WO2008044722A1 - Oil extended rubber composition, method for producing the same, tire member, and tire - Google Patents

Abstract

Disclosed is a rubber composition excellent in wear resistance and low heat generation property. Also disclosed is a method for producing such a rubber composition, a tire member using such a rubber composition, and a tire. Specifically disclosed is an oil extended rubber composition containing 100 parts by weight of a rubber component essentially containing a conjugated diene polymer (P1) having at least a butadiene unit and 10-120 parts by weight of a process oil. The conjugated diene polymer (P1) has a Mooney viscosity of 65-200 (ML1+4, 100˚C) and a molecular weight distribution of 1.5-4.0, while having a cis-1,4-bond content of not less than 96.5% and a vinyl bond content of not more than 1.0% in the butadiene unit portion.

Description

 Specification

 Oil-extended rubber composition, method for producing the same, tire member and tire

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to an oil-extended rubber composition, a method for producing the same, a tire member and tire obtained therefrom. In more detail, an oil-extended rubber composition comprising a rubber component whose essential component is a specific conjugate polymer having a specific monomer composition, a specific microstructure and a specific molecular weight characteristic, and a method for producing the same The present invention also relates to a tire member comprising the oil-extended rubber composition and a tire provided with the tire member.

 Background art

 [0002] In general, rubber for tires needs to have an excellent balance of impact resilience, wear resistance, and low heat build-up, and as a result, polybutadiene with a molecular weight distribution that is as high as possible in the cis 1,4 bond content and narrow in molecular weight distribution. Is required. It is known that the use of a polymerization catalyst containing a lanthanum series metal such as neodymium is advantageous for the production of such polybutadiene (hereinafter sometimes referred to as “BR”). Has been done.

 [0003] For example, Patent Document 1 discloses a rubber composition containing a rubber having a glass transition temperature of 50 ° C or lower and a paraffin oil having a weight average molecular weight force of S500 or higher. Patent Document 2 discloses a rubber composition obtained by mixing paraffin oil with polybutadiene having a cis 1,4 bond content of 96% and a weight average molecular weight of 400,000. However, these rubber compositions have a problem in wear resistance although they are excellent in low temperature characteristics.

 Patent Documents 3 and 4 disclose rubber compositions containing polybutadiene having a high cis 1,4 bond content and oil having a roma content of 10% or less. However, this rubber composition had a problem of V and poor wear and low heat build-up.

 [0004] Patent Document 1: Japanese Patent Laid-Open No. 04-81438

 Patent Document 2: JP 2004 277506 A

 Patent Document 3: JP 2005-36065 A

 Patent Document 4: Japanese Patent Laid-Open No. 2005-154754

Disclosure of the invention Problems to be solved by the invention

[0005] Therefore, an object of the present invention is to provide an oil-extended rubber composition excellent in wear resistance and low heat build-up, and a method for producing the same.

 Another object of the present invention is to provide a tire member using the oil-extended rubber composition.

 Still another object of the present invention is to provide a tire provided with the tire member.

 Means for solving the problem

[0006] The present inventors have conducted extensive research to achieve the above object, and as a result, obtained lanthanum-based IJ metal compounds (A), organoaluminum compounds (B), organoaluminum hydride compounds (C), and halogen compounds. By using a polymerization catalyst comprising a specific ratio of organoaluminum compound and organoaluminum hydride compound in the polymerization catalyst comprising (D), a higher cis 1, 4 bond content and a narrower As a result of finding that a conjugated phene polymer having a molecular weight distribution can be obtained, and further research based on this finding, it is possible to obtain wear resistance by blending a specific amount of a specific process oil into the conjugated gen polymer. The present invention has been completed by finding that an oil-extended rubber composition excellent in heat resistance and low heat buildup can be obtained.

[0007] In other words, according to the present invention, a conjugated diene polymer having at least a butadiene unit, having a viscosity of 65 to 200 (ML, 100 ° C) and 1.5 to 4 ···. 0 molecular weight distribution

 1 + 4

And a conjugated unit polymer (P1) having a cis-1,4 bond content of 96.5% or more and a butyl bond content of 1.0% or less in the butadiene unit portion as an essential component 100 parts by weight and the process oil 10 to contain Aroma content of 5 wt _^0/0 or more; oil-extended rubber composition comprising 120 parts by weight is provided.

 In the oil-extended rubber composition of the present invention, the conjugate polymer (P1) has a Mooney viscosity (Μ L, 100 ° C) force of S75 to 175 and a molecular weight distribution of 2.0 to 3.5. Butadiene unit

1 + 4

 It is preferable that the cis 1,4 bond content in the portion is 97.5% or more and the bull bond content is 0.9% or less! /.

In the oil-extended rubber composition of the present invention, the butadiene in the conjugated polymer (P1) The unit ratio is preferably 80% by weight or more.

 In the oil-extended rubber composition of the present invention, the conjugate polymer (P1) is composed of a lanthanum series metal compound (A), an organoaluminum compound (B), an organoaluminum hydride compound (C), and a halogen compound (D). It is preferably obtained by polymerizing a monomer containing butadiene as an essential component using a polymerization catalyst.

 In the oil-extended rubber composition of the present invention, the conjugate polymer (P1) is composed of a lanthanum series metal compound (A), an organoaluminum compound (B), an organoaluminum hydride compound (C), and a halogen compound (D). It is preferably obtained by polymerizing a conjugated diene monomer using a polymerization catalyst, and then modifying it with an organometallic halide (E) represented by the following general formula (1). Masle.

[Chemical 1]

(In the formula, M is Si, Ge, Sn or Ti, and X is a halogen atom. When a plurality of X are present, they may be the same or different from each other. R ¹ is a single bond. Or a hydrocarbon group having 1 to 20 carbon atoms that may contain a heteroatom R ² represents hydrogen or a hydrocarbon having 1 to 20 carbon atoms that may contain a hetero atom When a plurality of R ² are present, they may be the same or different from each other, and g and h each represent an integer of !! to 4. When h force, f is 0 When h force is ~ 4, f is 1, and at least one R ² is bonded to R ¹ ! /, The force S, and R ² may be a single bond! /, ).

 Furthermore, in the oil-extended rubber composition of the present invention, the polymerization catalyst is composed of a lanthanum series metal compound (A), an organic alkylaluminum compound (B), an organic aluminum hydride compound (C), and a halogen compound (D). It is preferable that the molar ratio (B / C) force of the organoalkylaluminum compound (B) to the organoaluminum hydride compound (C) is 5≤ (B / C) ≤1,000.

 In the oil-extended rubber composition of the present invention, it is preferred that the process oil contains 10 to 40% by weight of aroma!

In the oil-extended rubber composition of the present invention, the rubber component is composed only of the conjugated diene polymer (P1). It is preferable to be! /

 Further, in the oil-extended rubber composition of the present invention, the rubber component is 5% by weight or more of the conjugated polymer (P1), and the polymer rubber (P2) other than this conjugated polymer (P1) is 95% by weight or less. It is preferred that it consists of,.

 Furthermore, in the oil-extended rubber composition of the present invention, the polymer rubber (P2) other than the conjugated polymer (P1) is a copolymer of an aromatic bur and a conjugated gene, 7 in conjugation units with one viscosity (ML, 100 ° C)

 Preferably, it has a bull bond content of 1 + 4 to 85%.

 [0010] According to the present invention, 5 to 120 parts by weight of silica, clay, talc, calcium carbonate, carbon black, carbon nanotube, fullerene, nylon short fiber, and water are further included in 100 to 100 parts by weight of the rubber component. An oil-extended rubber composition further comprising at least one compounding agent selected from the group consisting of aluminum oxide is provided.

 [0011] According to the present invention, there is provided a method for producing an oil-extended rubber composition in which a process oil is mixed with an organic solvent solution of a rubber component containing a conjugated diene polymer (P1) as an essential component and then desolvated. .

 Further, according to the present invention, there is provided a tire member obtained by crosslinking the oil-extended rubber composition of the present invention.

 Furthermore, according to this invention, the tire provided with the said member for tires is provided.

 The invention's effect

 [0012] A crosslinked rubber (vulcanized product) obtained by crosslinking the oil-extended rubber composition of the present invention is excellent in low heat buildup and wear resistance.

 Accordingly, a tire member having excellent practicality and a tire provided with the tire member can be obtained from the oil-extended rubber composition.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0013] The oil-extended rubber composition of the present invention comprises 10 to 120 parts by weight of a specific process oil in 100 parts by weight of a rubber component containing a specific conjugated polymer (P1) as an essential component.

[0014] The conjugated diene polymer (P1) used in the present invention is a co-polymer having at least a butadiene unit, that is, a butadiene homopolymer or copolymerizable with butadiene. Copolymers with various monomers having specific microstructure and molecular weight characteristics.

 The conjugation polymer (P 1) is a homopolymer of butadiene (polybutadiene) or a copolymer of butadiene and a monomer copolymerizable therewith.

 The monomer copolymerizable with butadiene is not particularly limited.

As a representative example of a monomer copolymerizable with butadiene, a conjugation monomer other than butadiene can be cited. Specific examples thereof include 1, 3-butadiene, isoprene (2-methyl-1, 3-butadiene); 2, 3-dimethyl-1, 3-butadiene, 2-chloro-1, 3 - butadiene, 1, ₃ - Pentajen, 1; 3-hexagen and the like can be mentioned. Of these, isoprene is preferred.

 These conjugation monomers can be used alone or in combination of two or more.

 [0016] Specific examples of monomers copolymerizable with butadiene other than conjugated diene include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o —Ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, α-methylstyrene, α-methyl-ρ-methylstyrene, ο-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, 2 —Aromatic vinyl monomers such as methyl-4,6-dichlorostyrene, 2,4-dibu-mouthed styrene, and burnaphthalene; carbon numbers 2 to 10 such as ethylene, propylene, 1-butene, cyclopentene, and 2-norbornene 1,5-hexagen, 1,6-hexabutadiene, 1,7-octadiene, dicyclopentadi N, 5-ethylidene-2-norbornene and other non-conjugated diene monomers having 5 to 10 carbon atoms; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, etc. 1 to 8 a, 13 -ethylenically unsaturated carboxylic acid alkyl ester monomers;

 [0017] The ratio of the butadiene units in the conjugated polymer (P 1) is 80% by weight or more, preferably S, more preferably 90% by weight or more, and more preferably 95% by weight or more. Is preferable.

In addition, when the conjugated diene polymer (P 1) is a copolymer, the bonding mode of the monomer is particularly It is not limited, and for example, it can be made with various coupling modes such as block shape, taper shape, random shape, and the like with force S.

 [0018] The conjugated diene polymer (P1) used in the present invention has a cis in the butadiene unit portion.

1, ₄ is a bond content should be at _96.5% or more, this and force S preferably 97.5% or more, and more preferably 98. be 0% or more.

 In addition, the conjugate polymer (P1) needs to have a bull bond content in the butadiene unit portion of 1.0% or less, and preferably 0.9% or less. More preferably, it is at most%.

[0019] Further, the conjugate polymer (P1) has a Mooney viscosity (ML, 100 ° C) force of 5 to 20

 1 + 4

 0 is required, and 75 to 175 is more preferable.

 [0020] Further, the conjugate polymer (P1) needs to have a molecular weight distribution of 1.5 to 4.0, preferably 2.0 to 3.5, and preferably 2.0 to A power of 3 is also preferable.

