WO2011114990A1 - ゴム組成物、架橋ゴム組成物および高減衰積層体 - Google Patents

ゴム組成物、架橋ゴム組成物および高減衰積層体 Download PDF

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WO2011114990A1
WO2011114990A1 PCT/JP2011/055675 JP2011055675W WO2011114990A1 WO 2011114990 A1 WO2011114990 A1 WO 2011114990A1 JP 2011055675 W JP2011055675 W JP 2011055675W WO 2011114990 A1 WO2011114990 A1 WO 2011114990A1
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rubber
rubber composition
parts
present
mass
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PCT/JP2011/055675
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English (en)
French (fr)
Japanese (ja)
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智行 酒井
康一 伊海
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横浜ゴム株式会社
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Priority to KR1020127018967A priority Critical patent/KR101186117B1/ko
Priority to JP2011522177A priority patent/JP4900538B1/ja
Priority to CN2011800073685A priority patent/CN102725343B/zh
Publication of WO2011114990A1 publication Critical patent/WO2011114990A1/ja

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    • 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/02—Layered products comprising a layer of natural or synthetic rubber with fibres or particles being present as additives in the layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/56—Damping, energy absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/744—Non-slip, anti-slip
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene

Definitions

  • the present invention relates to a rubber composition, a crosslinked rubber composition, and a high attenuation laminate.
  • vibration isolation devices In recent years, anti-vibration devices, vibration isolation devices, seismic isolation devices, and the like are rapidly spreading as vibration energy absorbing devices.
  • a rubber composition having vibration energy damping performance is used.
  • laminated rubber for seismic isolation used in bridge bearings and building seismic isolation devices has high damping (attenuates vibration energy by converting vibration into more heat) and has a desired rigidity. It is required to be expressed.
  • Patent Document 1 As a rubber composition used for such a seismic isolation laminated rubber, the present applicant has disclosed in Patent Document 1 “100 parts by mass of a diene rubber, 40 to 75 parts by mass of carbon black, 5 to 35 parts by mass of silica, , A rubber composition for a high attenuation laminate comprising 5 to 55 parts by weight of an inorganic filler and 5 to 50 parts by weight of a petroleum resin.
  • a vulcanized rubber comprising a vulcanized diene-containing rubber in which polypropylene fibrils are randomly dispersed.
  • the polypropylene fibrils form a blend of (1) (a) a polymer alloy containing polypropylene and (b) an unvulcanized rubber material, wherein the polypropylene is in the blend from about 5 to about Present in an amount in the range of 25 phr; and (2) vulcanizing the rubber stock in the blend after orienting the polypropylene by applying heat and flowing the rubber stock through a molding cavity
  • a polymer alloy containing polypropylene and (b) an unvulcanized rubber material, wherein the polypropylene is in the blend from about 5 to about Present in an amount in the range of 25 phr
  • the present invention provides a rubber composition or a crosslinked rubber composition for a highly attenuated laminate that can achieve both improvement in damping properties and rigidity, and a highly attenuated laminate using at least one of these. For the purpose.
  • the present inventor formulated a specific amount of an inorganic filler having a silanol group, a polylactic acid resin, and polypropylene with respect to two or more types of crosslinkable rubber components. It has been found that a rubber composition and a crosslinked rubber composition obtained by crosslinking the rubber composition can achieve both improvement in damping property and rigidity.
  • the inventor of the present application also provides a rubber composition in which a specific amount of an inorganic filler having a silanol group, a polylactic acid resin, and polypropylene are blended with two or more kinds of crosslinkable rubber components, and a crosslinked rubber obtained by crosslinking the rubber composition.
  • the present inventors have found that the composition can simultaneously improve the grip performance and rigidity of the tire, and have completed the present invention. That is, the present invention provides the following 1 to 18.
  • the rubber component includes rubber A and rubber B, the rubber A is at least one selected from the group consisting of natural rubber and polyisoprene, and the rubber B is selected from the group consisting of polybutadiene and a butadiene copolymer. 4.
  • the rubber composition as described in 2. 11. 11.
  • 12 The rubber composition according to any one of 1 to 11, further comprising a silane coupling agent, wherein the amount of the silane coupling agent is 1 to 10 parts by mass with respect to 100 parts by mass of the inorganic filler having the silanol group. object. 13. 13.
  • 14 A crosslinked rubber composition containing a crosslinked rubber obtained by crosslinking the rubber composition according to any one of 1 to 13 above.
  • 15. A rubber composition for a high attenuation laminate, wherein the rubber composition according to any one of 1 to 13 or the crosslinked rubber composition according to 14 is used for a high attenuation laminate.
  • 16. 15.
  • a rubber composition for a pneumatic tire wherein the rubber composition according to any one of 1 to 13 or the crosslinked rubber composition according to 14 is used for a pneumatic tire.
  • 17. 16 A high attenuation laminate obtained by alternately laminating the rubber composition for a high attenuation laminate according to 15 and a hard plate. 18.
  • the rubber composition of the present invention and the crosslinked rubber composition of the present invention can achieve both improvement in damping property or grip performance and rigidity.
  • the highly attenuated laminate of the present invention has both excellent attenuation and excellent rigidity.
  • the pneumatic tire of the present invention combines excellent grip performance and excellent rigidity.
  • the rigidity of the high-damping laminate and the rigidity of the tire are the same in the sense that they are difficult to deform.
  • FIG. 1 is a schematic cross-sectional view of a highly attenuated laminate that represents an example of an embodiment of the laminate of the present invention.
  • FIG. 2 is a schematic side view of a sample for a lap shear type shear test.
  • FIG. 3 is a graph showing an example of a hysteresis curve obtained by a lap shear type shear test.
  • FIG. 4 is a graph showing the relationship between damping property and rigidity obtained in the example of the present invention.
  • FIG. 5 is a cross-sectional view of a rubber composition schematically showing an example of the morphology that the rubber composition of the present invention can have.
