JP4134732B2 - Rubber composition - Google Patents

Description

【００８３】

【００８４】
［素ゴム物性評価］
ミクロ構造は、赤外吸収スペクトル分析によって行った。シス７４０ｃｍ^-1、トランス９６７ｃｍ^-1、ビニル９１０ｃｍ^-1の吸収強度比からミクロ構造を算出した。
【００８５】
［η］は、トルエン溶液で３０℃の温度で測定した。
ムーニー粘度（ＭＬ₁₊₄）は、JIS K６３００に準拠して測定した。
【００８６】
トルエン溶液粘度（Ｔｃｐ）は、ポリマー２．２８gをトルエン５０mlに溶解した後、標準液として粘度計校正用標準液（JIS Z８８０９）を用い、キャノンフェンスケ粘度計No．４００を使用して、２５℃で測定した。
【００８７】
［配合物物性］
ダイスウェル
測定装置；モンサント社製加工性測定装置（MPT）
ダイ形状；円形
Ｌ／Ｄ；１ , １０（Ｄ＝１．５ｍｍ）
測定温度；１００℃
せん断速度；１０，１００ｓｅｃ^−１
【００８８】
ムーニー粘度は、ＪＩＳ−Ｋ−６３００に規定されている測定方法に従って測定した。
カーボンゲル
トルエンに配合物を室温で１日間浸漬抽出後、残存不溶解分を７０℃で１時間減圧乾燥する。
カーボンゲル（％）＝（残存不溶解分の乾燥物重量／配合物の重量）×１００
【００８９】
［加硫物物性］
硬度、反発弾性及び引張強度は、ＪＩＳ−Ｋ−６３０１に規定されている測定法に従って測定した。
【００９０】
動的粘弾性のｔａｎδは、レオメトリックス社製ＲＳＡ２を用いて、温度７０℃、周波数１０Ｈｚ、動歪２％の条件で測定した。
【００９１】
発熱特性 グッドリッチフレクソメーターを用い、ＡＳＴＭ Ｄ６２３に従い、歪み０．１７５インチ、荷重５５ポンド、１００℃２５分の条件で測定した。
【００９２】
耐摩耗性指数：ＪＩＳ Ｋ６２６４に準じてランボーン摩耗試験機を用いてスリップ率２０％で測定し、比較例１を１００として指数で評価した。指数が大きいほど耐摩耗性は良好である。
【００９３】
上記の実施例から明らかなように、ＨＣＨＶの相溶化の効果によりカーボンに物理及び化学吸着するNR/BRゴム成分が増加する（カーボンゲル量の増加）ことにより、加硫物の諸物性が向上する。（耐摩耗・発熱性の低下等）
【００９４】
【表１】