 [0021] The conjugated diene polymer (P1) used in the present invention is a polymer composed of a lanthanum series metal compound (Α), an organic alcohol compound (Β), an organoaluminum hydride compound (C), and a halogen compound (D). It can be obtained by polymerizing a monomer containing butadiene as an essential component using a catalyst.

 [0022] The lanthanum series metal compound (Α), which is the first component of the polymerization catalyst, is a lanthanum series metal salt, alkoxide, phenoxide or complex, with the salt being preferred.

 [0023] The lanthanum-based metal is at least one selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, pylorium, gadolinium, tenolebium, dysprosium, honorium, enolebium, thulium, ytterbium and lutetium. It is a kind of metal. Among these, lanthanum, cerium, praseodymium, neodymium, samarium, and gadolinium are preferred for easy access and high polymerization activity. From the viewpoint, neodymium is particularly preferable.

 [0024] The salt of the lanthanum series metal is not particularly limited, but a carboxylate salt that is preferably a carboxylate salt or a salt of phosphoric acid is more preferable.

In addition, lanthanum metal salts are complex salts of carboxylate and phosphorus-containing organic acid salts ( It may be a complex salt structure consisting of different bonding modes, such as [rubonate] [phosphorus-containing organic acid salt]).

 [0025] The carboxylic acid forming the carboxylate is not particularly limited! /, But usually has 2 to 20 carbon atoms. Specific examples include acetic acid, octanoic acid, otathenic acid, lauric acid, versatic acid (aliphatic monocarboxylic acid having 6 to 20 carbon atoms having a carboxyl group on a tertiary carbon in which three alkyl groups having 1 or more carbon atoms are bonded). Aliphatic carboxylic acid such as phenylacetic acid; Alicyclic carboxylic acid such as cyclopentanecarboxylic acid; Aromatic carboxylic acid such as benzoic acid and naphthenic acid; etc. Is mentioned. Among these, versatic acid is more preferable because a catalyst having a high polymerization activity, which is preferably an aliphatic carboxylic acid having 6 to 20 carbon atoms, is obtained.

 [0026] The phosphoric acid that forms a salt of phosphoric acid is not particularly limited, but a compound represented by the following general formula (2) is preferable.

 [0027] [Chemical 2]

 0

R ³ \ ll

 P-OH (2)

 R

(Wherein R ³ and R ⁴ are each a hydrogen atom, a hydroxyl group, a carbon number;! To 20 alkyl group or an alkoxy group, a C 6-20 aryl group or a phenoxy group, or a carbon number 7 to 20 represents an aralkyl group or an alkylphenoxy group.)

[0028] Specific examples of the compound represented by the general formula (2) include phosphoric acid; dibutyl phosphate, dihexyl phosphate, dioctyl phosphate, bis (2-ethylhexyl phosphate), bis ( Phosphoric acid dialkyl esters such as 1-methylheptyl), dioleyl phosphate, butyl phosphate (2-ethylhexyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl); phosphorus such as diphenyl phosphate Acid diaryl ester; 2-ethylhexylphosphonate mono-2-ethylhexyl, monoalkylphosphonate monoalkyl ester such as 2-butylhexylphosphonate monobutyl; monoalkyl such as 2-ethylhexylphosphonate monophenyl Phosphonates such as monophosphonophosphonates; phosphonates such as mono-2-ethylenohexenole phosphonate and monomethyl eptyl phosphonate Monoalkyl esters; phosphonate Monofueniru Phosphonic acid monoaryl esters such as: dibutylphosphinic acid, bis (2-ethylhexylole) phosphinic acid, bis (1 methylheptynole) phosphinic acid, dioleylphosphinic acid, (2-ethylhexyl) (1 methyl Heptyl) phosphinic acid and other dialkylphosphinic acids; diphenylphosphinic acid and other diarylphosphinic acids; and the like.

 [0029] The phenol for forming the lanthanum series metal phenoxide is not particularly limited. Specific examples thereof include alkyl-substituted monophenols such as 2,6-di-t-butylphenol and 2,6-di-t-butyl-4-methylphenol. Can be mentioned.

 [0030] The alcohol for forming the alkoxide of the lanthanum series metal is not particularly limited. Specific examples thereof include methanol, ethanol, isopropanol, t-butanol, tamyl alcohol, 2 butyr alcohol, 3 Hexenyl alcohol and other carbon atoms 1 to 10; aliphatic alcohols; cyclohexyl alcohols and other carbon atoms 3 to 6 alicyclic alcohols; benzyl alcohol and other carbon atoms 7 to 10; aryl substituted aliphatic alcohols And the like.

 The lanthanum series metal complex is not particularly limited, but specific examples thereof include a / 3-diketon complex.

 Specific examples of 0-diketone for forming a complex include / 3-diketones having 5 to 12 carbon atoms such as acetylacetone, benzoylacetone, ethylacetylacetone and the like.

Yes

 [0031] In the above polymerization catalyst, the amount of component (A) used is such that lanthanum-based IJ metal strength in component (A) is usually 0.001 to 100 millimonoles, preferably The range is 0.005 to 50 millimoles.

 If this amount is excessively small, the polymerization activity may be insufficient, and if it is excessively large, the molecular weight of the resulting polymer may be too small, or removal of the catalyst residue may be difficult.

[0032] The organoaluminum compound (B), which is the second component of the polymerization catalyst, has the general formula

 It is represented by (3), (4) or (5).

A1R ⁵ R ⁶ R ⁷ (3)

[0033] [Chemical 3] ( Four)

 [0034] [Chemical 4]

In the general formulas (3), (4), and (5), R ^{5 to} R ¹³ are each a hydrocarbon group having! r and s are each an integer of 2 to 100;

 Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n propinole group, isopropyl group, n butyl group, isobutyl group, sec butyl group, t butyl group, n pentyl group, and n hexyl group. , N-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other alkyl groups having 1 to 20 carbon atoms; cyclopentyl group, cyclohexyl group and other cycloalkyl groups having 3 to 6 carbon atoms; benzyl group, And aralkyl groups having 7 to 20 carbon atoms such as 2 phenylethyl group and 3 phenylpropyl group; aryl groups having 6 to 20 carbon atoms such as phenyl group, 1 naphthyl group, and 2-naphthyl group; and the like. Of these, an alkyl group is most preferred. In addition, the alkyl group, the aralkyl group, and the aryl group have a substituent at any position! /, Or may be! /.

 Of these hydrocarbon groups, those having 2 or more carbon atoms are preferred because of their high solubility in saturated hydrocarbon solvents used for polymerization and excellent control of the polymer molecular weight!

[0036] Specific examples of the organoaluminum compound represented by the general formula (3) include trimethylaluminum, triethinorenoreminium, tri-n-propylaluminum, triisopropylaluminum, tri-n-butyl. Noreanolium, triisobutylaluminum, methyldiisobutylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, tricyclohexylurenoreminimum, tribenzenorenoreminium, dimethylbenzylaluminum, jetyl

, Minium, triphenylaluminum, tri (4 methylphenol) aluminum Um and so on.

 [0037] The organoaluminum compound represented by the general formula (4) or (5) is, for example, a trianolenoquinoleminoleum or dialkylaluminum in a solvent such as benzene, tolylene or cyclohexane. It can be obtained by adding a salt having water of crystallization, such as water, copper sulfate pentahydrate, aluminum sulfate salt 16 hydrate, etc. after adding mumonochloride or the like.

 [0038] Specific examples of the organoaluminum compound represented by the general formula (4) or (5) include methylanoloxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane, t-butylalumoxane. Hexylalumoxane, octylalumoxane and the like. Of these, isobutylalumoxane, t-butylalumoxane, hexylalumoxane and octylalumoxane are preferred.

 [0039] Among the organoaluminum compounds, those represented by the general formula (3) are preferable because they give a polymer having high living properties. Ease of availability and handling, high catalyst activity, etc. From this point, triethyl aluminum and triisobutyl aluminum are preferred!

 [0040] The amount of component (B) in the above polymerization catalyst is usually 0.5 to 500 monolayers, preferably 5 to 250 monolayers, more preferably 1 mol of the lanthanum series metal in component (A). ίma 20 ~; 100 moles.

 [0041] The organoaluminum hydride compound (C), which is the third component of the polymerization catalyst, is a compound represented by the following formula (6).

A1H R ¹⁴ (6)

 k 3— k

(R ¹⁴ represents a hydrocarbon group having from 10 to 10 carbon atoms, k is 1 or 2, and preferably 1. When k is 1, two R ¹⁴ may be the same or different. May be.)

[0042] Specific examples of the hydrocarbon group R ¹⁴ having carbon atoms of! To 10 include methyl group, ethyl group, n propylene group, isopropyl group, n butyl group, isobutyl group, sec butyl group, t butyl group, n C1-C10 alkyl groups such as pentyl group and n-hexyl group; C3-C6 cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Carbons such as benzyl group and 2 phenylethyl group A aralkyl group having 7 to 10; a 6 to 10 carbon atom such as a phenyl group; an aryl group having 10; and the like. Among these, an alkyl group is preferable. In addition, the alkyl group, the aralkyl group, and the aryl group each have a substituent at any position, and may be V! /. [0043] Specific examples of the organoaluminum hydride compound (C) include methylaluminum hydride, hydrogenated chilled aluminum, hydrogenated n-propylaluminum, hydrogenated isopropylaluminum hydride, n-butylaluminum hydride, isobutylaluminum hydride, Formulas such as hydrogenated n-pentylaluminum, hydrogenated neopentylaluminum, hydrogenated n-hexanolenoreluminium, hydrogenated isohexylaluminum, hydrogenated cyclohexylaluminum, hydrogenated phenylaluminum, etc .: Hydrocarbyl aluminum represented by A1H R ¹⁴

 2

Umdino, idide; dimethylaluminum hydride, dimethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-pentylaluminum hydride, hydrogenated Di (hydrocarbyl) aluminum hydra represented by the formula: A1HR ¹⁴ , such as dineopentylaluminum, di-n-hexylaluminum hydride, diisohexylaluminum hydride, dicyclohexylaluminum hydride, diphenylaluminum hydride, etc.

 2

 Id; and the like.

 [0044] The amount of the component (C) in the above polymerization catalyst is usually 0.;! To 100 monolayers, preferably (or 0.5 to 25 monolayers) per mol of the lanthanum series metal in the component (A). More preferably (ma;! To 3 monoles.

 [0045] In the above polymerization catalyst, the molar ratio (B / C) between the organoaluminum compound (Β) and the organoaluminum hydride compound (C) is 5≤ (B / C) ≤l, 000 It is preferable to satisfy. This molar ratio (B / C) is preferably 10 or more, more preferably 12 or more, preferably 500 or less, more preferably 100 or less.

 Conjugated polymers (P1) having a narrower molecular weight distribution and a higher cis 1,4 bond content in the butadiene unit portion when the molar ratio (B / C) in the above polymerization catalyst is within the above range Can be obtained.

[0046] The halogen compound (D) as the fourth component of the polymerization catalyst may be a compound containing a halogen atom, and preferred specific examples thereof include metal halide compounds, halogenated compounds. Mention may be made of organic compounds and organoaluminum halide compounds.

As the halogen contained in the halogen compound, the chlorine, bromine or iodine atom is preferred. Yes.

