JP6701434B2 - Rubber composition and tire - Google Patents

Description

  The present invention relates to a rubber composition and a tire.

  In recent years, due to environmental considerations, carbon dioxide emission regulations have become strict worldwide, and demands for low fuel consumption of automobiles have increased significantly. Fuel efficiency is greatly contributed by the efficiency of the drive system and transmission system of the engine, etc., but the rolling resistance of tires is also greatly involved, and it is important to reduce the rolling resistance to reduce fuel consumption of automobiles. . Further, in heavy-duty tires for large automobiles such as trucks and buses, it is necessary not only to have low rolling resistance but also to have wear resistance.

  As a method of reducing the rolling resistance of a tire, it is known to apply a rubber composition having low heat generation to the tire. Examples of such a low exothermic rubber composition include, for example, (1) a rubber composition containing a functionalized polymer having an increased affinity for filler carbon black and silica (Patent Document 1); ) A rubber composition containing a diene elastomer, an inorganic filler as a reinforcing filler, a polysulfide alkoxysilane as a coupling agent, 1,2-dihydropyridine, and a guanidine derivative (Patent Document 2); (3) Rubber component, aminopyridine derivative And a rubber composition containing an inorganic filler (Patent Document 3); and (4) a rubber composition containing a terminal-modified polymer and an inorganic filler (Patent Documents 4 and 5).

  According to the inventions described in these Patent Documents 1 to 5, by increasing the affinity between the filler and the rubber component, the exothermic property of the rubber composition can be reduced, and as a result, the hysteresis loss (rolling A tire with low resistance) can be obtained.

  However, even if these rubber compositions of Patent Documents 1 to 5 are used, the improvement in low heat buildup was insufficient. Further, it is unavoidable that the wear resistance is lowered by improving the low heat buildup of the rubber composition.

  The demand for low fuel consumption of automobiles is further increasing, and there is a strong demand for the development of tires having extremely low heat generation.

Japanese Patent Laid-Open No. 2003-514079 Japanese special table 2003-523472 gazette Japanese Patent Laid-Open No. 2013-108004 Japanese Patent Laid-Open No. 2000-169631 Japanese Patent Laid-Open No. 2005-220323

  An object of the present invention is to provide a rubber composition which is excellent in wear resistance and low heat build-up and is suitable for manufacturing a heavy-duty tire for a large automobile.

  Another object of the present invention is to provide a tire having excellent wear resistance and low heat buildup.

  The present inventors have conducted extensive studies in order to solve the above problems, the rubber component containing natural rubber, and the rubber composition containing a tetrazine compound, by adding a specific amount of carbon black, We found that we could solve the problem. The present inventors have completed the present invention as a result of further studies based on such findings.

The present invention provides the following rubber composition, tire, and the like.
Item 1.
Rubber component, the following general formula (1):

[In the formula, X ¹ and X ² represent a heterocyclic group which may have a substituent. ]
A tetrazine compound represented by or a salt thereof, and a rubber composition containing carbon black,
40 parts by mass or more of natural rubber is contained in 100 parts by mass of the rubber component,
0.1 to 10 parts by mass of the tetrazine compound or a salt thereof and 30 to 120 parts by mass of carbon black with respect to 100 parts by mass of a rubber component,
Rubber composition.
Item 2.
Item ^2. The rubber composition according to Item 1, wherein the nitrogen adsorption specific surface area of carbon black is 50 to 160 m ² /g.
Item 3.
The rubber composition according to Item 1 or 2, further containing an inorganic filler.
Item 4.
Item 4. The rubber composition according to Item 3, wherein the inorganic filler is silica.
Item 5.
Item 5. The rubber composition according to Item 4, wherein the silica is wet silica having a BET specific surface area (m ² /g) of 40 to 350.
Item 6.
Item 6. The rubber composition according to any one of Items 3 to 5, wherein the compounding amount of the inorganic filler is 20 to 150 parts by mass with respect to 100 parts by mass of the rubber composition.
Item 7.
Item 7. The rubber composition according to any one of items 1 to 6, which is used for the tread portion.
Item 8.
Item 9. A tread for tire produced using the rubber composition according to any one of items 1 to 6.
Item 9.
A pneumatic tire using the tire tread according to item 8.
Item 10.
Item 10. The tire according to Item 9, which is used as a heavy-duty tire for large vehicles.

  According to the present invention, by combining a specific rubber component with a tetrazine compound represented by the general formula (1) or a salt thereof and carbon black, not only the tire has excellent low heat buildup but also excellent wear resistance. It is possible to provide a rubber composition capable of imparting

  Further, by producing a tire using the rubber composition of the present invention, it is possible to reduce the rolling resistance of the tire, reduce the heat generation of the tire, and improve the wear resistance, therefore, for large automobiles. It is possible to provide low fuel consumption tires.

  The present invention will be described in detail below.

1. Rubber composition The present invention relates to a rubber component, the following general formula (1):

[In the formula, X ¹ and X ² represent a heterocyclic group which may have a substituent. ]
A rubber composition containing a tetrazine compound represented by or a salt thereof (hereinafter, also referred to as “tetrazine compound (1)”) and carbon black,
40 parts by mass or more of natural rubber is contained in 100 parts by mass of the rubber component,
0.1 to 10 parts by mass of the tetrazine compound or a salt thereof and 30 to 120 parts by mass of carbon black with respect to 100 parts by mass of a rubber component,
It is a rubber composition.

Rubber Component The rubber component to be blended in the rubber composition of the present invention is not particularly limited, and examples thereof include diene rubbers such as natural rubber (NR), synthetic diene rubber, and a mixture of natural rubber and synthetic diene rubber. Examples of the rubber include non-diene rubbers other than these.

  Examples of natural rubber include natural rubber latex, technically graded rubber (TSR), smoked sheet (RSS), gutta percha, natural rubber derived from Tochu, natural rubber derived from guayule, natural rubber derived from dandelion, fermented rubber derived from plant components, and the like. In addition, modified natural rubber such as epoxidized natural rubber, methacrylic acid modified natural rubber, and styrene modified natural rubber can be used.

  As the synthetic diene rubber, styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), nitrile rubber (acrylonitrile-butadiene copolymer rubber) (NBR), chloroprene rubber (CR) Ethylene-propylene-diene terpolymer rubber (EPDM), styrene-isoprene-styrene terpolymer (SIS), styrene-butadiene-styrene terpolymer (SBS), and the like. Examples include modified synthetic diene rubber. Examples of the modified synthetic diene rubber include a diene rubber obtained by a modification method such as main chain modification, one-end modification, and both-end modification. Here, the modified functional group of the modified synthetic diene rubber includes at least one kind of functional group containing a hetero atom such as epoxy group, amino group, alkoxy group, hydroxyl group, alkoxysilyl group, polyether group, and carboxyl group. There are things. Further, the ratio of cis/trans/vinyl in the diene moiety is not particularly limited, and any ratio can be preferably used. The average molecular weight and molecular weight distribution of the diene rubber are not particularly limited, and the average molecular weight of 5 to 3,000,000 can be preferably used. Also, the method for producing the synthetic diene rubber is not particularly limited, and examples thereof include those synthesized by emulsion polymerization, solution polymerization, radical polymerization, anion polymerization, cation polymerization and the like.

