WO2019123879A1 - Masterbatch production method, rubber composition production method and tire production method - Google Patents

Masterbatch production method, rubber composition production method and tire production method Download PDF

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Publication number
WO2019123879A1
WO2019123879A1 PCT/JP2018/041479 JP2018041479W WO2019123879A1 WO 2019123879 A1 WO2019123879 A1 WO 2019123879A1 JP 2018041479 W JP2018041479 W JP 2018041479W WO 2019123879 A1 WO2019123879 A1 WO 2019123879A1
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Prior art keywords
rubber
rubber latex
mass
masterbatch
carbon black
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PCT/JP2018/041479
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French (fr)
Japanese (ja)
Inventor
優也 近野
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Ｔｏｙｏ Ｔｉｒｅ株式会社
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Publication of WO2019123879A1 publication Critical patent/WO2019123879A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00—Producing pneumatic or solid tyres or parts thereof
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C08L7/02—Latex

Definitions

  • the present disclosure relates to a method of producing a masterbatch, a method of producing a rubber composition, and a method of producing a tire.
  • a wet masterbatch in which carbon black is dispersed in natural rubber has a high Mooney viscosity and poor processability.
  • the wet masterbatch can be obtained, for example, by mixing natural rubber latex and carbon black slurry, coagulating and dewatering.
  • a plasticizer can be added when kneading the wet masterbatch in order to improve the processability. Kneading is performed by a kneader, for example, a Banbury mixer.
  • the physical properties of the vulcanized rubber for example, the tear strength and the abrasion resistance should be considered.
  • tear strength and abrasion resistance there is room for improvement in the method of adding a plasticizer when kneading a wet master batch.
  • An object of the present disclosure is to provide a method for producing a masterbatch that can improve the tear strength and abrasion resistance of vulcanized rubber.
  • the method for producing a masterbatch in the present disclosure includes the steps of preparing a pre-coagulation treatment mixture with at least a natural rubber latex, a liquid rubber latex and a filler slurry, and coagulating the pre-coagulation treatment mixture.
  • the method for producing a masterbatch includes the steps of preparing a pre-coagulation mixture with at least a natural rubber latex, a liquid rubber latex and a filler slurry, and coagulating the pre-coagulation mixture.
  • the method of producing a masterbatch according to the embodiments of the present disclosure can improve the tear strength and the abrasion resistance of a vulcanized rubber.
  • By preparing the pre-coagulation mixed liquid with natural rubber latex, liquid rubber latex and filler slurry it is possible to disperse liquid rubber in the pre-coagulation mixed liquid, and a master batch in which liquid rubber is dispersed is obtained. be able to.
  • the uniformity of the distribution state of the crosslinking points is enhanced.
  • the method for producing a masterbatch according to the embodiment of the present disclosure can improve the tear strength and the abrasion resistance of the vulcanized rubber, as compared to such a method.
  • the step of preparing the pre-coagulation treatment mixture includes adding a liquid rubber latex to the natural rubber latex, obtaining a natural rubber latex after the addition, and mixing the natural rubber latex and the filler slurry after the addition. it can.
  • the step of preparing the pre-solidification mixture may include mixing natural rubber latex and filler slurry and adding liquid rubber latex.
  • the method of producing the rubber composition of the embodiment in the present disclosure includes the method of producing the master batch of the embodiment in the present disclosure.
  • the method for producing a rubber composition according to an embodiment of the present disclosure comprises the steps of preparing a mixed liquid before coagulation treatment with at least a natural rubber latex, liquid rubber latex and filler slurry, and coagulating the mixed liquid before coagulation treatment. And the step of
  • a method of manufacturing a tire of an embodiment in the present disclosure includes a method of manufacturing a master batch of an embodiment in the present disclosure.
  • the method for manufacturing a tire according to an embodiment of the present disclosure includes the steps of preparing a mixed liquid before coagulation treatment with at least a natural rubber latex, liquid rubber latex and filler slurry, and coagulating the mixed liquid before coagulation treatment. And.
  • the filler can be an inorganic filler such as carbon black, silica, clay, talc, calcium carbonate, magnesium carbonate, aluminum hydroxide and the like. One or more of these can be selected and used.
  • Embodiment 1 From here, Embodiment 1 of the present disclosure will be described. Embodiment 1 uses carbon black as a filler for the masterbatch.
  • a step of preparing a pre-coagulation treatment mixture a step of coagulating the pre-solidification treatment mixture to obtain a masterbatch, and kneading at least a masterbatch and a compounding agent to obtain a rubber mixture
  • a step of kneading the vulcanized compounding agent into the rubber mixture to obtain a rubber composition
  • a step of vulcanizing and molding an unvulcanized tire produced from the rubber composition
  • the manufacturing method of the tire in the embodiment 1 includes the step of preparing the pre-coagulation treatment mixture, that is, the step of preparing the pre-coagulation treatment mixture with the natural rubber latex, the liquid rubber latex and the carbon black slurry.
  • the natural rubber latex rubber particles containing natural rubber are dispersed in water in the form of colloid.
  • the number average molecular weight of the natural rubber in the natural rubber latex is, for example, 2,000,000 or more.
  • the dry rubber content of the natural rubber latex is preferably 10% by mass or more, more preferably 20% by mass or more.
  • the upper limit of the dry rubber content in the natural rubber latex is, for example, 60% by mass, preferably 40% by mass, and more preferably 30% by mass.
  • liquid rubber latex rubber particles containing liquid rubber are dispersed in water in the form of colloid.
  • the liquid rubber can be, for example, a diene rubber such as isoprene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber and the like. That is, the liquid rubber latex can be a liquid diene rubber latex, for example, a liquid isoprene rubber latex.
  • the number average molecular weight of the liquid rubber is, for example, 0.5000 to 600000.
  • the dry rubber content of the liquid rubber latex can be, for example, 10% by mass or more, can be 30% by mass or more, and can be 50% by mass or more.
  • the upper limit of the dry rubber content in the liquid rubber latex is, for example, 90% by mass, 80% by mass, 70% by mass or the like.
  • the carbon black may be granulated carbon black granulated in consideration of its handling property, or may be non-granulated carbon black.
  • Carbon black and water can be mixed by a general dispersing machine such as a high shear mixer, homomixer, ball mill, bead mill, high pressure homogenizer, ultrasonic homogenizer, colloid mill and the like.
  • the liquid mixture before coagulation treatment contains rubber particles containing natural rubber, rubber particles containing liquid rubber, and carbon black. In the pre-coagulation mixed solution, these are dispersed in water.
  • the amount of natural rubber in the pre-coagulation mixed solution can be, for example, 80% by mass or more, can be 85% by mass or more, and can be 90% by mass in 100% by mass of the dried rubber content of the pre-coagulation treated liquid mixture It can be more than.
  • the amount of natural rubber in the pre-coagulation mixed solution can be, for example, 99 mass% or less, can be 98 mass% or less, and can be 97 mass% in 100 mass% of the dry rubber content of the pre-coagulation mixture.
  • the amount of liquid rubber in the pre-coagulation mixed liquid can be, for example, 1 mass% or more, and can be 2 mass% or more in 100 mass% of the dry rubber content of the pre-coagulation mixed liquid, It can be mass% or more.
  • the amount of liquid rubber in the pre-coagulation mixed liquid can be, for example, 20 mass% or less, can be 15 mass% or less, and can be 10 mass% in 100 mass% of dry rubber content of the pre-coagulation mixed liquid.
  • the amount of carbon black in the pre-coagulation mixed solution can be, for example, 10 parts by mass or more, and can be 20 parts by mass or more with respect to 100 parts by mass of the dry rubber of the pre-coagulation mixed liquid.
  • the amount of carbon black in the mixed solution before coagulation treatment can be, for example, 80 parts by mass or less, and can be 70 parts by mass or less, with respect to 100 parts by mass of the dried rubber of the mixed solution before coagulation treatment, It can be less than or equal to parts by weight.
  • the step of preparing the pre-coagulation treatment mixed liquid is replaced with natural rubber latex in place of the above-mentioned first procedure (adding liquid rubber latex to natural rubber latex and mixing natural rubber latex and carbon black slurry after addition)
  • the method may include mixing with a carbon black slurry and adding a liquid rubber latex (this procedure is hereinafter referred to as "second procedure").
  • first natural rubber latex and carbon black slurry are mixed.
  • the natural rubber latex and the carbon black slurry can be mixed by a general dispersing machine such as a high shear mixer, homomixer, ball mill, bead mill, high pressure homogenizer, ultrasonic homogenizer, colloid mill and the like.
  • a liquid rubber latex is added to the liquid obtained by this mixing, and if necessary, the mixture is stirred to obtain a mixed liquid before coagulation treatment.
  • the method for manufacturing a tire according to the first embodiment includes the steps of coagulating the pre-coagulation treatment liquid mixture to obtain a masterbatch.
  • Solidification can be caused by drying the pre-solidification mixture.
  • a coagulant may be added to the pre-coagulation mixture to cause coagulation.
  • the coagulant is, for example, an acid. Examples of the acid include formic acid and sulfuric acid.
  • the coagulated material obtained by coagulating the mixture before coagulation treatment contains water.
  • this step can include dewatering the solid.
