WO2019130800A1 - Procédé de production d'un mélange-maître humide de caoutchouc, procédé de fabrication d'une composition de caoutchouc pour pneus - Google Patents

Procédé de production d'un mélange-maître humide de caoutchouc, procédé de fabrication d'une composition de caoutchouc pour pneus Download PDF

Info

Publication number
WO2019130800A1
WO2019130800A1 PCT/JP2018/040477 JP2018040477W WO2019130800A1 WO 2019130800 A1 WO2019130800 A1 WO 2019130800A1 JP 2018040477 W JP2018040477 W JP 2018040477W WO 2019130800 A1 WO2019130800 A1 WO 2019130800A1
Authority
WO
WIPO (PCT)
Prior art keywords
rubber
carbon black
latex solution
rubber latex
producing
Prior art date
Application number
PCT/JP2018/040477
Other languages
English (en)
Japanese (ja)
Inventor
惇 田中
野村　健治
Original Assignee
Ｔｏｙｏ Ｔｉｒｅ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017247660A external-priority patent/JP7067917B2/ja
Priority claimed from JP2017247640A external-priority patent/JP7066398B2/ja
Priority claimed from JP2017247655A external-priority patent/JP2019112543A/ja
Application filed by Ｔｏｙｏ Ｔｉｒｅ株式会社 filed Critical Ｔｏｙｏ Ｔｉｒｅ株式会社
Publication of WO2019130800A1 publication Critical patent/WO2019130800A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to a method for producing a rubber wet masterbatch obtained using at least carbon black, a dispersion solvent, and a rubber latex solution as raw materials.
  • the present invention also relates to a method of producing a rubber composition for a tire.
  • a rubber wet masterbatch When a rubber wet masterbatch is used, it has excellent carbon black dispersibility and rubber physical properties such as processability and reinforcement, as compared with a rubber dry masterbatch obtained by mixing carbon black and rubber in a solid phase.
  • the rubber composition which is excellent in is obtained.
  • rolling resistance can be reduced, and a rubber product (vulcanized rubber) such as a pneumatic tire having excellent fatigue resistance can be manufactured.
  • the abrasion resistance and low heat buildup can be achieved by adjusting the pH in the preparation step of the above-mentioned carbon black-containing slurry solution or the above-mentioned preparation step of the carbon black-containing rubber coagulated material to a predetermined range. It is known that rubber products (vulcanized rubber) having improved rubber properties such as are obtained (Patent Documents 1 to 4).
  • rubber products such as pneumatic tires obtained from a rubber composition containing a rubber wet masterbatch have the above-mentioned reduction in rolling resistance, fatigue resistance, low heat buildup, wear resistance, and resistance What is excellent in tear resistance such as cracking is required (Patent Documents 5 and 6).
  • vulcanized rubber obtained from a rubber composition containing a rubber wet masterbatch as in the above-mentioned patent documents has room for improvement in the abrasion resistance and tear resistance.
  • a vulcanized rubber obtained from a rubber composition containing a rubber wet masterbatch as in the above-mentioned patent documents is particularly used for pre-papping (member for covering a cord in a carcass ply of a pneumatic tire or a belt ply). It turned out that there is room for improvement in low heat build-up and fatigue resistance.
  • the first object of the present invention is made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a method for producing a rubber wet masterbatch having good dispersibility (homogeneity) of carbon black.
  • the second object of the present invention is made in view of the above situation, and provides a method for producing a rubber composition for a tire from which a vulcanized rubber having excellent abrasion resistance and tear resistance can be obtained. It is to be.
  • the third object of the present invention is made in view of the above-mentioned circumstances, and it is a method for producing a rubber composition for pretipping which can obtain a vulcanized rubber having excellent low heat buildup and fatigue resistance. It is to provide.
  • the present invention is a method for producing a rubber wet masterbatch obtained using at least carbon black, a dispersion solvent, and a rubber latex solution as raw materials, wherein the carbon black, the dispersion solvent, and the rubber latex solution are mixed to obtain carbon.
  • the mechanical stability of the rubber latex solution measured according to ASTM D 1076-59 is 300 seconds or more, and in the step (II), the pH of the carbon black-containing latex solution before coagulation is 6.
  • Rubber wet master bag characterized in that it is 0 to 8.5 Method of manufacture, related to.
  • the present invention further includes a step (IV) of dry mixing using the rubber wet masterbatch obtained by the method of producing a rubber wet masterbatch, and a method of producing a rubber composition for a tire. About.
