WO2014129564A1 - Procédé de production de mélange maître humide et mélange maître humide obtenu ainsi - Google Patents

Procédé de production de mélange maître humide et mélange maître humide obtenu ainsi Download PDF

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Publication number
WO2014129564A1
WO2014129564A1 PCT/JP2014/054089 JP2014054089W WO2014129564A1 WO 2014129564 A1 WO2014129564 A1 WO 2014129564A1 JP 2014054089 W JP2014054089 W JP 2014054089W WO 2014129564 A1 WO2014129564 A1 WO 2014129564A1
Authority
WO
WIPO (PCT)
Prior art keywords
wet masterbatch
producing
acid
natural rubber
carbon black
Prior art date
Application number
PCT/JP2014/054089
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English (en)
Japanese (ja)
Inventor
染野　和明
Original Assignee
株式会社ブリヂストン
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
Application filed by 株式会社ブリヂストン filed Critical 株式会社ブリヂストン
Priority to CN201480010365.0A priority Critical patent/CN105026464B/zh
Priority to JP2015501508A priority patent/JP6412491B2/ja
Publication of WO2014129564A1 publication Critical patent/WO2014129564A1/fr

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Classifications

    • 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
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00—Characterised by the use of natural rubber
    • C08J2307/02—Latex
    • 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
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C08J2321/02—Latex

