JP2011079876A - Rubber composition and tire using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition which can hold a balance between reduced rolling resistance and abrasion resistance in a tire at a high level, and is especially excellent in the improvement of the abrasion resistance, and to provide the tire using the rubber composition. <P>SOLUTION: The rubber composition comprising 100 pts.mass of a rubber component containing an aromatic vinyl compound-conjugated dienic compound copolymer (A) and 10 to 250 pts.mass of carbon black (B) is characterized in that the aromatic vinyl compound-conjugated dienic compound copolymer (A) is an aromatic vinyl compound-conjugated dienic compound copolymer which is obtained by a specific production method and in which the cis-1,4-bond content of the conjugated dienic compound portion is ≥80%, and the carbon black (B) is obtained by a specific production method, has specified properties, and satisfies specific conditions. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a rubber composition that includes a rubber component containing a specific copolymer and carbon black and that can exhibit particularly excellent wear resistance, and a high-performance tire obtained by using the rubber composition.

  In recent years, tires with low rolling resistance have been demanded in order to save fuel consumption of automobiles under the social demand for energy saving and resource saving. In response to such demands, as a method of reducing the rolling resistance of the tire, by reducing the amount of carbon black used or by using lower carbon black, a rubber composition having a reduced hysteresis loss can be used as a tire member, In particular, a method used for tread rubber is known. Such a rubber composition with reduced hysteresis loss can effectively reduce rolling resistance when used in a tire, but it is not easy to maintain wear resistance that is in contradiction to this at a useful level, Various attempts have been made.

  Under these circumstances, for example, Patent Document 1 focuses on the surface characteristics of carbon black, particularly the hydrogen content and the residual amount of undecomposed polycyclic aromatic hydrocarbons, and by optimizing the thermal history of carbon black, A rubber composition that can suppress a decrease in wear and the like is disclosed, thereby achieving both the wear resistance and the hysteresis loss characteristic of the tire.

  On the other hand, various studies have also been made on copolymers contained in rubber components. Patent Documents 2 to 4 disclose stereoregularity of a conjugated diene compound part, for example, the inclusion of a cis-1,4 structure. In order to control the rate, a technique for producing an aromatic vinyl compound-conjugated diene compound copolymer using a metal catalyst composed of a ligand and a metal atom is disclosed.

JP 2005-272734 A Japanese Patent No. 3207502 JP 2006-137897 A Japanese Patent No. 3738315

  However, even with carbon black as described above, there is still room for improvement from the viewpoint of further improving these two contradictory performances of durability and rolling resistance. In addition, regarding an aromatic vinyl compound-conjugated diene compound copolymer that can be employed as a rubber component, if the copolymer is obtained by the above-described method, the aromatic vinyl compound portion is blocked or reduced in molecular weight. If the amount of cis-1,4 bonds in the conjugated diene compound portion is high, the tire tends to impart more wear resistance and wet skid resistance than those containing other microstructures. It is not possible to sufficiently respond to the views of the present inventors.

  Accordingly, the present invention provides a rubber composition that is particularly excellent in improving wear resistance while maintaining a high level of balance between reduced rolling resistance and wear resistance in the tire, and a tire using the rubber composition. It is an object.

In order to solve the above problems, the present inventor has blended an aromatic vinyl compound-conjugated diene compound copolymer obtained by a specific production method and a carbon black having a specific property obtained by a specific production method. The present invention has been found and the present invention has been completed.
That is, the rubber composition of the present invention is
A rubber composition obtained by blending carbon black (B) in an amount of 10 to 250 parts by mass with respect to 100 parts by mass of a rubber component containing an aromatic vinyl compound-conjugated diene compound copolymer (A). ,
The aromatic vinyl compound-conjugated diene compound copolymer (A) is represented by the following general formula (I):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式(II)；

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II);

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ^’は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、並びに下記一般式(III)；

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ^′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and the following general formula (III );

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、[Ｂ]⁻は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からなる群より選択される少なくとも１種類の錯体を含む重合触媒組成物の存在下、芳香族ビニル化合物及び共役ジエン化合物を付加重合して得られた、共役ジエン化合物部分のシス-１,４結合量が８０％以上の芳香族ビニル化合物−共役ジエン系化合物共重合体であり、かつ
前記カーボンブラック（Ｂ）が、燃焼ガス生成帯域と、反応帯域と、反応停止帯域とが連設されてなる反応装置を用い、前記燃焼ガス生成帯域内で高温燃焼ガスを生成させ、次いで前記反応帯域に原料を噴霧導入してカーボンブラックを含む反応ガス流を形成させた後、反応停止帯域にて、多段急冷媒体導入手段により、該反応ガス流を急冷して、反応を終結させることにより得られ、該多段急冷媒体導入手段でのトルエン着色透過度が、下記式(１)及び(２)；
１０＜Ｘ＜４０ ・・・ (１)
９０＜Ｚ＜１００ ・・・ (２)
（式中、Ｘは原料導入位置から第１番目の急冷媒体導入後のカーボンブラックのトルエン着色透過度(％)で、Ｚは最後の急冷媒体導入後のカーボンブラックのトルエン着色透過度(％)である）の関係を満たすことを特徴とする。

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating Obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex represented by , An aromatic vinyl compound-conjugated diene compound copolymer in which the cis-1,4 bond content of the conjugated diene compound portion is 80% or more, and the carbon black (B However, using a reactor in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are connected in series, high-temperature combustion gas is generated in the combustion gas generation zone, and then the raw material is sprayed into the reaction zone The reaction gas flow containing carbon black is formed, and then the reaction gas flow is quenched in the reaction stop zone by the multistage rapid refrigerant introduction means to terminate the reaction. The toluene coloring transmittance in the introducing means is represented by the following formulas (1) and (2);
10 <X <40 (1)
90 <Z <100 (2)
(In the formula, X is the toluene coloring permeability (%) of carbon black after introduction of the first quenching medium from the raw material introduction position, and Z is the toluene coloring permeability (%) of carbon black after the last quenching medium introduction. It is characterized by satisfying the relationship of

The carbon black (B)
The residence time in the zone from when the raw material is sprayed into the reaction zone until the first quenching medium is introduced is t ₁ (seconds), the average reaction temperature in this zone is T ₁ (° C.), The residence time in the zone from the introduction of the first quenching medium to the introduction of the quenching medium by the second quenching medium introduction means (12-Y in FIG. 1) is t ₂ (seconds). The average reaction temperature in the zone is T ₂ (° C.), and the residence time in the zone from the introduction of the second quenching medium until the last quenching medium is introduced (ie, until the reaction stop zone passes) The residence time in this zone is t ₃ (seconds) and the average reaction temperature in this zone is T ₃ (° C.).
The following formula (3), formula (4) and formula (5);
2.00 ≦ α1 ≦ 5.00 (3)
5.00 ≦ α2 ≦ 9.00 (4)
−2.5 × (α1 + α2) + 85.0 ≦ β ≦ 90.0 (5)
It may be obtained by controlling so as to satisfy the relationship (where α1 = t ₁ × T ₁ , α2 = t ₂ × T ₂ , β = t ₃ × T ₃ ).

