WO2022176502A1 - Pneumatique - Google Patents

Pneumatique Download PDF

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Publication number
WO2022176502A1
WO2022176502A1 PCT/JP2022/002140 JP2022002140W WO2022176502A1 WO 2022176502 A1 WO2022176502 A1 WO 2022176502A1 JP 2022002140 W JP2022002140 W JP 2022002140W WO 2022176502 A1 WO2022176502 A1 WO 2022176502A1
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Prior art keywords
thermoplastic elastomer
less
elastomer composition
tire
mass
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PCT/JP2022/002140
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English (en)
Japanese (ja)
Inventor
康揮 森田
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住友ゴム工業株式会社
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Publication of WO2022176502A1 publication Critical patent/WO2022176502A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • 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
    • B60C19/00—Tyre parts or constructions not otherwise provided for
    • 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
    • B60C5/00—Inflatable pneumatic tyres or inner tubes
    • B60C5/01—Inflatable pneumatic tyres or inner tubes without substantial cord reinforcement, e.g. cordless tyres, cast tyres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers

Definitions

  • the present disclosure relates to tires.
  • Vulcanized rubber compositions generally account for most of the constituent members of tires, and vulcanized rubber compositions are difficult to recycle. Therefore, in order to improve recyclability, tires using, for example, thermoplastic elastomers are being studied. . However, there are few examples of practical use of tires using the above thermoplastic elastomers, and it is considered that problems still remain in the present situation toward practical use.
  • thermoplastic elastomer As a tire using a thermoplastic elastomer, for example, various tires using a thermoplastic elastomer in the tread portion and the side portion have been studied. Due to the lack of strong bonding, it is thought that permanent deformation will occur if it is left standing in a state where force is applied. There is a concern that the ride comfort will be deteriorated due to the partial deformation during the next driving. Such deformation also affects durability and noise, and there is concern that these performances may deteriorate.
  • An object of the present disclosure is to solve the above problems and to provide a tire using a thermoplastic elastomer that exhibits excellent ride comfort performance after long-term storage.
  • the present disclosure is a tire comprising a tread portion and a sidewall portion, The tread portion and/or the sidewall portion are made of a thermoplastic elastomer composition
  • the thermoplastic elastomer composition relates to a tire characterized by having a compression set (cps) at 70°C represented by the following formula of 40% or less.
  • cps (%) ⁇ (t0-t1)/(t0) ⁇ x 100 (Wherein, cps is compression set at 70° C. (%), t0 is the initial thickness (mm) of the test piece (thermoplastic elastomer composition), t1 is the test piece after compression set test for 24 hours (thermoplastic represents the thickness (mm) of the elastomer composition).
  • a tire comprising a tread portion and a sidewall portion, wherein the tread portion and/or the sidewall portion is composed of a thermoplastic elastomer composition, the thermoplastic elastomer composition having the formula
  • the compression set (cps) at 70° C. indicated by is 40% or less, so it is possible to provide a tire excellent in riding comfort performance after long-term storage.
  • FIG. 2 is a cross-sectional view showing a portion of the pneumatic tire;
  • FIG. 2 is an enlarged sectional view showing the vicinity of the tread 4 of the tire 2 of FIG. 1;
  • the tire of the present disclosure includes a tread portion and a sidewall portion, and the tread portion and/or the sidewall portion is made of a thermoplastic elastomer composition, and the thermoplastic elastomer composition is The compression set (cps) in is 40% or less.
  • the tire is excellent in ride comfort performance after long-term storage.
  • thermoplastic elastomer composition used only for the sidewall portion, the tread portion connected to the sidewall portion is pushed back when the sidewall portion recovers from deformation, so the deformation of the tread portion is eliminated and the tire is allowed to stand still. It is considered that the subsequent ride comfort performance is improved.
  • the tread portion and the sidewall portion are restored at the same time, making it easier to form the original shape of the tire. It is considered that the ride comfort performance after installation is improved. Therefore, it is presumed that a tire using a thermoplastic elastomer composition satisfying the above formula for at least one of the tread portion and the sidewall portion is excellent in riding comfort after long-term storage.
  • the tire has a tread portion and/or a sidewall portion made of a thermoplastic elastomer composition having a compression set (cps) of 40% or less at 70°C.
  • a compression set (cps) of 40% or less at 70°C This is to solve the problem (purpose) of providing ride comfort performance after long-term storage. That is, the configuration that the compression set (cps) at 70 ° C. is 40% or less does not define the problem (purpose), but the problem of the present application is to provide excellent ride comfort performance after long-term storage.
  • a configuration is provided that satisfies the parameters.
  • the thermoplastic elastomer composition constituting the tread portion and/or the sidewall portion has a compression set (cps) at 70°C represented by the following formula of 40% or less.
  • cps (%) ⁇ (t0-t1)/(t0) ⁇ x 100
  • cps represents compression set (%) at 70°C.
  • t0 is the initial thickness (mm) of the test piece (thermoplastic elastomer composition), that is, the thickness of the test piece (thermoplastic elastomer composition before being subjected to the compression set test) before being subjected to the compression set test. (mm).
  • t1 is the thickness (mm) of the test piece (thermoplastic elastomer composition) after the 24-hour compression set test, that is, the test piece after the 24-hour compression set test (24-hour compression set It represents the thickness (mm) of the thermoplastic elastomer composition after being subjected to the test.
  • the thermoplastic elastomer composition constituting the tread portion and/or sidewall portion has a cps of 40% or less, preferably 35% or less, more preferably 33% or less, even more preferably 31% or less, and 29%.
  • the following are particularly preferred.
  • the cps is preferably as small as possible.
  • the lower limit is not particularly limited.
  • the compression set (cps) at 70°C is a value conforming to JIS K6262:2013, and can be measured by the method described in Examples below.
  • a test piece for cps measurement is, in principle, taken from a tire. If the size of the sample that can be taken is less than the size of the test piece, take multiple samples, use the thermoplastic elastomer, seal them in a predetermined mold, and apply heat and pressure to the test piece. It can be remolded into the shape of The heating and pressing conditions are not particularly limited as long as the temperature is higher than the melting point of the thermoplastic elastomer composition and no gap is generated in the sample mold. If the thermoplastic elastomer is a thermoplastic polyurethane elastomer, it can be remolded into a test piece at a temperature of 190° C., for example.
  • Methods for adjusting the compression set (cps) at 70°C include a method of appropriately selecting the types of hard segments and soft segments in the thermoplastic elastomer, and adjusting the amount of structural units of the hard segments and soft segments in the thermoplastic elastomer. a method of combining two or more types of soft segments, a method of combining the thermoplastic elastomer with a cross-linking agent as an additive, and a method of adjusting the type and content of fillers. Specifically, blending a thermoplastic elastomer having a hard segment and a soft segment or combining a thermoplastic elastomer and a cross-linking agent (additive) tends to impart elasticity and reduce cps.
  • Techniques that satisfy "40% or less compression set (cps) at 70°C" include a method of combining two or more types of soft segments, a method of adjusting the constituent units of hard segments and soft segments, a thermoplastic elastomer, For example, a method of combining with a cross-linking agent as an additive can be used alone or in combination as appropriate.
  • thermoplastic elastomer composition in the present disclosure uses a thermoplastic elastomer, and the sulfur-crosslinked diene rubber component does not correspond to the thermoplastic elastomer.
  • a pneumatic tire 2 is shown in FIG.
  • the vertical direction is the radial direction of the tire 2
  • the horizontal direction is the axial direction of the tire 2
  • the direction perpendicular to the paper surface is the circumferential direction of the tire 2 .
  • the dashed-dotted line CL represents the equatorial plane of the tire 2 .
  • the shape of this tire 2 is symmetrical with respect to the equatorial plane, except for the tread pattern.
  • the tire 2 has a tread 4 (tread portion) and a pair of sidewalls 6 (sidewall portions). This tire 2 is of the tubeless type. This tire 2 is mounted on a passenger car.
  • the tire 2 may further have a base tread and a rubber layer that functions as other members (clinches, beads, carcasses, belts, bands, inner liners, chafers, etc.).
  • the tread 4 has a shape that is convex radially outward.
  • the tread 4 forms a tread surface 24 that contacts the road surface.
  • the tread 4 (tread portion) may be a single thermoplastic elastomer composition, a laminate of a plurality of thermoplastic elastomer compositions, or a laminate of a vulcanized rubber composition and a thermoplastic elastomer composition.
