Process for producing wet rubber masterbatch, wet rubber masterbatch, and rubber composition containing wet rubber masterbatch

Abstract

A method for producing a wet rubber masterbatch uses a single-screw extruder. The single-screw extruder includes a screw, and an external cylinder in which a slit extended along the length direction of the external cylinder (the screw-shaft direction) is formed in an internal wall surface of the external cylinder, and when the width of the slit is represented by A and the clearance between a crest of the screw and the internal wall surface of the external cylinder is represented by B, the following expression (1) is satisfied:
0<AB(Y)/AB(X)<0.9(1)
wherein AB (Y) is the product of A and B at a downstream side along the screw-shaft direction of the external cylinder, and AB (X) is the product of A and B at an upstream side along the screw-shaft direction of the external cylinder.

Claims

1. A method for producing a wet rubber masterbatch obtained using at least a filler, a dispersing solvent and a rubber latex solution as raw materials, wherein the method comprises: a coagulation step of mixing a slurry solution containing the filler and the dispersing solvent, and the rubber latex solution with each other to be coagulated, thereby producing a filler-containing rubber coagulate, and a heating step of using a single-screw extruder to heat the filler-containing rubber coagulate to 160 C. to 200 C., thereby dehydrating, drying and plasticizing the filler-containing rubber coagulate in a single step, wherein the single-screw extruder includes a screw, and an external cylinder in which a slit extended along the length direction of the external cylinder, in the screw-shaft direction, is formed in an internal wall surface of the external cylinder, and when the width of the slit is represented by A and the clearance between a crest of the screw and the internal wall surface of the external cylinder is represented by B, the following expression (1) is satisfied:
0<AB(Y)/AB(X)<0.9(1) wherein AB (Y) is the product of A and B at a downstream side along the screw-shaft direction of the external cylinder, and AB (X) is the product of A and B at an upstream side along the screw-shaft direction of the external cylinder.

2. The wet rubber masterbatch producing method according to claim 1, wherein the screw is a screw having a shaft diameter that increases from the upstream side toward the downstream side along the screw-shaft direction.

3. The wet rubber masterbatch producing method according to claim 1, wherein the screw is a screw having at least one step permitting the shaft diameter of the screw to become larger toward a downstream side of the screw.

4. A wet rubber masterbatch produced by the producing method claim 1.

5. A rubber composition comprising the wet rubber masterbatch according to claim 4.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates an example of an external appearance of a single-screw extruder usable in the present invention.

(2) FIG. 2 is a sectional view of the extruder in FIG. 1 taken along line A-A when viewed in an arrow direction.

(3) FIG. 3 illustrates an example of a development diagram of an internal wall surface of an external cylinder.

(4) FIG. 4 is an explanatory view of the clearance B between a crest of a screw and an internal wall surface of an external cylinder.

MODE FOR CARRYING OUT THE INVENTION

(5) The wet rubber masterbatch producing method according to the present invention has at least a coagulation step and a heating step. Hereinafter, each of the steps will be described.

(6) Coagulation Step

(7) In the coagulation step, a slurry solution containing a filler and a dispersing solvent, and a rubber latex solution are mixed with each other to be coagulated, thereby producing a filler-containing rubber coagulate. It is preferred that the coagulation step has, particularly, the following steps: a step (I) in which when the filler is dispersed into the dispersing solvent, at least one portion of the rubber latex solution is added thereto to produce a slurry solution containing the filler to which rubber latex particles adhere; a step (II) of mixing the slurry solution with the rest of the rubber latex solution to produce a rubber latex solution containing the filler, to which the rubber latex particles adhere; and a step (III) of coagulating the rubber latex solution containing the filler, to which the rubber latex particles adhere, to produce a filler-containing rubber coagulate.

(8) In the present invention, the filler denotes an inorganic filler used usually in the rubber industry, such as carbon black, silica, clay, talc, calcium carbonate, magnesium carbonate, or aluminum hydroxide. Among these inorganic fillers, carbon black is in particular preferably usable in the present invention.

(9) As the carbon black, an electroconductive carbon black, such as acetylene black or Ketchen black may be used, in addition to a carbon black used in an ordinary rubber industry, such as SAF, ISAF, HAF, FEF, or GPF. The carbon black may be granulated carbon black, which is granulated in an ordinary rubber industry, considering the handleability thereof, or may be non-granulated carbon black.

(10) The dispersing solvent is in particular preferably water. The solvent may be, for example, water containing an organic solvent.

(11) As the rubber latex solution, a natural rubber latex solution and a synthetic rubber latex solution are usable.

(12) The natural rubber latex solution is a natural product obtained by metabolic effect of a plant. Particularly preferred is a natural-rubber/water system latex solution in which a dispersing solvent is water. The number-average molecular weight of the natural rubber in the natural rubber latex used in the present invention is preferably 2000000 or more, preferably 2500000 or more. The synthetic rubber latex solution is, for example, a latex solution of styrene-butadiene rubber, butadiene rubber, nitrile rubber or chloroprene rubber produced by emulsion polymerization.

