JP4415822B2 - Method for producing conjugated diolefin (co) polymer, conjugated diolefin (co) polymer, rubber composition, and tire - Google Patents

Description

  The present invention relates to a method for producing a conjugated diolefin (co) polymer, a conjugated diolefin (co) polymer, a rubber composition, and a tire. More specifically, the production of a conjugated diolefin (co) polymer that has a good workability and can provide an automobile tire tread having a balance of wear resistance, fracture characteristics, low hysteresis loss, and wet skid characteristics. The present invention relates to a method, a conjugated diolefin (co) polymer obtained therefrom, a rubber composition, and a tire.

  In response to the recent demand for fuel efficiency reduction in automobiles, conjugated diolefin rubbers with low rolling resistance as tire rubber materials, excellent wear resistance and fracture characteristics, and also handling stability typified by wet skid resistance Is desired.

  In order to reduce the rolling resistance of the tire, it is only necessary to reduce the hysteresis loss of the vulcanized rubber. The evaluation index of the vulcanized rubber is 50-80 ° C rebound resilience, 50-80 ° C tan δ, Goodrich heat generation, etc Is used. A rubber material having a large rebound resilience at 50 to 80 ° C., a tan δ at 50 to 80 ° C. or a small Goodrich heat generation is preferred.

  Natural rubber, polyisoprene rubber, polybutadiene rubber or the like is known as a rubber material having a small hysteresis loss. However, these have a problem of low wet skid resistance.

  As a method of reducing hysteresis loss without impairing wet skid resistance, there is a method of introducing a functional group into a polymer terminal of a styrene-butadiene copolymer having various structures polymerized with an organolithium initiator in a hydrocarbon solvent. Proposed. Styrene-butadiene copolymer obtained by modifying or coupling a polymer terminal with a tin compound (see Patent Document 1: Japanese Patent Laid-Open No. 57-55912), Styrene having a polymer terminal modified with an isocyanate compound or the like Butadiene copolymers are known (see Patent Document 2: Japanese Patent Application Laid-Open No. 61-141741). These modified polymers exhibit an effect of reducing hysteresis loss without impairing wet skid resistance, and further being excellent in wear resistance and fracture characteristics, particularly in a composition containing carbon black as a reinforcing agent.

  On the other hand, as a tire rubber material, a method of using a rubber composition in which silica or a mixture of silica and carbon black is mixed with a reinforcing agent has been proposed recently. Tire treads containing silica or a mixture of silica and carbon black have low rolling resistance and good handling stability, as typified by wet skid resistance, but on the other hand, the vulcanizate has low tensile strength and wear resistance. There is. The above modified styrene-butadiene copolymer is a rubber material for tires having excellent wear resistance and fracture characteristics in a composition using carbon black as a reinforcing agent, but in a composition using silica as a reinforcing agent, The improvement effect is small.

In order to improve the tensile strength and wear resistance of vulcanizates containing silica or a mixture of silica and carbon black, rubber compositions containing polymers having functional groups having an affinity for silica have been proposed. . Patent Document 3 (Japanese Patent Publication No. 49-36957) proposes a method of producing a polymer by reacting silicon tetrahalide or trihalosilane.
Further, the dispersion of silica described in Patent Document 4 (JP-A-1-188501), Patent Document 5 (JP-A-8-53513), and Patent Document 6 (JP-A-8-53576). A technique using an alkoxysilane that is effective for improving the effect and reinforcing properties is disclosed.

  By using these modified polymers in a composition containing silica or a mixture of silica and carbon black, improvement in the tensile strength and wear resistance of the vulcanizate is still sufficient, although some improvement in physical properties can be seen. However, the hysteresis loss was not sufficiently reduced. In general, the silica compounded composition is inferior in processability to the carbon black compounded composition, so that the processing cost is high. Use of the above-described polymer having a functional group having an affinity for silica is not preferable because the processability tends to be further deteriorated.

JP-A-57-55912 Japanese Patent Application Laid-Open No. 61-141741 Japanese Patent Publication No.49-36957 JP-A-1-188501 JP-A-8-53513 JP-A-8-53576

An object of the present invention is to provide a method for producing a novel conjugated diolefin (co) polymer.
Another object of the present invention is that it has good processability even when blending silica or a mixture of silica and carbon black, and at the same time, low hysteresis loss and wet skid characteristics are improved without impairing wear resistance and fracture characteristics. As a fuel efficient tire, large tire, high-performance tire tread material, and sidewall member, with low hysteresis loss, wear resistance, and fracture characteristics improved in a balanced manner without impairing wet skid characteristics. The object is to provide a process for producing a conjugated diolefin (co) polymer which can be used.

Still another object of the present invention is to provide an industrially advantageous method for producing the conjugated diolefin (co) polymer of the present invention.
Still another object of the present invention is to provide a rubber composition having the above-mentioned properties containing the conjugated diolefin (co) polymer of the present invention.
Still another object of the present invention is to provide a tire using the rubber composition of the present invention for a tire tread member or a sidewall member.

The present invention relates to a conjugated diolefin, or a conjugated diolefin and a fragrance in a hydrocarbon solvent using at least one compound selected from the group consisting of an organic alkali metal-containing compound and an organic alkaline earth metal-containing compound as an initiator. After anionic polymerization of the group vinyl compound, an alkoxysilyl group (—SiOR) (wherein R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms) at the polymer terminal and at the molecular terminal. And kinematic viscosity (25 ° C., mm ² / s) measured at 25 ° C. is 1 to 500 , and (a) General formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, when two R ¹ are present, they are the same or different and each represents a monovalent organic group having 1 to 10 carbon atoms; R ² is the same or different and is an alkyl group or carbon having 1 to 5 carbon atoms; At least one selected from an organosilane represented by the formula 1-6, and n is an integer of 0-1) and a hydrolyzate of the organosilane, or (b) an SiO bond And a silicone oligomer having a siloxane three-dimensional skeleton (hereinafter also referred to as “silicone oligomer”) , which is a trifunctional organosiloxane oligomer having a weight average molecular weight of 300 to 100,000 (hereinafter referred to as “terminal modification reaction”). And a method for producing a conjugated diolefin (co) polymer .
Here, the content of the alkoxysilyl group of the silicone oligomer bonded to the conjugated diolefin (co) polymer is preferably 0.5 to 200 mmol / kg · (co) polymer polymer.
Next, in the present invention, the conjugated diolefin (co) polymer contains 20 to 120 parts by weight of a filler such as silica with respect to 100 parts by weight of the total rubber component occupying 30% by weight or more of the total rubber component. The present invention relates to a rubber composition.
Next, the present invention relates to a tire using the rubber composition as a tread member or a sidewall member.

  According to the present invention, in addition to excellent workability, when vulcanized to give a vulcanized rubber, it has a good balance of wet skid characteristics, low hysteresis loss, wear resistance, and breaking strength, and for low fuel consumption. A conjugated diolefin (co) polymer useful as a tread material for tires, large tires, and high performance tires, a method for producing the same, a rubber composition, and a tire can be provided.

