Patent Application
20230226856
The present invention relates to a tire having a tread part provided with a main groove.
Patent documents 1 and 2 disclose a tire having a tread part provided with a main groove. One groove wall of the main groove is inclined to the groove outer side with respect to the normal line of a tread of the tread part when viewed from the tread side to the groove bottom side of the tread part. The main groove having such a groove wall becomes advantageous in maintaining drainability after wear of the tread part, and thereby improving wet performance.
However, with the above-described tire, there is a room for improvement with respect to steering stability performance after wear of the tread part.
An object of the invention is to provide a tire having good steering stability performance after wear and in which a decrease in wet performance after wear is suppressed.
As a result of intensive studies, the inventor has found that wet performance and steering stability performance after wear could be improved by producing a tire comprising a tread being composed of a rubber layer in which change in hardness after thermal deterioration is within a predetermined range and having a groove shape such that a sea ratio after wear with respect to a sea ratio as when the tire is newly used is within a predetermined range, and has completed the invention.
That is, the present invention relates to:
[1] A tire having a tread part, wherein the tread part is provided with at least one main groove extending continuously in the tire circumferential direction, wherein, when a sea ratio at a tread ground contact surface of the tire being newly used is defined as S0 (%) and a sea ratio when the tread part is worn so that the depth of the main groove is 50% of that of the tire being newly used is defined as S50 (%), S50/S0 is 1.05 to 1.40, and wherein, when a rubber hardness measured by pressing a type A durometer against a rubber piece from the ground contact surface side at 23° C. in accordance with JIS K 6253-3:2012, which the rubber piece is obtained by cutting out all the rubber forming the tread part in a tire radial direction from a land part closest to the equatorial plane of the tire being newly used, is defined as Hs0 and a rubber hardness measured by pressing a type A durometer against a rubber piece from the ground contact surface side, which the rubber piece is obtained by subjecting the rubber piece of the new tire to heat aging in an atmosphere of 80° C. for 168 hours and allowing it to cool to 23° C., is defined as Hs50, Hs50/Hs0 is 1.10 to 1.25,
[2] The tire of [1] above, wherein the tread part has at least a first rubber layer constituting a tread surface and a second rubber layer being arranged adjacent on the inner side of the first rubber layer in the radial direction,
[3] The tire of [2] above, wherein a difference (AET-AEB) between an acetone extraction amount AET of a rubber composition constituting the first rubber layer and an acetone extraction amount AEB of a rubber composition constituting the second rubber layer is 5 to 20% by mass,
[4] The tire according to [2] or [3] above, wherein a rubber composition constituting the first rubber layer comprises a liquid polymer,
[5] The tire of any one of [1] to [4] above, wherein at least one groove wall of the main groove is provided with a recessed part being recessed on the outer side of a groove edge appearing on a tread of the tread part in the groove width direction; and a total amount of recess of the main groove is 0.10 to 0.90 times the groove width being the length between groove edges of the main groove,
[6] The tire of any one of [1] to [5] above, wherein a first groove wall being one groove wall of the main groove is provided with at least one first recessed part being recessed on the outer side of a groove edge appearing on a tread of the tread part in the groove width direction; and the first recessed part has a deepest part being recessed most outwardly in the groove width direction in which an amount of recess from the groove edge gradually decreases toward both sides in the tire circumferential direction from the deepest part,
[7] The tire of [6] above, wherein the amount of recess of the deepest part is 0.10 to 0.50 times the groove width being the length between groove edges of the main groove,
[8] The tire of [6] or [7] above, wherein the first groove wall is provided with at least one second recessed part being recessed on the outer side of the groove edge in the groove width direction and having the amount of recess from the groove edge being constant in the tire circumferential direction,
[9] The tire of [8] above, wherein a maximum amount of recess of the second recessed part is less than the amount of recess of the deepest part of the first recessed part.
According to the invention, a tire comprising a tread being composed of a rubber layer in which change in hardness after thermal deterioration is within a predetermined range and having a groove shape such that a sea ratio after wear with respect to a sea ratio as when the tire is newly used is within a predetermined range is produced to provide a tire having good steering stability performance after wear and in which a decrease in wet performance after wear is suppressed.
A tire being one embodiment of the present disclosure is a tire having a tread part, wherein the tread part is provided with at least one main groove extending continuously in the tire circumferential direction, wherein, when a sea ratio at a tread ground contact surface of the tire being newly used is defined as S0 (%) and a sea ratio when the tread part is worn so that the depth of the main groove is 50% of that of the tire being newly used is defined as S0 (%), S50/S0 is 1.05 to 1.40, preferably 1.07 to 1.37, more preferably 1.10 to 1.35, further preferably 1.15 to 1.33, and particularly preferably 1.18 to 1.31, and wherein, when a rubber hardness measured by pressing a type A durometer against a rubber piece from the ground contact surface side at 23° C. in accordance with JIS K 6253-3:2012, which the rubber piece is obtained by cutting out all the rubber forming the tread part in a tire radial direction from a land part closest to the equatorial plane of the tire being newly used, is defined as Hs0 and a rubber hardness measured by pressing a type A durometer against a rubber piece from the ground contact surface side, which the rubber piece is obtained by subjecting the rubber piece of the new tire to heat aging in an atmosphere of 80° C. for 168 hours and allowing it to cool to 23° C., is defined as Hs50, Hs50/Hs0 is 1.10 to 1.25, more preferably 1.10 to 1.22, further preferably 1.10 to 1.19, and particularly preferably 1.10 to 1.17.
Note that “a sea ratio S0” in the specification means the ratio (%) of the total of the groove area for all grooves that can remain when the main groove is worn to 50%, with respect to the total of the tread ground contact area with all grooves of a tread part 2 as when the tire is newly used being buried. In other words, the groove area for the groove that does not remain when the main groove is worn to 50% is not to be included in the total of the groove area. Moreover, “a sea ratio S50” means the ratio (%), with respect to the total of the tread ground contact area with all grooves of the tread part 2 as when the main groove is worn to 50% being buried, of the total of the groove area for all grooves that remain then. Moreover, in a case that the tread part is provided with a plurality of main grooves, the depths of which main grooves differ, “the main groove” being referred to here refers to the deepest thereof, while the state in which the main groove is worn to 50% is the state in which each of land parts within the ground contact surface is worn by a thickness corresponding to the main groove being brought to be 50%.
While the method of determining the sea ratio S0 and the sea ratio S50 is not particularly limited, they can be calculated by the following method, for example. The ground contact shape of a tire can be obtained by mounting the tire to a normal rim, then filling the tire with 230 kPa for a passenger car tire or with a normal internal pressure (a maximum internal pressure) for a light weight truck or a van truck, then applying ink to the tread part 2, vertically pressing the tread part 2 against paper, etc., with a load of 70% of the maximum load capability for the passenger car tire or with a load of 80% of the maximum load capability for the light weight truck or the van truck, and transferring thereto ink applied to the tread part 2. The sea ratio S0 can be calculated by setting an area obtained by an outer ring of the ground contact shape obtained to be the total of the tread ground contact area with all grooves thereof being buried and determining the total of the groove area for all grooves that can remain when the main groove is worn to 50%, of the portion to which ink is not affixed. Moreover, with a technique similar to what is described above, the sea ratio S50 can be calculated by determining the total of the tread ground contact area with all grooves of the tread part 2 as when the main groove is worn to 50% being buried and the total of the groove area for all grooves that remain then.
Change in the sea ratio before and after the tread is worn and change in hardness of the rubber layer constituting the tread satisfying the above-described requirements makes it possible for an obtained tire to exhibit wet performance and steering stability performance over a long period of time, Although it is not intended to be bound by theory with respect to the reason therefor, it can be considered as follows:
It is considered that change in the sea ratio before and after the tread is worn being set to be within the above-described range makes it possible to secure an opening area of the main groove of the tread of the tread part even when the tread part is worn, exhibiting good wet performance over a long period of time.
Moreover, it is considered that, while an increase in groove area due to wear causes the rigidity of the tread surface to decrease, a decrease in rigidity of the overall tread part can be suppressed by rubber being hardened due to heat dissipation by traveling, making it possible to maintain drainability and steering stability performance for a long period of time.
