JP6190711B2 - Process for producing modified conjugated diene polymer composition - Google Patents

Description

  The present invention relates to a method for producing a modified conjugated diene polymer composition.

  In recent years, with the emphasis on resource saving and environmental measures, the level of demand for automobile tires with excellent fuel efficiency is increasing.

  Various methods for manufacturing tires with excellent fuel efficiency have been proposed from the following viewpoints. That is, in order to reduce rolling resistance, it is known to use a rubber material capable of forming a crosslinked rubber as a material constituting a tread that becomes a contact surface with a road surface in a tire. When the crosslinked rubber is used, there is an advantage that energy loss of the tire can be suppressed and excellent rolling resistance characteristics are excellent.

  Also, in view of the growing demand for low fuel consumption for tires, a technique for improving the rolling resistance characteristics of the rubber material constituting the base tread has been studied in order to obtain a tire with better fuel efficiency. Yes.

  As a method for improving the rolling resistance characteristics of a tire, for example, a technique for improving wet skid resistance and rolling resistance characteristics by adding silica to a rubber composition is known.

  However, silica has a problem that particles tend to aggregate due to hydrogen bonding of silanol groups, which are functional groups on the surface thereof, and the viscosity of the compound increases due to the aggregation of silica particles, which deteriorates workability. In addition, the silica high-mixing system has a problem that the vulcanization speed is slow.

  In order to solve the problem caused by blending silica into these rubber compositions, for example, techniques for blending various liquid polymers into the rubber composition are disclosed in Patent Documents 1 to 3 below.

JP 2009-126987 A JP 2010-77233 A JP 2010-174101 A

  However, these conventional techniques still have room for improvement in the balance of physical properties including workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance.

  Therefore, in the present invention, in view of the above-described problems of the prior art, dispersibility and vulcanization characteristics of compounding agents such as silica are good, workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance. An object of the present invention is to provide a method for producing a modified conjugated diene polymer composition having an excellent physical property balance.

  As a result of intensive studies to solve the above problems, the present inventors have used a modified conjugated diene polymer in a method for producing a modified conjugated diene polymer composition containing a silica-based inorganic filler. By blending the modified liquid polymer and specifying the kneading timing and kneading conditions, the dispersibility and vulcanization characteristics of compounding agents such as silica are improved, processability and rolling resistance. It has been found that the properties, wet skid resistance, tensile properties and wear resistance are excellent in balance of physical properties, and the present invention has been completed.

That is, the present invention is as follows.
[1]
A method for producing a modified conjugated diene polymer composition, comprising the following step (1) and step (2) in this order.
Step (1): A step of blending and kneading the following (A) and (B).
(A) 100 parts by mass of a rubber component containing a modified conjugated diene polymer (B) A modified liquid polymer having at least one functional group selected from the group consisting of an amino group, a carboxyl group and an epoxy group , 0.5 to 50 parts by mass with respect to 100 parts by mass of the rubber component Step (2): A step of blending and kneading the following (C) and (D).
(C) 10 to 200 parts by mass of silica inorganic filler with respect to 100 parts by mass of (A) rubber component (D) Silane coupling agent with respect to 100 parts by mass of (C) silica-based inorganic filler. 1-20 parts by mass
[2]
The method for producing a modified conjugated diene polymer composition according to [1] , wherein the functional group is an amino group.
[ 3 ]
The method for producing a modified conjugated diene polymer composition according to [1] or [2] , wherein kneading is performed at 120 to 170 ° C. in the step (2).
[ 4 ]
The method for producing a modified conjugated diene polymer composition according to any one of [1] to [ 3 ], wherein kneading is performed at 150 to 160 ° C in the step (2).
[ 5 ]
The method for producing a modified conjugated diene polymer composition according to any one of [1] to [ 3 ], wherein kneading is performed at 140 to 150 ° C in the step (2).
[ 6 ]
In the step (2), the kneading time after reaching the temperature range of 150 to 160 ° C. or 140 to 150 ° C. is 0.5 to 20 minutes, according to [ 4 ] or [ 5 ]. A method for producing a modified conjugated diene polymer composition.
[ 7 ]
The modified conjugated diene system according to any one of [1] to [ 6 ], further including a step of further blending (E) carbon black in an amount of 0.5 to 100 parts by mass with respect to 100 parts by mass of the rubber component (A). A method for producing a polymer composition.
[ 8 ]
In the step (2), when the (C) silica inorganic filler and the (D) silane coupling agent are blended, the (E) carbon black is blended, and the modified conjugated diene-based weight according to [ 7 ] A method for producing a combined composition.

  According to the present invention, a modified conjugated diene polymer having good dispersibility and vulcanization characteristics of a compounding agent such as silica and excellent balance of workability, rolling resistance characteristics, wet skid resistance, tensile characteristics and wear resistance. The manufacturing method from which a composition is obtained can be provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to this embodiment, It can implement in various deformation | transformation within the range of the summary.

[Method for Producing Modified Conjugated Diene Polymer Composition]
The manufacturing method of the modified conjugated diene polymer composition of this embodiment is a manufacturing method of the modified conjugated diene polymer composition including the following step (1) and step (2) in this order.
Step (1): Step of blending and kneading the following (A) and (B): (A) 100 parts by mass of a rubber component containing a modified conjugated diene polymer (B) 0.5-50 mass parts with respect to 100 mass parts of components Process (2): The process of mix | blending and knead | mixing following (C) and (D).
(C) The silica inorganic filler is 10 to 200 parts by mass with respect to 100 parts by mass of the (A) rubber component. (D) The silane coupling agent is based on 100 parts by mass of the (B) silica-based inorganic filler.
0.1 to 20 parts by mass Since it is configured as described above, according to the method for producing a modified conjugated diene polymer composition according to this embodiment, dispersibility and vulcanization characteristics of a compounding agent such as silica are obtained. A modified conjugated diene polymer composition that is good and excellent in workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and abrasion resistance can be obtained.

  Hereinafter, (A), (B) used in step (1), and (C), (D) used in step (2) will be described, and then production of the modified conjugated diene polymer composition of this embodiment will be described. Step (1) and step (2) constituting the method will be described.

(Raw material used in step (1))
<(A) Rubber component containing modified conjugated diene polymer>
In step (1) of the production method of the modified conjugated diene polymer composition of the present embodiment, (A) a rubber component containing a modified conjugated diene polymer (hereinafter simply referred to as “(A) rubber component”, “( A) component ”or“ (A) ”may be used). (A) The modified conjugated diene polymer contained in the rubber component is preferably a terminal-modified conjugated diene polymer.

  (A) The weight average molecular weight Mw of the modified conjugated diene polymer in the rubber component is preferably 200,000 to 2,000,000. (C) Silica-based inorganic filler to be described later is sufficiently dispersed, and (B) modified liquid polymer to be added (additional effects (improvement of workability, rolling resistance characteristics, wet skid resistance, tensile characteristics and wear resistance) described later) From the viewpoint of sufficient expression, it is preferably 200,000 or more, and from the viewpoint of making workability practically sufficient, it is preferably 2 million or less. More preferably, it is 250,000 to 1,500,000.

  The weight average molecular weight (Mw) can be measured as follows using gel permeation chromatography (GPC).

  As the column, three columns using polystyrene gel as a filler are connected and tetrahydrofuran (THF) is used as an eluent. For the column, in particular, Tosoh TSKguardcolumnHHR-H as a guard column, Tosoh TSKgel G6000HHR, TSKgel G5000HHR, and TSKgel G4000HHR as other columns, an oven temperature of 40 ° C., a THF flow rate of 1.0 mL / min, RI A detector (HLC8020 manufactured by Tosoh Corporation) is used. The sample is measured by dissolving 10 mg in 20 mL of THF and injecting 200 μL. A calibration curve using standard polystyrene is prepared as described above and used for conversion of molecular weight. Specifically, it can measure by the method described in the Example mentioned later.

  Examples of the conjugated diene compound constituting the modified conjugated diene polymer include, but are not limited to, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1, Examples include 3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability. In particular, 1,3-butadiene is preferable. These may be used alone or in combination of two or more.

  The aromatic vinyl compound constituting the modified conjugated diene polymer may be any monomer that can be copolymerized with the conjugated diene compound, and is not limited to the following. For example, styrene, p-methyl Examples thereof include styrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene and the like. Among these, styrene is preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

  The modified conjugated diene polymer may be a random copolymer or a block copolymer.

  Examples of the random copolymer include, but are not limited to, for example, butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer, butadiene-isoprene-styrene random. A copolymer etc. are mentioned.

  The composition distribution of each monomer in the copolymer chain is not particularly limited. For example, a completely random copolymer close to a statistical random composition, a taper (gradient) random in which the composition is distributed in a tapered shape. A copolymer etc. are mentioned. The bonding mode of the conjugated diene, that is, the composition of 1,4-bonds, 1,2-bonds, etc. may be uniform or distributed.

  Examples of the block copolymer include, but are not limited to, for example, a 2 type block copolymer composed of 2 blocks, a 3 type block copolymer composed of 3 blocks, and a 4 type composed of 4 blocks. Examples thereof include block copolymers.

  For example, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. Then, although not limited to the following, for example, it is represented by an S—B2 type block copolymer, an S—B—S3 type block copolymer, a S—B—S—B4 type block copolymer, or the like. In the notation, the boundaries between the blocks do not necessarily have to be clearly distinguished. For example, when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape. Further, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or portions where the aromatic vinyl compound is distributed in a tapered shape may coexist in the block B. Furthermore, a plurality of segments having different aromatic vinyl compound contents may coexist in the block B. When a plurality of blocks S and blocks B are present in the copolymer, the structures such as molecular weight and composition thereof may be the same or different.

  The modified conjugated diene polymer contained in the rubber component (A) is one in which all or part of the double bonds are hydrogenated in an inert solvent to be converted into saturated hydrocarbons. May be. By hydrogenating, heat resistance and weather resistance are improved, and the product tends to be prevented from being deteriorated when processed at a high temperature. As a result, it tends to exhibit even better performance in various applications such as automotive applications.

