CN103998508A - Tyre comprising a composition essentially free of guanidine derivative and comprising a hydroxylated diamine - Google Patents

Tyre comprising a composition essentially free of guanidine derivative and comprising a hydroxylated diamine Download PDF

Info

Publication number
CN103998508A
CN103998508A CN201280062619.4A CN201280062619A CN103998508A CN 103998508 A CN103998508 A CN 103998508A CN 201280062619 A CN201280062619 A CN 201280062619A CN 103998508 A CN103998508 A CN 103998508A
Authority
CN
China
Prior art keywords
tire
composition
group
diene elastomer
diamines
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201280062619.4A
Other languages
Chinese (zh)
Other versions
CN103998508B (en
Inventor
C·达尔诺
K·隆尚邦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie Generale des Etablissements Michelin SCA
Original Assignee
Michelin Recherche et Technique SA Switzerland
Compagnie Generale des Etablissements Michelin SCA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Michelin Recherche et Technique SA Switzerland, Compagnie Generale des Etablissements Michelin SCA filed Critical Michelin Recherche et Technique SA Switzerland
Publication of CN103998508A publication Critical patent/CN103998508A/en
Application granted granted Critical
Publication of CN103998508B publication Critical patent/CN103998508B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • B60C1/0016—Compositions of the tread
    • 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
    • B60C2001/0066—Compositions of the belt layers

Landscapes

  • 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)

Abstract

The invention therefore relates to a tyre comprising a rubber composition based on at least one diene elastomer, a reinforcing filler predominantly comprising silica, a crosslinking system, said composition being essentially free of guanidine derivative and also comprising a hydroxylated diamine of formula (I): in which R1 represents a linear or branched alkylene group comprising from 1 to 18 carbon atoms, R2 and R3 independently represent a linear or branched alkyl group comprising from 1 to 18 carbon atoms, it being understood that the hydroxylated diamine of formula (I) bears one or more hydroxyl groups on at least one carbon-based chain selected from R1, R2 and R3.

Description

Comprise the tire of the composition that does not basically contain guanidine derivative and comprise hydroxylation diamines
Technical field
The present invention relates to tire, relate more particularly to those tires that composition comprises hydroxylation diamines.
Background technology
Because need to becoming of saving of fuel and protection of the environment is preferential, confirm to be necessary that preparation has the rolling resistance of reduction and can not adversely affect the tire of other character of tire.Producer has developed tire composition, and described tire composition likely reduces this rolling resistance especially by introducing silicon-dioxide as reinforcing filler in mixture.
However, producer always finds the solution of the rolling resistance of further reduction tire, under this background, applicant company is found unexpectedly, introduces hydroxylation diamines and likely reduces and comprise the hysteresis quality of silicon-dioxide as the diene rubber compsns of main reinforcing filler as the substitute of guanidine derivative.
In addition, described solution goes out many other advantages than the composition exhibiting of prior art, particularly more cheaply and likely improves the use of the compound of environment footprint.
In implication of the present invention, hydroxylation diamines is the tertiary diamine being replaced by alkyl chain, and in described alkyl chain one is with primary amine functional group, and at least one in described alkyl chain is with at least one hydroxy functional group.
These hydroxylation diamines are never used to replace comprising silicon-dioxide as the guanidine derivative in the diene elastomer mixture of main stuffing and have above-mentioned advantage as proposed in the application company.
Summary of the invention
Therefore the present invention relates to a kind of tire that comprises rubber combination, described rubber combination is based at least one diene elastomer, mainly wrap silica containing reinforcing filler and cross-linking system, described composition does not basically contain guanidine derivative, and the hydroxylation diamines of contained (I) in addition:
Wherein R 1represent the straight or branched alkylidene group that comprises 1 to 18 carbon atom, R 2and R 3represent independently the straight or branched alkyl that comprises 1 to 18 carbon atom, the hydroxylation diamines that should understand formula (I) is being selected from R 1, R 2and R 3at least one carbon back chain on there are one or more hydroxyls.
Preferably, the present invention relates to one tire as defined above, the composition that wherein comprises hydroxylation diamines comprises and is less than 0.45phr, is preferably less than the guanidine derivative of 0.4phr.
Also preferably, the present invention relates to one tire as defined above, wherein the content of hydroxylation diamines is 0.1 to 8phr, is preferably and exceedes 0.15phr to 7phr.More preferably, the content of hydroxylation diamines is 0.2 to 5phr, is preferably and exceedes 0.25phr to 4phr.
More preferably, the present invention relates to one tire as defined above, wherein R 1, R 2and R 3comprise 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, extremely preferably 2 to 4 carbon atoms.Also preferably, R 1, R 2and R 3represent straight chain carbon back chain.Also preferably, the hydroxyl value that the hydroxylation diamines of formula (I) has is 1 to 4, more preferably 1,2 or 3.Described hydroxyl or these hydroxyls are preferably by R 2and R 3institute has.Most preferably, R 2there is hydroxyl, R 3there is hydroxyl, and R 1do not there is hydroxyl.
Preferably, the present invention relates to one tire as defined above, wherein dioxide-containing silica is 30 to 150phr.
Also preferably, the present invention relates to one tire as defined above, wherein said reinforcing filler comprises a small amount of carbon black.Preferably, the content of carbon black is 0.5 to 50phr.
More preferably, the present invention relates to one tire as defined above, wherein said diene elastomer is selected from polyhutadiene, synthetic polyisoprenes, natural rubber, butadienecopolymer, isoprene copolymer (as butadiene/styrene copolymers, isoprene/butadiene multipolymer, isoprene/styrol copolymer and isoprene/butadiene/styrol copolymer) and these elastomeric mixtures.
According to a preferred form, the present invention relates to one tire as defined above, wherein said diene elastomer is mainly made up of the diene elastomer of non-isoprene.
Preferably, the present invention relates to one tire as defined above, wherein said diene elastomer is made up of the diene elastomer of the non-isoprene of 100phr.
Also preferably, the present invention relates to one tire as defined above, the diene elastomer of wherein said non-isoprene is selected from polyhutadiene, butadienecopolymer, isoprene copolymer (as butadiene/styrene copolymers, isoprene/butadiene multipolymer, isoprene/styrol copolymer and isoprene/butadiene/styrol copolymer) and these elastomeric mixtures.
More preferably, the present invention relates to one tire as defined above, wherein said composition comprises softening agent in addition, and described softening agent is preferably selected from resin of plastification, extending oil and their mixture.
Preferably, the present invention relates to one tire as defined above, wherein plasticizer loading is 5 to 100phr.
Preferably, the present invention relates to one tire as defined above, wherein said composition is in addition containing zinc, or comprises and be less than 0.5phr, is preferably less than the zinc of 0.3phr.