  • the sidewall portion can be sufficiently restored if the compression set of any layer of the tread portion is 40% or less.
  • the compression set of any one of the thermoplastic elastomer layers bonded to the sidewall portion is preferably 40% or less, and the compression set of all the elastomer layers bonded to the sidewall portion is 40%. More preferably, the compression set of all layers constituting the tread portion is 40% or less.
  • each sidewall 6 (sidewall portion) is joined to the edge of the tread 4 and extends substantially inward in the radial direction.
  • the sidewall 6 may be a single thermoplastic elastomer composition, a laminate of a plurality of thermoplastic elastomer compositions, or a laminate of a vulcanized rubber composition and a thermoplastic elastomer composition. good.
  • the sidewall 6 is joined to the tread portion in the tire axial direction. It may be joined so as to cover the outside.
  • the bead portion of the radially inner portion of the sidewall 6 may be provided with a member corresponding to a chafer or a bead reinforcing layer from the viewpoint of fitting with the rim and steering stability.
  • the sidewall 6 may have a laminated structure composed of a plurality of different compositions from the tire surface to the inner surface.
  • the compression set of the tread portion is more than 40%, and if the compression set of any thermoplastic elastomer layer of the sidewall 6 is 40% or less, the deformation of the tread 4 is restored.
  • the compression set of at least one layer of the thermoplastic elastomer composition bonded to the tread 4 is 40% or less, and all the thermoplastic elastomer compositions bonded to the tread 4 More preferably, the compression set of the article is 40% or less, and even more preferably all layers of the sidewall 6 have a compression set of 40% or less.
  • the tire 2 may be provided with a composition layer, such as clinch or bead apex, which plays the same role as a rubber composition that a conventional tire can take, in the bead portion.
  • a core of non-stretchable wire wound with steel cord may be provided.
  • the bead portion is also desirably composed of the thermoplastic elastomer composition that constitutes the tread portion and/or the sidewall portion from the viewpoint of obtaining the effect.
  • the tire 2 may have a carcass in the tread portion and the sidewall portion, like a conventional tire.
  • the carcass consists of carcass plies, and the carcass plies consist of a number of parallel cords and covering layers.
  • the absolute value of the angle formed by each cord with respect to the tire equatorial plane is preferably 75° to 90°.
  • the carcass preferably has a radial structure.
  • the cord consists of organic fibers.
  • Preferred organic fibers include polyester fibers, nylon fibers, rayon fibers, polyethylene naphthalate fibers and aramid fibers. From the viewpoint of obtaining the effect, it is preferable that the sidewall portion has a cord member that contacts the wheel.
  • the tire 2 may be provided with a belt layer and a belt reinforcing layer in the tread portion.
  • the belt layer (belt portion) is also desirably composed of the thermoplastic elastomer composition that constitutes the tread portion and/or the sidewall portion from the viewpoint of obtaining the effect.
  • the belt layer and the belt reinforcement layer may each include a number of juxtaposed cords and cover layers.
  • each cord is preferably inclined with respect to the equatorial plane, and the general absolute value of the inclination angle is 10° or more and 35° or less.
  • a preferred material for the cords of the belt layers is steel.
  • Organic fibers may be used for the cord.
  • the organic fibers are exemplified by polyester fibers, nylon fibers, rayon fibers, polyethylene naphthalate fibers and aramid fibers.
  • the belt reinforcing layer When the belt reinforcing layer is provided, it is preferably provided outside the belt layer in the tire radial direction.
  • the belt reinforcing layer includes cords and covering layers.
  • the cord is spirally wound and may have a so-called jointless structure.
  • the cords extend substantially in the circumferential direction and the angle of the cords with respect to the circumferential direction is 5° or less, or even 2° or less. Since the belt layers are constrained by the cords, lifting of the belt layers is suppressed.
  • the cord consists of organic fibers.
  • Preferred organic fibers include nylon fibers, polyester fibers, rayon fibers, polyethylene naphthalate fibers and aramid fibers.
  • any one of the carcass, belt layer, and belt reinforcing layer it is possible to reduce the deformation applied to the tire, reduce the permanent deformation of the tire during storage, and improve the riding comfort after storage. It may be possible to make it easier.
  • the innermost layer of the tire may be provided with an elastomer layer having excellent air permeation resistance.
  • This elastomer layer may be a so-called inner liner containing butyl rubber, or a thermoplastic elastomer layer using styrene-isobutylene-styrene copolymer or the like. It is thought that providing such a layer makes it easier to maintain the air pressure, makes it easier to prevent the tire from deforming due to the weight of the vehicle during storage, and makes it easier to maintain ride comfort performance after long-term storage.
  • At least one of the tread 4 (tread portion) and sidewall 6 (sidewall portion) is made of a thermoplastic elastomer composition having a compression set (cps) of 40% or less at 70°C.
  • FIG. 1 shows an example of the two-layer structure tread 4 (tread portion) composed of the cap layer 30 and the base layer 28, but in the case of the single-layer structure tread 4, the single-layer structure tread 4 ( tread portion) and a tire having a tread 4 (tread portion) having a structure of three or more layers.
  • any of the layers constituting the tread portion (the tread 4 with a single-layer structure, the cap layer 30 and the base layer of the tread 4 with a two-layer structure 28, each layer of the tread 4 having a structure of three or more layers, etc.) may be composed of the thermoplastic elastomer composition.
  • the cap layer 30 of the tread 4 having a single-layer structure, the cap layer 30 of the tread 4 having a two-layer structure, the cap layer (outermost layer) in the case of the tread 4 having a structure of three or more layers, etc.) is composed of the thermoplastic elastomer composition. is desirable.
  • the thermoplastic elastomer composition forming the tread 4 (tread portion) and the sidewall 6 (sidewall portion) preferably has a creep rate of 40% or less from the viewpoint of riding comfort after long-term storage.
  • the creep rate is more preferably 30% or less, still more preferably 27% or less, and particularly preferably 26% or less.
  • the creep rate is desirably as small as possible, preferably 22% or less, or 20% or less. Since a smaller creep rate is desirable, the lower limit is not particularly limited.
  • Both the tread 4 (tread portion) and the sidewall 6 (sidewall portion) are made of a thermoplastic elastomer composition from the viewpoint of ride comfort after long-term storage, and the tread 4 (tread portion) is constructed. It is preferable that the difference in creep rate between the thermoplastic elastomer composition that forms the sidewall 6 (sidewall portion) and the thermoplastic elastomer composition that forms the sidewall 6 (sidewall portion) is 10% or less.
  • the difference in creep rate is more preferably 8% or less, still more preferably 6% or less, particularly preferably 5% or less, and most preferably 4% or less. It is desirable that the difference in the creep rate is as small as possible, preferably 2% or less, 1% or less, or even 0%. Since it is desirable that the difference in creep rate is as small as possible, the lower limit is not particularly limited.
  • the creep rate can be measured by the following method.
  • thermoplastic elastomer composition can be used without any particular limitation as long as it has a compression set (cps) of 40% or less at 70°C.
  • a composition containing a thermoplastic elastomer can be preferably used from the viewpoint of ride comfort performance after long-term storage.
  • thermoplastic elastomers include olefinic thermoplastic elastomers, styrene thermoplastic elastomers (elastomer styrene-isobutylene-styrene block copolymer (SIBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene Block copolymer (SIB), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS) , styrene-ethylene/ethylene/propylene-styrene block copolymer (SEEPS), styrene-butadiene/butylene-styrene block copolymer (S
  • thermoplastic elastomers thermoplastic polyurethane elastomers (TPU)
  • TPU thermoplastic polyurethane elastomers
  • thermoplastic polyurethane elastomers examples include those composed of isocyanate, polyol, and, if necessary, a chain extender.
  • the isocyanate constituting the thermoplastic polyurethane elastomer is not particularly limited as long as it is an isocyanate compound having two or more isocyanate groups.
  • Polyols (high molecular weight polyols) constituting thermoplastic polyurethane elastomers include polyether polyols such as polyoxyethylene glycol (PEG), polyoxypropylene glycol (PPG), polyoxytetramethylene glycol (PTMG); polyethylene adipate (PEA); ), polybutylene adipate (PBA), polyhexamethylene adipate (PHMA) and other condensed polyester polyols; poly- ⁇ -caprolactone (PCL) and other lactone polyester polyols; polyhexamethylene carbonate and other polycarbonate polyols; is mentioned.
