JP2019070085A - Rubber composition, method for producing rubber composition and tire - Google Patents

Abstract

To provide a rubber composition having excellent low-loss properties, without causing a deterioration of other physical properties such as scorch time.SOLUTION: A rubber composition according to the present invention contains a rubber component containing a diene rubber, a tetrazine compound, and a thiuram vulcanization accelerator.SELECTED DRAWING: None

Description

  The present invention relates to a rubber composition, a method for producing the rubber composition, and a tire.

  Recently, the demand for low fuel consumption of automobiles has been increasing, and a tire having a small rolling resistance is required. Therefore, as a rubber composition used for a tread etc. of a tire, what has low tan-delta and is excellent in low heat buildup is desired.

  The low heat buildup described above can be realized, for example, by reducing the content of a reinforcing filler such as carbon black or silica. However, in the case of reducing the content of the reinforcing filler in the rubber composition, there is a problem that the wear resistance of the tread rubber is lowered simultaneously, and the reinforcing properties such as cut resistance and chipping resistance of the rubber are lowered. was there.

Therefore, development of a technique capable of improving low heat buildup without reducing other physical properties such as strength and processability has been desired. For example, Patent Document 1 enhances the chemical interaction between the rubber component and the filler by containing a rubber component having a diene rubber, a reinforcing filler, and a compound having a specific amidine structure, Improvement of high elastic modulus and tan δ is achieved.
However, in the technique of Patent Document 1, although a certain effect is obtained in terms of high elastic modulus and low loss, further reduction in loss has been desired.

JP-A-2014-501827

  Therefore, an object of the present invention is to provide a rubber composition excellent in low loss property and a method for producing the rubber composition which can obtain the rubber composition without reducing other physical properties such as scorch time. It is in. Another object of the present invention is to provide a tire in which rolling resistance is reduced.

As a result of investigations to achieve the above-mentioned problems, the present inventors have obtained a strong interaction with a reinforcing filler such as silica by containing a tetrazine-based compound as a modifier in the rubber composition. Since the dispersibility of the reinforcing filler is improved, the low loss property can be greatly improved. However, it was also found that when the tetrazine compound is contained, the scorch time of the rubber composition becomes short, and the processability and productivity deteriorate. Therefore, in order to extend the scorch time, methods such as reducing the amount of vulcanization accelerator were also considered, but in that case, it was found that there is a problem such as a decrease in the breaking strength of the rubber composition after vulcanization. The
Therefore, as a result of further intensive researches, the inventors of the present invention have found that, for the vulcanization accelerator contained in the rubber composition, the use of a thiuram-based vulcanization accelerator improves the above-mentioned tetrazine for the purpose of improving the low loss property. Even in the case of containing a base compound, it becomes possible to keep the scorch time long, and it is not necessary to reduce the amount of the vulcanization accelerator, and the physical properties of the rubber composition after vulcanization are also adversely affected. It has been found that there is no problem, and the present invention has been completed.

That is, the rubber composition of the present invention is characterized by containing a rubber component containing a diene rubber, a tetrazine compound and a thiuram vulcanization accelerator.
By providing the above configuration, the low loss property of the rubber composition can be improved without causing the deterioration of the scorch time.

  Moreover, in the rubber composition of the present invention, it is preferable to further include a reinforcing filler. This is because low loss can be realized at a higher level.

  Furthermore, in the rubber composition of the present invention, the diene rubber preferably contains butadiene rubber and / or styrene butadiene rubber, and more preferably further contains natural rubber. It is because abrasion resistance can be improved more.

  Furthermore, in the rubber composition of the present invention, the diene rubber preferably contains a modified diene rubber. This is because low loss can be realized at a higher level.

  Further, in the rubber composition of the present invention, the reinforcing filler preferably contains silica, and further preferably contains carbon black. This is because low loss can be realized at a higher level.

  Furthermore, in the rubber composition of the present invention, the thiuram-based vulcanization accelerator is preferably tetrakis (2-ethylhexyl) thiuram disulfide. It is because a better scorch time can be obtained.

  In the rubber composition of the present invention, the mass ratio of the content of the vulcanization accelerator other than the thiuram vulcanization accelerator relative to the content of the thiuram vulcanization accelerator (the addition of the other than the thiuram vulcanization accelerator) It is preferable that content of a vulcanization accelerator / thiuram type vulcanization accelerator is 0-1.5. This is because the scorch time and the strength of the rubber composition after crosslinking can be compatible at a higher level.

  Furthermore, in the rubber composition of the present invention, the content of the tetrazine compound is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the rubber component. This is because low loss can be achieved at a higher level without causing deterioration in the scorch time.

  Furthermore, in the rubber composition of the present invention, it is preferable that the substituent in the tetrazine structure of the tetrazine compound has at least one element selected from N, O and F, and 3,6-di (2 It is more preferable that it is at least one selected from -pyridyl) -1,2,4,5-tetrazine and 3,6-di (4-pyridyl) -1,2,4,5-tetrazine. This is because low loss can be realized at a higher level.

The method for producing a rubber composition according to the present invention comprises the step of kneading compounding components including a rubber component containing a diene rubber, a reinforcing filler, a tetrazine compound and a thiuram vulcanization accelerator. It is characterized by
By including the above-mentioned constitution, a rubber composition excellent in low loss property can be obtained without causing deterioration of scorch time.

  Further, in the method for producing a rubber composition according to the present invention, a preliminary prepared by mixing at least a part of the rubber component and the tetrazine compound with the silica contained in at least the reinforcing filler. It is preferred to make a masterbatch. It is because the low loss property of the rubber composition can be realized at a higher level.

  Furthermore, in the method for producing a rubber composition of the present invention, it is preferable that the rubber component used for producing the preliminary masterbatch is 10% by mass or more of the rubber component. It is because the low loss property of the rubber composition can be realized at a higher level.

The tire of the present invention is characterized by using the above-mentioned rubber composition of the present invention.
By providing the above configuration, reduction in rolling resistance can be realized.

  In the tire according to the present invention, preferably, the rubber composition is used for tread rubber, side rubber, side reinforcing rubber, cord-coated rubber, bead filler or gum chafer. This is because the benefits of the excellent low loss property of the rubber composition of the present invention can be sufficiently enjoyed.

  Furthermore, the tire of the present invention is preferably a passenger car tire, a studless tire, a run flat tire or a truck / bus tire. It is because reduction of rolling resistance is exhibited more effectively.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the rubber composition which can obtain the rubber composition excellent in low loss property, and this rubber composition can be provided, without reducing other physical properties, such as scorch time. . Further, according to the present invention, it is possible to provide a tire in which rolling resistance can be simultaneously reduced.

Hereinafter, the rubber composition of the present invention, the method for producing the rubber composition, and one embodiment of the tire will be specifically described.
<Rubber composition>
The rubber composition of the present invention is characterized by containing a rubber component containing a diene rubber, a tetrazine compound and a thiuram vulcanization accelerator.
As a result of the strong interaction with a reinforcing filler such as silica being obtained by modifying the rubber component by the tetrazine compound contained in the rubber composition part, the dispersibility of the reinforcing filler is improved, Low loss and abrasion resistance can be improved.
However, since the rubber composition containing the tetrazine compound has a problem that the scorch time of the rubber composition becomes short, a good scorch time can be obtained by using a thiuram vulcanization accelerator as a vulcanization accelerator. Excellent low loss performance can be realized.

(Rubber component)
The rubber composition of the present invention contains a rubber component containing a diene rubber.
By containing a certain amount of diene rubber as a rubber component, the abrasion resistance of the rubber composition can be improved. Moreover, strong interaction with the reinforcing filler can also be obtained by being modified with a tetrazine-based compound described later.

Here, the rubber component may be composed of 100% of diene rubber, but may contain rubber other than diene rubber as long as the object of the present invention is not impaired.
The content of the diene rubber in the rubber component is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more.

  About the kind of rubber | gum which comprises the said rubber component, it does not specifically limit except containing a diene based rubber, According to the performance requested | required, it can select suitably. For example, natural rubber (NR), butadiene rubber (BR) (note that BR means polybutadiene which is a polymer of 1,3-butadiene, and includes copolymers of butadiene and other polymers, etc.) ), Isoprene rubber (IR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), diene rubber such as acrylonitrile butadiene rubber (NBR), ethylene propylene diene rubber (EPDM) And non-diene rubbers such as ethylene propylene rubber (EPM) and butyl rubber (IIR). From these, 1 type (s) or 2 or more types containing a diene based rubber can be selected suitably, and can be used.