  The hydrogenation rate of the unsaturated double bond based on the conjugated diene compound (ie, “hydrogenation rate”) can be arbitrarily selected according to the purpose, and is not particularly limited. When used as a vulcanized rubber, it is preferable that the double bond of the conjugated diene part partially remains from the viewpoint of improving the above-described performance balance. From this viewpoint, the hydrogenation rate of the conjugated diene part in the polymer is preferably 3 to 70%, more preferably 5 to 65%, and still more preferably 10 to 60%. The hydrogenation rate can be determined by a nuclear magnetic resonance apparatus (NMR).

  In addition, the hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but the viewpoint of making the above-described performance balance better. Therefore, it is preferably 50% or less, more preferably 30% or less, and further preferably 20% or less.

  The method for hydrogenating all or part of the double bonds of the modified conjugated diene polymer used in the present embodiment and the method for hydrogenating the aromatic group are not particularly limited, and known methods can be used. As a particularly suitable hydrogenation method, a method of hydrogenation by blowing gaseous hydrogen into a polymer solution in the presence of a catalyst may be mentioned.

  The catalyst used for hydrogenation of the double bond or aromatic group is not limited to the following. For example, a heterogeneous catalyst such as a catalyst in which a noble metal is supported on a porous inorganic material; nickel, cobalt And homogeneous catalysts such as a catalyst obtained by solubilizing a salt such as organoaluminum and a catalyst using a metallocene such as titanocene. The hydrogenation of the aromatic group can be effectively performed by using a noble metal supported catalyst.

  Specific examples of the catalyst for hydrogenating an unsaturated double bond based on a conjugated diene compound are not limited to the following. For example, (a) a metal such as Ni, Pt, Pd, Ru, etc. A supported heterogeneous hydrogenation catalyst supported on alumina, diatomaceous earth, etc., (b) organic acid salts such as Ni, Co, Fe, Cr or transition metal salts such as acetylacetone salts and reducing agents such as organic aluminum And so-called Ziegler-type hydrogenation catalysts, and (c) so-called organometallic complexes such as organometallic compounds such as Ti, Ru, Rh, and Zr. Also, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-35381, Japanese Patent Publication No. 2-9041, A hydrogenation catalyst described in JP-A-8-109219 can also be used. As a preferable hydrogenation catalyst, a titanocene catalyst is preferable from the viewpoint of selecting mild hydrogenation conditions, and specifically, a reaction mixture of a titanocene compound and a reducing organometallic compound can be mentioned.

  In producing the conjugated diene polymer, an anionic polymerization initiator can be used. Although it does not specifically limit as an anionic polymerization initiator, For example, an organic alkali metal compound is mentioned. The organic alkali metal compound is not particularly limited, but an organic lithium compound is preferable.

  Examples of the organolithium compound include, but are not limited to, a compound composed of a carbon-lithium bond, a compound composed of a nitrogen-lithium bond, and a compound composed of a tin-lithium bond in the bonding mode between the organic group and lithium.

  Examples of the compound composed of the carbon-lithium bond include, but are not limited to, for example, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, and stilbene. Lithium etc. are mentioned.

  Examples of the compound comprising a nitrogen-lithium bond include, but are not limited to, for example, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium di-n-hexylamide, lithium diisopropylamide, lithium hexamethyleneimide. , Lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium morpholide and the like.

  Examples of the compound comprising a tin-lithium bond include, but are not limited to, tributyltin lithium and the like. As the organic lithium compound, n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and ease of control of the polymerization reaction.

  The above-described organolithium compounds may be used as a mixture of not only one type but also two or more types.

  Furthermore, examples of other organic alkali metal compounds include, but are not limited to, organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specific examples include sodium naphthalene and potassium naphthalene. In addition, alkoxides such as lithium, sodium, and potassium, sulfonates, carbonates, amides, and the like can be given. Moreover, you may use together with another organometallic compound.

  Although it does not specifically limit as an anionic polymerization initiator used in order to manufacture the said conjugated diene type polymer, An alkaline-earth metal compound is also applicable. Examples of the alkaline earth metal compound include organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Further, alkaline earth metal alkoxides, sulfonates, carbonates, amides and other compounds may be used. These organic alkaline earth metal compounds may be used in combination with alkali metal compounds or other organic metal compounds.

  In this embodiment, the conjugated diene polymer that can be used in obtaining the modified conjugated diene polymer grows by an anionic polymerization reaction using the above-described alkali metal compound and / or alkaline earth metal compound as a polymerization initiator. It is preferable to be obtained. In particular, the conjugated diene polymer is more preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Thereby, it exists in the tendency which can obtain the modified conjugated diene type polymer of a high modification rate.

  Although it does not specifically limit as a polymerization mode, For example, it can carry out by polymerization modes, such as a batch type and a continuous type. In the continuous mode, one or two or more connected reactors can be used. As the reactor, a tank type with a stirrer, a tube type or the like is used.

  In the present embodiment, from the viewpoint of sufficient efficiency of the modification reaction for obtaining the modified conjugated diene polymer, the conjugated diene compound does not contain allenes, acetylenes or the like as impurities. Is preferred. From this viewpoint, the total content concentration (mass) of these impurities is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less. Examples of the allenes include propadiene and 1,2-butadiene. Examples of the acetylenes include ethyl acetylene and vinyl acetylene.

  The polymerization reaction of the conjugated diene polymer is preferably performed in a solvent. As the solvent, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons can be used, and are not limited to the following. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, cyclopentane, etc. , Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and hydrocarbons composed of mixtures thereof.

  Treatment of allenes and acetylenes that become impurities in the polymerization monomer with an organometallic compound before the polymerization reaction tends to yield a polymer having a high concentration of active terminals, and even higher. This is preferable because the modification rate tends to be achieved.

  In the polymerization reaction of the conjugated diene polymer, a polar compound may be added. By using a polar compound, an aromatic vinyl compound tends to be randomly copolymerized with a conjugated diene compound, and the polar compound is also used as a vinylating agent for controlling the microstructure of the conjugated diene part. Tend to be able to. It also tends to contribute to an improvement in the polymerization rate.

  Examples of the polar compound include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2 Ethers such as -oxolanyl) propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butyrate, sodium-t- Examples include alkali metal alkoxide compounds such as butyrate and sodium amylate; and phosphine compounds such as triphenylphosphine. These polar compounds may be used alone or in combination of two or more.

  The usage-amount of the said polar compound is not specifically limited, According to the objective etc., it can select. Usually, it is preferable that it is 0.01-100 mol with respect to 1 mol of polymerization initiators mentioned above.

  The polar compound as the vinylating agent can be used in an appropriate amount as a regulator of the microstructure of the polymer conjugated diene moiety depending on the desired amount of vinyl bonds.

  Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can be used as an adjustment of the distribution of the aromatic vinyl compound and as an adjuster of the styrene block amount. .

  The method for randomizing the conjugated diene compound and the aromatic vinyl compound is not particularly limited. For example, a polar compound as described in JP-A-59-140221 is used, and the copolymerization is in progress. Alternatively, a method of intermittently adding a part of 1,3-butadiene may be used.

  The polymerization temperature in the polymerization step of the conjugated diene polymer is not particularly limited as long as the living anion polymerization proceeds. From the viewpoint of productivity, the polymerization temperature is preferably 0 ° C. or higher, and the active terminal after completion of the polymerization. From the viewpoint of sufficiently ensuring the reaction amount of the modifier with respect to the temperature, it is preferably 120 ° C. or lower.

  The amount of bound conjugated diene in the modified conjugated diene polymer used in the production method of the present embodiment is not particularly limited, but is preferably 40 to 100% by mass. For example, physical properties preferable for the purpose of tire base tread applications. From the viewpoint of presenting, it is more preferably 60 to 80% by mass.

  Moreover, the amount of bonded aromatic vinyl in the modified conjugated diene polymer used in the production method of the present embodiment is not particularly limited, but is preferably 0 to 90% by mass, and preferably 20 to 70% by mass. More preferred. When the amount of bound conjugated diene and amount of bound aromatic vinyl are in the above ranges, there is a tendency that a vulcanizate having an excellent balance of rolling resistance rolling resistance and wet skid resistance and satisfying wear resistance can be obtained. . Here, the amount of bonded aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, and the amount of bonded conjugated diene can also be obtained from this. Specifically, it can be measured by a method according to an example described later according to a method for measuring the amount of bound styrene.

  Moreover, the vinyl bond amount in the conjugated diene bond unit of the modified conjugated diene polymer is not particularly limited, but is preferably 10 to 85 mol%, more preferably 15 to 70 mol%. When the vinyl bond amount is in the above range, a vulcanizate having a further excellent balance between rolling resistance and wet skid resistance and satisfactory wear resistance tends to be obtained. Here, when the modified conjugated diene-based polymer is a copolymer of butadiene and styrene, it is determined by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). A vinyl bond amount (1,2-bond amount) can be determined.

  The microstructure (bound conjugated diene content, bound aromatic vinyl content, 1,2-bond content in the modified conjugated diene copolymer) is in the above range, and the glass transition temperature of the modified conjugated diene polymer is -45. When the temperature is in the range of -15 ° C, a more excellent vulcanizate tends to be obtained due to the balance between rolling resistance and wet skid resistance. Regarding the glass transition temperature, according to ISO 22768: 2006, a DSC curve can be recorded while raising the temperature in a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve can be obtained as the glass transition temperature.

  The conjugated diene polymer in the present embodiment preferably has few or no blocks in which 30 or more aromatic vinyl units are linked. Specifically, in the case where the conjugated diene polymer is a butadiene-styrene copolymer, the Kolthoff method (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)) is used. In the case of evaluating by a known method of decomposing a polymer by the method described in the above and analyzing the amount of polystyrene insoluble in methanol, a block in which 30 or more aromatic vinyl units are chained is represented by a modified conjugated diene polymer. Preferably it is 5 mass% or less with respect to the total amount, More preferably, it is 3 mass% or less.