  • the rubber measured according to ASTM D 1076-59 in the step (I) for producing the carbon black-containing rubber latex solution described above The mechanical stability of the latex solution is 300 seconds or more, and in the step (II) of producing the carbon black-containing rubber coagulated product as described above, the pH of the carbon black-containing latex solution before coagulation is 6.0 to It is 8.5.
  • the mechanical stability is an index showing colloidal stability, and in the case of the small mechanical stability, rubber latex particles are aggregated by a small stimulus.
  • the carbon black-containing rubber latex solution obtained by using the rubber latex solution having high mechanical stability has high stability of latex particles, the reactivity between the rubber latex particles and carbon black is low. It is estimated that the dispersibility of carbon black in the medium is insufficient.
  • a carbon black-containing rubber latex solution is coagulated, coagulation due to shearing or heat during mixing occurs more dominantly than coagulation due to reaction between latex particles and carbon black, and the obtained rubber wet masterbatch The dispersibility (homogeneity) of carbon black will become inadequate.
  • the pH of the carbon black-containing rubber latex solution is adjusted to a range of 6.0 to 8.5 before coagulation with a coagulant.
  • the reactivity between the rubber latex particles and the carbon black can be kept optimum, and the dispersibility of the carbon black can be improved.
  • rapid solidification can be prevented in the subsequent solidification step, it is presumed that carbon black is uniformly incorporated into the coagulated body of the rubber latex particles while maintaining its dispersibility. As a result, it is considered that a rubber wet masterbatch having good carbon black dispersibility (homogeneity) can be obtained.
  • the rubber composition containing such a rubber wet masterbatch is presumed to have good dispersibility (homogeneity) of carbon black in the rubber composition, so that the resulting vulcanized rubber has excellent abrasion resistance and resistance. It is excellent in tearability or low heat buildup and fatigue resistance.
  • the method for producing a rubber wet masterbatch of the present invention uses at least carbon black, a dispersion solvent, and a rubber latex solution as raw materials.
  • conductive carbon blacks such as acetylene black and ketjen black
  • carbon black used by usual rubber industry such as SAF, ISAF, HAF, FEF, GPF, for example.
  • the carbon black may be granulated carbon black or non-granulated carbon black which is granulated in consideration of its handling property in ordinary rubber industry.
  • the carbon black may be used alone or in combination of two or more.
  • the carbon black from the viewpoint of improving the wear resistance of the vulcanized rubber, the nitrogen adsorption specific surface area, is preferably 50 m 2 / g or more, more preferably 60 m 2 / g or more, 70m 2 / more preferably g or more, and is preferably at 200 meters 2 / g or less, more preferably 190 m 2 / g or less, and more preferably not more than 180 m 2 / g.
  • the carbon black preferably has a nitrogen adsorption specific surface area of 20 m 2 / g or more, more preferably 25 m 2 / g or more, from the viewpoint of improving the low heat buildup of the vulcanized rubber, and more preferably 30 m. still more preferably 2 / g or more, and is preferably from 100 m 2 / g, more preferably 95 m 2 / g or less, and more preferably not more than 90m 2 / g.
  • the content of the carbon black is preferably 20 to 100 parts by weight, preferably 30 to 90 parts by weight, with respect to 100 parts by weight of the rubber component contained in the rubber composition, from the viewpoint of improving the reinforcing property of the vulcanized rubber. It is more preferably part, and still more preferably 40 to 80 parts by weight.
  • the content of the carbon black is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the rubber component contained in the rubber wet master batch, from the viewpoint of improving the reinforcing property of the vulcanized rubber.
  • the amount is more preferably 90 parts by weight, further preferably 20 to 80 parts by weight.
  • Water is particularly preferably used as the dispersion solvent, but it may be, for example, water containing an organic solvent.
  • the dispersion solvents may be used alone or in combination of two or more.
  • the rubber latex solution a natural rubber latex solution and a synthetic rubber latex solution can be used.
  • the natural rubber latex solution is a natural product produced by the metabolism of plants, and a natural rubber / water system in which the dispersion solvent is water is particularly preferable.
  • the number average molecular weight of the natural rubber contained in the natural rubber latex is preferably 2,000,000 or more, and more preferably 2,500,000 or more.
  • As the natural rubber latex solution concentrated latex, fresh latex called field latex, etc. can be used without distinction.
  • Examples of the synthetic rubber latex solution include those prepared by emulsion polymerization of styrene-butadiene rubber, butadiene rubber, nitrile rubber and chloroprene rubber.
