JP2015113424A - Production method for modified conjugated diene-type polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method for modified conjugated diene-type polymer composition that can realize excellent low-hysteresis-loss property, wet skid resistance and wear resistance while ensuring sufficient processability.SOLUTION: The production method for modified conjugated diene-type polymer composition includes carrying out the following step (1) and step (2) in the same stage. Step (1): a step of blending the following (A) to (C) and kneading the same at 120 to 170°C. (A) a rubber component comprising modified conjugated diene-type polymer having a weight average molecular weight of 400,000 or more and 2,000,000 or less. (B) a silica-inorganic filler by 30 to 300 pts.mass per 100 pts.mass of the (A) rubber component. (C) a silane coupling agent by 0.1 to 30 pts.mass per 100 pts.mass of the (B) silica-based inorganic filler. Step (2): a step of blending (D) a vulcanization promotion auxiliary and (E) an antiaging agent into the mix obtained in the step (1) and kneading the same.

Description

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

  In recent years, environmental considerations such as the suppression of carbon dioxide emissions have become social demands. Specifically, demand for low fuel consumption for automobiles is increasing. Under such circumstances, there has been a demand for the development of a material having low rolling resistance as a material for automobile tires, particularly tire treads in contact with the ground. On the other hand, from the viewpoint of safety, development of materials having excellent wet skid resistance and practically sufficient wear resistance and fracture characteristics is required.

  Conventionally, carbon black, silica, and the like have been used as reinforcing fillers for tire treads. When silica is used, there is an advantage that low hysteresis loss and wet skid resistance can be improved.

  However, on the other hand, hydrophilic surface silica has a disadvantage that its affinity with conjugated diene rubber is low and its dispersibility is poor compared to carbon black, compared to hydrophobic surface carbon black. . Therefore, it has been proposed to use a silane coupling agent. That is, the dispersibility is improved by chemically reacting the hydroxyl group on the silica surface and the silanol group of the silane coupling agent during kneading. Furthermore, when the silane coupling agent is crosslinked with rubber during vulcanization, excellent low hysteresis loss and wet skid resistance can be obtained. Therefore, an important technical issue is how the chemical reaction of the silica-silane coupling agent-rubber can proceed.

  In order to improve low hysteresis loss and wet skid resistance, various manufacturing methods have been studied so far. For example, Patent Document 1 discusses a method of kneading only with a polymer, silica, and a silane coupling agent in the first stage kneading. Patent Document 2 discusses a method of kneading with a polymer, silica, carbon black, and a silane coupling agent in the first stage kneading, and then adding a blending aid.

Japanese Patent No. 2635881 Patent No. 3933207 Specification

  However, in the invention described in Patent Document 1, while a rubber composition excellent in low hysteresis loss and wet skid resistance can be obtained, the discharged rubber is poorly organized and difficult to process. Further, in the invention described in Patent Document 2, since the kneading temperature is set as low as 100 to 130 ° C., the reaction between silica and the silane coupling agent is insufficient, and a high level of low hysteresis required in recent years. Loss and wet skid resistance cannot be obtained.

  The present invention has been made in view of the above-described problems of the prior art, and a modified conjugated diene that can exhibit excellent low hysteresis loss, wet skid resistance, and wear resistance while ensuring sufficient workability. It aims at providing the manufacturing method of a polymer composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has determined the specific kneading timing and kneading in the method for producing a modified conjugated diene polymer composition containing a large amount of silica-based filler. By adopting the conditions, the dispersibility and vulcanization of compounding agents such as silica, etc., compared with the conventional one, without impairing the processability, without inhibiting the reaction between the silica-based inorganic filler and the silane coupling agent The present inventors have found that the properties are improved and the balance between rolling resistance properties, wet skid resistance, and wear resistance is excellent, 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, wherein the following step (1) and step (2) are carried out in the same step.
Process (1): The process of mix | blending the following (A)-(C) and knead | mixing at 120-170 degreeC.
(A) Rubber component containing a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less (B) Silica inorganic filler is added in an amount of 30 to 300 parts by mass with respect to 100 parts by mass of the (A) rubber component. (C) 0.1-30 mass parts of silane coupling agent with respect to 100 mass parts of said (B) silica type inorganic filler Process (2): The kneaded material obtained in the said process (1) to (D) A step of blending and kneading a vulcanization acceleration aid and (E) an anti-aging agent.
[2]
The method for producing a modified conjugated diene polymer composition according to [1], wherein kneading is performed at 150 to 160 ° C. in the step (1).
[3]
The (C) silane coupling agent comprises bis- [3- (triethoxysilyl) -propyl] -disulfide, S- [3- (triethoxysilyl) -propyl] octanethioate and S- [3- (tri The modified conjugated diene copolymer according to [1] or [2], which is at least one selected from condensates of ethoxysilyl) -propyl] octanethioate and [(triethoxysilyl) -propyl] thiol A method for producing the composition.
[4]
The method for producing a modified conjugated diene polymer composition according to [1], wherein kneading is performed at 140 to 150 ° C. in the step (1).
[5]
[1] or [4], wherein the (C) silane coupling agent is bis- [3- (triethoxysilyl) -propyl] -tetrasulfide and / or a compound represented by the following formula (1): The manufacturing method of the composition of the modified | denatured conjugated diene type copolymer as described in any one of.

[6]
The method for producing a modified conjugated diene polymer composition according to [1], wherein the kneading time in the temperature range of 120 to 170 ° C. is 2 to 8 minutes in the step (1).
[7]
The method for producing a modified conjugated diene polymer composition according to [2] or [3], wherein the kneading time in the temperature range of 150 to 160 ° C. is 2 to 8 minutes in the step (1).
[8]
The method for producing a modified conjugated diene polymer composition according to [4] or [5], wherein the kneading time in the temperature range of 140 to 150 ° C. is 2 to 8 minutes in the step (1).
[9]
The modification | denaturation as described in any one of [1]-[8] including the process of further mix | blending 0.5-100 mass parts (F) carbon black with respect to 100 mass parts of said (A) rubber components. A method for producing a conjugated diene copolymer composition.
[10]
In the step (1), when the (A) to (C) are blended, the (F) carbon black is blended, and the method for producing the modified conjugated diene copolymer composition according to [9].

  According to the present invention, it is possible to obtain a modified conjugated diene polymer composition that can exhibit excellent low hysteresis loss, wet skid resistance, and wear resistance while ensuring sufficient processability. Therefore, for example, by using this as a tread material, a tire having an excellent balance of rolling resistance characteristics, wet skid resistance, and wear resistance can be obtained without deteriorating workability.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

[Method for Producing Modified Conjugated Diene Polymer Composition]
The manufacturing method of the modified conjugated diene polymer composition of the present embodiment includes the following steps (1) and (2) to obtain a modified conjugated diene polymer composition.
Process (1): The process of mix | blending the following (A)-(D) and knead | mixing at 120-170 degreeC.
(A) Rubber component containing a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less (B) Silica inorganic filler is added in an amount of 30 to 300 parts by mass with respect to 100 parts by mass of the (A) rubber component. (C) 0.1-30 mass parts of silane coupling agent with respect to 100 mass parts of said (B) silica type inorganic filler Process (2): The kneaded material obtained in the said process (1) to (D) A step of blending and kneading a vulcanization acceleration aid and (E) an anti-aging agent.
(In the step (1), (D) vulcanization acceleration aid and (E) anti-aging agent are not included.)
Step (1) and step (2) are performed in the same stage. The “same stage” will be described in detail later. Since it is configured as described above, according to the method for producing the modified conjugated diene polymer composition of the present embodiment, while ensuring sufficient processability, excellent low hysteresis loss, wet skid resistance, In addition, a modified conjugated diene polymer composition that can exhibit wear resistance can be obtained.

  Hereinafter, (A) to (C) used in step (1) and (D) and (E) 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 a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less>
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 having a weight average molecular weight of 400,000 or more and 2,000,000 or less (hereinafter referred to as “a”). , (A) rubber component, (A) component, and (A) may be described). (A) The modified conjugated diene polymer contained in the rubber component is a terminal modified conjugated diene polymer and / or a both terminal modified conjugated diene polymer.

  (A) The weight average molecular weight Mw of the modified conjugated diene polymer in the rubber component is obtained by sufficiently dispersing (B) a silica-based inorganic filler described later, processability, rolling resistance characteristics, wet skid resistance characteristics, tensile characteristics. And, from the viewpoint of sufficiently improving the wear resistance, it is set to 400,000 or more, and from the viewpoint of making workability practically sufficient, it is set to 2 million or less. Preferably it is 450,000 or more and 1.5 million or less, More preferably, it is 500,000-1.3 million.

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

[Modified Conjugated Diene Polymer]
The terminal modified conjugated diene polymer and the both terminal modified conjugated diene polymer of the modified conjugated diene polymer used in the production method of this embodiment will be described.

  It is preferable that the modified conjugated diene polymer contains a terminal modified conjugated diene polymer or a both terminal modified conjugated diene polymer from the viewpoint of rolling resistance characteristics, wet skid resistance, and tensile characteristics. 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 30% by mass or more.

