WO2014123249A1 - Composition de caoutchouc et pneumatique - Google Patents

Composition de caoutchouc et pneumatique Download PDF

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Publication number
WO2014123249A1
WO2014123249A1 PCT/JP2014/053571 JP2014053571W WO2014123249A1 WO 2014123249 A1 WO2014123249 A1 WO 2014123249A1 JP 2014053571 W JP2014053571 W JP 2014053571W WO 2014123249 A1 WO2014123249 A1 WO 2014123249A1
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WO
WIPO (PCT)
Prior art keywords
plant resource
extraction residue
rubber
rubber composition
resource extraction
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PCT/JP2014/053571
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English (en)
Japanese (ja)
Inventor
良彦 鈴木
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株式会社ブリヂストン
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Publication of WO2014123249A1 publication Critical patent/WO2014123249A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the present invention relates to a rubber composition and a tire.
  • a rubber composition used for tires or the like contains a large amount of rubber as a raw material.
  • the rubber composition is usually 50% by mass or more of the rubber composition is a blend of natural rubber and synthetic rubber. Consists of ingredients. Therefore, these rubber compositions and tires using the rubber compositions are affected by rising crude oil prices, rubber failure due to bad weather, etc., which may increase raw material costs and make it difficult to supply stable products. There is a risk of becoming.
  • Patent Document 1 As a rubber composition and a tire in which the amount of the rubber component used is reduced, a rubber composition in which a plant resource extraction residue such as coffee cake or tea husk is blended with the rubber component And a tire using the rubber composition at least partially.
  • the present invention has been made to solve the above-described problems, and provides a rubber composition that can improve tire performance, particularly rolling resistance, using a material having a low environmental load and low cost. With the goal. Furthermore, an object of the present invention is to provide a tire that uses such a material and has improved tire performance, particularly rolling resistance.
  • the rubber composition according to the present invention contains 0.2 to 9 parts by mass of the plant resource extraction residue with respect to 100 parts by mass of the rubber component, and the maximum major axis of the plant resource extraction residue is 50 to 240 ⁇ m. It is characterized by.
  • the plant resource extraction residue in the present invention is obtained by immersing a plant resource (solid) in a solvent and extracting a desired component in the solvent (solid-liquid extraction), and then filtering the solvent (extract solution) containing the component, etc. Refers to the residue remaining after separation.
  • the term “major axis” is on the outer periphery of the plant resource extraction residue (containing the rubber composition) dispersed in the rubber composition. It means the length of the longest line segment connecting two points, and the term “particle size” is the longest line segment connecting two points on the outer periphery of the plant resource extraction residue before blending with the rubber component. It means length.
  • the maximum major axis of the plant resource extraction residue in the present invention means the largest value among the major axes of plant resource extraction residues of various diameters dispersed in the rubber composition.
  • the maximum major axis is 5 cm ⁇ 5 cm obtained by cutting the rubber vulcanized under general vulcanization conditions (for example, 150 ° C., 30 minutes) in a direction perpendicular to and parallel to the rubber flow direction.
  • the cross-sectional area can be measured by observing the plant resource extraction residue in the entire cross-section of the cross-sectional area at a magnification of 50 to 500 times using a microscope (for example, VHX digital microscope manufactured by Keyence Corporation).
  • the average particle size of the plant resource extraction residue to be blended with the rubber component in the present specification is obtained by observing the target plant resource extraction residue using the above-mentioned microscope, and 100 plant resources selected arbitrarily. It means the average value of the particle size of the extraction residue.
  • containing means that the rubber composition contains a component such as a plant resource extraction residue.
  • blending means adding a component such as a plant resource extraction residue to a rubber component in order to obtain a rubber composition.
  • the mass of the plant resource extraction residue contained in the rubber composition after blending means the mass of the solid content of the plant resource extraction residue that does not contain water or a solvent such as an organic solvent.
  • the mass of the plant resource extraction residue to be blended with the rubber component is the mass of the plant resource extraction residue in a state where the plant resource extraction residue contains water or a solvent such as an organic solvent.