(13) Hereinafter, a description will be made about a preferred example of the coagulation step on the basis of an example in which carbon black is used as the filler, and a natural rubber latex solution is used as the rubber latex solution. This case makes it possible to produce a wet rubber masterbatch which is very high in carbon black dispersion degree and is further improved in low exothermic performance, durability performance and rubber strength when the masterbatch is made into vulcanized rubber. About the natural rubber latex, concentrated latex, fresh latex named field latex, and other latexes are usable without being distinguished from each other.

(14) In the wet rubber masterbatch producing method according to the present invention, it is unnecessary to use an additive called a viscosity stabilizer, which has a purpose for restraining a rise in the viscosity of any wet rubber masterbatch at an initial time of the storage thereof. Examples of the viscosity stabilizer include hydrazide compounds such as acetic acid hydrazide, propionic acid hydrazide, butyric acid hydrazide, caproic acid hydrazide, and cyclopropylhydrazide; hydroxyamine sulfate; semicarbazide; and dimedone (1,1-dimethylcyclohexane-3,5-dione).

(15) (1) Step (I)

(16) In the step (I), at the time of dispersing the carbon black into the dispersing solvent, at least one portion of a natural rubber latex solution is added thereto to produce a slurry solution containing the carbon black to which natural rubber latex particles adhere. It is allowable to mix the natural rubber latex solution beforehand with the dispersing solvent, and then add the carbon black to the mixture to disperse the carbon black in the mixture. It is also allowable to add the carbon black to the dispersing solvent; and next add the natural rubber latex solution thereto at a predetermined adding-speed and simultaneously disperse the carbon black in the dispersing solvent. Alternatively, it is allowable to add the carbon black to the dispersing solvent; and next add thereto a predetermined volume of the natural rubber latex solution several times through operations separated from each other and simultaneously disperse the carbon black in the dispersing solvent. By dispersing the carbon black into the dispersing solvent in the presence of the natural rubber latex solution, a slurry solution can be produced which contains the carbon black to which natural rubber latex particles adhere. The addition amount of the natural rubber latex solution in the step (I) is, for example, from 0.075% to 12% by mass of the total amount of the natural rubber latex solution to be used (the amount of the whole of the solutions to be added in the step (I) and in the step (II).

(17) In the step (I), the solid (rubber) content in the natural rubber latex solution to be added is preferably from 0.25% to 15%, more preferably from 0.5% to 6% by mass of the carbon black. The concentration of the solid (rubber) in the natural rubber latex solution to be added is preferably from 0.2% to 5% by mass, more preferably from 0.25% to 1.5% by mass. In these cases, a wet rubber masterbatch can be produced in which the dispersion degree of the carbon black is heightened while the carbon black is surely caused to adhere to the natural rubber latex particles.

(18) In the step (I), the method for mixing the carbon black and the dispersing solvent with each other in the presence of the natural rubber latex solution is, for example, a method of dispersing the carbon black, using an ordinary dispersing machine such as a highly shearing mixer, a high shear mixer, a homo-mixer, a ball mill, a bead mill, a high-pressure homogenizer, an ultrasonic homogenizer or a colloid mill.

(19) The highly shearing mixer means a mixer having a high-speed-rotatable rotor and a fixed stator in which in the state of making a precise clearance between the rotor and the stator, the rotor is rotated to act a highly shearing effect. In order to produce such a highly shearing effect, it is preferred to set the clearance between the rotor and the stator to 0.8 mm or less, and set the circumferential speed of the rotor to 5 m/s or more. Such a highly shearing mixer may be a commercially available product. An example thereof is a mixer, High Shear Mixer, manufactured by Silverson.

(20) In the present invention, at the time of mixing the carbon black with the dispersing solvent in the presence of the natural rubber latex solution, thereby producing the slurry solution containing the carbon black, to which the rubber latex particles adhere, a surfactant may be added thereto in order to improve the carbon black in dispersibility. The surfactant may be a surfactant known in the rubber industry. Examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric ionic surfactants. Instead of the surfactant or in addition to the surfactant, an alcohol such as ethanol may be used. However, when the surfactant is used, it is feared that the finally obtained vulcanized rubber is lowered in rubber physical properties. Thus, the blend amount of the surfactant is preferably 2 parts or less by mass, more preferably 1 part or less by mass for 100 parts by mass of the solid (rubber) content in the natural rubber latex solution. It is preferred not to use any surfactant substantially. In order to restrain a deterioration of the solid (rubber) in the natural rubber latex solution in the steps (I) and (II), an anti-aging agent may be added to the latex solution. As the anti-aging agent, known anti-aging agent in the rubber industry may be used. Examples thereof include amine-based anti-aging agent, phenolic-based anti-aging agent, organic phosphite-based anti-aging agent and thioether-based anti-aging agent.

(21) In the slurry solution produced in the step (I), the 90% volume particle diameter (m) (D90) of the carbon black, to which the natural rubber latex particles adhere, is preferably 31 m or more, more preferably 35 m or more. This case makes the carbon black excellent in dispersibility in the slurry solution and makes it possible to prevent the carbon black from re-aggregating, so that the slurry solution is excellent in storage stability and further the finally obtained vulcanized rubber is also excellent in low exothermic property, durability performance and rubber strength. In the present invention, the D90 of the carbon black, to which the natural rubber latex particles adhere, denotes a value obtained by measuring the whole including not only the carbon black but also the adhering natural rubber latex particles.

