WO2017061605A1 - Procédé de production d'une composition de caoutchouc - Google Patents

Procédé de production d'une composition de caoutchouc Download PDF

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Publication number
WO2017061605A1
WO2017061605A1 PCT/JP2016/079963 JP2016079963W WO2017061605A1 WO 2017061605 A1 WO2017061605 A1 WO 2017061605A1 JP 2016079963 W JP2016079963 W JP 2016079963W WO 2017061605 A1 WO2017061605 A1 WO 2017061605A1
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Prior art keywords
cellulose
rubber composition
cellulose nanofiber
water
dispersion
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PCT/JP2016/079963
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English (en)
Japanese (ja)
Inventor
康太郎 伊藤
丈史 中谷
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日本製紙株式会社
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Application filed by 日本製紙株式会社 filed Critical 日本製紙株式会社
Priority to JP2017514370A priority Critical patent/JP6153694B1/ja
Priority to CN201680055972.8A priority patent/CN108026289B/zh
Publication of WO2017061605A1 publication Critical patent/WO2017061605A1/fr

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    • 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
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C08L21/02—Latex

Definitions

  • the present invention relates to a method for producing a rubber composition.
  • cellulose nanofiber which improves various strengths in a rubber composition, such as tensile strength, has been known by incorporating into a rubber composition a material produced by finely pulverizing plant fibers to the nano level. .
  • Patent Document 1 discloses a rubber / short fiber masterbatch obtained by stirring and mixing cellulose short fibers having an average diameter of less than 0.5 ⁇ m and rubber latex.
  • a short fiber having an average fiber diameter of less than 0.5 ⁇ m is preliminarily fibrillated in water, and this is mixed with a rubber latex and dried to uniformly distribute the short fiber in the rubber. It is said that by using this rubber / short fiber master batch, a rubber composition having a balance between rubber reinforcement and fatigue resistance can be obtained.
  • Patent Document 2 shows a method for redispersing dried solids of cellulose nanofibers in water.
  • an object of the present invention is to provide a method for producing a rubber composition having a sufficiently improved reinforcing property by containing cellulose nanofibers at a relatively high solid content concentration.
  • the present invention provides the following.
  • a method for producing a rubber composition containing cellulose nanofibers The manufacturing method of a rubber composition including the process of mixing the dry solid substance containing a cellulose nanofiber, and the aqueous dispersion containing a rubber component.
  • the method for producing a rubber composition according to (1) further comprising a step of removing the dispersion medium from the dispersion of cellulose nanofibers to prepare the dry solid.
  • (3) The production of the rubber composition according to (1), wherein the dry solid containing the cellulose nanofiber contains 5 to 50% by weight of a water-soluble polymer based on the absolutely dry solid content of the cellulose nanofiber.
  • the dry solid containing the cellulose nanofiber is obtained by removing the dispersion medium from the dispersion containing the cellulose nanofiber and the water-soluble polymer with a drum dryer. (1) or (3) The manufacturing method of the rubber composition of description. (5) The dry solid containing the cellulose nanofiber is obtained by adjusting the pH of the dispersion containing the cellulose nanofiber and the water-soluble polymer to 9 to 11, and then removing the dispersion medium. ), (3) or (4). The method for producing a rubber composition according to any one of (4). (6) The method for producing a rubber composition according to (2), wherein the dispersion of cellulose nanofibers contains 5 to 50% by weight of a water-soluble polymer based on the absolutely dry solid content of cellulose nanofibers.
  • the dispersion of the cellulose nanofiber contains a water-soluble polymer, and in the adjusting step, the dispersion medium is removed from the dispersion containing the cellulose nanofiber and the water-soluble polymer by a drum dryer.
  • the method for producing a rubber composition according to (6) Or the method for producing a rubber composition according to (6).
  • the dispersion of the cellulose nanofiber contains a water-soluble polymer, and after adjusting the pH of the dispersion containing the cellulose nanofiber and the water-soluble polymer to 9 to 11 in the preparation step,
  • the cellulose nanofiber has a degree of carboxymethyl substitution of 0.01 to 0.50 per glucose unit of the cellulose nanofiber.
  • X to Y includes X and Y which are their end values. “X or Y” means either X or Y, or both.
  • the cellulose nanofiber is a fine fiber having an average fiber diameter of about 4 to 500 nm and an average aspect ratio of 100 or more, and can be obtained by fibrillating an unmodified or chemically modified cellulose raw material.
