JP2000154279A - Conjugated diene rubber composition containing crystalline segment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition which, in spite of its being a mixture of different rubber components, has a good compatibility between the components, exerts an excellent low-temperature impact resilience and tensile strength and has a sufficient wear factor. SOLUTION: The titled composition contains (i) from 2 to 90 pts.wt. block copolymer rubber, which is a partially crystalline block copolymer rubber which comprises (A) from 10 to 98 wt.% conjugated diene polymer segment having a high cis-content of 40% or larger and (B) from 90 to 2 wt.% crystalline segment and has a molecular weight distribution of 4 or smaller and a weight average molecular weight, in terms of polystyrene, of from 20,000 to 10,000,000, and (ii) from 98 to 2 pts.wt. (co)polymer of from 0 to 50 wt.% aromatic monovinyl monomer and from 100 to 50 wt.% conjugated diene monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel rubber composition containing a conjugated diene block copolymer rubber containing a crystalline segment.

[0002]

2. Description of the Related Art The following techniques are disclosed in a method for producing polybutadiene having a cis content of 35% or more. JP-A-61-85414 discloses a 1,2-vinyl bond 7
５０50%, cis-1,4 bond> 50%, trans-1,
A method for making a polybutadiene rubber with 4 bonds <5% is disclosed. Japanese Patent Application Laid-Open No. 9-316118 discloses a method for producing an amorphous random copolymer by copolymerizing an olefin and butadiene. The random copolymer has a lower Tg than the high cis-butadiene rubber.
Due to the high g, the improvement of the wear characteristics is not sufficient, and since it is amorphous, the improvement of the processing characteristics is not sufficient.

On the other hand, JP-A-57-15415 and JP-A-59-164313 disclose methods for producing reinforcing polybutadiene. The polymer is polybutadiene having a boiling n-hexane insoluble content of 5 to 30%, and cis-
Polybutadiene with high 1,4 bonds was produced, followed by 1,4
2. Polybutadiene obtained by a method of performing polymerization. JP-A-5-194658 discloses a polybutadiene rubber composition containing 10 to 25% by weight of n-hexane insoluble matter. As is evident in this,
There is a description that syndiotactic polybutadiene and 1,4-cis polybutadiene may be separately polymerized and these products may be blended. The polybutadiene obtained by the production method and the composition thereof are different from each other in two kinds of rubbers. Is a blended rubber composition.

However, it is common general knowledge in the art that blends of different rubbers are mostly incompatible and that there is an interface between the two polymers, reducing their reinforcing properties.

On the other hand, a polybutadiene rubber having a high cis content can obtain only a crosslinked product having a small tensile stress even when reinforcing particles such as carbon black are blended. In addition, there are also problems such as large bagging and swell in processing characteristics.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a mixture of different rubber components, which have good compatibility, excellent low-temperature rebound resilience, excellent tensile stress, and a sufficient wear index. Another object of the present invention is to provide a rubber composition.

[0007]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and as a result, have found that a new conjugated diene polymer segment having a high cis content and a crystalline segment such as ethylene are obtained. It has been found that the problem can be solved by using a copolymer having the same.

That is, the present invention relates to (i) 10 to 98% by weight of (A) a conjugated diene polymer segment having a high cis content of 40% or more and (B) 90 to 2% by weight of a crystalline segment. A partially crystalline block copolymer rubber having a molecular weight distribution of 4 or less and a polystyrene equivalent weight average molecular weight of 20,000 to 10,000,
2 to 90 parts by weight of a block copolymer rubber of 000, and (2) 98 to 2 parts by weight of a (co) polymer of 0 to 50% by weight of an aromatic monovinyl monomer and 100 to 50% by weight of a conjugated diene monomer. And a conjugated diene rubber composition containing a crystalline segment.

[(I) Partially crystalline block copolymer rubber] In the partially crystalline block copolymer (i) of the present invention, the weight ratio of the conjugated diene segment to the crystalline segment is usually 10 conjugated diene segments. ~ 98
% By weight and 90 to 2% by weight of the crystalline segment, preferably 50 to 98% by weight of the conjugated diene segment and 50 to 3% by weight of the crystalline segment, and more preferably 70 to 96% by weight of the conjugated diene segment. 30 to 4% by weight. If the crystal part is too small, the processing characteristics are not good, and if it is too large, the strength characteristics are not good.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the partially crystalline block copolymer (i) of the present invention is usually 1.1 or more and 4 or less.
Preferably 1.2 or more and 3 or less, more preferably 1.3.
It is 2 or less. If the molecular weight distribution is too narrow, processability is poor, and if the distribution is too wide, heat build-up is poor.

If the weight average molecular weight of the partially crystalline block copolymer (i) of the present invention is too small, the tensile strength is poor, and if it is too large, the processability is poor. 000 to 10,000
It is necessary to be 0,000, preferably 50,
000-5,000,000, more preferably 10
It is from 2,000 to 2,500,000.

In the partially crystalline block copolymer (i) of the present invention, if the cis content in the polybutadiene segment is excessively low, the abrasion characteristics deteriorate, which is not desirable. It is necessary that the content be at least 40% by weight or more. , Preferably at least 50% by weight, more preferably at least 70% by weight.

In the block copolymerization method, a conjugated diene polymer block (A) may be prepared first, and then a monomer forming a crystalline segment (B) may be block-copolymerized. The monomer to be formed may be separately polymerized, and the polymerization terminal of the conjugated diene polymer segment (A) may be reacted with the polymerization terminal of the crystalline segment (B) or a reactive portion in the molecular chain. Alternatively, a reaction starting point may be formed in the molecular chain of the conjugated diene polymer segment (A) by an organometallic catalyst, and a monomer serving as a component of the crystalline segment (B) may be graft-copolymerized.

[Regarding the high cis content conjugated diene polymer segment (A)]
The conjugated diene polymer segment which is a segment can be produced as follows. That is, (a) a carbonyl group,
A transition metal compound belonging to Group IV of the periodic table having a cyclopentadienyl skeleton having a substituent having at least one atomic group selected from a sulfonyl group, an ether group, and a thioether group; (ii) aluminoxane; An ionic compound capable of producing a cationic transition metal compound by reacting with a), a Lewis acid compound capable of producing a cationic transition metal compound by reacting with the transition metal compound (a), or a group I to III of the periodic table A conjugated diene monomer or conjugated diene in the presence of a catalyst obtained by contacting at least one cocatalyst selected from organometallic compounds of the main element metal under the conditions satisfying the following formulas α and β: It can be produced by polymerizing a monomer and a monomer copolymerizable therewith.

Formula α-100 <T <80 Formula β 0.017 <t <6000exp (−0.0921T) T is the contact temperature (° C.), t is the contact time (min.) The polymer rubber (i) is copolymerizable for forming the crystalline segment (B) by utilizing the living property of the active terminal of the conjugated diene polymer segment (A) obtained as described above. It can be obtained by block copolymerization by adding a monomer.

Group IV transition of the periodic table having a cyclopentadienyl skeleton having a substituent having at least one atomic group selected from the above-mentioned component (a), ie, carbonyl group, sulfonyl group, ether group and thioether group. The metal compound is preferably a compound represented by the following general formula (1) or (2). General formula (1)

Embedded image (Wherein, M is a transition metal of Group IV of the periodic table, X ¹ , X ² , X
³ is a group independently selected from the group consisting of a hydrogen atom, a halogen, a hydrocarbon group having 1 to 12 carbon atoms and a hydrocarbonoxy group having 1 to 12 carbon atoms, and Y is a hydrogen atom or a carbon atom having 1 to 12 carbon atoms. A hydrocarbon group of 1 to 20, which may itself form a ring with a cyclopentadienyl group, wherein Z ¹ and Z ² are each a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; Each independently selected groups, A is an oxygen atom or a sulfur atom, R ¹ is a hydrogen atom,
It is a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon oxy group having 1 to 12 carbon atoms, or a hydrocarbon sulfide group having 1 to 12 carbon atoms, and n is an integer of 0 to 5. ) General formula (2)

Embedded image (Wherein, M is a transition metal of Group IV of the periodic table, X ¹ , X ² , X
³ is a group independently selected from the group consisting of a hydrogen atom, a halogen, a hydrocarbon group having 1 to 12 carbon atoms and a hydrocarbonoxy group having 1 to 12 carbon atoms, and Y is a hydrogen atom or a carbon atom having 1 to 12 carbon atoms. 1 to 20 hydrocarbon groups, which may themselves form a ring with a cyclopentadienyl group, wherein Z ¹ and Z ² are each a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. A and B are independently selected groups, A is an oxygen atom or a sulfur atom, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 to 5. )

The transition metal compound represented by the general formula (1) or (2) is more preferably a cyclopentadienyl group; a cyclopentadienyl group having a substituent such as an alkyl, aryl or cycloalkyl group. It is a so-called metallocene compound having a dienyl group or a plurality of condensed cyclic substituents as ligands, and the cyclopentadienyl group of the ligand has> C = O structure,> C = S structure, -C-
The substituent has at least one atomic group selected from the group consisting of an OC-structure and a -CSC-structure. Further, a transition metal of Group IV of the periodic table (M in the formula) is
Preferably Ti, Zr or Hf, more preferably Ti
It is. Desirable X ¹ , X ² , and X ³ are chlorine atoms as halogens, alkyl groups such as methyl and neopentyl as hydrocarbon groups, aralkyl groups such as benzyl, and hydrocarbon oxy groups such as methoxy, ethoxy, and isopropoxy. And aralkyloxy groups such as an alkoxy group and a benzyloxy group. Particularly, an alkoxy group as a hydrocarbonoxy group is preferred. Y includes, for example, a hydrogen atom, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl; an aryl group such as phenyl; an aralkyl group such as benzyl; and a silicon atom such as a trimethylsilyl group. Hydrocarbon groups. Y bonded to the cyclopentadienyl ring may form a polycyclic group such as an indenyl group or a fluorenyl group together with the cyclopentadienyl ring. As Z ¹ and Z ² , for example, a hydrogen atom,
Methyl, ethyl, propyl, isopropyl, butyl, t
-Alkyl groups such as -butyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. R
Examples of ¹ include a hydrogen atom and a hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, t-
Alkyl groups such as butyl, aryl groups such as phenyl,
Aralkyl groups such as benzyl, alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy and t-butoxy as hydrocarbon oxy groups, aryloxy groups such as phenyloxy groups, aralkyloxy groups such as benzyloxy groups, and hydrocarbons Alkyl sulfide groups such as methylthio, ethyl thio, propyl thio, isopropyl thio, butyl thio, t-butyl thio, etc., and aryl sulfide groups such as phenyl thio group,
And aralkyl sulfide groups such as a benzylthio group. R ¹ is preferably a hydrocarbon oxy group,
Among them, an alkoxy group is particularly preferred. Examples of R ² include hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. n is preferably 1 or 2, more preferably 1.