  Here, the process of polymerizing the terminal-modified conjugated diene polymer will be described. The terminal-modified conjugated diene polymer is not limited to the following. For example, the polymerization activity of the conjugated diene polymer obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound using an anionic polymerization initiator. It can be obtained by reacting a compound having an amino group, an epoxy group or an alkoxysilane group at the terminal.

  Examples of the anionic polymerization initiator include organolithium compounds, which are not limited to the following. For example, n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium Monoorganolithium compounds such as benzyl lithium, 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,1,0-dilithiodecane, 1,1, -dilithiophenylene, dilithiopolybutadiene , Dilithiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1, Polyfunctional organolithium compounds such as 3,5-trilithio-2,4,6-triethylbenzene Etc. The. In particular, a monoorganolithium compound of n-butyllithium, sec-butyllithium, or tert-butyllithium is preferable from the viewpoint of reactivity.

  The conjugated diene compound used for polymerizing the conjugated diene polymer constituting the terminal-modified conjugated diene polymer may be any monomer that can be polymerized, and is not limited to the following. Examples include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-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. These may be used alone or in combination of two or more. In particular, 1,3-butadiene is preferable.

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

  The 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 limited to the following, for example, a completely random copolymer close to a statistical random composition, a taper (gradient) in which the composition is distributed in a tapered shape A random 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.

  The conjugated diene polymer for obtaining the terminal-modified conjugated diene polymer used in the production method of the present embodiment is preferably obtained through growth by an anionic polymerization reaction using an anionic polymerization initiator. In particular, a copolymer having an active end obtained by a growth reaction by living anionic polymerization is more preferable. In this case, a modified conjugated diene polymer having a high modification rate tends to be obtained by a modification step described later.

  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. The reactor is not particularly limited, and for example, a tank type with a stirrer, a tube type, or the like is used.

  In this embodiment, from the viewpoint of sufficient efficiency of the modification reaction for obtaining a modified conjugated diene polymer, allenes, acetylenes, etc. are contained as impurities in the conjugated diene compound used in the polymerization step. Preferably not. 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 allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.

  The polymerization reaction of the conjugated diene polymer is preferably performed in a solvent. Examples of the solvent include, but are not limited to, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. More specifically, but not limited to, for example, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; Examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, and hydrocarbons composed of mixtures thereof.

  Treatment of allenes and acetylenes, which are impurities, with an organometallic compound in a polymerization monomer before being subjected to a 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. The use of a polar compound is preferable from the viewpoint of randomly copolymerizing an aromatic vinyl compound with a conjugated diene compound. The polar compound can also be used as a vinylating agent for controlling the microstructure of the conjugated diene part. Polar compounds are also effective in improving 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- Alkali metal alkoxide compounds such as butyrate and sodium amylate; phosphine compounds such as triphenylphosphine can be usedThese 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. Such a polar compound (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 vinyl bond amount. 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, as described in JP-A No. 59-140212, a polar compound is used, and then a common method is used. A method of intermittently adding a part of 1,3-butadiene during the polymerization 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, but is preferably 0 ° C. or higher and 120 ° C. or lower. That is, from the viewpoint of productivity, it is preferably 0 ° C. or higher, and from the viewpoint of sufficiently ensuring the reaction amount of the modifier with respect to the active terminal after the completion of polymerization, 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 50 to 100% by mass. For example, when used for tire tread applications, 60 to More preferably, it is 80 mass%.

  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 50% by mass, and preferably 20 to 40% by mass. More preferred.

  When the amount of bound conjugated diene and amount of bound aromatic vinyl are in the above ranges, a vulcanizate having an excellent balance between low hysteresis loss and wet skid resistance and satisfactory 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 measure by the method according to the Example mentioned later.

  Moreover, the amount of vinyl bonds in the conjugated diene bond unit of the modified conjugated diene polymer is not particularly limited, but is preferably 10 to 75 mol%, and more preferably 25 to 65 mol%. When the vinyl bond amount is in the above range, a vulcanizate having a further excellent balance between low hysteresis loss 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 can be obtained due to the balance between low hysteresis loss and wet skid resistance. Regarding the glass transition temperature, in accordance with ISO 22768: 2006, a DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve is defined as the glass transition temperature.

  The terminal-modified conjugated diene polymer is obtained by, for example, a compound having an amino group, an epoxy group or an alkoxysilane group at the polymerization active terminal after obtaining a conjugated diene polymer having an active terminal by the method as described above. It is obtained by reacting (also called a modifier). The modifier is a compound having an amino group and an epoxy group, or one or more alkoxy groups bonded to a silyl group, and a compound having two or more tertiary amino groups, or an alkoxy group bonded to a silyl group. Is preferably a compound having one or more nitrogen atoms.

  The low molecular organic compound having an amino group and an epoxy group in the molecule used as a modifier for producing a terminal-modified conjugated diene polymer is a tertiary amino group as an amino group, and a molecular weight of 1000 or less. In some cases, a low molecular compound that does not need to have a repeating unit is preferable. Specifically, although not limited to the following, for example, epoxy group-containing tertiary amines such as 4,4′-diglycidyl-diphenylmethylamine, 4,4′-diglycidyl-dibenzylmethylamine, diglycidylaniline, diglycidyl Diglycidylamino compounds such as orthotoluidine, tetraglycidylmetaxylenediamine, tetraglycidylaminodiphenylmethane, tetraglycidyl-p-phenylenediamine, diglycidylaminomethylcyclohexane, tetraglycidyl-1,3-bisaminomethylcyclohexane, and amino groups thereof Examples include oligomers of contained epoxy compounds. A compound having an amino group and a plurality of epoxy groups in the molecule is preferred. More preferred are diglycidylamino group-containing polyfunctional compounds. A particularly suitable compound is tetraglycidyl-1,3-bisaminomethylcyclohexane. When these low molecular weight organic compounds having amino groups and epoxy groups are reacted with the active lithium of the polymer, some epoxy groups become alkoxy groups, and when a plurality of epoxy groups react, a plurality of polymers are bonded to form a cup. Ringing occurs, and the alkoxy lithium further reacts with the epoxy group, and a part of the epoxy group remains and is in a state of being bonded to the polymer.

  Further, the compound used in the modifier is one or more alkoxy groups bonded to a silyl group and has two or more tertiary amino groups, but is not limited to the following, for example, N- [2- ( Trialkoxysilanyl) -ethyl] -N, N ′, N′-trialkylethane-1,2-diamine, N- [2- (alkyldialkoxysilanyl) -ethyl] -N, N ′, N ′ -Trialkylethane-1,2-diamine, N- [3- (trialkoxysilanyl) -propyl] -N, N ', N'-trialkylpropane-1,3-diamine, N- [3- ( Alkyldialkoxysilanyl) -propyl] -N, N ′, N′-trialkylpropane-1,3-diamine, N- [3- (trialkoxysilanyl) -propyl] -2, N, N ′, N'-tetraalkylpro Down-1,3-diamine, N- [3- (alkyl dialkoxy -lH) - propyl] -2, N, N ', N'- tetraalkyl-1,3-diamine, and the like. 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 And killed-1,2,3,4-tetrahydropyrimidine and the like. 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) -1,3-dialkylhexahydropyrimidine and the like can also be mentioned.

  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 - trimethylsilanyl hexahydropyrimidine and the like. Preferred compounds include N- [2- (trimethoxysilanyl) -ethyl] -N, N ′, N′-trimethylethane-1,2-diamine and 1- [3- (triethoxysilanyl). -Propyl] -4-methylpiperazine, 2- (trimethoxysilanyl) -1,3-dimethylimidazolidine.

  Further, the “compound having a total number of alkoxy groups bonded to a silyl group of 4 or more and having one or more nitrogen atoms” used in the modifier is not limited to the following, but for example, the following formula (1 -1), (1-2), and (1-3).

  In General Formula (1-1), R1 to R4 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R5 represents an alkylene group having 1 to 10 carbon atoms. , R6 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 (1-2), R7 to R10 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R11 and R12 each independently represent a carbon number. R1 and R14 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, And q each independently represents an integer of 2 or 3.

  In General Formula (1-3), X1 and X2 are alkoxy groups having 1 to 20 carbon atoms, R15 and R16 are each a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A1 and A2 Are each a single bond or a C1-C20 divalent hydrocarbon group, and A3 is a group represented by the following formulas (a) and (b). When a plurality of X1, X2, R15, R16, A1, A2 or A3 are present, they may be the same or different. R and s are integers of 0 to 3, respectively. Furthermore, t is an integer of 0 to 20, and when t is 2 or more, the plurality of repeating units represented by (A1-A3-A2) may be different from each other.

In general formula (a), R17 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
In addition, when A3 is represented by Formula (a), (r + s) is 5 or 6.

  In general formula (b), A4 is a single bond or a C1-C20 bivalent hydrocarbon group, and X3 is a C1-C20 alkoxy group. R18 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of X4 or R18 are present, they may be the same or different from each other. u is an integer of 0-3. When A3 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, 1,4-bis [3- (triethoxysilyl) propyl] piperazine Masui.