  • chemical modification methods include oxidation, etherification, Phosphorylation, esterification, silane coupling, fluorination, cationization and the like can be performed, but from the viewpoint of affinity with rubber, it is preferably chemically modified, and among them, an N-oxyl compound is used.
  • the cellulose raw material may be a plant (for example, wood, bamboo, hemp, jute, kenaf, farmland waste, cloth, pulp (coniferous unbleached kraft pulp (NUKP), coniferous bleached kraft pulp (NBKP), broadleaf tree not yet).
  • NUKP unbleached kraft pulp
  • NKP coniferous bleached kraft pulp
  • cellulose fibers derived from plants or microorganisms More preferably, it is a cellulose fiber derived from a plant.
  • the fiber diameter of the cellulose fiber raw material used in the present invention is not particularly limited, and the number average fiber diameter is 1 ⁇ m to 1 mm. What has undergone general purification is about 50 ⁇ m. For example, when a chip or the like having a size of several centimeters is refined, it is preferable to perform a mechanical treatment with a disintegrator such as a refiner or a beater to make it about 50 ⁇ m.
  • the cellulose raw material dispersion is preferably water.
  • the oxidation of the cellulose raw material can be performed using a known method, and is not particularly limited. However, the amount of the carboxyl group is 0.6 mmol / g to 2.0 mmol with respect to the absolute dry weight of the cellulose nanofiber. It is preferable to adjust to / g.
  • oxidized cellulose is obtained by oxidizing cellulose in water in the presence of an N-oxyl compound and a compound selected from the group consisting of bromide, iodide or a mixture thereof. Can do.
  • an N-oxyl compound refers to a compound capable of generating a nitroxy radical.
  • any compound can be used as long as it promotes the target oxidation reaction.
  • the amount of the N-oxyl compound used is not particularly limited as long as it is a catalytic amount capable of oxidizing the cellulose as a raw material.
  • 0.01 to 10 mmol is preferable, 0.01 to 1 mmol is more preferable, and 0.05 to 0.5 mmol is more preferable with respect to 1 g of absolutely dry cellulose. Further, it is preferably about 0.1 to 4 mmol / L with respect to the reaction system.
  • Bromide is a compound containing bromine, examples of which include alkali metal bromides that can dissociate and ionize in water.
  • an iodide is a compound containing iodine, and examples thereof include alkali metal iodide.
  • the amount of bromide or iodide used can be selected as long as the oxidation reaction can be promoted.
  • the total amount of bromide and iodide is, for example, preferably 0.1 to 100 mmol, more preferably 0.1 to 10 mmol, and further preferably 0.5 to 5 mmol with respect to 1 g of absolutely dry cellulose.
  • oxidizing agent known ones can be used, and for example, halogen, hypohalous acid, halous acid, perhalogen acid or salts thereof, halogen oxide, peroxide and the like can be used.
  • sodium hypochlorite is preferable because it is inexpensive and has a low environmental impact.
  • the appropriate amount of the oxidizing agent used is, for example, preferably 0.5 to 500 mmol, more preferably 0.5 to 50 mmol, still more preferably 1 to 25 mmol, and most preferably 3 to 10 mmol with respect to 1 g of absolutely dry cellulose. . Further, for example, 1 to 40 mol is preferable with respect to 1 mol of the N-oxyl compound.
  • the reaction temperature is preferably 4 to 40 ° C., and may be room temperature of about 15 to 30 ° C.
  • a carboxyl group is generated in the cellulose, so that the pH of the reaction solution is reduced.
  • an alkaline solution such as an aqueous sodium hydroxide solution is added to maintain the pH of the reaction solution at about 8 to 12, preferably about 10 to 11.
  • the reaction medium is preferably water because it is easy to handle and hardly causes side reactions.
  • the reaction time in the oxidation reaction can be appropriately set according to the progress of the oxidation, and is usually 0.5 to 6 hours, for example, about 0.5 to 4 hours.
  • the oxidation reaction may be performed in two stages. For example, by oxidizing the oxidized cellulose obtained by filtration after the completion of the first-stage reaction again under the same or different reaction conditions, the efficiency is not affected by the reaction inhibition by the salt generated as a by-product in the first-stage reaction. Can be oxidized well.
  • Another example of the carboxylation (oxidation) method is a method of oxidizing by contacting a gas containing ozone and a cellulose raw material.
  • oxidation reaction By this oxidation reaction, at least the hydroxyl groups at the 2nd and 6th positions of the glucopyranose ring are oxidized and the cellulose chain is decomposed.
  • the ozone concentration in the gas containing ozone is preferably 50 to 250 g / m 3 , more preferably 50 to 220 g / m 3 .
