JP2013256630A - Rubber composition for tread - Google Patents
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- JP2013256630A JP2013256630A JP2012135001A JP2012135001A JP2013256630A JP 2013256630 A JP2013256630 A JP 2013256630A JP 2012135001 A JP2012135001 A JP 2012135001A JP 2012135001 A JP2012135001 A JP 2012135001A JP 2013256630 A JP2013256630 A JP 2013256630A
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Abstract
Description
本発明は、トレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for a tread.
タイヤトレッド部で起こる代表的なクレームにブロック部においてゴム部材がめくれるチッピング現象が挙げられる。この現象は、ゴム肌に見られるクラック現象とは異なり、路面から受ける比較的大きな変形によってゴム架橋体が直接破壊を起こすことで発生すると考えられている。 A typical complaint that occurs in a tire tread portion is a chipping phenomenon in which a rubber member turns over in a block portion. Unlike the crack phenomenon seen in rubber skin, this phenomenon is considered to occur when the rubber crosslinked body directly breaks due to a relatively large deformation received from the road surface.
このような破壊現象を抑えるためには、車重による繰り返し圧縮変形と旋回時に路面から受けるねじり変形の複合変形に対して耐久性の高いゴム材料を開発することが必要と考えられるが、現状では、単純な一軸引張試験により得られる破断応力や破断ひずみ、破断エネルギーを高める改良しか行われていない。 In order to suppress such destruction, it is considered necessary to develop a rubber material with high durability against the combined deformation of repeated compression deformation due to vehicle weight and torsional deformation received from the road surface during turning. However, only improvements have been made to increase the breaking stress, breaking strain, and breaking energy obtained by a simple uniaxial tensile test.
そのため、このような改良を行ったゴム組成物を実車のタイヤトレッド部に適用してもチッピング現象が発生するケースも散見されることから、実車に適用した際のチッピング現象を抑制し、耐久性が高いゴム組成物を提供することが望まれている。 Therefore, there are some cases where chipping phenomenon occurs even when the rubber composition with such improvements is applied to the tire tread part of an actual vehicle, so that the chipping phenomenon when applied to an actual vehicle is suppressed and durability is improved. It is desired to provide a rubber composition having a high value.
本発明は、前記課題を解決し、耐チッピング性能に優れたトレッド用ゴム組成物を提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems and to provide a rubber composition for a tread excellent in chipping resistance.
本発明は、動的圧縮変形中に圧縮ひずみと同期させた動的ねじり変形を印加した際に、動的ねじり振幅が３００％以上で破壊されるトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for a tread that is broken when a dynamic torsional amplitude is 300% or more when a dynamic torsional deformation synchronized with a compressive strain is applied during the dynamic compressive deformation.
前記動的圧縮変形及び前記動的ねじり変形が、該動的圧縮変形の最大変位点と該動的ねじり変形の最大変位点とが同期するように印加される複合変形であることが好ましい。
前記動的圧縮変形の周期が１〜１００Ｈｚであることが好ましい。
前記動的圧縮変形の圧縮荷重が５０ｋＰａ〜１０ＭＰａであることが好ましい。
It is preferable that the dynamic compression deformation and the dynamic torsion deformation are composite deformations applied so that the maximum displacement point of the dynamic compression deformation and the maximum displacement point of the dynamic torsion deformation are synchronized.
The period of the dynamic compression deformation is preferably 1 to 100 Hz.
It is preferable that the compressive load of the dynamic compressive deformation is 50 kPa to 10 MPa.
本発明によれば、動的圧縮変形中に圧縮ひずみと同期させた動的ねじり変形を印加した際に、動的ねじり振幅が３００％以上で破壊されるトレッド用ゴム組成物であるので、該ゴム組成物を用いて作製したトレッドは、耐チッピング性能に優れている。 According to the present invention, when a dynamic torsional deformation synchronized with the compressive strain is applied during the dynamic compressive deformation, the rubber composition for a tread is broken at a dynamic torsional amplitude of 300% or more. A tread produced using a rubber composition is excellent in chipping resistance.
本発明は、動的圧縮変形中に圧縮ひずみと同期させた動的ねじり変形を印加した際に、動的ねじり振幅が３００％以上で破壊されるトレッド用ゴム組成物である。つまり、タイヤ走行時に実際に路面から入力される変形様式である動的な圧縮変形とせん断変形を同期させながらゴム組成物に入力した場合に、動的ねじり振幅が３００％以上で破壊される性質を有するゴム組成物であるので、実車における耐チッピング性能に優れている。 The present invention is a rubber composition for a tread that is broken when a dynamic torsional amplitude is 300% or more when a dynamic torsional deformation synchronized with a compressive strain is applied during the dynamic compressive deformation. In other words, when dynamic compression deformation and shear deformation, which are deformation modes actually input from the road surface during tire travel, are input to the rubber composition while being synchronized, the dynamic torsional amplitude is destroyed at 300% or more. Therefore, the chipping resistance in an actual vehicle is excellent.