(22) (2) Step (II)

(23) In the step (II), the slurry solution is mixed with the rest of the natural rubber latex solution to produce a rubber latex solution containing the carbon black, to which the natural rubber latex particles adhere. The method for mixing the slurry solution with the rest of the natural rubber latex solution in a liquid phase is not particularly limited, and may be a method of mixing the slurry solution with the rest of the natural rubber latex solution, using an ordinary dispersing machine such as a highly shearing mixer, a High Shear Mixer, a homo-mixer, a ball mill, a bead mill, a high-pressure homogenizer, an ultrasonic homogenizer or a colloid mill. As required, the whole of the dispersing machine or some other mixing system may be heated at the time of the mixing.

(24) When the drying period and labor are considered in the next step (III), it is preferred that the rest of the natural rubber latex solution is higher in solid (rubber) concentration than the natural rubber latex solution added in the step (I). Specifically, the solid (rubber) concentration is preferably from 10 to 60% by weight, more preferably from 20 to 30% by weight.

(25) (3) Step (III)

(26) In the step (III), the rubber latex solution containing the carbon black, to which the natural rubber latex particles adhere, is coagulated to produce a filler-containing rubber coagulate. The method for the coagulation may be, for example, a method of adding a coagulant to the rubber latex solution containing the carbon black, to which the natural rubber latex particles adhere, to coagulate the rubber latex solution.

(27) The coagulant used in the coagulation step may be a substance used ordinarily to coagulate a rubber latex solution, for example, an acid such as formic acid or sulfuric acid, or a salt such as sodium chloride.

(28) About the ratio between the rubber component and the filler in the filler-containing rubber coagulate obtained through/after the step (III), it is preferred that the filler-containing rubber coagulate contains 30 to 80 parts by mass of the filler for 100 parts by mass (solid content) of the rubber. This case makes it possible to finally produce a wet rubber masterbatch in which improvements good in balance are made in the dispersion degree of the filler and in the low exothermic performance and durability performance of a vulcanized rubber produced from this masterbatch.

(29) Heating Step

(30) In the heating step, a single-screw extruder is used to heat the filler-containing rubber coagulate to 160 C. to 200 C., thereby dehydrating, drying and plasticizing this coagulate in a single step. FIG. 1 illustrates an example of a single-screw extruder usable in the present invention.

(31) A single-screw extruder 20 has a screw 23, and an external cylinder 27 composed of a first external cylinder 25 positioned at a supplying-opening-29 side (upstream side) of the extruder 20 and a second external cylinder 26 positioned at a discharging-opening-30 side (downstream side) thereof. The filler-containing rubber coagulate obtained through/after the coagulation step is charged through the supplying opening 29 into the extruder, and is advanced along a length direction 1 of the external cylinder (screw-shaft direction) while kneaded. Finally, the filler-containing rubber coagulate is discharged through the discharging opening 30. The upstream side part of the extruder 20 is also called a dehydrating section 21, and the downstream side part thereof is also called a drying section (expander section) 22. As required, a jacket 28 may be fitted to the drying section 22 to adjust the temperature of this section. In the present invention, however, it is preferred that the extruder 20 has no pin moieties projected from an internal wall surface of the external cylinder in the drying section 22 toward the inside thereof. If the extruder 20 has, in the drying section 22, such pin moieties, a high shearing force acts onto the rubber component passing between the pin moieties to cleave chains of the polymer in the rubber component so that a deterioration of the rubber component advances easily. As a result, the finally obtained vulcanized rubber may be deteriorated in tearing resistant performance and stress property at the high-strain region. The length (L) of the external cylinder (barrel) of this single-screw extruder and the diameter (D) of the external cylinder may be equivalent to those of any single-screw extruder used in an ordinary rubber industry. Furthermore, the ratio (L/D) of the external cylinder length to the external cylinder diameter may be set at will.

(32) The internal wall surface of the external cylinder 27 has at least one slit 24 extended along a length direction 1 of the external cylinder (as illustrated in FIGS. 2 and 3, in the present embodiment, plural slits 24 are formed at regular intervals in the internal wall surface of the external cylinder). In the single-screw extruder 20 described in the embodiment, the slits 24 are formed in the internal wall surface of the dehydrating section 21 while the slits 24 are not formed in the drying section (expander section) 22. It is therefore preferred in the embodiment that A and B at the downstream side along the screw-shaft direction of the external cylinder are preferably the following, respectively: the slit width of each of the slits 24 positioned at the downmost stream side of the dehydrating section 21; and the clearance between the crest of the screw 23 that is positioned at the downmost stream side of the dehydrating section 21 and the internal wall surface of the external cylinder 27 that is positioned at the same side. As illustrated in FIG. 3, in the embodiment, an example is illustrated in which the slits 24 are continuously extended along the external cylinder length direction 1. However, slits may be extended while inclined to the external cylinder length direction 1. Furthermore, the slits 24 may be extended from a supplying-opening-29 side end of the external cylinder 27 to a discharging-opening-30 side end thereof. The slits 24 may be formed only in the dehydrating section 21, or may be intermittently extended along the external cylinder length direction 1. It is preferred to set the slit width A in the internal wall surface of the external cylinder into the range of 0.1 mm to 0.9 mm. If the width A is less than 0.1 mm, flow channels for water that are generated by dehydrating the wet rubber masterbatch become narrow so that the water content by percentage in the wet rubber masterbatch may be insufficiently lowered. If the width A is more than 0.9 mm, the contact area between the wet rubber masterbatch and the internal wall surface of the external cylinder becomes small so that the water content by percentage in the wet rubber masterbatch may be insufficiently lowered.