  Regarding the glass transition point of the diene rubber, a glass transition point in the range of −120° C. to −15° C. is effective from the viewpoint of achieving both wear resistance and rolling resistance. In the rubber composition of the present invention, 50% by mass or more of the diene rubber is preferably a diene rubber having a glass transition point in the range of -70°C to -20°C.

  A wide variety of known non-diene rubbers can be used.

  From the viewpoint of abrasion resistance, it is essential that the rubber component used in the rubber composition of the present invention contains natural rubber. Specifically, 40 parts by mass or more of natural rubber is preferably contained in 100 parts by mass of the rubber component, and more preferably 60 parts by mass or more.

  The rubber component may be used singly or as a mixture (blend) of two or more. Among them, the preferred rubber component is natural rubber, IR, SBR, BR or a mixture of two or more selected from these, and more preferably natural rubber, SBR, BR or a mixture of two or more selected from these. .. The blending ratio of these is not particularly limited, but it is preferable to mix SBR, BR or a mixture thereof in a ratio of 60 parts by mass or less, and 40 parts by mass or less in 100 parts by mass of the rubber component. Is more preferable. When blending a mixture of SBR and BR, the total amount of SBR and BR is preferably within the above range. The SBR at this time is preferably 50 to 100 parts by mass, and the BR is preferably in the range of 0 to 50 parts by mass.

Tetrazine compound (1)
The rubber composition of the present invention contains a compound represented by the following general formula (1) or a salt thereof.
General formula 1:

[In the formula, X ¹ and X ² represent a heterocyclic group which may have a substituent. ]

  In the present specification, the "heterocyclic group" is not particularly limited, and includes, for example, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group, 3-pyridazyl group, 4-pyridazyl group, 4-(1,2,3-triazyl) group, 5-(1,2,3-triazyl) group, 2-(1,3,5- Triazyl) group, 3-(1,2,4-triazyl) group, 5-(1,2,4-triazyl) group, 6-(1,2,4-triazyl) group, 2-quinolyl group, 3- Quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6- Isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalyl group, 3-quinoxalyl group, 5-quinoxalyl group, 6-quinoxalyl group, 7-quinoxalyl group, 8-quinoxalyl group, 3-cinnolyl group, 4- Cinnolyl group, 5-cinnolyl group, 6-cinnolyl group, 7-cinnolyl group, 8-cinnolyl group, 2-quinazolyl group, 4-quinazolyl group, 5-quinazolyl group, 6-quinazolyl group, 7-quinazolyl group, 8- Quinazolyl group, 1-phthalazyl group, 4-phthalazyl group, 5-phthalazyl group, 6-phthalazyl group, 7-phthalazyl group, 8-phthalazyl group, 1-tetrahydroquinolyl group, 2-tetrahydroquinolyl group, 3-tetrahydro Quinolyl group, 4-tetrahydroquinolyl group, 5-tetrahydroquinolyl group, 6-tetrahydroquinolyl group, 7-tetrahydroquinolyl group, 8-tetrahydroquinolyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3 -Pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 1-imidazolyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 1-pyrazolyl group, 3 -Pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isoxazolyl group, 4 -Isoxazolyl group, 5-isoxazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 4-(1,2,3-thiadiazolyl) group, 5-(1,2,3-thiadiazolyl) group, 3-(1,2,5-thiadiazolyl) group, 2-(1,3,4-thiadiazolyl) Group), 4-(1,2,3-oxadiazolyl) group, 5-(1,2,3-oxadiazolyl) group, 3-(1,2,4-oxadiazolyl) group, 5-(1,2,2) 4-oxadiazolyl) group, 3-(1,2,5-oxadiazolyl) group, 2-(1,3,4-oxadiazolyl) group, 1-(1,2,3-triazolyl) group, 4-(1, 2,3-triazolyl) group, 5-(1,2,3-triazolyl) group, 1-(1,2,4-triazolyl) group, 3-(1,2,4-triazolyl) group, 5-( 1,2,4-triazolyl) group, 1-tetrazolyl group, 5-tetrazolyl group, 1-indolyl, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7 -Indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 1-benzimidazolyl group, 2-benzimidazolyl group, 4 -Benzimidazolyl group, 5-benzimidazolyl group, 6-benzimidazolyl group, 7-benzimidazolyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1 -Isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofurnyl group, 2-benzothienyl group, 3-benzothienyl group, 4-benzothienyl group, 5-benzothienyl group, 6-benzothienyl group, 7-benzothienyl group, 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzoxa Zolyl group, 6-benzoxazolyl group, 7-benzoxazolyl group, 2-benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 1-indazolyl group, 3-indazolyl group, 4-indazolyl group, 5-indazolyl group, 6-indazolyl group, 7-indazolyl group, 2-morpholyl group, 3-morpholyl group, 4-morpholyl group, 1-piperazyl group, 2-piperazyl group, 1-piperidyl group, 2-piperidyl group, 3-piperidyl group, 4-piperidyl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-tetrahydrothiopyranyl group Group, 3-tetrahydrothiopyranyl group, 4-tetrahydrothiopyranyl group, 1-pyrrolidyl group, 2-pyrrolidyl group, 3-pyrrolidyl group, 2-tetrahydrofuranyl group, 3-tetrahydrofuranyl group, 2-tetrahydrothienyl group , 3-tetrahydrothienyl group and the like. Among them, the preferable heterocyclic group is a pyridyl group, a furanyl group, a thienyl group, a pyrimidyl group or a pyrazyl group, and a pyridyl group is more preferable.

  The heterocyclic group may have one or more substituents at substitutable positions. The substituent is not particularly limited, and examples thereof include a halogen atom, amino group, aminoalkyl group, alkoxycarbonyl group, acyl group, acyloxy group, amide group, carboxyl group, carboxyalkyl group, formyl group, nitrile group, nitro group. Examples thereof include a group, an alkyl group, a hydroxyalkyl group, a hydroxyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a thiol group, an alkylthio group and an arylthio group. The substituent may have preferably 1 to 5, more preferably 1 to 3.

  In the present specification, examples of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom and an iodine atom.