Specific examples of the transition metal compound of Group IV of the periodic table (a) include those represented by the general formula (1):
MeO (CO) CH ₂ CpTiCl ₃ , MeO (CO)
CH (Me) CpTiCl ₃ , {3- [MeO (CO)
CH ₂ ]｝ (1-Me) CpTiCl 3, general formula (2)
Include MeOCH ₂ CH ₂ CpTi
Cl _{3 and the} like (Me in the formula is a methyl group, Cp
Represents a cyclopentadienyl structure).

The method for preparing the Group IV transition metal compound of the periodic table represented by the general formula (1) or (2) is not particularly limited. For example, in the case of MeO (CO) CH ₂ CpTiCl ₃ , Macromol. Symposia, 1997
Year, Vol. 118, pp. 55-60, Me
In the case of OCH ₂ CH ₂ CpTiCl ₃ , see JP-A-9-77.
It may be prepared based on the description in JP-A-818.

Group IV transition metal compound of the periodic table (a)
The aluminoxane used in combination with is a linear or cyclic polymer represented by the following general formula (3), and is an organic aluminum oxy compound.

Embedded image [—Al (R ³ ) O—] n (3) (R ³ is a hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, and isobutyl. R ³ may be substituted with a halogen atom and / or an R ⁴ O group, and R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, and isobutyl, and among them, a methyl group is preferable.
The above is preferably 10 or more, and there is no particular upper limit, but it is preferably 100 or less, more preferably 50 or less. )

Examples of the ionic compound for forming a cationic complex by reacting with the transition metal compound (a) include an anion of tetrakis (pentafluorophenyl) borate and, for example, (CH ₃ ) ₂ N (C ₆ H ₅₎ A) an amine cation having an active proton such as H ⁺ , (C ₆ H ₅ ) ₃
An ionic compound with a trisubstituted carbonium cation such as C ⁺ , a carborane cation, a metal carborane cation, or a ferrocenium cation having a transition metal can be used.

The conjugated diene polymer segment (A)
In order to obtain the catalyst component, a metal hydride compound, an organometallic compound of a main element metal of Groups I to III of the periodic table, an organometallic halogen compound, an organometallic hydride compound, or the like may be used in combination. . Examples of the metal hydride compound include, for example, NaH, LiH, CaH ₂ , LiAlH ₄ , NaB
Such as H _4, and the like. Examples of the organometallic compound of the main element metal include methyllithium, butyllithium, phenyllithium, dibutylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. Examples of the organometallic halogen compound include ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride, and ethyl aluminum dichloride. Examples of the hydrogenated organometallic compound include diethyl aluminum hydride and sesquiethyl aluminum hydride.

In order to obtain the conjugated diene polymer segment (A), the transition metal compound and / or cocatalyst can be used by being supported on a carrier. Examples of the carrier include an inorganic compound and an organic polymer compound. The inorganic compound is preferably an inorganic oxide, an inorganic chloride, an inorganic hydroxide, or the like, and may contain a small amount of a carbonate or a sulfate. Particularly preferred are inorganic oxides, and specific examples include silica, alumina, magnesia, titania, zirconia, calcia, and the like. These inorganic oxides have an average particle size of 5-1.
Porous fine particles having a specific surface area of 50 μm and a specific surface area of ² to 800 m ² / g are preferable. The organic polymer compound preferably has an aromatic ring, a substituted aromatic ring, or a functional group such as a hydroxy group, a carboxyl group, an ester group, or a halogen atom in a side chain. Specific examples of the organic polymer compound include ethylene, propylene, an α-olefin homopolymer having a functional group introduced by chemical modification such as polybutene, an α-olefin copolymer, acrylic acid, methacrylic acid, vinyl chloride, Examples include homopolymers and copolymers of vinyl alcohol, styrene, divinylbenzene, and the like, and further, chemically modified products thereof. As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 μm are used. By supporting the transition metal compound and / or the cocatalyst, it is possible to prevent the catalyst from adhering to the polymerization reactor.

The conjugated diene monomer for forming the conjugated diene polymer segment (A) of the present invention includes:
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,
3-hexadiene and the like are included. Among the conjugated dienes, 1,3-butadiene and 2-methyl-1,3-butadiene are preferred, and 1,3-butadiene is more preferred. These conjugated diene monomers can be used alone or in combination of two or more.
-It is preferred to use butadiene alone.

The monomers which can be copolymerized with the conjugated diene monomer to form the conjugated diene polymer segment (A) include styrene, o-methylstyrene, p-methylstyrene, m -Methylstyrene,
2,4-dimethylstyrene, ethylstyrene, p-te
rt-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, 2-methyl-1,4-dichlorostyrene , 2,4-
Dibromostyrene, aromatic vinyl such as vinylnaphthalene, ethylene, propylene, olefins such as 1-butene, cyclopentene, dicyclopentadiene, 2-norbornene, cyclic olefins such as 5-ethylidene-2-norbornene, 1,5-hexadiene, Non-conjugated dienes such as 1,6-heptadiene and 1,7-octadiene;
Methyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide and the like are included.

In the production of the conjugated diene polymer segment (A) of the present invention, the conjugated diene-based polymer segment (a) and the co-catalyst (b) are conjugated with a conjugated diene in the presence of a catalyst which has been previously contacted (aged). The monomer or conjugated diene monomer and a monomer copolymerizable therewith are polymerized. By performing aging in advance in this way, not only the polymerization activity and the efficiency of the initiator are improved, but also the obtained polymer is obtained. The molecular weight distribution of the coalescence can be further narrowed. In particular,
Aging and polymerization are performed by the following methods (1) to (7), and each component is a solution (1), (5) to
(7) is preferred, and (1) is most preferred.

(1) After the component solution (a) and the component solution (b) are brought into contact in advance, polymerization is carried out by bringing the solution into contact with a monomer. (2) After the component solution (a) and the component slurry (b) are brought into contact in advance, polymerization is carried out by bringing the component solution into contact with the monomer. (3) After the component (a) component slurry and the component solution (b) are brought into contact in advance, polymerization is carried out by further contacting with the monomer. (4) After the component slurry (a) and the component slurry (b) are brought into contact in advance, polymerization is carried out by further contacting with a monomer. (5) bringing the (a) component solution into contact with the (b) component solution;
After further contact with the carrier, the generated supported catalyst is separated, and the supported catalyst is brought into contact with the monomer to carry out polymerization. (6) After bringing the component solution and the carrier into contact, the component (b) is further brought into contact with the component solution to separate the generated supported catalyst, and the supported catalyst is brought into contact with the monomer to carry out polymerization. (7) After bringing the component solution and the carrier into contact with each other, the component (a) is further brought into contact with the component solution, the generated supported catalyst is separated, and the supported catalyst is brought into contact with the monomer to carry out polymerization.

The component (a) and the component (b) can be used in the form of either a solution or a slurry, respectively, but are preferably in the form of a solution in order to obtain a higher polymerization activity. Solvents used for preparing solutions or slurries include hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene, xylene, and halogens such as chloroform, methylene chloride, dichloroethane, and chlorobenzene. It is a chlorinated hydrocarbon solvent. Preferred solvents are aromatic hydrocarbons such as toluene and benzene.

The contact temperature of component (a) with component (b) (T,
C) is from -100 to 80C, preferably from -80 to 70C. The contact time (t, min.) Is 0.017 <t <6.
000 exp (−0.0921 T), and 0.083 <t <4000 exp (−0.092 T).
1T), more preferably 0.17 <t <
It is particularly preferable to satisfy 2000 exp (-0.0921T). At a high temperature of 80 ° C. or higher, the desired aging effect cannot be obtained, and at a low temperature of −100 ° C. or lower, there is a disadvantage in economy. t> 6000exp (-0.0921T)
The desired aging effect cannot be obtained with the aging time of, and the aging time of 0.017> t makes it difficult to perform a practical operation.

The amount of the catalyst used for forming the conjugated diene polymer segment (A) in the present invention is usually in the range of 100 parts per mole of the monomer.
-0.01 mmol, preferably 10-0.1 mmol, more preferably 5-0.2 mmol.
The polymerization reaction when a specific polymerization temperature is applied is a so-called living polymerization system. Therefore, the molecular weight of the resulting polymer can be regulated by the ratio of the transition metal compound to the monomer. The amount of the transition metal compound (a) per 1 mol of the monomer is particularly preferably 5 to 0.2 mmol per mol of the monomer to obtain a polymer which is preferable as a rubber material. Then, with this amount of catalyst used, a polymer having a particularly narrow molecular weight distribution can be obtained.

The molar ratio of aluminum / transition metal compound in the aluminoxane is usually 10 to 10,000, preferably 100 to 5,000, and the molar ratio of ionic compound / transition metal compound is usually 0.01 to 100, preferably Is 0.
1 to 10. Further, when the organic metal compound is used in common, the molar ratio of the organic metal compound / transition metal compound is usually 0.1 to 10,000, preferably 1 to 1,000.

