JP2016030762A - Rubber composition and method for producing thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition which is improved in low loss property and provide a method for producing thereof.SOLUTION: There is provided a modified diene-based polymer which is obtained by reacting a compound represented by the formula (I), a quinolinethiol or quinolinethione derivative with a diene-based polymer. (Rrepresents H or a substituent containing H; Rand Reach independently represents N or C and at least one of which represents N; Rto Reach independently represents H or a substituent containing H and arbitrary two adjacent may be bonded and formed; and when Rand/or Rare N, Rand/or Rmay not be present.)SELECTED DRAWING: None

Description

  The present invention relates to a rubber composition containing a modified diene polymer and a method for producing the same.

In recent years, there is an increasing demand for lower fuel consumption of automobiles, and tires with low rolling resistance are required. In order to reduce the rolling resistance of the tire, a method using a rubber composition excellent in low heat build-up is common. Therefore, as a rubber composition used for a tire tread or the like, a rubber composition having a low tan δ (hereinafter, referred to as a low loss property) and an excellent low heat generation property is required.
Conventionally, by using a rubber composition containing a specific modified diene polymer, silica and a specific liquid resin, a tire with improved fuel economy, wet grip performance, and wear resistance can be obtained. Known (for example, Patent Document 1). However, there is still room for improvement in tire rolling resistance.

JP 2013-87181 A

  An object of this invention is to provide the rubber composition which improved the low loss property, and its manufacturing method.

［一般式（Ｉ）及び（ＩＩ）中、
Ｒ¹は、水素原子又は水素原子を含む任意の置換基を表し、Ｒ²及びＲ³は、それぞれ独立に窒素原子又は炭素原子を表し、少なくともいずれか一方が窒素原子であり、Ｒ⁴〜Ｒ⁸は、それぞれ独立に水素原子又は水素原子を含む任意の置換基を表し、Ｒ⁴〜Ｒ⁸のうちの隣接する任意の２つからなる少なくとも１つの組み合わせにおいて、前記任意の２つが互いに連結して芳香環を形成し、Ｒ²及び／又はＲ³が窒素原子のときは、Ｒ⁴及び／又はＲ⁸は存在しなくてもよい。］
本発明のゴム組成物によれば、ゴム組成物の低ロス性を改善することができる。 The rubber composition of the present invention comprises a modified diene polymer obtained by reacting a compound represented by the following general formula (I) or (II) with a diene polymer.

[In the general formulas (I) and (II),
R ¹ represents a hydrogen atom or an arbitrary substituent containing a hydrogen atom, R ² and R ³ each independently represent a nitrogen atom or a carbon atom, at least one of which is a nitrogen atom, R ^{4 to} R ⁸ each independently represents a hydrogen atom or an arbitrary substituent containing a hydrogen atom, and in at least one combination of adjacent two of R ^{4 to} R ⁸ , the arbitrary two are connected to each other. When R ² and / or R ³ are nitrogen atoms, R ⁴ and / or R ⁸ may not be present. ]
According to the rubber composition of the present invention, the low loss property of the rubber composition can be improved.

In the rubber composition of the present invention, it is preferable that only one of R ² and R ^{3 in} the general formula (I) or (II) is a nitrogen atom. According to this structure, the low loss property of a rubber composition can be improved more.

  In the rubber composition of the present invention, the aromatic ring is preferably an aromatic 6-membered ring. According to this structure, the low loss property of a rubber composition can be improved more.

  In the rubber composition of the present invention, the compound represented by the general formula (I) or (II) is preferably quinoline thiol, isoquinoline thiol, quinoline thione, isoquinoline thione, or a derivative thereof. According to this structure, the low loss property of a rubber composition can be improved more.

  In the rubber composition of the present invention, the compound represented by the general formula (I) or (II) is 2-quinolinethiol, 1-isoquinolinethiol, quinoline-2-thione, isoquinoline-1-thione, or these A derivative is preferred. According to this configuration, the low loss property of the rubber composition can be further improved.

