JP2003155398A - Rubber composition - Google Patents

Abstract

(57) Abstract: The present invention provides a diene-based rubber composition having improved balance between low rolling resistance and wet skid resistance in a silica blend. The conjugated diene-based monomer polymerized by using an anionic polymerization initiator as an initiator, or the polymerization active terminal of a conjugated diene-based monomer and an aromatic vinyl compound is added to two or more epoxy groups in the molecule. 100 parts by weight of a rubbery polymer (A) obtained by reacting a polyfunctional compound having the following formula, 25 to 100 parts by weight of silica (B), and 0.1 to 20 parts by weight of an organic silane coupling agent (C). A modified conjugated diene rubber composition comprising an organic silane compound (D) represented by the following general formula (1) in an amount of 0.1 to 20% by weight based on the amount of silica. SiR ¹ _n (OR ² ) _4-n (1) (In the above formula, R ¹ and R ² are an alkyl group, an alkenyl group, a cycloalkenyl group, or an aromatic hydrocarbon group, which may be different or the same. .N is an integer of 0 to 3.)

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a rubber composition containing a conjugated diene rubber having excellent hysteresis loss characteristics of a rubber composition containing silica as a filler. More specifically, the present invention relates to a novel conjugated diene polymer rubber composition obtained by blending a diene rubber modified with an epoxy polyfunctional compound and a specific silane compound. The sulfide has a better balance between low rolling resistance and wet skid resistance, and is suitably used for applications where a conjugated diene polymer rubber composition has been conventionally used mainly for tires.

[0002]

2. Description of the Related Art The technique of using silica as a reinforcing filler in rubber for tire tread is widely known. A typical technique thereof is shown, for example, in U.S. Pat. No. 5,227,425, in which silica is used as a reinforcing filler in SBR having a specific structure, and the kneading conditions of the rubber composition are specified to obtain a tread rubber. A method for improving the balance between the fuel saving performance and the wet skid resistance performance of the composition has been proposed. However, since silica has a lower affinity for rubber than conventional carbon black, its dispersibility in rubber is not necessarily good, and this poor dispersibility tends to cause insufficient wear resistance and insufficient strength characteristics. Is. In order to improve the dispersibility of silica, it is necessary to improve the dispersion of silica by using a silane coupling agent represented by bis- (triethoxysilylpropyl) -tetrasulfide.

In order to improve the dispersibility of silica in rubber, JP-A-10-273559 discloses that
A rubber composition for a tire tread comprising 100 parts by weight of a diene rubber, 5 to 80 parts by weight of silica and a polysiloxane obtained by condensing a specific alkoxysilane, or 60% by weight or more of a specific alkoxysilane and sulfur. A rubber composition for a tire tread has been proposed which comprises a polysiloxane obtained by cohydrolyzing and condensing 40% by weight or less of a silane coupling agent.

Furthermore, Japanese Patent Laid-Open No. 2001-240700
In the report, natural rubber and / or diene-based synthetic rubber 10
5 to 100 parts by weight of silica and silane relative to 0 parts by weight
1 to 20% by weight of the coupling agent based on the weight of silica,
And the formula (R¹O)_nSiR _2n-4Organic kei represented by
Containing 1 to 25% by weight of elementary compound relative to the weight of silica
A rubber composition characterized by the following is proposed. But Naga
In both cases, the affinity between silica and rubber is insufficient, and practical
It was not satisfactory.

[0005]

Under these circumstances,
An object of the present invention is to provide a diene-based rubber composition having an improved balance between low rolling resistance and wet skid resistance in silica compounding.

[0006]

SUMMARY OF THE INVENTION In order to solve the above problems, the present inventors have found that a rubber-like polymer containing silica and a specific modifying component is added to an organic silane coupling agent and a specific organic silane compound. It has been found that the combined use of and and has excellent performance, and the present invention has been completed.

That is, the present invention is as follows: 1. A polymerization active terminal obtained by polymerizing a conjugated diene monomer in a hydrocarbon solvent using an anionic polymerization initiator as an initiator or a conjugated diene monomer and an aromatic compound. 100 parts by weight of a modified conjugated diene polymer (component A) obtained by reacting a polyfunctional compound having two or more epoxy groups in the molecule with a polymerization active terminal obtained by copolymerization with a group vinyl compound , Silica (B component) 25 to 100 parts by weight, and an organic silane coupling agent (C component) in an amount of silica of 0.1 to 20.
A modified conjugated diene rubber composition for vulcanization, which comprises 0.1% to 20% by weight of an organic silane compound (component D) represented by the following general formula (1) with respect to the amount of silica. SiR ¹ _n (OR ² ) _4-n (1) (In the above formula, R ¹ and R ² are an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, and they may be different or the same. n is an integer of 0 to 3.)