  The modifying agent represented by the general formula (3) is not limited to the following when A3 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-tri Ethoxysilylpropyl) propylamine, bis (3-trimethoxysilylpropyl) butylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3-trimethoxysilylpropyl) phenylamine, bis (3-triethoxysilylpropyl) Phenylamine, bis (3-trimethoxysilyl group) Pyr) 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 A3 is the general formula (b). For example, tris (trimethoxysilylmethyl) amine, tris (2- Examples include triethoxysilylethyl) amine, tris (3-trimethoxysilylpropyl) amine, and tris (3-triethoxysilylpropyl) amine.

  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. For example, the reaction is performed at 0 ° C to 120 ° C for 30 seconds or longer. Is preferred.

  The content of the polymer having a functional group component of the modified conjugated diene polymer, that is, the modification rate is low hysteresis loss and wet skid when the composition using the modified conjugated diene polymer is a vulcanized product. From the viewpoint of further improving the balance with resistance and obtaining 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. % Or more is more preferable. 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-mentioned modification reaction is 400,000 or more and 2 million or less. That is, the inorganic filler is sufficiently dispersed, and the processability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance are set to be 400,000 or more from the viewpoint of improving the workability, From the viewpoint of practically sufficient, it should be 2 million or less. From this viewpoint, Preferably, it is 400,000 or more and 1 million or less.

  Next, the process of polymerizing the both terminal-modified conjugated diene polymer will be described. For example, by using a polyfunctional anionic polymerization agent as the polymerization initiator, a both-end modified conjugated diene polymer can be obtained. The polyfunctional anionic polymerization initiator used in the step of polymerizing the conjugated diene polymer in the previous step of modifying the polymerization active terminal of the conjugated diene polymer with an alkoxylane compound (modifier) described later will be described. In addition, the conjugated diene polymer of the previous stage which modifies | denatures can be superposed | polymerized by the method similar to the modified conjugated diene polymer mentioned above except using a polyfunctional anion polymerization initiator.

  The polyfunctional anionic polymerization initiator used in the polymerization step of the conjugated diene polymer can be prepared by reacting a polyvinyl aromatic compound and an organolithium compound using a predetermined solvent. The method for preparing the polyfunctional anionic polymerization initiator is not limited to the following. For example, a method of reacting an organolithium compound and a polyvinyl aromatic compound in a hydrocarbon solvent, an organolithium compound and a conjugated diene. A method of reacting a polyvinyl aromatic compound after reacting with a compound, a method of reacting an organolithium compound with a monovinyl aromatic compound and then reacting the polyvinyl aromatic compound, a conjugated diene compound and / or a monovinyl aromatic compound, and There is a method of reacting an organolithium compound in the presence of two or three polyvinyl aromatic compounds. In particular, a method of reacting an organolithium compound and a polyvinyl aromatic compound in a hydrocarbon solvent, a method of reacting an organolithium compound and a conjugated diene compound and then reacting the polyvinyl aromatic compound, a conjugated diene compound and a polyvinyl compound A polyfunctional anionic polymerization initiator prepared by a method of reacting a monoorganolithium compound in the presence of is preferred from the viewpoints of rolling resistance characteristics, wet skid resistance, tensile characteristics, and abrasion resistance. In order to promote and stabilize the formation of the polyfunctional anionic polymerization initiator, it is preferable to add a Lewis base to the system during the preparation.

  The monomer of the polyvinyl aromatic compound used for the preparation of the polyfunctional anionic polymerization initiator is not limited to the following, but examples thereof include o, m and p-divinylbenzene, o, m and p-diiso Propenylbenzene, 1,2,4-trivinylbenzene, 1,2-vinyl-3,4-dimethylbenzene, 1,3-divinylnaphthalene, 1,3,5-trivinylnaphthalene, 2,4-divinylbiphenyl, 3,5,4′-trivinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,5,6-trivinyl-3,7-diethylnaphthalene and the like can be mentioned. These may be used alone or in combination of two or more. In particular, divinylbenzene and diisopropenylbenzene are preferable, and a mixture of these o-, m-, and p-isomers may be used.

  For the preparation of the polyfunctional anionic polymerization initiator, a conjugated diene compound and / or a monoaromatic vinyl compound may be used together with the polyvinyl aromatic compound.

  Examples of the conjugated diene compound include, but are not limited to, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1 1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like, and in particular, 1,3-butadiene, isoprene from the viewpoint of rolling resistance characteristics, wet skid resistance, tensile characteristics, and abrasion resistance. Is preferred.

  Examples of the monoaromatic vinyl compound include, but are not limited to, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and the like. Styrene is preferred from the viewpoint of rolling resistance characteristics, wet skid resistance, tensile characteristics, and abrasion resistance.

  The addition amount of the conjugated diene compound and / or the monoaromatic vinyl compound may be adjusted so that the weight average molecular weight in terms of polystyrene of the polyfunctional anionic polymerization initiator measured by GPC is 1,000 to 10,000. preferable.

  The organolithium compound used for the preparation of the polyfunctional anionic polymerization initiator is not limited to the following, but examples include n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso- Monoorganolithium compounds such as propyllithium and benzyllithium, 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,1,0-dilithiodecane, 1,1, -dilithiophenylene, Thiopolybutadiene, dilithiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, Polyfunctional organic lithium such as 1,3,5-trilithio-2,4,6-triethylbenzene Beam compounds. In particular, a monoorganolithium compound of n-butyllithium, sec-butyllithium, or tert-butyllithium is preferable from the viewpoint of reactivity.

  The solvent used for the preparation of the polyfunctional anionic polymerization initiator is not limited to the following, but examples thereof include aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, and alicyclic carbonization such as cyclopentane and cyclohexane. Examples thereof include aromatic hydrocarbons such as hydrogen, benzene, toluene, and xylene.

  In addition, it is effective to add a Lewis base in the system during the preparation process of the polyfunctional anionic polymerization initiator. Examples of the Lewis base include, but are not limited to, tertiary monoamines, tertiary diamines, chain or cyclic ethers, and the like.

  Examples of the tertiary monoamine include, but are not limited to, trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytrimethylamine, N, Examples thereof include N-dimethylformamide diisopropyl acetal and N, N-dimethylformamide dicyclohexyl acetal.

  Examples of the tertiary diamine include, but are not limited to, for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N , N ′, N′-tetramethylpropanediamine, N, N, N ′, N′-tetramethyldiaminobutane, N, N, N ′, N′-tetramethyldiaminopentane, N, N, N ′, N Examples thereof include compounds such as' -tetramethylhexanediamine and dipiperidinoethane.

  Examples of chain ethers include, but are not limited to, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.

  Examples of the cyclic ether include, but are not limited to, tetrahydrofuran, bis (2-oxoranyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane. 2,2-bis (2-oxolanylbutane), 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane, etc. The compound of this is mentioned.

  Among the Lewis bases, tertiary monoamine trimethylamine, triethylamine, tertiary diamine N, N, N ′, N′-tetramethylethylenediamine, and cyclic ether tetrahydrofuran, 2,2-bis (2-oxasolanyl). Propane is preferred from the viewpoint of promoting the generation and stabilization of the polyfunctional anionic polymerization initiator. The Lewis bases may be used alone or in combination of two or more.

  In addition, when a Lewis base is added when preparing a polyfunctional anionic polymerization initiator, it is preferably added within a range of 30 to 50,000 ppm with respect to the solvent used when preparing the polymerization initiator. More preferably, it is added within the range of 200 to 20,000 ppm. That is, from the viewpoint of sufficiently expressing the effect of promoting and stabilizing the reaction, 30 ppm or more is preferable, ensuring the freedom of microstructure adjustment in the subsequent polymerization step, recovering the solvent after polymerization, and in the purification step In consideration of separation from the polymerization catalyst, it is preferably added at 50,000 ppm or less.

  About the polyfunctional anionic polymerization initiator used in the polymerization step of the conjugated diene polymer, the molar ratio of the polyvinyl aromatic compound to the organic lithium is in the range of 0.01 to 1.0 with the polyvinyl aromatic compound / organic lithium. It is preferable to adjust so that it becomes. The greater the amount of polyvinyl aromatic compound used relative to the organic lithium, the greater the proportion of molecular chain ends to which functional groups are imparted by the modification reaction of the conjugated diene polymer described above, and the affinity and reactivity with silica particles. Thus, the balance between the low hysteresis loss property and the wet skid resistance in the modified conjugated diene polymer composition is further improved, and the wear resistance tends to be improved. From this viewpoint, the amount of the polyvinyl aromatic compound relative to 1 mol of the organic lithium compound is preferably 0.01 mol or more. On the other hand, the smaller the amount of the polyvinyl aromatic compound used relative to the organolithium compound, the better the workability such as kneading of the modified conjugated diene polymer composition of this embodiment. It is in. From this viewpoint, the amount of the polyvinyl aromatic compound relative to 1 mol of the organic lithium compound is preferably 1.0 mol or less.

  In general, when considering only the improvement of low hysteresis loss, the Mooney viscosity of the modified conjugated diene polymer composition tends to increase and the processability tends to deteriorate, but the viewpoint of obtaining good processability Therefore, it is preferable to appropriately adjust the amount of the polyvinyl aromatic compound used relative to the organolithium compound. From the viewpoint of achieving a good balance between the low hysteresis loss and workability, the amount of the polyvinyl aromatic compound is preferably in the range of 0.02 to 0.1 mol with respect to 1 mol of the organic lithium compound. , More preferably in the range of 0.02 to 0.5 mol.