  • FIG. 6 is a photograph of one example of the morphology of the rubber composition of the present invention observed with a scanning probe microscope (SMP).
  • SMP scanning probe microscope
  • the present invention is described in detail below.
  • the rubber composition of the present invention comprises 100 parts by weight of two or more crosslinkable rubber components, 10 to 100 parts by weight of an inorganic filler having a silanol group, 0.1 to 30 parts by weight of a polylactic acid resin, polypropylene A rubber composition containing 0.1 to 10 parts by mass.
  • the rubber composition of the present invention can be used as a rubber composition for a high-damping laminate and a rubber composition for a pneumatic tire.
  • the rubber component contained in the rubber composition of the present invention is not particularly limited as long as it is a rubber component that can be crosslinked with a sulfur compound or a peroxide. Specific examples thereof include a diene rubber and a heat having a double bond. Examples thereof include a plastic elastomer.
  • diene rubber examples include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), vinyl-cis butadiene rubber (VCR), and styrene-butadiene copolymer rubber (SBR). ), Acrylonitrile-butadiene copolymer rubber (NBR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR), chloroprene rubber (CR), and the like.
  • NR natural rubber
  • IR isoprene rubber
  • BR butadiene rubber
  • VCR vinyl-cis butadiene rubber
  • SBR styrene-butadiene copolymer rubber
  • NBR Acrylonitrile-butadiene copolymer rubber
  • IIR butyl rubber
  • Br-IIR halogenated butyl rubber
  • Cl-IIR chloroprene rubber
  • thermoplastic elastomer having a double bond examples include ethylene-propylene-diene rubber (EPDM), styrene-butadiene-styrene block copolymer (SBS), and hydrogenation (hydrogenation) thereof.
  • EPDM ethylene-propylene-diene rubber
  • SBS styrene-butadiene-styrene block copolymer
  • SEBS styrene-ethylene-propylene-styrene block copolymer
  • SEPS styrene-isoprene-styrene block copolymer
  • SIBS styrene-isobutylene-styrene block copolymer
  • the resulting rubber composition of the present invention has good physical properties such as tensile strength after vulcanization and elongation at break, and the rubber composition of the present invention.
  • laminate of the present invention obtained by alternately laminating and hard plates, a rubber composition and a hard plate (for example, general structural steel plate, A diene rubber is preferred because it has good adhesion to a hot rolled steel sheet and the like and is excellent in repeated deformation as a pneumatic tire.
  • two or more types of crosslinkable rubber components can be used as a rubber component containing two or more types of crosslinkable rubber.
  • a case where the rubber component contains rubber A and rubber B can be mentioned.
  • gum B are incompatible from a viewpoint that the improvement of damping property or grip performance and rigidity can be made to make compatible further.
  • Examples of the rubber A include at least one selected from the group consisting of natural rubber and polyisoprene.
  • Examples of the rubber B include at least one selected from the group consisting of polybutadiene and butadiene copolymers.
  • Examples of the butadiene copolymer include styrene butadiene copolymer and vinyl-cis butadiene rubber.
  • the mass ratio of rubber A and rubber B can improve both damping performance and grip performance and rigidity, and can ensure rigidity with a small amount of polypropylene and durability. From the standpoint of superiority, it is preferably 90/10 to 10/90, and more preferably 70/30 to 30/70.
  • rubber A contains natural rubber and rubber B contains vinyl-cis butadiene rubber from the viewpoint that both improvement in damping property and rigidity can be achieved, and that damping property at low temperature is excellent.
  • rubber B contains vinyl-cisbutadiene rubber
  • the mass ratio with rubber B is preferably 90/10 to 10/90, and more preferably 70/30 to More preferably, it is 30/70.
  • the vinyl-cis butadiene rubber is a polybutadiene rubber composite composed of cis-1,4-polymerization and syndiotactic-1,2 polymerization in an inert organic solvent mainly composed of a C 4 fraction. It is.
  • Specific examples of the vinyl-cis butadiene rubber include, for example, 97-80% by mass of cis-1,4-polybutadiene rubber having a cis 1,4-bond content of 90% or more, and syndiotactic-1,2-polybutadiene. Examples include composites composed of 3 to 20% by mass.
  • vinyl-cis butadiene rubber for example, commercially available products such as UBEPOL-VCR manufactured by Ube Industries, Ltd. can be used.
  • rubber A contains natural rubber
  • rubber B can be improved in both grip performance and rigidity, and excellent in grip performance at low temperatures. It preferably contains a styrene butadiene copolymer.
  • the mass ratio to rubber B is preferably 20/80 to 80/20, and more preferably 30/70 to 80/20 from the viewpoint that both improvement in grip performance and rigidity can be achieved. More preferably, it is 70/30.
  • the styrene butadiene copolymer preferably has a styrene content of 5 to 40% by weight and more preferably 5 to 30% by weight from the viewpoint that both improvement in grip performance and rigidity can be achieved. .
  • the inorganic filler having a silanol group contained in the rubber composition of the present invention is not particularly limited as long as it is an inorganic filler having a silanol group (Si—OH) on at least a part of the surface.
  • examples of the inorganic filler having a silanol group include silica, clay, talc and the like, and these may be used alone or in combination of two or more.
  • silica examples include fumed silica, calcined silica, precipitated silica, pulverized silica, fused silica, and colloidal silica.
  • Silica preferably has an average aggregate particle size of 5 to 50 ⁇ m, more preferably 5 to 30 ⁇ m.
  • the BET specific surface area of silica is preferably 50 to 300 m 2 / g from the viewpoints of reinforcing property, high damping property and excellent tire grip.
  • the clay is not particularly limited as long as it is a white powdery product, for example, industrially refined from natural ore containing hydrous aluminum silicate as a main component.
  • Specific examples of the clay include T-clay, kaolin clay, waxite clay, sericite clay, calcined clay, and silane-modified clay.
