WO2011125637A1 - Rubber composition and tire using same - Google Patents

Abstract

Disclosed is a rubber composition that when made into a tire improves durability such as wear resistance, tear resistance, and the like, and that enables a reduction in rolling resistance, by using a rubber composition that includes: a rubber component comprising a conjugated diene polymer that includes at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom, and a titanium atom in either a polymerization-active terminal, a polymerization initiating terminal, or a polymer chain, and a carbon black used for rubber compounding that was obtained by using a reactor comprising a combustion gas generation zone, a reaction zone, and a reaction termination zone provided in a linked manner, generating a high-temperature combustion gas within the aforementioned combustion gas generation zone, and subsequently spraying a starting material into the aforementioned reaction zone and quenching a reactant gas stream comprising a carbon black to terminate the reaction, wherein the aforementioned carbon black used for rubber compounding satisfies specific relations (1) and (2). Also disclosed is a tire using the same.

Description

Rubber composition and tire using the same

The present invention relates to a rubber composition and a pneumatic tire using the same. More specifically, the present invention relates to a rubber composition capable of reducing rolling resistance while improving durability such as wear resistance and tear resistance, and a tire including 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, a rubber composition having reduced hysteresis loss by reducing the amount of carbon black used or using lower carbon black, that is, exothermic property. A method is known in which a rubber composition having a low viscosity is used for tire members, particularly tread rubber.
However, simple weight loss of the carbon black used can reduce the wear resistance of the rubber composition.

On the other hand, in Patent Documents 1 and 2, a rubber using a modified conjugated diene polymer in which an amino group is introduced at a polymerization active terminal as a rubber component and carbon black as a filler in order to reduce rolling resistance. Compositions have been proposed. Patent Document 3 discloses a rubber composition that can achieve both tire wear resistance and rolling resistance by improving the dispersibility of carbon black using a terminal-modified polymer such as terminal-modified polybutadiene rubber. Things are disclosed.

JP-A-8-225604 JP-A-8-231658 Japanese Patent Laying-Open No. 2005-041975

In general, the improvement in tire wear resistance is thought to be governed by the particle size and structure of the carbon black compounded in the rubber composition of the tire. The smaller the carbon black particle size, the greater the wear resistance. However, it is known that if the particle size of the carbon black is extremely small, poor dispersion occurs in the rubber and the heat generation increases. When a tire tread is produced with such a rubber composition, it is excellent in wear resistance but inferior in fuel efficiency. That is, regarding the particle size of carbon black, wear resistance and low heat build-up are in a trade-off relationship.
From the above viewpoint, according to the rubber composition using the terminal-modified polymer as a rubber component, the hysteresis loss of the terminal-modified polymer is reduced, and a certain effect is obtained with respect to wear resistance and rolling resistance. There is still room for improvement regarding the two contradictory performances.

The present invention has been made under such circumstances, and provides a rubber composition capable of reducing rolling resistance while improving durability such as wear resistance and tear resistance when used as a tire. The purpose is to do. Another object of the present invention is to provide a tire using such a rubber composition, in which wear resistance and rolling resistance are highly balanced.

As a result of intensive studies to achieve the above object, the present inventor has found that the object can be achieved by a rubber composition containing carbon black having a specific property obtained by a specific process. I found it. The present invention has been completed based on such findings.
That is, the present invention
[1] A rubber component containing a conjugated diene polymer having at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom, and a titanium atom in any one of a polymerization active terminal, a polymerization start terminal, and a polymerization chain When,
Using a reaction apparatus 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 a raw material is sprayed into the reaction zone. A carbon black for rubber compounding obtained by quenching the reaction gas stream containing the carbon black in the reaction stop zone and terminating the reaction,
A rubber composition in which the carbon black for rubber blending satisfies the following relational expressions (1) and (2):
10 <X <40 (1)
90 <Z <100 (2)
(However, X represents the toluene coloring permeability (%) of carbon black after introduction of the first quenching medium from the raw material introduction position, and Z represents the toluene coloring permeability of carbon black after the last quenching medium introduction ( %).)
[2] Modification obtained by subjecting the conjugated diene polymer to a modification reaction between a polymerization active terminal and a compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom after the polymerization reaction The rubber composition according to [1], which is a conjugated diene polymer,

[3] The modified conjugated diene polymer has the following general formula (I) at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
R _a MX _b (I)
Wherein R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. , M is tin or silicon, X is independently chlorine, bromine or iodine, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4). A compound represented by formula (II)
R ¹ _a M (OR ² ) _b (II)
Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aralkyl having 7 to 20 carbon atoms. M is tin or silicon, X is independently chlorine, bromine or iodine, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4 A rubber composition according to [2], which is a modified conjugated diene polymer obtained by reacting at least one modifier selected from compounds represented by
[4] The modified conjugated diene polymer has, in the active site of the conjugated diene polymer having an organometallic active site in the molecule, the following general formula (III):

(Wherein, a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and A is a saturated cyclic tertiary amine compound residue, Unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group, pyridine group , (Thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, carboxylic acid halogen A compound residue, and at least one functional group selected from a secondary amino group or a mercapto group having a hydrolyzable group, and when A is plural, they may be the same It may be made to.
R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R ¹ is plural. May be different. R ² is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ² is plural, they are the same or different. May be. R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ³ is plural, they may be the same or different. Good. The rubber composition according to [2], which is a modified conjugated diene polymer obtained by reacting a modifier represented by
[5] A modified conjugated diene polymer obtained by reacting a condensate of a compound represented by the following general formula (II) with a modifier represented by the following general formula (III): The rubber composition according to [2], which is a polymer,
R ¹ _a M (OR ² ) _b (II)
Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aralkyl having 7 to 20 carbon atoms. M is tin or silicon, X is independently chlorine, bromine or iodine, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4 Is)

(Wherein, a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and A is a saturated cyclic tertiary amine compound residue, Unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group, pyridine group , (Thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, carboxylic acid halogen A compound residue, and at least one functional group selected from a secondary amino group or a mercapto group having a hydrolyzable group, and when A is plural, they may be the same It may be made to.
R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R ¹ is plural. May be different. R ² is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ² is plural, they are the same or different. May be. R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ³ is plural, they may be the same or different. Good. )
[6] The rubber composition according to any one of [2] to [5], wherein the modified conjugated diene polymer further contains a nitrogen atom,

[7] The rubber composition according to [1], wherein the conjugated diene polymer is a (co) polymer of a conjugated diene compound.
[8] The rubber composition according to [1], wherein the conjugated diene polymer is a copolymer of an aromatic vinyl compound and a conjugated diene compound.
[9] The conjugated diene polymer contains 1% by mass or more and 60% by mass or less of a structural unit derived from an aromatic vinyl compound, and the vinyl bond content in the conjugated diene part is 5% by mass or more and 80% by mass or less. [1] or the rubber composition according to [8],
[10] 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)), the residence time in the zone from the introduction of the first quenching medium to the introduction of the second quenching medium is t ₂ (seconds), and the average reaction temperature in this zone is T ₂ ( Furthermore, the residence time in the zone from the introduction of the second quenching medium to the introduction of the last quenching medium is t ₃ (seconds), and the average reaction temperature in this zone is T _3. (° C.), the rubber compounding carbon black has the following relational expressions (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)
(However, α1 = t ₁ × T ₁ , α2 = t ₂ × T ₂ , β = t ₃ × T _3. )
The rubber composition according to any one of [1] to [9], which is obtained by controlling so as to satisfy
[11] The carbon black for rubber blending has the following relational expressions (6), (7) and (8):
20 <X <40 (6)
50 <Y <60 (7)
90 <Z <95 (8)
(In the formula, Y represents the toluene coloring permeability of carbon black after introduction of the second quenching medium, and X and Z are the same as described above.)
The rubber composition according to any one of [1] to [10], which is obtained by controlling so as to satisfy
[12] The rubber composition according to any one of [1] to [11], wherein the hydrogen release rate of the carbon black for rubber blending is higher than 0.3% by mass;
[13] Dibutyl phthalate absorption amount (DBP) in the carbon black for rubber compounding is 95 mL / 100 g or more and 220 mL / 100 g or less, compression DBP absorption amount (24M4DBP) is 90 mL / 100 g or more and 200 mL / 100 g or less, and cetyl The rubber composition according to any one of [1] to [12], wherein a trimethylammonium bromide adsorption specific surface area (CTAB) is 70 m ² / g or more and 200 m ² / g or less,
[14] The rubber composition according to any one of [1] to [13], wherein the rubber composition contains 5 to 80 parts by mass of the conjugated diene polymer with respect to 100 parts by mass of a rubber component.
[15] The rubber composition according to any one of [1] to [14], wherein the rubber composition contains 10 parts by weight or more and 250 parts by weight or less of the carbon black for rubber blending with respect to 100 parts by weight of a rubber component. And [16] A tire using the rubber composition according to any one of [1] to [15],
Is to provide.