Moreover, about the said diene based rubber, it is preferable to contain a butadiene rubber and / or a styrene butadiene rubber among the specific examples mentioned above. It is because low loss and abrasion resistance can be compatible at a higher level.
Furthermore, the total content of these butadiene rubber and / or styrene butadiene rubber is preferably 20% by mass or more of the diene rubber, and more preferably 30% by mass or more. This is because both low loss and wear resistance can be achieved at a higher level.

Furthermore, in addition to the butadiene rubber and / or the styrene butadiene rubber, it is more preferable that the diene rubber further contain a natural rubber and / or an isoprene rubber. This is because the abrasion resistance of the rubber composition and other physical properties can be improved.
The content of the natural rubber and / or isoprene rubber is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more in the rubber component.

  In addition, about the said diene based rubber, even if it is unmodified | non-modified diene based rubber (Hereinafter, it may be mentioned "unmodified diene based rubber."), The diene based rubber modified (following, "modified diene based rubber") It may be said that). However, it is preferable that the diene-based rubber contains a modified diene-based rubber from the viewpoint of achieving both low loss and wear resistance at a higher level. The diene rubber is modified with a tetrazine compound to be described later, and the interaction with a reinforcing filler such as silica is enhanced, but a reinforcing filler (for example, with which the interaction is hardly obtained by modification with a tetrazine compound) , Carbon black, etc., and diene rubbers modified to increase interaction with other fillers (fillers other than reinforcing fillers), thereby enhancing the dispersibility of many fillers , Can achieve better low loss.

  The diene-based rubber may be composed only of an unmodified diene-based rubber, or may be composed only of a modified diene-based rubber. However, from the viewpoint of realizing low loss property at a higher level, the ratio of the content (mass) of the modified diene-based rubber to the content (mass) of the unmodified diene-based rubber (modified diene-based rubber The content / the unmodified diene rubber content) is preferably 0.5 to 1, and more preferably 0.75 to 1.

Here, the diene rubber which has been modified is one having a modifying functional group in a diene rubber such as the butadiene rubber, the styrene butadiene rubber, and the natural rubber.
The position of the modified functional group is not particularly limited, and may be, for example, the end of the main chain, or may be in the main chain or only from the end of the main chain to a quarter of the total chain length. .
Further, the number of modified functional groups is not particularly limited, and can be appropriately selected depending on the purpose.

The modifier for modifying the diene rubber can be appropriately selected according to the type of modifying functional group required.
For example, for the purpose of enhancing the interaction of modified rubber with silica, modifiers having at least one of the compounds represented by the following general formulas (I) to (X) can be mentioned.

前記一般（Ｉ）式中、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１〜２０の一価の脂肪族炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基を示し、ａは０〜２の整数であり、ＯＲ^２が複数ある場合、複数のＯＲ^２は互いに同一でも異なっていても良く、また分子中には活性プロトンは含まれない。

In the general formula (I), R ¹ and R ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, a is an integer of 0 to 2, if the OR ² there is a plurality, the plurality of OR ² may be the same or different from each other, also in the molecule does not include active proton.

  Here, specific examples of the compound (alkoxysilane compound) represented by the general formula (I) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n. -Butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, butylto Mention methoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydimethylsilane, methylphenyldimethoxysilane, dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldiethoxysilane, etc. Among these, tetraethoxysilane, methyltriethoxysilane and dimethyldiethoxysilane are preferred. One of these may be used alone, or two or more of these may be used in combination.

前記一般式（ＩＩ）中、Ａ^１はエポキシ、イソシアネート、イミン、カルボン酸エステル、カルボン酸無水物、環状三級アミン、非環状三級アミン、ピリジン、シラザン及ジスルフィドからなる群より選択される少なくとも一種の官能基を有する一価の基であり、Ｒ^３は単結合又は二価の炭化水素基であり、Ｒ^４及びＲ^５は、それぞれ独立に炭素数１〜２０の一価の脂肪族炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｂは０〜２の整数であり、ＯＲ^５が複数ある場合、複数のＯＲ^５は互いに同一であっても異なっていても良く、また分子中には活性プロトンは含まれない。

In the above general formula (II), A ¹ is at least one selected from the group consisting of epoxy, isocyanate, imine, carboxylic acid ester, carboxylic acid anhydride, cyclic tertiary amine, noncyclic tertiary amine, pyridine, silazane and disulfide R ³ is a single bond or a divalent hydrocarbon group, and R ⁴ and R ⁵ are each independently a monovalent aliphatic carbon having from 1 to 20 carbon atoms an aromatic hydrocarbon group of monovalent hydrocarbon group or a C6-18, b is an integer of 0 to 2, if the oR ⁵ there is a plurality, the plurality of oR ⁵ are be the same or different from each other And the molecule does not contain active protons.

  Specific examples of the alkoxysilane compound represented by the above general formula (II) include epoxy group-containing alkoxysilane compounds such as 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2 -Glycidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxy) Examples include cyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane and the like. Among these, 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane can be suitably used.

前記一般式（ＩＩＩ）中、ｎ１＋ｎ２＋ｎ３＋ｎ４＝４（但し、ｎ１、ｎ２、ｎ３及びｎ４は０〜４．０の整数であり、且つｎ１＋ｎ２＝1以上の整数）であり、Ａ¹は、飽和環状３級アミン化合物残基、不飽和環状３級アミン化合物残基、ケチミン残基、ニトリル基、（チオ）イソシアナート基（イソシアナート基又はチオイソシアナート基を示す。以下、同様。）、（チオ）エポキシ基、イソシアヌル酸トリヒドロカルビルエステル基、炭酸ジヒドロカルビルエステル基、ニトリル基、ピリジン基、（チオ）ケトン基、（チオ）アルデヒド基、アミド基、（チオ）カルボン酸エステル基、（チオ）カルボン酸エステルの金属塩、カルボン酸無水物残基、カルボン酸ハロゲン化合物残基、並びに、加水分解性基を有する第一若しくは第二アミノ基又はメルカプト基の中から選択される少なくとも１種の官能基であり、Ｒ²¹は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｎ１が2以上の場合には同一でも異なっていても良く、Ｒ²³は、炭素数1〜20の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又はハロゲン原子（フッ素、塩素、臭素、ヨウ素）であり、ｎ３が２以上の場合には同一でも異なっていても良く、Ｒ²²は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、いずれも窒素原子及び／又はケイ素原子を含有していても良く、ｎ２が2以上の場合には、互いに同一若しくは異なっていても良く、或いは、一緒になって環を形成しており、Ｒ²⁴は、炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、ｎ４が２以上の場合には同一でも異なっていても良い。
前記加水分解性基を有する第一若しくは第二アミノ基又は前記加水分解性基を有するメルカプト基における加水分解性基としては、トリメチルシリル基又はｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。
なお、本発明において、「炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基」とは、「炭素数１〜２０の一価の脂肪族炭化水素基若しくは炭素数３〜２０の一価の脂環式炭化水素基」をいう。二価の炭化水素基の場合も同様である。

In the general formula (III), n1 + n2 + n3 + n4 = 4 (wherein n1, n2, n3 and n4 are integers of 0 to 4.0, and n1 + n2 is an integer of 1 or more), and A ¹ represents a saturated cyclic group Secondary amine compound residue, unsaturated cyclic tertiary amine compound residue, ketimine residue, nitrile group, (thio) isocyanate group (shows isocyanate group or thioisocyanate group. The same applies hereinafter), (thio) Epoxy group, isocyanuric acid trihydrocarbyl ester group, dihydrocarbyl carbonate ester group, nitrile group, pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid ester group, (thio) carboxylic acid Metal salt of an ester, a carboxylic acid anhydride residue, a carboxylic acid halogen compound residue, and a primary or secondary amide having a hydrolyzable group At least one functional group selected from among group or a mercapto group, R ²¹ is a monovalent C1-20 aliphatic or cycloaliphatic hydrocarbon group or a monovalent 6 to 18 carbon atoms an aromatic hydrocarbon group may be the same or different when n1 is 2 or more, R ²³ is an aliphatic or alicyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, carbon atoms 6 to 18 monovalent aromatic hydrocarbon group or a halogen atom (fluorine, chlorine, bromine, iodine), and when n3 is 2 or more, they may be the same or different, and R ²² has 1 carbon atom To 20 monovalent aliphatic or alicyclic hydrocarbon groups or C 6-18 monovalent aromatic hydrocarbon groups, each of which may contain a nitrogen atom and / or a silicon atom, When n2 is 2 or more, they may be the same or different from each other, or together R ²⁴ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, When n4 is 2 or more, they may be the same or different.
As a hydrolysable group in the primary or secondary amino group which has the said hydrolysable group, or the mercapto group which has the said hydrolysable group, a trimethylsilyl group or a tert- butyl dimethyl silyl group is preferable, and a trimethylsilyl group is especially preferable.
In the present invention, “a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms” means “a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or 3 to 20 carbon atoms”. "Monovalent alicyclic hydrocarbon group". The same applies to the case of divalent hydrocarbon groups.

