JP5436051B2 - Rubber composition and tire using the same - Google Patents

Description

  The present invention relates to a rubber composition and a tire using the rubber composition, and particularly relates to a rubber composition having a high storage elastic modulus and excellent in low loss performance and crack growth resistance.

  In recent years, tires with low rolling resistance have been demanded in order to save automobile fuel consumption in response to social demands for energy and resource savings, and rubber with lower heat generation (low loss performance) and superior fracture characteristics than before. A composition is desired. For example, in International Publication No. 2006/112450 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2007-191611 (Patent Document 2), cis-1 is used as a rubber component in order to improve the low heat buildup and fracture characteristics of the rubber composition. Thus, a technique using a modified conjugated diene polymer having a high 4-bond amount is disclosed.

  On the other hand, a rubber composition capable of improving steering stability is desired from the demand for the driving surface of automobiles. In order to improve the steering stability of the tire, a method using a rubber composition having a high storage elastic modulus (G ′) is generally used. For example, Japanese Unexamined Patent Application Publication No. 2005-298804 (Patent Document 3) discloses a technique using a rubber composition obtained by blending a rubber component with a low molecular weight aromatic vinyl compound-conjugated diene compound copolymer. ing.

  From the above, in order to improve the rolling resistance and steering stability of the tire, a low molecular weight aromatic vinyl compound-conjugated diene compound copolymer is used for a modified conjugated diene polymer having a high cis-1,4 bond amount. A technique using a rubber composition formed by blending a coalescence can be expected. In fact, Japanese Patent Application Laid-Open No. 2007-326942 (Patent Document 4) discloses such a rubber composition.

  However, the rubber composition disclosed in Japanese Patent Application Laid-Open No. 2007-326942 is described to improve the wet grip performance, braking performance on ice and snow, and dry grip performance of the tire, but can sufficiently exhibit low loss performance. However, even when the rubber composition was applied to a tire, the effect of improving rolling resistance could not be sufficiently obtained.

International Publication No. 2006/112450 JP 2007-191611 A JP 2005-298804 A JP 2007-326942 A

  Accordingly, an object of the present invention is to solve the above-described problems of the prior art, and to provide a rubber composition having a high storage elastic modulus and excellent in low loss performance and crack growth resistance. Another object of the present invention is to provide a tire using such a rubber composition, which is excellent in handling stability, low rolling resistance and fracture characteristics.

  As a result of intensive studies to achieve the above object, the present inventor has found that the rubber component containing a modified conjugated diene polymer having a specific modification rate and a high cis-1,4 bond amount has a low molecular weight. By blending a specific amount of the conjugated diene compound polymer, it was found that a rubber composition having a high storage elastic modulus and excellent in low loss performance and crack growth resistance was obtained, and the present invention was completed.

That is, the rubber composition of the present invention has a cis-1,4 bond amount of 80.0% or more, a number average molecular weight (Mn) of 200,000 or more obtained by modifying an active polymer with a modifier. Less than 1 million, the rubber component containing the modified conjugated diene polymer (A) having at least one functional group has a cis-1,4 bond amount of 80.0% or more and a weight average molecular weight (Mw). A low molecular weight conjugated diene compound polymer (B) having a molecular weight of 5,000 to 150,000 is blended.

  The cis-1,4 bond amount is the ratio of cis-1,4 bond in the conjugated diene compound unit in the polymer, and the vinyl bond amount is the vinyl bond in the conjugated diene compound unit in the polymer. It is a ratio. Moreover, a weight average molecular weight (Mw), a number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are shown by the value converted into polystyrene by gel permeation chromatography (GPC). Furthermore, the conjugated diene polymer refers to a homopolymer of a conjugated diene compound or a copolymer of an aromatic vinyl compound and a conjugated diene compound, and the conjugated diene compound polymer refers to only a homopolymer of a conjugated diene compound. Point to.

  In the rubber composition of the present invention, the modified conjugated diene polymer (A) preferably has a modification rate of 10% or more.

Here, the modification rate is defined as described in Japanese Patent Application Laid-Open No. 2007-191611, and will be described in detail with reference to FIG. FIG. 1 is an explanatory diagram showing an example of a calibration curve for calculating the modification rate of a polymer. Here, the vertical axis represents the UV / RI value obtained by GPC measurement, and the horizontal axis represents the value of (1 / Mn) × 10 ³ . Mn is an absolute molecular weight (number average molecular weight). Further, UV indicates a peak area value obtained from the UV absorbance caused by the modifier that has reacted with the active polymer, and RI indicates a peak area value obtained from the differential refractive index (RI) of the polymer itself. LowCisBR + DEAB shown in FIG. 1 is a polymer obtained by anionic polymerization of 1,3-butadiene using a Li-based catalyst and modifying the resulting active polymer with a modifier [4,4′-bis (diethylamino) benzophenone (DEAB)]. In FIG. 1, three types of UV / RI values having different absolute molecular weights (number average molecular weights) (Mn) are plotted, and an approximate straight line is drawn with respect to the plots. In this case, since all active polymers are modified (modification rate is 100%), the UV / RI of LowCisBR + DEAB is defined as 100%, and is expressed by the following formula.
A = UV (Li-Br) / RI (Li-Br)
On the other hand, HighCisBR + DEAB shown in FIG. 1 refers to a polymer obtained by coordinating 1,3-butadiene with a catalyst containing a lanthanum series rare earth element (Nd) -containing compound and modifying the resulting active polymer with DEAB. In FIG. 1, five types of UV / RI values having different absolute molecular weights (number average molecular weights) (Mn) are plotted, and approximate lines are drawn with respect to the plots. Then, UV / RI of HighCisBR + DEAB is expressed by the following formula:
B = UV (Nd-Br) / RI (Nd-Rr)
In this case, the modification rate of HighCisBR + DEAB is defined as follows.
Denaturation rate (%) = B / A x 100
The modification rate is calculated using the A value and B value of a polymer having the same absolute molecular weight (number average molecular weight).

  The unmodified BR shown in FIG. 1 is a polymer obtained by polymerizing 1,3-butadiene with n-butyllithium and deactivating the resulting active polymer with isopropanol. Similarly, an approximate curve is drawn. It is. Here, the UV (Li-Br) / RI (Li-Br) and UV (Nd-Br) / RI (Nd-Rr) are obtained by subtracting the UV / RI value of unmodified BR from the respective values. Used as true value. Actually, since the UV absorption due to the main chain is extremely small, the true value is obtained by setting the UV / RI value of the unmodified BR to zero. Moreover, when using different denaturing agents, it is necessary to create a calibration curve each time.

  In the rubber composition of this invention, it is preferable that the compounding quantity of the said low molecular weight conjugated diene compound polymer (B) is 5-100 mass parts with respect to 100 mass parts of said rubber components.

  In the rubber composition of the present invention, the rubber component preferably contains 10% by mass or more of the modified conjugated diene polymer (A).

  In a preferred embodiment of the rubber composition of the present invention, the rubber component further contains at least one of natural rubber and synthetic diene rubber, and the modified conjugated diene polymer (A) is contained in the rubber component. It is compatible with at least one of natural rubber and synthetic diene rubber. “Compatible” means having the ability to mix homogeneously without causing separation and without causing a chemical reaction.

  In another preferred embodiment of the rubber composition of the present invention, 10 to 100 parts by mass of a filler is further contained with respect to 100 parts by mass of the rubber component. Here, the filler is preferably an inorganic filler and / or carbon black.

  In another preferred embodiment of the rubber composition of the present invention, the functional group is a functional group containing at least one atom selected from the group consisting of a nitrogen atom, a tin atom, a silicon atom, a sulfur atom and an oxygen atom. is there.

In another preferred embodiment of the rubber composition of the present invention, the modifier has a site P ₁ that is reactive with the active polymer and a site P ₂ that is reactive with the filler. It is a compound (provided that the site P ₁ and the site P ₂ may be the same or different and do not contain an active proton in the modification reaction) or a precursor of the compound. Here, the site P ₁ is preferably reactive with the chain end of the active polymer.

［式中、Ｘ¹〜Ｘ⁵は水素原子、ハロゲン原子、カルボニル基、チオカルボニル基、イソシアネート基、チオイソシアネート基、エポキシ基、チオエポキシ基、ハロゲン化シリル基、ヒドロカルビルオキシシリル基及びスルホニルオキシ基よりなる郡から選択される少なくとも一種を含む官能基を示し、Ｘ¹〜Ｘ⁵は互いに同一でも異なっていてもよいが、それらの中の少なくとも一つは水素原子ではない。Ｒ¹〜Ｒ⁵は、それぞれ独立して単結合又は炭素数１〜１８の二価の炭化水素基を示す。また、Ｘ¹〜Ｘ⁵及びＲ¹〜Ｒ⁵のいずれかを介して複数のアジリジン環が結合されていてもよい。］で表される化合物（（ａ）成分）から選ばれる少なくとも一種である。なお、前記（ａ）成分は、一般式(I)において、Ｘ¹＝水素原子及びＲ¹＝単結合を同時に満たさないことが好ましい。 In another preferred embodiment of the rubber composition of the present invention, the modifier is represented by the general formula (I):

[Wherein, X ^{1 to} X ⁵ are each a hydrogen atom, a halogen atom, a carbonyl group, a thiocarbonyl group, an isocyanate group, a thioisocyanate group, an epoxy group, a thioepoxy group, a halogenated silyl group, a hydrocarbyloxysilyl group, and a sulfonyloxy group. A functional group containing at least one selected from the group, and X ^{1 to} X ⁵ may be the same or different from each other, but at least one of them is not a hydrogen atom. R ^{1 to} R ⁵ each independently represent a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms. It may also be coupled a plurality of aziridine rings through any of X ¹ to X ⁵ and R ¹ to R ^5. ] It is at least 1 type chosen from the compound ((a) component) represented by this. The component (a) preferably does not simultaneously satisfy X ¹ = hydrogen atom and R ¹ = single bond in the general formula (I).

［式中、Ｙ'は、酸素原子、窒素原子又は硫黄原子である］で表される結合を分子中に含有するヘテロ３員環化合物
（ｅ）成分：ハロゲン化イソシアノ化合物
（ｆ）成分：Ｒ¹⁰−(ＣＯＯＨ)_m、Ｒ¹¹(ＣＯＺ)_m、Ｒ¹²−(ＣＯＯ−Ｒ¹³）、Ｒ¹⁴−ＯＣＯＯ−Ｒ¹⁵、Ｒ¹⁶−(ＣＯＯＣＯ−Ｒ¹⁷)_m、又は一般式(III)：

［式中、Ｒ¹⁰〜Ｒ¹⁸は、同一でも異なってもよいが、炭素数１〜５０の炭素原子を含む炭化水素基で、Ｚはハロゲン原子で、ｍは１〜５の整数である］に対応するカルボン酸、酸ハロゲン化物、エステル化合物、炭酸エステル化合物又は酸無水物
（ｇ）成分：Ｒ¹⁹ _kＭ''(ＯＣＯＲ²⁰)_4-k、Ｒ²¹ _kＭ''(ＯＣＯ−Ｒ²²−ＣＯＯＲ²³)_4-k又は一般式(IV)：

［式中、Ｒ¹⁹〜Ｒ²⁵は、同一でも異なってもよいが、炭素数１〜２０の炭素原子を含む炭化水素基で、Ｍ''はスズ原子、ケイ素原子又はゲルマニウム原子で、ｋは０〜３の整数で、ｐは０又は１である］に対応するカルボン酸の金属塩
（ｈ）成分：Ｎ−置換アミノケトン、Ｎ−置換アミノチオケトン、Ｎ−置換アミノアルデヒド、Ｎ−置換アミノチオアルデヒド、又は分子中に−Ｃ(＝Ｙ'')−Ｎ＜結合［Ｙ''は酸素原子又は硫黄原子である］を有する化合物 In another preferred embodiment of the rubber composition of the present invention, the modifier is at least one selected from the following compounds (b) to (h).
Component _{^{(b): R 6 n M'Z 4-n}} , M'Z 4, M'Z 3, R 7 n M '(- R 8 -COOR 9) 4-n or R ⁷ _n M' (- R ⁸ —COR ⁹ ) _4-n [wherein R ^{6 to} R ⁸ may be the same or different, but are hydrocarbon groups containing a carbon atom having 1 to 20 carbon atoms, wherein R ⁹ is 1 carbon atom] A hydrocarbon group containing ˜20 carbon atoms, and R ^{6 to} R ⁹ may contain a carbonyl group or an ester group in the side chain, and M ′ is a tin atom, a silicon atom, a germanium atom or a phosphorus atom. , Z is a halogen atom, and n is an integer of 0 to 3.] (C) Component: Y = C = Y ′ bond in the molecule [Wherein Y is a carbon atom, oxygen atom, nitrogen atom or sulfur atom, and Y ′ is an oxygen atom, nitrogen atom or sulfur atom] Compound component (d): formula (II):

[Wherein Y ′ is an oxygen atom, a nitrogen atom or a sulfur atom] A hetero 3-membered ring compound containing in its molecule a bond represented by (e) component: a halogenated isocyano compound (f) component: R _{^{10 - (COOH) m, R}} 11 (COZ) m, R 12 - (COO-R 13), R 14 -OCOO-R 15, R 16 - (COOCO-R 17) m, or general formula (III):

[Wherein, R ^{10 to} R ¹⁸ may be the same or different, but a hydrocarbon group containing a carbon atom having 1 to 50 carbon atoms, Z is a halogen atom, and m is an integer of 1 to 5] Carboxylic acid, acid halide, ester compound, carbonate compound or acid anhydride corresponding to (g) Component: R ¹⁹ _k M ″ (OCOR ²⁰ ) _4-k , R ²¹ _k M ″ (OCO-R ²² -COOR ²³ ) _4-k or general formula (IV):

[In the formula, R ^{19 to} R ²⁵ may be the same or different, but a hydrocarbon group containing a carbon atom having 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom, and k is Metal salt of carboxylic acid corresponding to an integer of 0 to 3, and p is 0 or 1. (h) Component: N-substituted aminoketone, N-substituted aminothioketone, N-substituted aminoaldehyde, N-substituted amino Thioaldehyde or a compound having —C (═Y ″) — N <bond [Y ″ is an oxygen atom or a sulfur atom] in the molecule

In another preferred embodiment of the rubber composition of the present invention, the modifier is represented by the following formula (V):
θ-C≡N (V)
Or the following formula (VI):
θ−R ²⁹ −C≡N (VI)
[In formulas (V) and (VI), θ represents a heterocyclic group, and R ²⁹ represents a divalent hydrocarbon group].