According to the present invention, a carbon black having a specific property obtained by a specific process is contained in a rubber component containing a modified conjugated diene polymer in a predetermined ratio, so that it has a wear resistance when used as a tire. In addition, it is possible to provide a rubber composition capable of reducing rolling resistance while improving durability such as tear resistance. Moreover, the tire obtained by using the rubber composition of the present invention has a high balance between wear resistance and rolling resistance.

It is a partial cross section explanatory drawing of an example of the carbon black manufacturing furnace for manufacturing carbon black for rubber compounding.

Hereinafter, the present invention will be described with reference to embodiments.
<Rubber composition>
First, the rubber composition of this embodiment is demonstrated.
The rubber composition of the present embodiment is a conjugated diene system having at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom in any one of a polymerization active terminal, a polymerization start terminal and a polymerization chain Using a reaction apparatus in which a rubber component containing a polymer, 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 reaction A raw material is sprayed into the zone to convert it to carbon black, and a reaction gas flow containing the carbon black is quenched in the reaction stop zone to terminate the reaction. It is a waste.

In general, in a rubber composition in which carbon black is compounded with a rubber component containing a modified conjugated diene polymer having a nitrogen-containing functional group or the like at the polymer terminal or the like, the dispersibility of carbon black with respect to the rubber component is improved, and In this case, since the hysteresis loss of the rubber component is reduced, the wear resistance and rolling resistance can be improved. However, when a rubber component in which natural rubber is blended with the modified conjugated diene polymer is used, it is necessary to further improve the effect of reducing hysteresis loss. This is because natural rubber obtained by a normal production method has a high loss tangent (tan δ) due to the remaining non-rubber component contained in the natural rubber latex, and the exothermic reduction effect may be low. is there.

On the other hand, the carbon black used in the rubber composition of the present embodiment has a toluene coloring transmittance satisfying a specific range, so that the tar content existing on the surface is sufficiently small, and the composite of carbon black and rubber molecules is efficient. As a result, the abrasion resistance and low heat build-up of the rubber composition can be improved. Furthermore, in the rubber composition of the present embodiment, the dispersibility of carbon black is greatly increased by using a modified conjugated diene-based polymer having a functional group having a specific structure together with carbon black having a small tar component present on the surface. In order to improve, the hysteresis loss in a rubber composition can be reduced, fully exhibiting the reinforcement effect of carbon black. For this reason, in the rubber composition of this embodiment, even if a natural rubber is blended with the modified conjugated diene polymer, the wear resistance, tear resistance and rolling resistance of the tire can be sufficiently improved. In addition, since the rubber composition of the present embodiment has high dispersibility of carbon black, even if a predetermined amount of carbon black is blended, it is possible to ensure the effect of reducing hysteresis loss. Abrasion and tear resistance can also be improved easily.

(Rubber component)
In the rubber composition of the present embodiment, the rubber component includes at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom, and a titanium atom, any one of a polymerization active terminal, a polymerization start terminal, and a polymerization chain. Conjugated diene polymers are included.

The conjugated diene polymer in the present embodiment can be produced as a polymer having an organometallic active site in the molecule, and the production method is not particularly limited, and is a solution polymerization method, a gas phase polymerization method, Any of the bulk polymerization methods can be used, but the solution polymerization method is particularly preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form.

The metal of the active site is preferably one selected from alkali metals and alkaline earth metals, and lithium metal is particularly preferable.
In the solution polymerization method, for example, a target polymer can be produced by anionic polymerization of a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound using a lithium compound as a polymerization initiator. As the conjugated diene polymer in the present embodiment, a polymer or copolymer of a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound are copolymerized from the viewpoint that the glass transition temperature can be controlled. A conjugated diene polymer is preferred.

Furthermore, it is also effective to mix a halogen-containing monomer and activate the halogen atom in the polymer with an organometallic compound. For example, it is also effective to lithiate the bromine moiety of a copolymer containing an isobutylene unit, a paramethylstyrene unit and a parabromomethylstyrene unit to form an active site.
The active site may be present in the polymer molecule, and may be present in any of the polymerization active terminal, the polymerization initiation terminal and the polymerization chain. When the polymer is obtained by anionic polymerization using an alkali metal compound and / or an alkaline earth metal compound as a polymerization initiator, generally, the active site is located at the end of the polymer.
For example, when the compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom is reacted with the active terminal, the conjugated diene polymer in the present embodiment can be obtained. .

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. These may be used alone or in combination of two or more, and among these, 1,3-butadiene and isoprene are particularly preferred.
Examples of aromatic vinyl compounds used for copolymerization with these conjugated diene compounds include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, and 4-cyclohexylstyrene. 2,4,6-trimethylstyrene and the like. These may be used singly or in combination of two or more, but among these, styrene is particularly preferable.
Further, when copolymerization is performed using a conjugated diene compound and an aromatic vinyl compound as monomers, the use of 1,3-butadiene and styrene, respectively, in terms of practicality such as the availability of monomers, And anionic polymerization characteristics are particularly preferred in view of the living property.
When the solution polymerization method is used, the monomer concentration in the solvent is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 30% by mass. When copolymerization is performed using a conjugated diene compound and an aromatic vinyl compound, the content of the aromatic vinyl compound in the charged monomer mixture is preferably in the range of 1 to 60% by mass, more preferably 5 to 45% by mass. % Range is preferred.

The lithium compound of the polymerization initiator is not particularly limited, but hydrocarbyl lithium and lithium amide compounds are preferably used. When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal. A conjugated diene polymer having a polymerization active site is obtained. When the latter lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained.

As the hydrocarbyl lithium, those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable. For example, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n-decyl. Examples include lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, and reaction products of diisopropenylbenzene and butyl lithium. Of these, n-butyllithium is preferred.

On the other hand, as the lithium amide compound, for example, lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium dipropyl amide, lithium Diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium methylbutyramide, lithium ethylbenzylamide, Examples include lithium methyl phenethyl amide.

Among these, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable from the viewpoint of the interaction effect on carbon black and the ability to initiate polymerization. Particularly preferred are lithium hexamethylene imide and lithium pyrrolidide.
These lithium amide compounds are generally prepared in advance from a secondary amine and a lithium compound in the polymerization, but can also be prepared in-polymerization in situ. The amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.