前記一般式（ＩＶ）中、ｐ１＋ｐ２＋ｐ３＝２（但し、ｐ１、ｐ２、ｐ３は０〜２の整数であり、且つｐ１＋ｐ２＝１以上の整数）であり、Ａ²は、ＮＲa（Ｒaは、一価の炭化水素基、加水分解性基又は含窒素有機基である。加水分解性基として、トリメチルシリル基又はｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。）、或いは、硫黄であり、Ｒ²⁵は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｐ１が２の場合には、互いに同一若しくは異なり、或いは、一緒になって環を形成しており、Ｒ²⁷は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又はハロゲン原子（フッ素、塩素、臭素、ヨウ素）であり、Ｒ²⁶は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又は含窒素有機基であり、いずれも窒素原子及び／又はケイ素原子を含有していても良く、ｐ２が２の場合には、互いに同一若しくは異なり、或いは、一緒になって環を形成しており、Ｒ²⁸は、炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基である。

In the general formula (IV), p1 + p2 + p3 = 2 (wherein p1, p2 and p3 are integers of 0 to 2 and p1 + p2 is an integer of 1 or more), and A ² is NRa (Ra is monovalent) As a hydrolyzable group, a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable as the hydrolyzable group, or sulfur, and R ²⁵ is a C1-C20 monovalent aliphatic or alicyclic hydrocarbon group or a C6-C18 monovalent aromatic hydrocarbon group, and when p1 is 2, they are the same as or different from each other And R ²⁷ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent aromatic carbonization having 6 to 18 carbon atoms. Hydrogen group or halogen atom (fluorine, salt , Bromine, iodine), and R ²⁶ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a nitrogen-containing organic group R ²⁸ may be a nitrogen atom and / or a silicon atom, and when p 2 is 2, they are identical to or different from each other, or form a ring together, and R ²⁸ is a group Or a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

前記一般式（Ｖ）中、ｑ１＋ｑ２＝３（但し、ｑ１は０〜２の整数であり、ｑ２は１〜３の整数である）であり、Ｒ³¹は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ³²及びＲ³³はそれぞれ独立して加水分解性基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ³⁴は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｑ１が２の場合には同一でも異なっていても良く、Ｒ³⁵は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｑ２が２以上の場合には同一でも異なっていても良い。

In the above general formula (V), q1 + q2 = 3 (wherein q1 is an integer of 0 to 2 and q2 is an integer of 1 to 3), and R ³¹ is a C1-C20 divalent fat Group or an alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³² and R ³³ each independently represent a hydrolyzable group and a monovalent one having 1 to 20 carbon atoms. An aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³⁴ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or carbon R 6 is a monovalent aromatic hydrocarbon group of 6 to 18 and may be the same or different when q 1 is 2; R ³⁵ is a C 1 to 20 monovalent aliphatic or alicyclic carbon A hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be the same or different when q2 is 2 or more

前記一般式（ＶＩ）中、ｒ１＋ｒ２＝３（但し、ｒ１は１〜３の整数であり、ｒ２は０〜２の整数である）であり、Ｒ³⁶は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ³⁷はジメチルアミノメチル基、ジメチルアミノエチル基、ジエチルアミノメチル基、ジエチルアミノエチル基、メチルシリル（メチル）アミノメチル基、メチルシリル（メチル）アミノエチル基、メチルシリル（エチル）アミノメチル基、メチルシリル（エチル）アミノエチル基、ジメチルシリルアミノメチル基、ジメチルシリルアミノエチル基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｒ１が２以上の場合には同一でも異なっていても良く、Ｒ³⁸は炭素数１〜２０のヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｒ２が２の場合には同一でも異なっていても良い。

In the above general formula (VI), r1 + r2 = 3 (wherein r1 is an integer of 1 to 3 and r2 is an integer of 0 to 2), and R ³⁶ is a C1-C20 divalent fat Group or alicyclic hydrocarbon group or divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³⁷ is dimethylaminomethyl group, dimethylaminoethyl group, diethylaminomethyl group, diethylaminoethyl group, methylsilyl (methyl) ) Aminomethyl group, methylsilyl (methyl) aminoethyl group, methylsilyl (ethyl) aminomethyl group, methylsilyl (ethyl) aminoethyl group, dimethylsilylaminomethyl group, dimethylsilylaminoethyl group, and having 1 to 20 carbon atoms An aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r1 is 2 or more, they may be the same or different; At best, R ³⁸ is a hydrocarbyloxy group, an aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, monovalent C1-20 C20 When r2 is 2, it may be the same or different.

前記一般式（ＶＩＩ）中、ＴＭＳはトリメチルシリル基であり、Ｒ⁴⁰はトリメチルシリル基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ⁴¹は炭素数１〜２０のヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ⁴²は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基である。

In the above general formula (VII), TMS is a trimethylsilyl group, R ⁴⁰ is a trimethylsilyl group, a C 1-20 monovalent aliphatic or alicyclic hydrocarbon group or a C 6-18 monovalent aromatic Hydrocarbon group, R ⁴¹ is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic ring having 6 to 18 carbon atoms R ⁴² is a hydrocarbon group, and R ⁴² is a C 1-20 divalent aliphatic or alicyclic hydrocarbon group or a C 6-18 divalent aromatic hydrocarbon group.

前記一般式（ＶＩＩＩ）中、ＴＭＳはトリメチルシリル基であり、Ｒ⁴³及びＲ⁴⁴はそれぞれ独立して炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ⁴⁵は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、複数のＲ⁴⁵は、同一でも異なっていても良い。

In the general formula (VIII), TMS is a trimethylsilyl group, and R ⁴³ and R ⁴⁴ each independently have a carbon number of 1 to 20, and a divalent aliphatic or alicyclic hydrocarbon group or a carbon number of 6 to 18 A divalent aromatic hydrocarbon group, and R ⁴⁵ is a C 1-20 monovalent aliphatic or alicyclic hydrocarbon group or a C 6-18 monovalent aromatic hydrocarbon group, Plural R ⁴⁵ may be the same or different.

前記一般式（ＩＸ）中、ｒ１＋ｒ２＝３（但し、ｒ１は０〜２の整数であり、ｒ２は１〜３の整数である。）であり、ＴＭＳはトリメチルシリル基であり、Ｒ⁴⁶は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ⁴⁷及びＲ⁴⁸はそれぞれ独立して炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、複数のＲ⁴⁷又はＲ⁴⁸は、同一でも異なっていても良い。

In the above general formula (IX), r1 + r2 = 3 (wherein r1 is an integer of 0 to 2 and r2 is an integer of 1 to 3), TMS is a trimethylsilyl group, and R ⁴⁶ is a carbon number 1 to 20 divalent aliphatic or alicyclic hydrocarbon group or divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, each of R ⁴⁷ and R ⁴⁸ independently having 1 to 20 carbon atoms It is a monovalent | monohydric aliphatic or alicyclic hydrocarbon group or a C6-C18 monovalent | monohydric aromatic hydrocarbon group, and several R ⁴⁷ or R ⁴⁸ may be same or different.

前記一般式（Ｘ）中、Ｘはハロゲン原子であり、Ｒ⁴⁹は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ⁵⁰及びＲ⁵¹はそれぞれ独立して、加水分解性基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であるか、或いは、Ｒ⁵⁰及びＲ⁵¹は結合して二価の有機基を形成しており、Ｒ⁵²及びＲ⁵³はそれぞれ独立してハロゲン原子、ヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基である。Ｒ⁵⁰及びＲ⁵¹としては、加水分解性基であることが好ましく、加水分解性基として、トリメチルシリル基又はｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。

In the above general formula (X), X is a halogen atom, and R ⁴⁹ is a C 1 to 20 divalent aliphatic or alicyclic hydrocarbon group or a C 6 to 18 divalent aromatic hydrocarbon. R ⁵⁰ and R ⁵¹ are each independently a hydrolyzable group, a C 1-20 monovalent aliphatic or alicyclic hydrocarbon group or a C 6-18 monovalent aromatic group R ⁵⁰ and R ⁵¹ are combined to form a divalent organic group, and R ⁵² and R ⁵³ each independently represent a halogen atom, a hydrocarbyloxy group, a carbon number of 1 to 5 20 monovalent aliphatic or alicyclic hydrocarbon groups or C6-18 monovalent aromatic hydrocarbon groups. As R ⁵⁰ and R ⁵¹ , a hydrolyzable group is preferable, and as the hydrolyzable group, a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable.