  • polyether polyols and polycarbonate polyols are preferable from the viewpoint of riding comfort performance after long-term storage. These may use 1 type and may use 2 or more types together.
  • chain extenders examples include low-molecular-weight polyols, polyamines, aminoalcohols, and the like. Among them, low-molecular-weight polyols are preferable from the viewpoint of ride comfort performance after long-term storage.
  • Examples of the low-molecular-weight polyol include triols such as glycerin, trimethylolethane, trimethylolpropane and hexanetriol; tetraols such as pentaerythritol; hexaols such as sorbitol; and ethylene glycol, diethylene glycol and triethylene glycol. , 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, aniline diol, bisphenol A diol, etc. diols of These may use 1 type and may use 2 or more types together.
  • triols such as glycerin, trimethylolethane, trimethylolpropane and hexanetriol
  • tetraols such as pentaerythrito
  • polyamines examples include triamines such as diethylenetriamine and dipropylenetriamine; aliphatic diamines such as ethylenediamine and hexamethylenediamine; alicyclic diamines such as isophoronediamine and piperazine; and diamines such as aromatic diamines.
  • the aromatic diamine may be, for example, a monocyclic aromatic diamine in which two amino groups are bonded to one aromatic ring, or an aminophenyl diamine in which at least one amino group is bonded to one aromatic ring. It may also be a polycyclic aromatic diamine containing two groups.
  • Monocyclic aromatic diamines include types in which an amino group is directly bonded to an aromatic ring, such as phenylenediamine, toluenediamine, diethyltoluenediamine, and dimethylthiotoluenediamine; amino groups such as xylylenediamine are lower alkylene groups; and a type that is bound to an aromatic ring via Polycyclic aromatic diamines include diaminodiphenylalkanes (4,4'-diaminodiphenylmethane and derivatives thereof, etc.). These may use 1 type and may use 2 or more types together.
  • thermoplastic polyurethane elastomer can be synthesized by a known method, and examples of synthesis methods include a one-shot method and a prepolymer method.
  • the one-shot method is a method in which isocyanate and polyol or the like are reacted all at once to increase the molecular weight.
  • the prepolymer method is a method of reacting an isocyanate with a polyol or the like in multiple steps to increase the molecular weight. It is a method of reacting with a chain extender to increase the molecular weight.
  • a known catalyst can be used for the synthesis of polyurethane.
  • catalysts include monoamines such as triethylamine and N,N-dimethylcyclohexylamine; polyamines such as N,N,N',N'-tetramethylethylenediamine; 1,8-diazabicyclo[5,4,0]. Cyclic diamines such as -7-undecene (DBU) and triethylenediamine; and tin-based catalysts such as dibutyltin dilaurate and dibutyltin diacetate. These may use 1 type and may use 2 or more types together.
  • DBU -7-undecene
  • tin-based catalysts such as dibutyltin dilaurate and dibutyltin diacetate.
  • the ratio of the isocyanate to the polyol in the polyurethane is not particularly limited, but the NCO/OH ratio (molar ratio) of the isocyanate group of the isocyanate to the hydroxyl group of the polyol is preferably 0.5 or more, more preferably 0.5. It is 7 or more, more preferably 0.8 or more. If the above lower limit is not reached, the mechanical strength of the urethane tends to decrease because the isocyanate component is too small. On the other hand, the NCO/OH ratio (molar ratio) is preferably 2.5 or less, more preferably 2.2 or less, and even more preferably 2.0 or less. When the above upper limit is exceeded, the isocyanate component becomes excessive, so that the urethane tends to absorb moisture, and the mechanical strength of the urethane may decrease.
  • the tread 4 (tread portion) and/or the sidewall 6 (sidewall portion) of the tire 2 are made of a thermoplastic elastomer composition having a compression set (cps) of 40% or less at 70°C.
  • the content of the thermoplastic elastomer in 100% by mass of the elastomer component is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. be.
  • the upper limit is not particularly limited, and may be 100% by mass. By setting it within the above range, there is a tendency to obtain good ride comfort performance after long-term storage.
  • the thermoplastic elastomer composition may contain elastomer components other than the thermoplastic elastomer.
  • a diene rubber can be used as another elastomer component. Diene rubbers include isoprene rubber, butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR). ) and the like.
  • butyl-based rubber, fluororubber, and the like can also be used. These may be used alone or in combination of two or more. SBR, BR, and isoprene-based rubbers are preferred as other elastomers from the viewpoint of being suitable for use in tire applications.
  • the diene rubber may be a non-modified diene rubber or a modified diene rubber.
  • the modified diene rubber may be any diene rubber having a functional group that interacts with a filler such as silica.
  • Terminal modified diene rubber modified with terminal modified diene rubber having the above functional group at the end
  • main chain modified diene rubber having the above functional group on the main chain and the above functional group on the main chain and terminal main chain end-modified diene rubber (for example, main chain end-modified diene rubber having the above functional group in the main chain and at least one end modified with the above modifier), or two or more in the molecule
  • a terminal-modified diene rubber modified (coupled) with a polyfunctional compound having an epoxy group and introduced with a hydroxyl group or an epoxy group is exemplified.
  • Examples of the functional groups include amino group, amido group, silyl group, alkoxysilyl group, isocyanate group, imino group, imidazole group, urea group, ether group, carbonyl group, oxycarbonyl group, mercapto group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, ammonium group, imide group, hydrazo group, azo group, diazo group, carboxyl group, nitrile group, pyridyl group, alkoxy group, hydroxyl group, oxy group, epoxy group and the like. .
  • these functional groups may have a substituent.
  • an amino group preferably an amino group in which the hydrogen atom of the amino group is substituted with an alkyl group having 1 to 6 carbon atoms
  • an alkoxy group preferably an alkoxy group having 1 to 6 carbon atoms
  • an alkoxysilyl group An alkoxysilyl group having 1 to 6 carbon atoms is preferred.
  • the SBR is not particularly limited, and for example, emulsion-polymerized styrene-butadiene rubber (E-SBR), solution-polymerized styrene-butadiene rubber (S-SBR), etc. can be used. These may be used alone or in combination of two or more.
  • E-SBR emulsion-polymerized styrene-butadiene rubber
  • S-SBR solution-polymerized styrene-butadiene rubber
  • the styrene content of SBR is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. Also, the styrene content is preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. Within the above range, the above effects can be obtained more favorably. In this specification, the styrene content of SBR is calculated by 1 H-NMR measurement.
  • SBR for example, SBR manufactured and sold by Sumitomo Chemical Co., Ltd., JSR Co., Ltd., Asahi Kasei Co., Ltd., Nippon Zeon Co., Ltd., etc. can be used.
  • SBR may be unmodified SBR or modified SBR.
  • modified SBR include modified SBR into which functional groups similar to those of modified diene rubber have been introduced.
  • the content of SBR in 100% by mass of the elastomer component is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of riding comfort after long-term storage. is.
  • the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
  • BR is not particularly limited, and for example, high cis BR having a high cis content, BR containing syndiotactic polybutadiene crystals, BR synthesized using a rare earth catalyst (rare earth BR), and the like can be used. These may be used alone or in combination of two or more. Among them, high-cis BR having a cis content of 90% by mass or more is preferable because it improves wear resistance.
  • BR may be non-denatured BR or denatured BR.
  • modified BR include modified BR into which functional groups similar to those of modified diene rubber have been introduced.
  • the content of BR in 100% by mass of the elastomer component is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of wear resistance and the like.
  • the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
  • As BR for example, products of Ube Industries, Ltd., JSR Corporation, Asahi Kasei Co., Ltd., Nippon Zeon Co., Ltd., etc. can be used.
  • the isoprene rubber includes natural rubber (NR), isoprene rubber (IR), modified NR, modified NR, modified IR, and the like.
  • NR natural rubber
  • IR isoprene rubber
  • modified NR those commonly used in the rubber industry, such as SIR20, RSS#3, and TSR20, can be used.
  • the IR is not particularly limited, and for example IR2200 or the like commonly used in the rubber industry can be used.
  • Modified NR includes deproteinized natural rubber (DPNR), high-purity natural rubber (UPNR), etc.
  • Modified NR includes epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), grafted natural rubber, etc.
  • modified IR include epoxidized isoprene rubber, hydrogenated isoprene rubber, grafted isoprene rubber, and the like. These may be used alone or in combination of two or more.
