CN110382612A

CN110382612A - Rubber composition and tire

Info

Publication number: CN110382612A
Application number: CN201880017080.8A
Authority: CN
Inventors: 佐藤崇; 汤浅宏昭; 中岛慎也
Original assignee: Otsuka Chemical Co Ltd
Current assignee: Otsuka Chemical Co Ltd
Priority date: 2017-03-10
Filing date: 2018-03-09
Publication date: 2019-10-25
Anticipated expiration: 2038-03-09
Also published as: WO2018164246A1; JP6701433B2; CN110382612B; JPWO2018164246A1

Abstract

Rubber composition, the resin that it contains rubber constituent, the tetrazine compound or its salt that the following general formula (1) indicates and softening point are 60~160 DEG C, in 100 mass parts rubber constituents, include more than 40 mass parts making comprising 1, diene series rubber obtained from the monomer polymerization of 3- divinylic monomer, for 100 mass parts rubber constituents, include the aforementioned tetramine compound of 0.1~10 mass parts or its salt and 2~60 mass parts aforementioned resins.[in formula, X¹And X²Expression can have the heterocycle of substituent group.]

Description

Rubber composition and tire

Technical field

The present invention relates to rubber composition and tires.

Background technique

In recent years, consider that the emission regulation of carbon dioxide has become strictly, to automobile in the world from the worry to environment The requirement of low fuel consumption becomes very high.For low fuel consumption, the drive systems such as engine and transmission system Efficiency contribution it is big, but the rolling resistance of tire also largely participates in, and in order to make automobile low fuel consumption, reduces rolling Dynamic resistance is important.

As the method for the rolling resistance for reducing tire, it is known that the low rubber composition of heat generation, which is applied to tire, 's.As the rubber composition of such low-heat-generation, for example, can enumerate: (1) comprising improve with as filler carbon black and The rubber composition (patent document 1) of the functionalized polymeric of the compatibility of silica；It (2) include diene elastomer, conduct The inorganic filler of reinforcing filler, more vulcanization alkoxy silanes as coupling agent, 1,2- dihydropyridine and guanidine derivatives rubber Composition (patent document 2)；(3) comprising rubber constituent, aminopyrazole derivatives and the rubber composition of inorganic filler (patent text It offers 3)；(4) rubber composition (patent document 4 and 5) comprising end-modified polymers and inorganic filler；Etc..

It can be dropped according to the invention recorded in above patent document 1~5 by improving the compatibility of filler and rubber constituent The heat generation of low rubber composition, as a result, the low tire of hysteresis loss (rolling resistance) can be obtained.

However, even if using above patent document 1~5 rubber composition, the improvement of low-heat-generation is also insufficient.Separately Outside, by improving the low-heat-generation of rubber composition, the braking ability for avoiding tire in wet road decline is also failed to.

The expectation of the low fuel consumption of automobile is further increased, it is very excellent that low-heat-generation is developed in urgent expectation Tire.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2003-514079 bulletin

Patent document 2: Japanese Unexamined Patent Application Publication 2003-523472 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2013-108004 bulletin

Patent document 4: Japanese Unexamined Patent Publication 2000-169631 bulletin

Patent document 5: Japanese Unexamined Patent Publication 2005-220323 bulletin

Summary of the invention

Problems to be solved by the invention

The purpose of the present invention is to provide can be well maintained tire while the braking ability in wet road, be in The rubber composition of existing low-heat-generation.

Another object of the present invention is to provide the tires that low-heat-generation is excellent.

Means for solving the problems

Further investigation has been repeated to solve aforementioned problems by present inventor, as a result, it has been found that, by containing Have and adds the specific of specific quantity in the rubber composition of the rubber constituent comprising specific diene series rubber and tetrazine based compound Resin can solve the above subject.Present inventor is based on above-mentioned discovery, further progress research, as a result, be finally completed The present invention.

The present invention provides rubber composition and tire etc. as follows.

Item 1.

Rubber composition, the tetrazine compound or its salt and softening point indicated containing rubber constituent, the following general formula (1) For 60~160 DEG C of resin,

[chemical formula 1]

[in formula, X¹And X²Expression can have the heterocycle of substituent group.]

In 100 mass parts rubber constituents, comprising more than 40 mass parts keeping the monomer comprising 1,3-butadiene monomer poly- Diene series rubber obtained from conjunction,

It include the aforementioned tetrazine compound or its salt of 0.1~10 mass parts and 2 for 100 mass parts rubber constituents ~60 mass parts aforementioned resins.

Item 2.

Rubber composition as described in item 1 also includes inorganic filler and/or carbon black.

Item 3.

Rubber composition as described in item 2, wherein for 100 mass parts rubber constituents, comprising total amount be 30~ The inorganic filler of 150 mass parts and/or carbon black.

Item 4.

Rubber composition as described in any one of item 1, wherein include 70 matter in 100 mass parts rubber constituents Measure the diene series rubber of part or more.

Item 5.

Rubber composition as described in item 4, wherein diene series rubber is selected from by natural rubber, isoprene rubber, benzene At least one of the group of ethylene-butadiene copolymer rubber and butadiene rubber composition.

Item 6.

Rubber composition as described in any one of item 2~5, wherein inorganic filler is silica.

Item 7.

Rubber composition as described in item 6, wherein silica is BET specific surface area (m²/ g) 40~350 range Interior wet silicon dioxide.

Item 8.

Rubber composition as described in any one of item 2~7, wherein for 100 mass parts rubber compositions, The use level of inorganic filler is 20~150 mass parts.

Item 9.

Rubber composition as described in any one of item 2~8, wherein for 100 mass parts rubber compositions, The use level of carbon black is 2~150 mass parts.

Item 10.

Rubber composition as described in any one of item 1~9, is used for fetus face.

Item 11.

Tire tyre surface is made using rubber composition described in any one of item 1~9.

Item 12.

Pneumatic tire, it uses tire tyre surfaces described in item 11.

Invention effect

Through the invention, the tetrazine compound or its salt and softening point by indicating specific rubber constituent, general formula (1) For 60~160 DEG C of resin combination, it is possible to provide can be well maintained tire while the braking ability in wet road, be in The rubber composition of existing low-heat-generation.

In addition, making tire by using rubber composition of the invention, the rolling resistance of tire, also, energy can be reduced The heat generation of tire is reduced, therefore, it is possible to provide low fuel consumption tire.

Specific embodiment

Hereinafter, the present invention will be described in detail.

1. rubber composition

The present invention is rubber composition, the tetrazine compound or its salt indicated containing rubber constituent, the following general formula (1) (hereinafter, otherwise referred to as " tetrazine compound (1) ".) and softening point be 60~160 DEG C resin (hereinafter, otherwise referred to as " resin ".),

[chemical formula 2]

Rubber constituent

It as the rubber constituent that can cooperate in rubber composition of the invention, is not particularly limited, such as day can be enumerated The diene series rubbers such as mixture of right rubber (NR), synthesis diene series rubber and natural rubber and synthesis diene series rubber and Non- diene series rubber other than them.

As natural rubber, can enumerate natural rubber latex, technically classified rubber (TSR), smoke sheet rubber (RSS), gutta-percha, Natural rubber from Cortex Eucommiae, the natural rubber from guayule rubber, the natural rubber from Russian dandelion, plant component hair The natural rubbers such as ferment rubber can also enumerate epoxy natural rubber, acrylic modified natural rubber, benzene second in addition to this Modified natural rubbers such as alkene modified natural rubber etc..

As synthesis diene series rubber, can enumerate styrene-butadiene copolymer rubber (SBR), butadiene rubber (BR), Isoprene rubber (IR), nitrile rubber (NBR), neoprene (CR), ethylene-propylene-diene terpolymer rubber (EPDM), styrene-isoprene-phenylethene ternary block polymer (SIS), s-B-S tri-block Copolymer (SBS) etc. and their modified synthesis diene series rubber.As modified synthesis diene series rubber, can enumerate based on master Chain modified, single terminal-modified, two method of modifying such as terminal-modified diene series rubber.Herein, as modified synthesis diene series rubber The property modifying functional group of glue can enumerate following property modifying functional groups, and it includes a kind or more of epoxy group, amino, alkoxy, hydroxyl, alkane Oxygroup silicyl, polyether-based, carboxyl etc. contain heteroatomic functional group.

