JP5649498B2 - Modified conjugated diene polymer, rubber composition and tire - Google Patents

Description

  The present invention is effective in reducing hysteresis loss, having at least one group that reacts with a polymer component and at least one group that has an affinity for a filler (filler) at different locations in a conjugated diene polymer. The present invention relates to a modified conjugated diene polymer excellent in low heat buildup and wear resistance, a rubber composition containing the modified conjugated diene polymer, and a tire using the rubber composition.

In recent years, demands for reducing the fuel consumption of automobiles are becoming more severe in connection with the movement of global carbon dioxide emission regulations due to the social demand for energy saving and the increasing interest in environmental problems.
In order to meet such demands, a reduction in rolling resistance has also been demanded for tire performance. As a method of reducing the rolling resistance of the tire, a method by optimizing the tire structure has been studied, but a material having a lower hysteresis loss, that is, a loss of mechanical energy to heat, should be used as a rubber composition. Is the most common method.

Hysteresis loss is often attributed to the separation of filler aggregates in addition to the free ends of the polymer within the crosslinked rubber network. Modified conjugated diene polymers are used to reduce hysteresis loss and increase bound rubber. It is believed that the functional groups of the modified conjugated diene polymer reduce the number of free ends of the polymer. Also, the functional groups interact with the filler particles to suppress filler agglomeration, thereby reducing hysteresis loss (ie, the Payne effect) due to separation of filler agglomerates. .
Conventionally, a modified conjugated diene polymer having a functionality at the tip of a polymer chain has been obtained by selecting a specific functional anionic polymerization initiator. It is also possible to attach a functional group to the end of the anionically polymerized polymer by stopping the living polymer with a functional compound.

In order to obtain such a rubber composition with low hysteresis loss, a method of modifying the polymerization active terminal of a diene polymer obtained by anionic polymerization using an organolithium compound with a functional group having an interaction with a filler. Is, for example, a method in which carbon black is used as a filler and a polymerization active terminal is modified with a tin compound (see, for example, Patent Document 1). Similarly, a method in which an amino group is introduced into a polymerization active terminal using carbon black ( For example, see Patent Document 2).
In addition, as a method of obtaining a rubber composition that gives tires both good fuel economy and good wet performance, hydrous silicic acid, etc., instead of carbon black, which has been generally used so far, as a reinforcing filler In the case of using silica, it is attempted to use a rubber material obtained by modifying the polymerization active terminal of a diene polymer obtained by anionic polymerization using an organolithium compound with a functional group having an interaction with the silica. ing. For example, a method is known in which silica is used as a filler and the polymerization active terminal is modified with a silicon compound having an alkoxyl group (see, for example, Patent Documents 3, 4, and 5).

  However, a copolymer obtained by modifying the polymerization active terminal of the above-mentioned diene polymer with a functional group having an interaction with a filler such as carbon black or silica is not necessarily satisfactory in reducing hysteresis loss. There was a problem that was not.

Therefore, the present applicant uses a sulfur-containing initiator for anionic polymerization of a monomer, thereby containing a functional polymer, which is a modified conjugated diene polymer having a leading group derived from a sulfur-containing initiator, the functionality. Have proposed a rubber compound and a tire component (see, for example, Patent Document 6). This modified conjugated diene polymer contains a sulfur (S) group, which enables cross-linking with other polymers, increases the network between polymers, suppresses movement of polymer ends, and reduces hysteresis loss. However, a modified conjugated diene polymer effective for further reduction of hysteresis loss and the like is desired. Further, this functional polymer of Patent Document 6, since a dithiane starting polymer terminating agent is a filler reactive modifier, such as DMI, fillers reactivity officers with functional group capable of bonding to the polymer main chain Although it has a functional group, it is different from the modified conjugated diene polymer of the present invention in that a strong polymer filler network that is the object of the present invention is not formed because the filler reactivity is weak, and it is differentiated. Is.

On the other hand, as a technique close to the present invention, living anion elastomer polymer, and an elastomer polymer chain-end modified with a silane-sulfide modifier represented by a specific formula {in the formula, R ₃ Si-S-R'-Si [(OR) x (R) y] -P (polymer)}, the elastomeric polymer, a vulcanized elastomeric polymer composition containing a filler (filler) such as carbon black and silica, and a vulcanizing agent, and the vulcanized elastomeric polymer Tire treads containing the composition (see, for example, Patent Document 7) are known.

  However, the elastomer polymer chain-end-modified with this silane-sulfide modifier contains a sulfur (S) group that is a main chain crosslinkable functional group, so that crosslinking with other polymers becomes possible, and a filler ( Filler) Containing SiOR groups that are reactive cross-linkable groups makes it compatible with fillers such as carbon black and silica, and is effective in reducing hysteresis loss by improving the dispersibility of fillers. However, since a single modifier (modifier) contains two functional groups, a large polymer / filler (filler) network by filler reaction + main chain crosslinking reaction is There is a problem that the effect of reducing hysteresis loss is limited and is not necessarily satisfactory.

Japanese Patent Publication No. 5-87530 (Claims, Examples, etc.) JP-A-62-207342 (Claims, Examples, etc.) Japanese Patent Publication No. 6-57767 (Claims, Examples, etc.) JP-A-7-233216 (Claims, Examples, etc.) JP-A-9-87426 (Claims, Examples, etc.) JP-T-2006-504866 (Claims, Examples, etc.) JP 2009-512762 A (Claims, Examples, etc.)

  The present invention is to solve this problem in view of the above-described conventional problems. By obtaining a large polymer / filler network by filler (filler) reaction + main chain crosslinking reaction, hysteresis loss can be reduced. A modified conjugated diene polymer having a special effect and excellent in low heat buildup and wear resistance, a rubber composition containing the modified conjugated diene polymer, and a low heat buildup using the rubber composition, An object is to provide a tire excellent in wear resistance and ride comfort.