  • the amount of ozone added to the cellulose raw material is preferably 0.1 to 30 parts by weight, and more preferably 5 to 30 parts by weight when the solid content of the cellulose raw material is 100 parts by weight.
  • the ozone treatment temperature is preferably 0 to 50 ° C., and more preferably 20 to 50 ° C.
  • the ozone treatment time is not particularly limited, but is about 1 to 360 minutes, and preferably about 30 to 360 minutes. When the conditions for the ozone treatment are within these ranges, the cellulose can be prevented from being excessively oxidized and decomposed, and the yield of oxidized cellulose is improved.
  • an additional oxidation treatment may be performed using an oxidizing agent.
  • the oxidizing agent used for the additional oxidation treatment is not particularly limited, and examples thereof include chlorine compounds such as chlorine dioxide and sodium chlorite, oxygen, hydrogen peroxide, persulfuric acid, and peracetic acid. For example, these oxidizing agents can be dissolved in a polar organic solvent such as water or alcohol to prepare an oxidizing agent solution, and a cellulose raw material can be immersed in the solution for additional oxidation treatment.
  • the amount of the carboxyl group, carboxylate group, and aldehyde group of the cellulose fiber can be adjusted by controlling the amount of the oxidizing agent added and the reaction time.
  • the carboxyl group content is measured, for example, by preparing 60 ml of a 0.5 wt% slurry (aqueous dispersion) of oxidized cellulose, adding 0.1 M hydrochloric acid aqueous solution to pH 2.5, and then adding 0.05 N sodium hydroxide.
  • the carboxymethylation of the cellulose raw material can be performed using a known method, and is not particularly limited.
  • the substitution degree of carboxymethyl group per anhydroglucose unit of cellulose is 0.01 to 0.50. It is preferable to adjust to.
  • the following production method can be mentioned, but it may be synthesized by a conventionally known method or a commercially available product may be used. Cellulose is used as a starting material, and 3 to 20 times by weight of water or lower alcohol or both are used as a solvent.
  • the lower alcohol examples include methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol, isobutanol, tertiary butanol and the like, or two or more mixed media.
  • the mixing ratio of the lower alcohol when used as a mixed solvent is 60 to 95% by weight.
  • the mercerizing agent 0.5 to 20 times moles of alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide is used per anhydroglucose residue of the bottoming material.
  • a bottoming raw material, a solvent, and a mercerizing agent are mixed, and a mercerization process is performed at a reaction temperature of 0 to 70 ° C., preferably 10 to 60 ° C., and a reaction time of 15 minutes to 8 hours, preferably 30 minutes to 7 hours.
  • a carboxymethylating agent is added in an amount of 0.05 to 10.0 times mol per glucose residue, a reaction temperature of 30 to 90 ° C., preferably 40 to 80 ° C., and a reaction time of 30 minutes to 10 hours, preferably 1 hour.
  • the etherification reaction is performed for ⁇ 4 hours.
  • the carboxymethyl substitution degree per glucose unit it can obtain by the following method, for example. That is, 1) About 2.0 g of carboxymethylated cellulose fiber (absolutely dry) is precisely weighed and put into a 300 mL conical stoppered Erlenmeyer flask. 2) Add 100 mL of a solution of 100 mL of special concentrated nitric acid to 1000 mL of nitric acid methanol and shake for 3 hours to convert the carboxymethyl cellulose salt (CM cellulose) into hydrogenated CM cellulose. 3) Weigh accurately 1.5 to 2.0 g of hydrogenated CM-modified cellulose (absolutely dry), and put into a 300 mL Erlenmeyer flask with a stopper.
  • CM cellulose carboxymethyl cellulose salt
  • the cationization of the cellulose raw material can be performed using a known method.
  • cationization for example, ammonium, phosphonium, sulfonium, groups having these ammonium, phosphonium or sulfonium can be present in the cellulose molecule, but groups having ammonium are preferred, and groups containing quaternary ammonium are particularly preferred.
  • the specific cationization method is not particularly limited.
  • a cellulose raw material may be prepared by using a cationizing agent such as glycidyltrimethylammonium chloride, 3-chloro-2hydroxypropyltrialkylammonium hydride or a halohydrin type thereof and a catalyst.
  • Cationic modification having a group containing quaternary ammonium by reacting an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) in the presence of water or an alcohol having 1 to 4 carbon atoms, or both.
  • Cellulose can be obtained.
  • the degree of cation substitution per glucose unit of the cation-modified cellulose obtained is controlled by controlling the addition amount of the cationizing agent to be reacted, the composition ratio of water and an alcohol having 1 to 4 carbon atoms. Can be adjusted.
  • the degree of substitution herein refers to the number of substituents introduced per unit structure (glucopyranose ring) constituting cellulose.
  • the degree of cation substitution per glucose unit of cationized cellulose is preferably 0.01 to 0.40.