 [0047] Specific examples of the metal halide compound include magnesium chloride, zinc chloride, calcium chloride, magnesium (II) iodide anhydride, manganese pentabromide bromide, manganese perchlorate (II) · 6 water Japanese, Manganese (II) chloride anhydrous, Manganese (II) chloride tetrahydrate, Manganese (II) bromide, Manganese (II) tetrahydrate, Rhenium chloride (111), Chloride Examples include rhenium (V), pentacarbonyl rhenium chloride, and pentacarbonyl rhenium bromide.

 Further, those obtained by reacting these metal halide compounds with Lewis bases such as phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds and alcohols can also be used.

 [0048] Specific examples of the halogenated organic compound include benzoyl chloride, xylylene dichloride, bropioyl chloride, benzyl chloride, benzylidene chloride, t-butyl chloride, t-amyl chloride, chlorodiphenylmethane, Organochlorine compounds such as chlorotriphenylmethane and methylchloroformate, hexaclonal butadiene; xylylene dibromide, benzoinorebromide, propioninorebromide, benzinorebromide, benzylidene bromide, t-butyl bromide, t- Organic bromine compounds such as amyl bromide and methyl bromoformate; and organic iodine compounds such as benzoyl iodide and xylylene diiodide.

 [0049] The organoaluminum halide compound is usually a compound represented by the general formula (7).

AIR ¹⁵ X (7)

 P 3— p

(R ¹⁵ is a hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, p is 1 or 2, and preferably 1. Further, when p force is applied, two R ¹⁵ The hydrocarbon group R ¹⁵ having 1 to 10 carbon atoms may be the same as the hydrocarbon group R ¹⁴ having 1 to 10 carbon atoms, An alkyl group is preferred.)

[0050] Specific examples of organoaluminum halide compounds include dialkylaluminum halides such as dimethylaluminum chloride, dimethylaluminum bromide, jetylaluminum chloride, jetylaluminum bromide, dibutylaluminum chloride, and dibutylaluminum bromide; Kuchiguchi Ride, Etyl Aluminum Yu Examples include alkylaluminum sesquihalides such as mussesquic mouthrides; alkylaluminum dinosides such as methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride.

 These can be used alone or in combination of two or more.

[0051] In the polymerization catalyst described above, the amount of component (D) used is usually from 0.;! To 20 monolayers, preferably from 0.5 to 1 monolayers of the lanthanum series metal in component (A). 10 monoles, more preferably (ma;! To 5 monoles.

 [0052] By using a polymerization catalyst composed of such components (i) to (D), cis 1, which is a butadiene unit portion having a higher Mooney viscosity and a narrower molecular weight distribution than conventional ones, 4 It is possible to obtain a conjugate polymer (P1) having a high bond content and a low bull bond content.

 [0053] The above polymerization catalyst is prepared by mixing the components (A) to (D) with the force S that can be obtained by mixing the components (A) to (D) in any order, and then mixing the components (A) and (B). It is preferred to add component (C) to the mixture.

 More preferably, the component (A) and the component (B) are first mixed, the component (C) is blended in the resulting mixture, and then the component (D) is blended.

 By mixing in this order, the polymerization activity is increased, the molecular weight distribution of the resulting conjugated polymer (P1) is narrowed, and the cis 1,4 bond content in the butadiene unit portion is further increased. Get higher.

[0054] Further, after mixing the component (A) and the component (B), it is preferable that the obtained mixture is aged for 1 minute or more and the component (C) is added to the aged mixture.

 Here, aging means that after a certain reaction component and another reaction component are mixed, a certain time is left until the next step.

 The time for aging is preferably 1 to 60 minutes, more preferably 5 to 30 minutes. If the aging time is too short, the molecular weight distribution of the resulting conjugate polymer (P1) may be widened. On the other hand, if this time is too long, the polymerization activity of the resulting polymerization catalyst may decrease.

[0055] Further, after mixing the component (A) and the component (B), conjugate conjugate is added to the resulting mixture, Thereafter, component (c) is preferably added.

 More preferably, after mixing component (A) and component (B), the conjugate is added to the resulting mixture, followed by component (C) and then component (D).

 The conjugation addition may be performed at any time point immediately after mixing of component (A) and component (B) to immediately before the addition of component (C). Preferably, after mixing component (A) and component (B), the mixture is aged for 1 to 20 minutes, then the conjugate is added; and further !! aged for 20 to 20 minutes before component (C) Add.

 The amount of conjugation addition at the time of catalyst preparation is not particularly limited, but is usually 1 to 200 mol, preferably 10 to 100 mol, per 1 mol of the lanthanum series metal in component (A). Presence of conjugation during catalyst preparation increases the polymerization activity of the catalyst, and the resulting conjugated 1, polymer (P1) has a higher cis 1,4 bond content, resulting in a narrower molecular weight distribution. .

 [0056] Conjugation used for preparing the catalyst used here may be used alone or in combination of two or more. Further, it may be the same as or different from the conjugation used as the monomer constituting the conjugation polymer (P1).

[0057] When the components (A) to (D) used as a polymerization catalyst are in a solid state, the ability to use each component as a solvent solution is preferable.

 The solvent used here is not particularly limited, but it may have 1 to carbon atoms which may be substituted with a halogen atom; a chain or cyclic saturated hydrocarbon having 10 carbon atoms which may be substituted with a halogen atom, or 6 to 6 carbon atoms which may be substituted with a halogen atom. ; 12 aromatic hydrocarbons, monoolefins and the like.

 Specific examples of linear or cyclic saturated hydrocarbons having 1 to 10 carbon atoms are substituted with halogen atoms such as η butane, η-pentane, η hexane, η-heptane, η-octane, and cyclohexane. Those not substituted; and those substituted with a rhogen atom such as chloroform, methylene chloride, dichloroethane and the like.

 Specific examples of the aromatic hydrocarbon include those not substituted with a halogen atom such as benzene, toluene and xylene; and those substituted with a halogen atom such as black benzene.

Specific examples of monoolefins include 1-butene and 2-butene. Among these, a linear or cyclic saturated hydrocarbon having 1 to 10 carbon atoms is particularly preferable, and n-butane, n-pentane, n hexane and cyclohexane are preferable.

[0058] The reaction temperature and reaction time for preparing the polymerization catalyst are not particularly limited, but are usually 78 ° C to + 100 ° C, preferably -20 ° C to + 80 ° C, usually 1 second to 24 hours. As the polymerization catalyst, a solution prepared as a solution can be used as it is, or it can be used by distilling off the solvent. Moreover, you may refine | purify as needed.

[0059] The polymerization catalyst may be supported on a carrier such as carbon black, an inorganic compound, or an organic polymer compound. By carrying it on a carrier, it is possible to prevent contamination due to catalyst adhesion in the polymerization reactor.

Preferable examples of the inorganic compound that can be used as the carrier include inorganic oxides such as silica, alumina, magnesia, titania, zircoure, strong rucia, and inorganic chlorides such as magnesium chloride. These inorganic compounds are preferably porous particles having an average particle size of 5 to; 150 ^ 111 and a specific surface area of ² to 800 m ² / g. Usually, heat treatment is performed at 100 to 800 ° C. Remove water to use as a carrier.

 Examples of the organic polymer compound that can be used as a carrier include a carboxy-modified crosslinked styrene copolymer composed of styrene-dibutylbenzene methacrylate. These organic polymer compounds are preferably spherical particles having an average particle diameter of 5 to 250 m.

 [0060] In addition to the components (A) to (D), the polymerization catalyst further contains an organometallic compound having at least one metal selected from Group 1 to 3, 12 and 13 elements of the periodic table May be. The organometallic compound is not particularly limited, and examples thereof include an organolithium compound, an organomagnesium compound, and an organomagnesium halide.

 Examples of the organic lithium compound include methyl lithium, butyl lithium, phenyl lithium and the like.

 Examples of the organic magnesium compound include dibutyl magnesium. Examples of the organomagnesium halide include ethylmagnesium chloride and butylmagnesium chloride.

[0061] In the present invention, the conjugated diene polymer (P1) is obtained by using the above polymerization catalyst and butadiene. Can be obtained by copolymerizing with other monomers copolymerizable with butadiene as required.

 [0062] The polymerization method is not particularly limited, and examples thereof include a bulk polymerization method, a solution polymerization method and a slurry polymerization method in an inert solvent, and a gas phase polymerization method using a gas phase stirring tank and a gas phase fluidized bed. I can get lost. Among these methods, the solution polymerization method that can narrow the molecular weight distribution is preferable. The solution polymerization method may be a batch type or a continuous type.

 [0063] The inert solvent used in the solution polymerization method is not particularly limited! /, But has 4 to 10 carbon atoms; a linear or cyclic saturated hydrocarbon having 10 to 10 carbon atoms; an aromatic hydrocarbon having 6 to 12 carbon atoms; Monoolefins such as 1-butene and 2-butene; and the like, which may be substituted with a halogen atom! /.

 Saturated hydrocarbons include n-butane, cyclopentane, n-pentane, 2-methylpentane, 2,3 dimethylpentane, n hexane, 2 methylheptane, 2,3 dimethylheptane, cycloheptane, n heptane, n Examples include octane, cyclooctane, and cyclohexane. Examples of the saturated hydrocarbon substituted with a halogen atom include black mouth form, methyl chloride, dichloroethane and the like.

 Examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Examples of the aromatic hydrocarbon substituted with a halogen atom include black benzene.

 Of these, chain-like or cyclic saturated hydrocarbons having 4 to 10 carbon atoms are particularly preferred, and n-butane, n-hexane, n-pentane, 2-methylpentane and cyclohexane are preferred.

 [0064] The polymerization temperature for obtaining the conjugation polymer (P1) is usually 50 ° C to + 200 ° C, preferably 0 ° C to 150 ° C, more preferably 20 ° C to 90 °. C, most preferably 40-70 ° C. When the polymerization temperature is within this range, the molecular weight can be easily controlled, which is industrially advantageous. The polymerization time is about 1 second to 20 hours, and the polymerization pressure is about 0.;! To 3 MPa.

 [0065] A chain transfer agent can be used to adjust the molecular weight of the conjugation polymer (P1).

Chain transfer agents have been used in the production of cis 1,4 polybutadiene rubber. Specific examples thereof include allenes such as 1,2-butadiene; cyclic gens such as cyclooctene; and the like. Moreover, the same effect can be obtained even if the polymerization reaction is carried out in the presence of hydrogen gas.

 [0066] The conjugation polymer (P1) may be modified with an organic metal halide (E) represented by the following general formula (1) following polymerization. This modification prevents the solidification of the polymer during the recovery of the polymer and improves the industrial productivity of the polymer.

[0067] [Chemical 5]

(In the formula, M is Si, Ge, Sn or Ti, and X is a halogen atom. When a plurality of X are present, they may be the same or different from each other. R ¹ is a single bond. Or a hydrocarbon group having 1 to 20 carbon atoms that may contain a heteroatom R ² represents hydrogen or a hydrocarbon having 1 to 20 carbon atoms that may contain a hetero atom When a plurality of R ² are present, they may be the same or different from each other, and g and h each represent an integer of !! to 4. When h force, f is 0 (When h force is ~ 4, f is 1, and at least one R ² is a force S bonded to R ^1, and R ² may be a single bond.)