The (co) polymer obtained by the terminal modification reaction of the present invention is a conjugated diolefin alone or a (co) polymer obtained by (co) polymerizing a conjugated diolefin and an aromatic vinyl compound, The (co) polymer has an alkoxysilyl group (—SiOR) (wherein R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms) at the molecular end, and further 25 ° C. The kinematic viscosity (25 ° C., mm ² / s) measured in (1) is 1 to 500 , and a silicone oligomer having a siloxane three-dimensional skeleton is bonded.
The alkoxysilyl group (—SiOR) is specifically described below.
｜
-SiOR
｜
It is group represented by these.

  Here, the content of the alkoxysilyl group bonded to the (co) polymer by the terminal modification reaction is preferably 0.5 to 200 mmol / kg · (co) polymer polymer. The content is more preferably 1 to 100 mmol / kg · (co) polymer polymer, and particularly preferably 2 to 50 mmol / kg · (co) polymer polymer.

  The alkoxysilyl group may be bonded to any of the polymerization initiation terminal, the polymerization termination terminal, the polymer main chain, and the side chain, but it can improve hysteresis loss characteristics by suppressing energy loss from the polymer terminal. It is preferably introduced at the end of polymerization.

  When the content of alkoxysilyl groups bonded to the polymer chain exceeds 200 mmol / kg · (co) polymer polymer, the interaction with the reinforcing agent such as carbon black and silica becomes too high, and the compounding viscosity is improved. Workability deteriorates. On the other hand, when the content of the alkoxysilyl group is less than 0.5 mmol / kg · (co) polymer polymer, the effect of introducing the alkoxysilyl group is not exhibited. That is, the improvement of the hysteresis loss characteristics, wear resistance, and fracture characteristics of the obtained (co) polymer is not sufficient, which is not preferable.

The (co) polymer of the present invention comprises a conjugated diolefin, or a conjugated diolefin and an aromatic vinyl compound, an organic alkali metal compound and / or an alkaline earth metal compound as a polymerization initiator in a hydrocarbon solvent. When the polymerization is substantially completed, the silicone oligomer can be added and reacted with the terminal of the living polymer.
With this production method, the silicone oligomer can be easily introduced at a high introduction rate into the copolymer terminal by a one-step reaction.

A specific example of the terminal modification reaction of the present invention is as shown in the following formula (1).
^{P - Li + + -SiOR → -Si} -P + RO - Li + ...... (1)
(In the formula, P is a polymer chain, P ^- Li ⁺ is a living polymer terminal, and R is the same as above)

In the present invention, the silicone oligomer used in the present invention has a relatively low molecular weight blocked with an alkoxysilyl group (—SiOR) at the molecular end, that is, a kinematic viscosity (25 ° C., mm ² / s) of 1 to 500, A relatively low molecular weight silicone oligomer of 1 to 300 is preferred.
Here, the viscosity is a value measured with a Canon-Fenske viscometer in a thermostatic bath at 25 ° C.
The kinematic viscosity of the silicone oligomer can be easily adjusted by adjusting the molecular weight of the silicone oligomer.

As described above, the silicone oligomer of the present invention is an organosiloxane oligomer having an alkoxysilyl group bonded to the molecular end and a kinematic viscosity (25 ° C., mm ² / s) of 1 to 500. In addition, since this silicone oligomer is an oligomer in which an alkoxysilyl group is partially condensed, it has a siloxane three-dimensional skeleton.
The silicone oligomer is: (a) the following general formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, when two R ¹ are present, they are the same or different and each represents a monovalent organic group having 1 to 10 carbon atoms; R ² is the same or different and is an alkyl group or carbon having 1 to 5 carbon atoms; indicates the number 1-6 acyl group, at least one n is selected from a hydrolyzate of organosilane and the organosilane represented from 0 to 1 of which is an integer) (hereinafter "component (a)" both Or (b) a trifunctional organosiloxane oligomer having a SiO bond and a weight average molecular weight of 300 to 100,000 (hereinafter also referred to as “component (b)”) .

Component (a) The component (a) is at least one selected from the organosilane represented by the general formula (1) (hereinafter referred to as “organosilane (1)”) and the hydrolyzate of the organosilane (1). It is.
Here, in the hydrolyzate of the organosilane (1), it is not necessary that all ² to 4 OR ² groups contained in the organosilane (1) are hydrolyzed. For example, only one hydrolyzate is hydrolyzed. Or two or more of them may be hydrolyzed, or a mixture thereof. As mentioned above, when the organosilane (1) is used as a hydrolyzate as the component (a), it can be hydrolyzed in advance and used as the component (a), but the organosilane (1) remains. It is preferable to hydrolyze organosilane (1) into component (a) by adding an appropriate amount of water when mixing with the above component.
The amount of water used for hydrolysis of the organosilane (1) is usually about 0.3 to 3 mol, preferably about 0.4 to 2 mol, per 1 mol of the organosilane (1).
In this invention, (a) component can be used individually or in mixture of 2 or more types.

In the general formula (1), examples of the monovalent organic group having 1 to 10 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. Group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group and other alkyl groups; acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group Acyl groups such as trioyl group and caproyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, epoxy group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group, etc. In addition to these, substituted derivatives of these groups can be mentioned.

Examples of the substituent in the substituted derivative of R ¹ include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a (meth) acryloxy group. Ureido group, ammonium base and the like. However, the carbon number of R ¹ composed of these substituted derivatives is 8 or less including the carbon atom in the substituent. In the general formula (1), when two R ^{1 s} are present, they may be the same as or different from each other.

Examples of the alkyl group having 1 to 5 carbon atoms of R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and n. -A pentyl group etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. can be mentioned, for example.
A plurality of R ² present in the general formula (1) may be the same as or different from each other.

  Specific examples of such organosilane (1) include tetramethoxysilane, tetraethoxysilane, tetrapropylsilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrisilane. Methoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxy Silane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltri Toxisilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxy Propyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimeth Sisilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-Epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Trialkoxysilanes such as silane;

In addition, methyltriacetyloxysilane and the like can be mentioned.

Of these, tetramethoxysilane and tetraethoxysilane are preferable as tetraalkoxysilanes, and methyltrimethoxysilane and methyltriethoxysilane are preferable as trialkoxysilanes . Moreover, as a part of (a) component, it is preferable to contain what R < ¹ > in the said General formula (1) is a C3-C10 organic group. Examples of the organic group having 3 to 10 carbon atoms include an alkyl group such as n-propyl group, i-propyl group, and butyl group, as well as 3-chloropropyl group, 3,3,3-trichloropropyl group, 3- Examples thereof include a glycidoxypropyl group, a 3-methacryloxypropyl group, a 3-mercapto group, a 3-mercaptopropyl group, a phenyl group, and a 3,4-epoxy cyclohexylethyl group. Specific examples of such organosilanes include ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3,4-epoxycyclohexylethylmethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, etc. Preferably, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and the like can be mentioned. These organosilanes are preferably contained in an amount of about 1 to 25% of the total component (a).