There is no restriction | limiting in particular as a method of manufacturing a conjugated diene polymer by anionic polymerization using the said lithium compound as a polymerization initiator, A conventionally well-known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, in a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound are used. The desired conjugated diene polymer can be obtained by subjecting the lithium compound as a polymerization initiator to anionic polymerization in the presence of a randomizer to be used, if desired.

The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms. For example, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2 -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.

The randomizer used as desired is a control of the microstructure of the conjugated diene polymer, such as an increase in 1,2 bonds in the butadiene moiety in the butadiene-styrene copolymer, an increase in 3,4 bonds in the isoprene polymer, or the like. It is a compound having an action of controlling the composition distribution of monomer units in a conjugated diene compound-aromatic vinyl compound copolymer, for example, randomizing butadiene units and styrene units in a butadiene-styrene copolymer. The randomizer is not particularly limited, and an arbitrary one can be appropriately selected from known compounds generally used as a conventional randomizer. Specifically, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, bistetrahydrofurylpropane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, 1, And ethers such as 2-dipiperidinoethane and tertiary amines. Further, potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can also be used.
One of these randomizers may be used alone, or two or more thereof may be used in combination. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of lithium compound.

The temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C, more preferably in the range of 20 to 130 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.
In this polymerization, it is desirable to use a material from which reaction-inhibiting substances such as water, oxygen, carbon dioxide, and protic compounds are removed as all raw materials involved in the polymerization, such as a polymerization initiator, a solvent, and a monomer. .
When a polymer is obtained as an elastomer, the glass transition point (Tg) obtained by differential thermal analysis of the obtained polymer or copolymer is preferably in the range of −110 ° C. to −15 ° C. It is difficult to obtain a polymer having a glass transition point of less than −110 ° C., and when the glass transition point exceeds −15 ° C., the viscosity becomes too high in the room temperature region, which may make handling difficult.

On the other hand, when the modified conjugated diene polymer is produced by coordination polymerization using a rare earth metal compound as a polymerization initiator, the following (A) component, (B) component, and (C) component may be used in combination. preferable.
The component (A) used for the coordination polymerization is selected from a rare earth metal compound, a complex compound of a rare earth metal compound and a Lewis base, and the like. Here, examples of rare earth metal compounds include rare earth element carboxylates, alkoxides, β-diketone complexes, phosphates and phosphites, and Lewis bases include acetylacetone, tetrahydrofuran, pyridine, N, N -Dimethylformamide, thiophene, diphenyl ether, triethylamine, organophosphorus compounds, monovalent or divalent alcohols, etc. As the rare earth element of the rare earth metal compound, lanthanum, neodymium, praseodymium, samarium and gadolinium are preferable, and among these, neodymium is particularly preferable. Specific examples of the component (A) include neodymium tri-2-ethylhexanoate, complex compounds thereof with acetylacetone, neodymium trineodecanoate, complex compounds thereof with acetylacetone, neodymium tri-n-butoxide, and the like. It is done. These (A) components may be used individually by 1 type, or 2 or more types may be mixed and used for them.

The component (B) used for the coordination polymerization is selected from organoaluminum compounds. As the organoaluminum compound, specifically, a trihydrocarbyl aluminum compound represented by the formula: R ¹² ₃ Al, a hydrocarbyl aluminum hydride represented by the formula: R ¹² ₂ AlH or R ¹² AlH ₂ (wherein R ¹² are each independently a hydrocarbon group having 1 to 30 carbon atoms), hydrocarbylaluminoxane compounds having a hydrocarbon group having 1 to 30 carbon atoms, and the like. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, and alkylaluminoxane. These compounds may be used individually by 1 type, or 2 or more types may be mixed and used for them. In addition, as (B) component, it is preferable to use aluminoxane and another organoaluminum compound together.

The component (C) used in the coordination polymerization is a compound having a hydrolyzable halogen or a complex compound thereof with a Lewis base; an organic halide having a tertiary alkyl halide, benzyl halide or allyl halide; a non-coordinating anion And an ionic compound comprising a counter cation. Specific examples of the component (C) include alkylaluminum dichloride, dialkylaluminum chloride, silicon tetrachloride, tin tetrachloride, complexes of zinc chloride with Lewis bases such as alcohol, magnesium chloride and Lewis such as alcohol. Examples thereof include complexes with bases, benzyl chloride, t-butyl chloride, benzyl bromide, t-butyl bromide, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. These components (C) may be used alone or in combination of two or more.

In addition to the components (A), (B), and (C), the polymerization initiator is preliminarily used by using the same conjugated diene compound and / or non-conjugated diene compound as the polymerization monomer, if necessary. May be prepared. Further, part or all of the component (A) or the component (C) may be supported on an inert solid and used. The amount of each of the above components can be appropriately set. Usually, the component (A) is 0.001 to 0.5 mmol (mmol) per 100 g of the monomer. The molar ratio of the component (B) / component (A) is preferably 5 to 1,000, and the component (C) / component (A) is preferably 0.5 to 10.

The polymerization temperature in the coordination polymerization is preferably in the range of −80 to 150 ° C., more preferably in the range of −20 to 120 ° C. Moreover, as a solvent used for coordination polymerization, a hydrocarbon solvent inert to the reaction exemplified in the above-mentioned anionic polymerization can be used, and the concentration of the monomer in the reaction solution is the same as in the case of anionic polymerization. . Furthermore, the reaction pressure in coordination polymerization is the same as that in the case of anionic polymerization, and it is desirable that the raw material used for the reaction substantially removes reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds.
The modified conjugated diene polymer is preferably an anion-polymerized organic alkali metal compound, particularly alkyllithium.

In the conjugated diene polymer in the present embodiment, the content of the structural unit derived from the aromatic vinyl compound is 1 mass as an unmodified and / or modified low molecular weight diene copolymer in the unmodified product or the property before modification. It is preferable that the vinyl bond content of the conjugated diene moiety is 5% by mass or more and 80% by mass or less. If the content of the structural unit derived from the aromatic vinyl compound and the vinyl bond content of the conjugated diene compound part are not within the above ranges, sufficient workability of the rubber composition and reduction of the loss tangent (tan δ) of the rubber composition are sufficient. May not be compatible.
The content of the structural unit derived from the aromatic vinyl compound is more preferably 10% by mass or more and 50% by mass or less, and the vinyl bond content of the conjugated diene moiety is preferably 10% by mass or more and 70% by mass or less.

The conjugated diene polymer in this embodiment is a modification obtained by subjecting a polymerization active end to a compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom after the polymerization reaction. A conjugated diene polymer is preferred.

Here, the conjugated diene polymer having a polymerizable active terminal is conjugated with an aromatic vinyl compound using an organic alkali metal compound, preferably a lithium compound, as described in the production of the conjugated diene polymer. The diene compound can be obtained by anionic polymerization in the same manner as described above. In this case, the reaction conditions are appropriately selected so that the resulting low molecular weight diene copolymer having an active terminal has the above-described properties.
Nitrogen-containing compounds, silicon-containing compounds, tin-containing compounds, and the like can be used as modifiers that are reacted with the active ends of the low molecular weight diene copolymer thus obtained. Nitrogen-containing compounds that can be used as the modifying agent include bis (diethylamino) benzophenone, dimethylimidazolidinone, N-methylpyrrolidone, 4-dimethylaminobenzylideneaniline, and the like. By using these nitrogen-containing compounds as modifiers, functional groups containing nitrogen such as substituted and unsubstituted amino groups, amide groups, imino groups, imidazole residues, nitrile groups, and pyridyl groups can be introduced.
In the modification reaction in the present embodiment, the low molecular weight diene copolymer having an active terminal to be used is preferably such that at least 10 mol% of the polymer chain has a living property.