Also preferably, the present invention relates to one tire as defined above, described tire comprises coupling agent in addition.
Preferably, the present invention relates to one tire as defined above, wherein said coupling agent is the silicol polysulfide corresponding to general formula (III):
(HO) aR (3-a)Si-R'-S x-R'-SiR (3-b)(OH) b (III)
Wherein:
-R group is identical or different, and is the alkyl that preferably comprises 1 to 15 carbon atom;
-R' group is identical or different, and is the divalent linker that preferably comprises 1 to 18 carbon atom;
-a and b are identical or different, and equal 1 or 2;
-x is more than or equal to 2 number.
More preferably, the present invention relates to one tire as defined above, wherein said coupling agent is monohydroxy silane, and wherein a and b equal 1.
Also more preferably, the present invention relates to one tire as defined above, wherein said R group is selected from straight or branched C 1-C 6alkyl, C 5-C 8cycloalkyl or phenyl; R' group is selected from C 1-C 18alkylidene group or C 6-C 12arylidene.More particularly, R group is selected from C 1-C 6alkyl, and R' group is selected from C 1-C 10alkylidene group.
Most preferably, the present invention relates to one tire as defined above, wherein said silicol is the monohydroxy silane polysulfide of formula (IV):
Wherein R group is C 1-C 3alkyl, is preferably methyl; R' group is C 1-C 4alkylidene group, preferably methylene radical, ethylidene or propylidene; X is more than or equal to 2.More particularly, described silicol is two (propyl-dimethyl silanol) polysulfides of concrete formula (IVa):
Preferably, the present invention relates to one tire as defined above, the composition that the composition that wherein comprises hydroxylation diamines is tire layer, described tire layer is selected from all or part of, tire belt all or part of of tyre surface and their combination.
Preferably, the present invention relates to one tire as defined above, all or part of composition that the composition that wherein comprises hydroxylation diamines is tyre surface.
Can for example, in one or more (cord body of tyre surface, tire belt, casingply or any other layers) of its various layers, comprise above-mentioned composition according to tire of the present invention.In the implication of present patent application, tire tread represents whole (on its whole thickness) or a part (comprising lower floor) for the rubber layer contacting with ground, described rubber layer, particularly in the time that described rubber layer forms by several layers.
Preferably, the present invention relates to one tire as defined above, the composition that the composition that wherein comprises hydroxylation diamines is tire layer, described tire layer is selected from all or part of, tire belt all or part of of tyre surface and their combination.
Preferably, the present invention relates to one tire as defined above, all or part of composition that wherein said composition is tyre surface.
Preferably, tire according to the present invention is selected from and is intended to assemble sulky vehicle, Passenger Vehicle or heavy vehicle (being subway, motorbus, off-road vehicle, heavy Road transport vehicle (as truck, tractor or trailer)), or the tire of flyer, Architectural Equipment, heavy agricultural vehicle or carrying vehicle.
Embodiment
the composition of I-composition
Rubber combination according to the present invention is based on following composition: at least one diene elastomer, reinforcing filler, cross-linking system and hydroxylation diamines.
Statement " based on ... composition " mixture that is interpreted as meaning comprising various basal component used and/or the composition of reaction in－situ product, some in these compositions can and/or be intended to manufacturing reaction each other at least in part in each phase process of composition or in solidification process subsequently, thus in the time starting to prepare composition improved composition.Therefore, for composition of the present invention at non-crosslinked state with can be different under cross-linked state.
In this manual, unless clearly indicated in addition, shown all per-cents (%) are all weight percentage.In addition, the interval representative of any value being represented by statement " between a to b " (does not comprise limit a and b), (comprises strict limit a and b) and the interval of any value being represented by statement " a to b " means by a until the scope of the value of b to the scope of the value that is less than b by being greater than a.
i-1 diene elastomer
Composition can only comprise a kind of diene elastomer, or the mixture that comprises several diene elastomers.
Here should remember, the elastomerics of " diene " type (or " rubber ", two terms are considered to synonym) should be interpreted as one (the being interpreted as one or more) elastomerics that means (being homopolymer or multipolymer) at least partly and be derived from diene monomers (with monomers two conjugation or unconjugated carbon-to-carbon double bond) in known manner.
Described diene elastomer can be divided into two classes: " substantially undersaturated " or " substantially saturated ".Conventionally, " substantially undersaturated " is interpreted as meaning to be derived from least partly the diene elastomer that unit, diene source (conjugated diolefine) content is greater than the conjugate diene monomer of 15% (mol%); Therefore, diene elastomer such as the EPDM type multipolymer of isoprene-isobutylene rubber or diene and alpha-olefin does not fall into aforementioned definitions, but can be described as especially " substantially saturated " diene elastomer (diene source unit content is low or very low, is less than all the time 15%).In the classification of " substantially undersaturated " diene elastomer, " highly undersaturated " diene elastomer is interpreted as meaning especially to have the diene elastomer of unit, diene source (conjugated diolefine) content that is greater than 50%.
According to these definition, can be used according to the diene elastomer in composition of the present invention and should more particularly be interpreted as and mean:
(a)-there is by polymerization any homopolymer that the conjugate diene monomer of 4 to 12 carbon atoms obtains;
(b)-by making the copolymerization or make one or more conjugated diolefines and any multipolymer that vinyl aromatic compounds copolymerization that one or more have 8 to 20 carbon atoms obtains each other of one or more conjugated diolefines;
(c)-terpolymer of obtaining by the alpha-olefin that makes ethene and there are 3 to 6 carbon atoms and the non-conjugated diene monomers copolymerization with 6 to 12 carbon atoms, for example, by the non-conjugated diene monomers of ethene and propylene and the above-mentioned type (especially, as Isosorbide-5-Nitrae-hexadiene, ethylidene norbornene or Dicyclopentadiene (DCPD)) obtain elastomerics;
(d) multipolymer (isoprene-isobutylene rubber) of-iso-butylene and isoprene, and the halogenated form of the multipolymer of described type, particularly chlorination or bromination form.
Although the present invention is applicable to the diene elastomer of any type, the technician in tire field should be understood that the present invention preferably uses substantially undersaturated diene elastomer, particularly as above type (a) or diene elastomer (b).
Be particularly suitable as follows conjugated diolefine: 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 2,3-bis-(C 1-C 5alkyl) and-1,3-butadiene (for example 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene or 2-methyl-3-sec.-propyl-1,3-butadiene), aryl-1,3-divinyl, 1,3-pentadiene or 2,4-hexadiene.For example, be suitable as follows vinyl aromatic compounds: vinylbenzene, o-, m-or p-vinyl toluene, " Vinyl toluene " commercial mixture, p-(tertiary butyl) vinylbenzene, methoxy styrene, chloro-styrene, vinyl mesitylene, Vinylstyrene or vinyl naphthalene.