In the present invention, the polymerization of the conjugated diene monomer for forming the conjugated diene-based polymer segment (A), or the conjugated diene monomer and a monomer copolymerizable therewith, is carried out by using an inert hydrocarbon. In addition to a solution polymerization method in a system solvent, a slurry polymerization method, and a bulk polymerization method using a monomer as a diluent, a gas phase polymerization method in a gas phase stirring tank or a gas phase fluidized bed can also be employed. Among these methods, the solution polymerization method is preferable in terms of maintaining living polymerizability and producing a polymer having a narrow molecular weight distribution. The polymerization temperature is -100 to 100C, preferably -80 to 80C, more preferably -60C to 60C.
It is. The temperature is preferably lower from the viewpoint of advancing living polymerization and the production of a polymer having a narrow molecular weight distribution by increasing the rate of the initiation reaction for the growth reaction. On the other hand, it is not preferable to use an extremely low temperature in terms of manufacturing cost. The polymerization time is 1 second to 360 minutes, and the polymerization pressure is normal pressure to 30 kg / cm ² . The inert hydrocarbon solvent used is the same as described above.

Further, the polymerization activity is improved, the shape of the solid catalyst of the produced polymer is maintained, the catalyst can be easily introduced into the polymerization reaction vessel,
For the purpose of preventing the catalyst from adhering to the polymerization reaction vessel, improving the fluidity in the gas phase reaction vessel, etc., butadiene may be preliminarily polymerized according to the above-mentioned various polymerization methods and used as a catalyst in the main polymerization. .

In order to adjust the molecular weight of the conjugated diene polymer segment (A), a chain transfer agent may be added. As the chain transfer agent, those generally used in the polymerization reaction of cis-1,4-polybutadiene rubber are used. In particular, allenes such as 1,2-butadiene, cyclic dienes such as cyclooctadiene, and hydrogen Is preferably used.

The termination of the polymerization reaction for obtaining the conjugated diene polymer segment (A) is usually carried out by adding a polymerization terminator to the polymerization system when a predetermined conversion is reached. Examples of the polymerization terminator include methanol,
Alcohols such as ethanol, propanol, butanol and isobutanol are used, and they may contain acids such as hydrochloric acid.

The method of recovering the conjugated diene-based polymer segment (A) after the termination of the polymerization reaction is not particularly limited, and for example, a steam stripping method, precipitation with a poor solvent, or the like may be used.

Among the above-mentioned conjugated diene-based polymer segments (A), particularly preferred conjugated diene-based polymer segments include a repeating unit derived from 1,3-butadiene of 50% by weight or more, preferably 70% by weight. The above, more preferably 80% by weight or more, particularly preferably 90% by weight or more of a copolymer segment or a 1,3-butadiene homopolymer segment, most preferably
It is a homopolymer segment of 1,3-butadiene. If the number of repeating units derived from butadiene is too small, preferable properties based on the large number of cis bonds are impaired. If the cis bond is too small, problems such as a decrease in tensile strength occur, and the rubber loses its desirable properties. Here, the cis bond is a 1,4-cis bond.

The weight average molecular weight (Mw) of the conjugated diene polymer segment (A) is from 1,000 to 9,500,000
0, preferably 5,000 to 4,500,000, more preferably 10,000 to 3,000,000, and particularly preferably 20,000 to 2,000,000. If the molecular weight is too small, the physical properties as a polymer such as low mechanical strength become insufficient, and conversely, if the molecular weight is too large, molding becomes difficult.

[Regarding Crystalline Segment (B)] The melting point of the crystalline segment (B) is not particularly limited, but is preferably room temperature or higher. Further, the crystalline segment may be a block copolymer or a part of the molecular chain.

The crystalline segment (B) is not particularly limited, but may be polyethylene, polypropylene, 1,2-polybutadiene, 1,2-syndiotactic polybutadiene, high cis polyisoprene, syndiotactic polystyrene, isotactic polystyrene, or the like. Saturated hydrocarbons, polyvinyl isobutyl ether, polyoxymethylene, polyethylene oxide, ethylene oxide-allyl glycidyl ether copolymer, ethylene oxide
Polyethers such as epichlorohydrin copolymer, ethylene oxide-propylene oxide copolymer, ethylene oxide-propylene oxide-epichlorohydrin copolymer, ethylene oxide-propylene oxide-allyl glycidyl ether copolymer, syndiotactic poly Polyamides such as methyl methacrylate, isotactic polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylene terephthalate, polyvinylidene chloride, nylon, triacetyl cellulose, tributyl cellulose, polyacrylonitrile, etc. Can be mentioned. Preferably, it has partial crystallinity having a melting point higher than room temperature, such as saturated hydrocarbons such as polyethylene, polyethers, syndiotactic polymethyl methacrylate, isotactic polymethyl methacrylate, and polyethylene terephthalate (co). Polymers are preferred, and polyethylene, polypropylene, syndiotactic polystyrene and polyethers are particularly preferred.

[(Co) polymer of (ii)] The (co) polymer (ii) is usually a diene-based polymer of 0 to 50% by weight of an aromatic monovinyl monomer and 100 to 50% by weight of a conjugated diene monomer. (Co) polymer. The amount of aromatic monovinyl monomer is preferably 0.1-45% by weight,
More preferably, the content is 0.5 to 40% by weight.

The terminal or / and part of the main chain of the polymer may be represented by -C (= M) -N <(where M represents an oxygen or sulfur atom), -C-N <bond, -OH group By using a (co) polymer modified with at least one selected from the group consisting of quaternary amino groups, the heat generation characteristics can be further improved.

The molecular weight of the (co) polymer (ii) is 100,000 to 2,000 in terms of weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography.
00,000, preferably 150,000 to 1,50
0000, more preferably 200,000 to 1,20
It is in the range of 0000. If the weight-average molecular weight (Mw) of the (co) polymer is too small, heat generation and abrasion resistance are poor, and if it is too large, processability is poor.

The method for producing the (co) polymer (ii) of the present invention is not particularly limited. For example, (a) a conjugated diene or a conjugated diene can be prepared by using an organic active metal as an initiator in a hydrocarbon solvent. A method of (co) polymerizing a conjugated diene and an aromatic vinyl is exemplified. As another method, a (co) polymer having an active metal bonded to a polymer chain terminal obtained by the above polymerization method is reacted with a modifier (Y) to introduce a tertiary amino group into the polymer chain terminal. And then reacting with an alkylating agent, or (b) (co) polymerizing a conjugated diene or a conjugated diene and aromatic vinyl as an organic active metal amide initiator in a hydrocarbon solvent, and then alkylating the alkylating agent. And the like. Other modification methods include the following. That is, the method of introducing an -OH group at the molecular chain terminal is disclosed in
It can be produced by reacting ethylene oxide and propylene oxide with the active terminal of living polymerization by the method of 188501 and the like. Further, when it is put in a molecular chain, it is necessary to add a -C (-M-) N <bond or a -CN <bond to JP-A-64-22940 and JP-A-1-101344.
JP, JP-A-59-191705, JP-A-60-191705
JP-137913, JP-A-62-86074, JP-A-62-109801, JP-A-62-1
It can be introduced into a polymer by a method such as that described in US Pat. A quaternizing method is disclosed in JP-A-9-227.
628 publication. Further, -OH group and-
Japanese Patent Laid-Open No. 9-1 describes a method for simultaneously introducing C—N <bonds.
No. 83820 and the like.

As the organic active metal used in the production method (a), those generally used in anionic polymerization are used, and examples thereof include organic alkali metals, organic alkaline earth metals, and organic acid lanthanoid series rare earth metals. . Among these, organic alkali metals are particularly preferred.

As the organic alkali metal, for example,
n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium,
Monoorganic lithium compounds such as stilbene lithium; polyfunctional organic lithium compounds such as dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene; sodium naphthalene, potassium And naphthalene. Among these, organolithium compounds are preferred,
Monoorganic lithium compounds are particularly preferred.

As the organic alkaline earth metal, for example,
n-butyl magnesium bromide, n-hexyl magnesium bromide, ethoxy calcium, calcium stearate, t-butoxystrontium, ethoxy barium, isopropoxy barium, ethyl mercapto barium, t-butoxy barium, phenoxy barium, diethyl amino barium, barium stearate, ethyl Barium and the like can be mentioned.

Examples of the organic acid lanthanoid series rare earth metals include a composite catalyst composed of neodymium versatate / triethylaluminum hydride / ethylaluminum sesquichloride as described in JP-B-63-64444.

These organic active metals can be used alone or in combination of two or more. The amount of the organic active metal used is appropriately selected depending on the required molecular weight of the produced polymer, and is usually 0.01 to 20 mmol, preferably 0.05 to 15 mmol per 100 g of the monomer.
Mmol, more preferably 0.1 to 10 mmol.

The polymerization reaction for obtaining the (co) polymer (ii) using the organic active metal as an initiator is carried out in a hydrocarbon solvent which does not destroy the initiator. Suitable hydrocarbon solvents are not particularly limited as long as they are used in ordinary solution polymerization. For example, n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, iso- Aliphatic hydrocarbons such as octane; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene and toluene; and the like, preferably n-hexane, cyclohexane, toluene and the like. is there. If necessary, an unsaturated hydrocarbon having a low polymerizability such as 1-butene, cis-2-butene and 2-hexene may be used.
These hydrocarbon solvents are used alone or in combination of two or more, and usually have a monomer concentration of 1 to 30.
It is used in an amount ratio that results in weight%.

In order to adjust the microstructure of the conjugated diene bond unit or the distribution of the aromatic vinyl to be copolymerized with the conjugated diene in the copolymer chain in the polymerization reaction for obtaining the (co) polymer (ii). A polar compound can be used. The polar compound is not particularly limited as long as it is used in ordinary anionic polymerization using an organic active metal as an initiator. Examples thereof include ethers; tertiary amines; potassium-t-amyl oxide, and potassium-t. Alkali metal alkoxides such as -butyl oxide; phosphines such as triphenylphosphine; and the like. Of these, tertiary amines and ethers are preferred.
Particularly preferred are secondary amines and diethers having two oxy groups.