In the present specification, the “amino group” includes not only an amino group represented by —NH ₂ but also, for example, a methylamino group, an ethylamino group, an n-propylamino group, an isopropylamino group, an n-butylamino group. , Isobutylamino group, s-butylamino group, t-butylamino group, 1-ethylpropylamino group, n-pentylamino group, neopentylamino group, n-hexylamino group, isohexylamino group, 3-methylpentyl group A linear or branched monoalkylamino group having 1 to 6 carbon atoms (particularly, 1 to 4 carbon atoms) such as amino group; 1 to 6 carbon atoms such as dimethylamino group, ethylmethylamino group, diethylamino group (particularly Substituted amino groups such as dialkylamino groups having two linear or branched alkyl groups having 1 to 4 carbon atoms are also included.

  In the present specification, the "aminoalkyl group" is not particularly limited, and examples thereof include aminoalkyl groups such as aminomethyl group, 2-aminoethyl group, 3-aminopropyl group (preferably having an amino group having 1 carbon atom). ~6 straight-chain or branched alkyl groups).

  In the present specification, the "alkoxycarbonyl group" is not particularly limited, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.

  In the present specification, the “acyl group” is not particularly limited and includes, for example, a linear or branched alkylcarbonyl group having 1 to 4 carbon atoms such as acetyl group, propionyl group, pivaloyl group and the like.

  In the present specification, the "acyloxy group" is not particularly limited, and examples thereof include an acetyloxy group, a propionyloxy group, an n-butyryloxy group and the like.

  In the present specification, the "amide group" is not particularly limited, and examples thereof include carboxylic acid amide groups such as acetamide group and benzamide group; thioamide groups such as thioacetamide group and thiobenzamide group; N-methylacetamide group, N -N-substituted amide group such as benzylacetamide group; and the like.

  In the present specification, the "carboxyalkyl group" is not particularly limited, and includes, for example, carboxymethyl group, carboxyethyl group, carboxy-n-propyl group, carboxy-n-butyl group, carboxy-n-pentyl group, carboxy. Examples thereof include a carboxy-alkyl group such as an -n-hexyl group (preferably an alkyl group having a carboxy group and having 1 to 6 carbon atoms).

  In the present specification, the “hydroxyalkyl group” is not particularly limited, and examples thereof include hydroxymethyl groups, hydroxyethyl groups, hydroxy-n-propyl groups, hydroxy-n-butyl groups, and other hydroxy-alkyl groups (preferably And an alkyl group having 1 to 6 carbon atoms having a hydroxy group).

  In the present specification, the “alkyl group” is not particularly limited and includes, for example, a linear, branched or cyclic alkyl group, and specifically, for example, methyl group, ethyl group, n-propyl group. Group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, n-pentyl group, neopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group A linear or branched alkyl group having 1 to 6 carbon atoms (especially 1 to 4 carbon atoms); a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like having a carbon number of 3 to Examples thereof include a cyclic alkyl group having 8 (particularly 3 to 6 carbon atoms).

  In the present specification, the “hydroxyalkyl group” is not particularly limited, and examples thereof include hydroxymethyl groups, hydroxyethyl groups, hydroxy-n-propyl groups, hydroxy-n-butyl groups, and other hydroxy-alkyl groups (preferably And an alkyl group having 1 to 6 carbon atoms having a hydroxy group).

  In the present specification, the “alkoxy group” is not particularly limited and includes, for example, a linear, branched or cyclic alkoxy group, and specifically, for example, methoxy, ethoxy group, n-propoxy group. , Isopropoxy group, n-butoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group having 1 to 6 carbon atoms (especially 1 to 4 carbon atoms), or A branched alkoxy group; a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, and the like, having 3 to 8 carbon atoms (in particular, 3 to 6 carbon atoms) An alkoxy group etc. are mentioned.

  In the present specification, the "aryl group" is not particularly limited, and examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a dihydroindenyl group, a 9H-fluorenyl group and the like.

  In the present specification, the “aryloxy group” is not particularly limited, and examples thereof include a phenoxy group, a biphenyloxy group and a naphthoxy group.

  In the present specification, the “alkylthio group” is not particularly limited and includes, for example, a linear, branched or cyclic alkylthio group, and specifically, for example, methylthio group, ethylthio group, n-propylthio group. Group, isopropylthio group, n-butylthio group, isobutylthio group, s-butylthio group, t-butylthio group, 1-ethylpropylthio group, n-pentylthio group, neopentylthio group, n-hexylthio group, isohexylthio group Group, a linear or branched alkylthio group having 1 to 6 carbon atoms (in particular, 1 to 4 carbon atoms) such as 3-methylpentylthio group; cyclopropylthio group, cyclobutylthio group, cyclopentylthio group, cyclohexylthio group And a cyclic alkylthio group having 3 to 8 carbon atoms (in particular, 3 to 6 carbon atoms) such as a group, a cycloheptylthio group and a cyclooctylthio group.

  In the present specification, the “arylthio group” is not particularly limited, and examples thereof include a phenylthio group, a biphenylthio group, a naphthylthio group and the like.

  The “salt” of the tetrazine compound represented by the general formula (1) is not particularly limited and includes all kinds of salts. Examples of such salts include inorganic acid salts such as hydrochloride, sulfate and nitrate; organic acid salts such as acetate and methanesulfonate; alkali metal salts such as sodium salt and potassium salt; magnesium salt, calcium Examples thereof include alkaline earth metal salts such as salts; ammonium salts such as dimethylammonium and triethylammonium.

In the preferable tetrazine compound (1), X ¹ and X ² are the same or different and each have a pyridyl group which may have a substituent, a furanyl group which may have a substituent, and a substituent. The compound is a thienyl group which may be substituted, a pyrazolyl group which may be substituted, a pyrimidyl group which may be substituted, or a pyrazyl group which may be substituted.

In a more preferred tetrazine compound (1), X ¹ and X ² are the same or different and may have a 2-pyridyl group which may have a substituent, a 3-pyridyl group which may have a substituent, or a substituent. 4-pyridyl group which may have a group, 2-furanyl group which may have a substituent, 2-thienyl group which may have a substituent, and which may have a substituent A compound which is a 1-pyrazolyl group, a 2-pyrimidyl group which may have a substituent, or a 2-pyrazyl group which may have a substituent, and specifically has a substituent. Optionally 2-pyridyl group, 3-pyridyl group optionally having substituents, 4-pyridyl group optionally having substituents, or 2-furanyl group optionally having substituents Particularly preferred are the compounds

Specific examples of the tetrazine compound (1) include:
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-bis(2-furanyl)-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(2-pyrimidinyl)-1,2,4,5-tetrazine,
3,6-bis(2-pyrazyl)-1,2,4,5-tetrazine and the like can be mentioned.