The first polymer in the present embodiment is the following general formula (III) with respect to the conjugated diene polymer having an organometallic active site in the molecule thus obtained:

(Wherein, a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and A is a saturated cyclic tertiary amine compound residue, Unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group, pyridine group , (Thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid ester residue, metal salt of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, carboxylic acid halogen compound residue , As well as at least one functional group selected from a secondary amino group or mercapto group having a hydrolyzable group, and when A is plural, they may be the same or different
R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R ¹ is plural. May be different. R ² is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ² is plural, they are the same or different. May be. R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ³ is plural, they may be the same or different. Good. And a condensate thereof.

In the general formula (III), R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. Etc. Here, the alkyl group and alkenyl group may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , Sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl, hexenyl, octenyl, cyclo A pentenyl group, a cyclohexenyl group, etc. are mentioned. The aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Furthermore, the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The divalent inert hydrocarbon group having 1 to 20 carbon atoms in R ³ is preferably an alkylene group having 1 to 20 carbon atoms. The alkylene group may be linear, branched or cyclic, but a linear one is particularly preferable. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.

Examples of the saturated cyclic tertiary amine compound residue in A include a hexamethyleneimino group, a pyrrolidinyl group, a piperidinyl group, a heptamethyleneimino group, a dodecamethyleneimino group, and the like, and an unsaturated cyclic tertiary amine Examples of the compound residue include an imidazole residue, a dihydroimidazole residue, an oxazole residue, and a pyridyl group.
The A includes a ketimine residue, a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, a pyridine group, a nitrile group, an isocyanate group, and a detachable functional group from the viewpoint of performance. It is preferably a monovalent group having at least one nitrogen-containing functional group selected from secondary amino groups, saturated cyclic tertiary amine compound residue, ketimine residue, imidazole residue, dihydroimidazole residue and It is more preferably a monovalent group having at least one selected from secondary amino groups having a detachable functional group.

In the general formula (III), among the functional groups in A, imine residues include ketimine, aldimine, and amidine residues, and (thio) carboxylic acid hydrocarbyl esters are unsaturated carboxylic acid esters such as acrylates and methacrylates. Of residues. Examples of the metal of the metal salt residue of (thio) carboxylic acid include alkali metals, alkaline earth metals, aluminum, tin, and zinc.

Among the functional groups in the monovalent group represented by A, examples of the secondary amino group having a hydrolyzable group include N- (trimethylsilyl) amino group. The (thio) isocyanate group is a —NCO group or a —NCS group.
Examples of the monovalent group containing a (thio) epoxy group include a glycidoxy group, a 3,4-epoxycyclohexyl group, and those obtained by replacing the epoxy ring in these groups with a thioepoxy ring.

The modifier used in the present embodiment is a bifunctional hydrocarbyloxysilane compound and / or a partial condensate thereof as described above. Here, the partial condensate refers to a product in which a part (not all) of the SiOR groups of the hydrocarbyloxysilane compound are converted into SiOSi bonds by condensation.
Further, when the modifier used in the present embodiment is a monofunctional hydrocarbyloxysilane compound having one hydrocarbyloxy group directly bonded to a silicon atom, the hydrocarbyloxy group is consumed by the modification reaction, and inorganic filler such as silica is filled. Since the modifying group that interacts with the material is not introduced, the object of the present invention cannot be achieved. On the other hand, in the case of a trifunctional hydrocarbyloxysilane compound having three hydrocarbyloxy groups directly bonded to a silicon atom, a conjugated diene polymer having a plurality of active ends reacts with one molecule of the modifier, whereby Highly efficient introduction of modified ends per molecule cannot be achieved.
In the modification reaction in the present embodiment, the conjugated diene polymer having an active terminal to be used is preferably such that at least 10 mol% of the polymer chain has a living property.

Examples of the hydrocarbyloxysilane compound represented by the general formula (III) include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (thio) epoxy group-containing hydrocarbyloxysilane compounds, (2-glycidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane and the epoxy groups in these compounds as thioepoxy groups Put in There may be mentioned a was example, among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyl triethoxysilane are particularly preferred.

Further, as imine residue-containing hydrocarbyloxysilane compounds, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (tri Ethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N -(4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine and their tris Trimethoxysilyl compounds corresponding to ethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds , Methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds, etc., among which N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine and N- (1, 3-Dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine is particularly preferred.

Examples of the imine (amidine) residue-containing compound include 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -4,5- Dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxysilylpropyl) Examples include -4,5-dihydroimidazole, and among these, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is preferable.

As the bifunctional hydrocarbyloxysilane compound represented by the general formula (III), for example, when A has an imidazole residue or a dihydroimidazole residue, a specific example is 1- [3- [diethoxy (methyl) silyl] propyl. ] -Imidazole, 1- [3- [diethoxy (ethyl) silyl] propyl] -imidazole, 1- [3- [dipropoxy (methyl) silyl] propyl] -imidazole, 1- [3- [dipropoxy (ethyl) silyl] Propyl] -imidazole, 1- [3- [diethoxy (methyl) silyl] propyl] -4,5-dihydroimidazole, 1- [3- [diethoxy (ethyl) silyl] propyl] -4,5-dihydroimidazole, 1 -[3- [Dipropoxy (methyl) silyl] propyl] -4,5-dihydroimidazo And 1- [3- [dipropoxy (ethyl) silyl] propyl] -4,5-dihydroimidazole, among which 1- [3- [diethoxy (methyl) silyl] propyl]- Imidazole, 1- [3- [dipropoxy (methyl) silyl] propyl] -imidazole, 1- [3- [diethoxy (methyl) silyl] propyl] -4,5-dihydroimidazole and 1- [3- [dipropoxy (methyl) ) Silyl] propyl] -4,5-dihydroimidazole is preferred.

As the bifunctional hydrocarbyloxysilane compound represented by the general formula (III), for example, when A has a pyridyl group or a nitrile group, as a specific example, 2- [2- [diethoxy (methyl) silyl] ethyl]- Pyridine, 2- [2- [dipropoxy (methyl) silyl] ethyl] -pyridine, 2- [3- [diethoxy (methyl) silyl] propyl] -pyridine, 2- [3- [diethoxy (ethyl) silyl] propyl] -Pyridine, 2- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 2- [3- [dipropoxy (ethyl) silyl] propyl] -pyridine, 4- [2- [diethoxy (methyl) silyl] ethyl ] -Pyridine, 4- [2- [dipropoxy (methyl) silyl] ethyl] -pyridine, 4- [3- [diethoxy (methyl)] Ril] propyl] -pyridine, 4- [3- [diethoxy (ethyl) silyl] propyl] -pyridine, 4- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 4- [3- [dipropoxy (ethyl) ) Pyridine compounds such as silyl] propyl] -pyridine, 1-cyano-3- [diethoxy (methyl) silyl] -propane, 1-cyano-3- [diethoxy (ethyl) silyl] -propane, 1-cyano-3- And cyano compounds such as [dipropoxy (methyl) silyl] -propane and 1-cyano-3- [dipropoxy (ethyl) silyl] -propane. Among these, 2- [3- [diethoxy (methyl) silyl] propyl] -pyridine, 2- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 4- [3- [diethoxy (methyl) silyl ] Propyl] -pyridine, 4- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 1-cyano-3- [diethoxy (methyl) silyl] -propane and 1-cyano-3- [dipropoxy (methyl) Silyl] -propane is preferred.