【００９５】
【表２】

【００９６】
【表３】

【００９７】
【表４】

【００９８】
【発明の効果】
本発明により、高シス−高ビニルポリブタジエンゴムによる変性基含有ゴムと非変性ゴム間のマクロな界面相溶性の改良、あるいは、ゴム間の界面相溶性の改良によるロール加工性、耐摩耗性、発熱性、引張・引裂き・破壊等の力学的特性の向上が図られる。[0001]
[Industrial application fields]
The present invention relates to a rubber composition comprising a modified group-containing rubber (a), an unmodified rubber (b) and a novel high cis high vinyl polybutadiene.
[0002]
[Prior art]
The polybutadiene has a so-called microstructure that includes a bond portion (1,4-structure) formed by polymerization at the 1,4-position and a bond portion (1,2-structure) formed by polymerization at the 1,2-position. Coexist in the molecular chain. The 1,4-structure is further divided into two types, a cis structure and a trans structure. On the other hand, the 1,2-structure has a structure in which a vinyl group is a side chain.
[0003]
It is known that polybutadienes having different microstructures described above are produced by polymerization catalysts, and they are used in various applications depending on their properties.
[0004]
As disclosed in JP-A-9-291108 (Patent Document 1) and the like, a metallocene complex of a vanadium metal compound and a polymerization catalyst comprising an ionic compound of a non-coordinating anion and a cation and / or an aluminoxane. The present applicant has found that a polybutadiene having a microstructure with a moderately high-cis structure and a 1,2-structure and a small number of trans structures and a high molecular linearity (linearity) can be produced. . Since this polybutadiene has excellent properties, its application to impact-resistant polystyrene resins, tires and the like has been studied.
[0005]
Japanese Patent Application Laid-Open No. 11-49924 (Patent Document 2) describes application of a composition comprising a specific high cis-high vinyl polybutadiene to a tire, which is useful for tread applications, and has a high impact resilience and skid resistance. It is described to have both.
[0006]
Further, various members of tires comprising 20 to 80% by weight of high cis-high vinyl polybutadiene produced by a metallocene catalyst by the present applicant, other diene rubbers, inorganic fillers, carbon black, silica, reinforcing materials and the like. Application to is disclosed. (For example, see Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, Patent Literature 7, Patent Literature 8, etc.)
[0007]
On the other hand, a rubber composition comprising a modified rubber obtained by modifying a diene rubber such as polybutadiene with various modifiers and its application to a tire are also disclosed. For example, Japanese Patent Laid-Open No. 2002-114872 (Patent Document 9) discloses a main chain-modified diene polymer obtained by reacting a diene rubber with an amine compound. JP-A-2001-40001 (Patent Document 10) discloses a modified polybutadiene modified with an organoalkoxysilane or an organoalloxysilane.
[0008]
JP-A-2001-247720 (Patent Document 11) discloses a modified butadiene rubber obtained by reacting an aliphatic compound having two amino groups. JP 2001-302703 A (Patent Document 12) discloses that polybutadiene is modified with an organosilicon compound having at least an epoxy group and an alkoxy group. JP 2000-1573 A (Patent Document 13) discloses a styrene-butadiene copolymer and / or a styrene-isoprene-butadiene copolymer having a nitrogen atom-containing group and a chlorosulfenyl group or chloro A modified diene rubber obtained by reacting with a compound having a sulfonyl group is disclosed. Japanese Unexamined Patent Publication No. 2000-178314 (Patent Document 14) discloses a modified polybutadiene characterized by modifying polybutadiene with a diamine compound.
[0009]
In recent years, demands for various properties of tires have been further increased, and further improvement of rubber compositions has been demanded.
[0010]
[Patent Document 1]
JP-A-9-291108
[Patent Document 2]
JP 11-49924 A
[Patent Document 3]
Japanese Patent Laid-Open No. 2002-265677
[Patent Document 4]
JP 2002-265678 A
[Patent Document 5]
JP 2002-265680 A
[Patent Document 6]
Japanese Patent Laid-Open No. 2002-265685
[Patent Document 7]
JP 2002-338740 A
[Patent Document 8]
JP 2002-338742 A
[Patent Document 9]
JP 2002-114872 A
[Patent Document 10]
Japanese Patent Laid-Open No. 2001-40001
[Patent Document 11]
JP 2001-302703 A
[Patent Document 12]
JP 2001-302703 A
[Patent Document 13]
JP 2000-1573 A
[Patent Document 14]
JP 2000-178314 A
[0011]
[Problems to be solved by the invention]
A composition comprising a rubber component having a unique microstructure composition possessed by a high cis-high vinyl polybutadiene, a modified group-containing rubber, and a non-modified rubber, wherein the high cis-high vinyl polybutadiene rubber has a modified group-containing rubber and an unmodified rubber. It aims to improve the interfacial compatibility of the rubber and improve the mechanical properties such as roll processability, wear resistance, heat generation, tension, tearing and fracture by improving the interfacial compatibility between rubbers.
[0012]
[Means for Solving the Problems]
  The present invention relates to an organic silicon compound having an amino group, an alkoxy group or the like, an aliphatic compound having an amino group such as a diamine compound, a compound having a nitrogen atom-containing group and having a chlorosulfenyl group or a chlorosulfonyl groupOr 2,3-dichloro-1,4-naphthoquinone or tetramethylthiuram sulfideAnd a high cis-high vinyl polybutadiene rubber (c) produced by a metallocene catalyst, the unmodified rubber (b) being polybutadiene and / or Natural rubber, wherein (c) is 1,2-structural unit content 4-30 mol%, cis-1,4-structural unit content 65-95 mol%, and trans-1,4-structural unit is contained The present invention relates to a rubber composition characterized by being polybutadiene having a rate of 5 mol% or less.