Component (b) The component (b) is a trifunctional siloxane oligomer having a SiO bond and having a polystyrene-equivalent weight average molecular weight of 300 to 100,000, and even if used alone, it is a mixture of two or more. May be.
The production method of the component (b) is not particularly limited, but mainly a chlorosilane condensate or an alkoxysilane condensate is preferable. In the siloxane oligomer, the terminal functional group of siloxane is a hydroxyl group, a halogen atom, an organic group having 1 to 15 carbon atoms [for example, an alkyl group, an acyl group, an alkoxyl group, an alkoxysilyl group, a vinyl group, an allyl group, an acetoxyl group, Acetoxysilyl group, cycloalkyl group, phenyl group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group] and-(R'O) _p -R "(formula A plurality of R's independently represent an alkyl group having 1 to 5 carbon atoms, R "represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p is an integer of 2 to 30). It is a group represented. These groups may be partially hydrolyzed / condensed or substituted derivatives.

Examples of the halogen atom include fluorine and chlorine. Moreover, as a C1-C15 alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n -Hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylhexyl, etc. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a valeryl group, a benzoyl group, and a trioyl group. Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the alkoxysilyl group include methoxysilyl group, ethoxysilyl group, propoxysilyl group, butoxysilyl group. Such as a group, and the like. The group represented by (R′O) _p —R ″ is preferably a polyoxyethylene group, a polyoxypropylene group, a poly (oxyethylene / oxypropylene) group, a polyoxyethylene-polyoxypropylene group or other polyoxy An alkylene group;

  Examples of the substituent in the substituted derivative include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, and a ureido. Groups, ammonium bases, ketoester groups and the like.

  As the component (b), two kinds of oligomers having different kinematic viscosities may be mixed and used. For example, an oligomer having a weight average molecular weight (Mw) of 400 to 2,800 and an Mw of 3,000 to 50, 000 oligomers may be mixed and used.

(B) Commercially available products include Toray Dow Corning Silicone Silicone Resin, GE Toshiba Silicone Silicone Resin, Shin-Etsu Chemical Silicone Resin, and Dow Corning Asia Limited hydroxyl group There are polydimethylsiloxane, a silicone oligomer manufactured by Nippon Unicar Company, etc., and these may be used as they are or after being condensed.
In this invention, (b) component can be used individually or in mixture of 2 or more types.

The kinematic viscosity (25 ° C., mm ² / S) of the silicone oligomer used in the present invention is usually 1 to 500, preferably 1 to 300. If it is less than 1, the effect of improving the fracture characteristics is insufficient. On the other hand, if it exceeds 500, the workability deteriorates.

  The (co) polymer of the present invention is a (co) polymer obtained by (co) polymerizing a conjugated diolefin, or a conjugated diolefin, an aromatic vinyl compound, and optionally a copolymerizable third monomer. And as above-mentioned, it has the alkoxy silyl group, It is characterized by the above-mentioned.

Examples of the conjugated diolefin used in the present invention include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, and the like. A mixture or the like is preferably used.
The amount of the conjugated diolefin used is usually 40 to 100% by weight, preferably 50 to 95% by weight, based on all monomers. If it is less than 40% by weight, the rolling resistance and wear resistance are deteriorated, and the rubber is cured at a low temperature to deteriorate grip performance and wet skid resistance.

Examples of the aromatic vinyl compound include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and 4-tert-butylstyrene. , Divinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4- Mention may be made of t-butylstyrene, vinylpyridine and mixtures thereof. Of these, styrene is particularly preferred.
The amount of the aromatic vinyl compound used is usually 60% by weight or less, preferably 50 to 5% by weight, based on all monomers.

Examples of the third monomer include acrylonitrile, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, hydroxyethyl methacrylate, and hydroxyethyl acrylate.
The amount of the third monomer used is usually less than 25% by weight, preferably 15% by weight or less, more preferably 10% by weight or less in the total monomers.

The (co) polymer of the present invention is the following (A), (B) or (C) (co) polymer:
(A) (1) The content of polymerized units of the aromatic vinyl compound is less than 30% by weight of the (co) polymer, and the content of polymerized units of the conjugated diolefin is 70% by weight of the (co) polymer. The content of the polymerized unit of the third monomer that is copolymerizable is greater than or equal to 0% by weight and less than 25% by weight of the (co) polymer, and (2) the vinyl bond content is 50 Mol% or more (hereinafter sometimes referred to as a first (co) polymer),
(B) (1) The content of the polymer unit of the aromatic vinyl compound is 30 to 50% by weight of the (co) polymer, and the content of the polymer unit of the conjugated diolefin is 50 to 70 of the (co) polymer. The content of polymerized units of the third monomer that can be copolymerized is 0 to 20% by weight of the (co) polymer, and (2) the vinyl bond content is 15 to 15 of the polymerized units of the conjugated diolefin. 50 mol% (hereinafter sometimes referred to as the second (co) polymer of the present invention), and (C) (1) the content of polymerized units of the conjugated diolefin is 80 to 100 of the (co) polymer. The copolymerizable third monomer polymerized unit is 20 to 0% by weight of the (co) polymer, and (2) the vinyl bond content is 50 mol% or more of the conjugated diolefin polymerized unit. (Hereinafter, it may be called the 3rd (co) polymer of this invention.)
Is included as a preferred embodiment.

  The content of the bonded aromatic vinyl compound bonded in the polymer chain, that is, the content of the polymerized unit of the aromatic vinyl compound is based on the (co) polymer in the first (co) polymer of the present invention. As described above, it is less than 30% by weight, more preferably 5% by weight or more and 27% by weight or less. When the content of the bonded aromatic vinyl compound is 30% by weight or more, the balance between hysteresis loss and wet skid characteristics deteriorates.

  The content of the conjugated diolefin bonded in the polymer chain, that is, the content of polymerized units of the conjugated diolefin is more than 70% by weight, preferably 95% by weight or less, more preferably 73% by weight or more and 90% by weight. It is as follows.

  The vinyl bond (1,2-bond and 3,4-bond) content in the polymerized unit of conjugated diolefin is based on the polymerized unit of conjugated diolefin in the first (co) polymer of the present invention. It is 50 mol% or more, preferably 50 mol% or more and 90 mol% or less. If the vinyl bond content is less than 50 mol%, the balance between hysteresis loss and wet skid characteristics deteriorates. In addition, it is difficult to exceed 90 mol% by a usual method for synthesizing a copolymer of an aromatic vinyl compound and a conjugated diolefin.

In the second (co) polymer of the present invention, the content of the bonded aromatic vinyl compound bonded in the polymer chain is 30 to 50% by weight, preferably 30 to 45% by weight. When the content of the bound aromatic vinyl compound is less than 30% by weight, wet skid characteristics, wear resistance and fracture characteristics are deteriorated. When it exceeds 50% by weight, hysteresis loss increases.
The content of the conjugated diolefin polymerization unit is 50 to 70% by weight, preferably 55 to 70% by weight.