  • dewatering of the coagulum for example, an extruder, a vacuum dryer, an air dryer, etc. can be used.
  • the water content of the dehydrated coagulated substance is preferably 15% by mass or less, more preferably 10% by mass or less.
  • This step can include shaping the coagulated material after dewatering.
  • the masterbatch thus obtained contains rubber and carbon black.
  • the masterbatch contains rubber.
  • the masterbatch rubber includes natural rubber and liquid rubber.
  • the amount of natural rubber in the masterbatch can be, for example, 80% by mass or more, can be 85% by mass or more, and can be 90% by mass or more in 100% by mass of rubber in the masterbatch.
  • the amount of natural rubber in the masterbatch can be, for example, 99% by weight or less, 98% by weight or less, and 97% by weight or less in 100% by weight of rubber in the masterbatch.
  • the masterbatch further comprises carbon black.
  • the amount of carbon black is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, with respect to 100 parts by mass of the rubber in the master batch.
  • the amount of carbon black is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the rubber in the masterbatch.
  • the method of manufacturing a tire according to the first embodiment includes the step of kneading the masterbatch and the compounding agent to obtain a rubber mixture.
  • the compounding agent include fillers, stearic acid, zinc oxide (zinc white), anti-aging agents and the like. One or more of these can be selected and kneaded with the master batch.
  • the ingredients added to the masterbatch in this step do not contain oil.
  • anti-aging agents aromatic amine anti-aging agents, amine-ketone anti-aging agents, monophenol anti-aging agents, bisphenol anti-aging agents, polyphenol anti-aging agents, dithiocarbamate anti-aging agents, thiourea anti-aging agents Anti-aging agents can be mentioned.
  • other rubbers can be kneaded together with the masterbatch and the compounding agent.
  • the rubber to be added to the masterbatch at the time of kneading include natural rubber, isoprene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber and the like.
  • the rubber added to the masterbatch at the time of kneading does not contain liquid rubber.
  • the liquid rubber here include diene-based liquid rubbers such as isoprene rubber, styrene-butadiene rubber, nitrile rubber and chloroprene rubber.
  • Kneading can be performed by a kneader.
  • a closed-type kneader, an open roll, etc. can be mentioned.
  • a Banbury mixer, a kneader etc. can be mentioned as a closed-type kneader.
  • the method of manufacturing a tire according to Embodiment 1 further includes the step of kneading the vulcanizing compound into the rubber mixture to obtain a rubber composition.
  • the vulcanizing compounding agent include sulfur, vulcanizing agents such as organic peroxides, vulcanization accelerators, vulcanization acceleration assistants, vulcanization retarders, and the like.
  • sulfur include powdered sulfur, precipitated sulfur, insoluble sulfur, highly dispersible sulfur and the like.
  • Sulfenamide-based vulcanization accelerator Sulfenamide-based vulcanization accelerator, thiuram-based vulcanization accelerator, thiazole-based vulcanization accelerator, thiourea-based vulcanization accelerator, guanidine-based vulcanization accelerator, dithiocarbamate-based vulcanization accelerator as vulcanization accelerator And the like.
  • the rubber composition comprises a rubber derived from a masterbatch.
  • the amount of rubber derived from the masterbatch can be, for example, 40% by mass or more, 60% by mass or more, and 80% by mass or more based on 100% by mass of the rubber in the rubber composition. It can be 100% by weight.
  • the rubber composition comprises carbon black.
  • the amount of carbon black is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber in the rubber composition.
  • the amount of carbon black is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the rubber in the rubber composition.
  • the rubber composition can further include stearic acid, zinc oxide, an antiaging agent, sulfur, a vulcanization accelerator and the like.
  • the amount of sulfur is preferably 0.5 to 5 parts by mass in terms of sulfur content with respect to 100 parts by mass of the rubber in the rubber composition.
  • the amount of the vulcanization accelerator is preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the rubber in the rubber composition.
  • the rubber composition can be used to make a tire. Specifically, it can be used for producing a tire member that constitutes a tire.
  • the rubber composition can be used to make tread rubber, sidewall rubber, chafer rubber, bead filler rubber and the like.
  • the method for producing a tire according to the first embodiment includes the step of vulcanizing and molding an unvulcanized tire produced with a rubber composition.
  • An unvulcanized tire comprises a tire member made of a rubber composition. That is, an unvulcanized tire includes a tire member including a rubber composition.
  • the tire obtained by the method of Embodiment 1 can be, for example, a pneumatic tire.
  • the method for producing a masterbatch in Embodiment 1 can improve the tear strength and the abrasion resistance of the vulcanized rubber.
  • the pre-coagulation mixed liquid By preparing the pre-coagulation mixed liquid with natural rubber latex, liquid rubber latex and carbon black slurry, it is possible to disperse liquid rubber in the pre-solidification mixed liquid, and a master batch in which liquid rubber is dispersed is obtained. be able to.
  • the uniformity of the distribution state of the crosslinking points is enhanced.
  • the manufacturing method of the masterbatch of Embodiment 1 in this indication can improve the tear strength and abrasion resistance of a vulcanized rubber compared with such a method.
  • the method for producing a masterbatch in Embodiment 1 can improve the processability.
  • By preparing the pre-coagulation mixed liquid with natural rubber latex, liquid rubber latex and carbon black slurry it is possible to disperse liquid rubber in the pre-solidification mixed liquid, and a master batch in which liquid rubber is dispersed is obtained. be able to. Therefore, it is possible to make liquid rubber exhibit the function as a plasticizer, and the manufacturing method of the masterbatch in Embodiment 1 can improve processability.
  • the method for producing the masterbatch in Embodiment 1 is different from the method using liquid rubber instead of liquid rubber latex (method for producing a mixture before coagulation treatment using natural rubber latex, liquid rubber and carbon black slurry)
  • the liquid rubber can be easily dispersed in the pre-solidification mixture, and the dispersion of the liquid rubber can be improved.
  • the step of preparing the pre-coagulation treatment is a first procedure (a procedure of adding a liquid rubber latex to a natural rubber latex and mixing a natural rubber latex and a carbon black slurry after the addition), or a second procedure (In the procedure of mixing a natural rubber latex and a carbon black slurry and adding a liquid rubber latex), in the third modification of the first embodiment, instead of the first procedure or the second procedure, a liquid is used as a carbon black slurry This step involves adding the rubber latex, stirring if necessary, and mixing it with the natural rubber latex.
  • Modification 4 In the first embodiment, carbon black and water are mixed to obtain a carbon black slurry, but in the fourth modification of the first embodiment, carbon black and rubber latex are used to obtain a carbon black slurry instead of this operation.
  • rubber latex for mixing with carbon black is referred to as "diluted rubber latex"
  • diluted rubber latex rubber latex for mixing with carbon black
  • the diluted rubber latex is, for example, a natural rubber latex, a synthetic rubber latex or the like.
  • the number average molecular weight of the natural rubber in the natural rubber latex is, for example, 2,000,000 or more.
  • Synthetic rubber latexes are, for example, styrene-butadiene rubber latex, butadiene rubber latex, nitrile rubber latex, chloroprene rubber latex.
  • the dry rubber content of the diluted rubber latex is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more.
  • the upper limit of the dry rubber content is, for example, 5% by mass, preferably 2% by mass, and more preferably 1% by mass.
  • Mooney Viscosity According to JIS K 6300, the unvulcanized rubber was preheated at 100 ° C. for 1 minute, and then the rotor was rotated, and the torque value 4 minutes after the start of rotation was recorded in Mooney units.
  • the Mooney viscosity of each example was indicated by an index based on the Mooney viscosity of Comparative Example 1 being 100. The smaller the index, the lower the Mooney viscosity and the better the processability.
  • Tear strength Unvulcanized rubber was vulcanized at 150 ° C. for 30 minutes to prepare test pieces from the vulcanized rubber. The force required to tear the test piece was measured according to JIS K6252. The tear strength of each example was indicated by an index based on the tear strength of Comparative Example 1 being 100. The larger the index, the better the tear strength.
  • Example 1 the Mooney viscosity and tear strength and abrasion resistance of Example 1 were superior to those of Example 4.
  • the Mooney viscosity of the unvulcanized rubber in Examples 1 to 4 was lower than that of the unvulcanized rubber in Comparative Example 1. That is, the processability of the unvulcanized rubber in Examples 1 to 4 was superior to that of the unvulcanized rubber in Comparative Example 1.
  • the Mooney viscosity, tear strength and abrasion resistance were evaluated by the methods already described.
  • the Mooney viscosity of each example was expressed as an index with the Mooney viscosity of Comparative Example 6 being 100. The smaller the index, the lower the Mooney viscosity and the better the processability.
  • the tear strength of each example was expressed as an index with the tear strength of Comparative Example 6 as 100. The larger the index, the better the tear strength.
  • the amount of wear of each example was indicated by an index with the amount of wear of Comparative Example 6 being 100. The smaller the index, the smaller the amount of wear and the better the wear resistance.

Abstract

This masterbatch production method comprises: a step for preparing a pre-solidification liquid mixture from at least a natural rubber latex, a liquid rubber latex and a filler slurry; and a step for solidifying the pre-solidification liquid mixture.