As the bifunctional hydrocarbyloxysilane compound represented by the general formula (III), for example, when A has a (thio) isocyanate group or an oxazole residue, as a specific example, 1-isocyanato-3- [diethoxy (methyl) Silyl] -propane, 1-isocyanato-3- [diethoxy (ethyl) silyl] -propane, 1-isocyanato-3- [dipropoxy (methyl) silyl] -propane, 1-isocyanato-3- [dipropoxy (ethyl) silyl] -Isocyanate compounds such as propane, thioisocyanate compounds in which the isocyanate in the above isocyanate compounds is replaced by thioisocyanate, 4- [3- [diethoxy (methyl) silyl] propyl] -oxazole, 4- [3- [diethoxy (ethyl) ) Silyl] propyl] -oxazo Le 4- [3- [dipropoxy (methyl) silyl] propyl] - oxazole, 4- [3- [dipropoxy (ethyl) silyl] propyl] - such as oxazole compounds such as oxazole and the like. Among these, 1-isocyanato-3- [diethoxy (methyl) silyl] -propane, 1-isocyanato-3- [dipropoxy (methyl) silyl] -propane, 4- [3- [diethoxy (methyl) silyl] propyl ] -Oxazole and 4- [3- [dipropoxy (methyl) silyl] propyl] -oxazole are preferred.
In the present embodiment, the oxazole residue also includes an isoxazole residue.

Furthermore, other hydrocarbyloxysilane compounds include the following. That is, as the carboxylic acid hydrocarbyl ester residue-containing compound, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyl Examples thereof include triisopropoxysilane, among which 3-methacryloyloxypropyltrimethoxysilane is preferable.

Examples of the isocyanate group-containing compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and 3-isocyanatopropyltriisopropoxysilane. Of these, 3-isocyanatopropyltriethoxysilane is preferred.

Further, as the carboxylic acid anhydride residue, 3-triethoxysilylpropyl succinic anhydride residue, 3-trimethoxysilylpropyl succinic anhydride residue, 3-methyldiethoxysilylpropyl succinic anhydride residue Among them, among them, 3-triethoxysilylpropyl succinic anhydride residue is preferable.

In this embodiment, the hydrocarbyloxysilane compound having the above characteristic structure is preferably in a stoichiometric amount or in excess of the active site, more preferably 0.3 molar equivalent or more of the apparent active site. In addition (usually, 1 mol of the modifying hydrocarbyloxysilane compound corresponds to several mole equivalents of the active site), the active site is reacted with the hydrocarbyloxysilane compound, and the active site is substantially hydrocarbyloxysilane. A method of adding a condensation accelerator after introducing a compound residue is used.

Examples of such a condensation accelerator include a compound containing a tertiary amino group, or among group 3, 4, 5, 12, 13, 14, and 15 of the periodic table (long period type). An organic compound containing one or more elements belonging to any of the above can be used. Further, as a condensation accelerator, an alkoxide, a carboxyl containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn). It is preferably an acid salt or an acetylacetonate complex salt.
The condensation accelerator used here can be added before the modification reaction, but is preferably added to the modification reaction system during and / or after the modification reaction. When added before the denaturation reaction, a direct reaction with the active end occurs, and for example, a hydrocarboxy group having a protected primary amino group at the active end may not be introduced.
It is preferable to add the condensation accelerator to the reaction system immediately after the modification in which the hydrocarbylsilane compound residue is introduced. However, the polymer modified by the reaction is dried and then blended, preferably blended. In the first stage, a condensation accelerator may be added.
In this modification reaction, the conjugated diene polymer used preferably has at least 20 mol% of the polymer chain having the active site.

The second modified conjugated diene polymer in this embodiment has the following general formula (I) at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
R _a MX _b (I)
Wherein R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. , M is tin or silicon, X is independently chlorine, bromine or iodine, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4). A compound represented by formula (II)
R ¹ _a M (OR ² ) _b (II)
Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aralkyl having 7 to 20 carbon atoms. M is tin or silicon, X is independently chlorine, bromine or iodine, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4 It is obtained by reacting at least one modifier selected from the compounds represented by formula (1) and a condensate thereof.

The method for producing the polymer having the organometallic active site in the molecule is the same as in the case of the first polymer.
The modified conjugated diene polymer modified with at least one of the coupling agents represented by the general formulas (I) and (II) has at least one tin-carbon bond or silicon-carbon bond. In the general formulas (I) and (II), R or R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group or an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-butyl group, a neophyll group, a cyclohexyl group, an n-octyl group, and a 2-ethylhexyl group. . Z is tin or silicon, and X is independently chlorine or bromine. In the general formulas (I) and (II), a is an integer of 0 to 3, and b is an integer of 1 to 4, provided that a + b = 4.
As the coupling agent represented by the general formula (I), tin tetrachloride, RSnCl ₃ , R ₂ SnCl ₂ , R ₃ SnCl and the like are preferable, and tin tetrachloride is particularly preferable. Moreover, as a coupling agent represented by general formula (II), tetraalkoxysilane, trialkoxysilane, and dialkoxysilane are preferable, and tetraethoxysilane is particularly preferable.

The third modified diene polymer in the present embodiment is obtained by reacting a condensate of an alkoxysilane compound represented by the general formula (II) and a modifying agent represented by the general formula (III). It is a modified conjugated diene polymer.
The alkoxysilane compound represented by the general formula (II) and the modifier represented by the general formula (III) are as described above.

The method for producing the polymer having the organometallic active site in the molecule is the same as in the case of the first polymer.
Further, the kind of the condensation accelerator and the condensation reaction conditions are also as described in the production of the first polymer.

The modified conjugated diene polymer in the present embodiment modified with the above-described modifier preferably contains a nitrogen atom. In general, in a rubber composition in which carbon black is blended with a rubber component containing a modified conjugated diene polymer having a nitrogen-containing functional group, the dispersibility of carbon black with respect to the rubber component is improved, and consequently hysteresis of the rubber component Since the loss is reduced, wear resistance and rolling resistance can be improved. Therefore, by using the modified conjugated diene polymer having a nitrogen-containing functional group together with the carbon black having a small tar component present on the surface in the present embodiment, the dispersibility of the carbon black is greatly improved. Hysteresis loss in the rubber composition can be reduced while sufficiently exerting the reinforcing effect.

As the modification reaction for obtaining the first polymer and the second polymer, both solution reaction and solid phase reaction can be used, but solution reaction (even if the unreacted monomer used at the time of polymerization is included). Is good). Moreover, there is no restriction | limiting in particular about the form of this modification | denaturation reaction, You may carry out using a batch type reactor, You may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor and an in-line mixer. In addition, it is important that the modification reaction is carried out after reaching the conversion rate at which the completion of the polymerization reaction is desired, and before performing a solvent removal treatment, a water treatment, a heat treatment or the like.

The temperature of the modification reaction is preferably 20 ° C. or higher, but the polymerization temperature of the conjugated diene polymer can be used as it is, and a more preferable range is 30 to 120 ° C. When the reaction temperature is lowered, the viscosity of the polymer is excessively increased and the dispersibility of the reaction product tends to be deteriorated. On the other hand, when the reaction temperature increases, the polymerization active site tends to be deactivated easily.
The amount of the modifier used is preferably in the range of 0.25 to 3.0 mol, more preferably in the range of 0.5 to 1.5 mol, relative to 1 mol of the polymerization initiator used for the production of the conjugated diene polymer. .

In this embodiment, the modification by the modifier is performed on the active site in the conjugated diene polymer, but the active site may be in the polymer molecule, and the position is not particularly limited. However, the rubber obtained may include a modified conjugated diene polymer obtained by modifying at least one molecular terminal with a modifier comprising a compound containing a functional group that interacts with carbon black. From the viewpoint of the balance between the wear resistance and the low rolling resistance of the composition, it is particularly preferable. From this viewpoint, the active site in the polymer is preferably present at the terminal of the conjugated diene polymer.