  • those forming an aggregate of fine particles of clay minerals such as pyrophyllite, kaolinite, halloysite, sericite, montmorillonite can be used.
  • aggregates of quartz and kaolinite, diatomaceous earth, and the like can be used.
  • the amount ratio of silica and clay is 25 to 150 parts by mass with respect to 100 parts by mass of silica from the viewpoint of excellent mixing properties. It is preferably 25 to 100 parts by mass.
  • the content of the inorganic filler having a silanol group is 10 to 100 parts by mass with respect to 100 parts by mass of the two or more types of crosslinkable rubber components described above, and the damping property or grip performance and rigidity are increased. And more preferably 10 to 90 parts by mass from the viewpoint of durability and low temperature performance (for example, damping property and grip performance at low temperature). More preferably, it is part.
  • the content of the inorganic filler having a silanol group can achieve both improvement in damping property and rigidity, and durability and low-temperature performance (for example, from the viewpoint of excellent attenuation at low temperatures, the amount is preferably 10 to 60 parts by weight, more preferably 15 to 50 parts by weight with respect to 100 parts by weight of the two or more crosslinkable rubber components described above. More preferably, it is 20 to 40 parts by mass.
  • the content of the inorganic filler having a silanol group can achieve both improvement in grip performance and rigidity, durability and low temperature performance (for example, From the viewpoint of excellent grip performance at low temperature), it is preferably 20 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of two or more kinds of crosslinkable rubber components. More preferably, it is 30 to 70 parts by mass.
  • the polylactic acid resin contained in the rubber composition of the present invention is a homopolymer of lactic acid and / or a copolymer of lactic acid.
  • the homopolymer of lactic acid is polylactic acid.
  • the lactic acid copolymer is a copolymer of lactic acid and one kind of monomer selected from the group consisting of hydroxy acids other than lactic acid, lactones and diene compounds copolymerizable with lactic acid.
  • hydroxy acids other than lactic acid include hydroxyacetic acid (glycolic acid), hydroxybutyric acid, malic acid, citric acid, ricinoleic acid, shikimic acid, salicylic acid, and coumaric acid.
  • lactones include ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -Propiolactone and the like are exemplified.
  • Specific examples of the diene compound copolymerizable with lactic acid include butadiene and isoprene.
  • the copolymer of these and lactic acid may be a block copolymer, a random block copolymer, a random copolymer, or a graft polymer as long as lactic acid is a main component. Preferably there is.
  • the resulting rubber composition of the present invention has excellent melting properties, such as tensile strength after vulcanization, elongation at break, etc., so that the melting point is 180 ° C. or less. However, it is preferably 160 ° C. or lower, and more preferably 135 ° C. or lower.
  • the number average molecular weight is preferably 1,000 to 200,000, more preferably 1,000 to 100,000.
  • the melting point is a value measured at a heating rate of 10 ° C./min by differential scanning calorimetry (DSC-Differential Scanning Calorimetry).
  • the number average molecular weight is a number average molecular weight (polystyrene conversion) measured by gel permeation chromatography (GPC). Tetrahydrofuran (THF), N, N-dimethylformamide (DMF) is used for the measurement. ), Chloroform is preferably used as a solvent.
  • the content of the polylactic acid-based resin is 0.1 to 30 parts by mass with respect to 100 parts by mass of the two or more cross-linkable rubber components described above. From the standpoint that both improvement in rigidity can be achieved and durability is excellent, the amount is more preferably 1 to 20 parts by mass, and still more preferably 3 to 15 parts by mass.
  • polylactic acid-based resin for example, LACEA H-440 (melting point: 155 ° C., number average molecular weight: 78000, weight average molecular weight: 150,000) manufactured by Mitsui Chemicals, Shimadzu Corporation
  • Lacti # 1012 melting point: 170 ° C., number average molecular weight: 180000
  • the rubber composition of the present invention obtained is excellent in processability
  • the laminate of the invention has a high damping property
  • the rubber obtained using the rubber composition of the invention has excellent grip performance and good rigidity.
  • the inorganic filler having a silanol group forms a crosslink by a siloxane bond, and due to the interaction between the remaining silanol group or the siloxane bond and the ester bond of the polylactic acid resin, This is probably because the polylactic acid resin collects around the crosslinked filler and crystallizes.
  • the processability of the resulting rubber composition of the present invention becomes better, the damping property of the laminate of the present invention is higher, and the rubber obtained using the rubber composition of the present invention has grip performance.
  • the mass ratio of the above-mentioned inorganic filler having a silanol group to the polylactic acid resin is 1/1 to 10 because / 1 is preferred.
  • the processability of the resulting rubber composition of the present invention becomes better, and the attenuation of the laminate of the present invention is also improved.
  • the mass ratio of the silanol group-containing inorganic filler to the polylactic acid resin is 1/1 to It is preferably 10/1, more preferably 8/1 to 4/1.
  • the processability of the resulting rubber composition of the present invention becomes better, and the rubber composition of the present invention is used.
  • the mass ratio of the above-mentioned inorganic filler having a silanol group to the polylactic acid resin is 1/1 to 8/1 is preferable, and 2/1 to 7/1 is more preferable.
  • the polypropylene contained in the rubber composition of the present invention is not particularly limited as long as it is a homopolymer or copolymer obtained from a monomer containing propylene.
  • a conventionally well-known thing is mentioned.
  • a propylene homopolymer and a polypropylene copolymer containing 50 mol% or more of a propylene monomer are preferable from the viewpoint of being able to achieve both improvement in damping property or grip performance and rigidity, and excellent durability.
  • Polypropylene is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. Polypropylenes can be used alone or in combination of two or more.
  • the amount of polypropylene is 0.1 to 10 parts by mass with respect to 100 parts by mass of two or more kinds of crosslinkable rubber components. In such a range, it is possible to achieve both improvement in damping performance or grip performance and rigidity, satisfy high breaking elongation required for a rubber composition for a high damping laminate, and excellent durability. .