In another preferred embodiment of the rubber composition of the present invention, the active polymer is component (i): a lanthanum series rare earth element-containing compound having an atomic number of 57 to 71 in the periodic table, or the lanthanum series rare earth element-containing substance. (Ii) Component: AlR ²⁶ R ²⁷ R ²⁸ [wherein R ²⁶ and R ²⁷ may be the same or different, but a hydrocarbon group or hydrogen atom having 1 to 10 carbon atoms] R ²⁸ is a hydrocarbon group having 1 to 10 carbon atoms, provided that R ²⁸ may be the same as or different from R ²⁶ or R ²⁷ ], and (iii) component: Lewis A conjugated diene compound is polymerized by a catalyst system comprising at least one of an acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen. Here, in the rubber composition of the present invention, the active polymer is preferably a terminal active polymer obtained by a catalyst system containing the lanthanum series rare earth element-containing compound. The lanthanum series rare earth element-containing compound in the component (i) is preferably a salt soluble in a neodymium hydrocarbon solvent, and is a branched carboxylate of neodymium or a reaction product of the salt and a Lewis base. Is more preferable. The conjugated diene compound refers to a conjugated diene compound or a mixture of a conjugated diene compound and an aromatic vinyl compound.

  In the rubber composition of the present invention, the modified conjugated diene polymer (A) preferably has a molecular weight distribution (Mw / Mn) of 1.6 to 3.5.

  In the rubber composition of the present invention, the modified conjugated diene polymer (A) preferably has a number average molecular weight (Mn) of 200,000 to 500,000, and more preferably 200,000 to 400,000.

  In the rubber composition of the present invention, the low molecular weight conjugated diene compound polymer (B) preferably has a weight average molecular weight (Mw) of 10,000 to 150,000.

  The tire of the present invention is characterized by using the above rubber composition.

  According to the present invention, a low molecular weight conjugated diene compound polymer is blended with a rubber component containing a high molecular weight modified conjugated diene polymer having a high cis-1,4 bond amount, thereby increasing storage modulus. Further, it is possible to provide a rubber composition excellent in low loss performance and crack growth resistance. Further, by using the rubber composition, it is possible to provide a tire excellent in handling stability, low rolling resistance, and fracture characteristics (crack growth resistance).

It is explanatory drawing which shows an example of the calibration curve for calculating the modification | denaturation rate of a polymer.

  The present invention is described in detail below. The rubber composition of the present invention has a cis-1,4 bond content of 80.0% or more and a number average molecular weight (Mn) of 200,000 or more and 1,000,000 or less obtained by modifying an active polymer with a modifier. The rubber component containing the modified conjugated diene polymer (A) having at least one functional group is blended with a low molecular weight conjugated diene compound polymer (B) having a weight average molecular weight (Mw) of 5,000 to 150,000. It is characterized by that. Here, in the present invention, in order to increase the storage elastic modulus (G ′) of the rubber composition, a polymer composed of one or more kinds of conjugated diene compounds (conjugated diene compound polymer) is used. The compatibility between the conjugated diene compound polymer and the modified conjugated diene polymer (A) can be improved. Therefore, as observed in the rubber composition described in JP-A-2007-326942, the low loss performance is not suppressed, and the low loss performance inherent in the modified conjugated diene polymer (A) is not suppressed. The improvement effect can be sufficiently exhibited. From the above, the rubber composition of the present invention improves the storage elastic modulus (G ′) without impairing the low loss performance and crack growth resistance improving effect obtained by the modified conjugated diene polymer (A). Can be made.

  The modified conjugated diene polymer (A) used in the rubber composition of the present invention requires a cis-1,4 bond content of 80.0% or more, and preferably 85% or more. When the cis-1,4 bond content is less than 80.0%, low loss performance and crack growth resistance cannot be sufficiently obtained. Further, the modified conjugated diene polymer (A) preferably has a modification rate of 10% or more, more preferably 15% or more. If the modification rate is less than 10%, low loss performance and crack growth resistance cannot be obtained sufficiently.

  The modified conjugated diene polymer (A) preferably has a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 1.6 to 3.5. More preferably, it is -2.7. When the molecular weight distribution (Mw / Mn) is within the above range, the workability of the rubber composition is not lowered.

  The modified conjugated diene polymer (A) requires a number average molecular weight (Mn) of 200,000 or more and 1,000,000 or less, preferably 200,000 to 500,000, and 200,000 to 400,000. Particularly preferred. When the number average molecular weight (Mn) is within the above range, the wear resistance is improved and the workability of the rubber composition is improved while suppressing the decrease in elastic modulus and the increase in hysteresis loss during vulcanization. . When the number average molecular weight (Mn) exceeds 1,000,000, it may be difficult to increase the modification rate of the conjugated diene polymer.

  In the modified conjugated diene polymer (A), the amount of the conjugated diene compound bonded is preferably 60% by mass or more, and more preferably 80% by mass or more. When the binding amount of the conjugated diene compound is 60% by mass or more, the compatibility with the low molecular weight conjugated diene compound polymer (B) can be greatly improved.

  The rubber component of the rubber composition of the present invention preferably contains 10% by mass or more of the modified conjugated diene polymer (A). When the ratio of the modified conjugated diene polymer (A) in the rubber component is less than 10% by mass, the effect of improving low loss performance and crack growth resistance is reduced. The rubber component can be blended with a general rubber component used in the rubber industry in addition to the modified conjugated diene polymer (A), specifically, natural rubber (NR). Styrene-butadiene copolymer rubber (SBR), polyisoprene rubber (IR), polybutadiene rubber (BR), ethylene-propylene copolymer, chloroprene rubber (CR), butyl rubber (IIR), halogenated butyl rubber, acryloni Synthetic diene rubbers such as little-butadiene rubber (NBR) can be blended. In addition, these general rubber components may be used individually by 1 type, and may blend and use 2 or more types. Further, when the rubber component is a blend of the modified conjugated diene polymer (A) and the general rubber component, the modified conjugated diene polymer (A) is a natural rubber (NR) contained in the rubber component. ) And at least one of synthetic diene rubbers.

  The modified conjugated diene polymer (A) is obtained by modifying an active polymer with a modifying agent and has at least one functional group. The functional group is preferably a functional group containing at least one atom selected from the group consisting of a nitrogen atom, a tin atom, a silicon atom, a sulfur atom and an oxygen atom. Moreover, as said modifier | denaturant, the following (a)-(h) component is mentioned, for example. The components (a) to (h) are all compounds that can be reacted with a polymer having an active end. Moreover, (a)-(h) component may be used individually by 1 type, and 2 or more types may be mixed and used for it.

［式中、Ｘ¹〜Ｘ⁵は水素原子、ハロゲン原子、カルボニル基、チオカルボニル基、イソシアネート基、チオイソシアネート基、エポキシ基、チオエポキシ基、ハロゲン化シリル基、ヒドロカルビルオキシシリル基及びスルホニルオキシ基よりなる郡から選択される少なくとも一種を含む官能基を示し、Ｘ¹〜Ｘ⁵は互いに同一でも異なっていてもよいが、それらの中の少なくとも一つは水素原子ではない。Ｒ¹〜Ｒ⁵は、それぞれ独立して単結合又は炭素数１〜１８の二価の炭化水素基を示す。また、Ｘ¹〜Ｘ⁵及びＲ¹〜Ｒ⁵のいずれかを介して複数のアジリジン環が結合されていてもよい。］で表される化合物である。なお、上記式(I)において、二価の炭化水素基として、具体的には、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、デカメチレン基等が挙げられる。また、上記（ａ）成分は、上記式(I)において、Ｘ¹＝水素原子及びＲ¹＝単結合を同時に満たさないことが好ましい。 First, the component (a) has the general formula (I):

[Wherein, X ^{1 to} X ⁵ are each a hydrogen atom, a halogen atom, a carbonyl group, a thiocarbonyl group, an isocyanate group, a thioisocyanate group, an epoxy group, a thioepoxy group, a halogenated silyl group, a hydrocarbyloxysilyl group, and a sulfonyloxy group. A functional group containing at least one selected from the group, and X ^{1 to} X ⁵ may be the same or different from each other, but at least one of them is not a hydrogen atom. R ^{1 to} R ⁵ each independently represent a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms. It may also be coupled a plurality of aziridine rings through any of X ¹ to X ⁵ and R ¹ to R ^5. It is a compound represented by this. In the above formula (I), as the divalent hydrocarbon group, specifically, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group, etc. Is mentioned. The component (a) preferably does not simultaneously satisfy X ¹ = hydrogen atom and R ¹ = single bond in the above formula (I).

  As the component (a), specifically, 1-acetylaziridine, 1-propionylaziridine, 1-butylaziridine, 1-isobutylaziridine, 1-valerylaziridine, 1-isovalerylaziridine, 1-pivaloyl Aziridine, 1-acetyl-2-methylaziridine, 2-methyl-1-propionylaziridine, 1-butyl-2-methylaziridine, 2-methyl-1-isobutylaziridine, 2-methyl-1-valerylaziridine, 1- Isovaleryl-2-methylaziridine, 2-methyl-1-pivaloylaziridine, ethyl 3- (1-aziridinyl) propionate, propyl 3- (1-aziridinyl) propionate, butyl 3- (1-aziridinyl) propionate, ethylene glycol Bis [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinini L) propionate], ethyl 3- (2-methyl-1-aziridinyl) propionate, propyl 3- (2-methyl-1-aziridinyl) propionate, butyl 3- (2-methyl-1-aziridinyl) propionate, ethylene glycol bis [3- (2-methyl-1-aziridinyl) propionate], trimethylolpropane tris [3- (2-methyl-1-aziridinyl) propionate], neopentyl glycol bis [3- (1-aziridinyl) propionate], neo Pentyl glycol bis [3- (2-methyl-1-aziridinyl) propionate], di (1-aziridinylcarbonyl) methane, 1,2-di (1-aziridinylcarbonyl) ethane, 1,3-di ( 1-aziridinylcarbonyl) propane, 1,4-di (1-aziridinylcarbonyl) butane, 1,5-di (1-aziridinylcarbonyl) pentane, di (2-methyl) -1-aziridinylcarbonyl) methane, 1,2-di (2-methyl-1-aziridinylcarbonyl) ethane, 1,3-di (2-methyl-1-aziridinylcarbonyl) propane, Examples include 4-di (2-methyl-1-aziridinylcarbonyl) butane, but are not limited thereto.

Next, (b) ^{_{component, R 6 n M'Z 4-n}} , M'Z 4, M'Z 3, R 7 n M '(- R 8 -COOR 9) 4-n or R ⁷ _n M '(-R ⁸ -COR ⁹⁾ in _4-n [wherein, R ⁶ to R ^8, which may be the same or different, a hydrocarbon group containing a carbon atom having 1 to 20 carbon atoms, R ⁹ Is a hydrocarbon group containing 1 to 20 carbon atoms, R ^{6 to} R ⁹ may contain a carbonyl group or an ester group in the side chain, and M ′ is a tin atom, silicon atom, germanium atom Or a phosphorus atom, Z is a halogen atom, and n is an integer of 0 to 3.], a halogenated organometallic compound, a halogenated metal compound, or an organometallic compound.

Specific examples of the component (b) R ⁶ _n M′Z _4-n include triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride, diphenyltin dichloride, dibutyltin dichloride. , Dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride, triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dioctyl Dichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, dimethyldichlorosilane, phenylchlorosilane, hexyl Examples include, but are not limited to, lichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, triphenylgermanium chloride, dibutylgermanium dichloride, diphenylgermanium dichloride, butylgermanium trichloride. Examples of M′Z ₄ include tin tetrachloride, silicon tetrachloride, and germanium tetrachloride. Examples of M′Z ₃ include phosphorus trichloride.