The hydrocarbyloxysilane compounds represented by the general formulas (III) to (X) are preferably alkoxysilane compounds.
Further, among the compounds represented by the formulas (I) to (X) described above, tetraoxysilane, N, N-bis (trimethylsilyl) -3-aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) -3 -Aminopropylmethyldiethoxysilane, 3-dimethylaminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, and N- (1,3-dimethylbutylidene) -3-triethoxysilyl-1-propyl At least one selected from among amines is particularly preferred.

  Further, in order to enhance the interaction between the modified rubber and the carbon black, the modified compounds represented by the following general formulas (XI), (XII-1), (XII-2), and (XIII) Agents.

R ' _a SnX _b ... (XI)
In the above general formula (XI), R ′ independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms X is each independently chlorine or bromine; a is 0 to 3 and b is 1 to 4, provided that a + b = 4. The diene-based rubber modified with the tin-containing compound of the formula (XI) has at least one tin-carbon bond.

Here, specific examples of R ′ include a methyl group, an ethyl group, an n-butyl group, a neophyl group, a cyclohexyl group, an n-octyl group and a 2-ethylhexyl group.
As the tin-containing compound of formula (XI), tin _{tetrachloride, R'SnCl 3, R '2 SnCl} 2, R' 3 SnCl , and the like are preferable, and tin tetrachloride is particularly preferred.

θ-C≡N (XII-1)
θ-R-C≡N (XII-2)
In the above formulas (XII-1) and (XII-2), θ represents a heterocyclic group. Further, it is preferable that θ is a heterocyclic group containing a nitrogen atom, and a heterocyclic group containing an oxygen atom, a heterocyclic group containing a sulfur atom, a heterocyclic group containing two or more hetero atoms, and one or more cyano groups And at least one heterocyclic group selected from the group consisting of heterocyclic groups containing Furthermore, it may be a heteroaromatic group or hetero nonaromatic group such as thiophene, pyridine, furan, piperidine, dioxane, etc., and further a monocyclic, bicyclic, tricyclic or polycyclic heterocyclic group It may be

  Specifically as such θ, for example, as a heterocyclic group containing a nitrogen atom, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl , 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, 1 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-pyrroline-3- , 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-indolizinyl, 2-indolizinyl, 3-indolizinyl, 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-carboline-1-yl, N-methyl-β-carboline-3-yl, N-methyl-β-carboline-4-yl, 9-acridinyl, 1,7-phenanthrolin-2-yl, 1,7-phenanthrolin-3-yl, 1,7-phenanthrolin-4-yl, 1,10-phenanthrolin-2-yl, 1,10-phenanthrolin- 3-yl, 1, 10-phenanthrolin-4-yl, 4, 7-phenanthrolin-1-yl, 4, 7-phenanthrolin-2-yl, 4, 7-phenanthrolin-3-yl, 1-phenazinyl, 2- Phenazinyl, pyrrolidino, piperidino can be mentioned.

2-furyl, 3-furyl, 2-benzo [b] furyl, 3-benzo [b] furyl, 1-isobenzo [b] furyl, 3-isobenzo [b] furyl, as a heterocyclic group containing an oxygen atom Naphtho [2,3-b] furyl and 3-naphtho [2,3-b] furyl are mentioned.
As a heterocyclic group containing a sulfur atom, 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 and 3-naphtho [2,3-b] thienyl can be mentioned.

As a heterocyclic group containing two or more hetero atoms, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-thiazolyl Isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,2,3-oxadiazol-4-yl, 1,2,3-oxadiazol-5-yl, 1,3,4-oxadiazole-2- , 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, isoxazolinyl, 2-thiazole 2-yl, 2-thiazoline-4-yl, 2-thiazoline-5-yl, 3-isothiazolinyl, 4-isothiazolinyl, 5- isothiazolinyl, 2-benzothiazolyl, and morpholino.
Among these, θ is preferably a nitrogen-containing heterocyclic group, particularly preferably 2-pyridyl, 3-pyridyl or 4-pyridyl.

  As such a heterocyclic nitrile compound, specifically, for example, as a compound having a heterocyclic group containing a nitrogen atom, 2-pyridinecarbonitrile, 3-pyridinecarbonitrile, 4-pyridinecarbonitrile, pyrazinecarbo 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-pyrazolecarbo Nitrile, N-Me Le-5-pyrazolecarbonitrile, N-methyl-1,2,3-triazole-4-carbonitrile, N-methyl-1,2,3-triazole-5-carbonitrile, N-methyl-1,2,3, 4-triazole-3-carbonitrile, N-methyl-1,2,4-triazole-5-carbonitrile, 1,2,4-triazine-3-carbonitrile, 1,2,4-triazine-5-carbo 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-carbo Nitrile, N-methyl-2-pyrazoline-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-methylisoyl Indole-3-carbonitrile, 1-indolizine carbonitrile, 2-indolizine carbonitrile, 3-indolizine carbonitrile, 1-phthalazine carbonitrile, 2-quinazoline carbonitrile, 4-quinazoline carbonitrile, 2-quinoxaline Carbonitrile, 3-cinnoline carbonitrile, 4-cinnoline carbonitrile, 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-pteridine carbonitrile, 4 -Pteridine carbonitrile, 6 Pteridine carbonitrile, 7-pteridine carbonitrile, 1-methylbenzimidazole-2-carbonitrile, phenanthridine-6-carbonitrile, N-methyl-2-purincarbonitrile, 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 -Acridine carbonitrile, 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-phenazine carbonitrile, 2 -Phenazine carbonitrile, 1-pyrrolidine carbonitrile, 1-piperidine carbonitrile are mentioned.

As a compound having a heterocyclic group containing an oxygen atom, 2-furonitrile, 3-furonitrile, 2-benzo [b] furancarbonitrile, 3-benzo [b] furancarbonitrile, 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 a compound having a heterocyclic group containing a sulfur atom, 2-thiophenecarbonitrile, 3-thiophenecarbonitrile, benzo [b] thiophene-2-carbonitrile, benzo [b] thiophene-3-carbonitrile, isobenzo [b] Thiophene-1-carbonitrile, isobenzo [b] thiophene-3-carbonitrile, naphtho [2,3-b] thiophene-2-carbonitrile, naphtho [2,3-b] thiophene-3-carbonitrile .

  Examples of compounds having a heterocyclic group containing two or more hetero atoms include 2-oxazolecarbonitrile, 4-oxazolecarbonitrile, 5-oxazolecarbonitrile, 3-isoxazole carbonitrile, 4-isoxazole carbonitrile, 5-iso. 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-isoxazoline carbonitrile, 4 -Isoxazoline carbonitrile, 5-isoxazoline carbonitrile, 2-thiazoline-2-carbonitrile, 2-thiazoline-4-carbonitrile, 2-thiazoline-5-carbonitrile, 3-isothiazoline carbonitrile, 4-isothiazoline carbo A nitrile, 5-isothiazoline carbonitrile, benzothiazole 2-carbonitrile, 4-morpholine carbonitrile is mentioned.

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-Flangedcarbonitrile, 2,4-Flangedcarbonitrile, 2,5-Flangedcarbonitrile, 2,3-Thiophenedicarbonitrile 2,4-thiophenedicarbonitrile, 2,5-thiophenedicarbonitrile, N-methyl -2,3-pyrrole dicarbonitrile, N-methyl-2,4-pyrrole dicarbonitrile, N-methyl-2,5-pyrrole dicarbonitrile, 1,3,5-triazine-2,4-dicarboxylic acid Nitrile, 1,2,4-triazine-3,5-dicarbonitrile, 3,2,4-triazine-3,6-dicarbonitrile, 2,3,4-pyridine tricarbonitrile, 2,3,5 -Pyridine tricarbonitrile, 2,3,6-pyridine tricarbonitrile, 2,4,5-pyridine tricarbonitrile, 2,4,6-pyridine tricarbonitrile, 3,4,5-pyridine tricarbonitrile, 2,4,5- pyrimidine tricarbonitrile, 2,4,6- pyrimidine tricarbonitrile, 4,5,6- pyrimidine tricarbonitrile, pyrazine tricarboni Ryl, 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- And triazine-3,5,6-tricarbonitrile.
Among these, 2-cyanopyridine (2-pyridinecarbonitrile), 3-cyanopyridine (3-pyridinecarbonitrile) and 4-cyanopyridine (4-pyridinecarbonitrile) are mentioned as a suitable thing.

（式中、各々のＲ^１は、独立して、１〜１２の炭素原子を有するアルキル、シクロアルキルまたはアラルキル基を示す。）

（式中、Ｒ_２は、３〜１６のメチレン基を有するアルキレン、置換アルキレン、オキシ−
またはＮ−アルキルアミノ−アルキレン基を示す。）］ (AM) Li (Q) y ... (XIII)
[Wherein, y is 0 or 0.5 to 3 and Q is a solubilizing component selected from the group consisting of hydrocarbons, ethers, amines or mixtures thereof, and AM is a general formula (XIII-1) or (XIII-2).