  • the rubber latex solution may be used alone or in combination of two or more.
  • the rubber latex solution has a mechanical stability (also referred to as mechanical stability) of 300 seconds or more, which is measured according to ASTM D 1076-59.
  • the mechanical stability is preferably 300 seconds or more, more preferably 400 seconds or more, from the viewpoint of improving the storage stability and the viewpoint of improving the homogeneity of carbon black in the rubber wet masterbatch. .
  • the mechanical stability is determined according to ASTM D 1076-59 by the time until a coagulated substance is found in the latex when the rotating plate is agitated at a predetermined rotation speed.
  • the mechanical stability is exemplified by, for example, 3600 seconds or less and 2400 seconds or less as the upper limit value.
  • the above-mentioned mechanical stability includes basic compounds such as ammonia, sodium hydroxide and potassium hydroxide; aromatic carboxylic acid salts such as sodium salicylate; long-chain fatty acid salts such as ammonium laurate; formic acid, acetic acid, propionic acid and the like Adjustment agents such as short-chain fatty acids; and the like can be adjusted to the above range by adding them to the raw material rubber latex solution. Among these, it is preferable to use ammonia. When these modifiers are used, the concentration of the rubber latex solution is not limited, but from the viewpoint of stabilization of the rubber latex solution, it is preferable to use the rubber latex solution after 12 hours or more after preparation.
  • the production method comprises the step (I) of mixing the carbon black, the dispersion solvent, and the rubber latex solution to produce a carbon black-containing rubber latex solution, and coagulating the obtained carbon black-containing rubber latex solution And the step (II) of producing a carbon black-containing rubber coagulated product.
  • the mechanical stability of the rubber latex solution measured according to ASTM D 1076-59 is 300 seconds or more, and in the step (II), the carbon black-containing before coagulation is contained.
  • the pH of the latex solution is 6.0 to 8.5.
  • step (I) of the present invention the carbon black, the dispersion solvent, and the rubber latex solution are mixed to produce a carbon black-containing rubber latex solution.
  • the step (I) comprises dispersing the carbon black in the dispersion solvent to produce a carbon black-containing slurry solution (hereinafter also referred to as a slurry solution) (I-a1) and It is preferable to include the step (I-b1) of producing a carbon black-containing rubber latex solution by mixing the obtained carbon black-containing slurry solution with the rubber latex solution.
  • the carbon black to which the rubber latex particles are attached by adding at least a part of the rubber latex solution when the carbon black is dispersed in the dispersion solvent in the step (I).
  • Step (I-a1) Examples of the method of mixing the carbon black and the dispersion solvent in the step (I-a1) include general methods such as high shear mixer, high shear mixer, homo mixer, homo mixer, ball mill, bead mill, high pressure homogenizer, ultrasonic homogenizer, colloid mill, etc. Of dispersing carbon black using a conventional dispersing machine.
  • the "high shear mixer” is a mixer including a rotor and a stator, and the rotor rotates in a state where a precise clearance is provided between the rotor capable of high speed rotation and the fixed stator.
  • a commercial item can be used for such a high shear mixer, For example, the "high shear mixer” by SILVERSON can be mentioned.
  • Step (I-a2) At the time of dispersing the carbon black in the dispersion solvent, at least a part of the rubber latex solution is added to produce a carbon black-containing slurry solution to which the rubber latex particles adhere.
  • the rubber latex solution may be mixed with a dispersion solvent in advance, and then carbon black may be added and dispersed.
  • carbon black may be added to the dispersion solvent, and then the carbon black may be dispersed in the dispersion solvent while adding the rubber latex solution at a predetermined addition rate, or carbon black may be added to the dispersion solvent. Then, the carbon black may be dispersed in the dispersing solvent while adding a constant amount of rubber latex solution in several divided portions.
  • the addition amount of the rubber latex solution in the step (I-a2) is 0.075 to the total amount of the rubber latex solution to be used (the total amount added in the step (I-a2) and the step (I-b2)). 12% by weight is exemplified.
  • the amount of rubber solid content of the rubber latex solution to be added is preferably 0.25 to 15% by weight ratio to carbon black, and is 0.5 to 6%. Is preferred.
  • the concentration of the rubber solids in the rubber latex solution to be added is preferably 0.2 to 5% by weight, and more preferably 0.5 to 1.5% by weight. In these cases, it is possible to produce a rubber wet masterbatch in which the degree of dispersion of carbon black is increased while the rubber latex particles are reliably attached to carbon black.
