WO2010050587A1 - Elastomer composition, method for producing same, and tire using the elastomer composition - Google Patents

Elastomer composition, method for producing same, and tire using the elastomer composition Download PDF

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Publication number
WO2010050587A1
WO2010050587A1 PCT/JP2009/068683 JP2009068683W WO2010050587A1 WO 2010050587 A1 WO2010050587 A1 WO 2010050587A1 JP 2009068683 W JP2009068683 W JP 2009068683W WO 2010050587 A1 WO2010050587 A1 WO 2010050587A1
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Prior art keywords
residue
elastomer composition
elastomer
moisture content
composition according
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PCT/JP2009/068683
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French (fr)
Japanese (ja)
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好秀 河野
誓志 今
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株式会社ブリヂストン
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Priority to JP2010535851A priority Critical patent/JPWO2010050587A1/en
Publication of WO2010050587A1 publication Critical patent/WO2010050587A1/en

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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
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • C08L1/02—Cellulose; Modified cellulose

Definitions

  • the present invention relates to an elastomer composition in which the amount of an elastomer component used is reduced, a method for producing the elastomer composition, and a tire using the elastomer composition.
  • Elastomer compositions used for tires, etc. contain a large amount of elastomer components (rubber etc.) as raw materials.
  • elastomer components rubber etc.
  • 50% by mass or more of the elastomer composition contains natural rubber and synthetic rubber. Made of rubber components. Therefore, these elastomer compositions and tires using the elastomer compositions are affected by rising crude oil prices, rubber failure due to bad weather, etc., resulting in increased raw material costs and a difficult supply of stable products. There is a risk of becoming.
  • Patent Document 1 describes a so-called eco-tire in which 75% by weight or more of the total weight is composed of raw materials made of resources other than petroleum.
  • the elastomer composition and tire according to the above prior art can reduce the amount of petroleum resources used, the manufacturing process becomes complicated and the unit price of alternative raw materials for petroleum resources is high, so the manufacturing cost is not necessarily reduced. could not.
  • the elastomer composition of the present invention is an elastomer composition in which a residue generated in an organic fermentation process is blended with an elastomer component.
  • the water content is 5 to 90% by mass, and the particle size of the residue is 0.02 to 600 ⁇ m.
  • an elastomer composition with low cost and low environmental load can be provided by blending the residue into the elastomer component.
  • the residue after the fermentation treatment also has an advantage that it is easy to handle because most of the decay factors such as proteins and lipids are decomposed during the fermentation treatment.
  • the fermentation of organic matter means that the organic matter is decomposed by the action of microorganisms, and includes both anaerobic fermentation and aerobic fermentation, and also includes decomposition of carbohydrates and the like. Also, if the moisture content of the residue to be blended is 5 to 90% by mass, the residue does not aggregate when blended into the elastomer component, and the residue is well dispersed in the elastomer composition.
  • the moisture content of the residue may be 90% by mass or less from the viewpoint of preventing agglomeration and improving dispersibility.
  • the amount of energy necessary to reduce the moisture content and the handleability of the residue From this point of view the content is preferably 5% by mass or more.
  • the moisture content is a value calculated by evaporating residual moisture with a known heater (temperature 120 ° C.) and measuring a change in weight before and after the evaporation with a known means such as a balance.
  • the particle size of the residue to be blended is 0.02 to 600 ⁇ m, an increase in manufacturing cost and a decrease in physical properties of the elastomer composition can be suppressed. If the particle size of the residue is less than 0.02 ⁇ m, the cost for pre-grinding becomes high, and if the particle size is more than 600 ⁇ m, the dispersibility in the elastomer component is poor and the physical properties of the elastomer composition are lowered. In addition, the amount of energy required to reduce the moisture content of the residue increases.
  • the particle diameter is obtained by measuring the particle diameter by laser diffraction (JIS Z8825-1), and is obtained by measuring the average of the major axis and the minor axis (taken as a sphere) of the particles in the laser diffraction method. Value.
  • the organic material is preferably biomass. This is because the use of biomass, which is an organic resource derived from renewable organisms, can further reduce the environmental load during the production of the elastomer composition.
  • the fermentation treatment is a fermentation treatment of an organic substance using a fermentation bacterium, and the residue contains a cell wall of the fermentation bacterium. Residues such as excess sludge generated during fermentation of organic matter using fermentative bacteria are low-use wastes that are present in large quantities and are inexpensive, and require complex processes and large processing energy when blending It is because it does not.
  • the main component of the residue is preferably peptidoglycan. This is because peptidoglycan is a substance that has little influence on the elastomer composition when blended with the elastomer component.
  • the main component of the residue refers to a main component constituting the residue, for example, a component constituting 50% by mass or more of the residue.
  • the elastomer composition of the present invention is preferably blended into the elastomer component after the residue is smoked or carbonized.
  • the soot treatment means that the residue is smoked with smoke generated when wood is heated.
  • the residue can be blended with the elastomer component in a state where desulfurization (deodorization) and sterilized handling are easy.
  • Carbonization means carbonization of the residue at a temperature of about 800 ° C. using a charcoal furnace.
  • the organic substance is an organic substance containing at least one of a plant cell wall and a short fiber connected with the plant cell wall, and the residue comprises at least one of the plant cell wall and the short fiber. It is preferable to contain.
  • those having an aspect ratio of 1 or more and 5 or less are called particles, and those having an aspect ratio of 5 or more and 50 or less are called short fibers.
  • the residue is preferably composed of at least one of cellulose particles and hemicellulose particles which are main components of the cell wall of the plant. This is because cellulose particles and hemicellulose particles are suitable as alternative materials in that they have good dispersibility and do not adversely affect the performance of the elastomer composition. Further, if at least one of cellulose particles and hemicellulose particles is blended into the elastomer composition alone, the cellulose particles and hemicellulose particles absorb moisture and function as micro drainage grooves.
  • an elastomer composition containing at least one of cellulose particles and hemicellulose particles is used in, for example, a studless tire, the performance (such as performance on ice) of the studless tire can be improved.
  • the cellulose particles and hemicellulose particles are aggregated to form a lump, the lump diameter is preferably 0.5 ⁇ m to 2 mm from the viewpoints of handleability and dispersibility.
  • the residue is preferably composed of the short fibers, and the short fibers are preferably composed of at least one of cellulose short fibers and hemicellulose short fibers. This is because cellulose or hemicellulose short fibers can also function as a fiber reinforcing material of an elastomer composition, and thus are suitable as an alternative material.
  • the diameter of the short fiber is preferably 1 ⁇ m to 150 ⁇ m, and the length of the short fiber is preferably 0.3 mm to 2 mm. This is because the dispersibility is poor when the diameter is large and the length is long, and the reinforcing effect is low when the diameter is small and the length is short. Further, it is preferable that 2 to 10 short fibers are gathered to form a bundle. This is because the reinforcing effect is increased by forming a bundle, but if the number of aggregated fibers is too large, the dispersibility deteriorates.
  • the residue contains at least one of cellulose particles and hemicellulose particles which are main components of the cell wall of the plant and short fibers in which the cell wall of the plant is continuous. This is because when both the particles and the short fibers are included, the particles are attached to the short fibers, and the accompanying particles cause fine irregularities on the surface of the short fibers and the like, thereby strengthening the physical adhesion with the elastomer component.
  • the fermentation treatment is a treatment using at least one of Aspergillus or yeast, and the cellulose particles and hemicellulose particles are accompanied by at least one cell wall of Aspergillus or yeast. Is preferred.
  • the fermentation treatment is a treatment using at least one of Aspergillus or yeast, and the short fiber is accompanied by at least one cell wall of Aspergillus or yeast. Is preferred.
  • the residue is preferably shochu shochu.
  • the shochu shochu is a soot generated in the manufacturing process of the soot shochu and includes, for example, a residue generated after distilling the secondary soot.
  • the shochu liquor contains cellulose particles, cellulose fibers, or a mixture thereof.
  • the method for producing an elastomer composition of the present invention is a method for producing an elastomer composition by blending a residue generated in an organic fermentation process with an elastomer component, the residue having a particle size of 0.02 to 600 ⁇ m.
  • an elastomer composition that is inexpensive, has a low environmental impact, and does not significantly reduce physical properties such as elongation at break as compared with an elastomer composition that does not use an alternative raw material. Things are obtained.
  • the manufacturing method of the elastomer composition of the present invention described above includes the pulverization step before the moisture content adjustment step.
  • the residue has a particle size of 0.02 to 600 ⁇ m when adjusting the moisture content. This is because the water content of the residue can be easily adjusted since the specific surface area is increased by grinding. That is, the energy and time required for adjusting the moisture content of the residue in the production of the elastomer composition can be greatly reduced.
  • the above-described method for producing an elastomer composition of the present invention includes a screening step of screening the residue into a screened residue and a screened residue before the kneading step.
  • the residue is preferably kneaded with the elastomer component.
  • the said selection process is included after the said crushing process and before the said moisture content adjustment process. This is because a residue having a desired particle diameter can be easily selected by sieving after the pulverization step.
  • the residue on the sieve becomes waste only in the sorting process, and residue having a uniform particle size cannot be obtained only in the pulverizing process. If the grinding process and the sorting process are combined in this way, the amount of waste can be reduced. This is because it is possible to obtain a residue having a uniform particle diameter while being reduced. Furthermore, the moisture content can be easily adjusted after pulverization and selection.
  • the method for producing an elastomer composition of the present invention is a method for producing an elastomer composition by blending a residue produced in an organic fermentation process with an elastomer component, wherein the moisture content of the residue is 5 to 90 mass%.
  • a kneading step in which the ingredients are mixed and kneaded.
  • the elastomer composition is inexpensive, has a low environmental impact, and does not significantly reduce physical properties such as elongation at break as compared with an elastomer composition that does not use an alternative raw material. Is obtained.
  • the method for producing an elastomer composition of the present invention is a method for producing an elastomer composition by blending a residue generated in an organic fermentation process with an elastomer component, wherein the residue is sieved with a mesh size of 600 ⁇ m or less.
  • a screening process including screening to a sieve residue and a sieve residue, a moisture content adjusting process in which the moisture content of the sieve residue is 5 to 90% by mass, and a sieve residue having an adjusted moisture content And a kneading step of kneading with an elastomer component.
  • the elastomer composition is inexpensive, has a low environmental impact, and does not significantly reduce physical properties such as elongation at break as compared with an elastomer composition that does not use an alternative raw material. Is obtained. Furthermore, according to this production method, an elastomer composition is produced by blending and kneading the elastomer component with a predetermined moisture content after passing through a sieve with a small particle diameter when passing through the sieve, Since the residue mixed and kneaded with the elastomer component after adjusting the water content has a small particle size and a large specific surface area, the water content of the residue can be easily adjusted.
  • the energy and time required for adjusting the moisture content of the residue in producing the elastomer composition can be greatly reduced.
  • the method for producing the elastomer composition it is preferable to sort the residue using at least two sieves having different mesh sizes in the sorting step. This is because residue having a large particle size can be reliably selected and removed by sieving using sieves having different mesh sizes.
  • the selection step passes the first sieve having a mesh size of 750 to 1500 ⁇ m through the residue after fermentation of the organic matter, and the first sieve. And a step of passing the residue over a second sieve having a mesh size of 90 to 600 ⁇ m. This is because a residue having a desired particle size (for example, 600 ⁇ m or less) whose water content can be easily adjusted can be selected and blended.
  • the moisture content adjusting step includes a drying step in which the moisture content is 5 to 90% by mass by drying, a pressing step in which the moisture content is 60 to 90% by mass by pressing, Alternatively, it is preferably a pressing / drying step in which the moisture content is 5 to 90% by mass by drying after pressing.
  • the moisture content adjustment step is a drying step
  • the moisture content can be easily reduced.
  • the moisture content can be reduced at a low cost. This is because the moisture content can be easily reduced at a low cost.
  • the moisture content adjusting step is preferably the drying step or the pressing / drying step, and the drying is preferably performed at a temperature of 130 to 250 ° C.
  • the residue after fermentation of the organic matter is dried at a temperature of 130 to 250 ° C., for example, at a temperature higher than the boiling point of the filtrate when the residue is filtered with a filtration device such as a stone mill method. This is because the time required for producing the elastomer composition can be shortened.
  • the tire of the present invention is characterized in that at least a part of the tire is composed of the elastomer composition or the elastomer composition produced by the production method.
  • the tire is composed only of an elastomer such as rubber, and the tire is composed of an elastomer composition containing a residue generated in the fermentation of organic matter and having a predetermined particle size and moisture content. It is possible to provide a tire capable of reducing the environmental load by reducing the amount of the elastomer component used while maintaining the performance as described above.
  • an elastomer composition that does not use an alternative raw material can be produced at low cost without using a complicated manufacturing process by blending a predetermined alternative raw material into the elastomer component. It can be provided without significantly reducing the physical properties as compared with the product. Moreover, the efficient manufacturing method of the said elastomer composition and the tire with a low environmental load at the time of manufacture using the said elastomer composition can be provided.
  • (A)-(c) is a flowchart which shows the example of the procedure which adjusts the moisture content of a residue.
  • the elastomer composition according to the present invention is kneaded with the elastomer component, which is a residue generated in the fermentation treatment of organic matter, having a water content of 5 to 90% by mass and a particle size of 0.02 to 600 ⁇ m.
  • the residue produced in the fermentation treatment of organic matter is preferably blended with a moisture content of 5 to 50% by mass, and more preferably with a moisture content of 5 to 30% by mass.
  • the elastomer component is a rubber component, the lower the moisture content of the residue, the less moisture present in the rubber composition.