In the tire of the present disclosure, the tread part preferably has at least a first rubber layer constituting a tread surface and a second rubber layer being arranged adjacent on the inner side of the first rubber layer in the radial direction.
In the tire of the present disclosure, a difference (AET-AEB) between an acetone extraction amount AET of a rubber composition constituting the first rubber layer and an acetone extraction amount AEB of a rubber composition constituting the second rubber layer is preferably 5 to 20% by mass.
In the tire of the present disclosure, the rubber composition constituting the first rubber layer preferably comprises a liquid polymer.
In the tire of the present disclosure, the sea ratio S0 at the tread ground contact surface as when the tire is newly used is preferably 10 to 40% and more preferably 20 to 35%.
In the tire of the present disclosure, preferably, at least one groove wall of the main groove is provided with a recessed part being recessed on the outer side of a groove edge appearing on a tread of the tread part in the groove width direction; and a total amount of recess of the main groove is 0.10 to 0.90 times the groove width being the length between groove edges of the main groove.
In the tire of the present disclosure, preferably, a first groove wall being one groove wall of the main groove is provided with at least one first recessed part being recessed on the outer side of a groove edge appearing on a tread of the tread part in the groove width direction, and the first recessed part has a deepest part being recessed most outwardly in the groove width direction in which an amount of recess from the groove edge gradually decreases toward both sides in the tire circumferential direction from the deepest part.
In the tire of the present disclosure, the first recessed part is preferably provided on the groove bottom side of the groove wall.
In the tire of the present disclosure, the first recessed part preferably has an arc-shaped contour portion in a cross section passing through the deepest part and being along the tread.
In the tire of the present disclosure, the first recessed part preferably has an amount of recess gradually decreasing outwardly in the tire radial direction from the deepest part in a groove lateral cross section passing through the deepest part.
In the tire of the present disclosure, the amount of recess of the deepest part is preferably 0.10 to 0.50 times the groove width being the length between groove edges of the main groove.
In the tire of the present disclosure, the first groove wall is preferably provided with at least one second recessed part being recessed on the outer side of the groove edge in the groove width direction and having the amount of recess from the groove edge being constant in the tire circumferential direction.
In the tire of the present disclosure, a maximum amount of recess of the second recessed part is preferably less than the amount of recess of the deepest part of the first recessed part.
In the tire of the present disclosure, preferably, the first groove wall is alternately provided with the first recessed part and the second recessed part in the tire circumferential direction.
In the tire of the present disclosure, a second groove wall being the other groove wall of the main groove is preferably provided with the at least one first recessed part.
In the tire of the present disclosure, preferably, each of the first groove wall and the second groove wall is provided with the first recessed part in a plurality, and the first recessed part, which the first groove wall is provided with, and the first recessed part, which the second groove wall is provided with, are alternately provided in the tire circumferential direction.
A procedure of producing the tire being one embodiment of the present disclosure will be described in detail below. Note the following description is exemplary for explaining the present disclosure and is not intended to limit the technical scope of the invention only to this description range. Besides, in the specification, a numerical range shown using the recitation “to” is to include the numerical values at both ends thereof.
While a tire according to one embodiment of the present disclosure is exemplified in
In the present disclosure, unless otherwise specified, dimensions and angles of each member of the tire are measured with the tire being incorporated into the normal rim and filled with air so as to achieve the normal internal pressure. Note that, at the time of measurement, no load is applied to the tire.
The “normal rim” is a rim defined, in a standard system including a standard on which the tire is based, for each tire by the standard, and is a “standard rim” for JATMA, a “Design Rim” for TRA, and a “Measuring Rim” for ETRTO. Besides, in a case of a tire having a size not specified in the standard system, it is to refer to what can be rim-assembled to the tire and has the least width of minimum diameter rims, causing no air leakage between the rim and the tire.
The “normal internal pressure” is an air pressure defined for each tire by each standard, in a standard system including a standard on which the tire is based, and is “a maximum air pressure” for JATMA, a maximum value described in the table “TIRE LOAD LIMITS AT VARIOUS COLD INFLATION PRESSURES” for TRA, or “INFLATION PRESSURE” for ETRTO. Note that, in a case of a tire having a size not specified in the standard system, the normal internal pressure is to be 250 kPa.
“The normal state” is a state in which a tire is rim-assembled to a normal rim and filled with a normal internal pressure, and is, even more, a non-load state. Note that, in a case of a tire having a size not specified in the standard system, it is to refer to a state in which the tire is rim-assembled to the minimum rim and filled with 250 kPa, and is, even more, a non-load state.
The “normal load” is a load defined for each tire by each standard, in a standard system including a standard on which the tire is based, and is “a maximum load capability” for JATMA, a maximum value described in the table “TIRE LOAD LIMITS AT VARIOUS COLD INFLATION PRESSURES” for TRA, or “LOAD CAPACITY” for ETRTO. Note that, in a case of a tire having a size not specified in the standard system, a normal load WL (kg) can be estimated using the below-described equations (4) and (5), where the tire cross-sectional width measured in the normal state is Wt (mm), the tire cross-sectional height is H1 (mm), and the tire outer diameter is Dt (mm):
V={(Dt/2)2−(Dt/2−H1)2}×π×Wt (4)
W
L=0.000011×V+175 (5)
As shown in
The tread pattern of the tire of the present disclosure is not particularly limited as long as it has a groove shape in which change in the sea ratio (S0/S50) before and after the tread part 2 is worn is within the previously-described range.
A groove width W1 of each of the main grooves 3 is preferably 3.0 to 6.0% of a tread width TW, for example. Note that, in the specification, unless otherwise specified, the groove width of the main groove means the length between groove edges appearing on a tread of the tread part 2. The tread width TW is the distance in the tire axial direction from one tread end Te to the other tread end Te in the normal state. The groove depth of each of the main grooves 3 is preferably 5 to 10 mm, for example, for a pneumatic tire for a passenger car.
In the tire according to one embodiment of the present disclosure, at least one groove wall of the main groove 3 is provided with a recessed part being recessed on the outer side of a groove edge 6 appearing on the tread of the tread part 2 in the groove width direction.
To secure the groove volume of the main groove 3, each of an amount of recess c1 and an amount of recess c2 of the deepest part 13 from the groove edge 6 independently is preferably 0.05 to 0.45 times, more preferably 0.07 to 0.40 times, and further preferably 0.10 to 0.35 times the groove width W1 being the length between groove edges of the main groove 3.
In
The first recessed part 11 has a deepest part 13 being recessed most outwardly in the groove width direction in which an amount of recess from the groove edge 6 gradually decreases toward both sides in the tire circumferential direction from the deepest part. In this way, the rigidity of the land part partitioned by the main groove 3 is secured on both sides of the deepest part 13 in the tire circumferential direction, making it possible to suppress collapsing of a land part groove edge side portion 8 (shown in
While the main groove extending continuously in the tire circumferential direction generally discharges water to the rear in the tire running direction when running on a wet road surface, in a case that the amount of water on the road surface is large, it tends to push away some of the water to the front in the tire running direction. With the main groove 3 of the present disclosure, the above-described first recessed part 11 can push away some of the water to the front in the tire running direction and outwardly in the tire axial direction, and, consequently, suppresses the pushed away water getting in between the tread part 2 and the road surface. Moreover, the groove area increases as wear progresses, so that a decrease in the groove volume in conjunction with the progress of wear can be delayed in comparison with the conventional groove,
With respect to the arc-shaped contour portion 7 in a cross section along the tread of the tread part 2, the first recessed part 11 preferably has the curvature thereof gradually increasing inwardly in the tire radial direction. The first recessed part 11 as such can secure a large groove volume of the main groove 3 while suppressing deformation of the groove edge side portion 8.
In the present disclosure, a radius of curvature r1 of the contour portion 7 is preferably 1.5 to 3.0 times the groove width W1. Moreover, a length L1 in the tire circumferential direction of the first recessed part 11 is preferably 2.0 to 3.0 times the groove width W1 of the main groove 3.
The first recessed part 11 of the present disclosure includes a concave surface part 17 being recessed outwardly in the groove width direction and a convex surface part 18 being connected to the concave surface part 17 on the outer side thereof in the tire radial direction and to be convex toward the groove center line side of the main groove 3, for example. Each of the concave surface part 17 and the convex surface part 18 is preferably curved in a smooth arc shape. Besides, the first recessed part 11 is not to be limited to such an aspect, so that it can be provided with a flat surface between the deepest part 13 and the groove edge 6, for example.