  • the rubber composition which can improve tire performance, especially rolling resistance can be provided using the material with small environmental impact and low cost. Furthermore, according to the present invention, it is possible to provide a tire with improved tire performance, particularly rolling resistance.
  • 6 is a microscope photograph of a cross section of a vulcanized product of a rubber composition of Example 5.
  • 6 is a microscope photograph of a cross section of a vulcanized product of a rubber composition of Example 5.
  • 6 is a microscope photograph of a cross section of a vulcanized product of a rubber composition of Example 5.
  • the rubber composition according to the present invention contains 0.2 to 9 parts by mass of a plant resource extraction residue with respect to 100 parts by mass of a rubber component, and the maximum major axis of the plant resource extraction residue is 50 to 240 ⁇ m. And Utilizing a material with low environmental impact and low cost by containing the specific amount of the plant resource extraction residue with respect to 100 parts by mass of the rubber component and the maximum major axis of the plant resource extraction residue being in the specific range. And the rubber composition which can improve tire performance, especially rolling resistance can be provided.
  • the rubber component is a rubber component such as natural rubber or synthetic rubber.
  • the synthetic rubber include styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (CR), butyl rubber ( IIR) and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the plant resource before extraction that can be a plant resource extraction residue may be a part of a plant containing any active ingredient that can be extracted by the extraction process.
  • Plant resources include, for example, tea leaves, coffee beans, aloe leaves, mugwort leaves, mulberry root, red grape skin, thistle fruit, tomorrow leaf leaves, acerola, chlorella, kudzu root (kudzu), roses Flowers, peach leaves, buckwheat, barley seeds.
  • Plant resources before extraction are crushed or crushed with a crusher or the like in order to increase the efficiency of the extraction work and to more easily blend the extracted plant resource extraction residue into the rubber component without going through the crushing and separating steps. It is preferable to pulverize and use for an extraction process. In the extraction process, for example, heating or stirring may be performed as necessary.
  • the solvent used for extraction can be selected according to the type of plant resource, the desired active ingredient and the use of the extract.
  • the solvent include water and organic solvents (ethyl alcohol, oil, etc.). You may mix and use extractants, such as a chelating agent, an acid, and an alkali, as needed. And the drink, skin lotion, emulsion, etc. containing the said active ingredient can be obtained by immersing the plant resource mentioned above in these solvents and extracting the active ingredient in a plant resource.
  • the tea leaves and coffee lees that are extracted from plant resources are wastes that are discharged in large quantities in the production process of tea and coffee beverages, and the environmental burden can be reduced by reusing them by mixing them with rubber components. ,preferable.
  • the tea husk and coffee mash usually contain a solvent such as water at the time of the waste discharged from the manufacturing process, and are crushed or crushed. This is preferable because it is not necessary to go through a drying step and a crushing or pulverizing step, and the environmental load can be reduced.
  • tea husk is used as the plant resource extraction residue, in addition to improving tire performance, particularly rolling resistance, there is an effect that the elongation at break of the vulcanizate of the rubber composition is hardly reduced.
  • the plant resource extraction residue is tea husk
  • the type of tea husks include tea husks such as green tea, hoji tea, and oolong tea.
  • the shape of the tea husk blended with the rubber component is not particularly limited.
  • the plant resource extraction residue to be blended with the rubber component may be used alone or in combination of two or more of different types and shapes.
  • the maximum major axis of the plant resource extraction residue contained in the rubber composition according to the present invention is 50 to 240 ⁇ m.
  • the maximum major axis is 50 ⁇ m or more, the hardness of the plant resource extraction residue is sufficiently exerted and heat generation is improved. Moreover, it is easy to maintain the dispersibility and exothermic property of the plant resource extraction residue in a rubber composition by making a maximum major axis into 240 micrometers or less. Thereby, it is easy to obtain a sufficient effect of improving the rolling resistance of a tire using the rubber composition at least partially.
  • the maximum major axis is preferably 65 to 220 ⁇ m, and more preferably 70 to 200 ⁇ m, from the viewpoint of securing exothermic properties.