  • the amount of polypropylene exceeds 10 parts by mass with respect to 100 parts by mass of the rubber component, the horizontal rigidity is increased, but the damping property or grip performance is not improved so much, and is required for a rubber composition for a high attenuation laminate.
  • the amount of polypropylene is 0.5 to 8 with respect to 100 parts by mass of the rubber component from the viewpoints that both the damping property and the improvement in grip performance and rigidity can be achieved, the durability is excellent, and the elongation at break is high.
  • the amount is preferably part by mass, and more preferably 1 to 5 parts by mass.
  • the rubber composition of the present invention preferably contains a petroleum resin from the viewpoint of improving physical properties such as tensile strength after vulcanization and elongation at break and improving the damping property of the laminate of the present invention.
  • a petroleum resin conventionally known ones can be used, for example, C5 aliphatic unsaturated hydrocarbon polymer, C9 aromatic unsaturated hydrocarbon polymer, C5 aliphatic unsaturated polymer. Copolymers of saturated hydrocarbons and C9 aromatic unsaturated hydrocarbons can be used.
  • C5 aliphatic unsaturated hydrocarbon examples include, for example, 1-pentene, 2-pentene, 2-methyl-1-butene contained in a C5 fraction obtained by thermal decomposition of naphtha, Olefinic hydrocarbons such as 3-methyl-1-butene and 2-methyl-2-butene; 2-methyl-1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, 3-methyl-1 , 2-olefin hydrocarbons such as 2-butadiene; and the like. These can be polymerized or copolymerized in the presence of a suitable catalyst.
  • the C5 aliphatic unsaturated hydrocarbon polymer is a co-polymer of a single C5 aliphatic unsaturated hydrocarbon homopolymer and two or more C5 aliphatic unsaturated hydrocarbons. It refers to any polymer.
  • the C9 aromatic unsaturated hydrocarbon include, for example, ⁇ -methylstyrene, o-vinyltoluene, m-vinyltoluene, p contained in a C9 fraction obtained by thermal decomposition of naphtha.
  • -Vinyl-substituted aromatic hydrocarbons such as vinyltoluene.
  • the C9 aromatic unsaturated hydrocarbon polymer is a co-polymer of a single C9 aromatic unsaturated hydrocarbon homopolymer and two or more C9 aromatic unsaturated hydrocarbons. It refers to any polymer.
  • a copolymer of a C5 aliphatic unsaturated hydrocarbon and a C9 aromatic unsaturated hydrocarbon is a C9 aromatic unsaturated hydrocarbon in that the softening point of the copolymer is high. What a unit is 60 mol% or more is preferable, and what is 90 mol% or more is more preferable.
  • a copolymer of a C5 aliphatic unsaturated hydrocarbon and a C9 aromatic unsaturated hydrocarbon can be copolymerized in the presence of a suitable catalyst.
  • the petroleum resin has a softening point (JIS K2207) of 100 ° C. or higher because the molecular weight and the reactivity of double bonds affect the physical properties of the crosslinkable rubber component (particularly diene rubber).
  • the thing of 120 degreeC or more is more preferable.
  • the content in the case of containing a petroleum resin as desired makes the physical properties such as tensile strength after vulcanization and elongation at break good, and the viewpoint of increasing the damping property of the laminate of the present invention. Therefore, the amount is preferably 5 to 50 parts by mass, more preferably 10 to 45 parts by mass with respect to 100 parts by mass of the crosslinkable rubber component described above.
  • the rubber composition of the present invention has a higher damping property of the laminate of the present invention, more excellent grip performance of rubber obtained by using the rubber composition of the present invention, and from the viewpoint of better rigidity. It is preferable to further contain an inorganic filler other than the inorganic filler having a silanol group described above. Specific examples of such inorganic fillers include calcium carbonate, heavy calcium carbonate, magnesium carbonate, aluminum hydroxide, and barium sulfate.
  • these inorganic fillers are calcium carbonate and heavy calcium carbonate because they can maintain particularly high damping properties and stability against long-term shear deformation and improve workability. Is preferred.
  • the content of the inorganic filler other than the inorganic filler having a silanol group is determined by the attenuation of the laminate of the present invention. From the viewpoint of higher grip performance of the rubber obtained using the rubber composition of the present invention and better rigidity, it is 5 to The amount is preferably 55 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 15 to 40 parts by mass.
  • the total amount of the inorganic filler having a silanol group and the inorganic filler other than the inorganic filler having a silanol group is higher in the attenuation of the laminate of the present invention, and the rubber composition of the present invention.
  • it is preferably 20 to 75 parts by mass with respect to 100 parts by mass of the crosslinkable rubber component described above. 30 to 65 parts by mass is more preferable.
  • the rubber composition with a good balance (high damping laminate) that has higher damping performance and grip performance, and more stable damping performance and rigidity against long-term repeated shear deformation. For body and pneumatic tire).
  • the mass ratio of the inorganic filler having a silanol group and the inorganic filler other than the inorganic filler having a silanol group is:
  • the ratio is preferably 1/1 to 1 / 2.5, more preferably 1/1 to 1 / 2.0. When the mass ratio is within this range, good workability can be obtained.
  • the rubber composition of the present invention has good physical properties such as tensile strength after vulcanization and elongation at break, higher damping properties of the laminate of the present invention, and the rubber composition obtained using the rubber composition of the present invention. From the viewpoint of improving grip performance and improving rigidity, it is preferable to further contain carbon black.
  • carbon black having a CTAB adsorption specific surface area of 100 m 2 / g or more is preferably used, and carbon black of 110 to 370 m 2 / g is more preferably used.
  • the CTAB adsorption specific surface area is in the range of 100 m 2 / g or more, the damping property of the obtained laminate of the present invention can be maintained higher, and the grip performance of the rubber obtained by using the rubber composition of the present invention. Can be made more excellent.
  • the CTAB adsorption specific surface area is a value obtained by measuring the surface area that carbon black can be used for adsorption with rubber molecules by adsorption of CTAB (cetyltrimethylammonium bromide). Examples of such carbon black include SAF, ISAF, and HAF.