The tertiary amines include, for example, tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, quinuclidine and the like, preferably tetramethylethylenediamine.

Examples of the ether compound include a monoether compound having one ether bond in the molecule, a diether compound having two ether bonds in the molecule, and a polyvalent ether compound having three or more ether bonds in the molecule. And most preferably a diether compound. The carbon number of the ether compound is not particularly limited, but is usually in the range of 2 to 100, preferably 3 to 50, more preferably 4 to 20, and most preferably 4 to 15.

Examples of the monoether compound include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, methyl butyl ether, methyl isoamyl ether, ethyl Aliphatic monoethers such as propyl ether, ethyl isopropyl ether and ethyl butyl ether; anisole;
Aromatic monoethers such as phenetole, diphenyl ether, dibenzyl ether; tetrahydrofuran,
Cyclic monoethers such as tetrahydropyran; among them, aliphatic monoethers and cyclic monoethers are preferable.

Examples of the diether compound include alkylene glycol diethers, cyclic diethers, etc., preferably alkylene glycol diethers. The carbon number of the diether compound is not particularly limited, but is usually 4 to 30, preferably 4 to 20, and more preferably 4 to 15.

As the alkylene glycol diether,
For example, alkylene glycol dialkyl ethers,
Examples thereof include alkylene glycol alkylaryl ethers, alkylene glycol diaryl ethers, and alkylene glycol diaralkyl ethers, and preferably alkylene glycol dialkyl ethers. Preferred alkylene glycol diethers include, for example, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol diamyl ether, ethylene glycol dioctyl ether, propylene glycol dimethyl ether Propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, isopropylene glycol dimethyl ether, isopropylene glycol diethyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether, butylene glycol dibutyl glycol, etc. Alkylene glycol diaryl ethers such as ethylene glycol methyl phenyl ether; alkylene glycol diaryl ethers such as ethylene glycol diphenyl ether; alkylene glycol diaralkyl ethers such as ethylene glycol dibenzyl ether; . Among these, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol diamyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene Glycol dibutyl ether and the like are particularly preferred, and ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol butyl t-butyl ether, ethylene glycol diamyl ether And Tel is most preferable.

Examples of the cyclic diether include dioxane, 1,10-phenanthroline and the like, and dioxolan alkanes described in US Pat. No. 4,429,091 such as bis (2-oxolanyl) methane.
2,2-bis (2-oxolanyl) propane, 1,1-
Bis (2-oxolanyl) ethane, 2,2-bis (5-
Methyl-2-oxolanyl) propane, and the like,
Among these, dioxane and dioxolane alkanes are preferable.

Examples of the polyvalent ether compound include oligooxyalkylene glycol dialkyl ethers, oxolanyl dioxane, oxolanyl dioxolan, crown ether and the like.

Examples of the oligooxyalkylene glycol dialkyl ether include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dihexyl ether, triethylene glycol dimethyl ether, triethylene glycol dipropyl glycol, and triethylene glycol dialkyl ether. Butyl ether,
Oligooxyethylene glycol dialkyl ethers such as tetraethylene glycol diethyl ether; oligooxypropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, diisopropylene glycol diamyl ether; Oligooxybutylene glycol dialkyl ethers such as dibutylene glycol dimethyl ether; and the like. Among these,
Oligooxyethylene glycol dialkyl ethers are preferred, and diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol dibutyl ether, tetraethylene glycol diethyl ether and the like are particularly preferred.

Examples of the polyoxyalkylene glycol dialkyl ethers include polyoxyethylene glycol dimethyl ether, polyoxyethylene glycol diethyl ether, polyoxyethylene glycol diisopropyl ether, polyoxyethylene glycol dibutyl ether, polyoxyethylene glycol dioctyl ether and the like. Polyoxyethylene glycol dialkyl ethers; polyoxypropylene glycol dialkyl ethers such as polyoxypropylene glycol dimethyl ether and polyoxypropylene glycol diethyl ether; and polyoxybutylene glycol dialkyl ethers such as polyoxybutylene glycol dimethyl ether.

The oxolanyl dioxane and oxolanyl dioxolane include, for example, Japanese Patent Publication No. 7-7424.
No. 5, No. 5, No. 5, and specifically, for example, 2- (2-oxolanyl) dioxane,
-(2-oxolanyl) -4,4,6-trimethyldioxane, 2- (5-methyl-2-oxolanyl) -4,
4,6-trimethyldioxane, 2- (2-oxolanyl) -5,5-dimethyldioxane, 2- (2-oxolanyl) dioxolan, 2- (2-oxolanyl) -4
-T-butyloxolane, 2- (2-oxolanyl)-
4,5-dimethyldioxolan, 2- (2-oxolanyl) -4,4,5,5-tetramethyldioxolan and the like can be mentioned.

The crown ethers include, for example, 1
8-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, dibenzo-1
8-crown ether, dibenzo-24-crown-8
-Ether, dicyclohexano-18-crown-6
Ether, 4'-nitrobenzo-15-crown-5
Ether and the like.

These polar compounds can be used alone or in combination of two or more. The amount of the polar compound to be used is generally 0 to 200 mol, preferably 0.1 to 100 mol, more preferably 0.5 to 50 mol, per 1 mol of the initiator (organic active metal or organic active metal amide). , Most preferably 0.8 to 20 mol.

When the conjugated diene and the aromatic vinyl are used in combination to obtain the (co) polymer (ii), the proportion of each monomer in all the monomers is such that the conjugated diene is usually 40 to 95%. % By weight, preferably 50-90% by weight, more preferably 55% by weight.
To 85% by weight, and the amount of the aromatic vinyl is usually 60 to 5% by weight, preferably 50 to 10% by weight, and more preferably 45 to 15% by weight.

The polymerization reaction for obtaining the (co) polymer (ii) is usually carried out in a batch mode or a continuous mode in a temperature range of -78 to 150 ° C. Further, when aromatic vinyl is copolymerized, in order to improve the randomness of the aromatic vinyl unit, for example, JP-A-59-14021
No. 1 and JP-A-56-143209, conjugated diene or conjugated diene so that the aromatic vinyl content in the composition ratio of aromatic vinyl and conjugated diene in the polymerization system falls within a specific concentration range. It is desirable to supply the mixture of the conjugated diene and the aromatic vinyl to the reaction system continuously or intermittently. Thus, a polymer having an active metal bonded to the terminal of the polymer chain (hereinafter referred to as an active polymer) is obtained.

Specific examples of the (co) polymer (ii) include polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, and styrene-butadiene-
An example is an isoprene copolymer.

Preferred examples of the modifying agent (Y) include, for example, a compound having a functional group that reacts with an active metal and a tertiary amino group in the molecule (hereinafter, referred to as "modifying agent Y-α"). Compound having an N-substituted nitrogen-carbon double bond in the molecule (hereinafter, referred to as "denaturing agent Y-β")
And the like.

The functional group in the modifying agent Y-α is not particularly limited as long as it reacts with the above-mentioned active polymer. Is mentioned. The tertiary amino group in the modifier Y-α is not particularly limited.

Preferred examples of the modifier Y-α include a compound having a vinyl group and a tertiary amino group in the molecule, and a compound having a carbonyl group and a tertiary amino group in the molecule.

Compounds having a vinyl group and a tertiary amino group in the molecule include, for example, N, N-disubstituted aminoalkyl acrylate, N, N-disubstituted aminoalkylacrylamide, N, N-disubstituted amino aromatic Group vinyl compounds and vinyl compounds having a pyridyl group.

Examples of the N, N-disubstituted amino acrylate include N, N-dimethylaminomethyl (meth) acrylate, N-methyl-N-ethylamino (meth) acrylate, and N, N-dimethylaminoethyl (meth) ) Acrylate, N, N-dimethylaminopropyl (meth)
Acrylate, N, N-dimethylaminobutyl (meth)
Acrylate, N, N-diethylaminoethyl (meth)
Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate N, N-dibutylaminoethyl (meth) acrylate, N, N-dibutylaminopropyl (meth) acrylate, N, N-dibutylaminobutyl (meth) acrylate, N, N-dihexylaminoethyl (meth) acrylate, N And esters of acrylic acid or methacrylic acid such as N, N-dioctylaminoethyl (meth) acrylate and acryloylmorpholine. Among them, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth) Acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate and the like are preferred.

Examples of the N, N-disubstituted aminoalkylacrylamide include N, N-dimethylaminomethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) ) Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N , N-diethylaminobutyl (meth) acrylamide, N-methyl-
N-ethylaminoethyl (meth) acrylamide, N,
N-dipropylaminoethyl (meth) acrylamide,
N, N-dibutylaminoethyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N-dibutylaminobutyl (meth) acrylamide, N, N-dihexylaminoethyl (meth) acrylamide, An acrylamide compound such as N-dihexylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide or a methacrylamide compound is exemplified. Among them, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide and the like are preferable.

Examples of the N, N-disubstituted amino aromatic vinyl compound include N, N-dimethylaminoethylstyrene, N-methyl-N-ethylaminoethylstyrene,
Styrene derivatives such as N, N-diethylaminoethylstyrene, N, N-dipropylaminoethylstyrene, and N, N-dioctylaminoethylstyrene are exemplified.

In the compound having a carbonyl group and a tertiary amino group in the molecule, both groups may be adjacent to or separated from each other. As an adjacent compound, for example, N
-Substituted amides, N-substituted imides, N-substituted ureas,
Examples thereof include N-substituted isocyanuric acids, and preferred are these cyclic compounds. Compounds in which both groups are separated include, for example, N-substituted amino ketones,
And substituted amino aldehydes.
-Substituted aminoketones.