(Wherein each R ¹ independently represents an alkyl, cycloalkyl or aralkyl group having 1 to 12 carbon atoms.)

(Wherein R ₂ represents an alkylene having 3 to 16 methylene groups, substituted alkylene, oxy-
Or N-alkylamino-alkylene group. )]

In formula (XIII), (Q) is a solubilizing component, which may be a hydrocarbon, an ether, an amine or a mixture thereof. The presence of this (Q) component makes the initiator soluble in hydrocarbon solvents.
The (Q) groups also include dienyl or vinyl aromatic polymers or copolymers having a degree of polymerization of from 3 to about 300 polymerized units. The above polymers include polybutadiene, polystyrene, polyisoprene and their copolymers.
Other examples of (Q) include polar ligands such as tetrahydrofuran (THF) and tetramethylethylenediamine (TMEDA).
The (AM) component represents an amino functional group, and is incorporated into, for example, the initiation site or head of the polymer, whereby a polymer having at least one functional group terminated is synthesized.
When the soluble component (Q) is an ether or amino compound, a solution of the functionalizing agent AM-H is prepared in an anhydrous aprotic solvent such as cyclohexane in the presence of (Q), Alternatively, the initiator can be generated by adding to this solution an organolithium compound in the same or similar solvent.
The organolithium compounds have the general formula RLi, where R is an alkyl having 1 to about 20 carbon atoms, cycloalkyl, alkenyl, aryl and aralkyl, and 25 obtained from diolefin and vinyl aryl monomers Selected from the group consisting of short chain length low molecular weight polymers having the following units:
For example, representative alkyls include n-butyl, s-butyl, methyl, ethyl, isopropyl and the like. Also, examples of cycloalkyl include cyclohexyl and menthyl, and examples of alkenyl include allyl and vinyl.
Additionally, aryl and aralkyl groups include phenyl, benzyl, oligo (styryl), etc. For short chain length polymers, oligos formed by initiating the oligomerization of appropriate monomers with organolithium ( Examples include butadienyls, oligo (isoprenyls), oligo (styryls) and the like. An in-situ method (the method described in JP-A-6-199921) is also suitably used. As an organic lithium compound, n-butyllithium is preferable.

The substituted amino group represented by formula (XIII-1) in formula (XIII) is not particularly limited as long as R ₁ group in the formula is an alkyl, cycloalkyl or aralkyl group having 1 to 12 carbon atoms. Are, for example, methyl, ethyl, butyl, octyl, cyclohexyl, 3-phenyl-1-propyl and isobutyl. Each R _{1 in} formula (XIII-1) may be the same or different.
Furthermore, in the formula (XIII), cyclic amino group represented by the formula (XIII-2) may, _{R 2} groups in the formula is a divalent alkylene having from 3 to 16 methylene groups, a substituted alkylene, oxy - There is no particular limitation as long as it is an N-alkylamino-alkylene group.
Here, substituted alkylenes include mono- to octa-substituted alkylenes. Preferred substituents are linear or branched alkyl having 1 to about 12 carbon atoms, cycloalkyl, bicycloalkyl, aryl and aralkyl. Preferred R2 groups include trimethylene, tetramethylene, hexamethylene, oxydiethylene, N-alkylazadiethylene, dodecamethylene and hexadecamethylene.
There are also many useful examples of cyclic amines including alkyl, cycloalkyl, aryl and aralkyl substituents of the cyclic and bicyclic amines, including but not limited to 2- (2-ethylhexyl). Pyrrolidine; 3- (2-propyl) pyrrolidine; 3,5-bis (2-ethylhexyl) piperidine; 4-phenylpiperidine; 7-decyl-1-azacyclotridecane; 3,3-dimethyl-1-azacyclo Tetradecane; 4-dodecyl-1-azacyclooctane; 4- (2-phenylbutyl) -1-azacyclooctane; 3-ethyl-5-cyclohexyl-1-azacycloheptane; 4-hexyl-1-azacycloheptane 9-isoamyl-1-azacycloheptadecane; 2-methyl-1-azacycloheptadec-9-a 3-isobutyl-1-azacyclododecane; 2-methyl-7-t-butyl-1-azacyclododecane; 5-nonyl-1-azacyclododecane; 8- (4'-methylphenyl) -5-pentyl 3-azabicyclo [5.4.0] undecane; 1-butyl-6-azabicyclo [3.2.1] octane; 8-ethyl-3-azabicyclo [3.2.1] octane; 1-propyl-3 -Azabicyclo [3.2.2] nonane; 3- (t-butyl) -7-azabicyclo [4.3.0] nonane; 1,5,5-trimethyl-3-azabicyclo [4.4.0] decane Etc.

  Furthermore, among the compounds represented by the above-mentioned formulas (XI), (XII-1), (XII-2) and (XIII), the modifier is tin tetrachloride, 2-cyanopyridine and hexamethyleneimine. It is particularly preferred to include at least one selected from among them.

  Furthermore, modification of the diene rubber includes modification of the compound represented by the general formulas (I) to (X) described above after modifying one end using an organic alkali metal compound as a polymerization initiator. The other end can also be denatured by the agent.

As an organic alkali metal compound used as the above-mentioned polymerization initiator, an organic lithium compound is preferable. The organic lithium compound is not particularly limited, but a hydrocarbyl lithium or a lithium amide compound is preferably used, and in the case of using the hydrocarbyl lithium, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal is a polymerization active site A modified diene rubber is obtained, and a hydrocarbyloxysilane compound containing a nitrogen atom and a silicon atom or a hydrocarbyloxysilane compound containing a silicon atom is reacted with an active end which is a polymerization active site to modify.
When the latter lithium amide compound is used, a modified diene rubber having a nitrogen-containing group at the polymerization initiation end and a polymerization active site at the other end is obtained. For example, hexamethylene at the polymerization initiation end It is also possible to obtain a modified diene-based rubber in which an imine is bonded and the alkoxysilane compound is bonded to the other end.

The hydrocarbyl lithium which is the polymerization initiator is preferably one having a hydrocarbyl group having a carbon number of 2 to 20, and examples thereof include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium and tert-octyl Lithium, n-decyllithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclophenyllithium, reactive organisms of diisopropenylbenzene and butyllithium, etc. Among these, n-butyllithium is particularly preferred.
Furthermore, as the lithium amide compound which is the above-mentioned polymerization initiator, for example, lithium hexamethylene imide, lithium pyrrolidine, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethylamide, lithium diethylamide, lithium dibutylamide , Lithium dipropylamide, lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazid, lithium ethyl propylamide, lithium ethyl butylamide, lithium ethyl benzyl Amide, lithium methyl phenethyl amide and the like can be mentioned. Among them, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidine, lithium piperidide, lithium hepta methylene imide, lithium dodecamethylene imide and the like are preferable from the viewpoint of interaction effect with carbon black and polymerization initiation ability. Particularly preferred are lithium hexamethylene imide and lithium pyrrolidine.
In addition, although these lithium amide compounds can generally be used for superposition | polymerization from what was previously prepared from the secondary amine and the lithium compound, they can also be prepared in the polymerization system (in-situ).

  As described above, the rubber component is denatured by a tetrazine-based compound described later. Therefore, a rubber composition containing the diene rubber and a rubber composition containing a tetrazine compound can be contained in the rubber composition as a diene rubber-containing modified rubber modified with the tetrazine compound. is there. That is, before kneading with a filler such as a reinforcing filler, the rubber component is denatured using the tetrazine compound to make a modified natural rubber, and then, other fillers are compounded and kneaded to obtain a rubber composition. You can also make things. When the reinforcing filler contains plural types of silica, silica and carbon black, the kneading step may be divided according to the type of silica, or the rubber component, tetrazine compound, vulcanization accelerator, and It is conceivable that the reinforcing filler such as carbon black is kneaded in the first stage and the silica is compounded in the subsequent kneading stage.

(Tetrazine compounds)
The rubber composition of the present invention is characterized by containing a tetrazine compound in addition to the above-mentioned rubber component.
When the tetrazine-based compound modifies the rubber component (in particular, a diene-based rubber), the interaction between the modified rubber and the reinforcing filler such as silica can be enhanced.

式中、テトラジン系化合物の側鎖にあるＲ^１及びＲ^２は、それぞれ、置換又は無置換の炭素数１〜１１の炭化水素基を示す。 Here, the tetrazine compound is a compound having a tetrazine structure, and in the present invention, a compound having a structure of 1,2,4,5-tetrazine as represented by the following formula: is there.