The rubber composition of the present embodiment contains the above-described modified conjugated diene polymer (first polymer, second polymer) as a rubber component. Here, the content of the modified conjugated diene polymer in the rubber component is preferably in the range of 5 to 80 parts by mass with respect to 100 parts by mass of the rubber component. When the content of the modified conjugated diene polymer in the rubber component is less than 5 parts by mass, the carbon black dispersibility cannot be sufficiently improved. On the other hand, when the content exceeds 80 parts by mass, the workability decreases. There is. The content is more preferably in the range of 15 parts by mass or more and 60 parts by mass or less.

In the rubber composition of the present embodiment, as rubber components other than the modified conjugated diene polymer, natural rubber (NR), unmodified styrene-butadiene copolymer (SBR), polybutadiene rubber (BR) ), Polyisoprene rubber (IR), butyl rubber (IIR), ethylene-propylene copolymer, etc., among which natural rubber and polyisoprene rubber are preferred. These rubber components may be used alone or as a blend of two or more.

(Carbon black for rubber compounding)
The rubber compounding carbon black in the present embodiment 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 sprayed and introduced into the reaction zone to form a reaction gas flow containing carbon black, and then the reaction gas flow is quenched in the reaction stop zone by a multistage rapid refrigerant introduction means to terminate the reaction. The following relational expressions (1) and (2) are satisfied.
10 <X <40 (1)
90 <Z <100 (2)
However, X shows the toluene coloring permeability (%) of carbon black after introduction of the first quenching medium from the raw material introduction position, and Z shows the toluene coloring permeability (%) of carbon black after the last quenching medium introduction. ).

First, the manufacturing method of the carbon black for rubber | gum mixing used for the rubber composition of this embodiment is demonstrated.
The interior of the carbon black production furnace has a structure in which a combustion zone, a reaction zone, and a reaction stop zone are connected, and the whole is covered with a refractory. The carbon black production furnace uses a rectifying plate to rectify the oxygen-containing gas introduced from the outer periphery of the furnace head and the oxygen-containing gas introduction pipe into the flammable fluid introduction chamber as a combustion zone. An oxygen-containing gas introduction cylinder to be introduced, and a fuel oil spraying device introduction pipe installed on the central axis of the oxygen-containing gas introduction cylinder and introducing the hydrocarbon for fuel into the combustible fluid introduction chamber. In the combustion zone, high-temperature combustion gas is generated by combustion of hydrocarbons for fuel.

The carbon black production furnace includes a reaction chamber in which a cylinder gradually converges, a raw material oil introduction chamber including, for example, four raw oil spray ports on the downstream side of the convergence chamber, and a reaction chamber on the downstream side of the raw material oil introduction chamber. With. 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.

FIG. 1 is a partial cross-sectional explanatory view of an example of a carbon black production furnace for producing the rubber compounding carbon black, and a reaction chamber into which a high-temperature gas containing a carbon black raw material (raw material hydrocarbon) is introduced. 10 and the reaction continuation / cooling chamber 11 are shown. As shown in FIG. 1, 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 color permeability X, Y and Z are set to desired values. Thereby, carbon black for rubber | gum mixing used for the rubber composition of this embodiment is obtained.

Here, each band in the present embodiment 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) ), For example, the upstream side (left side in FIG. 1) from the point where the feedstock is introduced.
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, for example, when the raw material oil is introduced at the third raw material oil spray port and 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.

In the present embodiment, the rubber compounding carbon black obtained as described above has the following relational expressions (1) and (2):
10 <X <40 (1)
90 <Z <100 (2)
It is necessary to satisfy.
X represents the toluene coloring permeability (%) of carbon black after introduction of the rapid refrigerant from the first material introduction position (12-X in FIG. 1) from the raw material introduction position, and Z represents the last 1 shows the toluene coloring permeability (%) of carbon black after the rapid refrigerant is introduced by the rapid refrigerant introduction means (12-Z in FIG. 1). That is, the carbon black after introduction of the first rapid refrigerant body has a toluene coloring permeability higher than 10% and less than 40%, and the carbon black after introduction of the final rapid refrigerant body (carbon black for rubber blending) is The toluene color transmission needs to be higher than 90% and lower than 100%. If the toluene coloring transmittance Z of the carbon black for rubber blending is 90% or less, the carbon black has a lot of heavy tar components contained therein, and gives sufficient reinforcement to the rubber. And the wear resistance is reduced.
Further, when X is 40 or more, the reinforcing property of the carbon black is lowered and the wear resistance is lowered.

The rubber compounding carbon black having such properties can be obtained by controlling the reaction temperature and residence time as described below.
That 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), and 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 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 following relational expressions (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)
(However, α1 = t ₁ × T ₁ , α2 = t ₂ × T ₂ , β = t ₃ × T _3. )
The carbon black for rubber | gum compounding can be obtained by controlling so that it may satisfy | fill.

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. In order to calculate the average reaction temperatures T ₁ , T ₂ , and T ₃ , it is preferable to measure temperatures at least at 2 points, preferably 3 to 4 points in each step (each zone).
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 equation. 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) = [reaction furnace 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) = [reaction furnace passage volume (m ³ ) from introduction position of first sudden refrigerant body to introduction of second sudden refrigerant body] / [volume of reactive gas fluid (m ³ / sec)]
Residence time t ₃ (sec) = [reaction furnace passage volume (m ³ ) from the second abrupt refrigerant introduction position until the last abrupt refrigerant is introduced] / [reaction gas fluid volume (m ³ / sec)]

Further, as the carbon black for rubber compounding, the following relational expressions (6), (7) and (8)
20 <X <40 (6)
50 <Y <60 (7)
90 <Z <95 (8)
(In the formula, Y represents the toluene coloring permeability of carbon black after introduction of the second quenching medium, and X and Z are the same as described above.)
What was obtained by controlling to satisfy | fill can be used suitably.
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 preferably has a hydrogen release rate exceeding 0.3% by mass. When this hydrogen release rate exceeds 0.3% by mass, the rubber composition of the present embodiment has high wear resistance and low heat generation. The hydrogen release rate is preferably 0.35% by mass or more. The upper limit is usually about 0.4% by mass.
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 and cooled to room temperature in a desiccator; Weigh accurately, crimp 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. .

Further, the carbon black for rubber blending has a dibutyl phthalate absorption (DBP) of 95 mL / 100 g or more and 220 mL / 100 g or less, a compressed DBP absorption (24M4DBP) of 90 mL / 100 g or more and 200 mL / 100 g or less, and cetyltrimethyl. Ammonium bromide adsorption specific surface area (CTAB) is preferably 70 m ² / g or more and 200 m ² / g or less. When DBP, 24M4DBP and CTAB are in the above ranges, the rubber composition can be sufficiently reinforced and the wear resistance of the rubber composition can be improved.

More preferably, the DBP is 100 mL / 100 g or more and 200 mL / 100 g or less, the 24M4DBP is 100 mL / 100 g or more and 180 mL / 100 g or less, and the CTAB is 80 m ² / g or more and 180 m ² / g or less.
The dibutyl phthalate absorption amount (DBP) and the compressed DBP absorption amount (24M4DBP) were measured by the method described in ASTM D2414-88 (JIS K6217-4: 2001), and dibutyl phthalate absorbed per 100 g of carbon black ( DBP) in mL. 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 composition of the present embodiment may contain 10 to 250 parts by mass of the rubber compounding carbon black with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer described above. preferable.
When the content of the carbon black is less than 10 parts by mass, the reinforcing effect of the rubber composition may not be sufficiently exhibited, and desired wear resistance may not be obtained. On the other hand, if it exceeds 250 parts by mass, a rubber composition having desired physical properties such as low rolling resistance may not be obtained. The content of the carbon black is preferably 20 parts by mass or more and 150 parts by mass or less, and more preferably 30 parts by mass or more and 120 parts by mass or less with respect to 100 parts by mass of the rubber component.
The rubber compounding carbon black is manufactured by the above-described method and has the above-described physical properties. Examples of the carbon black include FEF, SRF, HAF, ISAF, ISAF-LS, SAF-LS etc. are mentioned.