  • the CATB adsorption specific surface area can be measured by the method described in ASTM D3765-80.
  • N 2 AB specific surface area by nitrogen adsorption method
  • carbon black is preferably 110 to 370 m 2 / g, and more preferably 150 to 350 m 2 / g.
  • examples of such carbon black include SAF class, ISAF class, and HAF class carbon blacks.
  • the carbon black content when carbon black is optionally contained, can maintain the damping property of the obtained laminate of the present invention higher, and the rubber composition of the present invention is used.
  • the amount is preferably 10 to 90 parts by mass with respect to 100 parts by mass of the crosslinkable rubber component described above. More preferably, the amount is 20 to 75 parts by mass.
  • the content of the carbon black when carbon black is optionally contained, can be crosslinked as described above from the viewpoint that the resulting laminate of the present invention can maintain a higher attenuation.
  • the amount is preferably 10 to 90 parts by weight, more preferably 10 to 75 parts by weight, and still more preferably 20 to 75 parts by weight with respect to 100 parts by weight of the rubber component. Further, in the present invention, when carbon black is optionally contained, the content of the carbon black is a viewpoint that the grip performance of the rubber obtained using the rubber composition of the present invention can be further improved. Therefore, the amount is preferably 10 to 90 parts by weight, more preferably 10 to 75 parts by weight, and still more preferably 20 to 75 parts by weight with respect to 100 parts by weight of the crosslinkable rubber component. .
  • the rubber composition of the present invention promotes the decomposition (hydrolysis) of the polylactic acid-based resin described above, and increases the number of sites where the polylactic acid-based resin and the inorganic filler having a silanol group interact with each other. It is preferable to contain.
  • a zinc compound, an aluminum compound, a copper compound etc. are mentioned, for example. Of these, zinc compounds are preferable, and specifically zinc oxide, organic zinc phosphate, and fatty acid zinc are more preferable. Of these, zinc oxide is more preferable.
  • the content in the case of containing a metal compound as desired is 0 with respect to 100 parts by mass of the crosslinkable rubber component described above from the viewpoint of excellent dispersion of the metal compound and mechanical strength of the crosslinked product.
  • the amount is preferably 1 to 10 parts by mass, more preferably 0.1 to 3 parts by mass.
  • the rubber composition of the present invention preferably contains a silane coupling agent from the viewpoint of improving physical properties such as tensile strength after vulcanization and elongation at break of the rubber composition of the present invention to be obtained.
  • silane coupling agent examples include bis- [3- (triethoxysilyl) -propyl] tetrasulfide, bis- [3- (trimethoxysilyl) -propyl] tetrasulfide, and bis- [ 3- (triethoxysilyl) -propyl] disulfide, mercaptopropyl-trimethoxysilane, mercaptopropyl-triethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercapto Benzothiazole tetrasulfide, triethoxysilylpropyl-methacrylate-monosulfide, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl-tetrasulfide, etc. may be mentioned,
  • the content of the silane coupling agent when a silane coupling agent is optionally contained, is 0.1 of the content of the inorganic filler having a silanol group described above from the viewpoint of excellent mechanical strength. It is preferably ⁇ 10% by mass, more preferably 1 to 8% by mass.
  • the content of the silane coupling agent when the rubber composition of the present invention is used as a rubber composition for a pneumatic tire, is an inorganic material having a silanol group described above from the viewpoint of excellent balance between grip performance and rolling resistance.
  • the content of the filler is preferably 0.1 to 10% by mass, and more preferably 1 to 8% by mass.
  • the amount of the silane coupling agent can be 5% by mass or more of the silanol group-containing inorganic filler.
  • the rubber composition of the present invention can contain other additives as necessary within a range not impairing the object of the present invention.
  • the additive include a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a plasticizer, a softening agent, a vulcanization aid, a flame retardant, a weathering agent, and a heat resistance agent.
  • the rubber composition of this invention can contain the additive which the rubber composition for high attenuation
  • Specific examples of the vulcanizing agent include sulfur; organic sulfur-containing compounds such as TMTD; organic peroxides such as dicumyl peroxide; and the like.
  • vulcanization accelerator examples include sulfenamides such as N-cyclohexyl-2-benzothiazole sulfenamide (CBS); thiazoles such as mercaptobenzothiazole; tetramethylthiuram monosulfide and the like. Thiurams; stearic acid; and the like.
  • Specific examples of the antiaging agent include ketone / amine condensates such as TMDQ; amines such as DNPD; monophenols such as styrenated phenol; and the like.
  • plasticizer examples include phthalic acid derivatives (for example, DBP, DOP and the like), sebacic acid derivatives (for example, DBS and the like) monoesters, and the like.
  • softening agent examples include paraffinic oil (process oil), aroma oil, stearic acid, and wax.
  • the method for producing the rubber composition of the present invention is not particularly limited.
  • a method of producing a rubber composition (for a high-attenuation laminate or for a pneumatic tire) by kneading an unvulcanized rubber composition containing at least the above-described essential components can be mentioned.
  • an unvulcanized rubber composition containing the above-described components can be prepared by kneading using a known method and apparatus (for example, a Banbury mixer, a kneader, a roll, etc.).
  • the vulcanization conditions (primary crosslinking) of the rubber composition of the present invention are not particularly limited, and vulcanization can be performed under conventionally known vulcanization conditions using a sulfur compound or a peroxide.
  • the primary crosslinking temperature is preferably from 130 to 200 ° C. from the viewpoint of being more excellent in rigidity (for example, horizontal rigidity).
  • the temperature condition of the heat treatment is not particularly limited as long as it is the same temperature as the primary crosslinking temperature, but is preferably in the range of a temperature 10 ° C. to 10 ° C. higher than the temperature of the primary crosslinking. More preferably, the temperature is in the range of 5 ° C. to 5 ° C., more preferably in the range of 2 ° C. to 2 ° C. higher than the temperature of primary crosslinking.
