when the temperature reaches 110 ° C., in Example 1 in which stirring is performed for a certain period of time while maintaining the state of 110 ° C. by PID control, stirring can be performed for a longer time than Comparative Example 1. Therefore, it can be seen that the dispersion of the vulcanizing agent is proceeding.

  When Example 1 and Comparative Example 2 are compared, the value of scorch time is significantly smaller in Comparative Example 2. When Example 1 and Comparative Example 1 are compared, the value of the scorch time hardly changes. That is, according to the method of Example 1, it is possible to perform a kneading process for a long time without proceeding with vulcanization.

  As described above, according to Example 1 in which the method of the present invention is employed, since it can be maintained for a certain time in a temperature environment lower than the lower limit temperature at which the crosslinking treatment is started, the vulcanizing agent is suppressed while suppressing the progress of crosslinking. It turns out that the effect which raises dispersion | distribution is acquired.

1: Kneading device according to the present invention 2: Cylinder 3: Loading port 4: Ram 5: Kneading chamber 6: Stirring rotor 7: Drop door 11: Control unit 12: Rotating shaft 13: Temperature sensor

Claims (4)

A slot for feeding materials;
An agitation rotor for agitating the material charged from the charging port in a sealed kneading chamber;
A control unit for automatically controlling the rotation speed of the stirring rotor;
A temperature sensor that detects the temperature in the kneading chamber and outputs information on the detected actual temperature to the control unit;
The control unit is based on the information on the measured temperature and the information on the set target temperature until the set control time elapses in a state where at least the rubber component and the vulcanizing agent exist in the kneading chamber. An apparatus for producing a rubber compounding composition, wherein the rotation speed is automatically controlled by PID control for setting the measured temperature to the target temperature only by rotation control of the stirring rotor . A method for producing a rubber compounding composition comprising:
A step of mixing at least a rubber component and a vulcanizing agent in a sealed kneading chamber that is equipped with a stirring rotor capable of automatically controlling the rotation speed by the control unit and capable of detecting and outputting the internal temperature;
Setting the control unit for the control time and the target temperature;
After the two steps are completed, until the control time elapses, the measured temperature is set as the target temperature only by rotation control of the stirring rotor based on the information about the measured temperature in the kneading chamber and the target temperature. And a step of stirring the interior of the kneading chamber while automatically controlling the rotation speed by performing the PID control for the purpose of manufacturing the rubber compounding composition.   The said target temperature is a temperature lower than the minimum temperature which a rubber component starts bridge | crosslinking, The manufacturing method of the rubber compounding composition of Claim 2 characterized by the above-mentioned. The target temperature, method for producing a rubber composition according to claim 3, characterized in that the lower than 120 ° C. temperature.

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