  In the rubber composition of the present invention, the modified diene polymer is preferably formed by bonding the S atom in the general formula (I) or (II) to the diene polymer. According to this structure, the low loss property of a rubber composition can be improved more.

  The rubber composition of the present invention preferably further contains a filler containing at least one of carbon black and silica. According to this structure, the low loss property of a rubber composition can be improved more.

  In the rubber composition of the present invention, the diene polymer is preferably natural rubber. According to this structure, the low loss property of a rubber composition can be improved more.

The rubber composition of the present invention is obtained by kneading the compound represented by the general formula (I) or (II) and the diene polymer.
According to the rubber composition of the present invention, a rubber composition having improved low loss properties can be obtained.

The method for producing a rubber composition of the present invention includes a step of kneading the compound represented by the general formula (I) or (II) and the diene polymer.
According to the method for producing a rubber composition of the present invention, a rubber composition having improved low loss properties can be obtained.

The method for producing a rubber composition of the present invention includes a step of kneading the compound represented by the general formula (I) or (II) and the diene polymer.
According to the method for producing a rubber composition of the present invention, a rubber composition having improved low loss properties can be obtained.

  The rubber composition of the present invention is preferably formed by compounding the compound represented by the general formula (I) or (II) during the kneading of the composition containing at least the diene polymer. According to this structure, the low loss property of a rubber composition can be improved more.

  In the rubber composition of the present invention, the compound represented by the general formula (I) or (II) is preferably blended in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the diene polymer. . According to this structure, the low loss property of a rubber composition can be improved more.

  ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which improved the low loss property and its manufacturing method can be provided.

  The form for implementing this invention is illustrated below.

(Rubber composition)
The rubber composition of the present invention includes at least a modified diene polymer, and further includes other components as necessary. According to the rubber composition of the present invention, the low loss property of the rubber composition can be improved.
There is no restriction | limiting in particular as content of the modified diene polymer in the said rubber composition, Although it can select suitably according to the objective, 10-100 mass% is preferable and 30-100 mass% is more preferable. When the content of the modified diene polymer is within the preferable range or the more preferable range, it is easy to ensure low loss of the rubber composition.

［一般式（Ｉ）及び（ＩＩ）中、Ｒ¹は、水素原子又は水素原子を含む任意の置換基を表し、Ｒ²及びＲ³は、それぞれ独立に窒素原子又は炭素原子を表し、少なくともいずれか一方が窒素原子であり、Ｒ⁴〜Ｒ⁸は、それぞれ独立に水素原子又は水素原子を含む任意の置換基を表し、Ｒ⁴〜Ｒ⁸のうちの隣接する任意の２つからなる少なくとも１つの組み合わせにおいて、前記任意の２つが互いに連結して芳香環を形成し、Ｒ²及び／又はＲ³が窒素原子のときは、Ｒ⁴及び／又はＲ⁸は存在しなくてもよい。］ <Modified diene polymer>
The modified diene polymer is obtained by reacting a compound represented by the following general formula (I) or (II) with a diene polymer. The method for producing the modified diene polymer is not particularly limited as long as at least the diene polymer and the compound represented by the general formula (I) or (II) are reacted, and is appropriately selected according to the purpose. For example, a diene polymer and a compound represented by the general formula (I) or (II) are charged into a reaction vessel and stirred at 50 to 120 ° C. for 10 minutes to 2 hours to obtain a reaction. Can do. If necessary, an organic peroxide or the like may be further blended and reacted.
It can also be produced by kneading the diene polymer and the compound represented by the general formula (I) or (II) at 50 to 150 ° C. for 1 to 10 minutes with a Banbury mixer.