  As a result of intensive studies on the above-described conventional problems, the present inventors have found that groups that react with the polymer component and groups that have an affinity for the filler (filler) at different locations in the conjugated diene polymer. By introducing at least one of each, a modified conjugated diene polymer for the above purpose, which can simultaneously generate a filler reaction and a polymer main chain crosslinking reaction in one polymer, a rubber composition containing the same, and the rubber The inventors have found that a tire using the composition can be obtained, and have completed the present invention.

〔上記式（Ｉ）中、Ａは、下記式（IV）で表される基であり、Ｂは硫黄原子を含み、かつポリマー成分と反応する基であり、Ｐはポリマー鎖である。〕

〔上記式（II）中、Ａは、下記式（IV）で表される基であり、ＣはＸ−Ｂの構造を有し、Ｘは共重合可能な部位、Ｂは硫黄原子を含み、かつポリマー成分と反応する基であり、Ｐはポリマー鎖である。〕

〔上記式（III）中、Ｂは硫黄原子を含み且つポリマー成分と反応する基であり、ＤはＸ−Ａの構造を有し、Ｘは共重合可能な部位、Ａは下記式（IV）で表される基であり、Ｐはポリマー鎖である。〕

〔上記式（IV）中、ｎは、０〜２、ｍは１〜２、３−ｎ−ｍ≧０を満たす整数であり、Ｒ^１は炭素数１〜２０の２価の炭化水素基または炭素数６〜１８の２価の芳香族炭化水素基であり、Ｒ^２及びＲ^３は、それぞれ炭素数１〜２０の１価の炭化水素基または炭素数６〜１８の１価の芳香族炭化水素基またはハロゲン原子または窒素原子を含む飽和炭化水素基であり、Ｚは飽和環状３級アミン化合物残基、不飽和環状３級アミン化合物残基、ケチミン残基、ニトリル基、（チオ）イソシアナート基、ピリジン基、アミド基、並びに加水分解可能な基を有する１級若しくは２級アミノ基から選択される少なくとも１種の官能基である。〕
（３） 前記式（Ｉ）〜（III）中の硫黄原子を含み、かつポリマー成分と反応する基Ｂが、それぞれ、ポリサルファイド基、チオエステル基、チオール基、ジチオカーボネート基、ジチオアセタール基、ヘミチオアセタール基、ビニルチオ基、α−チオカルボニル基、β−チオカルボニル基、Ｓ−ＣＯ_２−Ｏ部分、Ｓ−ＣＯ−ＣＯ部分、及びＳ−ＣＨ_２―Ｓｉ部分からなる群から選択される少なくとも１種を含むことを特徴とする上記（２）記載の変性共役ジエン系重合体。
（４） 平均分子量が１５，０００〜１，０００，０００であり、ガラス転移温度（Ｔｇ）が−９０℃〜０℃であることを特徴とする上記（１）〜（３）の何れか一つに記載の変性共役ジエン系重合体。
（５） 上記（１）〜（４）の何れか一つに記載の変性共役ジエン系重合体を少なくとも１０質量部以上含むゴム成分１００質量部に対して、無機充填材１０〜１５０質量部を含有することを特徴とするゴム組成物。
（６） 上記（５）記載のゴム組成物をタイヤ構成部材の何れか一つに用いたことを特徴とするタイヤ。 That is, the present invention resides in the following (1) to (6).
(1) A modified conjugated diene polymer having, as a modifying group, a group that reacts with a polymer component and a group that has an affinity for a filler, and the group that has an affinity includes a nitrogen atom and a silicon atom. A modified conjugated diene polymer characterized by having both.
(2) The modified conjugated diene polymer according to the above (1), which is represented by any one of the following formulas (I) to (III).

[In the above formula (I), A is a group represented by the following formula (IV), B is a group containing a sulfur atom and reacting with a polymer component, and P is a polymer chain. ]

[In the above formula (II), A is a group represented by the following formula (IV), C has a structure of X-B, X is a copolymerizable site, B contains a sulfur atom, And a group that reacts with the polymer component, and P is a polymer chain. ]

[In the above formula (III), B is a group containing a sulfur atom and reacting with the polymer component, D has a structure of X-A, X is a copolymerizable site, A is the following formula (IV) And P is a polymer chain. ]

[In the above formula (IV), n is an integer satisfying 0 to 2, m is 1 to 2, and 3-nm ≧ 0, and R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms or A divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ² and R ³ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic carbon group having 6 to 18 carbon atoms. A hydrogen group or a saturated hydrocarbon group containing a halogen atom or a nitrogen atom, and Z is a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a ketimine residue, a nitrile group, (thio) isocyanate It is at least one functional group selected from a group, a pyridine group, an amide group, and a primary or secondary amino group having a hydrolyzable group. ]
(3) The groups B containing a sulfur atom in the formulas (I) to (III) and reacting with the polymer component are respectively polysulfide group, thioester group, thiol group, dithiocarbonate group, dithioacetal group, hemithio At least one selected from the group consisting of an acetal group, a vinylthio group, an α-thiocarbonyl group, a β-thiocarbonyl group, an S—CO ₂ —O moiety, an S—CO—CO moiety, and an S—CH ₂ —Si moiety. The modified conjugated diene polymer according to (2) above, comprising a seed.
(4) Any one of the above (1) to (3), wherein the average molecular weight is 15,000 to 1,000,000 and the glass transition temperature (Tg) is −90 ° C. to 0 ° C. The modified conjugated diene polymer described in 1.
(5) 10 to 150 parts by mass of the inorganic filler with respect to 100 parts by mass of the rubber component containing at least 10 parts by mass or more of the modified conjugated diene polymer according to any one of (1) to (4) above. A rubber composition containing the rubber composition.
(6) A tire characterized by using the rubber composition described in (5) above as any one of tire constituent members.

  According to the present invention, at least one group each having both a nitrogen atom and a silicon atom having an affinity for the filler and a group that reacts with the polymer component and a group that reacts with the filler are introduced into different locations in the conjugated diene polymer. As a result, the filler reaction and the polymer main chain cross-linking reaction can occur simultaneously in one polymer, so that the modified conjugated diene has a remarkable effect in reducing hysteresis loss, and has low heat buildup and excellent wear resistance. There are provided a polymer, a rubber composition containing the modified conjugated diene polymer, and a tire excellent in low heat build-up, wear resistance and riding comfort using the rubber composition.