  The temperature at which the polyfunctional anionic polymerization initiator is prepared is preferably 10 ° C. or higher from the viewpoint of production, and 140 ° C. or lower from the viewpoint of suppressing side effects due to high temperature, and more preferably in the range of 35 to 110 ° C. .

  The reaction time for preparing the polyfunctional anionic polymerization initiator depends on the reaction temperature, but is in the range of 5 minutes to 24 hours.

  The polystyrene equivalent weight average molecular weight (Mw) measured by GPC of the polyfunctional anionic polymerization initiator is preferably in the range of 500 to 20,000, more preferably in the range of 1,000 to 10,000. .

  The molecular weight distribution (Mw / Mn) of the polyfunctional anionic polymerization initiator is preferably in the range of 1.2 to 3.5, more preferably in the range of 1.2 to 2.5, still more preferably 1. In the range of 2 to 2.0. A modified conjugated diene polymer composition containing a conjugated diene polymer obtained using a polyfunctional anionic polymerization initiator having a molecular weight distribution in this range has a reduced Mooney viscosity, low hysteresis loss, and wetness. It tends to be a vulcanizate with an even better balance between skid resistance and wear resistance. The above Mw (weight average molecular weight) and Mn (number average molecular weight) can also be determined by GPC measurement.

  Both terminal-modified conjugated diene polymers are polymerized at the polymerization active terminal of the conjugated diene polymer obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound using the above-mentioned polyfunctional anionic polymerization initiator. It can be obtained by reacting the above modifier.

  In the modifier described above, the total number of moles of alkoxy groups bonded to the silyl group in the added modifier is 0.1 to 3 times the total number of moles of lithium contained in the polyfunctional anionic polymerization initiator described above. Is preferably added so as to be in a range of 0.2 to 2 times, more preferably added in a range of 0.2 to 1 times. preferable.

  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 making the processability better, the peak area on the lowest molecular side is preferably 10 to 70%. By adjusting the molar ratio of the polyvinyl aromatic compound to the organolithium compound and the addition amount of the modifier in preparing the polyfunctional anionic polymerization initiator within the aforementioned range, the lowest molecular weight as described above. The peak area on the side can be 10 to 70%.

  In the modified conjugated diene polymer used in the above-described embodiment, in any of the terminal modified conjugated diene polymer and the both terminal modified conjugated diene polymer, after the modification reaction, If necessary, a deactivator, a neutralizing agent, etc. 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.

  Further, the modified conjugated diene polymer used in the present embodiment is a main chain modified conjugated diene polymer and a terminal from the viewpoint of preventing gel formation in the finishing step after polymerization and improving stability during processing. In any of the modified conjugated diene polymers, 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.

  Further, in order to further improve the processability of the modified conjugated diene polymer, in both the terminal-modified conjugated diene polymer and the both-end modified conjugated diene polymer, an extender oil is modified as necessary. It can be added to the copolymer.

  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), as described in Kautschuk Gummi Kunststoff 52 (12) 799 (1999) 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 for both the terminal modified conjugated diene polymer and the both terminal modified conjugated diene polymer. For example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, further dehydrated and dried to obtain the polymer, concentrated in a flushing tank, and further devolatilized by a vent extruder or the like. The method, the method of devolatilizing directly with a drum dryer etc. are 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. Such other rubbery polymer is not particularly limited, for example, a conjugated diene polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and a vinyl aromatic compound, or a hydrogenated product thereof. And a block copolymer of a conjugated diene compound and a vinyl aromatic compound, a hydrogenated product thereof, a non-diene polymer, or the like. Specifically, butadiene rubber or its hydrogenated product, styrene-butadiene rubber or its hydrogenated product, styrene-butadiene block copolymer or its hydrogenated product, styrene-isoprene block copolymer or its hydrogenated product, etc. Examples thereof include styrene 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 2,000 to 2,000,000, more preferably 5,000 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) Silica-based inorganic filler>
In the production method of the modified conjugated diene polymer composition of the present embodiment, in step (1), the silica-based inorganic filler is used with respect to 100 parts by mass of the rubber component containing the above-described (A) modified conjugated diene polymer. 30 to 300 parts by mass. (A) The compounding amount of the silica-based inorganic filler with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer is 30 parts by mass or more from the viewpoint of better expressing the desired effect of the present embodiment, From the viewpoint of sufficiently dispersing the inorganic filler and practically sufficient workability and mechanical strength in the composition, the amount is set to 300 parts by mass or less. From this viewpoint, it is preferably 40 to 200 parts by mass, and more preferably 55 to 100 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, a main component means the component contained in a silica type inorganic filler 50 mass% or more, Preferably it is 70 mass% or more, More preferably, it is 80 mass% or more.

  (B) Specific examples of the silica-based inorganic filler include, but are not limited to, for example, inorganic fibrous materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. Can be mentioned. In addition, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica inorganic filler 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 modified conjugated diene polymer composition, from the viewpoint of obtaining more excellent rolling resistance characteristics, the nitrogen adsorption specific surface area determined by the BET adsorption method of (B) silica-based inorganic filler is 100 to 300 m ² / g. It is preferable that it is 160-250 m < ² > / g, and it is still more preferable that it is 170-190 m < ² > / g.

<(C) Silane coupling agent>
In the manufacturing method of the modified conjugated diene polymer composition of this embodiment, in step (1), (C) silane coupling agent 0.1-30 with respect to 100 parts by mass of (B) silica-based inorganic filler. A mass part is mix | blended. (C) 0.5-20 mass parts is preferable with respect to 100 mass parts of (B) silica type inorganic filler mentioned above, and, as for the compounding quantity of a silane coupling agent, 1-15 mass parts is more preferable. When the blending amount of the silane coupling agent is within the above range, the addition effect of the silane coupling agent tends to be more remarkable.

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

  Specific examples of the (C) silane coupling agent include, but are not limited to, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide and 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-tri Toxisilylpropyl-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, Methoxymethylsilylpropylbenzothiazolyl tetrasulfide, reaction product of 3-triethoxysilylpropanethiol and ethoxylate C13 alcohol represented by the following formula (1), S- [3- (triethoxysilyl) -propyl] Examples include octanethioate, [(triethoxysilyl) -propyl] thiol, a condensate of S- [3- (triethoxysilyl) -propyl] octanethioate and [(triethoxysilyl) -propyl] thiol, and the like. Among them, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, reaction production of 3-triethoxysilylpropanethiol and ethoxylate C13 alcohol Product (compound represented by the following formula (1)), S- [3- (triethoxysilyl) -propyl] octanethioate, S- [3- (triethoxysilyl) -propyl] octanethioate and [( At least one selected from condensates of (triethoxysilyl) -propyl] thiol is preferable because of its high reinforcing effect. These silane coupling agents can be used singly or in combination of two or more.

(Raw material used in step (2))
<(D) Vulcanization acceleration aid>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, (D) a vulcanization acceleration aid is blended in step (2). (D) The vulcanization accelerating aid is not limited to the following, but includes, for example, metal oxide salts such as zinc oxide and magnesium oxide, fatty acids such as stearic acid and dehydrated castor oil fatty acid, and zinc carbonate. It is done. These vulcanization accelerating aids can be used alone or in combination of two or more. From the viewpoint of effectively completing vulcanization by using a combination of zinc oxide and stearic acid. preferable. (D) From the viewpoint of effectively completing vulcanization, the blending amount of the vulcanization accelerating auxiliary is 0.5 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing (A) the modified conjugated diene polymer. Is preferable, 1.0-10 mass parts is more preferable, and 1.5-5 mass parts is further more preferable.

<(E) Anti-aging agent>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, (E) an anti-aging agent is blended in step (2). (E) Anti-aging agents are not limited to the following, but include, for example, p- (p-toluenesulfonylamide) -diphenylamine, diphenylamines such as octylated diphenylamine, N- (1,3-dimethylbutyl) P) such as -N'-phenyl-p-phenylenediamine (6PPD), N-phenyl-N'-isopropyl-p-phenylenediamine (IPPD), N, N'-di-2-naphthyl-p-phenylenediamine -A phenylenediamine type | system | group etc. are mentioned. These (E) antiaging agents can be used individually by 1 type or in combination of 2 or more types. (E) The blending amount of the anti-aging agent is (A) a rubber containing a modified conjugated diene polymer from the viewpoint of anti-aging (improvement in heat oxidation resistance, ozone deterioration resistance and resistance to display deterioration) and economy. 0.1-15 mass parts is preferable with respect to 100 mass parts of components, 0.5-10 mass parts is more preferable, and 1-5 mass parts is further more preferable.

(Step (1) and Step (2))
In the method for producing a modified conjugated diene polymer composition of the present embodiment, in step (1), (A) a rubber component containing a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less, (B) 30 to 300 parts by mass of silica-based inorganic filler with respect to 100 parts by mass of (A), and (C) silane coupling agent with respect to 100 parts by mass of (B) silica-based inorganic filler. -30 mass parts, and knead | mixing at 120-170 degreeC. Subsequently, in step (2), the kneaded product obtained in step (1) is blended with (D) a vulcanization accelerating aid and (E) an anti-aging agent, and kneaded to obtain a modified conjugated diene polymer. A composition is obtained. In addition, in the manufacturing method of the modified conjugated diene polymer of this embodiment, (D) vulcanization | cure acceleration | stimulation adjuvant and (E) anti-aging agent shall not be included at a process (1).