詳しくは、前記ゴム組成物は、周期的に圧力（圧縮荷重）を印加し、動的な圧縮変形を繰り返し与えることで、自動車走行時に車重によりタイヤに繰り返し入力される圧縮変形を与えるとともに、これと同期して、周期的にねじり変形を印加し、動的なねじり変形を繰り返し与えることで、旋回時にタイヤに入力されるねじり変形を与えた場合に、所定以上の動的ねじり振幅、すなわち機械的強度を有している。従って、従来の一軸引張試験のみによる評価法に比べて、より使用条件に近い環境下での破壊試験を実施した場合に所定の機械的強度を有するゴム組成物であるため、実車での耐チッピング性能も優れている。 Specifically, the rubber composition periodically applies pressure (compression load) and repeatedly gives dynamic compressive deformation, thereby giving compressive deformation that is repeatedly input to the tire due to the vehicle weight during vehicle travel, Synchronously with this, by applying torsional deformation periodically and repeatedly applying dynamic torsional deformation, when torsional deformation input to the tire during turning, a dynamic torsional amplitude greater than a predetermined value, that is, It has mechanical strength. Therefore, compared to the conventional evaluation method based only on the uniaxial tensile test, since it is a rubber composition having a predetermined mechanical strength when a destructive test is performed in an environment closer to the use conditions, chipping resistance in an actual vehicle is reduced. The performance is also excellent.
具体的には、動的ねじり振幅を大きくしながら、動的圧縮変形と動的ねじり変形を同期させながら入力し、ゴム組成物の破壊時における動的ねじり振幅（ねじり変位）が３００％以上のゴム組成物である。 Specifically, the dynamic torsional amplitude is increased and the dynamic compression deformation and the dynamic torsional deformation are input while being synchronized, and the dynamic torsional amplitude (torsional displacement) at the time of breaking the rubber composition is 300% or more. It is a rubber composition.
特に、動的圧縮変形が最大変位点になる時点（動的圧縮変形の最大ひずみ）において動的ねじり変形が最大変位点（動的ねじり変形の最大ひずみ）になるように同期させて入力することで実車の耐チッピング性能との相関性がより高められるので、その場合に所定以上の動的ねじり振幅を有するゴム組成物は当該性能が非常に優れている。 In particular, when dynamic compression deformation reaches the maximum displacement point (maximum strain of dynamic compression deformation), input is to be synchronized so that dynamic torsion deformation becomes the maximum displacement point (maximum strain of dynamic torsion deformation). Therefore, the correlation with the chipping performance of the actual vehicle is further enhanced, and in this case, the rubber composition having a dynamic torsional amplitude greater than or equal to a predetermined value is very excellent.
本発明のゴム組成物は、動的圧縮変形中に圧縮ひずみと同期させた動的ねじり変形を印加した際に、動的ねじり振幅が３００％以上で破壊されるものであるが、動的圧縮変形は、車重による繰り返し変形に対応し、動的ねじり変形は、旋回時に路面から受ける変形に対応している。 The rubber composition of the present invention is one that is broken when the dynamic torsion amplitude is 300% or more when a dynamic torsion deformation synchronized with the compression strain is applied during the dynamic compression deformation. The deformation corresponds to repeated deformation due to vehicle weight, and the dynamic torsion deformation corresponds to deformation received from the road surface during turning.
ここで、前記ゴム組成物において、動的圧縮変形と動的ねじり変形を同期させているが、具体的には、実車条件を再現するために、動的圧縮変形の最大変位点がねじり変形の最大変位点と一致し、動的圧縮変形の最小変位点（無荷重点）が動的ねじり変形の変位０点と一致することが望ましい。 Here, in the rubber composition, the dynamic compression deformation and the dynamic torsional deformation are synchronized. Specifically, in order to reproduce the actual vehicle conditions, the maximum displacement point of the dynamic compression deformation is the torsional deformation. It is desirable to match the maximum displacement point, and the minimum displacement point (no load point) of dynamic compressive deformation matches the zero displacement point of dynamic torsional deformation.
動的圧縮変形、動的ねじり変形ともに上記条件を満たす繰り返し変形であれば、その波形は規定されないが、より実車の力学的な入力に即した正弦波であることが好ましい。 If both dynamic compression deformation and dynamic torsional deformation are repetitive deformations that satisfy the above conditions, the waveform is not defined, but is preferably a sine wave that matches the dynamic input of the actual vehicle.
動的圧縮変形の周期は、実車走行時の転動周期に対応し、レースを含む実用レベルで１００Ｈｚ以下が好ましく、より好ましくは通常の使用条件である１２０ｋｍ／ｈ以下に対応する２０Ｈｚ以下である。該周期の下限は特に限定されないが、交差点における徐行運転を考慮すると、好ましくは速度１０ｋｍ／ｈに対応する１Ｈｚ以上、より好ましくは速度２０ｋｍ／ｈに相当する２Ｈｚ以上である。 The cycle of dynamic compression deformation corresponds to the rolling cycle during actual vehicle travel, and is preferably 100 Hz or less at a practical level including a race, and more preferably 20 Hz or less corresponding to 120 km / h or less which is a normal use condition. . The lower limit of the cycle is not particularly limited, but considering slow driving at the intersection, it is preferably 1 Hz or more corresponding to a speed of 10 km / h, more preferably 2 Hz or more corresponding to a speed of 20 km / h.