The first recessed part 11 preferably has an amount of recess gradually decreasing outwardly in the tire radial direction from the deepest part 13 in a groove lateral cross section passing through the deepest part 13. To secure the groove volume of the main groove 3, an amount of recess d1 of the deepest part 13 from the groove edge 6 is preferably 0.10 or more times, more preferably 0.20 or more times, and further preferably 0.30 or more times the groove width W1 being the length between groove edges of the main groove 3. Moreover, while the amount of recess d1 is not particularly limited, it is preferably 0.50 or less times the groove width W1 from the viewpoint of making it easy to take out, from the tread part, ribs for forming the main groove of a vulcanization mold.
As shown in
The second recessed part 12 preferably has a length in the tire circumferential direction being less than that of the first recessed part 11, for example. A length L2 of the second recessed part 12 in the tire circumferential direction is preferably 0.45 to 0.60 times the length L1 of the first recessed part 11 in the tire circumferential direction, for example. The second recessed part 12 as such can increase steering stability performance and wet performance in a well-balanced manner.
An angle ⊖1 of the flat surface 15 of the second recessed part 12 is preferably 5 to 15°, for example. Note that the angle ⊖1 is an angle between the tread normal line passing through the groove edge 6, and the flat surface 15. The recessed part 12 as such can improve wet performance after the tread part is worn.
From the similar viewpoint, a maximum amount of recess d2 of the second recessed part 12 is preferably less than the amount of recess d1 of the deepest part 13 of the first recessed part 11. Moreover, the maximum amount of recess d2 of the second recessed part 12 is preferably 0.01 to 0.25 times, more preferably 0.03 to 0.20 times, and further preferably 0.05 to 0.15 times the groove width W1 of the main groove 3.
As shown in
As shown in
In the present disclosure, the first recessed part 11, which the second groove wall 20 is provided with, faces the second recessed part 12, which the first groove wall 10 is provided with, for example. The second recessed part 12, which the second groove wall 20 is provided with, faces the first recessed part 11, which the first groove wall 10 is provided with, for example. In this way, the first recessed part 11, which the first groove wall 10 is provided with, and the first recessed part 11, which the second groove wall is provided with, are alternately provided in the tire circumferential direction, for example. Such an arrangement of the recessed parts makes it possible to suppress an increase in the air column resonance tone of the main groove.
The groove width gradually decreasing part 21 extends in the tire circumferential direction with a constant cross-sectional shape, for example. A depth d4 of the groove width gradually decreasing part 21 is preferably 0.30 to 0.50 times a depth d3 of the main groove 3, for example.
The first recessed part 11 is provided in a plurality in the tire circumferential direction on the inner side of the groove width gradually decreasing part 21 in the tire radial direction, for example. In this embodiment, the first recessed part 11, which the first groove wall 10 is provided with, and the first recessed part 11, which the second groove wall 20 is provided with, are alternately provided in the tire circumferential direction on the inner side of the groove width gradually decreasing part 21 in the tire radial direction. The main groove 3 as such can exhibit wet performance over a long period of time while suppressing local deformation of the land part and securing good steering stability.
To secure the groove volume of the main groove 3, the total amount of recess of the main groove 3 is preferably 0.10 to 0.90 times, more preferably 0.15 to 0.80 times, and further preferably 0.20 to 0.70 times the groove width W1 of the main groove 3. Note that, in the specification, “the total amount of recess of the main groove” refers to c1+c2 for the main groove being the aspect in
While the sunken groove 4 communicates with the tread surface through a sipe 5 in
While the groove width W1 of the main groove 3 is constant in the tire radial direction in
A tread of the present disclosure preferably has at least a first rubber layer constituting a tread surface and a second rubber layer being arranged adjacent on the inner side of the first rubber layer in the radial direction thereof. The first rubber layer typically corresponds to a cap tread. The second rubber layer typically corresponds to a base tread or an under tread. Moreover, as long as the object of the present disclosure is realized, it can further have one or a plurality of rubber layers between the second rubber layer and a belt outer layer.
The rubber composition constituting the first rubber layer will be described below.
The rubber composition constituting the first rubber layer preferably comprises at least one selected from the group consisting of an isoprene-based rubber, a styrene-butadiene rubber (SBR), and a butadiene rubber (BR) as rubber components. The rubber component may be a rubber component comprising a SBR and a BR, or may be a rubber component comprising an isoprene-based rubber, a SBR, and a BR. Moreover, the rubber component may be a rubber component consisting only of a SBR and a BR, or may be a rubber component consisting only of an isoprene-based rubber, a SBR, and a BR.
As the isoprene-based rubbers, those common in the tire industry such as an isoprene rubber (IR), a natural rubber and the like can be used, for example. In the natural rubber, in addition to a non-modified natural rubber (NR), an epoxidized natural rubber (ENR), a hydrogenated natural rubber (HNR), a deproteinized natural rubber (DPNR), an ultra pure natural rubber, a modified natural rubber including a grafted natural rubber, etc., and the like are also included. These isoprene-based rubbers may be used alone or two or more thereof may be used in combination.
The NR is not particularly limited, and, as the NR, those common in the tire industry such as, for example, SIR20, RSS #3, TSR20, and the like can be used.
When the rubber composition comprises the isoprene-based rubber (preferably the natural rubber and more preferably the non-modified natural rubber (NR)), a content of the isoprene-based rubber in 100% by mass of the rubber component is, from the viewpoint of wet performance, preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. Moreover, while a lower limit of a content of the isoprene-based rubber when the rubber composition comprises the isoprene-based rubber is not particularly limited, it may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, for example.
The SBR is not particularly limited, and examples thereof include a solution-polymerized SBR (S-SBR), an emulsion-polymerized SBR (E-SBR), modified SBRs thereof (a modified S-SBR, a modified E-SBR), and the like. Examples of the modified SBR include an SBR modified at its terminal and/or main chain, a modified SBR coupled with tin, a silicon compound, etc. (a modified SBR of condensate or having a branched structure, etc.), and the like. Furthermore, hydrogenated additives of these SBRs (hydrogenated SBRs) and the like may also be used. Among them, an S-SBR is preferable, and a modified S-SBR is more preferable.
Examples of the modified SBR include a modified SBR into which a functional group commonly used in this field is introduced. Examples of the above-described functional group include, for example, an amino group (preferably an amino group in which a hydrogen atom of the amino group is substituted with a C1-6 alkyl group), an amide group, a silyl group, an alkoxysilyl group (preferably a C1-6 alkoxysilyl group), an isocyanate group, an imino group, an imidazole group, an urea group, an ether group, a carbonyl group, an oxycarbonyl group, a mercapto group, a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, an ammonium group, an imide group, a hydrazo group, an azo group, a diazo group, a carboxyl group, a nitrile group, a pyridyl group, an alkoxy group (preferably a C1-6 alkoxy group), a hydroxyl group, an oxy group, an epoxy group, and the like. Besides, these functional groups may have a substituent. Examples of the substituent include, for example, a functional group such as an amino group, an amide group, an alkoxysilyl group, a carboxyl group, and a hydroxyl group. Moreover, examples of the modified SBR may include a hydrogenated SBR, an epoxidized SBR, a tin-modified SBR, and the like.
As the SBR, an oil-extended SBR can be used, or a non-oil-extended SBR can be used. When the oil-extended SBR is used, an oil-extended amount of SBR, that is, a content of an oil-extended oil comprised in the SBR, is preferably 10 to 50 parts by mass based on 100 parts by mass of a rubber solid content of the SBR.
The SBRs listed above may be used alone or two or more thereof may be used in combination. As the SBRs listed above, for example, those commercially available from Sumitomo Chemical Co., Ltd., JSR Corporation, Asahi Kasei Corporation, Zeon Corporation, ZS Elastomer Co., Ltd., etc. can be used.
A styrene content of the SBR is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more, from the viewpoints of securing damping in the tread part and wet grip performance. Moreover, it is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 45% by mass or less, from the viewpoints of temperature dependence of grip performance, and abrasion resistance. Besides, in the specification, the styrene content of the SBR is calculated by 1H-NMR measurement.