  Next, the modified conjugated diene polymer used in the production method of the present embodiment will be described. The modified conjugated diene polymer used in the present embodiment is preferably a terminal-modified conjugated diene polymer. It is preferable that the modified conjugated diene polymer contains a terminal-modified conjugated diene polymer because rolling resistance characteristics, wet skid resistance and tensile characteristics tend to be improved. The content of the terminal modified conjugated diene polymer in the modified conjugated diene polymer is preferably 10% by mass or more, and more preferably 20% by mass or more.

  The modified conjugated diene polymer is bonded to a silyl group at the polymerization active terminal of the conjugated diene polymer obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound using an anionic polymerization initiator. A compound having one or more alkoxy groups and having two or more tertiary amino groups, or a compound having a total of four or more alkoxy groups bonded to a silyl group and having one or more nitrogen atoms It is preferably obtained by reacting and terminal-modifying.

  Specific examples of the compound having at least one alkoxy group bonded to a silyl group and having two or more tertiary amino groups, preferably used as a modifier for producing a terminal-modified conjugated diene polymer, Although not limited to the following, for example, N- [2- (trialkoxysilanyl) -ethyl] -N, N ′, N′-trialkylethane-1,2-diamine, N- [2- (alkyldialkoxy) Silanyl) -ethyl] -N, N ′, N′-trialkylethane-1,2-diamine, N- [3- (trialkoxysilanyl) -propyl] -N, N ′, N′-trialkyl Propane-1,3-diamine, N- [3- (alkyldialkoxysilanyl) -propyl] -N, N ′, N′-trialkylpropane-1,3-diamine, N- [3- (trialkoxy) Shirani ) -Propyl] -2, N, N ′, N′-tetraalkylpropane-1,3-diamine, N- [3- (alkyldialkoxysilanyl) -propyl] -2, N, N ′, N ′ -Tetraalkylpropane-1,3-diamine etc. are mentioned. In addition, 1- [3- (trialkoxysilanyl) -propyl] -4-alkylpiperazine, 1- [3- (alkyldialkoxysilanyl) -propyl] -4-alkylpiperazine, 1- [3- (tri Alkoxysilanyl) -propyl] -3-alkylimidazolidine, 1- [3- (alkyldialkoxysilanyl) -propyl] -3-alkylimidazolidine, 1- [3- (trialkoxysilanyl) -propyl] -3-alkylhexahydropyrimidine, 1- [3- (alkyldialkoxysilanyl) -propyl] -3-alkylhexahydropyrimidine, 3- [3- (trialkoxysilanyl) -propyl] -1-alkyl- 1,2,3,4-tetrahydropyrimidine, 3- [3- (alkyldialkoxysilanyl) -propyl] -1-a Kill-1,2,3,4-tetrahydropyrimidine or the like can be mentioned. Furthermore, 2- (trialkoxysilanyl) -1,3-dialkylimidazolidine, 2- (alkyldialkoxysilanyl) -1,3-dialkylimidazolidine, 2- (trialkoxysilanyl) -1,4- Dialkylpiperazine, 2- (alkyldialkoxysilanyl) -1,4-dialkylpiperazine, 5- (trialkoxysilanyl) -1,3-dialkylhexahydropyrimidine, 5- (alkyldialkoxysilanyl) -1, Examples also include 3-dialkylhexahydropyrimidine.

  Specific examples of the compound having one or more alkoxyl groups bonded to a silyl group and having two or more tertiary amino groups include, but are not limited to, for example, N- [2- (trimethoxysilane). Nyl) -ethyl] -N, N ′, N′-trimethylethane-1,2-diamine, N- [2- (dimethoxymethylsilanyl) -ethyl] -N-ethyl-N ′, N′-dimethylethane -1,2-diamine, N- [3- (trimethoxysilanyl) -propyl] -N, N ′, N′-trimethylpropane-1,3-diamine, N- [3- (dimethoxymethylsilanyl) -Propyl] -N-ethyl-N ', N'-dimethylpropane-1,3-diamine, N- [3- (triethoxysilanyl) -propyl] -N, N', N'-triethyl-2- Methylpropane-1,3-di Min, N- [3- (dimethoxymethylsilanyl) -propyl] -2, N, N ′, N′-tetramethylpropane-1,3-diamine, N- (2-dimethylaminoethyl) -N′- [2- (Trimethoxysilanyl) -ethyl] -N, N′-dimethylethane-1,2-diamine, N- [2- (diethoxypropylsilanyl) -ethyl] -N ′-(3-ethoxy Propyl) -N, N'-dimethylethane-1,2-diamine, N- [2- (trimethoxysilanyl) -ethyl] -N'-methoxymethyl-N, N'-dimethylethane-1,2- Diamine, N- [2- (trimethoxysilanyl) -ethyl] -N, N′-dimethyl-N ′-(2-trimethylsilanylethyl) -ethane-1,2-diamine, N- [2- ( Triethoxysilanyl) -ethyl] -N N'- diethyl--N '- (2-dibutyl-methoxy -lH-ethyl) - 1,2-diamine, and the like. Also, 1- [3- (triethoxysilanyl) -propyl] -4-methylpiperazine, 1- [3- (diethoxyethylsilanyl) -propyl] -4-methylpiperazine, 1- [3- (tri Methoxysilanyl) -propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilanyl) -propyl] -3-ethylimidazolidine, 1- [3- (triethoxysilanyl) -propyl] -3-methylhexahydropyrimidine, 1- [3- (dimethoxymethylsilanyl) -propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxysilanyl) -propyl] -1-methyl-1 , 2,3,4-tetrahydropyrimidine, 3- [3- (dimethoxymethylsilanyl) -propyl] -1-ethyl-1,2,3,4-tetrahydropyrimidine Gin, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilanyl) -propyl] -imidazolidine, (2- {3- [3- (trimethoxysilanyl) -propyl] -tetrahydropyrimidine -1-yl} -ethyl) dimethylamine and the like. Furthermore, 2- (trimethoxysilanyl) -1,3-dimethylimidazolidine, 2- (diethoxyethylsilanyl) -1,3-diethylimidazolidine, 2- (triethoxysilanyl) -1,4- Diethylpiperazine, 2- (dimethoxymethylsilanyl) -1,4-dimethylpiperazine, 5- (triethoxysilanyl) -1,3-dipropylhexahydropyrimidine, 5- (diethoxyethylsilanyl) -1, 3-diethylhexahydropyrimidine, {2- [3- (2-dimethylaminoethyl) -2- (ethyldimethoxysilanyl) -imidazolidin-1-yl] -ethyl} -dimethylamine, 5- (trimethoxysila Nyl) -1,3-bis- (2-methoxyethyl) -hexahydropyrimidine, 5- (ethyldimethoxysilanyl) -1,3- Scan - also include trimethylsilanyl hexahydropyrimidine like. Among the compounds described above, preferred compounds include N- [2- (trimethoxysilanyl) -ethyl] -N, N ′, N′-trimethylethane-1,2-diamine, 1- [3- (triethoxysila). Nyl) -propyl] -4-methylpiperazine, 2- (trimethoxysilanyl) -1,3-dimethylimidazolidine.

  In addition, the total number of alkoxy groups bonded to the silyl group, which is preferably used as a modifier, is 4 or more, and the compound having one or more nitrogen atoms is not limited to the following. For example, the following formula (1) , (2), and (3).

(In General Formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁵ is an alkylene group having 1 to 10 carbon atoms. R ⁶ represents an alkylene group having 1 to 20 carbon atoms, m is an integer of 1 or 2, and n is an integer of 2 or 3.)

(In General Formula (2), R ^{7 to} R ¹⁰ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹¹ and R ¹² are each independently Represents an alkylene group having 1 to 20 carbon atoms, R ¹³ and R ¹⁴ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and a ring structure having a 5-membered ring or more together with two adjacent N atoms And p and q each independently represents an integer of 2 or 3.)

In General Formula (3), X ¹ and X ² are each an alkoxy group having 1 to 20 carbon atoms, R ¹⁵ and R ¹⁶ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A ¹ and A ² are each a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and A ³ is a group represented by the following formulas (a) and (b). When a plurality of X ¹ , X ² , R ¹⁵ , R ¹⁶ , A ¹ , A ² or A ³ are present, they may be the same or different. r and s are each an integer of 0 to 3. t is an integer of 0 to 20, and when t is 2 or more, the plurality of repeating units represented by (A ¹ -A ³ -A ² ) may be different from each other.

In the general formula (a), R ¹⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. In the case ^{where A 3} is of formula (a), (r + s ) is 5 or 6.

In the general formula (b), ^{A 4} is a divalent hydrocarbon group of a single bond or a C 1-20, ^{X 3} is an alkoxy group having 1 to 20 carbon atoms. R ¹⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of X ⁴ or R ¹⁸ are present, they may be the same or different from each other. u is an integer of 0-3. In the case ^{where A 3} is represented by the formula (b), [r + ( t × u) + s] is an integer of 5 or more.

  The modifying agent represented by the general formula (1) is not limited to the following, but for example, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2- Silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1- Aza-2-silacyclohexane, 2,2-dimethoxy-1- (5-trimethoxysilylpentyl) -1-aza-2-silacycloheptane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, -Methyl-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2-sila Cyclopentane, 2-methoxy, 2-methyl-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-diethoxyethylsilylpropyl) ) -1-aza-2-silacyclopentane and the like. Among these, those in which m is 2 and n is 3 are more preferable from the viewpoints of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability. Specifically, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1 -Aza-2-silacyclopentane is more preferred.

