JP2011116920A - Rubber composition and tire using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition that exhibits an excellent traction performance, while retaining the balance between reduced rolling resistance and wear resistance at a high level, and a tire using the composition. <P>SOLUTION: The rubber composition includes (A) a diene rubber, (B) a metal soap expressed by formula (I), and (C) a carbon black for rubber compounding that has specific characteristics obtained by a specific production process and meets specific requirements [wherein, M is a metal having an oxidation state of +3 or +4; R is an each independently selected organic portion; and n is the valency of M]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a rubber composition containing a specific metal soap and carbon black and capable of exhibiting particularly excellent wear resistance and wet performance, 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, not only carbon black but also an additive capable of improving tire traction performance and durability while keeping rolling resistance low is highly desired.

JP 2005-272734 A

  However, even with carbon black as described above, there is still room for improvement from the standpoint of further improving the two contradictory performances of durability and rolling resistance, and there is a significant improvement in these performances. Additives that can contribute have not yet been realized.

  Accordingly, the present invention provides a rubber composition capable of exhibiting excellent traction performance while maintaining a high balance between reduced rolling resistance and wear resistance in a tire, and a tire using the rubber composition. It is an object.

  In order to solve the above problems, the present inventor has found a rubber composition containing a specific metal soap and carbon black having a specific property obtained by a specific manufacturing method, and has completed the present invention.

That is, the rubber composition of the present invention is
(A) Diene rubber,
(B) a metal soap represented by the following formula (I);

［式中、Ｍは酸化状態が＋３又は＋４の金属であり、Ｒはそれぞれ独立して選択された有機部分であり、ｎはＭの原子価である］、及び
（Ｃ）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たゴム配合用カーボンブラックを含有し、かつ
前記ゴム配合用カーボンブラック（Ｃ）が、下記条件（ｉ）及び（ii）；
（ｉ）前記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；
（ii）前記ジエン系ゴム（Ａ）１００質量部に対して、ゴム配合用カーボンブラック（Ｃ）を、１０〜２５０質量部の量で含有する；
を満たすことを特徴とする。

[Wherein M is a metal with an oxidation state of +3 or +4, R is an independently selected organic moiety, and n is the valence of M], and (C) a combustion gas generation zone; , A reaction apparatus in which a reaction zone and a reaction stop zone are connected to each other, a high-temperature combustion gas is generated in the combustion gas generation zone, and then a raw material is sprayed into the reaction zone to contain carbon black. Containing a carbon black for rubber compounding obtained by quenching the reaction gas stream by a multistage rapid refrigerant introduction means in the reaction stop zone after forming the gas stream, and terminating the reaction, and Carbon black for rubber compounding (C) has the following conditions (i) and (ii);
(I) The toluene coloring permeability in the multistage rapid refrigerant introduction 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. Satisfy the relationship of
(Ii) The rubber compounding carbon black (C) is contained in an amount of 10 to 250 parts by mass with respect to 100 parts by mass of the diene rubber (A);
It is characterized by satisfying.

In the formula (I), n-1 may be 2 or 3, and the (O ₂ CR) group may be derived from a fatty acid having 6 or more carbon atoms.
Moreover, it is preferable that the said metal soap (B) is a thing which does not melt | dissolve in water.
The diene rubber (A) is preferably selected from the group consisting of styrene-butadiene rubber, butadiene rubber, isoprene rubber, natural rubber, and combinations thereof.
Furthermore, the metal soap (B) is desirably contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the diene rubber (A), and is a soap of aluminum and a carboxylic acid derivative. It may also be selected from the group consisting of diethylhexanoic acid aluminum soap and dilauric acid aluminum soap.

The rubber composition preferably further contains a silica filler (D), and the silica filler (D) is preferably silane-treated silica.
Moreover, it is desirable that the molecules of the metal soap (B) form a micelle structure or a structure represented by the formula (II) in a nonpolar solvent.

［式中、ｘは自然数である］。

[Wherein x is a natural number].

In the formula (I), R may comprise an alkyl chain having at least one unsaturated unit, and R may comprise an alkyl chain having one or more sulfur curable double bonds, such double The bond may be between two non-terminal carbons in the alkyl chain.
Further, the metal soap (B) is preferably an aluminum soap of dioleic acid.

The carbon black for rubber compounding (C) is
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 formulas (3), (4) and (5);
2.00 ≦ α1 ≦ 5.00 (3)
5.00 ≦ α2 ≦ 9.00 (4)
−2.5 × (α1 + α2) + 85.0 ≦ β ≦ 90.0 (5)
It is desirable to obtain it by controlling so as to satisfy the relationship [where α1 = t ₁ × T ₁ , α2 = t ₂ × T ₂ , β = t ₃ × T ₃ ], and the following equation (6 ), (7) and (8);
20 <X <40 (6)
50 <Y <60 (7)
90 <Z <95 (8)
It is desirable that Y be obtained by controlling so as to satisfy the relationship [wherein Y represents the toluene coloring permeability of carbon black after introduction of the second quenching medium, and X and Z are as defined above].