  • Step (I-b1) of the present invention the slurry solution and the rubber latex solution are mixed to produce a carbon black-containing rubber latex solution.
  • the method of mixing the slurry solution and the rubber latex solution in the liquid phase is not particularly limited, and the slurry solution and the rubber latex solution may be mixed, for example, with a high shear mixer, high shear mixer, homo mixer, homo mixer, ball mill, bead mill, Examples of the mixing method include a common disperser such as a high pressure homogenizer, an ultrasonic homogenizer, and a colloid mill, and a mixer using a mixer whose blades rotate in a cylindrical container. If necessary, the entire mixing system such as a dispersing machine may be heated during mixing.
  • the rubber latex solution preferably has a concentration of rubber solids of preferably 10 to 60% by weight, and more preferably 20 to 30% by weight, in consideration of dehydration time and labor in step (III) described later. It is more preferable that
  • Step (I-b2) In the step (I-b2), the carbon black-containing slurry solution to which the rubber latex particles are attached and the remaining rubber latex solution are mixed to produce a carbon black-containing rubber latex solution to which the rubber latex particles are attached.
  • the method of mixing the carbon black-containing slurry solution to which the rubber latex particles adhere and the remaining rubber latex solution in the liquid phase is the same as the method of mixing the slurry solution and the rubber latex solution in the liquid phase described above. The method is mentioned.
  • the remaining rubber latex solution preferably has a higher rubber solids concentration than the rubber latex solution added in step (I-a2), considering the dehydration time and labor in step (III) described later, Specifically, the concentration of rubber solids is preferably 10 to 60% by weight, and more preferably 20 to 30% by weight.
  • a surfactant may be added to improve the dispersibility of carbon black.
  • surfactants known in the rubber industry can be used.
  • nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, etc. Can be mentioned.
  • an alcohol such as ethanol may be used instead of the surfactant or in addition to the surfactant.
  • the surfactant is used, there is a concern that the final rubber physical properties of the vulcanized rubber may be reduced. Therefore, the blending amount of the surfactant is 100 parts by weight of the rubber solid content of the rubber latex solution. The amount is preferably 2 parts by weight or less, more preferably 1 part by weight or less, and it is preferable that the surfactant is not used substantially.
  • step (II) of the present invention the carbon black-containing rubber latex solution obtained above is coagulated to produce a carbon black-containing rubber coagulated product.
  • the pH of the carbon black-containing latex solution before coagulation is 6.0 to 8.5.
  • the pH of the carbon black-containing latex solution before coagulation is preferably 6.5 or more from the viewpoint of improving the ease of control of the size of the rubber wet masterbatch after coagulation, and in the rubber wet masterbatch From the viewpoint of improving the homogeneity of carbon black, 8.0 or less is preferable and 7.4 or less is more preferable.
  • the carbon black-containing rubber latex solution in the step (I) may be prepared appropriately.
  • Methods of heating, methods of vacuum degassing, methods of adding an acid such as formic acid, sulfuric acid, boric acid, citric acid, lactic acid and the like, and the like can be mentioned.
  • Examples of the method of coagulation include a method of incorporating a coagulant in the carbon black-containing rubber latex solution.
  • a coagulant an acid such as formic acid or sulfuric acid, a salt such as sodium chloride or the like that is usually used for coagulating a rubber latex solution can be used.
  • Step (III)> In the method for producing a rubber wet masterbatch of the present invention, it is preferable to provide a step (III) of dehydrating and drying the carbon black-containing rubber coagulated material obtained above.
  • various dehydration and drying apparatuses such as a single screw extruder, a twin screw extruder, a screw press, an oven, a conveyor type dryer, a vacuum dryer, an air dryer, can be used, for example .
  • a solid-liquid separation step using centrifugation or a vibrating screen may be provided before the step (III), for the purpose of appropriately reducing the amount of water contained in the carbon black-containing rubber coagulated material.
  • a washing process such as a water washing method may be provided.
  • the rubber wet masterbatch of the present invention is suitable for use in a rubber composition for tires because the carbon black contained therein has good dispersibility (homogeneity).
  • the method for producing a rubber composition for a tire according to the present invention includes the step (IV) of dry mixing using the rubber wet masterbatch obtained above.