[In General Formulas (I) and (II), R ¹ represents a hydrogen atom or an arbitrary substituent containing a hydrogen atom, R ² and R ³ each independently represent a nitrogen atom or a carbon atom, and One of them is a nitrogen atom, and R ^{4 to} R ⁸ each independently represent a hydrogen atom or an arbitrary substituent containing a hydrogen atom, and at least one of any two adjacent R ^{4 to} R ⁸ In one combination, when any two of the above are linked to each other to form an aromatic ring and R ² and / or R ³ are nitrogen atoms, R ⁴ and / or R ⁸ may not be present. ]

<< Diene polymer >>
The diene polymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, and chloroprene. Rubber, etc. These may be used individually by 1 type and may use 2 or more types together.
Among these, natural rubber and polyisoprene rubber are advantageous in that they have excellent breaking strength, and natural rubber is further advantageous in that it can further improve the low loss property of the rubber composition.
When the diene polymer is synthesized, the conjugated diene compound (diene monomer) is polymerized alone, or the conjugated diene compound is copolymerized with another monomer (for example, an aromatic vinyl compound). Can do.

-Conjugated diene compounds-
The conjugated diene compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. These may be used individually by 1 type and may use 2 or more types together.

-Aromatic vinyl compounds-
The aromatic vinyl compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexyl styrene, 2,4,6-trimethyl styrene, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

-Natural rubber (NR)-
The number average molecular weight of the natural rubber molecule is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 150,000 to 3,000,000, more preferably 250,000 to 2,000,000. .
When the number average molecular weight of the natural rubber molecule is within the preferable range or the more preferable range, it is advantageous in terms of a balance between low loss and compounding workability.
The number average molecular weight of the natural rubber molecule can be calculated, for example, by measuring a natural rubber molecule obtained by dissolving in tetrahydrofuran with gel permeation chromatography (GPC).

-Polyisoprene rubber-
The polyisoprene rubber preferably has a number average molecular weight of 300,000 or more and a cis bond content of 95% or more. Such polyisoprene rubber is advantageous in terms of a balance between low loss and compounding workability.
The number average molecular weight of the polyisoprene rubber molecule can be calculated, for example, by measuring polyisoprene rubber molecules obtained by dissolving in tetrahydrofuran with gel permeation chromatography (GPC).

<< Modification >>
The diene polymer is modified with a compound represented by the following general formula (I) or (II). In the modified diene polymer, the S atom in the following general formula (I) or (II) is preferably bonded to the diene polymer.

R ^{1 to} R ⁸ in the general formulas (I) and (II) will be described below.

-R ^1-
R ¹ is not particularly limited as long as it is a hydrogen atom or an arbitrary substituent containing a hydrogen atom, and can be appropriately selected depending on the purpose. Examples include a hydrogen atom; an amino group; an alicyclic hydrocarbon group, an aliphatic hydrocarbon group, a heterocyclic aromatic hydrocarbon group which may be unsubstituted or substituted; and the substitution may be, for example, , An alkyl group, an alkoxy group, and the like, and the position and number of the substitution are arbitrary.
The group represented by SR ¹ is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include thiol, disulfide, sulfenamide, and the like.

-R ² and R ^3-
R ² and R ³ each independently represent a nitrogen atom or a carbon atom, and as long as at least one of them is a nitrogen atom, there is no particular limitation and can be appropriately selected according to the purpose. Examples of the compound represented by I) or (II), only one of R ² and R ³ are compounds of nitrogen atom, both R ² and R ³ include compounds of nitrogen atoms.
Among these, a compound in which only one of R ² and R ³ is a nitrogen atom is advantageous in that the low loss property of the rubber composition can be further improved.

−R ^{4 to} R ⁸ −
R ^{4 to} R ⁸ each independently represent a hydrogen atom or an arbitrary substituent containing a hydrogen atom, and in the at least one combination of any two adjacent R ^{4 to} R ⁸ , Are linked to each other to form an aromatic ring, and when R ² and / or R ³ is a nitrogen atom, R ⁴ and / or R ⁸ are not particularly limited as long as they do not exist. It can be appropriately selected depending on the case. For example, at least one combination of R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ is linked to each other to form an aromatic ring. Compounds, and the like. The “arbitrary substituent containing a hydrogen atom” is the same as that described for R ¹ .