Description

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Method of producing masterbatch, method of producing rubber composition, and method of producing tire
　本開示は、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に関する。 The present disclosure relates to a method of producing a masterbatch, a method of producing a rubber composition, and a method of producing a tire.
　天然ゴムにカーボンブラックが分散したウェットマスターバッチは、ムーニー粘度が高く、加工性が悪い。ウェットマスターバッチは、たとえば、天然ゴムラテックスとカーボンブラックスラリーとを混合し、凝固し、脱水して得ることができる。 A wet masterbatch in which carbon black is dispersed in natural rubber has a high Mooney viscosity and poor processability. The wet masterbatch can be obtained, for example, by mixing natural rubber latex and carbon black slurry, coagulating and dewatering.
　加工性を向上するために、ウェットマスターバッチを混練りする際に、可塑剤を添加することができる。混練りは、混練機、たとえばバンバリーミキサーでおこなわれる。 A plasticizer can be added when kneading the wet masterbatch in order to improve the processability. Kneading is performed by a kneader, for example, a Banbury mixer.
特開平１１－４９８９５号公報Unexamined-Japanese-Patent No. 11-49895 gazette
　しかしながら、加工性の向上だけでなく、加硫ゴムの物性、たとえば引裂強さや耐摩耗性も考慮すべきである。引裂強さや耐摩耗性について、ウェットマスターバッチを混練りする際に可塑剤を添加する手法には改善の余地がある。 However, in addition to the improvement of the processability, the physical properties of the vulcanized rubber, for example, the tear strength and the abrasion resistance should be considered. With regard to tear strength and abrasion resistance, there is room for improvement in the method of adding a plasticizer when kneading a wet master batch.
　本開示の目的は、加硫ゴムの引裂強さと耐摩耗性とを向上することができるマスターバッチの製造方法を提供することである。 An object of the present disclosure is to provide a method for producing a masterbatch that can improve the tear strength and abrasion resistance of vulcanized rubber.
　本開示におけるマスターバッチの製造方法は、少なくとも天然ゴムラテックス、液状ゴムラテックスおよび充てん剤スラリーで凝固処理前混合液を作製する工程と、凝固処理前混合液を凝固する工程とを含む。 The method for producing a masterbatch in the present disclosure includes the steps of preparing a pre-coagulation treatment mixture with at least a natural rubber latex, a liquid rubber latex and a filler slurry, and coagulating the pre-coagulation treatment mixture.
　本開示における実施形態のマスターバッチの製造方法は、少なくとも天然ゴムラテックス、液状ゴムラテックスおよび充てん剤スラリーで凝固処理前混合液を作製する工程と、凝固処理前混合液を凝固する工程とを含む。 The method for producing a masterbatch according to an embodiment of the present disclosure includes the steps of preparing a pre-coagulation mixture with at least a natural rubber latex, a liquid rubber latex and a filler slurry, and coagulating the pre-coagulation mixture.
　本開示における実施形態のマスターバッチの製造方法は、加硫ゴムの引裂強さと耐摩耗性とを向上することができる。凝固処理前混合液を、天然ゴムラテックス、液状ゴムラテックスおよび充てん剤スラリーで作製することで、凝固処理前混合液に液状ゴムを分散させることが可能であり、液状ゴムが分散したマスターバッチを得ることができる。このようなマスターバッチで加硫ゴムを作製することによって、混練り時に液状ゴムをはじめて使用（添加）して加硫ゴムを作製する手法にくらべて、架橋点の分布状態の均一性を高めることができる。よって、本開示における実施形態のマスターバッチの製造方法は、そのような手法にくらべて、加硫ゴムの引裂強さと耐摩耗性とを向上することができる。 The method of producing a masterbatch according to the embodiments of the present disclosure can improve the tear strength and the abrasion resistance of a vulcanized rubber. By preparing the pre-coagulation mixed liquid with natural rubber latex, liquid rubber latex and filler slurry, it is possible to disperse liquid rubber in the pre-coagulation mixed liquid, and a master batch in which liquid rubber is dispersed is obtained. be able to. Compared with the method of producing a vulcanized rubber by using (adding) a liquid rubber for the first time during kneading by making a vulcanized rubber with such a masterbatch, the uniformity of the distribution state of the crosslinking points is enhanced. Can. Therefore, the method for producing a masterbatch according to the embodiment of the present disclosure can improve the tear strength and the abrasion resistance of the vulcanized rubber, as compared to such a method.
　凝固処理前混合液を作製する工程は、天然ゴムラテックスに液状ゴムラテックスを添加し、添加後天然ゴムラテックスを得ることと、添加後天然ゴムラテックスおよび充てん剤スラリーを混合することとを含むことができる。いっぽう、このような手順に代えて、凝固処理前混合液を作製する工程は、天然ゴムラテックスおよび充てん剤スラリーを混合し、液状ゴムラテックスを添加することを含むことができる。 The step of preparing the pre-coagulation treatment mixture includes adding a liquid rubber latex to the natural rubber latex, obtaining a natural rubber latex after the addition, and mixing the natural rubber latex and the filler slurry after the addition. it can. On the other hand, instead of such a procedure, the step of preparing the pre-solidification mixture may include mixing natural rubber latex and filler slurry and adding liquid rubber latex.
　本開示における実施形態のゴム組成物の製造方法は、本開示における実施形態のマスターバッチの製造方法を含む。具体的には、本開示における実施形態のゴム組成物の製造方法は、少なくとも天然ゴムラテックス、液状ゴムラテックスおよび充てん剤スラリーで凝固処理前混合液を作製する工程と、凝固処理前混合液を凝固する工程とを含む。 The method of producing the rubber composition of the embodiment in the present disclosure includes the method of producing the master batch of the embodiment in the present disclosure. Specifically, the method for producing a rubber composition according to an embodiment of the present disclosure comprises the steps of preparing a mixed liquid before coagulation treatment with at least a natural rubber latex, liquid rubber latex and filler slurry, and coagulating the mixed liquid before coagulation treatment. And the step of
　本開示における実施形態のタイヤの製造方法は、本開示における実施形態のマスターバッチの製造方法を含む。具体的には、本開示における実施形態のタイヤの製造方法は、少なくとも天然ゴムラテックス、液状ゴムラテックスおよび充てん剤スラリーで凝固処理前混合液を作製する工程と、凝固処理前混合液を凝固する工程とを含む。 A method of manufacturing a tire of an embodiment in the present disclosure includes a method of manufacturing a master batch of an embodiment in the present disclosure. Specifically, the method for manufacturing a tire according to an embodiment of the present disclosure includes the steps of preparing a mixed liquid before coagulation treatment with at least a natural rubber latex, liquid rubber latex and filler slurry, and coagulating the mixed liquid before coagulation treatment. And.
　本開示の実施形態において、充てん剤は、カーボンブラック、シリカ、クレー、タルク、炭酸カルシウム、炭酸マグネシウム、水酸化アルミニウムなどの無機充てん剤であることができる。これらのうち、一つまたは複数を選択して、使用することができる。 In embodiments of the present disclosure, the filler can be an inorganic filler such as carbon black, silica, clay, talc, calcium carbonate, magnesium carbonate, aluminum hydroxide and the like. One or more of these can be selected and used.
　実施形態１
　ここからは、本開示の実施形態１について説明する。実施形態１は、マスターバッチのための充てん剤としてカーボンブラックを使用する。 Embodiment 1
From here, Embodiment 1 of the present disclosure will be described. Embodiment 1 uses carbon black as a filler for the masterbatch.
　実施形態１におけるタイヤの製造方法は、凝固処理前混合液を作製する工程と、凝固処理前混合液を凝固し、マスターバッチを得る工程と、少なくともマスターバッチおよび配合剤を混練りし、ゴム混合物を得る工程と、ゴム混合物に加硫系配合剤を練り込み、ゴム組成物を得る工程と、ゴム組成物で作製した未加硫タイヤを加硫成型する工程とを含む。 In the tire manufacturing method according to the first embodiment, a step of preparing a pre-coagulation treatment mixture, a step of coagulating the pre-solidification treatment mixture to obtain a masterbatch, and kneading at least a masterbatch and a compounding agent to obtain a rubber mixture And a step of kneading the vulcanized compounding agent into the rubber mixture to obtain a rubber composition, and a step of vulcanizing and molding an unvulcanized tire produced from the rubber composition.
　実施形態１におけるタイヤの製造方法は、凝固処理前混合液を作製する工程、すなわち、天然ゴムラテックス、液状ゴムラテックスおよびカーボンブラックスラリーで凝固処理前混合液を作製する工程を含む。 The manufacturing method of the tire in the embodiment 1 includes the step of preparing the pre-coagulation treatment mixture, that is, the step of preparing the pre-coagulation treatment mixture with the natural rubber latex, the liquid rubber latex and the carbon black slurry.
