WO2009116543A1 - Process for producing wet masterbatch and wet masterbatch - Google Patents

Abstract

A process for producing a wet masterbatch by mixing and coagulating a slurry solution and a rubber solution. The wet masterbatch comprises coagulated particles produced from these solutions, the coagulated particles being uniform in size and composition. Also provided are the wet masterbatch formed by the process, a rubber composition, and a tire. The process for wet-masterbatch production comprises mixing a slurry solution containing a filler with a rubber solution and coagulating the mixture, and is characterized by metering these solutions to a coagulation tank (2) in respective amounts corresponding to one batch of the wet masterbatch and stirring and mixing the solutions while pulverizing the mixture.

Description

Wet masterbatch manufacturing method and wet masterbatch

The present invention relates to a method for producing a wet masterbatch, a wet masterbatch formed by this method, a rubber composition, and a tire, and in particular, a method for producing a wet masterbatch that improves the blending ratio and the accuracy of solidified particle size. It is about.

Conventionally, a method using a wet masterbatch is known in order to improve the processability and dispersibility of forming a rubber composition containing a filler. This wet masterbatch is a mixture of a rubber solution, a slurry solution containing a filler such as carbon black and silica, and a coagulant to coagulate and separate only the solid content from the coagulation liquid containing these coagulum, The separated solid is produced by dehydration and drying.

In order to improve the productivity in the production process of the wet master batch, a method of producing this in a continuous process is generally used. As a method of mixing and coagulating the slurry solution and the rubber solution, the slurry solution is added to the coagulation tank. And a rubber solution are continuously supplied, these are coagulated in a coagulation tank, and a coagulation liquid containing a coagulum formed from these is continuously discharged from the coagulation tank. In addition, the coagulating tank agitating apparatus at that time is generally a method of agitating at a relatively low rotational speed with paddles or propeller-shaped blades in order to efficiently mix the input raw materials.

However, in this wet masterbatch manufacturing method, the solidification time from charging to discharging cannot be quantitatively controlled, and the resulting solidified product is insufficiently mixed and solidified. There was a risk that the particle size and blending ratio were not satisfied.
Immediately after the slurry solution and the rubber solution are put into the coagulation tank, neither of them is mixed and solidified. However, when the number of contact between the slurry solution and the rubber solution increases by mixing, the slurry solution is solidified. Acting as an agent, primary agglomerated particles are formed in which a small amount of the slurry solution and the rubber solution are associated. When the mixing time is further increased, the primary aggregated particles are associated with each other to form secondary aggregated particles. When the mixing time is further increased, the secondary aggregated particles are associated with each other, and a giant coagulum is generated. In some cases, this coagulated material grows larger than the pipe diameter, making it difficult to flow, or entangled with the stirring blade and cannot flow.

Accordingly, an object of the present invention is to produce a wet masterbatch having a uniform size and composition of the solidified product produced from these solutions, particularly when producing a wet masterbatch for mixing and solidifying the slurry solution and the rubber solution. A wet masterbatch, a rubber composition, and a tire formed by the method are provided.

The method for producing a wet masterbatch according to the present invention is a method in which a slurry solution containing a filler and a rubber solution are mixed and coagulated, and the solution for one wet masterbatch is measured and coagulated. It is characterized by being stirred and mixed while being pulverized.

More preferably, the rubber solution is a natural rubber solution in such a wet masterbatch production method.

Also preferably, a coagulant containing acid is introduced into the coagulation tank.

More preferably, the grinding blade rotates at a speed of 500 rpm or a peripheral speed of 5 m / s or more.

More preferably, the slurry solution and the rubber solution are simultaneously added to the coagulation tank and mixed with stirring.

By the way, the particle size of the wet masterbatch is controlled in the range of 0.001 to 10 cm.

Preferably, the mixture is stirred and mixed at a slurry solid content concentration of 0.5 to 20% and a rubber solution solid content concentration of 1% to 60%.

The wet masterbatch according to the present invention is formed by any of the wet masterbatch manufacturing methods described above.

The rubber composition according to the present invention is formed using the wet master batch described above.

The tire according to the present invention is formed using the rubber composition described above.

In the conventional continuous wet masterbatch manufacturing method, the coagulation time from when the slurry solution and the rubber solution are charged into the coagulation tank to when the rubber solution is discharged as coagulum cannot be controlled quantitatively. Some products were insufficiently mixed and solidified, and did not have the intended particle size and blending ratio. Further, they were entangled with stirring blades, and it was difficult to flow and discharge.