  The modifying agent represented by the general formula (2) is not limited to the following, and examples thereof include 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [ 3- (triethoxysilyl) propyl] piperazine, 1,4-bis [3- (dimethoxymethylsilyl) propyl] piperazine, 1,3-bis [3- (trimethoxysilyl) propyl] imidazolidine, 1,3- Bis [3- (triethoxysilyl) propyl] imidazolidine, 1,3-bis [3- (diemethoxyethylsilyl) propyl] imidazolidine, 1,3-bis [3- (trimethoxysilyl) propyl] hexahydro Pyrimidine, 1,3-bis [3- (triethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [3- (tributoxysilyl) propyl Propyl] -1,2,3,4-tetrahydropyrimidine-like. Among these, those in which p and q are 3 are more preferable from the viewpoints of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability. Specifically, 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) propyl] piperazine, 1,3-bis [3- (trimethoxy Silyl) propyl] imidazolidine, 1,3-bis [3- (triethoxysilyl) propyl] imidazolidine, 1,3-bis [3- (trimethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [ 3- (triethoxysilyl) propyl] hexahydropyrimidine and 1,3-bis [3- (tributoxysilyl) propyl] -1,2,3,4-tetrahydropyrimidine are preferred, and among these, 1,4 -Bis [3- (trimethoxysilyl) propyl] piperazine and 1,4-bis [3- (triethoxysilyl) propyl] piperazine Preferred.

The modifying agent represented by the general formula (3) is not limited to the following when A ³ is the general formula (a), for example, bis (3-trimethoxysilylpropyl) methylamine, Bis (3-triethoxysilylpropyl) methylamine, bis (3-trimethoxysilylpropyl) ethylamine, bis (3-triethoxysilylpropyl) ethylamine, bis (3-trimethoxysilylpropyl) propylamine, bis (3- Triethoxysilylpropyl) propylamine, bis (3-trimethoxysilylpropyl) butylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3-trimethoxysilylpropyl) phenylamine, bis (3-triethoxysilylpropyl) ) Phenylamine, bis (3-trimethoxysilyl group) (Ropyl) benzylamine, bis (3-triethoxysilylpropyl) benzylamine, bis (trimethoxysilylmethyl) methylamine, bis (triethoxysilylmethyl) methylamine, bis (2-trimethoxysilylethyl) methylamine, bis (2-Triethoxysilylethyl) methylamine, bis (triethoxysilylmethyl) propylamine, bis (2-triethoxysilylethyl) propylamine and the like can be mentioned.

The modifying agent represented by the general formula (3) is not limited to the following when A ³ is the general formula (b). For example, tris (trimethoxysilylmethyl) amine, tris (2 -Triethoxysilylethyl) amine, tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) amine and the like.

  Among the above-described modifiers represented by the general formula (3), from the viewpoint of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability, r, s, And those in which u is 3 are more preferred. Specifically, bis (3-trimethoxysilylpropyl) methylamine, bis (3-triethoxysilylpropyl) methylamine, bis (3-trimethoxysilylpropyl) ethylamine, bis (3-triethoxysilylpropyl) ethylamine Bis (3-trimethoxysilylpropyl) propylamine, bis (3-triethoxysilylpropyl) propylamine, bis (3-trimethoxysilylpropyl) butylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3 -Trimethoxysilylpropyl) phenylamine, bis (3-triethoxysilylpropyl) phenylamine, bis (3-trimethoxysilylpropyl) benzylamine, bis (3-triethoxysilylpropyl) benzylamine, bis (trimethoxy Rylmethyl) methylamine, bis (triethoxysilylmethyl) methylamine, bis (2-trimethoxysilylethyl) methylamine, bis (2-triethoxysilylethyl) methylamine, bis (triethoxysilylmethyl) propylamine, bis (2-triethoxysilylethyl) propylamine, tris (trimethoxysilylmethyl) amine, tris (2-triethoxysilylethyl) amine, tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) ) Amine is more preferred.

  A modification reaction in which a conjugated diene polymer is modified using the above-described modifier to obtain a terminal-modified conjugated diene polymer will be described. In the modification reaction, the above-described modifiers may be used alone or in combination of two or more.

  There are no particular limitations on the reaction temperature, reaction time, and the like when the above-described modifier is reacted with the polymerization active terminal of the conjugated diene polymer, but it is preferable to react at 0 ° C. to 120 ° C. for 30 seconds or longer. .

  The above-mentioned modifier has a range in which the total number of moles of alkoxy groups bonded to silyl groups in the added modifier is 0.1 to 5 times the total number of moles of lithium contained in the above-described anionic polymerization initiator. It is preferable to add so that it may become, and it is more preferable to add so that it may become the range which becomes 0.2-3 times.

  The content of the polymer having a functional group component of the modified conjugated diene polymer, that is, the modification rate, when the composition using the modified conjugated diene polymer is a vulcanized product, rolling resistance and wet skid resistance. From the standpoint of obtaining a practically sufficient wear resistance and tensile properties, it is preferably 6% by mass or more, more preferably 80% by mass or more, and 90% by mass. More preferably, it is the above.

  The content of the polymer having a functional group component, that is, the modification rate, is determined by a chromatographic measurement method capable of separating the functional group-containing modified portion and the non-modified portion. This chromatographic measurement method uses a gel permeation chromatography (GPC) column with a polar substance such as silica adsorbing a functional group component as a filler, and uses an internal standard for non-adsorbed components for comparison. It is a method to do.

  The weight average molecular weight (polystyrene conversion) measured using GPC of the modified conjugated diene polymer obtained through the above-described modification reaction is preferably 200,000 to 2,000,000 from the following viewpoints. That is, from the viewpoint of sufficiently dispersing the inorganic filler and more preferably expressing the effect of addition by the modified liquid polymer (improving processability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance). On the other hand, it is preferably 2 million or less from the viewpoint of practically sufficient workability. From this viewpoint, it is more preferably 250,000 to 1.5 million.

  In addition, when the conjugated diene polymer is polymerized by a batch process, a plurality of peaks are observed in the molecular weight distribution of GPC. It is considered that the peak on the lowest molecular side is mainly a component produced by polymerization initiated by a monofunctional component mixed in the anionic polymerization initiator. Moreover, it exists in the tendency for physical properties, such as rolling resistance and abrasion resistance, to be excellent, so that there are many amounts by the side of the polymer in an anionic polymerization initiator. On the other hand, from the viewpoint of improving the workability, the peak area on the lowest molecular side is preferably 10 to 70% with respect to the peak area of the entire GPC.

  In the case of using the terminal-modified conjugated diene polymer described above as the modified conjugated diene polymer used in the present embodiment, after performing the modification reaction, the copolymer solution may be deactivated, neutralized as necessary. An agent or the like may be added. Examples of the deactivator include, but are not limited to, water; alcohols such as methanol, ethanol, and isopropanol. Examples of the neutralizing agent include, but are not limited to, carboxylic acids such as stearic acid, oleic acid, and versatic acid; aqueous solutions of inorganic acids, carbon dioxide gas, and the like.

  In addition, the modified conjugated diene polymer used in the present embodiment is any of terminal-modified conjugated diene polymers from the viewpoint of preventing gel formation in the finishing step after polymerization and improving stability during processing. However, it is preferable to add a stabilizer for rubber. The stabilizer for rubber is not particularly limited, and known ones can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3- (4 ′ -Hydroxy-3 ', 5'-di-tert-butylphenol) propinate, 2-methyl-4,6-bis [(octylthio) methyl] phenol and the like are preferable.

  In order to further improve the processability of the modified conjugated diene polymer, an extension oil can be added to the modified conjugated diene copolymer as necessary in any of the terminal-modified conjugated diene polymers. . The method of adding the extending oil to the modified conjugated diene polymer is not particularly limited, but a method of adding the extending oil to the polymer solution and mixing to remove the solvent from the oil-extended copolymer solution is preferable. . Examples of the extending oil include, but are not limited to, aroma oil, naphthenic oil, paraffin oil, and the like. Among these, from the viewpoint of environmental safety, oil bleed prevention and wet grip characteristics, an aromatic substitute oil having a polycyclic aromatic (PCA) component of 3% by mass or less by the IP346 method is preferable. Examples of the aroma substitute oil include, but are not limited to, for example, TDAE (Treated Distillate Aromatic Extracts), MES (Mild ExtractR), MES (Mild ExtractR) Extracts) and the like. Although the addition amount of extending oil is not specifically limited, Usually, it is 10-60 mass parts with respect to 100 mass parts of modified conjugated diene polymers, and 20-37.5 mass parts is preferable.

  As a method for obtaining the modified conjugated diene polymer from the polymer solution, a known method can be used also in the terminal modified conjugated diene polymer, and is not limited to the following, but for example, a solvent such as steam stripping is used. After separating the polymer, the polymer is filtered off and further dehydrated and dried to obtain the polymer; the polymer is concentrated in a flushing tank and then devolatilized with a vent extruder, etc .; The method of volatilizing is mentioned.

[Rubber polymer]
In the rubber component containing the (A) modified conjugated diene polymer used in the method for producing the modified conjugated diene polymer composition of the present embodiment, the modified conjugated diene system described above is within the range satisfying the characteristics of the present invention. In addition to the polymer, other rubbery polymers may be included. Examples of such rubber-like polymers include, but are not limited to, for example, conjugated diene polymers or hydrogenated products thereof; random copolymers of conjugated diene compounds and vinyl aromatic compounds or hydrogenated products thereof; Examples include block copolymers of conjugated diene compounds and vinyl aromatic compounds or hydrogenated products thereof; non-diene polymers. Specifically, butadiene rubber or hydrogenated product thereof; styrene-butadiene rubber or hydrogenated product thereof; styrene-butadiene block copolymer or hydrogenated product thereof; styrene-isoprene block copolymer or hydrogenated product thereof Examples thereof include styrene-based elastomers; acrylonitrile-butadiene rubber or hydrogenated products thereof.

  Examples of the non-diene polymer include, but are not limited to, olefins such as ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, and ethylene-octene rubber. Elastomer, butyl rubber, brominated butyl rubber, acrylic rubber, fluoro rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber, etc. Is mentioned.