In addition, cis/trans/vinyl ratio for diene portions is not particularly limited, arbitrary ratio can be closed It uses suitablely., it is preferable to use trans content is the SBR of 25~70 weight % in SBR.In addition, the mean molecule of diene series rubber Amount and molecular weight distribution are not particularly limited, and preferably average molecular weight is 500~3,000,000, and molecular weight distribution is 1.5~15.Separately Outside, for synthesize diene series rubber manufacturing method it is not also specifically limited, can enumerate using emulsion polymerization, polymerisation in solution, from The case where being synthesized by base polymerization, anionic polymerisation, cationic polymerization etc..

As non-diene series rubber, known non-diene series rubber can be widely used.

For the rubber constituent used in the rubber composition of the invention, from the viewpoint of low-heat-generation, it is necessary to Comprising diene series rubber, especially make diene series rubber obtained from the monomer polymerization comprising 1,3- divinylic monomer.It is specific and Speech, in 100 mass parts rubber constituents, preferably comprise 40 mass parts or more makes the monomer polymerization comprising 1,3-butadiene monomer Obtained from diene series rubber, more preferably comprising more than 75 mass parts, particularly preferably with the cooperation of 80~100 mass parts ratios.Make To make diene series rubber obtained from the monomer polymerization comprising 1,3-butadiene monomer, SBR, BR, NBR etc., preferably SBR can be enumerated And BR.

In addition, for the glass transition temperature of diene series rubber, from realizing wear resistance and braking characteristic simultaneously From the viewpoint of, the glass transition temperature of -120 DEG C~-15 DEG C of range is effective.For rubber composition of the invention For, the above are glass transition temperatures in the range of -70 DEG C~-20 DEG C two by 50 mass % preferably in diene series rubber Alkene system rubber.

It about rubber constituent, can be used alone a kind, or two or more mixed into (blending) and is used.Wherein, as preferred Rubber constituent, be natural rubber, IR, SBR, BR or the mixture of more than two kinds selected from them, more preferably natural rubber Glue, SBR, BR or the mixture of more than two kinds selected from them.In addition, their blending ratio is not particularly limited, In 100 mass parts rubber constituents, preferably cooperate SBR, BR or their mixture with 70~100 mass parts ratios, more preferably with The ratio of 75~100 mass parts cooperates their mixture.In the case where the mixture for cooperating SBR and BR, preferably SBR and BR's Total amount is within the above range.Additionally, it is preferred that SBR at this time is the range of 50~100 mass parts, BR is the model of 0~50 mass parts It encloses.

Tetrazine compound (1)

In rubber composition of the invention, the compound or its salt of cooperation the following general formula (1) expression.

General formula (1):

[chemical formula 3]

It in this specification, as " heterocycle ", is not particularly limited, such as 2- pyridyl group, 3- pyridyl group, 4- pyrrole can be enumerated Piperidinyl, 2- pyrazinyl, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- pyrimidine radicals, 3- pyridazinyl, 4- pyridazinyl, 4- (1,2,3- triazine) base, 5- (1,2,3- triazine) base, 2- (1,3,5- triazine) base, 3- (1,2,4- triazine) base, 5- (1,2,4- triazine) base, 6- (1,2,4- Triazine) base, 2- quinolyl, 3- quinolyl, 4- quinolyl, 5- quinolyl, 6- quinolyl, 7- quinolyl, 8- quinolyl, 1- isoquinoline Quinoline base, 3- isoquinolyl, 4- isoquinolyl, 5- isoquinolyl, 6- isoquinolyl, 7- isoquinolyl, 8- isoquinolyl, 2- quinoline Quinoline base, 3- quinoxalinyl, 5- quinoxalinyl, 6- quinoxalinyl, 7- quinoxalinyl, 8- quinoxalinyl, 3- cinnoline base, 4- cinnolines Base, 5- cinnoline base, 6- cinnoline base, 7- cinnoline base, 8- cinnoline base, 2- quinazolyl, 4- quinazolyl, 5- quinazolyl, 6- quinoline Oxazoline base, 7- quinazolyl, 8- quinazolyl, 1- phthalazinyl, 4- phthalazinyl, 5- phthalazinyl, 6- phthalazinyl, 7- phthalazinyl, 8- Phthalazinyl, 1- tetrahydric quinoline group, 2- tetrahydric quinoline group, 3- tetrahydric quinoline group, 4- tetrahydric quinoline group, 5- tetrahydric quinoline group, 6- tetra- Hydrogen quinolyl, 7- tetrahydric quinoline group, 8- tetrahydric quinoline group, 1- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, 2- furyl, 3- furans Base, 2- thienyl, 3- thienyl, 1- imidazole radicals, 2- imidazole radicals, 4- imidazole radicals, 5- imidazole radicals, 1- pyrazolyl, 3- pyrazolyl, 4- Pyrazolyl, 5- pyrazolyl, 2- oxazolyl, 4- oxazolyl, 5- oxazolyl, 2- thiazolyl, 4- thiazolyl, 5- thiazolyl, the different evil of 3- Oxazolyl, 4- isoxazolyl, 5- isoxazolyl, 3- isothiazolyl, 4- isothiazolyl, 5- isothiazolyl, 4- (1,2,3- thiadiazoles) Base, 5- (1,2,3- thiadiazoles) base, 3- (1,2,5- thiadiazoles) base, 2- (1,3,4- thiadiazoles) base, 4- (1,2,3- oxadiazoles) Base, 5- (1,2,3- oxadiazoles) base, 3- (1,2,4- oxadiazoles) base, 5- (1,2,4- oxadiazoles) base, 3- (1,2,5- oxadiazoles) Base, 2- (1,3,4- oxadiazoles) base, 1- (1,2,3- triazole) base, 4- (1,2,3- triazole) base, 5- (1,2,3- triazole) base, 1- (1,2,4- triazole) base, 3- (1,2,4- triazole) base, 5- (1,2,4- triazole) base, 1- tetrazole radical, 5- tetrazole radical, 1- indyl, 2- indyl, 3- indyl, 4- indyl, 5- indyl, 6- indyl, 7- indyl, 1- isoindolyl, 2- isoindolyl, 3- isoindolyl, 4- isoindolyl, 5- isoindolyl, 6- isoindolyl, 7- isoindolyl, 1- benzimidazolyl, 2- benzo miaow Oxazolyl, 4- benzimidazolyl, 5- benzimidazolyl, 6- benzimidazolyl, 7- benzimidazolyl, 2- benzofuranyl, 3- benzo Furyl, 4- benzofuranyl, 5- benzofuranyl, 6- benzofuranyl, 7- benzofuranyl, 1- isobenzofuran-base, 3- Isobenzofuran-base, 4- isobenzofuran-base, 5- isobenzofuran-base, 6- isobenzofuran-base, 7- isobenzofuran-base, 2- benzene Bithiophene base, 3- benzothienyl, 4- benzothienyl, 5- benzothienyl, 6- benzothienyl, 7- benzothienyl, 2- Benzoxazolyl, 4- benzoxazolyl, 5- benzoxazolyl, 6- benzoxazolyl, 7- benzoxazolyl, 2-[4-morpholinodithio base, 4- benzothiazolyl, 5- benzothiazolyl, 6- benzothiazolyl, 7- benzothiazolyl, 1- indazolyl, 3- indazolyl, 4- indazole Base, 5- indazolyl, 6- indazolyl, 7- indazolyl, 2- morpholinyl, morpholinyl, 4- morpholinyl, 1- piperazinyl, 2- piperazinyl, 1- Piperidyl, 2- piperidyl, 3- piperidyl, 4- piperidyl, 2- THP trtrahydropyranyl, 3- THP trtrahydropyranyl, 4- THP trtrahydropyranyl, 2- tetra- Hydrogen thiapyran base, 3- tetrahydro thiapyran base, 4- tetrahydro thiapyran base, 1- pyrrolidinyl, 2- pyrrolidinyl, 3- pyrrolidinyl, 2- tetrahydro furan It mutters base, 3- tetrahydrofuran base, 2- tetrahydro-thienyl, 3- tetrahydro-thienyl etc..Wherein, as preferred heterocycle, be pyridyl group, Furyl, thienyl, pyrimidine radicals or pyrazinyl, more preferable pyridyl group.

Heterocycle can have 1 or more substituent group in the position that can be replaced.As the substituent, without special Limitation, can enumerate such as halogen atom, amino, aminoalkyl, alkoxy carbonyl, acyl group, acyloxy, amide groups, carboxyl, carboxylic Base alkyl, formoxyl, itrile group, nitro, alkyl, hydroxy alkyl, hydroxyl, alkoxy, aryl, aryloxy, heterocycle, mercaptan Base, alkyl sulfenyl, artyl sulfo etc..Can have preferably 1~5, more preferable 1~3 substituent group.