Here, the hydrogen release rate of the carbon black for rubber blending (C) 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 tread rubber and tire of the present invention are obtained by using the above rubber composition.

  According to the present invention, by blending a specific metal soap (B) with a tar component present on the surface, particularly carbon black (C) having a small amount of polycyclic aromatic components, these synergistic effects result in the tire. While maintaining a high level of balance between reduced rolling resistance and wear resistance, it can also exhibit excellent traction performance, and in particular, it is possible to obtain a rubber composition that greatly improves wear resistance and wet performance It becomes.

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

It is a vertical front explanatory drawing of an example of the carbon black manufacturing furnace for manufacturing carbon black (C) used for the 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) Diene rubber,
(B) a metal soap represented by the following formula (I);

［式中、Ｍは酸化状態が＋３又は＋４の金属であり、Ｒはそれぞれ独立して選択された有機部分であり、ｎはＭの原子価である］、及び
（Ｃ）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たゴム配合用カーボンブラックを含有し、かつ
前記ゴム配合用カーボンブラック（Ｃ）が、下記条件（ｉ）及び（ii）；
（ｉ）前記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；
（ii）前記ジエン系ゴム（Ａ）１００質量部に対して、ゴム配合用カーボンブラック（Ｃ）を、１０〜２５０質量部の量で含有する；
を満たすことを特徴としている。

[Wherein M is a metal with an oxidation state of +3 or +4, R is an independently selected organic moiety, and n is the valence of M], and (C) a combustion gas generation zone; , A reaction apparatus in which a reaction zone and a reaction stop zone are connected to each other, a high-temperature combustion gas is generated in the combustion gas generation zone, and then a raw material is sprayed into the reaction zone to contain carbon black. Containing a carbon black for rubber compounding obtained by quenching the reaction gas stream by a multistage rapid refrigerant introduction means in the reaction stop zone after forming the gas stream, and terminating the reaction, and Carbon black for rubber compounding (C) has the following conditions (i) and (ii);
(I) The toluene coloring permeability in the multistage rapid refrigerant introduction 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. Satisfy the relationship of
(Ii) The rubber compounding carbon black (C) is contained in an amount of 10 to 250 parts by mass with respect to 100 parts by mass of the diene rubber (A);
It is characterized by satisfying.

  In the present specification, “di-soap” means a soap having two carboxylic acid groups. Thus, “mono-soap” and “tri-soap” mean soaps having one and three carboxylic acid groups.

[Diene rubber (A)]
The diene rubber (A) used in the present invention is a rubber component in the rubber composition of the present invention, and is, for example, one or more conjugated dienes such as styrene-butadiene rubber, butadiene rubber, isoprene rubber, or natural rubber. be able to. The diene rubber can be any treadstock rubber conventionally used. Such rubbers are well known to those skilled in the art and include, but are not limited to, natural rubber, synthetic polyisoprene rubber, styrene-butadiene rubber (SBR), styrene-isoprene rubber, styrene-isoprene-butadiene rubber, butadiene-isoprene. Rubber, polybutadiene (BR), acrylonitrile-butadiene rubber (NBR), silicone rubber, fluoroelastomer, ethylene / acrylic rubber, ethylene propylene rubber (EPR), ethylene / propylene / diene monomer (EPDM) rubber, butyl rubber, polychloroprene, hydrogen Nitrile rubber, and mixtures thereof. Among these, it is desirable to be selected from the group consisting of styrene-butadiene rubber, butadiene rubber, isoprene rubber, natural rubber, and combinations thereof.

[Metal soap (B)]
The metal soap (B) used in the present invention is represented by the above formula (I). In formula (I), M is a metal having an oxidation state of +3 or +4. For example, scandium (Sc), yttrium (Y), lanthanum (La), actinium (Ac), chromium (Cr), iron (Fe) , Cobalt (Co), ruthenium (Ru), iridium (Ir), gallium (Ga), indium (In), titanium (Ti), manganese (Mn), germanium (Ge), tin (Sn), aluminum (Al) And lead (Pb). M may be a group III metal (group 13 of IUPAC) or a transition metal excluding zinc, copper and nickel, and may be iron, titanium, aluminum or cobalt.

  Especially, it is preferable that it is a metal which does not melt | dissolve in polar solvents, such as water, and can form the metal soap (B) which does not dissociate into ion in polar solvents, such as water. The metal soap (B) that does not dissolve in water dissolves well in the rubber composition containing the diene rubber component. As the metal of the metal soap (B) dissolved in the polar solvent, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr); beryllium (Be), Alkaline metals such as magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra) and most alkaline earth metals, zinc (Zn), mercury (Hg) and cadmium ( Some transition metals such as Cd) are mentioned.

  In formula (I), each R is an independently selected organic moiety, may contain a hydrogen atom, and may contain an alkyl chain having at least one or more unsaturated units. “Organic moiety” means any chemical group consisting primarily of carbon, oxygen, nitrogen or hydrogen, including organic groups that may contain heteroatoms. Since each R group can be independently selected, for example, one R group can be a hydrocarbon chain of 6 carbon atoms, and the other R group can be carbonized with 7 carbon atoms. It can be a hydrogen chain. Specific examples include hydrogen, linear or branched hydrocarbon chains, and linear or branched hydrocarbon chains containing various organic or inorganic functional groups.