In the formula, R ¹ and R ^{2 in} the side chain of the tetrazine compound each represent a substituted or unsubstituted hydrocarbon group having 1 to 11 carbon atoms.

Examples of the tetrazine-based compound include the following.

Moreover, as a specific example of the said tetrazine type-compound,
1,2,4,5-tetrazine,
3,6-bis (2-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (3-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (4-pyridyl) -1,2,4,5-tetrazine,
3,6-Diphenyl-1,2,4,5-tetrazine,
3,6-dibenzyl-1,2,4,5-tetrazine,
3,6-bis (2-furanyl) -1,2,4,5-tetrazine,
3-Methyl-6- (3-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (3,5-dimethyl-1-pyrazolyl) -1,2,4,5-tetrazine,
3,6-bis (2-thienyl) -1,2,4,5-tetrazine,
3-Methyl-6- (2-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (4-hydroxyphenyl) -1,2,4,5-tetrazine,
3,6-bis (3-hydroxyphenyl) -1,2,4,5-tetrazine,
3,6-bis (2-pyrimidinyl) -1,2,4,5-tetrazine,
3,6-bis (2-pyrazyl) -1,2,4,5-tetrazine etc. are also mentioned.

Further, among the tetrazine compounds described above, at least one of R ¹ and R ² contains at least one element selected from N, O and F (substituents in the tetrazine structure are N, O and F) Preferably have at least one element selected from the group consisting of at least N, more preferably at least N, still more preferably a nitrogen-containing heterocyclic ring, and both of R ¹ and R ² are nitrogen-containing heterocyclic rings Is particularly preferred.
After modifying the rubber component, the interaction between the rubber component and the silica can be increased, and more excellent low loss can be realized.

From the same viewpoint, the tetrazine compound is
3,6-bis (2-pyridyl) -1,2,4,5-tetrazine (hereinafter, also referred to as "3,6-di (2-pyridyl) -1,2,4,5-tetrazine"),
3,6-bis (3-pyridyl) -1,2,4,5-tetrazine (hereinafter also referred to as "3,6-di (3-pyridyl) -1,2,4,5-tetrazine")
3,6-bis (2-furanyl) -1,2,4,5-tetrazine (hereinafter also referred to as "3,6-di (2-furanyl) -1,2,4,5-tetrazine")
3-methyl-6- (3-pyridyl) -1,2,4,5-tetrazine, and
More preferably, it is at least one selected from 3-methyl-6- (2-pyridyl) -1,2,4,5-tetrazine.
Furthermore, from the same point of view, the tetrazine compounds are 3,6-di (2-pyridyl) -1,2,4,5-tetrazine, and 3,6-di (4-pyridyl) -1,2 Particularly preferred is at least one selected from 4,5-tetrazine.

  The content of the tetrazine compound is not particularly limited as long as the rubber component can be modified. However, from the viewpoint of achieving low loss and high wear resistance without causing deterioration of scorch time, the content of the tetrazine compound is 0 with respect to 100 parts by mass of the rubber component. The amount is preferably from 1 to 5 parts by mass, more preferably from 0.5 to 4 parts by mass, and particularly preferably from 1 to 3 parts by mass. By making content of the said tetrazine type-compound into 0.1 mass part or more with respect to 100 mass parts of said rubber components, modification | denaturation of the said rubber component can be performed more reliably, and it shall be 5 mass parts or less. You can prevent the deterioration of the scorch time.

(Vulcanization accelerator)
The rubber composition of the present invention contains a thiuram-based vulcanization accelerator in addition to the rubber component and the tetrazine-based compound described above.
However, since the rubber composition containing the tetrazine compound has a problem that the scorch time of the rubber composition becomes short, a good scorch time can be obtained by using a thiuram vulcanization accelerator as a vulcanization accelerator. Excellent low loss performance can be realized.
In the case of using a vulcanization accelerator other than a thiuram type, it is difficult to extend the scorch time, and the productivity and processability of the rubber composition will be deteriorated. Further, in the rubber composition of the present invention, since it is not necessary to reduce the compounding amount of the vulcanization accelerator by containing the above-mentioned thiuram vulcanization accelerator, physical properties such as strength of the rubber composition after vulcanization are improved. There is no decline.

Here, the type of the thiuram-based vulcanization accelerator is not particularly limited, and examples thereof include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetradodecylthiuram disulfide, tetraoctylthiuram disulfide, and tetrabenzylthiuram. Disulfide, dipentamethylenethiuram tetrasulfide, tetrakis (2-ethylhexyl) thiuram disulfide and the like can be mentioned.
Among them, the thiuram vulcanization accelerator is preferably tetrakis (2-ethylhexyl) thiuram disulfide. It is because a better scorch time can be obtained.

  Here, the content of the thiuram vulcanization accelerator is preferably 0.5 to 2.0 parts by mass, and 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the rubber component. And more preferably 0.5 to 1.0 parts by mass. By setting the content of the thiuram vulcanization accelerator to at least 0.5 parts by mass with respect to 100 parts by mass of the rubber component, the strength of the rubber composition after crosslinking can be maintained at a high level, and By setting the amount to 2.0 parts by mass or less with respect to 100 parts by mass of the rubber component, the scorch time can be extended to a more preferable range.

In addition, the rubber composition of the present invention can further contain a vulcanization accelerator other than the above-mentioned thiuram vulcanization accelerator. There is no particular limitation on vulcanization accelerators other than the above-mentioned thiuram vulcanization accelerator, and, for example, thiazole vulcanization accelerators such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide; N-cyclohexyl-2-benzo Sulfenamide-based vulcanization accelerators such as thiazylsulfenamide, N-t-butyl-2-benzothiazylsulfenamide; guanidine-based vulcanization accelerators such as diphenylguanidine; dithiocarbamic acids such as zinc dimethyldithiocarbamate A salt-based vulcanization accelerator; zinc dialkyl dithiophosphate etc. may be mentioned.
When the rubber composition of the present invention contains a vulcanization accelerator other than the above-mentioned thiuram-based vulcanization accelerator, the content of the above-mentioned thiuram-based vulcanization accelerator relative to the content of the above-mentioned thiuram-based vulcanization accelerator is The mass ratio of the content of the vulcanization accelerator (content of the vulcanization accelerator / thiuram vulcanization accelerator other than the thiuram vulcanization accelerator) is preferably 0 to 4.0, and 0 to 1. More preferably, it is 5. By setting the mass ratio of the content of the vulcanization accelerator / thiuram vulcanization accelerator other than the thiuram vulcanization accelerator to 4.0 or less, the scorch time can be extended to a more preferable range. .

(Reinforcing filler)
The rubber composition of the present invention preferably contains a reinforcing filler in addition to the rubber component, the tetrazine compound and the vulcanization accelerator described above.
As a result of an increase in the interaction with the modified rubber component, the reinforcing filler can improve the dispersibility in the rubber composition, and can improve the low loss property and the abrasion resistance of the rubber composition.

  Here, the reinforcing filler may be any reinforcing filler generally used in the rubber field, and examples thereof include carbon black, silica, talc, clay, aluminum hydroxide, titanium oxide and the like.

Further, among the reinforcing fillers described above, it is preferable that at least silica be contained. By the tetradiene compound, the interaction with the rubber component is particularly high, and low loss and abrasion resistance can be achieved at a higher level.
And from the viewpoint of achieving both the loss property and the wear resistance at a higher level, the reinforcing filler more preferably contains carbon black in addition to the silica.

  Furthermore, the ratio of the content (mass) of the silica to the total amount (mass) of the reinforcing filler (content of silica / total amount of reinforcing filler × 100%) is 10 to 100%. Is preferably 50 to 100%. It is because loss property and abrasion resistance can be compatible at a higher level.

In addition, about the said silica, limitation in particular is not carried out. For example, wet silica, colloidal silica, calcium silicate, aluminum silicate and the like can be mentioned.
Among the above, the silica is preferably wet silica, and more preferably precipitated silica. These silicas have high dispersibility and can further improve the low loss and abrasion resistance of the rubber composition. In addition, with precipitated silica, the reaction is allowed to proceed in a relatively high temperature, neutral to alkaline pH range at the initial stage of production to grow primary silica particles, and then control is made to the acidic side to aggregate primary particles. It is the silica obtained as a result of

Here, the CTAB specific surface area (cetyltrimethylammonium bromide adsorption specific surface area) of the silica is preferably 70 m ² / g or more, more preferably 150 m ² / g or more, and 180 m ² / g or more. Is more preferred. The surface area should be as large as possible in order to make the surface of the silica favorable to dispersion, and by setting the CTAB specific surface area to 70 m ² / g or more, better abrasion resistance and low loss can be obtained. This is because the vulcanized viscosity can also be reduced.
In addition, the said CTAB specific surface area means the value measured based on ASTMD3765-92. However, the adsorption cross section per molecule of cetyltrimethylammonium bromide on the silica surface is 0.35 nm ² , and the specific surface area (m ² / g) calculated from the adsorption amount of CTAB is the CTAB specific surface area.