  • the celluloses repel each other electrically. For this reason, the cellulose which introduce
  • the cation substitution degree per glucose unit is smaller than 0.01, nano-defibration cannot be sufficiently performed.
  • the degree of cation substitution per glucose unit is larger than 0.40, the fiber form cannot be maintained because it swells or dissolves and may not be obtained as a nanofiber.
  • the degree of cation substitution per glucose unit is calculated by the following formula after measuring the nitrogen content with a total nitrogen analyzer TN-10 (Mitsubishi Chemical Corporation) after drying the sample (cation-modified cellulose). can do.
  • the degree of substitution referred to here represents the average value of the number of moles of substituents per mole of anhydroglucose unit.
  • an apparatus for defibrating is not particularly limited, but a strong shearing force is applied to the aqueous dispersion using an apparatus such as a high-speed rotation type, a colloid mill type, a high pressure type, a roll mill type, or an ultrasonic type. Is preferred.
  • a wet high-pressure or ultrahigh-pressure homogenizer that can apply a pressure of 50 MPa or more to the aqueous dispersion and can apply a strong shearing force.
  • the pressure is more preferably 100 MPa or more, and further preferably 140 MPa or more.
  • the cellulose nanofibers are pretreated using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. Is also possible.
  • the solid content concentration as the cellulose fiber raw material is 0.1 wt% or more, preferably 0.2 wt% or more, particularly 0.3 wt% or more, and 10 wt% or less, particularly 6 It is preferable that it is below wt%.
  • the solid content concentration is too low, the amount of liquid is too large with respect to the amount of the cellulose fiber raw material to be processed, resulting in poor efficiency, and when the solid content concentration is too high, the fluidity is deteriorated.
  • the water-soluble polymer refers to a polymer compound that dissolves in water, such as cellulose derivatives (carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, ethylcellulose), xanthan gum, xyloglucan, dextrin, dextran, carrageenan, locust bean.
  • the dry solid refers to a solid obtained by removing the dispersion medium from a dispersion of cellulose nanofibers.
  • the dry solid refers to a completely dry or wet state, and refers to a solid medium having a dispersion medium of 12% by weight or less.
  • the dry solid substance which consists of a cellulose nanofiber or this and a dispersion medium below this amount or the dry solid substance which consists of a cellulose nanofiber and a water-soluble polymer or these and a dispersion medium below this amount is mentioned.
  • the dispersion medium include water and aqueous organic solvents, but water is preferable. Removing the dispersion medium means removing the dispersion medium by dehydrating (dedispersing medium) or drying the dispersion.
  • a solid or liquid water-soluble polymer may be dissolved or dispersed in the aqueous dispersion. Further, by adjusting the pH of the dispersion to 9 to 11 and then dehydrating or drying, a dry solid having good affinity between the rubber composition and the cellulose nanofiber can be obtained.
  • the dispersion of cellulose nanofibers refers to a liquid in which cellulose nanofibers are dispersed in a dispersion medium.
  • the blending amount of the water-soluble polymer in the dry solid containing the cellulose nanofiber and the water-soluble polymer is 5 to 50% by weight with respect to the absolutely dry solid content of the cellulose nanofiber. preferable. If it is less than 5% by weight, the effect of sufficient redispersibility is hardly exhibited. On the other hand, when it exceeds 50% by weight, problems such as a decrease in viscosity characteristics and dispersion stability, which are characteristics of cellulose nanofibers, may occur.
  • the method for dehydrating or drying the dispersion or mixed solution may be any conventionally known method, and examples thereof include spray drying, pressing, air drying, hot air drying, and vacuum drying.
  • Examples of the drying apparatus specifically used in the method of the present invention are as follows. That is, continuous tunnel dryer, band dryer, vertical dryer, vertical turbo dryer, multi-stage disk dryer, aeration dryer, rotary dryer, air dryer, spray dryer dryer, spray dryer , Cylindrical dryers, drum dryers, screw conveyor dryers, rotary dryers with heating tubes, vibration transport dryers, batch-type box dryers, aeration dryers, vacuum box dryers, stirring dryers, etc.
  • These drying apparatuses can be used alone or in combination of two or more. Among these, it is preferable to use a drum drying apparatus from the viewpoint of energy efficiency because the heat energy is uniformly supplied directly to an object to be dried.
  • the drum drying apparatus is also preferable in that it can immediately collect a dried product without applying heat more than necessary.
  • the rubber component is a raw material of rubber and is crosslinked to become rubber.