Further, the carbon black (B) has the following formulas (6), (7) and (8);
20 <X <40 (6)
50 <Y <60 (7)
90 <Z <95 (8)
(Where Y represents the toluene-colored permeability of carbon black after introduction of the second quenching medium, and X and Z have the same meanings as described above). Also good.

Here, the hydrogen release rate of the carbon black for rubber compounding (B) is preferably more than 0.3% by mass, the dibutyl phthalate absorption amount (DBP) is 95 to 220 mL / 100 g, and the compressed DBP absorption amount ( 24M4DBP) is desirably 90 to 200 mL / 100 g, and cetyltrimethylammonium bromide adsorption specific surface area (CTAB) is desirably 70 to 200 m ² / g.

  The vinyl bond content of the conjugated diene compound portion of the aromatic vinyl compound-conjugated diene compound copolymer (A) is desirably 10% or less, and NMR measurement of the repeating unit of the aromatic vinyl compound portion is performed. It is desirable that the block amount of is 10% or less of the total aromatic vinyl compound portion.

Furthermore, in the DSC measurement of the aromatic vinyl compound-conjugated diene compound copolymer (A), it is desirable to have a melting point (Tm), and the aromatic vinyl compound-conjugated diene compound copolymer (A) is A styrene-butadiene copolymer is desirable.
The tread rubber and tire of the present invention are obtained by using the above rubber composition.

  According to the present invention, an aromatic vinyl compound-conjugated diene compound copolymer (A) obtained by a specific production method, and a carbon black (B) having a small amount of tar components, particularly polycyclic aromatic components, present on the surface. By blending, it is possible to obtain a rubber composition that particularly improves wear resistance while maintaining a high balance between reduced rolling resistance and wear resistance in the tire due to these synergistic effects. Become.

  By using such a rubber composition, it is possible to realize a high-performance tire in which wear resistance and rolling resistance are highly balanced.

It is a longitudinal front explanatory view of an example of a carbon black manufacturing furnace for manufacturing carbon black (B) used for a rubber composition of the present invention.

Hereinafter, the present invention will be specifically described with reference to the drawings as necessary.
The rubber composition of the present invention is
A rubber composition obtained by blending carbon black (B) in an amount of 10 to 250 parts by mass with respect to 100 parts by mass of a rubber component containing an aromatic vinyl compound-conjugated diene compound copolymer (A). ,
The aromatic vinyl compound-conjugated diene compound copolymer (A) is represented by the following general formula (I):

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｒ^a〜Ｒ^fは、それぞれ独立して炭素数１〜３のアルキル基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、及び下記一般式(II)；

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II);

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^Rは、それぞれ独立して無置換もしくは置換インデニルを示し、Ｘ^’は、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示す）で表されるメタロセン錯体、並びに下記一般式(III)；

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ^′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and the following general formula (III );

（式中、Ｍは、ランタノイド元素、スカンジウム又はイットリウムを示し、Ｃｐ^R’は、無置換もしくは置換シクロペンタジエニル、インデニル又はフルオレニルを示し、Ｘは、水素原子、ハロゲン原子、アルコキシド基、チオラート基、アミド基、シリル基又は炭素数１〜２０の炭化水素基を示し、Ｌは、中性ルイス塩基を示し、ｗは、０〜３の整数を示し、[Ｂ]⁻は、非配位性アニオンを示す）で表されるハーフメタロセンカチオン錯体からなる群より選択される少なくとも１種類の錯体を含む重合触媒組成物の存在下、芳香族ビニル化合物及び共役ジエン化合物を付加重合して得られた、共役ジエン化合物部分のシス-１,４結合量が８０％以上の芳香族ビニル化合物−共役ジエン系化合物共重合体であり、かつ
前記カーボンブラック（Ｂ）が、燃焼ガス生成帯域と、反応帯域と、反応停止帯域とが連設されてなる反応装置を用い、前記燃焼ガス生成帯域内で高温燃焼ガスを生成させ、次いで前記反応帯域に原料を噴霧導入してカーボンブラックを含む反応ガス流を形成させた後、反応停止帯域にて、多段急冷媒体導入手段により、該反応ガス流を急冷して、反応を終結させることにより得られ、該多段急冷媒体導入手段でのトルエン着色透過度が、下記式(１)及び(２)；
１０＜Ｘ＜４０ ・・・ (１)
９０＜Ｚ＜１００ ・・・ (２)
(式中、Ｘは原料導入位置から第１番目の急冷媒体導入後のカーボンブラックのトルエン着色透過度(％)で、Ｚは最後の急冷媒体導入後のカーボンブラックのトルエン着色透過度(％)である)の関係を満たすことを特徴とする。

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating Obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex represented by , An aromatic vinyl compound-conjugated diene compound copolymer in which the cis-1,4 bond content of the conjugated diene compound portion is 80% or more, and the carbon black (B However, using a reactor in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are connected in series, high-temperature combustion gas is generated in the combustion gas generation zone, and then the raw material is sprayed into the reaction zone The reaction gas flow containing carbon black is formed, and then the reaction gas flow is quenched in the reaction stop zone by the multistage rapid refrigerant introduction means to terminate the reaction. The toluene coloring transmittance in the introducing means is represented by the following formulas (1) and (2);
10 <X <40 (1)
90 <Z <100 (2)
(In the formula, X is the toluene coloring permeability (%) of carbon black after introduction of the first quenching medium from the raw material introduction position, and Z is the toluene coloring permeability (%) of carbon black after the last quenching medium introduction. It is characterized by satisfying the relationship of