A vinyl content of the SBR is preferably 10 mol % or more, more preferably 13 mol % or more, and further preferably 16 mol % or more, from the viewpoints of ensuring reactivity with silica, rubber strength, and abrasion resistance. Moreover, the vinyl content of the SBR is preferably 70 mol % or less, more preferably 65 mol % or less, and further preferably 60 mol % or less, from the viewpoints of preventing temperature dependence from increasing, wet grip performance, elongation at break, and abrasion resistance. Besides, in the specification, the vinyl content (1,2-bond butadiene unit amount) of the SBR is measured by infrared absorption spectrometry.
A weight-average molecular weight (Mw) of the SBR is preferably 150,000 or more, more preferably 200,000 or more, and further preferably 250,000 or more, from the viewpoint of abrasion resistance. Moreover, the Mw is preferably 2,500,000 or less, more preferably 2,000,000 or less, and further preferably 1,500,000 or less, from the viewpoints of cross-linking uniformity and the like. Besides, the Mw of the SBR can be determined in terms of a standard polystyrene based on measurement values obtained by a gel permeation chromatography (GPC) (for example, GPC-8000 Series, manufactured by Tosoh Corporation, Detector: differential refractometer, Column: TSKGEL SUPERMULTIPORE HZ-M, manufactured by Tosoh Corporation).
A content of the SBR in 100% by mass of the rubber component when the rubber composition comprises the SBR is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, and particularly preferably 50% by mass or more, from the viewpoint of wet performance. Moreover, an upper limit of a content of the SBR in the rubber component is not particularly limited and may be 100% by mass.
The BR is not particularly limited, and those commonly used in the tire industry can be used, such as, for example, a BR having a cis content of less than 50% by mass (a low cis BR), a BR having a cis content of 90% or more by mass (a high cis BR), a rare earth-based butadiene rubber synthesized using a rare earth element-based catalyst (a rare earth-based BR), a BR containing a syndiotactic polybutadiene crystal (an SPB-containing BR), a modified BR (a high cis modified BR, a low cis modified BR), and the like. Examples of the modified BR include a BR modified with a functional group or the like similar to that described in the SBRs above. These BRs may be used alone or two or more thereof may be used in combination.
As the high cis BR, those commercially available from Zeon Corporation, Ube Industries, Ltd., JSR Corporation, etc. can be used, for example. When a high cis BR is comprised, low temperature characteristics and abrasion resistance can be improved. The cis content is preferably 95% by mass or more, more preferably 96% by mass or more, further preferably 97% by mass or more, and particularly preferably 98% by mass or more. Besides, in the specification, the cis content (cis-1,4-bond butadiene unit amount) is a value calculated by infrared absorption spectrometry.
As the rare earth-based BR, those synthesized using a rare earth element-based catalyst and having a vinyl content of preferably 1.8 mol % or less, more preferably 1.0 mol % or less, and further preferably 0.8 mol % or less, and a cis content of preferably 95 mol % by mass or more, more preferably 96 mol % by mass or more, further preferably 97 mol % by mass or more, and particularly preferably 98 mol % by mass or more can be used. As the rare earth-based BR, those commercially available from LANXESS, etc. can be used, for example.
Examples of the SPB-containing BR include those in which a 1,2-syndiotactic polybutadiene crystal is chemically bonded with the BR and dispersed, but not those in which the crystal is simply dispersed in the BR. As such an SPB-comprising BR, those commercially available from Ube Industries, Ltd., etc., can be used.
As the modified BR, a modified butadiene rubber (modified BR) modified with a functional group comprising at least one element selected from the group consisting of silicon, nitrogen, and oxygen at its terminal and/or main chain is suitably used.
Examples of other modified BRs include those obtained by polymerizing 1,3-butadiene with a lithium initiator and then adding a tin compound and in which a modified BR molecule is bonded by a tin-carbon bond at its terminal (a tin-modified BR), and the like. Moreover, the modified BR may be hydrogenated or may not be hydrogenated.
The BRs listed above may be used alone or two or more thereof may be used in combination.
The glass transition temperature (Tg) of the BR is preferably −14 C or lower, more preferably −17 C or lower, and further preferably −20 C or lower from the viewpoint of preventing low temperature fragility. On the other hand, while a lower limit of the above-mentioned Tg is not particularly limited, from the viewpoint of abrasion resistance, it is preferably −150 C or higher, more preferably −120 C or higher, and further preferably −110 C or higher. Besides, the glass transition temperature of the BR is a value measured under the condition of a temperature increase rate of 10° C./min using differential scanning calorimetry (DSC) in accordance with Japanese Industrial Standard JIG K 7121.
A weight-average molecular weight (Mw) of the BR is preferably 300,000 or more, more preferably 350,000 or more, and further preferably 400,000 or more, from the viewpoint of abrasion resistance. Moreover, it is preferably 2,000,000 or less and more preferably 1,000,000 or less, from the viewpoints of cross-linking uniformity and the like. Besides, the Mw can be determined in terms of a standard polystyrene based on measurement values obtained by a gel permeation chromatography (GPC) (for example, GPC-8000 Series, manufactured by Tosoh Corporation, Detector: differential refractometer, Column: TSKGEL SUPERMULTIPORE HZ-M, manufactured by Tosoh Corporation).
A content of the BR in 100% by mass of the rubber component when the rubber composition comprises the BR is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less, from the viewpoint of wet performance. Moreover, while a lower limit of a content of the BR when the rubber composition comprises the BR is not particularly limited, it may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, for example.
As the rubber component according to the present disclosure, rubber components other than the above-described isoprene-based rubbers, SBRs, and BRs may be contained. As other rubber components, a cross-linkable rubber component commonly used in the tire industry can be used, such as, for example, a styrene-isoprene-butadiene copolymer rubber (SIBR), a styrene-isobutylene-styrene block copolymer (SIBS), a chloroprene rubber (CR), an acrylonitrile-butadiene rubber (NBR), a hydrogenated nitrile rubber (HNBR), a butyl rubber (IIR), an ethylene propylene rubber, a polynorbornene rubber, a silicone rubber, a polyethylene chloride rubber, a fluororubber (FKM), an acrylic rubber (ACM), a hydrin rubber, and the like. These other rubber components may be used alone or two or more thereof may be used in combination.
The rubber composition constituting the first rubber layer preferably comprises, as a filler, carbon black and/or silica. Moreover, the filler may be a filler consisting only of carbon black and silica.
As carbon black, those common in the tire industry can be appropriately used. Examples thereof include GPF, FEF, HAF, ISAF, SAF, and the like, for example. These carbon blacks may be used alone or two or more thereof may be used in combination.
A nitrogen adsorption specific surface area (N2SA) of carbon black is preferably 50 m2/g or more, and more preferably 70 m2/g or more, from the viewpoint of elongation at break. Moreover, from the viewpoints of fuel efficiency and processability, it is preferably 200 m2/g or less and more preferably 150 m2/g or less. Besides, the N2SA of carbon black is a value measured according to Japanese Industrial Standard JIS K 6217-2 “Carbon black for rubber-Fundamental characteristics-Part 2: Determination of specific surface area-Nitrogen adsorption methods-Single-point procedures”.
The dibutyl phthalate (DBP) oil absorption amount of carbon black is preferably 30 ml/100 g or more and more preferably 50 ml/100 g or more from the viewpoint of reinforcing property. Moreover, from the viewpoints of fuel efficiency and processability, it is preferably 400 ml/100 g or less and more preferably 350 ml/100 g or less. Besides, the DBP oil absorption amount of carbon black is measured according to Japanese Industrial Standard JIS K 6221.
When the rubber composition comprises the carbon black, the content thereof based on 100 parts by mass of the rubber component is, from the viewpoints of weather resistance and reinforcing property, preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more. Moreover, from the viewpoints of fuel efficiency and abrasion resistance, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.
Silica is not particularly limited, and for example, those common in the tire industry can be used, such as silica prepared by a dry process (anhydrous silica), silica prepared by a wet process (hydrous silica), and the like, for example. Among them, hydrous silica prepared by a wet process is preferable because it has many silanol groups. These silicas may be used alone or two or more thereof may be used in combination.