Furthermore, the vinyl bond (1,2-bond and / or 3,4-bond) content in the polymerized unit of conjugated diolefin is such that the polymer unit of conjugated diolefin in the second (co) polymer of the present invention. Is 15 to 50 mol%, preferably 18 to 47 mol%. If the vinyl bond content is less than 15 mol%, the wet skid characteristics are lowered and the handling stability is poor. On the other hand, if it exceeds 50 mol%, the fracture strength and wear resistance are deteriorated, and the hysteresis loss is increased.
Furthermore, the third (co) polymer of the present invention does not have a bonded aromatic vinyl compound. When the aromatic vinyl compound is bonded in the (co) polymer, the low temperature characteristics and low hysteresis loss are deteriorated.

Next, the manufacturing method of this invention is demonstrated.
The polymerization reaction and the reaction with the silicone resin for obtaining the (co) polymer of the present invention are usually performed in a temperature range of 0 to 120 ° C., and may be performed under a constant temperature condition or an elevated temperature condition. The polymerization method may be either a batch polymerization method or a continuous polymerization method.

  Examples of initiators of organic alkali metal compounds and organic alkaline earth metal compounds used for polymerization include alkyllithiums such as n-butyllithium, sec-butyllithium, and t-butyllithium, and 1,4-dilithiobutane. Alkylenedilithium, phenyllithium, stilbenelithium, lithium naphthalene, sodium naphthalene, potassium naphthalene, n-butylmagnesium, n-hexylmagnesium, ethoxycalcium, calcium stearate, t-butoxystrontium, ethoxybarium, isopropoxybarium, ethyl mercaptobarium Examples thereof include t-butoxybarium, phenoxybarium, diethylaminobarium, and barium stearate.

  The organic alkali metal compound as the initiator can be used for copolymerization of a conjugated diolefin and an aromatic vinyl compound as a reaction product with a secondary amine compound or a tertiary amine compound. As the organic alkali metal compound to be reacted with the secondary amine compound or the tertiary amine compound, an organic lithium compound is preferable. More preferably, n-butyl lithium, sec-butyl lithium, or t-butyl lithium is used.

  Examples of secondary amine compounds to be reacted with organic alkali metal compounds include dimethylamine, diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, dipentylamine, dihexylamine, di-n-octylamine. , Di- (2-ethylhexyl) amine, dicyclohexylamine, N-methylbenzylamine, diallylamine, morpholine, piperazine, 2,6-dimethylmorpholine, 2,6-dimethylpiperazine, 1-ethylpiperazine, 2-methylpiperazine, 1 -Benzylpiperazine, piperidine, 3,3-dimethylpiperidine, 2,6-dimethylpiperidine, 1-methyl-4- (methylamino) piperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 2,5- Dimethylpyrrolidine, azetidine, Hexamethylene imine, heptamethylene imine, 5-benzyloxy-indole, 3- azaspiro [5.5] undecane, 3-azabicyclo [3.2.2] nonane, carbazole and the like.

  Examples of the tertiary amine compound to be reacted with the organic alkali metal compound include N, N-dimethyl-o-toluidine, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, α -Picoline, β-picoline, γ-picoline, benzyldimethylamine, benzyldiethylamine, benzyldipropylamine, benzyldibutylamine, (o-methylbenzyl) dimethylamine, (m-methylbenzyl) dimethylamine, (p-methylbenzyl) ) Dimethylamine, N, N-tetramethylene-o-toluidine, N, N-heptamethylene-o-toluidine, N, N-hexamethylene-o-toluidine, N, N-trimethylenebenzylamine, N, N- Tetramethylenebenzylamine, N, N-hexamethylenebenzylamine, N, N-tetramethylene (O-methylbenzyl) amine, N, N-tetramethylene (p-methylbenzyl) amine, N, N-hexamethylene (o-methylbenzyl) amine, N, N-hexamethylene (p-methylbenzyl) amine, etc. Is mentioned.

  For the polymerization, diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, tetrahydrofuran, 2 , 2- (bistetrahydrofurfuryl) propane, bistetrahydrofurfuryl formal, methyl ether of tetrahydrofurfuryl alcohol, ethyl ether of tetrahydrofurfuryl alcohol, butyl ether of tetrahydrofurfuryl alcohol, α-methoxytetrahydrofuran, dimethoxybenzene, dimethoxyethane Ether compounds and / or triethylamine , Pyridine, N, N, N ′, N′-tetramethylethylenediamine, dipiperidinoethane, methyl ether of N, N-diethylethanolamine, ethyl ether of N, N-diethylethanolamine, N, N-diethyl A tertiary amine compound such as butyl ether of ethanolamine can be added to the polymerization system to adjust the microstructure (vinyl bond content) of the conjugated diolefin portion of the diolefin (co) polymer.

  Examples of the hydrocarbon solvent used when polymerizing the (co) polymer of the present invention include pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, toluene, xylene and the like. Of these, cyclohexane and heptane are preferred.

When trying to improve the reactivity of the initiator used in the present invention, or to arrange the aromatic vinyl compound introduced into the polymer randomly or to give a single chain of the aromatic vinyl compound In this case, a potassium compound may be added together with the polymerization initiator.
Examples of the potassium compound added together with the polymerization initiator include potassium isopropoxide, potassium t-butoxide, potassium t-amyloxide, potassium n-heptaoxide, potassium benzyloxide, potassium alkoxide represented by potassium phenoxide, Potassium phenoxide; potassium salts such as isovaleric acid, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, benzoic acid, phthalic acid, 2-ethylhexanoic acid; dodecylbenzenesulfonic acid, tetradecylbenzenesulfone Potassium salt of organic sulfonic acid such as acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid; diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibutyl phosphite, phosphorus phosphite Such as dilauryl, potassium salts of organic phosphorous acid partial esters are used.

  These potassium compounds can be added in an amount of 0.005 to 0.5 mole per gram atomic equivalent of alkali metal in the initiator. If it is less than 0.005 mol, the effect of adding a potassium compound (improved initiator reactivity, randomization of aromatic vinyl compound or imparting a single chain) does not appear, while if it exceeds 0.5 mol, the polymerization activity decreases. The productivity is greatly reduced, and the modification efficiency in the reaction of modifying the polymer terminal with a functional group is lowered.

The living polymer terminal thus obtained is reacted with a silicone oligomer (terminal modification reaction).
This reaction time is usually about 1 to 30 minutes, preferably about 1 to 15 minutes.
By this reaction, a polymer in which the silicone oligomer is bonded to the end of the living polymer is generated [see the above formula (1)].
Here, the amount of the silicone oligomer used for the terminal modification reaction is, for example, 0.001 g to 50 g, preferably 0.01 to 30 g with respect to 100 g of the living polymer. If it is less than 0.001 g, the effect of introducing the silicone oligomer will not be exhibited. That is, the improvement of the hysteresis loss property, wear resistance, and fracture property of the obtained (co) polymer is not sufficient, which is not preferable. On the other hand, when it exceeds 50 g, the interaction with the filler becomes too high, the compounding viscosity is improved, and the workability is deteriorated.