2. Polymerization of a conjugated diene monomer obtained by polymerizing a conjugated diene monomer in a hydrocarbon solvent using an anionic polymerization initiator as an initiator, and an aromatic vinyl compound. 100 parts by weight of a modified conjugated diene polymer (A component) obtained by reacting a polyfunctional compound having two or more epoxy groups in the molecule with a polymerization active terminal obtained by copolymerization, silica (B component) ) 25 to 100 parts by weight and 10 to 90% by weight of the organic silane coupling agent
And an organic silane compound 90 represented by the following general formula (1)
The siloxane compound (component E) obtained by hydrolyzing and condensing a mixture of 10% by weight and 0.1% of the amount of silica.
It is a modified conjugated diene rubber composition for vulcanization consisting of ˜20% by weight. SiR ¹ _n (OR ² ) _4-n (1) (In the above formula, R ¹ and R ² are an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, and they may be different or the same. . N is an integer of 0 to 3.)

3. A polyfunctional compound having two or more epoxy groups in its molecule is a modified conjugated diene rubber composition for vulcanization represented by a polyfunctional compound of the following general formula.

[0010]

[Chemical 2]

(However, R ¹ and R ² have 1 to 10 carbon atoms.
Hydrocarbon group or ether and / or a hydrocarbon group having 1 to 10 carbon atoms having a tertiary amine, R ³ and R ⁴ are
Hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or an ether, and or a hydrocarbon group having 1 to 20 carbon atoms having a tertiary amine, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms or an ether, a tertiary amine, It is a hydrocarbon group having 1 to 20 carbon atoms and at least one kind of epoxy, carbonyl, and halogen, and n is 1 to 6. )

4, modified conjugated diene polymer (component A) 9
Modified conjugation for vulcanization consisting of 9 to 20% by weight and 1 to 80% by weight of at least one rubber selected from natural rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, polyisoprene rubber and butyl rubber. It is a diene rubber composition. 5, silica (B component), organic silane coupling agent (C
Component), a silane compound (D component) and one or more kinds of siloxane compounds (E component) are pre-mixed silica for use in the modified conjugated diene rubber composition for vulcanization. 6, kneading discharge temperature of raw rubber (component A), silica (B) component, organic silane coupling agent (C) component, silane compound (D) component, siloxane compound (E component) and, if necessary, other compounding ingredients Is a modified conjugated diene rubber composition for vulcanization obtained by kneading once or more under the condition that the temperature is 135 to 180 ° C.

The present invention will be described in detail below. The modified conjugated diene rubber composition for vulcanization of the present invention is a rubber-like polymer,
A modified conjugated diene-based polymer (component A) obtained by reacting a polyfunctional compound having two or more epoxy groups in the molecule is used. Modified conjugated diene polymer (component A) of the present invention
Is a specific conjugated diene rubbery polymer or conjugated diene-styrene rubbery copolymer, in an inert solvent,
Modification obtained by reacting a conjugated diene-based rubbery polymer having an active end obtained by anionic polymerization or a conjugated diene-styrene-based rubbery copolymer with a polyfunctional compound having two or more epoxy groups in the molecule The content of ingredients is 40
It is more than weight%.

In the present invention, the conjugated diene of the conjugated diene rubber-like polymer or the conjugated diene-styrene rubber-like copolymer is preferably 1,3-butadiene or isoprene, and the copolymerized styrene is a random copolymer. It is preferable that If necessary, other copolymerizable monomers may be copolymerized in an amount of 10% by weight or less.
In the method for producing the conjugated diene rubber-like polymer or the conjugated diene-styrene rubbery copolymer (hereinafter sometimes abbreviated as rubbery polymer), the inert solvent may be saturated hydrocarbon, aromatic carbon Hydrogen, an aliphatic hydrocarbon such as butane, pentane, hexane, pentane and heptane, an alicyclic hydrocarbon such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane, and an aromatic hydrocarbon such as benzene, toluene and xylene. And hydrocarbons consisting of mixtures thereof.