Hereinafter, embodiments of the present invention will be described in detail.
(Modified conjugated diene polymer)
The modified conjugated diene polymer of the present invention has, as a modifying group, a group that reacts with a polymer component and a group that has an affinity for a filler, and the affinity group contains both a nitrogen atom and a silicon atom. It is characterized by having.

〔上記式（Ｉ）中、Ａは、下記式（IV）で表される基であり、Ｂは硫黄原子を含み、かつポリマー成分と反応する基であり、Ｐはポリマー鎖である。〕

〔上記式（II）中、Ａは、下記式（IV）で表される基であり、ＣはＸ−Ｂの構造を有し、Ｘは共重合可能な部位、Ｂは硫黄原子を含み、かつポリマー成分と反応する基であり、Ｐはポリマー鎖である。〕

〔上記式（III）中、Ｂは硫黄原子を含み且つポリマー成分と反応する基であり、ＤはＸ−Ａの構造を有し、Ｘは共重合可能な部位、Ａは下記式（IV）で表される基であり、Ｐはポリマー鎖である。〕

〔上記式（IV）中、ｎは、０〜２、ｍは１〜２、３−ｎ−ｍ≧０を満たす整数であり、Ｒ^１は炭素数１〜２０の２価の炭化水素基または炭素数６〜１８の２価の芳香族炭化水素基であり、Ｒ^２及びＲ^３は、それぞれ炭素数１〜２０の１価の炭化水素基または炭素数６〜１８の１価の芳香族炭化水素基またはハロゲン原子または窒素原子を含む飽和炭化水素基であり、Ｚは飽和環状３級アミン化合物残基、不飽和環状３級アミン化合物残基、ケチミン残基、ニトリル基、（チオ）イソシアナート基、ピリジン基、アミド基、並びに加水分解可能な基を有する１級若しくは２級アミノ基から選択される少なくとも１種の官能基である。〕 The modified conjugated diene-based polymer of the present invention has, as a modifying group, a group that reacts with a polymer component and a group that has an affinity for a filler, and the affinity group includes both a nitrogen atom and a silicon atom. For example, a modified conjugated diene polymer represented by any one of the following formulas (I) to (III) may be used.

[In the above formula (I), A is a group represented by the following formula (IV), B is a group containing a sulfur atom and reacting with a polymer component, and P is a polymer chain. ]

[In the above formula (II), A is a group represented by the following formula (IV), C has a structure of X-B, X is a copolymerizable site, B contains a sulfur atom, And a group that reacts with the polymer component, and P is a polymer chain. ]

[In the above formula (III), B is a group containing a sulfur atom and reacting with the polymer component, D has a structure of X-A, X is a copolymerizable site, A is the following formula (IV) And P is a polymer chain. ]

[In the above formula (IV), n is an integer satisfying 0 to 2, m is 1 to 2, and 3-nm ≧ 0, and R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms or A divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ² and R ³ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic carbon group having 6 to 18 carbon atoms. A hydrogen group or a saturated hydrocarbon group containing a halogen atom or a nitrogen atom, and Z is a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a ketimine residue, a nitrile group, (thio) isocyanate It is at least one functional group selected from a group, a pyridine group, an amide group, and a primary or secondary amino group having a hydrolyzable group. ]

  The modified conjugated diene polymer of the above formula (I) is obtained by introducing a group A having an affinity for a filler and a group B that reacts with a polymer component into both ends of a polymer chain P, respectively. In the formula (II), a group A having an affinity for a filler is introduced into one end of the polymer chain P, and a group C having an XB structure that reacts with a polymer component is branched in the middle of the polymer chain P. In the formula (III), a group B that reacts with the polymer component is introduced into one of the ends of the polymer chain P, and X- A group D having an A structure is branched.

C in the formula (II) has an X-B structure, X is a copolymerizable site such as aromatic vinyl and conjugated diene, and B is the above (I) and (III). The same group containing a sulfur atom and reacting with the polymer component.
Further, D in the above formula (III) has an X-A structure, X is the same copolymerizable site as described above, and A is the same as (I) and (II) above. is there.
The group A having an affinity for the filler in the formulas (I) to (III) has both a nitrogen atom (N) and a silicon atom (Si), and is represented by, for example, the formula (IV). In the formula (IV), n is an integer satisfying 0 to 2, m is 1 to 2, and 3-nm ≧ 0, and R ¹ is a divalent having 1 to 20 carbon atoms. A hydrocarbon group or a bivalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ² and R ³ are monovalent hydrocarbon groups having 1 to 20 carbon atoms or monovalent hydrocarbon groups having 6 to 18 carbon atoms. An aromatic hydrocarbon group or a saturated hydrocarbon group containing a halogen atom or a nitrogen atom, and Z is a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a ketimine residue, a nitrile group, (thio ) Is primary or secondary amino group having an isocyanate group, a pyridine group, an amide group, and a hydrolyzable group? At least one functional group selected from the above.
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in which R ¹ in the above formula (IV) includes ¹ to 20 carbon atoms include, for example, a methylene group, an ethylene group, a trimethylene group, Examples include a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group. Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms include a ferene group. , A tolylene group, a xylylene group, a naphthylene group, and the like, and examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms of R ² and R ³ include an alkyl group having 1 to 20 carbon atoms and 2 to 2 carbon atoms. There may be mentioned 20 alkenyl groups, which may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, iso Propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl Hexenyl group, octenyl group, cyclopentenyl group, cyclohexenyl group and the like. The monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms may have a substituent such as a lower alkyl group in the aromatic ring, and examples thereof include a phenyl group, a tolyl group, and a xylyl group. , Naphthyl group, benzyl group, phenethyl group, naphthylmethyl group, and the like, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Furthermore, as the saturated cyclic tertiary amine compound residue of Z, hexamethyleneimine or a (thio) ether bond as a part of the ring can be included, and as the unsaturated cyclic tertiary amine compound residue, 1, Examples include N, N-disubstituted aromatic amines such as 2,3,6-tetrahydropyridine, N-disubstituted aniline, ketimine residue (-N = C =), nitrile group (-CN). , (Thio) isocyanate group (—NCO), pyridine group (C ₅ H ₅ N), amide group (—CONH ₂ ), primary or secondary amino groups having hydrolyzable groups include ditrimethylsilylamine And so on.
As the group A having an affinity for the preferred filler of the above formula (IV), n is 1 to 2 and m is 1 from the strength of interaction with the filler (filler) such as carbon black and silica. , R ¹ is a saturated hydrocarbon having 1 to 5 carbon atoms, R ² is a saturated hydrocarbon having 1 to 7 carbon atoms, and R ³ is a saturated hydrocarbon having 1 to 5 carbon atoms.
The group A having an affinity for the filler represented by the above formula (IV) or D having an X-A structure is used for polymerizing various modifiers that give a filler-reactive functional group described later. It can introduce by using for.