  • the content of the isoprene-based rubber in 100% by mass of the elastomer component is preferably 10% by mass or more, more preferably 20% by mass, from the viewpoint of fuel efficiency and the like. % or more.
  • the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
  • the thermoplastic elastomer composition preferably contains a cross-linking agent from the viewpoint of riding comfort performance after long-term storage.
  • a cross-linking agent a known cross-linking agent can be used as appropriate, but one having the action of partially bonding the thermoplastic elastomers to form a network can be preferably used.
  • a crosslinking agent is added afterward, kneaded with a twin-screw extruder, and heat-treated, thereby suppressing changes in hardness and crosslinking. It is possible to change state.
  • the aforementioned isocyanate can be preferably used from the viewpoint of ride comfort performance after long-term storage.
  • isocyanates MDI (4,4'-diphenylmethane diisocyanate, methylenebis(4,1-phenylene) diisocyanate) is preferred, and MDI is more preferred. These may be used alone or in combination of two or more. good.
  • the thermoplastic elastomer composition contains isocyanate as the cross-linking agent in addition to the isocyanate constituting the thermoplastic polyurethane elastomer. That is, in this case, the thermoplastic elastomer composition contains a cross-linked thermoplastic polyurethane elastomer and isocyanate (another cross-linking agent).
  • the content of the cross-linking agent is preferably 1.0 parts by mass or more, relative to 100 parts by mass of the elastomer component. It is preferably 2.0 parts by mass or more, more preferably 2.5 parts by mass or more, and particularly preferably 3.0 parts by mass or more.
  • the upper limit is preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, even more preferably 7.0 parts by mass or less, and particularly preferably 5.0 parts by mass or less.
  • the content of isocyanate (an isocyanate separately blended in addition to the isocyanate constituting the thermoplastic elastomer) as a cross-linking agent is preferably 1.0 parts by mass with respect to 100 parts by mass of the elastomer component. Above, more preferably 2.0 parts by mass or more, still more preferably 2.5 parts by mass or more, and particularly preferably 3.0 parts by mass or more.
  • the upper limit is preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, even more preferably 7.0 parts by mass or less, and particularly preferably 5.0 parts by mass or less.
  • the content of MDI as a cross-linking agent is preferably 1.0 parts by mass with respect to 100 parts by mass of the elastomer component. Above, more preferably 2.0 parts by mass or more, still more preferably 2.5 parts by mass or more, and particularly preferably 3.0 parts by mass or more.
  • the upper limit is preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, even more preferably 7.0 parts by mass or less, and particularly preferably 5.0 parts by mass or less.
  • thermoplastic elastomer composition can be appropriately blended with a filler such as a fiber.
  • a filler such as a fiber.
  • Fibrous fillers that are generally difficult to disperse in thermoplastic elastomers can also be used.
  • difficult-to-disperse fillers such as microfibrillated plant fibers, short fibrous cellulose, and gel compounds can be suitably applied.
  • microfibrillated plant fibers are preferable from the viewpoint of riding comfort performance after long-term storage.
  • Cellulose microfibrils are preferable as the microfibrillated plant fibers because they provide good reinforcing properties.
  • Cellulose microfibrils are not particularly limited as long as they are derived from natural products. Examples include resource biomass such as fruits, grains, and root vegetables, wood, bamboo, hemp, jute, kenaf, and pulp obtained from these as raw materials.
  • resource biomass such as fruits, grains, and root vegetables, wood, bamboo, hemp, jute, kenaf, and pulp obtained from these as raw materials.
  • waste biomass such as paper, cloth, agricultural waste, food waste and sewage sludge, unused biomass such as rice straw, wheat straw, and thinned wood, those derived from cellulose produced by sea squirts, acetic acid bacteria, etc. be done.
  • waste biomass such as paper, cloth, agricultural waste, food waste and sewage sludge, unused biomass such as rice straw, wheat straw, and thinned wood, those derived from cellulose produced by sea
  • cellulose microfibrils typically mean cellulose fibers having an average fiber diameter of 10 ⁇ m or less, more typically an average fiber diameter formed by aggregation of cellulose molecules. Cellulose fibers with a microstructure of 500 nm or less are meant. A typical cellulose microfibril is formed, for example, as an aggregate of cellulose fibers having an average fiber diameter as described above.
  • the method for producing the microfibrillated plant fiber is not particularly limited. extruder), twin-screw kneading extruder, high-pressure homogenizer, medium stirring mill, stone mill, grinder, vibrating mill, sand grinder and the like.
  • extruder twin-screw kneading extruder
  • high-pressure homogenizer medium stirring mill
  • stone mill stone mill
  • grinder vibrating mill
  • sand grinder sand grinder and the like.
  • lignin is separated from the raw material by chemical treatment, resulting in microfibrillated plant fibers substantially free of lignin.
  • microfibrillated plant fiber for example, products of Sugino Machine Co., Ltd. can be used.
  • the microfibrillated plant fibers include those obtained by the above production method and further subjected to oxidation treatment and various chemical modification treatments, and natural products from which the cellulose microfibrils can be derived (for example, Wood, pulp, bamboo, hemp, jute, kenaf, agricultural waste, cloth, paper, sea squirt cellulose, etc.) are used as cellulose raw materials, and subjected to oxidation treatment and various chemical modification treatments, and then defibration treatment as necessary. can also be used.
  • oxidized microfibrillated plant fibers can be preferably used.
  • Examples of the oxidation treatment include oxidation treatment using an N-oxyl compound.
  • the oxidation treatment using the N-oxyl compound can be carried out, for example, by a method in which the N-oxyl compound is used as an oxidation catalyst in water and a co-oxidizing agent acts on the microfibrillated plant fibers.
  • Examples of the N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and derivatives thereof.
  • Examples of the co-oxidizing agent include sodium hypochlorite.
  • the average fiber diameter of the microfibrillated plant fibers is preferably 10 ⁇ m or less. Within the above range, the dispersibility of the microfibrillated plant fibers in the elastomer can be improved. In addition, breakage of microfibrillated plant fibers during processing tends to be suppressed.
  • the average fiber diameter is more preferably 500 nm or less, still more preferably 100 nm or less, and particularly preferably 50 nm or less. Although the lower limit of the average fiber diameter is not particularly limited, it is preferably 4 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more because the microfibrillated plant fibers are difficult to untangle and disperse.
  • the average fiber length of the microfibrillated plant fibers is preferably 100 nm or longer, more preferably 300 nm or longer, and still more preferably 500 nm or longer. Also, it is preferably 5 mm or less, more preferably 1 mm or less, still more preferably 50 ⁇ m or less, particularly preferably 3 ⁇ m or less, and most preferably 2 ⁇ m or less. When the average fiber length is less than the lower limit or exceeds the upper limit, there is a tendency similar to the aforementioned average fiber diameter.
  • the average fiber diameter and the average fiber length are calculated as the average of the microfibrillated plant fibers as a whole.
  • the average fiber diameter and average fiber length of the microfibrillated plant fibers are determined by image analysis using scanning electron micrographs, image analysis using transmission electron micrographs, image analysis using atomic force micrographs, X-ray It can be measured by scattering data analysis, pore electrical resistance method (Coulter principle method), or the like.
  • the short fibrous cellulose has good dispersibility in the elastomer, it can be maintained or improved without impairing the breaking strength of the elastomer, resulting in good elastomer physical properties.
  • the fiber width of the short fibrous cellulose is preferably 3 to 200 ⁇ m.
  • fibrous fillers that are blended in thermoplastic elastomer composites are preferred to have a smaller fiber width in terms of reinforcing properties of the elastomer.
  • the fiber width is preferably 10 ⁇ m or more, more preferably 15 ⁇ m or more, and still more preferably 20 ⁇ m or more, from the viewpoint of the balance between the reinforcing properties of the elastomer and the orientation of the fibers, and from the viewpoint of dispersibility in the elastomer.
  • it is preferably 120 ⁇ m or less, more preferably 80 ⁇ m or less, and even more preferably 50 ⁇ m or less.
  • the fiber length of the short fibrous cellulose is preferably 20 to 1000 ⁇ m. Similar to the fiber width, the fiber length is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, and 200 ⁇ m or more, from the viewpoint of the balance between the reinforcing properties of the elastomer and the orientation of the fibers, and from the viewpoint of dispersibility in the elastomer. is more preferred. Moreover, 700 micrometers or less are preferable and 500 micrometers or less are more preferable.