In this specification, as " halogen atom ", fluorine atom, chlorine atom, bromine atom and iodine atom can be enumerated, preferably Chlorine atom, bromine atom and iodine atom.

In this specification, " amino " not only includes-NH₂The amino of expression, further include for example methylamino, ethylamino, N-propyl amino, isopropylamino, n-butylamino, isobutylamino, s-butylamino, tert-butylamino, 1- ethyl propyl The carbon atom numbers such as amino, n-pentyl amino, neopentyl amino, n-hexyl amino, isohesyl amino, 3- methylpentylamino are 1 The straight-chain of~6 (especially carbon atom number is 1~4) or the alkyl monosubstituted amino of branched；Dimethylamino, ethyl-methyl ammonia It is the straight-chain or branched of 1~6 (especially carbon atom number is 1~4) that base, diethylamino etc., which have 2 carbon atom numbers, The substituted-aminos such as the dialkyl amido of alkyl.

In this specification, as " aminoalkyl ", be not particularly limited, can enumerate for example amino methyl, 2- amino-ethyl, The aminoalkyls such as 3- aminopropyl (preferably straight-chain or branched-chain alkyl of the carbon atom number with amino for 1~6).

It in this specification, as " alkoxy carbonyl ", is not particularly limited, such as methoxycarbonyl, ethyoxyl can be enumerated Carbonyl etc..

It in this specification, as " acyl group ", is not particularly limited, can enumerate such as acetyl group, propiono, pivaloyl group The straight-chain or branched-chain alkyl carbonyl that carbon atom number is 1~4.

It in this specification, as " acyloxy ", is not particularly limited, such as acetyl group oxygroup, propiono oxygen can be enumerated Base, positive bytyry oxygroup etc..

It in this specification, as " amide groups ", is not particularly limited, can enumerate such as acetamido, benzamido Carboxylic acid amide group；The thioamides bases such as thioacetyl amido, thiobenzamide base；N- methyl vinyl amido, N- benzyl acetyl The N substituted amides base such as amido；Etc..

It in this specification, as " carboxyalkyl ", is not particularly limited, such as carboxymethyl group, carboxy ethyl, carboxylic can be enumerated (preferably the carbon atom number with carboxyl is 1 to the carboxyalkyls such as base n-propyl, carboxyl normal-butyl, carboxyl n-pentyl, carboxyl n-hexyl ~6 alkyl).

It in this specification, as " hydroxy alkyl ", is not particularly limited, such as hydroxymethyl, hydroxyethyl, hydroxyl can be enumerated The hydroxy alkyls such as base n-propyl, hydroxy-n-butyl (preferably have the alkyl that the carbon atom number of hydroxyl is 1~6).

It in this specification, as " alkyl ", is not particularly limited, such as straight-chain, branched or cricoid alkane can be enumerated Base, specifically, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, 1- can be enumerated The carbon atom numbers such as ethyl propyl, n-pentyl, neopentyl, n-hexyl, isohesyl, 3- methyl amyl are 1~6 (especially carbon atom Number be 1~4) straight-chain or branched-chain alkyl；The carbon such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl are former Subnumber is the cyclic alkyl etc. of 3~8 (especially carbon atom number is 3~6).

It in this specification, as " alkoxy ", is not particularly limited, such as straight-chain, branched or cricoid can be enumerated Alkoxy, specifically, can enumerate for example methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, The carbon atom numbers such as n-pentyl oxygroup, neopentyl epoxide, n-hexyl oxygroup are the straight chain of 1~6 (especially carbon atom number is 1~4) The alkoxy of shape or branched；Cyclopropyl oxygroup, cyclobutyl oxygroup, cyclopentyloxy, cyclohexyl oxygroup, suberyl oxygroup, ring The carbon atom numbers such as octyl oxygroup are the cyclic alkoxy etc. of 3~8 (especially carbon atom number is 3~6).

It in this specification, as " aryl ", is not particularly limited, such as phenyl, xenyl, naphthalene, indane can be enumerated Base, 9H- fluorenyl etc..

It in this specification, as " aryloxy ", is not particularly limited, such as phenoxy group, xenyl oxygroup, naphthalene can be enumerated Oxygroup etc..

It in this specification, as " alkyl sulfenyl ", is not particularly limited, such as straight-chain, branched or ring-type can be enumerated Alkyl sulfenyl, specifically, such as methylsulfany, ethylsulfanyl, n-propyl sulfenyl, isopropylsulfanyl, normal-butyl can be enumerated Sulfenyl, i-butylthio, s-butylthio, tert. butyl-sulphenyl, 1- ethyl propyl sulfenyl, n-pentyl sulfenyl, neopentyl sulfenyl, just The carbon atom numbers such as hexyl sulfenyl, isohesyl sulfenyl, 3- methyl amyl sulfenyl are the straight of 1~6 (especially carbon atom number is 1~4) The alkyl sulfenyl of chain or branched；Cyclopropylsulfanyl, cyclobutyl sulfenyl, cyclopentylthio, cyclohexylthio, suberyl sulphur The carbon atom numbers such as base, cyclooctyl sulfenyl are the cyclic alkyl sulfenyl etc. of 3~8 (especially carbon atom number is 3~6).

In this specification, as " artyl sulfo ", be not particularly limited, can enumerate for example phenylsulfartyl, xenyl sulfenyl, Naphthylthio etc..

As " salt " of the tetrazine compound that general formula (1) indicates, it is not particularly limited, the salt comprising all kinds.As Such salt can enumerate the inorganic acid salt such as hydrochloride, sulfate, nitrate；The acylates such as acetate, mesylate； The alkali metal salts such as sodium salt, sylvite；The alkali salts such as magnesium salts, calcium salt；Ammonium salts such as dimethyl ammonium, triethyl ammonium etc..

Preferred tetrazine compound (1) is following compounds: X¹And X²It is identical or different, for the pyrrole that can have substituent group Piperidinyl, the furyl that can have substituent group, the thienyl that can have substituent group, the pyrazolyl that can have substituent group, can With the pyrimidine radicals with substituent group or it can have substituent group pyrazinyl.

Preferred tetrazine compound (1) is following compounds: X¹And X²It is identical or different, to can have substituent group 2- pyridyl group, the 3- pyridyl group that can have substituent group, the 4- pyridyl group that can have substituent group, the 2- that can have substituent group Furyl, the 2- thienyl that can have substituent group, the 1- pyrazolyl that can have substituent group, the 2- that can have substituent group are phonetic Piperidinyl or the 2- pyrazinyl that can have substituent group, specifically, particularly preferably following compounds: X¹And X²It is identical or not Together, to can have the 2- pyridyl group of substituent group, can have the 3- pyridyl group of substituent group, can have the 4- pyridine of substituent group Base or the 2- furyl that can have substituent group.

As the concrete example of tetrazine compound (1), can enumerate

Bis- (2- the pyridyl group) -1,2,4,5- tetrazines of 3,6-,

Bis- (3- the pyridyl group) -1,2,4,5- tetrazines of 3,6-,

Bis- (4- the pyridyl group) -1,2,4,5- tetrazines of 3,6-,

Bis- (2- the furyl) -1,2,4,5- tetrazines of 3,6-,

Bis- (3,5- dimethyl -1- the pyrazolyl) -1,2,4,5- tetrazines of 3,6-,

Bis- (2- the thienyl) -1,2,4,5- tetrazines of 3,6-,

3- methyl -6- (2- pyridyl group) -1,2,4,5- tetrazine,

Bis- (2- the pyrimidine radicals) -1,2,4,5- tetrazines of 3,6-,

Bis- (2- pyrazinyl) -1,2,4,5- tetrazines of 3,6- etc..

Wherein, preferred tetrazine compound (1) is bis- (the 2- pyridyl groups) -1 of 3,6-, bis- (the 3- pyridines of 2,4,5- tetrazines, 3,6- Base) -1,2,4,5- tetrazine, bis- (2- the furyl) -1,2,4,5- tetrazines of 3,6- and bis- (4- the pyridyl group) -1,2,4,5- four of 3,6- Piperazine, further preferred tetrazine compound (1) are bis- (the 2- pyridyl groups) -1 of 3,6-, 2,4,5- tetrazines, 3,6- bis- (3- pyridyl groups) - 1,2,4,5- tetrazine and bis- (4- the pyridyl group) -1,2,4,5- tetrazines of 3,6-.