  • the residue produced in the fermentation treatment of organic matter is preferably blended with a particle size of 0.02 to 500 ⁇ m, and more preferably blended with a particle size of 0.02 to 400 ⁇ m. Further, in the elastomer composition of the present invention, the amount of the residue is preferably 0.5 to 90 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the elastomer component.
  • Elastomer that can sufficiently reduce the environmental load by making the blending amount of the residue 0.5 parts by mass or more, and does not use an alternative raw material by making the blending amount of the residue 90 parts by mass or less. This is because an elastomer composition having performance equivalent to that of the composition can be provided.
  • the elastomer component is composed of a rubber component such as natural rubber or synthetic rubber, a resin such as a thermoplastic elastomer or a thermosetting elastomer, or a mixture thereof.
  • a rubber component such as natural rubber or synthetic rubber
  • a resin such as a thermoplastic elastomer or a thermosetting elastomer, or a mixture thereof.
  • synthetic rubber 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.
  • Thermoplastic elastomers include ethylene-methyl acrylate copolymers, styrene elastomers, urethane elastomers, and polyolefin elastomers.
  • Thermosetting elastomers include phenol elastomers, urea elastomers, melamine elastomers, and epoxy. Based elastomers and the like.
  • the elastomer composition of the present invention is optionally added to reinforcing fillers such as carbon black and silica, softeners such as aroma oil, vulcanization accelerators, vulcanization accelerators, anti-aging agents, etc. Additive may be included.
  • organic substances to be fermented include paper, livestock waste, food waste, shochu (potato, rice, barley shochu), construction-generated wood, black liquor, excess sludge (eg, sewage sludge, manure sludge) , Methane fermentation sludge), waste-based biomass such as beverage component extraction residue (such as tea husk and coffee straw), and unused biomass such as rice straw, straw, rice husk, and forest land residues (thinned wood, damaged wood, etc.) Including forage crops, fruits (grape, apples, cherries, palm nuts, etc.), cereals (rice, wheat, corn, etc.), root vegetables (potatoes, sweet potatoes, etc.), and resource crop biomass such as starch crops Biomass, which is an organic resource derived from a living organism, can be mentioned. If such biomass is used, the environmental load at the time of elastomer composition manufacture can be reduced more. In addition, it is preferable to use waste biomass as organic matter from the viewpoint of effective utilization of resources
  • a fermentation treatment method of organic matter there are, for example, methane fermentation using methanogen, ethanol fermentation using ethanol fermenter, hydrogen fermentation using hydrogen producer, etc.
  • Examples of fermentation treatment using aerobic microorganisms include acetic acid fermentation using acetic acid-producing bacteria, and wastewater treatment using various oxidizing bacteria such as ammonia oxidizing bacteria.
  • the aerobic fermentation treatment using aerobic microorganisms is preferable as a fermentation treatment method in that the deodorization treatment at the time of blending is unnecessary because the odor of the residue is small.
  • methane fermentation treatment, ethanol fermentation treatment, or hydrogen fermentation treatment the residue after efficiently removing the fuel from the resources can be used, and the resources can be reduced and the resources can be effectively utilized. Therefore, it is preferable as a fermentation treatment method.
  • the residue to be blended in the elastomer component for example, surplus sludge generated when biological treatment (fermentation) of organic substances under aerobic or anaerobic conditions can be used.
  • sludge is used as a residue, from the viewpoint of reducing the weight of the elastomer composition and preventing adverse effects on the elastomer composition due to metal inclusion, sludge containing no iron-based flocculant, for example, sludge using an aluminum compound as the flocculant is used.
  • sludge containing no flocculant is more preferable.
  • the residue preferably contains at least one of cellulose particles and hemicellulose particles alone. Further, it is more preferable that at least one of cellulose particles and hemicellulose particles and short fibers are included.
  • the cellulose particles and hemicellulose particles can absorb moisture and serve as a micro drainage groove. This is because the performance (such as on-ice performance) of the studless tire can be improved when used in the above.
  • the residue preferably contains at least one of peptidoglycan, cellulose particles and hemicellulose particles, and at least one of cellulose short fibers and hemicellulose short fibers. This is because by including peptidoglycan, particles, and short fibers, for example, when an elastomer composition is used in a studless tire, an effect of absorbing moisture can be achieved.
  • cellulose particles and hemicellulose particles are the main components of plant cell walls and have an aspect ratio of 1 or more and 5 or less.
  • the short cellulose fiber and the short hemicellulose fiber are a series of plant cell walls, and have an aspect ratio of more than 5 and 50 or less.
  • the diameter of the short fiber is preferably 1 ⁇ m to 150 ⁇ m, and the length of the short fiber is preferably 0.3 mm to 2 mm. This is because the dispersibility is poor when the diameter is large and the length is long, and the reinforcing effect is low when the diameter is small and the length is short. It is also preferable that 2 to 10 short fibers are assembled into a bundle. Further, when the cellulose particles and hemicellulose particles are aggregated in the residue to form a lump, the diameter of the lump is preferably 0.5 ⁇ m to 2 mm from the viewpoint of handleability and dispersibility.
  • the fermentation treatment of the organic substance is a treatment using at least one of koji mold or yeast
  • at least one cell wall of koji mold or yeast is attached to the cellulose particles and hemicellulose particles
  • at least one cell wall of Neisseria gonorrhoeae and yeast is also attached to the short fiber.
  • the accompanying koji mold or yeast causes fine irregularities on the surface of particles, short fibers, etc., and physical adhesion with the elastomer component is strengthened. It is.
  • the above-mentioned residue has an moisture content of 5 to 90% by mass, preferably 80% by mass or less, more preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. Is blended into the product.
  • the moisture content of the residue can be adjusted using known techniques such as drying with hot air drying, drum drying, hot plate drying, smoke treatment, etc., and pressing with a filter press, etc.
  • the moisture content of the residue remaining immediately after the fermentation treatment is in the desired moisture content range, it may be blended into the elastomer component without adjusting the moisture content.
  • the temperature at which the residue is dried and the water content is adjusted is preferably 130 to 250 ° C. from the viewpoint of workability, and is higher than the boiling point of the filtrate when the residue is filtered with a filtration device such as a stone mill method. Higher temperatures are even more preferred.
  • a smoke process for removing residue with smoke generated when wood is heated, or a carbonization process for carbonizing the residue at a high temperature of about 800 ° C. is preferred. This is because by performing the soot treatment, the residue can be blended with the elastomer component in a state where desulfurization (deodorization) and sterilized handling are easy.
  • the above-mentioned residue needs to have a particle size of 600 ⁇ m or less, particularly 0.02 to 600 ⁇ m, from the viewpoint of blendability into the elastomer component and ease of adjustment of the moisture content. Therefore, for those containing a residue having a particle size larger than 600 ⁇ m, as shown in FIGS. 2 (a) to (c), for example, water is optionally contained after sieving, pulverizing, or both. The rate can be adjusted (pressed, dried) and then blended into the elastomer component.
  • pulverization or adjustment of the moisture content is performed after sieving, the pulverization and adjustment of the moisture content are performed with respect to the residue under the sieve.
  • the moisture content may be adjusted before pulverization or sieving.
  • the residue whose moisture content has been adjusted may be further pulverized and sieved as necessary.
  • blend may contain the residue of less than 0.02 micrometer in particle size. This is because when the residue having a particle size of less than 0.02 ⁇ m is separated by sieving, the number of times the residue is sieved increases.
  • the particle size of the residue is preferably 0.02 to 500 ⁇ m, and particularly preferably 0.02 to 400 ⁇ m.
  • the residue is pulverized with a known wet pulverizer, or the residue is sieved using a known wet sieve to obtain a residue having a desired particle size, and the moisture content of the residue is adjusted. And then blended into the elastomer component.
  • pulverization is preferred as a method for adjusting the particle size of the residue to be blended in the elastomer component.
  • sieving is carried out in multiple times using sieves with different mesh sizes in order to reliably obtain a residue having a desired particle size, or the mesh size becomes smaller as the sieves with different mesh sizes are moved downward.
  • a sieve having different mesh sizes for example, a sieve having a mesh size of 750 to 1500 ⁇ m and a sieve having a mesh size of 90 to 600 ⁇ m can be used.
  • the elastomer composition of the present invention is obtained by blending the residue after pulverization or sieving by the above-described method and adjusting the moisture content into the elastomer component together with an optional filler (carbon black, etc.) and additives. It can be prepared by kneading.
  • an optional filler carbon black, etc.
  • the residue and the various compounding agents selected suitably as needed are kneaded into an elastomer component using a Banbury mixer, a roll, etc. Can be prepared.
  • the tire of the present invention is characterized in that at least a part thereof is composed of the above-mentioned elastomer composition, and other than that, it can be manufactured using the same manufacturing method as that of a normal tire.
  • 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 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 portion 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 can be provided between the belt reinforcing layer and the belt reinforcing layer.
  • the tire of the illustrated example is characterized by using an elastomer composition in which at least the tread portion 3 is blended with a residue containing cellulose short fibers having the above-described moisture content and particle size.
  • an elastomer composition containing cellulose short fibers in the tread portion 3 it is possible to provide a tire capable of improving running stability, wet performance, and ice / snow performance due to the interaction between the cellulose short fibers and the road surface. .
  • examples of the member using the elastomer composition include a tread rubber, a side rubber, a bead filler or a stiffener located outside the bead wire in the radial direction, a coating rubber for a carcass and a belt, and the like.
  • an inert gas such as nitrogen, argon, helium, etc. can be used in addition to air having normal or oxygen partial pressure adjusted.
  • Example 1 A rubber composition was prepared in the same manner as in Comparative Example 1 except that the soot shochu that had been pulverized after the moisture content was adjusted, and the elongation at break of the vulcanized rubber was measured and evaluated in the same manner as in Comparative Example 1. . The results are shown in Table 1.
  • Example 2 A rubber composition was prepared in the same manner as in Comparative Example 1 except that the soot shochu, which was adjusted in moisture content after pulverization, was mixed in a different amount, and vulcanized rubber was prepared in the same manner as in Comparative Example 1. The elongation at break was measured and evaluated. The results are shown in Table 1.
  • Examples 5 to 7 A rubber composition was prepared in the same manner as in Comparative Example 1 except that the shochu shochu, which had been adjusted in moisture content after sieving, was blended while changing the blending amount. The elongation at break was measured and evaluated. The results are shown in Table 1.
  • the rubber component was blended with the shochu shochu adjusted to a water content of 8% by mass without greatly reducing the physical properties (elongation at break) of the rubber composition. It was found that the usage amount of can be reduced.
  • Example 3 A rubber composition was prepared in the same manner as in Example 4 except that the soot shochu, which was adjusted in moisture content after pulverization, was blended while changing the particle size, and vulcanized rubber was prepared in the same manner as in Example 4. The elongation at break was measured and evaluated. The results are shown in Table 2.
  • Example 8 A rubber composition was prepared in the same manner as in Example 4 except that the shochu shochu, which was adjusted in moisture content after pulverization, was blended while changing the moisture content. The elongation at break was measured and evaluated. The results are shown in Table 2.
  • Shochu F After pulverizing with a wet pulverizer (made by Masuko Sangyo Co., Ltd.) until the particle size becomes 1 to 400 ⁇ m, dry mash shochu using a CD dryer (manufactured by Nishimura Steel) so that the water content becomes 20% by mass.
  • ⁇ G After pulverization with a wet pulverizer (made by Masuko Sangyo Co., Ltd.) until the particle size becomes 1 to 400 ⁇ m, dry mash shochu using a CD dryer (manufactured by Nishimura Steel Co., Ltd.) so that the water content becomes 40% by mass.
  • the shochu liquor is pulverized or sieved to a predetermined particle size (500 ⁇ m or less, preferably 400 ⁇ m or less) and then blended. It was found that the physical properties of were difficult to decrease. In Example 10, moisture was vaporized during the kneading of the rubber composition, and air bubbles sometimes entered the prepared rubber composition.
  • an elastomer composition that does not use an alternative raw material can be produced at low cost without using a complicated manufacturing process by blending a predetermined alternative raw material into the elastomer component. It can be provided without significantly reducing the physical properties as compared with the product. Moreover, the efficient manufacturing method of the said elastomer composition and the tire with a low environmental load at the time of manufacture using the said elastomer composition can be provided.

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Abstract

Disclosed is an environmentally friendly elastomer composition which can be produced at low cost without requiring complicated production processes and without significantly deteriorating the physical properties.  Also disclosed are a method for efficiently producing the elastomer composition, and a tire using the elastomer composition.  The elastomer composition is obtained by blending a residue produced during the fermentation of an organic material into an elastomer component, and is characterized in that the residue contains 5-90% by mass of water and has a particle size of 0.02-600 μm.  The tire is characterized by using the composition.  A method for producing the elastomer composition and a tire using the elastomer composition which is produced by the method are also disclosed.

Description

エラストマー組成物およびその製造方法並びに該エラストマー組成物を用いたタイヤELASTOMER COMPOSITION, PROCESS FOR PRODUCING THE SAME, AND TIRE USING THE ELASTOMER COMPOSITION
　本発明は、エラストマー成分の使用量を低減したエラストマー組成物および該エラストマー組成物の製造方法、並びに該エラストマー組成物を使用したタイヤに関するものである。 The present invention relates to an elastomer composition in which the amount of an elastomer component used is reduced, a method for producing the elastomer composition, and a tire using the elastomer composition.
