CN110392713A - Rubber composition and tire - Google Patents
Rubber composition and tire Download PDFInfo
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- CN110392713A CN110392713A CN201880017043.7A CN201880017043A CN110392713A CN 110392713 A CN110392713 A CN 110392713A CN 201880017043 A CN201880017043 A CN 201880017043A CN 110392713 A CN110392713 A CN 110392713A
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- mass parts
- rubber composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Rubber composition, the tetrazine compound or its salt and carbon black that it contains rubber constituent, the following general formula (1) indicates, in 100 mass parts rubber constituents, include natural rubbers more than 40 mass parts, it include the aforementioned tetrazine compound or its salt of 0.1~10 mass parts and 30~120 mass parts of carbon black for 100 mass parts rubber constituents.[in formula, X1And X2Expression can have the heterocycle of substituent group.]
Description
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.In addition, not only needing to roll resistance for the tyre for heavy load of the full-sized cars such as truck, bus
Power is small, but also needs with wear resistance.
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, hysteresis loss (hysteresis loss) (rolling resistance) low tire 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, it is not avoided that wear resistance declines.
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
Heavy duty that is excellent, being suitable for manufacture full-sized car that the object of the present invention is to provide wear resistances and low-heat-generation
The rubber composition of lotus tire.
Another object of the present invention is to provide the tires that wear resistance and low-heat-generation are 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
There is the carbon black for adding specific quantity in the rubber composition of the rubber constituent comprising natural rubber and tetrazine based compound, can solve
Above-mentioned project.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, tetrazine compound or its salt and carbon black containing rubber constituent, the following general formula (1) expression,
[chemical formula 1]
[in formula, X1And X2Expression can have the heterocycle of substituent group.]
In 100 mass parts rubber constituents, comprising natural rubbers more than 40 mass parts,
For 100 mass parts rubber constituents, comprising the aforementioned tetrazine compound or its salt of 0.1~10 mass parts and
30~120 mass parts of carbon black.
Item 2.
Rubber composition as described in item 1, wherein the N2 adsorption specific surface area of carbon black is 50~160m2/g。
Item 3.
Rubber composition as described in item 1 or 2 also includes inorganic filler.
Item 4.
Rubber composition as described in item 3, wherein inorganic filler is silica.
Item 5.
Rubber composition as described in item 4, wherein silica is BET specific surface area (m2/ g) 40~350 range
Interior wet silicon dioxide.
Item 6.
Rubber composition as described in any one of item 3~5, wherein for 100 mass parts rubber compositions,
The use level of inorganic filler is 20~150 mass parts.
Item 7.
Rubber composition as described in any one of item 1~6, can be used for fetus face.
Item 8.
Tire tyre surface is made using rubber composition described in any one of item 1~6.
Item 9.
Pneumatic tire, it uses tire tyre surfaces described in item 8.
Item 10.
Tire as described in item 9 is used for the tyre for heavy load of full-sized car.
The effect of invention
Through the invention, the tetrazine compound or its salt and carbon black by indicating specific rubber constituent, general formula (1)
Combination, it is possible to provide excellent low-heat-generation can not only be assigned to tire and excellent wear resistance can also be assigned to tire
Rubber composition.
In addition, make tire by using rubber composition of the invention, thus can not only reduce the rolling resistance of tire,
And the heat generation of tire is reduced, and wear resistance can be improved, therefore, it is possible to provide the low fuel consumption wheel of full-sized car
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 also referred to as " tetrazine compound (1) ".) and carbon black,
[chemical formula 2]
[in formula, X1And X2Expression can have the heterocycle of substituent group.]
In 100 mass parts rubber constituents, comprising natural rubbers more than 40 mass parts,
For 100 mass parts rubber constituents, comprising the aforementioned tetrazine compound or its salt of 0.1~10 mass parts and
30~120 mass parts of carbon black.