  As described above, the component (c) is a Y = C = Y ′ bond in the molecule [wherein Y is a carbon atom, oxygen atom, nitrogen atom or sulfur atom, and Y ′ is an oxygen atom, nitrogen atom or It is a heterocumulene compound containing a sulfur atom. Specific examples of the component (c) include ketene compounds such as ethyl ketene, butyl ketene, phenyl ketene and toluyl ketene; thioketene compounds such as ethylene thioketene, butyl thioketene, phenyl thioketene and toluyl thioketene; phenyl isocyanate, 2, 4 -Isocyanate compounds such as tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric type diphenylmethane diisocyanate, hexamethylene diisocyanate; phenylthioisocyanate, 2,4-tolylene diene Thioisocyanate compounds such as thioisocyanate and hexamethylenedithioisocyanate; carbodiimide compounds such as N, N′-diphenylcarbodiimide and N, N′-ethylcarbodiimide, etc. The present invention is not limited to these.

［式中、Ｙ'は、酸素原子、窒素原子又は硫黄原子である］で表される結合を分子中に含有するヘテロ３員環化合物である。上記（ｄ）成分として、具体的には、エチレンオキシド、プロピレンオキシド、シクロヘキセンオキシド、スチレンオキシド、エポキシ化大豆油、エポキシ化天然ゴム等のエポキシ化合物；エチレンイミンの他、プロピレンイミン、Ｎ-フェニルエチレンイミン、Ｎ-(β-シアノエチル)エチレンイミン等のエチレンイミン誘導体；チイラン、メチルチイラン、フェニルチイラン等のチイラン化合物等が挙げられるが、これらに限定されるものではない。 The component (d) has the general formula (II):

[Wherein Y ′ is an oxygen atom, nitrogen atom or sulfur atom] is a hetero three-membered ring compound containing in the molecule a bond represented by the formula: Specific examples of the component (d) include epoxy compounds such as ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, epoxidized soybean oil, and epoxidized natural rubber; in addition to ethyleneimine, propyleneimine, N-phenylethyleneimine And ethylene-imine derivatives such as N- (β-cyanoethyl) ethyleneimine; and thiirane compounds such as thiirane, methylthiirane, and phenylthiirane, but are not limited thereto.

  The component (e) is a halogenated isocyano compound as described above, for example, 2-amino-6-chloropyridine, 2,5-dibromopyridine, 4-chloro-2-phenylquinazoline, 2,4,5 -Tribromoimidazole, 3,6-dichloro-4-methylpyridazine, 3,4,5-trichloropyridazine, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine 2-amino-4,6-dichloropyrimidine, 6-chloro-2,4-dimethoxypyrimidine, 2-chloropyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2- (methylthio) Pyrimidine, 2,4,5,6-tetrachloropyrimidine, 2,4,6-trichloropyrimidine, 2-amino-6-chloropyrazine, 2,6-dichloropyrazine, 2,4-bis (methylthio) -6- Chloro-1,3,5-triazi , 2,4,6-trichloro-1,3,5-triazine, 2-bromo-5-nitro-thiazole, 2-chloro-benzothiazole, 2-chloro-benzoxazole, and the like.

［式中、Ｒ¹⁰〜Ｒ¹⁸は、同一でも異なってもよいが、炭素数１〜５０の炭素原子を含む炭化水素基で、Ｚはハロゲン原子で、ｍは１〜５の整数である］に対応するカルボン酸、酸ハロゲン化物、エステル化合物、炭酸エステル化合物又は酸無水物である。上記（ｆ）成分として、具体的には、酢酸、ステアリン酸、アジピン酸、マレイン酸、安息香酸、アクリル酸、メタアクリル酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸、メリット酸の他、ポリメタクリル酸エステル化合物又はポリアクリル酸エステル化合物のエステルを全部又は部分的に加水分解した化合物等のカルボン酸；酢酸クロリド、プロピオン酸クロリド、ブタン酸クロリド、イソブタン酸クロリド、オクタン酸クロリド、アクリル酸クロリド、安息香酸クロリド、ステアリン酸クロリド、フタル酸クロリド、マレイン酸クロリド、オキサリン酸クロリド、ヨウ化アセチル、ヨウ化ベンゾイル、フッ化アセチル、フッ化ベンゾイル等の酸ハロゲン化物；酢酸エチル、ステアリン酸エチル、アジピン酸ジエチル、マレイン酸ジエチル、安息香酸メチル、アクリル酸エチル、メタアクリル酸エチル、フタル酸ジエチル、テレフタル酸ジメチル、トリメリット酸トリブチル、ピロメリット酸テトラオクチル、メリット酸ヘキサエチル、酢酸フェニル、ポリメチルメタクリレート、ポリエチルアクリレート、ポリイソブチルアクリレート等のエステル化合物；炭酸ジメチル、炭酸ジエチル、炭酸ジプロピル、炭酸ジヘキシル、炭酸ジフェニル等の炭酸エステル化合物；無水酢酸、無水プロピオン酸、無水イソ酪酸、無水イソ吉草酸、無水ヘプタン酸、無水安息香酸、無水ケイ皮酸、無水コハク酸、無水メチルコハク酸、無水マレイン酸、無水グルタル酸、無水シトラコン酸、無水フタル酸、スチレン−無水マレイン酸共重合体等の酸無水物等が挙げられるが、これらに限定されるものではない。 Component _{^{(f), R 10 - (COOH) m}} , R 11 (COZ) m, R 12 - (COO-R 13), R 14 -OCOO-R 15, R 16 - (COOCO-R 17) m, Or general formula (III):

[Wherein, R ^{10 to} R ¹⁸ may be the same or different, but a hydrocarbon group containing a carbon atom having 1 to 50 carbon atoms, Z is a halogen atom, and m is an integer of 1 to 5] The carboxylic acid, acid halide, ester compound, carbonate compound or acid anhydride corresponding to As the component (f), specifically, acetic acid, stearic acid, adipic acid, maleic acid, benzoic acid, acrylic acid, methacrylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, Carboxylic acids such as compounds obtained by fully or partially hydrolyzing esters of polymethacrylic acid ester compounds or polyacrylic acid ester compounds in addition to merit acid; acetic acid chloride, propionic acid chloride, butanoic acid chloride, isobutanoic acid chloride, octanoic acid Acid halides such as chloride, acrylic acid chloride, benzoic acid chloride, stearic acid chloride, phthalic acid chloride, maleic acid chloride, oxalic acid chloride, acetyl iodide, benzoyl iodide, acetyl fluoride, benzoyl fluoride; ethyl acetate, Ethyl stearate, adip Diethyl acid, diethyl maleate, methyl benzoate, ethyl acrylate, ethyl methacrylate, diethyl phthalate, dimethyl terephthalate, tributyl trimellitic acid, tetraoctyl pyromellitic acid, hexaethyl meritate, phenyl acetate, polymethyl methacrylate, Ester compounds such as polyethyl acrylate and polyisobutyl acrylate; carbonate compounds such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dihexyl carbonate and diphenyl carbonate; acetic anhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, heptane anhydride Acid, benzoic anhydride, cinnamic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, glutaric anhydride, citraconic anhydride, phthalic anhydride, acid anhydrides such as styrene-maleic anhydride copolymer, etc. But it is lower, but the invention is not limited thereto.