  The various rubber-like polymers described above may be modified rubbers to which functional groups having polarity such as hydroxyl groups and amino groups are added. The weight average molecular weight is preferably 200,000 to 2,000,000, more preferably 250,000 to 1,500,000, from the viewpoint of the balance between performance and processing characteristics. These rubbery polymers may be used alone or in combination of two or more.

<(B) Modified liquid polymer>
In the production method of the modified conjugated diene polymer composition of the present embodiment, in step (1), (B) modified liquid with respect to 100 parts by mass of the rubber component containing (A) the modified conjugated diene polymer described above. 0.5 to 50 parts by mass of the polymer is blended. (A) The blending amount of the modified liquid polymer (B) with respect to 100 parts by mass of the rubber component has the effect of adding the modified liquid polymer (improving processability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance). From the viewpoint of expression, 0.5 part by mass or more, and from the viewpoints of suppression of reaction inhibition between the (C) silica-based inorganic filler and the (D) silane coupling agent described later, wear resistance, and the like, 50 parts by mass. The following. From this viewpoint, it is preferably 0.5 parts by mass or more and 45 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, and further preferably 5 parts by mass or more and 35 parts by mass or less.

  In the present embodiment, the modified liquid polymer is liquid at ordinary temperature (5 ° C. to 35 ° C.), has two or more monomer units constituting the polymer, has a specific functional group, An average molecular weight is 200-20000. Examples of the monomer constituting the polymer include butadiene, ethylene, propylene, and acrylonitrile. In the present embodiment, the term “liquid” means that the viscosity at 30 ° C. in the 2000 version JIS K 2283 test method is 0.1 to 2000 Pa · S, and preferably 0.5 to 1000 Pa · S. The number average molecular weight is more preferably 500 to 10,000. Here, the number average molecular weight (Mn) is a value measured at 40 ° C. by using THF (tetrohydrofuran) as a solvent by GPC (gel permeation chromatography).

  As the specific functional group of the modified liquid polymer, one having at least one functional group selected from the group consisting of an amino group, a carboxyl group (—COOH), an epoxy group, and a hydroxyl group (—OH) is preferably used. It is done. By using such a modified liquid polymer having a functional group that interacts well with silica, there is a tendency that it can bind to silica and improve its dispersibility. Here, the interaction means that the functional group is bonded to the silanol group on the silica surface by a chemical bond or a hydrogen bond by a chemical reaction. In the case of having the above-described functional group, the modified liquid polymer tends to be more strongly bonded to the silica surface, and therefore, the dispersibility of the silica in the rubber component is further improved and the heat generation tends to be low.

Regarding the functional group, the amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group, and is not limited to the following, but is not limited to methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, Allyl isopropylamine, acyclic polyamine and derivatives thereof and salts thereof; ethylenediamine (NH ₂ CH ₂ CH ₂ NH ₂ ) and salts thereof; hexamethylene diamine, saturated alicyclic monoamine, unsaturated alicyclic monoamine, cycloterpene Examples include those derived from monoamines, saturated alicyclic polyamines, unsaturated finger ring polyamines, cycloterpene polyamines and derivatives thereof, and salts thereof, and these include cyclohexylamine, dimethylaminocyclohexane, and the like. In addition, aromatic monoamines and derivatives thereof and salts thereof; aniline (C ₆ H ₅ NH ₂ ) (phenylamine), salts of aniline, halogenated derivatives of aniline (chloroaniline), sulfonated derivatives of aniline (meta-amino) Benzenesulfonic acid, para-aminobenzenesulfonic acid), nitrated derivatives of aniline (nitroaniline, etc.), nitrosated derivatives of aniline, sulfohalogenated derivatives of aniline, nitrohalogenated derivatives of aniline, nitrosulfonated derivatives of aniline, alkyl derivatives of aniline (N- methylaniline, N, N- dimethylaniline, N- ethylaniline and N, N- diethylaniline); toluidine, diphenylamine, 1-naphthylamine (alpha - _{naphthylamine) (C 10 H 7 NH 2} ) , 2-Naphth Amine, xylidine, aromatic polyamines and their derivatives; salts thereof; ortho - phenylenediamine, meta - phenylenediamine, para - phenylenediamine _{(C 6 H 4 (NH 2} ) 2), ortho - phenylenediamine, meta - phenylenediamine , para - phenylenediamine, diaminotoluene _{(CH 3 C 6 H 3 (} NH 2) 2), N- alkyl phenylenediamines (e.g., N, N- dimethyl - p - phenylenediamine, N- alkyl tolylenediamine, benzidine ( _{NH 2 C 6 H 4 C 6} H 4 NH 2)); diphenylmethane or triphenylmethane or their homologues or tetramethyl-diaminodiphenylmethane obtained from these derivatives, derived polyamine such as tetraethyl-diaminodiphenylmethane Those that can be mentioned.

Examples of the carboxyl group include, but are not limited to, those derived from maleic acid, phthalic acid, acrylic acid, methacrylic acid, and the like. The hydroxyl group includes a phenol group as well as a methylol group (—CH ₂ OH) and an ethylol group.

  As said modified liquid polymer, if it has 1 or more types of functional groups in the molecule | numerator, it can be used conveniently. More preferably, an end-modified liquid polymer in which the functional group is introduced at the end of the polymer is used. When it has a functional group at the polymer terminal, there is a tendency that the effect of improving the dispersibility of the surface-treated silica can be further improved by interaction with silica or interaction with an aminosilane coupling agent bonded to silica. As the functional group, an amino group is preferably used from the viewpoint of the bonding reaction between silica and the polymer.

  The modified liquid polymer is preferably a diene liquid polymer. That is, a diene liquid polymer as a base polymer and a functional group introduced therein is preferably used. Examples of the diene liquid polymer include, but are not limited to, liquid polybutadiene, liquid polyisoprene, liquid styrene-butadiene rubber, liquid styrene-isoprene rubber, and liquid nitrile rubber. Such a modified liquid polymer can be obtained, for example, by introducing the functional group by reacting a compound having the functional group with an unmodified liquid polymer synthesized by anionic polymerization or the like. Alternatively, a liquid polymer having a functional group can be obtained by polymerization using a polymerizable monomer having the functional group. Such a polymerization method and modification method of the polymer itself can be a conventionally known method.

(Raw material used in step (2))
<(C) Silica-based inorganic filler>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, in step (2), (C) silica-based rubber with respect to 100 parts by mass of the rubber component containing the (A) modified conjugated diene polymer described above. The inorganic filler is blended in an amount of 10 to 200 parts by mass. (A) The compounding quantity of (C) silica type inorganic filler with respect to 100 mass parts of rubber components containing a modified conjugated diene type polymer shall be 10 mass parts or more from a viewpoint which the desired effect of this embodiment expresses, From the standpoint of sufficiently dispersing the inorganic filler and making the composition have practically sufficient workability and mechanical strength, the amount is set to 200 parts by mass or less. From this viewpoint, it is preferably 20 to 180 parts by mass, more preferably 30 to 160 parts by mass, and still more preferably 35 to 150 parts by mass.

The silica-based inorganic filler is not particularly limited, but may be a known, SiO _2, or _Si 3 solid particles preferably contains Al as a constituent unit, SiO _2, or _Si 3 Al constituent units It is more preferable to use as a main component. Here, the “main component” means a component contained in (C) the silica-based inorganic filler in an amount of 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more. Specific examples of (C) silica-based inorganic fillers include, but are not limited to, inorganic inorganic substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, glass fiber, and the like. Can be mentioned.

  Moreover, the mixture of (C) silica type inorganic filler which hydrophobized the surface, and (C) silica type inorganic filler and inorganic fillers other than a silica type can also be used. Among these, silica and glass fiber are preferable from the viewpoints of strength, wear resistance, and the like, and silica is more preferable. Examples of silica include, but are not limited to, dry silica, wet silica, and synthetic silicate silica. Among these, wet silica is preferable.

In the present embodiment, from the viewpoint of obtaining superior rolling resistance characteristics, the nitrogen adsorption specific surface area determined by the BET adsorption method of (C) silica-based inorganic filler is preferably 10 to 500 m ² / g, More preferably, it is -400 m < ² > / g.

<(D) Silane coupling agent>
In the production method of the modified conjugated diene polymer composition of the present embodiment, in step (2), (D) silane coupling agent 0.1-20 with respect to 100 parts by mass of (C) silica-based inorganic filler. A mass part is mix | blended. (D) As for the compounding quantity of a silane coupling agent, 0.1-20 mass parts is preferable with respect to 100 mass parts of (C) silica type inorganic filler mentioned above, 0.5-18 mass parts is more preferable, 1 More preferably, it is 0-15 mass parts. (D) When the compounding quantity of a silane coupling agent is the said range, the said addition effect by (D) silane coupling agent can be made more remarkable.

  The (D) silane coupling agent has a function of tightly interacting the rubber component containing the (A) modified conjugated diene polymer and the (C) silica-based inorganic filler. It has an affinity or binding group for each of the rubber component containing the conjugated diene polymer and the (C) silica-based inorganic filler, and generally has a sulfur bond portion, an alkoxysilyl group, and a silanol group portion. Are used in a molecule.

  (D) Although a silane coupling agent is not limited to the following, for example, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl ] -Disulfide, bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis- [2- (triethoxysilyl) -ethyl] -tetrasulfide, Bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2- Mercaptoethyltriethoxysilane, 3-trimeth Sisilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3- Trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilyl) Propyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethyl Methyl silyl propyl benzothiazolyl tetrasulfide, and the like. Among these, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide and bis- [3- (triethoxysilyl) -propyl] -disulfide are preferable because of their high reinforcing effect. These silane coupling agents can be used singly or in combination of two or more.

  Then, the process (1) which comprises the manufacturing method of the modified conjugated diene type polymer composition of this embodiment is demonstrated.