Here, the BET specific surface area of the silica is preferably 150 m ² / g or more, and more preferably 190 m ² / g or more. The surface area should be as large as possible in order to make the surface of the silica advantageous for dispersion, and by setting the BET specific surface area to 150 m ² / g or more, the unvulcanized viscosity can be reduced, and at the same time the abrasion resistance and the low resistance. Loss can be realized.
In addition, the said BET specific surface area is a specific surface area calculated | required by BET method, and it can measure based on ASTMD4820-93 by this invention.

  In addition, the carbon black is not particularly limited. For example, any hard carbon and soft carbon produced by the oil furnace method can be used. Among them, it is preferable to use GPF, FEF, SRF, HAF, ISAF, IISAF, SAF grade carbon black from the viewpoint of achieving more excellent low loss and abrasion resistance.

(Other ingredients)
In addition, the rubber composition of the present invention can contain additives (other components) usually blended in the rubber composition to such an extent that the effects of the invention are not impaired. For example, addition of anti-aging agent, cross-linking agent, vulcanization acceleration auxiliary agent, silane coupling agent, glycerin fatty acid ester, softener, stearic acid, anti-ozonant, surfactant, etc. usually used in the rubber industry An agent can be suitably blended.

  The anti-aging agent may be a known one, and is not particularly limited. For example, a phenolic antioxidant, an imidazole antioxidant, an amine antioxidant etc. can be mentioned. These antiaging agents can be used alone or in combination of two or more.

The crosslinker is also not particularly limited. For example, sulfur, bismaleimide compounds and the like can be mentioned.
As to the type of the bismaleimide compound, for example, N, N′-o-phenylenebismaleimide, N, N′-m-phenylenebismaleimide, N, N′-p-phenylenebismaleimide, N, N ′-( Exemplifies 4,4'-diphenylmethane) bismaleimide, 2,2-bis- [4- (4-maleimidophenoxy) phenyl] propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and the like Can. In the present invention, N, N'-m-phenylenebismaleimide, N, N '-(4,4'-diphenylmethane) bismaleimide and the like can be suitably used.

  Examples of the vulcanization acceleration assistant include zinc white (ZnO) and fatty acids. The fatty acid may be any saturated or unsaturated, linear or branched fatty acid, and the carbon number of the fatty acid is not particularly limited, and is, for example, a fatty acid having 1 to 30 carbon atoms, preferably 15 to 30 carbon atoms, More specifically, naphthenic acids such as cyclohexane acid (cyclohexanecarboxylic acid), alkyl cyclopentane having a side chain; hexanoic acid, octanoic acid, decanoic acid (including branched carboxylic acids such as neodecanoic acid), dodecanoic acid, tetradecane Saturated fatty acids such as acids, hexadecanoic acid and octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid and linolenic acid; resin acids such as rosin, tall oil acid and abietic acid. These may be used singly or in combination of two or more. In the present invention, zinc flower and stearic acid can be suitably used.

  Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-trithiosilyl). Ethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthio Carbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilyl Propyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide , Dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, 3-octanoylthiopropyltriethoxysilane, 3-mercap Propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, γ-gly Cidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3- [ethoxybis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silyl] -1-propanethiol ( Examples include trade name "Si 363" manufactured by Evonik Degussa. In addition, these silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more types.

In the case where the rubber composition of the present invention contains silica as the reinforcing filler, it is preferable that the rubber composition further contains a glycerin fatty acid ester. The processability of the rubber composition is improved, and the rolling resistance of the tire can be further reduced by applying the rubber composition to the tire.
The glycerin fatty acid ester is an ester of glycerin and two or more fatty acids. In addition, glycerine fatty acid ester is a compound which ester bond forms with at least one of three OH groups of glycerol, and the COOH group of a fatty acid.
Here, even if the glycerin fatty acid monoester (monoester component) formed by esterifying one glycerol and one fatty acid molecule, the glycerol fatty acid ester is a glycerin fatty acid diester formed by esterifying one glycerol and two fatty acid molecules ( It may be a diester component) or a glycerol fatty acid triester (triester component) formed by esterifying one molecule of glycerol and three molecules of fatty acid, or a mixture thereof, but a glycerol fatty acid monoester is preferable. In addition, when glycerol fatty acid ester is a mixture of glycerol fatty acid monoester, glycerol fatty acid diester, and glycerol fatty acid triester, the content rate of each ester can be measured by gel permeation chromatography (GPC). Moreover, two fatty acids which comprise glycerol fatty-acid diester, and three fatty acids which comprise glycerol fatty-acid triester may be same or different.
The two or more types of fatty acids (that is, the constituent fatty acids of glycerin fatty acid esters) that are the raw materials of the above glycerin fatty acid esters have 8 to 22 carbon atoms from the viewpoint of processability, low loss property, and destruction characteristics of the rubber composition. Certain fatty acids are preferable, fatty acids having 12 to 18 carbon atoms are more preferable, fatty acids having 14 to 18 carbon atoms are more preferable, and fatty acids having 16 carbon atoms and fatty acids having 18 carbon atoms are more preferable. Further, among the two or more types of fatty acids that are the raw materials of the glycerin fatty acid ester, one of the most abundant fatty acid component and the second most abundant fatty acid component is a C16 fatty acid and the other is a C18 fatty acid More preferable.
When the glycerin fatty acid ester is an ester of glycerin and a fatty acid having 16 carbon atoms and a fatty acid having 18 carbon atoms, the mass ratio of the fatty acid having 16 carbon atoms to the fatty acid having 18 carbon atoms (carbon number 16) The range of 90/10 to 10/90 is preferable, the range of 80/20 to 20/80 is more preferable, and the range of 75/25 to 25/75 is still more preferable. If the mass ratio of the fatty acid having 16 carbon atoms to the fatty acid having 18 carbon atoms is within this range, the processability, the low loss property, and the fracture characteristics of the rubber composition can be further improved.

In addition, the rubber composition of the present invention preferably further includes a softener from the viewpoint of achieving excellent low loss and abrasion resistance. Examples of the softener include naphthenic base oil, paraffinic base oil, and aromatic base oil. Here, the content of the softener is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the rubber component. When the content of the softener exceeds 30 parts by mass with respect to 100 parts by mass of the rubber component, the softener may be exuded to the surface of the rubber product, or the abrasion resistance may be reduced. Moreover, since it interacts with the tetrazine site in the modified rubber component and shields it, the reactivity may be lowered, and the low loss performance and the abrasion resistance may be lowered.
Furthermore, among the above-mentioned softeners, it is preferable to use naphthene base oil or paraffin base oil, and it is most preferable to use naphthene base oil. Aroma oil has a large amount of aromatic components, so it has high affinity with the drug which is an aromatic compound and is not preferable because it further inhibits the reaction with the polymer. On the other hand, naphthenic base oil and paraffinic base oil have an effect of helping to diffuse and react in the polymer, and an oil having a low pour point diffuses in the polymer better.
The classification of the naphthenic base oil, the paraffinic base oil and the aromatic base oil is determined by the CA value, the CP value and the CN value. For example, the naphthenic base oil may be classified into TDAE, SRAE, RAE, Black Oil, and the like. In addition, spindle oil and paraffin oil are classified as the paraffin base oil.
Furthermore, a more preferable effect can be obtained even with a mixed oil such as A / O Mix (Sanko Yuka Kogyo Co., Ltd.) in which the naphthenic base oil and the naphthenic asphalt are mixed.
There is no particular limitation on the timing of blending these lubricating oils, and for example, it may be oil-extended at the stage of production of the rubber component, or may be added at the time of kneading the rubber composition.

<Method of producing rubber composition>
Next, the method for producing a rubber composition of the present invention will be described.
The method for producing a rubber composition according to the present invention comprises the step of kneading compounding components including a rubber component containing a diene rubber, a reinforcing filler, a tetrazine compound and a thiuram vulcanization accelerator. It is characterized by

It is possible to improve the dispersibility of the reinforcing filler and to obtain a rubber composition excellent in low loss property by blending the tetrazine compound as the blending component and kneading together with the rubber component and the reinforcing filler. it can.
Further, by blending the thiuram vulcanization accelerator as the blending component, it is possible to keep the scorch time long even when the tetrazine compound is included to improve the low loss property. The present invention has been completed.