A nitrogen adsorption specific surface area (N2SA) of silica is preferably 140 m2/g or more, more preferably 170 m2/g or more, and further preferably 200 m2/g or more, from the viewpoints of fuel efficiency and abrasion resistance. Moreover, it is preferably 350 m2/g or less, more preferably 300 m2/g or less, and further preferably 250 m2/g or less, from the viewpoints of fuel efficiency and processability. Besides, the N2SA of silica in the specification is a value measured by the BET method according to ASTM D3037-93.
The average primary particle size of silica is preferably 20 nm or less, and more preferably 18 nm or less. The lower limit of the average primary particle size is not particularly limited and is preferably 1 nm or more, more preferably 3 nm or more, and further preferably 5 nm or more. When the average primary particle size of silica is in the above-described ranges, the dispersibility of silica can be improved more, and the reinforcing property, fracture properties, and abrasion resistance can be further improved. Besides, the average primary particle size of silica can be determined by observing it with a transmission or scanning electron microscope, measuring or more primary particles of silica observed in the field of view, and averaging them.
A content of silica in the rubber composition based on 100 parts by mass of the rubber component when the rubber composition comprises silica is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and further preferably 50 parts by mass or more, from the viewpoint of wet performance. Moreover, it is preferably 130 parts by mass or less, more preferably 110 parts by mass or less, and further preferably 95 parts by mass or less, from the viewpoint of abrasion resistance.
As fillers other than carbon black and silica, other fillers can further be used. While such fillers are not particularly limited, any one of fillers commonly used in this field, such as aluminum hydroxide, alumina (aluminum oxide), calcium carbonate, magnesium sulfate, talc, clay, and the like, for example, can be used. These fillers may be used alone or two or more thereof may be used in combination.
From the viewpoint of wet performance, a total content of the filler based on 100 parts by mass of the rubber component is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and further preferably 60 parts by mass or more. Moreover, from the viewpoints of fuel efficiency and elongation at break, it is preferably 150 parts by mass or less, more preferably 130 parts by mass or less, and further preferably 110 parts by mass or less.
A content of the silica in 100 parts by mass of the silica and carbon black is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. Moreover, a content of the silica is preferably 99% by mass or less, more preferably 97% by mass or less, and further preferably 95% by mass or less.
Silica is preferably used in combination with a silane coupling agent. The silane coupling agent is not particularly limited, and any silane coupling agent conventionally used in combination with silica in the tire industry can be used, and examples thereof include, for example, a mercapto-based silane coupling agent as follows: a sulfide-based silane coupling agent such as bis(3-triethoxysilylpropyl)disulfide and bis(3-triethoxysilylpropyl)tetrasulfide; a thioester-based silane coupling agent such as 3-octanoylthio-1-propyltriethoxysilane, 3-hexanoylthio-1-propyltriethoxysilane, and 3-octanoylthio-1-propyltrimethoxysilane; a vinyl-based silane coupling agent such as vinyltriethoxysilane and vinyltrimethoxysilane; an amino-based silane coupling agent such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-(2-aminoethyl) aminopropyltriethoxysilane; a glycidoxy-based silane coupling agent such as γ-glycidoxypropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane; a nitro-based silane coupling agent such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane; a chloro-based silane coupling agent such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane, and the like. Among them, the silane coupling agent containing a sulfide-based silane coupling agent and/or a mercapto-based silane coupling agent is preferable. These silane coupling agents may be used alone or two or more thereof may be used in combination.
The mercapto-based silane coupling agent is preferably a compound represented by the following Formula (1) and/or a compound comprising a bond unit A represented by the following Formula (2) and a bond unit B represented by the following Formula (3):
(Wherein, each of R101, R102, and R103 independently represents a group represented by a C1-12 alkyl, a C112 alkoxy, or a —O—(R111—O)zR112 (Each of z R111s independently represents a divalent hydrocarbon group having 1 to carbon atoms; R112 represents a C1-30 alkyl, a C2-30 alkenyl, a C6-30 aryl, or a C7-30 aralkyl; z represents an integer of 1 to 30); and R104 represents a C1-6 alkylene.)
(Wherein, x represents an integer of 0 or more; y represents an of 1 or more; R201 represents a C1-30 alkyl, a C2-30 alkenyl, or a C2-30 alkynyl, which may be substituted with a hydrogen atom, a halogen atom, hydroxyl or carboxyl; R212 represents a C1-30 alkylene, a C2-3-0 alkenylene, or a C2-30 alkynylene; wherein R201 and R212 may form a ring structure.)
Examples of the compound represented by Formula (1) include, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mearcaptoethyltrimethoxysilanie, 2-mercaptoethyltriethoxysilane, and a compound represented by Formula (4) below (Si363, manufactured bv Evonik Deaussa), and the compound represented by Formula (4) below can be suitably used. They may be used alone or two or more thereof may be used in combination.
Examples of the compound comprising the bond unit A represented by Formula (2) and the bond unit B represented by Formula (3) include those commercially available from Momentive Performance Materials, and the like, for example. They may be used alone or two or more thereof may be used in combination.
A content of the silane coupling agent based on 100 parts by mass of silica when the rubber composition comprises the silane coupling agent is, from the viewpoint of enhancing the dispersibility of silica, preferably 1.0 part by mass or more, more preferably 3.0 parts by mass or more, and further preferably 5.0 parts by mass or more. Moreover, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably parts by mass or less, from the viewpoint of preventing deterioration of abrasion resistance.
Change in hardness after thermal deterioration of the rubber layer can be appropriately adjusted by changing the type and content of the filler and silane coupling agent described above.
The rubber composition constituting the first rubber layer is preferably compounded with plasticizers to obtain a high wet performance. Examples of a softener include a resin component, oil, a liquid polymer, an ester-based plasticizer, and the like, for example.
The resin component is not particularly limited, and examples thereof include a petroleum resin, a terpene-based resin, a rosin-based resin, a phenol-based resin, and the like being commonly used in the tire industry. These resin components may be used alone or two or more thereof may be used in combination.
Examples of the petroleum resin include a C5-based petroleum resin, an aromatic-based petroleum resin, and a C5-C9-based petroleum resin, for example. These petroleum resins may be used alone or two or more thereof may be used in combination.
In the specification, the “C5-based petroleum resin” refers to a resin obtained by polymerizing a C5 fraction. Examples of the C5 fraction include, for example, a petroleum fraction equivalent to 4 to 5 carbon atoms such as cyclopentadiene, pentene, pentadiene, isoprene, and the like. As the C5-based petroleum resin, a dicyclopentadiene resin (DCPD resin) is suitably used.
In the specification, the “aromatic-based petroleum resin” refers to a resin obtained by polymerizing a C9 fraction, and may be hydrogenated or modified. Examples of the C9 fraction include, for example, a petroleum fraction equivalent to 8 to 10 carbon atoms such as vinyltoluene, alkylstyrene, indene, and methyl indene. As specific examples of the aromatic-based petroleum resin, for example, a coumarone indene resin, a coumarone resin, an indene resin, and an aromatic vinyl-based resin are suitably used. As the aromatic vinyl-based resin, a homopolymer of α-methylstyrene or styrene or a copolymer of α-methylstyrene and styrene is preferable, and a copolymer of α-methylstyrene and styrene is more preferable, because it is economical, easy to be processed, and good in heat generation. As the aromatic vinyl-based resin, for example, those commercially available from Kraton Corporation, Eastman Chemical Company, etc. can be used.
In the specification, a “C5-C9-based petroleum resin” refers to a resin obtained by copolymerizing the C5 fraction and the C9 fraction, and may be hydrogenated or modified. Examples of the C5 fraction and the C9 fraction include the above-described petroleum fractions. As the C5-C9-based petroleum resin, for example, those commercially available from Tosoh Corporation, Zibo Luhua Hongjin New Material Co., Ltd., etc., can be used.
Examples of the terpene-based resin include a polyterpene resin consisting of at least one selected from terpene compounds such as α-pinene, β-pinene, limonene, and dipentene; an aromatic-modified terpene resin made from the terpene compound and an aromatic compound; a terpene phenol resin made from a terpene compound and a phenol-based compound; and those obtainable by hydrogenating these terpene-based resins (hydrogenated terpene-based resins). Examples of the aromatic compound used as a raw material for the aromatic-modified terpene resin include, for example, styrene, α-methylstyrene, vinyltoluene, divinyltoluene, and the like. Examples of the phenol-based compound used as a raw material for the terpene phenol resin include, for example, phenol, bisphenol A, cresol, xylenol, and the like.