  • a rubber component for natural rubber and a rubber component for synthetic rubber, either one may be used in the present invention, or both may be combined.
  • a rubber component for natural rubber or the like is referred to as “natural rubber polymer” or the like.
  • Natural rubber (NR) polymer is a natural rubber polymer in a narrow sense without chemical modification; natural rubber polymer chemically modified such as chlorinated natural rubber polymer, chlorosulfonated natural rubber polymer, epoxidized natural rubber polymer; Rubber polymer; deproteinized natural rubber polymer.
  • Synthetic rubber polymers include, for example, butadiene rubber (BR) polymer, styrene-butadiene copolymer rubber (SBR) polymer, isoprene rubber (IR) polymer, acrylonitrile-butadiene rubber (NBR) polymer, chloroprene rubber polymer, styrene-isoprene copolymer.
  • Diene rubber polymers such as polymer rubber polymer, styrene-isoprene-butadiene copolymer rubber polymer, isoprene-butadiene copolymer rubber polymer; butyl rubber (IIR) polymer, ethylene-propylene rubber (EPM, EPDM) polymer, acrylic rubber (ACM) polymer, epichlorohydrin rubber (CO, ECO) polymer, fluoro rubber (FKM) polymer, silicone rubber (Q) polymer, urethane rubber (U) polymer, chlorosulfonated polyethylene Down (CSM) non-diene-based rubber polymers such as polymers.
  • These rubber polymers may be used alone or in combination. Among these, diene rubber is preferable. These may be used alone or in combination of two or more.
  • the rubber component is preferably used as an aqueous dispersion (latex) of the rubber component.
  • the aqueous dispersion (latex) containing a rubber component is a system (emulsion) in which fine particles of the rubber component are stably dispersed in an aqueous solution, and the solid content concentration of the rubber component is usually 30 to 70. %.
  • the aqueous dispersion of the rubber component preferably has a pH of 7-12.
  • the weight ratio of the cellulose nanofiber is 1 to 50% by weight with respect to the absolutely dry solid content of the rubber component. Is preferred. When the ratio is less than 1% by weight, a sufficient tensile strength improvement effect is not exhibited when a crosslinked rubber composition is obtained. On the other hand, when the ratio exceeds 50% by weight, the processability of the rubber composition decreases.
  • the lower limit of the total solid concentration of the mixture obtained in this step is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 40% by weight or more. Further, the upper limit of the concentration is preferably 100% by weight or less, more preferably 90% by weight or less, and further preferably 80% by weight or less.
  • the production method of the present invention prepares a mixture having a high solid content concentration by subjecting a dry solid obtained by removing a dispersion medium from a dispersion containing cellulose nanofibers, which has not been studied in the past, to mixing with a rubber component. To do. For this reason, the manufacturing method of this invention is excellent in work efficiency and productivity. Also, by dispersing at a high solid content concentration, sufficient shear stress is applied to the cellulose nanofibers, and redispersibility is improved to produce a rubber composition with excellent mechanical strength with high work efficiency and productivity. Achieved that.
  • the rubber composition of the present invention is produced by removing water or the like derived from latex or dry solid from a mixture of the rubber component and the dry solid.
  • the dry solid contains a dispersion medium other than water
  • the water and the dispersion medium are removed from the mixture of the rubber component and the dry solid.
  • water or a dispersion medium is also referred to as a “liquid medium”.
  • the method for removing the liquid medium is not particularly limited, and the mixture may be dried as it is in an oven, or may be dehydrated or dried after coagulation. At this time, the pH may be adjusted to 2-6.
  • the rubber composition and other necessary rubbers and compounding agents are mixed by a conventionally known method using, for example, a rubber kneader or the like, and crosslinked by a conventionally known method (when sulfur is used, “ Vulcanization)).
  • the rubber composition includes a composition before crosslinking and a crosslinked composition.
  • the composition before crosslinking is referred to as “uncrosslinked rubber composition”, and the composition after crosslinking is also referred to as “crosslinked rubber composition”.
  • compounding agents conventionally used in the rubber industry include, for example, reinforcing agents, silane coupling agents, vulcanizing agents, stearic acid, vulcanization accelerators, Vulcanization accelerators, oils, curing resins, waxes, anti-aging agents, and the like can be blended.
  • any of those used for tires can be suitably used, but it is particularly preferable to use at least one of carbon black and silica.