Definitions

  • the present invention relates to a method for producing a wet masterbatch (hereinafter also simply referred to as “manufacturing method”) and a wet masterbatch obtained thereby, and more specifically, production while reducing the outflow of carbon black into a coagulating liquid.
  • the present invention relates to a method for producing a wet masterbatch having improved properties and a wet masterbatch obtained thereby.
  • a method using a wet masterbatch is known in order to improve processability and dispersibility when producing a rubber composition containing a filler.
  • This wet masterbatch mixes and solidifies a latex solution and a slurry solution containing a filler such as carbon black and silica, and separates the coagulated product from the coagulated liquid containing these coagulated products.
  • the product is dehydrated and dried (for example, Patent Document 1).
  • the solidification of the natural rubber latex and the slurry solution was started by putting both into the coagulation tank and mixing them, and the coagulation time was set until the carbon black in the coagulation tank became uniform.
  • the coagulation of the uncoagulated natural rubber latex was promoted by adding an acid.
  • the coagulation of the slurry solution and the natural rubber latex starts before the two are uniformly mixed, and the composition tends to be non-uniform, causing variations in the physical properties of the obtained coagulated product.
  • even in the case of adding an acid there is a case in which solidification progresses partly rapidly and the solidified product becomes a large mass in the solidification tank, which makes it difficult to discharge the solidified product. .
  • Patent Document 2 a stirring blade and a crushing blade are provided in a coagulation tank, and a solidified product is produced while stirring the slurry solution and the rubber solution with the stirring blade.
  • Manufacture of a wet masterbatch that improves the uniformity of the composition of the masterbatch and the convenience of taking out the coagulum by crushing with the crushing blades provided in the coagulation tank and adjusting the size of the coagulum. A method has been proposed.
  • the solidified product is separated from the coagulated liquid and dehydrated and dried as the final step.
  • drying of the coagulated material is performed using hot air, but it is performed while applying mechanical shearing force in order to efficiently dehydrate and further improve the dispersibility and uniformity of the filler.
  • a twin screw extruder to which a slit for dehydration is added may be used.
  • the solidified product is charged into the twin-screw extruder with the carbon black released into the coagulating liquid as described above, the carbon black flows out from the dehydration slit together with the coagulating liquid, and the quality is not stable. Had a problem.
  • the amount of solidified product added to the twin-screw extruder is increased in order to increase the production volume of wet masterbatch, the solidified water contained in the solidified material overflows in the charging unit, and at the same time carbon black The problem of leaking occurs.
  • This problem can be avoided by widening the gap of the dehydration slit of the twin-screw extruder, but if the gap of the dehydration slit is widened, the carbon black flowing out together with the coagulating liquid further increases, which is not preferable. . Therefore, in order to prevent the carbon black from flowing out, it is necessary to maintain the gap of the dewatering slit and suppress the amount of the solidified material so that water does not overflow from the charging part of the twin screw extruder. It is difficult to balance productivity.
  • an object of the present invention is to provide a method for producing a wet masterbatch with improved productivity while reducing the outflow of carbon black into the coagulating liquid, and a wet masterbatch obtained thereby.
  • the present inventor As a result of earnestly examining the manufacturing process of the wet masterbatch in order to solve the above problems, the present inventor said that after mixing the natural rubber latex and the slurry solution, the moisture content of the coagulum decreases as the mixing time increases. Obtained knowledge. In addition, after increasing the mixing time before acid addition and reducing the moisture content of the coagulated product, the coagulated product is crushed to release insufficiently incorporated carbon black into the coagulating solution, and then the acid is removed. Further knowledge was obtained that carbon black can be sufficiently incorporated into the coagulated material by adding and coagulating the natural rubber latex.
  • the method for producing the wet masterbatch of the present invention comprises a coagulating step of coagulating the slurry and the natural rubber latex by adding an acid after mixing the slurry solution containing carbon black and the natural rubber latex.
  • a drying step of drying the obtained solidified product comprising a drying step of drying the obtained solidified product, The solidified product generated before the addition of the acid is crushed, and then the solidified product is crushed even after the acid is added.
  • the coagulate of the slurry and the natural rubber latex is crushed after the coagulum formed before the acid is added has grown to a diameter of 70 to 200 mm.
  • the diameter of the solidified product is an average value calculated by arbitrarily taking 10 solidified products and measuring the maximum diameter and the minimum diameter of each solidified product with a ruler.
  • the wet masterbatch of the present invention is manufactured by the method for manufacturing a wet masterbatch of the present invention.
  • the wet masterbatch mixes a slurry solution in which fillers such as carbon black and silica are dispersed and natural rubber latex to coagulate to form a coagulated product, which is separated and taken out. It is manufactured by removing impurities such as a coagulant from the product, and then dehydrating and drying.
  • the wet masterbatch production method of the present invention was obtained by mixing a slurry solution containing carbon black and natural rubber latex, and then adding an acid to coagulate the slurry and natural rubber latex. And a drying step for drying the coagulated product.
  • the solidified material produced before adding an acid is crushed, and also the solidified material after adding an acid is also crushed.
  • natural rubber latex is a natural product. Therefore, even if it is mixed with a slurry solution containing a filler under the same conditions to form a coagulated product, it is always carbon. Black capture is not always the same. Therefore, even if the filler is apparently taken into the solidified product, carbon black may be released again when the solidified product is pulverized during mixing. Therefore, before adding the acid to promote the coagulation of the natural rubber latex and the slurry solution, the coagulated product is crushed, and carbon black that has not been sufficiently taken into the coagulated product is released into the coagulated liquid. By adding and coagulating the uncoagulated natural rubber latex, the carbon black is sufficiently taken into the coagulated product.
  • the diameter of the coagulum is preferably grown to 70 to 200 mm, and the moisture content of the coagulum is 45 to 70% by mass, more preferably the diameter of the coagulum is increased.
  • the water content is 55 to 65% by mass. If the water content of the coagulated product exceeds 70% by mass, the effect of the present invention cannot be sufficiently obtained.
  • the coagulated product is stirred in the liquid even if the moisture content is less than 45% by mass. is there.
  • the coagulated product is further crushed after the acid addition.
  • the size of the obtained solidified product can be made uniform, and a master batch having a uniform composition can be manufactured.