[0013]
  The present invention also provides theModified with denaturing agentThe rubber composition is characterized in that the rubber (a) is polybutadiene.
[0014]
  Used for (a)An organosilicon compound having an amino group or an alkoxy group, an aliphatic compound having an amino group such as a diamine compound, a nitrogen atom-containing group and a chlorosulfenyl group or a chlorosulfonyl groupThe modifying agent is 3- (2-aminoethylaminopropyl) trimethoxysilane.
[0016]
The present invention also relates to 100 parts by weight of a rubber mixture comprising 10 to 90% by weight of the modified group-containing rubber (a) and 90 to 10% by weight of the unmodified rubber (b) and a high cis produced by the metallocene catalyst. -It is preferable to consist of 0.1-10 weight part of high vinyl polybutadiene rubber (c).
[0017]
The present invention also relates to a tire rubber composition comprising the above rubber composition.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The (a) modified group-containing rubber of the present invention is obtained by modifying various raw rubbers by introducing a modified group. Examples of the raw rubber include natural rubber, high cis-polybutadiene, low cis-polybutadiene, styrene-butadiene rubber, polyisoprene, isoprene-isobutylene copolymer and other isoprene rubber, butyl rubber, acrylonitrile-butadiene rubber, and the like. Among these, high cis-polybutadiene is preferable.
[0019]
High cis-polybutadiene can be produced by polymerization using a transition metal compound catalyst system as a polymerization catalyst. Examples of transition metal compound catalyst systems include Ziegler-Natta catalysts such as cobalt-based catalyst compositions and nickel-based catalyst compositions, metallocene-based catalysts, and rare earth element catalysts.
[0020]
As the cobalt-based catalyst composition, a catalyst system comprising a cobalt compound, a halogen-containing organoaluminum compound and water, and as the nickel-based catalyst composition, a nickel-based catalyst composition comprising a nickel compound, an organoaluminum compound and a fluorine compound, Examples of the metallocene catalyst include a metallocene complex of a Group 5 transition metal compound in the periodic table, an ionic compound of a non-coordinating anion and a cation, an organoaluminum compound, and water. The rare earth element catalyst includes a composite catalyst system composed of a rare earth metal compound such as a neodymium compound and a group I to III organometallic compound such as an organoaluminum compound. Among these, a cobalt-based catalyst composition is preferable.
[0021]
Examples of the modifier for introducing the modifying group in the modifying group-containing rubber of the present invention include, for example, organoalkoxysilanes, among them, organosilicon compounds having amino groups, alkoxy groups, etc., aliphatic compounds having amino groups such as diamine compounds, A compound having a nitrogen atom-containing group and having a chlorosulfenyl group or a chlorosulfonyl group,
[0022]
Examples of specific compounds of organoalkoxysilane or organoalloxysilane include ethyltrimethoxysilane, triethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, Examples include hexyltrimethoxysilane, tetrabutoxysilane, and tetraphenoxysilane.
[0023]
There is no restriction | limiting in particular as organosilicon containing an alkoxy group etc., What is necessary is just a thing which can carry out an addition reaction to the double bond in a diene rubber. Examples thereof include those having an amino group and an alkoxy group in the molecule, those generally used as a silane coupling agent, and silane (alkoxysilane).
[0024]
Specifically, as an organosilicon compound containing an amino group and an alkoxy group in the molecule, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethylbutoxysilane, 3-aminopropylmethyldibutoxysilane, 3- (2 -Aminoethylaminopropyl) dimethoxymethylsilane, 3- (2-aminoethylaminopropyl) dimethoxyethylsilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) Triethoxysilane, and 3 (2-aminoethyl-aminopropyl) tributoxysilane silane and the like. Among these compounds, 3- (2-aminoethylaminopropyl) trimethoxysilane is preferably used particularly from the viewpoint of the modification effect.
[0025]
Examples of the aliphatic hydrocarbon having an amino group include ethylenediamine, trimethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,2-diaminomethane, 1,2-propanediamine, 1,3-propanediamine, 1, Examples include 4-diaminobutane, 2,7-diaminoheptane, 1,6-diaminohexane, and the like.
[0026]
Examples of the compound containing a chlorosulfenyl group include 2,4-dinitrobenzenesulfenyl chloride.
[0027]
Examples of the compound containing a chlorosulfonyl group include 4-nitrobenzenesulfonyl chloride.
[0028]
Moreover, you may use unsaturated carboxylic acid or its derivative (s), for example, maleic acid, fumaric acid, acrylic acid, methacrylic acid, and derivatives thereof. Specifically, an acid anhydride such as maleic anhydride and phthalic anhydride, an alkyl ester such as methyl acrylate and 2-ethylhexyl acrylate, an alkoxyalkyl ester such as methoxy acrylate, ethoxyethyl acrylate, and methoxyethoxyethyl acrylate, Examples include acrylamide, methacrylamide, N-methyl (meth) acrylamide, and the like.