The rosin-based resin is not particularly limited, and examples thereof include, for example, a natural resin rosin, and a rosin modified resin being the natural resin rosin modified by hydrogenation, disproportionation, dimerization, or esterification.
The phenol-based resin is not particularly limited, and examples thereof include a phenolformaldehyde resin, an alkylphenolformaldehyde resin, an alkylphenol acetylene resin, an oil-modified phenolformaldehyde resin, and the like.
A softening point of the resin component is preferably 60° C. or higher and more preferably 65° C. or higher, from the viewpoint of grip performance. Moreover, it is preferably 150° C. or lower, more preferably 140° C. or lower, and further preferably 130° C. or lower, from the viewpoints of processability and improvement in dispersibility of a rubber component with a filler. Besides, in the specification, the softening point can be defined as a temperature at which a sphere drops when the softening point specified in Japanese Industrial Standard JIS K 6220-1: 2001 is measured with a ring and ball softening point measuring device.
When the rubber composition comprises the resin component, the content thereof based on 100 parts by mass of the rubber component is, from the viewpoints of riding comfort performance and wet performance, preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2.0 parts by mass or more. Moreover, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, from the viewpoint of abrasion resistance.
Examples of oil include, for example, a process oil, a vegetable oil and fat, an animal oil and fat, and the like. Examples of the process oil include a paraffin-based process oil, a naphthene-based process oil, an aromatic-based process oil, and the like. Moreover, as an environmental measure, a process oil having a low content of a polycyclic aromatic compound (PCA) can also be used. Examples of the process oil having a low content of a PCA include a treated distillate aromatic extract (TDAE), which is an oil aromatic-based process oil being reextracted; an aromatic substitute oil being a mixed oil of asphalt and naphthenic oil; mild extraction solvates (MES); a heavy naphthenic oil; and the like.
When the rubber composition comprises the oil, the content thereof based on 100 parts by mass of the rubber component is, from the viewpoint of processability, preferably 1 part by mass or more, more preferably parts by mass or more, and further preferably 3 parts by mass or more. Moreover, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 75 parts by mass or less, from the viewpoints of fuel efficiency and durability. Besides, in the specification, the content of oil also includes an amount of oil contained in an oil-extended rubber.
Examples of the liquid polymer include, for example, a liquid styrene-butadiene polymer, a liquid butadiene polymer, a liquid isoprene polymer, a liquid styrene-isoprene polymer, a liquid farnesene rubber, and the like, and is preferably the liquid farnesene rubber. These may be used alone or two or more thereof may be used in combination.
The liquid farnesene rubber can be a homopolymer of farnesene (farnesene homopolymer) or a copolymer of farnesene and a vinyl monomer (farnesene-vinyl monomer copolymer). Examples of the vinyl monomer include aromatic vinyl compounds such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropyl styrene, 4-tert-butylstyrene, 5-t-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethylether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, vinylxylene, vinylnaphthalene, vinyltoluene, vinylpyridyne, diphenylethylene, tertiary amino group containing diphenylethylene, and the like; and conjugated diene compounds such as butadiene, isoprene, and the like. Among these, styrene and butadiene are preferable. In other words, as the copolymer of farnesene and the vinyl monomer, a copolymer of farnesene and styrene (farnesene-styrene copolymer) and a copolymer of farnesene and butadiene (farnesene-butadiene copolymer) are preferable. The farnesene-styrene copolymer can be compounded to increase an effect of improving wet performance, and the farnesene-butadiene copolymer can be compounded to increase an effect of improving fuel efficiency and abrasion resistance.
When the rubber composition comprises the liquid polymer, the content thereof based on 100 parts by mass of the rubber component is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more. Moreover, a content of the liquid polymer is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and further preferably 40 parts by mass or less.
When the rubber composition comprises the plasticizer, a content of the plasticizer (when the plasticizer is used in a plurality in combination, a total content of all of the plasticizers) based on 100 parts by mass of the rubber component is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, further preferably 30 parts by mass or more, and particularly preferably 35 parts by mass or more, from the viewpoint of wet performance. Moreover, it is preferably 130 parts by mass or less, more preferably 110 parts by mass or less, and further preferably 95 parts by mass or less, from the viewpoint of processability,
The rubber composition constituting the first rubber layer can appropriately comprise compounding agents commonly used in the tire industry, such as, for example, an antioxidant, wax, stearic acid, zinc oxide, a vulcanizing agent, a vulcanization accelerator, and the like, in addition to the previously-described components.
The antioxidant is not particularly limited, and examples thereof include, for example, each amine-based, quinoline-based, quinone-based, phenol-based, and imidazole-based compound, and an antioxidant such as a carbamate metal salt, preferably a phenylenediamine-based antioxidant such as N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-di-2-naphthyl-p-phenylenediamine, and N-cyclohexyl-N′-phenyl-p-phenylenediamine, and a quinoline-based antioxidant such as 2,2,4-trimethyl-1,2-dihydroquinolin polymer and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinolin. These antioxidants may be used alone or two or more thereof may be used in combination.
When the rubber composition comprises the antioxidant, the content thereof based on 100 parts by mass of the rubber component is, from the viewpoint of ozone crack resistance of a rubber, preferably 0.5 parts by mass or more and more preferably 1 part by mass or more. Moreover, it is preferably 10 parts by mass or less and more preferably 5 parts by mass or less, from the viewpoints of abrasion resistance and wet performance.
When the rubber composition comprises the wax, the content thereof based on 100 parts by mass of the rubber component is, from the viewpoint of weather resistance of a rubber, preferably 0.5 parts by mass or more and more preferably 1 part by mass or more. Moreover, it is preferably parts by mass or less and more preferably 5 parts by mass or less, from the viewpoint of preventing whitening of a tire due to bloom.
When the rubber composition comprises the stearic acid, the content thereof based on 100 parts by mass of the rubber component is, from the viewpoint of vulcanization rate, preferably 0.2 parts by mass or more and more preferably 1 part by mass or more. Moreover, it is preferably 10 parts by mass or less and more preferably 5 parts by mass or less, from the viewpoint of processability.
When the rubber composition comprises the zinc oxide, the content thereof based on 100 parts by mass of the rubber component is, from the viewpoint of vulcanization rate, preferably 0.5 parts by mass or more and more preferably 1 part by mass or more. Moreover, it is preferably 10 parts by mass or less and more preferably 5 parts by mass or less, from the viewpoint of abrasion resistance.
Sulfur is suitably used as the vulcanizing agent. As sulfur, a powdered sulfur, an oil-treated sulfur, a precipitated sulfur, a colloidal sulfur, an insoluble sulfur, a highly dispersible sulfur, and the like can be used.
A content of sulfur based on 100 parts by mass of the rubber component when the rubber composition comprises sulfur as the vulcanizing agent is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and further preferably 0.5 parts by mass or more, from the viewpoint of securing a sufficient vulcanization reaction. Moreover, it is preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, and further preferably 3.0 parts by mass or less, from the viewpoint of preventing deterioration. Besides, a content of a vulcanizing agent when using an oil-containing sulfur as the vulcanizing agent shall be a total content of pure sulfur amounts comprised in the oil-containing sulfur.
Examples of vulcanizing agents other than sulfur include, for example, alkylphenol-sulfur chloride condensate, 1,6-hexamethylene-sodium dithiosulfate dehydrate, 1,6-bis(N,N′-dibenzylthiocarbamoyldithio)hexane, and the like. As these vulcanizing agents other than sulfur, those commercially available from Taoka Chemical Co., Ltd., LANXESS, Flexsys, etc. can be used.
The vulcanization accelerator is not particularly limited, and examples of the vulcanization accelerators include, for example, sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamic acid-based, aldehyde-amine-based or aldehyde-ammonia-based, imidazoline-based, and xanthate-based vulcanization accelerators, and, among them, sulfenamide-based, thiazole-based, and guanidine-based vulcanization accelerators are preferable from the viewpoint that desired effects are more suitably obtained.