Described multipolymer can comprise the vinyl aromatic units between diene units and 1 % by weight to 80 % by weight between 99 % by weight to 20 % by weight.Described elastomerics can have and depends on the existence of polymerizing condition used, particularly properties-correcting agent and/or randomization reagent or do not exist and any microstructure of the amount of properties-correcting agent used and/or randomization reagent.Described elastomerics can be, for example block, random, sequence or micro-sequence elastomerics, and can in dispersion or in solution, make; They can be coupling and/or star-branched, or available coupling agent and/or star-branched reagent or functionalized reagent carry out functionalized.For example, for being coupled to carbon black, can mention the functional group or aminated functional group, for example aminobenzophenone that comprise C-Sn key, for the enhancing mineral filler being coupled to such as silicon-dioxide, the polysiloxane functional group that can mention for example silanol or have a silanol end (is for example described in FR2 740 778, in US6 013 718 and WO2008/141702), alkoxysilane groups (being for example described in FR2 765 882 or US5 977 238), carboxyl (is for example described in WO01/92402 or US6 815 473, in WO2004/096865 or US2006/0089445) or polyether group (be for example described in EP1 127 909, US6 503 973, in WO2009/000750 and WO2009/000752).Also can mention that the elastomerics (as SBR, BR, NR or IR) of epoxidation type is as other examples of functionalized elastomeric body.
These can be used as the elastomeric blend functionalized with blend inclusive NAND each other through functionalized elastomerics.For example, likely use to there is the silanol of silanol end-or polysiloxane-functionalized elastomerics as with use tin coupling and/or star-branched elastomeric mixture (being described in WO11/042507), the described coupling of use tin and/or star-branched elastomerics have 5% to 50%, for example 25% to 50% content.
It is suitable as follows: polyhutadiene, particularly 1, 2-unit content (mol%) is those or cis-1 between 4% to 80%, 4-unit content (mol%) is greater than those of 80%, polyisoprene, butadiene/styrene copolymers, particularly Tg (second-order transition temperature, Tg, record according to ASTM D3418) be between 0 DEG C to-70 DEG C and be more particularly between-10 DEG C to-60 DEG C, styrene content is between 5 % by weight to 60 % by weight and is more particularly between 20 % by weight to 50 % by weight, 1 of divinyl part, 2-linkage content (mol%) is between 4% to 75% and anti-form-1, 4-linkage content (mol%) is those between 10% to 80%, divinyl/isoprene copolymer, particularly isoprene content is between 5 % by weight to 90 % by weight and Tg is those of-40 DEG C to-80 DEG C, or isoprene/styrol copolymer, particularly styrene content is between 5 % by weight to 50 % by weight and Tg is those between-5 DEG C to-60 DEG C.In the situation of Butadiene/Styrene/isoprene copolymer, specially suitable is that styrene content is between 5 % by weight to 50 % by weight, be more particularly between 10 % by weight to 40 % by weight, isoprene content is between 15 % by weight to 60 % by weight, be more particularly between 20 % by weight to 50 % by weight, butadiene content is between 5 % by weight to 50 % by weight, be more particularly between 20 % by weight to 40 % by weight, 1 of divinyl part, the content (mol%) of 2-unit is between 4% to 85%, trans 1 of divinyl part, the content (mol%) of 4-unit is between 6% to 80%, 1 of isoprene part, 2-adds 3, the content (mol%) of 4-unit is between 5% to 70%, the anti-form-1 of isoprene part, the content (mol%) of 4-unit is those between 10% to 50%, more generally Tg is any Butadiene/Styrene/isoprene copolymer between-20 DEG C to-70 DEG C.
In a word, the diene elastomer of composition is preferably selected from the group by the undersaturated diene elastomer of height forming as follows: polyhutadiene (being abbreviated as " BR "), synthetic polyisoprenes (IR), natural rubber (NR), butadienecopolymer, isoprene copolymer and these elastomeric mixtures.This multipolymer is more preferably selected from two or more the mixture in butadiene/styrene copolymers (SBR), isoprene/butadiene multipolymer (BIR), isoprene/styrol copolymer (SIR), isoprene/butadiene/styrol copolymer (SBIR), butadiene/acrylonitrile copolymer (NBR), Butadiene/Styrene/acrylonitrile copolymer (NSBR) or these compounds.
According to a specific embodiments, described composition comprises 50 to 100phr SBR elastomerics, and no matter it is the SBR (" ESBR ") making in milk sap or is the SBR (" SSBR ") making in solution.
According to another particular, described diene elastomer is SBR/BR blend (mixture).
The embodiment possible according to other, described diene elastomer is SBR/NR (or SBR/IR), BR/NR (or BR/IR) or SBR/BR/NR (or SBR/BR/IR) blend.
In the elastomeric situation of SBR (ESBR or SSBR), use especially and there is medium styrene content (for example, between 20 % by weight to 35 % by weight) or high-phenylethylene content (for example 35% to 45%), the content of the vinyl bonds of divinyl part is between 15% to 70%, anti-form-1, the content (mol%) of 4-key is between 15% to 75%, and Tg is the SBR between-10 DEG C to-55 DEG C; This SBR can be advantageously used for and the mixture of BR preferably with the cis-Isosorbide-5-Nitrae-key that is greater than 90% (mol%).
According to another specific embodiments, described diene elastomer is mainly isoprene elastomerics (that is, than other elastomeric weight fractions, the elastomeric weight fraction maximum of the isoprene of described diene elastomer)." isoprene elastomerics " should be interpreted as in known manner and mean isoprene homopolymer or multipolymer, in other words, be selected from natural rubber (NR) (its can be through plasticising or through dispergation), the diene elastomer of synthetic polyisoprenes (IR), various isoprene copolymer and these elastomeric mixtures.In isoprene copolymer, to mention especially iso-butylene/isoprene copolymer (isoprene-isobutylene rubber-IIR), isoprene/styrol copolymer (SIR), isoprene/butadiene multipolymer (BIR) or isoprene/butadiene/styrol copolymer (SBIR).Described isoprene elastomerics is preferably natural rubber or synthesizing cis-Isosorbide-5-Nitrae-polyisoprene; In these synthetic polyisoprenes, preferably use the content (mol%) of cis-Isosorbide-5-Nitrae-key to be greater than 90%, also more preferably greater than 98% polyisoprene.