[0068] Specific examples of the compound represented by the general formula (1) include silicon tetrachloride, trichlorosilane, dichlorosilane, diphenyldichlorosilane, dibutyldichlorosilane, triphenylchlorosilane, tributylchlorosilane, 1 , 2-Di (trichlorosilyl) ethane, trichlorodisilane and other halogenated silicon compounds; triphenylgermanium chloride, dibutylgermanium dichloride, halogenated germanium compounds such as diphenylgermanium dichloride, butylgermanium trichloride; tetrachloride Tin, tin tetrabromide, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, diphenyltin chloride, dioctyltin dichloride, dibutyltin dichloride, phenyltin trichloride, butyltin trichloride Fluorogen tin compounds such as Loride; Titanium halide compounds such as Tetrachrome Titanium, Trichrome Titanium, Dicyclopentadienyl No-Dichloro Titanium; and the like.

Among these, tin tetrachloride, silicon tetrachloride, 1,2-bis (trichlorosilyl) ethane, trichlorodisilane, etc., which are preferred as halogenated tin compounds and halogenated silicon compounds, are preferred. Those with 4 or more halogen atoms are preferred!

[0069] The addition amount of the compound (E) is preferably 0.001-1 mol with respect to 1 mol of the lanthanum series metal compound (A). Further preferred. When the addition amount is within this range, a rejuvenating effect can be obtained if the exothermic property, wear property and coagulation property of the conjugated diene polymer are excellent.

 [0070] The reaction temperature when the compound (E) is reacted is usually 20 to 100 ° C, preferably 40 to 8 ° C.

0 ° C, more preferably 50 to 70 ° C. The reaction time is usually;! -120 minutes, preferably 5

~ 60 minutes, more preferably. ~ 30 minutes.

[0071] At the end of the modification reaction with compound (1), at least one compound selected from the group consisting of isocyanate compounds, quinone compounds, ester compounds, carbonate compounds, carboxylic acids and acid compounds, and rogenates may be added. .

[0072] The rubber component used in the oil-extended rubber composition of the present invention may be only the conjugated diene polymer (P1), but a heavy component other than the conjugated diene polymer (P1) and the conjugated diene polymer (P1). Combined rubber (

May contain P2)! /.

[0073] In the oil-extended rubber composition of the present invention, the polymer rubber (P2) that can be used in combination with the conjugated polymer (P1) as a rubber component is not particularly limited! /.

 A specific example of this is a conjugated gen polymer, which has molecular weight characteristics (molecular viscosity and molecular weight distribution) and microstructure of the butadiene unit (P1

) And polymer rubbers other than conjugated polymer can be mentioned.

Specific examples of the polymer rubber (P2) include emulsion polymerization SBR (styrene butadiene copolymer rubber), solution polymerization random SBR (bonded styrene 5 to 50% by weight, 1,2 bond content of butadiene unit part 10 to 80% ), High trans SBR (trans bond content of butadiene part 70 to 95%), low cis BR (polybutadiene rubber), high trans BR (trans bond content of butadiene part 70 to 95%), high bull SBR low Bull SBR block copolymer rubber, other conjugated polymer that does not meet the requirements of conjugated polymer (P1) in terms of micro structure or molecular weight, such as natural rubber (NR), polyisoprene rubber (IR), polybutadiene rubber ( BR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, emulsification Examples thereof include a polymerized styrene / acrylonitrile / butadiene copolymer rubber, an acrylonitrile / butadiene copolymer rubber, a polyisoprene SBR block copolymer rubber, and a polystyrene / polybutadiene / polystyrene block copolymer.

 Specific examples of the polymer rubber (P2) other than the conjugate polymer include acrylic rubber, epichlorohydrin rubber, fluorine rubber, silicon rubber, ethylene propylene rubber, urethane rubber and the like.

 The polymer rubber (P2) is usually a solid one, but a liquid one may be used. These polymer rubbers (P2) can be used alone or in combination of two or more.

 [0074] Among these, as the polymer rubber (P2), among these, an aromatic bur-conjugated rubber copolymer, a natural rubber, a polybutadiene rubber, and a polyisoprene rubber are preferable. preferable. The viscosity of the aromatic bis-conjugate copolymer rubber is 1 to 100 (ML, 100 ° C).

 It is preferably 1 +4 to 200. The content of butyl in the conjugated gen unit part of the aromatic butyl-conjugated gen copolymer rubber is 7 to 85%, preferably S, and more preferably 20 to 70%. In addition, the aromatic bull unit content in the aromatic bull-conjugated conjugated copolymer rubber is St (wt%), and the bull content V (%) in the conjugated gen unit portion is In this case, the direct force of (2St + V) is preferably an amount satisfying 30≤ (2St + V) ≤170, and particularly preferably an amount satisfying 60≤ (2St + V) ≤140. If the (2St + V) value of the aromatic butyl-conjugate copolymer is in the above range, the compatibility with the conjugated polymer (P1) will be good, and the vulcanizate obtained from the oil-extended rubber composition Good wear resistance.

[0075] In the oil-extended rubber composition of the present invention, when the conjugated polymer (P1) and the polymer rubber (P2) are used in combination as the rubber component, the rubber component is 5% by weight of the conjugated polymer (P1). % or more and the polymer rubber (P2) 95 weight _^0/0 follows is preferable is made of tool rubber component conjugated diene polymer (P1) polymer rubber with 80 to 30 wt% (P2) is More preferably, it is 20 to 70% by weight.

When the oil-extended rubber composition of the present invention is used for tire applications, the ratio of the conjugated polymer (P1) is preferably 1% by weight or more with respect to the total amount of the rubber component. 5 to 95% by weight It is more preferable that it is 30 to 80% by weight.

[0076] The method for producing the polymer rubber (P2) used in the present invention is not particularly limited, and a conventionally known method can be employed. For example, a method of polymerizing using an organic active metal as an initiator is mentioned. That's the power S.

 The polymer rubber (P2) may have been subjected to a coupling agent treatment subsequent to the polymerization. The treatment with the coupling agent further improves the wear characteristics when the oil-extended rubber composition of the present invention is a crosslinked rubber (vulcanized product).

 [0077] Examples of the coupling agent include a silicon-containing coupling agent, a tin-containing coupling agent, a phosphorus-containing coupling agent, an epoxy group-containing coupling agent, an isocyanate group-containing force coupling agent, and an ester group-containing coupling agent. Alkenyl group-containing coupling agents, halogenated hydrocarbons and the like.

 Of these, a cage-containing coupling agent and an epoxy group-containing coupling agent are preferred, with a cage-containing coupling agent, an epoxy group-containing coupling agent, and an isocyanate group-containing coupling agent being preferred.

 [0078] Examples of the caustic-containing coupling agent include alkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and alkyltriphenoxysilane; silicon tetrachloride, silicon tetrabromide, tetra Halogenated silane compounds such as silicon iodide, monomethyltrichlorosilane, monoethyltrichlorosilane, monobutyltrichlorosilane, monohexyltrichlorosilane, monomethyltritribromosilane, bistrichlorosilylethane, etc .; monochrome oxysilane, trichloromethoxysilane And alkoxyhalogenated silane compounds such as tribromomethoxysilane;

 Of these, tetramethoxysilane and silicon tetrachloride are more preferred, and alkoxysilane compounds and halogenated silane compounds are preferred!

[0079] Examples of the tin-containing coupling agent include, for example, tin tetrachloride, tin tetrabromide, monomethyltrichlorozose, monoethinoretrichlorotin, monobutinoretrichlorotin, monohexinoretrichlorosu, bistrichlorostani. And tin halide compounds such as ruthetan; alkoxytin compounds such as tetramethoxytin, tetraethoxytin, and tetrabutoxytin; Examples of the phosphorus-containing coupling agent include trisnoylphenyl phosphite, trimethyl phosphite, triethyl phosphite and the like.

[0080] Examples of the epoxy group-containing coupling agent include tetraglycidyl 1,1,3-bisaminomethylcyclohexane, tetraglycidyl 1,3-bisaminomethylbenzene, epoxy-modified silicone, epoxidized soybean oil, and epoxidation. Linseed oil etc. are mentioned.

 Of these, tetraglycidyl 1,3-bisaminomethylcyclohexane is preferable. Examples of the isocyanate group-containing coupling agent include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylenomethane diisocyanate, diphenylenoethane diisocyanate, 1, 3 , 5-benzene triisocyanate and the like.

 Of these, 2,4-tolylene diisocyanate is preferable.

[0081] Examples of the ester group-containing coupling agent include dimethyl adipate, dimethyl adipate, dimethyl terephthalate, jetyl terephthalate, dimethyl phthalate, and dimethyl isophthalenoate.

 Examples of the alkenyl group-containing coupling agent include dibutylbenzene and diisopropenylbenzene.

 Examples of the halogenated hydrocarbon include chlorophonerem, tribromomethane, trichloromethane, trichloropropane, tribromopropane, carbon tetrachloride, and tetrachloroethane.

 These coupling agents can be used alone or in combination of two or more.

 [0082] The amount of the coupling agent to be used can be appropriately selected according to the required weight average molecular weight, coupling rate, reactivity of the coupling agent, etc., but with respect to the organic active metal in the polymerization catalyst. The number of moles of the functional group is preferably 0.

 Here, the coupling rate is a ratio (% by weight) of a polymer (coupling polymer) produced by coupling a plurality of living polymers to one molecule of coupling agent with respect to the total amount of the polymer. Yes, it can be measured by gel 'permeation' chromatographic analysis.

The coupling rate in the case of coupling the polymer rubber (P2) is preferably 10% by weight or more, more preferably 30 to 90% by weight, still more preferably 40 to 80% by weight, particularly preferably 55 to 80% by weight. If the coupling rate is too low, the processability may be inferior, and low heat build-up and wear resistance may be inferior.

 The coupling reaction is preferably carried out at 0 to; 150 ° C. under reaction conditions for 0.5 to 20 hours.

 [0083] The oil-extended rubber composition of the present invention comprises 10 to 120 parts by weight of a process oil with respect to 100 parts by weight of a rubber component containing the conjugated polymer (P1) as an essential component. is there.

 [0084] As the process oil, mineral oil or synthetic oil can be used. As mineral oil, t-DAE, s RAE, MES, aroma oil, naphthenic oil, paraffin oil, etc. are usually used.

 In the present invention, the aroma content of the process oil needs to be 5% by weight or more. The aromatic content is preferably 10 to 40% by weight, more preferably 20 to 35% by weight.

 The aroma content is the ratio of the aroma content to the total of 100 aroma content, naphthene content, and paraffin content measured by ASTM D 2140 ring analysis method.

 If the aroma content is low, the wear resistance is inferior, and if it is excessively high, the heat resistance is inferior to the low heat build-up.In the present invention, an oil expansion obtained by using a process oil having an aroma content in the above range is used. Rubber composition strength Excellent balance between wear resistance and low heat build-up.

 [0085] The oil-extended rubber composition of the present invention may contain an anti-aging agent. The anti-aging agent may be added at the time of preparing the polymers (conjugation polymer (P1) and polymer rubber (P2)) used as the rubber component in the present invention. It can be added at any stage in the process of preparing the product! /.

 The total amount of the anti-aging agent added at the time of preparation of each polymer used in the present invention (before the addition of the crosslinking agent) is not particularly limited, but is generally 0.01 to 2 parts by weight.

 [0086] The anti-aging agent is not particularly limited, but specific examples thereof include phenol-based, thio-based, and phosphorus-based anti-aging agents.