Examples of the sulfenamide-based vulcanization accelerator include, for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (TBBS), N-oxyethylene-2-benzothiazolylsulfenamide, N,N′-diisopropyl-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-2-benzothiazolylsulfenamide, and the like. Examples of the thiazole-based vulcanization accelerator include 2-niercaptobenzothiazole, dibenzothiazolyl disulfide, and the like. Examples of the guanidine-based vulcanization accelerator include diphenylguanidine (DPG), di-o-tolylguanidine, o-tolylbiguanidine, and the like. These vulcanization accelerators may be used alone or two or more thereof may be used in combination.
When the rubber composition comprises the vulcanization accelerator, the content thereof based on 100 parts by mass of the rubber component is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2.0 parts by mass or more. Moreover, the content of the vulcanization accelerator based on 100 parts by mass of the rubber component is preferably 8.0 parts by mass or less, more preferably 7.0 parts by mass or less, further preferably 6.0 parts by mass or less, and particularly preferably 5.0 parts by mass or less. When the content of the vulcanization accelerators is within the above-described ranges, there is a tendency to be able to secure breaking strength and elongation.
Change in hardness after thermal deterioration of the rubber layer can be appropriately adjusted by changing the type and content of the vulcanizing agent and vulcanization accelerator described above.
The rubber composition constituting the second rubber layer will be described below.
The rubber composition constituting the second rubber layer preferably comprises at least one selected from the group consisting of an isoprene-based rubber, a styrene-butadiene rubber (SBR), and a butadiene rubber (BR) as rubber components. The rubber component may be a rubber component comprising an isoprene-based rubber and a BR, and may be a rubber component comprising an isoprene-based rubber, a SBR, and a BR. Moreover, the rubber component may be a rubber component consisting only of an isoprene-based rubber and a BR, or may be a rubber component consisting only of an isoprene-based rubber, a SBR, and a BR.
When the rubber composition comprises the isoprene-based rubber, a content of the isoprene-based rubber in 100% by mass of the rubber component is, from the viewpoint of steering stability performance, preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. Moreover, a content of the isoprene-based rubber in the rubber component is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less.
A content of the SBR in 100% by mass of the rubber component when the rubber composition comprises the SBR is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less. Moreover, a lower limit of a content of the SBR when the rubber composition comprises the SBR is not particularly limited and may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, for example.
A content of the BR in 100% by mass of the rubber component when the rubber composition comprises the BR is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, and particularly preferably 35% by mass or less. Moreover, a lower limit of a content of the BR when the rubber composition comprises the BR is not particularly limited and may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 15% by mass or more, for example.
The rubber composition constituting the second rubber layer preferably comprises carbon black and/or silica as a filler. Moreover, the filler may be a filler consisting only of carbon black and silica, or may be a filler composed of only carbon black. Furthermore, as the filler, the other fillers other than carbon black and silica may be used. As carbon black, silica, the silane coupling agent, and the other fillers, those being similar to the rubber composition constituting the first rubber layer may be suitably used in a similar aspect.
When the rubber composition comprises the carbon black, the content thereof based on 100 parts by mass of the rubber component is, from the viewpoints of weather resistance and reinforcing property, preferably 20 parts by mass or more, more preferably 25 parts by mass or more, further preferably 30 parts by mass or more, and particularly preferably 35 parts by mass or more. Moreover, while an upper limit of the content of the carbon black is not particularly limited, from the viewpoint of fuel efficiency and processability, it is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 90 parts by mass or less.
When the rubber composition comprises the silica, the content thereof based on 100 parts by mass of the rubber component is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and further preferably 20 parts by mass or less. Moreover, while a lower limit of the content of the silica when the rubber composition comprises the silica is not particularly limited, it may be 1 part by mass or more, 3 parts by mass or more, parts by mass or more, 10 parts by mass or more, or 15 parts by mass or more, for example.
The rubber composition constituting the second rubber layer can appropriately comprise, as needed, compounding agents and additives conventionally used in the tire industry, such as, for example, a plasticizer, an antioxidant, wax, stearic acid, zinc oxide, a vulcanizing agent, a vulcanization accelerator, and the like, in addition to the previously-described rubber components and filler. As the previously-described compounding agents and additives, those being similar to the rubber composition constituting the first rubber layer may be suitably used in a similar aspect.
A difference (AET-AEB) between an acetone extraction amount AET of the rubber composition constituting the first rubber layer and an acetone extraction amount AEs of the rubber composition constituting the second rubber layer is preferably 3 to 20% by mass, more preferably 5 to 20% by mass, further preferably 10 to 20% by mass, and particularly preferably 12 to 16% by mass. It is considered that the difference in the acetone extraction amounts being set within the previously-mentioned range makes it easy to transfer the acetone extraction component such as an oil and the like from the first rubber layer to the second rubber layer during traveling due to the concentration gradient and makes it easy to harden the first rubber layer.
A ratio (AET/AEB) of the acetone extraction amount AET of the rubber composition constituting the first rubber layer with respect to an acetone extraction amount AEB of the rubber composition constituting the second rubber layer is preferably 1.25 to 5.0 and more preferably 1.5 to 5.0. It is considered that the ratio of the acetone extraction amounts being set within the previously-mentioned range makes it easy to transfer the acetone extraction component such as an oil and the like from the first rubber layer to the second rubber layer during traveling due to the concentration gradient and makes it easy to harden the first rubber layer.
Besides, the acetone extraction amount is to be an indicator of the concentration of an organic low-molecular compound within a plasticizer comprised in the vulcanized rubber composition. In accordance with Japanese Industrial Standard JIS K 6229-3:2015, the acetone extraction amount can be determined using the below-described equation by soaking each of vulcanized rubber test pieces in acetone for 24 hours to extract the soluble component and measuring mass of each of the vulcanized rubber test pieces before and after extraction:
Acetone extraction amount (%)={(Mass of rubber test piece before extraction-Mass of rubber test piece after extraction)/(Mass of rubber test piece before extraction)}×100.
The content of the plasticizer based on 100 parts by mass of the rubber component constituting the first rubber layer is preferably greater than the content of the plasticizer based on 100 parts by mass of the rubber component constituting the second rubber layer. Increasing the content of the plasticizer in the first rubber layer makes it easy for the plasticizer to be transferred to the second rubber layer during traveling and makes it possible to suitably exhibit hardening of a rubber layer during traveling.
The rubber composition according to the present disclosure can be manufactured by a known method. For example, it can be manufactured by kneading each of the previously-described components using a rubber kneading apparatus such as an open roll and a closed type kneader (Bunbury mixer, kneader, etc.).
The kneading step comprises, for example, a base kneading step of kneading compounding agents and additives other than vulcanizing agents and vulcanization accelerators, and a final kneading (F kneading) step of adding vulcanizing agents and vulcanization accelerators to the kneaded product obtained in the base kneading step and kneading them. Furthermore, the base kneading step can be divided into a plurality of steps, if desired. Kneading conditions are not particularly limited, and, for example, a method of kneading at a discharge temperature of 150 to 170° C. for 3 to 10 minutes in the base kneading step and kneading at 70 to 110° C. for 1 to 5 minutes in the final kneading step is exemplified.
The tire according to the present disclosure comprises a tread preferably composed of the first rubber layer and the second rubber layer and may be a pneumatic tire or a non-pneumatic tire. Moreover, examples of the pneumatic tire include a tire for a passenger car, a tire for a truck/bus, a tire for a motorcycle, a high-performance tire, and the like. Besides, the high-performance tire in the specification is a tire having a particularly good grip performance and is a concept even including a racing tire used for a racing vehicle.
The tire comprising the tread composed of the first rubber layer and the second rubber layer can be manufactured by a usual method using the previously-described rubber composition. In other words, the tire can be manufactured by extruding unvulcanized rubber compositions compounded with each of the above-described components based on the rubber component as necessary into shapes of the tread, attaching them together with other tire members on a tire molding machine, and molding them by a usual method to form an unvulcanized tire, followed by heating and pressurizing this unvulcanized tire in a vulcanizing machine.
Although the present disclosure will be described based on Examples, it is not to be limited to these Examples.
Various chemicals used in Examples and Comparative examples are shown below:
NR: TSR20
SBR: Tufdene 4850 (non-modified S-SBR, styrene content: 40% by mass, vinyl content: 46 mol %, Mw: 350,000, comprises 50 parts by mass of an oil content based on 100 parts by mass of a rubber solid content), manufactured by Asahi Kasei Corporation
BR: UBEPOL BR (registered trademark) 150B (vinyl content: 1.5 mol %, cis content: 97% by mass, Tg: −108° C., Mw: 440,000), manufactured by Ube Industries, Ltd.