Preferably, according to another embodiment, described rubber combination mainly comprises the diene elastomer of (having the highest weight content) non-isoprene.In the implication of present patent application, " diene elastomer of non-isoprene " is interpreted as representing that at least part of (being homopolymer or multipolymer) is derived from the elastomerics of the diene monomers (having the monomer of two carbon-to-carbon double bonds) except isoprene.Therefore,, in the implication of this definition, therefore the diene elastomer of non-isoprene also comprises and comprises the multipolymer of isoprene as comonomer.Natural rubber and isoprene homopolymer (by forming through functionalized or non-functionalized isoprene monomer) are excluded outside this definition.According to described preferred embodiment, all above-mentioned elastomerics except natural rubber and polyisoprene is suitable as the diene elastomer of non-isoprene.Especially, likely use the diene elastomer being preferably selected from by the non-isoprene of the group of the undersaturated diene elastomer of height forming as follows: polyhutadiene (being abbreviated as " BR "), butadienecopolymer, isoprene copolymer and these elastomeric mixtures.This multipolymer is more preferably selected from butadiene/styrene copolymers (SBR), isoprene/butadiene multipolymer (BIR), isoprene/styrol copolymer (SIR) and isoprene/butadiene/styrol copolymer (SBIR).Also, according to described preferred embodiment, in the situation of elastomer blend, the elastomeric total content of " non-isoprene " must be greater than the elastomeric total content that is selected from natural rubber, synthetic polyisoprenes and their mixture.Preferably, according to described embodiment, the content of the diene elastomer of non-isoprene exceedes 50phr, more preferably 60phr at least, more preferably 70phr at least, also more preferably 80phr at least, and extremely preferred 90phr at least.Especially, according to described embodiment, the content utmost point of the diene elastomer of non-isoprene is preferably 100phr.
According to another preferred embodiment of the present invention, the blend that rubber combination comprises one (one or more) " high Tg " diene elastomer and one (one or more) " low Tg " diene elastomer, described " high Tg " diene elastomer shows the Tg between-70 DEG C to 0 DEG C, between described " low Tg " diene elastomer shows-110 DEG C to-80 DEG C, the Tg between more preferably-105 DEG C to-90 DEG C.Described high Tg elastomerics be preferably selected from S-SBR, E-SBR, natural rubber, synthetic polyisoprenes (demonstration be preferably greater than cis-Isosorbide-5-Nitrae-linker of 95% ( ) content (mol%)), BIR, SIR, SBIR and these elastomeric mixtures.Described low Tg elastomerics preferably comprises content (mol%) and at least equals 70% butadiene unit; Its polyhutadiene (BR) that is preferably greater than the content (mol%) of cis-Isosorbide-5-Nitrae-linker of 90% by demonstration forms.
According to another specific embodiments of the present invention, described rubber combination comprises, for example, between 30 to 90phr, especially the high Tg elastomerics between 40 to 90phr as with the elastomeric blend of low Tg.
According to another specific embodiments of the present invention, the blend of the BR (as low Tg elastomerics) that comprises the content (mol%) that shows the cis-Isosorbide-5-Nitrae-linker that is greater than 90% according to the diene elastomer of composition of the present invention and one or more S-SBR or E-SBR (as high Tg elastomerics).
i-2 reinforcing filler
Tire according to the present invention comprises and mainly comprises the composition of silicon-dioxide as reinforcing filler.Term " main reinforcing filler " is interpreted as meaning to show in the reinforcing filler being present in composition the reinforcing filler of maximum level.Especially, term " main reinforcing filler " is interpreted as meaning to account at least 50 % by weight of existing reinforcing filler, preferably exceedes 50% and more preferably exceed any reinforcing filler of 60%.
Which kind of physical condition providing reinforcing filler unimportant with, no matter it is form or any other suitable densification form of powder, microballon, particle, bead.
The volume fraction of reinforcing filler in rubber combination is defined as the ratio of the volume of the volume of reinforcing filler and all the components of composition, should understand by each the volume in the composition of composition is added together to the volume that calculates all the components.Therefore, the volume fraction of reinforcing filler in composition is defined as each the ratio of summation of volume in the volume of reinforcing filler and the composition of composition; Conventionally, described volume fraction is between 10% to 30%, is preferably between 15% to 25%.To be equal to preferred mode, the content of all reinforcing fillers (carbon black and/or strengthen mineral filler (as silicon-dioxide)) is 30 to 200phr, and more preferably 30 to 150phr, and extremely preferably 50 to 135phr.
According to a preferred embodiment of the invention, use and comprise 30 to 150phr silicon-dioxide, more preferably the reinforcing filler of 50 to 130phr silicon-dioxide and optional carbon black; In the time there is carbon black, carbon black is with 0.5 to 50phr, and also more preferably content and the silicon-dioxide of 1 to 20phr (particularly between 1 to 10phr) are used in combination.
Composition can comprise the silicon-dioxide of one type or the blend of several silicon-dioxide.Silicon-dioxide used can be any enhancing silicon-dioxide, particularly BET specific surface area well known by persons skilled in the art and CTAB specific surface area is all less than 450m 2/ g, is preferably 30 to 400m 2any precipitated silica or the pyrogenic silica of/g.As high dispersion precipitated silica (" HDS "), can mention for example Ultrasil7000 and the Ultrasil7005 silicon-dioxide from Degussa, from the Zeosil1165MP of Rhodia, 1135MP and 1115MP silicon-dioxide, from the Hi-Sil EZ150G silicon-dioxide of PPG, from the Zeopol8715 of Huber, 8745 and 8755 silicon-dioxide, treated precipitated silica (for example applying for the silicon-dioxide of " doping " aluminium described in EP-A-0735088), or as the silicon-dioxide with high-specific surface area described in application WO03/16837.
Silicon-dioxide preferably has 45 to 400m 2between/g, more preferably 60 to 300m 2bET specific surface area between/g.
Except coupling agent, these compositions also optionally comprise coupling activator, it is for covering reagent or the processing aid more usually of mineral filler, it can be in known manner improves the processed ability of composition in undressed state by the viscosity of improving the dispersion of filler in rubber matrix and reducing composition, these reagent are for example hydrolyzable silane (as alkylalkoxy silane), polyvalent alcohol, lipid acid, polyethers, primary amine, secondary amine or tertiary amine, hydroxylated or hydrolyzable organopolysiloxane.
Use especially silane polysulfide, depend on their concrete structure and be called " symmetry " or " asymmetric ", as for example applied for described in WO03/002648 (or US2005/016651) and WO03/002649 (or US2005/016650).