For 100 mass parts of rubber constituent in rubber composition, the use level of tetrazine compound (1) is usually 0.1~10 mass parts, preferably 0.25~5 mass parts, more preferably 0.5~2 mass parts.

When tetrazine compound (1) is powder, volume average particle size is not particularly limited.From the viewpoint that low-heat-generation is presented Consider, volume average particle size be preferably 300 μm hereinafter, further preferably 150 μm hereinafter, particularly preferably 75 μm or less.

It should be noted that the particle size distribution device based on laser diffractometry etc. can be used in volume average particle size, make It is found out to be equivalent to 50% partial size of integral distribution curve in volume reference size distribution.

In addition, from operability when processing and from the viewpoint of reducing ignitability or explosive risk, usable oil, tree Rouge, stearic acid etc. powder is surface-treated after product, or powder and calcium carbonate, silica etc. can also be filled Agent etc. is mixed and is used.

Resin

In rubber composition of the invention, cooperating softening point is 60~160 DEG C of resin.By in rubber of the invention Include the resin in composition, the braking ability in braking characteristic, especially wet road can be improved.

As resin, specifically, the natural resins such as rosin series resin, terpenic series resin can be enumerated；C 5 fraction, C9 fraction Equal petroleum line resins；The resins such as phenolic aldehyde system resin, coal measures resin, diformazan benzene series resin.

As rosin series resin, such as gum rosin (gum rosin), toll oil rosin (tall oil can be enumerated Rosin), wood rosin (wood rosin), hydrogenated rosin, disproportionated rosin disproportionated rosin), newtrex, Modified rosins such as glycerol or pentaerythritol ester etc..They can be used alone, and can also be used in combination of two or more.

As terpenic series resin, the terpene resin such as australene system, nopinene system, cinene system can be enumerated；Aromatic series Modified terpene resin；Terpene phenolic resin；Hydrogenated terpene resin, polyterpene-limonene resin, poly- limonene resin etc..They It can be used alone, can also be used in combination of two or more.In addition, it is possible to use with product made of other kinds of resin polymerization.

As C 5 fraction, such as 1- amylene, 2- amylene, 2-methyl-1-butene alkene, 2- methyl-2-butene, 3- first can be enumerated The olefin-baseds hydrocarbon such as base -1- butylene；2- methyl-1,3- butadiene, 1,2- pentadiene, 1,3- pentadiene, 3- methyl-1,2- fourth two Dienes hydrocarbon such as alkene, the homopolymer of cyclopentadiene (CPD) or copolymer etc..They can be used alone, can also and with 2 Kind or more.

As C9 fraction, the styrene such as α-methylstyrene, Beta-methyl styrene, γ-methyl styrene can be enumerated Isomers；The indenes analogs such as indenes, 1- benzofuran (coumarone), the homopolymer of bicyclopentadiene (DCPD) or copolymer etc..It Can be used alone, can also be used in combination of two or more.

As phenolic aldehyde system resin, such as alkylphenol formaldehyde system resin and its Abietyl modified object, alkyl phenol second can be enumerated Alkyne series resin, modified alkyl phenol resin, terpene phenolic resin etc..They can be used alone, and can also be used in combination of two or more.

As coal measures resin, can enumerate such as coumarone indene resin.

As diformazan benzene series resin, can enumerate such as xylene formaldehyde resin.

The range that the softening point of resin is 60~160 DEG C.Softening point is that the resin of above range has braking ability excellent The advantage that.The softening point can usually be measured by the global formula of JIS K2207.

Consider from the viewpoint, is resin of softening point in the range of 90~150 DEG C, more preferably as preferred resin For resin of softening point in the range of 100~140 DEG C.

ExxonMobil Chemical Company can be enumerated as C5 system as the commercially available product of such resin, Inc. trade name " ECR1102 " processed can enumerate ExxonMobil Chemical Company, Inc. quotient as C5~C9 system The name of an article " ECR213 " can enumerate Yasuhara Chemical Co., Ltd. trade name " YS Polyster as terpenic series T100 " (100 DEG C of softening point), trade name " YS Resin PX1250 ", trade name " YS Polyster UH115 " and trade name " YS Resin PX300N ", Arizona Chemical trade name " Polylimonene SYLVARES TR-5147 ", ball Kind petrochemistry (strain) trade name processed " Marukarez M-890A ", Tonen General Sekiyu K.K. T-REZ system Column, trade name " T-REZ HB103 " and trade name " T-REZ RA100 ", JXTG Nippon Oil&Energy Corporation trade name " Nisseki Neopolymer 150 " and trade name " Nisseki Neopolymer L90 ", Japanese Zeon Corporation trade name " Quintone 1105 " etc..

As the use level for the resin that softening point is 60~160 DEG C, for 100 mass parts rubber constituents, usually For 2~60 mass parts, preferably 5~40 mass parts, more preferably 10~30 mass parts.

60 DEG C of resin can also be lower than using softening point in the range of not interfering effect of the invention and softening point is higher than 160 DEG C of resin.The glass transition temperature of these resins does not specify, but glass transition temperature is -10 DEG C~90 Braking characteristic of the resin in wet road in DEG C is excellent.

It is preferred that rubber composition of the invention other than comprising above-mentioned rubber constituent, tetrazine compound (1) and resin, is gone back Include inorganic filler and/or carbon black.

For 100 mass parts rubber constituents, the use level of inorganic filler is usually 20~150 mass parts, preferably For 30~120 mass parts, more preferably 40~90 mass parts.

For 100 mass parts rubber constituents, the use level of carbon black is usually 2~150 mass parts, preferably 4~ 120 mass parts, more preferably 6~100 mass parts.

It should be noted that in rubber composition of the invention, for inorganic filler and/or carbon black, with following sides Formula carries out appropriate adjustment in the range of the above-mentioned use level of each ingredient: in terms of the total amount of two-component, for example, relative to For 100 mass parts rubber constituents, become usual 30~150 mass parts, preferably 40~130 mass parts, more preferable 45~100 matter Measure part.

When total use level of inorganic filler and/or carbon black is 30 mass parts or more, from the enhancement of rubber composition Be from the viewpoint of raising it is preferred, be 150 below the mass when, be preferred from the viewpoint of reducing rolling resistance.It needs It is noted that when cooperation inorganic filler and/or carbon black, it is possible to use first pass through wet type or dry type in advance and formed with mixed with polymers Masterbatch polymer.

Inorganic filler

It as inorganic filler, is not particularly limited, as long as inorganic compound usually used in rubber industry circle is It can.As workable inorganic compound, the aluminium oxide such as silica, gama-alumina, Alpha-alumina can be enumerated (Al₂O₃)；The alumina monohydrates such as boehmite, diaspore (Al₂O₃·H₂O)；The aluminium hydroxides such as zirlite, bayerite [Al(OH)₃]；Aluminium carbonate [Al₂(CO₃)₃], magnesium hydroxide [Mg (OH)₂], magnesia (MgO), magnesium carbonate (MgCO₃), talcum (3MgO·4SiO₂·H₂O), attapulgite (5MgO8SiO₂·9H₂O), titanium white (TiO₂), the black (TiO of titanium_2n-1), calcium oxide (CaO), calcium hydroxide [Ca (OH)₂], magnesium aluminium oxide (MgOAl₂O₃), clay (Al₂O₃·2SiO₂), kaolin (Al₂O₃· 2SiO₂·2H₂O), pyrophyllite (Al₂O₃·4SiO₂·H₂O), bentonite (Al₂O₃·4SiO₂·2H₂O), alumina silicate (Al₂SiO₅、 Al₄·3SiO₄·5H₂O etc.), magnesium silicate (Mg₂SiO₄、MgSiO₃Deng), calcium silicates (Ca₂·SiO₄Deng), calcium aluminosilicate (Al₂O₃·CaO·2SiO₂Deng), calcium magnesium silicate (CaMgSiO₄), calcium carbonate (CaCO₃), zirconium oxide (ZrO₂), zirconium hydroxide [ZrO(OH)₂·nH₂O], zirconium carbonate [Zr (CO₃)₂], such hydrogen, alkali metal or the alkaline earth comprising compensation charge of various zeolites Crystallized silicon aluminate of metal etc..It, can be to this in order to improve the compatibility with rubber constituent for these inorganic fillers The surface of inorganic filler carries out organic process.

Since rubbery intensity can be assigned, silica is preferably added.As silica, can be used commercially available all Silica.It wherein, is wet silicon dioxide, dry type silica or colloidal silica as preferred silica Silicon, more preferably wet silicon dioxide.It, can be right in order to improve the compatibility with rubber constituent for these silica The surface of the inorganic filler carries out organic process.