Examples of the group B containing a sulfur atom that is a functional group capable of binding to the polymer main chain P in the formulas (I) to (III) and reacting with the polymer component include, for example, a polysulfide group, a thioester group, a thiol group, a dithio group. Carbonate group, dithioacetal group, hemithioacetal group, vinylthio group, α-thiocarbonyl group, β-thiocarbonyl group, S—CO ₂ —O moiety, S—CO—CO moiety, and S—CH ₂ —Si moiety And at least one selected from the group consisting of, preferably, containing at least one of a polysulfide group and a thioester group.
The group B containing these sulfur atoms and reacting with the polymer component, or C of the X-B structure, is used for the polymerization of various modifiers that contain a sulfur atom and reacting with the polymer component described later. It can be introduced by using.

The polymer main chain P in the formulas (I) to (III) in the present invention is obtained according to a polymerization technique such as anionic polymerization of a monomer containing a conjugated diene. Examples of the monomer used include conjugated dienes having 4 to 12 carbon atoms, monovinyl aromatic monomers having 4 to 18 carbon atoms, and trienes having 6 to 20 carbon atoms. Examples of conjugated diene monomers include, but are not limited to, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. An example of a triene includes, but is not limited to, myrcene. Aromatic vinyl monomers include, but are not limited to, styrene, α-methyl styrene, p-methyl styrene, and vinyl naphthalene.
When producing a copolymer such as an elastomer copolymer containing a conjugated diene monomer and an aromatic vinyl monomer, the conjugated diene monomer and aromatic vinyl monomer are 95: 5 to 50:50, preferably 95: 5 to Usually used in a ratio of 65:35.

(Method for producing modified conjugated diene polymer)
In the present invention, a modified conjugated diene polymer having a group that reacts with a polymer component and a group having an affinity for a filler as the modifying group, and the affinity group has both a nitrogen atom and a silicon atom For example, in the anionic polymerization of a monomer containing a conjugated diene, a group A having an affinity for a filler or an X-A structure can be bonded to one end or branch of the polymer main chain P A functional group B that contains a sulfur atom at the other end or branch of the polymer main chain P and is capable of binding to the polymer main chain that reacts with the polymer component, and C of the XB structure are bonded. It can be manufactured by using a modifying agent that can be used.

〔上記式（IV）中、ｎは、０〜２、ｍは１〜２、３−ｎ−ｍ≧０を満たす整数であり、Ｒ^１は炭素数１〜２０の２価の炭化水素基または炭素数６〜１８の２価の芳香族炭化水素基であり、Ｒ^２及びＲ^３は、それぞれ炭素数１〜２０の１価の炭化水素基または炭素数６〜１８の１価の芳香族炭化水素基またはハロゲン原子であり、Ｚは飽和環状３級アミン化合物残基、不飽和環状３級アミン化合物残基、ケチミン残基、ニトリル基、（チオ）イソシアナート基、ピリジン基、アミド基、並びに加水分解可能な基を有する１級若しくは２級アミノ基から選択される少なくとも１種の官能基である。〕で表されるシラン化合物及び／その部分縮合物を用いることができる。
具体的には、アミノプロピルメチルジエトキシシラン、Ｎ−（１，３−ジメチル−１−ブチリデン）−３−（トリエトキシシリル）−１−プロパンアミン、ヘキサメチルシクロトリシロキサン、または、１級アミノ基及びケイ素原子に結合したアルコキシ基を少なくとも有する２官能性ケイ素原子を含む化合物、例えば、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルジメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルジエトキシシラン、および１−トリメチルシリル−２−エトキシ−２−メチル−１−アザ−２−シラシクロペンタンなどを挙げることができる。
また、例えば、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルメトキシクロロシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルエトキシクロロシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルメトキシクロロシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルエトキシクロロシランなどが挙げられる。
これらの変性剤は、１種単独で用いてもよく、２種以上組み合わせて用いてもよい。 Examples of the modifying agent capable of binding the group A having an affinity to the filler or an X-A structure to the terminal of the polymer main chain include the group A having an affinity for the various fillers described above, or X -A structure is not particularly limited as long as the structure can be bonded to the end or branch of the polymer main chain. For example, the following formula (IV),

[In the above formula (IV), n is an integer satisfying 0 to 2, m is 1 to 2, and 3-nm ≧ 0, and R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms or A divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ² and R ³ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic carbon group having 6 to 18 carbon atoms. A hydrogen group or a halogen atom, Z is a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a ketimine residue, a nitrile group, a (thio) isocyanate group, a pyridine group, an amide group, and It is at least one functional group selected from a primary or secondary amino group having a hydrolyzable group. Or a partial condensate thereof can be used.
Specifically, aminopropylmethyldiethoxysilane, N- (1,3-dimethyl-1-butylidene) -3- (triethoxysilyl) -1-propanamine, hexamethylcyclotrisiloxane, or primary amino And compounds containing at least a bifunctional silicon atom having an alkoxy group bonded to the silicon atom, such as N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxy Silane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, and 1-trimethylsilyl-2-ethoxy-2-methyl-1-aza-2- Name silacyclopentane, etc. It can be.
Further, for example, N, N-bis (trimethylsilyl) aminopropylmethylmethoxychlorosilane, N, N-bis (trimethylsilyl) aminopropylmethylethoxychlorosilane, N, N-bis (trimethylsilyl) aminoethylmethylmethoxychlorosilane, N, N— Examples thereof include bis (trimethylsilyl) aminoethylmethylethoxychlorosilane.
These modifiers may be used alone or in combination of two or more.