動的圧縮変形は、車重による変形に対応するものであるため、その振幅は圧力によって規定され、最大振幅において印加される圧力（圧縮荷重）は、１０ＭＰａ以下が好ましく、３ＭＰａ以下がより好ましい。該圧力の下限は、車重の半分相当の圧力の点から、好ましくは５０ｋＰａ以上、より好ましくは１５０ｋＰａ以上、更に好ましくは３００ｋＰａ以上である。圧力を上記範囲内とすることにより、タイヤに使用した際の耐チッピング性能を良好に評価できる。 Since dynamic compression deformation corresponds to deformation due to vehicle weight, the amplitude is defined by pressure, and the pressure (compression load) applied at the maximum amplitude is preferably 10 MPa or less, and more preferably 3 MPa or less. The lower limit of the pressure is preferably 50 kPa or more, more preferably 150 kPa or more, and still more preferably 300 kPa or more from the viewpoint of a pressure corresponding to half the vehicle weight. By setting the pressure within the above range, it is possible to satisfactorily evaluate the chipping resistance performance when used in a tire.
動的ねじり変形の周期は、動的圧縮変形とねじり変形を同期させるという点から、上記動的圧縮変形の周期によって定めることが望ましい。具体的には、動的ねじり変形の中心位置に変位０の原点を置く場合は動的圧縮変形の半分の周期を、動的ねじり変形の最小変位位置に変位０の原点を置く場合は動的圧縮変形と同じ周期にすることが好ましい。 The period of the dynamic torsional deformation is preferably determined by the period of the dynamic compression deformation from the viewpoint of synchronizing the dynamic compression deformation and the torsional deformation. Specifically, when the origin of displacement 0 is placed at the center position of dynamic torsional deformation, half the period of dynamic compression deformation is used. When the origin of displacement 0 is placed at the minimum displacement position of dynamic torsional deformation, dynamic is applied. It is preferable to have the same cycle as the compression deformation.
動的圧縮変形と動的ねじり変形との複合変形を同期させて印加する際に、動的ねじり振幅（動的ねじり変形の振幅）を大きくしながらゴム組成物を破壊させる方法を使用する。具体的には、ゴム組成物が破壊するまで動的ねじり変形の振幅を徐々に大きくしながら測定を行い、破壊時のねじり変位（動的ねじり振幅）によって耐チッピング性能の優劣を決定でき、その時の動的ねじり振幅が３００％以上であれば当該性能が優れていると評価できる。 A method of breaking the rubber composition while increasing the dynamic torsional amplitude (the amplitude of the dynamic torsional deformation) when applying the combined deformation of dynamic compressive deformation and dynamic torsional deformation in synchronism is used. Specifically, measurement is performed while gradually increasing the amplitude of dynamic torsional deformation until the rubber composition breaks, and the superiority or inferiority of chipping resistance can be determined by the torsional displacement (dynamic torsional amplitude) at the time of destruction. If the dynamic torsional amplitude is 300% or more, it can be evaluated that the performance is excellent.
ここで、動的ねじり振幅とは、ゴム組成物の動的圧縮方向に最大荷重を印加した時点における動的圧縮方向の厚み（最大荷重印加時の圧縮変形方向の長さ）に対する動的ねじり変位量であり、例えば、図１に示す円柱状のゴム組成物では、圧縮方向に最大荷重を印加した時点におけるゴム組成物の圧縮方向の厚み（圧縮方向の長さ）ＡＢに対する、Ｂ点からＣ点に変位させるねじり変形における最外径の移動量ＢＣ、すなわちＢＣ／ＡＢを意味する。 Here, the dynamic torsional amplitude is the dynamic torsional displacement with respect to the thickness in the dynamic compression direction when the maximum load is applied in the dynamic compression direction of the rubber composition (the length in the compression deformation direction when the maximum load is applied). For example, in the columnar rubber composition shown in FIG. 1, from the point B to the thickness (length in the compression direction) AB of the rubber composition when the maximum load is applied in the compression direction. It means the movement amount BC of the outermost diameter in torsional deformation displaced to a point, that is, BC / AB.
動的ねじり振幅を徐々に大きくしながら複合変形を繰り返し印加する際、１つの動的ねじり振幅における動的変形の継続時間を、動的変形が安定する１０秒以上、好ましくは充分に安定する３０秒以上に、またゴム試験片が硬化するような通常の疲労破壊を起こさない１時間以内、好ましくは総測定時間を考慮して１０分以内、より好ましくは５分以内になるように調整する。つまり、動的ねじり振幅が３００％以上の複合変形を上記範囲の時間印加し、破壊が生じなければ、耐チッピング性能が優れていると判断できる。 When the composite deformation is repeatedly applied while gradually increasing the dynamic torsional amplitude, the duration of the dynamic deformation at one dynamic torsional amplitude is 10 seconds or more when the dynamic deformation is stabilized, preferably sufficiently stabilized 30 It is adjusted to be within 10 minutes, more preferably within 5 minutes, taking into consideration the total measurement time, within 1 hour, which does not cause normal fatigue failure such that the rubber specimen is cured. That is, it can be determined that chipping resistance is excellent if a composite deformation having a dynamic torsional amplitude of 300% or more is applied for a time in the above range and no breakdown occurs.
前記複合変形において、測定温度は、使用環境に則するという理由から、好ましくは−２０〜８０℃、より好ましくは０〜６０℃である。 In the composite deformation, the measurement temperature is preferably −20 to 80 ° C., more preferably 0 to 60 ° C., because it conforms to the use environment.
複合変形を入力するゴム組成物の大きさは特に規定されないが、トレッドのブロック相当の大きさであることが好ましい。また、形状は、動的圧縮変形と動的ねじり変形からなる複合変形を印加できるものであれば特に限定されないが、円筒状（円柱状）であることが望ましい。このため、試料は、直径５〜２０ｍｍ程度の円筒状で、その高さは５〜２０ｍｍ程度が好ましい。 The size of the rubber composition for inputting the composite deformation is not particularly limited, but is preferably a size corresponding to a tread block. The shape is not particularly limited as long as it can apply a composite deformation composed of dynamic compressive deformation and dynamic torsional deformation, but is preferably cylindrical (columnar). For this reason, a sample is a cylindrical shape about 5-20 mm in diameter, and the height is preferable about 5-20 mm.