[0029]
Carboxylic acid esters or carbonate esters may be used. For example, the ester compound of carboxylic acid and alcohol or phenol, the ester compound of carbonic acid and alcohol or phenol, etc. are mentioned. Specific examples thereof include ethyl acetate, butyl stearate, diethyl adipate, diethyl maleate, methyl benzoate, ethyl acrylate, methyl methacrylate, diethyl phthalate, diethyl isophthalate, diethyl terephthalate, or dimethyl carbonate. And carbonate esters such as diethyl carbonate, dipropyl carbonate, dihexyl carbonate, dicyclohexyl carbonate and diphenyl carbonate.
[0030]
A compound such as 2,3-dichloro-1,4-naphthoquinone may also be used.
[0031]
Further, a compound such as tetramethyl thiuram sulfide may be used.
[0032]
Rubber-modified epoxy or maleated rubber may be used.
[0033]
As a modification method, a modification reaction may be performed immediately after the production of the diene rubber, or a modification and a diene rubber may be contacted and modified in an organic solvent. As other methods, it is also possible to directly knead and modify by an extrusion kneader. The modification may be main chain modification or terminal modification.
[0034]
Examples of the unmodified rubber (b) of the present invention include natural rubber, high cis-polybutadiene, low cis-polybutadiene, styrene-butadiene rubber, polyisoprene, isoprene-isobutylene copolymer and the like isoprene rubber, butyl rubber, chlorinated butyl rubber, bromine Butyl rubber, acrylonitrile-butadiene rubber and the like. Among these, natural rubber is preferable.
[0035]
The high cis-high vinyl polybutadiene rubber (HCHV) (c) produced by the metallocene catalyst of the present invention has a cis-1,4-structural unit content in the microstructure of 65 to 95 mol%, preferably 70 to 90 mol% and 1,2-structural unit content are 4-30 mol%, preferably 5-25 mol%, more preferably 7-15 mol%. Further, the trans-1,4-structural unit content is preferably 5 mol% or less, particularly preferably 0.5 to 4.0 mol%.
[0036]
Moreover, 5% toluene solution viscosity (T-cp) and Mooney viscosity (ML) at 25 ° C. of HCHV_{1 + 4}) Is preferably in a range satisfying the following formula (I).
1 ≦ T-cp / ML_{1 + 4}≦ 6. . . (I)
Particularly preferably, 2 ≦ T-cp / ML_{1 + 4}≦ 6 is satisfied.
[0037]
Moreover, 20-500 are preferable and, as for the toluene solution viscosity (Tcp) of HCHV, 30-300 are especially preferable.
[0038]
HCHV Mooney Viscosity (ML_{1 + 4}) Is preferably 10 to 200, particularly preferably 25 to 100.
[0039]
The molecular weight of HCHV is preferably 0.1 to 10, particularly preferably 0.1 to 3, as the intrinsic viscosity [η] measured in toluene at 30 ° C.
[0040]
The molecular weight of HCHV is preferably in the following range as the molecular weight in terms of polystyrene.
Number average molecular weight (Mn): 0.2 × 10^Five-10x10^Five, More preferably 0.5 × 10^Five~ 5x10^Five
Weight average molecular weight (Mw): 0.5 × 10^Five~ 20x10^Five, More preferably 1 × 10^Five-10x10^Five
[0041]
Moreover, the molecular weight distribution (Mw / Mn) of HCHV of this invention becomes like this. Preferably it is 1.5-3.5, More preferably, it is 1.6-3.
[0042]
The above HCHV is, for example,
It can be produced by polymerizing butadiene using (A) a metallocene complex of a transition metal compound and (B) an ionic compound of a non-coordinating anion and a cation and / or a catalyst obtained from an aluminoxane.
[0043]
Or (A) a metallocene complex of a transition metal compound,
(B) an ionic compound of a non-coordinating anion and a cation,
(C) an organometallic compound of Group 1-3 elements of the periodic table, and
(D) Water
Can be produced by polymerizing butadiene using a catalyst obtained from
[0044]
Examples of the metallocene complex of the transition metal compound (A) include metallocene complexes of Group 4-8 transition metal compounds of the periodic table.
[0045]
For example, metallocene complexes of Group 4 transition metals such as titanium and zirconium (for example, CpTiCl_ThreeMetallocene type complexes of group 5 transition metals such as vanadium, niobium and tantalum, group 6 transition metal metallocene type complexes such as chromium, and metallocene type complexes of group 8 transition metals such as cobalt and nickel. Can be mentioned.
[0046]
Among these, metallocene type complexes of group 5 transition metals of the periodic table are preferably used.
[0047]
As the metallocene complex of the Group 5 transition metal compound of the above periodic table,
(1) RM.La, that is, a group 5 transition metal compound having an oxidation number of +1 having a ligand of a cycloalkadienyl group
(2) R_n MX_2-n La, that is, a group 5 transition metal compound with an oxidation number of +2 having a ligand of at least one cycloalkadienyl group
(3) R_n MX_3-n ・ La
(4) RMX_Three ・ La
(5) RM (O) X₂ ・ La
(6) R_n MX_3-n (NR ')
(In the formula, n is 1 or 2, and a is 0, 1 or 2).
[0048]
Above all, RM / La, R_n MX_2-n ・ La, R₂ M ・ La 、 RMX_Three ・ La and RM (O) X₂ -La etc. are mentioned preferably.
[0049]
M is preferably a Group 5 transition metal compound in the periodic table.
[0050]
(A) As the metallocene complex of the Group 5 transition metal compound of the periodic table, a vanadium compound in which M is vanadium is particularly preferable. For example, RV · La, RVX · La, R₂ M ・ La 、 RMX₂ ・ La and RMX_Three ・ La and RM (O) X₂ -La etc. are mentioned preferably. In particular, RV / La, RMX_Three -La is preferred.