(About step (1))
In the method for producing the modified conjugated diene polymer composition of the present embodiment, in step (1), the rubber component containing the modified conjugated diene polymer of (A) and (B) the modified liquid polymer are combined with (A ) By blending 0.5 to 50 parts by mass with respect to 100 parts by mass and kneading in advance, the dispersibility of the silica can be improved, and the respective physical properties can also be improved.

(About step (2))
By blending (C) silica-based inorganic filler and (D) silane coupling agent into the compound kneaded in step (1), the dispersibility of silica is improved, and each physical property is also improved. Can do.

  The kneading temperature in the step (2) is preferably 120 to 170 ° C, preferably 150 to 160 ° C, or 140 to 150 ° C. In addition, it is also preferable to select according to the kind of (D) silane coupling agent. By kneading at 120 to 170 ° C. in the step (2), the reaction rate of (C) silica-based inorganic filler and (D) silane coupling agent is improved, dispersibility is improved, and the balance of physical properties is further improved. It tends to increase.

  For example, when the number of sulfur atoms in the molecular structure of the (D) silane coupling agent is 3 or more, the kneading temperature is preferably in the range of 120 to 160 ° C, and in the range of 140 to 150 ° C. It is more preferable. Specific examples of the (D) silane coupling agent having 3 or more sulfur atoms in the molecular structure include, but are not limited to, for example, bis- [2- (triethoxysilyl) -ethyl] -tetra And sulfide, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, and the like.

  When (D) the number of sulfur atoms in the molecular structure of the silane coupling agent is 1 to 2, the kneading temperature is preferably in the range of 140 to 170 ° C, and the range of 150 to 160 ° C. More preferably. Specific examples of the (D) silane coupling agent having 1 to 2 sulfur atoms in the molecular structure are not particularly limited. For example, bis- [3- (triethoxysilyl) -propyl] -disulfide Etc.

  In step (2), as described above, it is preferable to select a kneading temperature according to the type of (D) silane coupling agent, but in this embodiment, all of step (2) are selected. The kneading need not be performed in the selected temperature range.

  In step (2), the kneading time after reaching the desired temperature, for example, the temperature range of 150 to 160 ° C. selected as described above, is 0.5 to 20 minutes during kneading. Is preferable, and more preferably 2 to 15 minutes. Furthermore, it is more preferable to set it as 2 to 8 minutes. Thereby, the balance of each physical property of a modified conjugated diene-type copolymer composition can be improved more. Furthermore, in step (2), during kneading, the kneading time after reaching a desired temperature, for example, the temperature range of 140 to 150 ° C. selected as described above, is 0.5 to 20 minutes. It is preferable that it is 2 to 15 minutes. Furthermore, it is more preferable to set it as 2 to 8 minutes. Thereby, the balance of each physical property of a modified conjugated diene-type copolymer composition can be improved more.

  In the method for producing the modified conjugated diene polymer composition of the present embodiment, the step (2) is carried out following the step (1). After the step (1), the kneaded product obtained in the step (1) is once discharged from a closed kneader such as a kneader or a banbury, and then discharged from the closed kneader at a predetermined stage. The blend may be charged, or the kneaded product may be continuously kneaded without being discharged from the closed kneader. In addition, it is preferable to knead | mix the said kneaded material, without discharging | emitting from a closed kneading machine from a viewpoint of the workability (processability of the discharge | release material) in a process (1). From the viewpoint of expressing the desired effect of the present embodiment, in the present embodiment, (B) the modified liquid polymer is blended and kneaded with the rubber component containing (A) the modified conjugated diene polymer (C). Dispersibility of silica is enhanced by blending and kneading the silica-based inorganic filler and (D) silane coupling agent.

  Moreover, although the temperature and kneading | mixing time in the said process (2) depend on the kneading | mixing time of the said process (1), 120-170 degreeC and 1 second-20 minutes are preferable from a silica dispersible viewpoint. .

  In the production method of the modified conjugated diene polymer composition of the present embodiment, as a method of mixing various materials, a conventionally known method can be applied, and is not limited to the following, for example, open roll, Banbury. A melt kneading method using a general mixer such as a mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, a method in which each solvent is dissolved and mixed, and then the solvent is removed by heating. Can be mentioned. Of these, a melt kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferred from the viewpoint of productivity and good kneading properties. In addition, any of a method of kneading various materials at once and a method of mixing in a plurality of times can be applied.

(Other materials)
<(E) Carbon black>
Moreover, the manufacturing method of the modified | denatured diene polymer composition of this embodiment is further from viewpoints of coloring property, workability, etc. with respect to 100 mass parts of rubber components containing the said (A) modified conjugated diene polymer. E) It is preferable to include the process of mix | blending 0.5-100 mass parts of carbon black. (A) The blending amount of (E) carbon black with respect to 100 parts by mass of a rubber component containing a modified conjugated diene polymer having a weight average molecular weight of 200,000 or more and 2,000,000 or less is suitable for applications such as dry grip and conductive tires. 0.5 mass% or more is preferable from the viewpoint of expressing the required performance, and 100 mass parts or less is preferable from the viewpoint of dispersibility, more preferably 3 to 100 mass parts, and even more preferably 5 to 80 mass parts. The carbon black is not limited to the following, but for example, carbon black of each class such as SRF, FEF, HAF, ISAF, and SAF can be used. Among these, from the viewpoint of workability and rolling resistance characteristics, the nitrogen adsorption specific surface area is preferably 50 m ² / g or more, and the dibutyl phthalate (DBP) oil absorption is 80 mL / 100 g or more, and the nitrogen adsorption ratio is preferred. More preferably, the surface area is 90 m ² / g or more and the DBP oil absorption is 80 mL / 100 g or more.

  Moreover, (E) The timing which mix | blends carbon black may be performed in the process (2) which mix | blends the (C) silica type inorganic filler and (D) silane coupling agent, or in a process (1). You may mix | blend with the obtained kneaded material. In addition, from the viewpoint of further improving rolling resistance characteristics and wet skid resistance, the rubber component is preferably blended with (C) a silica-based inorganic filler and (D) a silane coupling agent (step (2)). It is preferable to blend in.

<Additives> [Vulcanizing agent]
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a vulcanized composition may be obtained by adding a vulcanizing agent and performing a vulcanization treatment. Examples of the vulcanizing agent include, but are not limited to, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur, and sulfur compounds. Examples of the sulfur compound include, but are not limited to, sulfur monochloride, sulfur dichloride, disulfide compounds, polymer polysulfur compounds, and the like. The amount of the vulcanizing agent is not particularly limited, and is usually 0.01 to 20 parts by mass with respect to 100 parts by mass of the rubber component containing (A) the modified conjugated diene polymer, and 0.1 to 15 Part by mass is preferred. The vulcanization method is not particularly limited, and a conventionally known method can be applied. The vulcanization temperature is not particularly limited, and is usually 120 to 200 ° C, preferably 140 to 180 ° C.

[Vulcanization aid]
In vulcanization, a vulcanization accelerator may be used as necessary. As the vulcanization accelerator, conventionally known materials can be used, and are not limited to the following, but for example, sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, Examples thereof include vulcanization accelerators such as thiazole, thiourea, and dithiocarbamate. The amount of the vulcanization accelerator used is not particularly limited, and is usually 0.01 to 20 parts by mass with respect to 100 parts by mass of the rubber component containing the (A) modified conjugated diene polymer. Part by mass is preferred.

[Other additives]
In the manufacturing method of the modified conjugated diene polymer composition of the present embodiment, other additives than those described above can be included within the range not impairing the object of the present embodiment. Examples of the additive include, but are not limited to, various additives such as a softener and a filler, and a heat resistance stabilizer, an antistatic agent, a weather resistance stabilizer, a colorant, and a lubricant. Other softeners are not particularly limited, and known softeners can be used. Specific examples of other fillers include, but are not limited to, calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. The heat resistance stabilizer, antistatic agent, weather resistance stabilizer, colorant, and lubricant are not particularly limited, and known materials can be used.

[Modified Conjugated Diene Polymer Composition]
In the step (1), the modified conjugated diene polymer composition obtained by the production method of the present embodiment is blended and kneaded with (A) a rubber component and (B) a modified liquid polymer. ) In (C) silica-based inorganic filler and (D) silane coupling agent are mixed and kneaded, the effect of improving the dispersibility of the compounding agent such as (C) silica-based inorganic filler is obtained, In the target modified conjugated diene polymer composition, the balance of workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and abrasion resistance can be improved as compared with the conventional one.

  The modified conjugated diene polymer obtained by the production method of the present embodiment can be used, for example, as a rubber composition for a base tread, and a tire can be produced by a usual method. That is, a tire can be manufactured by manufacturing a base tread using the rubber composition, pasting together with other members, and heating and pressing using a tire molding machine.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

  First, a method for structural analysis of the modified conjugated diene polymers used in Examples and Comparative Examples and a method for measuring physical properties of the modified conjugated diene polymer compositions of Examples and Comparative Examples are shown below.

[(1) Bonded styrene content]
100 mg of a measurement sample (modified conjugated diene polymer used as a raw material for the composition) was made up to 100 mL with chloroform and dissolved to prepare a measurement sample. Using UV-2450 manufactured by Shimadzu Corporation as a measuring instrument, the amount of ultraviolet (UV) absorbed at a wavelength of 254 nm by the phenyl group of styrene was measured, and the amount of bound styrene (% by mass) was measured.

[(2) Microstructure of butadiene moiety (1,2-vinyl bond amount)]
50 mg of the measurement sample (modified conjugated diene polymer used as a raw material for the composition) was dissolved in 10 mL of carbon disulfide to obtain a measurement sample. A solution cell is manufactured, and an infrared spectrum is measured in the range of 600 to 1000 cm ⁻¹ using FT-IR230 manufactured by JASCO Corporation as a measuring instrument, and the calculation formula of the Hampton method is determined by absorbance at a predetermined wave number. Thus, the microstructure (1,2-vinyl bond amount) of the butadiene portion was determined.