The N-substituted cyclic amides include, for example,
N-methyl-β-propiolactam, N-phenyl-β
-Propiolactam, N-methyl-2-pyrrolidone, N
-Vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, Nt-butyl-2-pyrrolidone, N-methyl-
5-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-vinyl-2-piperidone, N-phenyl-2
-Piperidone, N-methyl-ε-caprolactam, N-
Phenyl-ε-caprolactam, N-methyl-ω-laurylolactam, N-vinyl-ω-laurylolactam and the like. Among these, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-
2-pyrrolidone, N-methyl-piperidone, N-vinyl-2-piperidone, N-methyl-ε-caprolactam,
N-phenyl-ε-caprolactam is preferred.

Examples of the N-substituted cyclic ureas include:
1,3-dimethylethylene urea, 1,3-divinylethylene urea, 1,3-diethyl-2-imidazolidinone,
1-methyl-3-ethyl-2-imidazolidinone and the like, preferably 1,3-dimethylethylene urea,
1,3-divinylethylene urea and the like.

Examples of the N-substituted amino ketones include, for example, 4-N, N-dimethylaminoacetophenone,
N-methyl-N-ethylaminoacetophenone, 4-
N, N-diethylaminoacetophenone, 1,3-bis (diphenylamino) -2-propanone, 1,7-bis (methylethylamino) -4-heptanone, 4-N, N
-Dimethylaminobenzophenone, 4-N, N-di-t
-Butylaminobenzophenone, 4-N, N-diphenylaminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (diphenylamino) benzophenone, etc. Is mentioned. Among these, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (diphenylamino) benzophenone and the like are particularly preferable.

The N-substituted aminoaldehydes include, for example, 4-N, N-dimethylaminobenzaldehyde,
4-N, N-diphenylaminobenzaldehyde, 4-
And N-substituted aminoaldehydes such as N, N-divinylaminobenzaldehyde.

In the compound having a carbonyl group and an amino group in the molecule, both groups may be adjacent to or separated from each other. Adjacent compounds include, for example, amides, imides, ureas, isocyanuric acids and the like, preferably these cyclic compounds, more preferably N-substituted cyclic amides, N-substituted cyclic ureas and the like. is there. Examples of the compound in which both groups are apart include aminoketones and aminoaldehydes, preferably N-substituted aminoketones and N-substituted aminoaldehydes, and more preferably N-substituted aminoketones. .

The N-substituted cyclic amides include, for example,
N-methyl-β-propiolactam, N-phenyl-β
-Propiolactam, N-methyl-2-pyrrolidone, N
-Vinyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, Nt-butyl-2-pyrrolidone, N-methyl-
5-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-vinyl-2-piperidone, N-phenyl-2
-Piperidone, N-methyl-ε-caprolactam, N-
Phenyl-ε-caprolactam, N-methyl-ω-laurylolactam, N-vinyl-ω-laurylolactam and the like. Among these, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl-
2-pyrrolidone, N-methyl-piperidone, N-vinyl-2-piperidone, N-methyl-ε-caprolactam,
N-phenyl-ε-caprolactam is preferred.

As the N-substituted cyclic ureas, for example,
1,3-dimethylethylene urea, 1,3-divinylethylene urea, 1,3-diethyl-2-imidazolidinone,
1-methyl-3-ethyl-2-imidazolidinone and the like, preferably 1,3-dimethylethylene urea,
1,3-divinylethylene urea and the like.

Examples of the N-substituted amino ketones include 4-N, N-dimethylaminoacetophenone,
N, N-diethylaminoacetophenone, 1,3-bis (diphenylamino) -2-propanone, 1,7-bis (methylethylamino) -4-heptanone, 4-N, N
-Dimethylaminobenzophenone, 4-N, N-di-t
-Butylaminobenzophenone, 4-N, N-diphenylaminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (diphenylamino) benzophenone, etc. Is mentioned. Among these, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (diphenylamino) benzophenone and the like are particularly preferable.

Examples of N-substituted aminoaldehydes include 4-N, N-dimethylaminobenzaldehyde,
4-N, N-diphenylaminobenzaldehyde, 4-
And N-substituted aminoaldehydes such as N, N-divinylaminobenzaldehyde.

Examples of the compound having an N-substituted nitrogen-carbon double bond of the modifier Y-β include N-substituted carbodiimide and Schiff base.

Examples of the N-substituted carbodiimide include dimethylcarbodiimide, diethylcarbodiimide, dipropylcarbodiimide, dibutylcarbodiimide, dihexylcarbodiimide, dicyclohexylcarbodiimide, dibenzylcarbodiimide, diphenylcarbodiimide, methylpropylcarbodiimide, butylcyclohexylcarbodiimide, and ethylbenzylcarbodiimide. Propylphenylcarbodiimide, phenylbenzylcarbodiimide and the like. Among them, dicyclohexylcarbodiimide, diphenylcarbodiimide and the like are preferable.

Examples of the Schiff base include N-ethylethylideneimine, N-methylbenzylideneimine and N-ethylbenzylideneimine.
-Hexylcinnamylideneimine, N-decyl-2-ethyl-1,2-diphenylbutylideneimine, N-phenylbenzylideneimine, N-dodecylcyclohexaneimine, N-propyl-2,5-cyclohexadienimine, N- Methyl-1-naphthalenimine and the like.

These modifiers (Y) are used alone or in combination of two or more. The amount of the modifier (Y) used is appropriately selected depending on the required characteristics of the diene rubber, but is usually 0.1 to 0.1 per organic active metal.
The range is from 50 to 50 equivalents, preferably from 0.2 to 20 equivalents, more preferably from 0.3 to 10 equivalents. When the diene rubber (i) having a quaternary ammonium group is produced, the amount of the modifier (Y) to be used is generally 1 to 50 equivalents, preferably 1 to 20 equivalents, more preferably 1 to 10 equivalents, per organic active metal. 10
The range of equivalents. Further, in the present invention, since the effect of the modification by the quaternary ammonium group is great, the object can be achieved even if it is slightly introduced into the rubber component. In that case, the amount of the modifying agent (Y) used in the case of producing a diene rubber (iii) comprising a quaternary ammonium group-containing diene rubber (ii) and an unmodified diene rubber (ii-i) is Usually 0.1 to 0.9 equivalent per organic active metal,
Preferably 0.2-0.8 equivalents, more preferably 0.3
~ 0.7 equivalents.

For the modification reaction, the active polymer having an active metal bonded to the molecule may be brought into contact with the modifying agent (Y). When an active polymer is produced by a polymerization reaction,
Usually, a modification reaction is performed by adding a predetermined amount of a modifying agent (Y) to the active polymer solution before the termination of the polymerization. The reaction temperature and reaction time in the denaturation reaction can be selected in a wide range,
Generally, room temperature to 120 ° C. for several seconds to several hours. The modification ratio is usually appropriately selected from the range of 10 to 100%. The denaturation rate was measured by measuring the absorption intensity with a GPC differential refractometer (RI) and an ultraviolet-visible spectrophotometer (UV).
RI) and can be determined by a calibration curve created in advance.

As the organic active metal amide used in the production method (b), those obtained by reacting the organic active metal with a secondary amine in advance may be used.
No. 921, at least one
The organic active metal may be added in the presence of a part of the monomer and the secondary amine to form a polymer in the polymerization reaction system.

The secondary amine includes, for example, an aliphatic secondary amine compound, an aromatic secondary amine compound, a cyclic imine compound and the like, and preferably an aliphatic secondary amine compound and a cyclic imine compound.

Examples of the aliphatic secondary amine compound include dimethylamine, methylethylamine, methylpropylamine, methylbutylamine, methylamylamine, amylhexylamine, diethylamine, ethylpropylamine, ethylbutylamine, ethylhexylamine, dipropylamine , Diisopropylamine, propylbutylamine, dibutylamine, diamylamine,
Examples include dihexylamine, diheptylamine, dioctylamine, methylcyclopentylamine, ethylcyclopentylamine, methylcyclohexylamine, dicyclopentylamine, dicyclohexylamine, and the like. Among them, dimethylamine, methylethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine and the like are preferable.

Examples of the aromatic secondary amine compound include diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine, N-methylbenzylamine and N-ethylphenethylamine.

Examples of the cyclic imine compound include, for example, aziridine, acetylidine, pyrrolidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, hexamethyleneimine, Heptamethyleneimine, dodecamethyleneimine, coniine, morpholine, oxazine, pyrroline, pyrrole, azepine and the like. Among these, pyrrolidine, piperidine, 3-
Preferred are methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, hexamethyleneimine, heptamethyleneimine and the like.

Each of these secondary amines is
Alternatively, two or more kinds are used in combination.

When an organic active metal amide prepared by reacting an organic active metal with a secondary amine in advance is used, the amount of the organic active metal amide used is appropriately selected depending on the required molecular weight of the produced polymer. Per 100 g of monomer
Usually 0.1 to 30 mmol, preferably 0.2 to 15 m
mol, more preferably in the range of 0.3 to 10 mmol.

When an organic active metal and a secondary amine are added to a polymerization system to form an organic active metal amide in the system, the amount of the organic active metal used is appropriately selected depending on the required molecular weight of the produced polymer. Is usually 0.1 to 30 mmol, preferably 0.2 to 15 mmol per 100 g of the monomer.
1, more preferably in the range of 0.3 to 10 mmol. The amount of the secondary amine used at this time is usually 0.5 to 2 equivalents, preferably 0.8 to 1.5 equivalents to the organic active metal.
The equivalent is more preferably 1 to 1.2 equivalent.

The polymerization reaction in the production method (b) may be carried out according to a conventional method. For example, according to the method disclosed in JP-A-6-199921, an organic active metal is present in the presence of at least a part of the monomer. And a secondary amine compound. Other polymerization conditions are the same as the polymerization conditions of the above-mentioned production method (a).