  • the average major axis of the plant resource extraction residue contained in the rubber composition according to the present invention is preferably 10 to 70 ⁇ m, and more preferably 10 to 40 ⁇ m. Thereby, it becomes difficult to impair the fracture resistance of rubber using the rubber composition at least in part.
  • the average of the major axis of the plant resource extraction residue dispersed in the rubber composition is perpendicular and parallel to the rubber flow direction for rubber vulcanized under general vulcanization conditions (for example, 150 ° C., 30 minutes).
  • the cross-section of the cross-sectional area is observed at a magnification of 50 to 500 times using a microscope (for example, VHX digital microscope manufactured by Keyence Co., Ltd.) It is determined by calculating the average of the major axis of 100 arbitrarily selected plant resource extraction residues.
  • the method for setting the maximum long diameter of the plant resource extraction residue contained in the rubber composition according to the present invention to 50 to 240 ⁇ m is not particularly limited, for example, the average particle diameter of the plant resource extraction residue to be blended in the rubber component is
  • the water content of the plant resource extraction residue is preferably 80% by mass or less, and is 600 to 4000 ⁇ m.
  • the moisture content of the said plant resource extraction residue shall be 80 mass% or less preferably.
  • the water content is preferably 5% by mass or more from the viewpoint of reducing the amount of energy necessary for reducing the water content and improving the handleability of the plant resource extraction residue.
  • the water content is preferably 60 to 80% by mass because the maximum major axis can be easily controlled.
  • the plant resource extraction residue is a residue generated by subjecting the plant resource to solid-liquid extraction treatment.
  • the method for adjusting the moisture content of the plant resource extraction residue is not particularly limited.
  • the moisture content of the plant resource extraction residue such as hot air drying, drum drying, hot plate drying, or pressing with a filter press is reduced.
  • a method is mentioned. What is necessary is just to adjust suitably as temperature at the time of drying a plant resource extraction residue and reducing a moisture content, for example, 130-250 degreeC is preferable from a viewpoint of workability
  • the plant resource extraction residue can be blended with the rubber component without undergoing a step of adjusting the moisture content of the plant resource extraction residue such as moisture.
  • the rubber composition according to the present invention contains 0.2 to 9 parts by mass of a plant resource extraction residue with respect to 100 parts by mass of the rubber component, and the maximum major axis of the plant resource extraction residue is 50 to 240 ⁇ m.
  • the content of the plant resource extraction residue is 0.2 parts by mass or more, the amount of the plant resource extraction residue contained in the rubber composition is secured, and the effect of suppressing heat generation is easily exhibited.
  • the content of the plant resource extraction residue is 9 parts by mass or less, the dispersibility and heat generation of the plant resource extraction residue contained in the rubber composition can be easily maintained.
  • the content of the plant resource extraction residue is preferably 1.5 to 6 parts by mass and preferably 2.3 to 4 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of ensuring exothermic properties. More preferred.
  • the rubber composition according to the present invention may optionally contain a reinforcing filler such as carbon black and silica, a softener such as aroma oil, a vulcanization accelerator, a vulcanization accelerator, an anti-aging agent, etc. Ingredients may be included.
  • the method for preparing the rubber composition according to the present invention is not particularly limited, and a plant resource extraction residue is blended with a rubber component together with other components such as the above-described carbon black as an optional component, for example, a Banbury mixer or a roll. Can be prepared by kneading.
  • the plant resource extraction residue may be blended in a desired amount all at once, or may be blended in a plurality of times.
  • the kneading method in preparing the rubber composition according to the present invention is not particularly limited, and for example, a Banbury mixer, a roll, or the like can be used.
  • the rubber composition according to the present invention is preferably obtained by kneading with a Banbury mixer.
  • the kneading conditions in the Banbury mixer are not particularly limited, and may be appropriately adjusted according to the desired maximum long diameter of the plant resource extraction residue, but from the viewpoint of improving the heat build-up, the maximum temperature of the rubber composition during kneading Is preferably 120 ° C. to 190 ° C., preferably 130 ° C. to 175 ° C., and more preferably 140 to 170 ° C.