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 (acrylonitrile-butadiene copolymer rubber) (NBR), neoprene (CR), ethylene-the third
Alkene-diene terpolymer rubber (EPDM), styrene-isoprene-phenylethene ternary block polymer (SIS), styrene-
Butadiene-styrene ternary block polymer (SBS) etc. and their modified synthesis diene series rubber.As modified synthesis two
Alkene system rubber can be enumerated based on backbone modification, single terminal-modified, two method of modifying such as terminal-modified diene series rubber.Herein,
As the property modifying functional group of modified synthesis diene series rubber, following property modifying functional groups can be enumerated, it includes a kind or more of epoxies
Base, amino, alkoxy, hydroxyl, alkoxysilyl, polyether-based, carboxyl etc. contain heteroatomic functional group.In addition, for
Cis/trans/vinyl ratio of diene portions is not particularly limited, and arbitrary ratio can be used suitably.In addition, diene
It is that the average molecular weight of rubber and molecular weight distribution are not particularly limited, the use of average molecular weight is preferably 500~3,000,000
Diene series rubber.In addition, being gathered it is not also specifically limited, can enumerate using lotion for the manufacturing method for synthesizing diene series rubber
The case where conjunction, polymerisation in solution, free radical polymerization, anionic polymerisation, cationic polymerization etc. synthesize.
For the glass transition temperature of diene series rubber, from the viewpoint for realizing wear resistance and rolling resistance simultaneously
Consider, the glass transition temperature of -120 DEG C~-15 DEG C of range is effective.For rubber composition of the invention,
It is preferred that diene series of the 50 mass % the above are glass transition temperature in the range of -70 DEG C~-20 DEG C in diene series rubber
Rubber.
As non-diene series rubber, known non-diene series rubber can be widely used.
From the viewpoint of wear resistance, rubber constituent used in rubber composition of the invention must include natural rubber
Glue.It more preferably include 60 specifically, preferably comprising the natural rubber of 40 mass parts or more in 100 mass parts rubber constituents
Natural rubbers more than mass parts.
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
In 100 mass parts rubber constituents, preferably with 60 ratio cooperation SBR, BR or their mixture below the mass, more preferably with
40 ratio below the mass cooperates their mixture.In the case where the mixture for cooperating SBR and BR, preferably SBR and BR's
Total amount is above range.Additionally, it is preferred that SBR at this time is the range of 50~100 mass parts, BR is the range of 0~50 mass parts.
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]
[in formula, X1And X2Expression can have the heterocycle of substituent group.]
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-triazines) 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-triazoles) base, 4- (1,2,3-triazoles) base, 5- (1,2,3-triazoles) 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 " 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 " 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
3,6- bis- (2- pyridyl groups) -1,2,4,5- tetrazines,
3,6- bis- (3- pyridyl groups) -1,2,4,5- tetrazines,
3,6- bis- (4- pyridyl groups) -1,2,4,5- tetrazines,
3,6- bis- (2- furyls) -1,2,4,5- tetrazines,
3,6- bis- (3,5- dimethyl -1- pyrazolyls) -1,2,4,5- tetrazines,
3,6- bis- (2- thienyls) -1,2,4,5- tetrazines,
3- methyl -6- (2- pyridyl group) -1,2,4,5- tetrazines,
3,6- bis- (2- pyrimidine radicals) -1,2,4,5- tetrazines,
3,6- bis- (2- pyrazinyls) -1,2,4,5- tetrazines 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, bis- (the 2- furyls) -1 of 2,4,5- tetrazines, 3,6-, 2,4,5- tetrazines and 3,6- bis- (4- pyridyl groups) -1,2,4,5- tetra-
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 3, bis- (the 4- pyridyl groups) -1 of 6-, 2,4,5- tetrazines.
From the viewpoint of assigning low-rolling-resistance to rubber constituent, relative to the rubber constituent 100 in rubber composition
For mass parts, the use level of tetrazine compound (1) is 0.1~10 mass parts.Relative to the rubber constituent in rubber composition
For 100 mass parts, the preferred use level of tetrazine compound (1) is 0.25~5 mass parts, more preferably 0.5~2 mass
Part.
In the case that tetrazine compound (1) is powder, volume average particle size is not particularly limited.From presentation low-heat-generation
From the viewpoint of, volume average particle size be preferably 300 μm hereinafter, further preferably 150 μm hereinafter, particularly preferably 75 μm with
Under.