An anionic polymerization initiator is used as the polymerization initiator, and an organic alkali metal compound or an organic alkaline earth metal is preferable, and an organic lithium compound is particularly preferable. Particularly preferred is n-butyllithium, sec
-Butyl lithium. These organolithium compounds may be used not only as one type but also as a mixture of two or more types. The polymerization reaction is carried out under the conditions usually performed, for example, 20 to
At a polymerization temperature of 150 ° C, the final polymer concentration is 5 to 3
It is carried out in a concentration range of 0% by weight, and the polymerization temperature is controlled by the feed temperature of the monomer and the solvent, the monomer concentration, and cooling or heating from the outside of the reactor in consideration of the fact that the polymerization is an exothermic reaction.

The rubber-like polymer used in the present invention (hereinafter sometimes referred to as raw rubber (component A)) is a diene-based polymer having an active terminal obtained by the above-mentioned method. It is obtained by reacting the above polyfunctional compound having an epoxy group. As the modifier used to obtain the polymer containing the modifying component of the present invention, a polyfunctional compound having two or more epoxy groups in the molecule is used, and examples thereof include the following.

Specifically, polyglycidyl ethers of polyhydric alcohols such as ethylene glycol diglycidyl ether and glycerin triglycidyl ether, polyglycidyl ethers of aromatic compounds having two or more phenol groups such as diglycidylated bisphenol A, 1,4-
Polyepoxy compounds such as diglycidylbenzene, 1,3,5-triglycidylbenzene and polyepoxidized liquid polybutadiene, epoxies such as 4,4′-diglycidyl-diphenylmethylamine and 4,4′-diglycidyl-dibenzylmethylamine Group-containing tertiary amine, diglycidylaniline, diglycidyl orthotoluidine, tetraglycidyl metaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane,
It is a diglycidylamino compound such as tetraglycidyl-1,3-bisaminomethylcyclohexane.

Polyfunctional compounds having two or more epoxy groups and one or more nitrogen-containing groups in the molecule are preferably used. More preferably, a polyfunctional compound represented by the following general formula is used.

[0019]

[Chemical 3]

However, R ¹ and R ² are hydrocarbon groups or ethers having 1 to 10 carbon atoms and / or hydrocarbon groups having 1 to 10 carbon atoms having a tertiary amine, and R ³ and R ⁴ are hydrogen and carbon numbers. A hydrocarbon group or ether having 1 to 20 and / or a hydrocarbon group having 1 to 20 carbon atoms having a tertiary amine, R ⁵ represents a hydrocarbon group or ether having 1 to 20 carbon atoms, a tertiary amine, epoxy, carbonyl, It is a hydrocarbon group having 1 to 20 carbon atoms having at least one kind of halogen, and n is 1 to 6.

More preferred are polyfunctional compounds having a diglycidylamino group. Further, the number of epoxy groups in the molecule needs to be 2 or more, more preferably 3 or more, and further preferably 4 or more. The specific rubbery polymer used in the present invention has a content of the modifying component by the polyfunctional compound of 40% by weight or more, preferably 60% by weight or more based on the whole polymer. More preferably, 70
It is recommended that more than 80% by weight, particularly preferably 80% by weight or more. When the content of the modifying component is large, the effect of the filler as silica is more exerted. The content of the modified component can be measured by chromatography capable of separating the modified component and the non-modified component.

As a method of this chromatography,
A method of quantifying using a GPC column that uses a polar substance such as silica that adsorbs modified components as a packing material, and uses an internal standard for non-adsorbed components, and measures the GPC of the polymer before modification and the polymer after modification And a method of calculating the amount of the modified portion based on the change in the molecular weight. The molecular weight distribution Mw / Mn of the rubbery polymer (component A) used in the present invention is in the range of 1.05 to 3.0. The molecular weight distribution is determined by the method of measuring the molecular weight of standard polystyrene using GPC. When the molecular weight distribution is less than 1.05, the workability is poor and it is difficult to industrially manufacture. 3.
When it exceeds 0, the mechanical strength of the obtained vulcanized rubber composition is poor.

Conventionally, polymers having a molecular weight distribution of 2.2 or more are excellent in workability at the time of kneading, the torque at the time of processing is not large, and the kneading time may be short. If the molecular weight distribution is less than 2.2, the workability is generally poor, and particularly in the case of silica blending, the torque at the time of processing becomes large. Therefore, it has conventionally been necessary to use a large amount of carbon black together. In the case of the present invention, the processability is excellent even within the range of the molecular weight distribution described above even when the compounding amount of carbon black is small because the affinity with silica is particularly enhanced, and the vulcanization obtained is further improved. The rubber composition has an excellent balance of low rolling resistance and wet skid resistance, and also has excellent strength characteristics.