The weight average molecular weight of the (co) polymer after the terminal modification reaction obtained in the present invention is usually 100,000 to 2,000,000, preferably 150,000 to 1,700,000. If the weight average molecular weight is less than 100,000, the fracture strength, abrasion resistance, low hysteresis loss and the like of the rubber composition obtained are not sufficient. On the other hand, if it exceeds 2 million, the processability is inferior, Filler dispersibility deteriorates, and fracture strength, wear resistance, low hysteresis loss, and wet skid properties deteriorate.
In addition, it is preferable that the Mooney viscosity (ML1 _{+ 4} , 100 degreeC) of the (co) polymer obtained by this invention is the range of 20-200 after terminal modification reaction. When the Mooney viscosity (ML _{1 + 4} , 100 ° C.) after the terminal modification reaction is less than 20, the fracture strength, wear resistance, and low hysteresis loss are deteriorated. On the other hand, when the Mooney viscosity exceeds 200, the workability is deteriorated.

A polymer having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of more than 100 of the (co) polymer of the present invention is not preferable because it is inferior in processability as it is, but is an aromatic process oil or naphthenic process. By adding an extending oil such as oil or a liquid polymer having a weight average molecular weight of 150,000 or less, the Mooney viscosity can be lowered to 100 or less so that it can be used without any problem in processing.
The extending oil to be used is not particularly limited as long as it is an extending oil or a softening agent that is usually used for diene rubbers, but a mineral oil-based extending oil is preferably used. Generally, mineral oil extension oils are aromatic oils, alicyclic oils, and mixtures of aliphatic oils, and aromatic (aromatic) or alicyclic oils depending on their proportions. (Naphthenic) and aliphatic (paraffinic), and any of them can be used. The extending oil is preferably 0.790 to 1.100, preferably 0.790 to 1.049, in terms of viscosity specific gravity constant (or referred to as viscosity specific gravity constant, hereinafter abbreviated as VGC). V. G. C. Of 0.790 to 0.999, particularly preferably V.V. G. C. Of 0.790 to 0.949. Among them, an aromatic mineral oil having a viscosity specific gravity constant (VGC value) of 0.900 to 1.049 and an aliphatic mineral oil having an aromatic mineral oil of 0.800 to 0.899 ( Naphthenic oil) is preferably used from the viewpoint of low hysteresis / wet skid resistance.

  Among these, as the aromatic extending oil satisfying the above-mentioned viscosity specific gravity constant, Diana Process Oil AC-12, AC460, AH-16, AH-58 manufactured by Idemitsu Kosan Co., Ltd., Mobil Sol K manufactured by ExxonMobil Co., Ltd. No. 22 and No. 130, Kyoishi Processes X50, X100, and X140 manufactured by Nippon Mining & Co., Ltd., Resox No. 3. Deutrex 729UK, manufactured by Mitsubishi Oil Corporation (former Nippon Oil Company), Komolex 200, 300, 500, 700, manufactured by ExxonMobil Corporation, Esso Process Oil 110, 120, Mitsubishi Corporation (former Mitsubishi) Petroleum Company] Mitsubishi 34 Heavy Process Oil, Mitsubishi 44 Heavy Process Oil, Mitsubishi 38 Heavy Process Oil, Mitsubishi 39 Heavy Process Oil, and the like.

  Moreover, as a naphthenic extension oil satisfying the above-mentioned viscosity specific gravity constant, Diana Process Oil NS-24, NS-100, NM-26, NM-280, NP-24, manufactured by Idemitsu Kosan Co., Ltd., manufactured by ExxonMobil, Inc. Naplex 38, manufactured by Fuji Kosan Co., Ltd., Fukkor FLEX # 1060N, # 1150N, # 1400N, # 2040N, # 2050N, manufactured by Nikko Kyoishi Co., Ltd., Kyoishi Process R25, R50, R200, R1000, manufactured by Shell Chemical Co., Ltd. , Shelf Rex 371JY, 371N, 451, 451, N-40, 22, 22, 22R, 32R, 100R, 100S, 100SA, 220RS, 220S, 260, 320R, 680, Sun Komolex No. 2 process oil manufactured by Ishi Mitsubishi Corporation (formerly Nippon Oil Co., Ltd.), Esso manufactured by ExxonMobil Rosesuoiru L-2, the same 765, and the like Oil & Mitsubishisha [former Mitsubishi Oil Co.] manufactured by Mitsubishi 20 Light Process Oil.

  Furthermore, as the paraffinic extending oil satisfying the above-mentioned viscosity specific gravity constant, Diana Process Oil PW-90, PW-380, PS-32, PS-90, PS-430 manufactured by Idemitsu Kosan Co., Ltd., manufactured by Fuji Kosan Co., Ltd. , Fukkor process P-100, P-200, P-300, P400, P-500, manufactured by Nikko Kyoishi Co., Ltd., Kyoishi process P-200, P-300, P-500, Kyoishi EPT750, 1000 , Kyoishi Process S90, manufactured by Shell Chemical, Lebrex 26, 100, 460, ExxonMobil, Esso Process Oil 815, 845, B-1, Naxlex 32, ExxonMobil Examples include Mitsubishi 10 Light Process Oil manufactured by Mitsubishi Oil Corporation (formerly Mitsubishi Oil Corporation).

  As described above, the conjugated diolefin (co) polymer of the present invention is oil-extended with an extending oil, so that fillers such as carbon black and silica can be uniformly finely dispersed in the (co) polymer. Therefore, processability and various properties of the vulcanizate can be remarkably improved. This also surprisingly improves the mechanical strength, in particular the wear resistance, of the oil-extended (co) polymers and vulcanizates obtained.

  The amount of the extender oil used in the present invention is 10 to 100 parts by weight, preferably 15 to 90 parts by weight, based on 100 parts by weight of the conjugated diolefin (co) polymer. If the amount is less than 10 parts by weight, the effect of improving the wear resistance and the workability are poor. On the other hand, if the amount exceeds 100 parts by weight, it becomes extremely soft and inferior in workability.

There is no restriction | limiting in particular as an oil-extended method, For example, the method of adding extending oil to the polymerization solution of the said (co) polymer, and mixing in a solution state can be mentioned. This method is preferable from the viewpoint that, in operation, the process of mixing the (co) polymer and the extending oil can be omitted, and the mixing uniformity of both is excellent. When the extender oil is added to the polymerization solution, it is preferably after the completion of polymerization, for example, after the addition of a terminal modifier or after the addition of a polymerization terminator. A required amount of extender oil is added to a polymer solution containing an organic solvent and mixed well in a solution state (first step). Next, (1) a crumb is obtained by a steam stripping method in which steam is blown into a polymer solution containing an extending oil, or (2) a polymer solution containing an extending oil is obtained by means of an extruder, a devolatizer, or the like. The solvent is removed directly to separate the oil-extended 1,2-polybutadiene and the solvent (second step). The obtained undried oil-extended (co) polymer is dried by a vacuum dryer, a hot air dryer or a roll, if necessary (third step), and the desired oil-extended (co) polymer is obtained. It can be isolated.
Moreover, as an oil-extended method, the conjugated diolefin (co) polymer of the present invention and an extender oil can be blended in a molten state to prepare an oil-extended (co) polymer. In this case, as a blending method, a single screw extruder, a twin screw extruder, a banbury, a roll, a kneader, a plast mill or the like is adopted, and a melt kneading temperature is preferably 50 to 200 ° C.