[(3) Molecular weight]
Using a GPC (gel permeation chromatography) measuring device in which three columns with polystyrene gel as a filler are connected, the chromatogram of the modified conjugated diene polymer is measured, and a calibration curve using standard polystyrene is obtained. Based on this, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined. Tetrahydrofuran (THF) was used as the eluent. As the column, TSK guard column HHR-H manufactured by Tosoh Corporation was used as the guard column, and TSK gel G6000HHR, TSKgel G5000HHR, and TSKgel G4000HHR manufactured by Tosoh Corporation were used as the other columns. Further, the molecular weight was measured using an RI detector (“HLC8020” manufactured by Tosoh Corporation) under conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min. 10 mg of a measurement sample (modified conjugated diene polymer used as a raw material of the composition) was dissolved in 20 mL of THF to prepare a measurement solution, and 200 μL of the measurement solution was injected into the GPC measurement apparatus.

[(4) Denaturation rate]
It measured by applying the characteristic that the modified | denatured component adsorb | sucks to the GPC column which used the silica gel as the filler. As shown below, the sample solution containing the sample and the low molecular weight internal standard polystyrene is transferred to the silica column from the difference between the chromatogram measured with the polystyrene gel column and the chromatogram measured with the silica column as described later. The amount of adsorption was measured to determine the modification rate. A commercially available standard polystyrene having a molecular weight of 5000 was used as the low molecular weight internal standard polystyrene.

<Preparation of sample solution>
A sample solution was prepared by dissolving 10 mg of a sample and 5 mg of standard polystyrene in 20 mL of THF.

<GPC measurement conditions using polystyrene column>
Using THF as an eluent, 200 μL of the sample solution was injected into the apparatus for measurement. The column used was Tosoh TSKguardcolumn HHR-H as the guard column, and Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR as the other columns. The chromatogram was obtained by measurement using a RI detector (HLC8020 manufactured by Tosoh Corporation) under conditions of a column oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min.

<GPC measurement conditions using silica column>
Using THF as an eluent, 200 μL of sample was injected into the apparatus for measurement. As the columns, DIOL 4.6 × 12.5 mm 5 micron was used as a guard column, and Zorbax PSM-1000S, PSM-300S, and PSM-60S were used as other columns. In addition, CCP8020 series build-up type GPC system manufactured by Tosoh Corporation: AS-8020, SD-8022, CCPS, CO-8020, RI-8021 at a column oven temperature of 40 ° C. and a THF flow rate of 0.5 mL / min. Was used to obtain a chromatogram.

<Calculation method of denaturation rate>
Sample with 100 as the total peak area of the chromatogram using the polystyrene column, P1 as the peak area of the sample, P2 as the peak area of the standard polystyrene, and 100 as the entire peak area of the chromatogram using the silica column Assuming that the peak area of P3 is P3 and the peak area of standard polystyrene is P4, the modification rate (%) was obtained from the following formula.
Denaturation rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100

[(5) Compound Mooney viscosity]
Using a Mooney viscometer, according to JIS K6300-1, after preheating at 100 ° C. for 1 minute, the viscosity after rotating the rotor at 2 revolutions per minute for 4 minutes was measured. Each measured value is the value of Example 2, Comparative Examples 3 and 7 with the value of Comparative Example 2 as 100, the values of Examples 1, Comparative Examples 1 and 7 are indexed, and the value of Comparative Example 4 is 100. Was indexed. Further, the value of Comparative Example 6 was set to 100, the values of Reference Example 3, Comparative Examples 5 and 7 were indexed, the value of Comparative Example 9 was set to 100, and the values of Comparative Examples 7 and 8 were indexed. The smaller the value, the lower the Mooney viscosity of the compound and the better the processability.

[(6) Collectability of waste]
Regarding the unvulcanized modified conjugated diene polymer composition produced by the method shown in the Examples and Comparative Examples, immediately after being discharged from the pressure kneader (the kneading by the pressure kneader in the first kneading is completed and discharged) The panel set (shape) immediately after the observation was visually observed by five panelists, and was evaluated based on the following criteria, with 20 points per panel being a perfect score and a total of 100 points being evaluated. The closer to 100 points, the better the workability after extrusion.
70 points: Poor 71 points 75 points: Very inferior.
76 to 80 points: Inferior.
81-85 points: Usually.
86 to 90 points: Excellent.
91 to 100 points: very good.

[(7) Tensile properties]
The tensile breaking strength (TB) and the tensile breaking elongation (EB) were measured by the tensile test method of JIS K6251. The product of the tensile strength at break (TB, unit: MPa) and the tensile elongation at break (EB, unit:%) was taken as tensile characteristics. Each measured value is the value of Example 2, Comparative Examples 3 and 7 with the value of Comparative Example 2 as 100, the values of Examples 1, Comparative Examples 1 and 7 are indexed, and the value of Comparative Example 4 is 100. Was indexed. Further, the value of Comparative Example 6 was set to 100, the values of Reference Example 3, Comparative Examples 5 and 7 were indexed, the value of Comparative Example 9 was set to 100, and the values of Comparative Examples 7 and 8 were indexed. Larger values indicate better tensile properties.

[(8) Abrasion resistance]
Using an Akron abrasion tester (manufactured by Yasuda Seiki Seisakusho), the amount of wear at a load of 44.1 N and 3000 rotations was measured according to JIS K6264-2. Each measured value is the value of Example 2, Comparative Examples 3 and 7 with the value of Comparative Example 2 as 100, the values of Examples 1, Comparative Examples 1 and 7 are indexed, and the value of Comparative Example 4 is 100. Was indexed. Further, the value of Comparative Example 6 was set to 100, the values of Reference Example 3, Comparative Examples 5 and 7 were indexed, the value of Comparative Example 9 was set to 100, and the values of Comparative Examples 7 and 8 were indexed. Smaller values indicate less wear and better wear resistance.

[(9) Wet skid resistance (WET)]
Using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments Japan, viscoelastic parameters were measured in torsion mode. Tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an indicator of wet skid resistance. Each measured value is the value of Example 2, Comparative Examples 3 and 7 with the value of Comparative Example 2 as 100, the values of Examples 1, Comparative Examples 1 and 7 are indexed, and the value of Comparative Example 4 is 100. Was indexed. Further, the value of Comparative Example 6 was set to 100, the values of Reference Example 3, Comparative Examples 5 and 7 were indexed, the value of Comparative Example 9 was set to 100, and the values of Comparative Examples 7 and 8 were indexed. Larger values indicate better wet skid resistance.

[(10) Rolling resistance characteristics (RR)]
Using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments Japan, viscoelastic parameters were measured in torsion mode. Tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of rolling resistance characteristics (fuel saving). Each measured value is the value of Example 2, Comparative Examples 3 and 7 with the value of Comparative Example 2 as 100, the values of Examples 1, Comparative Examples 1 and 7 are indexed, and the value of Comparative Example 4 is 100. Was indexed. Further, the value of Comparative Example 6 was set to 100, the values of Reference Example 3, Comparative Examples 5 and 7 were indexed, the value of Comparative Example 9 was set to 100, and the values of Comparative Examples 7 and 8 were indexed. A smaller value indicates better rolling resistance characteristics.

[Modified Conjugated Diene Polymer]
[Production example]
An autoclave having an internal volume of 10 liters having a stirrer and a jacket and capable of temperature control was used as a reactor. 637 g of butadiene from which impurities were removed, 213 g of styrene, 5500 g of cyclohexane, and 0.82 g of 2,2-bis (2-oxolanyl) propane as a polar substance were put into the reactor, and the reactor internal temperature was maintained at 30 ° C. A cyclohexane solution containing 6.75 mmol of n-butyllithium as a polymerization initiator was supplied to the reactor. After the start of the reaction, the temperature in the reactor began to rise due to the exotherm caused by the polymerization. Over 7 to 12 minutes after addition of the polymerization initiator, 50 g of butadiene was additionally supplied at a rate of 10 g / min. As a result, the final temperature in the reactor reached 77 ° C. After completion of the polymerization reaction, 13.5 mmol of 1- [3- (triethoxysilanyl) -propyl] -4-methylpiperazine was added to the reactor, and the modification reaction was carried out by stirring at 75 ° C. for 5 minutes. After 1.8 g of an antioxidant (BHT; 2,6-di-tertbutyl-4-methylphenol) was added to this polymer solution, the solvent was removed and a styrene-butadiene copolymer having a modifying component (Sample A) )

  As a result of analyzing the sample A by the above method, the amount of bound styrene was 25% by weight, the amount of bound butadiene was 75% by weight, the styrene single chain content of one styrene unit was 45%, and the number of styrene units was 8 or more. The content of the continuous styrene long chain was 0.5%. The Mooney viscosity of the polymer was 60, and the 1,2-bond content of the microstructure of the butadiene portion was 55%. As for the molecular weight in terms of polystyrene, the weight average molecular weight (Mw) was 400,000, the number average molecular weight (Mn) was 310,000, and the molecular weight distribution (Mw / Mn) was 1.29. The modification rate was 87%.

  Table 1 below shows the structure and physical properties of the above-described modified conjugated diene polymer (hereinafter also simply referred to as “modified SBR”).