In the method (b), after the completion of the polymerization reaction, it can be reacted with the modifying agent (X) and / or the polyfunctional coupling agent. Modifier (X) in this case
May use the above modifier (Y), or may use another modifier (Z). When the modifier (Y) is used, a polymer in which a tertiary amino group is introduced at two terminals of a polymer chain is obtained.

As the other modifier (Z), those used in ordinary anionic polymerization can be used.
No. 137913, JP-A-62-86074,
JP-A-62-109801, JP-A-62-149
Various modifiers disclosed in JP-A-708-708 and JP-A-64-22940 can be used.

Specific examples of the other modifier (C) include:
For example, ketones such as acetone, benzophenone and acetylacetone; aldehydes such as benzaldehyde; epoxies; cyclic imine compounds having 2 to 3 carbon atoms;

Examples of epoxies include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-iso-butane, 2,3-epoxybutane, 1,2-epoxyhexane, 1,2 -Epoxy octane, 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane,
1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy-2-pentylpropane,
3,4-epoxy-1-butene, 1,2-epoxy-5
-Hexene, 1,2-epoxy-9-decene, 1,2-
Epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclododecane, 1,2-epoxyethylbenzene, 1,2-epoxy-1-methoxy-2-methylpropane, glycidyl methyl ether, glycidyl ethyl ether, glycidyl Isopropyl d
And glycidyl allyl ether, glycidyl phenyl ether, glycidyl butyl ether and the like. Among these, ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-iso-butane, 2,3-epoxybutane, 1,2
-Epoxyhexane, 3,4-epoxy-1-butene,
Preferred are 1,2-epoxy-5-hexene, glycidyl methyl ether, glycidyl ethyl ether, glycidyl isopropyl ether, glycidyl allyl ether, glycidyl phenyl ether, glycidyl butyl ether and the like.

As the epoxies, epihalohydrins obtained by substituting at least one hydrogen atom of the epoxies with a halogen atom can be used. Examples of epihalohydrins include, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, 2,3-epoxy-1,1,1-trifluoropropane, 1,2-epoxy-1H, 1H, 2H, 3H, 3H, -heptadecafluoroundecane and the like are preferable, and epichlorohydrin and epibromohydrin are preferable.

Examples of the cyclic imine compound having 2 to 3 carbon atoms include N-unsubstituted aziridine compounds such as ethyleneimine and propyleneimine, and N-unsubstituted aziridine compounds such as trimethyleneimine.

These modifying agents (X) can be used alone or in combination of two or more. The amount of the modifier (X) used and the reaction conditions are the same as those of the specific example of the modifier (Y).

As the polyfunctional coupling agent, for example,
JP-A-56-143209, JP-A-56-173
No. 62, Japanese Patent Application Laid-Open No. 57-55912, Japanese Patent Application Laid-Open
Various polyfunctional coupling agents disclosed in, for example, JP-A-8-162605 can be used.

As specific examples of the polyfunctional coupling agent,
For example, tin dichloride, tin tetrachloride, tin tetrabromide, monomethyltrichlorotin, monoethyltrichlorotin, monobutyltrichlorotin, monohexyltrichlorotin,
Tin-based coupling agents such as dimethyldichlorotin, diethyldichlorotin, dibutyldichlorotin, dibutyldibromotin, tetramethoxytin, tetraethoxytin, tetrabutoxytin, bistrichlorostannylethane; silicon dichloride, silicon dibromide , Silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, monomethyltrichlorosilicon, monoethyltrichlorosilicon, monobutyltrichlorosilicon, monohexyltrichlorosilicon, monomethyltribromosilicon, dimethyldichlorosilicon, diethyldichlorosilicon, butyltrichlorosilicon , Dibutyldichlorosilicon, dihexyldichlorosilicon, dimethyldibromosilicon, tetramethoxysilicon, tetraethoxysilicon, tetrabutoxysilicon, diphenyldimethoxysilicon, diphenyl Jietokishikei arsenide, monochloro trimethoxy silicon, monobromo trimethoxy silicon, dichloro-dimethoxy silicon, dibromo-dimethoxy silicon, trichloromethoxy silicon, tribromometoxy silicon,
Silicon-based coupling agents such as alkyltriphenoxysilicon and bistrichlorosilylethane; metal halide-based coupling agents such as lead dichloride and germanium tetrachloride; unsaturated nitrile-based coupling agents such as ethylacrylonitrile; dichloromethane and dibromomethane , Dichloroethane, dibromoethane, dichloropropane, dibromopropane, dibromobenzene, dichlorobenzene,
Chloroform, tribromomethane, trichloroethane,
Halogenated hydrocarbon-based coupling agents such as trichloropropane, tribromopropane, carbon tetrachloride, and tetrachloroethane; methyl formate, ethyl formate, methyl acetate;
Ethyl acetate, propyl acetate, isopropyl acetate, amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, ethyl trimethyl acetate, methyl caproate, ethyl caproate, methyl benzoate, ethyl benzoate, dimethyl adipate, Diethyl adipate,
Ester coupling agents such as dimethyl terephthalate, diethyl terephthalate, dimethyl phthalate and dimethyl isophthalate; halide coupling agents such as terephthalic acid dichloride, phthalic dichloride, isophthalic dichloride, adipic dichloride; trisnonylphenylphospho Fight, trimethyl phosphite,
Phosphorus-based coupling agents such as triethyl phosphite; and the like. Among these, tin-based coupling agents, silicon-based coupling agents, ester-based coupling agents, halogenated hydrocarbon-based coupling agents, and the like are preferable, and tin-based coupling agents and silicon-based coupling agents are particularly preferable.

These polyfunctional coupling agents can be used alone or in combination of two or more. The amount of the polyfunctional coupling agent used can be appropriately selected depending on the required weight average molecular weight and the coupling ratio, the reactivity of the polyfunctional coupling agent, and the like.
The amount is usually 0.1 to 10 equivalents, preferably 0.2 to 5 equivalents, more preferably 0.3 to 2 equivalents, per organic active metal. The coupling reaction is usually performed at 0 to 150 ° C.
For 0.5 to 20 hours. The coupling ratio can be appropriately selected, but is usually 10 to 10.
The range is 100%. The coupling ratio can be determined from the area ratio between the high molecular weight and the low molecular weight of the differential refractometer by GPC measurement.

The reaction of the alkylating agent can be carried out in the same manner in any of the production method (a) and the production method (b).

Examples of the alkylating agent include alkyl nitrates such as methyl nitrate, ethyl nitrate, propyl nitrate and butyl nitrate; potassium alkyl sulfates such as potassium methyl sulfate and potassium ethyl sulfate; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; Aryl sulfonic acid alkyl esters such as aryl sulfonic acid methyl ester, aryl sulfonic acid ethyl ester and aryl sulfonic acid propyl ester; monohalides; and the like, preferably monohalides.

As the monohalide, for example, the following general formula (4)

Embedded image R ⁸ X (4) (wherein, R ⁸ represents a lower alkyl group, an aryl group or an aralkyl group, and X represents a halogen atom). R ⁸ in the general formula (4) is the same as the specific example of R ^{3 in} the general formula (1). X in the general formula (4) is the same as the specific example of X in the general formula (1).

Preferred examples of the monohalide include:
For example, alkyl halides such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl iodide, butyl iodide, butyl bromide, hexyl iodide; benzyl chloride, benzyl bromide And benzyl halides such as benzyl iodide; and the like, and alkyl halides are preferable. Of the alkyl halides, lower alkyl halides are preferred, and methyl halide is particularly preferred. As the halogen atom, a chlorine atom, a bromine atom, an iodine atom and the like are preferable, and an iodine atom is particularly preferable.

These alkylating agents can be used alone or in combination of two or more. The amount of the alkylating agent to be used can be appropriately selected according to the requirement of the degree of quaternization, but it is usually 0.1 to 50 equivalents, preferably 0.1 to 50 equivalents per tertiary amino group contained in the diene polymer rubber.
The range is 2 to 20 equivalents, more preferably 0.3 to 10 equivalents. When the diene rubber (i) having a quaternary ammonium group of the present invention is produced, the amount of the alkylating agent is usually 1 to 50 per tertiary amino group contained in the diene polymer rubber. Equivalent, preferably in the range of 1 to 20 equivalents, more preferably 1.2 to 10 equivalents. Further, in the present invention, since the effect of the modification by the quaternary ammonium group is great, the object can be achieved even if it is slightly introduced into the rubber component. In this case, the amount of the alkylating agent used in the case of producing a diene rubber (iii) comprising a quaternary ammonium group-containing diene rubber (i) and a tertiary amine-containing diene rubber (ii-ii) is as follows: Usually 0.1 to 0.9 equivalent, preferably 0.2 to 0.8 equivalent, more preferably 0.3 to 0.7 equivalent per tertiary amino group content in the diene polymer rubber. is there.

The reaction of the alkylating agent is not particularly limited and may be carried out in accordance with a conventional method.
90 ° C., preferably 20-80 ° C., and the reaction time is:
It is usually 0.1 to 10 hours, preferably 0.5 to 5 hours.

Confirmation of quaternization after the completion of the reaction may be carried out by a conventional method, for example, by an ultraviolet (UV) absorption spectrum or a qualitative reaction of quinhydrone.

In the present invention, the quaternary ammonium group-containing diene rubber (ii) is obtained by (1) using a conjugated diene or a conjugated diene and aromatic vinyl in an organic solvent as an initiator in a hydrocarbon solvent. A (co) polymer having an active metal bonded to a polymer chain end obtained by (co) polymerization, and a tertiary amino group introduced into the polymer chain end by reacting with a modifier (Y), A production method for reacting an agent,
(2) a production method in which a conjugated diene or a conjugated diene and aromatic vinyl are (co) polymerized with an alkylating agent using an organic active metal amide as an initiator in a hydrocarbon solvent, (3) A) a conjugated diene or a (co) polymerization of a conjugated diene and aromatic vinyl in a hydrocarbon solvent using an organic active metal amide as an initiator, followed by a modifier (X) and / or a polyfunctional coupling agent; And then reacting with an alkylating agent.