  • various compounding agents can be further used.
  • examples of usable compounding agents include rubber, carbon black, sulfur-based vulcanizing agent, vulcanization accelerator, anti-aging agent, silica, silane coupling agent, zinc oxide, methylene acceptor and methylene donor, stearic acid
  • examples of such additives include vulcanization accelerators, vulcanization retarders, organic peroxides, softeners such as waxes and oils, and processing aids and the like, which are commonly used in the rubber industry.
  • the rubber is used separately from the rubber component derived from the rubber wet masterbatch.
  • the rubber include synthetic dienes such as natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber (CR) and nitrile rubber (NBR). Rubber is mentioned.
  • the rubber may be used alone or in combination of two or more.
  • the weight ratio of the rubber component of the rubber latex solution in the wet master batch to the rubber (rubber component of the rubber latex solution / rubber) is the resistance of the vulcanized rubber From the viewpoint of improving physical properties such as abrasion, it is preferably 60/40 or more, more preferably 65/35 or more, and from the viewpoint of improving physical properties such as the abrasion resistance of vulcanized rubber, It is preferably 90/10 or less, more preferably 80/20 or less.
  • the weight ratio of the rubber component of the rubber latex solution in the wet master batch to the rubber (rubber component of the rubber latex solution / rubber) is fatigue resistance. Or more, preferably 40/60 or more, more preferably 45/55 or more, and 80/20 or less from the viewpoint of improving physical properties such as fatigue resistance. Is preferable and 60/40 or less is more preferable.
  • the sulfur as the sulfur-based vulcanizing agent may be any conventional sulfur for rubber, and for example, powder sulfur, precipitated sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used.
  • the sulfur-based vulcanizing agent may be used alone or in combination of two or more.
  • the content of sulfur is preferably 0.3 to 6.5 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition. If the content of sulfur is less than 0.3 parts by weight, the crosslink density of the vulcanized rubber will be insufficient to lower the rubber strength, etc. If it exceeds 6.5 parts by weight, both the heat resistance and the durability will be particularly good. Getting worse.
  • the sulfur content is 1.0 to 5.5 with respect to 100 parts by weight of the rubber component in the rubber composition. It is more preferable that it is a weight part.
  • any conventional vulcanization accelerator for rubber may be used, and a sulfenamide-based vulcanization accelerator, a thiuram-based vulcanization accelerator, a thiazole-based vulcanization accelerator, a thiourea-based vulcanization accelerator And guanidine-based vulcanization accelerators and dithiocarbamate-based vulcanization accelerators.
  • the vulcanization accelerators may be used alone or in combination of two or more.
  • the content of the vulcanization accelerator is preferably 1 to 5 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition.
  • the anti-aging agent may be any conventional anti-aging agent for rubber, such as aromatic amine based anti-aging agent, amine-ketone based anti-aging agent, monophenol based anti-aging agent, bisphenol based anti-aging agent, polyphenol based Antiaging agents, dithiocarbamate antiaging agents, thiourea antiaging agents, etc. may be mentioned.
  • the antioxidant may be used alone or in combination of two or more.
  • the content of the anti-aging agent is preferably 1 to 5 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition.
  • the method of blending (adding) the rubber wet masterbatch and the various compounding agents is, for example, using a kneader used in a usual rubber industry such as a Banbury mixer, a kneader, or a roll.
  • a knead used in a usual rubber industry such as a Banbury mixer, a kneader, or a roll.
  • mixing is mentioned.
  • the method of kneading is not particularly limited, for example, a method of adding and kneading components other than a vulcanizing component such as a sulfur-based vulcanizing agent and a vulcanization accelerator in any order, and a method of simultaneously adding and kneading Also, a method of simultaneously adding and kneading all the components may be mentioned.
  • the number of times of kneading may be one or more. Although the time for kneading varies depending on the size of the kneader used, etc., it may usually be about 2 to 5 minutes.
  • the discharge temperature of the kneader is preferably 120 to 170 ° C., and more preferably 120 to 150 ° C.
  • the discharge temperature of the kneader is preferably 80 to 110 ° C., more preferably 80 to 100 ° C., when the above-mentioned vulcanization system component is contained.