Wherein, as inorganic filler, from the viewpoint of braking characteristic, preferred silica, the BET as silica Specific surface area is not particularly limited, and can enumerate such as 40~350m²The range of/g.BET specific surface area is the dioxy of above range SiClx has the advantage that capable of realizing rubber reinforcement and dispersibility in rubber constituent simultaneously.The BET specific surface area can It is measured according to ISO 5794/1.

Consider from the viewpoint, is BET specific surface area in 50~250m as preferred silica²In the range of/g Silica, more preferably BET specific surface area are 100~230m²The silica of/g, particularly preferably BET specific surface area exist 110~210m²Silica in the range of/g.

As the commercially available product of such silica, Quechen Silicon Chemical Co., Ltd. system can be enumerated Trade name " HD165MP " (BET specific surface area=165m²/ g), " HD115MP " (BET specific surface area=115m²/g)、 " HD200MP " (BET specific surface area=200m²/ g), " HD250MP " (BET specific surface area=250m²/g)、Tosoh Silica Trade name " Nipsil AQ " (BET specific surface area=205m of Corporation²/ g), " Nipsil KQ " (BET specific surface Product=240m²/ g), trade name " Ultrasil VN3 " (BET specific surface area=175m of Degussa AG²/ g), Solvay it is public Take charge of trade name " Z1085Gr " (BET specific surface area=90m of system²/ g), " Z Premium200MP " (BET specific surface area= 215m²/ g), " Z HRS 1200MP " (BET specific surface area=200m²/ g) etc..

As the use level of silica, for 100 mass parts rubber constituents, usually 20~120 mass parts, Preferably 30~100 mass parts, more preferably 40~90 mass parts.

Carbon black

It as carbon black, is not particularly limited, carbon black, the carbon-silicon dual phase filler (Carbon- of such as commercially available product can be enumerated Silica Dual phase filler) etc..

Specifically, as carbon black, can enumerate it is for example high, in or SAF, ISAF of low structure, IISAF, N110, N134, The carbon black etc. of N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, SRF grade.Wherein, as preferred charcoal It is black, it is the carbon black of SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF or FEF grade.

As the DBP uptake of carbon black, it is not particularly limited, preferably 60~200cm³/ 100g, more preferably 70~ 180cm³/ 100g or more, particularly preferably 80~160cm³/100g。

In addition, the N2 adsorption specific surface area (N2SA is measured according to JIS K 6217-2:2001) of carbon black is preferably 30 ~200m²/ g, more preferably 40~180m²/ g, particularly preferably 50~160m²/g。

By cooperating tetrazine compound (1) in the rubber composition of cooperation carbon black, the dispersibility of carbon black can be made substantially to mention Height can significantly improve the low-heat-generation of rubber composition.

Other compounding agents

In rubber composition of the invention, in addition to above-mentioned tetrazine compound (1), resin and inorganic filler and/or charcoal Other than black, it can also cooperate the vulcanizing agents such as usually used compounding agent in rubber industry circle, such as sulphur.Building rubber compound of the invention In object, it can further cooperate other compounding agents, such as antiaging agent, antiozonant, softening agent, processing aid, wax, foaming Agent, oil, stearic acid, the flowers of zinc (ZnO), vulcanization accelerator, vulcanization retarder etc..These compounding agents can not interfere mesh of the invention In the range of suitably select and cooperated.As these compounding agents, commercially available product can be suitably used.

In addition, purpose or raising rubber composition for the enhancement for improving the rubber composition based on silica Low-heat-generation and wear resistance purpose, silicon can be cooperated in the rubber composition for being combined with the inorganic fillers such as silica Alkane coupling agent.

As that can be not particularly limited with the silane coupling agent of inorganic filler, commercially available product can be suitably used.As Such silane coupling agent can enumerate such as thioether system, polythiaether system, thioesters system, mercaptan system, olefin-based, epoxy, amino The silane coupling agent of system, alkyl system.

As the silane coupling agent of thioether system, such as bis- (3- triethoxysilylpropyltetrasulfides) four thioethers, double can be enumerated (3- trimethoxy-silylpropyl) four thioethers, bis- (3- methyl dimethoxy oxygroup silylpropyls) four thioethers, bis- (tri- second of 2- Oxygroup silyl ether) four thioethers, bis- (3- triethoxysilylpropyltetrasulfide) disulfides, bis- (3- trimethyoxysilanes Base propyl) disulfide, bis- (3- methyl dimethoxy oxygroup silylpropyl) disulfides, bis- (2- triethoxysilylethyls) It is disulfide, bis- (3- triethoxysilylpropyltetrasulfide) trithioethers, bis- (3- trimethoxy-silylpropyl) trithioethers, double (3- methyl dimethoxy oxygroup silylpropyl) trithioether, bis- (2- triethoxysilylethyl) trithioethers, bis- (mono- second of 3- Oxygroup dimetylsilyl propyl) four thioethers, bis- (3- monosubstituted ethoxy dimetylsilyl propyl) trithioethers, bis- (3- is mono- Ethoxydimethylsilylpropyl) disulfide, bis- (3- mono methoxy dimetylsilyl propyl) four thioethers, bis- (3- Mono methoxy dimetylsilyl propyl) it is trithioether, bis- (3- mono methoxy dimetylsilyl propyl) disulfides, double (2- monosubstituted ethoxy dimetylsilyl ethyl) four thioethers, bis- (2- monosubstituted ethoxy dimetylsilyl ethyl) trithioethers, Bis- (2- monosubstituted ethoxy dimetylsilyl ethyl) disulfides etc..In these, particularly preferred bis- (3- triethoxysilyls Propyl) four thioethers.

As the silane coupling agent of thioesters system, such as 3- caproyl mercaptopropyl triethoxysilane, 3- decoyl can be enumerated Base mercaptopropyl triethoxysilane, 3- capryl mercaptopropyl triethoxysilane, three ethoxy of 3- lauroyl sulfopropyl Base silane, 2- caproyl sulfenyl ethyl triethoxysilane, 2- octanoylthio ethyl triethoxysilane, 2- capryl sulfenyl Ethyl triethoxysilane, 2- lauroyl thio-ethyl triethoxysilane, 3- caproyl mercaptopropyl trimethoxy silane, 3- octanoylthio propyl trimethoxy silicane, 3- capryl mercaptopropyl trimethoxy silane, 3- lauroyl sulfopropyl Trimethoxy silane, 2- caproyl sulfenyl ethyl trimethoxy silane, 2- octanoylthio ethyl trimethoxy silane, 2- caprinoyl Base sulfenyl ethyl trimethoxy silane, 2- lauroyl thio-ethyl trimethoxy silane etc..

As the silane coupling agent of mercaptan system, such as 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi three can be enumerated Ethoxysilane, 3- mercapto propyl methyl dimethoxy silane, 3- [bis- (the five oxa- octacosanes of 3,6,9,12,15--of ethyoxyl 1- base oxygroup) silicyl] -1- propanethiol etc..

As the silane coupling agent of olefin-based, such as dimethoxymethylvinylchlane, vinyl trimethoxy can be enumerated Base silane, dimethylethyloxy vinyl silanes, diethoxymethylvinylschane, Triethoxyvinylsilane, ethylene Base three (2- methoxy ethoxy) silane, allyltrimethoxysilanis, allyltriethoxysilane, to styryl front three Oxysilane, acrylic acid 3- (dimethoxy-methyl silicyl) propyl ester, acrylic acid 3- (trimethoxysilyl) propyl ester, first Base acrylic acid 3- [dimethoxy (methyl) silicyl] propyl ester, methacrylic acid 3- (trimethoxysilyl) propyl ester, first Base acrylic acid 3- [dimethoxy (methyl) silicyl] propyl ester, methacrylic acid 3- (triethoxysilyl) propyl ester, first Base acrylic acid 3- [three (trimethylsiloxy) silicyls] propyl ester etc..

As the silane coupling agent of epoxy, such as 3- glycidyloxypropyl (dimethoxy) methyl silicon can be enumerated Alkane, 3- glycidyloxypropyl trimethoxy silane, diethoxy (3- glycidyloxypropyl) methyl-monosilane, three Ethyoxyl (3- glycidyloxypropyl) silane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane etc..In these, It is preferred that 3- glycidyloxypropyl trimethoxy silane.