［式中、Ｒ¹⁹〜Ｒ²⁵は、同一でも異なってもよいが、炭素数１〜２０の炭素原子を含む炭化水素基で、Ｍ''はスズ原子、ケイ素原子又はゲルマニウム原子で、ｋは０〜３の整数で、ｐは０又は１である］に対応するカルボン酸の金属塩である。上記（ｇ）成分として、具体的には、トリフェニルスズラウレート、トリフェニルスズ-２-エチルヘキサテート、トリフェニルスズナフテート、トリフェニルスズアセテート、トリフェニルスズアクリレート、トリ-ｎ-ブチルスズラウレート、トリ-ｎ-ブチルスズ-２-エチルヘキサテート、トリ-ｎ-ブチルスズナフテート、トリ-ｎ-ブチルスズアセテート、トリ-ｎ-ブチルスズアクリレート、トリ-ｔ-ブチルスズラウレート、トリ-ｔ-ブチルスズ-２-エチルヘキサテート、トリ-ｔ-ブチルスズナフテート、トリ-ｔ-ブチルスズアセテート、トリ-ｔ-ブチルスズアクリレート、トリイソブチルスズラウレート、トリイソブチルスズ-２-エチルヘキサテート、トリイソブチルスズナフテート、トリイソブチルスズアセテート、トリイソブチルスズアクリレート、トリイソプロピルスズラウレート、トリイソプロピルスズ-２-エチルヘキサテート、トリイソプロピルスズナフテート、トリイソプロピルスズアセテート、トリイソプロピルスズアクリレート、トリヘキシルスズラウレート、トリヘキシルスズ-２-エチルヘキサテート、トリヘキシルスズアセテート、トリヘキシルスズアクリレート、トリオクチルスズラウレート、トリオクチルスズ-２-エチルヘキサテート、トリオクチルスズナフテート、トリオクチルスズアセテート、トリオクチルスズアクリレート、トリ-２-エチルヘキシルスズラウレート、トリ-２-エチルヘキシルスズ-２-エチルヘキサテート、トリ-２-エチルヘキシルスズナフテート、トリ-２-エチルヘキシルスズアセテート、トリ-２-エチルヘキシルスズアクリレート、トリステアリルスズラウレート、トリステアリルスズ-２-エチルヘキサテート、トリステアリルスズナフテート、トリステアリルスズアセテート、トリステアリルスズアクリレート、トリベンジルスズラウレート、トリベンジルスズ-２-エチルヘキサテート、トリベンジルスズナフテート、トリベンジルスズアセテート、トリベンジルスズアクリレート、ジフェニルスズジラウレート、ジフェニルスズ-２-エチルヘキサテート、ジフェニルスズジステアレート、ジフェニルスズジナフテート、ジフェニルスズジアセテート、ジフェニルスズジアクリレート、ジ-ｎ-ブチルスズジラウレート、ジ-ｎ-ブチルスズジ-２-エチルヘキサテート、ジ-ｎ-ブチルスズジステアレート、ジ-ｎ-ブチルスズジナフテート、ジ-ｎ-ブチルスズジアセテート、ジ-ｎ-ブチルスズジアクリレート、ジ-ｔ-ブチルスズジラウレート、ジ-ｔ-ブチルスズジ-２-エチルヘキサテート、ジ-ｔ-ブチルスズジステアレート、ジ-ｔ-ブチルスズジナフテート、ジ-ｔ-ブチルスズジアセテート、ジ-ｔ-ブチルスズジアクリレート、ジイソブチルスズジラウレート、ジイソブチルスズジ-２-エチルヘキサテート、ジイソブチルスズジステアレート、ジイソブチルスズジナフテート、ジイソブチルスズジアセテート、ジイソブチルスズジアクリレート、ジイソプロピルスズジラウレート、ジイソプロピルスズ-２-エチルヘキサテート、ジイソプロピルスズジステアレート、ジイソプロピルスズジナフテート、ジイソプロピルスズジアセテート、ジイソプロピルスズジアクリレート、ジヘキシルスズジラウレート、ジヘキシルスズジ-２-エチルヘキサテート、ジヘキシルスズジステアレート、ジヘキシルスズジナフテート、ジヘキシルスズジアセテート、ジヘキシルスズジアクリレート、ジ-２-エチルヘキシルスズジラウレート、ジ-２-エチルヘキシルスズ-２-エチルヘキサテート、ジ-２-エチルヘキシルスズジステアレート、ジ-２-エチルヘキシルスズジナフテート、ジ-２-エチルヘキシルスズジアセテート、ジ-２-エチルヘキシルスズジアクリレート、ジオクチルスズジラウレート、ジオクチルスズジ-２-エチルヘキサテート、ジオクチルスズジステアレート、ジオクチルスズジナフテート、ジオクチルスズジアセテート、ジオクチルスズジアクリレート、ジステアリルスズジラウレート、ジステアリルスズジ-２-エチルヘキサテート、ジステアリルスズジステアレート、ジステアリルスズジナフテート、ジステアリルスズジアセテート、ジステアリルスズジアクリレート、ジベンジルスズジラウレート、ジベンジルスズジ-２-エチルヘキサテート、ジベンジルスズジステアレート、ジベンジルスズジナフテート、ジベンジルスズジアセテート、ジベンジルスズジアクリレート、フェニルスズトリラウレート、フェニルスズトリ-２-エチルヘキサテート、フェニルスズトリナフテート、フェニルスズトリアセテート、フェニルスズトリアクリレート、ｎ-ブチルスズトリラウレート、ｎ-ブチルスズトリ-２-エチルヘキサテート、ｎ-ブチルスズトリナフテート、ｎ-ブチルスズトリアセテート、ｎ-ブチルスズトリアクリレート、ｔ-ブチルスズトリラウレート、ｔ-ブチルスズトリ-２-エチルヘキサテート、ｔ-ブチルスズトリナフテート、ｔ-ブチルスズトリアセテート、ｔ-ブチルスズトリアクリレート、イソブチルスズトリラウレート、イソブチルスズトリ-２-エチルヘキサテート、イソブチルスズトリナフテート、イソブチルスズトリアセテート、イソブチルスズトリアクリレート、イソプロピルスズトリラウレート、イソプロピルスズトリ-２-エチルヘキサテート、イソプロピルスズトリナフテート、イソプロピルスズトリアセテート、イソプロピルスズトリアクリレート、ヘキシルスズトリラウレート、ヘキシルスズトリ-２-エチルヘキサテート、ヘキシルスズトリナフテート、ヘキシルスズトリアセテート、ヘキシルスズトリアクリレート、オクチルスズトリラウレート、オクチルスズトリ-２-エチルヘキサテート、オクチルスズトリナフテート、オクチルスズトリアセテート、オクチルスズトリアクリレート、２-エチルヘキシルスズトリラウレート、２-エチルヘキシルスズトリ-２-エチルヘキサテート、２-エチルヘキシルスズトリナフテート、２-エチルヘキシルスズトリアセテート、２-エチルヘキシルスズトリアクリレート、ステアリルスズトリラウレート、ステアリルスズトリ-２-エチルヘキサテート、ステアリルスズトリナフテート、ステアリルスズトリアセテート、ステアリルスズトリアクリレート、ベンジルスズトリラウレート、ベンジルスズトリ-２-エチルヘキサテート、ベンジルスズトリナフテート、ベンジルスズトリアセテート、ベンジルスズトリアクリレート、ジフェニルスズビスメチルマレート、ジフェニルスズビス-２-エチルヘキサテート、ジフェニルスズビスオクチルマレート、ジフェニルスズビスオクチルマレート、ジフェニルスズビスベンジルマレート、ジ-ｎ-ブチルスズビスメチルマレート、ジ-ｎ-ブチルスズビス-２-エチルヘキサテート、ジ-ｎ-ブチルスズビスオクチルマレート、ジ-ｎ-ブチルスズビスベンジルマレート、ジ-ｔ-ブチルスズビスメチルマレート、ジ-ｔ-ブチルスズビス-２-エチルヘキサテート、ジ-ｔ-ブチルスズビスオクチルマレート、ジ-ｔ-ブチルスズビスベンジルマレート、ジイソブチルスズビスメチルマレート、ジイソブチルスズビス-２-エチルヘキサテート、ジイソブチルスズビスオクチルマレート、ジイソブチルスズビスベンジルマレート、ジイソプロピルスズビスメチルマレート、ジイソプロピルスズビス-２-エチルヘキサテート、ジイソプロピルスズビスオクチルマレート、ジイソプロピルスズビスベンジルマレート、ジヘキシルスズビスメチルマレート、ジヘキシルスズビス-２-エチルヘキサテート、ジヘキシルスズビスオクチルマレート、ジヘキシルスズビスベンジルマレート、ジ-２-エチルヘキシルスズビスメチルマレート、ジ-２-エチルヘキシルスズビス-２-エチルヘキサテート、ジ-２-エチルヘキシルスズビスオクチルマレート、ジ-２-エチルヘキシルスズビスベンジルマレート、ジオクチルスズビスメチルマレート、ジオクチルスズビス-２-エチルヘキサテート、ジオクチルスズビスオクチルマレート、ジオクチルスズビスベンジルマレート、ジステアリルスズビスメチルマレート、ジステアリルスズビス-２-エチルヘキサテート、ジステアリルスズビスオクチルマレート、ジステアリルスズビスベンジルマレート、ジベンジルスズビスメチルマレート、ジベンジルスズビス-２-エチルヘキサテート、ジベンジルスズビスオクチルマレート、ジベンジルスズビスベンジルマレート、ジフェニルスズビスメチルアジテート、ジフェニルスズビス-２-エチルヘキサテート、ジフェニルスズビスオクチルアジテート、ジフェニルスズビスベンジルアジテート、ジ-ｎ-ブチルスズビスメチルアジテート、ジ-ｎ-ブチルスズビス-２-エチルヘキサテート、ジ-ｎ-ブチルスズビスオクチルアジテート、ジ-ｎ-ブチルスズビスベンジルアジテート、ジ-ｔ-ブチルスズビスメチルアジテート、ジ-ｔ-ブチルスズビス-２-エチルヘキサテート、ジ-ｔ-ブチルスズビスオクチルアジテート、ジ-ｔ-ブチルスズビスベンジルアジテート、ジイソブチルスズビスメチルアジテート、ジイソブチルスズビス-２-エチルヘキサテート、ジイソブチルスズビスオクチルアジテート、ジイソブチルスズビスベンジルアジテート、ジイソプロピルスズビスメチルアジテート、ジイソプロピルスズビス-２-エチルヘキサテート、ジイソプロピルスズビスオクチルアジテート、ジイソプロピルスズビスベンジルアジテート、ジヘキシルスズビスメチルアジテート、ジヘキシルスズビス-２-エチルヘキサテート、ジヘキシルスズビスメチルアジテート、ジヘキシルスズビスベンジルアジテート、ジ-２-エチルヘキシルスズビスメチルアジテート、ジ-２-エチルヘキシルスズビス-２-エチルヘキサテート、ジ-２-エチルヘキシルスズビスオクチルアジテート、ジ-２-エチルヘキシルスズビスベンジルアジテート、ジオクチルスズビスメチルアジテート、ジオクチルスズビス-２-エチルヘキサテート、ジオクチルスズビスオクチルアジテート、ジオクチルスズビスベンジルアジテート、ジステアリルスズビスメチルアジテート、ジステアリルスズビス-２-エチルヘキサテート、ジステアリルスズビスオクチルアジテート、ジステアリルスズビスベンジルアジテート、ジベンジルスズビスメチルアジテート、ジベンジルスズビス-２-エチルヘキサテート、ジベンジルスズビスオクチルアジテート、ジベンジルスズビスベンジルアジテート、ジフェニルスズマレート、ジ-ｎ-ブチルスズマレート、ジ-ｔ-ブチルスズマレート、ジイソブチルスズマレート、ジイソプロピルスズマレート、ジヘキシルスズマレート、ジ-２-エチルヘキシルスズマレート、ジオクチルスズマレート、ジステアリルスズマレート、ジベンジルスズマレート、ジフェニルスズアジテート、ジ-ｎ-ブチルスズアジテート、ジ-ｔ-ブチルスズアジテート、ジイソブチルスズアジテート、ジイソプロピルスズアジテート、ジヘキシルスズジアセテート、ジ-２-エチルヘキシルスズアジテート、ジオクチルスズアジテート、ジステアリルスズアジテート、ジベンジルスズアジテート等が挙げられるが、これらに限定されるものではない。 The component (g) is R ¹⁹ _k M ″ (OCOR ²⁰ ) _4-k , R ²¹ _k M ″ (OCO—R ²² —COOR ²³ ) _4-k or the general formula (IV):

[In the formula, R ^{19 to} R ²⁵ may be the same or different, but a hydrocarbon group containing a carbon atom having 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom, and k is A metal salt of a carboxylic acid corresponding to an integer of 0 to 3 and p is 0 or 1. Specific examples of the component (g) include triphenyltin laurate, triphenyltin-2-ethyl hexatate, triphenyltin naphthate, triphenyltin acetate, triphenyltin acrylate, and tri-n-butyltin laurate. , Tri-n-butyltin-2-ethylhexarate, tri-n-butyltin naphthate, tri-n-butyltin acetate, tri-n-butyltin acrylate, tri-t-butyltin laurate, tri-t-butyltin-2 -Ethyl hexatate, tri-t-butyltin naphthate, tri-t-butyltin acetate, tri-t-butyltin acrylate, triisobutyltin laurate, triisobutyltin-2-ethylhexamate, triisobutyltin naphthate, tri Isobutyltin acetate, triisobutyltin accelerator , Triisopropyl tin laurate, triisopropyl tin-2-ethyl hexatate, triisopropyl tin naphthate, triisopropyl tin acetate, triisopropyl tin acrylate, trihexyl tin laurate, trihexyl tin-2-ethyl hexatate, Trihexyltin acetate, trihexyltin acrylate, trioctyltin laurate, trioctyltin-2-ethylhexamate, trioctyltin naphthate, trioctyltin acetate, trioctyltin acrylate, tri-2-ethylhexyltin laurate , Tri-2-ethylhexyltin-2-ethylhexarate, tri-2-ethylhexyltin naphthate, tri-2-ethylhexyltin acetate, tri-2-ethylhexyltin acrylate, tristeare Rutin laurate, tristearyl tin-2-ethyl hexatate, tristearyl tin naphthate, tristearyl tin acetate, tristearyl tin acrylate, tribenzyl tin laurate, tribenzyl tin-2-ethyl hexatate, tribenzyl tin naphthate, Tribenzyltin acetate, tribenzyltin acrylate, diphenyltin dilaurate, diphenyltin-2-ethylhexarate, diphenyltin distearate, diphenyltin dinaphthate, diphenyltin diacetate, diphenyltin diacrylate, di-n-butyltin dilaurate, di-n- Butyltin di-2-ethylhexarate, di-n-butyltin distearate, di-n-butyltin dinaphthate, di-n-butyltin diacetate, di-n-butyltin dia Chlorate, di-t-butyltin dilaurate, di-t-butyltin di-2-ethylhexarate, di-t-butyltin distearate, di-t-butyltin dinaphthate, di-t-butyltin diacetate, di-t -Butyltin diacrylate, diisobutyltin dilaurate, diisobutyltin di-2-ethylhexarate, diisobutyltin distearate, diisobutyltin dinaphthate, diisobutyltin diacetate, diisobutyltin diacrylate, diisopropyltin dilaurate, diisopropyltin-2- Ethyl hexatate, diisopropyl tin distearate, diisopropyl tin dinaphthate, diisopropyl tin diacetate, diisopropyl tin diacrylate, dihexyl tin dilaurate, dihexyl tin di-2-ethylhexate , Dihexyltin distearate, dihexyltin dinaphthate, dihexyltin diacetate, dihexyltin diacrylate, di-2-ethylhexyltin dilaurate, di-2-ethylhexyltin-2-ethylhexarate, di-2-ethylhexyl Tin distearate, di-2-ethylhexyltin dinaphthate, di-2-ethylhexyltin diacetate, di-2-ethylhexyltin diacrylate, dioctyltin dilaurate, dioctyltin di-2-ethylhexarate, dioctyltindi Stearate, dioctyltin dinaphthate, dioctyltin diacetate, dioctyltin diacrylate, distearyltin dilaurate, distearyltin di-2-ethylhexarate, distearyltin distearate, distearyltin dinaphthate Tate, distearyl tin diacetate, distearyl tin diacrylate, dibenzyltin dilaurate, dibenzyltin di-2-ethylhexarate, dibenzyltin distearate, dibenzyltin dinaphthate, dibenzyltin diacetate, dibenzyltin Diacrylate, phenyltin trilaurate, phenyltin tri-2-ethylhexarate, phenyltin trinaphthate, phenyltin triacetate, phenyltin triacrylate, n-butyltin trilaurate, n-butyltin tri-2-ethylhexa Tate, n-butyltin trinaphthate, n-butyltin triacetate, n-butyltin triacrylate, t-butyltin trilaurate, t-butyltin tri-2-ethylhexarate, t-butyltin trinaphthate, t-butyl Rutin triacetate, t-butyltin triacrylate, isobutyltin trilaurate, isobutyltin tri-2-ethyl hexatate, isobutyltin trinaphthate, isobutyltin triacetate, isobutyltin triacrylate, isopropyltin trilaurate, isopropyltin tri -2-ethyl hexatate, isopropyl tin trinaphthate, isopropyl tin triacetate, isopropyl tin triacrylate, hexyl tin trilaurate, hexyl tin tri-2-ethyl hexatate, hexyl tin trinaphthate, hexyl tin triacetate, hexyl tin Triacrylate, octyltin trilaurate, octyltin tri-2-ethyl hexatate, octyltin trinaphthate, octyltin triacetate, Octyltin triacrylate, 2-ethylhexyltin trilaurate, 2-ethylhexyltin tri-2-ethylhexarate, 2-ethylhexyltin trinaphthate, 2-ethylhexyltin triacetate, 2-ethylhexyltin triacrylate, stearyltin trilaurate , Stearyltin tri-2-ethylhexarate, stearyltin trinaphthate, stearyltin triacetate, stearyltin triacrylate, benzyltin trilaurate, benzyltin tri-2-ethylhexarate, benzyltin trinaphthate, benzyl Tin triacetate, benzyltin triacrylate, diphenyltin bismethylmalate, diphenyltin bis-2-ethylhexarate, diphenyltin bisoctylmalate, diphenyls Bisbisoctylmalate, diphenyltin bisbenzylmalate, di-n-butyltin bismethylmalate, di-n-butyltin bis-2-ethylhexarate, di-n-butyltin bisoctylmalate, di-n-butyltin Bisbenzyl malate, di-t-butyltin bismethylmalate, di-t-butyltin bis-2-ethylhexarate, di-t-butyltin bisoctylmalate, di-t-butyltin bisbenzylmalate, diisobutyltin Bismethyl malate, diisobutyltin bis-2-ethylhexarate, diisobutyltin bisoctylmalate, diisobutyltin bisbenzylmalate, diisopropyltin bismethylmalate, diisopropyltin bis-2-ethylhexarate, diisopropyltin bisoctyl Malate, diisopropyl tin bis N-diethyl malate, dihexyltin bismethylmalate, dihexyltin bis-2-ethylhexarate, dihexyltin bisoctylmalate, dihexyltin bisbenzylmalate, di-2-ethylhexyltin bismethylmalate, di-2-ethylhexyltin Bis-2-ethylhexarate, di-2-ethylhexyltin bisoctyl malate, di-2-ethylhexyltin bisbenzylmalate, dioctyltin bismethylmalate, dioctyltin bis-2-ethylhexarate, dioctyltin bis Octylmalate, dioctyltin bisbenzylmalate, distearyltin bismethylmalate, distearyltin bis-2-ethylhexarate, distearyltin bisoctylmalate, distearyltin bisbenzylmalate, dibenzyltin Smethyl malate, dibenzyltin bis-2-ethyl hexatate, dibenzyl tin bis octyl malate, dibenzyl tin bis benzyl malate, diphenyl tin bismethyl agitate, diphenyl tin bis-2-ethyl hexatate, diphenyl tin bis octyl azate , Diphenyltin bisbenzyl agitate, di-n-butyltin bismethyl agitate, di-n-butyltin bis-2-ethylhexaate, di-n-butyltin bisoctyl agitate, di-n-butyltin bisbenzyl agitate, di-t- Butyltin bismethyl agitate, di-t-butyltin bis-2-ethyl hexatate, di-t-butyltin bisoctyl agitate, di-t-butyltin bisbenzyl agitate, diisobutyltin bismethyl agitate, diisobutyltin bis-2-ethyl Tilhexate, diisobutyltin bisoctyl agitate, diisobutyltin bisbenzyl agitate, diisopropyltin bismethyl agitate, diisopropyltin bis-2-ethylhexate, diisopropyltin bisoctyl agitate, diisopropyltin bisbenzyl agitate, dihexyltin bismethyl agitate, Dihexyltin bis-2-ethyl hexatate, dihexyl tin bismethyl agitate, dihexyl tin bisbenzyl agitate, di-2-ethylhexyl tin bismethyl agitate, di-2-ethylhexyl tin bis-2-ethyl hexatate, di-2- Ethylhexyltin bisoctyl agitate, di-2-ethylhexyltin bisbenzyl agitate, dioctyltin bismethyl agitate, dioctyltin bis-2- Ethyl hexatate, dioctyltin bisoctyl agitate, dioctyltin bisbenzyl agitate, distearyl tin bismethyl agitate, distearyl tin bis-2-ethyl hexatate, distearyl tin bisoctyl agitate, distearyl tin bisbenzyl agitate, dibenzyl Tin bismethyl agitate, dibenzyltin bis-2-ethylhexarate, dibenzyltin bisoctyl agitate, dibenzyltin bisbenzyl agitate, diphenyltin malate, di-n-butyltin malate, di-t-butyltin maleate, Diisobutyltin maleate, diisopropyltin maleate, dihexyltin maleate, di-2-ethylhexyltin maleate, dioctyltin maleate, distearyl tin maleate, dibenzyltin maleate Diphenyltin agitate, di-n-butyltin agitate, di-t-butyltin agitate, diisobutyltin agitate, diisopropyltin agitate, dihexyltin diacetate, di-2-ethylhexyltin agitate, dioctyltin agitate, distearyltin agitate, di Examples include, but are not limited to, benzyl tin agitate.