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.
Carbon black
Cooperate carbon black in rubber composition of the invention.By including carbon black, energy in rubber composition of the invention
Improve wear resistance.
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,
Carbon black of N220, N234, N330, N339, N375, N550, HAF, FEF, GPF, SRF grade etc. can be enumerated.Wherein, as preferred
Carbon black, be SAF, ISAF, IISAF, N134, N234, N330, N339, N375, HAF or FEF grade carbon black.
The N2 adsorption specific surface area (N2SA is measured according to JIS K 6217-2:2001) of carbon black is preferably 50~
160m2/g.As the N2 adsorption specific surface area of carbon black, more preferably 60~140m2/ g, further preferably 80~135m2/g。
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。
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.
For 100 mass parts rubber constituents, cooperate 30~120 mass parts of carbon black.Relative to 100 mass parts rubber
For ingredient, the use level of carbon black is preferably 35~80 mass parts, more preferably 40~70 mass parts.
It is preferred that rubber composition of the invention is other than comprising above-mentioned rubber constituent, tetrazine compound (1) and carbon black,
It also include inorganic filler.
For 100 mass parts rubber constituents, the use level of inorganic filler is usually 0~100 mass parts, preferably
0~60 mass parts, more preferably 0~40 mass parts.
It should be noted that for carbon black and inorganic filler, existing in the following manner in rubber composition of the invention
Appropriate adjustment is carried out 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 100 matter
For measuring part rubber constituent, become usual 30~150 mass parts, preferably 35~130 mass parts, more preferable 40~100 mass parts.
When carbon black and total use level of inorganic filler are 30 mass parts or more, mentioned from the wear resistance of rubber composition
Be from the viewpoint of height it is preferred, be 150 below the mass when, be preferred from the viewpoint of reducing rolling resistance.It needs
Illustrate, when cooperating carbon black and inorganic filler, it is possible to use first pass through mother made of wet type or dry type and mixed with polymers in advance
Expect 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 titanium2n-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.
In order to assign rubbery intensity, silica is preferably added.As silica, it can be used commercially available all two
Silica.It wherein, is wet silicon dioxide, dry type silica or colloidal silicon dioxide as preferred silica, more
Preferably wet silicon dioxide.It, can be inorganic to this in order to improve the compatibility with rubber constituent for these silica
The surface of filler carries out organic process.
Wherein, as inorganic filler, from the viewpoint of wear resistance, preferred silica.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.
Other compounding agents
In rubber composition of the invention, other than above-mentioned tetrazine compound (1), carbon black and inorganic filler, also
The vulcanizing agents such as usually used compounding agent in rubber industry circle, such as sulphur can be cooperated.It, can be in rubber composition of the invention
Further cooperate other compounding agents, for example, antiaging agent, antiozonant, softening agent, processing aid, wax, resin, foaming agent, oil,
Stearic acid, the flowers of zinc (ZnO), vulcanization accelerator, vulcanization retarder etc..These compounding agents can be in the model for not interfering the purpose of the present invention
It encloses interior appropriate selection and is 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- (3,6,9,12, the 15- five oxa- octacosanes-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- (3,6,9,12, the 15- five oxa- octacosane -1- base oxygen 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, resin etc. can be added in the case where especially paying attention to braking characteristic.Specifically, rosin series tree can be enumerated
The tree of the natural resins such as rouge, terpenic series resin, petroleum line resin, phenolic aldehyde system resin, coal measures resin, diformazan benzene series resin etc
Rouge.As rosin series resin, gum rosin (gum rosin), toll oil rosin (tall oil rosin), wood rosin can be enumerated
(wood rosin), hydrogenated rosin, disproportionated rosin (disproportionated rosin), newtrex, modified rosin it is sweet
The resin of oil, pentaerythritol ester etc can enumerate the terpenes such as australene system, nopinene system, cinene system as terpenic series resin
The resin of resin, aromatic modified terpene resin, terpene phenolic resin, hydrogenated terpene resin etc.