  Step (1) and step (2) are performed in the same stage. Here, in the process of kneading to obtain a composition, the stage is defined as one stage from putting the first component (which may be a composition) into an apparatus used for one mixing until discharging. That is, “performing the same step” in step (1) and step (2) means that the kneaded material after step (1) is continuously discharged from the device used for mixing without being discharged from the device used for mixing. In step (2). For example, when the composition kneaded with an apparatus used for one mixing is discharged and the composition is kneaded again with an apparatus used for the same mixing, the kneading process has two stages.

  In step (1), (A) a rubber component containing a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less, (B) a silica-based inorganic filler, and (C) a silane coupling agent By blending and kneading at 120 to 170 ° C., the dispersibility of silica can be improved, and each physical property can also be improved. In the step (1), the kneading time in the temperature range of 120 to 170 ° C. is preferably 2 to 8 minutes.

  The kneading temperature in the step (1) is preferably 150 to 160 ° C or 140 to 150 ° C. In addition, it is preferable that the above suitable temperature ranges are suitably selected according to the kind of (C) silane coupling agent. For example, when the number of sulfur atoms in the molecular structure of (C) the silane coupling agent is 1 to 2, or when the number of mercapto groups in one molecular structure is less than 1, the kneading temperature is 140 to It is preferable that it is the range of 170 degreeC, and it is more preferable to set it as the range of 150-160 degreeC. The (C) silane coupling agent having 1 to 2 sulfur atoms in the molecular structure is not limited to the following, and examples thereof include bis- [3- (triethoxysilyl) -propyl] -disulfide. Can be mentioned. Examples of the silane coupling agent having less than one mercapto group in one molecular structure include, but are not limited to, for example, S- [3- (triethoxysilyl) -propyl] octanethioate, S- [3 [(Triethoxysilyl) -propyl] octanethioate and [(triethoxysilyl) -propyl] thiol condensate with [(triethoxysilyl) -propyl] octanethioate The case where the ratio of the number of molecules of (silyl) -propyl] thiol is 50% or less is mentioned.

  When the number of sulfur atoms in the molecular structure of the (C) silane coupling agent is 3 or more, or when there are 1 or more mercapto groups in one molecular structure, the kneading temperature is 120 to 160. It is preferable that it is the range of ° C, and it is more preferable to set it as the range of 140-150 degreeC. Examples of the (C) 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] -tetrasulfide, bis -[3- (triethoxysilyl) -propyl] -tetrasulfide and the like. Examples of the case where there are one or more mercapto groups in the molecular structure include, but are not limited to, a reaction product of 3-triethoxysilylpropanethiol and ethoxylate C13 alcohol.

  In step (1), as described above, it is preferable to select a kneading temperature according to the type of (C) silane coupling agent, but in this embodiment, all of step (1) are selected. The kneading need not be performed within the selected temperature range, and may be performed within the range of 120 to 170 ° C. and according to the type of (C) silane coupling agent. Further, in the step (1), during the kneading, the kneading time after reaching a desired temperature, for example, the temperature range of 150 to 160 ° C. or 140 to 150 ° C. selected as described above is 2 to 8 hours. It is preferable to set it as minutes, and it is more preferable to set it as 2 to 5 minutes. Thereby, it exists in the tendency which can improve the balance of each physical property of a modified conjugated diene type-copolymer composition more.

  By kneading at 120 to 170 ° C. in step (1) as described above, the reaction rate of (B) silica-based inorganic filler and (C) silane coupling agent can be improved, and dispersibility can be improved. The balance of physical properties of the modified conjugated diene polymer composition can be increased.

  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). In the step (2), the kneaded product obtained in the step (1) is blended with (D) a vulcanization acceleration aid and (E) an anti-aging agent. That is, after the step (1), from the viewpoint of workability (groupability of discharged materials), the kneaded product obtained in the step (1) is not discharged from a closed kneader such as a Banbury mixer, and continues. Then, (D) a vulcanization accelerating aid and (E) an antioxidant are blended and kneaded.

  The timing of blending and kneading (D) the vulcanization acceleration aid and (E) the anti-aging agent does not hinder the reaction between (B) the silica-based inorganic filler and (C) the silane coupling agent. From the viewpoint of sufficiently ensuring the stability of the reaction, enhancing the dispersibility, and sufficiently expressing the desired effect of this embodiment, (B) silica is added to the rubber component containing the (A) modified conjugated diene polymer. As long as the inorganic inorganic filler and (C) the silane coupling agent are mixed and kneaded at 120 to 170 ° C., any timing may be used, (D) vulcanization acceleration aid, and (E) aging prevention From the viewpoint of the dispersibility of the agent, it is more preferably immediately after kneading at 120 to 170 ° C.

  The temperature and kneading time in the step (2) depend on the kneading time in the step (1), but (D) the vulcanization accelerating aid and (E) the dispersibility of the anti-aging agent, And from a viewpoint of a tensile characteristic, 120-170 degreeC and 1 minute-6 minutes are preferable.

  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)
<(F) Carbon black>
Moreover, the manufacturing method of the modified diene polymer composition of this embodiment is colored with respect to 100 parts by mass of the rubber component containing (A) the modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2,000,000 or less. From the viewpoints of properties, workability, etc., it is preferable to further include a step of blending (F) 0.5 to 100 parts by mass of carbon black. (A) The compounding amount of (F) carbon black with respect to 100 parts by mass of the rubber component containing a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less is suitable for applications such as dry grip properties 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 still more preferably 5 to 50 mass parts. Although it does not specifically limit as carbon black, For example, carbon black of each class, such as SRF, FEF, HAF, ISAF, 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, the dibutyl phthalate (DBP) oil absorption is preferably 80 mL / 100 g or more, and the nitrogen adsorption specific surface area is 90 m ² / g or more, and DBP oil absorption is more preferably 80 mL / 100 g or more. In addition, dibutyl phthalate (DBP) oil absorption can be measured according to JIS-K6217-4. More specifically, dibutyl phthalate is added to carbon black that has been stirred using an absorber, and the amount at which the detected torque reaches a certain set value can be obtained as the oil absorption.

  Moreover, the timing which mix | blends (F) carbon black is (B) silica-type inorganic filler, (C) to the rubber component containing (A) modified conjugated diene type | system | group polymer whose weight average molecular weights are 400,000 or more and 2 million or less. ) The silane coupling agent is blended in the step (1) or may be blended in the kneaded product obtained in the step (1), but the viewpoint of further improving the rolling resistance characteristics and wet skid resistance. More preferably, in the step (1), (B) a silica-based inorganic filler and (C) a silane coupling agent are blended with the rubber component.

<Metal oxide and metal hydroxide>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a metal oxide or a metal hydroxide may be contained in addition to (B) the silica-based inorganic filler and carbon black. The metal oxide refers to solid particles having the chemical formula M _x O _y (M represents a metal atom, and x and y each represent an integer of 1 to 6) as a main component of a structural unit. Although not limited, for example, alumina, titanium oxide, magnesium oxide, zinc oxide, or the like can be used. A mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used. Examples of the metal hydroxide include, but are not limited to, aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

<Rubber softener>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a rubber softener may be contained in order to improve processability. As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is suitable.

  A mineral oil-based rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic rings, naphthene rings, and paraffin chains. A paraffin chain having 50% or more carbon atoms in the total carbon is called paraffinic, a naphthene ring having 30 to 45% carbon is naphthenic, and an aromatic carbon having more than 30% aromatic is aromatic. It is called a system. As the rubber softener used with the (A) modified conjugated diene polymer used in the production method of the present embodiment, those having an appropriate aromatic content are preferred because they tend to be familiar with the copolymer.

  The blending amount of the rubber softener is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component containing (A) a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less. A mass part is more preferable and 30-90 mass parts is further more preferable. When the blending amount of the rubber softener is 100 parts by mass or less with respect to 100 parts by mass of the rubber component, bleeding out can be more reliably prevented and stickiness on the composition surface can be effectively prevented.

<Wax>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a wax may be blended. Conventionally known waxes can be used as the wax, and include, but are not limited to, natural waxes and petroleum waxes.

<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 used is usually 0.01 to 20 parts by mass with respect to 100 parts by mass of the rubber component containing (A) a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less. 0.1 to 15 parts by mass is preferable. A conventionally known method can be applied as the vulcanization method, and the vulcanization temperature 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 usually 0.01 to 20 parts by mass with respect to 100 parts by mass of the rubber component containing (A) a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less. 0.1 to 15 parts by mass is preferable.