  • the rubber composition for a tire according to the present invention comprises each part of a pneumatic tire. In particular, it is suitable for tire treads. Moreover, according to the method for producing a rubber composition for a tire of the present invention, a vulcanized rubber having excellent low heat buildup and fatigue resistance can be obtained. Therefore, the rubber composition for a tire of the present invention is a pneumatic tire although it can be used at each site, it is particularly suitable for pre-papping.
  • Example 1 Preparation of rubber latex solution> Ammonia was added to the natural rubber latex concentrated latex solution at normal temperature so that the following mechanical stability was 1000 seconds. Subsequently, water was added at normal temperature to prepare a rubber latex solution having a rubber component of 25% by weight. [Measurement of mechanical stability of rubber latex solution] The mechanical stability of the rubber latex solution was measured by rotating the rotating plate at 14000 rpm according to ASTM D 1076-59, and measuring the time (seconds) until visually apparent coagulated material was found in the latex. . In addition, the density
  • the rubber latex solution (25% by weight) having the predetermined mechanical stability obtained above is added in an amount of 100 parts by weight of solid content (rubber) Were mixed using a SANYO household mixer SM-L 56 (mixer conditions: 11300 rpm, 1 minute) to produce a carbon black-containing rubber latex solution (step (I-b1)) ).
  • the carbon black-containing rubber coagulated material produced in the above step (II) is dewatered and dried with a squeezer type single-screw extrusion dehydrator (V-02 type made by Suehiro EPM) until the water content becomes 1.5% or less Thus, a rubber wet masterbatch was produced (step (III)).
  • Examples 2 to 11 and Comparative Examples 1 to 3 In ⁇ Preparation of rubber latex solution> of Example 1, the mechanical stability of the rubber latex was changed to a value shown in Table 1, and ⁇ Step (I) of Example 1: Production of carbon black-containing rubber latex solution In ⁇ >, the carbon black to be used was changed to the type and blending amount shown in Table 1, and in ⁇ Step (II) of Example 1: Production of carbon black-containing rubber coagulant>, carbon black-containing before solidification. Rubber wet masterbatches of Examples 2 to 11 and Comparative Examples 1 to 3 were produced in the same manner as in Example 1 except that the pH of the rubber latex solution was changed to the values shown in Table 1. In addition, the compounding quantity in Table 1 shows a weight part (phr) when the whole quantity of the rubber component contained in a rubber wet masterbatch is 100 weight part.
  • Example 12 In ⁇ Step (I): Preparation of Carbon Black-Containing Rubber Latex Solution> of Example 1, a part of the rubber latex solution was added (step (I-a2)), and the remaining rubber latex solution was added. A rubber wet masterbatch was produced in the same manner as in Example 1 except for (Step (I-b2)). In the step (I-a2), 0.5% by weight of the rubber latex solution is used based on the total amount of the rubber latex solution to be used (the total amount added in the step (I-a2) and the step (I-b2)). Added.
  • the difference between the carbon black content of the median sample and the carbon black content of the sample farthest from the median is less than 1 part by weight
  • ⁇ The carbon black content of the median sample and the median
  • the difference between the carbon black content of the farthest sample and the carbon black content of the farthest sample is 1 part by weight or more and less than 2 parts by weight. But 2 parts by weight or more
  • Example 1 Preparation of rubber latex solution> Ammonia was added to the natural rubber latex-concentrated latex solution at room temperature so that the following mechanical stability was 600 seconds. Subsequently, water was added at normal temperature to prepare a rubber latex solution having a rubber component of 25% by weight. [Measurement of mechanical stability of rubber latex solution] The mechanical stability of the rubber latex solution was measured by rotating the rotating plate at 14000 rpm according to ASTM D 1076-59, and measuring the time (seconds) until visually apparent coagulated material was found in the latex. . In addition, the density
  • the remaining carbon latex-containing slurry solution to which the rubber latex particles produced in the step (I-a2) have been adhered is treated with the remaining rubber latex solution (25% by weight) having the predetermined mechanical stability obtained above.
  • the carbon black-containing rubber coagulated material produced in the above step (II) is dewatered and dried with a squeezer type single-screw extrusion dehydrator (V-02 type made by Suehiro EPM) until the water content becomes 1.5% or less Thus, a rubber wet masterbatch was produced (step (III)).
  • Examples 2 to 10 and Comparative Examples 1 to 5 In ⁇ Preparation of rubber latex solution> of Example 1, the mechanical stability of the rubber latex was changed to the value shown in Table 2, and ⁇ Step (I) of Example 1: Production of carbon black-containing rubber latex solution In ⁇ >, the carbon black to be used was changed to the type and blending amount shown in Table 2, and in ⁇ Step (II) of Example 1: Production of carbon black-containing rubber coagulated substance>, carbon black-containing before solidification.