  • the solidified product is prevented from becoming a large lump in the solidification tank, resulting in a decrease in stirring efficiency and difficulty in discharging the solidified product.
  • the drying step in the method for producing a wet masterbatch of the present invention can be carried out using a general hot air type that has been usually employed in a method for producing a conventional wet masterbatch. From the viewpoint of productivity, and in order to further improve the dispersibility and uniformity of the filler, it is preferable to use a continuous extruder or a continuous multi-screw extruder, particularly preferably a twin-screw extruder having a dewatering slit. Can be used.
  • the wet masterbatch production method of the present invention was obtained by mixing a slurry solution containing carbon black and natural rubber latex, and then adding an acid to coagulate the slurry and natural rubber latex.
  • the method for producing a wet masterbatch of the present invention since the incorporation of carbon black into the coagulated product is excellent, a metal mesh, a centrifugal dehydrator, etc.
  • a dehydration treatment may be performed in advance using a metal mesh, a stretching dehydrator, or the like.
  • the concentration of the rubber component in the natural rubber latex is preferably 15 to 40% by mass. If the concentration of the rubber component is less than 15% by mass, a huge mixing and stirring vessel is required, which is not practical. If the concentration exceeds 40% by mass, the viscosity of the natural rubber latex increases so much that it is used during transportation and mixing in the manufacturing process. There is a risk of deteriorating workability.
  • a surfactant, an emulsifier, and the like may be appropriately selected and added to the natural rubber latex from the viewpoint of quality improvement and stabilization.
  • the slurry solution may be formed by dispersing a filler in a solvent.
  • a solvent In addition to water as a solvent, alcohols such as methanol, ethanol, isopropyl alcohol, aromatic, aliphatic, alicyclic, halogen
  • An organic solvent such as a fluorinated hydrocarbon solvent can be mentioned. These solvents may be used alone or in combination of two or more.
  • an inorganic filler such as silica may be added as a filler. These fillers may be used alone or in combination of two or more.
  • those of SRF, GPF, FEF, HAF, ISAF, and SAF grade can be suitably used, but those of HAF, ISAF, and SAF grade are preferred.
  • silica wet silica, dry silica, colloidal silica, and the like can be preferably used, but wet silica is preferable.
  • formic acid, sulfuric acid or the like can be used as the acid as the coagulant.
  • the concentration of the filler in the slurry solution is preferably 5 to 15% by mass. If the concentration of the filler is less than 5% by mass, a huge mixing and stirring vessel is required, which is not practical. If the concentration exceeds 15% by mass, the viscosity of the slurry solution is very high, and it is added during transportation and mixing in the manufacturing process. There is a risk of hindrance.
  • the slurry solution may contain, for example, a surfactant, an emulsifier, a pH adjuster, and the like from the viewpoint of quality improvement and stabilization. It can select suitably and mix
  • the slurry solution can be produced using a known method, and is not particularly limited, and is a rotor-stator type high shear mixer, high-pressure homogenizer, ultrasonic homogenizer, colloid mill. Etc. may be used.
  • a slurry solution can be prepared by adding water to a colloid mill, slowly dropping the filler while stirring, and then circulating the mixture with a surfactant in a homogenizer at a constant pressure and a constant temperature.
  • the pressure is usually in the range of 10 to 1000 kPa, preferably in the range of 200 to 800 kPa. It is also possible to mix a filler and water at a certain ratio, introduce these mixed solutions from one end of an elongated conduit, and generate a continuous flow of slurry having a homogeneous composition under the condition of vigorous hydraulic stirring. it can.
  • the wet masterbatch of the present invention is manufactured by the method for manufacturing a wet masterbatch of the present invention.
  • the wet masterbatch of the present invention can be used as a rubber composition by mixing with other rubber components, but preferably contains 30% by mass or more of the rubber component in the wet masterbatch of the present invention with respect to the entire rubber component.
  • examples of other rubber components used in addition to the wet masterbatch of the present invention include ordinary natural rubber and diene-based synthetic rubber.
  • diene-based synthetic rubber examples include a styrene-butadiene copolymer ( SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, and mixtures thereof.
  • SBR styrene-butadiene copolymer
  • BR polybutadiene
  • IR polyisoprene
  • IIR butyl rubber
  • a vulcanizing agent such as a vulcanizing agent, a vulcanization accelerator, anti-aging agent, a scorch inhibiting agent, zinc white, and a stearic acid
  • the rubber composition can be used for applications such as anti-vibration rubber, belts, hoses, and other industrial products as well as tire applications.
  • it is suitably used as tire rubber, and can be applied to all tire members such as tread rubber, side rubber, ply coating rubber, bead filler rubber, and belt coating rubber.
  • Examples 1 to 5 400 kg of natural rubber latex and 500 kg of the carbon slurry solution were put into a coagulation tank (MX1500 manufactured by Tsukishima Kikai Co., Ltd.), mixed and coagulated at 60 rpm.
  • the mixing time is as shown in Tables 1 and 2.
  • the crushing blade in the coagulation tank was rotated at 1500 rpm for 10 minutes to crush the solidified product.
  • formic acid was added until the coagulation solution had a pH of 4.7 while continuing stirring at 60 rpm.
  • the coagulated material was crushed by rotating the crushing blade in the coagulation tank at 1500 rpm for 10 minutes while continuing the stirring.
  • the obtained solidified product was put into a twin-screw extruder, dehydrated and dried to produce a wet masterbatch.
  • KTX46 manufactured by Kobe Steel, Ltd. was used, and the operating conditions were 350 rpm and the temperature was 120 ° C.
  • Tables 1 and 2 show the width of the dehydration slit and the amount of the coagulated product.
  • MX1500 manufactured by Tsukishima Kikai Co., Ltd.
  • the operating conditions of the twin screw extruder were 350 rpm, the temperature was 120 ° C., and the width of the dehydration slit and the amount of solidified product were as shown in Tables 1 and 2.
  • the wet masterbatch production method of the present invention can improve the productivity of the wet masterbatch while reducing the outflow of carbon black into the coagulation liquid.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de production d'un mélange maître humide qui améliore la productivité tout en réduisant l'écoulement de noir de carbone dans le liquide de coagulation, et un mélange maître humide obtenu ainsi. Le procédé a : une étape de coagulation pour mélanger un latex de caoutchouc naturel et une solution de bouillie contenant du noir de carbone, puis coaguler la bouillie et le latex de caoutchouc naturel par ajout d'acide ; et une étape de séchage pour séparer le coagulum obtenu à partir du liquide de coagulation, éliminer l'humidité dans le coagulum à l'aide d'un malaxeur ayant une fente de déshydratation et sécher le coagulum. Le coagulum produit ainsi est broyé avant que l'acide ne soit ajouté, puis le coagulum est également broyé après que l'acide est ajouté.
PCT/JP2014/054089 2013-02-25 2014-02-20 Procédé de production de mélange maître humide et mélange maître humide obtenu ainsi WO2014129564A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201480010365.0A CN105026464B (zh) 2013-02-25 2014-02-20 湿法母炼胶的制造方法和因此获得的湿法母炼胶
JP2015501508A JP6412491B2 (ja) 2013-02-25 2014-02-20 ウエットマスターバッチの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013034844 2013-02-25
JP2013-034844 2013-02-25