[0051]
RMX_Three Specific examples of the compound represented by La include the following:
And cyclopentadienyl vanadium trichloride.
[0052]
RM (O) X₂ Specific compounds represented by the formula: cyclopentadienyloxovanadium dichloride, methylcyclopentadienyloxovanadium dichloride, benzylcyclopentadienyloxovanadium dichloride, (1,3-dimethylcyclopentadienyl) oxovanadium Examples include dichloride.
[0053]
Examples of the non-coordinating anion constituting the ionic compound of the non-coordinating anion and the cation as the component (B) include tetra (phenyl) borate and tetra (fluorophenyl) borate. It is done.
[0054]
On the other hand, examples of the cation include trisubstituted carbonium cations such as triphenylcarbonium cation.
[0055]
Moreover, you may use an alumoxane as (B) component. The alumoxane is obtained by bringing an organoaluminum compound and a condensing agent into contact with each other, and includes a chain aluminoxane represented by the general formula (—Al (R ′) O—) n or a cyclic aluminoxane. (R ′ is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an alkoxy group. N is the degree of polymerization and is 5 or more, preferably 10 or more) . Examples of R ′ include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and a methyl group is preferable.
[0056]
The (A) component and the (B) component may be further combined with an organometallic compound of Group 1 to 3 elements of the periodic table as the (C) component to polymerize a conjugated diene. The addition of component (C) has the effect of increasing the polymerization activity. Examples of organometallic compounds of Group 1 to 3 elements of the periodic table include organoaluminum compounds, organolithium compounds, organomagnesium compounds, organozinc compounds, and organoboron compounds.
[0057]
As a combination of the above catalyst components, (A) component cyclopentadienyl vanadium trichloride (CpVCl)_Three) Etc. RMX_ThreeOr cyclopentadienyloxovanadium dichloride (CpV (O) Cl₂) RM (O) X₂The combination of trialkylcarbenium tetrakis (pentafluorophenyl) borate as component (B) and trialkylaluminum such as triethylaluminum as component (C) is preferably used.
[0058]
Moreover, when using an ionic compound as (B) component, you may use combining said alumoxane as (C) component.
The order of addition of the catalyst components is not particularly limited.
[0059]
In the present invention, it is preferable to add water as the component (D) as the catalyst system. The molar ratio (C) / (D) between the organoaluminum compound (C) and the water (D) is preferably 0.66 to 5, and more preferably 0.7 to 1.5. .
[0060]
Moreover, hydrogen can coexist as needed at the time of superposition | polymerization.
[0061]
Here, the butadiene monomer to be polymerized may be the whole amount or a part thereof. In the case of part of the monomer, the above contact mixture can be mixed with the remaining monomer or the remaining monomer solution.
[0062]
The polymerization method is not particularly limited, and solution polymerization, bulk polymerization using 1,3-butadiene itself as a polymerization solvent, or the like can be applied. Aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, 1-butene, 2-butene and the like Examples thereof include hydrocarbon solvents such as olefinic hydrocarbons, mineral spirits, solvent naphtha and kerosene, and halogenated hydrocarbon solvents such as methylene chloride.
[0063]
A mixture of a low molecular weight HCHV component and a high molecular weight HCHV component may also be used.
[0064]
Examples of the method for adjusting the molecular weight in the present invention include polymerizing a conjugated diene compound in the presence of a chain transfer agent such as hydrogen using the above catalyst.
[0065]
In addition to various types of carbon black, rubber reinforcing agents include inorganic reinforcing agents such as white carbon, activated calcium carbonate, and ultrafine magnesium silicate, syndiotactic 1.2 polybutadiene resin, polyethylene resin, polypropylene resin, high styrene resin, and phenol. Organic reinforcing agents such as resin, lignin, modified melamine resin, coumarone indene resin and petroleum resin may be added. Particularly preferred is carbon black having a particle size of 90 nm or less and a dibutyl phthalate (DBP) oil absorption of 70 ml / 100 g or more, and examples thereof include FEF, FF, GPF, SAF, ISAF, SRF, and HAF.
[0066]
In the present invention, the proportion of the rubber composition comprising the modified group-containing rubber (a), the unmodified rubber (b) and the HCHV (c) is 10 to 90% by weight of the modified group-containing rubber (a) and the unmodified rubber ( b) It is preferably composed of 100 parts by weight of a rubber mixture comprising 90 to 10% by weight and 0.1 to 10 parts by weight of a high cis-high vinyl polybutadiene rubber (c) produced by the metallocene catalyst.
[0067]
The rubber composition of the present invention can be obtained by kneading the above components using a conventional Banbury, open roll, kneader, biaxial kneader or the like.
[0068]
The rubber composition of the present invention is kneaded with a compounding agent usually used in the rubber industry, such as a vulcanizing agent, a vulcanization aid, an anti-aging agent, a filler, process oil, zinc white, and stearic acid, if necessary. May be.
[0069]