Specific examples of phenolic anti-aging agents include tetrakis [methylene 3 (3 ', 5' —T-Butyl-4'-Hydroxyphenol) propionate] methane, 1, 3, 5-trimethyl

2, 4, 6 tris (3,5 di-tert-butyl-4-hydroxybenzyl) benzene, 2,4bis (n-octylthio) -6 (4-hydroxy-3,5-di-tert-butylanilino) 1,

3, 5-triazine, Octadecyl 3- (3, 5-di-butinoleol 4-hydroxyphenol) propionate, triethylene glycol bis [3- (3-t-butyl 5-methyl

4-Hydroxyphenyl) propionate], 1, 3, 5-tris (4-tert-butyl 3-hydroxy-1,2,6-dimethylbenzyl) isocyanuric acid, 2,2'-methylene monobis (4-me 6-t-butylphenol), 3, 9 bis [2- {3 -— (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} 1,1-dimethylethyl] 2, 4, 8, 10 tetraoxa Spiro [5 · 5] undecane, 4-hydroxymethyl-2,6 di-tert-butylphenol, 2,6 di-tert-butyl-4-ethylphenol, butylated hydroxyanisole, 2,2'-dihydroxy-3,3'-dicyclo Hexiru 5, 5 'dimethyl-diphenylmethane, 1, 1, 3-tris (2-methyl 4-hydroxy-5-t-butylphenyl) butane, 4, 4, -butylidenebis (6-t-butyl-m cresol, 4, 4, thiobi (3-methyl-6- t-butylphenol), hexyl 2-hydroxy-one to bis (3 cyclo

5 Methylphenol) methane, 2,2,1-methylenebis (4-ethyl-1-6-butyl-phenol), 1,1-bis (2-methyl-4'-hydroxy-5'-t-butyl-phenol) butane, etc. Power S can be.

 The phenolic anti-aging agent may have a thioether group described later.

Specific examples of anti-aging agents for phosphorus compounds include tris (noyulpheninole) phosphite, tris (2,4 di-t-butylphenol) phosphite, tris having one phosphorus atom in the molecule. (2,5-dibutyl butylphenol) phosphite, tris (2,4 bis (1,1 dimethinole propinole) phosphinole) phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) Monophenyl phosphite, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, tris (mono-di mixed phenylphenyl) phosphite, 2,2, -methylenebis (4,6-di-t-butylphenyl) -2-ethylhexyl Phosphite, 2,2, -methylenebis (4,6 di-t-butylphenyl) -2 octadecyl phosphite, 2, 2-Ethylidenebis (4, 6 di-t-butylphenyl) fluorophosphite, etc.

 [0088] Specific examples of the phosphorus compound anti-aging agent having two or more phosphorus atoms in the molecule include dialkylpentaerythritol diphosphites such as di (tridecyl) pentaerythritol diphosphite and distearyl pentaerythritol diphosphite. Phytite; Di (Noyulfeninore) Pentaerythritol Diphosphite, Bis (2,4G t-Butylphenol) Pentaerythritol Diphosphite, Bis (2,6G t-Butylphenolinore) Pentaerythritol Diphosphite, Bis (2,6 di-tert-butyl-4-methylphenol) pentaerythritol diphosphite, bis (2,4 di-tert-butyl-6-methylphenol) pentaerythritol diphosphite, bis (2,6 di-tert-butyl-4-isopropylphenol) Pentaerythritol diphosphie Diaryl pentaerythritol diphosphite, such as bis (2,6 di-tert-butyl-4-sec butylphenyl) pentaerythritol diphosphite, bis (2,4,6 tri-t-butylphenyl) pentaerythritol diphosphite The power of pentaerythritol diphosphite, such as tetra (tridecyl) isopropylidenediphenyldiphosphite, tetra (tridecyl) mono-1,1,3-tris (2-methyl 5-tbutyl 4-hydroxyphenyl) ) Butanediphosphite, tetra (mixed alkyl from C to C) — 4, 4 '

 12 15

 Isopropylidene diphenyl diphosphite, tetra (tridecyl) 4,4'-butylidene bis (2-t-butyl-5-methylphenyl) diphosphite, tetra (tridecyl) 4,4, -butylidene bis (3-methyl-6-tert-butylphenol) diphosphite, bis (Octinorefeninore) Bis [4,4, -butylidenebis (3-methyl-6-t-butylphenol)] 1,6-hexanediol diphosphite and the like can be mentioned.

 A phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule is tris [2-t-butyltinole 4- (3-t-butyl-4-hydroxy 5-methylphenylthio) 5-methylphenyl] phosphite. It may have two or more thioether structures in the molecule.

[0089] Specific examples of the thioether-based anti-aging agent include dilauryl 3, 3 'thiodipropionate, dimyristyl 3, 3' thiodipropionate, distearyl 3, 3'-thiodipropionate, laurinorestearinore 3, 3 'Thiodipropionate, Pentaeryth Ritol-tetrakis (3 lauryl thiopropionate), 3, 9 bis (2 dodecylthioethinole) 2, 4, 8, 10 tetraoxaspiro [5,5] undecane; 4, 6 bis (octinoretiomethyl) o-talesole 2, 2 Thiodiethylenebis [3- (3,5 di-t-butyl-4-hydroxyphenol) propionate], 2,4 Bis (n-octylthio) 6- (4-hydroxy-3,5-di-tert-butylanilino ) ―1, 3, 5-Triazine;

 [0090] The oil-extended rubber composition of the present invention further includes a reinforcing filler such as silica, carbon black, talc, calcium carbonate, clay, carbon nanotube, fullerene, nylon short fiber, aluminum hydroxide. Can be blended.

 The oil-extended rubber composition of the present invention includes a crosslinking agent; a crosslinking accelerator such as zinc white; a crosslinking accelerator such as sulfamide; a processing assistant such as stearic acid and its salt; a silane coupling agent; Stabilizers; active agents such as diethylene glycol, polyethylene glycol and silicone oil; tackifiers such as petroleum resin and coumarone resin; wax; These compounding amounts are usually 5 to 120 parts by weight with respect to 100 parts by weight in total of the rubber components (conjugation polymer (P 1) and polymer rubber (P2)) used in the present invention.

 [0091] Examples of the silica compounded in the oil-extended rubber composition of the present invention include dry method white carbon, wet method white carbon, colloidal silica, and precipitated silica. Among these, wet method white carbon mainly containing hydrous key acid is preferable. Alternatively, a carbon silica dual 'phase' filler in which silica is supported on the carbon black surface may be used. These silicas can be used alone or in combination of two or more.

[0092] The nitrogen adsorption specific surface area of silica (measured by BET method according to ASTM D3037-81) is preferably 50 to 400 m ² / g, more preferably 50 to 250 m ² / g. Within this range, the resulting oil-extended rubber composition is more excellent in wear resistance and low heat build-up. Also, silica CDBP absorption! : Power of 50 to 400 ml / 100 g, preferably (80 to 300 ml / 100 g. Silica preferably has a pH of less than 7, more preferably ρΗ5 to 6.9. The amount of silica is preferably 5 to 120 parts by weight, more preferably 20 to 100 parts by weight, and particularly preferably 40 parts by weight with respect to 100 parts by weight of all rubber components in the oil-extended rubber composition. ~ 90 parts by weight.

 [0093] In the present invention, when silica is used in the conjugate polymer (P1), low heat build-up and wear resistance are further improved by adding a silane coupling agent.

 Examples of silane coupling agents include butyltriethoxysilane, 0- (3,4-epoxy

 Ν ~ (β-aminoethyl) γ-aminop

 Rasulfide; a mercapto-type silane coupling agent having an alkylene ether bond represented by the general formula (8) (wherein t is an integer of! To 5);

 HS -C H-SiOC H (C H O) CH (8)

 [0094] Among these silane coupling agents, mercapto silane coupling agents having an alkylene ether group and disulfides are more preferable, which are preferred to tetrasulfide, disulfide and mercapto silane coupling agents having an alkyl ether group. . These silane coupling agents can be used alone or in combination of two or more.

 The amount of the silane coupling agent is preferably 0.;! To 30 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of silica.

[0095] Examples of carbon black to be blended in the oil-extended rubber composition of the present invention include furnace black, acetylene black, thermal black, channel black, and graphite. Of these, specific examples of which furnace black is preferred include SAF, IS AF, ISAF—HS, ISAF—LS, IISAF—HS, HAF, HAF—HS, HAF—LS, and FEF. These carbon blacks can be used alone or in combination of two or more.

 The compounding amount of carbon black is usually 150 parts by weight or less with respect to 100 parts by weight of all rubber components in the rubber composition. The total amount of silica and carbon black is 100 parts by weight of all rubber components. It is preferable to be 5 to 150 parts by weight!

[0096] The nitrogen adsorption specific surface area (N SA) of carbon black is preferably 5 to 200 m ² / g, Preferably 80 to 130 m ² / g, and dibutyl phthalate (DBP) adsorption amount is preferably 5 to 300 ml / 100 g, more preferably 80 to 160 ml / 100 g. Within this range, the resulting rubber composition is excellent in mechanical properties and wear resistance. Furthermore, as carbon black, cetyltrimethylammonium bromide (CTAB) has an adsorption specific surface area of 110-; 170 m ² / g, and DBP (24M4DBP) oil absorption after repeated compression four times at a pressure of 165 MPa Wear resistance is further improved by using high structure carbon black in an amount of 110-130 ml / 100 g.

[0097] The oil-extended rubber composition of the present invention may further contain a crosslinking agent.

 Cross-linking agents include sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; dicumyl peroxide, and dibutyl butyl peroxide. Organic peroxides such as xoxides; p-quinone dioxime, p, p'-dibenzoy / lequinone diximes and other quinone dioximes; triethylenetetramine, hexamethylenediamine carbamate, 4, 4, -methylenebis o chloroadiline, etc. Examples thereof include polyvalent amine compounds; alkylphenol resins having a methylol group; among these, powdered sulfur, in which sulfur is preferred, is more preferred.

 These crosslinking agents are used alone or in combination of two or more. The amount of the crosslinking agent is preferably from 0.5 to 15 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of all rubber components.

[0098] The crosslinking agent is preferably used in combination with a crosslinking accelerator and a crosslinking activator.

Examples of the cross-linking accelerator include N cyclohexyl lu 2-benzothiazyl sulfenamide, N-t-butyl-2-benzothiazole sulfenamide, N oxyethylene 2-benzothiazole sulfenamide, N Sulfenamide-based crosslinking accelerators such as oxyethylene 2-benzothiazonolesulfenamide, N, N, 1-diisopropyl-1-benzothiazolesulfenamide; diphenyldanidine, diortolylguanidine, orthotolylbiguanidine Guanidine-based cross-linking accelerators such as: thiolear cross-linking accelerators such as jetylthiourea; thiazole-based cross-linking accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and 2-mercaptobenzothiazole zinc salt; Tetrame Accelerators: Dithiocarbamate crosslinking accelerators such as sodium dimethyldithiocarbamate and zinc jetyldithiocarbamate; Xanthogenate crosslinking accelerators such as sodium isopropylxanthate, zinc isopropylxanthate and zinc butylxanthate A crosslinking accelerator such as an agent; Of these, those containing a sulfenamide-based crosslinking accelerator are particularly preferred. These crosslinking accelerators may be used alone or in combination of two or more. The blending amount of the crosslinking accelerator is preferably 0.5;! To 15 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of all rubber components.