[Aromatic vinyl compound-conjugated diene compound copolymer (A)]
The aromatic vinyl compound-conjugated diene compound copolymer (A) of the present invention “hereinafter also referred to as copolymer (A)” has a very high cis-1,4 bond amount in the conjugated diene compound portion, and A rubber composition using an aromatic vinyl compound-conjugated diene compound copolymer (A) as a rubber component is a rubber composition using a conventional aromatic vinyl compound-conjugated diene compound copolymer obtained by anionic polymerization. Wet skid resistance compared to a rubber composition using a blend of an aromatic vinyl compound-conjugated diene compound copolymer and a homopolymer of a conjugated diene compound having a high cis-1,4 bond amount The wear resistance can be improved while maintaining the property at a high level. The reason for this is not necessarily clear, but it seems to be due to the effect of improving the wear resistance due to the crystallinity derived from the amount of cis-1,4 bonds in the conjugated diene compound portion. Here, the amount of cis-1,4 bonds in the conjugated diene compound portion needs to be 80% or more, and preferably 90% or more. When the amount of cis-1,4 bonds in the conjugated diene compound portion is less than 80%, the cis chain is insufficient, so the melting point (Tm) is not measured, and the wear resistance decreases. The amount of cis-1,4 bonds in the conjugated diene compound portion can be determined from the integration ratio of ¹ H-NMR spectrum and ¹³ C-NMR spectrum, and the specific method is disclosed in JP-A-2004-27179. It is disclosed.

  In the aromatic vinyl compound-conjugated diene compound copolymer (A) of the present invention, the vinyl bond content of the conjugated diene compound portion is preferably 10% or less, and more preferably 5% or less. If the amount of vinyl bonds in the conjugated diene compound portion exceeds 10%, the amount of cis-1,4 bonds decreases and the effect of improving wear resistance cannot be sufficiently obtained.

  The aromatic vinyl compound-conjugated diene compound copolymer (A) is not particularly limited except that a polymerization catalyst composition described in detail later is used. For example, an addition polymer using a normal coordination ion polymerization catalyst. In the same manner as in the above production method, it can be obtained by copolymerizing a mixture of a monomeric aromatic vinyl compound and a conjugated diene compound. As a polymerization method, any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used. When a solvent is used for the polymerization reaction, the solvent used may be inert in the polymerization reaction, and the amount of the solvent used is arbitrary, but the concentration of the complex contained in the polymerization catalyst composition is 0.1 to The amount is preferably 0.0001 mol / l. Here, examples of the aromatic vinyl compound include styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like. Among these, styrene Is preferred. On the other hand, examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene is preferable. Therefore, a styrene-butadiene copolymer is particularly preferable as the aromatic vinyl compound-conjugated diene compound copolymer (A) of the present invention.

  The polymerization catalyst composition used for the synthesis of the aromatic vinyl compound-conjugated diene compound copolymer (A) of the present invention includes a metallocene complex represented by the above general formula (I) and formula (II), and the above general formula ( It is necessary to include at least one complex selected from the group consisting of the half metallocene cation complexes represented by III), and further, other components contained in the polymerization catalyst composition including a normal metallocene complex, such as an auxiliary It preferably contains a catalyst or the like.

In the metallocene complexes represented by the above general formulas (I) and (II), Cp ^R in the formula is unsubstituted indenyl or substituted indenyl. Cp ^R having an indenyl ring as a basic skeleton can be represented by C ₉ H _7-X R _X or C ₉ H _11-X R _X. Here, X is an integer of 0-7 or 0-11. In addition, each R is preferably independently a hydrocarbyl group or a metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of the substituted indenyl include 2-phenylindenyl, 2-methylindenyl and the like. In addition, two Cp ^R in the general formula (I) and the formula (II) may be the same or different from each other.

In the half metallocene cation complex represented by the general formula (III), Cp ^{R ′} in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton is represented by C ₅ H _5-X R _X. Here, X is an integer of 0-5. Moreover, it is preferable that R is respectively independently a hydrocarbyl group; metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group. Specific examples of Cp ^{R ′} having a cyclopentadienyl ring as a basic skeleton include the following.

（式中、Ｒは水素原子、メチル基又はエチル基を示す。）

(In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)

In the general formula (III), Cp ^{R ′} having the indenyl ring as a basic skeleton is defined in the same manner as Cp ^{R in the} general formula (I), and preferred examples thereof are also the same.

In the general formula (III), Cp ^{R ′} having the fluorenyl ring as a basic skeleton can be represented by C ₁₃ H _9-X R _X or C ₁₃ H _17-X R _X. Here, X is an integer of 0-9 or 0-17. Moreover, it is preferable that R is respectively independently a hydrocarbyl group; metalloid group. The hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms. Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. On the other hand, examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there. Specific examples of the metalloid group include a trimethylsilyl group.

  The central metal M in the general formula (I), formula (II) and formula (III) is a lanthanoid element, scandium or yttrium. The lanthanoid elements include 15 elements having atomic numbers 57 to 71, and any of these may be used. Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.

The metallocene complex represented by the general formula (I) contains a bistrialkylsilylamide ligand [—N (SiR ₃ ) ₂ ]. The alkyl groups R (R ^{a to} R ^f in the general formula (I)) contained in the bistrialkylsilylamide are each independently an alkyl group having 1 to 3 carbon atoms, and is preferably a methyl group.

The metallocene complex represented by the general formula (II) contains a silyl ligand [—SiX ^′ ₃ ]. X ^′ contained in the silyl ligand [—SiX ^′ ₃ ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.

  In the general formula (III), X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms. Here, examples of the alkoxide group include aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group; phenoxy group and 2,6-di- -tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.

  In the general formula (III), the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thio sec-butoxy group, a thio tert-butoxy group and the like Thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group is preferable.

  In the general formula (III), the amide group represented by X includes aliphatic amide groups such as dimethylamide group, diethylamide group and diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2 2,6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamide groups such as 6-neopentylphenylamide group, 2,4,6-tert-butylphenylamide group; and bistrialkylsilylamide groups such as bistrimethylsilylamide group. Among these, bistrimethylsilylamide group is preferable.

  In the general formula (III), examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like. Among these, a tris (trimethylsilyl) silyl group is preferable.

  In the general formula (III), the halogen atom represented by X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc. Others: Examples include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.