　タイヤ等に使用するエラストマー組成物は多量のエラストマー成分（ゴム等）を原料として含んでおり、例えば乗用車用空気入りタイヤの場合、エラストマー組成物の５０質量％以上が天然ゴムと合成ゴムとを配合したゴム成分からなる。従って、これらのエラストマー組成物および当該エラストマー組成物を使用したタイヤは、原油価格の高騰や天候不良によるゴムの不作等の影響を受け、原料コストが上昇したり、安定した製品の供給が困難となったりする恐れがある。 Elastomer compositions used for tires, etc. contain a large amount of elastomer components (rubber etc.) as raw materials. For example, in the case of pneumatic tires for passenger cars, 50% by mass or more of the elastomer composition contains natural rubber and synthetic rubber. Made of rubber components. Therefore, these elastomer compositions and tires using the elastomer compositions are affected by rising crude oil prices, rubber failure due to bad weather, etc., resulting in increased raw material costs and a difficult supply of stable products. There is a risk of becoming.
　また、近年では世界的に環境問題が重視される傾向にあり、特に地球温暖化防止の観点からＣＯ２の排出量の規制が強化され、石油資源の使用量の低減が求められていると共に、資源循環型社会の形成が求められている。 Moreover, in recent years, environmental problems tend to be emphasized globally. In particular, from the viewpoint of preventing global warming, regulations on CO 2 emissions have been strengthened, and reductions in the use of petroleum resources have been demanded. The formation of a resource recycling society is required.
　そこで、タイヤ製造時の石油資源の使用量を低減するため、例えば特許文献１には、全重量の７５重量％以上を石油外資源からなる原材料で構成した、いわゆるエコタイヤが記載されている。 Therefore, in order to reduce the amount of petroleum resources used when manufacturing tires, for example, Patent Document 1 describes a so-called eco-tire in which 75% by weight or more of the total weight is composed of raw materials made of resources other than petroleum.
特開２００３－６３２０６号公報JP 2003-63206 A
　しかし、上記従来技術にかかるエラストマー組成物およびタイヤでは、石油資源の使用量は低減できるものの、製造工程が複雑になったり、石油資源の代替原料の単価が高かったりするため、必ずしも製造コストを低減できなかった。 However, although the elastomer composition and tire according to the above prior art can reduce the amount of petroleum resources used, the manufacturing process becomes complicated and the unit price of alternative raw materials for petroleum resources is high, so the manufacturing cost is not necessarily reduced. could not.
　また、天然繊維等を代替原料として使用した場合には、代替原料自体に燃料・資源等としての利用可能性があるという観点等から、代替原料に改良および選択の余地があった。 In addition, when natural fiber or the like is used as an alternative raw material, there is room for improvement and selection of the alternative raw material from the viewpoint that the alternative raw material itself can be used as a fuel / resource.
　更に、配合する代替原料としては、エラストマー成分への分散性が良好で、ゴム等の代わりに配合してもエラストマー組成物の物性を大幅に低下させることが無いものが求められていた。また、そのような代替原料を用いたエラストマー組成物の効率的な製造方法も求められていた。 Furthermore, as an alternative raw material to be blended, a material that has good dispersibility in the elastomer component and does not significantly reduce the physical properties of the elastomer composition even when blended in place of rubber or the like has been demanded. There has also been a demand for an efficient method for producing an elastomer composition using such an alternative raw material.
　この発明は、上記課題を有利に解決することを目的とするものであり、本発明のエラストマー組成物は、エラストマー成分に対して有機物の発酵処理において生じる残滓を配合したエラストマー組成物において、前記残滓の含水率を５～９０質量％とし、前記残滓の粒径を０．０２～６００μｍとしたことを特徴とする。
　このように、有機物の発酵処理において生じる残滓等の、資源を利用した後に残る残滓を配合すれば、エラストマー組成物中のエラストマー成分の使用量を低減することができる。また、有機物の発酵処理において生じる残滓は安価な残物であるから、代替原料として適している。よって、該残滓をエラストマー成分に配合することで、安価且つ環境負荷の低いエラストマー組成物を提供することができる。更に、発酵処理後の残滓は、発酵処理の過程で腐敗要因、例えば蛋白質や脂質の大部分が分解されているので扱い易いという利点も有している。なお、有機物の発酵とは、微生物の働きで有機物を分解することを意味し、嫌気的発酵および好気的発酵の双方を含み、糖質等が分解されることも含む概念である。
　また、配合する残滓の含水率を５～９０質量％とすれば、エラストマー成分に配合する際に残滓が凝集することが無く、エラストマー組成物中で残滓が良好に分散するので、代替原料を使用しないエラストマー組成物と比較して破断伸び等の物性が大幅に低下することが無いエラストマー組成物を提供することができる。ここで、残滓の含水率は、凝集を防止して分散性を良好にする観点からは９０質量％以下とすれば良いが、含水率を低下させるために必要なエネルギー量や、残滓の取り扱い性の観点からは、５質量％以上とすることが好ましい。なお、含水率とは、残滓の水分を既知のヒーターで蒸発（温度１２０℃）させ、その蒸発前後の重量変化を天秤等の既知の手段で測定することにより算出される値である。
　更に、配合する残滓の粒径を０．０２～６００μｍとすれば、製造コストの増加およびエラストマー組成物の物性低下を抑制することができる。残滓の粒径が０．０２μｍ未満の場合には事前粉砕等にかかるコストが高くなり、また、粒径が６００μｍより大きい場合にはエラストマー成分中での分散性が悪くエラストマー組成物の物性が低下すると共に残滓の含水率を低下させるために必要なエネルギー量が大きくなるからである。なお、粒径は、レーザー回折による粒子径測定（ＪＩＳ Ｚ８８２５－１）で求められ、該レーザー回折による方法において、粒子等の長軸－短軸の平均（球形と捉えられる）を測定して得られる値である。 An object of the present invention is to advantageously solve the above-mentioned problems, and the elastomer composition of the present invention is an elastomer composition in which a residue generated in an organic fermentation process is blended with an elastomer component. The water content is 5 to 90% by mass, and the particle size of the residue is 0.02 to 600 μm.
Thus, if the residue which remains after utilizing resources, such as the residue which arises in the fermentation process of organic substance, is mix | blended, the usage-amount of the elastomer component in an elastomer composition can be reduced. Moreover, since the residue produced in the fermentation process of organic matter is an inexpensive residue, it is suitable as an alternative raw material. Therefore, an elastomer composition with low cost and low environmental load can be provided by blending the residue into the elastomer component. Furthermore, the residue after the fermentation treatment also has an advantage that it is easy to handle because most of the decay factors such as proteins and lipids are decomposed during the fermentation treatment. The fermentation of organic matter means that the organic matter is decomposed by the action of microorganisms, and includes both anaerobic fermentation and aerobic fermentation, and also includes decomposition of carbohydrates and the like.
Also, if the moisture content of the residue to be blended is 5 to 90% by mass, the residue does not aggregate when blended into the elastomer component, and the residue is well dispersed in the elastomer composition. It is possible to provide an elastomer composition in which physical properties such as elongation at break do not significantly decrease as compared with an elastomer composition that does not. Here, the moisture content of the residue may be 90% by mass or less from the viewpoint of preventing agglomeration and improving dispersibility. However, the amount of energy necessary to reduce the moisture content and the handleability of the residue From this point of view, the content is preferably 5% by mass or more. The moisture content is a value calculated by evaporating residual moisture with a known heater (temperature 120 ° C.) and measuring a change in weight before and after the evaporation with a known means such as a balance.
Furthermore, if the particle size of the residue to be blended is 0.02 to 600 μm, an increase in manufacturing cost and a decrease in physical properties of the elastomer composition can be suppressed. If the particle size of the residue is less than 0.02 μm, the cost for pre-grinding becomes high, and if the particle size is more than 600 μm, the dispersibility in the elastomer component is poor and the physical properties of the elastomer composition are lowered. In addition, the amount of energy required to reduce the moisture content of the residue increases. The particle diameter is obtained by measuring the particle diameter by laser diffraction (JIS Z8825-1), and is obtained by measuring the average of the major axis and the minor axis (taken as a sphere) of the particles in the laser diffraction method. Value.
　ここで、本発明のエラストマー組成物は、前記有機物がバイオマスであることが好ましい。再生可能な生物由来の有機性資源であるバイオマスを用いれば、エラストマー組成物製造時の環境負荷をより低減することができるからである。 Here, in the elastomer composition of the present invention, the organic material is preferably biomass. This is because the use of biomass, which is an organic resource derived from renewable organisms, can further reduce the environmental load during the production of the elastomer composition.
　本発明のエラストマー組成物は、前記発酵処理が発酵菌を用いた有機物の発酵処理であり、前記残滓が前記発酵菌の細胞壁を含有することが好ましい。発酵菌を用いた有機物の発酵処理の際に生じる余剰汚泥等の残滓は多量に存在する利用可能性の低い廃棄物であるので安価であり、また、配合に際して複雑な工程や大きな加工エネルギーを必要としないからである。 In the elastomer composition of the present invention, it is preferable that the fermentation treatment is a fermentation treatment of an organic substance using a fermentation bacterium, and the residue contains a cell wall of the fermentation bacterium. Residues such as excess sludge generated during fermentation of organic matter using fermentative bacteria are low-use wastes that are present in large quantities and are inexpensive, and require complex processes and large processing energy when blending It is because it does not.
　本発明のエラストマー組成物は、前記残滓の主成分がペプチドグリカンであることが好ましい。ペプチドグリカンは、エラストマー成分に配合した際にエラストマー組成物に与える影響が少ない物質だからである。ここで、残滓の主成分とは残滓を構成する成分の主なものをいい、例えば残滓の５０質量％以上を構成する成分をいう。 In the elastomer composition of the present invention, the main component of the residue is preferably peptidoglycan. This is because peptidoglycan is a substance that has little influence on the elastomer composition when blended with the elastomer component. Here, the main component of the residue refers to a main component constituting the residue, for example, a component constituting 50% by mass or more of the residue.
　本発明のエラストマー組成物は、前記残滓を燻煙処理または炭化処理した後に前記エラストマー成分に配合することが好ましい。ここで、燻煙処理とは木材を熱した時に出る煙で残滓を燻すことを言う。燻煙処理を行うことにより、脱硫（消臭）および殺菌した取り扱いが容易な状態で残滓をエラストマー成分に配合することができる。また、炭化処理とは炭焼炉を用いて８００℃程度の温度で残滓を炭化することを言う。 The elastomer composition of the present invention is preferably blended into the elastomer component after the residue is smoked or carbonized. Here, the soot treatment means that the residue is smoked with smoke generated when wood is heated. By performing the soot treatment, the residue can be blended with the elastomer component in a state where desulfurization (deodorization) and sterilized handling are easy. Carbonization means carbonization of the residue at a temperature of about 800 ° C. using a charcoal furnace.
　また、本発明のエラストマー組成物は、前記有機物が植物の細胞壁および該植物の細胞壁が連なった短繊維の少なくとも一方を含有する有機物であり、前記残滓が前記植物の細胞壁および短繊維の少なくとも一方を含有することが好ましい。なお、本明細書では、アスペクト比が１以上５以下のものを粒子、５超５０以下のものを短繊維と呼んでいる。 Further, in the elastomer composition of the present invention, the organic substance is an organic substance containing at least one of a plant cell wall and a short fiber connected with the plant cell wall, and the residue comprises at least one of the plant cell wall and the short fiber. It is preferable to contain. In the present specification, those having an aspect ratio of 1 or more and 5 or less are called particles, and those having an aspect ratio of 5 or more and 50 or less are called short fibers.
　本発明のエラストマー組成物は、前記残滓が、前記植物の細胞壁の主成分であるセルロース粒子およびヘミセルロース粒子の少なくとも一方からなることが好ましい。セルロース粒子およびヘミセルロース粒子は、分散性が良くエラストマー組成物の性能に悪影響を与えないという点で代替材料として適しているからである。また、セルロース粒子およびヘミセルロース粒子の少なくとも一方を単体でエラストマー組成物に配合すれば、セルロース粒子およびヘミセルロース粒子が水分を吸収してミクロな排水溝として働くからである。従って、セルロース粒子およびヘミセルロース粒子の少なくとも一方を配合したエラストマー組成物を例えばスタッドレスタイヤに使用すれば、スタッドレスタイヤの性能（氷上性能等）を向上することができる。なお、前記セルロース粒子およびヘミセルロース粒子が凝集して塊状となっている場合、取り扱い性および分散性の観点から、該塊の直径は０．５μｍ～２ｍｍであることが好ましい。 In the elastomer composition of the present invention, the residue is preferably composed of at least one of cellulose particles and hemicellulose particles which are main components of the cell wall of the plant. This is because cellulose particles and hemicellulose particles are suitable as alternative materials in that they have good dispersibility and do not adversely affect the performance of the elastomer composition. Further, if at least one of cellulose particles and hemicellulose particles is blended into the elastomer composition alone, the cellulose particles and hemicellulose particles absorb moisture and function as micro drainage grooves. Therefore, if an elastomer composition containing at least one of cellulose particles and hemicellulose particles is used in, for example, a studless tire, the performance (such as performance on ice) of the studless tire can be improved. When the cellulose particles and hemicellulose particles are aggregated to form a lump, the lump diameter is preferably 0.5 μm to 2 mm from the viewpoints of handleability and dispersibility.
　本発明のエラストマー組成物は、前記残滓が前記短繊維からなり、該短繊維は、セルロース短繊維およびヘミセルロース短繊維の少なくとも一方からなることが好ましい。セルロースまたはヘミセルロースの短繊維は、エラストマー組成物の繊維補強材としても機能し得るので、代替材料として適しているからである。 In the elastomer composition of the present invention, the residue is preferably composed of the short fibers, and the short fibers are preferably composed of at least one of cellulose short fibers and hemicellulose short fibers. This is because cellulose or hemicellulose short fibers can also function as a fiber reinforcing material of an elastomer composition, and thus are suitable as an alternative material.