  • the use of the vulcanized rubber composition of the present invention is not particularly limited, but is suitable for tires due to its characteristics.
  • it can be used as a pneumatic tire for passenger cars, trucks, buses, heavy vehicles and the like.
  • the oxidized pulp obtained in the above step was adjusted to 1.0% (w / v) with water and treated three times with an ultrahigh pressure homogenizer (20 ° C., 150 MPa) to obtain a cellulose nanofiber dispersion.
  • the obtained fiber had an average fiber diameter of 4 nm and an aspect ratio of 150.
  • the carboxymethylated pulp was made into 1% (w / v) solid content with water, and fibrillated by treating with a high pressure homogenizer 5 times at 20 ° C. and a pressure of 150 MPa to obtain carboxymethylated cellulose fibers.
  • the obtained fiber had an average fiber diameter of 50 nm and an aspect ratio of 120.
  • the cation-modified pulp was treated at a solid concentration of 1% (w / v) and treated twice with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa.
  • the obtained fiber had an average fiber diameter of 50 nm and an aspect ratio of 120.
  • Carboxymethyl cellulose (trade name: F350HC-4) was added to the 0.7% by weight aqueous dispersion of the above oxidized cellulose nanofibers in an amount of 30% by weight with respect to the cellulose nanofibers, and 60% by a TK homomixer (12,000 rpm). Stir for minutes. To this aqueous dispersion, 0.5% by weight of an aqueous sodium hydroxide solution was added to adjust the pH to 9, and then a vapor pressure of 0.5 MPa.
  • the obtained unvulcanized rubber composition sheet was sandwiched between molds and press vulcanized at 150 ° C. for 10 minutes to obtain a vulcanized rubber sheet having a thickness of 2 mm.
  • the obtained vulcanized rubber sheet was cut into a test piece having a predetermined shape, and in accordance with JIS K6251 “vulcanized rubber and thermoplastic rubber—determining tensile properties”, the tensile strength was determined at 100% strain. The stress at 300% strain and the breaking strength were measured. The larger each value, the better the vulcanized rubber composition is reinforced and the better the mechanical strength.
  • a vulcanized rubber composition was produced using a mixture having a total solid content of 68.25% by weight, which was very high, and the cellulose nanofibers were well dispersed in the rubber matrix. As shown, excellent mechanical properties were obtained.
  • Example 2> It carried out similarly to Example 1 except having changed the cellulose nanofiber into the carboxymethylated cellulose nanofiber manufactured by said method.
  • Example 3> It carried out similarly to Example 1 except having changed the cellulose nanofiber into the cationized cellulose nanofiber manufactured by said method.
  • Example 4> When the aqueous dispersion of cellulose nanofibers was dried, the same procedure as in Example 1 was carried out except that the cellulose nanofibers were dried alone without mixing carboxymethylcellulose.
  • Example 1 when obtaining a masterbatch, it carried out like Example 1 except not using the mixed dry solid substance of a cellulose nanofiber and carboxymethylcellulose.
  • Example 2 when obtaining a master batch, instead of using a dried cellulose nanofiber solid material, an undried cellulose nanofiber aqueous dispersion (solid content concentration: 1.0% by weight) was used. 1 was performed. The amount of cellulose nanofibers relative to the rubber component was the same as in Example 1.
  • Example 3 when obtaining a masterbatch, instead of using a dried cellulose nanofiber solid material, an undried cellulose nanofiber aqueous dispersion (solid content concentration: 1.0% by weight) was used except that Performed in the same manner as 2. The amount of cellulose nanofibers relative to the rubber component was the same as in Example 2.
  • Example 4 when obtaining a masterbatch, instead of using a dried cellulose nanofiber solid material, an undried cellulose nanofiber aqueous dispersion (solid content concentration: 1.0% by weight) was used. This was carried out in the same manner as in 3. The amount of cellulose nanofibers relative to the rubber component was the same as in Example 3.
  • Example 1 to 3 using a mixed dry solid of cellulose nanofibers and a water-soluble polymer and in Example 4 using a dry solid of cellulose nanofibers comparison was made without using cellulose nanofibers.
  • Example 1 and Comparative Examples 2 to 4 using an undried cellulose nanofiber aqueous dispersion the stress at 100% and 300% strain and the breaking strength are clearly large, so that the vulcanized rubber composition is excellent. It can be seen that it is reinforced and has excellent mechanical strength. This is presumably because the mixture of the rubber component and the cellulose nanofiber has a high solid content concentration, so that a sufficient shear stress (shear stress) is generated at the time of stirring and the dispersibility of the cellulose nanofiber is increased.
  • the vulcanized rubber composition can be obtained from the mixture having a high solid content concentration, the present invention is clearly excellent in productivity and workability.