As to give a definition not be in restrictive situation, specially suitable is to be called " symmetrical " silane polysulfide corresponding to following general formula (II):
(II) Z-A-S x-A – Z, wherein:
-x is 2 to 8 integer of (preferably 2 to 5);
-A is that bivalent hydrocarbon radical (is preferably C 1-C 18alkylidene group or C 6-C 12arylidene is more particularly C 1-C 10alkylidene group, is in particular C 1-C 4alkylidene group, particularly propylidene);
-Z is corresponding to one of following formula:
Wherein:
-R 1group is that replace or unsubstituted and is same to each other or different to each other, and represents C 1-C 18alkyl, C 5-C 18cycloalkyl or C 6-C 18aryl (is preferably C 1-C 6alkyl, cyclohexyl or phenyl, be in particular C 1-C 4alkyl, is more particularly methyl and/or ethyl);
-R 2group is that replace or unsubstituted and is same to each other or different to each other, and represents C 1-C 18alkoxyl group or C 5-C 18cycloalkyloxy (is preferably and is selected from C 1-C 8alkoxyl group or C 5-C 8the group of cycloalkyloxy, is also more preferably selected from C 1-C 4the group of alkoxyl group, particularly methoxyl group and oxyethyl group).
In the mixture of the organoalkoxysilane polysulfide corresponding to above formula (II), the particularly situation of standard available mixture, the mean value of " x " index is for being preferably between 2 to 5, more preferably about 4 mark.But the present invention also can advantageously use for example organoalkoxysilane disulphide (x=2) and carry out.
As the example of silane polysulfide, will more particularly mention two ((C 1-C 4) alkoxyl group (C 1-C 4) alkyl silyl (C 1-C 4) alkyl) polysulfide (particularly disulphide, trisulphide or tetrasulfide), for example two (3-trimethoxy-silylpropyl) or two (3-triethoxysilylpropyltetrasulfide) polysulfides.In these compounds, use and there is formula [(C especially 2h 5o) 3si (CH 2) 3s 2] 2two (3-triethoxysilylpropyltetrasulfide) tetrasulfides of being abbreviated as TESPT or there is formula [(C 2h 5o) 3si (CH 2) 3s] 2two (3-triethoxysilylpropyltetrasulfide) disulphide of being abbreviated as TESPD.As preferred example, also can mention two (single (C 1-C 4) alkoxyl group two (C 1-C 4) alkyl silyl propyl group) polysulfide (particularly disulphide, trisulphide or tetrasulfide), more particularly two (monosubstituted ethoxy dimetylsilyl propyl group) tetrasulfides, described in patent application WO02/083782 (or US2004/132880).
As the coupling agent except organoalkoxysilane polysulfide, also mention difunctionality POS (organopolysiloxane) or silicol polysulfide (R in above formula II 2=OH) (described at patent application WO02/30939 (or US6774255) and WO02/31041 (or US2004/051210)), or with silane or the POS (for example, described in patent application WO2006/125532, WO2006/125533 and WO2006/125534) of azo dicarbapentaborane functional group.
Especially and preferably, coupling agent can be corresponding to the silicol polysulfide of general formula (III) (described at above-mentioned document):
(HO) aR (3-a)Si-R'-S x-R'-SiR (3-b)(OH) b (III)
Wherein:
-R group is identical or different, and is the alkyl that preferably comprises 1 to 15 carbon atom;
-R' group is identical or different, and is the divalent linker that preferably comprises 1 to 18 carbon atom;
-a and b are identical or different, and equal 1 or 2;
-x is more than or equal to 2 number.
R group is identical or different and for straight or branched, and preferably comprises 1 to 15 carbon atom, is more preferably selected from alkyl, cycloalkyl or aryl, is selected from especially C 1-C 6alkyl, C 5-C 8cycloalkyl and phenyl.In these groups; for example, mention especially and be selected from following those: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, neo-pentyl, n-hexyl, 2-ethylhexyl, n-octyl, iso-octyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, phenyl, toluyl and benzyl.
Also more preferably, R group is identical or different, and is C 1-C 3alkyl (being methyl, ethyl, n-propyl or sec.-propyl), the utmost point is selected from methyl and ethyl especially.
R ' group is identical or different and that be replacement or unsubstituted, and is preferably the saturated or unsaturated alkyl that comprises 1 to 18 carbon atom, and these R ' groups are likely interrupted by least one heteroatoms (as O, S or N) in hydrocarbon chain.Specially suitable is C 1-C 18alkylidene group or C 6-C 12arylidene is more particularly C 1-C 10, particularly C 1-C 4alkylidene group, is especially selected from those of methylene radical, ethylidene and propylidene.
Preferably, in the silicol polysulfide corresponding to general formula (III), silicol is monohydroxy silane, and a and b equal 1.Again preferably, R group is selected from straight or branched C 1-C 6alkyl, C 5-C 8cycloalkyl or phenyl; R ' group is selected from C 1-C 18alkylidene group or C 6-C 12arylidene, and more particularly, R group is selected from C 1-C 6alkyl and R ' group are selected from C 1-C 10alkylidene group.
Therefore, most preferably, described silicol is the monohydroxy silane polysulfide of formula (IV):
Wherein R group is C 1-C 3alkyl, is preferably methyl; R' group is C 1-C 4alkylidene group, preferably methylene radical, ethylidene or propylidene; X is more than or equal to 2.More particularly, described silicol can be two (propyl-dimethyl silanol) polysulfides of concrete formula (IVa):
The described product of formula (IVa) is corresponding to the product D in above-mentioned document WO02/31041 (or US2004/051210).
In rubber combination according to the present invention, the content of coupling agent is preferably between 2 to 15phr, more preferably between 3 to 13phr, also more preferably between 5 to 10phr.
Except silicon-dioxide, can use the known reinforcing filler that can strengthen any type that can be used for the rubber combination of manufacturing tire, for example organic filler (as carbon black), strengthens mineral filler (as aluminum oxide), or the blend of this two classes filler.
All carbon blacks, particularly " tire level " carbon black, is suitable for as carbon black.In " tire level " carbon black, more particularly mention the enhancing carbon black of 100,200 or 300 series (ASTM level), for example N115, N134, N234, N326, N330, N339, N347 or N375 carbon black, or, depend on intended application, the carbon black (for example N660, N683 or N772) of higher series.Carbon black can for example be introduced in isoprene elastomerics (referring to for example applying for WO97/36724 or WO99/16600) with the form of masterbatch.
As the particle of the organic filler except carbon black, can mention as application described in WO-A-2006/069792, WO-A-2006/069793, WO-A-2008/003434 and WO-A-2008/003435 through functionalized polyvinyl organic filler.