  • the heat treatment time is obtained from a vulcanization curve obtained from a rheometer torque defined in JIS K6300-2: 2001 using the rubber composition of the present invention before primary crosslinking (unvulcanized). Is preferably 0.5 to 3 times, more preferably 0.5 to 2 times.
  • the vulcanization curve is based on JIS K6300-2: 2001 “How to determine vulcanization characteristics using a vibration vulcanization tester”, using a rotorless vulcanization tester as a rheometer at a predetermined test temperature.
  • the obtained torque is on the vertical axis and the vulcanization time is on the horizontal axis.
  • the rheometer test temperature is the above-described primary crosslinking temperature.
  • the damping property of the laminate of the present invention can be further improved, and excellent vibration damping properties can be secured in a wide temperature range, which is obtained using the rubber composition of the present invention.
  • the grip performance of the obtained rubber can be made more excellent. This is because the polylactic acid-based resin described above is decomposed (hydrolyzed) during vulcanization, for example, by moisture in the system, so that the polylactic acid-based resin after decomposition and an inorganic filler having a silanol group interact with each other. It is thought that it can be done.
  • FIG. 5 is a cross-sectional view of a rubber composition schematically showing an example of the morphology that the rubber composition of the present invention (for example, for a high-damping laminate and for a pneumatic tire) can have.
  • the rubber composition of the present invention for example, for a high-damping laminate and for a pneumatic tire
  • the rubber composition 100 of the present invention has rubber A (reference numeral 10) as a matrix, rubber B (reference numeral 20) as a domain, and polypropylene (reference numeral 30).
  • the rubber A10 and the rubber B20 form a sea-island structure (that is, the rubber A and the rubber B are incompatible), and the polypropylene 30 is added to the rubber A10 and the rubber B20 by adding a small amount of the polypropylene 30 thereto.
  • the rubber composition 100 forms a continuous phase (network) 30 of polypropylene 30 in the rubber composition 100.
  • the continuous phase 30 can form a substantially continuous continuous phase.
  • the inventors of the present application infer that the continuous phase 30 of the polypropylene 30 hardens the rubber composition 100 in an appropriate range, and as a result, the rigidity (shear elastic modulus, horizontal rigidity) is improved.
  • Such a continuous phase of polypropylene also applies to the crosslinked rubber composition of the present invention, the highly attenuated laminate of the present invention, and the pneumatic tire of the present invention.
  • the said mechanism is a presumption of this inventor to the last, and it is in the scope of the present invention even if the mechanism is other than the above.
  • Rubber composition of the present invention examples include, for example, a rubber composition for a high damping laminate, a rubber composition for a pneumatic tire, a damping industrial belt, and the like.
  • the crosslinked rubber composition of the present invention is a crosslinked rubber composition containing a crosslinked rubber obtained by crosslinking the rubber composition of the present invention.
  • the crosslinked rubber composition of the present invention can contain polypropylene in addition to the crosslinked rubber.
  • the crosslinked rubber composition of the present invention is not particularly limited as long as it uses the rubber composition of the present invention as a raw material.
  • Examples of the vulcanization conditions include the same as described above.
  • the contained polypropylene is contained in the crosslinked rubber (especially rubber A and rubber B are incompatible with each other) from the viewpoint that both the damping property and the improvement in grip performance and rigidity can be achieved. Forming a continuous phase (network) is a preferred embodiment.
  • the rubber composition of the present invention or the crosslinked rubber composition of the present invention can achieve both improvement in damping property or grip performance and rigidity. Therefore, according to the rubber composition of the present invention or the crosslinked rubber composition of the present invention. For example, it is possible to reduce the size of the high attenuation laminate required to obtain the same characteristics (for example, attenuation).
  • Applications of the crosslinked rubber composition of the present invention include, for example, a rubber composition for a high damping laminate, a rubber composition for a pneumatic tire, a damping industrial belt, and the like.
  • the highly attenuated laminate of the present invention will be described below.
  • the high damping laminate of the present invention is obtained by alternately laminating the rubber composition of the present invention (the rubber composition for a high damping laminate of the present invention) or the crosslinked rubber composition of the present invention and a hard plate. It is a laminate.
  • the highly attenuated laminate of the present invention (hereinafter sometimes referred to as “the laminate of the present invention”) is formed by alternately laminating the above-described rubber composition of the present invention or the crosslinked rubber composition of the present invention and a hard plate. It is a high-damping laminate obtained by the above, and is a structure used for bridge support and building base isolation.
  • FIG. 1 shows a schematic cross-sectional view of a highly attenuated laminate that represents an example of an embodiment of the laminate of the present invention.
  • symbol 1 represents a high attenuation
  • symbol 2 represents a hard board
  • symbol 3 represents the rubber composition (rubber composition for high attenuation
  • the high attenuation laminate 1 of the present invention includes a rubber composition (rubber composition for a high attenuation laminate) 3 of the present invention and a hard plate 2 (for example, a general structural steel plate, Cold rolled steel sheets and the like) are alternately laminated.
  • the high attenuation laminate 1 may be configured by providing an adhesive layer between the rubber composition (rubber composition for a high attenuation laminate) 3 of the present invention and the hard plate 2. You may comprise by vulcanizing directly, without providing.
  • the high attenuation laminate 1 of the present invention shows a state in which the rubber composition (rubber composition for a high attenuation laminate) 3 of the present invention and hard plates 2 are alternately laminated.
  • the rubber composition (rubber composition for a high attenuation laminate) 3 may have a structure in which two or more layers are laminated.
  • FIG. 1 shows an example of a total of 13 layers including 6 layers for the rubber composition (rubber composition for high attenuation laminate) 3 of the present invention and 7 layers for the hard plate 2.
  • the number of laminations of the rubber composition (rubber composition for high attenuation laminate) 3 of the present invention and the hard plate 2 of the damping laminate 1 is not limited to this, depending on the application used, required characteristics, etc.