The modifying agent capable of bonding the group B that reacts with the polymer component or the XYB structure to the end of the polymer main chain, etc. includes a modifying agent that contains a sulfur atom and can react with the polymer component. If it is, it will not specifically limit, However, The sulfur containing lithio compound containing a thioether containing a thioether, a thioether, a thioether, a thioether, a thioether, a thioether, and a thioether which will be mentioned as a polymerization initiator.
Specific examples of the sulfur-containing lithio compounds include 2-thiothio-2-methyl-1,3-dithiane, such as lithioalkylthiothioacetal, 2-lithio-2-phenyl-1,3-dithiane, and 2-lithio. -2- (4-dimethylamino) phenyl-1,3-dithiane and the like. These sulfur-containing lithio compounds such as 2-lithio-2-methyl-1,3-dithiane, 2-lithio-2-phenyl-1,3-dithiane are 2-methyl-1,3-dithiane, 2- It can be synthesized from a phenyl-1,3-dithiane or the like and an organic lithium compound such as n-butyllithium by a known production method.

As a method for producing a modified conjugated diene polymer modified at both ends represented by the above formula (I), a conjugated diene monomer such as 1,3-butadiene and an aromatic vinyl monomer such as styrene may be used such as tetrahydrofuran (THF). 2,2-ditetrahydrofurylpropane in polar solvents or in various cyclic and acyclic hexane, heptane, octane, pentane, their alkylated derivatives, and mixtures thereof, and nonpolar hydrocarbons such as benzene Polymerization of linear and cyclic oligomers such as oxolanyl alkane, dipiperidylethane, dipiperidylmethane, hexamethylphosphoramide, NN'-dimethylpiperazine, diazabicyclooctane, dimethyl ether, diethyl ether, tributylamine Add a modifier, and further contain sulfur atoms and polymers -Sulfur-containing lithio such as 2-lithio-2-methyl-1,3-dithiane and 2-lithio-2-phenyl-1,3-dithiane which can bind the group B that reacts with the component and serves as a polymerization initiator After adding a modifier such as a compound, a polymerization reaction is performed in a warm water bath at a temperature of 30 to 150 ° C. for 0.1 to 10 hours. In addition, although the compounding quantity of the said polymerization regulator and modifier changes with monomers to be used and the functional group kind to introduce | transduce, it is about 0.05-20 mmol of modifier | denaturants with respect to 100g of said monomer use whole quantity.
Next, the above-mentioned polymerization reaction system is mixed with the above-mentioned aminopropylmethyldiethoxysilane, N- (1,3-dimethyl-1-butylidene) -3- (triethoxysilyl) -1-propanamine, hexamethylcyclotrisiloxane, etc. 0.05 to 20 mmol of a modifier imparting a group A having both nitrogen atoms and silicon atoms having an affinity for the filler is added to 100 g of the monomer, and a hot water bath at a temperature of 30 to 150 ° C. By subjecting to a polymerization reaction for 0.1 to 5 hours, a modified conjugated diene polymer having both ends modified can be obtained.

As a method for producing the modified conjugated diene polymer represented by the above formula (II), the same modifier as the above (I) is used as a polymerization initiator, the same polymerization regulator as (I) is added, and the temperature is increased. The reaction is carried out in a warm water bath at 30 to 150 ° C. for 0.1 to 10 hours, 0.05 to 20 mmol of the modifying agent having the X-A structure is added, and polymerization is carried out for 0.1 to 5 hours. After reacting for 10 hours, it can be produced by stopping the reaction with a large excess of isopropyl alcohol (IPA).
Moreover, as a manufacturing method of the modified conjugated diene polymer represented by the above formula (III), BuLi is used as a polymerization initiator, a polymerization regulator similar to (I) is added, and hot water at a temperature of 30 to 150 ° C. The reaction is performed in a bath for 0.5 to 10 hours, 0.05 to 20 mmol of the modifier having the X-B structure is added, the polymerization is performed for 0.1 to 5 hours, and the reaction is further performed for 0.5 to 10 hours. It was. Hereinafter, the modification termination reaction can be produced in the same manner as the production method of the modified conjugated diene polymer of the above formula (I).

In the present invention, the modified conjugated diene polymer represented by the above formulas (I) to (III) has a number average molecular weight (Mn) of 15,000 to 1,000 from the viewpoint of processability and physical properties of vulcanized rubber. And a glass transition temperature (Tg) of −90 ° C. to 0 ° C. is desirable.
The modified conjugated diene polymer having a number average molecular weight (Mn) and a glass transition temperature (Tg) within this preferred range can be obtained by adjusting the monomer species used, each modifier species, the polymerization reaction temperature, time, etc. Can be prepared.

In the present invention, the modified conjugated diene polymer represented by any one of the above formulas (I) to (III) obtained by the above production method has an affinity for the filler in a separate place in the conjugated diene polymer. Introducing a group A having both a nitrogen atom and a silicon atom, or D that becomes an XA structure, and a group B that reacts with a polymer component, or C of an XB structure, respectively, A modified conjugated diene that has a remarkable effect in reducing hysteresis loss and has low heat buildup and wear resistance, because the filler reaction and the polymer main chain crosslinking reaction can occur simultaneously in one polymer. It becomes a system polymer.
In the modified conjugated diene polymer represented by the above formula (I), A which becomes a filler-binding functional group when kneaded with rubber is bonded to a filler (an inorganic filler such as carbon black or silica) and has a main chain bond. When the group B serving as a functional group is bonded to the main chain of another polymer, a polymer filler network larger than that used alone can be obtained.