In addition, in the case where paying attention to processability, as processing aid, mineral oil, vaseline, paraffin, petroleum tree can be enumerated
Rouge, fatty acid, aliphatic ester, fatty alcohol, metallic soap, fatty acid amide, phenolic resin, polyethylene, polybutene, peptizing agent, again
The processing aid of raw agent, organosiloxane 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 alkane hydrocarbon system
Technical oil, aromatic series technical oil.
The purposes of rubber composition
It as the purposes of rubber composition of the invention, is not particularly limited, can enumerate such as the rubber part of tire.
Wherein, preferred purposes is the fetus face of the tyre for heavy load such as tire, truck.
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), carbon black and the raw material of inorganic filler as needed at
The process (II) divided the process (I) being kneaded and be kneaded mixture obtained in process (I) and vulcanizing agent.
Process (I)
Process (I) be will include rubber constituent, tetrazine compound (1), carbon black and the raw material of inorganic filler as needed
The process that ingredient 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), charcoal
The method that the composition of black and as needed inorganic filler is kneaded.It, can be once by the complete of each ingredient in the mixing method
Portion's amount is kneaded, and the purpose of can also being adjusted according to viscosity, each ingredient is put by several times and is kneaded.Furthermore it is possible to by rubber
It after ingredient and carbon black are kneaded, put into tetrazine compound (1) and is kneaded, or rubber constituent and tetrazine compound (1) is mixed
After refining, puts into carbon black and be kneaded.For process (I), mixing can be repeated in multiple times.Cooperate inorganic filler
In the case of, inorganic filler can put into together with carbon black and is kneaded.
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.
In process (I), for 100 mass parts rubber constituents, cooperate 0.1~10 mass parts tetrazine compound (1).
As the use level of tetrazine compound (1), for 100 mass parts rubber constituents, preferably 0.25~5 mass parts, more
Preferably 0.5~2 mass parts.
In process (I), for 100 mass parts rubber constituents, cooperate 30~120 mass parts of carbon black.As carbon black
Use level, for 100 mass parts rubber constituents, preferably 35~80 mass parts, more preferably 40~70 mass parts.
In the case where comprising inorganic filler, as the use level of the inorganic filler in process (I), relative to 100 mass parts
For rubber constituent, usually 20~150 mass parts, preferably 35~120 mass parts, more preferably 40~90 mass parts.
It should be noted that in process (I), for carbon black and inorganic filler, in the following manner in the upper of each ingredient
State and carry out appropriate adjustment in the range of use level: in terms of the total amount of two-component, for example, relative to 100 mass parts rubber at
For point, 30~150 mass parts are usually become.
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), carbon black and nothing as needed obtained in process (I-1)
The two stage mixing method for the process (I-2) that machine filler is 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.
In process (I-1), for 100 mass parts rubber constituents, cooperate 0.1~10 mass parts tetrazine compound
(1).As the use level of tetrazine compound (1), for 100 mass parts rubber constituents, preferably 0.25~5 mass
Part, more preferably 0.5~2 mass parts.
Pass through the diene series rubber by the process (I-1) of the rubber constituent and tetrazine compound (1) mixing, in rubber constituent
Double bond reacted with tetrazine compound (1), formed it is polymer-modified.
As when mixture (polymer-modified) obtained in process (I-1) and carbon black being mixed in process (I-2)
Temperature is not particularly limited, for example, the upper limit of the temperature of mixture is 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.
For 100 mass parts of mixture (polymer-modified) obtained in process (I-1), in process (I-2)
The use level of carbon black is 30~120 mass parts.As the use level of carbon black, (change relative to mixture obtained in process (I-1)
Property polymer) for 100 mass parts, preferably 35~80 mass parts, more preferably 40~70 mass parts.
In process (I-2) in the case where cooperation inorganic filler, as its use level, relative to obtained in process (I-1)
For 100 mass parts of mixture (polymer-modified), usually 20~150 mass parts, preferably 30~120 mass parts, more excellent
It is selected as 40~90 mass parts.