　ここで、前記短繊維の直径は１μｍ～１５０μｍであることが好ましく、前記短繊維の長さは０．３ｍｍ～２ｍｍであることが好ましい。直径が大きい場合および長さが長い場合には分散性が悪く、直径が小さい場合および長さが短い場合には補強効果が低いからである。更に、前記短繊維は、２～１０本集合して束状となっていることが好ましい。束状となることで補強効果が大きくなるが、集合する繊維数が多すぎると分散性が悪くなるからである。 Here, the diameter of the short fiber is preferably 1 μm to 150 μm, and the length of the short fiber is preferably 0.3 mm to 2 mm. This is because the dispersibility is poor when the diameter is large and the length is long, and the reinforcing effect is low when the diameter is small and the length is short. Further, it is preferable that 2 to 10 short fibers are gathered to form a bundle. This is because the reinforcing effect is increased by forming a bundle, but if the number of aggregated fibers is too large, the dispersibility deteriorates.
　本発明のエラストマー組成物は、前記残滓が、前記植物の細胞壁の主成分であるセルロース粒子およびヘミセルロース粒子の少なくとも一方と、前記植物の細胞壁が連なった短繊維とを含むことが好ましい。粒子と短繊維との双方を含む場合、短繊維に粒子が付随し、そして付随した粒子により短繊維等の表面に微細な凹凸が生じてエラストマー成分との物理的接着が強まるからである。 In the elastomer composition of the present invention, it is preferable that the residue contains at least one of cellulose particles and hemicellulose particles which are main components of the cell wall of the plant and short fibers in which the cell wall of the plant is continuous. This is because when both the particles and the short fibers are included, the particles are attached to the short fibers, and the accompanying particles cause fine irregularities on the surface of the short fibers and the like, thereby strengthening the physical adhesion with the elastomer component.
　本発明のエラストマー組成物は、前記発酵処理が麹菌および酵母菌の少なくとも一方を用いた処理であり、前記セルロース粒子およびヘミセルロース粒子には、麹菌および酵母菌の少なくとも一方の細胞壁が付随していることが好ましい。また、本発明のエラストマー組成物は、前記発酵処理が麹菌および酵母菌の少なくとも一方を用いた処理であって、前記短繊維には、麹菌および酵母菌の少なくとも一方の細胞壁が付随していることが好ましい。このように麹菌および酵母菌の少なくとも一方の細胞壁が付随している場合、付随した麹菌および酵母菌により短繊維等の表面に微細な凹凸が生じ、エラストマー成分との物理的接着が強まるからである。 In the elastomer composition of the present invention, the fermentation treatment is a treatment using at least one of Aspergillus or yeast, and the cellulose particles and hemicellulose particles are accompanied by at least one cell wall of Aspergillus or yeast. Is preferred. In the elastomer composition of the present invention, the fermentation treatment is a treatment using at least one of Aspergillus or yeast, and the short fiber is accompanied by at least one cell wall of Aspergillus or yeast. Is preferred. This is because when the cell wall of at least one of koji molds and yeasts is attached, fine irregularities are generated on the surface of short fibers and the like due to the accompanying koji molds and yeasts, and physical adhesion with the elastomer component is strengthened. .
　また、本発明のエラストマー組成物は、前記残滓が芋焼酎粕であることが好ましい。ここで、芋焼酎粕とは、芋焼酎の製造過程において発生する粕であり、例えば二次醪を蒸留した後に生じる残渣等が含まれる。なお、一般に芋焼酎粕には、セルロース粒子またはセルロース繊維、或いは、それらの混合物が含まれている。 Further, in the elastomer composition of the present invention, the residue is preferably shochu shochu. Here, the shochu shochu is a soot generated in the manufacturing process of the soot shochu and includes, for example, a residue generated after distilling the secondary soot. In general, the shochu liquor contains cellulose particles, cellulose fibers, or a mixture thereof.
　更に、本発明のエラストマー組成物の製造方法は、エラストマー成分に対して有機物の発酵処理において生じる残滓を配合してエラストマー組成物を製造する方法であって、前記残滓を粒径０．０２～６００μｍまで粉砕する粉砕工程と、前記残滓の含水率を５～９０質量％とする含水率調整工程と、含水率の調整および粉砕を行った残滓をエラストマー成分に配合して混練する混練工程とを含むことを特徴とする。このような製造方法によれば、上述したような、安価で、環境負荷が低く、且つ代替原料を使用しないエラストマー組成物と比較して破断伸び等の物性が大幅に低下することが無いエラストマー組成物が得られる。 Furthermore, the method for producing an elastomer composition of the present invention is a method for producing an elastomer composition by blending a residue generated in an organic fermentation process with an elastomer component, the residue having a particle size of 0.02 to 600 μm. A pulverizing step of pulverizing the residue to a moisture content of 5 to 90% by mass, and a kneading step of mixing and kneading the adjusted moisture content and pulverized residue in an elastomer component. It is characterized by that. According to such a production method, an elastomer composition that is inexpensive, has a low environmental impact, and does not significantly reduce physical properties such as elongation at break as compared with an elastomer composition that does not use an alternative raw material. Things are obtained.
　ここで、上述した本発明のエラストマー組成物の製造方法は、前記粉砕工程を、前記含水率調整工程より前に含むことが好ましい。このように、粉砕して粒径を小さくした残滓を所定の含水率とした後にエラストマー成分に配合・混練してエラストマー組成物を製造すれば、含水率調整時には残滓が粒径０．０２～６００μｍまで粉砕されて比表面積が大きくなっているので、容易に残滓の含水率を調整することができるからである。即ち、エラストマー組成物の製造にあたって残滓の含水率の調整に要するエネルギーおよび時間を大幅に少なくすることができるからである。 Here, it is preferable that the manufacturing method of the elastomer composition of the present invention described above includes the pulverization step before the moisture content adjustment step. In this way, if an elastomer composition is produced by blending and kneading the elastomer, which has been pulverized to reduce the particle size, to a predetermined moisture content and then blended and kneaded with the elastomer component, the residue has a particle size of 0.02 to 600 μm when adjusting the moisture content. This is because the water content of the residue can be easily adjusted since the specific surface area is increased by grinding. That is, the energy and time required for adjusting the moisture content of the residue in the production of the elastomer composition can be greatly reduced.
　上述した本発明のエラストマー組成物の製造方法は、前記残滓を篩に掛けて篩上残滓と篩下残滓とに選別する選別工程を、前記混練工程より前に含み、前記混練工程で前記篩下残滓をエラストマー成分に配合して混練することが好ましい。なお、本発明のエラストマー組成物の製造方法は、前記選別工程を、前記粉砕工程の後、且つ、前記含水率調整工程の前に含むことが更に好ましい。粉砕工程の後に篩い分けを行えば所望の粒径の残滓を容易に選別することができるからである。また、選別工程のみでは篩上残滓が廃棄物となってしまい、粉砕工程のみでは粒径の揃った残滓を得ることができないところ、このように粉砕工程と選別工程とを組み合わせれば廃棄物量を低減しつつ粒径の揃った残滓を得ることができるからである。更に、粉砕および選別を行った後であれば含水率を容易に調整できるからである。 The above-described method for producing an elastomer composition of the present invention includes a screening step of screening the residue into a screened residue and a screened residue before the kneading step. The residue is preferably kneaded with the elastomer component. In addition, as for the manufacturing method of the elastomer composition of this invention, it is still more preferable that the said selection process is included after the said crushing process and before the said moisture content adjustment process. This is because a residue having a desired particle diameter can be easily selected by sieving after the pulverization step. In addition, the residue on the sieve becomes waste only in the sorting process, and residue having a uniform particle size cannot be obtained only in the pulverizing process. If the grinding process and the sorting process are combined in this way, the amount of waste can be reduced. This is because it is possible to obtain a residue having a uniform particle diameter while being reduced. Furthermore, the moisture content can be easily adjusted after pulverization and selection.
　また、本発明のエラストマー組成物の製造方法は、エラストマー成分に対して有機物の発酵処理において生じる残滓を配合してエラストマー組成物を製造する方法であって、前記残滓の含水率を５～９０質量％とする含水率調整工程と、含水率を調整した残滓をメッシュサイズが６００μｍ以下の篩に掛けて篩上残滓と篩下残滓とに選別することを含む選別工程と、前記篩下残滓をエラストマー成分に配合して混練する混練工程とを含むことを特徴とする。このような製造方法によれば、上述したような、安価で、環境負荷が低く、代替原料を使用しないエラストマー組成物と比較して破断伸び等の物性が大幅に低下することが無いエラストマー組成物が得られる。 The method for producing an elastomer composition of the present invention is a method for producing an elastomer composition by blending a residue produced in an organic fermentation process with an elastomer component, wherein the moisture content of the residue is 5 to 90 mass%. A moisture content adjusting step, a screening step including screening the residue after adjusting the moisture content on a sieve having a mesh size of 600 μm or less to obtain an on-screen residue and an under-screen residue, and the above-mentioned under-screen residue as an elastomer And a kneading step in which the ingredients are mixed and kneaded. According to such a manufacturing method, as described above, the elastomer composition is inexpensive, has a low environmental impact, and does not significantly reduce physical properties such as elongation at break as compared with an elastomer composition that does not use an alternative raw material. Is obtained.
　更に、本発明のエラストマー組成物の製造方法は、エラストマー成分に対して有機物の発酵処理において生じる残滓を配合してエラストマー組成物を製造する方法であって、前記残滓をメッシュサイズが６００μｍ以下の篩に掛けて篩上残滓と篩下残滓とに選別することを含む選別工程と、前記篩下残滓の含水率を５～９０質量％とする含水率調整工程と、含水率を調整した篩下残滓をエラストマー成分に配合して混練する混練工程とを含むことを特徴とする。このような製造方法によれば、上述したような、安価で、環境負荷が低く、代替原料を使用しないエラストマー組成物と比較して破断伸び等の物性が大幅に低下することが無いエラストマー組成物が得られる。更に、この製造方法によれば、篩い分けした際に篩を通過した粒径の小さい篩下残滓を所定の含水率とした後にエラストマー成分に配合・混練してエラストマー組成物を製造しており、含水率を調整してエラストマー成分に配合・混練する残滓は粒径が小さく比表面積が大きいものであるので、容易に残滓の含水率を調整することができる。即ち、エラストマー組成物の製造にあたって残滓の含水率の調整に要するエネルギーおよび時間を大幅に少なくすることができる。なお、配合する残滓の粒径を篩い分けにより調整する場合、篩い分けに要するコストの観点からは、エラストマー成分に配合する残滓の粒径を０．０２μｍ以上とする必要は無い。 Furthermore, the method for producing an elastomer composition of the present invention is a method for producing an elastomer composition by blending a residue generated in an organic fermentation process with an elastomer component, wherein the residue is sieved with a mesh size of 600 μm or less. A screening process including screening to a sieve residue and a sieve residue, a moisture content adjusting process in which the moisture content of the sieve residue is 5 to 90% by mass, and a sieve residue having an adjusted moisture content And a kneading step of kneading with an elastomer component. According to such a manufacturing method, as described above, the elastomer composition is inexpensive, has a low environmental impact, and does not significantly reduce physical properties such as elongation at break as compared with an elastomer composition that does not use an alternative raw material. Is obtained. Furthermore, according to this production method, an elastomer composition is produced by blending and kneading the elastomer component with a predetermined moisture content after passing through a sieve with a small particle diameter when passing through the sieve, Since the residue mixed and kneaded with the elastomer component after adjusting the water content has a small particle size and a large specific surface area, the water content of the residue can be easily adjusted. That is, the energy and time required for adjusting the moisture content of the residue in producing the elastomer composition can be greatly reduced. In addition, when adjusting the particle size of the residue to mix | blend by sieving, it is not necessary to make the particle size of the residue mix | blended with an elastomer component 0.02 micrometer or more from a viewpoint of the cost required for sieving.
　ここで、上記エラストマー組成物の製造方法は、前記選別工程でメッシュサイズの異なる少なくとも２つの篩を使用して残滓を選別することが好ましい。メッシュサイズの異なる篩を使用して篩い分けを行う事により、粒径の大きい残滓を確実に選別して取り除くことができるからである。 Here, in the method for producing the elastomer composition, it is preferable to sort the residue using at least two sieves having different mesh sizes in the sorting step. This is because residue having a large particle size can be reliably selected and removed by sieving using sieves having different mesh sizes.
　具体的には、上記エラストマー組成物の製造方法は、前記選別工程が、有機物の発酵処理後の残滓をメッシュサイズ７５０～１５００μｍの第１の篩に掛ける工程と、前記第１の篩を通過した残滓をメッシュサイズ９０～６００μｍの第２の篩に掛ける工程とを含むことが好ましい。このようにすれば、含水率を調整し易い所望の粒径（例えば、６００μｍ以下）の残滓を選択して配合することができるからである。 Specifically, in the method for producing the elastomer composition, the selection step passes the first sieve having a mesh size of 750 to 1500 μm through the residue after fermentation of the organic matter, and the first sieve. And a step of passing the residue over a second sieve having a mesh size of 90 to 600 μm. This is because a residue having a desired particle size (for example, 600 μm or less) whose water content can be easily adjusted can be selected and blended.