It will be appreciated by those skilled in the art that, can use the reinforcing filler of another character (particularly organic nature) as the filler that is equal to the silicon-dioxide of describing in this part, prerequisite is that this reinforcing filler is covered by silicon dioxide layer, or this reinforcing filler comprises and need to use the functional site, particularly hydroxyl group sites of coupling agent with the combination between formation filler and elastomerics on its surface.
i-3 cross-linking system
Cross-linking system can be vulcanization system; It is preferably based on sulphur or sulfur donor and main vulcanization accelerator (preferably 0.5 to 10.0phr primary accelerator).Except this vulcanization system, optional various known inferior vulcanization accelerator or vulcanization activators, as zinc oxide (preferably 0.5 to 10.0phr) or stearic acid or other (preferably respectively doing for oneself 0.5 to 5.0phr).In the time that the present invention is applied to tire tread, sulphur is with between 0.5 to 10phr, and more preferably, between 0.5 to 5.0phr, for example the preferred content between 0.5 to 3.0phr uses.
Can use any compound of the promotor that can serve as the sulfuration of diene elastomer under the existence of sulphur as (main or inferior) promotor, particularly thiazole type accelerator and their derivative and thiuram and zinc dithiocarbamate type promotor.These promotor are more preferably selected from 2-mercaptobenzothiazole based bisulfide (being abbreviated as " MBTS "), N cyclohexyl 2 benzothiazole sulfenamide (being abbreviated as " CBS "), N, the mixture of N-dicyclohexyl-2-[4-morpholinodithio sulphenamide (being abbreviated as " DCBS "), N tert butyl benzothiazole 2 sulfenamide (being abbreviated as " TBBS "), the N-tertiary butyl-2-[4-morpholinodithio sulfenamide (being abbreviated as " TBSI "), zinc dibenzyldithiocarbamate (being abbreviated as " ZBEC ") and these compounds.Preferably, use sulphenamide type primary accelerator.
On the other hand, in tire according to the present invention, comprise for the composition that requires essential hydroxylation diamines of the present invention and do not contain guanidine derivative, or comprise the guanidine derivative that is less than 0.5phr.Preferably, composition or completely containing this compound, or it comprises and be less than 0.45phr, is preferably less than 0.4phr, is more preferably less than 0.3phr, is preferably less than 0.2phr and is extremely preferably less than this compound of 0.1phr.Term " guanidine derivative " is interpreted as meaning to have the organic compound of guanidine functional group as main functional group, for example, as known those as vulcanization accelerator especially in tire composition, vulkacit D (DPG) or two (o-tolyl) guanidine (DOTG).
According to a preferred form, in tire according to the present invention, the composition that comprises the amino ether alcohol essential for requirement of the present invention is also containing zinc, or comprises and be less than 0.5phr, preferably be less than 0.3phr, be more preferably less than 0.2phr and be extremely preferably less than the zinc of 0.1phr.
i-4 hydroxylation diamines
In order advantageously to replace above-mentioned guanidine derivative, the hydroxylation diamines of tire according to the present invention contained (I):
Wherein R 1represent the straight or branched alkylidene group that comprises 1 to 18 carbon atom, R 2and R 3represent independently the straight or branched alkyl that comprises 1 to 18 carbon atom, should understand described hydroxylation diamines and be selected from R 1, R 2and R 3at least one carbon back chain on there are one or more hydroxyls.
Preferably, R 1, R 2and R 3comprise 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, extremely preferably 2 to 4 carbon atoms.
Also preferably, R 1, R 2and R 3represent straight chain carbon back chain.
Preferably, the hydroxyl value that the hydroxylation diamines of formula (I) has is 1 to 4, more preferably 1,2 or 3.Described hydroxyl or these hydroxyls are preferably by R 2and R 3have.Most preferably, R 2there is hydroxyl, R 3there is hydroxyl, and R 1do not there is hydroxyl.
Preferably, in composition, the content of hydroxylation diamines is 0.1 to 8phr, and more preferably 0.15 to 7phr, preferably exceedes in 0.2 to 5phr and more preferably 0.25 to 4phr scope.
For example, the hydroxylation diamines of formula (I) can be for example aminopropyl diethanolamine of buying with liquid form from Arkema:
It should be noted that as undefined hydroxylation diamines and introduce with the form of free alkali, do not form salt with inorganic or organic acid.
other possible additives of I-5
Also optionally also comprise all or part of in the conventional additives in the elastic composition that is generally used for being intended to especially manufacture tyre surface according to rubber combination of the present invention, for example pigment, protective material (as anti-ozone wax, chemical antiozonidate or antioxidant), softening agent (as provided below those), fatigue protective agent, enhancing resin or methylene acceptor (for example linear phenolic resin) or give body (for example HMT or H3M).
According to a preferred embodiment, comprise in addition softening agent according to composition of the present invention.Preferably, described softening agent is solid hydrocarbons resin (or resin of plastification), extending oil (or plasticizing oil) or both mixtures.
In the time that softening agent is contained in composition, all the content of softening agent is preferably greater than or equal to 5phr, and more preferably 5 to 100phr, is in particular 10 to 80phr, and for example 15 to 70phr.
According to the first preferred embodiment of the present invention, described softening agent is the extending oil of liquid for what be called low " Tg " at 20 DEG C, is less than-20 DEG C by defining its demonstration, is preferably less than the Tg of-40 DEG C.
Can use known any extending oil (no matter it has aromatics character or non-aromatic character) with the plasticising character to diene elastomer.(20 DEG C) at ambient temperature, these oil (being viscosity more or less) for liquid (, in this prompting, there is the material of the ability of the shape of the container of finally taking them), this is contrary with the plasticising hydrocarbon resin that is innately at ambient temperature solid especially.
The extending oil that is selected from the mixture of naphthenic oil (low viscosity or high viscosity, particularly hydrogenation or unhydrided), paraffin oil, MES (medium extraction solvate) oil, TDAE (the distillation aromatics extract of processing) oil, mineral oil, vegetables oil, ether plasticizer, ester plasticizer, phosphate plasticizer, sulphonate softening agent and these compounds is specially suitable.For example, can mention those of the carbon atom that comprises between 12 to 30, for example trioctyl phosphate.As the example of non-aqueous and water-insoluble ester plasticizer, can mention especially and be selected from following compound: trimellitate, Pyromellitic Acid ester, phthalic ester, 1, the mixture of 2-cyclohexanedicarboxyester ester, adipic acid ester, azelate, sebate, triglyceride level and these compounds.In as above three esters, can mention especially that preferably main (exceed 50 % by weight, more preferably exceed 80 % by weight) is by C 18the triglyceride level of unsaturated fatty acids (being selected from oleic acid, linolic acid, linolenic acid and these sour mixtures) composition.More preferably, no matter be synthetic source or natural source (for example sunflower plants oil or Semen Brassicae campestris plant oil condition), lipid acid used, by exceeding 50 % by weight, also more preferably exceedes the oleic acid composition of 80 % by weight.This three esters (trioleate) with the oleic acid of high-content are known; They are for example described as the softening agent in tire tread in application WO02/088238.