--Aromatic ring--
There is no restriction | limiting in particular as said aromatic ring, According to the objective, it can select suitably, For example, aromatic 6-membered ring; Condensed aromatic rings, such as a naphthalene ring, a phenanthrene ring, an anthracene ring; Heterocycles containing one or more heteroatoms such as nitrogen, oxygen, sulfur; and the like.

--- Aromatic 6-membered ring ---
There is no restriction | limiting in particular as said aromatic 6-membered ring, According to the objective, it can select suitably, For example, the benzene ring etc. which are hydrocarbon rings are mentioned.
Among these, a benzene ring is preferable. In particular, when the compound represented by the general formula (I) or (II) is quinoline thiol, isoquinoline thiol, quinoline thione, isoquinoline thione, or a derivative thereof, the low loss property of the rubber composition is further improved. This is advantageous in that

The quinoline thiol means a thiol compound in which at least one hydrogen atom bonded to the carbon atom of quinoline is substituted with an —SH group (thiol group), and 2-quinoline thiol is preferably used.
The quinoline thiol derivative is not particularly limited as long as it is a derivative having the quinoline thiol skeleton, and can be appropriately selected according to the purpose. For example, a derivative of 2-quinoline thiol, 4-methyl-2- Examples include quinoline thiol, 3-methyl-2-quinoline thiol, and 3-hydroxy-2-quinoline thiol. These may be used individually by 1 type and may use 2 or more types together.
Among these, 2-quinolinethiol derivatives are advantageous in that the low loss property of the rubber composition can be further improved.

The 2-quinoline thiol is represented by the following formula (III).

［式中、Ｒ⁹は、水素原子又は水素原子を含む任意の置換基を表す。］ The 2-quinolinethiol derivative may be a compound represented by the following general formula (IV).

[Wherein R ⁹ represents a hydrogen atom or an arbitrary substituent containing a hydrogen atom. ]

  The quinoline thione means a compound in which at least one hydrogen atom bonded to the carbon atom of the quinoline is replaced by = S, and quinoline-2-thione and its derivatives are preferably used.

The quinoline-2-thione is represented by the following formula (V).

  2-Quinolinethiol and quinoline-2-thione are tautomers and coexist. For example, the thiol represented by the general formula (I) such as the 2-quinoline thiol and the tautomer of the thiol such as the quinoline-2-thione are both represented by the general formula (I). ) Or (II).

The isoquinoline thiol means a thiol compound in which at least one hydrogen atom bonded to a carbon atom of isoquinoline is substituted with an —SH group (thiol group), and 1-isoquinoline thiol is preferably used.
The isoquinoline thiol derivative is not particularly limited as long as it is a derivative having the above-described isoquinoline thiol skeleton, and can be appropriately selected according to the purpose. Etc. These may be used individually by 1 type and may use 2 or more types together.
Among these, 1-isoquinoline thiol derivatives are advantageous in that the low loss property of the rubber composition can be further improved.

The 1-isoquinoline thiol is represented by the following formula (VI).

［式中、Ｒ¹⁰は、水素原子又は水素原子を含む任意の置換基を表す。］ The derivative of the 1-isoquinoline thiol may be, for example, a compound represented by the following general formula (VII).

[Wherein, R ¹⁰ represents a hydrogen atom or an arbitrary substituent containing a hydrogen atom. ]

The isoquinoline thione means a thione in which at least one hydrogen atom bonded to a carbon atom of isoquinoline is replaced by = S, and isoquinoline-1-thione and its derivatives are preferably used.
1-isoquinoline thiol and isoquinoline-1-thione are tautomers and exist together. For example, the thiol represented by the general formula (I) such as the 1-isoquinoline thiol and the tautomer of the thiol such as the quinoline-2-thione are both represented by the general formula (I) of the present application. ) Or (II).