Therefore, the diene rubber (ii) of the present invention
Is simply a copolymer of an aromatic vinyl monomer and a conjugated diene monomer, a diene rubber having a quaternary ammonium group at its terminal, a diene rubber at least part of which is coupled with a polyfunctional coupling agent, and And / or a diene rubber modified at least in part with a modifier X, and mixtures thereof.

[Conjugated Diene Rubber Composition Containing (i) and (ii)] The diene rubber mixture of the present invention contains the polymer (i) having the crystalline segment and the modifying group. Or diene rubber (ii)
And The polymer (i) and the diene polymer (ii) each having a crystalline segment may be used alone or
More than one species can be used in combination. Other diene rubbers (iii) can be used alone or in combination of two or more in the above (i) and (ii). The diene rubber composition of the present invention comprises 2 to 90 parts by weight of the block copolymer (i), preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight, and 98 to 98 parts by weight of the diene polymer (ii). The amount is 2 parts by weight, preferably 98 to 10 parts by weight, more preferably 95 to 20 parts by weight, particularly preferably 90 to 30 parts by weight. If the amount of the block copolymer (i) is too large and the amount of the diene-based polymer (ii) is too small, abrasion and rebound resilience at 60 ° C. are deteriorated, and the amount of the block copolymer (i) is too small. If the amount of the system polymer (ii) is too large, abrasion, tensile stress, and rebound resilience at 0 ° C deteriorate.

Other diene rubbers (iii) include:
Although there is no particular limitation, a diene rubber used in a general rubber industry can be used. Specifically, for example,
Natural rubber (NR), polyisoprene rubber (IR), emulsion-polymerized styrene-butadiene copolymer rubber (SBR), solution-polymerized random SBR (bonded styrene 5 to 50% by weight, 1,2-vinyl bond amount in butadiene bond unit portion) 10-8
0%), high trans SBR (70-95% of 1,4-trans bond in butadiene bond unit portion), low cis polybutadiene rubber (BR), high cis BR, high trans BR
(Amount of 1,4-trans bond of butadiene bond unit portion is 7)
0-95%), styrene-isoprene copolymer rubber (SI
R), butadiene-isoprene copolymer rubber, solution-polymerized random styrene-butadiene-isoprene copolymer rubber (SIBR), emulsion-polymerized SIBR, emulsion-polymerized styrene-
Block copolymers such as acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, high vinyl SBR-low vinyl SBR block copolymer rubber, polystyrene-polybutadiene-polystyrene block copolymer, etc. Can be selected as appropriate. Among these, NR, BR, IR, SBR, S
IBR and the like are preferred. These other rubbers can be used alone or in combination of two or more.

In the present invention, the unmodified diene rubber (ii-i),
Includes tertiary amino group-containing diene rubbers (ii-ii), other modified diene rubbers, and mixtures thereof.

[Reinforcing Agent] The reinforcing agent that can be blended in the rubber composition of the present invention is not particularly limited. For example, silica, carbon black, calcium carbonate, magnesium carbonate, titanium oxide, or a surface-treated thereof is used. And the like.

The silica is not particularly limited, and examples thereof include dry-process white carbon, wet-process white carbon, colloidal silica, and precipitated silica disclosed in JP-A-62-62838. Among these, wet-process white carbon containing hydrated silicic acid as a main component is particularly preferable. These silicas can be used alone or in combination of two or more.

The specific surface area of silica is not particularly limited, but is usually 50 to 40 in terms of nitrogen adsorption specific surface area (BET method).
0 m ² / g, preferably from 100 to 250 m ² / g, when more preferably in the range of 120~190m ² / g, reinforcing property, wear resistance, is sufficiently achieved improvements in such heat build-up and processability, It is suitable. Here, the nitrogen adsorption specific surface area is a value measured by a BET method according to ASTM D3037-81.

The carbon black is not particularly limited. For example, furnace black, acetylene black, thermal black, channel black, graphite and the like can be used. Among these, furnace black is particularly preferred, and specific examples thereof include:
SAF, ISAF, ISAF-HS, ISAF-LS,
IISAF-HS, HAF, HAF-HS, HAF-L
Examples include various grades such as S and FEF. These carbon blacks can be used alone or in combination of two or more.

The nitrogen adsorption specific surface area of carbon black (N
2SA) is not particularly limited, but is usually 5 to 200 m ² /
g, preferably in the range of 50 to 150 m ² / g, more preferably in the range of 80 to 130 m ² / g, since the tensile strength and abrasion resistance are improved at a high level, which is suitable. The DBP adsorption amount of carbon black is not particularly limited, but is usually 5 to 300 ml / 100 g, preferably 50 to 200 ml.
ml / 100 g, more preferably 80-160 ml / 1
When it is in the range of 00 g, the tensile strength and abrasion resistance are improved at a high level, which is preferable.

As carbon black, JP-A-5-23
No. 0290, the adsorption (CTAB) specific surface area of cetyltrimethylammonium bromide is 110 to 110.
Abrasion resistance can be further improved by using high-structure carbon black having a DBP (24M4DBP) oil absorption of 110 to 130 ml / 100 g after being repeatedly compressed at 170 m ² / g at a pressure of 24,000 psi four times. .

As surface-modified carbon, JP-A-10-7
If a composite carbon black containing a silica component is used as in JP-A-929-129, the modifying effect is further improved.

The mixing ratio of the reinforcing agent is not particularly limited, but is usually 10 parts by weight or more based on 100 parts by weight of the rubber component.
It is preferably at least 20 parts by weight, more preferably at least 30 parts by weight, and usually at most 200 parts by weight, preferably at most 1 part by weight.
The amount is 50 parts by weight or less, more preferably 120 parts by weight or less.

To achieve the object of the present invention to a high degree,
As the reinforcing agent, it is preferable to use silica alone or in combination with silica and other reinforcing agents such as carbon black, calcium carbonate, magnesium carbonate, and titanium oxide. When silica and another reinforcing agent such as carbon black are used in combination, the mixing ratio is appropriately selected according to the application and purpose, but usually, silica: another reinforcing agent such as carbon black = 10: 90 to 99. : 1, preferably 30:70 to 95: 5, more preferably 50:50 to 9
0:10 (weight ratio).

In the present invention, the addition of a silane coupling agent further improves the heat generation and abrasion resistance.
It is suitable.

The silane coupling agent is not particularly restricted but includes, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl)- γ-aminopropylmethyldimethoxysilane, N
-Phenyl-γ-aminopropyltrimethoxysilane,
γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis [3- (triethoxysilyl)
Propyl] tetrasulfide and JP-A-6-2481
There can be mentioned tetrasulfides such as γ-trimethoxysilylpropyldimethylthiocarbamyltetrasulfide and γ-trimethoxysilylpropylbenzothiazyltetrasulfide described in JP-A-16.

[0130] These silane coupling agents can be used alone or in combination of two or more. The mixing ratio of the silane coupling agent is usually 0.1 to 30 parts by weight with respect to 100 parts by weight of silica,
Preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight
It is in the range of parts by weight.

The rubber composition of the present invention comprises, in addition to the above components,
According to a conventional method, necessary amounts of other compounding agents such as a vulcanizing agent, a vulcanization accelerator, a vulcanizing activator, an antioxidant, an activator, a plasticizer, a lubricant, and a filler can be respectively contained.

The vulcanizing agent is not particularly restricted but includes, for example, powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur,
Sulfur such as highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; organic peroxides such as dicumyl peroxide and ditert-butyl peroxide; p-quinone dioxime, p, p'-di Quinone dioximes such as benzoylquinone dioxime; organic polyamine compounds such as triethylenetetramine, hexamethylenediamine carbamate and 4,4'-methylenebis-o-chloroaniline; alkylphenol resins having a methylol group; Of these, sulfur is preferred, and powdered sulfur is particularly preferred. These vulcanizing agents are used alone or in combination of two or more.

The compounding ratio of the vulcanizing agent is usually 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the rubber component. Range. When the compounding ratio of the vulcanizing agent is in this range, it is particularly preferable because it is excellent in tensile strength and wear resistance and also excellent in properties such as heat resistance and residual strain.

Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide,
-T-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N, N'-diisopropyl-2-
Sulfenamide-based vulcanization accelerators such as benzothiazolesulfenamide; guanidine-based vulcanization accelerators such as diphenylguanidine, diortitolylguanidine, ortho-tolylbiguanidine; thiocarbanilide, diortitolylthiourea, ethylenethiourea, diethyl Thiourea-based vulcanization accelerators such as thiourea and trimethylthiourea; 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole sodium salt,
Thiazole vulcanization accelerators such as mercaptobenzothiazole cyclohexylamine salt and 2- (2,4-dinitrophenylthio) benzothiazole; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, Thiuram-based vulcanization accelerators such as dipentamethylenethiuram tetrasulfide; sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butyldithiocarbamate, lead dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, -Zinc n-butyldithiocarbamate, zinc pentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, Acceleration of dithiocarbamic acid vulcanization such as tellurium tildithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, diethylamine diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, and pipecoline methylpentamethylenedithiocarbamate. Vulcanization accelerators such as sodium isopropyl xanthogenate, zinc isopropyl xanthate and zinc butyl xanthate; and the like.

Each of these vulcanization accelerators can be used alone.
Alternatively, two or more kinds are used in combination, and those containing at least a sulfenamide-based vulcanization accelerator are particularly preferable. The compounding ratio of the vulcanization accelerator is usually 0.1 to 15 parts by weight, preferably 0.1 part by weight, per 100 parts by weight of the rubber component.
It is in the range of 3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

The vulcanization activator is not particularly limited. For example, higher fatty acids such as stearic acid and zinc oxide can be used. As zinc oxide, for example,
It is preferable to use one having a high surface activity and a particle size of 5 μm or less.
Active zinc white of 5 to 0.2 μm and zinc white of 0.3 to 1 μm can be exemplified. As the zinc oxide, a zinc oxide surface-treated with an amine-based dispersant or wetting agent can be used.