In the formula (I), the carboxylic acid group ((O ₂ CR) group) may be derived from, for example, a C ₂ to C ₅ acid, a C ₆ to C ₂₂ fatty acid, or a C ₂₃ to C _50. Higher fatty acids such as those described above may be used, and those derived from C ₆ or higher fatty acids are preferred. Specific examples of the acid include lauric acid and ethylhexanoic acid, and the M (O ₂ CR) _n group is preferably formed from these carboxylic acid derivatives and metals. That is, the metal soap (B) is preferably a soap of a metal and a carboxylic acid derivative, and is optimally a soap of aluminum and a carboxylic acid derivative, for example, an aluminum soap of dilauric acid, An aluminum soap of diethylhexanoic acid may be used, and an aluminum soap of dioleic acid is preferable.

  In formula (I), n is the valence of M, indicates the number of R groups, and can be, for example, 1, 2, 3, 4, 5, or 6, depending on the metal element used. Specifically, for example, when M is aluminum, n-1 can be 2, and when M is titanium, n-1 can be 2 or 3.

  It has been found that by adding the metal soap (B) to the tire tread composed of the diene rubber (A), a significant improvement is obtained in tensile strength, tear strength and wet traction properties. In addition, the rolling resistance is maintained at a similar level. Such metal soap (B) preferably includes aluminum di-soap and the like, when dispersed in a non-polar organic solvent, the metal soap (B) is somewhat similar to an elastic liquid polymer. Shows behavior. Furthermore, in a nonpolar solvent, the metal soap (B) forms a somewhat cluster-like aggregate like the structure represented by the following formula (II).

式（II）中、ｘは自然数である。

In formula (II), x is a natural number.

  The hydrogen bond represented by formula (II) further allows the molecular aggregate of metal soap (B) to become micelles and other forms. This produces a very viscous elastic liquid or gel. When the metal soap (B) is an aluminum di-soap, the adjacent di-soap chains are composed of van der Waals forces between hydrocarbon chains, hydrogens of shared hydroxyl ions and oxygen atoms of carboxyl groups. Are held together by both hydrogen bonds between. In addition to the above aluminum soaps, other metal soaps having a +3 or +4 oxidation state are also considered to exhibit similar types of unique aggregates in nonpolar solvents as well. Among these metals, preferred metals are those that can be dissolved in a non-polar solvent and form cluster-like aggregates when the metal soap (B) is formed. Specific examples of metals that can form the structure of formula (II) or other cluster-like structures are aluminum and iron and titanium. Other metals that may be able to form such a structure are metals in the +3 or +4 oxidation state. Among these, aluminum di-soaps such as dioleic acid aluminum soaps are the only aluminum soaps known to be associated with the structure of formula (II) above.

It is particularly effective when the metal soap (B) containing at least one unsaturated unit in the R group, that is, an O ₂ CR group containing one or more double bonds, is combined with a rubber matrix and vulcanized. . Without being bound by theory, it is believed that the double bond contributes to improving cross-linking with the diene rubber matrix. The acid preferably contains at least one unsaturated unit. For example, the acid may be a C ₂ to C ₅ monounsaturated acid, a C ₆ to C ₂₂ monounsaturated fatty acid, such as C ₂₃ to C ₅₀ It may be a monounsaturated higher fatty acid. Specific examples include oleic acid. The acid may also contain multiple double bonds, such as two or three double bonds, in the alkyl chain. The one or more double bonds must be sulfur curable double bonds. In the example including a plurality of double bonds, the double bonds may be conjugated. At least one double bond or all double bonds may be between two non-terminal carbons in the alkyl chain. For example, the double bond may be in the center of the alkyl chain as in oleic acid or in the vicinity thereof.

  Without being bound by theory, improved cross-linking due to double bonds in the R group, tensile strength at 25 ° C. and 100 ° C., 170 ° C., while maintaining good rolling resistance. Tear strength and wet traction characteristics are improved.

  The metal soap (B) is usually 1 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 100 parts by weight, more preferably 100 parts by weight of the diene rubber (A). It is contained in the rubber composition in an amount of 5 to 30 parts by mass or 15 to 50 parts by mass. These amounts are in contrast to zinc soaps that have been used for many years in the rubber industry. Such zinc soap dissolves in a typical diene rubber only up to about 4 parts by mass with respect to 100 parts by mass of the diene rubber. Above about 4 parts by weight, the zinc soap floats on the rubber surface and acts as "bloom". The metal soap (B) described here is preferably used in an amount up to 200 parts by weight avoiding any “bloom”.

  The metal soap (B) is prepared by the following method. A polar solvent, a base, and an organic species including a carboxylic acid are combined and mixed together to form solution A. A base is added to neutralize the acid and promote dissolution. The base may be added so that the pH of the solution A before adding the solution of the metal ion source becomes basic. For example, the metal may have an oxidation state of +3 or +4, and in other embodiments may be a group III (group 13 of IUPAC) or a transition metal excluding zinc, nickel and copper. . The metal may be selected from the group consisting of aluminum, iron, titanium and cobalt.