　また、本発明のエラストマー組成物の製造方法は、前記含水率調整工程が、乾燥により含水率を５～９０質量％とする乾燥工程、圧搾により含水率を６０～９０質量％とする圧搾工程、または圧搾した後に乾燥することにより含水率を５～９０質量％とする圧搾・乾燥工程であることが好ましい。含水率調整工程が、乾燥工程の場合には含水率を容易に低下させることができ、圧搾工程の場合には低コストで含水率を低下させることができ、圧搾・乾燥工程である場合には低コストで容易に含水率を低下させることができるからである。 Further, in the method for producing an elastomer composition of the present invention, the moisture content adjusting step includes a drying step in which the moisture content is 5 to 90% by mass by drying, a pressing step in which the moisture content is 60 to 90% by mass by pressing, Alternatively, it is preferably a pressing / drying step in which the moisture content is 5 to 90% by mass by drying after pressing. In the case where the moisture content adjustment step is a drying step, the moisture content can be easily reduced. In the case of a pressing step, the moisture content can be reduced at a low cost. This is because the moisture content can be easily reduced at a low cost.
　ここで、上記エラストマー組成物の製造方法においては、前記含水率調整工程が、前記乾燥工程または前記圧搾・乾燥工程であり、乾燥を、温度１３０～２５０℃で行うことが好ましい。有機物の発酵処理後の残滓を、１３０～２５０℃の温度、例えば石臼方式等のろ過装置で残滓をろ過した際のろ液の沸点よりも高い温度で乾燥することにより、所望の含水率の残滓を迅速に得て、エラストマー組成物の製造に要する時間を短縮することができるからである。 Here, in the method for producing the elastomer composition, the moisture content adjusting step is preferably the drying step or the pressing / drying step, and the drying is preferably performed at a temperature of 130 to 250 ° C. The residue after fermentation of the organic matter is dried at a temperature of 130 to 250 ° C., for example, at a temperature higher than the boiling point of the filtrate when the residue is filtered with a filtration device such as a stone mill method. This is because the time required for producing the elastomer composition can be shortened.
　また、本発明のタイヤは、少なくとも一部を、上記エラストマー組成物、或いは、上記製造方法で製造したエラストマー組成物で構成したことを特徴とする。従来のタイヤではゴム等のエラストマーのみで構成していた部分を、有機物の発酵処理において生じる残滓であって所定の粒径および含水率としたものを配合したエラストマー組成物で構成することにより、タイヤとしての性能を維持しつつエラストマー成分の使用量を低減して環境負荷を低減可能なタイヤを提供することができる。 Further, the tire of the present invention is characterized in that at least a part of the tire is composed of the elastomer composition or the elastomer composition produced by the production method. In the conventional tire, the tire is composed only of an elastomer such as rubber, and the tire is composed of an elastomer composition containing a residue generated in the fermentation of organic matter and having a predetermined particle size and moisture content. It is possible to provide a tire capable of reducing the environmental load by reducing the amount of the elastomer component used while maintaining the performance as described above.
　本発明によれば、所定の代替原料をエラストマー成分に配合することにより、複雑な製造工程を用いることなく低コストで製造が可能で且つ環境に優しいエラストマー組成物を、代替原料を使用しないエラストマー組成物と比較して物性を大幅に低下させることなく提供することができる。また、当該エラストマー組成物の効率的な製造方法、並びに当該エラストマー組成物を用いた、製造時の環境負荷が低いタイヤを提供することができる。 According to the present invention, an elastomer composition that does not use an alternative raw material can be produced at low cost without using a complicated manufacturing process by blending a predetermined alternative raw material into the elastomer component. It can be provided without significantly reducing the physical properties as compared with the product. Moreover, the efficient manufacturing method of the said elastomer composition and the tire with a low environmental load at the time of manufacture using the said elastomer composition can be provided.
本発明のタイヤの一例の断面図である。It is sectional drawing of an example of the tire of this invention. （ａ）～（ｃ）は、残滓の含水率を調整する手順の例を示すフローチャートである。(A)-(c) is a flowchart which shows the example of the procedure which adjusts the moisture content of a residue.
＜エラストマー組成物＞
　以下に、本発明のエラストマー組成物を詳細に説明する。本発明に従うエラストマー組成物は、エラストマー成分に、有機物の発酵処理において生じる残滓であって含水率を５～９０質量％とし、且つ、粒径を０．０２～６００μｍとしたものを配合して混練することで、エラストマー成分の使用量を低減したことを特徴とする。なお、有機物の発酵処理において生じる残滓は、含水率を５～５０質量％として配合することが好ましく、含水率を５～３０質量％として配合することが更に好ましい。例えばエラストマー成分がゴム成分の場合、残滓の含水率が低いほどゴム組成物中に存在する水分が少なくなるため、ゴム組成物を混練や加硫した際に水分が蒸発してゴム組成物中で気泡が発生する可能性を低減することができ、ゴム組成物の物性低下を抑制し得ると共に、ゴム組成物の混練がし易いからである。また、有機物の発酵処理において生じる残滓は、粒径を０．０２～５００μｍとして配合することが好ましく、粒径を０．０２～４００μｍとして配合することが更に好ましい。更に、本発明のエラストマー組成物は、残滓の配合量が、エラストマー成分１００質量部に対して０．５～９０質量部、好ましくは０．５～１０質量部であることが好ましい。残滓の配合量を０．５質量部以上とすることで環境負荷の低減を十分に達成することができ、また、残滓の配合量を９０質量部以下とすることで、代替原料を使用しないエラストマー組成物と同程度の性能を有するエラストマー組成物を提供することができるからである。 <Elastomer composition>
Below, the elastomer composition of this invention is demonstrated in detail. The elastomer composition according to the present invention is kneaded with the elastomer component, which is a residue generated in the fermentation treatment of organic matter, having a water content of 5 to 90% by mass and a particle size of 0.02 to 600 μm. Thus, the amount of the elastomer component used is reduced. The residue produced in the fermentation treatment of organic matter is preferably blended with a moisture content of 5 to 50% by mass, and more preferably with a moisture content of 5 to 30% by mass. For example, when the elastomer component is a rubber component, the lower the moisture content of the residue, the less moisture present in the rubber composition. Therefore, when the rubber composition is kneaded or vulcanized, the moisture evaporates and is contained in the rubber composition. This is because the possibility of bubbles being generated can be reduced, the physical properties of the rubber composition can be suppressed from being lowered, and the rubber composition can be easily kneaded. The residue produced in the fermentation treatment of organic matter is preferably blended with a particle size of 0.02 to 500 μm, and more preferably blended with a particle size of 0.02 to 400 μm. Further, in the elastomer composition of the present invention, the amount of the residue is preferably 0.5 to 90 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the elastomer component. Elastomer that can sufficiently reduce the environmental load by making the blending amount of the residue 0.5 parts by mass or more, and does not use an alternative raw material by making the blending amount of the residue 90 parts by mass or less. This is because an elastomer composition having performance equivalent to that of the composition can be provided.
　ここで、エラストマー成分は、天然ゴム、合成ゴム等のゴム成分、熱可塑性エラストマー、熱硬化性エラストマー等の樹脂、或いは、それらを混合したものからなり、合成ゴムとしては、具体的には、スチレン－ブタジエン共重合体ゴム（ＳＢＲ）、ポリブタジエンゴム（ＢＲ）、ポリイソプレンゴム（ＩＲ）、アクリロニトリル－ブタジエン共重合体ゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）等が挙げられる。また、熱可塑性エラストマーとしては、エチレン－メチルアクリレート共重合体、スチレン系エラストマー、ウレタン系エラストマー、ポリオレフィン系エラストマー等が、熱硬化性エラストマーとしては、フェノール系エラストマー、ウレア系エラストマー、メラミン系エラストマー、エポキシ系エラストマー等が挙げられる。なお、本発明のエラストマー組成物は、任意に、カーボンブラックおよびシリカ等の補強性充填剤や、アロマオイル等の軟化剤、加硫促進剤、加硫促進助剤、老化防止剤等の一般に添加される添加剤等を含んでも良い。 Here, the elastomer component is composed of a rubber component such as natural rubber or synthetic rubber, a resin such as a thermoplastic elastomer or a thermosetting elastomer, or a mixture thereof. Specifically, as the synthetic rubber, 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. Thermoplastic elastomers include ethylene-methyl acrylate copolymers, styrene elastomers, urethane elastomers, and polyolefin elastomers. Thermosetting elastomers include phenol elastomers, urea elastomers, melamine elastomers, and epoxy. Based elastomers and the like. The elastomer composition of the present invention is optionally added to reinforcing fillers such as carbon black and silica, softeners such as aroma oil, vulcanization accelerators, vulcanization accelerators, anti-aging agents, etc. Additive may be included.
　発酵処理される有機物としては、例えば、紙、家畜***物、食品廃棄物、焼酎粕（芋、米、麦焼酎の粕）、建設発生木材、黒液、余剰汚泥（例えば、下水汚泥、屎尿汚泥、メタン発酵汚泥）、飲料成分の抽出残渣（茶殻やコーヒー粕など）等の廃棄物系バイオマスと、稲わら、麦わら、籾殻、林地残材（間伐材・被害木など）等の未利用バイオマスと、飼料作物、果実（ブドウ、リンゴ、サクランボ、ヤシの実など）、穀物（米、麦、トウモロコシなど）、根菜類（ジャガイモ、サツマイモなど）、でんぷん系作物等の資源作物バイオマスとを含む、再生可能な生物由来の有機性資源であるバイオマスが挙げられる。このようなバイオマスを用いれば、エラストマー組成物製造時の環境負荷をより低減できる。なお、資源の有効活用および環境負荷の低減という観点から、廃棄物系バイオマスを有機物として用いることが好ましい。 Examples of organic substances to be fermented include paper, livestock waste, food waste, shochu (potato, rice, barley shochu), construction-generated wood, black liquor, excess sludge (eg, sewage sludge, manure sludge) , Methane fermentation sludge), waste-based biomass such as beverage component extraction residue (such as tea husk and coffee straw), and unused biomass such as rice straw, straw, rice husk, and forest land residues (thinned wood, damaged wood, etc.) Including forage crops, fruits (grape, apples, cherries, palm nuts, etc.), cereals (rice, wheat, corn, etc.), root vegetables (potatoes, sweet potatoes, etc.), and resource crop biomass such as starch crops Biomass, which is an organic resource derived from a living organism, can be mentioned. If such biomass is used, the environmental load at the time of elastomer composition manufacture can be reduced more. In addition, it is preferable to use waste biomass as organic matter from the viewpoint of effective utilization of resources and reduction of environmental burden.
　また、有機物の発酵処理方法としては、嫌気性微生物を用いた発酵処理として、例えばメタン生成菌を用いたメタン発酵、エタノール発酵菌を用いたエタノール発酵、水素生成菌を用いた水素発酵等があり、好気性微生物を用いた発酵処理として、例えば酢酸産生菌を用いた酢酸発酵、アンモニア酸化細菌等の各種酸化細菌を用いた排水処理等がある。ここで、好気性微生物を利用した好気性発酵処理は、残滓の臭気が少ないので、配合時の消臭処理が不要であるという点で発酵処理方法として好ましい。一方、メタン発酵処理、エタノール発酵処理、または水素発酵処理は、資源から効率的に燃料等を取り出した後の残滓を用いることができ、環境への負荷低減と共に資源の有効活用を図ることができるという点で発酵処理方法として好ましい。 Moreover, as a fermentation treatment method of organic matter, there are, for example, methane fermentation using methanogen, ethanol fermentation using ethanol fermenter, hydrogen fermentation using hydrogen producer, etc. Examples of fermentation treatment using aerobic microorganisms include acetic acid fermentation using acetic acid-producing bacteria, and wastewater treatment using various oxidizing bacteria such as ammonia oxidizing bacteria. Here, the aerobic fermentation treatment using aerobic microorganisms is preferable as a fermentation treatment method in that the deodorization treatment at the time of blending is unnecessary because the odor of the residue is small. On the other hand, in methane fermentation treatment, ethanol fermentation treatment, or hydrogen fermentation treatment, the residue after efficiently removing the fuel from the resources can be used, and the resources can be reduced and the resources can be effectively utilized. Therefore, it is preferable as a fermentation treatment method.
　なお、上述した通り、エラストマー成分に配合する残滓としては、例えば、好気または嫌気条件下で有機物の生物学的処理（発酵）を行った際に生じる余剰汚泥等を用いることができるが、余剰汚泥を残滓として用いる場合にはエラストマー組成物の軽量化および金属含有によるエラストマー組成物への悪影響防止という観点から、鉄系の凝集剤を含まない汚泥、例えばアルミ化合物を凝集剤として使用した汚泥が好ましく、凝集剤を含まない汚泥がより好ましい。 As described above, as the residue to be blended in the elastomer component, for example, surplus sludge generated when biological treatment (fermentation) of organic substances under aerobic or anaerobic conditions can be used. When sludge is used as a residue, from the viewpoint of reducing the weight of the elastomer composition and preventing adverse effects on the elastomer composition due to metal inclusion, sludge containing no iron-based flocculant, for example, sludge using an aluminum compound as the flocculant is used. Preferably, sludge containing no flocculant is more preferable.