 [0099] As the crosslinking activator, for example, higher fatty acids such as stearic acid, zinc oxide and the like can be used. For example, zinc oxide having a high surface activity particle size of 5 m or less is preferred. Examples include zinc oxide with a particle size of 0.05-0.2 m and zinc oxide with a particle size of 0.3-1111. Power S can be. In addition, zinc oxide that has been surface-treated with an amine-based dispersant or wetting agent can also be used.

 The amount of the crosslinking activator is appropriately selected. The amount of the higher fatty acid is preferably from 0.05 to 15 parts by weight, more preferably from 0.5 to 100 parts by weight based on 100 parts by weight of the total rubber component. The amount of zinc oxide is preferably 0.05 to 10 parts by weight, more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the total rubber component.

 In addition, when the crosslinking agent is blended in the oil-extended rubber composition, an additional anti-aging agent may be blended in addition to the anti-aging agent that can be blended in advance in the oil-extended rubber composition.

 [0100] The oil-extended rubber composition of the present invention can be obtained by kneading each component according to a conventional method. When a cross-linking agent is included as a component of the oil-extended rubber composition, a compounding agent excluding the cross-linking agent and the cross-linking accelerator is kneaded, and then the cross-linking agent and the cross-linking accelerator are mixed into the kneaded product to crosslink the oil-extended A rubber composition can be obtained.

 The kneading temperature of the compounding agent and rubber excluding the crosslinking agent and the crosslinking accelerator is preferably 80 to 200 ° C, more preferably 110 to 180 ° C, and the kneading time is preferably 30 seconds to 30 minutes. It is. The mixing of the crosslinking agent and crosslinking accelerator with the kneaded product is usually performed after cooling to 100 ° C or lower, preferably 80 ° C or lower.

[0101] The crosslinking method for crosslinking the crosslinkable oil-extended rubber composition is not particularly limited, and may be selected according to the shape, size, etc. of the vulcanizate. Fill mold with crosslinkable oil-extended rubber composition It may be crosslinked at the same time as molding by filling and heating, or a preliminarily molded crosslinkable oil-extended rubber composition may be heated and crosslinked. The crosslinking temperature is preferably 120 to 200 ° C, more preferably 140 to 180 ° C, and the crosslinking time is usually about 1 to 120 minutes.

[0102] In order to obtain the oil-extended rubber composition of the present invention in an industrially advantageous manner, it is possible to employ a method of removing the solvent after mixing the process oil into the organic solvent solution of the rubber component.

 In addition to the process oil, each compounding agent may be added to and mixed with the organic solvent of the rubber component, and then the solvent may be removed.

 Examples of the solvent removal method include a spray drying method, a steam stripping method, a direct drying method by solvent separation using supercritical carbon dioxide, and the like. The steam stripping method is preferably employed industrially.

[0103] Applications of the oil-extended rubber composition of the present invention include tire treads, under treads, side treads, beads, bead fillers, tire carcass; hoses, belts, mats, anti-vibration rubbers, and other various industries. Articles; adhesives; impact resistance improvers for resins; resin film buffers; shoe soles, rubber shoes; golf ball cores; toys and the like.

 In particular, since the oil-extended rubber composition of the present invention is excellent in low heat buildup and wear resistance, for example, tire members such as treads, carcass, sidewalls, and bead parts are used as footwear, particularly tire reds for low fuel consumption tires. It can be suitably used for use.

 Example

 [0104] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples and comparative examples, parts and% are based on mass unless otherwise specified.

 [0105] (1) 1, 4 bond content (cis, trans) and 1, 2 Bull bond content

丄 ^ 1 Determined by NMR and ¹³ C-PST-NMR analysis.

 (2) Mw and Mn

 Two GMH columns manufactured by Tosoh Corporation are used in combination, and tetrahydrofuran is used as the eluent, and is obtained based on a calibration curve prepared using a standard polystyrene sample.

 (3) Molecular weight distribution (Mw / Mn)

Gel, permeation, chromatographic method to measure Mw and Mn of the polymer. And decide.

[0106] (4) Branching rate (coupling rate) of polymer rubber (P2)

 Determined based on a calibration curve created using a standard polystyrene sample with two analytical columns GMH-HR-H connected by Tosoh Corporation and tetrahydrofuran as the eluent (40 ° C, 1 ml / min). . The branching rate of the polymer rubber (P2) is determined from the area ratio of the high molecular weight side peak to the low molecular weight side peak in the obtained analysis chart. Measured by NMR.

[0107] (6) Solidification

 Judgment is made based on the following criteria based on the condition of clogging of the transfer line when pumping the crumb obtained by steam stripping the polymerization solution at 105 ° C.

 1: No clogging occurs.

 2: The pump pressure varies from time to time, but transfer is possible.

 3: Since the transfer line is sometimes clogged, it is necessary to switch to a spare pump and operate.

4: Repeated clogging 10 times or more per hour

 (7) Mooney viscosity of polymer (ML, 100 ° C)

 1 + 4

 Use a Mooney viscometer (manufactured by Shimadzu Corporation) and measure according to JIS K6300.

[8108] (8) Low exothermic property of oil-extended rubber composition

 Using a viscoelasticity measuring device (Rheometrics, trade name “RDA-11”), tan δ at 60 ° C. is measured under the conditions of 0.5% twist and 20 Hz. The result is displayed as an index for each group of the same composition. In other words, Table 3 shows the measured values of Comparative Example 1 and Table 4 shows the measured values of Comparative Example 3 as 100. The smaller this index, the better the low heat buildup.

[0109] (9) Abrasion resistance of oil-extended rubber composition (for tires)

Measured according to JIS Κ6264 using a Lambourn abrasion tester. The result is displayed as an index for each group of the same composition. In other words, Table 3 shows the measured values of Comparative Example 1 and Table 4 shows the measured values of Comparative Example 3 as 100. The higher this value, Shows excellent wear resistance.

[Synthesis Example 1]

 (Example of production of neodymium salt versatic acid)

 Versatic acid (Versatic 10, manufactured by Shell Co.) (3.5 parts) was added to 15 parts of an aqueous solution in which 0.8 parts of sodium hydroxide had been dissolved to prepare an aqueous solution of sodium versatate. Then, the above-mentioned sodium versatate aqueous solution was added dropwise to an aqueous solution in which 4 parts of neodymium chloride had been dissolved with vigorous stirring. The blue-violet viscous product formed in the aqueous solution was sufficiently washed with water and dried to obtain a neodymium versatate salt.

[Synthesis Example 2]

 (Preparation of catalyst solution)

1 mol of neodymium versatate obtained in Synthesis Example 1 (component (A)) is dissolved in 200 parts of n-hexane, and 37 mol of triisobutylaluminum (TIBAU (component (B)) is added thereto. , after aging (early aging). 7.5 minutes, 1, was added 3-butadiene 15 molar (hexane solution n-), under stirring, and further _7.5 minutes aging (late aging). then , Diisobutylaluminum hydride (DIBAH) ((component) 1.8 mol and jetyl aluminum chloride (DEAC) (component (D)) 2 mol were added at room temperature.At this time, component (B) and component (C) And the molar ratio (B / C) is 20 · 6.

 The resulting mixture was further stirred at room temperature for 1 hour to obtain catalyst solution 1.

[Production Example 11]

 (Production of Conjugated Polymer (P 1))

A jacketed reactor with a capacity of 2,000 liters was charged with 567 kg of cyclohexane and 100 kg of 1,3 butadiene so that the monomer concentration was 15%. Next, the catalyst solution 1 was added so that the molar amount of neodymium salt was 0 · 15 mol, and the polymerization reaction was performed at 60 ° C for 120 minutes with stirring (the polymerization start temperature and the maximum temperature during polymerization are described in the table). ), After the polymerization conversion of the polymer reached almost 100%, 0.006 mol (0.04 mol per 1 mol of neodymium (Nd)) tin tetrachloride in cyclohexane was added, Denaturation reaction was performed for 1 minute. The reaction was stopped by adding 3 times mole of ethanol to Nd to obtain a polymer solution having a concentration of 15% containing the conjugate polymer P11 as the conjugate polymer (P1). In addition In the denaturation reaction, the Sn content in the polymer obtained by reprecipitation of PI twice was determined using the ICP internal standard method, confirming that the reaction rate of the denaturation reaction was 100%.

 Conjugated polymer P11 yield is 99.2%, cis 1,4 bond content and 1,2 bule bond content of butadiene unit moiety are 98.4% and 0.5%, Mooney, respectively. The viscosity (ML, 100 ° C) was 81.2 and the molecular weight distribution was 2.73. Also, tetrachloride

 1 + 4

 The coagulation properties before and after denaturation were 3 and 1, respectively.

[Production Examples 12 to 13]

 Except for changing the amount of diisobutylaluminum hydride (DIBAH) (component (C)) as shown in Table 1, the same procedure as in Production Example 11 was carried out to prepare polymers P 12 to P13 as conjugated diene polymers (P1). Obtained. These yields, cis-1,4 bond content and 1,2-bule bond content, Mooney viscosity (ML, 100 ° C) and molecular weight distribution of butadiene unit

 1 + 4

 Table 1 shows the solidification properties before and after modification with tin tetrachloride.

[0114] [Comparative Production Example C14]

 Polymer PC14 was obtained as a control conjugated diene polymer (P1) except that the amount of diisobutylaluminum hydride (DIBAH) (component (C)) was changed as shown in Table 1 and the same procedure as in Production Example 11 was performed. . These yields, cis-1,4 bond content and 1,2-bule bond content, Mooney viscosity (ML, 100 ° C) and molecular weight distribution of butadiene units.

 1 + 4

 Table 1 shows.

 In each table, “cis bond content” and “bull bond content” are respectively “cis bond content”.

“1, 4 bond content” and “1, 2 Bull bond content”.

[0115] [Table 1]

Comparative manufacturing

 Production Example 11 Production Example 12 Production Example 13

 Example C14 Conjugated polymer (P1) P11 P12 P13 PC14 Butadiene ZNd (kgZmol) 750 750 1500 750 Polymerization catalyst

 (A) component [mol] 1 1 1 1

Component (B) [Mole] 37 37 37 37 Butadiene (for aging) [Mole] 15 15 15 15

Component (C) [mol] 1.8 1.4 7 3

Component (D) [mol] 2 2 2 2

Component (B) Component (C) Molar ratio 20.6 26.4 5.3 12.3 Starting temperature (° c) 50 50 50 50

 ¾ trw; dish degree (.) 60 60 60 60 coupling agent (* 1) SnCI4 SnCI4 SnCI4 SnCI4 Amount used [mol] 0.04 0.04 0.04 0.04 w / Mn 2. 73 2.51 3.04 2.86 Mooney viscosity 81.2 99. 6 79.6 60. 5 Cis bond content (%) 98.4 98. 5 96.9 98.1 Vinyl bond content (%) 0.5 0.4 1.0 0. 6 Solidification

 Before denaturation 3 2 3 4 After denaturation 1 1 1 1

* 1 SnCI4: Tin tetrachloride (Production Examples 21-25)

 A stainless steel autoclave polymerization reactor is charged with different amounts of styrene, 1,3-butadiene, cyclohexane and a small amount of tetramethylenediamine as solvents, and then n-butyllithium is added as a polymerization catalyst. Polymerization was started at 40 ° C while stirring the contents. The internal temperature of the polymerization reactor rose to 60 ° C. After the polymerization reaction, the compounds shown in Table 2 as the coupling agent were each 0 · 13 monolayers (P21, coupling symmetric IJ fffi number (4), 0 to 1 mol of n-butyllithium used as the polymerization catalyst). 13 monoles (P22, the valence of the coupling agent is 4), 0.125 monoles (P23, the valence of the coupling agent is 6), 0.13 monoles (P2 4, the valence of the coupling agent is 4), and 0 · 13 moles (P25, coupling agent valence is 4) was added and reacted for 30 minutes, then methanol was added to stop the reaction, and the polymer was recovered by steam stripping. As a polymer (P2), a polymer P2;! To P25 was obtained.