Examples of polar solvents include, but are not limited to, water, THF, acetone, acetonitrile, DMF, DMSO, acetic acid, n-butanol, isopropanol, n-propanol, ethanol, or methanol. Typical bases include but are not limited to sodium hydroxide, potassium hydroxide, potassium carbonate, calcium carbonate and ammonia. Typical chemical species containing a carboxylic acid group correspond to those described above in the discussion of the metal soap, C ₂ -C ₅ acid, C ₆ fatty acids -C _22, exclusive of such acids C ₂₃ -C ₅₀ Fatty acids, preferably C ₆ or higher fatty acids. Specific examples include lauric acid and ethylhexanoic acid.

The metal ion source solution is then added to solution A and mixed to form product A. The metal ion source solution may be prepared by adding a metal ion source in a polar solvent such as water to form the solution B. The metal ion source can be, for example, formula (III);
M _l Z _m (III)
Where M is the above metal, Z is selected from the group consisting of potassium sulfate, hydroxide, sulfate and phosphate, and l and m are each independently And an integer of 1-20. For example, potassium aluminum sulfate is known to be inexpensive and effective as a metal ion source for aluminum.

  Solution A and solution B are then mixed together to form product A. Stirring and heating may be used to encourage the metal ions in solution B to bind to the carboxylic acid group-containing species, thereby creating a metal soap that is insoluble in polar solvents. Product A contains metal soap (B) and may contain other reaction residues such as potassium sulfate and / or water.

  The metal soap (B) may be synthesized by a technique that promotes the formation of a cluster-like structure such as a micelle type structure or a structure of formula (II) with a high proportion of molecules. For example, in aluminum soap, di-soap is a molecule that is believed to form the structure of formula (II). However, mono- and tri-aluminum soaps do not associate with these structures. Therefore, in this respect it is beneficial to maximize the formation of aluminum di-soap. For other metal soaps generally represented by formula (I), it is preferred that one OH is hanging from the metal ion and the remaining valence is filled with organic moieties.

Aluminum di-soap molecules can be promoted by slowly adding solution B to solution A as opposed to abruptly combining the two solutions. Changing the temperature and concentration of solutions A and B is another method that affects the production of mono-, di-, or tri-soap. The number of (O ₂ CR) groups can be adjusted by changing the relative amounts of metal ions and O ₂ CR molecules. For example, the formation of aluminum di-soap can be achieved by using an aluminum source and an O ₂ CR molecular source, an aluminum ion to O ₂ CR molecule ratio of about 1: 2, eg, 1: 1.5 to 1: 2.5. It can be encouraged by adding in ratio.

  In a further step, product A is isolated from the solvent. For example, in the case of dilauric acid aluminum soap, diethylhexanoic acid aluminum soap, and dioleic acid aluminum soap, product A can be isolated by washing it with water and drying it, thereby reducing the purity. About 99% of a powdered product is produced. Wash off all other reaction residues in product A with water.

  In another step, the isolated metal soap (B) is dissolved in a nonpolar solvent to form solution X. The nonpolar solvent can be, for example, hexane, benzene, cyclohexane or toluene. Agitation and heating may be used to facilitate dissolution. The metal soap (B) molecule may form a cluster-like structure, for example, a structure represented by the formula (II) in a basic nonpolar solvent, and as a result, a very viscous elastic material. Will be generated.

  In a further step, the solution X is combined with a diene rubber composition containing the diene rubber (A) described later. Any of the diene rubbers described above may be selected. Again, stirring and heating may be used to help the metal soap (B) solution dissolve in the rubber composition.

[Carbon black for rubber compounding (C)]
The carbon black for rubber blending (C) 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 the high temperature combustion gas is generated in the combustion gas generation zone. Then, after the raw material is sprayed and introduced into the reaction zone to form a reaction gas flow containing carbon black, the reaction gas flow is quenched in the reaction stop zone by the multistage rapid refrigerant introduction means, In the following, a method for producing the carbon black will be described in detail 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 (C) for rubber compounding. 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. And by making Z into a desired value, carbon black (C) for rubber | gum compounding is obtained.

  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 rubber compounding carbon black (C) 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 (C) for rubber blending satisfies the relationship of the following formulas (1) and (2), the particle size and surface physical properties of the carbon black are determined by defining the toluene coloring permeability step by step. Balance can be achieved, reinforcing property can be improved, and wear resistance can be improved.
10 <X <40 (1)
90 <Z <100 (2)

As described above, the rubber compounding carbon black (C) having such properties can be obtained by controlling the reaction temperature and the 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)
Carbon black for rubber blending (C) by controlling so as to satisfy the relationship [where α1 = t ₁ × T ₁ , α2 = t ₂ × T ₂ , β = t ₃ × T ₃ ] Can be definitely obtained.