　本発明のエラストマー組成物に配合し得る、有機物の発酵処理において生じる残滓の他の例としては、発酵菌等の細胞壁に含まれるペプチドグリカン、植物の細胞壁に含まれるセルロース粒子、ヘミセルロース粒子、リグニン、植物の細胞壁が連なった短繊維（セルロース短繊維、ヘミセルロース短繊維等）、またはそれらの混合物を含有する残滓が挙げられる。なお、残滓は、セルロース粒子およびヘミセルロース粒子の少なくとも一方を単体で含むことが好ましい。また、セルロース粒子およびヘミセルロース粒子の少なくとも一方と、短繊維との双方を含むことが更に好ましい。セルロース粒子およびヘミセルロース粒子の少なくとも一方を単体でエラストマー組成物に配合することにより、セルロース粒子およびヘミセルロース粒子が水分を吸収してミクロな排水溝として働くことができるので、該エラストマー組成物を例えばスタッドレスタイヤに用いた場合にスタッドレスタイヤの性能（氷上性能等）を向上することができるからである。また、粒子と短繊維との双方を含むことにより、例えばエラストマー組成物をスタッドレスタイヤに使用した場合に、水分を吸収するという効果を奏することが可能だからである。更に、残滓は、ペプチドグリカン、セルロース粒子およびヘミセルロース粒子の少なくとも一方、並びにセルロース短繊維およびヘミセルロース短繊維の少なくとも一方を含むことが好ましい。ペプチドグリカンと、粒子と、短繊維とを含むことにより、例えばエラストマー組成物をスタッドレスタイヤに使用した場合に、水分を吸収するという効果を奏することが可能だからである。 Other examples of residues generated in the fermentation treatment of organic matter that can be blended in the elastomer composition of the present invention include peptidoglycan contained in the cell wall of fermenting bacteria, cellulose particles contained in the cell wall of plants, hemicellulose particles, lignin, plants And a residue containing short fibers (cellulosic short fibers, hemicellulose short fibers, etc.) in which the cell walls are continuous, or a mixture thereof. The residue preferably contains at least one of cellulose particles and hemicellulose particles alone. Further, it is more preferable that at least one of cellulose particles and hemicellulose particles and short fibers are included. By blending at least one of cellulose particles and hemicellulose particles into the elastomer composition alone, the cellulose particles and hemicellulose particles can absorb moisture and serve as a micro drainage groove. This is because the performance (such as on-ice performance) of the studless tire can be improved when used in the above. In addition, by including both particles and short fibers, for example, when an elastomer composition is used in a studless tire, it is possible to achieve an effect of absorbing moisture. Furthermore, the residue preferably contains at least one of peptidoglycan, cellulose particles and hemicellulose particles, and at least one of cellulose short fibers and hemicellulose short fibers. This is because by including peptidoglycan, particles, and short fibers, for example, when an elastomer composition is used in a studless tire, an effect of absorbing moisture can be achieved.
　ここで、セルロース粒子およびヘミセルロース粒子とは、植物の細胞壁の主成分であり、アスペクト比が１以上５以下のものである。またセルロース短繊維およびヘミセルロース短繊維とは、植物の細胞壁が連なったものであり、アスペクト比が５超５０以下のものである。 Here, cellulose particles and hemicellulose particles are the main components of plant cell walls and have an aspect ratio of 1 or more and 5 or less. In addition, the short cellulose fiber and the short hemicellulose fiber are a series of plant cell walls, and have an aspect ratio of more than 5 and 50 or less.
　なお、短繊維の直径は１μｍ～１５０μｍであることが好ましく、短繊維の長さは０．３ｍｍ～２ｍｍであることが好ましい。直径が大きい場合および長さが長い場合には分散性が悪く、直径が小さい場合および長さが短い場合には補強効果が低いからである。なお、短繊維は、２～１０本集合して束状となっていることも好ましい。また、残滓中でセルロース粒子およびヘミセルロース粒子が凝集して塊状となっている場合、取り扱い性および分散性の観点から、該塊の直径は０．５μｍ～２ｍｍであることが好ましい。更に、有機物の発酵処理が麹菌および酵母菌の少なくとも一方を用いた処理である場合、セルロース粒子およびヘミセルロース粒子には、麹菌および酵母菌の少なくとも一方の細胞壁が付随していることが好ましく、また、短繊維にも、麹菌および酵母菌の少なくとも一方の細胞壁が付随していることが好ましい。このように麹菌および酵母菌の少なくとも一方の細胞壁が付随している場合、付随した麹菌および酵母菌により粒子や短繊維等の表面に微細な凹凸が生じ、エラストマー成分との物理的接着が強まるからである。 In addition, the diameter of the short fiber is preferably 1 μm to 150 μm, and the length of the short fiber is preferably 0.3 mm to 2 mm. This is because the dispersibility is poor when the diameter is large and the length is long, and the reinforcing effect is low when the diameter is small and the length is short. It is also preferable that 2 to 10 short fibers are assembled into a bundle. Further, when the cellulose particles and hemicellulose particles are aggregated in the residue to form a lump, the diameter of the lump is preferably 0.5 μm to 2 mm from the viewpoint of handleability and dispersibility. Furthermore, when the fermentation treatment of the organic substance is a treatment using at least one of koji mold or yeast, it is preferable that at least one cell wall of koji mold or yeast is attached to the cellulose particles and hemicellulose particles, It is preferable that at least one cell wall of Neisseria gonorrhoeae and yeast is also attached to the short fiber. In this way, when the cell wall of at least one of koji mold or yeast is attached, the accompanying koji mold or yeast causes fine irregularities on the surface of particles, short fibers, etc., and physical adhesion with the elastomer component is strengthened. It is.
　そして、上述した残滓は、その含水率を５～９０質量％、好ましくは８０質量％以下、更に好ましくは７０質量％以下、より好ましくは５０質量％以下、特に好ましくは３０質量％以下としてエラストマー組成物に配合される。ここで、残滓の含水率は、例えば熱風乾燥、ドラム乾燥、熱板乾燥、燻煙処理等の乾燥や、フィルタープレス等の圧搾など、既知の手法を用いて調整することができるが、有機物の発酵処理を行った直後に残っている残滓の含水率が所望の含水率の範囲にある場合には、含水率の調整を行うことなくエラストマー成分に配合しても良い。 The above-mentioned residue has an moisture content of 5 to 90% by mass, preferably 80% by mass or less, more preferably 70% by mass or less, more preferably 50% by mass or less, and particularly preferably 30% by mass or less. Is blended into the product. Here, the moisture content of the residue can be adjusted using known techniques such as drying with hot air drying, drum drying, hot plate drying, smoke treatment, etc., and pressing with a filter press, etc. When the moisture content of the residue remaining immediately after the fermentation treatment is in the desired moisture content range, it may be blended into the elastomer component without adjusting the moisture content.
　なお、残滓を乾燥させて含水率を調整する際の温度としては、作業性の観点から、１３０～２５０℃が好ましく、石臼方式等のろ過装置で残滓をろ過した際のろ液の沸点よりも高い温度が更に好ましい。また、発酵処理が嫌気性発酵処理の場合、残滓の含水率の調整手段としては、木材を熱した時に出る煙で残滓を燻す燻煙処理や、残滓を８００℃程度の高温で炭化する炭化処理が好ましい。燻煙処理を行うことにより、脱硫（消臭）および殺菌した取り扱いが容易な状態で残滓をエラストマー成分に配合することができるからである。 The temperature at which the residue is dried and the water content is adjusted is preferably 130 to 250 ° C. from the viewpoint of workability, and is higher than the boiling point of the filtrate when the residue is filtered with a filtration device such as a stone mill method. Higher temperatures are even more preferred. In addition, when the fermentation process is an anaerobic fermentation process, as a means for adjusting the moisture content of the residue, a smoke process for removing residue with smoke generated when wood is heated, or a carbonization process for carbonizing the residue at a high temperature of about 800 ° C. Is preferred. This is because by performing the soot treatment, the residue can be blended with the elastomer component in a state where desulfurization (deodorization) and sterilized handling are easy.
　更に、上述した残滓は、エラストマー成分への配合性および含水率の調整の容易性の観点から、粒径が６００μｍ以下、特には０．０２～６００μｍであることが必要である。そのため、粒径が６００μｍより大きい残滓を含むものについては、例えば図２（ａ）～（ｃ）に示すように、任意に、篩い分け、粉砕、またはその両方を行った後に必要に応じて含水率を調整（圧搾、乾燥）した上でエラストマー成分に配合することができる。ここで、篩い分けを行った後に粉砕または含水率の調整を行う場合には、粉砕および含水率の調整は篩下残滓に対して行う。なお、含水率の調整は粉砕または篩い分けの前に行っても良い。また、含水率を調整した残滓（含水率調整残滓）は、必要に応じて更に粉砕、篩い分けを行っても良い。因みに、エラストマー成分に配合する残滓の粒径を篩い分けにより調整する場合には、配合する残滓は粒径０．０２μｍ未満の残滓を含むものであっても良い。篩い分けにより粒径０．０２μｍ未満の残滓を分離する場合、残滓を篩に掛ける回数が増加してしまうからである。なお、エラストマー組成物の物性低下防止の観点からは、残滓の粒径は、０．０２～５００μｍであることが好ましく、０．０２～４００μｍであることが特に好ましい。 Further, the above-mentioned residue needs to have a particle size of 600 μm or less, particularly 0.02 to 600 μm, from the viewpoint of blendability into the elastomer component and ease of adjustment of the moisture content. Therefore, for those containing a residue having a particle size larger than 600 μm, as shown in FIGS. 2 (a) to (c), for example, water is optionally contained after sieving, pulverizing, or both. The rate can be adjusted (pressed, dried) and then blended into the elastomer component. Here, when pulverization or adjustment of the moisture content is performed after sieving, the pulverization and adjustment of the moisture content are performed with respect to the residue under the sieve. The moisture content may be adjusted before pulverization or sieving. Further, the residue whose moisture content has been adjusted (moisture content adjustment residue) may be further pulverized and sieved as necessary. Incidentally, when adjusting the particle size of the residue mix | blended with an elastomer component by sieving, the residue to mix | blend may contain the residue of less than 0.02 micrometer in particle size. This is because when the residue having a particle size of less than 0.02 μm is separated by sieving, the number of times the residue is sieved increases. From the viewpoint of preventing deterioration of the physical properties of the elastomer composition, the particle size of the residue is preferably 0.02 to 500 μm, and particularly preferably 0.02 to 400 μm.
　具体的には、例えば既知の湿式粉砕機で残滓を粉砕し、或いは、既知の湿式篩を用いて残滓を篩い分けすることにより所望の粒径の残滓を得て、該残滓の含水率を調整した上でエラストマー成分に配合することができる。ここで、篩い分けでは篩上に残った残滓が廃棄物となってしまうので、エラストマー成分に配合する残滓の粒径の調整方法としては粉砕が好ましい。なお、篩い分けは、所望の粒径の残滓を確実に得るために、メッシュサイズの異なる篩を用いて複数回に分けて実施し、或いは、メッシュサイズの異なる篩を下方に行くほどメッシュサイズが小さい篩となるように積み重ねたものを用いて実施することができる。因みに、メッシュサイズの異なる篩としては、例えばメッシュサイズが７５０～１５００μｍの篩と９０～６００μｍの篩とを用いることができる。 Specifically, for example, the residue is pulverized with a known wet pulverizer, or the residue is sieved using a known wet sieve to obtain a residue having a desired particle size, and the moisture content of the residue is adjusted. And then blended into the elastomer component. Here, since the residue remaining on the sieve becomes waste in sieving, pulverization is preferred as a method for adjusting the particle size of the residue to be blended in the elastomer component. In addition, sieving is carried out in multiple times using sieves with different mesh sizes in order to reliably obtain a residue having a desired particle size, or the mesh size becomes smaller as the sieves with different mesh sizes are moved downward. It can implement using what was piled up so that it might become a small sieve. Incidentally, as a sieve having different mesh sizes, for example, a sieve having a mesh size of 750 to 1500 μm and a sieve having a mesh size of 90 to 600 μm can be used.
　本発明のエラストマー組成物は、上述した方法で粉砕または篩い分けを行い、その後に含水率の調整を行った残滓を、任意の充填剤（カーボンブラック等）および添加剤とともにエラストマー成分に配合して混練することにより調製することができる。なお、本発明のエラストマー組成物の調製方法に特に制限はなく、例えば、バンバリーミキサーやロール等を用いて、エラストマー成分に、残滓と、必要に応じて適宜選択した各種配合剤とを練り込んで調製することができる。 The elastomer composition of the present invention is obtained by blending the residue after pulverization or sieving by the above-described method and adjusting the moisture content into the elastomer component together with an optional filler (carbon black, etc.) and additives. It can be prepared by kneading. In addition, there is no restriction | limiting in particular in the preparation method of the elastomer composition of this invention, For example, the residue and the various compounding agents selected suitably as needed are kneaded into an elastomer component using a Banbury mixer, a roll, etc. Can be prepared.
＜タイヤ＞
　本発明のタイヤは、少なくとも一部を上記エラストマー組成物で構成したことを特徴とし、それ以外は通常のタイヤと同様の製造方法を用いて製造することができる。 <Tire>
The tire of the present invention is characterized in that at least a part thereof is composed of the above-mentioned elastomer composition, and other than that, it can be manufactured using the same manufacturing method as that of a normal tire.
　次に、本発明のタイヤを、図を参照しながら詳細に説明する。図１は、本発明のタイヤの一例の断面図である。図１に示すタイヤは、一対のビード部１及び一対のサイドウォール部２と、両サイドウォール部２に連なるトレッド部３とを有し、上記一対のビード部１間にトロイド状に延在してこれら各部１，２，３を補強するカーカス４と、該カーカス４のクラウン部のタイヤ半径方向外側に位置するベルト５とを具える。 Next, the tire of the present invention will be described in detail with reference to the drawings. 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 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 portion of the carcass 4 are provided.
　図示例のタイヤにおいて、カーカス４は、一枚のカーカスプライからなり、また、上記ビード部１内に夫々配設した一対のビードコア（ワイヤ）６間にトロイド状に延在する本体部と、各ビードコア６の周りでタイヤ幅方向の内側から外側に向けて半径方向外方に巻上げた折り返し部とからなる。なお、図示例のカーカス４は、一枚のカーカスプライよりなるが、本発明のタイヤにおいては、カーカスプライの枚数は複数であってもよい。 In the illustrated tire, 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; 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. In the illustrated example, the carcass 4 is composed of one carcass ply. However, in the tire of the present invention, a plurality of carcass plies may be provided.