Abstract

La présente invention concerne le problème de fournir un procédé de production d'une composition de caoutchouc contenant des nanofibres de cellulose dans laquelle les nanofibres de cellulose présentent une dispersibilité encore améliorée et qui a une résistance à la traction améliorée et une concentration en solides relativement élevée. Le problème est résolu par un procédé de production d'une composition de caoutchouc contenant des nanofibres de cellulose, le procédé comprenant une étape dans laquelle une matière solide séchée comprenant des nanofibres de cellulose est mélangée avec une dispersion aqueuse contenant un ingrédient de caoutchouc.
PCT/JP2016/079963 2015-10-07 2016-10-07 Procédé de production d'une composition de caoutchouc WO2017061605A1 (fr)

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JP2017514370A JP6153694B1 (ja) 2015-10-07 2016-10-07 ゴム組成物の製造方法
CN201680055972.8A CN108026289B (zh) 2015-10-07 2016-10-07 橡胶组合物的制造方法

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JP2015-199659 2015-10-07
JP2015199659 2015-10-07

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WO2017061605A1 true WO2017061605A1 (fr) 2017-04-13

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017171764A (ja) * 2016-03-23 2017-09-28 日本ゼオン株式会社 ラテックス組成物
JP2020012069A (ja) * 2018-07-19 2020-01-23 住友ゴム工業株式会社 分散体、製造方法、ゴム組成物及び空気入りタイヤ
WO2020054342A1 (fr) * 2018-09-14 2020-03-19 日本製紙株式会社 Procédé de production d'une composition de caoutchouc
JP2020158700A (ja) * 2019-03-27 2020-10-01 大王製紙株式会社 繊維状セルロース複合樹脂及びその製造方法、並びに樹脂の補強材
JP7346525B2 (ja) 2020-11-27 2023-09-19 株式会社スギノマシン ゴム複合化物、ゴム複合化物の製造方法、ゴム－バイオマスナノファイバーマスターバッチ