Therefore, the manufacturing method of the wet masterbatch of the present invention is to measure the solution for one wet masterbatch and put it into the coagulation tank, so that the raw materials are not continuously charged, but the batch is charged for a certain time, By discharging after mixing and coagulation, a coagulated product with the intended particle size and blending ratio can always be reliably produced.

In addition, by stirring and mixing while pulverizing, the shear force F by the pulverization blade is applied in the coagulation step as shown in FIG. 1B to suppress aggregation and make the size of the generated coagulum uniform. Thus, a wet masterbatch having a uniform composition can be obtained without generating a giant coagulated product in which aggregated particles are associated with each other as shown in FIG. As a result, the coagulated material becomes a large mass in the coagulation tank, so that the stirring efficiency can be reduced and the decrease in discharge of the coagulated material can be prevented.

It is the schematic which showed the grinding | pulverization of the grinding | pulverization part of the wet masterbatch of this invention. It is process drawing which illustrates the process of the manufacturing method of the wet masterbatch of this invention. It is the schematic which shows the wet masterbatch stirring apparatus used for the manufacturing method of the wet masterbatch of this invention which mixes and solidifies a slurry solution and a rubber solution. It is a figure which shows a twin-screw extruder typically. (A)-(d) is a figure which shows the result of having measured the particle size distribution by the Example. (A)-(d) is a figure which shows the result of having measured the carbon black compounding quantity by the Example. It is the schematic which shows the wet masterbatch stirring apparatus used for the manufacturing method of the conventional wet masterbatch which mixes and solidifies a slurry solution and a rubber solution.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Stirring apparatus 2 Coagulation tank 3, 13 Stirrer 4, 14 Slurry solution supply port 5, 15 Rubber solution supply port 6, 16 Coagulant supply port 7, 17 Discharge port 8 Grinding part 20 Overall process 21 Filler slurry solution preparation process 22 Rubber solution preparation process 23 Mixing / coagulation process 24 Solid-liquid separation process 25 Cleaning process 26 Dehydration process 27 Drying process 28 Molding process 29 Coagulant preparation process 31 Twin screw extruder

Below, the manufacturing method of the wet masterbatch of this invention is demonstrated in detail, referring drawings.
FIG. 2 is a process diagram illustrating the process of the method for producing a wet masterbatch of the present invention.
In the figure, the overall process 20 includes a filler slurry solution preparation process 21 prepared by preparing a slurry solution in which a filler such as carbon or silica is dispersed, a natural rubber or synthetic rubber solution, a surfactant, and the like. A rubber solution compounding step 22 for preparing a rubber solution by stirring in a solvent such as water, and a coagulating liquid containing a coagulated product by mixing and coagulating the slurry solution and the rubber solution prepared in these steps A mixing / coagulation step 23 to be formed, and a solid-liquid separation step 24, a washing step 25, and a dehydration step 26, in which only the solid content is separated from the formed coagulation liquid and the separated solid content is washed and dehydrated; The drying step 27 for drying the solid content, and the molding step 28 for forming the wet solid batch as a product by molding the dried solid content into a desired shape such as a granular shape or a bale shape.
In the mixing / coagulation step 23, only the slurry solution and the rubber solution can be mixed and coagulated, but in order to accelerate the coagulation reaction, a coagulant preparation step 29 for preparing and preparing an acid such as formic acid, It can also be included before the mixing / solidifying step 23.

FIG. 3 is a schematic view showing a wet master batch stirring device for mixing and coagulating the slurry solution and the rubber solution in the mixing and coagulating step 23.
In the figure, a stirrer 1 includes a coagulation tank 2 that contains a slurry solution, a rubber solution, and a coagulation liquid, and a radial type agitator 3 that is disposed at the bottom of the coagulation tank 2 with the axis of rotation directed vertically. Have. Further, at a position above the coagulation tank 2, the slurry solution supply port 4 that supplies the slurry solution prepared in the filler slurry solution preparation process 21 to the coagulation tank 2 and the rubber solution prepared in the rubber solution preparation process 22. And a coagulant supply port for supplying the coagulant prepared in the coagulant preparation step 29 made of an acid such as formic acid or sulfuric acid or a salt such as sodium chloride to the coagulation tank The coagulation tank 2 is further provided with a discharge port 7 for discharging a coagulation liquid containing a coagulated product formed by mixing and coagulation of the coagulation tank.