　また、図示例のタイヤにおいて、ベルト５は、二枚のベルト層からなるが、本発明のタイヤにおいて、ベルトを構成するベルト層の枚数は一枚以上であればよく、これに限られるものではない。更に、本発明のタイヤは、ベルト５のタイヤ半径方向外側に、タイヤ周方向に対し実質的に平行に配列したコードのゴム引き層からなるベルト補強層を具えてもよく、ベルト５の端部と該ベルト補強層との間に更に層間ゴムを具えることもできる。 In the illustrated tire, the belt 5 is composed of two belt layers. However, in the tire of the present invention, the number of belt layers constituting the belt may be one or more, and is not limited thereto. Absent. Furthermore, 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 can be provided between the belt reinforcing layer and the belt reinforcing layer.
　そして、図示例のタイヤは、少なくともトレッド部３に、上述した含水率および粒径のセルロース短繊維を含む残滓を配合したエラストマー組成物を用いることを特徴とする。セルロース短繊維を配合したエラストマー組成物をトレッド部３に使用することで、セルロース短繊維と路面との相互作用により走行安定性、ウェット性能、氷雪性能の向上が可能なタイヤを提供することができる。 And, the tire of the illustrated example is characterized by using an elastomer composition in which at least the tread portion 3 is blended with a residue containing cellulose short fibers having the above-described moisture content and particle size. By using an elastomer composition containing cellulose short fibers in the tread portion 3, it is possible to provide a tire capable of improving running stability, wet performance, and ice / snow performance due to the interaction between the cellulose short fibers and the road surface. .
　なお、上記エラストマー組成物を用いる部材としては、トレッドゴムの他、サイドゴム、ビードワイヤの半径方向外側に位置するビードフィラーないしスティフナー、カーカスやベルトのコーティングゴム等が挙げられる。 In addition, examples of the member using the elastomer composition include a tread rubber, a side rubber, a bead filler or a stiffener located outside the bead wire in the radial direction, a coating rubber for a carcass and a belt, and the like.
　また、本発明のタイヤに充填する気体としては、通常の或いは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウム等の不活性ガスを用いることができる。 Further, as a gas filled in the tire of the present invention, an inert gas such as nitrogen, argon, helium, etc. can be used in addition to air having normal or oxygen partial pressure adjusted.
　以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
（比較例１）
　含水率を調整した芋焼酎粕を配合したゴム組成物（エラストマー組成物）を、表１に示す配合処方でバンバリーミキサーを用いて調製した。そして、調製したゴム組成物に対し既知の加硫剤等を配合して後述の条件で加硫した後に、以下の方法で当該加硫ゴムの破断伸びを測定、評価した。 (Comparative Example 1)
A rubber composition (elastomer composition) in which shochu shochu having an adjusted water content was blended was prepared using a Banbury mixer with the blending formulation shown in Table 1. Then, after blending a known vulcanizing agent and the like with the prepared rubber composition and vulcanizing under the conditions described later, the elongation at break of the vulcanized rubber was measured and evaluated by the following method.
（実施例１）
　含水率の調整後に粉砕処理を行った芋焼酎粕を配合した以外は比較例１と同様にしてゴム組成物を調製し、比較例１と同様にして加硫ゴムの破断伸びを測定、評価した。結果を表１に示す。 Example 1
A rubber composition was prepared in the same manner as in Comparative Example 1 except that the soot shochu that had been pulverized after the moisture content was adjusted, and the elongation at break of the vulcanized rubber was measured and evaluated in the same manner as in Comparative Example 1. . The results are shown in Table 1.
（実施例２～４）
　粉砕処理を行った後に含水率を調整した芋焼酎粕を、配合量を変化させて配合した以外は比較例１と同様にしてゴム組成物を調製し、比較例１と同様にして加硫ゴムの破断伸びを測定、評価した。結果を表１に示す。 (Examples 2 to 4)
A rubber composition was prepared in the same manner as in Comparative Example 1 except that the soot shochu, which was adjusted in moisture content after pulverization, was mixed in a different amount, and vulcanized rubber was prepared in the same manner as in Comparative Example 1. The elongation at break was measured and evaluated. The results are shown in Table 1.
（実施例５～７）
　篩い分けを行った後に含水率を調整した芋焼酎粕を、配合量を変化させて配合した以外は比較例１と同様にしてゴム組成物を調製し、比較例１と同様にして加硫ゴムの破断伸びを測定、評価した。結果を表１に示す。 (Examples 5 to 7)
A rubber composition was prepared in the same manner as in Comparative Example 1 except that the shochu shochu, which had been adjusted in moisture content after sieving, was blended while changing the blending amount. The elongation at break was measured and evaluated. The results are shown in Table 1.
（従来例１）
　芋焼酎粕を含まないゴム組成物を、表１に示す配合処方でバンバリーミキサーを用いて調製した。そして、調製したゴム組成物に対し既知の加硫剤等を配合して後述の条件で加硫した後に、比較例１と同様にして加硫ゴムの破断伸びを測定、評価した。結果を表１に示す。 (Conventional example 1)
A rubber composition containing no shochu shochu was prepared using a Banbury mixer with the formulation shown in Table 1. The prepared rubber composition was blended with a known vulcanizing agent and vulcanized under the conditions described below, and the elongation at break of the vulcanized rubber was measured and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 1.
（破断伸びの測定）
　比較例１、実施例１～７および従来例１で作製したゴム組成物を１６０℃で１５分加硫して得た加硫ゴムに対し、株式会社東洋精機製作所製のストログラフを用いて、温度２５℃、引張速度１００ｍｍ／ｍｉｎの条件で破断伸びを測定した。 (Measurement of elongation at break)
For the vulcanized rubber obtained by vulcanizing the rubber composition produced in Comparative Example 1, Examples 1 to 7 and Conventional Example 1 at 160 ° C. for 15 minutes, using a strograph made by Toyo Seiki Seisakusho Co., Ltd. The elongation at break was measured under the conditions of a temperature of 25 ° C. and a tensile speed of 100 mm / min.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（配合物）
*1　乳化重合ＳＢＲ、ゴム成分１００質量部に対して３７．５質量部のアロマ油で油展
*2　旭カーボン株式会社製、Ｎ１１０
*3　芋麹：米麹＝４：１の割合で発酵処理を行い製造した芋焼酎の粕、粕中の固形分の組成は芋短繊維：芋細胞壁＝１：４
（芋焼酎粕の処理方法）
芋焼酎粕Ａ：含水率が８質量％となるようにＣＤドライヤー（西村鐡工所製）で乾燥、粒径５ｍｍ以上の粕を含む
芋焼酎粕Ｂ：含水率が８質量％となるようにＣＤドライヤー（西村鐡工所製）で乾燥した後に、乾式粉砕機（増幸産業株式会社製）で粒径１～４００μｍとなるまで粉砕
芋焼酎粕Ｃ：湿式粉砕機（増幸産業株式会社製）で粒径１～４００μｍとなるまで粉砕した後に、含水率が８質量％となるようにＣＤドライヤー（西村鐡工所製）で乾燥
芋焼酎粕Ｄ：メッシュサイズ１０００μｍの篩で篩い分けした際の篩下を、メッシュサイズ５００μｍの篩で更に篩い分けし、その篩下（粒径１～５００μｍ）を含水率が８質量％となるようにＣＤドライヤー（西村鐡工所製）で乾燥 (Compound)
* 1 Emulsion polymerization SBR, 37.5 parts by mass of aroma oil for 100 parts by mass of rubber component
* 2 N110 manufactured by Asahi Carbon Co., Ltd.
* 3 Koji: rice koji = koji of koji shochu manufactured by fermentation at a ratio of 4: 1, the composition of the solid content in koji is koji short fiber: koji cell wall = 1: 4
(Processing method for shochu)
Shochu shochu A: dried with a CD dryer (manufactured by Nishimura Seiko Co., Ltd.) so that the moisture content is 8% by mass, shochu shochu containing soot with a particle size of 5 mm or more B: so that the moisture content is 8% by mass After drying with a CD dryer (manufactured by Nishimura Seiko), pulverized shochu shochu C: wet mill (manufactured by Masuko Sangyo Co., Ltd.) until the particle size becomes 1 to 400 μm with a dry pulverizer (manufactured by Masuko Sangyo Co., Ltd.) After pulverizing to a particle size of 1 to 400 μm, dried soju shochu with a CD dryer (manufactured by Nishimura Steel Co., Ltd.) so that the water content is 8% by mass D: sieve when sieving with a sieve having a mesh size of 1000 μm The bottom is further sieved with a sieve having a mesh size of 500 μm, and the sieve (particle size: 1 to 500 μm) is dried with a CD dryer (manufactured by Nishimura Steel) so that the water content is 8% by mass.
　表１の従来例１および実施例１～７より、含水率を８質量％に調整した芋焼酎粕を配合することで、ゴム組成物の物性（破断伸び）を大きく低下させることなく、ゴム成分の使用量を低減することができることが分かった。 From the conventional example 1 and examples 1 to 7 in Table 1, the rubber component was blended with the shochu shochu adjusted to a water content of 8% by mass without greatly reducing the physical properties (elongation at break) of the rubber composition. It was found that the usage amount of can be reduced.
　また、表１の比較例１および実施例１～７より、芋焼酎粕は粉砕または篩い分けをして所定の粒径（５００μｍ以下）とした上で配合したほうが、ゴム組成物の物性が低下し難いことが分かった。 Also, from Comparative Example 1 and Examples 1 to 7 in Table 1, the physical properties of the rubber composition decrease when the shochu is blended after pulverization or sieving to obtain a predetermined particle size (500 μm or less). I found it difficult.
（比較例２）
　ロールを用いて、含水率が９０％超の芋焼酎粕を含むゴム組成物の調製を試みたが、ロールが滑ってしまい、ゴム成分と芋焼酎粕との混練ができなかった。そのため、破断伸びを測定することができなかった。 (Comparative Example 2)
An attempt was made to prepare a rubber composition containing shochu shochu having a water content of more than 90% using a roll. However, the roll slipped and the rubber component and shochu shochu could not be kneaded. Therefore, the elongation at break could not be measured.
（比較例３）
　粉砕処理を行った後に含水率を調整した芋焼酎粕を、粒径を変化させて配合した以外は実施例４と同様にしてゴム組成物を調製し、実施例４と同様にして加硫ゴムの破断伸びを測定、評価した。結果を表２に示す。 (Comparative Example 3)
A rubber composition was prepared in the same manner as in Example 4 except that the soot shochu, which was adjusted in moisture content after pulverization, was blended while changing the particle size, and vulcanized rubber was prepared in the same manner as in Example 4. The elongation at break was measured and evaluated. The results are shown in Table 2.
（実施例８～９）
　粉砕処理を行った後に含水率を調整した芋焼酎粕を、含水率を変化させて配合した以外は実施例４と同様にしてゴム組成物を調製し、実施例４と同様にして加硫ゴムの破断伸びを測定、評価した。結果を表２に示す。 (Examples 8 to 9)
A rubber composition was prepared in the same manner as in Example 4 except that the shochu shochu, which was adjusted in moisture content after pulverization, was blended while changing the moisture content. The elongation at break was measured and evaluated. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
（配合物）
*1　乳化重合ＳＢＲ、ゴム成分１００質量部に対して３７．５質量部のアロマ油で油展
*2　旭カーボン株式会社製、Ｎ１１０
*3　芋麹：米麹＝４：１の割合で発酵処理を行い製造した芋焼酎の粕、粕中の固形分の組成は芋短繊維：芋細胞壁＝１：４
（芋焼酎粕の処理方法）
芋焼酎粕Ｅ：湿式粉砕機（増幸産業株式会社製）で粒径１～８００μｍとなるまで粉砕した後に、含水率が８質量％となるようにＣＤドライヤー（西村鐡工所製）で乾燥
芋焼酎粕Ｆ：湿式粉砕機（増幸産業株式会社製）で粒径１～４００μｍとなるまで粉砕した後に、含水率が２０質量％となるようにＣＤドライヤー（西村鐡工所製）で乾燥
芋焼酎粕Ｇ：湿式粉砕機（増幸産業株式会社製）で粒径１～４００μｍとなるまで粉砕した後に、含水率が４０質量％となるようにＣＤドライヤー（西村鐡工所製）で乾燥
芋焼酎粕Ｈ：湿式粉砕機（増幸産業株式会社製）で粒径１～４００μｍとなるまで粉砕した後に、含水率が６０質量％となるようにＣＤドライヤー（西村鐡工所製）で乾燥 (Compound)
* 1 Emulsion polymerization SBR, 37.5 parts by mass of aroma oil for 100 parts by mass of rubber component
* 2 N110 manufactured by Asahi Carbon Co., Ltd.
* 3 Koji: rice koji = koji of koji shochu manufactured by fermentation at a ratio of 4: 1, the composition of the solid content in koji is koji short fiber: koji cell wall = 1: 4
(Processing method for shochu)
Shochu shochu E: After milling to a particle size of 1 to 800 μm with a wet mill (made by Masuko Sangyo Co., Ltd.), dry koji using a CD dryer (manufactured by Nishimura Seiko Co., Ltd.) so that the water content becomes 8% by mass. Shochu F: After pulverizing with a wet pulverizer (made by Masuko Sangyo Co., Ltd.) until the particle size becomes 1 to 400 μm, dry mash shochu using a CD dryer (manufactured by Nishimura Steel) so that the water content becomes 20% by mass.粕 G: After pulverization with a wet pulverizer (made by Masuko Sangyo Co., Ltd.) until the particle size becomes 1 to 400 μm, dry mash shochu using a CD dryer (manufactured by Nishimura Steel Co., Ltd.) so that the water content becomes 40% by mass. H: After pulverizing with a wet pulverizer (made by Masuko Sangyo Co., Ltd.) until the particle size becomes 1 to 400 μm, dry with a CD dryer (manufactured by Nishimura Steel Co., Ltd.) so that the water content becomes 60 mass%
　比較例１、比較例３および実施例１～１０より、芋焼酎粕は粉砕または篩い分けをして所定の粒径（５００μｍ以下、好ましくは４００μｍ以下）とした上で配合したほうが、ゴム組成物の物性が低下し難いことが分かった。なお、実施例１０では、ゴム組成物の混練中に水分が気化し、調製したゴム組成物中に気泡が入ることがあった。 From Comparative Example 1, Comparative Example 3 and Examples 1 to 10, it is more preferable that the shochu liquor is pulverized or sieved to a predetermined particle size (500 μm or less, preferably 400 μm or less) and then blended. It was found that the physical properties of were difficult to decrease. In Example 10, moisture was vaporized during the kneading of the rubber composition, and air bubbles sometimes entered the prepared rubber composition.