(Preparation of rubber composition)
In addition to the rubber component containing the modified conjugated diene polymer and the carbon black for rubber blending, the rubber composition of the present embodiment includes other components such as an inorganic filler, a vulcanizing agent, a vulcanization accelerator, and zinc oxide. The compounding agents usually used in the rubber industry such as stearic acid and anti-aging agent can be appropriately selected and blended within a range not impairing the object of the present invention. As these compounding agents, commercially available products can be suitably used. Further, the rubber composition is prepared by blending a rubber component, carbon black for blended rubber, and various appropriately selected blending agents, and kneading using a Banbury mixer, roll, internal mixer, intensive mixer, etc. It can be prepared by heating, extruding or the like.

<Tire>
The tire according to this embodiment is characterized in that the rubber composition is applied to any of the tire members. Here, in the tire of the present embodiment, it is particularly preferable to use the rubber composition of the present embodiment for a tread, and the tire using the rubber composition for a tread has excellent wear resistance and low rolling resistance. Excellent fuel economy. In addition, as gas with which the tire of this embodiment is filled, normal or the air which changed oxygen partial pressure, or inert gas, such as nitrogen, is mentioned. When the rubber composition in the present embodiment is used for a tread, for example, the rubber composition is extruded onto a tread member, and pasted and molded by a normal method on a tire molding machine to form a raw tire. The green tire is heated and pressed in a vulcanizer to obtain a tire.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
The tire wear resistance and the low heat build-up of the rubber composition were evaluated according to the following methods.
(1) Abrasion resistance The test tire was mounted on a vehicle, and the groove weight loss at the time when the vehicle traveled 40,000 km was measured. The larger this value, the better the wear resistance.
(2) Low exothermic property (tan δ)
Using a dynamic spectrometer manufactured by Rheometrics, Inc. in USA, the measurement was carried out under the conditions of 3% tensile dynamic strain, frequency 10 Hz, 50 ° C. It shows that the low exothermic property (rolling resistance) of a tire is excellent, so that the value of an index | exponent is small.

<Manufacture of carbon black>
(Carbon black A)
Carbon black A was manufactured using the carbon black manufacturing furnace shown in FIG. However, in FIG. 1, as the multistage rapid refrigerant introduction means 12, a three-stage comprising a first rapid refrigerant introduction means 12-X, a second rapid refrigerant introduction means 12-Y, and a final rapid refrigerant introduction means 12-Z. The rapid refrigerant introduction means was used.
Moreover, in order to monitor the temperature in a manufacturing furnace, the said manufacturing furnace provided with the structure where a thermocouple can be inserted in a furnace in arbitrary several places 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. Table 2 shows the operating conditions of the carbon black production furnace and the characteristics of the carbon black.

(Carbon black BK)
Carbon blacks B to K were produced in the same manner as the production of carbon black A except that the operating conditions shown in Table 2 were adopted. Table 2 shows the characteristics of each carbon black.

<Production of Modified Conjugated Diene Polymer>
(Modified Conjugated Diene Polymer (1))
A 5 liter autoclave reactor purged with nitrogen was charged with 2750 g of cyclohexane, 0.0285 mmol of 2,2-ditetrahydrofurylpropane, 375 g of 1,3-butadiene and 2.85 mmol of n-butyllithium as a cyclohexane solution and stirred. Polymerization was carried out for 4.5 hours in a 50 ° C. hot water bath equipped with an apparatus.
When the polymerization conversion rate reached 99%, 2.08 mmol of tributyltin chloride was added and the modification reaction was performed for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Subsequently, the solvent was removed by steam stripping, and the rubber was dried by a hot roll adjusted to 110 ° C. to obtain a modified conjugated diene polymer (1). In addition, the weight average molecular weight (Mw) of polystyrene conversion by GPC of the conjugated diene polymer before modification was 510,000, and the vinyl bond amount was 14%.

(Modified Conjugated Diene Polymer (2))
The modified conjugated diene polymer (1) was prepared in the same manner as the modified conjugated diene polymer (1) except that tributyltin chloride was changed to 0.52 mmol of tin tetrachloride in the production of the modified conjugated diene polymer (1). Combined (2) was obtained.

(Modified conjugated diene polymer (3))
In the production of the modified conjugated diene polymer (1), the modified conjugated diene polymer (1) was modified in the same manner as in the production of the modified conjugated diene polymer (1) except that tributyltin chloride was changed to 2.08 mmol of tetraethoxysilane. Combined (3) was obtained.

(Modified Conjugated Diene Polymer (4))
In the production of the modified conjugated diene polymer (1), except that tributyltin chloride was changed to 2.08 mmol of N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, In the same manner as in the production of the modified conjugated diene polymer (1), a modified conjugated diene polymer (4) was obtained.

(Modified Conjugated Diene Polymer (5))
After adding 2750 g of cyclohexane, 375 g of 1,3-butadiene, 2.85 mmol of n-butyllithium and 2.85 mmol of hexamethyleneimine to an autoclave reactor with an internal volume of 5 liters purged with nitrogen, 0.0285 mmol of tetrahydrofuran was added to the cyclohexane solution. The polymerization was carried out for 4.5 hours in a 50 ° C. warm water bath equipped with a stirrer.
When the polymerization conversion rate reached 99%, 2.08 mmol of tributyltin chloride was added and the modification reaction was performed for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Next, the solvent was removed by steam stripping, and the rubber was dried by a hot roll adjusted to 110 ° C. to obtain a modified conjugated diene polymer (5). In addition, the polystyrene equivalent weight average molecular weight (Mw) by GPC of the conjugated diene polymer before modification was 560,000.

(Modified Conjugated Diene Polymer (6))
・ Production of modifying agent 3.4 g (0.05 mol) of imidazole was melted at 95 ° C., and 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane was added over 30 minutes while stirring in an argon atmosphere. And dripped. After completion of the dropwise addition, the reaction was further carried out at 95 ° C. for 1 hour. This reaction product A was obtained as a dark brown viscous liquid. When used in a modification reaction of anionic polymerization, 5 g of this reaction product A is dissolved in 18 mL of cyclohexane, and 10 mL of n-butyllithium (1.6 N hexane solution) is added and stirred thoroughly immediately before use in the modification reaction. A denaturant solution A was obtained.
-Production of polymer The production of the modified conjugated diene polymer (1) was the same as that of the modified conjugated diene polymer (1) except that tributyltin chloride was changed to 5.7 mL of the above modifier solution A. Thus, a modified conjugated diene polymer (6) was obtained.

(Modified Conjugated Diene Polymer (7))
In a 5 liter autoclave reactor purged with nitrogen, 2750 g of cyclohexane, 0.05 mmol of 2,2-ditetrahydrofurylpropane, 75 g of styrene, 300 g of 1,3-butadiene, and 2.85 mmol of n-butyllithium as a cyclohexane solution The polymerization was carried out for 4.5 hours in a 50 ° C. warm water bath equipped with a stirring device.
When the polymerization conversion rate reached 99%, 2.08 mmol of tetraethoxysilane was added and the modification reaction was performed for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Next, the solvent was removed by steam stripping, and the rubber was dried by a hot roll adjusted to 110 ° C. to obtain a modified conjugated diene polymer (7). In addition, the weight average molecular weight (Mw) of polystyrene conversion by GPC of the conjugated diene polymer before modification was 490,000, and the vinyl bond amount was 20%.