Here, the radiant flow type agitator 3 rotates at a low speed so as to expose the bottom of the container, and can agitate the entire inside of the tank and extrude the generated coagulum to the discharge port 7. This can improve productivity and stabilize product quality.
The discharge port 7 is disposed in the lower part of the side wall of the coagulation tank 2 and can discharge and collect the solidified material in the coagulation tank by opening and closing the piston.

The side wall of the coagulation tank 2 is provided with a pulverizing section 8 that is arranged orthogonal to the radial flow stirrer 3 and crushes the generated coagulated product in the coagulating liquid with pulverization blades.
In the stirring device 1 shown in FIG. 3, the rotating shaft of the stirrer 3 and the rotating shaft of the pulverizing unit 8 are arranged orthogonal to each other, but the rotating shafts of the stirrer 3 and the pulverizing unit 8 are arranged in parallel. You can also.

In order to mix and coagulate the slurry solution and the rubber solution using the stirring device 1 configured as described above, the slurry solution and the rubber solution are supplied into the coagulation tank 2 containing the coagulation liquid, and the agitator 3 is mixed. Further, while rotating the pulverizing unit 8, water, a coagulant, a solution containing various additives, and the like may be supplied, and the coagulation liquid may be discharged after stirring.

FIG. 4 is a diagram schematically showing a twin-screw extruder that cleans and dewaters the solidified product in the dewatering step 26 and the drying step 27.
The twin-screw extruder 31 in the figure is configured to include two screws and a cylinder, and when the solidified material is introduced from the hopper of the extruder 31, the screw rotates under heating to dehydrate the solidified material. dry.

In this wet masterbatch manufacturing method, one wet masterbatch of these solutions is weighed and charged into the coagulation tank 2, and stirred and mixed while being pulverized.

In such a production method, more preferably, by using a natural rubber solution as the rubber solution, it is possible to obtain a material that is excellent in mechanical properties, low heat generation, and wear resistance and is environmentally friendly during the production process.

A surfactant may be added for the purpose of improving the stability of the natural rubber solution. For example, anionic, cationic, nonionic and amphoteric surfactants can be used, and anionic and nonionic surfactants are particularly preferable. The addition amount of the surfactant is appropriately adjusted according to the properties of the natural rubber solution.

Moreover, the solidification yield can be improved by introducing a coagulant containing an acid such as formic acid or sulfuric acid into the coagulation tank.
Further improvement in coagulation yield by combining acids such as sulfuric acid and formic acid, salts such as NaCl and KCl, polymer flocculants, and liquid temperature control (60-100 ° C) used in the mixing / coagulation step 23 Can be achieved.

By rotating the pulverization blade of the pulverization unit 8 at a speed of 500 rpm or a peripheral speed of 5 m / s or more, the enlargement of the solidified product can be suppressed.
By controlling the solidification time and selecting the rotation speed of the pulverization blades, the particle size of the solidified product can be controlled to produce a solidified product having a desired particle size and blending ratio.

By simultaneously adding and mixing the slurry solution and the rubber solution into the coagulation tank 2, the coagulation where the slurry solution and the rubber solution come into contact partially starts, resulting in variations in the carbon black compounding ratio and poor carbon black uptake. Can be prevented. Moreover, since the slurry solution and the rubber solution are not mixed in the vicinity of the pipe, clogging of the pipe can be prevented.

Preferably, the slurry solution and the rubber solution are simultaneously added to the coagulation tank 2 from separate pipes and mixed by stirring. These charging speeds can be controlled to the intended mixing ratio of the rubber and carbon black of the coagulated product to be produced by adding the same amount according to the mixing ratio. When the slurry solution and the rubber solution are mixed, the coagulation reaction proceeds in about a few minutes in the case of a natural rubber solution. Therefore, the charging time is 10 minutes, more preferably 5 minutes, and even more preferably within 2 minutes. . Further, depending on the capacity of the coagulation tank 2, a preliminary mixing tank can be provided.

By controlling the wet masterbatch particle size within the range of 0.001 to 10 cm, preferably 0.2 to 1.0 cm, there is an advantage that the workability of dehydration and drying in the post-process is improved.