  • the rubber composition of the present invention (rubber composition for highly attenuated laminate) is molded into a sheet and then vulcanized to obtain a sheet-like rubber composition.
  • a layer containing an adhesive may be provided and alternately laminated with a hard plate, or an unvulcanized rubber composition of the present invention (a rubber composition for a high attenuation laminate) is formed into a sheet shape in advance, After alternately laminating with the hard plate, heating and vulcanization and adhesion may be performed simultaneously.
  • the laminated body of the present invention uses the above-described rubber composition of the present invention, it has an effect of high damping and excellent rigidity.
  • the equivalent damping constant (Heq) which is an index of damping performance measured by a lap shear shear test described later, is 0.21 or more, and the stiffness (Geq) measured similarly is 0.78 to 0.96. Can be.
  • FIG. 2 is a schematic side view of a sample for a lap shear type shear test.
  • symbol 4 represents the sample for a lap shear type shear test
  • symbol 5 represents the rolled unvulcanized rubber composition
  • symbol 6 represents a steel plate.
  • the unvulcanized rubber composition 5 is an unvulcanized rubber composition of the rubber composition of the present invention that has been rolled to a size of 25 mm wide ⁇ 25 mm long ⁇ 5 mm thick.
  • the steel plate 6 is a steel plate (width 25 mm ⁇ length 100 mm ⁇ thickness 20 mm) having a surface sandblasted and coated with a metal adhesive.
  • the sample 4 for lap shear type shear test is obtained by placing (stacking) the unvulcanized rubber composition 5 and the steel plate 6 as shown in FIG. 2 and then press vulcanizing at 130 ° C. for 120 minutes.
  • the lap shear shear test is performed under the following conditions using a vibrator (manufactured by Saginomiya), an input signal oscillator, and an output signal processor.
  • a vibrator manufactured by Saginomiya
  • an input signal oscillator an input signal oscillator
  • an output signal processor an output signal processor.
  • ⁇ W is the area of the hysteresis loop (the shaded area in FIG. 3).
  • Keq is represented by the following formula (3), H represents the total thickness of the rubber layer laminated in the high attenuation laminate, and A is the cross-sectional area of the rubber layer.
  • the high damping laminate of the present invention is formed by using the rubber composition of the present invention (rubber composition for a high damping laminate) or the crosslinked rubber composition of the present invention, both the damping property and the rigidity are improved. Therefore, according to the high attenuation laminate of the present invention, the size of the high attenuation laminate required to obtain the same characteristic (eg, attenuation) can be reduced.
  • the use, application conditions, and the like of the high attenuation laminate are not particularly limited as long as the high attenuation laminate is used as a vibration energy absorber. Among these, since it has the above-described excellent characteristics, it is preferably used as a vibration energy absorption device for buildings. For example, various vibration energy absorption devices for vibration isolation, vibration isolation, vibration isolation, etc. Is suitably used for, for example, support of road bridges, basic isolation of bridges and buildings, seismic isolation of detached houses, metal bearings, and replacement of bearings.
  • the pneumatic tire of the present invention is a pneumatic tire formed using the rubber composition of the present invention. If the rubber composition used when forming the pneumatic tire of this invention is a rubber composition of this invention, it will not restrict
  • By forming the pneumatic tire of the present invention using the rubber composition of the present invention both the grip performance and the rigidity can be improved.
  • a tread part, a side part, and a belt part of a pneumatic tire can be formed using the rubber composition of the present invention.
  • the pneumatic tire of the present invention is not particularly limited except that the rubber composition of the present invention is used for a pneumatic tire, and can be produced, for example, according to a conventionally known method.
  • inert gas such as nitrogen, argon, helium other than the air which adjusted normal or oxygen partial pressure, can be used.
  • ⁇ Lap shear test> The lap shear type shear test sample obtained as described above was subjected to a lap shear shear test using a vibrator (manufactured by Saginamiya), an input signal oscillator, and an output signal processor.
  • the number of lap shear type shear test samples used in each example was ten. Specifically, the shear characteristics of each time when 175% strain was applied 10 times at a deformation frequency of 0.5 Hz by a biaxial shear tester and a measurement temperature of 23 ° C. with respect to the lap shear type shear test sample. The average of the values was obtained.
  • Rubber A1 Natural rubber, TSR20, manufactured by SIAM INDO RUBBER
  • Rubber B1 Vinyl-cisbutadiene rubber, UBEPOL-VCR412, Ube Industries, Ltd.
  • Rubber B2 Styrene-butadiene copolymer, Nipol 1502, manufactured by Nippon Zeon Carbon black 1: Diamond black I, manufactured by Mitsubishi Chemical Co., Ltd.
  • Silanol group-containing inorganic filler 1 Silica, nip seal VN3, manufactured by Tosoh Silica, BET specific surface area 215 m 2 / g Silanol group-containing inorganic filler 2: Clay, SUPREX PLAY, manufactured by Kentucky Tennessee Clay Company, Ltd.
  • Inorganic filler not containing silanol group 1 Calcium carbonate
  • Inorganic filler not containing silanol group 2 Magnesium carbonate Petroleum resin 1 : High Resin # 120S (softening point 120 ° C., manufactured by Toho Chemical Co., Ltd.) ⁇ Metal compound 1: Zinc oxide, Zinc Hana No. 3, manufactured by Shodo Chemical Industry Co., Ltd.
  • Polylactic acid 1 LACEA H-440 (melting point: 155 ° C., number average molecular weight: 78000, weight average molecular weight: 150,000, manufactured by Mitsui Chemicals, Inc. )
  • Polylactic acid 2 NatureWorks 4060D (softening point 81 ° C., weight average molecular weight 180000, manufactured by NatureWorks)
  • Polypropylene 1 Propylene homopolymer, trade name E-333GV, manufactured by Prime Polymer Co., Ltd.