  The component (h) is an N-substituted aminoketone, N-substituted aminothioketone, N-substituted aminoaldehyde, N-substituted aminothioaldehyde, or —C (═Y ″) — N <bond [Y ′ 'Is an oxygen atom or a sulfur atom]. As the component (h), specifically, 4-dimethylaminoacetophenone, 4-diethylaminoacetophenone, 1,3-bis (diphenylamino) -2-propanone, 1,7-bis (methylethylamino) -4- Heptanone, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4-di-t-butylaminobenzophenone, 4-diphenylaminobenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) N-substituted aminoketones such as benzophenone and 4,4'-bis (diphenylamino) benzophenone and the corresponding N-substituted aminothioketones; N- such as 4-dimethylaminobenzaldehyde, 4-diphenylaminobenzaldehyde and 4-divinylaminobenzaldehyde Substituted amino aldehydes and corresponding N-substituted aminos Oaldehyde; N-methyl-β-propiolactam, N-phenyl-β-propiolactam, N-methyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, Nt-butyl-2-pyrrolidone, N -Phenyl-5-methyl-2-pyrrolidone, N-methyl-2-piperidone, N-phenyl-2-piperidone, N-methyl-ε-caprolactam, N-phenyl-ε-caprolactam, N-methyl-ω-caprolactam N-substituted lactams such as N-phenyl-ω-caprolactam, N-methyl-ω-laurylactam, N-vinyl-ω-laurylactam and the corresponding N-substituted thiolactams; 1,3-dimethylethyleneurea N- such as 1,3-divinylethyleneurea, 1,3-diethyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone Substituted cyclic ureas and corresponding N-substitutions Although cyclic thiourea etc. are mentioned, it is not limited to these.

  Examples of the modifier include heterocyclic nitrile compounds represented by the following formula (V) or formula (VI). In the formulas (V) and (VI), θ represents a heterocyclic group. Also, θ is a heterocyclic group containing a nitrogen atom, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a sulfur atom, a heterocyclic group containing two or more heteroatoms, and a heterocyclic group containing one or more cyano groups It is preferably at least one heterocyclic group selected from the group consisting of Further, it may be a heteroaromatic group or a heteroaromatic group such as thiophene, pyridine, furan, piperidine, dioxane, and also a monocyclic, bicyclic, tricyclic, or polycyclic heterocyclic ring. It may be a group.

  Conventionally, the modifying groups that can be introduced into the butadiene-based polymer have been limited to specific groups such as —CN, —SiCl, —SiOR, and C═O. However, in the present invention, more excellent low heat generation is realized. From the viewpoint of conversion, a more preferable conjugated modifying group can be introduced. Such a conjugated modification group can more reliably conjugated a butadiene copolymer or the like, and contributes to an improvement in affinity for carbon black. The heterocyclic nitrile compound component represented by the formula (V) or the formula (VI) is a compound that can be reacted with a polymer having an active end.

  Specific examples of such θ include, for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl as a heterocyclic group containing a nitrogen atom. 4-pyridazinyl, N-methyl-2-pyrrolyl, N-methyl-3-pyrrolyl, N-methyl-2-imidazolyl, N-methyl-4-imidazolyl, N-methyl-5-imidazolyl, N-methyl-3 -Pyrazolyl, N-methyl-4-pyrazolyl, N-methyl-5-pyrazolyl, N-methyl-1,2,3-triazol-4-yl, N-methyl-1,2,3-triazol-5-yl N-methyl-1,2,4-triazol-3-yl, N-methyl-1,2,4-triazol-5-yl, 1,2,4-triazin-3-yl, 2,4-triazin-5-yl, 1,2,4-triazin-6-yl, 1,3,5-triazinyl, N-methyl-2-pyrrolin-2-yl, N-methyl-2-pyrroline- 3-yl, N-methyl-2-pyrrolin-4-yl, N-methyl-2-pyrrolin-5-yl, N-methyl-3-pyrrolin-2-yl, N-methyl-3-pyrrolin-3- Yl, N-methyl-2-imidazolin-2-yl, N-methyl-2-imidazolin-4-yl, N-methyl-2-imidazolin-5-yl, N-methyl-2-pyrazolin-3-yl, N-methyl-2-pyrazolin-4-yl, N-methyl-2-pyrazolin-5-yl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, N- Methylindol-2-yl N-methylindol-3-yl, N-methylisoindol-1-yl, N-methylisoindol-3-yl, 1-indolidinyl, 2-indolidinyl, 3-indolidinyl, 1-phthalazinyl, 2-quinazolinyl, 4-quinazolinyl, 2-quinoxalinyl, 3-cinnolinyl, 4-cinnolinyl, 1-methylindazol-3-yne, 1,5-naphthyridin-2-yl, 1,5-naphthyridin-3-yl, 1,5-naphthyridine -4-yl, 1,8-naphthyridin-2-yl, 1,8-naphthyridin-3-yl, 1,8-naphthyridin-4-yl, 2-pteridinyl, 4-pteridinyl, 6-pteridinyl, 7-pteridinyl 1-methylbenzimidazol-2-yl, 6-phenanthridinyl, N-methyl-2-purinyl, N Methyl-6-purinyl, N-methyl-8-purinyl, N-methyl-β-carbolin-1-yl, N-methyl-β-carbolin-3-yl, N-methyl-β-carbolin-4-yl, 9-acridinyl, 1,7-phenanthroline-2-yl, 1,7-phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,10-phenanthroline-2-yl, 1,10-phenanthroline- 3-yl, 1,10-phenanthroline-4-yl, 4,7-phenanthroline-1-yl, 4,7-phenanthroline-2-yl, 4,7-phenanthroline-3-yl, 1-phenazinyl, 2- Examples include phenazinyl, pyrrolidino and piperidino.

  Examples of the heterocyclic group containing an oxygen atom include 2-furyl, 3-furyl, 2-benzo [b] furyl, 3-benzo [b] furyl, 1-isobenzo [b] furyl, 3-isobenzo [b] furyl, 2 -Naphtho [2,3-b] furyl, 3-naphtho [2,3-b] furyl.

  Examples of the heterocyclic group containing a sulfur atom include 2-thienyl, 3-thienyl, 2-benzo [b] thienyl, 3-benzo [b] thienyl, 1-isobenzo [b] thienyl, 3-isobenzo [b] thienyl, 2 -Naphtho [2,3-b] thienyl, 3-naphtho [2,3-b] thienyl.

  Examples of the heterocyclic group containing two or more heteroatoms include 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3- Isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,3,4-oxadiazol-2- Yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 2-oxazolin-2-yl, 2-oxazoline- 4-yl, 2-oxazolin-5-yl, 3-isoxazolinyl, 4-isoxazolinyl, 5-isoxazolinyl, 2-thia Phosphorus-2-yl, 2-thiazoline-4-yl, 2-thiazoline-5-yl, 3-isothiazolinyl, 4-isothiazolinyl, 5- isothiazolinyl, 2-benzothiazolyl, and morpholino.

  Among these, it is preferable that (theta) is a heterocyclic group containing a nitrogen atom, and it is especially preferable that they are 2-pyridyl, 3-pyridyl, and 4-pyridyl.

In the above formulas (V) and (VI), R ²⁹ represents a divalent hydrocarbon group, and corresponds to an alkylene group, alkenylene group, arylene group or the like corresponding to a heterocyclic nitrile compound described later.

  Specific examples of such a heterocyclic nitrile compound include, for example, 2-pyridinecarbonitrile, 3-pyridinecarbonitrile, 4-pyridinecarbonitrile, pyrazinecarbohydrate as compounds having a heterocyclic group containing a nitrogen atom. Nitrile, 2-pyrimidinecarbonitrile, 4-pyrimidinecarbonitrile, 5-pyrimidinecarbonitrile, 3-pyridazinecarbonitrile, 4-pyridazinecarbonitrile, N-methyl-2-pyrrolecarbonitrile, N-methyl-3-pyrrolecarb Nitrile, N-methyl-2-imidazolecarbonitrile, N-methyl-4-imidazolecarbonitrile, N-methyl-5-imidazolecarbonitrile, N-methyl-3-pyrazolecarbonitrile, N-methyl-4-pyrazolecarbonitrile Nitrile, N-me Ru-5-pyrazolecarbonitrile, N-methyl-1,2,3-triazole-4-carbonitrile, N-methyl-1,2,3-triazole-5-carbonitrile, N-methyl-1,2, 4-triazole-3-carbonitrile, N-methyl-1,2,4-triazole-5-carbonitrile, 1,2,4-triazine-3-carbonitrile, 1,2,4-triazine-5-carbonitrile Nitrile, 1,2,4-triazine-6-carbonitrile, 1,3,5-triazinecarbonitrile, N-methyl-2-pyrroline-2-carbonitrile, N-methyl-2-pyrroline-3-carbonitrile N-methyl-2-pyrroline-4-carbonitrile, N-methyl-2-pyrroline-5-carbonitrile, N-methyl-3-pyrroline-2-carbonitrile N-methyl-3-pyrroline-3-carbonitrile, N-methyl-2-imidazoline-2-carbonitrile, N-methyl-2-imidazoline-4-carbonitrile, N-methyl-2-imidazoline-5-carbonitrile Nitrile, N-methyl-2-pyrazolin-3-carbonitrile, N-methyl-2-pyrazoline-4-carbonitrile, N-methyl-2-pyrazoline-5-carbonitrile, 2-quinolinecarbonitrile, 3-quinoline Carbonitrile, 4-quinolinecarbonitrile, 1-isoquinolinecarbonitrile, 3-isoquinolinecarbonitrile, 4-isoquinolinecarbonitrile, N-methylindole-2-carbonitrile, N-methylindole-3-carbonitrile, N-methyl Isoindole-1-carbonitrile, N-methylisoi Ndole-3-carbonitrile, 1-indolizinecarbonitrile, 2-indolizinecarbonitrile, 3-indolizinecarbonitrile, 1-phthalazinecarbonitrile, 2-quinazolinecarbonitrile, 4-quinazolinecarbonitrile, 2-quinoxaline Carbonitrile, 3-cinnolinecarbonitrile, 4-cinnolinecarbonitrile, 1-methylindazole-3-carbonitrile, 1,5-naphthyridine-2-carbonitrile, 1,5-naphthyridine-3-carbonitrile, 1 , 5-naphthyridine-4-carbonitrile, 1,8-naphthyridine-2-carbonitrile, 1,8-naphthyridine-3-carbonitrile, 1,8-naphthyridine-4-carbonitrile, 2-pteridinecarbonitrile, 4 -Pteridinecarbonitrile, 6 Pteridinecarbonitrile, 7-pteridinecarbonitrile, 1-methylbenzimidazole-2-carbonitrile, phenanthridine-6-carbonitrile, N-methyl-2-purinecarbonitrile, N-methyl-6-purinecarbonitrile, N-methyl-8-purinecarbonitrile, N-methyl-β-carboline-1-carbonitrile, N-methyl-β-carboline-3-carbonitrile, N-methyl-β-carboline-4-carbonitrile, 9 -Acridinecarbonitrile, 1,7-phenanthroline-2-carbonitrile, 1,7-phenanthroline-3-carbonitrile, 1,7-phenanthroline-4-carbonitrile, 1,10-phenanthroline-2-carbonitrile, 1 , 10-phenanthroline-3-carbonitrile, , 10-phenanthroline-4-carbonitrile, 4,7-phenanthroline-1-carbonitrile, 4,7-phenanthroline-2-carbonitrile, 4,7-phenanthroline-3-carbonitrile, 1-phenazinecarbonitrile, 2, -Phenazinecarbonitrile, 1-pyrrolidinecarbonitrile, 1-piperidinecarbonitrile are mentioned.