(33) FIG. 2 has illustrated an example of the slits formed to widen the slit width from the internal wall surface of the external cylinder toward the depth direction of the slits. In the present invention, however, the slits formed in the internal wall surface of the external cylinder may be slits formed to make the slit width constant or narrow from the internal wall surface of the external cylinder toward the depth direction of the slits.

(34) The shape of the screw 23 included in the single-screw extruder 20 may be any shape. In the present invention, however, at the time of representing the clearance between the crest of the screw 23 and the internal wall surface of the external cylinder 27 by B, the screw 23 is designed to satisfy the following expression (1) about a relationship between the clearance B and the slit width A of each of the slits 24 formed in the internal wall surface of the external cylinder:
0<AB(Y)/AB(X)<0.9(1)
wherein AB (Y) is the product of A and B at the downstream side along the screw-shaft direction of the external cylinder 27, and AB (X) is the product of A and B at the upstream side along the screw-shaft direction of the external cylinder 27. The clearance B is preferably from 1 mm to 10 mm both inclusive. If the clearance B is less than 1 mm, the flow channels for the rubber component become narrow so that an excessive shearing force acts onto the rubber component. Thus, the finally obtained vulcanized rubber may be deteriorated in rubber physical properties. If the clearance B is more than 10 mm, the flow channels for the rubber component become wide so that the shearing force given to the rubber component becomes short. Thus, the water content by percentage in the wet rubber masterbatch may be insufficiently lowered. The screw may be a heating mode screw. FIG. 4 each illustrate an example of a screw shape adoptable in the present invention.

(35) FIG. 4(a) illustrates an example of the screw 23 in which the shaft diameter is made large from an upstream side along the screw-shaft direction toward a downstream side along the screw-shaft direction (the screw shaft diameter D.sub.L at the downstream side along the screw-shaft direction is larger than the screw shaft diameter D.sub.U at the upstream side along the screw-shaft direction). This structure makes it possible to gradually heighten shearing force given to the rubber component toward the downstream side to restrain the shearing force from being given excessively to the rubber component. Thus, the water content by percentage in the wet rubber masterbatch can be further decreased while the rubber component in the wet rubber masterbatch is restrained from being deteriorated. The screw 23 illustrated in FIG. 4(a) is formed to make the height of a crest 41 of the screw gradually small from the upstream side toward the downstream side along the screw-shaft direction (the height H.sub.L of the screw crest 41 at the downstream side along the screw-shaft direction is smaller than the height H.sub.U of the screw crest 41 at the upstream side along the screw-shaft direction). This structure makes it possible to moderate, to an appropriate extent, shearing force given to the rubber component at the downstream side along the screw-shaft direction, this side being a side where the shearing force acts strongly to the rubber component. Thus, the water content by percentage in the wet rubber masterbatch can be further decreased while the rubber component in the wet rubber masterbatch is restrained from being deteriorated. Moreover, the screw illustrated in FIG. 4(a) is formed to make the clearance B.sub.L between the crest 41 of the screw 23 at the downstream side along the screw-shaft direction and an internal wall surface of the external cylinder 27 smaller than the clearance B, between the crest 41 of the screw 23 at the upstream side along the screw-shaft direction and the internal wall surface of the external cylinder 27. However, in the present invention, the screw may be formed to make the crest height of the screw constant from the upstream side toward the downstream side along the screw-shaft direction as far as the expression (1) is satisfied.

(36) FIG. 4(b) illustrates an example of the screw having at least one step 42 (referred to also as collar) permitting the shaft diameter of the screw to become larger toward a downstream side of the screw 23. When this screw is adopted, the rubber component is blocked by the step in the heating step so that the rubber component receives shearing force while the rubber component remains and stays in an appropriate extent inside the single-screw extruder. Thus, the water content by percentage in the wet rubber masterbatch can be further decreased while the rubber component in the wet rubber masterbatch is restrained from being deteriorated. Since the screw 23 illustrated in FIG. 4(b) has the step 42, the shaft diameter D.sub.L of the screw at the downstream side along the screw-shaft direction is larger than the shaft diameter D.sub.U of the screw at the upstream side along the screw-shaft direction. Moreover, the example illustrated in FIG. 4(b) is formed to make the height H.sub.L of a crest 41 of the screw at the downstream side along the screw-shaft direction smaller than the height H.sub.U of the crest 41 of the screw at the upstream side along the screw-shaft direction; and make the clearance B.sub.L between the crest 41 of the screw 23 at the downstream side along the screw-shaft direction and an internal wall surface of an external cylinder 27 smaller than the clearance B.sub.U between the crest 41 of the screw 23 at the upstream side along the screw-shaft direction and the internal wall surface of the external cylinder 27. However, in the present invention, the screw may be formed to make the crest height of the screw constant from the upstream side toward the downstream side along the screw-shaft direction as far as the expression (1) is satisfied.