The Mooney viscosity (MV-M) of the (A) component rubbery polymer of the present invention is preferably in the range of 20 to 200. The Mooney viscosity is Mooney viscosity (ML1 + 4 (100 ° C)) measured at 100 ° C using a Mooney viscometer specified in the standard. However, when the Mooney viscosity (ML1 + 4 (100 ° C)) value exceeds about 150 and it is difficult to measure at 100 ° C, for example, measure at 130 ° C and convert it to the value at 100 ° C. . Mooney viscosity (MV-
When M) is less than 20, the strength and abrasion resistance of the obtained vulcanized rubber composition are reduced, and when it exceeds 200, the processing performance is extremely reduced and it becomes difficult to obtain a rubber composition. The Mooney viscosity (MV-M) is more preferably in the range of 25 to 180.

The glass transition temperature of the rubbery polymer of the component (A) of the present invention is preferably in the range of -100 to 0 ° C. so that the finally obtained vulcanized rubber composition exhibits rubber elasticity. Furthermore, the range of −95 to −10 ° C. is more preferable. The glass transition temperature of the rubber-like polymer used in the present invention is selected within the range depending on the intended use of the rubber composition. For example, in applications where low-temperature performance is more important, the rubber-like polymer having a low glass transition temperature is used. Is mainly selected, and a rubber-like polymer having a glass transition temperature in a high range is mainly selected in applications where braking ability is required.

The glass transition temperature is controlled by the composition of the constituent conjugated diene monomer and aromatic vinyl monomer, and when the conjugated diene monomer is butadiene or isoprene, it has a microstructure in the polymer chain. It can be controlled by the ratio of (1,4-bond and 1,2- and 3,4-bond). When the rubber-like polymer of the present invention is polybutadiene, the amount of 1,2-bonds of butadiene micro-bonds is 10 to 80%, preferably 10 to 70%, and the rubber-like polymer of the present invention is a styrene-butadiene random copolymer. In the case of a polymer, the amount of styrene is 5 to 45%, preferably 5 to 35%.

The rubber-like polymer of the component (A) of the present invention may be added with a usual extender oil for rubber in order to make the processing easier. As extender oils for rubber, in addition to the aromatic, naphthenic and paraffinic extender oils that have been conventionally used, there are few polynuclear aromatic components such as MES, T-DAE and T-RAE, and environmentally friendly rubber. Extender oil can also be used. In the present invention, the extender oil for rubber is used in an amount of 1 to 100 parts by weight per 100 parts by weight of the raw rubber. The amount of the extender oil for rubber is increased or decreased according to the amounts of the reinforcing silica filler and the reinforcing carbon black, which will be described later, and is used to control the elastic modulus of the compound after vulcanization. When the amount of the extender oil for rubber exceeds 100 parts by weight, the hysteresis loss performance and wear resistance of the obtained rubber composition are deteriorated, which is not preferable. The amount of the extender oil for rubber is preferably in the range of 5 to 60 parts by weight.

The rubber-like polymer of the component (A) of the present invention is 1
Not only one kind, but also a mixture of two or more kinds of modified rubbery polymers may be used. In the present invention, it is also possible to use a raw material rubber composed of 99 to 20% by weight of the (A component) and 1 to 80% by weight of a vulcanizable rubber-like polymer as the raw material rubber. As the other component, one or more of synthetic rubber and natural rubber may be used, if necessary.

Specifically, butadiene rubber, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, synthetic polyisoprene rubber, butyl rubber,
One or more rubbers selected from natural rubbers. For example, as butadiene rubber, high cis butadiene rubber using various catalysts such as cobalt type, nickel type, neodymium type and uranium type, low cis butadiene using lithium type catalyst Rubber, medium / high vinyl butadiene rubber, styrene-
As the butadiene rubber, emulsion-polymerized styrene-butadiene rubber having a styrene content of 3 to 50% by weight, and solution-polymerized styrene-butadiene having a styrene content of 3 to 50% by weight and a 1,2-bond amount of a butadiene portion of 10 to 80%. The rubber and the styrene-isoprene-butadiene rubber have a styrene content of 3 to 40% by weight and an isoprene content of 3 to 4
0% by weight of styrene-isoprene-butadiene rubber,
Examples of the synthetic polyisoprene rubber include synthetic polyisoprene rubber having a cis 1,4-bond content of 90% or more.