(Rubber composition of the present invention)
The rubber composition of the present invention is characterized by containing 10 to 150 parts by mass of an inorganic filler with respect to 100 parts by mass of a rubber component containing at least 10 parts by mass of a modified conjugated diene polymer.
If the content of the modified conjugated diene polymer is less than 10 parts by mass, a rubber composition having desired physical properties cannot be obtained, and the object of the present invention cannot be exhibited. The preferable content of the modified conjugated diene polymer in the rubber component (100% by mass) is 20% by mass or more, and particularly preferably 30 to 100% by mass.
One kind of this modified conjugated diene polymer may be used, or two or more kinds may be used in combination. The rubber component used in combination with the modified conjugated diene polymer includes natural rubber and diene synthetic rubber. Examples of the diene synthetic rubber include styrene-butadiene copolymer (SBR), polybutadiene (BR). ), Polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, and mixtures thereof.

  Examples of the inorganic filler used in the rubber composition of the present invention include at least one filler selected from carbon black, silica, aluminum hydroxide, alumina, clay, and calcium carbonate, preferably carbon black alone, silica Single or a combination of carbon black and silica is desirable.

The silica used in the present invention is not particularly limited, and includes, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. In addition, wet silica is most preferable because it has the most remarkable effect of achieving both wet grip properties and low rolling resistance.
In this case, the silica is used in an amount of 10 to 150 parts by weight with respect to 100 parts by weight of the rubber component, and is preferably 30 to 90 parts by weight from the viewpoint of reinforcing properties and efficiency of improving various physical properties thereby. If the silica content is less than 10 parts by mass, the fracture characteristics and the like are not sufficient, and if it exceeds 150 parts by mass, the workability is poor.

The carbon black used in the present invention is not particularly limited, and various grades of carbon black are used. Carbon black having N ₂ SA of 10 m ² / g or more and dibutyl phthalate oil absorption (DBP) of 50 ml / 100 g or more is preferable. The use of carbon black increases the effect of improving various physical properties, but grades such as FEF, SRF, HAF, ISAF, and SAF that are particularly excellent in wear resistance are preferred.

In the rubber composition of the present invention, when silica is used, a silane coupling agent can be further contained as desired. The silane coupling agent is not particularly limited, and known ones conventionally used in rubber compositions such as bis (3-triethoxysilylpropyl) polysulfide, γ-mercaptopropyltriethoxysilane, γ-amino Propyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and the like can be used.
The content of the silane coupling agent to be used is usually selected in the range of 1 to 20% by weight with respect to the silica. If this amount is less than 1% by weight, the effect as a coupling agent is not sufficiently exhibited, and if it exceeds 20% by weight, the rubber component may be gelled. In view of the effect as a coupling agent and the prevention of gelation, the preferable content of this silane coupling agent is in the range of 5 to 15% by weight.

In the rubber composition of the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, and an anti-aging agent, as long as the effects of the present invention are not impaired. , Scorch inhibitor, zinc white, stearic acid and the like. As said vulcanizing agent, sulfur etc. are mentioned, The usage-amount is 0.1-10.0 mass parts as a sulfur content with respect to 100 mass parts of rubber components, More preferably, it is 1.0-5. 0 parts by mass.
The vulcanization accelerator that can be used in the present invention is not particularly limited. For example, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and other guanidine-based vulcanization accelerators such as DPG (diphenylguanidine) can be used, and the amount used is 0.1-5. 0 mass part is preferable, More preferably, it is 0.2-3.0 mass part.
Examples of the process oil that can be used in the rubber composition of the present invention include paraffinic, naphthenic, and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low-temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and if it exceeds 100 parts by mass, the tensile strength and low heat build-up of the vulcanized rubber tend to deteriorate.

  The rubber composition of the present invention is obtained by kneading using a kneader such as a roll or an internal mixer. After molding, vulcanization is performed, and tire tread, under tread, carcass, sidewall, bead It can be used not only for tire applications such as parts, but also for applications such as anti-vibration rubber, belts, hoses and other industrial products, but it is particularly suitably used as rubber for tire treads.

  The tire of the present invention is produced by an ordinary method using the rubber composition of the present invention. That is, if necessary, the rubber composition of the present invention containing various chemicals as described above is extruded as a tire member at an unvulcanized stage, for example, a tread member, and is usually used on a tire molding machine. The green tire is molded by pasting and molding by the above method. The green tire is heated and pressed in a vulcanizer to obtain a tire. The pneumatic tire of the present invention thus obtained has a remarkable effect in reducing the hysteresis loss, and effectively uses a modified conjugated diene polymer excellent in low heat generation and wear resistance as a rubber component. Since it contains, the fuel efficiency is good, and in particular, the destructive properties, wear resistance and ride comfort are excellent, and the processability of the rubber composition is good, so the productivity is also excellent. It becomes.

  Next, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to the following manufacture example and Example at all.

[Example of production of modified conjugated diene polymer, comparative production example]
Example 1 (phenyldithiane: aminopropylmethyldiethoxysilane)
(Preparation of denaturing agent)
In a syringe, THF solution (5 ml) containing 10.69 mmol of 2-phenyl-1,3-dithiane and 10 ml of hexane were added to n-butyllithium (6.37 ml. 1.68 M hexane solution) at -78 ° C. The dropped solution was further stirred at 0 ° C. for 3 hours. The obtained 0.5M 2-lithio-2-phenyl-1,3-dithiane (hereinafter simply referred to as “phenyldithiane”) is used as an initiator for anionic polymerization and is placed in a refrigerator in a nitrogen atmosphere. Stored.
(Preparation of modified conjugated diene polymer)
Add 1,3-butadiene in cyclohexane and styrene in cyclohexane to 800 g pressure-resistant glass that has been dried and purged with nitrogen, and add 1,3-butadiene 60 g and styrene 15 g to give 2,2-ditetrahydrofuryl. After adding 0.70 mmol of propane and further adding 0.70 mmol of 2-lithio-2-phenyl-1,3-dithiane, polymerization was carried out in warm water at 50 ° C. for 1.5 hours. The polymerization addition rate at this time was almost 100%.
Next, 0.63 mmol of aminopropylmethyldiethoxysilane as a modifier was added to the polymerization reaction system, and a modification reaction was further performed at 50 ° C. for 30 minutes to obtain a modified conjugated diene polymer.