The compound represented by the general formula (I) or (II) is not particularly limited as long as it is represented by the general formula (I) or (II), and can be appropriately selected according to the purpose. The compound represented by the following formula (VIII) (compound 1), the compound represented by the following formula (IX) (compound 2), the compound represented by the following formula (X) (compound 3), the following formula (XI) And the like (compound 4). These may be used individually by 1 type and may use 2 or more types together.

The bond between the compound represented by the general formula (I) or (II) and the diene polymer is, for example, the S atom in the general formula (I) or (II) is bonded to the diene polymer. That is, it may be a covalent bond via an S atom or a covalent bond not via the S atom.
Among these, the covalent bond through the S atom in the general formula (I) or (II) is advantageous in that the low loss property of the rubber composition can be further improved.
In addition, the compound represented by the above general formula (I) or (II) may undergo an addition reaction with a carbon-carbon double bond of the main chain of the diene polymer molecule, or the diene polymer molecule. You may couple | bond with the terminal of.

<Other ingredients>
Other components contained in the rubber composition are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fillers, anti-aging agents, softeners, silane coupling agents, stearic acid, and zinc. For example, white, vulcanization accelerator, and vulcanizing agent. These may be used individually by 1 type and may use 2 or more types together.
Among these, blending a filler is particularly advantageous in that the low loss property of the rubber composition can be further improved.

<< Filler >>
There is no restriction | limiting in particular as a filler used for the rubber composition of this invention, According to the objective, it can select suitably, For example, carbon black, an inorganic filler, etc. are mentioned. Examples of the inorganic filler include silica and an inorganic compound represented by the following general formula (XII):
nM · xSiO _y · zH ₂ O (XII)
[Wherein M is a metal selected from the group consisting of aluminum, magnesium, titanium, calcium and zirconium, an oxide or hydroxide of these metals, and a hydrate thereof, or a carbonate of these metals. N, x, y and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10]
Etc. These may be used individually by 1 type and may use 2 or more types together.
Among these, carbon black and silica are advantageous in that the low loss property of the rubber composition can be further improved.

-Blending amount of filler-
There is no restriction | limiting in particular as a compounding quantity of a filler, Although it can select suitably according to the objective, The range of 5-100 mass parts is preferable with respect to 100 mass parts of said modified diene polymers, 10-70. The range of parts by mass is more preferable.
It is advantageous in that the reinforcing property of the rubber composition can be improved when the blending amount of the filler is within the preferable range and the more preferable range.

-Carbon black-
There is no restriction | limiting in particular as said carbon black, According to the objective, it can select suitably, For example, carbon black whose grade name is GPF, FEF, SRF, HAF, ISAF, SAF etc. is mentioned. These may be used individually by 1 type and may use 2 or more types together.

-Silica-
There is no restriction | limiting in particular as said silica, According to the objective, it can select suitably, For example, wet silica, dry silica, colloidal silica, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

<Method for producing rubber composition>
The rubber composition can be produced by kneading a diene polymer previously modified with the compound represented by the general formula (I) or (II) and other components.
The rubber composition can also be obtained by a production method including a step of kneading the compound represented by the general formula (I) or (II) and the diene polymer. For example, the rubber composition of this invention can be manufactured by mix | blending the compound represented with the said general formula (I) or (II) with the composition containing an unmodified diene type polymer. Moreover, it can also manufacture by mix | blending the compound represented by the said general formula (I) or (II) in the kneading | mixing of the composition containing a diene polymer at least. In such a case, the compounding amount of the compound represented by the general formula (I) or (II) with respect to 100 parts by mass of the diene polymer is not particularly limited and can be appropriately selected depending on the purpose. However, 0.01-5 mass parts is preferable. Within the above preferred range, it is advantageous in that the low loss property of the rubber composition can be further improved.

<< Kneading >>
The kneading means is not particularly limited and may be appropriately selected depending on the purpose. For example, kneading can be performed using a Banbury mixer, a roll, an intensive mixer, a kneader, biaxial extrusion, or the like. . These may be used individually by 1 type and may use 2 or more types together.