　本発明によれば、所定の代替原料をエラストマー成分に配合することにより、複雑な製造工程を用いることなく低コストで製造が可能で且つ環境に優しいエラストマー組成物を、代替原料を使用しないエラストマー組成物と比較して物性を大幅に低下させることなく提供することができる。また、当該エラストマー組成物の効率的な製造方法、並びに当該エラストマー組成物を用いた、製造時の環境負荷が低いタイヤを提供することができる。 According to the present invention, an elastomer composition that does not use an alternative raw material can be produced at low cost without using a complicated manufacturing process by blending a predetermined alternative raw material into the elastomer component. It can be provided without significantly reducing the physical properties as compared with the product. Moreover, the efficient manufacturing method of the said elastomer composition and the tire with a low environmental load at the time of manufacture using the said elastomer composition can be provided.
１　ビード部
２　サイドウォール部
３　トレッド部
４　カーカス
５　ベルト
６　ビードコア 1 Bead part 2 Side wall part 3 Tread part 4 Carcass 5 Belt 6 Bead core

Claims (28)

  1. 　エラストマー成分に対して有機物の発酵処理において生じる残滓を配合したエラストマー組成物において、
    　前記残滓の含水率を５～９０質量％とし、
    　前記残滓の粒径を０．０２～６００μｍとしたことを特徴とする、エラストマー組成物。     In an elastomer composition in which a residue generated in an organic fermentation process is blended with an elastomer component,
    The water content of the residue is 5 to 90% by mass,
    An elastomer composition, wherein the particle size of the residue is 0.02 to 600 μm.
  2. 　前記有機物がバイオマスである、請求項１に記載のエラストマー組成物。 The elastomer composition according to claim 1, wherein the organic substance is biomass.
  3. 　前記発酵処理が発酵菌を用いた有機物の発酵処理であり、
    　前記残滓が前記発酵菌の細胞壁を含有することを特徴とする、請求項１または２に記載のエラストマー組成物。     The fermentation treatment is a fermentation treatment of organic matter using a fermenting bacterium,
    The elastomer composition according to claim 1 or 2, wherein the residue contains a cell wall of the fermenting bacterium.
  4. 　前記残滓の主成分がペプチドグリカンであることを特徴とする、請求項３に記載のエラストマー組成物。 The elastomer composition according to claim 3, wherein the main component of the residue is peptidoglycan.
  5. 　前記残滓を燻煙処理または炭化処理した後に前記エラストマー成分に配合することを特徴とする、請求項３に記載のエラストマー組成物。 4. The elastomer composition according to claim 3, wherein the residue is mixed with the elastomer component after being smoked or carbonized.
  6. 　前記有機物が植物の細胞壁および該植物の細胞壁が連なった短繊維の少なくとも一方を含有する有機物であり、
    　前記残滓が前記植物の細胞壁および短繊維の少なくとも一方を含有することを特徴とする、請求項１に記載のエラストマー組成物。     The organic substance is an organic substance containing at least one of a plant cell wall and a short fiber connected to the plant cell wall;
    2. The elastomer composition according to claim 1, wherein the residue contains at least one of a cell wall and a short fiber of the plant.
  7. 　前記残滓が、前記植物の細胞壁の主成分であるセルロース粒子およびヘミセルロース粒子の少なくとも一方からなることを特徴とする、請求項６に記載のエラストマー組成物。 The elastomer composition according to claim 6, wherein the residue comprises at least one of cellulose particles and hemicellulose particles which are main components of the cell wall of the plant.
  8. 　前記残滓が前記短繊維からなり、
    　該短繊維は、セルロース短繊維およびヘミセルロース短繊維の少なくとも一方からなることを特徴とする、請求項６に記載のエラストマー組成物。     The residue consists of the short fibers,
    The elastomer composition according to claim 6, wherein the short fibers are composed of at least one of cellulose short fibers and hemicellulose short fibers.
  9. 　前記残滓が、前記植物の細胞壁の主成分であるセルロース粒子およびヘミセルロース粒子の少なくとも一方と、前記植物の細胞壁が連なった短繊維とを含むことを特徴とする、請求項６に記載のエラストマー組成物。 The elastomer composition according to claim 6, wherein the residue includes at least one of cellulose particles and hemicellulose particles which are main components of the cell wall of the plant, and short fibers in which the cell wall of the plant is continuous. .
  10. 　前記発酵処理が麹菌および酵母菌の少なくとも一方を用いた処理であり、
    　前記セルロース粒子およびヘミセルロース粒子には、麹菌および酵母菌の少なくとも一方の細胞壁が付随していることを特徴とする、請求項７に記載のエラストマー組成物。     The fermentation treatment is a treatment using at least one of Aspergillus or yeast;
    The elastomer composition according to claim 7, wherein the cellulose particles and hemicellulose particles are accompanied by at least one cell wall of gonococci and yeast.
  11. 　前記発酵処理が麹菌および酵母菌の少なくとも一方を用いた処理であって、
    　前記短繊維には、麹菌および酵母菌の少なくとも一方の細胞壁が付随していることを特徴とする、請求項６または８に記載のエラストマー組成物。     The fermentation process is a process using at least one of Aspergillus or yeast,
    The elastomer composition according to claim 6 or 8, wherein the short fiber is accompanied by at least one cell wall of Neisseria gonorrhoeae or yeast.
  12. 　前記短繊維が、２～１０本集合して束状となっていることを特徴とする、請求項６または８に記載のエラストマー組成物。 The elastomer composition according to claim 6 or 8, wherein 2 to 10 short fibers are aggregated to form a bundle.
  13. 　前記残滓が芋焼酎粕であることを特徴とする、請求項１～３および５～１２の何れかに記載のエラストマー組成物。 The elastomer composition according to any one of claims 1 to 3 and 5 to 12, wherein the residue is shochu shochu.
  14. 　前記エラストマー成分がゴム成分であることを特徴とする、請求項１～１３の何れかに記載のエラストマー組成物。 The elastomer composition according to any one of claims 1 to 13, wherein the elastomer component is a rubber component.
  15. 　前記エラストマー成分が樹脂であることを特徴とする、請求項１～１３の何れかに記載のエラストマー組成物。 14. The elastomer composition according to claim 1, wherein the elastomer component is a resin.
  16. 　エラストマー成分に対して有機物の発酵処理において生じる残滓を配合してエラストマー組成物を製造する方法であって、
    　前記残滓を粒径０．０２～６００μｍまで粉砕する粉砕工程と、
    　前記残滓の含水率を５～９０質量％とする含水率調整工程と、
    　含水率の調整および粉砕を行った残滓をエラストマー成分に配合して混練する混練工程と、
    を含むことを特徴とする、エラストマー組成物の製造方法。     A method for producing an elastomer composition by blending a residue generated in a fermentation process of an organic substance with an elastomer component,
    Crushing step of crushing the residue to a particle size of 0.02 to 600 μm;
    A moisture content adjusting step in which the moisture content of the residue is 5 to 90% by mass;
    A kneading step of mixing and kneading the residue after adjusting the moisture content and pulverizing the elastomer component;
    A process for producing an elastomer composition, comprising:
  17. 　前記粉砕工程を、前記含水率調整工程より前に含むことを特徴とする、請求項１６に記載のエラストマー組成物の製造方法。 The method for producing an elastomer composition according to claim 16, wherein the pulverizing step is included before the moisture content adjusting step.
  18. 　前記残滓を篩に掛けて篩上残滓と篩下残滓とに選別する選別工程を、前記混練工程より前に含み、
    　前記混練工程で前記篩下残滓をゴム成分に配合して混練することを特徴とする、請求項１６に記載のエラストマー組成物の製造方法。     Including a screening step of screening the residue into a sieve residue and a sieve residue before the kneading step,
    The method for producing an elastomer composition according to claim 16, wherein the under-screen residue is mixed with a rubber component and kneaded in the kneading step.
  19. 　前記選別工程を、前記粉砕工程の後、且つ、前記含水率調整工程の前に含むことを特徴とする、請求項１８に記載のエラストマー組成物の製造方法。 The method for producing an elastomer composition according to claim 18, wherein the selection step is included after the pulverization step and before the moisture content adjustment step.
  20. 　エラストマー成分に対して有機物の発酵処理において生じる残滓を配合してエラストマー組成物を製造する方法であって、
    　前記残滓の含水率を５～９０質量％とする含水率調整工程と、
    　含水率を調整した残滓をメッシュサイズが６００μｍ以下の篩に掛けて篩上残滓と篩下残滓とに選別することを含む選別工程と、
    　前記篩下残滓をエラストマー成分に配合して混練する混練工程と、
    を含むことを特徴とする、エラストマー組成物の製造方法。     A method for producing an elastomer composition by blending a residue generated in a fermentation process of an organic substance with an elastomer component,
    A moisture content adjusting step in which the moisture content of the residue is 5 to 90% by mass;
    A sorting step including sorting the residue whose moisture content has been adjusted through a sieve having a mesh size of 600 μm or less into a residue on the sieve and a residue under the sieve;
    A kneading step of blending and kneading the under-screen residue with an elastomer component;
    A process for producing an elastomer composition, comprising:
  21. 　エラストマー成分に対して有機物の発酵処理において生じる残滓を配合してエラストマー組成物を製造する方法であって、
    　前記残滓をメッシュサイズが６００μｍ以下の篩に掛けて篩上残滓と篩下残滓とに選別することを含む選別工程と、
    　前記篩下残滓の含水率を５～９０質量％とする含水率調整工程と、
    　含水率を調整した篩下残滓をエラストマー成分に配合して混練する混練工程と、
    を含むことを特徴とする、エラストマー組成物の製造方法。     A method for producing an elastomer composition by blending a residue generated in a fermentation process of an organic substance with an elastomer component,
    A screening step comprising screening the residue to a sieve having a mesh size of 600 μm or less and separating the residue into an on-screen residue and an under-screen residue;
    A moisture content adjusting step in which the moisture content of the under-screen residue is 5 to 90% by mass;
    A kneading step of blending and kneading the under-screen residue with adjusted water content into the elastomer component;
    A process for producing an elastomer composition, comprising:
  22. 　前記選別工程でメッシュサイズの異なる少なくとも２つの篩を使用して残滓を選別することを特徴とする、請求項２０または２１に記載の製造方法。 The method according to claim 20 or 21, wherein the residue is sorted using at least two sieves having different mesh sizes in the sorting step.
  23. 　前記選別工程が、
    　前記残滓をメッシュサイズ７５０～１５００μｍの第１の篩に掛ける工程と、
    　前記第１の篩を通過した残滓をメッシュサイズ９０～６００μｍの第２の篩に掛ける工程と、
    を含むことを特徴とする、請求項２０または２１に記載の製造方法。     The sorting step is
    Passing the residue on a first sieve having a mesh size of 750 to 1500 μm;
    Applying the residue that has passed through the first sieve to a second sieve having a mesh size of 90 to 600 μm;
    The manufacturing method of Claim 20 or 21 characterized by including.
  24. 　前記含水率調整工程が、乾燥により含水率を５～９０質量％とする乾燥工程、圧搾により含水率を６０～９０質量％とする圧搾工程、または圧搾した後に乾燥することにより含水率を５～９０質量％とする圧搾・乾燥工程であることを特徴とする、請求項１６～２３の何れかに記載の製造方法。 The moisture content adjusting step is a drying step in which the moisture content is 5 to 90% by mass by drying, a pressing step in which the moisture content is 60 to 90% by mass by pressing, or a moisture content of 5 to 5 by drying after pressing. The production method according to any one of claims 16 to 23, which is a pressing / drying step of 90 mass%.
  25. 　前記含水率調整工程が、前記乾燥工程または前記圧搾・乾燥工程であり、
    　乾燥を、温度１３０～２５０℃で行うことを特徴とする、請求項２４に記載の製造方法。     The moisture content adjusting step is the drying step or the pressing / drying step,
    The production method according to claim 24, wherein the drying is performed at a temperature of 130 to 250 ° C.
  26. 　前記エラストマー成分がゴム成分であることを特徴とする、請求項１６～２５の何れかに記載の製造方法。 The production method according to any one of claims 16 to 25, wherein the elastomer component is a rubber component.
  27. 　前記エラストマー成分が樹脂であることを特徴とする、請求項１６～２５の何れかに記載の製造方法。 The production method according to any one of claims 16 to 25, wherein the elastomer component is a resin.
  28. 　少なくとも一部を、請求項１～１５の何れかに記載のエラストマー組成物、或いは、請求項１６～２７の何れかに記載の製造方法で製造したエラストマー組成物で構成したことを特徴とする、タイヤ。 At least a part of the elastomer composition according to any one of claims 1 to 15 or the elastomer composition produced by the production method according to any one of claims 16 to 27, tire.
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