Preferably, the content of extending oil is between 2 to 50phr, more preferably between 3 to 40phr, also more preferably between 5 to 35phr.
According to another preferred embodiment of the present invention, described softening agent is thermoplastic hydrocarbon resin, and its Tg is greater than 0 DEG C, is preferably greater than 20 DEG C.Contrary with liquid plasticized compound (as oil), this resin is lower in envrionment temperature (23 DEG C) is solid.
Preferably, described thermoplasticity plasticising hydrocarbon resin show below in characteristic at least any one:
-be greater than 20 DEG C, more preferably greater than the Tg of 30 DEG C;
Between-400 to 2000g/mol, the more preferably number-average molecular weight between 500 to 1500g/mol (Mn);
-be less than 3, be more preferably less than 2 polydispersity index (PI (French is abbreviated as " IP ")) (at this prompting: PI=Mw/Mn, Mw is weight-average molecular weight).
More preferably, described thermoplasticity plasticising hydrocarbon resin shows all as above preferred characteristic.
The macrostructure (Mw, Mn and PI) of hydrocarbon resin is determined by spatial exclusion chromatography (SEC): solvents tetrahydrofurane; 35 DEG C of temperature; Concentration 1g/l; Flow rate 1ml/min; Before injecting, be the strainer of 0.45 μ m by porosity by solution filter; Carry out a mole calibration by polystyrene standards; 3 Waters posts (Styragel HR4E, HR1 and HR0.5) of one group of series connection; Detect by differential refractor (Waters2410) and associated function software (Waters Empower) thereof.
Described thermoplastic hydrocarbon resin can be aliphatic series or aromatics or aliphatic series/aromatics type, based on aliphatic series and/or aromatic monomer.They can be natural or synthetic, based on or not based on oil (if based on stone oil condition, it is also referred to as petroleum resin).
As aromatic monomer, suitable for for example: vinylbenzene, alpha-methyl styrene, o-, m-and p-methylstyrene, Vinyl toluene, p-(tertiary butyl) vinylbenzene, methoxy styrene, chloro-styrene, vinyl mesitylene, Vinylstyrene, vinyl naphthalene, or derive from C 9cut (or more generally derives from C 8to C 10cut) any vi-ny l aromatic monomers.Preferably, vi-ny l aromatic monomers is vinylbenzene or derives from C 9cut (or more generally derives from C 8to C 10cut) vi-ny l aromatic monomers.Preferably, vi-ny l aromatic monomers is relatively small number of monomers (representing with molar fraction) in considered multipolymer.
According to a particularly preferred embodiment, described plasticising hydrocarbon resin is selected from cyclopentadiene (being abbreviated as CPD) or dicyclopentadiene (being abbreviated as DCPD) homopolymer or copolymer resin, terpenes homopolymer or copolymer resin, terpenes/phenol homopolymer or copolymer resin, C 5cut homopolymer or copolymer resin, C 9the mixture of cut homopolymer or copolymer resin, alpha-methyl styrene homopolymer or copolymer resin and these resins, it can be used alone or for example, is used in combination with liquid plasticizer (MES oil or TDAE oil).Term " terpenes " combines α-pinene, beta-pinene He limonene monomer herein in known manner; Preferably Shi limonene monomer, this compound exists with the form of three kinds of possible isomer in known manner: L-limonene (levo-enantiomer), orange limonene (dextrorotation enantiomorph) or limonene (racemoid of dextrorotation and levo-enantiomer).In as above plasticising hydrocarbon resin, mention especially α-pinene, beta-pinene, limonene Huo Ju limonene homopolymer or copolymer resin.
As above preferred resin is well known to a person skilled in the art and can buy, for example, about following sale:
Ju limonene resin: sell (Mn=625g/mol with title Dercolyte L120 by DRT; Mw=1010g/mol; PI=1.6; Tg=72 DEG C) or sell (Mn=630g/mol by Arizona with title Sylvagum TR7125C; Mw=950g/mol; PI=1.5; Tg=70 DEG C);
C 5cut/vinyl aromatic copolymers resin, particularly C 5cut/vinylbenzene or C 5cut/C 9cut copolymer resin: sold with title Super Nevtac78, Super Nevtac85 or Super Nevtac99 by Neville Chemical Company, sold with title Wingtack Extra by Goodyear Chemicals, sold with title Hikorez T1095 and Hikorez T1100 by Kolon, or sold with title Escorez2101 and Escorez1273 by Exxon;
Limonene/styrene copolymer resin: sold with title Dercolyte TS105 by DRT, or sold with title ZT115LT and ZT5100 by Arizona Chemical Company.
As the example of other preferred resins, also can mention phenol-modified alpha-methyl styrene resin.In order to characterize these phenol-modified resins, should remember to use in known manner the numeral (measure and represent with mg KOH/g according to standard ISO 4326) that is called " hydroxyl value ".Alpha-methyl styrene resin, particularly phenol-modified those are to well known to a person skilled in the art and can buy, for example by Arizona Chemical with title Sylvares SA100 (Mn=660g/mol; PI=1.5; Tg=53 DEG C), Sylvares SA120 (Mn=1030g/mol; PI=1.9; Tg=64 DEG C), Sylvares540 (Mn=620g/mol; PI=1.3; Tg=36 DEG C; Hydroxyl value=56mg KOH/g), and Sylvares600 (Mn=850g/mol; PI=1.4; Tg=50 DEG C; Hydroxyl value=31mg KOH/g) sell.
According to a specific embodiments of the present invention, in the time that plasticising hydrocarbon resin is contained in composition, the content of plasticising hydrocarbon resin is between 5 to 50phr, is preferably between 7 to 40phr, also more preferably between 10 to 35phr.Also preferably, the content of resin of plastification is between 5 to 20phr, more preferably between 5 to 15phr.
Certainly, composition according to the present invention can be used alone or as and the blend (as mixture) that can be used for any other rubber combination of manufacturing tire use.
It is evident that, the present invention relates to " undressed " or non cross-linked state (sulfuration before) and " through solidifying " or through crosslinked or through the above-mentioned rubber combination of sulfided state (after crosslinked or sulfuration).
the preparation of II-rubber combination
Use well known to a person skilled in the art that two continuous production stages manufacture composition in suitable mixing tank: until between 110 DEG C to 190 DEG C, preferably under the high temperature of the maximum temperature between 130 DEG C to 180 DEG C, carry out the first stage (being sometimes referred to as " non-preparation " stage) of thermomechanical operation or kneading, then be usually less than 110 DEG C, for example under the lesser temps between 60 DEG C to 100 DEG C, carry out mechanically operated subordinate phase (being sometimes referred to as " preparation " stage), in this precision work phase process, mix crosslinked or vulcanization system; This stage has been described in for example applies in EP-A-0 501 227, EP-A-0 735 088, EP-A-0 810 258, WO00/05300 or WO00/05301.