These vulcanization activators can be used alone or in combination of two or more.
The mixing ratio of the vulcanization activator is appropriately selected depending on the type of the vulcanization activator. When higher fatty acids are used, rubber component 1
Usually, 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 00 parts by weight.
Parts by weight. When zinc oxide is used, the rubber component 10
The amount is usually 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight with respect to 0 parts by weight. When the mixing ratio of zinc oxide is within this range,
Properties such as workability, tensile strength and abrasion resistance are highly balanced and suitable.

Examples of other compounding agents include, for example, coupling agents other than silane coupling agents; activators such as diethylene glycol, polyethylene glycol and silicone oil; fillers such as calcium carbonate, talc and clay; process oils; Wax and the like.

The rubber composition of the present invention can be obtained by kneading the components according to a conventional method. For example, a rubber composition can be obtained by mixing a compounding agent excluding a vulcanizing agent and a vulcanization accelerator and a rubber component, and then mixing the mixture with a vulcanizing agent and a vulcanization accelerator. The mixing temperature of the compounding agent excluding the vulcanizing agent and the vulcanization accelerator and the rubber component is usually 80 to 200 ° C, preferably 100 to 190 ° C, and more preferably 140 to 18 ° C.
0 ° C., and the mixing time is usually 30 seconds or longer, preferably 1 to 30 minutes. Mixing of the vulcanizing agent and the vulcanization accelerator is usually performed after cooling to 100 ° C. or less, preferably from room temperature to 80 ° C., and then usually press-vulcanized at a temperature of 120 to 200 ° C., preferably 140 to 180 ° C. The rubber composition of the present invention can be obtained

[0140]

EXAMPLES The present invention will be described below with reference to Production Examples, Comparative Examples and Examples, but the present invention is not limited thereto.

Production Example 1 (Production Example of Polybutadiene of Comparative Example) In a 15-liter autoclave equipped with a jacket and a stirrer, 510 g of 1,3-butadiene dehydrated with Molecular Sieve 4A was added to 5100 cc of benzene.
The temperature was adjusted to 30 ° C. by adding 4.2 mmol of water. To this solution was added 28 parts of diethyl aluminum chloride (DEAC).
Mmol, cyclooctadiene (COD) 29.4 mmol, and cobalt octenoate 0.12 mmol were added and stirred for about 30 minutes. The polymer obtained at this time is 96
% Cis-butadiene rubber. Subsequently, 2.1 mmol of carbon disulfide, 8.4 mmol of acetone,
And 0.7 mmol of cobalt octenoate were added, and the mixture was further stirred for 30 minutes. The polymerization was stopped by adding 30 cc of methanol containing an antioxidant (BHT) and hydrochloric acid. After removing the solvent by a steam stripping method, the sample was dried under vacuum to obtain a sample. The thus obtained sample had a boiling n-hexane insoluble content of 9%, a 1,2 bond content of 90%, and a melting point of 199 ° C. The polymer is a mixture of high cis butadiene rubber and 9% partially crystalline 1,2-syndiotactic butadiene.

Production Example 2 (Production of Segment Copolymer of the Present Invention) In a sealed pressure-resistant glass ampoule having an internal volume of 800 ml, a toluene solution of 130 g of toluene and 33.5 mmol of methylaluminosane (MAO) was placed under a nitrogen atmosphere ( Tosoh Akzo). 2-methoxyethyl-cyclopentadienyl trichloro titanium (MeOCH ₂ CH ²
CpTiCl ₃ , hereinafter abbreviated as TiES) 0.0335 m
mol of a toluene solution was added dropwise and aged at 25 ° C. for 10 minutes. Thereafter, the temperature was lowered to -25 ° C, and
And a solution of 30 g of toluene were added thereto and polymerized at -25 ° C for 30 minutes. Continue adding 5 kg / cm of ethylene to this container.
A pressure of ² was applied to react for about 1 hour. Thereafter, the polymerization reaction was stopped with a small amount of acidic methanol solution, and then the polymerization solution was poured into a large amount of acidic methanol, and the precipitated white solid was collected by filtration and dried to obtain a block copolymer having a polybutadiene block and a polyethylene block. .

EXAMPLES, COMPARATIVE EXAMPLES, REFERENCE EXAMPLES Table 1 shows the compounding ratios of the compositions of the examples, comparative examples, and reference examples of the present invention (the compounding ratios are shown in parts by weight). The physical properties are shown in Tables 2 and 3, respectively.

The method of measuring the physical property data in the following table is as follows. The rebound resilience is JIS K630
According to No. 1, it was measured using a Lupke rebound resilience tester. For the 300% tensile stress, a 300% stress (kgf / cm ² ) was measured according to JIS K6301. The number of flex fatigue resistance is 2 mm according to JIS K6301.
The number of times until the cracks became 15 mm was measured. Abrasion resistance was measured using a pico abrasion tester according to ASTM D2228. Tables 2 and 3 are represented by relative indexes with Comparative Example 1 being 100. The processability was determined as follows: (a) the winding property of the rubber composition on a roll, (b) the smoothness of the molding surface, and (c) the shape maintenance during extrusion forming, the best point was 5 points, and the lowest point was 1 point. The points were evaluated on a 5-point scale, and indicated by the total points of (a), (b), and (c).

[0145]

[Table 1] Carbon black N220 is ASTM D1765-9
Carbon black satisfying the standard specified in
O # 1 is Zinc Hua No. 1, Nocrack 6C is Ouchi Emerging, Fuccoal M is Fujikosan, Sansera NS
Is a brand name of Sanshin Chemical Co., Ltd., and sulfur # 325 is mesh #
It is a sulfur powder having a particle size passing through 325.

[0146] Special notes concerning the following Tables 2 and 3 are as follows. * 1) BR1220 is a polybutadiene having a cis content of 95.2%, vinyl of 2.5%, Mw / Mn = 2.8 and Mw = 440,000, and Nipol BR1220 of Zeon Corporation.
(Product name). * 2) Polyethylene; high-density polyethylene, melting point 125
* 3) Production Example 2 is a segment copolymer comprising a butadiene block and an ethylene block corresponding to (i) the partially crystalline block copolymer rubber of the present invention, and the cis content of the butadiene segment is 92%. %, Tm = 127 ° C., and the ethylene segment accounts for 4.8% by weight of the whole. M
w / Mn = 1.4, Mw = 300,000 * 4), * 5), * 6) and * 7) all correspond to (ii) (co) polymer of the present invention. * 4) Nipol IR2200 is manufactured by Zeon Corporation.
High cis isoprene rubber with a cis content of 98% or more. * 5) Nipol 9529 is a high oil-extended styrene-butadiene rubber manufactured by Zeon Corporation, and is obtained by adding 50 parts by weight of a highly aromatic oil to 100 parts by weight of a styrene-butadiene rubber having a bound styrene content of about 43%. * 6), * 7) Solution polymerization SBR-A and B
The solution-polymerized SBR-A is made of 25% styrene, 50% vinyl,
A random SBR having a weight-average molecular weight Mw of 600,000 obtained by performing a 52% coupling reaction with nCl ₄ .
4'-bis- (diethylamino) benzophenone (EA
SBR modified in B).

[0147]

[Table 2] The vulcanization property values in Tables 2 and 3 are as follows except for the workability section.
This is a relative value when the data of rubber in proportional example 1 is set to 100.

[0148]

[Table 3]

(Discussion) Each physical property value is represented by an index with Comparative Example 1 being 100. However, the rebound at 0 ° C. is represented by a reciprocal index. The higher the value, the better. The workability was evaluated on a scale of 5 out of 5 points for roll winding property, surface smoothness, and die swell. As is clear from the comparison between Comparative Example 1 and Example 1, the balance of viscoelastic properties and strength properties,
It can be seen that both processability is excellent. Since the physical properties are not improved by blending the crystalline polyethylene as in Reference Example 1, and the processing characteristics are improved in the blend of 1,2-syndiotactic polybutadiene as in Comparative Example 2, It can be seen that the balance of the high physical properties by the block copolymer of the present invention cannot be maintained. From the above, it can be seen that the rubber composition of the present invention shows excellent balance of physical properties because it is a block copolymer of a crystalline segment. From the comparison between Examples 2 and 3, it can be seen that blending with the polymer obtained by the solution polymerization method has a better balance of physical properties, and Example 4 in which the molecular terminal is chemically modified has further improved physical properties. .

[0150]

According to the present invention, it is possible to provide a rubber composition which has good compatibility, excellent low-temperature rebound resilience, excellent tensile stress, and a sufficient wear index despite the composition comprising different rubber components. did it.

Claims (2)

[Claims] 1. (i) (A) a conjugated diene-based polymer segment having a high cis content of 40% or more,
A partially crystalline block copolymer rubber comprising 98% by weight and (B) 90 to 2% by weight of a crystalline segment, having a molecular weight distribution of 4 or less and a weight average molecular weight in terms of polystyrene of 20,000 to 10,000. 2,000,000 to 90 parts by weight of a block copolymer rubber of 0,000,000, and 98-2 parts by weight of a (co) polymer of (ii) 0-50% by weight of an aromatic monovinyl monomer and 100-50% by weight of a conjugated diene monomer. A conjugated diene-based rubber composition containing a crystalline segment, characterized by being contained. 2. The (co) polymer (ii) has a —C (＝ M) —N <bond (where M represents oxygen or sulfur) at its terminal and / or in the molecular chain. -N <bond,-
The conjugated diene rubber composition containing a crystalline segment according to claim 1, wherein the rubber composition contains at least one selected from the group consisting of an OH group and a quaternary amino group.