  • the short fibrous cellulose preferably has a ratio of fiber width to fiber length (fiber length/fiber width) of 5 to 1,000. Similar to the fiber width, the ratio of the fiber width to the fiber length is preferably 6 or more, more preferably 10 or more, from the viewpoint of the balance between the reinforcing properties of the elastomer and the orientation of the fibers. Moreover, it is preferably 800 or less, more preferably 500 or less, still more preferably 400 or less, and particularly preferably 300 or less.
  • the fiber width and fiber length of the short fibrous cellulose are determined by image analysis of scanning atomic force micrographs, image analysis of scanning electron micrographs, image analysis of transmission micrographs, analysis of X-ray scattering data, pore It can be measured by an electrical resistance method (Coulter principle method) or the like.
  • a gel compound is a substance obtained by gelling microfibrillated plant fibers or short fibrous cellulose. Even when such a gelled product is used, the gelled compound can be well dispersed.
  • the gelation method is not particularly limited, and includes a method of stirring using an ultra-high pressure homogenizer or the like.
  • the content of the hard-to-disperse filler is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more with respect to 100 parts by mass of the elastomer component.
  • the upper limit of the content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less.
  • the thermoplastic elastomer composition may contain silica as a filler.
  • silica examples include dry silica (anhydrous silica) and wet silica (hydrous silica).
  • wet-process silica is preferable because it has many silanol groups.
  • Commercially available products of Degussa, Rhodia, Tosoh Silica, Solvay Japan, Tokuyama, etc. can be used. These may be used alone or in combination of two or more.
  • the content of silica is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 50 parts by mass or more with respect to 100 parts by mass of the elastomer component. By making it more than the lower limit, there is a tendency that good ride comfort performance after long-term storage can be obtained.
  • the upper limit of the content is not particularly limited, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 170 parts by mass or less, particularly preferably 100 parts by mass or less, and most preferably 80 parts by mass or less. be. By making it below the upper limit, there is a tendency that good dispersibility can be obtained.
  • the nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 70 m 2 /g or more, more preferably 140 m 2 /g or more, still more preferably 160 m 2 /g or more. By making it more than the lower limit, there is a tendency that good ride comfort performance and breaking strength after long-term storage can be obtained.
  • the upper limit of N 2 SA of silica is not particularly limited, but is preferably 500 m 2 /g or less, more preferably 300 m 2 /g or less, and still more preferably 250 m 2 /g or less. By making it below the upper limit, there is a tendency that good dispersibility can be obtained.
  • the N 2 SA of silica is a value measured by the BET method according to ASTM D3037-93.
  • the thermoplastic elastomer composition contains silica, it preferably further contains a silane coupling agent.
  • the silane coupling agent is not particularly limited, and examples thereof include bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, Bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (2-triethoxysilylethyl) trisulfide, bis (4-trimethoxysilylbutyl) trisulfide, bis ( 3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) disulfide, bis(4-triethoxysilylbutyl) disulf
  • the content of the silane coupling agent is preferably 3 parts by mass or more, more preferably 6 parts by mass or more, relative to 100 parts by mass of silica. When it is 3 parts by mass or more, there is a tendency that good breaking strength and the like can be obtained. Moreover, 20 mass parts or less are preferable, and, as for the said content, 15 mass parts or less are more preferable. When the amount is 20 parts by mass or less, there is a tendency to obtain an effect commensurate with the blending amount.
  • thermoplastic elastomer composition may contain carbon black as a filler.
  • carbon black tends to increase the viscosity of the elastomer composition, apply shear, and improve filler dispersibility.
  • Examples of carbon black include, but are not limited to, N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, and N762.
  • Commercially available products include Asahi Carbon Co., Ltd., Cabot Japan Co., Ltd., Tokai Carbon Co., Ltd., Mitsubishi Chemical Co., Ltd., Lion Corporation, Shin Nikka Carbon Co., Ltd., and Columbia Carbon Co., Ltd. can. These may be used alone or in combination of two or more.
  • the content of carbon black is preferably 1 part by mass or more, more preferably 3 parts by mass or more, relative to 100 parts by mass of the elastomer component. By making it more than the lower limit, there is a tendency that good abrasion resistance, ride comfort performance after long-term storage, etc. can be obtained. Moreover, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. By making it below the upper limit, there is a tendency to obtain good processability of the elastomer composition.
  • the nitrogen adsorption specific surface area (N 2 SA) of carbon black is preferably 50 m 2 /g or more, more preferably 80 m 2 /g or more, and even more preferably 100 m 2 /g or more.
  • the N 2 SA is preferably 200 m 2 /g or less, more preferably 150 m 2 /g or less, and even more preferably 130 m 2 /g or less. By making it below the upper limit, there is a tendency for good dispersion of carbon black to be obtained.
  • the nitrogen adsorption specific surface area of carbon black is determined according to JIS K6217-2:2001.
  • the thermoplastic elastomer composition may contain fillers other than the flame-retardant filler, silica, and carbon black.
  • Other fillers include calcium carbonate, talc, alumina, clay, aluminum hydroxide, aluminum oxide, mica, and the like.
  • the thermoplastic elastomer composition may contain a plasticizer.
  • the plasticizer is not particularly limited, but liquid plasticizers having liquid plasticity at 25 ° C. such as oils and liquid resins, resins (polymers in a solid state at normal temperature (25 ° C.)), etc. Solid plasticity at 25 ° C. and solid plasticizers having One type of these plasticizers may be used, or two or more types may be used in combination.
  • the plasticizer content (total amount of liquid plasticizer, solid plasticizer, etc.) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass, per 100 parts by mass of the elastomer component. That's it. Also, the content is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. By setting it within the above range, there is a tendency that good ride comfort performance after long-term storage can be obtained.
  • the above oils are not particularly limited, and process oils such as paraffinic process oils, aromatic process oils, and naphthenic process oils, low PCA (polycyclic aromatic) process oils such as TDAE and MES, vegetable oils and fats, and Conventionally known oils such as mixtures thereof can be used.
  • aromatic process oils are preferable in terms of wear resistance and fracture properties.
  • Specific examples of the aromatic process oil include the Diana process oil AH series manufactured by Idemitsu Kosan Co., Ltd., and the like.
  • liquid resin examples include, but are not limited to, liquid aromatic vinyl polymers, coumarone-indene resins, indene resins, terpene resins, rosin resins, and hydrogenated products thereof.
  • a liquid aromatic vinyl polymer is a resin obtained by polymerizing ⁇ -methylstyrene and/or styrene.
  • examples include liquid resins such as copolymers.
  • a liquid coumarone-indene resin is a resin containing coumarone and indene as main monomer components constituting the skeleton (main chain) of the resin. , styrene, ⁇ -methylstyrene, methylindene, vinyltoluene, and the like.
  • a liquid indene resin is a liquid resin containing indene as a main monomer component that constitutes the skeleton (main chain) of the resin.
  • Liquid terpene resins are resins obtained by polymerizing terpene compounds such as ⁇ -pinene, ⁇ -pinene, camphor, and dipetene, and liquids represented by terpene phenol, which is a resin obtained from a terpene compound and a phenolic compound as raw materials. It is a terpene resin.
  • the liquid rosin resin is a liquid rosin resin represented by natural rosin, polymerized rosin, modified rosin, ester compounds thereof, or hydrogenated products thereof.
  • the content of the liquid plasticizer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more with respect to 100 parts by mass of the elastomer component. Also, the content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. By setting it within the above range, there is a tendency to obtain good ride comfort performance after long-term storage.
  • the solid resin is not particularly limited, but for example, solid styrene-based resin, coumarone-indene resin, terpene-based resin, pt-butylphenolacetylene resin, acrylic resin, dicyclopentadiene-based resin (DCPD-based resin). , C5 petroleum resin, C9 petroleum resin, C5C9 petroleum resin, and the like. These may be used alone or in combination of two or more.
  • the solid styrenic resin is a solid polymer using a styrenic monomer as a constituent monomer, and examples thereof include polymers polymerized with a styrenic monomer as a main component (50% by mass or more).
  • styrene monomers styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-Chlorostyrene, m-chlorostyrene, p-chlorostyrene, etc.), homopolymers obtained by polymerizing each alone, copolymers obtained by copolymerizing two or more styrene monomers, and styrene monomers and copolymers of other monomers copolymerizable therewith.