That is, if it is less than 0.001 cm, when dehydrating, the filter cloth is clogged with particles and the dehydration efficiency is lowered, or the ratio of solidified particles passing through the filter cloth tends to increase and the yield tends to decrease. . In addition, the moisture content of the coagulated product due to the water adhering to the surface of the coagulated product increases, the moisture content of the extrudate after the extrusion (dehydration + drying) process increases, the workability decreases, and the heat generation characteristics of the kneaded rubber increase. At the same time, the solidified material adheres to the hopper portion of the extruder, and the biting into the extruder tends to deteriorate.
On the other hand, if it exceeds 10 cm, it tends to be bulky and stagnant at a small inlet or the like, or the biting into the extruder will deteriorate, and the extrusion process will not be performed.

Preferably, the slurry solid content concentration is 0.5 to 20%, the rubber solution solid content concentration is 1% to 60%, more preferably the slurry solid content concentration is 3% to 10%, and the rubber solution solid content concentration is 10% to 30%. To do.

By stirring and mixing with this blend, a solidified product having a uniform blend ratio and particle size can be produced with high productivity. When each liquid has a concentration higher than this range, the liquid viscosity becomes too high, and the liquid cannot be uniformly stirred, and a non-uniform solidified product may be generated. On the other hand, when the concentration is lower than this range, the amount of the solidified product produced per unit volume becomes low, and there is a possibility that sufficient productivity cannot be obtained.

In the filler slurry solution preparation step 21, a known method can be used as a method for preparing the slurry solution, and is not particularly limited, but is a rotor-stator type high shear mixer, high pressure homogenizer, ultrasonic homogenizer. A bead mill, a colloid mill, or the like can be used. For example, a slurry solution can be prepared by putting a predetermined amount of filler such as carbon black and water in a colloid mill and stirring at high speed for a certain time.

Here, as the slurry solution, it is preferable to use carbon black, silica, or a dispersion in which at least one filler represented by the general formula (1) is dispersed in water in advance.
nM ₁ xSiO _y zH ₂ O (1)
[Wherein M ₁ is a metal selected from the group consisting of aluminum, magnesium, titanium, calcium and zirconium, an oxide or hydroxide of these metals, and a hydrate thereof, or a carbonate of these metals. N, x, y and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10]

The filler represented by the general formula (1), .gamma.-alumina, alpha-alumina, such as alumina _{(Al 2 O} 3), boehmite, alumina monohydrate such as diaspore _{(Al 2 O 3 · H 2} O ), Gibbsite, Bayerite, etc. Aluminum hydroxide [Al (OH) ₃ ], Aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], Magnesium hydroxide [Mg (OH) ₂ ], Magnesium oxide (MgO), Magnesium carbonate (MgCO ₃ ), talc (3MgO · 4SiO ₂ · H ₂ O), attapulgite (5MgO · 8SiO ₂ · 9H ₂ O), titanium white (TiO ₂ ), titanium black (TiO _2n-1 ), calcium oxide (CaO) , calcium hydroxide [Ca _(OH) 2], magnesium aluminum oxide _{(MgO · Al 2 O 3)} , clay _(Al 2 _{O 3} · SiO _2), kaolin _{(Al 2 O 3 · 2SiO 2} · 2H 2 O), pyrophyllite _{(Al 2 O 3 · 4SiO 2} · H 2 O), bentonite _{(Al 2 O 3 · 4SiO 2} · 2H 2 O) Aluminum silicate (Al ₂ SiO ₅ , Al ₄ · 3SiO ₄ · 5H ₂ O etc.), magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ etc.), calcium silicate (Ca ₂ · SiO ₄ etc.), silicic acid Aluminum calcium (Al ₂ O ₃ · CaO · 2SiO ₂ etc.), magnesium calcium silicate (CaMgSiO ₄ ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), zirconium hydroxide [ZrO (OH) ₂ · nH ₂ O], zirconium carbonate _{[Zr (CO 3) 2]} , hydrogen to correct electric charge as various zeolites, Such as crystalline aluminosilicates including alkali metal or alkaline earth metal can be used. Further, it is preferable that M ₁ in the general formula (1) is at least one selected from aluminum metal, aluminum oxide or hydroxide, hydrates thereof, and aluminum carbonate.

Note that the slurry concentration of the filler containing at least one of the carbon black, silica, and the filler represented by the general formula (1) is preferably 0.5% by weight to 20% by weight, and particularly preferably. The range is 3% to 10% by weight.