  Among them, preferred tetrazine compounds (1) are 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine and 3,6-bis(3-pyridyl)-1,2,4,5-tetrazine. Tetrazine, 3,6-bis(2-furanyl)-1,2,4,5-tetrazine, and 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, and more preferable tetrazine. The compound (1) includes 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, 3,6-bis(3-pyridyl)-1,2,4,5-tetrazine, and 3 , 6-bis(4-pyridyl)-1,2,4,5-tetrazine.

  From the viewpoint of imparting low rolling resistance to the rubber component, the compounding amount of the tetrazine compound (1) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component in the rubber composition. The preferred blending amount of the tetrazine compound (1) is 0.25 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the rubber component in the rubber composition.

  When the tetrazine compound (1) is a powder, its volume average diameter is not particularly limited. From the viewpoint of low heat buildup, the volume average diameter is preferably 300 μm or less, more preferably 150 μm or less, and particularly preferably 75 μm or less.

  The volume average diameter can be obtained as a particle diameter corresponding to 50% of the cumulative distribution curve from the volume standard particle size distribution by using a particle size distribution measuring device such as a laser beam diffraction method.

  Further, from the viewpoint of handling property during handling and risk of ignitability or explosiveness reduction, powder may be surface-treated with oil, resin, stearic acid or the like, or powder may be used such as calcium carbonate or silica. You may use it, mixing with the filler etc. of.

Carbon Black Carbon black is compounded in the rubber composition of the present invention. By including carbon black in the rubber composition of the present invention, abrasion resistance can be improved.

  The carbon black is not particularly limited, and examples thereof include commercially available carbon black and Carbon-Silica Dual phase filler.

  Specifically, examples of the carbon black include high, medium or low structure SAF, ISAF, IISAF, N110, N134, N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, and SRF grade carbon. Examples include black. Among them, preferable carbon black is SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF, or FEF grade carbon black.

The nitrogen adsorption specific surface area of carbon black (measured according to N2SA, JIS K 6217-2:2001) is preferably 50 to 160 m ² /g. The nitrogen adsorption specific surface area of carbon black is more preferably 60 to 140 m ² /g, further preferably 80 to 135 m ² /g.

The DBP absorption amount of carbon black is not particularly limited and is preferably 60 to 200 cm ³ /100 g, more preferably 70 to 180 cm ³ /100 g or more, and particularly preferably 80 to 160 cm ³ /100 g.

  By blending the tetrazine compound (1) in the rubber composition containing carbon black, the dispersibility of the carbon black is significantly improved, and the low heat buildup of the rubber composition can be significantly improved.

  30 to 120 parts by mass of carbon black is blended with 100 parts by mass of the rubber component. The blending amount of carbon black is preferably 35 to 80 parts by mass, and more preferably 40 to 70 parts by mass with respect to 100 parts by mass of the rubber component.

  The rubber composition of the present invention preferably further contains an inorganic filler in addition to the rubber component, the tetrazine compound (1), and carbon black.

  The compounding amount of the inorganic filler is usually 0 to 100 parts by mass, preferably 0 to 60 parts by mass, and more preferably 0 to 40 parts by mass with respect to 100 parts by mass of the rubber component.

  In the rubber composition of the present invention, the total amount of both carbon black and the inorganic filler is, for example, 30 to 150 parts by mass, preferably 35 to 130 parts by mass, relative to 100 parts by mass of the rubber component. However, more preferably, it may be appropriately adjusted within the above-mentioned blending amount range of each component so as to be 40 to 100 parts by mass.

  If the total amount of carbon black and the inorganic filler is 30 parts by mass or more, it is preferable from the viewpoint of improving the wear resistance of the rubber composition, and if it is 150 parts by mass or less, it is preferable from the viewpoint of reducing rolling resistance. When blending the carbon black and the inorganic filler, a masterbatch polymer preliminarily mixed with the polymer in a wet or dry manner may be used.

Inorganic Filler The inorganic filler is not particularly limited as long as it is an inorganic compound that is usually used in the rubber industry. Examples of inorganic compounds that can be used include alumina (Al ₂ O ₃ ) such as silica, γ-alumina, and α-alumina; alumina monohydrate (Al ₂ O ₃ .H ₂ O) such as boehmite and diaspore; gibbsite. , Aluminum hydroxide [Al(OH) ₃ ] such as bayerite; aluminum carbonate [Al ₂ (CO ₃ ) ₃ ], magnesium hydroxide [Mg(OH) ₂ ], magnesium oxide (MgO), magnesium carbonate (MgCO ₃ ). ), talc _{(3MgO · 4SiO 2 · H 2} O), attapulgite _{(5MgO · 8SiO 2 · 9H 2} O), titanium white _(TiO 2), titanium black _{(TiO 2n-1),} calcium oxide (CaO), hydroxide Calcium [Ca(OH) ₂ ], aluminum magnesium oxide (MgO·Al ₂ O ₃ ), clay (Al ₂ O ₃ ·2SiO ₂ ), kaolin (Al ₂ O ₃ ·2SiO ₂ ·2H ₂ O), pyrophyllite _{(Al 2 O 3 · 4SiO 2} · H 2 O), bentonite _{(Al 2 O 3 · 4SiO 2} · 2H 2 O), aluminum silicate _{(Al 2 SiO 5, Al 4} · 3SiO 4 · 5H 2 O , etc.), Magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ etc.), calcium silicate (Ca ₂ ·SiO ₄ etc.), aluminum calcium silicate (Al ₂ O ₃ ·CaO·2SiO ₂ etc.), magnesium calcium silicate (CaMgSiO _{4 ).} ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), zirconium hydroxide [ZrO(OH) ₂ ·nH ₂ O], zirconium carbonate [Zr(CO ₃ ) ₂ ], and various zeolites to correct the charge. And a crystalline aluminosilicate containing an alkali metal or an alkaline earth metal. In these inorganic fillers, the surface of the inorganic filler may be organically treated in order to improve the affinity with the rubber component.

  Silica is preferably added because it can impart rubber strength. Any commercially available silica can be used. Among them, preferable silica is wet silica, dry silica, or colloidal silica, more preferably wet silica. The surface of the inorganic filler of these silicas may be organically treated in order to improve the affinity with the rubber component.

Among them, silica is preferable as the inorganic filler from the viewpoint of wear resistance. The BET specific surface area of silica is not particularly limited, and examples thereof include a range of 40 to 350 m ² /g. Silica having a BET specific surface area within this range is advantageous in that it can achieve both rubber-reinforcing properties and dispersibility in rubber components. The BET specific surface area is measured according to ISO 5794/1.