The said rubber composition can be used for tire manufacture, It is preferable to use the said rubber composition for the tread of a tire especially. A tire using the rubber composition of the present invention for a tread is particularly excellent in fuel efficiency.
The method for producing a tire using the rubber composition of the present invention is not particularly limited and can be appropriately changed.For example, the rubber composition is extruded in an extrusion process and molded as a tread member. A green tire can be formed by pasting and molding on a tire molding machine by a usual method. The green tire can be heated and pressurized in a vulcanizer to obtain a tire.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to the following Example at all, In the range which does not change the summary of this invention, an Example can be changed suitably.

  The compound represented by the general formula (I) or (II) was synthesized by the following method.

<Synthesis Example 1>
Synthesis of Compound 1 Represented by the following Formula (VIII) A 1000 mL 4-necked flask was charged with 24.1 g of isoquinoline-1-thione, 400 mL of 2-propanol, and 100 mL of water under a nitrogen atmosphere. Sodium hydroxide 13.6g was added there, and it stirred for 15 minutes at room temperature. Next, 74.0 g of cyclohexylamine was added, and the mixture was further stirred for 10 minutes. 320 mL of sodium hypochlorite aqueous solution (effective chlorine 5%) was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 2 hours. After the reaction, 2-propanol was distilled off with an evaporator and extraction was performed with ethyl acetate / water. After collecting and concentrating the organic layer, silica gel chromatography was performed with ethyl acetate / hexane = 1/5 to obtain 32.0 g of Compound 1.

<Synthesis Example 2>
Synthesis of Compound 2 Represented by Formula (IX) below Synthesis was performed in the same manner as in Synthesis Example 1 except that isoquinoline-1-thione was changed to 2-quinolinethiol in Synthesis Example 1.

<Synthesis Example 3>
Synthesis of Compound 3 Represented by Formula (X) below To a 1000 mL four-necked flask, 24.1 g of isoquinoline-1-thione and 500 mL of 2-propanol were added under a nitrogen atmosphere and stirred at room temperature for 15 minutes. Thereto, 320 mL of an aqueous sodium hypochlorite solution (effective chlorine 5%) was added dropwise over 1 hour, and the mixture was further stirred at room temperature for 2 hours. After the reaction, the deposited precipitate was collected by filtration to obtain 46.3 g of Compound 3.

<Synthesis Example 4>
Synthesis of Compound 4 Represented by Formula (XI) below Synthesis was performed in the same manner as in Synthesis Example 3 except that isoquinoline-1-thione was changed to 2-quinolinethiol in Synthesis Example 3.

<Synthesis Example 5>
Synthesis of compound 5 represented by the following formula (XIII) (an example of a compound not included in the compound represented by the above general formula (I) or (II)) In the above synthesis example 1, isoquinoline-1-thione was changed to 8 -Synthesis was performed in the same manner as in Synthesis Example 1 except that mercaptoquinoline was used.

<Synthesis Example 6>
Synthesis of Compound 6 Represented by Formula (XIV) below (Example of Compound Not Included in Compound Represented by General Formula (I) or (II)) In Synthesis Example 1 above, isoquinoline-1-thione is converted to 2 -Synthesis was performed in the same manner as in Synthesis Example 1 except that it was changed to mercaptopyridine.

<Synthesis Example 7>
Synthesis of Compound 7 Represented by Formula (XV) below (Example of Compound Not Included in Compound Represented by General Formula (I) or (II)) In Synthesis Example 3 above, isoquinoline-1-thione was changed to 8 -Synthesis was performed in the same manner as in Synthesis Example 3 except that mercaptoquinoline was used.

<Synthesis Example 8>
Synthesis of Compound 8 Represented by Formula (XVI) below (Example of Compound Not Included in Compound Represented by General Formula (I) or (II)) In Synthesis Example 3 above, isoquinoline-1-thione is converted to 2 Synthesis was performed in the same manner as in Synthesis Example 3, except that the amount was changed to -mercaptopyridine.