  Thus, according to the present invention, an oil-extended (co) polymer containing 10 to 100 parts by weight of the extended oil is preferably provided with respect to 100 parts by weight of the conjugated diolefin (co) polymer of the present invention.

  The polymerization reaction solution containing the (co) polymer obtained in the present invention is a method used for a normal solution polymerization method, for example, after adding a stabilizer or the like in a solution state, and if necessary, as described above. Add an extender oil such as aromatic process oil or naphthenic process oil or a liquid polymer with a weight average molecular weight of 100,000 or less (or a solution of the above liquid polymer) to the rubber by direct drying or steam stripping. The solvent can be separated and washed, and dried with a vacuum dryer, hot air dryer, roll or the like, and the desired (co) polymer of the present invention can be isolated.

  The (co) polymer of the present invention is used alone or blended with natural rubber, polyisoprene rubber, polybutadiene rubber, emulsion-polymerized styrene butadiene rubber, etc., and reinforcing agents such as carbon black and silica and various compounding agents, rolls, and banbury. After kneading with a mixer, sulfur, a vulcanization accelerator, and the like can be added and used for tires such as treads, sidewalls, carcass, belts, anti-vibration rubbers, and other industrial products.

  Examples of the reinforcing material filled when the (co) polymer of the present invention is used for a tire, particularly a tire tread, include fillers such as carbon black and silica.

In particular, when the vulcanized product is effectively reinforced and good wear resistance and fracture strength are expected, carbon black is preferably used. The filling amount of the filler is preferably 20 to 120 parts by weight, more preferably 30 to 110 parts by weight with respect to 100 parts by weight of the total rubber component. Carbon black produced by a furnace method is preferably carbon black having a nitrogen adsorption specific surface area of 50 to 200 m ² / g and a DBP oil absorption of 80 to 200 ml / 100 g. FEF, HAF, ISAF, SAF Class members can be preferably used, and those of high aggregation type are particularly preferable.

  In particular, in the use of fuel-efficient tires, it is preferable to use silica for the purpose of reducing the hysteresis loss of the vulcanizate to give good rolling resistance and improving wet skid resistance. As the silica, any of wet method silica, dry method silica, and synthetic silicate silica can be used. A silica having a small particle system has a high reinforcing effect, and a small particle / highly agglomerated type (high surface area, high oil absorption) has good dispersibility in rubber, and is particularly preferable in terms of physical properties and processability. It is also preferable to use high-dispersion type silica to improve the dispersibility in rubber and improve physical properties and processability. The average particle size of silica is preferably 5 to 60 μm, particularly preferably 10 to 35 μm in terms of primary particle size. The filling amount of silica is preferably 20 to 120 parts by weight, more preferably 30 to 110 parts by weight with respect to 100 parts by weight of the total rubber component.

Furthermore, when silica is used for the filler, various known silane coupling agents can be used for the purpose of enhancing the reinforcing effect. A silane coupling agent includes a component capable of reacting with a silica surface such as an alkoxysilyl group in a molecule and a component capable of reacting with a rubber, particularly a carbon-carbon double bond, such as a polysulfide, a mercapto group, and an epoxy group. It refers to a compound that has both. For example, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide and 3-mercaptopropyltrimethoxysilane are well known as silane coupling agents.
In addition, when using a silica as a filler, it is desirable to use at least 1 weight part in a filler as a silica, and also to contain 0.5-20 weight% of silane coupling agents with respect to this silica. By doing so, the dispersibility of silica is improved and the bonding ratio between silica and rubber is improved, so that the effect of improving the breaking strength, wear resistance, and low hysteresis loss can be obtained.

  Also, by using carbon black and silica in combination within the range of 20 to 120 parts by weight with respect to 100 parts by weight of all rubber components, good wear resistance, breaking strength and excellent low hysteresis performance, wet grip It is also possible to balance performance.

  Also, by blending a carbon-silica dual phase filler with the (co) polymer of the present invention, the same excellent advantages as when carbon black and silica are used in combination can be obtained.

The carbon-silica dual phase filler is a so-called silica-coated carbon black in which silica is chemically bonded to the surface of carbon black, and is sold under the trade names CRX2000, CRX2002, and CRX2006 by Cabot Corporation.
The compounding amount of the carbon-silica dual phase filler is preferably 1 to 100 parts by weight, more preferably 5 to 95 parts by weight, with respect to 100 parts by weight of the total rubber component.

In the present invention, the carbon-silica dual phase filler can be used in combination with other fillers. Examples of fillers that can be used in combination include carbon black, silica, calcium carbonate, and magnesium carbonate, but these are not limited. Of these, carbon black and silica are preferred.
These fillers that can be used in combination are preferably 3 to 100 parts by weight, particularly 5 to 95 parts by weight, based on 100 parts by weight of the total amount of rubber components.

On the other hand, when preparing a rubber composition using the oil-extended (co) polymer, the oil-extended (co) polymer is contained in an amount of 30% by weight or more based on the total rubber component, and as a filler, 2-100 parts by weight of carbon black and / or 30-100 parts by weight of silica per 100 parts by weight of the total rubber component, and when silica is contained, 5-20% by weight of the silane coupling agent with respect to silica It is preferable to contain. By doing so, the dispersibility of silica is improved and the bonding ratio between silica and rubber is improved, so that the effect of improving the breaking strength, wear resistance, and low hysteresis loss can be obtained.
Further, when preparing a rubber composition using the oil-extended (co) polymer, the oil-extended (co) polymer is contained in an amount of 30% by weight or more based on the total rubber components, Per 100 parts by weight of rubber component,
(A) 30 to 100 parts by weight of carbon black and silica as a total amount thereof,
(B) 30 to 100 parts by weight of carbon-silica dual phase filler, or (c) 30 to 100 parts by weight of carbon-silica dual phase filler and carbon black and / or silica as their total amount,
And 5 to 20% by weight of a silane coupling agent based on the total amount of silica and / or carbon-silica dual phase filler,
This is also a preferred embodiment.
By doing so, the dispersibility of silica is improved and the bonding ratio between silica and rubber is improved, so that the effect of improving the breaking strength, wear resistance, and low hysteresis loss can be obtained.

  The kneading method of the rubber composition obtained using the (co) polymer of the present invention (including the oil-extended (co) polymer) is not particularly limited, but when the filler contains silica, reinforcement with silica For the purpose of further improving the physical properties of the vulcanized rubber, it can be kneaded by the following method.

  As a kneading method of the rubber composition containing the (co) polymer of the present invention (including an oil-extended (co) polymer), silica, silane coupling agent, zinc white and vulcanizing agent, (a) ( Co) Polymer is blended with silica and kneaded to prepare a first rubber compound, then a silane coupling agent is blended with the first rubber compound and kneaded to obtain a second rubber compound. And then blending the second rubber compound with zinc white and vulcanizing agent and kneading, or (b) blending silica into the (co) polymer and kneading the first rubber. A blend is prepared, and then a silane coupling agent is blended into the first rubber blend and kneaded, further zinc white is blended, and kneading is continued to prepare a second rubber blend, A method of blending and kneading a vulcanizing agent in the second rubber compound can be mentioned.