本発明における複合変形を入力可能な測定装置としては、ゴム組成物に対して、動的圧縮変形及び動的ねじり変形を同時に印加し続けることが可能な装置であれば特に限定されず、例えば、特開２００６−１７７７３４号公報に記載の粘弾性測定装置等を使用できる。 The measuring device capable of inputting the composite deformation in the present invention is not particularly limited as long as it can continuously apply dynamic compression deformation and dynamic torsion deformation to the rubber composition, for example, The viscoelasticity measuring device described in JP-A-2006-177734 can be used.
複合変形は、具体的には、二枚の平行に置かれた金属プレート間に円柱又は直方体形状の試料を接着剤にて固定したものを測定用試料として使用し、金属プレートを測定治具に固定した後、金属プレート間に圧縮とねじりの周期的な変形を同時に与え、試料が破壊するまでねじり変形の振幅を大きくしながら測定することで実施できる。 Specifically, compound deformation uses a cylindrical or rectangular parallelepiped-shaped sample fixed between two metal plates placed in parallel with an adhesive as a measurement sample, and the metal plate is used as a measurement jig. After fixing, cyclic deformation of compression and torsion is simultaneously applied between the metal plates, and measurement is performed while increasing the amplitude of torsional deformation until the sample breaks.
複合変形について、図面を用い、更に具体的に説明する。
図２は、測定用試料１の一例を示す模式図である。測定用試料１は、円柱形状のゴム組成物１１及び一対の金属プレート１２Ａ及び１２Ｂからなる。一対の金属プレート１２Ａ及び１２Ｂは、それぞれゴム組成物１１の円形状の上面１１Ａ及び下面１１Ｂに貼着されている。
The composite deformation will be described more specifically with reference to the drawings.
FIG. 2 is a schematic diagram illustrating an example of the
図２に示す測定用試料１を上述の装置にセットし、本発明における複合変形を行うことが可能である。具体的には、図２に示すように、一対の金属プレート１２Ａ及び１２Ｂを介し、ゴム組成物１１の円形状の上面１１Ａ及び下面１１Ｂに対して円柱軸方向（図２のＸ方向）に繰り返し圧縮変形を入力することにより、上面１１Ａ及び下面１１Ｂからゴム組成物１１に動的圧縮変形が印加される。更に、金属プレート１２Ａを介して上面１１Ａを円周方向（図２のＴ方向）に繰り返しねじり変形を入力し、原点ＯＲ（変位０点）を中心にＲＡ点、ＲＢ点に繰り返し変位させることにより、動的ねじり変形が印加される。
The
動的圧縮変形が車重による変形に、動的ねじり変形が旋回時に路面から受ける変形にそれぞれ対応しているので、動的圧縮変形の最大変位点、すなわち最も圧縮されて一対の金属プレート１２Ａ及び１２Ｂの距離が最小になる時点と、動的ねじり変形の最大変位点、すなわち最もねじられて動的ねじれひずみ角αが最大になる時点とが一致するように同期させることで、実車におけるタイヤの変形を良好に再現できる。
Since the dynamic compression deformation corresponds to the deformation due to the vehicle weight, and the dynamic torsion deformation corresponds to the deformation received from the road surface during turning, the maximum displacement point of the dynamic compression deformation, that is, the pair of
そして、動的ねじり振幅を徐々に大きくしながら、動的圧縮変形、動的ねじり変形をゴム組成物１１に入力し続け、ゴム組成物１１の破壊時における動的ねじり振幅（ねじり変位）を測定することにより、ゴム組成物１１と同一の組成の試料をタイヤのトレッドに使用した際の耐チッピング性能を予測でき、３００％以上であれば当該性能に優れていると評価できる。なお、「破壊」とは、「亀裂が生じること(外観上)」、「応力の低下(物性)」であり、本試験では、動的ねじりを印加した際の応力が低下する時点を「破壊」と判定する。
Then, while gradually increasing the dynamic torsional amplitude, the dynamic compression deformation and dynamic torsional deformation are continuously input to the
図２に示す測定用試料において、金属プレート１２Ａ及び１２Ｂの材質は特に規定されず、例えば、ステンレスや鉄、真鍮などが挙げられる。ゴム組成物１１と金属プレート１２Ａ及び１２Ｂとの接着は、例えば、金属−ゴム間を接着可能な一般的な接着剤（エポキシ系の接着剤、ウレタン系の接着剤、加硫接着剤等）を用いて実施でき、加硫後の試料を接着する手法や加硫と同時に金属プレートとゴム組成物を接着する手法などが挙げられる。いずれの手法であれ、試料が破壊するまでに金属プレート−ゴム間の剥離が生じなければよく、これにより、測定したゴム試料をタイヤに使用した際の耐チッピング性能を良好に評価できる。
In the measurement sample shown in FIG. 2, the material of the
本発明のゴム組成物としては、ゴム成分、カーボンブラックやシリカなどの充填剤を含むものなどが挙げられる。 Examples of the rubber composition of the present invention include those containing a rubber component and a filler such as carbon black and silica.