  • the kneading time is preferably 10 seconds to 20 minutes, more preferably 10 seconds to 10 minutes, and further preferably 30 seconds to 5 minutes.
  • the tire according to the present invention is characterized in that the rubber composition according to the present invention is used at least in part. As a result, the tire according to the present invention has improved tire performance, particularly rolling resistance.
  • the tire according to the present invention can be manufactured by the same manufacturing method as that of a normal tire except that the vulcanized product of the rubber composition is used.
  • FIG. 1 is a cross-sectional view of an example of the tire of the present invention.
  • the tire shown in FIG. 1 has a pair of bead portions 1, a pair of sidewall portions 2, and a tread portion 3 connected to both sidewall portions 2, and extends in a toroid shape between the pair of bead portions 1.
  • the carcass 4 that reinforces each of the parts 1, 2, and 3 and the belt 5 that is located on the outer side in the tire radial direction of the crown part of the carcass 4 are provided.
  • the carcass 4 is composed of a single carcass ply, and a main body portion extending in a toroidal shape between a pair of bead cores (wires) 6 respectively disposed in the bead portion 1;
  • the bead core 6 Around the bead core 6, it consists of a folded portion wound up radially outward from the inside in the tire width direction toward the outside.
  • the carcass 4 is composed of one carcass ply.
  • a plurality of carcass plies may be provided.
  • the belt 5 is composed of two belt layers.
  • the number of belt layers constituting the belt may be one or more, and is not limited thereto. Absent.
  • the tire of the present invention may further include a belt reinforcing layer made of a rubberized layer of cords arranged substantially parallel to the tire circumferential direction on the outer side in the tire radial direction of the belt 5. Further, an interlayer rubber may be provided between the belt and the belt reinforcing layer.
  • Examples of the member using the rubber composition include tread rubber, side rubber, bead filler or stiffener located outside the bead wire in the radial direction, carcass, and belt coating rubber.
  • an inert gas such as nitrogen, argon, helium, or the like can be used in addition to normal or air having an adjusted oxygen partial pressure.
  • the rubber compounding agents used in this study are as follows. The abbreviations in the table are shown in parentheses. ⁇ Polybutadiene rubber (BR: rubber component): Ube Industries, Ltd., trade name UBEPOL BR150L ⁇ Natural rubber (NR: rubber component): Trade name TSR Styrene-butadiene copolymer rubber (SBR: rubber component): Emulsion polymerization SBR Product name: SBR1500 ⁇ Carbon black (CB: filler): Asahi Carbon Co., Ltd., trade name ISAF grade, SAF grade ⁇ Oil (oil: softener): Process oil ⁇ Tea shell (plant resource extraction residue): Discharged from beverage manufacturing plant Tea leaves
  • Components such as a vulcanizing agent used when vulcanizing the rubber composition in this study were as follows (parts by mass of each component are parts by mass with respect to 100 parts by mass of the rubber component).
  • -Sulfur 1.5 parts by mass-Vulcanization accelerator (N-cyclohexyl-2-benzothiazylsulfenamide): 1.5 parts by mass-Vulcanization accelerator (diphenylguanidine): 1.2 parts by mass Sulfur accelerator (dibenzothiazyl disulfide): 0.2 parts by mass, zinc white (ZnO): 2.0 parts by mass, stearic acid: 1.0 part by mass, anti-aging agent (manufactured by Ouchi Shinsei Chemical Co., Ltd.)
  • Product name NOCRACK 6C N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine): 1.0 part by mass
  • the vulcanizing agent is used for vulcanization of
  • the rubber composition shown in Table 1 was obtained by kneading the blended composition as described above using a 4000 mL Banbury mixer. In the first stage of the kneading, the plant resource extraction residue (tea husk) was blended. The product was discharged at 160 ° C., mixed with a vulcanizing agent at the final stage, and discharged at 110 ° C.