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 for rubber blending (C), the following relational expressions (6), (7) and (8)
20 <X <40 (6)
50 <Y <60 (7)
90 <Z <95 (8)
Preferred are those obtained by controlling so as to satisfy the relationship [wherein Y represents the toluene-colored permeability 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 for rubber blending (C) 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 for rubber blending (C) 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, a cetyltrimethylammonium bromide adsorption specific surface area (CTAB). ) Is preferably 70 to 200 m ² / g.

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.

  The rubber compounding carbon black (C) is manufactured by the above-described method and has the above-described physical properties. Examples of the carbon black include FEF, SRF, HAF, ISAF, and ISAF-LS. , SAF-LS and the like.

  Carbon black for rubber compounding (C) is contained in an amount of 10 to 250 parts by weight, preferably 20 to 150 parts by weight, more preferably 30 to 120 parts by weight with respect to 100 parts by weight of the diene rubber (A). Is done. If the blending amount of the carbon black for rubber blending (C) is less than 10 parts by mass, sufficient reinforcement of the rubber composition cannot be ensured. On the other hand, if it exceeds 250 parts by mass, the carbon black for blending rubber (C ) May decrease, and the rubber composition may have reduced wear resistance, tear resistance, and heat resistance.

  Here, the rubber composition of the present invention preferably contains a silica filler (D) in addition to the rubber compounding carbon black (C) as a filler, specifically, a rubber compounding carbon black. The silica filler (D) is added to 100 parts by mass of the diene rubber (A) in a rubber composition in which the blending amount of (C) is less than 60 parts by mass with respect to 100 parts by mass of the diene rubber (A). By blending in the range of 20 parts by mass or less, preferably in the range of 20 to 80 parts by mass, it is possible to ensure the reinforcing property (abrasion resistance) of the rubber composition, and further greatly reduce the hysteresis loss of the rubber composition. can do. That is, the silica filler can be blended in a suitable amount without reducing the blending amount of the carbon black for rubber blending (C) more than necessary, and the low loss and reinforcing properties (wear resistance) of the rubber composition Compatibility) is possible at a high level.

  The silica filler (D) is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), and calcium silicate. Among these, hydrous silica by a precipitated amorphous wet process is preferable. The upper limit of useful usage is limited by the high viscosity provided by this type of filler. Some of the commercially available silicas that can be used are not particularly limited, but include HiSil (R) 190, HiSil (R) 210, HiSil (R) produced by PPG Industries (Pittsburgh, PA). (Trademark) 215, HiSil (registered trademark) 233, HiSil (registered trademark) 243, and the like. Many useful commercial grades of various silicas are also available from Evonik (eg, VN2, VN3), Rhodia (eg, Zeosil® 1165MP0), and J. Org. M.M. Available from Hoover.

  When the silica filler (D) is used, it is desirable to perform a silane treatment using a coupling agent in order to bind the silica to the polymer. Many coupling agents are known and include, but are not limited to, organic sulfide polysulfides. Any organosilane polysulfide may be used.

  Although it does not specifically limit as a polysulfide of a suitable organosilane, 3,3'-bis (trimethoxysilylpropyl) disulfide, 3,3'-bis (triethoxysilylpropyl) disulfide, 3,3 ' -Bis (triethoxysilylpropyl) tetrasulfide, 3,3'-bis (triethoxysilylpropyl) octasulfide, 3,3'-bis (trimethoxysilylpropyl) tetrasulfide, 2,2'-bis (triethoxy Silylethyl) tetrasulfide, 3,3′-bis (trimethoxysilylpropyl) trisulfide, 3,3′-bis (triethoxysilylpropyl) trisulfide, 3,3′-bis (tributoxysilylpropyl) disulfide, 3,3′-bis (trimethoxysilylpropyl) hexasulfi 3,3′-bis (trimethoxysilylpropyl) octasulfide, 3,3′-bis (trioctoxysilylpropyl) tetrasulfide, 3,3′-bis (trihexoxysilylpropyl) disulfide, 3, 3'-bis (tri-2 "-ethylhexoxysilylpropyl) trisulfide, 3,3'-bis (triisooctoxysilylpropyl) tetrasulfide, 3,3'-bis (tri-t-butoxysilylpropyl) ) Disulfide, 2,2′-bis (methoxydiethoxysilylethyl) tetrasulfide, 2,2′-bis (tripropoxysilylethyl) pentasulfide, 3,3′-bis (tricycloneoxysilylpropyl) tetrasulfide, 3,3′-bis (tricyclopentoxysilylpropyl) trisulfide, 2, '-Bis (tri-2 "-methylcyclohexoxysilylethyl) tetrasulfide, bis (trimethoxysilylmethyl) tetrasulfide, 3-methoxyethoxypropoxysilyl 3'-diethoxybutoxy-silylpropyl tetrasulfide, 2,2' -Bis (dimethylmethoxysilylethyl) disulfide, 2,2'-bis (dimethylsecbutoxysilylethyl) trisulfide, 3,3'-bis (methylbutylethoxysilylpropyl) tetrasulfide, 3,3'-bis (di t-butylmethoxysilylpropyl) tetrasulfide, 2,2′-bis (phenylmethylmethoxysilylethyl) trisulfide, 3,3′-bis (diphenylisopropoxysilylpropyl) tetrasulfide, 3,3′-bis (diphenyl) Cyclohexo Sisilylpropyl) disulfide, 3,3′-bis (dimethylethylmercaptosilylpropyl) tetrasulfide, 2,2′-bis (methyldimethoxysilylethyl) trisulfide, 2,2′-bis (methylethoxypropoxysilylethyl) Tetrasulfide, 3,3′-bis (diethylmethoxysilylpropyl) tetrasulfide, 3,3′-bis (ethyldi-secbutoxysilylpropyl) disulfide, 3,3′-bis (propyldiethoxysilylpropyl) disulfide, 3, , 3′-bis (butyldimethoxysilylpropyl) trisulfide, 3,3′-bis (phenyldimethoxysilylpropyl) tetrasulfide, 3′-trimethoxysilylpropyltetrasulfide, 4,4′-bis (trimethoxysilylbutyl) ) Tetra Sulfide, 6,6′-bis (triethoxysilylhexyl) tetrasulfide, 12,12′-bis (triisopropoxysilyldodecyl) disulfide, 18,18′-bis (trimethoxysilyloctadecyl) tetrasulfide, 18,18 '-Bis (tripropoxysilyloctadecenyl) tetrasulfide, 4,4'-bis (trimethoxysilyl-buten-2-yl) tetrasulfide, 4,4'-bis (trimethoxysilylcyclohexylene) tetrasulfide 5,5′-bis (dimethoxymethylsilylpentyl) trisulfide, 3,3′-bis (trimethoxysilyl-2-methylpropyl) tetrasulfide, 3,3′-bis (dimethoxyphenylsilyl-2-methylpropyl) ) Disulfide and 3-octanoylthio 1-propyltriethoxysilane (NXT) may be mentioned. Also, a mixture of these various polysilane compounds of organosilanes can be used.