The filler is preferably added in an amount of 5 to 100 parts by weight, particularly 10 to 70 parts by weight, with respect to 100 parts by weight of the rubber component of the wet masterbatch. This is because if the amount of the filler is less than 5 parts by weight, sufficient reinforcement may not be obtained, and if it exceeds 100 parts by weight, the workability may be deteriorated. Furthermore, the said carbon black, a silica, and the filler represented by General formula (1) can also be used individually or in mixture of 2 or more types.

Furthermore, in addition to fillers, solutions containing various additives such as surfactants, vulcanizing agents, anti-aging agents, coloring agents, dispersants, and the like, water, and the like can also be added.

The wet masterbatch formed by the manufacturing method of the present invention co-solidifies after mixing the rubber particles finely dispersed in water and the carbon black particles, so that the dispersibility of carbon black is improved compared to the dry-mixed mixture To do. Further, since the particle size is controlled as fine particles, workability in subsequent processes such as dehydration and drying can be improved.

The rubber composition obtained by using this wet masterbatch has excellent dispersibility of carbon black due to the factors of wet mixing and the shape factor of fine particles, and the resulting improvement in rubber properties (reduction of energy loss, wear / durability) Improvement) is realized.

The rubber composition obtained by the production method of the present invention includes various chemicals usually used in the rubber industry, such as a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a scorch, as long as the object of the present invention is not impaired. An inhibitor, zinc white, stearic acid and the like can be added.

The pneumatic tire obtained by using this rubber composition is improved in rolling resistance (fuel consumption), wear and durability.

Using the stirring device shown in the figure, a natural rubber (clone type GT-1) solution, a carbon black (LS-SAF) slurry solution, and a coagulant (formic acid diluted to 20% by weight with water) are put into a coagulation tank. As shown in Table 1, the particle size distribution was evaluated for each of Example Batch 1 to Example Batch 3 and Comparative Example Batch 1 in which the respective specifications were changed.
In addition, the stirring apparatus of the comparative example batch 1 shown in FIG. 7 is an apparatus in which a rubber solution (35 kg / hour) and a slurry solution (30 kg / hour) are joined together through a pipe and continuously added. A universal mixer manufactured by Tsukishima Kikai Co., Ltd. was used as the stirring device shown in FIG.

(Particle size distribution)
About each of Example Batch 1 to Example Batch 3 and Comparative Example Batch 1, the produced coagulum was sampled by about 1 L, stirred uniformly, and then sieved with 1 to 3000 mesh, and the coagulation remaining on each sieve The average particle size was calculated from the amount of the product and the size of the mesh. The evaluation results are shown in Table 2 and FIG.

From the results of Table 2 and FIG. 5, in Example Batch 1 to Example Batch 3, the solidified particle size is controlled to a constant size, and the average particle size can be adjusted by the number of rotations of the grinding blades. On the other hand, the size of the patch 1 of Comparative Example could not be controlled because the coagulated material became a lump.

(Carbon black content)
Each of Example Batch 1 to Example Batch 3 and Comparative Example Batch 1 was sampled from three different locations in each batch of the coagulated material produced under the conditions of Example Batch and Comparative Example Batch 1, and solidified at each location. About 1 g of the product was dried to remove moisture, then cut into a size of 1 to 2 mm in diameter, and the content of carbon black was measured by a pyrolysis method according to ASTM D297-39 using a crucible.
The average of batches sampled at three different locations is defined as carbon black blending amount B, and the difference (AB) between the value and target blending amount A is defined as the center value deviation of the batch. When a plurality of batches are manufactured under the same manufacturing conditions and the same target blending amount, and the blending amount of each batch is measured, (center value deviation) and (variation) in the manufacturing conditions are expressed by Equation 1. The evaluation results are shown in Table 3 and FIG.

[N: number of batches, B _k : K = 1 to N batch carbon black content measurement result]
(Dispersion): Standard deviation of B _k Here, N = 21 for Example Batch 1, N = 24 for Example Batch 2, N = 19 for Example Batch 3, and N = 34 for Comparative Batch 1 Calculated from the data.

From the results of Table 3 and FIG. 6, Example Batch 1 to Example Batch 3 have a significantly reduced center value deviation and variation compared to Comparative Example Batch 1, and are stably master batches at the intended carbon black content. Could be manufactured.