The composition is used by optimizing the physical properties and processability according to the purpose of use of the rubber composition. A particularly preferable other component is a solution-polymerized styrene-butadiene rubber, and in this case, the balance between low rolling resistance and wet skid resistance, which is the object of the present invention, is the best. As the silica of the (B component) of the present invention, any of wet process silica, dry process silica, and synthetic silicate silica can be used. It is silica having a small particle size that has a high reinforcing effect and a high grip performance improving effect, and a small particle size / high aggregation type is preferable. The silica of the present invention is used as a filler having a reinforcing effect in an amount of 25 per 100 parts by weight of raw rubber.
~ 100 parts by weight are used. If it is less than 25 parts by weight, the strength and other physical properties are inferior, and if it exceeds 100 parts by weight, it becomes too hard, the strength is rather lowered, and the rubber performance is deteriorated. The amount of silica is preferably 30 to 90 parts by weight.

In the present invention, in order to make the coupling action (mutual coupling action) between silica and the raw rubber close, (C
An organic silane coupling agent is used as a component). The organic silane coupling agent is 0.1 to 20 times the amount of silica.
%, Preferably 0.5 to 17% by weight, more preferably 1 to 15% by weight. The organic silane coupling agent used in the present invention has a group having an affinity or a bonding group in the molecule for the double bond of the polymer and the surface of silica. A preferred organic silane coupling agent is one having a silanol group or an alkoxysilane and at the same time a mercapto group or / and a polysulfide bond in which two or more sulfurs are linked, and examples thereof include bis- [3- (triethoxysilyl). ) -Propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2-
(Triethoxysilyl) -ethyl] -tetrasulfide, 3-mercaptopropyl-trimethoxysilane, 3
-Triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide and the like can be mentioned.

From the viewpoint of the effect of addition, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide and the like are preferable. These organic silane coupling agents may be used alone or in combination of two or more. The (D component) of the present invention comprises an organosilane compound represented by the following general formula (1). SiR ¹ _n (OR ² ) _4-n (1) (In the above formula, R ¹ and R ² are an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, and they may be different or the same. n is an integer of 0 to 3.)

As a specific example, tetraethoxysilane,
Tetramethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane,
Methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, octyltrimethoxysilane, octyltrimethoxysilane, ethyltriacetoxysilane, and the like, and particularly preferably tetraethoxysilane. As the D component, one kind may be used, or two or more kinds of compounds having different structures may be used.

The compounding amount of the organic silane compound contained in the rubber composition of the present invention is 0.1 to 20% by weight, preferably 2 to 15% by weight based on the amount of silica. If the compounding amount of the organic silane compound is less than 0.1% by weight, the effect of adding the silane compound is not sufficient, and if it exceeds 20% by weight, the rolling resistance property tends to be deteriorated. In the present invention,
(Component C) organosilane coupling agent and / or (D
It is also recommended to use silica in which the silane compound of (Component) is premixed with the silica of (Component B).

The organosilane coupling agent and the organosilane compound of the present invention may be used by mixing them in advance, or may be used without mixing. Further, as the (E component) of the present invention, a mixture of 10 to 90% by weight of the above-mentioned organic silane coupling agent and 90 to 10% by weight of the organic silane compound represented by the following general formula (1) is hydrolyzed, The siloxane compound obtained by condensation can be used in the range of 0.1 to 20% by weight based on the amount of silica. SiR ¹ _n (OR ² ) _4-n (1) (In the above formula, R ¹ and R ² are an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, and they may be different or the same. n is an integer of 0 to 3.)

The method of synthesizing the siloxane compound is described in JP-A-6-
It is already known in Japanese Patent Laid-Open No. 200331 and the like, and is synthesized by hydrolyzing and condensing an organic silane coupling agent and an organic silane compound using an acid or a base as a catalyst. In order to improve the bonding property between silica and rubber, the organosilane coupling agent is 10 to 90% by weight or less, preferably 10 to 90% by weight.
70% by weight or less, more preferably 20 to 60% by weight or less is copolymerized. The organosilane coupling agent used for the copolymerization may be used alone or in combination of two or more.

The organosilane compound used for the copolymerization may be one kind or two or more kinds. The synthesized siloxane compound is added in an amount of 0.1 to 20% by weight, preferably 0.5 to 17% by weight, and more preferably 1 to 15% by weight based on the amount of silica. In addition to the above rubber component, silica, organic silane coupling agent, organic silane compound, and siloxane compound, the rubber composition of the present invention may optionally contain carbon black, extender oil for rubber, zinc white, stearin. Compounding agents used in ordinary rubber industry, such as acids, antioxidants, vulcanizing agents, vulcanization accelerators, vulcanization accelerating aids, etc., can be appropriately added. Zinc white, stearic acid, an antioxidant, a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerating aid and the like are generally used in the range of 0.1 to 20 parts by weight.