  The amount of the coupling agent in the rubber composition is based on the mass of the silica filler (D) in the rubber composition. The amount of the coupling agent is 0.1% by mass to 20% by mass, preferably 1% by mass to 15% by mass, of the silica filler (D).

[Rubber composition]
The rubber composition of the present invention comprises the above diene rubber (A), metal soap (B), carbon black for rubber blending (C), and optionally a silica filler (D), vulcanizing agent, vulcanizing agent. Accelerator, oil, tackifier resin, anti-aging agent, fatty acid, wax, peptizer, vulcanization retarder, activator, processing additive, plasticizer, pigment, and antiozonant Contains one or more components.

  Examples of vulcanizing agents include sulfur and sulfur donating compounds. The compounding quantity of this vulcanizing agent is 0.1-10 mass parts with respect to 100 mass parts of diene rubber (A), Preferably it is 1-5 mass parts. Specific examples include 1.5 parts by mass, 1.7 parts by mass, 1.87 parts by mass, and 2.0 parts by mass.

  The vulcanization accelerator is not particularly limited. A number of accelerators are known in the art and include, but are not limited to, diphenylguanidine (DPG), tetramethylthiuram disulfide (TMTD), 4,4′-dithiodimorpholine (DTDM), tetrabutyl Examples include thiuram disulfide (TBTD), benzothiazyl disulfide (MBTS), and 2- (morpholinothio) benzothiazole (MBS). Examples of the blending amount of the accelerator include 0.25 parts by mass, 0.5 parts by mass, 1.0 part by mass, 1.5 parts by mass, and 1. parts by mass with respect to 100 parts by mass of the diene rubber (A). 65 mass parts and 2.0 mass parts are mentioned. Two or more of these accelerators may be used in combination.

  Oil has been conventionally used as a compounding aid in rubber compositions. Examples of oils include, but are not limited to, aromatic process oils, naphthenic process oils, and / or paraffinic process oils. For some applications, it is preferred to use low polycyclic aromatic (PCA) oils, particularly oils having a PCA content of less than 3%. The suitable amount of oil used is usually in a wide range of 0 to 100 parts by weight, preferably 0 to 70 parts by weight, more preferably 0 to 50 parts by weight, with respect to 100 parts by weight of the rubbery matrix in the rubber composition. For example, the amount can be 15 parts by mass, 20 parts by mass, or 30 parts by mass. In a typical embodiment, metal soap (B) is used to replace part of the oil in the rubber compound or all of the oil. For example, 1% to 100%, 5% to 50%, or 10% to 40% of the oil may be replaced with metal soap (B).

  Certain additional fillers may also be used, including mineral fillers such as clay, talc, aluminum hydrate, aluminum hydroxide and mica. These additional fillers are optional, and can be used in an amount of 0.5 to 40 parts by mass with respect to 100 parts by mass of the diene rubber (A), for example.

  Further, the anti-aging agent is, for example, 0.5 parts by mass, 1 part by mass, 1.5 parts by mass, 2.0 parts by mass, 2.5 parts by mass, etc. with respect to 100 parts by mass of the diene rubber (A). May be used in an amount of. Two or more of such anti-aging agents may be used simultaneously.