It should be noted that in process (I-2) in the case where cooperation inorganic filler, for carbon black and inorganic filler,
Appropriate adjustment is carried out in the range of the above-mentioned use level of each ingredient in the following manner: in terms of the total amount of two-component, for example,
For 100 mass parts of mixture (polymer-modified) obtained in process (I-1), 35~150 mass parts are usually become.
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 carbon black and according to circumstances be dispersed with the mixture of inorganic filler.
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 the vulcanization accelerators such as stearic acid, the flowers of zinc that can often cooperate in rubber composition, antiaging agent.
By above-mentioned process (I) and process (II), can manufacture containing useful tetrazine compound (1) to two in rubber constituent
Polymer-modified, carbon black obtained from alkene system rubber is handled and the rubber composition of inorganic filler as needed.
It should be noted that rubber composition of the invention includes both following rubber compositions: be combined with rubber at
Point, the composition of tetrazine compound (1), carbon black and inorganic filler as needed；And using tetrazine compound (1) to rubber
Diene series rubber in glue ingredient rubber of polymer-modified, carbon black and inorganic filler as needed obtained from being handled
Glue composition.
Process (I) or the polymer-modified of (I-1) middle formation can be by carrying out shown in following -1~reaction equations of reaction equation -4
Such reaction is to 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 and wear resistance.
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 top load tire 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
Mode.
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 refers to that the downside of the slave shoulder portion in such as Pneumatic belt tire to the part of bead part, is
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 the structure for 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, In are 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 is obtained and slightly ties product 19g.
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)
Examples 1 to 6 and comparative example 1~6
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 carry out while being adjusted
It is kneaded, manufactures each rubber composition.
Abrasion test
For the rubber composition (subject composition) made in Examples 1 to 6 and comparative example 1~6, at room temperature, In
Slip rate (slip rate) implements LAMBOURN wear test (JIS K 6264) under conditions of being 24%.It will be made in comparative example 1
The rubber composition of work is based on following formula as reference, calculates wear resistance index.
Show the result in table 1 and 2.
Formula:
Wear resistance index={ (abrasion loss of reference)/(abrasion loss of subject composition) } × 100
Low-heat-generation (tan δ index) test
For the rubber composition (subject composition) made in Examples 1 to 6 and comparative example 1~6, surveyed using viscoplasticity
Determine device (Metravib corporation), tan δ is measured under conditions of temperature is 40 DEG C, dynamic strain 5%, frequency are 15Hz.
Using the rubber composition made in comparative example 1 as reference, it is based on following formula, calculates low-heat-generation sex 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.In addition,
Using the low-heat-generation of the vulcanized rubber composition of reference 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
[table 1]
[table 2]
[explanation of the symbol in table]
Raw material used in table 1 and 2 is as follows.
※ 1:JSR Co. Ltd. system, kind " SB R1502 "
※ 2: Ube Industries, Ltd's system, trade name " BR150B "
3: Zhong Hua international corporation's system of ※, trade name " RSS#3 "
※ 4:Tokai Carbon Co., Ltd., system, trade name " Seast 6 " (N2 adsorption specific surface area 119m2/g)
※ 5:Tokai Carbon Co., Ltd., system, trade name " Seast 3 " (N2 adsorption specific surface area 79m2/g)
※ 6: Kawaguchi's chemical industry Co. Ltd. system, trade name " Antage 6C "
※ 7:Sakai Chemical Industry Co., Ltd. system, zinc oxide kind " a kind "
※ 8:Sichuan Tianyu Grease Chemical Co., Ltd. system
※ 9: Japan Sekiscoat Co., Ltd.'s system, trade name " OZOACE-0355 "
※ 10:JXJXTG Nippon Oil&Energy Corporation system, trade name " X-140 (aromatic oil) "
Bis- (the 3- pyridyl groups) -1 of ※ 11:3,6-, 2,4,5- tetrazines (compound manufactured in Production Example 1)
Bis- (the 2- pyridyl groups) -1 of ※ 12: 3,6-, 2,4,5- tetrazines, Tokyo Chemical Industry Co., Ltd's system
Bis- (the 4- pyridyl groups) -1 of ※ 13: 3,6-, 2,4,5- tetrazines, Tokyo Chemical Industry Co., Ltd's system
※ 14: thin well chemical industry Co. Ltd. system, trade name " HK200-5 "
※ 15: Ouchi Shinko Chemical Ind Co., Ltd.'s system, trade name " Nocceler CZ-G "
※ 16: Ouchi Shinko Chemical Ind Co., Ltd.'s system, trade name " CTP "
Industrial availability
Rubber composition of the invention since wear resistance and low-heat-generation are excellent, use the rubber composition
When, the pneumatic tire of various automobiles, the fetus face (tire tread) of especially top load tire can be manufactured.