ゴム成分としては、例えば、天然ゴム（ＮＲ）、エポキシ化天然ゴム（ＥＮＲ）等の改質天然ゴム、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、ブチルゴム（ＩＩＲ）、イソブチレン−ｐ−メチルスチレン共重合体の臭素化物、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、エチレン−プロピレンゴム（ＥＰＭ）、エチレン−プロピレン−ジエン共重合ゴム（ＥＰＤＭ）、スチレン−イソプレンゴム、スチレン−イソプレン−ブタジエンゴム共重合ゴム（ＳＩＢＲ）、イソプレン−ブタジエンゴム、クロロスルホン化ポリエチレン（ＣＳＭ）、アクリルゴム（ＡＣＭ、ＡＮＭ）、エピクロルヒドリンゴム（ＣＯ、ＥＣＯ、ＧＥＣＯ）、多硫化ゴム（Ｔ）、シリコーンゴム（Ｑ）、フッ素ゴム（ＦＫＭ）、ウレタンゴム（Ｕ）などが挙げられる。これらは単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Examples of rubber components include modified natural rubber such as natural rubber (NR) and epoxidized natural rubber (ENR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), and butyl rubber (IIR). Brominated product of isobutylene-p-methylstyrene copolymer, acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), ethylene-propylene rubber (EPM), ethylene-propylene-diene copolymer rubber (EPDM), styrene- Isoprene rubber, styrene-isoprene-butadiene rubber copolymer rubber (SIBR), isoprene-butadiene rubber, chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO, GECO), polysulfide rubber (T), Silico Rubber (Q), fluorine rubber (FKM), and the like urethane rubber (U). These may be used alone or in combination of two or more.
カーボンブラックには、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、グラファイトなどが挙げれられ、具体例としては、ＳＡＦ−ＨＳ、ＳＡＦ、ＩＳＡＦ、ＩＳＡＦ−ＨＳ、ＩＳＡＦ−ＬＳ、ＩＩＳＡＦ−ＨＳ、ＨＡＦ、ＨＡＦ−ＨＳ、ＨＡＦ−ＬＳ、ＦＥＦ、ＧＰＦ、ＳＲＦなどがある。これらのカーボンブラックは、それぞれ単独で又は２種以上を組み合わせて使用できる。 Carbon black includes furnace black, acetylene black, thermal black, channel black, graphite and the like, and specific examples include SAF-HS, SAF, ISAF, ISAF-HS, ISAF-LS, IISAF-HS, HAF, There are HAF-HS, HAF-LS, FEF, GPF, SRF and the like. These carbon blacks can be used alone or in combination of two or more.
カーボンブラックの配合量は、ゴム成分１００質量部に対して１０〜１５０質量部が好ましい。１０質量部未満では、充分な補強性が得られない傾向があり、１５０質量部を超えると、発熱が増大して転がり抵抗が悪化したり、加工性が悪化し、かえって補強性が低下するおそれもある。該配合量は、３０〜１００質量部が更に好ましい。 The compounding amount of carbon black is preferably 10 to 150 parts by mass with respect to 100 parts by mass of the rubber component. If the amount is less than 10 parts by mass, sufficient reinforcing property tends not to be obtained. If the amount exceeds 150 parts by mass, heat generation increases and rolling resistance deteriorates, workability deteriorates, and the reinforcement property may decrease. There is also. The blending amount is more preferably 30 to 100 parts by mass.
シリカとしては、従来ゴム補強用として慣用されているもの、たとえば、乾式法シリカ、湿式法シリカなどのなかから適宜選択して使用できるが、なかでも、湿式法シリカが好ましい。湿式法シリカの好適例としては、デグッサ製ウルトラジルＶＮ３、東ソー・シリカ（株）製ニップシールＡＱなどがあげられる。 Silica can be appropriately selected and used from those conventionally used for reinforcing rubber, for example, dry silica, wet silica, etc. Among them, wet silica is preferable. Preferable examples of the wet process silica include Degussa Ultrasil VN3, Tosoh Silica Co., Ltd. nip seal AQ, and the like.
シリカの配合量は、ゴム成分１００質量部に対して、好ましくは５質量部以上、より好ましくは３０質量部以上である。５質量部未満であると、シリカを用いることによる転がり抵抗低減効果やウエットグリップ向上効果が得られにくくなる。該配合量は、好ましくは１５０質量部以下、より好ましくは８０質量部以下である。１５０質量部を超えると、加工性が低下する傾向がある。 The compounding amount of silica is preferably 5 parts by mass or more, more preferably 30 parts by mass or more with respect to 100 parts by mass of the rubber component. When the amount is less than 5 parts by mass, it is difficult to obtain a rolling resistance reduction effect and a wet grip improvement effect by using silica. The amount is preferably 150 parts by mass or less, more preferably 80 parts by mass or less. When it exceeds 150 mass parts, there exists a tendency for workability to fall.
シリカを配合する場合、更にシランカップリング剤を添加することが望ましい。シランカップリング剤としては特に限定されず、従来から用いられている一般的なものを使用できる。 When silica is blended, it is desirable to further add a silane coupling agent. It does not specifically limit as a silane coupling agent, The general thing used conventionally can be used.