From the results of Tables 2 and 3 and FIGS. 5 and 6, Example Batch 1 to Example Batch 3 are compared with Comparative Example Batch 1 with a solidified particle size of a certain size and the target carbon black content. It was possible to stably produce a masterbatch controlled at a constant temperature.

Example batch 4 in which natural rubber solution, carbon black slurry solution, and formic acid as a coagulant are simultaneously charged into the coagulation tank, and comparative example batch 1 in which pipe mixing is performed, using the stirring apparatus shown in the figure, The comparative example batch 2 to be introduced first was made as a prototype, and the others were changed as shown in Table 4 to evaluate the dispersion and variation of carbon black.

In each of Example Batch 4, Comparative Example Batch 1, and Comparative Example Batch 2, the produced coagulated product was drained, dried, compounded with rubber chemicals, mixed with a banbury mixer except the vulcanizing agent, and added. The mixture was mixed with the sulfurizing agent. Thereafter, the sample was cut into an appropriate size, placed in a mold, and vulcanized at 145 ° C. for 30 minutes with a vulcanizer to prepare a test specimen for measurement. Using the test piece, the dispersion of carbon black with TECHPRO dispersGRADER + and the variation with the above formula 1 were measured by a method according to ASTM D2663-95a. The evaluation results are shown in Table 5.
The dispersion is performed by comparison with standard samples of 1 to 10, and the larger the value in the table, the greater the dispersion and variation.

From the results shown in Table 5, in Example Batch 4, the dispersion of carbon black was higher than that in Comparative Example Batch 1 and Comparative Example Batch 2, and the variation in carbon black was greatly improved.

Using the stirrer shown in FIG. 3, the produced coagulum was sampled approximately 1 L and stirred uniformly, and sieved with 1 to 3000 mesh. From the amount of coagulum remaining on each sieve and the size of the mesh After calculating the average particle size, the moisture content was measured for each of the solidified products having an average particle size as shown in Table 6. Thereafter, in the Kobe Steel twin-screw extruder KTX-59 shown in FIG. 4, when the dehydration and drying are performed at a barrel temperature of 160 ° C. and a screw rotation speed of 400 rpm, The moisture content of the extrudate after extrusion was measured, and the evaluation results are shown in Table 6.

Here, the biting property to the extruder was evaluated by visual observation of the fluidity of the solidified product with the screw of the extruder and the adherence of the solidified product to the hopper.
The moisture content of the coagulated product and the extrudate was determined to be 2.0% or less by measuring the moisture content by weight with a heat-drying moisture meter MX-50 manufactured by A & D.

From the results in Table 6, when the particle size of the wet masterbatch is in the range of 0.001 to 10 cm, the biting property into the extruder and the moisture content of the coagulated substance are improved, especially in the range of 0.2 to 1.0 cm. Even better results were obtained.

Claims (10)

1. In a method for producing a wet masterbatch in which a slurry solution containing a filler and a rubber solution are mixed and solidified,
   A method for producing a wet masterbatch, characterized in that a solution of one wet masterbatch is weighed and charged into a coagulation tank and stirred and mixed while being pulverized.
2. The method for producing a wet masterbatch according to claim 1, wherein the rubber solution is a natural rubber solution.
3. The method for producing a wet masterbatch according to claim 1 or 2, wherein a coagulant containing an acid is introduced into a coagulation tank.
4. The method for producing a wet masterbatch according to claims 1 to 3, wherein the grinding blade is rotated at a speed of 500 rpm or a peripheral speed of 5 m / s or more.
5. The method for producing a wet masterbatch according to any one of claims 1 to 4, wherein the slurry solution and the rubber solution are simultaneously charged into a coagulation tank and stirred and mixed.
6. The method for producing a wet masterbatch according to any one of claims 1 to 5, wherein the particle size of the wet masterbatch is controlled within a range of 0.001 to 10 cm.
7. The method for producing a wet masterbatch according to any one of claims 1 to 6, wherein stirring solid mixing is performed at a slurry solid content concentration of 0.5 to 20% and a rubber solution solid content concentration of 1% to 60%.
8. A wet masterbatch formed by the production method according to any one of claims 1 to 7.
9. A rubber composition formed using the wet masterbatch according to claim 8.
10. A tire formed using the rubber composition according to claim 9.

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