From this viewpoint, preferred silica is a silica having a BET specific surface area of 50 to 250 m ² /g, more preferably a silica having a BET specific surface area of 100 to 230 m ² /g, and particularly preferably. , BET specific surface area is in the range of 110 to 210 m ² /g.

As commercial products of such silica, trade names “HD165MP” (BET specific surface area =165 m ² /g), “HD115MP” (BET specific surface area =115 m ² /g) manufactured by Quechen Silicon Chemical Co., Ltd., "HD200MP" (BET specific surface area = 200 m ² /g), "HD250MP" (BET specific surface area = 250 m ² /g), trade name "Nipseal AQ" manufactured by Tosoh Silica Corporation (BET specific surface area = 205 m ² /g) ), "Nipseal KQ" (BET specific surface area = 240 m ² /g), trade name "Ultrasil VN3" manufactured by Degussa (BET specific surface area = 175 m ² /g), trade name "Z1085Gr" manufactured by Solvay (BET). Specific surface area=90 m ² /g), “Z Premium 200MP” (BET specific surface area=215 m ² /g), “Z HRS 1200 MP” (BET specific surface area=200 m ² /g) and the like.

  The amount of silica to be added is usually 20 to 120 parts by mass, preferably 30 to 100 parts by mass, and more preferably 40 to 90 parts by mass with respect to 100 parts by mass of the rubber component.

Other compounding agents In addition to the tetrazine compound (1), carbon black, and the inorganic filler, the rubber composition of the present invention may further contain compounding agents commonly used in the rubber industry, such as sulfur. A sulfurizing agent can be added. The rubber composition of the present invention further includes other compounding agents such as antiaging agent, antiozonant, softening agent, processing aid, wax, resin, foaming agent, oil, stearic acid, zinc white (ZnO). A vulcanization accelerator, a vulcanization retarder or the like may be added. These compounding agents can be appropriately selected and compounded within a range not impairing the object of the present invention. Commercially available products can be preferably used as these compounding agents.

  Further, in a rubber composition containing an inorganic filler such as silica, a silane coupling agent is used for the purpose of enhancing the reinforcing property of the rubber composition by silica, or for enhancing the abrasion resistance as well as the low heat generation property of the rubber composition. You may mix an agent.

  The silane coupling agent that can be used in combination with the inorganic filler is not particularly limited, and commercially available products can be preferably used. Examples of such silane coupling agents include sulfide-based, polysulfide-based, thioester-based, thiol-based, olefin-based, epoxy-based, amino-based, and alkyl-based silane coupling agents.

  Examples of the sulfide-based silane coupling agent include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(3-methyldimethoxysilylpropyl)tetrasulfide, bis( 2-triethoxysilylethyl) tetrasulfide, bis(3-triethoxysilylpropyl) disulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(3-methyldimethoxysilylpropyl) disulfide, bis(2-triethoxysilyl) Ethyl) disulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-trimethoxysilylpropyl) trisulfide, bis(3-methyldimethoxysilylpropyl) trisulfide, bis(2-triethoxysilylethyl)tri Sulfide, bis(3-monoethoxydimethylsilylpropyl) tetrasulfide, bis(3-monoethoxydimethylsilylpropyl) trisulfide, bis(3-monoethoxydimethylsilylpropyl) disulfide, bis(3-monomethoxydimethylsilylpropyl) Tetrasulfide, bis(3-monomethoxydimethylsilylpropyl) trisulfide, bis(3-monomethoxydimethylsilylpropyl) disulfide, bis(2-monoethoxydimethylsilylethyl) tetrasulfide, bis(2-monoethoxydimethylsilylethyl) ) Trisulfide, bis(2-monoethoxydimethylsilylethyl) disulfide and the like. Of these, bis(3-triethoxysilylpropyl) tetrasulfide is particularly preferable.

  Examples of the thioester-based silane coupling agent include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, and 3-lauroylthiopropyltriethoxysilane. , 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2 -Decanoylthioethyltrimethoxysilane, 2-lauroylthioethyltrimethoxysilane and the like can be mentioned.

  Examples of the thiol-based silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-[ethoxybis(3,6,9,12,15). -Pentaoxaoctacosan-1-yloxy)silyl]-1-propanethiol and the like.

  Examples of the olefin-based silane coupling agent include dimethoxymethylvinylsilane, vinyltrimethoxysilane, dimethylethoxyvinylsilane, diethoxymethylvinylsilane, triethoxyvinylsilane, vinyltris(2-methoxyethoxy)silane, allyltrimethoxysilane, and allyltrisilane. Ethoxysilane, p-styryltrimethoxysilane, 3-(dimethoxymethylsilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(trimethoxysilyl)propyl Methacrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate and the like can be mentioned.

  Examples of the epoxy-based silane coupling agent include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, and triethoxy(3-glycidyloxypropyl)silane. , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and the like. Of these, 3-glycidyloxypropyltrimethoxysilane is preferable.

  Examples of amino-based silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyl. Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-ethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)- 2-aminoethyl-3-aminopropyl trimethoxysilane etc. can be mentioned. Of these, 3-aminopropyltriethoxysilane is preferable.

  Examples of the alkyl silane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, and isobutyltriethoxy. Examples thereof include silane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, and n-decyltrimethoxysilane. Of these, methyltriethoxysilane is preferred.

  Among these silane coupling agents, bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) disulfide, and 3-[ethoxybis(3,6,9,12,15-pentaoxaoctaoctane Cosan-1-yloxy)silyl]-1-propanethiol can be used particularly preferably.

  In the present invention, one type of silane coupling agent may be used alone, or two or more types may be used in combination.

  The compounding amount of the silane coupling agent of the rubber composition of the present invention is preferably 0.1 to 20 parts by mass, and particularly preferably 3 to 15 parts by mass with respect to 100 parts by mass of the inorganic filler. If it is 0.1 parts by mass or more, the effect of low heat build-up of the rubber composition can be exhibited more suitably, and if it is 20 parts by mass or less, the cost of the rubber composition is reduced and the economical efficiency is improved. Because it does.

  Further, in a case where the braking characteristic is particularly emphasized, a resin or the like may be added. Specific examples thereof include natural resins such as rosin-based resins and terpene-based resins, petroleum-based resins, phenol-based resins, coal-based resins, and xylene-based resins. Examples of rosin-based resins include gum rosin, tall oil rosin, wood rosin, hydrogenated rosin, disproportionated rosin, polymerized rosin, glycerin of modified rosin, and pentaerythritol ester, and terpene-based resins include α-pinene-based resins. , Β-pinene-based and dipentene-based terpene resins, aromatic modified terpene resins, terpene phenol resins, hydrogenated terpene resins and the like.