(37) In the wet rubber masterbatch producing method according to the present invention, after the heating step, a kneading step and a vulcanization compounding agent kneading step are performed to blend various blending agents into the wet rubber masterbatch. In this way, a rubber composition can be produced.

(38) Kneading Step:

(39) This is a step of: incorporating, into the wet rubber masterbatch obtained through/after the heating step, compounding agents other than any vulcanization compounding agent, examples of the agents including stearic acid, zinc white, an anti-aging agent, silica, a silane coupling agent, softeners such as wax and oil, and a processing aid; and then using a mixing and dispersing machine to knead the individual components. In the kneading step, these blending agents are mixed with the rubber component to produce, for example, the following advantageous effects: after the masterbatch is vulcanized, the resultant rubber product is heightened in strength; the rubber is made good in kneadability and workability; and the rubber is prevented from being deteriorated by radicals generated by the cleavage of molecular chains of the rubber. In the mixing and kneading step, for example, a mesh-type type Bunbury mixer, a tangential type Bunbury mixer, or a kneader is usable. The use of the mesh-type Bunbury mixer is particularly preferred.

(40) As the anti-aging agent, usually used for rubbers, aromatic amine-based anti-aging agent, amine-ketone-based anti-aging agent, monophenolic-based anti-aging agent, bisphenolic-based anti-aging agent, polyphenolic-based anti-aging agent, dithiocarbamic acid salt-based anti-aging agent, and thiourea-based anti-aging agent may be used singly or used by appropriately mixing. The content of the anti-aging agent(s) is more preferably from 0.3 to 3 parts by mass, even more preferably from 0.5 to 1.5 parts by mass for 100 parts by mass of the rubber component (solid) in the wet rubber masterbatch.

(41) Vulcanization Compounding Agent Kneading Step:

(42) Vulcanization compounding agents, for example, a vulcanizing agent such as sulfur, and a vulcanization accelerator are incorporated into the rubber composition obtained through/after the kneading step, and then the whole is kneaded. When the rubber composition obtained through/after the vulcanization compounding agent kneading step is heated to a predetermined temperature or higher, the vulcanizing agent in the rubber composition reacts with molecules of the rubber to form a crosslinkage structure between the rubber molecules, so that the molecules are made into a three-dimensional network structure to give rubbery elasticity to the composition.

(43) Sulfur may be any ordinary sulfur for rubbers. Examples thereof include powdered sulfur, precipitated sulfur, insoluble sulfur, and highly dispersible sulfur. The content of the sulfur in the rubber composition according to the present invention is preferably from 0.3 to 6 parts by mass for 100 parts by mass of the rubber component. If the content of the sulfur is less than 0.3 part by mass, the vulcanized rubber is short in crosslinkage density to be lowered in rubber strength and others. If the content is more than 6.5 parts by mass, the rubber is deteriorated, particularly, in both of heat resistant performance and durability performance. In order to keep the rubber strength of the vulcanized rubber good and further improve the heat resistant performance and the durability performance, the content of the sulfur is more preferably set into the range of 1.5 to 5.5 parts by mass for 100 parts by mass of the rubber component.

(44) As the vulcanization accelerator, usually used for vulcanizing rubbers, sulfenamide-based vulcanization accelerator, thiuram-based vulcanization accelerator, thiazole-based vulcanization accelerator, thiourea-based vulcanization accelerator, guanidine-based vulcanization accelerator, and dithiocarbamate-based vulcanization accelerator may be used singly or used by appropriately mixing.

(45) The content of the vulcanization accelerator(s) is more preferably from 1 to 5 parts by mass, even more preferably from 1.5 to 4 parts by mass for 100 parts by mass of the rubber component.

EXAMPLES

(46) Hereinafter, the present invention will be more specifically described through a description of examples thereof. Raw materials and apparatuses used therein are as follows:

(47) Raw Materials Used:

(48) a) Carbon black:

(49) Carbon black N330: SEAST 3 (manufactured by Tokai Carbon Co., Ltd.)

(50) Carbon black N110: SEAST 9 (manufactured by Tokai Carbon Co., Ltd.)

(51) Carbon black N774: SEAST SO (manufactured by Tokai Carbon Co., Ltd.)