　天然ゴムラテックスでは、天然ゴムを含むゴム粒子が、コロイド状に水に分散している。天然ゴムラテックス中の天然ゴムの数平均分子量は、たとえば２００万以上である。天然ゴムラテックスの乾燥ゴム分は、好ましくは１０質量％以上、より好ましくは２０質量％以上である。天然ゴムラテックスにおける乾燥ゴム分の上限は、たとえば６０質量％、好ましくは４０質量％、さらに好ましくは３０質量％である。 In the natural rubber latex, rubber particles containing natural rubber are dispersed in water in the form of colloid. The number average molecular weight of the natural rubber in the natural rubber latex is, for example, 2,000,000 or more. The dry rubber content of the natural rubber latex is preferably 10% by mass or more, more preferably 20% by mass or more. The upper limit of the dry rubber content in the natural rubber latex is, for example, 60% by mass, preferably 40% by mass, and more preferably 30% by mass.
　液状ゴムラテックスでは、液状ゴムを含むゴム粒子が、コロイド状に水に分散している。液状ゴムは、たとえば、イソプレンゴム、スチレン－ブタジエンゴム、ニトリルゴム、クロロプレンゴムなどのジエン系ゴムであることができる。すなわち、液状ゴムラテックスは、液状ジエン系ゴムラテックスであることができ、たとえば液状イソプレンゴムラテックスであることができる。液状ゴムの数平均分子量は、たとえば０．５万～６．０万である。液状ゴムラテックスの乾燥ゴム分は、たとえば１０質量％以上であることができ、３０質量％以上であることもでき、５０質量％以上であることもできる。液状ゴムラテックスにおける乾燥ゴム分の上限は、たとえば９０質量％、８０質量％、７０質量％などである。 In liquid rubber latex, rubber particles containing liquid rubber are dispersed in water in the form of colloid. The liquid rubber can be, for example, a diene rubber such as isoprene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber and the like. That is, the liquid rubber latex can be a liquid diene rubber latex, for example, a liquid isoprene rubber latex. The number average molecular weight of the liquid rubber is, for example, 0.5000 to 600000. The dry rubber content of the liquid rubber latex can be, for example, 10% by mass or more, can be 30% by mass or more, and can be 50% by mass or more. The upper limit of the dry rubber content in the liquid rubber latex is, for example, 90% by mass, 80% by mass, 70% by mass or the like.
　カーボンブラックスラリーでは、カーボンブラックが水中に分散している。カーボンブラックスラリーにおけるカーボンブラックの量は、カーボンブラックスラリー１００質量％において、好ましくは１質量％以上、より好ましくは３質量％以上である。カーボンブラックスラリーにおけるカーボンブラック量の上限は、好ましくは１５質量％、より好ましくは１０質量％である。カーボンブラックスラリーは、たとえばカーボンブラックと水とを混合することで得ることができる。カーボンブラックとしては、たとえばＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＦＥＦ、ＧＰＦなどのカーボンブラックのほか、アセチレンブラックやケッチェンブラックなどの導電性カーボンブラックを使用することができる。カーボンブラックは、そのハンドリング性を考慮して造粒された、造粒カーボンブラックであってもよく、未造粒カーボンブラックであってもよい。カーボンブラックと水とは、高せん断ミキサー、ホモミキサー、ボールミル、ビーズミル、高圧ホモジナイザー、超音波ホモジナイザー、コロイドミルなどの一般的な分散機で混合できる。 In the carbon black slurry, carbon black is dispersed in water. The amount of carbon black in the carbon black slurry is preferably 1% by mass or more, more preferably 3% by mass or more, in 100% by mass of the carbon black slurry. The upper limit of the amount of carbon black in the carbon black slurry is preferably 15% by mass, more preferably 10% by mass. The carbon black slurry can be obtained, for example, by mixing carbon black and water. As carbon black, for example, carbon black such as SAF, ISAF, HAF, FEF, GPF and the like, or conductive carbon black such as acetylene black and ketjen black can be used. The carbon black may be granulated carbon black granulated in consideration of its handling property, or may be non-granulated carbon black. Carbon black and water can be mixed by a general dispersing machine such as a high shear mixer, homomixer, ball mill, bead mill, high pressure homogenizer, ultrasonic homogenizer, colloid mill and the like.
　凝固処理前混合液は、天然ゴムを含むゴム粒子と、液状ゴムを含むゴム粒子と、カーボンブラックとを含む。凝固処理前混合液では、これらが水中に分散している。凝固処理前混合液における天然ゴムの量は、凝固処理前混合液の乾燥ゴム分１００質量％において、たとえば８０質量％以上であることができ、８５質量％以上であることができ、９０質量％以上であることができる。凝固処理前混合液における天然ゴムの量は、凝固処理前混合液の乾燥ゴム分１００質量％において、たとえば９９質量％以下であることができ、９８質量％以下であることができ、９７質量％以下であることができる。いっぽう、凝固処理前混合液における液状ゴムの量は、凝固処理前混合液の乾燥ゴム分１００質量％において、たとえば１質量％以上であることができ、２質量％以上であることができ、３質量％以上であることができる。凝固処理前混合液における液状ゴムの量は、凝固処理前混合液の乾燥ゴム分１００質量％において、たとえば２０質量％以下であることができ、１５質量％以下であることができ、１０質量％以下であることができる。いっぽう、凝固処理前混合液におけるカーボンブラックの量は、凝固処理前混合液の乾燥ゴム分１００質量部に対して、たとえば１０質量部以上であることができ、２０質量部以上であることができ、３０質量部以上であることができ、４０質量部以上であることができる。凝固処理前混合液におけるカーボンブラックの量は、凝固処理前混合液の乾燥ゴム分１００質量部に対して、たとえば８０質量部以下であることができ、７０質量部以下であることができ、６０質量部以下であることができる。 The liquid mixture before coagulation treatment contains rubber particles containing natural rubber, rubber particles containing liquid rubber, and carbon black. In the pre-coagulation mixed solution, these are dispersed in water. The amount of natural rubber in the pre-coagulation mixed solution can be, for example, 80% by mass or more, can be 85% by mass or more, and can be 90% by mass in 100% by mass of the dried rubber content of the pre-coagulation treated liquid mixture It can be more than. The amount of natural rubber in the pre-coagulation mixed solution can be, for example, 99 mass% or less, can be 98 mass% or less, and can be 97 mass% in 100 mass% of the dry rubber content of the pre-coagulation mixture. It can be On the other hand, the amount of liquid rubber in the pre-coagulation mixed liquid can be, for example, 1 mass% or more, and can be 2 mass% or more in 100 mass% of the dry rubber content of the pre-coagulation mixed liquid, It can be mass% or more. The amount of liquid rubber in the pre-coagulation mixed liquid can be, for example, 20 mass% or less, can be 15 mass% or less, and can be 10 mass% in 100 mass% of dry rubber content of the pre-coagulation mixed liquid. It can be On the other hand, the amount of carbon black in the pre-coagulation mixed solution can be, for example, 10 parts by mass or more, and can be 20 parts by mass or more with respect to 100 parts by mass of the dry rubber of the pre-coagulation mixed liquid. , 30 parts by mass or more, and 40 parts by mass or more. The amount of carbon black in the mixed solution before coagulation treatment can be, for example, 80 parts by mass or less, and can be 70 parts by mass or less, with respect to 100 parts by mass of the dried rubber of the mixed solution before coagulation treatment, It can be less than or equal to parts by weight.
　凝固処理前混合液を作製する工程は、天然ゴムラテックスに液状ゴムラテックスを添加し、添加後天然ゴムラテックスを得ることと、添加後天然ゴムラテックスおよびカーボンブラックスラリーを混合することとを含む（この手順を、以下、「第一手順」という。）。具体的には、まず、天然ゴムラテックスに液状ゴムラテックスを添加し、必要に応じて撹拌し、添加後天然ゴムラテックスを得る。次いで、添加後天然ゴムラテックスとカーボンブラックスラリーとを混合し、凝固処理前混合液を得る。添加後天然ゴムラテックスとカーボンブラックスラリーとは、高せん断ミキサー、ホモミキサー、ボールミル、ビーズミル、高圧ホモジナイザー、超音波ホモジナイザー、コロイドミルなどの一般的な分散機で混合できる。 The step of preparing the pre-coagulation treatment mixture includes adding a liquid rubber latex to the natural rubber latex, obtaining a natural rubber latex after the addition, and mixing the natural rubber latex and the carbon black slurry after the addition (this The procedure is hereinafter referred to as the "first procedure." Specifically, first, a liquid rubber latex is added to a natural rubber latex, and if necessary, the mixture is stirred to obtain a natural rubber latex after addition. Then, after addition, the natural rubber latex and the carbon black slurry are mixed to obtain a mixed solution before coagulation treatment. After the addition, natural rubber latex and carbon black slurry can be mixed by a general dispersing machine such as a high shear mixer, homomixer, ball mill, bead mill, high pressure homogenizer, ultrasonic homogenizer, colloid mill and the like.