  • Polypropylene 2 Propylene homopolymer, trade name E-2900H, manufactured by Prime Polymer Co., Ltd.
  • Polyethylene 1 Low density polyethylene (Homo polymer), trade name YF30, manufactured by Nippon Polyethylene Co., Ltd.
  • Sulfur 1 powder sulfur, manufactured by Hosoi Chemical Co., Ltd.
  • Vulcanization accelerator 1 Noxeller CZ, manufactured by Ouchi Shinsei Chemical Co., Ltd.
  • FIG. 4 is a graph showing the relationship between damping property and rigidity obtained in the example of the present invention
  • the rubber compositions (Comparative Examples 2 and 3) in which a polylactic acid resin was added to the prepared rubber composition for highly attenuated laminates showed improved rigidity as compared with Comparative Example 1, but reduced rigidity.
  • the comparative example 4 which does not contain a polypropylene and contains polyethylene instead also improved the damping property as compared with the comparative example 1, the rigidity was lowered, and it was impossible to achieve both the damping property and the improvement in rigidity.
  • the rubber compositions (rubber compositions for highly attenuated laminates) produced in Examples 1 to 10 have higher attenuation than Comparative Example 1, and the rigidity is improved without decreasing the rigidity.
  • the rubber composition of the present invention (the rubber composition for a high-damping laminate) has a high damping property, and accordingly the rigidity is improved without decreasing the stiffness. Can be improved at the same time.
  • the rubber composition for highly attenuated laminates of the present invention is excellent in damping property, rigidity and durability at low temperature (23 ° C.), and excellent in low temperature performance.
  • Rubber B3 Styrene butadiene rubber (SBR), N9520 manufactured by Nippon Zeon Co., Ltd. (bonded styrene content: 35.0% by weight)
  • Carbon black 2 Dia Black SA manufactured by Mitsubishi Chemical Corporation (N 2 SA: 137 m 2 / g)
  • Silanol group-containing inorganic filler 3 sica: Silica, Ultraseal VN3 (BET: 175 m 2 / g) manufactured by Degussa Silane coupling agent 1: bis- [3- (triethoxysilyl) -propyl] tetrasulfide, trade name Si69, manufactured by DEGGUSA ⁇
  • Aroma oil 1 Process X-140 manufactured by Japan Energy Co., Ltd.
  • ⁇ Stearic acid manufactured by Nippon Oil & Fats Co., Ltd.
  • Metal compound 2 (zinc flower) Zinc flower, manufactured by Mitsui Mining & Smelting Co., Ltd.
  • ⁇ Wax Ozoace 0355 manufactured by Nippon Seiwa Co., Ltd.
  • Anti-aging agent 1 Antigen 6c (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
  • Sulfur 2 manufactured by Tsurumi Chemical Co., Ltd.
  • rubber A1, polylactic acid 1, polypropylene 1, and vulcanization accelerator 1 in Table 2 are the same as those used in Table 1.
  • Comparative Examples 6 and 7 not containing polypropylene had 100% modulus, low hardness and poor rigidity, and low grip performance.
  • Examples 11 and 12 had 100% modulus, high hardness and excellent rigidity, and were able to achieve both grip performance and rigidity.
  • FIG. 6 is a photograph of one example of the morphology of the rubber composition of the present invention observed with a scanning probe microscope (SMP).
  • the rubber composition sample (unvulcanized) used in FIG. 6 is composed of 61 parts by mass of rubber A1 (NR) shown in Table 1 and rubber shown in Table 1 as two or more types of crosslinkable rubber components. 36 parts by mass of B1 (BR) and polypropylene 1 (3 parts by mass) shown in Table 1 are contained. Measurement with a scanning probe microscope was performed at 23 ° C. The obtained photograph is an enlarged cross section of the sample 3500 times.
  • SMP scanning probe microscope
  • the phase portion of the same color reflects the same hardness in the measurement result by the scanning probe microscope.
  • the rubber composition 60 has a soft phase 61 as a matrix, and has a hard phase 63 that is elongated in the matrix. Since the hardest of the rubber component and polypropylene contained in the sample is polypropylene, the phase 63 that is elongated in the phase 61 is considered to be polypropylene.
  • the results of FIG. 6 are believed to suggest that polypropylene forms a continuous phase (network) of polypropylene in the rubber composition.
  • the phase 63 in FIG. 6 occupies a relatively wide part and forms a substantially continuous continuous phase. This is believed to prove that polypropylene is unevenly distributed at the interface between incompatible rubber A and rubber B to form a continuous phase of polypropylene in the rubber composition, as shown in FIG. .
  • Rubber composition of the present invention (rubber composition for highly attenuated laminate) 4 Sample for lap shear type shear test 5 Rolled unvulcanized rubber composition 6 Steel plate 10 Rubber A 20 Rubber B 30 Polypropylene (continuous phase) 60 Rubber composition 61, 63 Phase 100 Rubber composition of the present invention (crosslinked rubber composition) (rubber composition for highly attenuated laminate)

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CN104159962A (zh) * 2012-03-05 2014-11-19 日东电工株式会社 减振片
WO2016088979A1 (ko) * 2014-12-05 2016-06-09 주식회사 불스원 젤쿠션 조성물 및 이로부터 제조된 젤쿠션
WO2017037636A1 (en) * 2015-08-31 2017-03-09 Bridgestone Corporation Rubber compound to produce treads
WO2017209263A1 (ja) * 2016-06-01 2017-12-07 株式会社ブリヂストン ゴム組成物、及びタイヤ
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JP2018083894A (ja) * 2016-11-24 2018-05-31 Ｊｘｔｇエネルギー株式会社 導電性熱可塑性エラストマー組成物
JP2018177836A (ja) * 2017-04-03 2018-11-15 住友ゴム工業株式会社 キャップトレッド用ゴム組成物及びスタッドレスタイヤ
JP2022535367A (ja) * 2019-05-29 2022-08-08 ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー タイヤトレッドゴム組成物及び関連方法

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