As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, resin vulcanizing agents, and metal oxides such as magnesium oxide are used.
[0070]
As the vulcanization aid, known vulcanization aids such as aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, xanthates and the like are used.
[0071]
Examples of the filler include inorganic fillers such as calcium carbonate, basic magnesium carbonate, clay, Lissajous and diatomaceous earth, and organic fillers such as recycled rubber and powder rubber.
.
[0072]
Examples of the anti-aging agent include amine / ketone series, imidazole series, amine series, phenol series, sulfur series and phosphorus series.
[0073]
The process oil may be any of aromatic, naphthenic, and paraffinic.
[0074]
The rubber composition of the present invention is used as a rubber composition suitable for applications such as treads and sidewalls of tires that are more balanced and have improved physical properties such as improved wear resistance and reduced heat generation. It is done.
[0075]
【Example】
(Reference Example 1) (Production of high cis-high vinyl polybutadiene)
A toluene solution (1.3-butadiene: 814 g) containing 30 wt% of 1.3-butadiene is charged into a 5 L autoclave equipped with a stirrer purged with nitrogen and stirred. Then, hydrogen gas was introduced to 0.092 kgG / cm²Only the pressure was increased. Triethylaluminum (2.25 mmol) was added successively at 30 ° C. over 3 minutes, followed by trityltetra (perfluorophenyl) borate (0.039 mmol) and cyclopentadienyl vanadium trichloride (0.026 mmol). Polymerization was carried out for minutes.
After the polymerization, an equivalent mixture of ethanol and heptane containing 2,6-di-t-butyl-p-cresol was injected to stop the reaction, and the solvent was evaporated and dried. The yield of the obtained polymer was 32%, and the microstructure, Mooney viscosity, and 5% toluene solution viscosity are shown in Table 1. It was shown to.
[0076]
As high cis-polybutadiene, UBEPOL made by Ube Industries, which was polymerized with a Co-based catalyst, was used. Further, those polymerized with an Nd-based catalyst were also used.
[0077]
Reference Example 2 Production of modified group-containing rubber (a)
Using a nitrogen-substituted 1.5 L autoclave, 670 g of cyclohexane and 260 g of 1,3-butadiene were charged under nitrogen. Next, distilled water (2.3 mmol), n-hexane solution of diethylaluminum chloride (2.9 mmol) and cyclooctadiene (4.24 mmol) were added and the temperature was raised. When the internal temperature reached approximately 58 ° C., a benzene solution of cobalt octenoate (0.0087 mmol) as a catalyst was charged, and polymerization was performed at 60 ° C. for 30 minutes. The reaction conversion of 1,3-butadiene was approximately 40%.
Next, the temperature of the polymerization solution was kept at 60 ° C., and 3- (2-aminoethylaminopropyl) trimethoxysilane (1.78 mmol) was added and reacted for 120 minutes. After completion of the reaction, discharge the unreacted gas out of the system, add a methanol solution containing 0.5 g of 2,4-di-tert-butyl-p-cresol, stop the polymerization, and vacuum dry at 100 ° C for 90 minutes. To obtain a polymer.
[0078]
Reference Example 3 Production of modified group-containing rubber (a)
Using a nitrogen-substituted 1.5 L autoclave, 670 g of cyclohexane and 85 g of 1,3-butadiene were charged under nitrogen. Next, a cyclohexane solution of neodymium versatate (0.0252 mmol), a toluene solution of methylalumoxane (4.032 nmol), a diisobutylaluminum hydride (2.2 mmol) and a toluene solution of diethylaluminum chloride (0.05 mmol), 5 times that of neodymium. An amount of 1,3-butadiene (1.146 mmol) was added to a catalyst which was aged at 50 ° C. for 30 minutes, and polymerization was carried out at 80 ° C. for 60 minutes. The reaction conversion of 1,3-butadiene was almost 100%.
Next, while maintaining the temperature of this polymerization solution at 50 ° C., 2,3-dichloro-1,4-naphthoquinone (1.26 mmol) was added and reacted for 30 minutes. Thereafter, a methanol solution containing 0.5 g of 2,4-di-tert-butyl-p-cresol was added, and after the polymerization was terminated, the polymer was obtained by vacuum drying at 100 ° C. for 90 minutes.
[0079]
Reference Example 4 Production of Modified Group-Containing Rubber (a)
Example-2 except that tetramethylthiuram disulfide (1.26 mmol) was added instead of 2,3-dichloro-1,4-naphthoquinone. In the same manner as above, a polymer was obtained.
[0080]
(Examples 1-3) (Comparative Examples 1-4)
Using a rubber composition comprising a modified group-containing high cis polybutadiene (a), natural rubber (b), and high cis high vinyl polybutadiene (HCHV) (c), according to the formulation shown in Table 1, the method described below Formulated and vulcanized. Each characteristic was shown to Tables 2-4. .
[0081]
Evaluation items and implementation conditions
Kneading method
Kneading according to the following procedure.
[Primary formulation]
Kneading device: Banbury mixer (capacity 1.7L)
Rotation speed: 77rpm
Start temperature: 90 ° C
Kneading procedure:
0 minutes; put rubber
1 minute; filler filling
3 minutes; Raise the ram and clean (15 seconds)
5 minutes; dump
The dumped material was continuously wound on a 10-inch roll for 1 minute, rounded 3 times, and then sheeted. The compound was cooled for 2 hours or more and then subjected to secondary blending according to the following procedure.
[0082]
[Secondary formulation]
After completion of the primary blending, secondary blending was performed according to the following procedure.