  In the general formula (III), X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.

In the general formula (III), [B] ^- The non-coordinating anion represented by, for example, a tetravalent boron anion. Specific examples of the tetravalent boron anion include tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaoundecaborate is exemplified, and among these, tetrakis (pentafluorophenyl) borate is preferable.

  The metallocene complex represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are further 0 to 3, preferably 0 to 1 neutral. Contains Lewis base L. Here, examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like. Here, when the complex includes a plurality of neutral Lewis bases L, the neutral Lewis bases L may be the same or different.

  Further, the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.

  The metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction examples for obtaining the metallocene complex represented by the general formula (I) are shown below.

（式中、Ｘ^’’はハライドを示す。）

(In the formula, X ^″ represents a halide.)

  The metallocene complex represented by the general formula (II) includes, for example, a lanthanoid trishalide, scandium trishalide or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt). In addition, since reaction temperature should just be about room temperature, it can manufacture on mild conditions. The reaction time is arbitrary, but is about several hours to several tens of hours. The reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. The reaction examples for obtaining the metallocene complex represented by the general formula (II) are shown below.

（式中、Ｘ^’’はハライドを示す。）

(In the formula, X ^″ represents a halide.)

  The half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.

Here, in the compound represented by the general formula (IV), M represents a lanthanoid element, scandium or yttrium, and Cp ^{R ′} independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl. , X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, and w represents 0 to 3 Indicates an integer. In the ionic compound represented by the general formula [A] ⁺ [B] ⁻ , [A] ⁺ represents a cation, and [B] ⁻ represents a non-coordinating anion.

Examples of the cation represented by [A] ⁺ include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal. Examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation. Examples of the tri (substituted phenyl) carbonyl cation include tri (methylphenyl). ) Carbonium cation and the like. Examples of amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation. Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. Among these cations, N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.

The ionic compound represented by the general formula [A] ⁺ [B] ⁻ used in the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Nitrotetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like are preferable. In general formula [A] ⁺ [B] ^- ionic compounds represented by is preferably added from 0.1 to 10 mol per mol of the metallocene complex, more preferably it added about 1 molar. When the half metallocene cation complex represented by the general formula (III) is used for the polymerization reaction, the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] ⁺ [B] ^- provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this. Further, by using a combination of a metallocene complex represented by the general formula (I) or the formula (II) and an ionic compound represented by the general formula [A] ⁺ [B] ⁻ , A half metallocene cation complex represented by the formula (III) can also be formed.

  The structures of the metallocene complexes represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are preferably determined by X-ray structural analysis.

  The co-catalyst that can be used in the polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex. Suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.

  The aluminoxane is preferably an alkylaluminoxane, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. As the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem Co., Ltd.) and the like are preferable. The content of aluminoxane in the polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable.

  On the other hand, examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable. Examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum. In addition, it is preferable that it is 1-50 times mole with respect to a metallocene complex, and, as for content of the organoaluminum compound in the said polymerization catalyst composition, it is still more preferable that it is about 10 times mole.

  Furthermore, in the polymerization catalyst composition, the metallocene complex represented by the general formula (I) and the formula (II), and the half metallocene cation complex represented by the general formula (III), respectively, are used as appropriate promoters. By combining them, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.

  The method for producing the aromatic vinyl compound-conjugated diene compound copolymer (A) is represented by the metallocene complex represented by the general formula (I) and the general formula (II), and the general formula (III). It includes a step of subjecting an aromatic vinyl compound and a conjugated diene compound to addition polymerization in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex. Moreover, this manufacturing method can be the same as the manufacturing method of the addition polymer by the addition polymerization reaction using the conventional coordination ion polymerization catalyst except using the polymerization catalyst composition mentioned above as a polymerization catalyst. Here, such a production method provides, for example, (1) a component of the polymerization catalyst composition separately in a polymerization reaction system containing an aromatic vinyl compound and a conjugated diene compound as monomers, May be a polymerization catalyst composition, or (2) a previously prepared polymerization catalyst composition may be provided in the polymerization reaction system. Moreover, (2) includes providing a metallocene complex (active species) activated by a cocatalyst. In addition, the usage-amount of the metallocene complex contained in a polymerization catalyst composition has the preferable range of 1/10000-1/100 times mole with respect to a monomer.

  Further, the number average molecular weight (Mn) of the obtained copolymer (A) of the present invention is not particularly limited, and the problem of lowering the molecular weight does not occur. Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 3 or less, and more preferably 2 or less. Here, the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).

  The addition polymerization reaction is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas.

  Although the polymerization temperature of the addition polymerization reaction is not particularly limited, for example, a range of −100 ° C. to 200 ° C. is preferable, and can be about room temperature. When the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered. On the other hand, the reaction time of the above addition polymerization reaction is not particularly limited, and is preferably in the range of, for example, 1 second to 10 days, but is appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature. Can do.

In the aromatic vinyl compound-conjugated diene compound copolymer (A) of the present invention, the amount of blocks in the NMR measurement of the repeating unit of the aromatic vinyl compound portion is 10% or less of the total aromatic vinyl compound portion. Preferably, it is more preferably 7% or less, particularly preferably 0%. The copolymer of the present invention obtained by using the polymerization catalyst composition tends to polymerize the aromatic vinyl compound at random, and can inhibit blocking of the aromatic vinyl compound. Here, the term “random” means that the amount of block in the NMR measurement of the repeating unit of the aromatic vinyl compound portion (hereinafter sometimes referred to as “block aromatic vinyl compound content”) is 10% or less of the total aromatic vinyl compound portion. The block refers to an aromatic vinyl compound portion having an aromatic vinyl compound-aromatic vinyl compound bond. When the content of the block aromatic vinyl compound exceeds 10%, the behavior of the aromatic vinyl compound as a homopolymer appears, the glass transition temperature increases, and the wear resistance may decrease. In addition, a block aromatic vinyl compound content rate can be calculated | required from the integral ratio of a < ¹ > H-NMR spectrum.

  Furthermore, the aromatic vinyl compound-conjugated diene compound copolymer (A) of the present invention exhibits a melting point (Tm) in DSC measurement (differential scanning calorimetry). Here, the melting point (Tm) in DSC measurement refers to the melting point of a static crystal derived from a chain of conjugated diene compound portions.