[Other additives]
In the production method of the modified conjugated diene polymer composition of the present embodiment, other softeners and fillers other than those described above, as well as a heat stabilizer, an antistatic agent, within the range not impairing the purpose of the present embodiment. Various additives such as a colorant, a weather stabilizer, a colorant, and a lubricant may be used. 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 step (1), the modified conjugated diene polymer composition obtained by the production method of the present embodiment contains (A) a rubber component, (B) a silica-based inorganic filler, and (C) a silane coupling agent. Kneading at 120 ° C. to 170 ° C., and kneading the kneaded product obtained in the step (1) with (D) a vulcanization acceleration aid and (E) an anti-aging agent, (B) The reaction proceeds stably without hindering the reaction between the silica-based inorganic filler and (C) the silane coupling agent, and (B) the dispersibility of the compounding agent such as the silica-based inorganic filler is improved. In the modified conjugated diene polymer composition of interest, an improved balance of workability, rolling resistance characteristics, wet skid resistance, and wear resistance can be obtained.

  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 tread, and the tire of the present invention can be produced by a usual method. That is, a tire can be manufactured by manufacturing a tread using the rubber composition, pasting together with other members, and heating and pressing using a tire molding machine.

  The present invention will be described in more detail with reference to the following 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 of the butadiene portion (1,2-vinyl bond amount: mol%) 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) was determined. Tetrahydrofuran (THF) was used as the eluent. As a column, TSKguardcolumn HHR-H manufactured by Tosoh Corporation was used as a guard column, and TSKgel G6000HHR, TSKgel G5000HHR, and TSKgel G4000HHR manufactured by Tosoh Corporation were used as other columns. 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 amount of adsorption of the sample solution containing the sample and the low molecular weight internal standard polystyrene on the silica column is measured from the difference between the chromatogram measured with the polystyrene gel column and the chromatogram measured with the silica column. Denaturation rate was determined. 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's TSKguardcolumn HHR-H as the guard column, and Tosoh TSKgel G6000HHR, TSKgel G5000HHR, and TSKgel G4000HHR were used 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 a column, 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. The smaller the value, the smaller the viscosity and the better the workability. The Mooney viscosity of the modified conjugated diene polymer shown in Table 1 was measured according to the method for measuring the Mooney viscosity of the compound.

[(6) Collectability of waste]
Regarding the unvulcanized modified conjugated diene polymer composition produced by the method shown in Examples and Comparative Examples, immediately after being discharged from the Banbury mixer (the kneading by the Banbury mixer in the first kneading was completed and discharged) Immediately after that, the panel members (shape) were visually observed by five panelists, and evaluated based on the following criteria, with a maximum score of 5 points per panel member and a total score of 25 points. The closer to 25 points, the better the kneading processability.
1 point: There is no lump in the discharged rubber and it is powdery.
2 points | pieces: The discharged | emitted rubber | gum is comprised by the lump (diameter 0.5-2cm), and it is not gathered but is disjoint.
3 points: The discharged rubber is composed of a medium lump (diameter 2 to 4 cm), and is untidy.
4 points: The discharged rubber is composed of a slightly large lump (diameter 4 to 20 cm), but it is disjointed and disjointed.
5 points: The discharged rubber is composed of a large lump (diameter of 20 cm or more), and is gathered as a whole.

[(7) Rolling resistance characteristics (RR)]
A viscoelasticity tester (ARES) manufactured by Rheometrics Scientific was used to measure viscoelastic parameters in torsional mode. That is, 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 (low fuel consumption). Each measured value was indexed by setting Comparative Example 1 as 100 for Examples 1 to 6 and Comparative Examples 2 to 11. A smaller value indicates better rolling resistance characteristics.

[(8) Wet skid resistance (WET)]
A viscoelasticity tester (ARES) manufactured by Rheometrics Scientific was used to measure viscoelastic parameters in torsional mode. That is, tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet skid resistance. Each measured value was indexed by setting Comparative Example 1 as 100 for Examples 1 to 6 and Comparative Examples 2 to 11. Larger values indicate better wet skid resistance.

[(9) Silica dispersibility (ΔG ′)]
A viscoelasticity tester (ARES) manufactured by Rheometrics Scientific was used to measure viscoelastic parameters in torsional mode. That is, G ′ was measured at 50 ° C. with a frequency of 10 Hz and a strain of 0.1 and 10%, and the difference between G ′ of 0.1% and 10% was used as an index of silica dispersion. Each measured value was indexed by setting Comparative Example 1 as 100 for Examples 1 to 6 and Comparative Examples 2 to 11. A smaller value indicates better silica dispersion and processability.

[(10) 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 was indexed by setting Comparative Example 1 as 100 for Examples 1 to 6 and Comparative Examples 2 to 11. Smaller values indicate less wear and better wear resistance.

[(11) Oil-extended glass transition temperature (° C)]
The oil-extended glass transition temperature (° C.) was measured by differential scanning calorimetry (DSC). The desired glass transition temperature varies depending on the required application, for example, the tire member to be applied, the summer tire and the winter tire, and depends on the amount of styrene and vinyl. About the said glass transition temperature, according to ISO22768: 2006, the DSC curve was recorded, heating up in a predetermined temperature range, and the peak top (Infection point) of the DSC differential curve was made into the glass transition temperature. For the measurement, DSC 3200S manufactured by Mac Science was used.

[Modified Conjugated Diene Polymer]
(Production Example 1)
Autoclave with internal volume of 10L, internal height (L) to diameter (D) ratio (L / D) of 4, inlet at the bottom, outlet at the top, stirrer and temperature adjustment jacket Were connected in series, the first group was a polymerization reactor and the second group was a denaturing reactor.

  In advance, impurities such as 1,3-butadiene, from which impurities such as moisture were removed, were mixed under the conditions of 16.38 g / min, styrene 8.88 g / min, and cyclohexane 132.3 g / min. A necessary amount of n-butyllithium was further mixed by a static mixer immediately before entering the first reactor, continuously fed to the bottom of the first reactor, and further, 2,2- Bis (2-oxolanyl) propane was supplied to the bottom of the first reactor at a rate of 0.15 g / min and n-butyllithium was used as a polymerization initiator at a rate of 0.0504 g / min (0.0788 mmol). The internal temperature of the reactor outlet was adjusted to 73 ° C., and the polymerization reaction was continued.

  The temperature of the second reactor was kept at 75 ° C., and tetraglycidyl-1,3-bisaminomethylcyclohexane, which is a tetrafunctional polyepoxy compound having an amino group in the molecule as a modifier, was 0.0394 mmol / min. Addition was made at the bottom from the bottom of the second reactor to carry out the modification (coupling) reaction.

  Antioxidant (BHT) was continuously added to the polymer solution flowing out from the top of the second reactor at a rate of 0.048 g / min (cyclohexane solution) at a rate of 0.2 g per 100 g of the polymer, and the modification reaction was performed. After completion, the solvent was removed to obtain a modified conjugated diene polymer solution.

  Further, process oil (manufactured by JX Nippon Mining & Energy Co., Ltd., trade name “NC140”) was mixed with the modified conjugated diene polymer (polymer) solution, and then the solvent was removed with a drum dryer, and modified SBR (1) Got.

  The resulting modified SBR (1), that is, the modified conjugated diene polymer (polymer) constituting the mixture of the modified conjugated diene polymer and process oil has a modification rate of 78%, and the modified SBR (1) has a Mooney viscosity of 77. The amount of bound styrene of the modified conjugated diene polymer (polymer) is 35% by mass, the amount of 1,2-vinyl bond of the modified conjugated diene polymer (polymer) is 39% by mass, and the modified conjugated diene polymer (polymer). The weight average molecular weight Mw was 1,10,000, and the process oil content of the modified SBR (1) was 27.3 mass%. These results are shown together in Table 1.

(Production Example 2)
The same operation as in Production Example 1 was repeated except that the modifier was changed to 0.045 mmol / min instead of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane. Modified SBR (2) was obtained.

  The modified conjugated diene polymer (polymer) constituting the modified SBR (2) thus obtained has a modification rate of 82%, the modified SBR (2) has a Mooney viscosity of 80, and the modified conjugated diene polymer (polymer) has bound styrene. The amount of the 1,2-vinyl bond in the modified conjugated diene polymer (polymer) is 39% by mass, the weight average molecular weight Mw of the modified conjugated diene polymer (polymer) is 900,000, and the modified SBR (2 ) Was 27.3 mass%. These results are shown together in Table 1.

  LANXESS unmodified SBR “BUNA VSL2438-2HM” was designated as SBR (3). The evaluation results of the SBR (3) are also shown in Table 1. The SBR (3) had a weight average molecular weight Mw of 830,000.

  Table 1 below shows the structures and physical properties of the modified SBR (1) to (2) and SBR (3) described above.