  • styrene monomers styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, p-methoxyst
  • Examples of the other monomers include acrylonitrile, methacrylonitrile, and other acrylonitrile, acrylic acid, methacrylic acid, and other unsaturated carboxylic acids, methyl acrylate, methyl methacrylate, and other unsaturated carboxylic acid esters, chloroprene, and butadiene. dienes such as isoprene; olefins such as 1-butene and 1-pentene; ⁇ , ⁇ -unsaturated carboxylic acids such as maleic anhydride and acid anhydrides thereof;
  • solid ⁇ -methylstyrene resins ( ⁇ -methylstyrene homopolymers, copolymers of ⁇ -methylstyrene and styrene, etc.) are preferred.
  • solid coumarone-indene resin examples include solid resins having the same structural units as those of the liquid coumarone-indene resin described above.
  • Solid terpene-based resins include polyterpene, terpenephenol, and aromatic modified terpene resins.
  • Polyterpenes are resins obtained by polymerizing terpene compounds and hydrogenated products thereof.
  • Terpene compounds are hydrocarbons represented by the composition (C 5 H 8 ) n and their oxygen-containing derivatives, such as monoterpene (C 10 H 16 ), sesquiterpene (C 15 H 24 ), diterpene (C 20 H 32 ) and the like, which are compounds having a terpene as a basic skeleton, such as ⁇ -pinene, ⁇ -pinene, dipentene, limonene, myrcene, alloocimene, ocimene, ⁇ -phellandrene, ⁇ -terpinene, ⁇ -terpinene, terpinolene , 1,8-cineole, 1,4-cineole, ⁇ -terpineol, ⁇ -ter
  • terpene resin such as ⁇ -pinene resin, ⁇ -pinene resin, limonene resin, dipentene resin, ⁇ -pinene/limonene resin made from the above-mentioned terpene compound as a raw material, and hydrogenation of the terpene resin
  • solid resins such as treated hydrogenated terpene resins.
  • the solid terpene phenol examples include a solid resin obtained by copolymerizing the terpene compound and a phenolic compound, and a solid resin obtained by hydrogenating the resin.
  • the terpene compound, the phenolic compound and A solid resin obtained by condensing formalin can be mentioned.
  • phenolic compounds include phenol, bisphenol A, cresol, and xylenol.
  • solid aromatic-modified terpene resins include solid resins obtained by modifying terpene resins with aromatic compounds, and solid resins obtained by hydrogenating the resins.
  • the aromatic compound is not particularly limited as long as it is a compound having an aromatic ring. Examples include phenol compounds such as phenol, alkylphenol, alkoxyphenol, unsaturated hydrocarbon group-containing phenol; naphthol compounds such as unsaturated hydrocarbon group-containing naphthol; styrene derivatives such as styrene, alkylstyrene, alkoxystyrene, unsaturated hydrocarbon group-containing styrene; coumarone, indene, and the like.
  • solid pt-butylphenol acetylene resins include solid resins obtained by condensation reaction of pt-butylphenol and acetylene.
  • the solid acrylic resin is not particularly limited, a solvent-free acrylic solid resin can be preferably used because it contains few impurities and provides a resin with a sharp molecular weight distribution.
  • a solid solvent-free acrylic resin is produced by a high-temperature continuous polymerization method (high-temperature continuous bulk polymerization method) (U.S. Pat. No. 4,414) without using polymerization initiators, chain transfer agents, organic solvents, etc. , 370, JP-A-59-6207, JP-B-5-58005, JP-A-1-313522, US Pat.
  • (meth)acryl means methacryl and acryl.
  • the solid acrylic resin preferably does not substantially contain auxiliary materials such as a polymerization initiator, a chain transfer agent, and an organic solvent. Further, the acrylic resin preferably has a relatively narrow composition distribution and molecular weight distribution obtained by continuous polymerization.
  • the solid acrylic resin preferably does not substantially contain auxiliary materials such as a polymerization initiator, a chain transfer agent, an organic solvent, etc., that is, has a high purity.
  • the purity of the solid acrylic resin (percentage of resin contained in the resin) is preferably 95% by mass or more, more preferably 97% by mass or more.
  • Examples of monomer components constituting solid acrylic resins include (meth)acrylic acid, (meth)acrylic acid esters (alkyl esters, aryl esters, aralkyl esters, etc.), (meth)acrylamide, and (meth) Examples include (meth)acrylic acid derivatives such as acrylamide derivatives.
  • styrene In addition to (meth)acrylic acid and (meth)acrylic acid derivatives, styrene, ⁇ -methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinyl are also used as monomer components constituting solid acrylic resins. Aromatic vinyls such as naphthalene may also be used.
  • the solid acrylic resin may be a resin composed only of a (meth)acrylic component, or a resin containing components other than the (meth)acrylic component as constituent elements. Moreover, the solid acrylic resin may have a hydroxyl group, a carboxyl group, a silanol group, or the like.
  • the content of the solid plasticizer is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more with respect to 100 parts by mass of the elastomer component. Also, the content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. By setting it within the above range, there is a tendency to obtain good ride comfort performance after long-term storage.
  • Liquid plasticizers and solid plasticizers include, for example, Maruzen Petrochemical Co., Ltd., Sumitomo Bakelite Co., Ltd., Yasuhara Chemical Co., Ltd., Tosoh Corporation, Rutgers Chemicals, BASF Corporation, Arizona Chemical Co., Nikko Chemical Co., Ltd. ), Nippon Shokubai Co., Ltd., ENEOS Co., Ltd., Arakawa Chemical Industry Co., Ltd., Taoka Chemical Industry Co., Ltd., etc. can be used.
  • thermoplastic elastomer composition preferably contains an anti-aging agent.
  • Antiaging agents are not particularly limited, but naphthylamine antiaging agents such as phenyl- ⁇ -naphthylamine; diphenylamine antiaging agents such as octylated diphenylamine and 4,4'-bis( ⁇ , ⁇ '-dimethylbenzyl)diphenylamine.
  • p-phenylenediamine-based antioxidants and quinoline-based antioxidants are preferable, and N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 2,2,4-trimethyl-1 , 2-dihydroquinoline polymers are more preferred.
  • products of Seiko Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., Ouchi Shinko Kagaku Kogyo Co., Ltd., Flexis, etc. can be used.
  • the content of the antioxidant is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the elastomer component. By making it more than the lower limit, there is a tendency that sufficient ozone resistance can be obtained.
  • the content is preferably 7.0 parts by mass or less, more preferably 4.0 parts by mass or less. By making it below the upper limit, there is a tendency that a good appearance can be obtained.
  • the thermoplastic elastomer composition may contain stearic acid.
  • the stearic acid content is preferably 0.5 to 10 parts by mass or more, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the elastomer component.
  • stearic acid conventionally known ones can be used, for example, products of NOF Corporation, Kao Corporation, FUJIFILM Wako Pure Chemical Industries, Ltd., Chiba Fatty Acids Co., Ltd., etc. can be used.
  • the thermoplastic elastomer composition preferably contains zinc oxide.
  • the content of zinc oxide is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the elastomer component.
  • zinc oxide conventionally known ones can be used. products can be used.
  • Wax may be blended into the thermoplastic elastomer composition.
  • the wax is not particularly limited, and examples thereof include petroleum waxes and natural waxes. Synthetic waxes obtained by refining or chemically treating a plurality of waxes can also be used. These waxes may be used alone or in combination of two or more.
  • Examples of petroleum wax include paraffin wax and microcrystalline wax.
  • the natural wax is not particularly limited as long as it is derived from a resource other than petroleum. Examples include plant waxes such as candelilla wax, carnauba wax, Japan wax, rice wax, and jojoba wax; beeswax, lanolin, spermaceti, and the like. animal waxes; mineral waxes such as ozokerite, ceresin and petrolactam; and refined products thereof.
  • plants such as candelilla wax, carnauba wax, Japan wax, rice wax, and jojoba wax
  • animal waxes mineral waxes such as ozokerite, ceresin and petrolactam
  • refined products thereof for example, products of Ouchi Shinko Kagaku Kogyo Co., Ltd., Nippon Seiro Co., Ltd., Seiko Kagaku Co., Ltd., etc. can be used.
  • thermoplastic elastomer composition contains a diene rubber component
  • sulfur may be added in order to form an appropriate crosslinked chain in the polymer chain of the diene rubber component and to provide the above-mentioned good balance of performance.
  • the sulfur content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 0.7 parts by mass or more with respect to 100 parts by mass of the diene rubber component.