(52) b) Dispersing solvent: Water

(53) c) Rubber latex solution:

(54) Natural rubber concentrated latex solution: latex solution obtained by adding water to a rubber manufactured by Regitex Co., Ltd (having a DRC (dry rubber content) of 60% and a mass-average molecular weight of 236000) at ambient temperature to give a rubber component concentration of 25% by mass; and

(55) Natural rubber fresh latex solution: latex solution obtained by adding water to a rubber manufactured by a company Golden Hope (having a DRC (dry rubber content) of 31.2% and a mass-average molecular weight of 232000) at ambient temperature to give a rubber component concentration of 25% by mass

(56) d) Coagulant: Formic acid (solution obtained by diluting a first-class 85% solution thereof into a 10% solution to adjust the pH of the diluted solution to 1.2), manufactured by Nacalai Tesque, Inc.

(57) e) Zinc white: Zinc white No. 1, manufactured by Mitsui Mining & Smelting Co., Ltd.

(58) f) Stearic acid, manufactured by NOF Corp.

(59) g) Anti-aging agent: Aromatic amine-based agent N-phenyl-N-(1,3-dimethylbutyl)-p-phenylenediamine 6PPD, manufactured by Monsanto Company; melting point: 44 C.;

(60) h) Sulfur, manufactured by Tsurumi Chemical Industry Co., Ltd.

(61) i) Vulcanization accelerator: CBS manufactured by Sanshin Chemical Industry Co., Ltd.

(62) Evaluations:

(63) Evaluations were made about a rubber obtained by using a predetermined mold to heat and vulcanize each of rubber compositions at 150 C. for 30 minutes.

(64) Water Content by Percentage in Each Filler-Containing Rubber Coagulate:

(65) In accordance with JIS K6238-2, the water content by percentage in a filler-containing rubber coagulate of each of the compositions was measured, using a heat-drying type moisture meter MX-50 manufactured by A & D Co., Ltd.

(66) Mooney Viscosity of Each Wet Rubber Masterbatch:

(67) In accordance with JIS K6300, the viscosity of the wet rubber masterbatch of each of the compositions was measured at 100 C. In the evaluation, the value of Comparative Example 1 was regarded as 100, and Examples 1 to 10 and Comparative Examples 2 to 5 were each evaluated through an index relative thereto; the value of Comparative Example 6 was regarded as 100, and Example 11 was evaluated through an index relative thereto; and the value of Comparative Example 7 was regarded as 100, and Example 12 was evaluated through an index relative thereto. It is shown that as the numerical value of the compositions is lower, the compositions are further plasticized to be better.

(68) 300% Elongation Modulus (M300) of Each Vulcanized Rubber:

(69) In accordance with JIS-K 6251, an evaluating sample was prepared from each of the vulcanized rubbers, and then the 300% elongation modulus (M300 (MPa)) thereof was measured, using a JIS#3 dumbbell. In the evaluation, the value of Comparative Example 1 was regarded as 100, and Examples 1 to 10 and Comparative Examples 2 to 5 were each evaluated through an index relative thereto; the value of Comparative Example 6 was regarded as 100, and Example 11 was evaluated through an index relative thereto; and the value of Comparative Example 7 was regarded as 100, and Example 12 was evaluated through an index relative thereto. It is shown that as the numerical value of the vulcanized rubbers is higher, the vulcanized rubbers are higher in rubber strength to be better.

Example 1

(70) To a diluted natural rubber latex solution, the concentration thereof being adjusted to 0.5% by mass, were added 50 parts by mass of one of the carbon blacks (about the solid amount (rubber amount) in the latex solution, the ratio by mass of the solid to the carbon black was 1 part by mass). A ROBOMIX manufactured by PRIMIX Corp. was then used to disperse the carbon black therein (conditions of the ROBOMIX: 9000 rpm for 30 minutes). In this way, produced was a slurry solution containing the carbon black to which natural rubber latex particles adhered (step (I)).

(71) Next, the rest of the natural rubber concentrated latex solution (latex solution into which water was added to adjust the solid (rubber) concentration therein to 25% by mass) was added to the slurry solution produced in the step (I) and containing the carbon black, to which the natural rubber latex particles adhered, to set the solid (rubber) content to 100 parts by mass in the total of the rest and the natural rubber latex solution used in the step (I). Thereafter, a mixer for household use, SM-L56 model, manufactured by SANYO Electric Co., Ltd. was used to mix the individual components with each other (mixer condition: 11300 rpm for 30 minutes) to produce a natural rubber latex solution containing the carbon black, to which the natural rubber latex particles adhered (step (II).

(72) Coagulation Step:

(73) A 10% by mass solution of formic acid in water was added as a coagulant to the natural rubber latex solution produced in the step (II) and containing the carbon black, to which the natural rubber latex particles adhered, until the pH of the latex solution was turned to 4. In this way, a natural rubber coagulate containing the carbon black was produced (step (III).