Production Example 2 [Phenyldithiane: N- (1,3-dimethyl-1-butylidene) -3- (triethoxysilyl) -1-propanamine]
In Example Production Example 1, N- (1,3-dimethyl-1-butylidene) -3- (triethoxysilyl)-was used instead of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system. A modified conjugated diene polymer was obtained in the same manner as in Production Example 1 using 0.63 mmol of 1-propanamine.

Production Example 3 (Dimethylaminophenyldithiane: aminopropylmethyldiethoxysilane)
Instead of the modifying agent 2-lithio-2-phenyl-1,3-dithiane (phenyldithiane) used in the above Production Example 1, the modifying agent prepared below [2-lithio-2- (4-dimethylamino) Phenyl-1,3-dithiane] (0.70 mmol) was used in the same manner as in Production Example 1 to obtain a modified conjugated diene polymer.
(Preparation of denaturing agent)
8 ml of THF solution containing 1.25 g of 2- (4-dimethylamino) phenyl-1,3-dithiane and 1 ml of Et ₃ N (triethylamine) were added to 3.1 ml of n-butyllithium and 1.68 M of hexane solution. , -78 ° C. The solution was further stirred at 0 ° C. for 4 hours. The obtained 0.43M 2-lithio-2- (4-dimethylamino) phenyl-1,3-dithiane was used as an initiator for anionic polymerization and was stored in a refrigerator in a nitrogen atmosphere.

Example Production Example 4 [Dimethylaminophenyldithiane: N- (1,3-dimethyl-1-butylidene) -3- (triethoxysilyl) -1-propanamine]
In the above Production Example 2, the modifier [2-lithio-2- (4-dimethylamino) phenyl prepared above was used instead of the modifier 2-lithio-2-phenyl-1,3-dithiane (phenyldithiane). -1,3-dithiane] (0.70 mmol) was used to obtain a modified conjugated diene polymer in the same manner as in Production Example 2 above.

Comparative Production Example 1 (Phenyldithiane: isopropyl alcohol)
In the above Production Example 1, modified conjugated in the same manner as in the above Production Example 1 using a large excess of isopropyl alcohol (IPA) instead of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system. A diene polymer was obtained.

Comparative Production Example 2 (Dimethylaminophenyl dithiane: isopropyl alcohol)
In Example Production Example 3 above, the modified conjugate was modified in the same manner as in Example Production Example 1 using a large excess of isopropyl alcohol (IPA) instead of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system. A diene polymer was obtained.

Comparative Production Example 3 (Phenyldithiane: tetraethoxysilane)
In Example Production Example 1 above, 0.63 mmol of tetraethoxysilane (TEOS) was used instead of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system. A conjugated diene polymer was obtained.

Comparative Production Example 4 (Dimethylaminophenyl dithiane: tetraethoxysilane)
In Example Production Example 3 above, 0.63 mmol of tetraethoxysilane (TEOS) was used instead of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system, and the modification was conducted in the same manner as in Example Production Example 1 above. A conjugated diene polymer was obtained.

Comparative Production Example 5 (Phenyldithiane: tributyltin chloride)
In Example Production Example 1, instead of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system, 0.63 mmol tributyltin chloride (Bu ₃ SnCl) was used in the same manner as Example Production Example 1 above. A modified conjugated diene polymer was obtained.

Comparative Production Example 6 (Dimethylaminophenyldithiane: tributyltin chloride)
In Example Production Example 3 above, 0.63 mmol of tributyltin chloride (Bu ₃ SnCl) was used instead of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system in the same manner as in Example Production Example 1 above. A modified conjugated diene polymer was obtained.

Comparative Production Example 7 (n-butyllithium: aminopropylmethyldiethoxysilane)
Add 1,3-butadiene in cyclohexane and styrene in cyclohexane to 800 g pressure-resistant glass that has been dried and purged with nitrogen, and add 1,3-butadiene 60 g and styrene 15 g to give 2,2-ditetrahydrofuryl. After adding 0.70 mmol of propane and further adding 0.70 mmol of n-butyllithium (BuLi), polymerization was performed in warm water at 50 ° C. for 1.5 hours. The polymerization addition rate at this time was almost 100%.
Next, 0.63 mmol of aminopropylmethyldiethoxysilane as a modifier was added to the polymerization reaction system, and a modification reaction was further performed at 50 ° C. for 30 minutes to obtain a modified conjugated diene polymer.

Comparative Production Example 8 [n-butyllithium: N- (1,3-dimethyl-1-butylidene) -3- (triethoxysilyl) -1-propanamine]
In Comparative Production Example 7, N- (1,3-dimethyl-1-butylidene) -3- (triethoxysilyl)-was used instead of 0.63 mmol of aminopropylmethyldithioxysilane as a modifier added to the polymerization reaction system. A modified conjugated diene polymer was obtained in the same manner as Comparative Production Example 7 using 0.63 mmol of 1-propanamine.

Comparative Production Example 9 (n-butyllithium: tetraethoxysilane)
In Comparative Production Example 7, in place of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system, 0.63 mmol of tetraethoxysilane (TEOS) was used to conjugate in the same manner as in Comparative Production Example 7. A diene polymer was obtained.

Comparative Production Example 10 (n-butyllithium: tributyltin chloride)
In the above Comparative Production Example 7, instead of 0.63 mmol of the aminopropylmethyldiethoxysilane modifier added to the polymerization reaction system, 0.63 mmol of tributyltin chloride (Bu ₃ SnCl) was used in the same manner as in the above Comparative Production Example 7. A conjugated diene polymer was obtained.

Comparative production example 11 (n-butyllithium: isopropyl alcohol)
In Comparative Production Example 7, conjugated diene was used in the same manner as in Comparative Production Example 7 using 0.63 mmol of isopropyl alcohol (IPA) instead of 0.63 mmol of aminopropylmethyldiethoxysilane as a modifier added to the polymerization reaction system. A polymer was obtained.