　凝固処理前混合液を作製する工程は、前述の第一手順（天然ゴムラテックスに液状ゴムラテックスを添加し、添加後天然ゴムラテックスおよびカーボンブラックスラリーを混合する手順）に代えて、天然ゴムラテックスとカーボンブラックスラリーとを混合し、液状ゴムラテックスを添加することを含んでもよい（この手順を、以下、「第二手順」という。）。この場合、まず、天然ゴムラテックスとカーボンブラックスラリーとを混合する。天然ゴムラテックスとカーボンブラックスラリーとは、高せん断ミキサー、ホモミキサー、ボールミル、ビーズミル、高圧ホモジナイザー、超音波ホモジナイザー、コロイドミルなどの一般的な分散機で混合できる。次いで、この混合で得られた液に、液状ゴムラテックスを添加し、必要に応じて撹拌し、凝固処理前混合液を得る。 The step of preparing the pre-coagulation treatment mixed liquid is replaced with natural rubber latex in place of the above-mentioned first procedure (adding liquid rubber latex to natural rubber latex and mixing natural rubber latex and carbon black slurry after addition) The method may include mixing with a carbon black slurry and adding a liquid rubber latex (this procedure is hereinafter referred to as "second procedure"). In this case, first, natural rubber latex and carbon black slurry are mixed. The natural rubber latex and the carbon black slurry can be mixed by a general dispersing machine such as a high shear mixer, homomixer, ball mill, bead mill, high pressure homogenizer, ultrasonic homogenizer, colloid mill and the like. Next, a liquid rubber latex is added to the liquid obtained by this mixing, and if necessary, the mixture is stirred to obtain a mixed liquid before coagulation treatment.
　凝固処理前混合液を凝固し、マスターバッチを得る工程を、実施形態１におけるタイヤの製造方法は含む。凝固は、凝固処理前混合液を乾燥させることで起こすことができる。いっぽう、凝固を起こすために、凝固処理前混合液に凝固剤を添加してもよい。凝固剤は、たとえば酸である。酸としてギ酸、硫酸などを挙げることができる。凝固処理前混合液を凝固することで得られた凝固物は水を含んでいる。よって、この工程（凝固処理前混合液を凝固し、マスターバッチを得る工程）は、凝固物を脱水することを含むことができる。凝固物を脱水するために、たとえば、押出機や真空乾燥機、エアドライヤーなどを使用できる。脱水された凝固物の水分量は、好ましくは１５質量％以下、より好ましくは１０質量％以下である。脱水後の凝固物を成形することをこの工程は含むことができる。このようにして得られたマスターバッチは、ゴム、カーボンブラックを含む。 The method for manufacturing a tire according to the first embodiment includes the steps of coagulating the pre-coagulation treatment liquid mixture to obtain a masterbatch. Solidification can be caused by drying the pre-solidification mixture. On the other hand, a coagulant may be added to the pre-coagulation mixture to cause coagulation. The coagulant is, for example, an acid. Examples of the acid include formic acid and sulfuric acid. The coagulated material obtained by coagulating the mixture before coagulation treatment contains water. Thus, this step (the step of solidifying the pre-solidification mixture to obtain the masterbatch) can include dewatering the solid. For dewatering of the coagulum, for example, an extruder, a vacuum dryer, an air dryer, etc. can be used. The water content of the dehydrated coagulated substance is preferably 15% by mass or less, more preferably 10% by mass or less. This step can include shaping the coagulated material after dewatering. The masterbatch thus obtained contains rubber and carbon black.
　マスターバッチはゴムを含む。マスターバッチのゴムは、天然ゴムと液状ゴムとを含む。マスターバッチにおける天然ゴムの量は、マスターバッチ中のゴム１００質量％において、たとえば８０質量％以上であることができ、８５質量％以上であることができ、９０質量％以上であることができる。マスターバッチにおける天然ゴムの量は、マスターバッチ中のゴム１００質量％において、たとえば９９質量％以下であることができ、９８質量％以下であることができ、９７質量％以下であることができる。 The masterbatch contains rubber. The masterbatch rubber includes natural rubber and liquid rubber. The amount of natural rubber in the masterbatch can be, for example, 80% by mass or more, can be 85% by mass or more, and can be 90% by mass or more in 100% by mass of rubber in the masterbatch. The amount of natural rubber in the masterbatch can be, for example, 99% by weight or less, 98% by weight or less, and 97% by weight or less in 100% by weight of rubber in the masterbatch.
　マスターバッチはカーボンブラックをさらに含む。カーボンブラックの量は、マスターバッチ中のゴム１００質量部に対して、好ましくは１０質量部以上、より好ましくは２０質量部以上、さらに好ましくは３０質量部以上である。カーボンブラックの量は、マスターバッチ中のゴム１００質量部に対して、好ましくは８０質量部以下、より好ましくは６０質量部以下である。 The masterbatch further comprises carbon black. The amount of carbon black is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more, with respect to 100 parts by mass of the rubber in the master batch. The amount of carbon black is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the rubber in the masterbatch.
　マスターバッチと配合剤とを混練りし、ゴム混合物を得る工程を、実施形態１におけるタイヤの製造方法は含む。配合剤としては、充てん剤、ステアリン酸、酸化亜鉛（亜鉛華）、老化防止剤など挙げることができる。これらのうち、一つまたは複数を選択して、マスターバッチと混練することができる。この工程でマスターバッチに添加する配合剤はオイルを含んでいない。老化防止剤として、芳香族アミン系老化防止剤、アミン－ケトン系老化防止剤、モノフェノール系老化防止剤、ビスフェノール系老化防止剤、ポリフェノール系老化防止剤、ジチオカルバミン酸塩系老化防止剤、チオウレア系老化防止剤などを挙げることができる。この混練りの工程では、マスターバッチおよび配合剤とともに、ほかのゴムを混練りすることができる。混練り時にマスターバッチに追加するゴムとして、たとえば、天然ゴム、イソプレンゴム、スチレン－ブタジエンゴム、ニトリルゴム、クロロプレンゴムなどを挙げることができる。混練り時にマスターバッチに追加するゴムは液状ゴムを含んでいない。ここでの液状ゴムとして、たとえば、イソプレンゴム、スチレン－ブタジエンゴム、ニトリルゴム、クロロプレンゴムなどのジエン系液状ゴムを挙げることができる。混練りは、混練機でおこなうことができる。混練機として密閉式混練機、オープンロールなどを挙げることができる。密閉式混練機としてバンバリーミキサー、ニーダーなどを挙げることができる。 The method of manufacturing a tire according to the first embodiment includes the step of kneading the masterbatch and the compounding agent to obtain a rubber mixture. Examples of the compounding agent include fillers, stearic acid, zinc oxide (zinc white), anti-aging agents and the like. One or more of these can be selected and kneaded with the master batch. The ingredients added to the masterbatch in this step do not contain oil. As anti-aging agents, aromatic amine anti-aging agents, amine-ketone anti-aging agents, monophenol anti-aging agents, bisphenol anti-aging agents, polyphenol anti-aging agents, dithiocarbamate anti-aging agents, thiourea anti-aging agents Anti-aging agents can be mentioned. In the kneading step, other rubbers can be kneaded together with the masterbatch and the compounding agent. Examples of the rubber to be added to the masterbatch at the time of kneading include natural rubber, isoprene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber and the like. The rubber added to the masterbatch at the time of kneading does not contain liquid rubber. Examples of the liquid rubber here include diene-based liquid rubbers such as isoprene rubber, styrene-butadiene rubber, nitrile rubber and chloroprene rubber. Kneading can be performed by a kneader. As a kneader, a closed-type kneader, an open roll, etc. can be mentioned. A Banbury mixer, a kneader etc. can be mentioned as a closed-type kneader.
　ゴム混合物に加硫系配合剤を練り込み、ゴム組成物を得る工程を、実施形態１におけるタイヤの製造方法はさらに含む。加硫系配合剤として硫黄、有機過酸化物などの加硫剤、加硫促進剤、加硫促進助剤、加硫遅延剤などを挙げることができる。硫黄として粉末硫黄、沈降硫黄、不溶性硫黄、高分散性硫黄などを挙げることができる。加硫促進剤としてスルフェンアミド系加硫促進剤、チウラム系加硫促進剤、チアゾール系加硫促進剤、チオウレア系加硫促進剤、グアニジン系加硫促進剤、ジチオカルバミン酸塩系加硫促進剤などを挙げることができる。 The method of manufacturing a tire according to Embodiment 1 further includes the step of kneading the vulcanizing compound into the rubber mixture to obtain a rubber composition. Examples of the vulcanizing compounding agent include sulfur, vulcanizing agents such as organic peroxides, vulcanization accelerators, vulcanization acceleration assistants, vulcanization retarders, and the like. Examples of sulfur include powdered sulfur, precipitated sulfur, insoluble sulfur, highly dispersible sulfur and the like. Sulfenamide-based vulcanization accelerator, thiuram-based vulcanization accelerator, thiazole-based vulcanization accelerator, thiourea-based vulcanization accelerator, guanidine-based vulcanization accelerator, dithiocarbamate-based vulcanization accelerator as vulcanization accelerator And the like.
　ゴム組成物は、マスターバッチに由来するゴムを含む。マスターバッチに由来するゴムの量は、ゴム組成物中のゴム１００質量％に対して、たとえば、４０質量％以上であることができ、６０質量％以上であることができ、８０質量％以上であることができ、１００質量％であることもできる。 The rubber composition comprises a rubber derived from a masterbatch. The amount of rubber derived from the masterbatch can be, for example, 40% by mass or more, 60% by mass or more, and 80% by mass or more based on 100% by mass of the rubber in the rubber composition. It can be 100% by weight.