As the silane coupling agent of amino system, such as N-2- (amino-ethyl) -3- amino propyl methyl dimethoxy can be enumerated Base silane, N-2- (amino-ethyl) -3- TSL 8330,3- TSL 8330,3- aminopropan Ethyl triethoxy silicane alkane, 3- triethoxysilyl-N- (1,3- dimethylbutylene (butylidene)) propyl amine, N- benzene Base -3- TSL 8330, N- (vinyl benzyl) -2- amino-ethyl -3- TSL 8330 etc.. In these, preferred 3-aminopropyltriethoxysilane.

As the silane coupling agent of alkyl system, can enumerate for example methyltrimethoxysilane, dimethyldimethoxysil,ne, Trimethylmethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, n-propyl trimethoxy silane, isobutyl group Trimethoxy silane, isobutyl triethoxy silane, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, cyclohexyl Methyl dimethoxysilane, n-octytriethoxysilane, positive decyl trimethoxy silane etc..In these, preferred three second of methyl Oxysilane.

In these silane coupling agents, bis- (3- triethoxysilylpropyltetrasulfides) four thioethers, bis- (3- can be particularly preferably used Triethoxysilylpropyltetrasulfide) disulfide and 3- [bis- (the five oxa- octacosane -1- base oxygen of 3,6,9,12,15- of ethyoxyl Base) silicyl] -1- propanethiol.

In the present invention, silane coupling agent be can be used alone, and also can be used in combination two or more.

For 100 mass parts inorganic fillers, the use level of the silane coupling agent of rubber composition of the invention is excellent It is selected as 0.1~20 mass parts, particularly preferably 3~15 mass parts.This is because when to be more than 0.1 mass parts, it can be more suitably The effect of the low-heat-generation of rubber composition is presented, be 20 below the mass when, the cost decline of rubber composition, economy mentions It is high.

In addition, maying be used in the fillers such as carbon black and dispersing made of silane coupling agent in advance from the viewpoint of processability Product.As such silane coupling agent, such as Evonik Resource Efficiency GmbH trade name can be enumerated " X-50S " etc..

In addition, in the case where paying attention to processability, as processing aid, mineral oil, vaseline, paraffin, petroleum tree can be added Rouge, fatty acid, aliphatic ester, fatty alcohol, metallic soap, fatty acid amide, phenolic resin, polyethylene, polybutene, peptizing agent, again Liquids rubber, the organosiloxanes such as raw agent, liquid isoprene rubber and liquid butadiene rubber etc..

In addition, oil etc. can also be added in order to adjust hardness.Can be used technical oil, vegetable fat, or mixtures thereof.As Technical oil can be used such as alkane hydrocarbon system technical oil, aromatic series technical oil, cycloalkanes hydrocarbon system technical oil.It, can as vegetable fat It is burnt to enumerate castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, rosin, pine tar, pine Oil, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower oil, palm-kernel oil, camellia oil, Jojoba Oil, macadimia nut oil, tung oil etc..Wherein, consider to the advantageous such reason of processability, can suitably use vegetable oil Rouge, alkane hydrocarbon system technical oil or aromatic series technical oil.

The purposes of rubber composition

It as the purposes of rubber composition of the invention, is not particularly limited, such as tire, vibration-proof rubber, biography can be enumerated Send band, their rubber part etc..Wherein, preferred purposes is tire.

The manufacturing method of rubber composition

As the manufacturing method of rubber composition of the invention, it is not particularly limited.The system of rubber composition of the invention Make method for example including will include rubber constituent, tetrazine compound (1), silica and silica as needed with Process (I) that the material composition of outer inorganic filler and/or carbon black is kneaded and by mixture and sulphur obtained in process (I) The process (II) that agent is kneaded.

Process (I)

Process (I) be will include rubber constituent, tetrazine compound (1), silica and silica as needed The process that the material composition of inorganic filler and/or carbon black in addition is kneaded refers to the process before cooperation vulcanizing agent.

In process (I), as needed, it can further cooperate above-mentioned other compounding agents etc..

As the mixing method in process (I), for example, can enumerate: will include rubber constituent, tetrazine compound (1) and two The method that the composition of inorganic filler and/or carbon black other than silica, silica is kneaded.It, can be with one in the mixing method The whole amount of each ingredient is kneaded secondaryly, the purpose of can also being adjusted according to viscosity, each ingredient is put by several times and is kneaded.Separately Outside, tetrazine can be put into after by the inorganic filler and/or carbon black mixing other than rubber constituent and silica, silica Compound (1) and be kneaded, or after being kneaded rubber constituent and tetrazine compound (1), put into silica, silica Inorganic filler and/or carbon black in addition and be kneaded.For process (I), mixing can be repeated in multiple times.

It as temperature when mixing rubber composition in process (I), is not particularly limited, for example, rubber composition The upper limit of temperature be preferably 120~190 DEG C, more preferably 130~175 DEG C, further preferably 140~170 DEG C.

It as the incorporation time in process (I), is not particularly limited, for example, it is preferable to be 10 seconds~20 minutes, more preferably 30 seconds~10 minutes, further preferably 2 minutes~7 minutes.

It in process (I), as the use level of tetrazine compound (1), is not particularly limited, for example, relative to 100 mass parts For rubber constituent, usually 0.1~10 mass parts, preferably 0.25~5 mass parts, more preferably 0.5~2 mass parts.

It in process (I), as the use level of silica, is not particularly limited, for example, relative to 100 mass parts rubber For ingredient, usually 15~150 mass parts, preferably 20~120 mass parts, more preferably 30~100 mass parts, further Preferably 40~90 mass parts.

When comprising inorganic filler other than silica, other than the silica and silica in process (I) Total use level of inorganic filler, for 100 mass parts rubber constituents, usually 20~150 mass parts, preferably 30~ 120 mass parts, more preferably 40~90 mass parts.

As the use level of the carbon black in process (I), for 100 mass parts rubber constituents, usually 2~150 Mass parts, preferably 4~120 mass parts, more preferably 6~100 mass parts.

It should be noted that in process (I), about other than silica, silica inorganic filler and/or carbon black, Appropriate adjustment in the range of the above-mentioned use level of each ingredient in the following manner: in terms of the total amount of whole components, for example, phase For 100 mass parts rubber constituents, 20~150 mass parts are usually become.It should be noted that silica, titanium dioxide Total amount can be divided into 2 times or more and mixed by inorganic filler and/or carbon black other than silicon.

In addition, as other mixing method in process (I), can enumerate including by rubber constituent and tetrazine compound (1) The process (I-1) of mixing and by mixture (polymer-modified) and silica and titanium dioxide obtained in process (I-1) The mixing method of two steps of the process (I-2) that inorganic filler and/or carbon black other than silicon are kneaded.

In process (I-1), as by the method for rubber constituent and tetrazine compound (1) mixing, rubber constituent is solid In the case of, it can enumerate the method (mixing method) of the rubber constituent and tetrazine compound (1) mixing；Rubber constituent is liquid In the case where (liquid), the side for mixing the solution of the rubber constituent or lotion (suspension) and tetrazine compound (1) can be enumerated Method (liquid mixed method) etc..

As melting temperature, it is not particularly limited, for example, in the case where above-mentioned mixing method, the temperature of rubber constituent The upper limit be preferably 80~190 DEG C, more preferably 90~160 DEG C, further preferably 100~150 DEG C.In liquid mixed method In the case where, the upper limit of the temperature of rubber constituent is preferably 80~170 DEG C, and more preferably 90~160 DEG C, further preferably 100~150 DEG C.

As incorporation time or mixing time, it is not particularly limited, for example, in the case where mixing method, preferably 10 Second~20 minutes, more preferably 30 seconds~10 minutes, further preferably 60 seconds~7 minutes.The liquid mixed method the case where Under, preferably 10 seconds~60 minutes, more preferably 30 seconds~40 minutes, further preferably 60 seconds~30 minutes.It is being based on liquid After the hybrid reaction of shape mixed method, for example, under reduced pressure, the solvent in mixture is purged into (removal), it can be by the rubber of solid Glue composition recycling.

It as the use level of the tetrazine compound (1) in process (I-1), is not particularly limited, for example, relative to 100 matter For measuring part rubber constituent, usually 0.1~10 mass parts, preferably 0.25~5 mass parts, more preferably 0.5~2 mass Part.

Diene series rubber by the process (I-1) for being kneaded the rubber constituent and tetrazine compound (1), in rubber constituent Double bond reacted with tetrazine compound (1), formed it is polymer-modified.