  In addition to the diene rubber (A), metal soap (B), carbon black for rubber blending (C), and optionally silica filler (D), vulcanizing agent, vulcanization accelerator, oil, tackifying resin One or more components selected from the group consisting of antioxidants, fatty acids, waxes, peptizers, vulcanization retarders, activators, processing additives, plasticizers, pigments and antiozonants, rubber May be compounded in a manner generally known in the art of blending techniques, for example, by using standard rubber mixing equipment and techniques, and mixing the above ingredients together in the desired amounts used. Further, for example, the diene rubber composition may be prepared by emulsion polymerization, solution polymerization, or bulk polymerization according to a known appropriate method. In general, ingredients can be mixed in an internal mixer such as a Brabender or a small Banbury mixer, and shearing forces are included, so the compounding process is generally exothermic and usually hot.

  In one embodiment, the rubber composition comprises (a) an elastomer, carbon black or carbon black and silica filler in the absence of added sulfur and curing agent at a temperature of 130 ° C. to 200 ° C. (fall temperature). (B) cooling the mixture below the mixing temperature, (c) lowering the mixture obtained in step (b) below the vulcanization temperature. In the step of mixing with a curing agent and an amount of sulfur effective to achieve a satisfactory cure, and (d) curing the mixture obtained in step (c). The formulation is usually cured at 140 ° C. to 190 ° C. for 5 to 120 minutes. Also, the drop temperature for mixing the components together can be 145 ° C to 190 ° C, or 155 ° C to 180 ° C.

  The initial mixing step can include at least two sub-steps. That is, the first mixing step is (i) a sub-step of mixing together elastomer and at least a part of the filler at a temperature of 130 ° C. to 180 ° C., and (ii) cooling the mixture to a temperature lower than the mixing temperature. Sub-steps, and (iii) if present, can include a sub-step of mixing the remaining filler with the mixture obtained in sub-step (ii). The temperature achieved by the at least two sub-processes may be the same or different from each other within the temperature range.

  The above method may further include a remilling step in which no components are added to the first mixture or uncured components are added to reduce the viscosity of the formulation and improve the dispersion of the reinforcing filler. The metal soap (B) can be added in the remill process. The drop temperature in the remill process is usually 130 ° C. to 175 ° C., for example, 145 ° C. to 165 ° C.

  The final step of the mixing process is the addition of a curing agent containing an amount of sulfur effective to achieve a satisfactory cure in the final formulation. The temperature at which the final mixture is mixed must be below the vulcanization temperature to avoid unwanted precuring of the formulation. Therefore, the temperature of the final mixing step should not exceed 120 ° C, and is usually 40 ° C to 120 ° C, preferably 60 ° C to 110 ° C, and more preferably 75 ° C to 100 ° C.

[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 excellent wear resistance, low rolling resistance, high traction performance, and particularly excellent wet performance. 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 black XY]
Carbon black XY was 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. Further, carbon blacks X to Y having the physical properties shown below were manufactured according to the operating conditions of the carbon black manufacturing furnace shown in Table 2.

The resulting carbon black X~Y, 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.

[Manufacture of metal soap Z (sodium dioleate)
To a 1.9 L glass bottle, 2000 mL of water and 40 g (1 mol) of sodium hydroxide (purity 99 +%, manufactured by Aldrich) were added. After the sodium hydroxide was completely dissolved, 313 g oleic acid (purity 90%, made by Aldrich) was added. The mixture was then mixed vigorously at 75 ° C. for 1 hour until the solution was completely clear. Hereinafter, this solution is referred to as “solution A”.

  To another 1.9 L glass bottle, 2000 mL of water and 238 g of potassium aluminum sulfate (purity 99 +%, Aldrich) were added. The mixture was then mixed vigorously at 75 ° C. for 1 hour until the solution was completely clear. Hereinafter, this solution is referred to as “solution B”.

  The warm solutions A and B were then combined and under vigorous stirring, this combination produced a gel-like material. In this case, Solution B was slowly added into Solution A at a rate of about 100 mL / min. This material was washed 8 times with deionized water and then vacuum dried at 65 ° C. overnight. The final product (aluminum dioleate soap) was a white powder, and was easily dissolved in toluene and mixed into a diene rubber.

[Example 1, Comparative Examples 1-3]
A rubber composition having the formulation shown in Table 3 was prepared according to a conventional method using the metal soap Z and carbon blacks X to Y as required, and the rubber composition was applied to a tread rubber. Size: 11R22. A heavy-duty tire No. 5 was prototyped according to a conventional method, and rolling resistance, abrasion resistance and tear resistance were evaluated by the following methods. The results are shown in Table 3.

《Abrasion resistance》
The amount of wear after the test tire was mounted on the drive shaft of the truck and traveled 100,000 km was measured. The larger the index value, the smaller the wear amount 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.

《Friction coefficient on wet road surface (WETμ)》
The resistance value when the wet concrete road surface was rubbed with a vulcanized rubber test piece using a British portable skid tester manufactured by Stanley London Co., Ltd. was indicated as an index with Comparative Example 1 being 100. The larger the value, the higher the coefficient of friction (μ) on the wet road surface, indicating better wet traction characteristics.