  In the above kneading method, since the silane coupling agent does not coexist when kneading the (co) polymer and silica, the kneading temperature can be increased to about 170 to 180 ° C. ) Since the reactivity between the polymer and silica is increased, the performance is improved.

  In the rubber composition of the present invention, the vulcanizing agent is preferably used in the range of 0.5 to 10 parts by weight, more preferably 1 to 6 parts by weight with respect to 100 parts by weight of the total rubber components. it can.

  Typical examples of the vulcanizing agent include sulfur, and other examples include sulfur-containing compounds and peroxides.

  Further, in combination with a vulcanizing agent, a vulcanization accelerator such as a sulfenamide-based, guanidine-based, or thiuram-based one may be used as needed. Further, zinc white, vulcanization aid, anti-aging agent, processing aid, and the like may be used as required.

  Further, various compounding agents of the rubber composition obtained by using the (co) polymer of the present invention are not particularly limited, but improvement in workability during kneading, wet skid characteristics, low hysteresis loss, abrasion resistance Vulcanizing agents, vulcanization accelerators, zinc oxide, anti-aging agents, anti-scorching agents, tackifiers, other fillers, etc., blended with other extender oils and ordinary rubber compositions for the purpose of further improving the balance of properties In addition to the various compounding agents, the following compatibilizers can be added during kneading.

  Preferred compatibilizers are organic compounds selected from epoxy group-containing compounds, carboxylic acid compounds, carboxylic ester compounds, ketone compounds, ether compounds, aldehyde compounds, hydroxyl group-containing compounds and amino group-containing compounds, or alkoxysilanes. A silicone compound selected from a compound, a siloxane compound and an aminosilane compound.

Specific examples of the organic compound of the compatibilizer include the following compounds.
Epoxy group-containing compounds: butyl glycidyl ether, diglycidyl ether, propylene oxide, neopentyl glycol siglycidyl ether, epoxy resin, epoxidized soybean oil, epoxidized fatty acid ester and the like.
Carboxylic acid compounds: adipic acid, octylic acid, methacrylic acid and the like.

Carboxylic acid ester compounds: acrylic acid ester, diethylene acrylate, ethyl methacrylate, orthoacetic acid ester, ethyl acetoacetate, butyl acetate, isopropyl acetate, dimethyl carbonate, p-hydroxyphenylacetic acid, polyester plasticizer, stearic acid plasticizer Such.
Ketone compounds: methylcyclohexanone, acetylacetone, etc.
Ether compounds: isopropyl ether, dibutyl ether and the like.
Aldehyde compounds: undecylenaldehyde, decylaldehyde, vanillin, 3,4-dimethoxybenzaldehyde, cuminaldehyde and the like.
Amino group-containing compounds: n-propylamine, isopropylamine, di-n-propylamine, diisopropylamine, triethylamine, 3-ethoxypropylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, isopropanolamine, ethylenediamine N-ethylethylenediamine, ethyleneimine, hexamethylenediamine, 3-lauryloxypropylamine, aminophenol, aniline, 3-isopropoxyaniline, phenylenediamine, aminopyridine, N-methyldiethanolamine, N-methylethanolamine, 3- Amino-1-propanol, ethylamine hydrochloride, hydrochloric acid-n-butylamine and the like.
Hydroxyl group-containing compounds: isopropyl alcohol, butanol, octanol, octanediol, ethylene glycol, methylcyclohexanol, 2-mercaptoethanol, 3-methyl-3-methoxy-1-butanol, 3-methyl-1,5-pentanediol, 1 -Octadecanol, diethylene glycol, butylene glycol, dibutylene glycol, triethylene glycol and the like.
Among these, an epoxy group-containing compound, an amino group-containing compound, and a hydroxyl group-containing compound are preferable.

Specific examples of the compatibilizer silicone compound include:
Alkoxysilane compounds: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, tetraethoxysilane, methyldiethoxysilane, vinyltrimethoxysilane and the like.
Siloxane compounds: dimethylsiloxane oligomer, silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, higher alkoxy-modified silicone oil, higher-grade Fatty acid-containing silicone oil etc.
Aminosilane compounds: hexamethylcisilazane, nonamethyltrisilazane, anilitrimethylsilane, bis (dimethylamino) dimethylsilane, bis (diethylamino) dimethylsilane, triethylaminosilane, among them, silazane compounds and bis (dimethylamino) dimethylsilane are preferable. .

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by these Examples.
Various measurements in the examples were based on the following methods.
(1) Vinyl content of the conjugated diolefin moiety It was determined by 270 MHz ¹ H-NMR.
(2) Bound styrene content Determined by 270 MHz ¹ H-NMR.
(3) Glass transition temperature Determined according to ASTM D3418.
(4) Weight average molecular weight It calculated | required in polystyrene conversion using the gel permeation chromatography (GPC) (the Tosoh company make, HLC-8120GPC).
(5) Mooney viscosity (ML _{1 + 4} , 100 ° C.)
According to JIS K6300, L rotor, preheating 1 minute, rotor operating time 4 minutes, temperature 100 ° C.

(6) Evaluation of physical properties of vulcanized rubber Using a copolymer rubber, kneaded with a 250 cc lab plast mill according to the formulation shown in Table 5, and then vulcanized at 145 ° C for a predetermined time. Various measurements (i) to (d) below were performed.
(I) Processability:
The mass of dump rubber after kneading and the appearance of gloss were visually inspected and evaluated.
(B) Tensile strength (300% modulus):
It measured according to JISK6301.
Expressed as an index, the larger the value, the greater the tensile strength and the better.
(C) tan δ (50 ° C.), tan δ (0 ° C.):
Tan δ (50 ° C.) was measured using a dynamic spectrometer manufactured by Rheometrics, USA under the conditions of tensile dynamic strain 1%, frequency 10 Hz, 50 ° C. Expressed as an index, the larger the value, the smaller the rolling resistance and the better. Further, tan δ (0 ° C.) was measured using the same apparatus at a tensile dynamic strain of 0.1%, a frequency of 10 Hz, and 0 ° C. Expressed as an index, the larger the value, the greater the wet skid resistance.
(D) Lambourn wear index (wear resistance):
A Lambourn type wear tester was used, and the slip rate was expressed as a wear amount of 25%, and the measurement temperature was room temperature. The higher the index, the better the wear resistance.