(Example 1)
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 produced in (Production Example 1), process oil content in 137.5 parts by mass of modified SBR (1) 37.5 parts by mass); 137.5 parts by mass Part / Silica (Evonik Degussa, Ultrasil 7000GR): 75 parts by mass Silane coupling agent Bis [3- (triethoxysilyl) -propyl] -tetrasulfide (Evonik Degussa, Si69): 6 parts by mass Process oil (JX Nippon Mining & Energy Co., Ltd., trade name “NC140”): 4.5 parts by mass, carbon black (manufactured by Tokai Carbon Co., Ltd., Seast KH (N339)): 5 parts by mass, vulcanization acceleration Auxiliary agent (zinc oxide): 2.5 parts by mass. Vulcanization accelerating auxiliary agent (stearic acid): 1.0 part by mass. Wax: (Onouchi Shin Chemical Co., Ltd., Sunnock): 5 parts by mass-Anti-aging agent (N-isopropyl-N'-phenyl-p-phenylenediamine): 2.0 parts by mass-Sulfur: 2.2 parts by mass-Vulcanization accelerator (N-cyclohexyl-2-benzothia Dilsulfinamide): 1.7 parts by mass / Vulcanization accelerator (diphenylguanidine): 2.0 parts by mass

  The above materials were kneaded by the following method to obtain an unvulcanized rubber composition and a vulcanized rubber sheet. Using a Kobe Steel Banbury mixer “Mixtron BB2” (with an internal capacity of 1430 cc) equipped with a temperature control device, the first stage kneading was carried out under conditions of a filling rate of 65% and a rotor rotation speed of 90 rpm. The coalescence (modified SBR (1)) was kneaded for 30 seconds. Thereafter, silica, Si69, and process oil were blended and kneaded.

  Next, after the material instruction temperature reached 140 ° C., kneading was performed for 2 minutes while controlling the material instruction temperature in the Banbury mixer to 140 to 150 ° C. by controlling the temperature of the mixer.

  After that, carbon black, vulcanization accelerators (stearic acid and zinc oxide), anti-aging agent, and wax are blended while discharging the kneaded material and continuously controlling the material temperature in Banbury to 140 to 150 ° C. The mixture was kneaded for 1 minute, cleaned by raising the ram, and further kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C.) was discharged from a Banbury mixer. 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.

  The total amount of process oil blended with the process oil and each modified SBR contained in each modified SBR with respect to 100 parts by mass of the pure modified SBR obtained by subtracting the process oil contained in each modified SBR in Examples and Comparative Examples. The total amount of process oil blended was 42 parts by mass.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 140 to 150 ° C. by controlling the temperature of the mixer. And after discharging | emitting the said compound from a Banbury mixer, the compound was immediately passed 6 times through a 10 inch (phi) 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 kneading stage, 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 was 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), and wear resistance of the vulcanized rubber composition were evaluated.

(Example 2)
Silica, Si69, process oil, and carbon black are blended and kneaded into the modified conjugated diene polymer (modified SBR (1)), and after the material indication temperature reaches 140 ° C., the Banbury is controlled by controlling the temperature of the mixer. Kneading was carried out for 2 minutes while controlling the indicated material temperature in the mixer at 140 to 150 ° C.

Then, without discharging the kneaded material, the vulcanization acceleration aid (stearic acid and zinc oxide), the antiaging agent, and the wax are blended while continuously controlling the material temperature in Banbury to 140 to 150 ° C. After kneading for a minute, raising the ram and cleaning, the mixture was further kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C.) was discharged from the Banbury mixer.
Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 140 to 150 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Example 3)
Modified conjugated diene polymer (modified SBR (1)), silica, silane coupling agent bis- [3- (triethoxysilyl) -propyl] -disulfide (Si75 manufactured by Evonik Degussa), process oil, and carbon black After the material instruction temperature reached 150 ° C., kneading was carried out for 2 minutes while controlling the material instruction temperature in the Banbury mixer to 150 to 160 ° C. by controlling the temperature of the mixer.

  Thereafter, without discharging the kneaded material, the vulcanization acceleration aid (stearic acid and zinc oxide), the anti-aging agent, and the wax are blended while continuously controlling the material temperature in the kneader to 150 to 160 ° C. The mixture (kneading temperature 150 to 160 ° C.) was discharged from a Banbury mixer. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 150 to 160 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

Example 4
Silica, Si75, process oil, and carbon black are blended and kneaded with the modified conjugated diene polymer (modified SBR (2)), and after the material indication temperature reaches 150 ° C., the Banbury is controlled by controlling the temperature of the mixer. Kneading was carried out for 2 minutes while controlling the indicated material temperature in the mixer at 150 to 160 ° C.

  Thereafter, without discharging the kneaded material, the vulcanization acceleration aid (stearic acid and zinc oxide), the anti-aging agent, and the wax are blended while continuously controlling the material temperature in the kneader to 150 to 160 ° C. The mixture (kneading temperature 150 to 160 ° C.) was discharged from a Banbury mixer. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 150 to 160 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Example 5)
Silica, Si69, and process oil are blended and kneaded into the modified conjugated diene polymer (modified SBR (1)), and after the material instruction temperature reaches 140 ° C, the material instruction in the Banbury mixer is controlled by controlling the temperature of the mixer. Kneading was carried out for 1 minute while controlling the temperature at 140 to 150 ° C.

  After that, carbon black, vulcanization accelerators (stearic acid and zinc oxide), anti-aging agent, and wax are blended while discharging the kneaded material and continuously controlling the material temperature in Banbury to 140 to 150 ° C. The mixture was kneaded for 1 minute, cleaned by raising the ram, and further kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C.) was discharged from a Banbury mixer. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 140 to 150 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Example 6)
Silica, Si69, and process oil are blended and kneaded into the modified conjugated diene polymer (modified SBR (1)), and after the material instruction temperature reaches 140 ° C, the material instruction in the Banbury mixer is controlled by controlling the temperature of the mixer. Kneading was carried out for 10 minutes while controlling the temperature at 140 to 150 ° C.

  After that, carbon black, vulcanization accelerators (stearic acid and zinc oxide), anti-aging agent, and wax are blended while discharging the kneaded material and continuously controlling the material temperature in Banbury to 140 to 150 ° C. The mixture was kneaded for 1 minute, cleaned by raising the ram, and further kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C.) was discharged from a Banbury mixer. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 140 to 150 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 1)
Silica, Si69, process oil, carbon black, vulcanization accelerating aid (stearic acid and zinc oxide), anti-aging agent, and wax were blended into the modified conjugated diene polymer (modified SBR (3)) and kneaded. .

  Next, after the material instruction temperature reached 140 ° C., kneading was performed for 2 minutes while controlling the material instruction temperature in the Banbury mixer to 140 to 150 ° C. by controlling the temperature of the mixer.

  After that, the ram is raised and cleaned, and then, while controlling the indicated material temperature in Banbury to 140 to 150 ° C, it is blended and kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C) is discharged from the Banbury mixer. did. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 140 to 150 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 2)
Silica, Si69, and process oil were blended and kneaded in the modified conjugated diene polymer (modified SBR (3)).

  Next, after the material instruction temperature reached 140 ° C., kneading was performed for 2 minutes while controlling the material instruction temperature in the Banbury mixer to 140 to 150 ° C. by controlling the temperature of the mixer.

  After that, the ram is raised and cleaned, and then, while controlling the indicated material temperature in Banbury to 140 to 150 ° C, it is blended and kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C) is discharged from the Banbury mixer. did. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like composition obtained by the first stage kneading is cooled to room temperature, and this is then added to the Banbury mixer with carbon black, a vulcanization accelerator (stearin). Acid and zinc oxide), anti-aging agent, and wax, and after reaching 150 ° C., raise the ram, clean it, knead for one minute, and mix the mixture (discharge temperature 140-150 ° C.) into a Banbury mixer More discharged.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 3)
Silica, Si69, and process oil are blended and kneaded into the modified conjugated diene polymer (modified SBR (3)), and after the material indication temperature reaches 140 ° C, the material indication in the Banbury mixer is controlled by controlling the temperature of the mixer. Kneading was carried out for 2 minutes while controlling the temperature at 140 to 150 ° C.

  After that, carbon black, vulcanization accelerators (stearic acid and zinc oxide), anti-aging agent, and wax are blended while discharging the kneaded material and continuously controlling the material temperature in Banbury to 140 to 150 ° C. The mixture was kneaded for 1 minute, cleaned by raising the ram, and further kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C.) was discharged from a Banbury mixer. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 140 to 150 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 4)
Silica, Si69, process oil, carbon black, vulcanization accelerators (stearic acid and zinc oxide), anti-aging agent, and wax were blended into the modified conjugated diene polymer (modified SBR (1)) and kneaded. .

  Next, after the material instruction temperature reached 140 ° C., kneading was performed for 2 minutes while controlling the material instruction temperature in the Banbury mixer to 140 to 150 ° C. by controlling the temperature of the mixer.

  After that, the ram is raised and cleaned, and then, while controlling the indicated material temperature in Banbury to 140 to 150 ° C, it is blended and kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C) is discharged from the Banbury mixer. did. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 140 to 150 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 5)
Silica, Si69, and process oil were blended and kneaded in the modified conjugated diene polymer (modified SBR (1)).

Next, after the material instruction temperature reached 140 ° C., kneading was performed for 2 minutes while controlling the material instruction temperature in the Banbury mixer to 140 to 150 ° C. by controlling the temperature of the mixer.
After that, the ram is raised and cleaned, and then, while controlling the indicated material temperature in Banbury to 140 to 150 ° C, it is blended and kneaded for 1 minute, and the mixture (discharge temperature 140 to 150 ° C) is discharged from the Banbury mixer. did. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like composition obtained by the first stage kneading is cooled to room temperature, and this is added to the Banbury mixer with carbon black, a vulcanization accelerator (stearin). Acid and zinc oxide), anti-aging agent, and wax, and after reaching 150 ° C., raise the ram, clean it, knead for one minute, and mix the mixture (discharge temperature 140-150 ° C.) into a Banbury mixer More discharged.