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6874411B2 (ja) * 2017-02-17 2021-05-19 日本製紙株式会社 ゴム組成物の製造方法
JP6874412B2 (ja) * 2017-02-17 2021-05-19 日本製紙株式会社 ゴム組成物の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09216952A (ja) * 1996-01-08 1997-08-19 Elf Atochem Sa 伝導性ミクロフィブリルセルロースと、それを含む複合材料
JP2012236906A (ja) * 2011-05-11 2012-12-06 Nissan Motor Co Ltd 樹脂組成物
JP2013203803A (ja) * 2012-03-27 2013-10-07 Toyo Tire & Rubber Co Ltd ゴム／セルロースマスターバッチ及びゴム組成物
WO2014115560A1 (fr) * 2013-01-24 2014-07-31 日本ゼオン株式会社 Dispersion de nanotubes de carbone, procédé de fabrication de cette dispersion, composition de nanotubes de carbone, et procédé de fabrication de cette composition
JP2016029169A (ja) * 2014-07-23 2016-03-03 日信工業株式会社 熱可塑性樹脂組成物の製造方法及び熱可塑性樹脂組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104169306A (zh) * 2012-03-14 2014-11-26 日本制纸株式会社 阴离子改性纤维素纳米纤维分散液的制造方法
US9567455B2 (en) * 2013-03-14 2017-02-14 Bridgestone Corporation Rubber composition, method for manufacturing same, vulcanized rubber, and tire
US11603415B2 (en) * 2014-01-17 2023-03-14 Nippon Paper Industries Co., Ltd. Dry solids of anionically modified cellulose nanofibers and processes for preparing them

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09216952A (ja) * 1996-01-08 1997-08-19 Elf Atochem Sa 伝導性ミクロフィブリルセルロースと、それを含む複合材料
JP2012236906A (ja) * 2011-05-11 2012-12-06 Nissan Motor Co Ltd 樹脂組成物
JP2013203803A (ja) * 2012-03-27 2013-10-07 Toyo Tire & Rubber Co Ltd ゴム／セルロースマスターバッチ及びゴム組成物
WO2014115560A1 (fr) * 2013-01-24 2014-07-31 日本ゼオン株式会社 Dispersion de nanotubes de carbone, procédé de fabrication de cette dispersion, composition de nanotubes de carbone, et procédé de fabrication de cette composition
JP2016029169A (ja) * 2014-07-23 2016-03-03 日信工業株式会社 熱可塑性樹脂組成物の製造方法及び熱可塑性樹脂組成物

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017171764A (ja) * 2016-03-23 2017-09-28 日本ゼオン株式会社 ラテックス組成物
JP2020012069A (ja) * 2018-07-19 2020-01-23 住友ゴム工業株式会社 分散体、製造方法、ゴム組成物及び空気入りタイヤ
JP7243060B2 (ja) 2018-07-19 2023-03-22 住友ゴム工業株式会社 分散体、製造方法、ゴム組成物及び空気入りタイヤ
WO2020054342A1 (fr) * 2018-09-14 2020-03-19 日本製紙株式会社 Procédé de production d'une composition de caoutchouc
JPWO2020054342A1 (ja) * 2018-09-14 2021-08-30 日本製紙株式会社 ゴム組成物の製造方法
JP2020158700A (ja) * 2019-03-27 2020-10-01 大王製紙株式会社 繊維状セルロース複合樹脂及びその製造方法、並びに樹脂の補強材
WO2020195908A1 (fr) * 2019-03-27 2020-10-01 大王製紙株式会社 Résine composite de cellulose fibreuse, son procédé de production, et matériau de renforcement de résine
JP7346525B2 (ja) 2020-11-27 2023-09-19 株式会社スギノマシン ゴム複合化物、ゴム複合化物の製造方法、ゴム－バイオマスナノファイバーマスターバッチ

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