  • the content is preferably 6.0 parts by mass or less, more preferably 4.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.
  • Sulfur includes powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, soluble sulfur and the like commonly used in the rubber industry.
  • products of Tsurumi Chemical Industry Co., Ltd., Karuizawa Io Co., Ltd., Shikoku Kasei Kogyo Co., Ltd., Flexis Co., Ltd., Nippon Kantan Kogyo Co., Ltd., Hosoi Chemical Industry Co., Ltd., etc. can be used. These may be used alone or in combination of two or more.
  • the thermoplastic elastomer composition may contain a vulcanization accelerator.
  • the content of the vulcanization accelerator is not particularly limited, and may be freely determined according to the desired vulcanization speed and crosslink density. , preferably 0.5 to 7 parts by mass.
  • Vulcanization accelerators include thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram disulfide (TMTD ), tetrabenzyl thiuram disulfide (TBzTD), tetrakis (2-ethylhexyl) thiuram disulfide (TOT-N) and other thiuram vulcanization accelerators; N-cyclohexyl-2-benzothiazolesulfenamide, Nt-butyl- Sulfenamide-based vulcanization accelerators such as 2-benzothiazolylsulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N,N'-diisopropyl-2-
  • thermoplastic elastomer composition may optionally contain additives such as release agents and pigments, which are commonly used for their use, according to the field of application.
  • thermoplastic elastomer composition A known method can be used as a method for producing the thermoplastic elastomer composition.
  • it can be manufactured using each component such as the above thermoplastic elastomer by using a known molding method such as injection molding.
  • a known molding method such as injection molding.
  • it can be produced by kneading each of the above components using a rubber kneading apparatus such as an open roll or Banbury mixer and, if necessary, cross-linking.
  • kneading conditions the kneading temperature is usually 50 to 200° C., preferably 80 to 190° C., and the kneading time is usually 30 seconds to 30 minutes, preferably 1 minute to 30 minutes.
  • thermoplastic elastomer composition is produced by subjecting a composition containing the thermoplastic elastomer and the like to heat treatment at 100° C. or higher. More preferably, it is produced by subjecting a composition containing the thermoplastic polyurethane elastomer and 4,4′-diphenylmethane diisocyanate to heat treatment at 100° C. or higher.
  • the heat treatment temperature is more preferably 130° C. or higher, still more preferably 140° C. or higher, and particularly preferably 150° C. or higher.
  • the heat treatment time is not particularly limited and may be set as appropriate, but is preferably 0.5 to 24 hours, more preferably 2 to 12 hours, and even more preferably 3 to 8 hours.
  • the tread 4 (tread portion) is made of the thermoplastic elastomer composition, and the thickness d ( mm) and the compression set cps (%) of the tread 4 (tread portion) preferably satisfy the following relationship. cps ⁇ d ⁇ 400 mm ⁇ %
  • the cps ⁇ d is preferably 320 mm ⁇ % or less, more preferably 310 mm ⁇ % or less, still more preferably 280 mm ⁇ % or less, particularly preferably 250 mm ⁇ % or less, and most preferably 230 mm ⁇ % or less.
  • the upper limit is preferably 217 mm ⁇ % or less and 161 mm ⁇ % or less.
  • the lower limit is not particularly limited, it is preferably 50 mm.% or more, more preferably 100 mm.% or more, still more preferably 130 mm.% or more, and particularly preferably 150 mm.% or more.
  • the crown portion 50 of the tread 4 refers to a portion of the tire cross section located on the tire equatorial plane CL.
  • the thickness of the crown portion 50 of the tread portion is the thickness of the tread portion in the radially inward direction of the tire 2 from the tread portion surface when the tread portion 4 does not have circumferential grooves. is the thickness of the tread portion in the radially inward direction of the tire 2 from the position of the tire equatorial plane CL on the extension line of the tread portion surface when has circumferential grooves.
  • the term “circumferential groove” refers to a groove having a width of 3 mm or more on the outermost surface of the tread and communicating in the tire circumferential direction. Also, the circumferential grooves may be straight and curved, or zigzag.
  • FIG. 2 is an enlarged sectional view showing the vicinity of the tread 4 (tread portion) of the tire 2 of FIG. 2 .
  • the vertical direction is the radial direction of the tire 2
  • the horizontal direction is the axial direction of the tire 2
  • the direction perpendicular to the paper surface is the circumferential direction of the tire 2 .
  • reference P is a point on the tread surface 24 .
  • a double arrow d is the thickness d of the tread 4 at the point P.
  • Thickness d is the sum of the thicknesses of cap layer 30 and base layer 28 at point P; This thickness d is measured along the normal to the tread surface 24 at point P. 1 and 2 show an example of the two-layer structure tread 4 consisting of the cap layer 30 and the base layer 28, but in the case of the single-layer structure tread 4, the thickness d of the tread is the single layer thickness at the point P.
  • the tread thickness d is the sum of the thicknesses of the three or more layers at that point P, in which case the thickness d at that point P is also Measured along the normal to the tread surface 24 .
  • the thickness d at the crown portion 50 of the tread 4 is the maximum thickness of the crown portion, and the thickness of each tread at each point on the tread surface 24 (in FIG. 1, the cap layer 30 and of the total thickness of the base layer 28).
  • the thickness d of the tread 4 at the crown portion 50 is preferably 13.0 mm or less, more preferably 12.0 mm or less, still more preferably 11.0 mm or less, and particularly preferably 10.0 mm or less.
  • the lower limit is preferably 5.5 mm or more, more preferably 6.0 mm or more, still more preferably 6.5 mm or more, and particularly preferably 7.0 mm or more. By setting it within the above range, there is a tendency to obtain good ride comfort performance after long-term storage.
  • the sidewall 6 (sidewall portion) is composed of the thermoplastic elastomer composition, and the sidewall 6 (sidewall portion) in the tire maximum width portion ) and the compression set cps (%) of the sidewall 6 (sidewall portion) preferably satisfy the following relationship. cps ⁇ s ⁇ 400 mm ⁇ %
  • the cps ⁇ s is preferably 350 mm ⁇ % or less, more preferably 200 mm ⁇ % or less, still more preferably 165 mm ⁇ % or less, particularly preferably 160 mm ⁇ % or less, most preferably 145 mm ⁇ % or less.
  • the cps ⁇ s is preferably 130 mm ⁇ % or less, 110 mm ⁇ % or less, or 87 mm ⁇ % or less.
  • the lower limit is not particularly limited, it is preferably 30 mm.% or more, more preferably 50 mm.% or more, still more preferably 70 mm.% or more, and particularly preferably 90 mm.% or more.
  • the thickness s of the sidewall 6 (sidewall portion) at the tire maximum width portion is the thickness of the sidewall at the tire maximum width position (outer end in the axial direction of the tire) when the tire is filled with a specified internal pressure.
  • the maximum width thickness of the wall 6 (the maximum width thickness of the sidewall) is indicated by s.
  • the lower limit of the thickness s is preferably 2.0 mm or more, more preferably 2.5 mm or more, still more preferably 2.8 mm or more, and particularly preferably 3.0 mm or more.
  • the upper limit is preferably 13.0 mm or less, more preferably 11.5 mm or less, still more preferably 10.5 mm or less, particularly preferably 10.0 mm or less, and most preferably 5.0 mm or less.
  • tire 2 is a pneumatic tire, it is also applicable to non-pneumatic tires.
  • pneumatic tires are preferred.
  • it can be suitably used as a summer tire (summer tire) and a winter tire (studless tire, snow tire, studded tire, etc.).
  • Tires can be used as tires for passenger cars, tires for large passenger cars, tires for large SUVs, tires for heavy loads such as trucks and buses, tires for light trucks, tires for two-wheeled vehicles, tires for racing (high performance tires), and the like.
  • a tire is manufactured by a normal method using the thermoplastic elastomer composition.
  • it can be manufactured by using the above components and using a known molding method such as injection molding.
  • the thermoplastic elastomer composition blended with various materials as necessary is extruded according to the shape of the tire member in the unvulcanized stage, and together with other tire members, it is processed by a normal method on a tire building machine.
  • a tire can be manufactured by heating and pressurizing in a vulcanizer.
  • TPU1 Elastollan C60A10WN manufactured by BASF (polyester thermoplastic polyurethane elastomer)
  • TPU2 Elastollan 1198ATR manufactured by BASF (polyether thermoplastic polyurethane elastomer)
  • TPU3 Lezamin P-6165 (thermoplastic polyurethane elastomer) manufactured by Dainichiseika Kogyo Co., Ltd.