Claims (5)
1. rubber composition, tetrazine compound or its salt and carbon black containing rubber constituent, the following general formula (1) expression,
[chemical formula 1]
In formula, X1And X2Expression can have the heterocycle of substituent group；
In 100 mass parts rubber constituents, comprising natural rubbers more than 40 mass parts,
For 100 mass parts rubber constituents, comprising tetrazine compound or its salt described in 0.1~10 mass parts and 30~
120 mass parts of carbon black.
2. rubber composition as described in claim 1, wherein the N2 adsorption specific surface area of carbon black is 50~160m2/g。
3. tire tyre surface is made using rubber composition described in as claimed in claim 1 or 22.
4. pneumatic tire, it uses tire tyre surfaces as claimed in claim 3.
5. tire as claimed in claim 4 is used for the tyre for heavy load of full-sized car.
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| CN112745542A (en) * | 2020-12-25 | 2021-05-04 | 大冢材料科技（上海）有限公司 | Rubber composition and preparation method thereof |
| CN112778592A (en) * | 2019-11-06 | 2021-05-11 | 大冢材料科技（上海）有限公司 | Low-hysteresis-loss rubber composition for tire |
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| WO2018169064A1 (en) * | 2017-03-17 | 2018-09-20 | 大塚化学株式会社 | Rubber composition for tire for icy and snowy roads, and studless tire |
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| CN1738837A (en) * | 2003-11-06 | 2006-02-22 | 横滨橡胶株式会社 | Thermoplastic elastomer and thermoplastic elastomer composition |
| CN102532622A (en) * | 2010-11-11 | 2012-07-04 | 固特异轮胎和橡胶公司 | Pneumatic tire having an innerliner of a rubber composition comprising diene based elastomer and resin |
| JP2015093928A (en) * | 2013-11-12 | 2015-05-18 | 東洋ゴム工業株式会社 | Inner liner rubber composition and pneumatic tire |
| CN104919609A (en) * | 2013-01-29 | 2015-09-16 | 富士胶片株式会社 | Thermoelectric conversion material, thermoelectric conversion element, and article for thermoelectric power generation and sensor power source using same |
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| KR102592174B1 (en) * | 2015-09-30 | 2023-10-19 | 오츠카 가가쿠 가부시키가이샤 | Additives to provide low heat generation properties to rubber components |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738837A (en) * | 2003-11-06 | 2006-02-22 | 横滨橡胶株式会社 | Thermoplastic elastomer and thermoplastic elastomer composition |
| CN102532622A (en) * | 2010-11-11 | 2012-07-04 | 固特异轮胎和橡胶公司 | Pneumatic tire having an innerliner of a rubber composition comprising diene based elastomer and resin |
| CN104919609A (en) * | 2013-01-29 | 2015-09-16 | 富士胶片株式会社 | Thermoelectric conversion material, thermoelectric conversion element, and article for thermoelectric power generation and sensor power source using same |
| JP2015093928A (en) * | 2013-11-12 | 2015-05-18 | 東洋ゴム工業株式会社 | Inner liner rubber composition and pneumatic tire |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778592A (en) * | 2019-11-06 | 2021-05-11 | 大冢材料科技（上海）有限公司 | Low-hysteresis-loss rubber composition for tire |
| CN112745542A (en) * | 2020-12-25 | 2021-05-04 | 大冢材料科技（上海）有限公司 | Rubber composition and preparation method thereof |
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| WO2018164247A1 (en) | 2018-09-13 |
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| JP6701434B2 (en) | 2020-05-27 |
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