  • the average particle size of the blended plant resource extraction residue (tea husk) in this study is determined by observing the target plant resource extraction residue (tea husk) using a microscope (VHX digital microscope manufactured by Keyence Co., Ltd.). It is an average value of the particle sizes of 100 plant resource extraction residues (tea husk) that are arbitrarily selected.
  • the maximum length of plant resource extraction residue (tea husk) using a microscope in this study was measured with a microscope cut into a cross section of 5 cm x 5 cm in a direction perpendicular to and parallel to the rubber flow direction. (VHX digital microscope manufactured by Keyence Co., Ltd.) was used to observe the plant resource extraction residue (tea husk) in the entire cross-sectional area at a magnification of 50 to 500 times.
  • Rolling resistance (RR) Measurement and evaluation of rolling resistance in this study were performed as follows. For a 275 / 80R22.5 size tire using a vulcanized rubber composition, the drum is rotated while the tire is in contact with an iron drum having a diameter of 1.7 m, and the drum drive switch is raised to 80 km / h. The drum was rotated freely, the rolling resistance was measured from the degree of deceleration, and the results were indexed. It shows that rolling resistance is so small that a numerical value is small and rolling resistance is favorable.
  • Example 1 to 6 and Comparative Examples 2 to 4 About the vulcanizate of each rubber composition, rolling resistance was measured and evaluated by the method mentioned above. In addition, the numerical value of rolling resistance is an index value when the performance of Comparative Example 1 is 100. Microscope photographs of the vulcanizate of Example 5 are shown in FIGS. 2 to 4, it can be seen that the major axis of the contained tea husk is 100 to 140 ⁇ m.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

L'invention concerne une composition de caoutchouc contenant 0,2-9 parties en masse d'un résidu d'extrait de plante par rapport à 100 parties en masse d'un constituant caoutchouc, et caractérisé en ce que la longueur maximale de l'axe principal du résidu d'extrait de plante est de 50-240 µm.
PCT/JP2014/053571 2013-02-08 2014-02-10 Composition de caoutchouc et pneumatique WO2014123249A1 (fr)

Applications Claiming Priority (2)

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JP2013-023692 2013-02-08
JP2013023692A JP2014152267A (ja) 2013-02-08 2013-02-08 ゴム組成物およびタイヤ

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WO2014123249A1 true WO2014123249A1 (fr) 2014-08-14

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009154118A1 (fr) * 2008-06-18 2009-12-23 株式会社ブリヂストン Composition de caoutchouc et pneumatiques fabriqués au moyen de la composition de caoutchouc
JP2010215706A (ja) * 2009-03-13 2010-09-30 Bridgestone Corp ゴム組成物および該ゴム組成物を用いたタイヤ
JP2010215713A (ja) * 2009-03-13 2010-09-30 Bridgestone Corp エラストマー組成物および該エラストマー組成物を用いたタイヤ
JP2010215720A (ja) * 2009-03-13 2010-09-30 Bridgestone Corp ゴム組成物および該ゴム組成物を用いたタイヤ
JP2012171998A (ja) * 2011-02-18 2012-09-10 Sumitomo Rubber Ind Ltd ゴム組成物およびそれを用いたタイヤ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009154118A1 (fr) * 2008-06-18 2009-12-23 株式会社ブリヂストン Composition de caoutchouc et pneumatiques fabriqués au moyen de la composition de caoutchouc
JP2010215706A (ja) * 2009-03-13 2010-09-30 Bridgestone Corp ゴム組成物および該ゴム組成物を用いたタイヤ
JP2010215713A (ja) * 2009-03-13 2010-09-30 Bridgestone Corp エラストマー組成物および該エラストマー組成物を用いたタイヤ
JP2010215720A (ja) * 2009-03-13 2010-09-30 Bridgestone Corp ゴム組成物および該ゴム組成物を用いたタイヤ
JP2012171998A (ja) * 2011-02-18 2012-09-10 Sumitomo Rubber Ind Ltd ゴム組成物およびそれを用いたタイヤ

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