In the method for producing a rubber composition according to the present invention, a preliminary masterbatch is formed by kneading at least a part of the rubber component and the tetrazine compound prior to kneading with at least the silica in the reinforcing filler. It is preferred to make With regard to the tetrazine-based compound, the state of being incorporated in the rubber component is suitable for enhancing the interaction with the reinforcing filler, and low loss and low loss can be obtained by preparing the preliminary masterbatch in advance. A rubber composition having more excellent wear resistance can be produced.
Here, the preliminary masterbatch may include at least the rubber component and the tetrazine compound, but the vulcanization accelerator, the reinforcing filler other than the silica, and the other components are components other than the silica. Additives can also be blended into the pre-masterbatch and incorporated.

  Furthermore, about the rubber component used for preparation of the said preliminary masterbatch, it is preferable that it is 10 mass% or more of the said rubber components, It is more preferable that it is 20 mass% or more, It is 100 mass% that Most preferred. A rubber composition which is suitable for enhancing the interaction with the reinforcing filler and is more excellent in low loss property and wear resistance can be produced.

  In addition, about the said compounding component, it is the same as the component (A rubber component, a tetrazine type-compound, a vulcanization accelerator, a reinforcing filler, and other components) described in description of the rubber composition mentioned above.

<Tire>
The tire of the present invention is characterized by using the above-mentioned rubber composition of the present invention. By including the rubber composition of the present invention as a tire material, the abrasion resistance can be improved.
The tire of the present invention is not particularly limited except that the above-described rubber composition of the present invention is used for any of tire members, and can be manufactured according to a conventional method. In addition, as a gas with which the tire is filled, an inert gas such as nitrogen, argon, helium or the like can be used in addition to a normal air or air whose oxygen partial pressure is adjusted.

  Moreover, in the tire of the present invention, although the rubber composition of the present invention described above is used for any tire member, among the tire members, tread rubber, sidewall rubber, cord or fiber-coated rubber, bead filler or gum chafer It is preferably used in If applied to these members, it is possible to fully enjoy the benefits of the excellent low loss property of the rubber composition of the present invention.

  The type of the tire according to the present invention is not particularly limited, but from the viewpoint of being able to more effectively exhibit both the improvement of the wear resistance and the reduction of the rolling resistance, tires for passenger cars, studless tires, run flat tires Or it is preferable that it is a tire for truck and bus.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

(Samples 1 to 4)
The blended components were kneaded using a blast mill to prepare samples of rubber compositions formulated as shown in Table 1. In addition, about kneading of a compounding component, all the compounding components were collectively knead | mixed, without preparing a preliminary | backup masterbatch previously.
The following evaluation was performed about the rubber composition of each obtained sample.

(1) tan δ (low loss property)
The rubber composition of each sample is vulcanized at 145 ° C. for 33 minutes to form a vulcanized rubber, and a temperature of 50 ° C. is obtained for the obtained vulcanized rubber using a spectrophotometer (manufactured by Ueshima Seisakusho Co., Ltd.) The loss tangent (tan δ) was measured under the conditions of an initial distortion of 5% and a frequency of 15 Hz.
About evaluation, it shows with an index when tandelta of sample 1 which is a comparative example is set to 100, and it shows that it is excellent in low exothermic nature, so that an index value is small. The evaluation results are shown in Table 1.

(2) M300 (strength)
The rubber composition of each sample was vulcanized at 145 ° C. for 33 minutes to form a vulcanized rubber, and the obtained vulcanized rubber was M300 at 300% elongation according to JIS K6251 (2010). Tensile stress (MPa) was measured.
About evaluation, it showed as an index when the measured value of M300 of the sample 1 which is a comparative example is set to 100. The larger the index value, the larger the tensile stress and the better the strength. The evaluation results are shown in Table 1.

(3) Scorch time The rubber composition of each sample is measured at 130 ° C. in accordance with JIS K 6300-1 (2001) “How to determine viscosity and scorch time with a Mooney viscometer”. The Mooney Scorch time was obtained by measuring the time (minutes) until the value from the start of the residual heat rises 5 units above the lowest value Vm.
About evaluation, the value of the Mooney Scorch time of sample 1 which is a comparative example is displayed as an index value when it is 100. As for index values, larger values indicate longer scorch times and better productivity.

＊６ 大内新興化学工業株式会社製 「ノクセラー ＣＺ−Ｇ」
＊７ 大内新興化学工業株式会社製 「ノクセラー Ｄ」
＊８ 大内新興化学工業株式会社製 「ノクセラーＴＯＴ−Ｎ」 * 1 Solution-polymerized butadiene rubber, manufactured by JSR Corporation, “JSR BR01”
* 2 “Nip seal AQ” manufactured by Tosoh Silica Corporation, BET surface area 205 m ² / g
* 3 Bis (3-triethoxysilylpropyl) disulfide, Evonik “Si75” (registered trademark), average sulfur chain length: 2.35
* 4 N- (1,3-Dimethylbutyl) -N'-phenyl-p-phenylenediamine, manufactured by Ouchi Shinko Chemical Co., Ltd. "NOCLAK 6C"
* 5 3,6-Bis (2-pyridyl) -1,2,4,5-tetrazine

* 6 "Noccellar CZ-G" manufactured by Ouchi Shinko Chemical Co., Ltd.
* 7 "Nocceler D" manufactured by Ouchi Shinko Chemical Co., Ltd.
* 8 "Noccellar TOT-N" manufactured by Ouchi Shinko Chemical Co., Ltd.

From the results of Table 1, it was found that each sample of the inventive example shows well-balanced excellent results in any of low loss property, strength and scorch time, as compared with each sample of the comparative example.
On the other hand, Sample 1 not containing the tetrazine compound is inferior to the sample of the Example in the point of low loss property and strength, and Sample 2 not containing the thiuram vulcanization accelerator is compared with the sample of the Example The scorch time was short, and it turned out that productivity is inferior.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the rubber composition which can obtain the rubber composition excellent in low loss property, and this rubber composition can be provided, without reducing other physical properties, such as scorch time. . Further, according to the present invention, it is possible to provide a tire in which rolling resistance can be simultaneously reduced.

Claims (18)

  A rubber composition comprising a rubber component containing a diene rubber, a tetrazine compound and a thiuram vulcanization accelerator.   The rubber composition according to claim 1, further comprising a reinforcing filler.   The rubber composition according to claim 1 or 2, wherein the diene rubber contains butadiene rubber and / or styrene butadiene rubber.   The rubber composition according to claim 3, wherein the diene rubber further contains natural rubber and isoprene rubber.   The rubber composition according to any one of claims 1 to 4, wherein the diene rubber contains a modified diene rubber.   The rubber composition according to claim 2, wherein the reinforcing filler comprises silica.   The rubber composition according to claim 6, wherein the reinforcing filler further comprises carbon black.   The rubber composition according to any one of claims 1 to 7, wherein the thiuram vulcanization accelerator is tetrakis (2-ethylhexyl) thiuram disulfide.   Mass ratio of the content of the vulcanization accelerator other than the thiuram vulcanization accelerator relative to the content of the thiuram vulcanization accelerator (the vulcanization accelerator other than the thiuram vulcanization accelerator / the thiuram vulcanization accelerator The rubber composition according to any one of claims 1 to 8, wherein the content of (A) is 0 to 1.5.   The rubber composition according to any one of claims 1 to 9, wherein the content of the tetrazine compound is 0.1 to 5 parts by mass with respect to 100 parts by mass of the rubber component. .   The rubber composition according to any one of claims 1 to 10, wherein the tetrazine compound has at least one element selected from N, O and F as a substituent in a tetrazine structure. .   The tetrazine compound is selected from 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine and 3,6-bis (4-pyridyl) -1,2,4,5-tetrazine The rubber composition according to claim 11, characterized in that it is at least one of   A method for producing a rubber composition, comprising the step of kneading a compounding component containing a rubber component containing a diene rubber, a reinforcing filler, a tetrazine compound and a thiuram vulcanization accelerator. .   A preliminary masterbatch is prepared by kneading at least a part of the rubber component and the tetrazine compound prior to kneading with the silica contained in at least the reinforcing filler. The manufacturing method of the rubber composition as described in 13.   The method for producing a rubber composition according to claim 14, wherein the rubber component used for producing the preliminary masterbatch is 10% by mass or more of the rubber component.   A tire comprising the rubber composition according to any one of claims 1 to 12.   The tire according to claim 16, wherein the rubber composition is used for tread rubber, side rubber, side reinforcing rubber, cord-coated rubber, bead filler or gum chafer. The tire according to claim 16 or 17, wherein the tire is a passenger car tire, a studless tire, a run flat tire or a truck / bus tire.