The method of obtaining the modified diene rubber composition for vulcanization of the present invention is not particularly limited, and known methods can be used. For example, Banbury mixer,
A melt-kneading method using a general kneader such as a dough roll, a screw type extruder or the like is used. Particularly preferred methods are (A component) raw material rubber, (B component) silica (carbon black if necessary), (C component) organic silane coupling agent, (D component) organic silane compound, and optionally other The compounding agent has a kneading discharge temperature of 135 to 18
This is a method of kneading once or more using a known closed kneader such as an internal mixer under the condition of 0 ° C, preferably 140 to 170 ° C.

In the case of kneading two or more times, compounding agents such as an antioxidant, a vulcanizing agent and a vulcanization accelerator may be added, if necessary. By adjusting the kneading method and the kneading discharge temperature, a modified diene rubber composition for vulcanization, which has the better balance between low rolling resistance and wet skid resistance, which is the object of the present invention, can be obtained. The amount of bound rubber is 3
It is necessary to be 0 to 70% by weight. If it is less than 30% by weight, a diene polymer rubber vulcanizate having an improved balance between low rolling resistance and wet skid resistance, which is the object of the present invention, cannot be obtained. On the other hand, if it exceeds 70% by weight, the torque during kneading becomes high and processing becomes difficult. The amount of bound rubber is preferably 40 to 70% by weight.

The modified diene rubber composition for vulcanization of the present invention is vulcanized by a commonly used vulcanization method, for example, 120 to 2
Vulcanized at a temperature of 00 ° C, preferably 140-180 ° C,
It exerts its performance in the state of the obtained diene polymer rubber vulcanizate. If necessary, carbon black, softener,
A compounding agent used in a usual rubber industry, such as an antioxidant, a vulcanizing agent, a vulcanization accelerator, and a vulcanization accelerating aid, can be appropriately mixed. The modified conjugated diene-based polymer composition of the present invention,
In the form of a rubber vulcanizate, it is preferably used for high performance tires and tire tread compounds typified by all-season tires, but also for other tire applications and anti-vibration rubbers, belts,
It can also be applied to industrial products and footwear by taking advantage of its features.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples and Comparative Examples, but these do not limit the scope of the present invention. Production method of sample A 1: An internal volume of 10 liters, a stirrer and a temperature-controllable autoclave equipped with a jacket were used as a reactor, and 6 parts of butadiene with impurities removed
45g, 280g of styrene, 550 of cyclohexane
0 g and 0.70 g of 2,2-bis (2-oxolanyl) propane as a polar substance were put into the reactor, and the temperature inside the reactor was kept at 30 ° C. A cyclohexane solution containing 0.85 g of n-butyllithium as a polymerization initiator was supplied to the reactor. After the reaction was started, the internal heat of the reactor gradually increased due to the heat generated by the polymerization. 7 to 5/12 minutes after addition of polymerization initiator
Over a period of 75 minutes, 75 g of butadiene was fed at a rate of 15 g / min. The final reactor internal temperature reached 75 ° C. After the completion of the polymerization reaction, a part of the polymer solution was collected. The Mooney viscosity of the polymer before modification reaction measured after removing the solvent is 10
It was 7 at 0 ° C.

1.2 g of tetraglycidyl-1,3-bisaminomethylcyclohexane was used as a modifier in the reactor.
The mixture was added and kept at 75 ° C. for 5 minutes to carry out a denaturing reaction.
After adding an antioxidant to this polymer solution, the solvent was removed to obtain a styrene-butadiene copolymer (Sample A) having a target modifying component. The Mooney viscosity of the polymer after this modification was 65 when measured at 100 ° C. As a result of analyzing the sample A, the amount of bound styrene was 28% and the amount of bound butadiene was 72%. Further, the 1,2-bond content of the microstructure of the butadiene portion calculated from the measurement results using the infrared spectrophotometer according to the Hampton method was 52%, and G
The polystyrene-equivalent molecular weight distribution measured by PC has a weight average molecular weight (Mw) of 563,000 and a number average molecular weight (Mn).
Was 42,000, the molecular weight distribution (Mw / Mn) was 1.33, and the modification ratio determined by GPC using a silica-based adsorption column was 83% by weight.