[0083]

[0084]
[Rubber properties evaluation]
The microstructure was performed by infrared absorption spectrum analysis. Cis 740cm^-1, Transformer 967cm^-1Vinyl 910cm^-1The microstructure was calculated from the absorption intensity ratio.
[0085]
[Η] was measured with a toluene solution at a temperature of 30 ° C.
Mooney viscosity (ML_{1 + 4}) Was measured according to JIS K6300.
[0086]
Toluene solution viscosity (Tcp) was obtained by dissolving 2.28 g of polymer in 50 ml of toluene, and using viscometer calibration standard solution (JIS Z 8809) as the standard solution. 400 was used and measured at 25 ° C.
[0087]
[Formulation properties]
Die swell
Measuring device: Processability measuring device (MPT) manufactured by Monsanto
Die shape; circular
L / D; 1, 10 (D = 1.5mm)
Measurement temperature: 100 ° C
Shear rate: 10,100 sec^-1
[0088]
The Mooney viscosity was measured according to a measurement method defined in JIS-K-6300.
Carbon gel
The mixture is extracted by immersion in toluene at room temperature for 1 day, and the remaining insoluble matter is dried under reduced pressure at 70 ° C. for 1 hour.
Carbon gel (%) = (dry weight of residual insoluble matter / weight of blend) × 100
[0089]
[Vulcanized physical properties]
Hardness, impact resilience, and tensile strength were measured according to the measurement method defined in JIS-K-6301.
[0090]
The tan δ of dynamic viscoelasticity was measured using a RSA2 manufactured by Rheometrics under the conditions of a temperature of 70 ° C., a frequency of 10 Hz, and a dynamic strain of 2%.
[0091]
Exothermic characteristics A Goodrich flexometer was used and measured according to ASTM D623 under conditions of strain 0.175 inch, load 55 pounds, 100 ° C. for 25 minutes.
[0092]
Abrasion resistance index: Measured with a slip rate of 20% using a Lambourn abrasion tester in accordance with JIS K6264, and Comparative Example 1 was evaluated as 100. The higher the index, the better the wear resistance.
[0093]
As is apparent from the above examples, the physical properties of the vulcanizate are improved by increasing the amount of NR / BR rubber components that are physically and chemically adsorbed on the carbon due to the compatibilizing effect of HCHV (increasing the amount of carbon gel). To do. (Abrasion resistance, exothermic deterioration, etc.)
[0094]
[Table 1]