  The other conditions were the same as in Comparative Example 2 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, and processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 6)
Silica, Si75, process oil, carbon black, vulcanization accelerators (stearic acid and zinc oxide), anti-aging agent, and wax were blended into the modified conjugated diene polymer (modified SBR (2)) 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 Banbury mixer to 150 to 160 ° C. by controlling the temperature of the mixer.

  After that, the ram is raised and cleaned, and the material temperature indicated in the Banbury is continuously controlled at 150 to 160 ° C., then mixed and kneaded for 1 minute, and the mixture (discharge temperature 150 to 160 ° C.) is discharged from the Banbury mixer. did. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 150 to 160 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 7)
Silica, Si75, and process oil were blended in the modified conjugated diene polymer (modified SBR (2)) 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 Banbury mixer to 150 to 160 ° C. by controlling the temperature of the mixer.
After that, the ram is raised and cleaned, and the material temperature indicated in the Banbury is continuously controlled at 150 to 160 ° C., then mixed and kneaded for 1 minute, and the mixture (discharge temperature 150 to 160 ° C.) is discharged from the Banbury mixer. did. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like composition obtained by the first stage kneading is cooled to room temperature, and this is added to the Banbury mixer with carbon black, a vulcanization accelerator (stearin). Acid and zinc oxide), anti-aging agent, and wax, and after reaching 160 ° C., raise the ram, clean it, knead for one minute, and mix the mixture (discharge temperature 150 to 160 ° C.) into a Banbury mixer More discharged.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 8)
Silica, Si75, process oil, and carbon black are blended and kneaded into the modified conjugated diene polymer (modified SBR (2)), and after the material indication temperature reaches 110 ° C., Banbury is controlled by controlling the temperature of the mixer. Kneading was carried out for 2 minutes while controlling the indicated material temperature in the mixer at 110 to 115 ° C.

  Then, without discharging the kneaded material, the vulcanization acceleration aid (stearic acid and zinc oxide), the antiaging agent, and the wax are blended while continuously controlling the material temperature in the kneader to 110 to 115 ° C. The mixture (kneading temperature 110 to 115 ° C.) was discharged from a Banbury mixer. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 110 to 115 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

(Comparative Example 9)
Silica, Si75, process oil, and carbon black are blended and kneaded with the modified conjugated diene polymer (modified SBR (2)), and after the material indication temperature reaches 180 ° C., Banbury is controlled by controlling the temperature of the mixer. Kneading was carried out for 2 minutes while controlling the indicated material temperature in the mixer at 180 to 190 ° C.

  Thereafter, without discharging the kneaded material, the vulcanization acceleration aid (stearic acid and zinc oxide), the anti-aging agent, and the wax are blended while continuously controlling the material temperature in the kneader to 180 to 190 ° C. The mixture (kneading temperature 180 to 190 ° C.) was discharged from a Banbury mixer. Then, the blend was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like blend.

  Next, as the second stage of kneading, the sheet-like compound obtained by the first stage of kneading was cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. Also in this case, the discharge temperature (formulation) was adjusted to 180 to 190 ° C. by controlling the temperature of the mixer.

  The other conditions were the same as in Example 1 to obtain an unvulcanized rubber composition and a vulcanized rubber composition, processability (concentration of discharged matter, blended Mooney viscosity), vulcanized physical properties ( Rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance) were evaluated.

  Results of evaluation of workability of Examples 1 to 6 and Comparative Examples 1 to 9 (collectability of discharged matter, blended Mooney viscosity), rolling resistance characteristics (RR), wet skid resistance (WET), and wear resistance Is shown in Table 2.

  From Table 2, it was found that the modified conjugated diene copolymer compositions produced in Examples 1 to 6 were excellent in balance between workability, rolling resistance characteristics, wet skid resistance, and wear resistance. On the other hand, it turned out that Comparative Examples 1-9 are inferior to the balance of workability, rolling resistance characteristics, wet skid resistance, and abrasion resistance. In particular, Comparative Examples 1 to 5 are inferior in the balance between rolling resistance characteristics and silica dispersibility and processability, and Comparative Examples 6 to 9 are results in which at least one of wear resistance and silica dispersibility and processability is remarkably inferior. It was.

  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.

That is, the present invention is as follows.
[1]
A method for producing a modified conjugated diene polymer composition, wherein the following step (1) and step (2) are carried out in the same step.
Process (1): The process of mix | blending the following (A)-(C) and knead | mixing at 120-170 degreeC.
(A) Rubber component containing a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less (B) Silica inorganic filler is added in an amount of 30 to 300 parts by mass with respect to 100 parts by mass of the (A) rubber component. (C) 0.1-30 parts by mass of the silane coupling agent with respect to 100 parts by mass of the (B) silica-based inorganic filler
(I) As the silane coupling agent, a silane coupling agent having 3 or more sulfur atoms in the molecular structure, or a silane coupling agent having one or more mercapto groups in one molecular structure. Use and knead at 140-150 ° C
(Ii) As the silane coupling agent, a silane coupling agent having 1 to 2 sulfur atoms in the molecular structure, or a silane coupling agent having less than 1 mercapto group in one molecular structure. And kneading at 150 to 160 ° C. (2): kneading the kneaded product obtained in the above step (1) with (D) a vulcanization accelerator and (E) an anti-aging agent. Process.
[2]
The (C) silane coupling agent comprises bis- [3- (triethoxysilyl) -propyl] -disulfide, S- [3- (triethoxysilyl) -propyl] octanethioate and S- [3- (tri Production of a composition of a modified conjugated diene copolymer according to [1] , which is at least one selected from condensates of [ethoxysilyl) -propyl] octanethioate and [(triethoxysilyl) -propyl] thiol Method.
[3]
The modification according to [1] , wherein the (C) silane coupling agent is bis- [3- (triethoxysilyl) -propyl] -tetrasulfide and / or a compound represented by the following formula (1). A method for producing a composition of a conjugated diene copolymer.

[4]
In the step (1), the kneading time in a temperature range of 150 to 160 ° C. is 2 to 8 minutes. The method for producing a modified conjugated diene polymer composition according to [2] .
[5]
In the step (1), the kneading time in the temperature range of 140 to 150 ° C. is 2 to 8 minutes. The method for producing a modified conjugated diene polymer composition according to [3] .
[6]
The modification | denaturation as described in any one of [1]-[ 5 ] including the process of further mix | blending 0.5-100 mass parts (F) carbon black with respect to 100 mass parts of said (A) rubber components. A method for producing a conjugated diene copolymer composition.
[7]
In the said process (1), when mix | blending said (A)-(C), the manufacturing method of the modified conjugated diene-type copolymer composition as described in [ 6 ] which mix | blends said (F) carbon black.

Claims (10)

A method for producing a modified conjugated diene polymer composition, wherein the following step (1) and step (2) are carried out in the same step.
Process (1): The process of mix | blending the following (A)-(C) and knead | mixing at 120-170 degreeC.
(A) Rubber component containing a modified conjugated diene polymer having a weight average molecular weight of 400,000 or more and 2 million or less (B) Silica inorganic filler is added in an amount of 30 to 300 parts by mass with respect to 100 parts by mass of the (A) rubber component. (C) 0.1-30 mass parts of silane coupling agent with respect to 100 mass parts of said (B) silica type inorganic filler Process (2): The kneaded material obtained in the said process (1) to (D) A step of blending and kneading a vulcanization acceleration aid and (E) an anti-aging agent.   The method for producing a modified conjugated diene polymer composition according to claim 1, wherein kneading is performed at 150 to 160 ° C in the step (1).   The (C) silane coupling agent comprises bis- [3- (triethoxysilyl) -propyl] -disulfide, S- [3- (triethoxysilyl) -propyl] octanethioate and S- [3- (tri The composition of the modified conjugated diene copolymer according to claim 1 or 2, which is at least one selected from condensates of ethoxysilyl) -propyl] octanethioate and [(triethoxysilyl) -propyl] thiol. Manufacturing method.   The method for producing a modified conjugated diene polymer composition according to claim 1, wherein kneading is performed at 140 to 150 ° C. in the step (1). The (C) silane coupling agent is bis- [3- (triethoxysilyl) -propyl] -tetrasulfide and / or a compound represented by the following formula (1). A process for producing a modified conjugated diene copolymer composition.
  The method for producing a modified conjugated diene polymer composition according to claim 1, wherein a kneading time in a temperature range of 120 to 170 ° C is 2 to 8 minutes in the step (1).   The method for producing a modified conjugated diene polymer composition according to claim 2 or 3, wherein a kneading time in a temperature range of 150 to 160 ° C in the step (1) is 2 to 8 minutes.   The method for producing a modified conjugated diene polymer composition according to claim 4 or 5, wherein a kneading time in a temperature range of 140 to 150 ° C is 2 to 8 minutes in the step (1).   The modified conjugated diene according to any one of claims 1 to 8, further comprising a step of blending 0.5 to 100 parts by mass of (F) carbon black with respect to 100 parts by mass of the rubber component (A). A method for producing a copolymer composition.   The method for producing a modified conjugated diene copolymer composition according to claim 9, wherein (F) carbon black is blended when blending the (A) to (C) in the step (1).