  • TPU4 Rezamin PB-2285 (thermoplastic polyurethane elastomer) manufactured by Dainichiseika Kogyo Co., Ltd.
  • TPU5 Rezamin P-2275 (thermoplastic polyurethane elastomer) manufactured by Dainichiseika Kogyo Co., Ltd.
  • TPU6 Elastollan 1180A manufactured by BASF (polyether-based thermoplastic polyurethane elastomer)
  • Cross-linking agent 4,4'-diphenylmethane diisocyanate (MDI, Crosnate EM-30 (MDI content: 30-40%) manufactured by Dainichiseika Kogyo Co., Ltd.
  • MDI 4,4'-diphenylmethane diisocyanate
  • thermoplastic elastomer composition (Preparation of thermoplastic elastomer composition) According to the formulation shown in Table 1, kneading was performed using a twin-screw extruder to obtain a thermoplastic elastomer composition (without heat treatment). Further, for those that were further heat treated, the thermoplastic elastomer composition (without heat treatment) was heat treated in a dryer at 100° C. for 6 hours to obtain a thermoplastic elastomer composition (with heat treatment).
  • thermoplastic elastomer compositions (with or without heat treatment) were evaluated by the following methods. Table 1 shows the results.
  • ⁇ Creep rate> For the obtained thermoplastic elastomer composition (with or without heat treatment), a No. 3 dumbbell-shaped test piece (thickness 1 mm ) was made. Then, a tensile test was performed under conditions of a temperature of 50° C. and a stress of 1 MPa (constant), and the creep rate (%) was obtained from the displacement after 30 seconds and the displacement after 1 hour.
  • thermoplastic elastomer composition (with heat treatment) and each TPU (without heat treatment) in Table 1 were injection molded according to the specifications in Table 2 into tread and sidewall shapes.
  • the bead wire is housed inside to improve the fit with the rim, forming the entire side part of the tire.
  • a test tire was obtained by welding each injection molded product afterward.
  • the present disclosure (1) is a tire comprising a tread portion and a sidewall portion, The tread portion and/or the sidewall portion are made of a thermoplastic elastomer composition
  • the thermoplastic elastomer composition is a tire characterized by having a compression set (cps) at 70° C. of 40% or less as shown by the following formula.
  • cps (%) ⁇ (t0-t1)/(t0) ⁇ x 100 (Wherein, cps is compression set at 70° C. (%), t0 is the initial thickness (mm) of the test piece (thermoplastic elastomer composition), t1 is the test piece after compression set test for 24 hours (thermoplastic represents the thickness (mm) of the elastomer composition).
  • the tread portion is made of the thermoplastic elastomer composition
  • the tire according to (1) of the present disclosure wherein the thickness d (mm) at the crown portion of the tread portion and the compression set cps (%) of the tread portion satisfy the following relationship. cps ⁇ d ⁇ 320 mm ⁇ %
  • the sidewall portion is made of the thermoplastic elastomer composition
  • the present disclosure (4) is any one of the present disclosure (1) to (3), wherein the thermoplastic elastomer composition constituting the tread portion and/or the sidewall portion has a creep rate of 40% or less. tires.
  • the tread portion and the sidewall portion are made of the thermoplastic elastomer composition, Any one of (1) to (4) of the present disclosure, wherein a difference in creep rate between the thermoplastic elastomer composition forming the tread portion and the thermoplastic elastomer composition forming the sidewall portion is 10% or less. It is a tire described in the above.
  • thermoplastic elastomer composition comprises a thermoplastic polyurethane elastomer.
  • thermoplastic elastomer composition comprises a thermoplastic polyurethane elastomer and 4,4'-diphenylmethane diisocyanate
  • thermoplastic elastomer composition comprises a thermoplastic polyurethane elastomer and 4,4'-diphenylmethane diisocyanate
  • the content of the 4,4'-diphenylmethane diisocyanate is 1.0 to 10.0 parts by mass with respect to 100 parts by mass of the elastomer component.
  • thermoplastic elastomer composition is obtained by heat-treating a composition containing the thermoplastic polyurethane elastomer and 4,4′-diphenylmethane diisocyanate at 100° C. or higher. (7) The tire described above.
  • (9) of the present disclosure is the tire according to any one of (1) to (8) of the present disclosure, wherein the sidewall portion is provided with a cord member that contacts the wheel.
  • (10) of the present disclosure is the tire according to any one of (1) to (9) of the present disclosure, which includes a belt portion.
  • the present disclosure (11) comprises a bead, The tire according to any one of the present disclosure (1) to (10), wherein the bead portion is made of the thermoplastic elastomer composition.
  • (12) of the present disclosure is the tire according to any one of (1) to (11) of the present disclosure, wherein the thickness d of the crown portion of the tread portion is 10.0 mm or less.
  • (13) of the present disclosure is the tire according to any one of (1) to (12) of the present disclosure, wherein the sidewall portion has a thickness s of 5.0 mm or less.
  • thermoplastic polyurethane elastomer includes at least one selected from the group consisting of polyester-based thermoplastic polyurethane elastomers and polyether-based thermoplastic polyurethane elastomers. It is a tire described in the above.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Tires In General (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un pneumatique ayant, entre autres, une qualité de conduite exceptionnelle après un stockage de longue durée. Ce pneumatique comprend une portion de bande de roulement et une portion de paroi latérale, le pneumatique étant caractérisé en ce que la portion de bande de roulement et/ou la portion de paroi latérale est composée d'une composition d'élastomère thermoplastique, et la composition d'élastomère thermoplastique est telle que la déformation permanente de compression (cps) à 70 °C représentée par la formule suivante est de 40 % ou moins. cps (%)=\{(t0–t1)/(t0)\}×100 (dans cette formule, cps représente la déformation permanente de compression (%) à 70 °C, t0 représente l'épaisseur initiale (mm) d'un échantillon d'essai (composition d'élastomère thermoplastique), et t1 représente l'épaisseur (mm) de l'échantillon d'essai (composition d'élastomère thermoplastique) après un test de déformation permanente de compression de 24 heures.)
PCT/JP2022/002140 2021-02-16 2022-01-21 Pneumatique WO2022176502A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56160202A (en) * 1980-04-11 1981-12-09 Goodyear Tire & Rubber Tire and its manufacture
WO2005044869A1 (fr) * 2003-11-06 2005-05-19 The Yokohama Rubber Co., Ltd. Elastomere thermoplastique et composition elastomere thermoplastique
WO2014133105A1 (fr) * 2013-02-28 2014-09-04 株式会社ブリヂストン Pneumatique
JP2016003265A (ja) * 2014-06-16 2016-01-12 横浜ゴム株式会社 非空気式タイヤ用熱可塑性エラストマー組成物および非空気式タイヤ
WO2017061268A1 (fr) * 2015-10-05 2017-04-13 株式会社ブリヂストン Pneu
WO2017104472A1 (fr) * 2015-12-16 2017-06-22 株式会社ブリヂストン Pneu
WO2017146069A1 (fr) * 2016-02-22 2017-08-31 株式会社ブリヂストン Pneumatique
JP2021191813A (ja) * 2020-06-05 2021-12-16 住友ゴム工業株式会社 タイヤ及び熱可塑性エラストマー複合体

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56160202A (en) * 1980-04-11 1981-12-09 Goodyear Tire & Rubber Tire and its manufacture
WO2005044869A1 (fr) * 2003-11-06 2005-05-19 The Yokohama Rubber Co., Ltd. Elastomere thermoplastique et composition elastomere thermoplastique
WO2014133105A1 (fr) * 2013-02-28 2014-09-04 株式会社ブリヂストン Pneumatique
JP2016003265A (ja) * 2014-06-16 2016-01-12 横浜ゴム株式会社 非空気式タイヤ用熱可塑性エラストマー組成物および非空気式タイヤ
WO2017061268A1 (fr) * 2015-10-05 2017-04-13 株式会社ブリヂストン Pneu
WO2017104472A1 (fr) * 2015-12-16 2017-06-22 株式会社ブリヂストン Pneu
WO2017146069A1 (fr) * 2016-02-22 2017-08-31 株式会社ブリヂストン Pneumatique
JP2021191813A (ja) * 2020-06-05 2021-12-16 住友ゴム工業株式会社 タイヤ及び熱可塑性エラストマー複合体

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