  • the rubber compositions and unvulcanized rubber compositions of Examples 2 to 10 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1 except that the pH of the rubber latex solution was changed to the values shown in Table 2. Manufactured. In addition, the compounding quantity in Table 2 shows a weight part (phr) when the whole quantity of the rubber component contained in a rubber wet masterbatch is 100 weight part.
  • a vulcanized rubber was produced by vulcanizing the unvulcanized rubber compositions obtained in the above Examples and Comparative Examples under the conditions of 150 ° C. and 30 minutes. The following evaluation was performed about the obtained vulcanized rubber. The evaluation results are shown in Table 2.
  • Example 1 Preparation of rubber latex solution> Ammonia was added to the natural rubber latex-concentrated latex solution at room temperature so that the following mechanical stability was 600 seconds. Subsequently, water was added at normal temperature to prepare a rubber latex solution having a rubber component of 25% by weight. [Measurement of mechanical stability of rubber latex solution] The mechanical stability of the rubber latex solution was measured by rotating the rotating plate at 14000 rpm according to ASTM D 1076-59, and measuring the time (seconds) until visually apparent coagulated material was found in the latex. . In addition, the density
  • the remaining carbon latex-containing slurry solution to which the rubber latex particles produced in the step (I-a2) have been adhered is treated with the remaining rubber latex solution (25% by weight) having the predetermined mechanical stability obtained above.
  • the carbon black-containing rubber coagulated material produced in the above step (II) is dewatered and dried with a squeezer type single-screw extrusion dehydrator (V-02 type made by Suehiro EPM) until the water content becomes 1.5% or less Thus, a rubber wet masterbatch was produced (step (III)).
  • Examples 2 to 10 and Comparative Examples 1 to 5 In ⁇ Preparation of rubber latex solution> of Example 1, the mechanical stability of the rubber latex was changed to a value shown in Table 3. Further, ⁇ Step (I) of Example 1: Production of carbon black-containing rubber latex solution In ⁇ >, the carbon black to be used was changed to the kind and compounding amount shown in Table 3, and in ⁇ Step (II) of Example 1: Production of carbon black-containing rubber coagulated material>, carbon black-containing before solidification.
  • the rubber compositions and unvulcanized rubber compositions of Examples 2 to 10 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1 except that the pH of the rubber latex solution was changed to the values shown in Table 3. Manufactured.
  • the compounding quantity in Table 3 shows a weight part (phr) when the whole quantity of the rubber component contained in a rubber wet masterbatch is 100 weight part.
  • a vulcanized rubber was produced by vulcanizing the unvulcanized rubber compositions obtained in the above Examples and Comparative Examples under the conditions of 150 ° C. and 30 minutes. The following evaluation was performed about the obtained vulcanized rubber. The evaluation results are shown in Table 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production d'un mélange-maître humide de caoutchouc qui est obtenu en utilisant au moins un noir de carbone, un solvant de dispersion et une solution de latex de caoutchouc en tant que matières premières. Ce procédé de production d'un mélange-maître humide de caoutchouc comprend : une étape (I) de production d'une solution de latex de caoutchouc contenant du noir de carbone par mélange du noir de carbone, du solvant de dispersion et de la solution de latex de caoutchouc ; et une étape (II) de production d'un coagulum de caoutchouc contenant du noir de carbone par coagulation de la solution de latex de caoutchouc contenant du noir de carbone ainsi obtenu. Dans l'étape (I), la stabilité mécanique de la solution de latex de caoutchouc telle que déterminée conformément à la norme ASTM D1076-59 est égale ou supérieure à 300 secondes ; et dans l'étape (II), le pH de la solution de latex contenant du noir de carbone avant la coagulation est compris entre 6,0 et 8,5. La présente invention permet de fournir un procédé de production d'un mélange-maître humide de caoutchouc qui a une bonne dispersibilité (homogénéité) de noir de carbone.
PCT/JP2018/040477 2017-12-25 2018-10-31 Procédé de production d'un mélange-maître humide de caoutchouc, procédé de fabrication d'une composition de caoutchouc pour pneus WO2019130800A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2017-247660 2017-12-25
JP2017247660A JP7067917B2 (ja) 2017-12-25 2017-12-25 ゴムウエットマスターバッチの製造方法
JP2017247640A JP7066398B2 (ja) 2017-12-25 2017-12-25 タイヤ用ゴム組成物の製造方法
JP2017-247640 2017-12-25
JP2017247655A JP2019112543A (ja) 2017-12-25 2017-12-25 プライトッピング用ゴム組成物の製造方法
JP2017-247655 2017-12-25