As in process (I-2) by mixture (polymer-modified) obtained in process (I-1) and silica, dioxy Temperature when inorganic filler and/or carbon black other than SiClx mix, is not particularly limited, for example, the upper limit of the temperature of mixture Preferably 120~190 DEG C, more preferably 130~175 DEG C, further preferably 140~170 DEG C.

It as the incorporation time in process (I-2), is not particularly limited, for example, it is preferable to be 10 seconds~20 minutes, more preferably It is 30 seconds~10 minutes, further preferably 2 minutes~7 minutes.

It as the use level of the silica in process (I-2), is not particularly limited, for example, relative to 100 mass parts rubbers For glue ingredient, usually 15~150 mass parts, preferably 20~120 mass parts, more preferably 30~100 mass parts, into one Step is preferably 40~90 mass parts.

As total use level of the inorganic filler other than the silica and silica in process (I-2), relative to For mixture (polymer-modified) obtained in 100 mass parts processes (I-1), usually 20~150 mass parts, preferably 30 ~120 mass parts, more preferably 40~90 mass parts.

As the use level of the carbon black in process (I-2), relative to mixture obtained in 100 mass parts processes (I-1) For (polymer-modified), usually 2~150 mass parts, preferably 4~120 mass parts, more preferably 6~100 mass parts.

It should be noted that in process (I-2), for other than silica and silica inorganic filler and/or charcoal For black, appropriate adjustment is carried out: in the range of the above-mentioned use level of each ingredient in the following manner with the total amount of two-component Meter, for example, for 100 mass parts of mixture (polymer-modified) obtained in process (I-1), usually become 20~ 150 mass parts.

By process (I), the double bond portion of rubber constituent (diene series rubber) is reacted with tetrazine compound (1), is formed and is modified Polymer can be suitably dispersed with the mixture of the inorganic filler and/or carbon black other than silica, silica.

Process (II)

Process (II) is that mixture obtained in process (I), the process mixed with vulcanizing agent are referred to the final rank of mixing Section.

In process (II), as needed, it can further cooperate vulcanization accelerator etc..

As mixing (or mixing) temperature of process (II), it is not particularly limited, for example, it is preferable to be 60~140 DEG C, it is more excellent It is selected as 80~120 DEG C, further preferably 90~120 DEG C.

As mixing (or be kneaded) time, be not particularly limited, for example, it is preferable to for 10 seconds~20 minutes, more preferably 30 Second~10 minutes, further preferably 60 seconds~5 minutes.

When from process (I) progress to process (II), the temperature preferably after from the process of previous stage reduces by 30 DEG C After above, carry out subsequent processing (II).

In the manufacturing method of rubber composition of the invention, as needed, addition it can lead in process (I) or process (II) The various compounding agents such as stearic acid, the flowers of zinc, vulcanization accelerator, the antiaging agent that can often cooperate in rubber composition.

By above-mentioned process (I) and process (II), following such rubber compositions can be manufactured, are contained: with four Piperazine compound (1) is polymer-modified obtained from handling the diene series rubber in rubber constituent；Silica；And two The rubber composition of inorganic filler and/or carbon black other than silica.

It should be noted that rubber composition of the invention includes both following rubber compositions: be combined with rubber at Point, tetrazine compound (1), silica and be combined with the inorganic filler other than silica and/or the group of carbon black as needed Close object；And modified poly obtained from handling containing useful tetrazine compound (1) the diene series rubber in rubber constituent The rubber composition of inorganic filler and/or carbon black other than object, silica and silica.

Process (I) or the polymer-modified of (I-1) middle formation can be such anti-shown in following reaction equations -1~4 by carrying out It should manufacture.

[chemical formula 4]

Reaction equation -1

[in formula, X¹And X²It is same as described above.]

In reaction equation -1, pass through the double bond position of formula (A-1) diene series rubber indicated and the anti-electricity of tetrazine compound (1) Sub- demand type Aza-Diels-Alder reaction, forms the bicyclo ring structure of formula (B-1) expression.- N=in the bicyclo ring structure The portion N- is easy to carry out denitrogenation, forms the six-membered ring structure of formula (C-1), (C-2) or (C-3) expression, can be further by air Oxygen oxidation, manufacture have formula (2-1) indicate six-membered ring structure it is polymer-modified.

[chemical formula 5]

Reaction equation -2

[in formula, X¹And X²It is same as described above.]

It is same as reaction equation -1 in reaction equation -2, double bond position and tetrazine by formula (A-2) diene series rubber indicated The bicyclo ring structure that object (1) forms formula (B-2) or (B-2 ') is indicated is closed, the hexatomic ring of formula (C-4)~(C-9) expression is then formed Then structure manufactures the polymer-modified of the six-membered ring structure that there is formula (2-2) or (2-3) to indicate.

[chemical formula 6]

Reaction equation -3

[in formula, X¹And X²It is same as described above.R indicates alkyl or halogen atom.]

In reaction equation -3, pass through the double bond position of formula (A-3) diene series rubber indicated and the anti-electricity of tetrazine compound (1) Sub- demand type Aza-Diels-Alder reaction, forms the bicyclo ring structure of formula (B-3) or (B-3 ') expression, then passes through denitrogenation Change and manufactures the polymer-modified of the six-membered ring structure that there is formula (2-4)~(2-7) to indicate.It should be noted that formula (A-3) table When R on the double bond position of the diene series rubber shown is halogen atom, the disengaging of the halogen atom, such case occur sometimes Under, by oxidation reaction, can manufacture with the polymer-modified of formula (2-1) six-membered ring structure indicated.

[chemical formula 7]

Reaction equation -4

[in formula, X¹、X²And R is same as described above.]

It is same as the reaction of reaction equation -3 in reaction equation -4, pass through the double bond position of formula (A-4) diene series rubber indicated With reacting for tetrazine compound (1), the bicyclo ring structure of formula (B-4) or (B-4 ') expression is formed, then, manufacture has formula (2- 8)~(2-11) six-membered ring structure of expression is polymer-modified.

What is manufactured in the manner described above is polymer-modified with hetero atoms such as nitrogen-atoms, and the hetero atom and inorganic filler are (outstanding It is silica) and the strong interaction of carbon black generation, therefore the dispersibility in rubber composition can be improved, it can assign high Low-heat-generation.

It should be noted that rubber composition of the invention includes following such rubber compositions, containing rubber at Point especially the double bond of diene series rubber reacted with tetrazine compound (1) and manufacture it is polymer-modified, preferably with being selected from down It states at least one kind of polymer-modified in the compound structure of formula (2-1)~(2-11) expression.

[chemical formula 8]

[in formula, X¹、X²And R is same as described above.]

3. tire

Tire of the invention is the tire made using the rubber composition of aforementioned present invention.

As tire of the invention, can enumerate such as pneumatic tire (radial, cross-ply), solid tyre etc. Tire.

It as the purposes of tire, is not particularly limited, for example riding tire for vehicles, top load tire, motor can be enumerated Vehicle (motorcycle) tire, studless tire etc., wherein riding tire for vehicles can be suitably used for.

It as the shape, structure, size and material of tire of the invention, is not particularly limited, can suitably be selected according to purpose It selects.

In tire of the invention, above-mentioned rubber composition be particularly useful for selected from fetus face, sidewall, bead region portion, At least one of banding portion, carcass portion and shoulder portion component.

Wherein, it is preferred that one of, can enumerate by the rubber composition formed pneumatic tire tire face or The mode of sidewall.

So-called tire face, refer to tread contour and with the part that road surface directly contacts, be not only to protect carcass And the sheath portion of the tire of abrasion and wound is prevented, refer to the crown part for constituting the grounding parts of tire and/or is arranged at The tread base of the inside of crown part.

So-called sidewall, such as the downside for referring to slave shoulder portion in Pneumatic belt tire is to the part of bead part It protects carcass and is bent most violent part in motion.

So-called bead region portion, refers to and fixes the both ends of body cord while playing the role of tire being fixed on wheel rim Part.Tyre bead refers to structure made of tying up high-carbon steel.

So-called banding portion refers to circumferentially extending enhancing band between the tyre surface and carcass of meridian cable architecture.Such as The hoop of bucket ties carcass tight securely like that improve the rigidity of tyre surface.

So-called carcass portion, refers to form the part of the cord ply of the skeleton of tire, play tolerance tire suffered by load, Impact and the effect of filling air pressure.

So-called shoulder portion refers to the shoulder of tire, plays the role of protecting carcass.

Tire of the invention can be manufactured according to the method being currently known in the field of tire.

In addition, air that is common or having adjusted partial pressure of oxygen can be used as the gas being filled into tire；Nitrogen, argon, helium Equal non-active gas.