  Modified diene polymers 1 to 4 were prepared by the following method.

<Preparation of Modified Diene Polymer 1>
JSR polyisoprene rubber (IR2200) 50.0 g was dissolved in 2 L of toluene, and 2-quinolinethiol 1.0 g and azobisisobutyronitrile 1.0 g were added and reacted at 80 ° C. for 2 hours. After the reaction, 2 L of methanol was added to precipitate the polymer, and the remaining polymer was dried to obtain 48.8 g of a modified diene polymer 1.

<Preparation of Modified Diene Polymer 2>
In the preparation of the modified diene polymer 1, a modified diene heavy polymer was prepared in the same manner as in the preparation of the modified diene polymer 1 except that isoquinoline-1-thione was used instead of 2-quinolinethiol. Combined 2 was obtained.

<Preparation of Modified Diene Polymer 3>
The modified diene polymer 1 was prepared in the same manner as the modified diene polymer 1 except that 8-mercaptoquinoline was used instead of 2-quinolinethiol in the preparation of the modified diene polymer 1. 3 was obtained.

<Preparation of Modified Diene Polymer 4>
The modified diene polymer 1 was prepared in the same manner as the modified diene polymer 1 except that 2-mercaptopyridine was used instead of 2-quinolinethiol in the preparation of the modified diene polymer 1. 4 was obtained.

(Examples 1-16 and Comparative Examples 1-15)
<Preparation of rubber composition>
The compounding agent described in the column A of Tables 1 to 5 below is kneaded using a Banbury mixer, and then the compounding agent described in the column B is blended with the obtained composition and mixed using the Banbury mixer. A rubber composition was prepared by kneading.

<Evaluation of rubber composition (tan δ)>
About the vulcanized rubber obtained by vulcanizing the obtained rubber composition at 145 ° C. for 33 minutes, using a spectrometer (dynamic viscoelasticity tester) manufactured by Ueshima Seisakusho, frequency 52 Hz, initial strain 10%, measurement Tan δ was measured under the conditions of a temperature of 50 ° C. and a dynamic strain of 1%. The evaluation results are shown in Tables 1 to 5 below. The results are shown in Table 1 for Comparative Example 3, Table 2 for Comparative Example 6, Table 3 for Comparative Example 9, Table 4 for Comparative Example 12, and Table 5 for Comparative Example 15. The index when the value of 100 is 100 is displayed. The smaller the index value, the lower the tan δ and the lower the loss.

＊１ ＪＳＲ製， ＩＲ２２００
＊２ 旭カーボン製， ＃８０
＊３ 大内新興化学工業製， ノクラック ６Ｃ
＊４ 大内新興化学工業製， ノクセラー ＣＺ−Ｇ
＊５ ＲＳＳ＃３
＊６ 日本シリカ工業製， ニップシールＡＱ
＊７ ビス（３−トリエトキシシリルプロピル）ジスルフィド
＊８ 大内新興化学工業製， ノクセラー ＤＭ−Ｐ
＊９ 大内新興化学工業製， ノクセラー Ｄ
＊１０ ２−キノリンチオール
＊１１ イソキノリン−１−チオン
＊１２ ８−キノリンチオール（８−メルカプトキノリン）
＊１３ ２−メルカプトピリジン
＊１４ ２−メルカプトベンゾチアゾール

* 1 JSR, IR2200
* 2 Asahi Carbon, # 80
* 3 Nouchi 6C, manufactured by Ouchi Shinsei Chemical
* 4 Nouchira CZ-G, manufactured by Ouchi Shinsei Chemical
* 5 RSS # 3
* 6 NIPSEAL AQ, manufactured by Nippon Silica Industry
* 7 Bis (3-triethoxysilylpropyl) disulfide * 8 Ouchi Shinsei Chemical Industries, Noxeller DM-P
* 9 Nouchira D, manufactured by Ouchi Shinsei Chemical Industry
* 10 2-quinolinethiol * 11 isoquinoline-1-thione * 12 8-quinolinethiol (8-mercaptoquinoline)
* 13 2-mercaptopyridine * 14 2-mercaptobenzothiazole