  In addition, as a rubber component used with the rubber composition of this invention, you may use combining the rubber component normally used in the rubber industry besides the said aromatic vinyl compound-conjugated diene compound copolymer (A). Specifically, for example, natural rubber, butadiene-isoprene rubber, polybutadiene (BR), acrylonitrile-butadiene rubber (NBR), silicone rubber, fluorine elastomer, ethylene / acrylic rubber, ethylene propylene rubber (EPR), ethylene / propylene / Examples include diene monomer (EPDM) rubber, butyl rubber, polychloroprene, hydrogenated nitrile rubber, and mixtures thereof.

[Carbon black (B)]
(B) carbon black used in the present invention uses a reaction apparatus in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are connected in series, and generates high-temperature combustion gas in the combustion gas generation zone, Next, the raw material is spray-introduced into the reaction zone to form a reaction gas stream containing carbon black, and then the reaction gas stream is rapidly cooled in the reaction stop zone by a multistage rapid refrigerant introduction means to terminate the reaction. The method for producing the carbon black will be described in detail below with reference to the drawings.

  FIG. 1 is a longitudinal front explanatory view of an example of a carbon black production furnace for producing carbon black (B). The interior of the carbon black production furnace 1 has a structure in which a combustion zone, a reaction zone, and a reaction stop zone are connected in series, and the whole is covered with a refractory. Moreover, the carbon black production furnace 1 rectifies the oxygen-containing gas introduced from the outer periphery of the furnace head and the oxygen-containing gas introduction pipe by the oxygen-containing gas introduction pipe as a combustion zone using a rectifying plate, and combustible fluid. An oxygen-containing gas introduction cylinder to be introduced into the introduction chamber, and a fuel oil spray device introduction pipe that is installed on the central axis of the oxygen-containing gas introduction cylinder and introduces combustion hydrocarbons into the combustible fluid introduction chamber. In the combustion zone, high-temperature combustion gas is generated by combustion of combustion hydrocarbons.

  The carbon black production furnace 1 includes, as a reaction zone, a condensing chamber in which a cylinder gradually converges, a raw material oil introducing chamber including four raw material oil spray ports on the downstream side of the converging chamber, and a reaction chamber on the downstream side of the raw material oil introducing chamber. 10. The feed oil spray port sprays feed hydrocarbons into the hot combustion gas stream from the combustion zone. In the reaction zone, the raw material hydrocarbon is sprayed into the high-temperature combustion gas stream, and the raw material hydrocarbon is converted into carbon black by incomplete combustion or thermal decomposition reaction.

  The carbon black production furnace 1 includes a reaction continuation / cooling chamber 11 having a multistage rapid refrigerant introduction means 12 as a reaction stop zone. The multistage rapid refrigerant introduction means 12 sprays a rapid refrigerant such as water on the high-temperature combustion gas flow from the reaction zone. In the reaction stop zone, the high-temperature combustion gas flow is quenched by the quenching refrigerant to terminate the reaction. The carbon black production furnace 1 may further include a device for introducing a gas body in the reaction zone or the reaction stop zone. Here, as the “gas body”, air, a mixture of oxygen and hydrocarbon, a combustion gas obtained by a combustion reaction thereof, or the like can be used. In this way, in the production of carbon black, the average reaction temperature and residence time in each zone until the reaction gas flow enters the reaction stop zone are controlled, and the toluene coloring permeability X, Y of carbon black at each stage is controlled. Carbon black (B) is obtained by setting Z and Z to desired values.

  Next, each zone in the carbon black production furnace 1 will be described. The combustion zone is a region where a high-temperature gas flow is generated by the reaction of fuel and air, and this downstream end is the point at which the feedstock is introduced into the reactor (the most upstream when introduced at multiple locations) ). The reaction zone refers to the multistage quench water spray means 12 in the reaction continuation / cooling chamber 11 from the point where the raw material hydrocarbon is introduced (the most upstream in the case of a plurality of positions) (these means are the reaction continuation / cooling chamber). 11 can be inserted and removed freely, and the use position is selected according to the type of product to be produced and the characteristics thereof) to the point of operation (introducing a cooling medium such as water). That is, when the raw material oil is introduced through the raw material oil spraying port and the water is introduced by the multistage rapid refrigerant introduction means 12, the region between these becomes the reaction zone. The reaction stop zone refers to a zone below (on the right side in FIG. 1) the point where the quenching water injection spray means is operated. In FIG. 1, the name of the reaction continuation / cooling chamber 11 is used because the reaction zone is from the raw material introduction time point to the operation time point of the quenching water injection spray means for stopping the reaction, and the reaction stop zone is thereafter. This is because the cold water introduction position may move depending on the required carbon black performance.

The carbon black (B) obtained by the above production method needs to satisfy the relationship of the following formulas (1) and (2). In FIG. 1, X is the toluene coloring permeability (%) of carbon black after the rapid refrigerant introduction from the first rapid refrigerant introduction means 12 -X, and Z is the final rapid refrigerant introduction means 12. -Z is the toluene coloring permeability (%) of carbon black after rapid refrigerant introduction. Here, if the carbon black (B) satisfies the relationship of the following formulas (1) and (2), the balance of the carbon black particle size and the surface physical properties can be achieved by defining the toluene coloring permeability step by step. This can increase the reinforcement and improve the wear resistance.
10 <X <40 (1)
90 <Z <100 (2)

As described above, the carbon black (B) having such properties can be obtained by controlling the reaction temperature and residence time. For example, the residence time in the zone from when the raw material is sprayed into the reaction zone until the first quenching medium is introduced is t ₁ (seconds), and the average reaction temperature in this zone is T ₁ (° C.). And the residence time in the zone from the introduction of the first quenching medium to the introduction of the quenching medium by the second quenching medium introducing means (12-Y in FIG. 1) is t ₂ (seconds). The average reaction temperature in this zone is T ₂ (° C.), and the residence time in the zone from the introduction of the second sudden refrigerant body to the introduction of the last sudden refrigerant body (ie, the reaction stop zone) When the residence time in the zone until passage) is t ₃ (seconds) and the average reaction temperature in this zone is T ₃ (° C.), the residence time and average reaction temperature are represented by the following formulas (3) and (3): (4) and formula (5):
2.00 ≦ α1 ≦ 5.00 (3)
5.00 ≦ α2 ≦ 9.00 (4)
−2.5 × (α1 + α2) + 85.0 ≦ β ≦ 90.0 (5)
By controlling to satisfy the relationship (where α1 = t ₁ × T ₁ , α2 = t ₂ × T ₂ , β = t ₃ × T ₃ ), the carbon black (B) can be reliably Obtainable.