シランカップリング剤の配合量は、シリカ１００質量部に対して０．５〜２０質量部が好ましく、２．５〜１０質量部がより好ましい。０．５質量部未満では、シランカップリング剤を入れてシリカの分散を改善する効果が充分に得られず、耐摩耗性や破壊エネルギーが低下する傾向があり、２０質量部を超えると、コストが上がる割に効果が得られず、更には、補強性、耐摩耗性がかえって低下する場合がある。 0.5-20 mass parts is preferable with respect to 100 mass parts of silica, and, as for the compounding quantity of a silane coupling agent, 2.5-10 mass parts is more preferable. If the amount is less than 0.5 parts by mass, the effect of improving the dispersion of silica by adding a silane coupling agent cannot be sufficiently obtained, and the wear resistance and fracture energy tend to decrease. However, there is a case where the effect is not obtained for the increase of the resistance, and further, the reinforcement property and the wear resistance are deteriorated.
本発明のゴム組成物は、軟化剤を配合してもよい。軟化剤としては、パラフィン系プロセスオイル、ナフテン系プロセスオイル、芳香族系プロセスオイルなどのプロセスオイル；ひまし油、綿実油、あまに油、なたね油、大豆油、パーム油、やし油、落花生湯、ロジン、パインオイル、パインタール、トール油、コーン油、こめ油、べに花油、ごま油、オリーブ油、ひまわり油、パーム核油、椿油、ホホバ油、マカデミアナッツ油、サフラワー油、桐油などの植物油脂などが挙げられる。軟化剤の配合量は、適宜選択すればよい。 The rubber composition of the present invention may contain a softening agent. Softeners include paraffinic process oil, naphthenic process oil, aromatic process oil, castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut water, rosin, Examples include vegetable oils such as pine oil, pine tar, tall oil, corn oil, rice bran oil, bean flower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, coconut oil, jojoba oil, macadamia nut oil, safflower oil, and tung oil. . What is necessary is just to select the compounding quantity of a softening agent suitably.
本発明のゴム組成物は、老化防止剤を配合してもよく、例えば、耐熱性老化防止剤、耐候性老化防止剤等でゴム組成物に通常使用されるものであれば特に限定されることなく使用できる。具体的には、ナフチルアミン系（フェニル−α−ナフチルアミン等）、ジフェニルアミン系（オクチル化ジフェニルアミン、４，４′−ビス（α，α′−ジメチルベンジル）ジフェニルアミン等）、ｐ−フェニレンジアミン系（Ｎ−イソプロピル−Ｎ′−フェニル−ｐ−フェニレンジアミン、Ｎ−（１，３−ジメチルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミン、Ｎ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン等）等のアミン系老化防止剤；２，２，４−トリメチル−１，２−ジヒドロキノリンの重合物等のキノリン系老化防止剤；モノフェノール系（２，６−ジ−ｔ−ブチル−４−メチルフェノール、スチレン化フェノール等）、ビス、トリス、ポリフェノール系（テトラキス−［メチレン−３−（３′，５′−ジ−ｔ−ブチル−４′−ヒドロキシフェニル）プロピオネート］メタン等）等のフェノール系老化防止剤が挙げられる。老化防止剤の配合量は、適宜選択すればよい。 The rubber composition of the present invention may be blended with an anti-aging agent, and is particularly limited as long as it is usually used in rubber compositions such as a heat-resistant anti-aging agent and a weather-resistant anti-aging agent. Can be used without Specifically, naphthylamine type (phenyl-α-naphthylamine etc.), diphenylamine type (octylated diphenylamine, 4,4′-bis (α, α′-dimethylbenzyl) diphenylamine etc.), p-phenylenediamine type (N- Isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, etc.) Amine-based anti-aging agents such as 2,2,4-trimethyl-1,2-dihydroquinoline and other quinoline anti-aging agents; monophenol-based (2,6-di-t-butyl-4-methyl) Phenol, styrenated phenol, etc.), bis, tris, polyphenol (tetrakis- [methylene-3- (3 ', 5'-di-t-butyl) Le-4'-hydroxyphenyl) propionate] methane) phenolic antioxidant, and the like. What is necessary is just to select the compounding quantity of an anti-aging agent suitably.
上記ゴム組成物には、前記成分の他に、従来ゴム工業で使用される配合剤、例えば、酸化防止剤、酸化亜鉛、硫黄、含硫黄化合物等の加硫剤、加硫促進剤等を含有してもよい。 In addition to the above components, the rubber composition contains compounding agents conventionally used in the rubber industry, such as antioxidants, vulcanizing agents such as zinc oxide, sulfur and sulfur-containing compounds, and vulcanization accelerators. May be.
本発明のトレッド用ゴム組成物は、一般的な方法で製造される。すなわち、バンバリーミキサーやニーダー、オープンロールなどの混練機で前記各成分を混練りし、その後加硫する方法等により製造できる。 The rubber composition for a tread of the present invention is produced by a general method. That is, it can be produced by a method of kneading each component with a kneader such as a Banbury mixer, a kneader, or an open roll, and then vulcanizing.
上記トレッド用ゴム組成物を用いて作製する空気入りタイヤは、通常の方法で製造される。すなわち、前記成分を配合したゴム組成物を、未加硫の段階でトレッドの形状にあわせて押出し加工し、他のタイヤ部材とともに、タイヤ成型機上にて通常の方法で成形することにより、未加硫タイヤを形成する。この未加硫タイヤを加硫機中で加熱加圧することにより、空気入りタイヤを製造できる。 A pneumatic tire produced using the rubber composition for a tread is produced by a normal method. That is, the rubber composition containing the above components is extruded in accordance with the shape of the tread at an unvulcanized stage and molded together with other tire members on a tire molding machine by a normal method. Form a vulcanized tire. A pneumatic tire can be manufactured by heating and pressing the unvulcanized tire in a vulcanizer.