(Modified Conjugated Diene Polymer (8))
Modified conjugated diene system, except that in the production of the modified conjugated diene polymer (7), tributyltin chloride was changed to 5.7 mL of the modifier solution A used in the production of the modified conjugated diene polymer (6). In the same manner as in the production of the polymer (1), a modified conjugated diene polymer (8) was obtained.

<Examples 1 to 16 and Comparative Examples 1 to 7>
Using each of the carbon blacks A to K shown in Table 2, 23 types of rubber compositions were prepared with a Banbury mixer according to the formulation shown in Table 3.
Next, 23 types of tires for tires having a tire size of 11R22.5 using these 23 types of rubber compositions as treads were produced according to a conventional method, and rolling resistance (low heat generation) and wear resistance were evaluated. The results are shown in Table 3.

[note]
1) Natural rubber: RSS # 1
2) Polybutadiene rubber: Ube Industries, Ltd., trade name "UBEPOL-BR150L" (vinyl bond content: 1%, weight average molecular weight (Mw): 520,000)
3) Modified diene polymer: Modified conjugated diene polymers (1) to (8) obtained by production of modified conjugated diene polymers.
4) Carbon black: Carbon black D and K obtained from carbon black production
5) Anti-aging agent 6C: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “NOCRACK 6C”
6) Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller CZ”

From the results shown in Table 3, the tires of Examples 1 to 16 using the rubber composition in which a predetermined amount of carbon black with a small amount of tar existing on the surface was blended with the rubber component containing the modified conjugated diene polymer, It can be seen that the rolling resistance and wear resistance are highly balanced.

Claims (16)

1. A rubber component containing a conjugated diene polymer having at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom in any one of a polymerization active terminal, a polymerization initiation terminal and a polymerization chain;
   Using a reaction apparatus 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 a raw material is sprayed into the reaction zone. A carbon black for rubber compounding obtained by quenching the reaction gas stream containing the carbon black in the reaction stop zone and terminating the reaction,
   A rubber composition in which the carbon black for rubber blending satisfies the following relational expressions (1) and (2).
   10 <X <40 (1)
   90 <Z <100 (2)
   (However, X represents the toluene coloring permeability (%) of carbon black after introduction of the first quenching medium from the raw material introduction position, and Z represents the toluene coloring permeability of carbon black after the last quenching medium introduction ( %).)
2. The conjugated diene polymer is a modified conjugated diene obtained by subjecting a polymerization active terminal to a compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom after the polymerization reaction. The rubber composition according to claim 1, which is a polymer.
3. The modified conjugated diene polymer has the following general formula (I) at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
   R _a MX _b (I)
   Wherein R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. , M is tin or silicon, X is independently chlorine, bromine or iodine, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4). A compound represented by formula (II)
   R ¹ _a M (OR ² ) _b (II)
   Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aralkyl having 7 to 20 carbon atoms. M is tin or silicon, X is independently chlorine, bromine or iodine, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4 The rubber composition according to claim 2, which is a modified conjugated diene polymer obtained by reacting at least one modifier selected from compounds represented by
4. The modified conjugated diene polymer has an active site of the conjugated diene polymer having an organometallic active site in the molecule, and the following general formula (III):
   

   

   
   (Wherein, a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and A is a saturated cyclic tertiary amine compound residue, Unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group, pyridine group , (Thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, carboxylic acid halogen A compound residue, and at least one functional group selected from a secondary amino group or a mercapto group having a hydrolyzable group, and when A is plural, they may be the same It may be made to.
   R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R ¹ is plural. May be different. R ² is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ² is plural, they are the same or different. May be. R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ³ is plural, they may be the same or different. Good. The rubber composition according to claim 2, which is a modified conjugated diene polymer obtained by reacting a modifier represented by formula (1) and a condensate thereof.
5. The modified conjugated diene polymer is a modified conjugated diene polymer obtained by reacting a condensate of a compound represented by the following general formula (II) with a modifier represented by the following general formula (III). The rubber composition according to claim 2.
   R ¹ _a M (OR ² ) _b (II)
   Wherein R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and an aralkyl having 7 to 20 carbon atoms. M is tin or silicon, X is independently chlorine, bromine or iodine, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4 Is)
   

   

   
   (Wherein, a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and A is a saturated cyclic tertiary amine compound residue, Unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group, pyridine group , (Thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, carboxylic acid halogen A compound residue, and at least one functional group selected from a secondary amino group or a mercapto group having a hydrolyzable group, and when A is plural, they may be the same It may be made to.
   R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R ¹ is plural. May be different. R ² is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ² is plural, they are the same or different. May be. R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ³ is plural, they may be the same or different. Good. )
6. 6. The rubber composition according to claim 2, wherein the modified conjugated diene polymer further contains a nitrogen atom.
7. The rubber composition according to claim 1, wherein the conjugated diene polymer is a polymer or copolymer of a conjugated diene compound.
8. The rubber composition according to claim 1, wherein the conjugated diene polymer is a copolymer of an aromatic vinyl compound and a conjugated diene compound.
9. The conjugated diene polymer contains 1% by mass or more and 60% by mass or less of a structural unit derived from an aromatic vinyl compound, and the vinyl bond content in the conjugated diene part is 5% by mass or more and 80% by mass or less. Or 9. The rubber composition according to 8.
10. The residence time in the zone from the introduction of the raw material 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.). The residence time in the zone from the introduction of the first quenching medium to the introduction of the second quenching medium is t ₂ (seconds), and the average reaction temperature in this zone is T ₂ (° C.). Furthermore, the residence time in the zone from the introduction of the second quenching medium to the introduction of the last quenching medium is t ₃ (seconds), and the average reaction temperature in this zone is T ₃ (° C.). In this case, the carbon black for rubber compounding has the following relational expressions (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)
    (However, α1 = t ₁ × T ₁ , α2 = t ₂ × T ₂ , β = t ₃ × T _3. )
    The rubber composition according to any one of claims 1 to 9, wherein the rubber composition is obtained by controlling to satisfy the above.
11. The rubber compounding carbon black has the following relational expressions (6), (7) and (8):
    20 <X <40 (6)
    50 <Y <60 (7)
    90 <Z <95 (8)
    (In the formula, Y represents the toluene coloring permeability of carbon black after introduction of the second quenching medium, and X and Z are the same as described above.)
    The rubber composition according to any one of claims 1 to 10, wherein the rubber composition is obtained by controlling to satisfy the above.
12. The rubber composition according to any one of claims 1 to 11, wherein a hydrogen release rate of the carbon black for rubber blending is higher than 0.3% by mass.
13. Dibutyl phthalate absorption (DBP) in the rubber compounding carbon black is 95 mL / 100 g or more and 220 mL / 100 g or less, compressed DBP absorption (24M4DBP) is 90 mL / 100 g or more and 200 mL / 100 g or less, and cetyltrimethylammonium bromide The rubber composition according to any one of claims 1 to 12, which has an adsorption specific surface area (CTAB) of 70 m ² / g or more and 200 m ² / g or less.
14. The rubber composition according to any one of claims 1 to 13, wherein the rubber composition contains 5 to 80 parts by mass of the conjugated diene polymer with respect to 100 parts by mass of a rubber component.
15. The rubber composition according to any one of claims 1 to 14, wherein the rubber composition contains 10 parts by weight or more and 250 parts by weight or less of the carbon black for rubber blending with respect to 100 parts by weight of a rubber component.
16. A tire comprising the rubber composition according to any one of claims 1 to 15.

Images