Preparation of sample B: Table 1 is prepared in the same manner as sample A.
The sample B shown in FIG. Table 1 shows the analytical values of the above samples. The sample was analyzed by the method described below. 1) Amount of bound styrene was used as a chloroform solution, and the amount of bound styrene [S] was determined by absorption of UV 254 nm by phenyl group of styrene.
(Wt%) was measured. 2) Microstructure of butadiene part The carbon disulfide solution was used as a sample, the infrared spectrum was measured in the range of 600 to 1000 cm ^-1 using a solution cell, and the microstructure of the butadiene part was calculated from the predetermined absorbance according to the calculation method of the method of Hampton. I asked. 3) Mooney viscosity, 10 according to JIS K 6300
Measure the viscosity 4 minutes after preheating 1 minute at 0 ° C.

4) Molecular weight and molecular weight distribution Chromatograms were measured using GPC using three columns with polystyrene gel as a packing material, and molecular weight and molecular weight distribution were calculated using standard polystyrene using a calibration curve. . 5) Modification rate Applying the property that the modified component is adsorbed to the GPC column using silica gel as the packing material, and regarding the sample solution containing the sample and the low molecular weight internal standard polystyrene, the polystyrene gel of 4 above (manufactured by Showa Denko) : Shodex) GPC
And silica-based column GPC (Zorba manufactured by DuPont)
Both chromatograms of x) were measured, and the amount of adsorption to the silica column was measured from the difference between them to determine the modification rate. A rubber compound was obtained by the following kneading method using the compounds shown in Table 1 as raw rubbers and the compounds shown in Table 2.

[Kneading method] A closed kneader equipped with a temperature control device using circulating water from the outside (internal volume 1.7 liters)
As the first stage kneading, the raw material rubber, the filler (silica and carbon black), the organic silane coupling agent, the organic silane compound, the siloxane compound under the conditions of a filling rate of 65% and a rotor rotation speed of 66/77 rpm. Aromatic oil, zinc white, and stearic acid were kneaded. At this time, the temperature of the closed mixer was controlled to adjust the discharge temperature of the compound to 160 ° C. After the above-obtained blends were cooled to room temperature, as a second stage of kneading, an antioxidant was added to each blend and kneaded again to improve the dispersion of silica. Also in this case, control the temperature of the mixer,
The discharge temperature of the formulation was adjusted to 160 ° C.

After cooling the mixture obtained above to room temperature, as the third stage of kneading, sulfur and a vulcanization accelerator were added and kneaded with an open roll set at 70 ° C. After that, each compound was vulcanized by a vulcanizing press (vulcanization condition: 160
C., 20 to 30 minutes), and the following physical properties were measured. 1) Formulation Mooney viscosity: Using a Mooney viscometer, J
According to IS K 6300, the viscosity was measured at 130 ° C after 1 minute of preheating and 4 minutes of rotation. If the Mooney viscosity is much higher than 80, the workability is poor. When the Mooney viscosity is 30 or less, the tackiness is large and it becomes difficult to process.

2) Fuel economy: Tanδ at 50 ° C
Tested in. With a rheometrics Ares viscoelasticity tester, the frequency was 10 Hz, strain was 3%, and
Measured at 50 ° C. The smaller the number, the better the fuel efficiency. 3) Wet skid resistance performance: Tan δ at 0 ° C
Tested in. With a rheometrics Ares viscoelasticity tester, the frequency was 10 Hz, strain was 3%, and
Measured at 0 ° C. The larger the number, the better the wet skid resistance performance. 4) Bound rubber amount: After the second stage kneading, 0.2 g of the sampled composition was cut into about 1 mm square and put into a Harris cage (made of 100 mesh wire mesh) to measure the weight. After soaking in toluene for 24 hours, the weight was measured, and the amount of rubber bound to the filler was calculated from the amount of non-dissolved components to obtain the bound rubber amount.

[0048]

Examples 1 to 5 and Comparative Examples 1 and 2 Sample A and Sample B,
A vulcanized rubber composition was prepared by using, and the results of evaluation of its performance are shown in Table 3. As is clear from Examples 1 to 5 in Table 3, the vulcanized rubber composition defined in the present invention has good fuel economy as compared with the compositions of Comparative Examples 1 and 2,
The wet skid property is also good.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