[0095]
[Table 2]

[0096]
[Table 3]

[0097]
[Table 4]

[0098]
【The invention's effect】
According to the present invention, high interfacial compatibility between modified group-containing rubber and non-modified rubber is improved by high cis-high vinyl polybutadiene rubber, or roll processability, wear resistance, heat generation by improving interfacial compatibility between rubbers. And mechanical properties such as tension, tearing, and fracture are improved.

Claims (5)

Organosilicon compounds having amino groups, alkoxy groups, etc., aliphatic compounds having amino groups such as diamine compounds, compounds having nitrogen atom-containing groups and having chlorosulfenyl or chlorosulfonyl groups, or 2,3-dichloro A rubber modified with a modifier of 1,4-naphthoquinone or tetramethylthiuram sulfide (a), an unmodified rubber (b) and a high cis-high vinyl polybutadiene rubber (c) produced by a metallocene catalyst, The unmodified rubber (b) is polybutadiene and / or natural rubber, and (c) has a 1,2-structural unit content of 4-30 mol% and a cis-1,4-structural unit content of 65-95 mol%. And a polybutadiene having a trans-1,4-structure unit content of 5 mol% or less. Composition. The rubber composition according to claim 1, wherein the rubber (a) modified with the modifier is polybutadiene. An organosilicon compound having an amino group or an alkoxy group used in (a), an aliphatic compound having an amino group such as a diamine compound, a nitrogen atom-containing group, and a chlorosulfenyl group or a chlorosulfonyl group The rubber composition according to claim 1 or 2, wherein the modifier is 3- (2-aminoethylaminopropyl) trimethoxysilane. A high cis-high vinyl polybutadiene rubber produced by 100 parts by weight of a rubber mixture comprising 10 to 90% by weight of the modified group-containing rubber (a) and 90 to 10% by weight of the unmodified rubber (b) and the metallocene catalyst ( The rubber composition according to any one of claims 1 to 3 , which comprises c) 0.1 to 10 parts by weight. A rubber composition for tires comprising the rubber composition according to any one of claims 1 to 4.