  Examples of the compound having a heterocyclic group containing an oxygen atom include 2-furonitrile, 3-furonitrile, 2-benzo [b] furancarbonitrile, 3-benzo [b] furancarbonitrile, and isobenzo [b] furan-1-carbo. Examples include nitrile, isobenzo [b] furan-3-carbonitrile, naphtho [2,3-b] furan-2-carbonitrile, and naphtho [2,3-b] furan-3-carbonitrile.

  As compounds having a heterocyclic group containing a sulfur atom, 2-thiophenecarbonitrile, 3-thiophenecarbonitrile, benzo [b] thiophene-2-carbonitrile, benzo [b] thiophene-3-carbonitrile, isobenzo [b] Examples include thiophene-1-carbonitrile, isobenzo [b] thiophene-3-carbonitrile, naphtho [2,3-b] thiophene-2-carbonitrile, and naphtho [2,3-b] thiophene-3-carbonitrile. .

  Compounds having a heterocyclic group containing two or more heteroatoms include 2-oxazolecarbonitrile, 4-oxazolecarbonitrile, 5-oxazolecarbonitrile, 3-isoxazolecarbonitrile, 4-isoxazolecarbonitrile, 5-isoxazole. Oxazolecarbonitrile, 2-thiazolecarbonitrile, 4-thiazolecarbonitrile, 5-thiazolecarbonitrile, 3-isothiazolecarbonitrile, 4-isothiazolecarbonitrile, 5-isothiazolecarbonitrile, 1,2,3-oxazole -4-carbonitrile, 1,2,3-oxazole-5-carbonitrile, 1,3,4-oxazole-2-carbonitrile, 1,2,3-thiazole-4-carbonitrile, 1,2,3 -Thiazole-5-carbo Tolyl, 1,3,4-thiazole-2-carbonitrile, 2-oxazoline-2-carbonitrile, 2-oxazoline-4-carbonitrile, 2-oxazoline-5-carbonitrile, 3-isoxazolinecarbonitrile, 4 -Isoxazoline carbonitrile, 5-isoxazoline carbonitrile, 2-thiazoline-2-carbonitrile, 2-thiazoline-4-carbonitrile, 2-thiazoline-5-carbonitrile, 3-isothiazoline carbonitrile, 4-isothiazoline carbonitrile Nitriles, 5-isothiazolinecarbonitriles, benzothiazole-2-carbonitriles, 4-morpholinecarbonitriles.

  As compounds having two or more cyano groups, 2,3-pyridinedicarbonitrile, 2,4-pyridinedicarbonitrile, 2,5-pyridinedicarbonitrile, 2,6-pyridinedicarbonitrile, 3,4- Pyridinedicarbonitrile, 2,4-pyrimidinedicarbonitrile, 2,5-pyrimidinedicarbonitrile, 4,5-pyrimidinedicarbonitrile, 4,6-pyrimidinedicarbonitrile, 2,3-pyrazinedicarbonitrile, 2,5-pyrazinedicarbonitrile, 2,6-pyrazinedicarbonitrile, 2,3-furandicarbonitrile, 2,4-furandicarbonitrile, 2,5-furandicarbonitrile, 2,3-thiophenedicarbonitrile 2,4-thiophene dicarbonitrile, 2,5-thiophene dicarbonitrile, N-methyl -2,3-pyrrole dicarbonitrile, N-methyl-2,4-pyrrole dicarbonitrile, N-methyl-2,5-pyrrole dicarbonitrile, 1,3,5-triazine-2,4-dicarb Nitrile, 1,2,4-triazine-3,5-dicarbonitrile, 3,2,4-triazine-3,6-dicarbonitrile, 2,3,4-pyridinetricarbonitrile, 2,3,5 -Pyridine tricarbonitrile, 2,3,6-pyridinetricarbonitrile, 2,4,5-pyridinetricarbonitrile, 2,4,6-pyridinetricarbonitrile, 3,4,5-pyridinetricarbonitrile, 2,4,5-pyrimidine tricarbonitrile, 2,4,6-pyrimidine tricarbonitrile, 4,5,6-pyrimidine tricarbonitrile, pyrazine tricarbonitrile Ril, 2,3,4-furantricarbonitrile, 2,3,5-furantricarbonitrile, 2,3,4-thiophenetricarbonitrile, 2,3,5-thiophenetricarbonitrile, N-methyl- 2,3,4-pyrrole tricarbonitrile, N-methyl-2,3,5-pyrrole tricarbonitrile, 1,3,5-triazine-2,4,6-tricarbonitrile, 1,2,4- Examples include triazine-3,5,6-tricarbonitrile.

  Among these, 2-cyanopyridine (2-pyridinecarbonitrile), 3-cyanopyridine (3-pyridinecarbonitrile), and 4-cyanopyridine (4-pyridinecarbonitrile) are preferable.

Further, as the modifier, a compound having a site P ₁ reactive to the active polymer and a site P ₂ reactive to the filler (provided that the site P ₁ and the site P ₂ are Which may be the same or different and does not contain active protons in the modification reaction) or precursors of the compounds. Here, the site P ₁ can be reactive with the chain end of the active polymer. Specific examples include dichloronaphthoquinone and the like. In addition, the said compound or the precursor of this compound can be directly reacted with the polymer which has an active terminal, or can be introduce | transduced into a polymer using the two-stage modification | denaturation method mentioned later.

  In order to modify the active polymer with a modifier, for example, a two-stage modification method may be used. The secondary modification method is (1) a step of reacting a primary modifier with an active polymer to obtain a primary modified polymer (primary modification reaction), and (2) a reaction of a secondary modifier with the primary modified polymer. And a step of obtaining a secondary modified polymer (secondary modification reaction). If this two-stage modification method is used, the primary amino acid has a very high affinity for fillers such as inorganic fillers and carbon black, and can effectively disperse the fillers even when the reaction efficiency is low. A group can be introduced into the modified conjugated diene polymer (A).

  The primary modifier is a compound having a functional group A that is reactive with an active polymer and at least one reactive functional group B. Here, the functional group A and the functional group B may be the same or different, and examples thereof include a ketene group, an isocyanate group, a thioisocyanate group, and a carbodiimide group. Specific examples include 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-dicyclohexyl. Methane diisocyanate, isopropylidenebis (4-cyclohexylisocyanate), xylylene diisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, 3,3′-dimethoxy-4,4′-biphenyl diisocyanate, 3,3 '-Dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, bis (2-isocyanatoethyl) fumarate, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane dithioisocyanate, 1,6- Hexamethylene dithioisocyanate Sulfonates can be preferably used. In addition, a primary modifier may be used individually by 1 type, and may be used in combination of 2 or more type.

  It is preferable that the usage-amount of a primary modifier is 0.02 mmol-20 mmol with respect to 100 g of monomers. This primary denaturation reaction is preferably performed by a solution reaction. This solution reaction may be, for example, a solution containing unreacted monomers used when polymerizing a conjugated diene polymer. Moreover, there is no restriction | limiting in particular about the form of primary denaturation reaction, You may carry out using a batch type reactor, and you may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor and an in-line mixer. In addition, it is important to carry out this primary modification reaction after the completion of the polymerization reaction and before performing various operations necessary for solvent removal, water treatment, heat treatment, polymer isolation, and the like. As the temperature of the primary modification reaction, the polymerization temperature of the conjugated diene polymer can be used as it is. Specifically, 0 ° C to 120 ° C is preferable, and 10 ° C to 100 ° C is more preferable. The time required for the primary denaturation reaction is preferably, for example, 5 minutes to 5 hours, and more preferably 15 minutes to 1 hour.

  In the primary modification reaction, the active polymer and the functional group A of the primary modifier are reacted to obtain a primary modified conjugated diene polymer. In the secondary modification reaction (step (2)) described later, In order to further react with the modifier, at least one of the functional groups B of the primary modifier must be left unreacted.

  The secondary modifier is a compound having a functional group C that is reactive with the reactive functional group B derived from the primary modifier and at least one primary amino group or protected primary amino group. It is. Here, examples of the functional group C include an amino group, an imino group, a mercapto group, and a hydroxyl group. The functional group C may be a primary amino group or a protected primary amino group. Specific examples include hexamethylenediamine, heptamethylenediamine, nonamethylenediamine, dodecamethylenediamine, decamethylenediamine, 1,5-naphthalenediamine, 1,8-naphthalenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethyldisilazane, N-chlorohexamethyldisilazane, N-bromohexamethyldisilazane, 1 -(3-Bromopropyl) -2,2,5,5-tetramethyl-1-aza-2,5-diciacyclopentane, 1- (3-chloropropyl) -2,2,5,5-tetra Preferable examples include methyl-1-aza-2,5-diciacyclopentane. In addition, a secondary modifier may be used individually by 1 type, and may be used in combination of 2 or more type.

  This secondary denaturation reaction can be carried out continuously with the above-mentioned primary denaturation reaction, and is preferably carried out by a solution reaction in the same manner as the primary denaturation reaction. This solution reaction may be, for example, a solution containing unreacted monomers used when polymerizing a conjugated diene polymer. Also, the type of secondary denaturation reaction is not particularly limited, and may be performed using a batch type reactor as in the case of the primary denaturation reaction, or a continuous type using an apparatus such as a multistage continuous reactor or an inline mixer. You may go on. Further, it is important to carry out this secondary modification reaction after completion of the polymerization reaction and before performing various operations necessary for solvent removal treatment, water treatment, heat treatment, polymer isolation, and the like. It is preferable that the usage-amount of a secondary modifier is 0.02 mmol-20 mmol with respect to 100 g of monomers. As the temperature of the secondary denaturation reaction, the temperature of the primary denaturation reaction can be used as it is. Specifically, 0 ° C to 120 ° C is preferable, and 10 ° C to 100 ° C is more preferable. The time required for the secondary denaturation reaction is preferably, for example, 5 minutes to 5 hours, and more preferably 15 minutes to 1 hour.

Next, the catalyst system used for the polymerization of the active polymer in the present invention will be described. Specifically, for example, component (i): a lanthanum series rare earth element-containing compound having an atomic number of 57 to 71 in the periodic table, or a reaction product of the lanthanum series rare earth element-containing material and a Lewis base, (ii) component: AlR ²⁶ R ²⁷ R ²⁸ [wherein R ²⁶ and R ²⁷ may be the same or different, but are a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, and R ²⁸ is a hydrocarbon having 1 to 10 carbon atoms. And R ²⁸ may be the same as or different from R ²⁶ or R ²⁷ ], and (iii) component: Lewis acid, complex compound of metal halide and Lewis base, and An active polymer, preferably a terminal active polymer is obtained by polymerizing a conjugated diene compound with a catalyst system comprising at least one organic compound containing an active halogen. In the present invention, the catalyst system preferably contains at least the lanthanum series rare earth element-containing compound. Furthermore, in addition to the components (i) to (iii), it is preferable to add an organoaluminum oxy compound, so-called aluminoxane, as the component (iv).

  Here, as the conjugated diene compound as a monomer, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3- Examples include hexadiene, myrcene, styrene, p-methylstyrene, m-methylstyrene, p-tert-butylstyrene, α-methylstyrene, chloromethylstyrene, vinyltoluene and the like.

  In the component (i), neodymium, praseodymium, cerium, lanthanum, gadolinium or a mixture thereof is preferable among the rare earth elements having atomic numbers 57 to 71 in the periodic table, and neodymium is particularly preferable. The lanthanum series rare earth element-containing compound is preferably a salt soluble in a hydrocarbon solvent. Specifically, the rare earth element carboxylate, alkoxide, β-diketone complex, phosphate and phosphorous acid. Among these, carboxylates and phosphates are preferable, and carboxylates are particularly preferable. Therefore, among the lanthanum series rare earth element-containing compounds, neodymium phosphate and neodymium carboxylate are preferable, and neodymium such as neodymium 2-ethylhexanoate, neodymium neodecanoate, neodymium versatate, etc. Branched carboxylates are more preferred.