According to the composition shown below, an unvulcanized rubber composition (unvulcanized product) and a vulcanized rubber composition (vulcanized product) were obtained.
Modified SBR (1) (modified conjugated diene copolymer prepared in (Production Example 1), modified SBR (1)): 100 parts by mass Silica (manufactured by Rhodia, ZEOSIL Premium 200MP): 45 parts by mass Ring agent (Evonik Degussa, Si75): 3.6 parts by mass, terminal amine-modified liquid polymer (manufactured by Ube Industries, trade name “ATBN 1300 × 16”, amine terminal-modified, number average molecular weight = 3400): 30 parts by mass / terminal carboxy-modified liquid polymer (manufactured by Ube Industries, trade name “CTBN 1300 × 31”, carboxy-terminal modified, number average molecular weight = 3500): 30 parts by mass / terminal hydroxyl-modified liquid polymer (Idemitsu Kosan ( Product name “R-45HT (Hydroxyl terminal-modified, number average molecular weight = 2800)”): 30 parts by mass Non-modified liquid poly MA (Kuraray Co., Ltd., trade name “LBR-307 (number average molecular weight = 8000)”): 30 parts by mass / carbon black (manufactured by Tokai Carbon Co., Ltd., Seast KH (N339)): 5 parts by mass Sulfur accelerating aid (zinc oxide, indicated as “zinc flower” in the table): 2.5 parts by mass. Vulcanization accelerating aid (stearic acid): 2.0 parts by mass. Wax: (Ouchi Shinsei Chemical Industry ( Sannok Co., Ltd.): 1.5 parts by mass / anti-aging agent (N-isopropyl-N′-phenyl-p-phenylenediamine): 2.0 parts by mass / sulfur: 1.7 parts by mass / acceleration of vulcanization Agent (N-cyclohexyl-2-benzothiazylsulfinamide): 1.7 parts by mass / Vulcanization accelerator (diphenylguanidine): 2.0 parts by mass

  The materials shown above were kneaded by the following method to obtain an unvulcanized rubber composition and a vulcanized rubber sheet.

(Examples 1 and 2 , Reference Example 3, and Comparative Example 7)
Using a Moriyama pressure kneader “DO.5-3” (with an internal volume of 500 cc) equipped with a temperature control device, the first stage kneading step was performed under the conditions of a filling rate of 65% and a rotor rotational speed of 50 rpm. The modified conjugated diene polymer (modified SBR) and the liquid polymer were kneaded for 60 seconds. That is, as Step 1, kneading was performed for 1 minute. Then, the process 2 was implemented as follows. First, silica, a silane coupling agent, and carbon black were blended and kneaded. Next, after the material instruction temperature reached 150 ° C., kneading was performed for 2 minutes while controlling the material instruction temperature in the pressure kneader to 150 to 160 ° C. by controlling the temperature of the mixer.

  Then, without discharging the kneaded material, the vulcanization acceleration aid (stearic acid and zinc oxide), anti-aging agent, and wax are blended while controlling the indicated material temperature in the pressure kneader to 150 to 160 ° C. The mixture (discharge temperature 150 to 160 ° C.) was discharged from the pressure kneader. At this time, the state of unity of the blend (unvulcanized product) was observed (the unity property of the discharged matter). Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend. As described above, in Step 1 and Step 2 in the first stage of kneading, the kneading was performed for a total of 8 minutes.

  Next, as the second kneading step, the sheet-like composition obtained by the first kneading described above was cooled to room temperature, and then kneaded again with the pressure kneader for 3 minutes. Also in this case, the discharge temperature (formulation) was adjusted to 150 to 160 ° C. by controlling the temperature of the mixer. And after discharging | emitting the said compound from a pressure kneader, the compound was immediately passed 6 times through the 10 inch diameter open roll, and it was set as the sheet-like unvulcanized rubber composition.

  Further, after heating the unvulcanized composition using an oven at 70 ° C. for 30 minutes, as a third stage of kneading, sulfur and a vulcanization accelerator were added with a 10 inch φ open roll set at 70 ° C. And kneaded for 2 minutes to obtain a composition. A part of this composition (unvulcanized product) was taken out, and the Mooney viscosity and vulcanization rate were measured.

  Thereafter, the other remaining part of the composition was vulcanized with a vulcanizing press at 160 ° C. for 20 minutes. After vulcanization, the rolling resistance characteristics (RR), wet skid resistance (WET), tensile characteristics, and wear resistance of the vulcanized rubber composition were evaluated.

(Comparative Examples 1, 3, 5, 8)
Using a Moriyama pressure type kneader “DO.5-3” (with an internal volume of 500 cc) equipped with a temperature control device, kneading in the first stage under the conditions of a filling rate of 65% and a rotor rotational speed of 50 rpm, The modified conjugated diene polymer (modified SBR) was kneaded for 60 seconds. That is, as Step 1, kneading was performed for 1 minute. Then, the process 2 was implemented as follows. First, a modified liquid polymer, silica, a silane coupling agent, and carbon black were blended and kneaded. Next, after the material instruction temperature reached 150 ° C., kneading was performed for 2 minutes while controlling the material instruction temperature in the pressure kneader to 150 to 160 ° C. by controlling the temperature of the mixer.

  Then, without discharging the kneaded material, the vulcanization acceleration aid (stearic acid and zinc oxide), anti-aging agent, and wax are blended while controlling the indicated material temperature in the pressure kneader to 150 to 160 ° C. The mixture (discharge temperature 150 to 160 ° C.) was discharged from the pressure kneader. At this time, the state of unity of the blend (unvulcanized product) was observed (the unity property of the discharged matter). Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend. As described above, in Step 1 and Step 2 in the first stage of kneading, the kneading was performed for a total of 8 minutes.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (exhaust cohesiveness, compound Mooney viscosity, vulcanization speed), vulcanization Sulfur physical properties (rolling resistance characteristics (RR), wet skid resistance (WET), tensile characteristics, and wear resistance were evaluated.

(Comparative Examples 2, 4, 6, 9)
Using a Moriyama pressure type kneader “DO.5-3” (with an internal volume of 500 cc) equipped with a temperature control device, kneading in the first stage under the conditions of a filling rate of 65% and a rotor rotational speed of 50 rpm, 8 minutes by blending modified conjugated diene polymer (modified SBR), modified liquid polymer, silica, silane coupling agent, carbon black, vulcanization accelerator (stearic acid and zinc oxide), anti-aging agent, and wax. The mixture (discharge temperature 150 to 160 ° C.) was discharged from a pressure kneader. At this time, the state of unity of the blend (unvulcanized product) was observed (the unity property of the discharged matter). Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend. As described above, in these examples, Step 1 and Step 2 were not performed separately, and kneading was performed for a total of 8 minutes.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (exhaust cohesiveness, compound Mooney viscosity, vulcanization speed), vulcanization Sulfur physical properties (rolling resistance characteristics (RR), wet skid resistance (WET), tensile characteristics, and wear resistance were evaluated.

  The production conditions in Example 1 and Comparative Examples 1, 2, and 7 are shown in Table 2. Processability (exhaust cohesiveness, compound Mooney viscosity, vulcanization speed), rolling resistance characteristics (RR), wet skid Table 3 shows the evaluation results of resistance (WET), tensile properties, and abrasion resistance.

  From Table 3, it was found that the modified conjugated diene copolymer composition produced in Example 1 was excellent in the balance of workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance. .

  The production conditions in Example 2 and Comparative Examples 3, 4 and 7 are shown in Table 4. Processability (exhaust cohesiveness, compound Mooney viscosity, vulcanization speed), rolling resistance characteristics (RR), wet skid Table 5 shows the evaluation results of resistance (WET), tensile properties, and abrasion resistance.

  From Table 5, it was found that the modified conjugated diene copolymer composition produced in Example 1 was excellent in the balance of workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance. .

The production conditions in Reference Example 3 and Comparative Examples 5, 6, and 7 are shown in Table 6. Processability (exhaust cohesiveness, compound Mooney viscosity, vulcanization speed), rolling resistance characteristics (RR), wet skid Table 7 shows the evaluation results of resistance (WET), tensile properties, and abrasion resistance.

  From Table 7, it was found that the modified conjugated diene copolymer composition produced in Example 1 was excellent in the balance of workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance. .

  The production conditions in Comparative Examples 7, 8, and 9 are shown in Table 8. Processability (exhaust cohesiveness, blended Mooney viscosity, vulcanization speed), rolling resistance characteristics (RR), wet skid resistance (WET) Table 9 shows the evaluation results of tensile properties and abrasion resistance.

  From Table 9, the modified conjugated diene copolymer composition produced in Comparative Examples 7, 8, and 9 has the same balance of workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance. I understood.

  The modified conjugated diene polymer composition obtained by the production method of the present invention has industrial applicability as a material for various members such as tire treads, footwear, and industrial articles.

Claims (8)

A method for producing a modified conjugated diene polymer composition, comprising the following step (1) and step (2) in this order.
Step (1): A step of blending and kneading the following (A) and (B).
(A) 100 parts by mass of a rubber component containing a modified conjugated diene polymer (B) A modified liquid polymer having at least one functional group selected from the group consisting of an amino group, a carboxyl group and an epoxy group , 0.5 to 50 parts by mass with respect to 100 parts by mass of the rubber component Step (2): A step of blending and kneading the following (C) and (D).
(C) 10 to 200 parts by mass of silica inorganic filler with respect to 100 parts by mass of (A) rubber component (D) Silane coupling agent with respect to 100 parts by mass of (C) silica-based inorganic filler. 1-20 parts by mass The method for producing a modified conjugated diene polymer composition according to claim 1 , wherein the functional group is an amino group. The method for producing a modified conjugated diene polymer composition according to claim 1 or 2 , wherein kneading is performed at 120 to 170 ° C in the step (2). The method for producing a modified conjugated diene polymer composition according to any one of claims 1 to 3 , wherein kneading is performed at 150 to 160 ° C in the step (2). The method for producing a modified conjugated diene polymer composition according to any one of claims 1 to 3 , wherein kneading is performed at 140 to 150 ° C in the step (2). The modified conjugate according to claim 4 or 5 , wherein the kneading time after reaching the temperature range of 150 to 160 ° C or 140 to 150 ° C in the step (2) is 0.5 to 20 minutes. A method for producing a diene polymer composition. The modified conjugated diene system according to any one of claims 1 to 6 , comprising a step of further blending (E) carbon black in an amount of 0.5 to 100 parts by mass with respect to 100 parts by mass of the rubber component (A). A method for producing a polymer composition. In step (2), in formulating the (C) silica inorganic filler and the (D) silane coupling agent, compounding the (E) carbon black, modified conjugated diene-based heavy according to claim 7 A method for producing a combined composition.