　ゴム組成物はカーボンブラックを含む。カーボンブラックの量は、ゴム組成物中のゴム１００質量部に対して、好ましくは１０質量部以上、より好ましくは２０質量部以上、さらに好ましくは３０質量部以上である。カーボンブラックの量は、ゴム組成物中のゴム１００質量部に対して、好ましくは８０質量部以下、より好ましくは６０質量部以下である。 The rubber composition comprises carbon black. The amount of carbon black is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber in the rubber composition. The amount of carbon black is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, based on 100 parts by mass of the rubber in the rubber composition.
　ゴム組成物は、ステアリン酸、酸化亜鉛、老化防止剤、硫黄、加硫促進剤などをさらに含むことができる。硫黄の量は、ゴム組成物中のゴム１００質量部に対して、硫黄分換算で好ましくは０．５質量部～５質量部である。加硫促進剤の量は、ゴム組成物中のゴム１００質量部に対して、好ましくは０．１質量部～５質量部である。 The rubber composition can further include stearic acid, zinc oxide, an antiaging agent, sulfur, a vulcanization accelerator and the like. The amount of sulfur is preferably 0.5 to 5 parts by mass in terms of sulfur content with respect to 100 parts by mass of the rubber in the rubber composition. The amount of the vulcanization accelerator is preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the rubber in the rubber composition.
　ゴム組成物は、タイヤの作製に使用できる。具体的には、タイヤを構成するタイヤ部材の作製に使用可能である。たとえば、トレッドゴム、サイドウォールゴム、チェーハーゴム、ビードフィラーゴムなどの作製にゴム組成物を使用できる。 The rubber composition can be used to make a tire. Specifically, it can be used for producing a tire member that constitutes a tire. For example, the rubber composition can be used to make tread rubber, sidewall rubber, chafer rubber, bead filler rubber and the like.
　ゴム組成物で作製した未加硫タイヤを加硫成型する工程を、実施形態１におけるタイヤの製造方法は含む。未加硫タイヤは、ゴム組成物で作製したタイヤ部材を備える。すなわち、未加硫タイヤが、ゴム組成物を含むタイヤ部材を備える。実施形態１の方法で得られたタイヤは、たとえば空気入りタイヤであることができる。 The method for producing a tire according to the first embodiment includes the step of vulcanizing and molding an unvulcanized tire produced with a rubber composition. An unvulcanized tire comprises a tire member made of a rubber composition. That is, an unvulcanized tire includes a tire member including a rubber composition. The tire obtained by the method of Embodiment 1 can be, for example, a pneumatic tire.
　ここまで説明したように、実施形態１におけるマスターバッチの製造方法は、加硫ゴムの引裂強さと耐摩耗性とを向上することができる。凝固処理前混合液を、天然ゴムラテックス、液状ゴムラテックスおよびカーボンブラックスラリーで作製することで、凝固処理前混合液に液状ゴムを分散させることが可能であり、液状ゴムが分散したマスターバッチを得ることができる。このようなマスターバッチで加硫ゴムを作製することによって、混練り時に液状ゴムをはじめて使用（添加）して加硫ゴムを作製する手法にくらべて、架橋点の分布状態の均一性を高めることができる。よって、本開示における実施形態１のマスターバッチの製造方法は、そのような手法にくらべて、加硫ゴムの引裂強さと耐摩耗性とを向上することができる。 As described above, the method for producing a masterbatch in Embodiment 1 can improve the tear strength and the abrasion resistance of the vulcanized rubber. By preparing the pre-coagulation mixed liquid with natural rubber latex, liquid rubber latex and carbon black slurry, it is possible to disperse liquid rubber in the pre-solidification mixed liquid, and a master batch in which liquid rubber is dispersed is obtained. be able to. Compared with the method of producing a vulcanized rubber by using (adding) a liquid rubber for the first time during kneading by making a vulcanized rubber with such a masterbatch, the uniformity of the distribution state of the crosslinking points is enhanced. Can. Therefore, the manufacturing method of the masterbatch of Embodiment 1 in this indication can improve the tear strength and abrasion resistance of a vulcanized rubber compared with such a method.
　実施形態１におけるマスターバッチの製造方法は、加工性を向上することができる。凝固処理前混合液を、天然ゴムラテックス、液状ゴムラテックスおよびカーボンブラックスラリーで作製することで、凝固処理前混合液に液状ゴムを分散させることが可能であり、液状ゴムが分散したマスターバッチを得ることができる。よって、液状ゴムに、可塑剤としての機能を発揮させることが可能であり、実施形態１におけるマスターバッチの製造方法は加工性を向上することができる。 The method for producing a masterbatch in Embodiment 1 can improve the processability. By preparing the pre-coagulation mixed liquid with natural rubber latex, liquid rubber latex and carbon black slurry, it is possible to disperse liquid rubber in the pre-solidification mixed liquid, and a master batch in which liquid rubber is dispersed is obtained. be able to. Therefore, it is possible to make liquid rubber exhibit the function as a plasticizer, and the manufacturing method of the masterbatch in Embodiment 1 can improve processability.
　さらに、実施形態１におけるマスターバッチの製造方法は、液状ゴムラテックスに代えて液状ゴムを用いる手法（凝固処理前混合液を、天然ゴムラテックス、液状ゴムおよびカーボンブラックスラリーで作製する手法）にくらべて、液状ゴムを凝固処理前混合液に容易に分散することが可能であり、液状ゴムの分散を向上できる。 Furthermore, the method for producing the masterbatch in Embodiment 1 is different from the method using liquid rubber instead of liquid rubber latex (method for producing a mixture before coagulation treatment using natural rubber latex, liquid rubber and carbon black slurry) The liquid rubber can be easily dispersed in the pre-solidification mixture, and the dispersion of the liquid rubber can be improved.
　変形例１
　実施形態１では、マスターバッチに添加する配合剤がオイルを含んでいないものの、実施形態１における変形例１では、マスターバッチに添加する配合剤がオイルを含んでいる。 Modification 1
In the first embodiment, although the combination added to the master batch does not contain an oil, in the first variation of the first embodiment, the combination added to the master batch includes an oil.
　変形例２
　実施形態１では、混練り時にマスターバッチにゴムを追加する場合、このゴムが液状ゴムを含んでいないものの、実施形態１における変形例２では、このゴムが液状ゴムを含んでいる。 Modification 2
In Embodiment 1, when rubber is added to the master batch at the time of kneading, although this rubber does not contain liquid rubber, in Modification 2 in Embodiment 1, this rubber contains liquid rubber.
　変形例３
　実施形態１では、凝固処理前混合液を作製する工程が、第一手順（天然ゴムラテックスに液状ゴムラテックスを添加し、添加後天然ゴムラテックスおよびカーボンブラックスラリーを混合する手順）、または第二手順（天然ゴムラテックスとカーボンブラックスラリーとを混合し、液状ゴムラテックスを添加する手順）を含むものの、実施形態１の変形例３では、第一手順または第二手順に代えて、カーボンブラックスラリーに液状ゴムラテックスを添加し、必要に応じて撹拌し、これと天然ゴムラテックスとを混合することを、この工程が含む。 Modification 3
In the embodiment 1, the step of preparing the pre-coagulation treatment is a first procedure (a procedure of adding a liquid rubber latex to a natural rubber latex and mixing a natural rubber latex and a carbon black slurry after the addition), or a second procedure (In the procedure of mixing a natural rubber latex and a carbon black slurry and adding a liquid rubber latex), in the third modification of the first embodiment, instead of the first procedure or the second procedure, a liquid is used as a carbon black slurry This step involves adding the rubber latex, stirring if necessary, and mixing it with the natural rubber latex.
　変形例４
　実施形態１では、カーボンブラックスラリーを得るためにカーボンブラックと水とを混合するものの、実施形態１の変形例４では、この操作に代えて、カーボンブラックスラリーを得るために、カーボンブラックとゴムラテックス（以下、カーボンブラックと混合するためのゴムラテックスを「希薄ゴムラテックス」という。）とを混合する。カーボンブラックと希薄ゴムラテックスとを混合することによって、カーボンブラックの再凝集を防止できる。カーボンブラックの表面の一部または全部に極薄いラテックス相が生成し、ラテックス相がカーボンブラックの再凝集を抑制すると考えられるからである。希薄ゴムラテックスでは、ゴム粒子が，コロイド状に水に分散している。希薄ゴムラテックスは、たとえば天然ゴムラテックス、合成ゴムラテックスなどである。天然ゴムラテックス中の天然ゴムの数平均分子量は、たとえば２００万以上である。合成ゴムラテックスは、たとえばスチレン－ブタジエンゴムラテックス、ブタジエンゴムラテックス、ニトリルゴムラテックス、クロロプレンゴムラテックスである。希薄ゴムラテックスの乾燥ゴム分は、好ましくは０．１質量％以上、より好ましくは０．２質量％以上、さらに好ましくは０．３質量％以上である。乾燥ゴム分の上限は、たとえば５質量％、好ましくは２質量％、さらに好ましくは１質量％である。 Modification 4
In the first embodiment, carbon black and water are mixed to obtain a carbon black slurry, but in the fourth modification of the first embodiment, carbon black and rubber latex are used to obtain a carbon black slurry instead of this operation. (Hereafter, rubber latex for mixing with carbon black is referred to as "diluted rubber latex"). By mixing the carbon black and the dilute rubber latex, reaggregation of the carbon black can be prevented. This is because an extremely thin latex phase is formed on part or all of the surface of carbon black, and the latex phase is considered to suppress reaggregation of carbon black. In the dilute rubber latex, rubber particles are dispersed in water in the form of colloid. The diluted rubber latex is, for example, a natural rubber latex, a synthetic rubber latex or the like. The number average molecular weight of the natural rubber in the natural rubber latex is, for example, 2,000,000 or more. Synthetic rubber latexes are, for example, styrene-butadiene rubber latex, butadiene rubber latex, nitrile rubber latex, chloroprene rubber latex. The dry rubber content of the diluted rubber latex is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more. The upper limit of the dry rubber content is, for example, 5% by mass, preferably 2% by mass, and more preferably 1% by mass.