  The component (i) may be a reaction product of the lanthanum series rare earth element-containing compound and a Lewis base. Here, examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, a monovalent or divalent alcohol, and the like.

  Specific examples of the component (ii) include triethylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutylaluminum hydride and the like.

  Specific examples of the Lewis acid as the component (iii) include diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide. It is done. The metal halide constituting the complex compound of the metal halide of component (iii) and Lewis base is preferably magnesium chloride, manganese chloride, zinc chloride, copper chloride or the like, and the Lewis base is triphosphate phosphate. -2-Ethylhexyl, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred. Furthermore, preferred examples of the organic compound containing an active halogen as the component (iii) include benzyl chloride.

  Examples of the component (iv) include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, chloroaluminoxane and the like.

  In addition, the said (i)-(iv) component may be used individually by 1 type, and may be used in combination of 2 or more type. The amount or composition ratio of each component of the catalyst system used in the present invention is appropriately selected according to the purpose or necessity.

  In the rubber composition of the present invention, the amount of the low molecular weight conjugated diene compound polymer (B) is preferably 5 to 100 parts by mass, and 10 to 70 parts by mass with respect to 100 parts by mass of the rubber component. Is more preferable. When the blending amount of the low molecular weight conjugated diene compound polymer (B) is less than 5 parts by mass with respect to 100 parts by mass of the rubber component, the storage elastic modulus (G ′) may not be sufficiently increased. When it exceeds the mass part, the dispersibility of the filler may be lowered.

  The low molecular weight conjugated diene compound polymer (B) requires a weight average molecular weight (Mw) of 5,000 to 150,000, preferably 10,000 to 150,000, more preferably 30,000 to 100,000, More preferred is ~ 100,000. When the weight average molecular weight (Mw) is less than 5,000, the storage elastic modulus (G ′) cannot be sufficiently increased. On the other hand, when it exceeds 150,000, the workability of the rubber composition is lowered.

  The low molecular weight conjugated diene compound polymer (B) preferably has a cis-1,4 bond content of 80.0% or more, more preferably 85% or more. If the amount of cis-1,4 bonds is 80.0% or more, the effect of improving the low loss performance and crack growth resistance can be enhanced.

  The low molecular weight conjugated diene compound polymer (B) is obtained by polymerizing one or more kinds of conjugated diene compounds. Here, the polymerization method of the polymer (B) is not particularly limited, but in order to increase the cis-1,4 bond amount of the polymer (B) to 80% or more, the catalyst system described above is used. Preferred examples include coordination polymerization using. Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, and the like. .

  The rubber composition of the present invention preferably further contains 10 to 100 parts by mass of a filler with respect to 100 parts by mass of the rubber component. When the content of the filler is less than 10 parts by mass with respect to 100 parts by mass of the rubber component, the fracture characteristics of the rubber composition may be reduced. On the other hand, when the content exceeds 100 parts by mass, the low exothermic property of the rubber composition may be reduced. May get worse.

As the filler, carbon black and inorganic filler are preferable. The carbon black is not particularly limited, it is preferable that the nitrogen adsorption specific surface area is in the range of 20~180m ² / g, and still more preferably in the range of 20 to 100 m ² / g. Carbon black having a nitrogen adsorption specific surface area in the range of ²⁰ to 180 m ² / g has a large particle size and a very high effect of improving low heat generation. Specifically, the carbon black is preferably of the grade below HAF, and examples thereof include HAF, FF, FEF, GPF, SRF, and FT grades. From the viewpoint of fracture characteristics, HAF, FEF, A GPF grade is particularly preferred. On the other hand, examples of the inorganic filler include silica, talc, and aluminum hydroxide. In addition, these fillers may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  In the rubber composition of the present invention, for example, the rubber component containing the modified conjugated diene polymer (A) is usually used in the rubber industry in addition to the low molecular weight conjugated diene compound polymer (B) and the filler. A compounding agent such as a softening agent, a silane coupling agent, stearic acid, an anti-aging agent, zinc white, a vulcanization accelerator, a vulcanizing agent, and the like can be appropriately blended depending on the purpose. As these compounding agents, commercially available products can be suitably used. In addition, the rubber composition is blended with a rubber component containing the modified conjugated diene polymer (A), together with various low-molecular-weight conjugated diene compound polymers (B) and various compounding agents appropriately selected as necessary, It can be produced by kneading, heating, extruding or the like.

  The tire of the present invention is characterized by using the above rubber composition in the tread portion, and is excellent in handling stability, low rolling resistance and fracture characteristics (crack growth resistance). The tire of the present invention is not particularly limited except that the above rubber composition is used, and can be manufactured according to a conventional method. Moreover, as gas with which this tire is filled, inert gas, such as nitrogen, argon, helium other than normal or the air which adjusted oxygen partial pressure, can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Production Example of Unmodified BR (Polymer A-1)>
A nitrogen-substituted 5 L autoclave was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene under a nitrogen atmosphere. To the autoclave, a cyclohexane solution of neodymium versatate (0.09 mmol) as a catalyst component, a toluene solution of methylalumoxane (hereinafter also referred to as “MAO”) (3.6 mmol), diisobutylaluminum hydride (hereinafter also referred to as “DIBAH”) (5.5 mmol) and diethylaluminum chloride (0.18 mmol) in toluene and 1,3-butadiene (4.5 mmol) were reacted and aged at 40 ° C. for 30 minutes, and the pre-prepared catalyst composition was charged at 60 ° C. Polymerization was performed for 60 minutes. The reaction conversion of 1,3-butadiene was almost 100%. 200 g of this polymer solution was extracted into a methanol solution containing 0.2 g of 2,4-di-tert-butyl-p-cresol, the polymerization was stopped, the solvent was removed by steam stripping, and the product was dried on a roll at 110 ° C. Thus, a polymer A-1 (conjugated diene polymer) before modification was obtained. The polymer A-1 thus obtained was measured by the following method. As a result, the number average molecular weight (Mn) was 230 × 10 ³ , the weight average molecular weight (Mw) was 440 × 10 ³ , and the molecular weight The distribution (Mw / Mn) was 1.9, the cis-1,4 bond content (Cis) was 98.5%, and the vinyl bond content (Vi) was 0.75%.

(1) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
Using gel permeation chromatography (trade name “HLC-8220GPC”, manufactured by Tosoh Corporation), a differential refractometer was used as a detector, and measurement was performed under the following conditions to calculate as a standard polystyrene equivalent value.
Column: Trade name “GMHXL” (manufactured by Tosoh Corporation) 2 Column temperature: 40 ° C.
Mobile phase: Tetrahydrofuran Flow rate: 1.0 ml / min
Sample concentration: 10mg / 20ml

［式中、ａは、フーリエ変換赤外分光法（ＦＴ−ＩＲ）による透過率スペクトルの1130cm^-1付近の山ピーク値であり、ｂは、967cm^-1付近の谷ピーク値であり、ｃは、911cm^-1付近の谷ピーク値であり、ｄは、736cm^-1付近の谷ピーク値である］から導かれるｅ、ｆ、ｇの値を用い、下記式(I')及び式(II')：
(シス-１,４結合量)＝ｅ／(ｅ＋ｆ＋ｇ)×100 ・・・ (I')
(ビニル結合量)＝ｇ／(ｅ＋ｆ＋ｇ)×100 ・・・ (II')
に従ってシス-１,４結合量及びビニル結合量を求めた。 (2) Microstructure [cis-1,4 bond amount (Cis) (%) and 1,2-vinyl bond amount (Vi) (%)]
Using the carbon disulfide of the same cell as a blank, the transmittance spectrum by FT-IR of a carbon disulfide solution of polybutadiene prepared to a concentration of 5 mg / mL was measured, and the following determinant:

[Wherein, a is a peak peak value near 1130 cm ⁻¹ of the transmittance spectrum by Fourier transform infrared spectroscopy (FT-IR), b is a valley peak value near 967 cm ⁻¹ , and c is a valley peak value around 911 cm ^-1, d uses the values of e, f, g derived from a valley peak value around 736cm ^-1], the following formula (I ') and formula (II' ):
(Cis-1,4 bond amount) = e / (e + f + g) × 100 (I ′)
(Amount of vinyl bond) = g / (e + f + g) × 100 (II ′)
The amount of cis-1,4 bonds and the amount of vinyl bonds were determined according to

<Production Example of Unmodified BR (Polymer A-2)>
Under a nitrogen atmosphere, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene and 0.0285 mmol of 2,2-ditetrahydrofurylpropane were injected as a cyclohexane solution into a nitrogen-substituted 5 L autoclave, and n-butyllithium (BuLi) 2.85 was injected into the autoclave. After the addition of mmol, polymerization was carried out for 4.5 hours in a 50 ° C. warm water bath equipped with a stirrer. The reaction conversion of 1,3-butadiene was almost 100%. Thereafter, 1.3 g of 2,6-di-t-butyl-p-cresol (BHT) is added to the polymerization reaction system to stop the polymerization reaction, and the solvent is removed by steam stripping, followed by drying with a roll at 110 ° C. Thus, a polymer A-2 was obtained. The polymer A-2 thus obtained was measured by the above method. The number average molecular weight (Mn) was 230 × 10 ³ , the weight average molecular weight (Mw) was 250 × 10 ³ , and the molecular weight The distribution (Mw / Mn) was 1.1, the cis-1,4 bond amount (Cis) was 30%, and the vinyl bond amount (Vi) was 20%.

<Production Example of Modified BR (Polymer A-3)>
After polymerizing in the same manner as in the production example of the polymer A-1, the polymer solution was further kept at a temperature of 60 ° C., and polymethylene polyphenyl polyisocyanate (trade name “PAPI * 135”, manufactured by Dow Chemical Japan Ltd.). ) (Hereinafter also referred to as “cMDI”) (4.16 mmol in terms of isocyanate group (NCO)) was added and allowed to react for 15 minutes (primary modification reaction). Subsequently, a toluene solution of hexamethylenediamine (hereinafter also referred to as “HMDA”) (2.08 mmol) was added and reacted for 15 minutes (secondary modification reaction). Thereafter, it was taken out in a methanol solution containing 1.3 g of 2,4-di-tert-butyl-p-cresol, and the polymerization was stopped. Then, the solvent was removed by steam stripping, and the polymer A was dried by a roll at 110 ° C. -3 (modified conjugated diene polymer) was obtained. The polymer A-3 thus obtained was measured by the above method. The number average molecular weight (Mn) was 230 × 10 ³ , the weight average molecular weight (Mw) was 470 × 10 ³ , and the molecular weight The distribution (Mw / Mn) was 2.1, the cis-1,4 bond content (Cis) was 98.5%, the vinyl bond content (Vi) was 0.72%, and the modification rate was 18%.

<Example of production of modified BR (polymer A-4)>
A solution before polymerization after polymerizing in the same manner as in Production Example of Polymer A-1 and a solution before performing solvent removal after performing polymerization in the same manner as in Production Example of Polymer A-3 Are mixed at a weight ratio of 1.0: 1.0, desolvated by steam stripping, dried on a roll at 110 ° C., and polymer A-4 (ie, polymers A-1 and A-3). Obtained). The polymer A-4 thus obtained was measured by the above method and the modification rate was 10%.

<Production Example of Modified BR (Polymer A-5)>
Polymerization was carried out in the same manner as in the production example of the polymer A-1, and then the polymer solution was kept at a temperature of 60 ° C., and trimethylolpropane tris [(3- (1-aziridinyl)) propionate] (2.08 mmol) Toluene solution was added and allowed to react for 15 minutes. Thereafter, it was taken out in a methanol solution containing 1.3 g of 2,4-di-tert-butyl-p-cresol, and the polymerization was stopped. Then, the solvent was removed by steam stripping, and the polymer A was dried by a roll at 110 ° C. I got -5. The thus obtained polymer A-5 was measured by the above method. As a result, the number average molecular weight (Mn) was 230 × 10 ³ , the weight average molecular weight (Mw) was 490 × 10 ³ , and the molecular weight The distribution (Mw / Mn) was 2.2, the cis-1,4 bond content (Cis) was 98.5%, the vinyl bond content (Vi) was 0.73%, and the modification rate was 18%.

<Production Example of Modified BR (Polymer A-6)>
A polymer A-6 was obtained in the same manner as the polymer A-5 except that the modifier was changed to 1-butylaziridine (Azl). The polymer A-6 thus obtained was measured by the above method. As a result, the number average molecular weight (Mn) was 230 × 10 ³ , the weight average molecular weight (Mw) was 440 × 10 ³ , and the molecular weight The distribution (Mw / Mn) was 1.9, the cis-1,4 bond amount (Cis) was 98.5%, the vinyl bond amount (Vi) was 0.76%, and the modification rate was 18%.

<Example of production of modified BR (polymer A-7)>
A polymer A-7 was obtained in the same manner as the polymer A-5 except that the modifier was changed to dichloronaphthoquinone (DCNQ). The thus obtained polymer A-7 was measured by the above method. As a result, the number average molecular weight (Mn) was 230 × 10 ³ , the weight average molecular weight (Mw) was 450 × 10 ³ , and the molecular weight The distribution (Mw / Mn) was 1.9, the cis-1,4 bond amount (Cis) was 98.5%, the vinyl bond amount (Vi) was 0.74%, and the modification rate was 18%.