Publications (1)

Publication Number Publication Date
WO2019130800A1 true WO2019130800A1 (fr) 2019-07-04

Family

ID=67063492

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/040477 WO2019130800A1 (fr) 2017-12-25 2018-10-31 Procédé de production d'un mélange-maître humide de caoutchouc, procédé de fabrication d'une composition de caoutchouc pour pneus

Country Status (1)

Country Link
WO (1) WO2019130800A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7329459B2 (ja) 2020-01-27 2023-08-18 Ｔｏｙｏ Ｔｉｒｅ株式会社 ゴムウエットマスターバッチの製造方法、およびゴム組成物の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012184354A (ja) * 2011-03-07 2012-09-27 Toyo Tire & Rubber Co Ltd 未加硫ゴム組成物およびその製造方法、ならびに空気入りタイヤ
JP2015048416A (ja) * 2013-09-02 2015-03-16 東洋ゴム工業株式会社 ゴムウエットマスターバッチおよびその製造方法、ゴム組成物ならびに空気入りタイヤ
JP2017039881A (ja) * 2015-08-21 2017-02-23 東洋ゴム工業株式会社 ゴムウエットマスターバッチの製造方法、ゴム組成物の製造方法およびタイヤの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012184354A (ja) * 2011-03-07 2012-09-27 Toyo Tire & Rubber Co Ltd 未加硫ゴム組成物およびその製造方法、ならびに空気入りタイヤ
JP2015048416A (ja) * 2013-09-02 2015-03-16 東洋ゴム工業株式会社 ゴムウエットマスターバッチおよびその製造方法、ゴム組成物ならびに空気入りタイヤ
JP2017039881A (ja) * 2015-08-21 2017-02-23 東洋ゴム工業株式会社 ゴムウエットマスターバッチの製造方法、ゴム組成物の製造方法およびタイヤの製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7329459B2 (ja) 2020-01-27 2023-08-18 Ｔｏｙｏ Ｔｉｒｅ株式会社 ゴムウエットマスターバッチの製造方法、およびゴム組成物の製造方法

Similar Documents

Publication Publication Date Title
US9796819B2 (en) Process for producing wet masterbatch, and wet masterbatch produced by said process
JP6030411B2 (ja) ゴムウエットマスターバッチおよびその製造方法、ゴム組成物ならびに空気入りタイヤ
JP2010209175A (ja) ウエットマスターバッチの製造方法、および該ウエットマスターバッチを用いて得られた加硫ゴム
JP6545481B2 (ja) ウェットマスターバッチの製造方法及びその方法により製造されたウェットマスターバッチ
JP6781603B2 (ja) タイヤ部材の製造方法
JP6910125B2 (ja) タイヤ部材の製造方法
JP7329459B2 (ja) ゴムウエットマスターバッチの製造方法、およびゴム組成物の製造方法
CN108350185B (zh) 橡胶湿法母炼胶及橡胶组合物的制造方法
CN107955217B (zh) 轮胎材料的制造方法
WO2019130800A1 (fr) Procédé de production d'un mélange-maître humide de caoutchouc, procédé de fabrication d'une composition de caoutchouc pour pneus
JP7066398B2 (ja) タイヤ用ゴム組成物の製造方法
JP2019112543A (ja) プライトッピング用ゴム組成物の製造方法
JP2019104860A (ja) 空気入りタイヤ用ゴム部材の製造方法および空気入りタイヤの製造方法
JP7125883B2 (ja) ゴムウエットマスターバッチの製造方法
CN109923154B (zh) 橡胶组合物及其制备方法
JP7125325B2 (ja) ゴムウエットマスターバッチの製造方法、およびゴム組成物の製造方法
JP7067917B2 (ja) ゴムウエットマスターバッチの製造方法
JP6761723B2 (ja) タイヤ部材の製造方法
WO2019130727A1 (fr) Procédé de production d'un mélange-maître humide de caoutchouc, et procédé de production d'une composition de caoutchouc
JP7125298B2 (ja) ゴムウエットマスターバッチの製造方法、およびゴム組成物の製造方法
US11584832B2 (en) Method for producing rubber wet masterbatch and method for producing rubber composition
JP2019104859A (ja) ゴムウエットマスターバッチの製造方法
JP7089431B2 (ja) タイヤトレッド用ゴム組成物の製造方法
JP6821382B2 (ja) タイヤ部材の製造方法
JP2020023645A (ja) ゴム組成物の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18895789

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18895789

Country of ref document: EP

Kind code of ref document: A1