Example 1 (Synthesis of copolymer rubber A and evaluation thereof)
An autoclave reactor with an internal volume of 5 liters purged with nitrogen was charged with 2,750 g of cyclohexane, 41.3 g of tetrahydrofuran, 125 g of styrene, and 365 g of 1,3-butadiene. After adjusting the temperature of the reactor contents to 10 ° C., 325 mg of n-butyllithium was added to initiate polymerization. The polymerization was conducted under adiabatic conditions and the maximum temperature reached 85 ° C.
When the polymerization conversion rate reached 99%, 10 g of butadiene was added and polymerization was further performed for 5 minutes. A small amount of the polymer solution from the reactor was sampled in 30 g of a cyclohexane solution to which 1 g of methanol was added, and then 886 mg of KC-89S (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a silicone oligomer, and a terminal modification reaction was performed for 15 minutes. Finally, 2,6-di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Next, the solvent was removed by steam stripping, and the rubber was dried by a hot roll adjusted to 110 ° C. to obtain a raw rubber. This raw rubber is referred to as copolymer rubber A. The composition and physical properties of the obtained copolymer rubber A are shown in Table 2. Moreover, the GPC curve before silicone oligomer addition is shown in FIG. 1, and the GPC curve after addition is shown in FIG.
Using the copolymer rubber A, the compounded rubber prepared by the compounding formulation shown in Table 3 was vulcanized, and the physical properties were evaluated. The results are shown in Table 4 as Example 5.

Example 2 (Synthesis of copolymer rubber B and evaluation thereof)
Copolymer rubber B was obtained in the same manner as in Example 1, except that KC-89S was changed to 972 mg of silicone oligomer X41-1053 (manufactured by Shin-Etsu Chemical Co., Ltd.). The composition and physical properties of the obtained copolymer rubber B are shown in Table 2.
Using the copolymer rubber B, the compounded rubber prepared by the compounding recipe shown in Table 3 was vulcanized, and the physical properties were evaluated. The results are shown in Table 4 as Example 6.

Example 3 (Synthesis of copolymer rubber C and evaluation thereof)
Copolymer rubber C was obtained in the same manner as in Example 1, except that KC-89S was changed to 1,054 mg of silicone oligomer X40-2308 (manufactured by Shin-Etsu Chemical Co., Ltd.). The composition and physical properties of the obtained copolymer rubber C are shown in Table 2.
Using the copolymer rubber C, the compounded rubber prepared by the compounding formulation shown in Table 3 was vulcanized, and the physical properties were evaluated. The results are shown in Table 4 as Example 7.

Example 4 (Synthesis of copolymer rubber D and evaluation thereof)
A copolymer rubber D was obtained in the same manner as in Example 1, except that KC-89S was changed to 1,064 mg of silicone oligomer X40-9238 (manufactured by Shin-Etsu Chemical Co., Ltd.). Table 2 shows the composition and physical properties of the obtained copolymer rubber D.
Using the copolymer rubber D, the compounded rubber prepared by the compounding formulation shown in Table 3 was vulcanized, and the physical properties were evaluated. The results are shown in Table 4 as Example 8.

Comparative Examples 1 and 2 (Synthesis of copolymer rubbers E to F and evaluation thereof)
In Example 1, copolymer rubbers E and F were obtained in the same manner as in Example 1 except that the coupling agent shown in Table 1 was used instead of the silicone oligomer. Table 2 shows the composition and physical properties of the obtained copolymer rubber.
Using the copolymer rubbers E and F, the compounded rubber prepared by the compounding formulation shown in Table 3 was vulcanized, and the physical properties were evaluated. The results are shown in Table 4 as Comparative Examples 3-4.

From the results of Table 1, Table 2, Table 3, Table 4, FIG. 1 and FIG.
From Table 2, Example 1 has a weight average molecular weight after the terminal modification reaction of 400,000, which is an increase compared to the weight average molecular weight of 220,000 before the reaction. Moreover, compared with FIG. 1 which showed the GPC curve before reaction, in FIG. 2, the area of the GPC curve which shows the molecular weight before reaction decreased, and the GPC curve appeared newly in the high molecular weight area | region. These results suggest that the silicone oligomer is bonded to the conjugated diolefin copolymer rubber A. Moreover, from the area ratio of FIG. 2, it turns out that the silicone oligomer has couple | bonded with 73% of a polymer terminal. Similarly, it can be seen from Table 2 that the silicone oligomer is also bound to the conjugated diolefin copolymer rubbers B to D of Examples 2 to 4.

Further, from the evaluation results in Table 4 using conjugated diolefin copolymer rubbers A to F, conjugated diolefin copolymer rubbers A to D in which silicone oligomers are bonded to conjugated diolefin copolymer rubbers as in the present invention. In the case of Examples 5 to 8 using the above, it has good workability, has a low hysteresis loss property (tan δ at 50 ° C.), and wear resistance without impairing fracture strength, wet skid characteristics (tan δ at 0 ° C.), and wear resistance Sex is balanced at a high level at the same time.
On the other hand, in Comparative Examples 3 and 4 using conjugated diolefin copolymer rubbers E and F coupled with tin tetrachloride or tetraethoxysilane, the effect of improving various physical properties is small, and the conjugated diolefin copolymer of the present invention is used. It does not extend to the improvement of the properties of rubber.

  The conjugated diolefin (co) polymer obtained by the present invention is excellent in processability, and when vulcanized to give vulcanized rubber, wet skid characteristics, low hysteresis loss, wear resistance, fracture strength Therefore, it is useful as a tread material for low fuel consumption tires, large tires, and high performance tires.

2 is a GPC curve of a copolymer rubber before a terminal modification reaction in Example 1. 2 is a GPC curve of a copolymer rubber after a terminal modification reaction in Example 1.

Claims (5)

In a hydrocarbon solvent, using at least one compound selected from the group consisting of an organic alkali metal-containing compound and an organic alkaline earth metal-containing compound as an initiator, a conjugated diolefin, or a conjugated diolefin and an aromatic vinyl compound After anionic polymerization, it has an alkoxysilyl group (—SiOR) (wherein R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms) at the polymer terminal and at the molecular terminal, Furthermore, kinematic viscosity (25 degreeC, mm < ² > / s) measured at 25 degreeC is 1-500, and (a) General formula (1)
(R ¹ ) _n Si (OR ² ) _4-n (1)
(In the formula, when two R ¹ are present, they are the same or different and each represents a monovalent organic group having 1 to 10 carbon atoms; R ² is the same or different and is an alkyl group or carbon having 1 to 5 carbon atoms; At least one selected from an organosilane represented by the formula 1-6, and n is an integer of 0-1) and a hydrolyzate of the organosilane, or (b) an SiO bond A conjugated diolefin (co) polymer production method comprising reacting a silicone oligomer having a siloxane three-dimensional skeleton, which is a trifunctional organosiloxane oligomer having a weight average molecular weight of 300 to 100,000 .   The conjugated diolefin (co) polymer according to claim 1, wherein the content of the alkoxysilyl group of the silicone oligomer bonded to the conjugated diolefin (co) polymer is 0.5 to 200 mmol / kg · (co) polymer polymer. Manufacturing method. The conjugated diolefin (co) polymer obtained by the production method according to claim 1 or 2 contains 20 to 120 parts by weight of filler with respect to 100 parts by weight of all rubber components occupying 30% by weight or more of all rubber components. A rubber composition characterized by comprising: The rubber composition according to claim 3 , wherein the filler is silica.   A tire using the rubber composition according to claim 3 for a tread member or a side wall member.

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