Using the modified conjugated diene polymers of Examples Production Examples 1 to 4 and Comparative Production Examples 1 to 11 obtained above, Mw / k and St / Vi were measured and calculated by the following methods.
The evaluation results of these modified conjugated diene polymers are shown in Table 1 below.

(Calculation method of Mw / k)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer are measured by gel permeation chromatography [GPC: HLC-8020 manufactured by Tosoh Corporation, column: GMH-XL manufactured by Tosoh Corporation (two in series)] Using the differential refractive index (R1), the measurement was performed in terms of polystyrene using monodisperse polystyrene as a standard.
(Calculation method of St / Vi)
The microstructure of the butadiene portion of the polymer was determined by the infrared method (Morero method). The styrene unit content in the polymer was calculated from the integral ratio of the 1H-NMR spectrum.

Preparation of rubber composition]
Each rubber composition was prepared by the following methods using a rubber composition having a silica formulation shown in Tables 1 and 2 and a rubber composition having a carbon black formulation shown in Table 3 below. About each obtained rubber composition, rolling resistance and abrasion resistance were evaluated by the following method.

(Examples 1-4 and Comparative Examples 1-8, preparation method of rubber composition of silica compounding prescription, Table 1 and Table 2)
The silica compounding formulation shown in the following Table 2 using each modified conjugated diene copolymer shown in the following Table 1, specifically, in the first stage, other than the vulcanization accelerator, the vulcanization acceleration aid, and the crosslinking agent These components were blended and kneaded with a Banbury mixer, and in the second stage, each component of a vulcanization accelerator, a vulcanization acceleration aid, and a crosslinking agent was blended and kneaded with a Banbury mixer to prepare a rubber composition.
(Method of preparing the rubber composition of mosquitoes over carbon black formulation, Table 3)
Using the modified conjugated diene copolymer shown in Table 1 below, the carbon black formulation shown in Table 3 below, specifically, in the first stage, other than the vulcanization accelerator, vulcanization acceleration aid, and crosslinking agent These components were blended and kneaded with a Banbury mixer, and in the second stage, each component of a vulcanization accelerator, a vulcanization acceleration aid, and a crosslinking agent was blended and kneaded with a Banbury mixer to prepare a rubber composition.

[Evaluation method for low loss (low heat generation)]
Using Rheometrics Co. viscoelasticity measuring device, the temperature 50 ° C., a frequency 10 Hz, the tanδ at strain 3% were measured and indexed to Table 1 Comparative Example 8 as 100. The larger the index, the better the low loss (low heat generation).
(Abrasion resistance evaluation method)
A Lambone-type friction tester was used, and the slip rate was expressed as a wear amount of 25%, and the measurement temperature was room temperature. In Table 1, the comparative example 8 was set as 100 and indicated as an index. The higher the index, the better the wear resistance.

As apparent from the results shown in Tables 1-2, rubber compositions of silica formulation with modified conjugated diene-based copolymer of Example 1-4 as a range of the present invention, the present invention range compared to silica-loaded prescription of rubber composition using the modified conjugated diene copolymers of Comparative examples 1 to 8, the low heat buildup (rolling resistance), it was found to have excellent wear resistance.

The modified conjugated diene copolymers obtained in Examples Production Examples 1 to 4 within the scope of the present invention are the above-mentioned modified groups A and B at different positions of the conjugated diene polymer, that is, at both ends of the polymer chain P. As a result, the filler reaction and the polymer main chain crosslinking reaction can occur simultaneously in one polymer, which has a remarkable effect on reducing hysteresis loss, and has excellent low heat buildup and wear resistance. It is a modified conjugated diene polymer.

  A modified conjugated diene polymer that has a remarkable effect in reducing hysteresis loss and has low heat build-up and excellent wear resistance can be obtained, so tire configurations such as tire treads, undertreads, carcass, sidewalls, bead parts, etc. It can be suitably used as a rubber component for vibration-insulating rubbers, belts, hoses and other rubber industrial products as well as member applications.

Claims (5)

A modified conjugated diene polymer, which is represented by the following formula (I), has modified groups A and B at both ends of the polymer chain P , and A is carbon black and / or silica. Having a group represented by the following formula (IV) having an affinity for a filler comprising: the group having an affinity has both a nitrogen atom and a silicon atom , and B binds to a conjugated diene polymer. modified copolymer conjugated diene polymer which is a functional group containing a sulfur reaction.
A-P-B ......... (I)

[In the above formula (IV), n is an integer satisfying 0 to 2, m is 1 to 2 , and 3-nm ≧ 0, and R ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms or A divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, wherein R ² and R ³ are each a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic carbon group having 6 to 18 carbon atoms. Z is a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a ketimine residue, a nitrile group, (thio) isocyanate, a hydrogen group or a saturated hydrocarbon group containing a halogen atom or a nitrogen atom And at least one functional group selected from a primary or secondary amino group having a group, a pyridine group, an amide group, and a hydrolyzable group. ] The modifying group B in the formula (I) is a polysulfide group, a thioester group, a thiol group, a dithiocarbonate group, a dithioacetal group, a hemithioacetal group, a vinylthio group, an α-thiocarbonyl group, and a β-thiocarbonyl group, respectively. , _S-CO 2 -O moiety, S-CO-CO moiety, and the modified conjugated diene according to claim 1, characterized in that it comprises at least one selected from the group consisting of _S-CH 2 -Si moiety Polymer. The modified conjugated diene polymer according to claim 1 or 2 , wherein the average molecular weight is 15,000 to 1,000,000, and the glass transition temperature (Tg) is -90 ° C to 0 ° C. It contains 10 to 150 parts by mass of an inorganic filler with respect to 100 parts by mass of a rubber component containing at least 10 parts by mass or more of the modified conjugated diene polymer according to any one of claims 1 to 3. Rubber composition. A tire comprising the rubber composition according to claim 4 as any one of tire constituent members.