本発明における複合変形の入力により、これまでの一軸引張試験では耐チッピング性能の判別が困難であるが、市場性能と差が見られる配合について、市場性能の序列どおりに比較ができるようになる。従って、本発明における動的ねじり振幅が所定以上という基準により、市場性能の序列を相対的に判別できるため、耐チッピング性能に優れたトレッド部を提供できる。 With the input of the composite deformation in the present invention, it is difficult to discriminate the chipping performance in the conventional uniaxial tensile test, but it becomes possible to compare the blends that are different from the market performance according to the order of the market performance. Accordingly, since the order of market performance can be relatively determined based on the criterion that the dynamic torsion amplitude in the present invention is not less than a predetermined value, a tread portion having excellent chipping resistance can be provided.
実施例に基づいて、本発明を具体的に説明するが、本発明はこれらのみに限定されるものではない。 The present invention will be specifically described based on examples, but the present invention is not limited to these examples.
以下、実施例及び比較例で使用した各種薬品について、まとめて説明する。
天然ゴム（ＮＲ）：ＴＳＲ２０
スチレンブタジエンゴム（ＳＢＲ）：ＪＳＲ（株）製のＳＢＲ１５０２（結合スチレン量：２３．５質量％）
ブタジエンゴム（ＢＲ）：宇部興産（株）製のＢＲ７００
カーボンブラック：キャボットジャパン（株）製のショウブラックＮ３３０（Ｎ２ＳＡ：７９ｍ２／ｇ）
シリカ：日本シリカ（株）製のニプシルＶＮ３
オイル：（株）ジャパンエナジー製のプロセスＸ−１４０
フェニレンジアミン系老化防止剤：大内新興化学工業（株）製のノクラック６Ｃ（Ｎ−１，３−ジメチルブチル−Ｎ’−フェニル−ｐ−フェニレンジアミン）
ワックス：日本精蝋（株）製のオゾエース０３５５
酸化亜鉛：東邦亜鉛（株）製の銀嶺Ｒ
ステアリン酸：日油（株）製の椿
硫黄：鶴見化学工業（株）製の５％オイル処理粉末硫黄（オイル分５質量％含む可溶性硫黄）
加硫促進剤：大内新興化学工業（株）製のノクセラーＮＳ（Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアジルスルフェンアミド）
Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
Natural rubber (NR): TSR20
Styrene butadiene rubber (SBR): SBR1502 (bonded styrene content: 23.5% by mass) manufactured by JSR Corporation
Butadiene rubber (BR): BR700 manufactured by Ube Industries, Ltd.
Carbon black: Show Black N330 (N 2 SA: 79 m 2 / g) manufactured by Cabot Japan
Silica: Nipsil VN3 manufactured by Nippon Silica Co., Ltd.
Oil: Process X-140 manufactured by Japan Energy Co., Ltd.
Phenylenediamine-based anti-aging agent: NOCRACK 6C (N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Wax: Ozoace 0355 manufactured by Nippon Seiwa Co., Ltd.
Zinc oxide: Silver candy R made by Toho Zinc Co., Ltd.
Stearic acid: Sulfur Sulfur manufactured by NOF Corporation: 5% oil-treated powdered sulfur manufactured by Tsurumi Chemical Co., Ltd. (soluble sulfur containing 5% by mass of oil)
Vulcanization accelerator: Noxeller NS (N-tert-butyl-2-benzothiazylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
（実施例及び比較例）
表１に示す配合処方にしたがい、工程１の材料を充填率が５８％になるように（株）神戸製鋼製の１．７Ｌバンバリーに充填し、８０ｒｐｍで１４０℃に到達するまで混練した。工程１で得られた混練物に、工程２に示す硫黄および加硫促進剤を表１に示す量配合し、１６０℃で２０分間加硫することにより、直径１０ｍｍ、高さ１０ｍｍの円柱状の加硫ゴム組成物を得た。
また、同配合をトレッドとした試験用タイヤも製造した。
(Examples and Comparative Examples)
According to the formulation shown in Table 1, the material of
In addition, a test tire having the same composition as a tread was also produced.
各ゴム組成物、各試験用タイヤについて下記の評価を行った。結果を表１に示す。 Each rubber composition and each test tire were evaluated as follows. The results are shown in Table 1.
＜測定用試料の作製＞
得られた各ゴム試験片（ゴム組成物）の上面及び下面のそれぞれに、金属プレート（ＳＵＳ３０４製、４０×４０（ｍｍ））を接着剤（Ｈｅｎｋｅｌ社製、ロックタイト４０７）を用いて接着し、図２に示す測定用試験片を作製した。
＜破壊試験（動的圧縮変形及び動的ねじり変形）＞
得られた測定用試料の金属プレートを測定治具に固定した後、金属プレート間に圧縮とねじりの周期的な変形を同期させながら入力し、ゴム試験片が破壊するまで動的ねじり変形の振幅を大きくしながら、破壊時の動的ねじり振幅（ねじり変位）を測定し、結果を表１に示した。測定装置、測定条件は、以下のとおりである。
測定装置：株式会社ヨシミズ製の大変形粘弾性試験装置（ゴム疲労試験機）
ひずみの入力：圧縮＋ねじりモード
動的圧縮変形の圧縮荷重：１００Ｎ
動的圧縮変形の周期：２０Ｈｚ（正弦波）
動的ねじり変形の動的ねじれひずみ角：±５〜±９０度
動的ねじり変形の周期：１０Ｈｚ（正弦波）
測定温度：４０℃
なお、試験は、動的圧縮変形の最大変位点とねじり変形の最大変位点を一致させ、動的圧縮変形の最小変位点（無荷重点）と動的ねじり変形の変位０点を一致させて行った。また、動的ねじり変形の周期は、動的ねじり変形の中心位置に変位０の原点を置いた値である。
<Preparation of measurement sample>
A metal plate (manufactured by SUS304, 40 × 40 (mm)) is bonded to each of the upper surface and the lower surface of each obtained rubber test piece (rubber composition) using an adhesive (manufactured by Henkel, Loctite 407), A test specimen for measurement shown in FIG. 2 was produced.