These bound styrene content (content of aromatic bul unit), branching rate, butadiene unit Partial 1,2-bule bond content, Mooney viscosity (ML, 100 ° C) and molecular weight distribution

 1 + 4

 Are shown in Table 2.

[0117] [Table 2]

 SiCI4: Cay tetrachloride

 HCDS: Hexachlordisilane

 TMOS: Tetramethoxysilane

 Bonded styrene content (9¾) +2 X vinyl bond content

[Example 1]

 To the cyclohexane solution containing 100 parts of the conjugated diene polymer P11 as the conjugated diene polymer (P1) obtained in Production Example 11, aroma oil (trade name “Fukol Flex M”, manufactured by Fuji Kosan Co., Ltd. Min. 45.5%, VGC (viscosity specific gravity constant) = 0.975) 37.5 parts, anti-aging agent 2, 4-bis (n-octylthiomethyl) -6-methylphenol (Ciba Specialty Chemicals) , Trade name "IRGANOX 1520L") 0.15 part was added and mixed at 60 ° C for 30 minutes, then the polymer was analyzed by the steam stripping method, dried and oil-extended rubber composition 1 was obtained. Obtained.

Next, the obtained oil-extended rubber composition 1 was mixed with 55 parts of silica (made by Rhodia, trade name “Zeosil (R) 1165MP”, BET specific surface area = 160 m ² pH = 6.5), silane coupling agent (dedasa 5 parts, zinc oxide (zinc white # 1) 1.5 parts, stearic acid 2.0 parts and anti-aging agent N (l, 3-dimethylbutyl) -N-Feniru p-Phenylenediamine (trade name “NOCRACK 6C”, manufactured by Ouchi Shinsei Co., Ltd.) 3 parts was blended and kneaded in a Banbury type mixer for 6 minutes so that the discharge temperature of the kneaded product was 120 ° C. Later, the resulting mixture was transferred to an open roll at 50 ° C., and 0.9 parts of sulfur (S # 325) and a crosslinking accelerator N- (tert-butyl) -2-benzothiazole sulfenamide (flexis) Product name "Santo" Cure TBBS ") 1.5 parts were added and kneaded to obtain a crosslinkable oil-extended rubber composition 1.

 This crosslinkable oil-extended rubber composition 1 was vulcanized at 150 ° C. for 30 minutes to obtain a vulcanized product 1. Table 3 shows the results of evaluating the low heat build-up and wear resistance of this vulcanizate 1.

 [Examples 2 to 4]

 Process oil was changed to modified aroma oil t DAE (manufactured by Nippon Oil Co., Ltd., aroma component 25 · 8%), and for Examples 3 and 4, the type of conjugated polymer (P1) is shown in Table 3. The oil-extended rubber compositions 2 to 4, the crosslinkable oil-extended rubber compositions 2 to 4 and the vulcanizates 2 to 4 were obtained in the same manner as in Example 1, except that the low exothermic property and abrasion resistance were obtained. Sex was evaluated. The results are shown in Table 3.

 [Comparative Example 1]

 Instead of conjugation polymer P11 as conjugation polymer (P1), commercially available cobalt-catalyzed butadiene rubber as a control conjugation polymer (cis 1,4 bond content 96%, 1,2 bull bond content 2. 8%, Mooney viscosity (ML, 100 ° C) 80.5, molecule

 1 + 4

 Quantity distribution 2.6, Enomoto Zeon, trade name “Nipol BR1441J: Also, 37.5 parts of aroma oil per 100 parts of rubber (Fujikosan Co., Ltd., trade name“ Fukol Flex M ”) and 0.15 Part of the anti-aging agent 2, 4 bis (n-octylthiomethyl) 6 methylphenol. The vulcanizate C1 was obtained in the same manner as in Example 1, except that the low heat generation and wear resistance were evaluated. The results are shown in Table 3.

[0121] [Comparative Example 2]

 Conjugated polymer as conjugate polymer (P1) Conjugated polymer as P1 Conjugated polymer as reference conjugated polymer (P1) in place of P11 C2 was obtained, and its low heat build-up and wear resistance were evaluated. The results are shown in Table 3.

[0122] [Table 3] Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Example 4 Oil-extended rubber composition C1 C2 1 2 3 4 Conjugated polymer (P1) (BR1441) PC14 P11 P11 P12 P13 60.5 81. 2 81. 2 99. 6 79.6 Cis bond content (<< ½) 96.0 98. 1 98.4 98.4 98. 5 96.9 Process oil

 Type (* 4) ArOI ArOI ArOI Ar02 Ar02 Ar02 Crosslinkable oil-extended rubber composition C1 C2 1 2 3 4 Vulcanized product C1 C2 1 2 3 4 Low heat generation 100 91 86 66 61 73 Abrasion resistance 100 102 122 133 147 116

* 4: Ar01: manufactured by Fujikosan Co., Ltd., trade name Γ Futskor Flex M ”V. G. C. = 0. 9758 Ar02: Reformed Aloma Oil t—DAE (manufactured by Nippon Oil Corporation)

[0123] From the results shown in Table 3, the oil-extended rubber compositions (Examples;! To 4) using the conjugated gen polymer (P1) satisfying the provisions of the present invention are control conjugates not satisfying the provisions of the present invention. Compared to the oil-extended rubber composition (Comparative Examples 1 and 2) using a gene polymer, it has a low heat build-up and excellent wear resistance. From the results of Example 1, it can be seen that the oil-extended gen rubber composition of the present invention is excellent in low exothermic property. Further, from comparison between Example 1 and Comparative Example 2 and comparison between Examples 4 and 3, it can be seen that a higher Mooney viscosity is better in balance between low heat buildup and wear resistance. Furthermore, it can be seen from the comparison between Example 2 and Example 4 that the higher the cis content, the better the wear resistance.

 [Examples 5 to 9, Comparative Example 3]

 Instead of 100 parts of the conjugate polymer PI 1 as the conjugate polymer (P1), 60 parts of the conjugate polymer PI 1 and 40 parts of the natural rubber (RSS # 3) as the polymer (P2) Oil-extended rubber compositions 5-9, C3 and crosslinkable oil-extended rubber compositions 5-9, as in Example 1, except that the mixture is used and the process oil used is as shown in Table 4. Got C3. Using these crosslinkable oil-extended rubber compositions, the amount of sulfur was 1.1 parts, and 1,3-diphenyldanidine (trade name “Noxeller D”, manufactured by Ouchi Shinsei Co., Ltd.) was used as a crosslinking accelerator. Except for the use of 0.3 part, the same operations as in Example 1 were carried out to obtain vulcanizates 5 to 9 and C3, and the low exothermic properties and wear resistance of the vulcanizates were evaluated. The results are shown in Table 4. In the table, CA, CN, and CP represent the aroma content, the naphthene content, and the paraffin content, respectively.

[0125] [Table 4]

 * 5: ArOI: Fuji Kosan Co., Ltd., trade name Γ Fuccole Flex M ”V. G. C. = 0. 9758

 Ar02: Reformed aroma oil t—DAE (manufactured by Nippon Oil Corporation)

 Ar03: Paraffin oil. Product name “PW-90”, manufactured by Idemitsu Kosan Co., Ltd.

 Ar04: Naphthenic oil. Made by Idemitsu Kosan Co., Ltd., trade name “Diana Process Oil NS—100” ArOS: Naphten Oil, V. G. C. = 0. 9220.

 Made by Idemitsu Kosan Co., Ltd., trade name “Diana Process Oil NM— 1 50J

 Ar06: Made by Idemitsu Kosan Co., Ltd., trade name "Diana Process Oil NP 700"

[0126] From the results in Table 4, the strength of the oil-extended rubber composition obtained using a process oil containing 5% by weight or more of the aroma content. The obtained vulcanizate has an excellent balance between low heat buildup and wear resistance. ! I understand the power S. However, when the aroma content exceeds 40% by weight, the low exothermicity slightly decreases (Example 9), so the aroma content is 5-40%. It can be said that it is preferably between / ₀ .

 [Example 10]

 Conjugated polymer P1 1 as conjugate polymer (P1) obtained in the same manner as in Production Example 11, 30.5 parts of process oil shown in Table 5, and anti-aging agent 2, 4 Bis (n-octylthiomethyl) 6— An oil-extended rubber composition 1A was obtained in the same manner as in Example 1 by using 0.2 part of methyl phenol (trade name “IRGA NOX 1520L” manufactured by Ciba Specialty Chemicals).

On the other hand, commercially available emulsion polymerized styrene butadiene copolymer rubber (P2) Cis-1,4—bond content 12%, 1,2-bule bond content 13%, styrene content 35%, Mooney viscosity (ML, 100 ° C) 135, molecular weight distribution 3.8, manufactured by Nippon Zeon ,Product

 1 + 4

 The oil-extended rubber composition 28A was obtained in the same manner except that a 15% solution of the name “Nipol SBR9528R”) in cyclohexane was used and 37.5 parts of the process oil shown in Table 5 was used.

Yes

 In the Banbury mixer, oil-extended rubber composition 1A and oil-extended rubber composition 28A, SAF carbon black 40 parts, siri force (trade name, manufactured by Degusa), each containing 50 parts of rubber component and 18.75 parts of process oil ": BV7000GR", BET specific surface area = 170m2 / g, pH = 6.5)) 40 parts, 4 parts of silane coupling agent (made by Dedasa, trade name "Si75"), wax (made by Ouchi Shinsei Co., Ltd., product) Name “Sannok”) 10 parts, zinc oxide (zinc flower # 1) 2-5 parts, stearic acid 1/5 parts and anti-aging agent N— (1,3-dimethylbutyl) —N—Henrirou p—Hue Add 2 parts of direnamine (Ouchi Shinsei Co., Ltd., trade name “NOCRACK 6C”) and knead for 6 minutes so that the discharge temperature of the kneaded product is 120 ° C. Move to C open roll and further sulfur (S # 325) 1. 8 parts and crosslinking accelerator 1,3-diphenyldanidine (Ouchi Shinsei Co., Ltd., trade name “Noxeller D”) 0.8 parts and N-cyclohexyloxy 2-benzothiazolylsulfenamide (Ouchi Shinsei Co., Ltd., trade name “Noxeller CZ-G”) l. 8 Part was added and kneaded to obtain a crosslinkable mixed oil-extended rubber composition 10.

 This crosslinkable mixed oil-extended rubber composition 10 was vulcanized at 160 ° C. for 20 minutes to obtain a vulcanized product 10. Table 5 shows the results of evaluating the low heat build-up and wear resistance of the vulcanizate 10.

 [Examples 11 to 13]

 Crosslinkable mixed oil-extended rubber compositions 11 to 13 were obtained in the same manner as in Example 10 except that the polymers (P2) and process oils shown in Table 5 were used. From this, vulcanizates 11 to 13 were obtained in the same manner as in Example 10. Table 5 shows the results of evaluating the low heat build-up and wear resistance of these vulcanizates 11 to 13.