The carbon black production furnace 1 has a structure in which thermocouples can be inserted into an arbitrary number of locations in order to monitor the temperature in the furnace. To calculate the average reaction temperature T _1, T _2, T _3, at each step (each band), at least two positions, preferably it is preferable to measure the temperature of 3-4 points. Further, the residence times t ₁ , t ₂ , and t ₃ are calculated by calculating the volume of the introduced reaction gas fluid by a known thermodynamic calculation method, and calculating by the following formula. Note that the increase in volume due to the decomposition reaction of the feedstock oil and the rapid cooling medium is ignored.
Residence time t ₁ (sec) = reactor passage volume from raw material hydrocarbon introduction position to first quenching medium introduction position (m ³ ) / reaction gas fluid volume (m ³ / sec)
Residence time t ₂ (sec) = reactor passage volume (m ³ ) / volume of reaction gas fluid (m ³ / sec) from the first abrupt refrigerant introduction position until the second abrupt refrigerant is introduced
Residence time t ₃ (sec) = reactor passage volume (m ³ ) / volume of reaction gas fluid (m ³ / sec) from the second abrupt refrigerant introduction position to the last abrupt refrigerant introduction

Further, as the carbon black (B), the following relational expressions (6), (7) and (8)
20 <X <40 (6)
50 <Y <60 (7)
90 <Z <95 (8)
(Where Y represents the toluene-colored transmittance of carbon black after introduction of the second quenching medium, and X and Z are as defined above) Can be used.
The toluene coloring transmittance is measured by the method described in Method B of Item 8 of JIS K 6218: 1997, and is expressed as a percentage with pure toluene.

  The carbon black (B) preferably has a hydrogen release rate of more than 0.3% by mass, more preferably 0.35% by mass or more. The upper limit is not particularly limited, but is usually about 0.4% by mass. When the hydrogen release rate exceeds 0.3% by mass, the wear resistance of the rubber composition of the present invention is further improved, and the heat generation is further reduced.

  The hydrogen release rate is as follows: (1) a carbon black sample is dried in a constant temperature dryer at 105 ° C. for 1 hour, cooled to room temperature in a desiccator, and (2) about 10 mg is added to a tubular tube sample container made of tin. Weigh accurately, press and seal, and (3) measure the amount of hydrogen gas generated when heated at 2000 ° C for 15 minutes under an argon stream with a hydrogen analyzer (Horiba EMGA621W), and display the mass fraction. The

Further, the carbon black (B) has a dibutyl phthalate absorption (DBP) of 95 to 220 mL / 100 g, a compressed DBP absorption (24M4DBP) of 90 to 200 mL / 100 g, and a cetyltrimethylammonium bromide adsorption specific surface area (CTAB) of 70. What is -200 m < ² > / g is preferable.

The dibutyl phthalate absorption amount (DBP) and the compressed DBP absorption amount (24M4DBP) are measured by the method described in ASTM D2414-88 (JIS K6217-4: 2001), and are absorbed per 100 g of carbon black. DBP) in mL. Further, the cetyltrimethylammonium bromide adsorption specific surface area (CTAB) is measured by the method described in JIS K6217-3: 2001 and is expressed as a specific surface area m ² / g per unit mass of carbon black.

  As the carbon black (B), those produced by the above-described method and having the above-mentioned physical properties are used. Examples of the carbon black include FEF, SRF, HAF, ISAF, ISAF-LS, SAF- LS etc. are mentioned.

  Carbon black (B) is 10 to 250 parts by weight, preferably 20 to 150 parts by weight, more preferably 100 parts by weight of rubber component containing the aromatic vinyl compound-conjugated diene compound copolymer (A). Is contained in an amount of 30 to 120 parts by mass. If the blending amount of the carbon black (B) is less than 10 parts by mass, the rubber composition cannot be sufficiently strengthened. On the other hand, if it exceeds 250 parts by mass, the dispersibility of the carbon black (B) decreases. In addition, the wear resistance, tear resistance and heat generation resistance of the rubber composition may be lowered.

[Rubber composition]
In addition to the aromatic vinyl compound-conjugated diene compound copolymer (A) and carbon black (B), the rubber composition of the present invention includes a compounding agent commonly used in the rubber industry, such as an anti-aging agent, A softener, a filler other than carbon black (B), a silane coupling agent, a vulcanization accelerator, a vulcanization accelerator, a vulcanizer, and the like are appropriately selected and blended within a range that does not impair the object of the present invention. can do. As these compounding agents, commercially available products can be suitably used. In addition, examples of the filler other than the carbon black (B) include silica, wet silica and dry silica are preferable, and wet silica is more preferable.

  The rubber composition of the present invention is prepared by blending an aromatic vinyl compound-conjugated diene compound copolymer (A) with carbon black (B) and various compounding agents appropriately selected as necessary, kneading and heating. It can be produced by extrusion or the like.

[Treads and tires]
The rubber composition can be applied to any tire member, but is preferably used for a tread. A tire employing such a tread has a low rolling resistance and is particularly excellent in wear resistance. The tire of the present invention is not particularly limited except that the above rubber composition is used for the tread, and can be produced according to a conventional method. Moreover, as gas with which this tire is filled, inert gas, such as nitrogen, argon, helium other than normal or the air which adjusted oxygen partial pressure, can be used.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Production of carbon blacks A to D]
Carbon blacks A to D were manufactured using the carbon black manufacturing furnace 1 shown in FIG. Here, as the multistage cooling medium introducing means 12, a three-stage rapid cooling comprising a first rapid refrigerant introducing means 12-X, a second rapid refrigerant introducing means 12-Y, and a final rapid refrigerant introducing means 12-Z. Media introduction means were used. Moreover, in order to monitor the temperature in a manufacturing furnace, the said manufacturing furnace provided with the structure which can insert a thermocouple in an arbitrary several places in a furnace was used. In the carbon black production furnace, A heavy oil having a specific gravity of 0.8622 (15 ° C / 4 ° C) was used as the fuel, and heavy oil having the properties shown in Table 1 was used as the raw material oil. In addition, carbon blacks A to D having the following physical properties were produced according to the operating conditions of the carbon black production furnace shown in Table 2, respectively.