* 1: Styrene-butadiene copolymer, Toughden 100, manufactured by Asahi Kasei Corporation
* 2: Carbon black X for rubber compound obtained by the above manufacturing method
* 3: Carbon black Y for rubber compound obtained by the above manufacturing method
* 4: NIPSEAL AQ, manufactured by Tosoh Silica
* 5: Metal soap obtained by the above production method
* 6: Nocrack 6C, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 7: Si69, bis- (3-triethoxysilylpropyl) tetrasulfide, manufactured by Degussa
* 8: Noxeller D, 1,3-diphenylguanidine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 9: Noxeller CZ, N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

  According to Table 3, Example 1 containing a specific metal soap (B) and carbon black (C) is in Comparative Example 1 that does not contain both, and Comparative Examples 2-3 that contain only one of them. In comparison, excellent results in all of wear resistance, rolling resistance and wet performance are clearly shown, and it can be seen that the metal soap (B) and the carbon black (C) exhibit a greatly improved synergistic effect.

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 (21)

(A) Diene rubber,
(B) a metal soap represented by the following formula (I);

[Wherein M is a metal with an oxidation state of +3 or +4, R is an independently selected organic moiety, and n is the valence of M], and (C) a combustion gas generation zone; , A reaction apparatus in which a reaction zone and a reaction stop zone are connected to each other, a high-temperature combustion gas is generated in the combustion gas generation zone, and then a raw material is sprayed into the reaction zone to contain carbon black. Containing a carbon black for rubber compounding obtained by quenching the reaction gas stream by a multistage rapid refrigerant introduction means in the reaction stop zone after forming the gas stream, and terminating the reaction, and Carbon black for rubber compounding (C) has the following conditions (i) and (ii);
(I) The toluene coloring permeability in the multistage rapid refrigerant introduction 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. Satisfy the relationship of
(Ii) The rubber compounding carbon black (C) is contained in an amount of 10 to 250 parts by mass with respect to 100 parts by mass of the diene rubber (A);
The rubber composition characterized by satisfy | filling.   2. The rubber composition according to claim 1, wherein n-1 is 2 or 3 in the formula (I). The rubber composition according to claim 1, wherein in the formula (I), the (O ₂ CR) group is derived from a fatty acid having 6 or more carbon atoms.   The rubber composition according to claim 1, wherein the metal soap (B) does not dissolve in water.   The rubber composition according to claim 1, wherein the diene rubber (A) is selected from the group consisting of styrene-butadiene rubber, butadiene rubber, isoprene rubber, natural rubber, and combinations thereof.   The rubber composition according to claim 1, wherein the metal soap (B) is contained in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the diene rubber (A).   The rubber composition according to claim 1, wherein the metal soap (B) is a soap of aluminum and a carboxylic acid derivative.   The rubber composition according to claim 7, wherein the metal soap (B) is selected from the group consisting of aluminum soap of diethylhexanoic acid and aluminum soap of dilauric acid.   Furthermore, the rubber composition of Claim 1 containing a silica filler (D).   The rubber composition according to claim 9, wherein the silica filler (D) is silane-treated silica. The rubber composition according to claim 1, wherein the molecule of the metal soap (B) forms a micelle structure or a structure represented by the formula (II) in a nonpolar solvent;

[Wherein x is a natural number].   The rubber composition according to claim 1, wherein in the formula (I), R includes an alkyl chain having at least one unsaturated unit.   2. The rubber composition according to claim 1, wherein R in the formula (I) includes an alkyl chain having one or more sulfur-curable double bonds.   The rubber composition according to claim 13, wherein the double bond is between two non-terminal carbons in an alkyl chain.   4. The rubber composition according to claim 3, wherein the metal soap (B) is a dioleic acid aluminum soap. The rubber compounding carbon black (C) is
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 formulas (3), (4) and (5);
2.00 ≦ α1 ≦ 5.00 (3)
5.00 ≦ α2 ≦ 9.00 (4)
−2.5 × (α1 + α2) + 85.0 ≦ β ≦ 90.0 (5)
Claim 1 characterized in that 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 rubber compounding carbon black (C) has the following formulas (6), (7) and (8):
20 <X <40 (6)
50 <Y <60 (7)
90 <Z <95 (8)
It is obtained by controlling so as to satisfy the relationship of [wherein Y represents the toluene coloring permeability of carbon black after the introduction of the second quenching medium, and X and Z are as defined above] The rubber composition according to claim 1.   2. The rubber composition according to claim 1, wherein a hydrogen release rate of the carbon black for rubber blending (C) exceeds 0.3 mass%. In the rubber compounding carbon black (C), dibutyl phthalate absorption (DBP) is 95 to 220 mL / 100 g, compression DBP absorption (24M4DBP) is 90 to 200 mL / 100 g, and cetyltrimethylammonium bromide adsorption specific surface area (CTAB) The rubber composition according to claim 1, wherein the rubber composition is 70 to 200 m ² / g.   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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