(74) Heating Step:

(75) The single-screw extruder illustrated in FIGS. 1 to 4 was used, this extruder being a squeezer type extruder [product No.: V-02 (manufactured by Suehiro EPM Corp.); barrel diameter: 90 mm; the ratio of the barrel length/the barrel diameter (L/D)=8.6; the width A of slits in an internal wall surface of its external cylinder: the slit width A (X) at an upstream side along the screw-shaft direction=0.9 mm, and the slit width A (Y) at a downstream side along the screw-shaft direction=0.7 mm; screw shape (2): a shape designed as follows: from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw was constant and further the shaft diameter of the screw was made gradually large; and the clearance B between the crest of the screw and the internal wall surface of the external cylinder: the clearance B (X) at the upstream side along the screw-shaft direction=8.0 mm, and the clearance B (Y) at the downstream side along the screw-shaft direction=7.0 mm. While the above-mentioned natural rubber coagulate was kneaded at a heating temperature of 200 C. (heating temperature of the heating type screw: 200 C.), the product was dehydrated, dried and plasticized through a single step.

(76) Kneading Step and Vulcanization Compounding Agent Kneading Step:

(77) A B-type Bunbury mixer (manufactured by Kobe Steel, Ltd.) was used to blend various additives shown in Table 1 into the resultant natural wet rubber masterbatch to prepare a rubber composition. Physical properties of a vulcanized rubber thereof were measured. The results are shown in Table 1.

Examples 2 to 4, and Comparative Example 5

(78) In each of the examples, a natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that one or more of A(X), A(Y), B(X) and B(Y) were varied to change the ratio of AB(Y)/AB(X).

Example 5

(79) A natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that the screw shape of the screw was changed to a screw shape (1) designed as follows: from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw was made gradually small and further the shaft diameter of the screw was made gradually large.

Example 6 and Comparative Example 2

(80) In each of the examples, a natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that the screw shape of the screw was changed to the screw shape (1) and further one or more of A(X), A(Y), B(X) and B(Y) were varied to change the ratio of AB(Y)/AB(X).

Example 7

(81) A natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that the screw shape of the screw was changed to a screw shape (3) designed as follows: from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw was constant and further at least one step was formed.

Example 8

(82) A natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that the screw shape of the screw was changed to a screw shape (4) designed as follows: from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw was made gradually small and further at least one step was formed.

Example 9

(83) A natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that the screw shape of the screw was changed to the screw shape (4) and further one or more of A(X), A(Y), B(X) and B(Y) were varied to change the ratio of AB(Y)/AB(X). Masterbatch, a rubber composition and a vulcanized rubber were produced.

Example 10

(84) A natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that the screw shape was changed to the screw shape (4) and further the heating temperature was changed into the range from 160 C. to 200 C.

Examples 11 and 12

(85) In each of the examples, a natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that the screw shape was changed to the screw shape (1) and further the species and the blend amount of the carbon black were changed.

Comparative Example 1

(86) A natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that: instead of the heating step, two steps were performed, the steps being a dehydrating step (dehydrating temperature (temperature of the heating type screw of the single-screw extruder used at the time of the dehydrating): 160 C.) and a drying and plasticizing step (drying and plasticizing temperature (temperature of the heating type screw of the single-screw extruder used at the time of the drying and plasticizing): 160 C.); and one or more of A(X), A(Y), B(X) and B(Y) were varied to change the ratio of AB(Y)/AB(X). Physical properties of the vulcanized rubber are shown in Table 1.

Comparative Example 3

(87) A natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that: the screw shape of the screw was changed to the screw shape (1); one or more of A(X), A(Y), B(X) and B(Y) were varied to change the ratio of AB(Y)/AB(X); and further as the single-screw extruder, the following was used: an extruder having pin moieties extended from an internal wall surface of a downstream side of its external cylinder toward the inside thereof.

Comparative Example 4

(88) A natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that: instead of the heating step, two steps were performed, the steps being a dehydrating step using a centrifugal separator, and a drying and plasticizing step (drying and plasticizing temperature (temperature of the heating type screw of the single-screw extruder used at the time of the drying and plasticizing): 200 C.); and one or more of A(X), A(Y), B(X) and B(Y) were varied to change the ratio of AB(Y)/AB(X). Physical properties of the vulcanized rubber are shown in Table 1.

Comparative Examples 6 and 7

(89) In each of the examples, a natural wet rubber masterbatch, a rubber composition and a vulcanized rubber were produced in the same way as in Example 1 except that: instead of the heating step, two steps were performed, the steps being a dehydrating step (dehydrating temperature (temperature of the heating type screw of the single-screw extruder used at the time of the dehydrating): 160 C.), and a drying and plasticizing step (drying and plasticizing temperature (temperature of the heating type screw of the single-screw extruder used at the time of the drying and plasticizing): 160 C.); one or more of A(X), A(Y), B(X) and B(Y) were varied to change the ratio of AB(Y)/AB(X); and the species and the blend amount of the carbon black were changed. Physical properties of the vulcanized rubber are shown in Table 1.