  Further, in the case where importance is attached to processability, as a processing aid, mineral oil, petrolatum, paraffin wax, petroleum resin, fatty acid, fatty acid ester, fatty alcohol, metal soap, fatty acid amide, phenol resin, polyethylene, polybutene, peptizer, Examples include processing aids such as a rejuvenating agent and an organosiloxane.

  Further, oil or the like may be added to adjust the hardness. Process oils, vegetable oils, or mixtures thereof can be used. As the process oil, for example, paraffin type process oil, aroma type process oil, naphthene type process oil and the like can be used. As vegetable oils and oils, castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, rosin, pine oil, pine tar, tall oil, corn oil, sesame oil, Beni flower oil, sesame oil, Examples include olive oil, sunflower oil, palm kernel oil, camellia oil, jojoba oil, macadamia nut oil, tung oil and the like. Among them, paraffin-based process oils and aroma-based process oils are preferably used because they are advantageous in processability.

Use of Rubber Composition The use of the rubber composition of the present invention is not particularly limited, and examples thereof include a rubber portion of a tire. Among them, a preferable application is a tread portion of a heavy-duty tire such as a tire or a truck.

Production Method of Rubber Composition The production method of the rubber composition of the present invention is not particularly limited. The method for producing a rubber composition of the present invention includes, for example, a step (I) of kneading a rubber component, a tetrazine compound (1), carbon black, and a raw material component containing an inorganic filler, and a step (I). The step (II) of kneading the mixture obtained in step 1 and the vulcanizing agent is included.

Process (I)
The step (I) is a step of kneading a raw material component including a rubber component, a tetrazine compound (1), carbon black, and an inorganic filler as necessary, and is a step before adding a vulcanizing agent. I mean.

  In the step (I), the above-mentioned other compounding agents and the like can be further compounded, if necessary.

  Examples of the kneading method in the step (I) include a method of kneading a composition containing a rubber component, a tetrazine compound (1), carbon black, and optionally an inorganic filler. In this kneading method, the entire amount of each component may be kneaded at once, or each component may be dividedly added and kneaded depending on the purpose of adjusting the viscosity and the like. Alternatively, after kneading the rubber component and carbon black, the tetrazine compound (1) may be added and kneaded, or the rubber component and the tetrazine compound (1) may be kneaded and then carbon black may be added and kneaded. Good. Step (I) may be repeatedly kneaded multiple times. When the inorganic filler is blended, the inorganic filler can be added together with carbon black and kneaded.

  The temperature for mixing the rubber composition in step (I) is not particularly limited, and for example, the upper limit of the temperature of the rubber composition is preferably 120 to 190°C, and 130 to 175°C. More preferably, it is more preferably 140 to 170°C.

  The mixing time in step (I) is not particularly limited and is, for example, preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, further preferably 2 minutes to 7 minutes. preferable.

  In the step (I), the tetrazine compound (1) is blended in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. As a compounding quantity of a tetrazine compound (1), 0.25-5 mass parts is preferable with respect to 100 mass parts of rubber components, and 0.5-2 mass parts is more preferable.

  In the step (I), 30 to 120 parts by mass of carbon black is blended with 100 parts by mass of the rubber component. The blending amount of carbon black is preferably 35 to 80 parts by mass, and more preferably 40 to 70 parts by mass with respect to 100 parts by mass of the rubber component.

  When an inorganic filler is contained, the compounding amount of the inorganic filler in the step (I) is usually 20 to 150 parts by mass, preferably 35 to 120 parts by mass, based on 100 parts by mass of the rubber component. It is preferably 40 to 90 parts by mass.

  In the step (I), the carbon black and the inorganic filler are contained in the above-mentioned respective amounts so that the total amount of both components is usually 30 to 150 parts by mass with respect to 100 parts by mass of the rubber component. It may be adjusted appropriately within the range.

  Further, as another kneading method in the step (I), a step (I-1) of kneading the rubber component and the tetrazine compound (1), and a mixture (modified polymer) obtained in the step (I-1) There can be mentioned a two-step kneading method including a step (I-2) of kneading carbon black and an inorganic filler as necessary.

  As a method for kneading the rubber component and the tetrazine compound (1) in the step (I-1), when the rubber component is solid, a method for kneading the rubber component and the tetrazine compound (1) (kneading method) When the rubber component is liquid (liquid), a method of mixing the solution or emulsion (suspension) of the rubber component with the tetrazine compound (1) (liquid mixing method) and the like can be mentioned.

  The kneading temperature is not particularly limited. For example, in the case of the above kneading method, the upper limit of the temperature of the rubber component is preferably 80 to 190°C, more preferably 90 to 160°C, and 100 to 100°C. More preferably, it is 150°C. In the case of the liquid mixing method, the upper limit of the temperature of the rubber component is preferably 80 to 170°C, more preferably 90 to 160°C, and further preferably 100 to 150°C.

  The mixing time or kneading time is not particularly limited. For example, in the case of the kneading method, it is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and 60 seconds to 7 minutes. It is more preferable that there is. In the case of a liquid mixing method, it is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 40 minutes, and further preferably 60 seconds to 30 minutes. After the mixing reaction by the liquid mixing method, the solvent in the mixture can be removed (removed) under reduced pressure to recover the solid rubber composition.

  In the step (I-1), the tetrazine compound (1) is blended in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. As a compounding quantity of a tetrazine compound (1), 0.25-5 mass parts is preferable with respect to 100 mass parts of rubber components, and 0.5-2 mass parts is more preferable.

  By the step (I-1) of kneading the rubber component and the tetrazine compound (1), the double bond of the diene rubber in the rubber component and the tetrazine compound (1) react with each other to form a modified polymer.

  In the step (I-2), the temperature at the time of mixing the mixture (modified polymer) obtained in the step (I-1) and carbon black is not particularly limited, and for example, the upper limit of the temperature of the mixture is 120. The temperature is preferably from 190 to 190°C, more preferably from 130 to 175°C, even more preferably from 140 to 170°C.

  The mixing time in the step (I-2) is not particularly limited and is, for example, preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and further preferably 2 minutes to 7 minutes. Is more preferable.

  The blending amount of carbon black in the step (I-2) is 30 to 120 parts by mass with respect to 100 parts by mass of the mixture (modified polymer) obtained in the step (I-1). The blending amount of carbon black is preferably 35 to 80 parts by mass, and more preferably 40 to 70 parts by mass, relative to 100 parts by mass of the mixture (modified polymer) obtained in step (I-1).

  When the inorganic filler is blended in the step (I-2), the blending amount is usually 20 to 150 parts by mass with respect to 100 parts by mass of the mixture (modified polymer) obtained in the step (I-1). It is preferably 30 to 120 parts by mass, more preferably 40 to 90 parts by mass.