The resulting carbon black A~D, ASTM D2414-88 (JIS K6217-97) to conform dibutyl phthalate (DBP) absorption amount, compliance with the nitrogen adsorption specific surface area ASTM D3037-88 (N ₂ SA) The specific coloring power (TINT) was measured according to ASTM D3265-88, and the toluene coloring transmittance was measured according to JIS K6218-97. The results are shown in Table 2.

[Synthesis of Half Metallocene Cation Complex Represented by General Formula (III)]
In the production of the polymers A to B shown below, a half metallocene cation complex represented by the general formula (III) ([(2-MeC ₉ H ₆ ) GdN (SiMe ₃ ) ₂ (THF) ₃ ) commonly used. ] [B (C ₆ F ₅ ) ₄ ]) was synthesized and its structure was confirmed by ¹ H-NMR and X-ray crystal structure analysis. ¹ H-NMR was measured at room temperature using THF-d8 as a solvent. X-ray crystal structure analysis was performed using RAXIS CS (Rigaku).

Under a nitrogen atmosphere, triethylanilinium tetrakisphenylborate (Et ₃ NHB (C ₆ H ₆ ) ₄ ) was added to 5 mL of a solution of (2-MeC ₉ H ₆ ) ₂ GdN (SiMe ₃ ) ₂ (0.150 g, 0.260 mmol) in THF. (0.110 g, 0.260 mmol) was added and stirred at room temperature for 12 hours. Thereafter, THF was distilled off under reduced pressure, and the resulting residue was washed three times with hexane to obtain an oily compound. The residue was recrystallized with a THF / hexane mixed solvent to produce [(2-MeC ₉ H ₆ ) GdN (SiMe ₃ ) ₂ (THF) ₃ ] [B (C ₆ F ₅ ) ₄ ] (150 mg as white crystals). 59%). The structure was confirmed by X-ray crystal analysis.

[Production of Polymer A]
In a glove box under a nitrogen atmosphere, 104 g (1 mol) of styrene and 50 g of toluene were added to a well-dried 1 L pressure-resistant glass bottle, and the bottle was stoppered. Thereafter, the bottle was taken out from the glove box, and 54 g (1 mol) of 1,3-butadiene was charged into a monomer solution. Meanwhile, in a glove box under a nitrogen atmosphere, 40 μmol of bis (2-methylindenyl) gadolinium (trimethylsilylamide) [(2-MeC ₉ H ₆ ) ₂ GdN (SiMe ₃ ) ₂ ] in a glass container ₄₀ μmol of phenylcarbonium tetrakis (pentafluorophenyl) borate (Ph ₃ CB (C ₆ F ₅ ) ₄ ) and 1 mmol of diisobutylaluminum halide were charged and dissolved in 10 ml of toluene to obtain a catalyst solution. Thereafter, the catalyst solution was taken out from the glove box, added to the monomer solution, and polymerized at 70 ° C. for 30 minutes. After polymerization, the reaction was stopped by adding 10 ml of a 10 mass% methanol solution of 2,6-bis (t-butyl) -4-methylphenol (BHT), and the polymer was separated with a large amount of methanol / hydrochloric acid mixed solvent. And vacuum dried at 60 ° C. The yield of the obtained polymer A was 47 g.

[Production of polymer B]
Polymerization was carried out in the same manner as for Polymer A, except that the amount of diisobutylaluminum halide used in the catalyst solution was 0.8 mmol. The yield of the obtained polymer B was 46 g.

  For the polymers A to B and the following polymers C to D produced as described above, the number average molecular weight (Mn), molecular weight distribution (Mw / Mn), microstructure, bound styrene content, block styrene content, glass transition The point (Tg) and the melting point (Tm) were measured by the following methods. The results are shown in Table 3.

<< Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) >>
Gel permeation chromatography [GPC: Tosoh HLC-8020, column: Tosoh GMH-XL (two in series), detector: differential refractometer (RI)], based on monodisperse polystyrene, The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) in terms of polystyrene were determined.

<< Microstructure and bound styrene content >>
The microstructure of the polymer was determined from the integration ratio of ¹ H-NMR spectrum and ¹³ C-NMR spectrum, and the amount of bound styrene of each polymer was determined from the integration ratio of ¹ H-NMR spectrum. ¹ H-NMR and ¹³ C-NMR were measured at 120 ° C. using 1,1,2,2-tetrachloroethane as a solvent.

<Block styrene content>
The ratio of the block amount (block styrene content) in the NMR measurement of the repeating unit of the styrene portion to the total styrene portion was determined from the integral ratio of the ¹ H-NMR spectrum.

<< Glass transition point (Tg) (° C) and melting point (Tm) (° C) >>
A sample weighing 10 mg ± 0.5 mg, put in an aluminum measuring pan and covered, was heated from room temperature to 50 ° C. with a DSC apparatus (TA Instruments) and stabilized for 10 minutes. After cooling to −80 ° C. and stabilizing at −80 ° C. for 10 minutes, the glass transition point (Tg) and melting point (Tm) were measured while raising the temperature to 50 ° C. at a rate of 10 ° C./min. .

  From the detailed NMR data of the sample, no styrene-styrene bond was particularly confirmed.

* 1: Styrene-butadiene copolymer, manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Toughden 1000
* 2: Styrene-butadiene copolymer, manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Toughden 2000

[Examples 1-2, Comparative Examples 1-4]
Using the carbon blacks A to D and the polymers A to D, a rubber composition having a compounding formulation shown in Table 4 was prepared, and the rubber composition was obtained by vulcanization under normal conditions. The wet skid resistance and abrasion resistance of each were measured by the following methods. The results are shown in Table 5.

《Abrasion resistance》
The amount of wear was measured at room temperature using a Lambone-type wear tester, the reciprocal of the amount of wear was calculated, and indexed with Comparative Example 1 being 100. The larger the index value, the smaller the amount of wear and the better the wear resistance.

《Rolling resistance》
The rolling resistance at 80 km / h was measured for the test tire under normal load and internal pressure, and the rolling resistance of Comparative Example 1 was indicated as 100 and indicated as an index. It shows that rolling resistance is so small that an index value is small.