Carbon black: Show Black N330 (N2SA: 75 m2/g, DBP oil absorption amount: 102 ml/10 g), manufactured by Cabot Japan K.K.
Silica: Ultrasil VN3 (N2SA: 175 m2/g, average primary particle size: nm), manufactured by Evonik Degussa
Silane coupling agent: NXT-Z45 (mercapto-based silane coupling agent), manufactured by Momentive Performance Materials
Resin component: PetroTac 100V (C5-C9-based petroleum resin, softening point: 96° C., Mw: 3,800, SP value: 8.3), manufactured by Tosoh Corporation
Liquid polymer: FB-823 (farnesene-butadiene copolymer, copolymerization ratio on a mass basis: farnesene/butadiene=80/20, Mw: 50,000, Tg: −78° C.), manufactured by Kuraray Co., Ltd.
Oil: Vivatec 500 (TDAE oil), manufactured by H&R Group
Antioxidant: Antigen 6C (N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine), manufactured by Sumitomo Chemical Co., Ltd.
Wax: Sunnock N, manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.
Stearic acid: Bead stearic acid “Tsubaki”, manufactured by NOF CORPORATION
Zinc oxide: Zinc oxide No. 2, manufactured by Mitsui Mining & Smelting Co., Ltd.
Sulfur: Powdered sulfur, manufactured by Karuizawa Iou Kabushiki Kaisha
Vulcanization accelerator: Nocceler CZ (N-cyclohexyl-2-benzothiazolylsulfenamide), manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.
According to the compounding formulations shown in Tables 1 and 2, using a 1.7 L closed Banbury mixer, chemicals other than the sulfur and vulcanization accelerator were kneaded for 1 to 10 minutes until a discharge temperature reached 150 to 160° C. to obtain a kneaded product. Next, using a twin-screw open roll, the sulfur and vulcanization accelerator were added to the obtained kneaded product, and the mixture was kneaded for 4 minutes until the temperature reached 105° C. to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was extruded into shapes of a cap tread (first rubber layer, thickness: 7 mm) and a base tread (second rubber layer, thickness: 3 mm) and attached together with other tire members to produce an unvulcanized tire, followed by vulcanization at 170° C. to obtain a test tire (size: 205/65R15, rim: 15×6.0 J, internal pressure: 230 kPa). Table 3 shows a tire in which the tread part 2 does not have a sunken groove and the shape in plan view and the cross-sectional shape of the main groove 3 are in any one of
The ground contact shape of a tire was obtained by mounting each of test tires to a normal rim, and then applying ink to the tread part, and vertically pressing the tread part against paper, with a load of 70% of the maximum load capability, and transferring thereto ink applied to the tread part. The sea ratio S0 was calculated by setting an area obtained by an outer ring of the ground contact shape obtained to be the total of the tread ground contact area with all grooves thereof being buried and determining the total of the groove area for all grooves that can remain when the main groove is worn to 50% of the portion to which ink is not affixed. Moreover, with the similar technique as what is described above, the sea ratio S50 was calculated by determining the total of the tread ground contact area with all grooves of the tread part as when the main groove is worn to 50% being buried and the total of the groove area for grooves that remain then. Besides, the base tread (the second rubber layer) is not exposed when the main groove is worn to 50%.
Each of vulcanized rubber test pieces was soaked in acetone for hours to extract the soluble component, Mass of each of the test pieces before and after extraction was measured and the acetone extraction amount was calculated using the below-described calculation equation:
Acetone extraction amount (%)={(Mass of rubber test piece before extraction-Mass of rubber test piece after extraction)/(Mass of rubber test piece before extraction)}×100.
Besides, for each of the rubber test pieces of the first rubber layer and the second rubber layer, what was cut out from the tread of each of the test tires was used. Values of the difference (AET-AEB) between the acetone extraction amount AET of the rubber composition constituting the first rubber layer and the acetone extraction amount AEB of the rubber composition constituting the second rubber layer are shown in Tables 3 and 4.
<Measurement of Rubber Hardness as when the Tire is Newly Used and after Thermal Deterioration>
The rubber hardness Hs0 was measured by pressing a type A durometer against a rubber piece from the ground contact surface (tread surface) side at 23° C. in accordance with JIS K 6253-3:2012, which the rubber piece is obtained by cutting out all the rubber forming the tread part in a tire radial direction from a land part closest to the equatorial plane of the tire being newly used. Moreover, the rubber hardness Hs50 was measured by pressing a type A durometer against a rubber piece from the ground contact surface side, which the rubber piece is obtained by subjecting the rubber piece of the new tire to heat aging in an atmosphere of 80° C. for 168 hours and allowing it to cool to 23° C. Values of Hs50/Hs0 of each of the test tires are shown in Tables 3 and 4.
<Steering Stability Performance after Wear>
Each of the test tires as at when the tire is newly used and each of the test tires after wear were mounted to all wheels of a domestic FF vehicle with a displacement of 2,000 cc, and the actual vehicle was made to run on a test course having a dry asphalt surface. Handling characteristics were evaluated based on feeling at each of the times of running straight, changing lanes, and accelerating/decelerating when running at 120 km/h by a test driver. Evaluation was performed using an integer value of 1 to 10 points, and a total score by 10 test drivers was calculated based on evaluation criteria in which the higher the score, the better the handling characteristics. The total score of a reference tire (Comparative example 2 in Table 3 and Comparative example 11 in Table 4) as when the tire is newly used was converted to a reference value (100), and evaluation results of each of the test tires after wear were indexed so as to be proportional to the total score, and shown.
Besides, each of the test tires after wear was produced by having the tread part worn so that the depth of the deepest main groove of the new tire is 50% of that when it is newly used, and then subjecting this tire to thermal deterioration at 80° C. for 7 days (the same below).
<Wet Performance Maintenance Performance Afterwear>
Each of the test tires as at when the tire is newly used and each of the test tires after wear were mounted to all wheels of a domestic FF vehicle with a displacement of 2,000 cc, and the actual vehicle was made to run on a test course having a wet asphalt surface. Wet performance was evaluated based on feeling for each of wet grip and drainability (hydroplaning) when running at 120 km/h by a test driver. Evaluation was performed using an integer value of 1 to 10 points, and a total score by 10 test drivers was calculated based on evaluation criteria in which the higher the score, the better the wet performance. For each of the test tires, a maintenance index of the score for the wet performance before and after wear was calculated using the below-described equations, the maintenance index was converted with the maintenance index of a reference tire (Comparative example 2 in Table 3 and Comparative example 11 in Table 4) as 100 to be set as the wet performance maintenance performance after wear of each of the test tires. The higher the score, the smaller the change in the Net performance before and after wear, so that the wet performance as when the tire is newly used is maintained and is good.
(Wet performance maintenance index of reference tire)=(Wet performance score of reference tire after wear)/(Wet performance score of reference tire as when the tire is newly used)
(Wet performance maintenance index of each of test tires)=(Wet performance score of each of test tires after wear)/(Wet performance score of each of test tires as when the tire is newly used)
(Wet performance maintenance performance of each of test tires)=(Wet performance maintenance index of each of test tires)/(Wet performance maintenance index of reference tire)×100.
For the overall performance of the steering stability performance after wear and the wet performance maintenance performance after wear (the total sum of the steering stability performance index after wear and the wet performance maintenance performance index after wear), over 200 is to be the performance target value.
Based on the results of Tables 1 to 4, with respect to a tire of the present disclosure comprising a tread being composed of a rubber layer in which change in hardness after thermal deterioration is within a predetermined range and having a groove shape such that the sea ratio after wear with respect to the sea ratio as when the tire is newly used is within a predetermined range, it is evident that the tire has good steering stability performance after wear and a decrease in wet performance after wear is suppressed.
With the tire of the present disclosure, it has good steering stability performance after wear and there is little decrease in wet performance after wear, so that it is useful as a tire that can exhibit steering stability performance and wet performance over a long period of time.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-108986 | Jun 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/006171 | 2/18/2021 | WO |