  In addition, when mix|blending an inorganic filler in a process (I-2), carbon black and an inorganic filler are the total amount of both components, for example, the mixture (modified polymer) 100 obtained by a process (I-1) 100. It may be appropriately adjusted within the range of the above blending amount of each component so that it is usually 35 to 150 parts by mass with respect to parts by mass.

  By the step (I), the double bond part of the rubber component (diene rubber) and the tetrazine compound (1) react with each other to form a modified polymer, and the carbon black and, in some cases, the inorganic filler are suitably dispersed. A mixture can be obtained.

Process (II)
Step (II) is a step of mixing the mixture obtained in step (I) and a vulcanizing agent, and means the final stage of kneading.

  In the step (II), a vulcanization accelerator and the like can be further compounded, if necessary.

  The mixing (or kneading) temperature in step (II) is not particularly limited and is, for example, preferably 60 to 140° C., more preferably 80 to 120° C., and 90 to 120° C. More preferable.

  The mixing (or kneading) time is not particularly limited and is, for example, preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, further preferably 60 seconds to 5 minutes. .

  When proceeding from step (I) to step (II), it is preferable to lower the temperature by 30° C. or more from the temperature after the end of the previous step, and then proceed to the next step (II).

  In the method for producing a rubber composition of the present invention, various compounding agents such as vulcanization accelerators such as stearic acid and zinc white, antioxidants and the like, which are usually compounded in the rubber composition, are added in the step (I ) Or in step (II).

  A rubber containing a modified polymer obtained by treating the diene-based rubber in the rubber component with the tetrazine compound (1) by the above steps (I) and (II), carbon black, and an inorganic filler as necessary. The composition can be manufactured.

  The rubber composition of the present invention contains a rubber component, a tetrazine compound (1), carbon black, and a composition containing an inorganic filler if necessary, and the diene rubber in the rubber component contains the tetrazine compound (1 Both the modified polymer obtained by treating the above), carbon black, and optionally a rubber composition containing an inorganic filler are included.

  The modified polymer formed in step (I) or (I-1) is produced by the progress of the reactions shown in the following reaction formulas-1 to 4.

[In the formula, X ¹ and X ² are the same as defined above. ]

  In the reaction formula-1, the double bond site of the diene rubber represented by the formula (A-1) and the tetrazine compound (1) are subjected to a reverse electron-requiring Aza-Diels-Alder reaction to obtain the formula (B-1). ) Form a bicyclo ring structure. The -N=N- moiety in this bicyclo ring structure facilitates denitrification and has a 6-membered ring structure represented by the formula (C-1), (C-2) or (C-3). Although formed, it is further oxidized by oxygen in the air to produce a modified polymer having a 6-membered ring structure represented by the formula (2-1).

[In the formula, X ¹ and X ² are the same as defined above. ]

  In the reaction formula-2, as in the reaction formula-1, from the double bond site of the diene rubber represented by the formula (A-2) and the tetrazine compound (1), the formula (B-2) or ( B-2′) and then the six-membered ring structure represented by formulas (C-4) to (C-9) are formed, and then the formula (2-2) or (2-3) A modified polymer having a six-membered ring structure represented by

[In the formula, X ¹ and X ² are the same as defined above. R represents an alkyl group or a halogen atom. ]

  In the reaction formula-3, the double bond site of the diene rubber represented by the formula (A-3) and the tetrazine compound (1) are subjected to a reverse electron-requiring Aza-Diels-Alder reaction to give the formula (B-3). ) Or (B-3′) is formed, and then a modified polymer having a 6-membered ring structure represented by formulas (2-4) to (2-7) by denitrification is formed. Manufactured. When R on the double bond site of the diene rubber represented by the formula (A-3) is a halogen atom, the elimination of the halogen atom may occur. A modified polymer having a 6-membered ring structure represented by (2-1) is produced.

[In formula, X< ¹ >, X< ² > and R are the same as the above. ]

  In the reaction formula-4, similarly to the reaction of the reaction formula-3, the double bond site of the diene rubber represented by the formula (A-4) and the tetrazine compound (1) are reacted to give the formula (B- 4) or after forming a bicyclo ring structure represented by (B-4′), a modified polymer having a 6-membered ring structure represented by formulas (2-8) to (2-11) is produced. It

  As described above, the produced modified polymer has a hetero atom such as a nitrogen atom, and since this hetero atom strongly interacts with the inorganic filler (particularly silica) and carbon black, the rubber composition It is possible to enhance the dispersibility in the inside and to impart high low heat buildup and abrasion resistance.

  The rubber composition of the present invention is a modified polymer produced by reacting a rubber component, in particular, a double bond of a diene rubber with a tetrazine compound (1), preferably the following formulas (2-1) to ( The rubber composition contains a modified polymer having at least one selected from the compound structures represented by 2-11).

[In the formula, X ¹ , X ² , and R are the same as defined above. ]

3. Tire The tire of the present invention is a tire produced by using the rubber composition of the present invention.

  Examples of the tire of the present invention include pneumatic tires (radial tires, bias tires, etc.) and solid tires.

  The use of the tire is not particularly limited, and examples thereof include passenger car tires, high-load tires, motorcycle (motorcycle) tires, studless tires, and the like, and among them, it can be suitably used for high-load tires.

  The shape, structure, size and material of the tire of the present invention are not particularly limited and can be appropriately selected according to the purpose.

  In the tire of the present invention, the rubber composition is used for at least one member selected from a tread portion, a sidewall portion, a bead area portion, a belt portion, a carcass portion and a shoulder portion.

  Among them, forming the tire tread portion of the pneumatic tire with the rubber composition is mentioned as one of the preferable embodiments.

  The tire tread portion is a portion that has a tread pattern and is in direct contact with the road surface, that is the outer skin portion of the tire that protects the carcass and prevents wear and damage, and the cap tread and/or cap tread that constitutes the ground contact portion of the tire. It is a base tread that is placed inside the.

  The sidewall portion is, for example, a portion from the lower side of the shoulder portion of the pneumatic radial tire to the bead portion, which protects the carcass and is the portion which is most bent when traveling.

  The bead area part is a part that fixes both ends of the carcass cord and at the same time fixes the tire to the rim. A bead is a structure in which high carbon steel is bundled.

  The belt portion is a reinforcing band stretched in the circumferential direction between the tread having a radial structure and the carcass. The carcass is tightened like a trough to increase the rigidity of the tread.

  The carcass portion is a portion of the cord layer forming the skeleton of the tire and plays a role of withstanding the load, impact, and filled air pressure of the tire.

  The shoulder portion is a shoulder portion of the tire and serves to protect the carcass.

  The tire of the present invention can be manufactured according to a method known so far in the field of tires.