* 3: Table 5 shows the types of polymers used in Examples 1-2 and Comparative Examples 1-4.
* 4: Table 5 shows the types of carbon blacks used in Examples 1-2 and Comparative Examples 1-4.
* 5: Nocrac 6C, N-(1,3-dimethylbutyl) -N ^'- phenyl -p- phenylenediamine, manufactured by Ouchi Shinko Chemical Industrial Co., Ltd.
* 6: Noxeller CZ, N-cyclohexyl-2-benzothiazylsulfenamide, Ouchi Shinsei Chemical Co., Ltd.

  According to Table 5, the copolymer (A) is included as compared with Examples 1 and 2 containing the specific aromatic vinyl compound-conjugated diene compound copolymer (A) and carbon black (B). Compared to Comparative Examples 1 to 2 and Comparative Examples 3 to 4 that do not contain such carbon black (B), the results clearly show superior results in both wear resistance and rolling resistance, and these copolymers (A) and It can be seen that carbon black (B) exhibits a very excellent synergistic effect particularly in improving the wear resistance.

DESCRIPTION OF SYMBOLS 1 Carbon black production furnace 10 Reaction chamber 11 Reaction continuation and cooling chamber 12 Multistage rapid refrigerant body introduction means 12-X First rapid refrigerant body introduction means 12-Y Second rapid refrigerant body introduction means 12-Z Last sudden refrigerant body introduction means

Claims (11)

A rubber composition obtained by blending carbon black (B) in an amount of 10 to 250 parts by mass with respect to 100 parts by mass of a rubber component containing an aromatic vinyl compound-conjugated diene compound copolymer (A). ,
The aromatic vinyl compound-conjugated diene compound copolymer (A) is represented by the following general formula (I):

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R independently represents unsubstituted or substituted indenyl, and R ^{a to} R ^f each independently represents an alkyl having 1 to 3 carbon atoms. A group, L represents a neutral Lewis base, w represents an integer of 0 to 3), and the following general formula (II);

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^R each independently represents an unsubstituted or substituted indenyl group, and X ^′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group. , A silyl group or a hydrocarbon group having 1 to 20 carbon atoms, L represents a neutral Lewis base, w represents an integer of 0 to 3, and the following general formula (III );

(In the formula, M represents a lanthanoid element, scandium or yttrium, Cp ^{R ′} represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group. represents an amide group, a silyl group or a hydrocarbon group having a carbon number of 1 to 20, L is a neutral Lewis base, w is, an integer of 0 to 3, [B] ^- is a non-coordinating Obtained by addition polymerization of an aromatic vinyl compound and a conjugated diene compound in the presence of a polymerization catalyst composition containing at least one complex selected from the group consisting of a half metallocene cation complex represented by , An aromatic vinyl compound-conjugated diene compound copolymer in which the cis-1,4 bond content of the conjugated diene compound portion is 80% or more, and the carbon black (B However, using a reactor in which a combustion gas generation zone, a reaction zone, and a reaction stop zone are connected in series, high-temperature combustion gas is generated in the combustion gas generation zone, and then the raw material is sprayed into the reaction zone The reaction gas flow containing carbon black is formed, and then the reaction gas flow is quenched in the reaction stop zone by the multistage rapid refrigerant introduction means to terminate the reaction. The toluene coloring transmittance in the introducing means is represented by the following formulas (1) and (2);
10 <X <40 (1)
90 <Z <100 (2)
(In the formula, X is the toluene coloring permeability (%) of carbon black after introduction of the first quenching medium from the raw material introduction position, and Z is the toluene coloring permeability (%) of carbon black after the last quenching medium introduction. The rubber composition characterized by satisfying the relationship of The carbon black (B)
The residence time in the zone from when the raw material is sprayed into the reaction zone until the first quenching medium is introduced is t ₁ (seconds), the average reaction temperature in this zone is T ₁ (° C.), The residence time in the zone from the introduction of the first quenching medium to the introduction of the quenching medium by the second quenching medium introduction means (12-Y in FIG. 1) is t ₂ (seconds). The average reaction temperature in the zone is T ₂ (° C.), and the residence time in the zone from the introduction of the second quenching medium until the last quenching medium is introduced (ie, until the reaction stop zone passes) The residence time in this zone is t ₃ (seconds) and the average reaction temperature in this zone is T ₃ (° C.).
The following formula (3), formula (4) and formula (5);
2.00 ≦ α1 ≦ 5.00 (3)
5.00 ≦ α2 ≦ 9.00 (4)
−2.5 × (α1 + α2) + 85.0 ≦ β ≦ 90.0 (5)
_2. It is obtained by controlling so as to satisfy the relationship (where α1 = t ₁ × T ₁ , α2 = t ₂ × T ₂ , β = t ₃ × T ₃ ). The rubber composition as described. The carbon black (B) has the following formulas (6), (7) and (8);
20 <X <40 (6)
50 <Y <60 (7)
90 <Z <95 (8)
(Wherein Y represents the toluene-colored permeability of carbon black after introduction of the second quenching medium, and X and Z have the same meanings as described above). The rubber composition according to claim 1 or 2.   2. The rubber composition according to claim 1, wherein a hydrogen release rate of the carbon black (B) exceeds 0.3 mass%. In the carbon black (B), dibutyl phthalate absorption (DBP) is 95 to 220 mL / 100 g, compressed DBP absorption (24M4DBP) is 90 to 200 mL / 100 g, and cetyltrimethylammonium bromide adsorption specific surface area (CTAB) is 70 to It is 200 m < ² > / g, The rubber composition of Claim 1 characterized by the above-mentioned.   2. The rubber composition according to claim 1, wherein the vinyl bond content of the conjugated diene compound portion of the aromatic vinyl compound-conjugated diene compound copolymer (A) is 10% or less.   The block amount in the NMR measurement of the repeating unit of the aromatic vinyl compound part of the aromatic vinyl compound-conjugated diene compound copolymer (A) is 10% or less of the total aromatic vinyl compound part, The rubber composition according to claim 1.   The rubber composition according to claim 1, which has a melting point (Tm) in DSC measurement of the aromatic vinyl compound-conjugated diene compound copolymer (A).   The rubber composition according to claim 1, wherein the aromatic vinyl compound-conjugated diene compound copolymer (A) is a styrene-butadiene copolymer.   A tread rubber obtained using the rubber composition according to claim 1.   A tire obtained using the rubber composition according to claim 1.

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