<Production Example of Modified BR (Polymer A-8)>
A polymer A-8 was obtained in the same manner as the polymer A-5 except that the modifier was changed to dioctyltin bisoctimarate (DOTBOM). The thus obtained polymer A-8 was measured by the above method. As a result, the number average molecular weight (Mn) was 230 × 10 ³ , the weight average molecular weight (Mw) was 470 × 10 ³ , and the molecular weight The distribution (Mw / Mn) was 2.1, the cis-1,4 bond content (Cis) was 98.5%, the vinyl bond content (Vi) was 0.75%, and the modification rate was 18%.

<Production Example of Low Molecular Weight BR (Polymer B-1)>
The amount of catalyst composition used so that the content of neodymium versatic acid as a catalyst component is 0.20 mmol, the content of MAO is 10.3 mmol, the content of DIBAH is 13.3 mmol, and the content of diethylaluminum chloride is 0.35 mmol. A polymer B-1 was obtained in the same manner as the polymer A-1, except that the above was changed. The results are shown in Tables 1-2.

<Production Example of Low Molecular Weight BR (Polymers B-2 to B-7)>
Polymers B-2 to B-7 were obtained in the same manner as the polymer B-1, except that the amounts of 1,3-butadiene and catalyst components were appropriately adjusted. The results are shown in Tables 1-2.

<Production Example of Low Molecular Weight BR (Polymers B-8 to B-9)>
A 800 mL pressure-resistant glass container that has been dried and purged with nitrogen is poured into a cyclohexane solution of butadiene (16%) to a concentration of 50 g of butadiene monomer, and 2,2-ditetrahydrofurylpropane (the amount used is polymer B). -8 is 0.40 mmol and polymer B-9 is 0.66 mmol), and 1.32 mmol of n-butyllithium (BuLi) is added thereto, followed by polymerization in a hot water bath at 50 ° C. for 1.5 hours. It was. The reaction conversion rate of the monomer was almost 100%. Thereafter, 0.5 mL of an isopropanol solution (BHT concentration: 5% by mass) of 2,6-di-t-butyl-p-cresol (BHT) was added to the polymerization reaction system to stop the polymerization reaction, and further according to a conventional method. It dried and obtained polymer B-8-B-9. The results are shown in Tables 1-2.

<Production Example of Low Molecular Weight SBR (Polymer B-10)>
Pour butadiene in cyclohexane solution (16%) and styrene in cyclohexane solution (21%) into an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, so as to be 40 g of butadiene monomer and 10 g of styrene monomer. 0.66 mmol of 2,2-ditetrahydrofurylpropane was injected, and 1.32 mmol of n-butyllithium (BuLi) was added thereto, followed by polymerization in a hot water bath at 50 ° C. for 1.5 hours. The reaction conversion rate of the monomer was almost 100%. Thereafter, 0.5 mL of an isopropanol solution (BHT concentration: 5% by mass) of 2,6-di-t-butyl-p-cresol (BHT) was added to the polymerization reaction system to stop the polymerization reaction, and further according to a conventional method. It dried and obtained polymer B-10. The results are shown in Tables 1-2.

  Next, a rubber composition having the formulation shown in Table 3 was prepared, and the vulcanized rubber obtained by vulcanization at 160 ° C. for 15 minutes was subjected to the following methods for crack growth resistance, storage elastic modulus and low loss performance. It was measured by. The results are shown in Tables 1-2.

(3) Crack growth resistance A 0.5 mm crack was formed at the center of a JIS No. 3 test piece, repeatedly fatigued at 50 to 100% strain at room temperature, and the number of times until the sample was cut was measured. The value at each strain was determined and the average value was used. Comparative example 1 was set to 100 and indicated as an index. A larger index value indicates better crack growth resistance.

(4) Storage elastic modulus (G ')
The storage elastic modulus (G ′) is measured at a temperature of 50 ° C., a frequency of 15 Hz, and a strain of 3% using a rheometrics viscoelasticity measuring device, and the storage elastic modulus (G ′) of Comparative Example 1 is taken as 100. displayed. A larger index value indicates a higher storage elastic modulus.

(5) Low loss performance A dynamic spectrometer (manufactured by Rheometrics, USA) was used, and measurement was performed under the conditions of tensile dynamic strain 3%, frequency 15 Hz, and 50 ° C. Comparative example 1 was set to 100 and indicated as an index. The smaller the index value, the better the low loss performance.

* 1 Polymers A-1 to A-8 and types of polymer A used are shown in Tables 1-2.
* 2 Polymers B-1 to B-10 and types of polymer B used are shown in Tables 1-2.
* 3 Tokai Carbon Co., Ltd., Seast SO (FEF), nitrogen adsorption specific surface area = 42 m ² / g.
* 4 Fukko AROMA # 3 manufactured by Fuji Kosan Co., Ltd.
* 5 “NOCRACK 224” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 6 Di-2-benzothiazolyl disulfide.
* 7 N-cyclohexyl-2-benzothiazolylsulfenamide.

From the results of Tables 1 and 2, the rubber compositions of Examples and Reference Examples are highly balanced in terms of crack growth resistance, storage elastic modulus, and low loss performance as compared with the rubber compositions of Comparative Examples. I understand. Moreover, if the weight average molecular weight (Mw) of the low molecular weight conjugated diene compound polymer (B) is in the range of 5,000 to 150,000 from the comparison of Example 7 and Comparative Examples 5 and 6, the low loss performance. It can be seen that the crack growth resistance and the storage elastic modulus can be improved while improving. Further, from the results of Examples and Comparative Example 7, when styrene is used as a monomer in the preparation of the polymer B, the low loss performance is greatly reduced, and the compatibility between the polymer A and the polymer B is remarkably high. It is clear that it is getting worse.

Claims (23)

At least one functional group having a cis-1,4 bond content of 80.0% or more and a number average molecular weight (Mn) of 200,000 or more and 1,000,000 or less obtained by modifying an active polymer with a modifier. Low molecular weight having a cis-1,4 bond amount of 80.0% or more and a weight average molecular weight (Mw) of 5,000 to 150,000 with respect to the rubber component containing the modified conjugated diene polymer (A) having A rubber composition comprising a conjugated diene compound polymer (B).   The rubber composition according to claim 1, wherein the modified conjugated diene polymer (A) has a modification rate of 10% or more.   2. The rubber composition according to claim 1, wherein the amount of the low molecular weight conjugated diene compound polymer (B) is 5 to 100 parts by mass with respect to 100 parts by mass of the rubber component.   The rubber composition according to claim 1, wherein the rubber component contains 10% by mass or more of the modified conjugated diene polymer (A). The rubber component further includes at least one of natural rubber and synthetic diene rubber,
2. The rubber composition according to claim 1, wherein the modified conjugated diene polymer (A) is compatible with at least one of natural rubber and synthetic diene rubber contained in the rubber component.   The rubber composition according to claim 1, further comprising 10 to 100 parts by mass of a filler with respect to 100 parts by mass of the rubber component.   The rubber composition according to claim 6, wherein the filler is an inorganic filler and / or carbon black.   The rubber composition according to claim 1, wherein the functional group is a functional group containing at least one atom selected from the group consisting of a nitrogen atom, a tin atom, a silicon atom, a sulfur atom, and an oxygen atom. object. A compound in which the modifier has a site P ₁ that is reactive with the active polymer and a site P ₂ that is reactive with a filler (provided that the site P ₁ and the site P ₂ are the same) However, it may be different and does not contain active protons in the modification reaction) or a precursor of the compound. The rubber composition according to claim 9, wherein the site P ₁ is reactive with a chain end of the active polymer. The denaturant is represented by the general formula (I):

[Wherein, X ^{1 to} X ⁵ are a hydrogen atom, a halogen atom, a carbonyl group, a thiocarbonyl group, an isocyanate group, a thioisocyanate group, an epoxy group, a thioepoxy group, a halogenated silyl group, a hydrocarbyloxysilyl group, and a sulfonyloxy group. A functional group containing at least one selected from the group, and X ^{1 to} X ⁵ may be the same or different from each other, but at least one of them is not a hydrogen atom. R ^{1 to} R ⁵ each independently represent a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms. It ^may also be coupled a plurality of aziridine rings through any of X 1 to X ⁵ and ^R 1 to R ^5. The rubber composition according to claim 1, wherein the rubber composition is at least one selected from compounds represented by formula (component (a)). The rubber composition according to claim 11, wherein the component (a) does not simultaneously satisfy X ¹ = hydrogen atom and R ¹ = single bond in the general formula (I). The rubber composition according to claim 1, wherein the modifier is at least one selected from compounds of the following components (b) to (h).
Component _{^{(b): R 6 n M'Z 4-n}} , M'Z 4, M'Z 3, R 7 n M '(- R 8 -COOR 9) 4-n or ^R _{7 n} M' (- ^{R 8-} COR ⁹ ) _4-n [wherein R ^{6 to} R ⁸ may be the same or different, but are hydrocarbon groups containing a carbon atom having 1 to 20 carbon atoms, and R ⁹ has 1 carbon atom. Is a hydrocarbon group containing 20 carbon atoms, and R ^{6 to} R ⁹ may contain a carbonyl group or an ester group in the side chain, and M ′ is a tin atom, a silicon atom, a germanium atom or a phosphorus atom. , Z is a halogen atom, and n is an integer of 0 to 3.] A halogenated organometallic compound, a halogenated metal compound or an organometallic compound (c) component: Y = C = Y ′ bond in the molecule [Wherein Y is a carbon atom, oxygen atom, nitrogen atom or sulfur atom, and Y ′ is an oxygen atom, nitrogen atom or Heterocumulene compound containing a sulfur atom] (d) component: formula (II):

[Wherein, Y ′ is an oxygen atom, a nitrogen atom or a sulfur atom] The hetero 3-membered ring compound (e) component containing a bond represented by the molecule: component: halogenated isocyano compound (f) component: R ^{_{10 - (COOH) m, R}} 11 (COZ) m, R 12 - (COO-R 13), R 14 -OCOO-R 15, R 16 - (COOCO-R 17) m, or general formula (III):

[Wherein, R ^{10 to} R ¹⁸ may be the same or different, but a hydrocarbon group containing a carbon atom having 1 to 50 carbon atoms, Z is a halogen atom, and m is an integer of 1 to 5] Carboxylic acid, acid halide, ester compound, carbonate compound or acid anhydride (g) component corresponding to: R ¹⁹ _k M ″ (OCOR ²⁰ ) _4-k , R ²¹ _k M ″ (OCO-R ²² -COOR ²³⁾ _4-k, or general formula (IV):

[Wherein, R ^{19 to} R ²⁵ may be the same or different, but a hydrocarbon group containing a carbon atom having 1 to 20 carbon atoms, M ″ is a tin atom, a silicon atom or a germanium atom, and k is Carboxylic acid metal salt (h) component corresponding to an integer of 0 to 3, p is 0 or 1]: N-substituted aminoketone, N-substituted aminothioketone, N-substituted aminoaldehyde, N-substituted amino Thioaldehyde or a compound having —C (═Y ″) — N <bond [Y ″ is an oxygen atom or a sulfur atom] in the molecule. The rubber composition according to claim 1, wherein the modifier is a heterocyclic nitrile compound represented by the following formula (V) or formula (VI).
θ-C≡N (V)
θ-R ²⁹ -C≡N (VI)
[In the formulas (V) and (VI), θ represents a heterocyclic group, and R ²⁹ represents a divalent hydrocarbon group. ] The active polymer comprises (i) component: a lanthanum series rare earth element-containing compound having atomic numbers 57 to 71 in the periodic table, or a reaction product of the lanthanum series rare earth element-containing material and a Lewis base, and (ii) component: AlR. ²⁶ R ²⁷ R ²⁸ [wherein R ²⁶ and R ²⁷ may be the same or different, but a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ²⁸ is a hydrocarbon group having 1 to 10 carbon atoms. Wherein R ²⁸ may be the same as or different from R ²⁶ or R ²⁷ ], and (iii) component: complex compound and activity of Lewis acid, metal halide and Lewis base The rubber composition according to claim 1, wherein the conjugated diene compound is polymerized by a catalyst system composed of at least one of halogen-containing organic compounds.   The rubber composition according to claim 15, wherein the active polymer is a terminal active polymer obtained by a catalyst system containing the lanthanum series rare earth element-containing compound.   16. The rubber composition according to claim 15, wherein the lanthanum series rare earth element-containing compound in the component (i) is a salt soluble in a neodymium hydrocarbon solvent.   18. The rubber composition according to claim 17, wherein the lanthanum rare earth element-containing compound in the component (i) is a neodymium branched carboxylate or a reaction product of the salt and a Lewis base.   The rubber composition according to claim 1, wherein the modified conjugated diene polymer (A) has a molecular weight distribution (Mw / Mn) of 1.6 to 3.5.   The rubber composition according to claim 1, wherein the modified conjugated diene polymer (A) has a number average molecular weight (Mn) of 200,000 to 500,000.   21. The rubber composition according to claim 20, wherein the modified conjugated diene polymer (A) has a number average molecular weight (Mn) of 200,000 to 400,000.   The rubber composition according to claim 1, wherein the low molecular weight conjugated diene compound polymer (B) has a weight average molecular weight (Mw) of 10,000 to 150,000.   A tire using the rubber composition according to any one of claims 1 to 22.

Images