　これらの変形例から、一つまたは複数を選択して、実施形態１に、組み合わせることはもちろん可能である。 Of course, it is possible to select one or more of these variations and combine them with the first embodiment.
　以下に、本開示の実施例を説明する。 Examples of the present disclosure will be described below.
　原料・薬品を次に示す。
       天然ゴムラテックス（乾燥ゴム分３０．５％のフィールドラテックス）　Ｇｏｌｄｅｎ　Ｈｏｐｅ社製
       液状イソプレンゴムラテックス　「ＬＩＲ－７００」（数平均分子量＝２８０００、乾燥ゴム分＝６０．０質量％、分散媒＝水）クラレ社製
       Ｎ３３０カーボンブラック（Ｎ２ＳＡ９３ｍ２／ｇ　フタル酸ジブチル吸収量１１９ｃｍ３／１００ｇ）東海カーボン社製
       Ｎ１１０カーボンブラック（Ｎ２ＳＡ１４２ｍ２／ｇ　フタル酸ジブチル吸収量１１５ｃｍ３／１００ｇ）東海カーボン社製
       天然ゴム　ＲＳＳ＃３を素練りしたもの
       酸化亜鉛　「酸化亜鉛２種」三井金属鉱業社製
       老化防止剤　「ノクラック６Ｃ」（６ＰＰＤ）大内新興化学工業社製
       ステアリン酸　「ルナックＳ－２０」花王社製
       オイル　「プロセスＮＣ－１４０」ＪＯＭＯ社製
       液状イソプレンゴムＡ　「ＬＩＲ－５０」（数平均分子量＝５４０００）クラレ社製
       液状イソプレンゴムＢ　「ＬＩＲ－３０」（数平均分子量＝２８０００）クラレ社製
       硫黄　「粉末硫黄」鶴見化学工業社製
       加硫促進剤　「ソクシールＣＺ」住友化学社製 Raw materials and chemicals are shown below.
Natural rubber latex (field latex with 30.5% dry rubber) Liquid isoprene rubber latex "LIR-700" (number average molecular weight = 28000, dry rubber = 60.0% by mass, dispersion medium = water) manufactured by Golden Hope manufactured by Kuraray Co., Ltd. N330 carbon black (N 2 SA93m 2 / g dibutylphthalate absorption 119cm 3 / 100g) manufactured by Tokai carbon Co., Ltd. N110 carbon black (N 2 SA142m 2 / g dibutylphthalate absorption 115cm 3 / 100g) Tokai carbon Co. Made of natural rubber RSS # 3 zinc oxide "Zinc oxide type 2" made by Mitsui Metal Mining Co., Ltd. Anti-aging agent "Nocrac 6C" (6PPD) made by Ouchi Emerging Chemical Industry Co., Ltd. Stearic acid "Lunak S-20" Kao Company oil Cess NC-140 "Liquid isoprene rubber A" LIR-50 "(number average molecular weight = 54000) manufactured by JOMO Liquid isoprene rubber B" LIR-30 "(number average molecular weight = 28000) manufactured by Kuraray "Tsurumi Chemical Industry Co., Ltd." Vulcanization accelerator "Sokushiel CZ" Sumitomo Chemical Co., Ltd.
　実施例１～３におけるマスターバッチの作製
　天然ゴムラテックスに、液状イソプレンゴムラテックスを表１にしたがって添加し、撹拌し、スラリー添加前ゴムラテックスを得た。いっぽう、カーボンブラックを水に添加し、撹拌し、カーボンブラックスラリーを得た。カーボンブラックスラリーを、スラリー添加前ゴムラテックスに表１にしたがって加え、撹拌し、凝固剤としてギ酸をｐＨ４になるまで添加し、凝固物を得た。凝固物を、スクイザー式１軸押出脱水機（スエヒロＥＰＭ社製スクリュープレスＶ－０２型）で２００℃で脱水し、マスターバッチを得た。 Preparation of Masterbatch in Examples 1 to 3 A liquid isoprene rubber latex was added to a natural rubber latex according to Table 1 and stirred to obtain a rubber latex before adding a slurry. On the other hand, carbon black was added to water and stirred to obtain a carbon black slurry. A carbon black slurry was added to the rubber latex before slurry addition according to Table 1 and stirred, and formic acid as a coagulant was added until pH 4 to obtain a coagulum. The coagulated material was dewatered at 200 ° C. with a squeezer type single screw extruder (screw press V-02 type manufactured by Suehiro EPM) to obtain a master batch.
　実施例４におけるマスターバッチの作製
　カーボンブラックを水に添加し、撹拌し、カーボンブラックスラリーを得た。カーボンブラックスラリーを、天然ゴムラテックスに表１にしたがって加え、撹拌した。これに、液状イソプレンゴムラテックスを表１にしたがって添加し、撹拌し、凝固剤としてギ酸をｐＨ４になるまで添加し、凝固物を得た。凝固物を、スクイザー式１軸押出脱水機で２００℃で脱水し、マスターバッチを得た。 Preparation of Masterbatch in Example 4 Carbon black was added to water and stirred to obtain a carbon black slurry. The carbon black slurry was added to natural rubber latex according to Table 1 and stirred. To this, liquid isoprene rubber latex was added according to Table 1 and stirred, and formic acid as a coagulant was added until pH 4 to obtain a coagulum. The coagulated material was dewatered at 200 ° C. with a squeezer type single screw extruder dehydrator to obtain a masterbatch.
　比較例２～５におけるマスターバッチの作製
　カーボンブラックを水に添加し、撹拌し、カーボンブラックスラリーを得た。カーボンブラックスラリーを、天然ゴムラテックスに表１にしたがって加え、撹拌し、凝固剤としてギ酸をｐＨ４になるまで添加し、凝固物を得た。凝固物を、スクイザー式１軸押出脱水機で２００℃で脱水し、マスターバッチを得た。 Preparation of Masterbatches in Comparative Examples 2 to 5 Carbon black was added to water and stirred to obtain a carbon black slurry. A carbon black slurry was added to a natural rubber latex according to Table 1 and stirred, and formic acid as a coagulant was added until pH 4 to obtain a coagulum. The coagulated material was dewatered at 200 ° C. with a squeezer type single screw extruder dehydrator to obtain a masterbatch.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　未加硫ゴムの作製
　マスターバッチまたは天然ゴムに、硫黄と加硫促進剤とを除く配合剤を表２にしたがって添加し、神戸製鋼社製のＢ型バンバリーミキサーで混練りし、ゴム混合物を排出した。ゴム混合物と硫黄と加硫促進剤とをＢ型バンバリーミキサーで混練りし、未加硫ゴムを得た。 Preparation of unvulcanized rubber Compounding agents other than sulfur and a vulcanization accelerator are added to a master batch or natural rubber according to Table 2 and kneaded with a B-type Banbury mixer manufactured by Kobe Steel Co., Ltd. to discharge a rubber mixture did. The rubber mixture, sulfur and vulcanization accelerator were kneaded with a B-type Banbury mixer to obtain an unvulcanized rubber.
　ムーニー粘度
　ＪＩＳ Ｋ６３００に準じて、未加硫ゴムを１００℃で１分間予熱した後にローターを回転させ、回転開始から４分後のトルク値をムーニー単位で記録した。比較例１のムーニー粘度を１００とした指数で、各例のムーニー粘度を表示した。指数が小さいほどムーニー粘度が低く、加工性に優れる。 Mooney Viscosity According to JIS K 6300, the unvulcanized rubber was preheated at 100 ° C. for 1 minute, and then the rotor was rotated, and the torque value 4 minutes after the start of rotation was recorded in Mooney units. The Mooney viscosity of each example was indicated by an index based on the Mooney viscosity of Comparative Example 1 being 100. The smaller the index, the lower the Mooney viscosity and the better the processability.
　引裂強さ
　未加硫ゴムを１５０℃で３０分間加硫し、加硫ゴムから試験片を作製した。試験片を引き裂くのに要する力を、ＪＩＳ Ｋ６２５２に準じて測定した。比較例１の引裂強さを１００とした指数で、各例の引裂強さを表示した。指数が大きいほど引裂強さに優れる。 Tear strength Unvulcanized rubber was vulcanized at 150 ° C. for 30 minutes to prepare test pieces from the vulcanized rubber. The force required to tear the test piece was measured according to JIS K6252. The tear strength of each example was indicated by an index based on the tear strength of Comparative Example 1 being 100. The larger the index, the better the tear strength.