  From Table 1, the rubber composition of the Example (Examples 1 and 2) containing the modified diene polymer obtained by reacting the compound represented by the general formula (I) or (II) with the diene polymer. It can be seen that the low loss property of the product is remarkably improved from the low loss property of the rubber compositions of Comparative Examples (Comparative Examples 1 to 3) in which the compound represented by the general formula (I) or (II) is not used. . That is, when Examples and Comparative Examples are compared, the low loss property of the rubber composition is improved by including the modified diene polymer modified with the compound represented by the general formula (I) or (II). It is suggested.

  From Tables 2-5, the low loss of the rubber composition of the Example (Examples 3-16) using the compounds 1-4, 9 and 10 which are the compounds represented by the said general formula (I) or (II). It can be seen that the property is remarkably improved from the low loss property of the rubber compositions of Comparative Examples (Comparative Examples 4 to 12) in which the compound represented by the general formula (I) or (II) is not used. That is, when an Example and a comparative example are compared, it is suggested that the low loss property of a rubber composition improves by using the compound represented by the said general formula (I) or (II).

  ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which improved the low loss property can be provided, and it can utilize for a tire use.

Claims (13)

A rubber composition comprising a modified diene polymer obtained by reacting a compound represented by the following general formula (I) or (II) with a diene polymer.

[In the general formulas (I) and (II),
R ¹ represents a hydrogen atom or an arbitrary substituent containing a hydrogen atom,
R ² and R ³ each independently represent a nitrogen atom or a carbon atom, at least one of which is a nitrogen atom,
R ^{4 to} R ⁸ each independently represent a hydrogen atom or an arbitrary substituent containing a hydrogen atom, and in at least one combination of adjacent two of R ^{4 to} R ⁸ , the arbitrary 2 When they are connected to each other to form an aromatic ring and R ² and / or R ³ are nitrogen atoms, R ⁴ and / or R ⁸ may not be present. ] The rubber composition according to claim 1, wherein only one of R ² and R ³ in the general formula (I) or (II) is a nitrogen atom.   The rubber composition according to claim 1 or 2, wherein the aromatic ring is an aromatic 6-membered ring.   The rubber according to any one of claims 1 to 3, wherein the compound represented by the general formula (I) or (II) is quinoline thiol, isoquinoline thiol, quinoline thione, isoquinoline thione, or a derivative thereof. Composition.   The compound represented by the general formula (I) or (II) is 2-quinolinethiol, 1-isoquinolinethiol, quinoline-2-thione, isoquinoline-1-thione, or a derivative thereof. 5. The rubber composition according to any one of 4 above.   The rubber composition according to any one of claims 1 to 5, wherein the modified diene polymer is formed by bonding an S atom in the general formula (I) or (II) to the diene polymer.   The rubber composition according to any one of claims 1 to 6, further comprising a filler containing at least one of carbon black and silica.   The rubber composition according to any one of claims 1 to 7, wherein the diene polymer is natural rubber.   A rubber composition obtained by kneading the compound represented by the general formula (I) or (II) and the diene polymer.   A method for producing a rubber composition, comprising a step of kneading the compound represented by the general formula (I) or (II) and the diene polymer.   It is a manufacturing method of the rubber composition which manufactures the rubber composition in any one of Claims 1-8, Comprising: The compound represented by the said general formula (I) or (II), and the said diene polymer are included. A method for producing a rubber composition, comprising a kneading step.   10. The compound according to claim 1, wherein the compound represented by the general formula (I) or (II) is blended during kneading of a composition containing at least the diene polymer. Rubber composition.   The rubber composition according to claim 12, wherein the compound represented by the general formula (I) or (II) is blended in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the diene polymer. .