According to the present invention, it is possible to provide a rubber composition excellent in workability, rolling resistance characteristics and wet grip performance. This vulcanized rubber composition is useful as a material for automobile tires and other industrial products that require fuel saving performance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 7/00 C08L 7/00 9/00 9/00 23/22 23/22 // (C08L 63/00 C08L 83:04 83:04) F-term (reference) 4F070 AA06 AA12 AA18 AA46 AA60 AB11 AB16 AC04 AC05 AC13 AC23 AC40 AC52 AC94 AE01 AE08 FA03 FA17 FB06 FB07 4J002 AC01X AC02W AC02W AC08W CD08W CD08W CD06W AC06W AC06W AC06W AC06X AC08W AC06W AC06W AC06X AC08W AC06W AC06W AC06W AC06W AC06W AC06W AC06W AC06W AC06X AC08W CD20W CP033 CP133 DJ016 EX038 EX087 FD010 FD016 FD140 FD207 GC00 GM01 GN01 GR00 4J031 AA13 AA29 AA47 AB01 AC04 AD01 AF05 AF18 AF20

Claims (7)

[Claims] 1. A polymerization active terminal or a conjugated diene monomer obtained by polymerizing a conjugated diene monomer in a hydrocarbon solvent using an anionic polymerization initiator as an initiator, and an aromatic vinyl compound. 100 parts by weight of a modified conjugated diene polymer (A component) obtained by reacting a polyfunctional compound having two or more epoxy groups in the molecule with a polymerization active terminal obtained by copolymerization, silica (B component) ) 25 to 100 parts by weight, an organic silane coupling agent (component C) in an amount of 0.1 to 20% by weight of the amount of silica, and an organic silane compound represented by the following general formula (1) (component D) in an amount of silica. 0.1
A modified conjugated diene rubber composition for vulcanization consisting of ˜20% by weight. SiR ¹ _n (OR ² ) _4-n (1) (In the above formula, R ¹ and R ² are an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, and they may be different or the same. . N is an integer of 0 to 3.) 2. A polymerization active terminal obtained by polymerizing a conjugated diene-based monomer in a hydrocarbon solvent using an anionic polymerization initiator as an initiator, or a conjugated diene-based monomer and an aromatic vinyl compound. 100 parts by weight of a modified conjugated diene polymer (A component) obtained by reacting a polyfunctional compound having two or more epoxy groups in the molecule with a polymerization active terminal obtained by copolymerization, silica (B component) ) 25 to 100 parts by weight, and organic silane coupling agent 10 to 90% by weight
And organosilane compounds 90-1 represented by the following general formula (1)
The siloxane compound (component E) obtained by hydrolyzing and condensing a mixture of 0% by weight and 0.1% by weight of silica is used.
20% by weight of a modified conjugated diene rubber composition for vulcanization. SiR ¹ _n (OR ² ) _4-n (1) (In the above formula, R ¹ and R ² are an alkyl group, an alkenyl group, a cycloalkenyl group or an aromatic hydrocarbon group, and they may be different or the same. . N is an integer of 0 to 3.) 3. The modified conjugated diene rubber composition for vulcanization according to claim 1 or 2, wherein the polyfunctional compound having two or more epoxy groups in the molecule is represented by a polyfunctional compound represented by the following general formula. object. [Chemical 1] (However, R ¹ and R ² are hydrocarbon groups or ethers having 1 to 10 carbon atoms and / or hydrocarbon groups having 1 to 10 carbon atoms having a tertiary amine, R ³ and R ⁴ are hydrogen, and 1 to carbon atoms. 20 hydrocarbon groups or ethers and / or 3
A hydrocarbon group having 1 to 20 carbon atoms having a primary amine, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms or an ether, a tertiary amine having at least one kind of a tertiary amine, epoxy, carbonyl and halogen; ~ 20 hydrocarbon groups,
n is 1 to 6. ) 4. A modified conjugated diene polymer (component A) 99.
20% by weight and 1 to 80% by weight of one or more rubbers selected from natural rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene-butadiene rubber, polyisoprene rubber, butyl rubber.
The modified conjugated diene rubber composition for vulcanization according to claim 2 or 3. 5. Silica (component B), an organic silane coupling agent (component C), a silane compound (component D) and a siloxane compound (component E) are used in combination with silica in advance. 4. The modified conjugated diene rubber composition for vulcanization according to any one of 4 above. 6. A modified conjugated diene polymer (component A), silica (component B), an organic silane coupling agent (component C), a silane compound (component D), a siloxane compound (E).
The modified conjugated diene rubber for vulcanization according to any one of claims 1 to 5, which is obtained by kneading the components) and optionally other compounding agents at least once under the condition that the kneading discharge temperature is 135 to 180 ° C. Composition. 7. A rubber product obtained by vulcanizing the modified conjugated diene rubber composition according to any one of claims 1 to 6.