Embodiment

Hereinafter, showing Production Example and embodiment to illustrate the present invention.But embodiment is only example, the present invention is not It is limited to embodiment.

Bis- (the 3- pyridyl groups) -1 of Production Example 1:3,6-, the manufacture of 2,4,5- tetrazines (1a)

Nicotinonitrile 24g (0.23 mole), hydrazine hydrate 15g (1.3 equivalent) and first are added into 200mL four-hole boiling flask Alcohol 48mL, is stirred at room temperature.Next, adding sulphur 3.6g (15 weight %) into the mixture, return pipe is installed, One night of heating stirring under 70 DEG C of external temperature.The reaction solution is cooled with ice, filtering for crystallizing is washed with a small amount of cold methanol. Coarse crystallization is dried under reduced pressure, orange dihydro tetrazine coarse crystallization 19g is obtained.

Obtained coarse crystallization 17.8g is dissolved in acetic acid 178g (40 equivalent), sulphur is filtered to remove.To tetra- mouthfuls of eggplant types of 1L In flask, dihydro tetrazine acetic acid solution and distilled water 178mL are added, is stirred under ice-cooling.By sodium nitrite 15.5g (3 equivalent) is added in distilled water 35mL, and acquired solution was added dropwise through 1 hour or so into reaction solution, is stirred at room temperature one Night.The crystallization of precipitation is filtered, crystallization is neutralized with 10% sodium bicarbonate aqueous solution, coarse crystallization is made.With silicagel column (acetic acid second Ester) coarse crystallization is purified, obtain tetrazine compound (1a) 8.4g (aubergine, acicular crystal) of title.

Fusing point: 200 DEG C,

¹H-NMR (300MHz, CDCl₃, δ ppm):

7.59 (ddd, J=0.9,5.1,7.8Hz, 2H), 8.89-8.96 (m, 4H), 9.88 (dd, J=0.9,2.4Hz, 2H)

Embodiment 1~11 and the Comparative Examples 1 to 5

The middle each ingredient recorded of the process (I) of following table 1 and 2 is mixed according to its ratio (mass parts), uses class Mixer in uncle carries out being kneaded for 5 minutes while adjusting revolving speed in such a way that the maximum temperature of mixture becomes 160 DEG C.Into Row maintenance until the temperature of mixture becomes 80 DEG C hereinafter, then, by each ingredient recorded in the process (II) of table 1 and 2 according to Its ratio (mass parts) investment, by the maximum temperature of mixture become 110 DEG C it is below in a manner of be adjusted general progress on one side It is kneaded, manufactures each rubber composition.

Low-heat-generation (tan δ index) test

For the rubber composition (subject composition) made in embodiment 1~11 and the Comparative Examples 1 to 5, viscoplasticity is used Measurement device (Metravib corporation) measures tan under conditions of temperature is 60 DEG C, dynamic strain 5%, frequency are 15Hz δ。

It should be noted that being based on following formula using the rubber composition of comparative example 1 or 3 as reference, low-heat-generation is calculated Index.

It should be noted that the value of low-heat-generation sex index is bigger, indicate that more low-heat-generation, hysteresis loss is smaller.It will ginseng The low-heat-generation of the vulcanized rubber composition of ratio is as 100.

Show the result in table 1 and 2.

Formula:

Low-heat-generation sex index={ (the tan δ of reference)/(the tan δ of subject composition) } × 100

Braking characteristic test

For the rubber composition (subject composition) made in embodiment 1~11 and the Comparative Examples 1 to 5, viscoplasticity is used Measurement device (Metravib corporation) measures under conditions of temperature is 0 DEG C, dynamic strain 0.25%, frequency are 10Hz The tan δ value of low vulcanized rubber.

It should be noted that being based on following formula using the rubber composition of comparative example 1 or 3 as reference, braking ability is calculated Index.The value is higher, indicates that braking characteristic is more excellent.In addition, the braking ability index of the vulcanized rubber composition of reference is made It is 100.

Show the result in table 1 and 2.

Formula:

Braking ability index={ (the tan δ of subject composition)/(the tan δ of reference) } × 100

[table 1]

[table 2]

[explanation of the symbol in table]

Raw material used in table 1 and 2 is as follows.

※ 1: Japanese Zeon Corporation system, trade name " NS116R "

※ 2: Asahi Kasei Corporation's system, trade name " Tufdene 2000R "

※ 3: Ube Industries, Ltd's system, trade name " BR150B "

4: Zhong Hua international corporation's system of ※, trade name " RSS#3 "

※ 5:Tosoh Silica Corporation system, trade name " Nipsil (kind AQ) "

※ 6:Evonik Industries AG system, trade name " Si69 "

※ 7:Evonik Industries AG system, trade name " Si75 "

※ 8:Evonik Industries AG system, trade name " Si363 "

※ 9:Tokai Carbon Co., Ltd., system, trade name " Seast 3 "

※ 10:JXTG Nippon Oil&Energy Corporation system, trade name " Nisseki Neopolymer 150 " (155 DEG C of softening points)

※ 11:JXTG Nippon Oil&Energy Corporation system, trade name " Nisseki Neopolymer L90 " (95 DEG C of softening point)

※ 12:Yasuhara Chemical Co., Ltd. Co. Ltd. system, trade name " YS Resin PX1250 " are (soft Change 125 DEG C of point)

※ 13:Yasuhara Chemical Co., Ltd. Co. Ltd. system, trade name " YS Polyster UH115 " (115 DEG C of softening point)

※ 14:Yasuhara Chemical Co., Ltd. Co. Ltd. system, trade name " YS Resin PX300N " are (soft Change 30 DEG C of point)

※ 15:TonenGeneral Sekiyu K.K. system, trade name " T-REZ HB103 " (103 DEG C of softening point)

※ 16: Japanese Zeon Corporation system, trade name " Quintone 1105 " (107 DEG C of softening point)

※ 17: Kawaguchi's chemical industry Co. Ltd. system, trade name " Antage 6C "

※ 18:Sakai Chemical Industry Co., Ltd. system, zinc oxide kind " a kind "

※ 19:Sichuan Tianyu Grease Chemical Co., Ltd. system

※ 20:Struktol corporation, trade name " HT254 "

※ 21:JXJXTG Nippon Oil&Energy Corporation system, trade name " X-140 (aromatic oil) "

Bis- (3- the pyridyl group) -1,2,4,5- tetrazines (compound manufactured in Production Example 1) of ※ 22:3,6-

Bis- (the 2- pyridyl groups) -1 of ※ 23:3,6-, 2,4,5- tetrazines, Tokyo Chemical Industry Co., Ltd's system

Bis- (the 4- pyridyl groups) -1 of ※ 24:3,6-, 2,4,5- tetrazines, Tokyo Chemical Industry Co., Ltd's system

※ 25: thin well chemical industry Co. Ltd. system, trade name " HK200-5 "

※ 26: Ouchi Shinko Chemical Ind Co., Ltd.'s system, trade name " Nocceler D "

※ 27: Ouchi Shinko Chemical Ind Co., Ltd.'s system, trade name " Nocceler CZ-G "

Industrial availability

Rubber composition of the invention is being well maintained tire while the braking ability in wet road, low-heat-generation Property is excellent, therefore, when using the rubber composition, can manufacture the fetus face (tire tread) of the pneumatic tire of various automobiles.

Claims

1. rubber composition, the tetrazine compound or its salt and softening point indicated containing rubber constituent, the following general formula (1) are 60~160 DEG C of resin,

[chemical formula 1]

In formula, X¹And X²Expression can have the heterocycle of substituent group；

In 100 mass parts rubber constituents, comprising it is more than 40 mass parts make comprising 1,3-butadiene monomer monomer polymerization and Obtained diene series rubber,

For 100 mass parts rubber constituents, include tetrazine compound or its salt and 2~60 described in 0.1~10 mass parts Resin described in mass parts.

2. rubber composition as described in claim 1 also includes inorganic filler and/or carbon black.

3. rubber composition as claimed in claim 2, wherein for 100 mass parts rubber constituents, be comprising total amount The inorganic filler of 30~150 mass parts and/or carbon black.

4. rubber composition as claimed in claim 2 or claim 3, wherein inorganic filler is silica.

5. rubber composition as described in any one of claims 1 to 4, is used for fetus face.

6. tire tyre surface is made using rubber composition described in any one of Claims 1 to 44.

7. pneumatic tire, it uses tire tyre surfaces as claimed in claim 6.