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WO2014129564A1 true WO2014129564A1 (fr) 2014-08-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108164768A (zh) * 2017-12-28 2018-06-15 浙江传化合成材料有限公司 一种石墨烯母炼胶的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07252364A (ja) * 1994-03-14 1995-10-03 Japan Synthetic Rubber Co Ltd 重合体ラテックスの凝固方法
JP2011032373A (ja) * 2009-07-31 2011-02-17 Toyo Tire & Rubber Co Ltd ウェットマスターバッチの製造方法
JP2012136574A (ja) * 2010-12-24 2012-07-19 Toyo Tire & Rubber Co Ltd ウェットマスターバッチの製造方法及びタイヤ用ゴム組成物及び空気入りタイヤ
JP2012153763A (ja) * 2011-01-24 2012-08-16 Sumitomo Rubber Ind Ltd 複合体、その製造方法、ゴム組成物及び空気入りタイヤ

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4909517B2 (ja) * 2005-02-03 2012-04-04 株式会社ブリヂストン タイヤ用ゴム組成物
WO2009116543A1 (fr) * 2008-03-18 2009-09-24 株式会社ブリヂストン Procédé de fabrication d'un mélange maître humide et mélange maître humide
US9616712B2 (en) * 2009-03-16 2017-04-11 Bridgestone Corporation Process for producing rubber wet master batch, rubber composition and tire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07252364A (ja) * 1994-03-14 1995-10-03 Japan Synthetic Rubber Co Ltd 重合体ラテックスの凝固方法
JP2011032373A (ja) * 2009-07-31 2011-02-17 Toyo Tire & Rubber Co Ltd ウェットマスターバッチの製造方法
JP2012136574A (ja) * 2010-12-24 2012-07-19 Toyo Tire & Rubber Co Ltd ウェットマスターバッチの製造方法及びタイヤ用ゴム組成物及び空気入りタイヤ
JP2012153763A (ja) * 2011-01-24 2012-08-16 Sumitomo Rubber Ind Ltd 複合体、その製造方法、ゴム組成物及び空気入りタイヤ

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108164768A (zh) * 2017-12-28 2018-06-15 浙江传化合成材料有限公司 一种石墨烯母炼胶的制备方法

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CN105026464A (zh) 2015-11-04
CN105026464B (zh) 2018-07-10
JP6412491B2 (ja) 2018-10-24
JPWO2014129564A1 (ja) 2017-02-02

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