(90) TABLE-US-00001 TABLE 1 Compar- Compar- Compar- Compar- Compar- ative ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- (Formulation) ple 1 ple 2 ple 3 ple 4 ple 5 ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 ple 9 ple 10 Wet rubber Carbon black N330 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 masterbatch N110 blending N774 components Natural rubber (solid) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Blending Zinc white 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 components at Stearic acid 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 rubber Anti-aging agent 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 composition Sulfur 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 production time Vulcanization 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 accelerator Dehydrating step conditions: Dehydrating temperature (heating type screw 160 Centrifugal temperature) separator Screw shape (1) used AB(Y)/AB(X) 1.0 A(X) (mm) 0.9 B(X) (mm) 8.0 A(Y) (mm) 0.9 B(Y) (mm) 8.0 Water content by percentage in 5.0 27 carbon-black-containing coagulate Drying and plasticizing step conditions: Drying and plasticizing temperature 160 200 (heating type screw temperature) Screw shape (1) (1) AB(Y)/AB(X) 1.0 1.0 A(X) (mm) 0.9 0.9 B(X) (mm) 8.0 8.0 A(Y) (mm) 0.9 0.9 B(Y) (mm) 8.0 8.0 Heating step conditions: Heating temperature (heating type screw 200 200 200 200 200 200 200 200 200 200 200 200 160-200 temperature) Screw shape (1) (1) (2) (2) (2) (2) (2) (1) (1) (3) (4) (4) (4) Step(s) of screw Not Not Not Not Not Not Not Not Not Formed Formed Formed Formed formed formed formed formed formed formed formed formed formed AB(Y)/AB(X) 1.0 1.0 1.1 0.7 0.5 0.3 0.1 0.7 0.6 0.7 0.7 0.6 0.7 A(X) (mm) 0.9 0.9 0.7 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 B(X) (mm) 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 A(Y) (mm) 0.9 0.9 0.9 0.7 0.6 0.4 0.4 0.7 0.5 0.7 0.7 0.5 0.7 B(Y) (mm) 8.0 8.0 7.0 7.0 6.0 5.0 1.0 7.0 8.0 7.0 7.0 8.0 7.0 Water content by percentage in 0.95 1.22 1.10 1.03 1.10 0.68 0.64 0.57 0.50 0.66 0.63 0.55 0.53 0.54 0.50 carbon-black-containing coagulate Viscosity (index) 100 110 83 80 105 90 85 7.9 70 94 90 80 80 81 81 Vulcanized rubber physical properties: M300(INDEX) 100 98 88 85 96 114 115 113 108 119 118 110 115 117 124 Screw shape(1): shape designed in such a manner that from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw is made gradually small, and further the shaft diameter of the screw is made gradually large. Screw shape(2): shape designed in such a manner that from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw is constant, and further the shaft diameter of the screw is made gradually large. Screw shape(3): shape designed in such a manner that from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw is constant, and further at least one step is formed. Screw shape(4): shape designed in such a manner that from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw is made gradually small, and further at least one step is formed.

(91) TABLE-US-00002 TABLE 2 Comparative Comparative (Formulation) Example 6 Example 11 Example 7 Example 12 Wet rubber masterbatch Carbon black N330 blending components N110 40 40 N774 80 80 Natural rubber (solid) 100 100 100 100 Blending components at Zinc white 3 3 3 3 rubber composition Stearic acid 2 2 2 2 production time Anti-aging agent 2 2 2 2 Sulfur 2 2 2 2 Vulcanization accelerator 1 1 1 1 Dehydrating step conditions: Dehydrating temperature (heating type screw temperature) 160 160 Screw shape (1) (1) AB(Y)/AB(X) 1.0 1.0 A(X) (mm) 0.9 0.9 B(X) (mm) 8.0 8.0 A(Y) (mm) 0.9 0.9 B(Y) (mm) 8.0 8.0 Water content by percentage in carbon-black-containing coagulate 4.0 5.6 Drying and plasticizing step conditions: Drying and plasticizing temperature (heating type screw temperature) 160 160 Screw shape (1) (1) AB(Y)/AB(X) 1.0 1.0 A(X) (mm) 0.9 0.9 B(X) (mm) 8.0 8.0 A(Y) (mm) 0.9 0.9 B(Y) (mm) 8.0 8.0 Heating step conditions: Heating temperature (heating type screw temperature) 200 200 Screw shape (1) (1) Step(s) of screw Not formed Not formed AB(Y)/AB(X) 0.7 0.7 A(X) (mm) 0.9 0.9 B(X) (mm) 8.0 8.0 A(Y) (mm) 0.7 0.7 B(Y) (mm) 7.0 8.0 Water content by percentage in carbon-black-containing coagulate 0.86 0.70 0.90 0.81 Viscosity (index) 100 89 100 87 Vulcanized rubber physical properties: M300 (INDEX) 100 113 100 110 Screw shape(1): shape designed in such a manner that from the upstream side toward the downstream side along the screw-shaft direction, the crest height of the screw is made gradually small, and further the shaft diameter of the screw is made gradually large.

(92) From Tables 1 and 2, in the wet rubber masterbatches according to Examples 1 to 12, only through a single step of the heating step, the water content by percentage is sufficiently made lower than in the wet rubber masterbatches according to Comparative Examples 1, 6 and 7. It is also understood that the Mooney viscosity is also made lower to attain the plasticization sufficiently. Furthermore, it is understood that also when the masterbatches of Examples 1 to 12 are each converted to the vulcanized rubber, the rubber is improved in strength.