  As the gas to be filled in the tire, normal air or air whose oxygen partial pressure is adjusted; inert gas such as nitrogen, argon or helium can be used.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples. However, the embodiments are merely examples, and the present invention is not limited to the embodiments.

Production Example 1: Production of 3,6-bis(3-pyridyl)-1,2,4,5-tetrazine (1a) In a 200 mL four-necked flask, 24 g (0.23 mol) of 3-cyanopyridine and water were added. 15 g (1.3 equivalents) of hydrazine and 48 mL of methanol were added, and the mixture was stirred at room temperature. Next, 3.6 g (15% by weight) of sulfur was added to this mixture, a reflux tube was attached, and the mixture was heated and stirred overnight at an external temperature of 70°C. The reaction solution was ice-cooled, the crystals were filtered and washed with a small amount of cold methanol. The crude crystals were dried under reduced pressure to obtain 19 g of orange crude dihydrotetrazine crystals.

The obtained crude crystals (17.8 g) were dissolved in acetic acid (178 g, 40 equivalents), and sulfur was filtered off. A dihydrotetrazine acetic acid solution and 178 mL of distilled water were added to a 1 L four-necked eggplant flask, and the mixture was stirred under ice cooling. Sodium nitrite (15.5 g, 3 equivalents) was dissolved in distilled water (35 mL), added dropwise to the reaction solution over about 1 hour, and stirred overnight at room temperature. The precipitated crystals were filtered and the crystals were neutralized with 10% multi-layered water to give crude crystals. The crude crystals were purified by a silica gel column (ethyl acetate) to obtain 8.4 g of the title tetrazine compound (1a) (reddish purple, needle crystals).
Melting point: 200°C,
¹ H-NMR (300 MHz, CDCl ₃ , δppm):
7.59 (ddd, J = 0.9, 5.1, 7.8 Hz, 2H), 8.89-8.96 (m, 4H), 9.88 (dd, J = 0.9, 2) .4Hz, 2H)

Examples 1-6 and Comparative Examples 1-6
The respective components described in step (I) of Tables 1 and 2 below were mixed in the ratio (parts by mass), and kneaded for 5 minutes while adjusting the rotation speed so that the maximum temperature of the mixture was 160° C. with a Banbury mixer. .. After curing until the temperature of the mixture becomes 80°C or lower, each component described in step (II) of Tables 1 and 2 is added in the ratio (parts by mass), and the maximum temperature of the mixture becomes 110°C or lower. Each rubber composition was manufactured by kneading while adjusting as described above.

Abrasion resistance test
With respect to the rubber compositions (test compositions) produced in Examples 1 to 6 and Comparative Examples 1 to 6, a Lambourn abrasion test (JISK62664) was performed at room temperature under a slip ratio of 24%. did. Using the rubber composition prepared in Comparative Example 1 as a reference, the abrasion resistance index was calculated based on the following formula.

  The results are shown in Tables 1 and 2.

formula:
Abrasion resistance index={(amount of wear of reference)/(amount of wear of test composition)}×100

Low exothermicity (tan δ index) test For the rubber compositions (test compositions) prepared in Examples 1 to 6 and Comparative Examples 1 to 6, a viscoelasticity measuring device (manufactured by Metravib) was used, and the temperature was 40° C. Tan δ was measured at a strain of 5% and a frequency of 15 Hz.

  Using the rubber composition prepared in Comparative Example 1 as a reference, the low exothermic index was calculated based on the following formula.

  The larger the value of the low heat buildup index, the lower the heat buildup and the smaller the hysteresis loss. The low heat buildup of the reference vulcanized rubber composition is 100.

  The results are shown in Tables 1 and 2.

formula:
Low exothermic index={(tan δ of reference)/(tan δ of test composition)}×100

[Explanation of symbols in the table]
The raw materials used in Tables 1 and 2 are shown below.
*1: JSR Corporation's product type "SBR1502"
*2: Product name "BR150B" manufactured by Ube Industries, Ltd.
*3: Made by Chuka Kokusai Co., Ltd., product name "RSS#3"
*4: Tokai Carbon Co., Ltd., trade name "SEAST 6" (nitrogen adsorption specific surface area 119 m ² /g)
*5: Tokai Carbon Co., Ltd., trade name "SEAST 3" (nitrogen adsorption specific surface area 79 m ² /g)
*6: Product name "Antage 6C" manufactured by Kawaguchi Chemical Industry Co., Ltd.
*7: Zinc oxide brand "1 type" manufactured by Sakai Chemical Industry Co., Ltd.
*8: Made by Sichuan Tianyu Grease Chemical Co., Ltd. *9: Made by Nippon Seiro Co., Ltd., product name "OZOACE-0355"
*10: JX Nikko Nisseki Energy Co., Ltd. product name "X-140 (aroma oil)"
*11: 3,6-bis(3-pyridyl)-1,2,4,5-tetrazine (compound produced in Production Example 1)
*12: 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, manufactured by Tokyo Chemical Industry Co., Ltd. *13: 3,6-bis(4-pyridyl)-1,2,4. 5-Tetrazine, manufactured by Tokyo Kasei Kogyo Co., Ltd. *14: Hosoi Chemical Co., Ltd., trade name "HK200-5"
*15: Product name "NOXCELLER CZ-G" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
*16: Product name “CTP” manufactured by Ouchi Shinko Chemical Co., Ltd.

  The rubber composition of the present invention is excellent in both wear resistance and low heat buildup. Therefore, by using the rubber composition, pneumatic tires of various automobiles, particularly tread portions (tire treads) of high-load tires can be obtained. It can be manufactured.

Claims (5)

Rubber component, the following general formula (1):

[In the formula, X ¹ and X ² represent a pyridyl group which may have a substituent. ]
A tetrazine compound represented by or a salt thereof, and a rubber composition containing carbon black,
40 parts by mass or more of natural rubber is contained in 100 parts by mass of the rubber component,
0.1 to 10 parts by mass of the tetrazine compound or a salt thereof and 30 to 120 parts by mass of carbon black with respect to 100 parts by mass of a rubber component,
Rubber composition. The substituent is a halogen atom, amino group, aminoalkyl group, alkoxycarbonyl group, acyl group, acyloxy group, amide group, carboxyl group, carboxyalkyl group, formyl group, nitrile group, nitro group, alkyl group, hydroxyalkyl group. The rubber composition according to claim 1, which is at least one selected from the group consisting of a hydroxyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a thiol group, an alkylthio group and an arylthio group. A tread for tire produced using the rubber composition according to claim 1. A pneumatic tire using the tire tread according to claim 3. The tire according to claim 4, which is used as a heavy-duty tire for a large automobile.