　耐摩耗性
　未加硫ゴムを１５０℃で３０分間加硫し、加硫ゴムから試験片を作製した。試験片の摩耗量を、岩本製作所製のランボーン摩耗試験機を用いて、荷重４０Ｎ、スリップ率３０％、温度２３℃、落砂量２０ｇ／分でＪＩＳ Ｋ６２６４に準じて測定した。比較例１の摩耗量を１００とした指数で、各例の摩耗量を表示した。指数が小さいほど摩耗量が少なく、耐摩耗性に優れる。 Abrasion resistance Unvulcanized rubber was vulcanized at 150 ° C. for 30 minutes to prepare a test piece from the vulcanized rubber. The amount of wear of the test piece was measured according to JIS K6264 at a load of 40 N, a slip ratio of 30%, a temperature of 23 ° C. and a falling sand amount of 20 g / min using a Lambourn wear tester manufactured by Iwamoto Seisakusho. The amount of wear of each example was indicated by an index with the amount of wear of Comparative Example 1 being 100. The smaller the index, the smaller the amount of wear and the better the wear resistance.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１・４における加硫ゴムの引裂強さと耐摩耗性とが、比較例４における加硫ゴムのそれらにくらべて優れていた。 The tear strength and abrasion resistance of the vulcanized rubber in Examples 1 and 4 were superior to those of the vulcanized rubber in Comparative Example 4.
　いっぽう、実施例１のムーニー粘度および引裂強さ・耐摩耗性は、実施例４のそれらより優れていた。 On the other hand, the Mooney viscosity and tear strength and abrasion resistance of Example 1 were superior to those of Example 4.
　実施例１～４における未加硫ゴムのムーニー粘度は、比較例１における未加硫ゴムのそれにくらべて低かった。すなわち、実施例１～４における未加硫ゴムの加工性は、比較例１における未加硫ゴムのそれにくらべて優れていた。 The Mooney viscosity of the unvulcanized rubber in Examples 1 to 4 was lower than that of the unvulcanized rubber in Comparative Example 1. That is, the processability of the unvulcanized rubber in Examples 1 to 4 was superior to that of the unvulcanized rubber in Comparative Example 1.
　なお、比較例５では、液状イソプレンゴムラテックスにおける分散媒の影響で、うまく混練りできなかった。 In Comparative Example 5, the kneading could not be carried out well due to the influence of the dispersion medium in the liquid isoprene rubber latex.
　実施例５～７におけるマスターバッチの作製
　天然ゴムラテックスに、液状イソプレンゴムラテックスを表３にしたがって添加し、撹拌し、スラリー添加前ゴムラテックスを得た。いっぽう、カーボンブラックを水に添加し、撹拌し、カーボンブラックスラリーを得た。カーボンブラックスラリーを、スラリー添加前ゴムラテックスに表３にしたがって加え、撹拌し、凝固剤としてギ酸をｐＨ４になるまで添加し、凝固物を得た。凝固物を、スクイザー式１軸押出脱水機で２００℃で脱水し、マスターバッチを得た。 Preparation of Masterbatch in Examples 5 to 7 A liquid isoprene rubber latex was added to a natural rubber latex according to Table 3 and stirred to obtain a rubber latex before adding a slurry. On the other hand, carbon black was added to water and stirred to obtain a carbon black slurry. The carbon black slurry was added to the rubber latex before slurry addition according to Table 3 and stirred, and formic acid as a coagulant was added until pH 4 to obtain a coagulum. The coagulated material was dewatered at 200 ° C. with a squeezer type single screw extruder dehydrator to obtain a masterbatch.
　比較例７におけるマスターバッチの作製
　カーボンブラックを水に添加し、撹拌し、カーボンブラックスラリーを得た。カーボンブラックスラリーを、天然ゴムラテックスに表３にしたがって加え、撹拌し、凝固剤としてギ酸をｐＨ４になるまで添加し、凝固物を得た。凝固物を、スクイザー式１軸押出脱水機で２００℃で脱水し、マスターバッチを得た。 Preparation of Masterbatch in Comparative Example 7 Carbon black was added to water and stirred to obtain a carbon black slurry. A carbon black slurry was added to a natural rubber latex according to Table 3, stirred, and formic acid as a coagulant was added until pH 4 to obtain a coagulum. The coagulated material was dewatered at 200 ° C. with a squeezer type single screw extruder dehydrator to obtain a masterbatch.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　未加硫ゴムの作製
　マスターバッチまたは天然ゴムに、硫黄と加硫促進剤とを除く配合剤を表４にしたがって添加し、神戸製鋼社製のＢ型バンバリーミキサーで混練りし、ゴム混合物を排出した。ゴム混合物と硫黄と加硫促進剤とをＢ型バンバリーミキサーで混練りし、未加硫ゴムを得た。 Preparation of unvulcanized rubber Compounding agents other than sulfur and a vulcanization accelerator are added to a master batch or natural rubber according to Table 4 and kneaded with a B-type Banbury mixer manufactured by Kobe Steel Co., Ltd. to discharge a rubber mixture did. The rubber mixture, sulfur and vulcanization accelerator were kneaded with a B-type Banbury mixer to obtain an unvulcanized rubber.
　未加硫ゴムおよび加硫ゴムの評価
　ムーニー粘度、引裂強さおよび耐摩耗性を、すでに述べた方法で評価した。各例のムーニー粘度は、比較例６のムーニー粘度を１００とした指数で表示した。指数が小さいほどムーニー粘度が低く、加工性に優れる。各例の引裂強さは、比較例６の引裂強さを１００とした指数で表示した。指数が大きいほど引裂強さに優れる。各例の摩耗量は、比較例６の摩耗量を１００とした指数で表示した。指数が小さいほど摩耗量が少なく、耐摩耗性に優れる。 Evaluation of Unvulcanized and Vulcanized Rubber The Mooney viscosity, tear strength and abrasion resistance were evaluated by the methods already described. The Mooney viscosity of each example was expressed as an index with the Mooney viscosity of Comparative Example 6 being 100. The smaller the index, the lower the Mooney viscosity and the better the processability. The tear strength of each example was expressed as an index with the tear strength of Comparative Example 6 as 100. The larger the index, the better the tear strength. The amount of wear of each example was indicated by an index with the amount of wear of Comparative Example 6 being 100. The smaller the index, the smaller the amount of wear and the better the wear resistance.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実施例５～７のムーニー粘度および引裂強さ・耐摩耗性は、比較例６のそれらより優れていた。
  The Mooney viscosity and tear strength / abrasion resistance of Examples 5 to 7 are superior to those of Comparative Example 6.

Claims (4)

  1. 　少なくとも天然ゴムラテックス、液状ゴムラテックスおよび充てん剤スラリーで凝固処理前混合液を作製する工程と、
    　前記凝固処理前混合液を凝固する工程とを含む、
    　マスターバッチの製造方法。     Preparing a mixed solution before coagulation treatment with at least natural rubber latex, liquid rubber latex and filler slurry,
    Solidifying the pre-solidification mixture, and
    Masterbatch production method.
  2. 　前記凝固処理前混合液を作製する前記工程は、前記天然ゴムラテックスに前記液状ゴムラテックスを添加し、添加後天然ゴムラテックスを得ることと、前記添加後天然ゴムラテックスおよび前記充てん剤スラリーを混合することとを含む、または
    　前記凝固処理前混合液を作製する前記工程は、前記天然ゴムラテックスおよび前記充てん剤スラリーを混合し、前記液状ゴムラテックスを添加することを含む、
    　請求項１に記載のマスターバッチの製造方法。     The step of preparing the mixed solution before the coagulation treatment is adding the liquid rubber latex to the natural rubber latex, obtaining a natural rubber latex after addition, and mixing the natural rubber latex and the filler slurry after the addition. Or the step of preparing the pre-solidification processing mixture includes mixing the natural rubber latex and the filler slurry and adding the liquid rubber latex.
    A method of producing a masterbatch according to claim 1.
  3. 　請求項１または２に記載のマスターバッチの製造方法で得られたマスターバッチと配合剤とを混練りする工程を含む、ゴム組成物の製造方法。 The manufacturing method of a rubber composition including the process of kneading | mixing the masterbatch obtained by the manufacturing method of the masterbatch of Claim 1 or 2, and a compounding agent.
  4. 　請求項１または２に記載のマスターバッチの製造方法を含む、タイヤの製造方法。
     
          A method for producing a tire, comprising the method for producing a masterbatch according to claim 1 or 2.

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013181051A (en) * 2012-02-29 2013-09-12 Toyo Tire & Rubber Co Ltd Rubber composition for tire base tread, method for manufacturing the same, and pneumatic tire
JP2017088747A (en) * 2015-11-11 2017-05-25 株式会社ブリヂストン Manufacturing method of wet master batch

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013181051A (en) * 2012-02-29 2013-09-12 Toyo Tire & Rubber Co Ltd Rubber composition for tire base tread, method for manufacturing the same, and pneumatic tire
JP2017088747A (en) * 2015-11-11 2017-05-25 株式会社ブリヂストン Manufacturing method of wet master batch

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