 The oils of the examples and comparative examples in Table 5 were adjusted with mineral oil t-DAE so that the total oil amount was 50.0 parts with respect to 100 parts of the total rubber amount, and were put into a Banbury mixer. .

[Example 14] A rubber composition 23B was prepared in the same manner as in Example 10 except that no process oil was used in preparing an oil-extended rubber composition from the polymer P23 as the polymer (P2). A crosslinkable mixed oil-extended rubber composition 14 was obtained in the same manner as in Example 10 except that the rubber composition 23B was used instead of the oil-extended rubber composition 28A. From this, a vulcanizate 14 was obtained in the same manner as in Example 10. The results of evaluating the low heat buildup and wear resistance of this vulcanizate 14 are shown in Table 5.

 [0130] [Comparative Example 4]

 A crosslinkable oil-extended rubber composition C4 was obtained in the same manner as in Example 11 except that the oil-extended rubber composition 1A was not used. From this, a vulcanizate C4 was obtained in the same manner as in Example 10. Table 5 shows the results of evaluating the low heat buildup and wear resistance of this vulcanizate C4.

[Examples 15 to 16]

 Conjugating polymer other than rubber component using 50 parts of polymer P23 instead of 40 parts of natural rubber as polymer (P2) with 50 parts of conjugating polymer P11 as conjugating polymer (P1) In the same manner as in Example 10 except that the conjugated polymer (P1) and the polymer (P2) were mixed in a solution and then an oil-extended rubber), Sexual mixed oil extended rubber composition 15 was obtained. From this, a vulcanizate 15 was obtained in the same manner as in Example 10. Table 5 shows the results of evaluating the low heat build-up and wear resistance of this vulcanizate 15.

 In addition, when obtaining a crosslinkable oil-extended rubber composition from the conjugate polymer PI 1 as the conjugate polymer (P1) and the polymer P23 as the polymer (P2), the amount of silica was increased by 40 parts. Then, a crosslinkable mixed oil-extended rubber composition 16 was obtained in the same manner as in Example 15 except that the amount of the silane coupling agent was increased by 4 parts. From this, a vulcanizate 16 was obtained in the same manner as in Example 10. Table 5 shows the results of evaluating the low heat buildup and wear resistance of the vulcanizate 16.

 From the results in Table 5, it can be seen that low heat buildup and wear resistance are better when the conjugated polymer (P1) and polymer rubber (P2) are mixed and then used as an oil-extended rubber ( Examples 15 and 16).

[0132] [Table 5] Comparative Example 4 Example 10 Example 11 Example 12 Oil-extended rubber composition-1A 1A 1A

 Conjugated polymer (P1)-P11 P11 P11

 Mooney viscosity-81. 2 81.2 81.2 Cis bond content (%)-98.4 98.4 98.4 Polymer rubber (P2)--■--Process oil

 Type (* 6)-Ar02 Ar02 Ar02 Oil-extended rubber composition 21A 28A 21A 22A

 Polymer rubber (P2) P21 (9528R) P21 P22 Process oil

 Type (* 6) Ar02 ArOI Ar02 Ar02 Amount (parts) 37.5 37.5 37.5 Crosslinkable mixed oil extended rubber composition C4 10 11 12 Vulcanizate O

 Low heat generation 100 97 94 90 Abrasion resistance 100 106 103 109

 * 6: ArOI: manufactured by Fuji Kosan Co., Ltd., trade name: ΓFoccole Flex MjV. G. C. = 0.9758 Ar02: Modified Aloma Oil t—DAE (manufactured by Nippon Oil Corporation)

 (Examples 17 to 22)

Cyclohexane solution containing 30 parts of the conjugate polymer P12 as the conjugate polymer (P1) obtained in Production Example 12 and 70 parts of the polymer P23 as the polymer (P2) obtained in Production Example 23 In addition, modified aroma oil t DAE (manufactured by Nippon Oil Co., Ltd. 25.8 parts), anti-aging agent 2, 4 bis (n-octylthiomethyl) 6 methylphenol (Ciba Specialty Chemicals, trade name “IRGANOX 1520L”), 0.2 part, and 60 ° C After mixing for 30 minutes, a polymer was precipitated by a steam stripping method and dried to obtain a mixed oil-extended rubber composition 17.

Subsequently, the obtained mixed oil-extended rubber composition 17 was mixed with silica (manufactured by Rhodia, trade name “Zeo sil (R) 1165MP”, BET specific surface area = 160 m ² / g, pH = 6.5) 80 parts, SAF 10 parts of carbon black, 5 parts of wax (made by Ouchi Shinsei Co., Ltd., trade name “Sannok”), silane coupling agent (made by Dedasa Co., Ltd., trade name “Si75”), 10% of silica, zinc oxide (zinc flower # 1 ) 2 parts, stearic acid 1.5 parts and anti-aging agent N— (1,3-dimethylbutyl) N Phenol p-Phenylenediamine (trade name “NOCRACK 6C” manufactured by Ouchi Shinsei Co., Ltd.) 2 parts And knead for 6 minutes so that the discharge temperature of the kneaded product becomes 120 ° C. Then, transfer the resulting mixture to an oven roll at 50 ° C, and further add 1. 9 parts of sulfur (S # 325) and Cross-linking accelerator 1,3-diphenino guanidine (made by Ouchi Shinsei Co., Ltd., trade name “Noxeller D”) 0.8 part and N cyclohexyl —2— 2 parts of benzothiazolylsulfenamide (made by Ouchi Shinsei Co., Ltd., trade name “Noxeller CZ-G”) was added and kneaded to obtain a crosslinkable (mixed) oil-extended rubber composition 17.

 This crosslinkable (mixed) oil-extended rubber composition 17 was vulcanized at 160 ° C. for 20 minutes to obtain a vulcanized product 17.

 Further, in the same manner as in Example 17, except that the types and amounts of the conjugated diene polymer (P1), the polymer (P2), and the process oil used are changed as shown in Table 6, Examples 18 to 22 Mixed oil-extended rubber compositions 18-22, crosslinkable (mixed) oil-extended rubber compositions 18-22, and carbonates 18-22 were obtained.

 Table 6 shows the results of evaluating the low heat buildup and wear resistance of vulcanizates 17-22.

(Comparative Example 5)

 Commercially available cobalt-catalyzed butadiene rubber (conjugated with a cis 1,4 bond content of 96%, 1,2 bulle bond content of 2.8%, Mooney viscosity) (ML, 100 ° C) 80.5, molecular weight distribution 2.6. Made by Nippon Zeon Co., Ltd.

 1 + 4

The mixed oil-extended rubber composition C5 and the crosslinkable (mixed) oil-extended rubber composition C5 were obtained in the same manner as in Example 17, except that the product name “Nipol BR1441”] was used. From this crosslinkable (mixed) oil-extended rubber composition C5, a vulcanizate C5 was obtained in the same manner as in Example 17, and the results of evaluating the low heat buildup and wear resistance are shown in Table 6.

[Table 6]

 * 7: Bonded styrene content (%) + 2 X vinyl bond content ()

 * 8: Ar02: Modified Aloma Oil t 1 DAE (manufactured by Nippon Oil Corporation) From the above results, the oil-extended rubber composition of the present invention exhibits excellent properties as a tire member. Therefore, it can be seen that a tire including a tire member obtained by using this oil-extended rubber composition is excellent in fuel efficiency and wear resistance.

Claims

The scope of the claims

 [1] Conjugated polymer having at least butadiene units, having a viscosity of 65 to 200 (ML, 100 ° C) and 1.5

 Conjugated polymer having a molecular weight distribution of 1 + 4 to 4.0 and having a cis 1,4 bond content of 96.5% or more and a butyl bond content of 1.0% or less in the butadiene unit portion. An oil-extended rubber composition comprising 100 parts by weight of a rubber component containing (P1) as an essential component and 10 to 120 parts by weight of a process oil containing 5% by weight or more of aroma.

 [2] Conjugated polymer (P1) has Mooney viscosity (ML, 100 ° C) of 75-;

 1 + 4

 2. The molecular weight distribution is 2.0 to 3.5, the cis 1,4 bond content in the butadiene unit portion is 97.5% or more and the bull bond content is 0.9% or less. The oil-extended rubber composition described in 1.

 [3] The oil-extended rubber composition according to claim 1 or 2, wherein the ratio of the butadiene units in the conjugate polymer (P1) is 80% by weight or more.

 [4] Using a polymerization catalyst in which the conjugation polymer (P1) is composed of a lanthanum series metal compound (A), an organoaluminum compound (B), an organoaluminum hydride compound (C), and a halogen compound (D). The oil-extended rubber composition according to any one of claims 1 to 3, which is obtained by polymerizing a monomer having butadiene as an essential component.

 [5] Conjugation polymer (P1) is composed of lanthanum series metal compound (A), organoaluminum compound (B), organoaluminum hydride compound (C), and halogen compound (D). The oil-extended rubber according to claim 4, which is obtained by polymerizing the monomer and further modifying with an organometallic halide (E) represented by the following general formula (1). Composition.

 [Chemical 1

R size R ² _{4. G} MX _g ) _h (l)

(In the formula, M is Si, Ge, Sn or Ti, and X is a halogen atom. When a plurality of X are present, they may be the same or different from each other. R ¹ is a single bond. Or a hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, and R ² represents hydrogen or It represents a hydrocarbon group having 1 to 20 carbon atoms which may contain a terror atom. When a plurality of R ² are present, they may be the same as or different from each other. g and h each represent an integer of !!-4. When h force, f is 0. When h-force ˜4, f is 1, and at least one R ² is bonded to R ¹ ! /, the force S, and R ² may be a single bond! /,).

 [6] The polymerization catalyst is composed of a lanthanum series metal compound (A), an organic alkylaluminum compound (B), an organic aluminum hydride compound (C), and a halogen compound (D). The molar ratio (B / C) force between B) and the organoaluminum hydride compound (C), which satisfies 5≤ (B / C) ≤1,000, Oil-extended rubber composition.

 [7] The oil-extended rubber composition according to any one of claims 1 to 6, wherein the process oil contains 10 to 40% by weight of aroma.

 [8] The oil-extended rubber composition according to any one of [1] to [7], wherein the rubber component is composed only of the conjugated polymer (P1).

 [9] The rubber component is a conjugation polymer ^ 1) of 5% by weight or more and a polymer rubber (P2) other than this conjugation polymer (P1) of 95% by weight or less. 8. The oil-extended rubber composition according to any one of items 1 to 7.

 [10] The polymer rubber (P2) other than the conjugated diene polymer (P1) is a copolymer of aromatic bur and conjugated diene, and has a viscosity of 100 to 200 (ML, 100 ° C) Conjugated Gen

 1 + 4

 The oil-extended rubber composition according to claim 9, which has a bull bond content of 7 to 85% in units.

[11] Rubber component 5 to 100 parts by weight; 120 parts by weight selected from the group consisting of silica, clay, talc, calcium carbonate, carbon black, carbon nanotubes, fullerenes, nylon short fibers, and aluminum hydroxide The oil-extended rubber composition according to any one of claims 1 to 10, further comprising at least one compounding agent.

[12] The method according to any one of claims 1 to 11, wherein the process oil is mixed with an organic solvent solution of a rubber component containing the conjugation polymer (P1) as an essential component, and then the solvent is removed. A method for producing an oil-extended rubber composition.

[13] The oil-extended rubber composition according to any one of claims 1 to 11 is crosslinked. A tire comprising the tire member according to claim 13.