<Destructive test (dynamic compressive deformation and dynamic torsional deformation)>
After fixing the metal plate of the obtained measurement sample to the measurement jig, input the cyclic deformation of compression and torsion between the metal plates while synchronizing them, and the amplitude of dynamic torsional deformation until the rubber specimen breaks The dynamic torsional amplitude (torsional displacement) at the time of fracture was measured while increasing, and the results are shown in Table 1. The measurement apparatus and measurement conditions are as follows.
Measuring device: Large deformation viscoelasticity testing device (Rubber Fatigue Testing Machine) manufactured by Yoshimizu Co., Ltd.
Strain input: Compression + torsion mode Compressive load of dynamic compression deformation: 100N
Dynamic compression deformation cycle: 20 Hz (sine wave)
Dynamic torsional strain angle of dynamic torsional deformation: ± 5 to ± 90 degrees Period of dynamic torsional deformation: 10 Hz (sine wave)
Measurement temperature: 40 ° C
In the test, the maximum displacement point of dynamic compression deformation is matched with the maximum displacement point of torsion deformation, and the minimum displacement point (no load point) of dynamic compression deformation is matched with zero displacement of dynamic torsion deformation. went. The dynamic torsional deformation period is a value obtained by placing the origin of zero displacement at the center position of the dynamic torsional deformation.
（実車試験）
作製した試験用タイヤについて、市場において６ヶ月間走行した後のチッピング発生状況を確認し、結果を表１に示した。
(Actual vehicle test)
The produced test tires were checked for chipping occurrence after running for 6 months in the market, and the results are shown in Table 1.
動的ねじり振幅が３００％以上で破壊された実施例は、実車試験のチッピングの発生が確認されず、３００％未満で破壊された比較例は、チッピングの発生が確認された。従って、複合変形における動的ねじり振幅を基準とすることで、耐チッピング性能を評価でき、３００％以上のものが良好な性能を持つことが確認された。 In the example in which the dynamic torsion amplitude was broken at 300% or more, the occurrence of chipping in the actual vehicle test was not confirmed, and in the comparative example broken at less than 300%, the occurrence of chipping was confirmed. Therefore, the chipping resistance can be evaluated by using the dynamic torsional amplitude in the composite deformation as a reference, and it has been confirmed that those having 300% or more have good performance.
１ 測定用試料
１１ ゴム組成物
１１Ａ ゴム組成物の上面
１１Ｂ ゴム組成物の下面
１２Ａ、１２Ｂ 金属プレート
DESCRIPTION OF
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220033644A1 (en) * | 2018-11-09 | 2022-02-03 | Bridgestone Corporation | Resin composition for tire, resin-metal composite member for tire, and tire |
| WO2022158423A1 (en) * | 2021-01-21 | 2022-07-28 | 横浜ゴム株式会社 | Rubber composition for tires, and tire |
| JP2022112200A (en) * | 2021-01-21 | 2022-08-02 | 横浜ゴム株式会社 | Rubber composition for tires and tire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08337688A (en) * | 1995-06-13 | 1996-12-24 | Sumitomo Rubber Ind Ltd | Rubber composition for tread |
| JP2004123926A (en) * | 2002-10-03 | 2004-04-22 | Bridgestone Corp | Tire |
| JP2005146078A (en) * | 2003-11-13 | 2005-06-09 | Yokohama Rubber Co Ltd:The | Rubber composition and pneumatic tire using the same |
-
2012
- 2012-06-14 JP JP2012135001A patent/JP5881542B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08337688A (en) * | 1995-06-13 | 1996-12-24 | Sumitomo Rubber Ind Ltd | Rubber composition for tread |
| JP2004123926A (en) * | 2002-10-03 | 2004-04-22 | Bridgestone Corp | Tire |
| JP2005146078A (en) * | 2003-11-13 | 2005-06-09 | Yokohama Rubber Co Ltd:The | Rubber composition and pneumatic tire using the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220033644A1 (en) * | 2018-11-09 | 2022-02-03 | Bridgestone Corporation | Resin composition for tire, resin-metal composite member for tire, and tire |
| WO2022158423A1 (en) * | 2021-01-21 | 2022-07-28 | 横浜ゴム株式会社 | Rubber composition for tires, and tire |
| JP2022112200A (en) * | 2021-01-21 | 2022-08-02 | 横浜ゴム株式会社 | Rubber composition for tires and tire |
| JP7251563B2 (en) | 2021-01-21 | 2023-04-04 | 横浜ゴム株式会社 | Tire rubber composition and tire |
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