The first (non-preparation) stage preferably carried out in several thermomechanical steps.In first step process, elastomerics and reinforcing filler (and optional coupling agent and/or other compositions) are introduced between 20 DEG C to 100 DEG C, preferably in the suitable mixing tank at the temperature between 25 DEG C to 100 DEG C (as common closed mixing tank).At several minutes (preferably 0.5 to 2min), and temperature rise to 90 DEG C or rise to after 100 DEG C, in the mixing process of 20 seconds to several minutes, simultaneously or portions adds other compositions except cross-linking system (i.e. remaining (if start do not add whole) those).In described non-preparatory phase, the total duration of kneading is preferably and is being less than or equal to 180 DEG C and be preferably less than or equal at the temperature of 170 DEG C between 2 to 10 minutes.
After cooling thus obtained mixture, conventionally in external mixer (as mill), under low temperature (being conventionally less than 100 DEG C), introduce subsequently vulcanization system; Then mix the mixture for several minute of (preparatory phase) combination, for example, between 5 to 15min.
Subsequently thus obtained final composition is for example rolled with the form of sheet material or sheet material, to characterize for laboratory especially, or thus obtained final composition is extruded, to form for example for the manufacture of half-finished rubber-moulding part, thereby acquisition product, as sidewall, casingply, crown plies (or tire belt), tyre surface, tyre bead line weighting material, tyre surface lower floor or other elastomer layers, preferably tyre surface.These products can be subsequently according to technology well known by persons skilled in the art and for the manufacture of tire.
Conventionally at the temperature between 130 DEG C to 200 DEG C, under pressure, vulcanize in known manner (or solidifying) and reach the sufficiently long time, the described time can be depended on solidification value especially, the sulfuration kinetics of the vulcanization system adopting, the composition of considering or tire size and for example between 5 to 90min, changing.
Following example has illustrated the present invention and has not limited the present invention.
iII-implements embodiments of the invention
the preparation of III-1 embodiment
In following embodiment, rubber combination makes as mentioned above.
the sign of III-2 embodiment
In an embodiment, before and after solidifying, characterize as mentioned below rubber combination.
-mooney viscosity or mooney plasticity (before solidifying):
Use the vibration consistometer of describing as in normes Francaises NF T43-005 (1991).Carry out mooney plasticity measurement according to following principle: the composition of undressed state (solidify before) is being heated in the cylindrical chamber of 100 DEG C molded.After preheating 1 minute, rotor rotates in test sample with 2 revs/min, measures the operation torque for maintaining this motion after rotating 4 minutes.Mooney plasticity (ML1+4) with " mooney unit " (MU, 1MU=0.83 newton. rice) represent.For better readability, result shows with radix 100, and 100 value is assigned to contrast.Be less than 100 result and represent that considered value reduces, on the contrary, be greater than 100 result and represent that considered value increases.
-Elongation test (after solidifying):
Elastic stress and breaking property are likely determined in these tests.Unless otherwise noted, otherwise these test the standard NF ISO37 based in December, 2005." nominal " secant modulus under 100% elongation (" M100 ") of measurement in extending (adjust circulation after) for the second time (or apparent stress, in MPa, with respect to the strain without unit).All these stretch to measure and carry out under the standard conditions of temperature (23 ± 2 DEG C) and humidity (50 ± 10% relative humidity).Also measure rupture stress (in MPa) and extension at break (in %).For better readability, result shows with radix 100, and 100 value is assigned to contrast.Be less than 100 result and represent that considered value reduces, on the contrary, be greater than 100 result and represent that considered value increases.
-kinetic property (after solidifying):
According to standard A STM D5992-96, at upper kinetic property G* and tan (δ) max of measuring of viscosity analyser (Metravib VA4000).According to standard A STM D1349-99, under standard temperature condition, (thickness is 4mm, and cross-sectional area is 400mm to record vulcanized composition sample 2cylindrical sample) stand the response of the simple AC sine shear-stress under 10Hz frequency.By 0.1% to 50% (to External Periodic), then carry out the strain amplitude scanning of crest to crest by 50% to 1% (return period).Result used is loss factor tan (δ).For return period, point out the maximum value (tan (δ) max) of the tan (δ) observing.Tan (δ) the max value providing as follows records at 23 DEG C.For better readability, result shows with radix 100, and 100 value is assigned to contrast.Be less than 100 result and represent that considered value reduces, on the contrary, be greater than 100 result and represent that considered value increases.
iII-3 embodiment
iII-3-1 example I
The object of this embodiment be compare composition with according to the various rubber properties of composition of the present invention, composition according to the present invention comprises diene elastomer, mainly wraps silica containing reinforcing filler, cross-linking system, and do not contain guanidine derivative or comprise the guanidine derivative that is less than 0.5phr, and comprising the hydroxylation diamines of formula (I) as defined above.
Especially, preparation test composition C-1 and C-2.The formula of composition C-1 and C-2 is only distinguished and is to replace DPG by aminopropyl diethanolamine (with equimolar amount), as shown in table 1.Compare according to composition C-2 of the present invention and reference composition C-1.
table 1
Composition C-1 C-2
SBR(1) 100 100
Carbon black (2) 3 3
Silicon-dioxide (3) 110 110
Coupling agent (4) 9 9
Antioxidant (5) 2 2
Plasticizing oil (6) 12 12
Resin of plastification (7) 46 46
Zinc oxide 1.2 1.2
DPG(8) 1.8 0
Aminopropyl diethanolamine 0 1.4
Stearic acid 2 2
Promotor (9) 2.3 2.3
Sulphur 1 1
(1) SBR (star-branched through Sn), its have 27% styrene units and 24% divinyl part 1,2-unit (Tg=-48 DEG C), and there is silanol functional in the end of elastomerics chain
(2) ASTM level N234 (Cabot)
(3) silicon-dioxide, from the Zeosil1165MP of Rhodia, " HDS " type
(4) coupling agent: TESPT (from the Si69 of Evonik-Degussa)
(5) N-(1,3-dimethylbutyl)-N '-phenyl-Ursol D (Santoflex6-PPD), from Flexsys
(6) sunflower oil of the oleic acid that comprises 85 % by weight, from the Lubrirob Tod1880 of Novance
(7) C 5/ C 9resin, from the Escorez1273 of Exxon
(8) vulkacit D (from the Perkacit DPG of Flexsys)
(9) N cyclohexyl 2 benzothiazole sulfenamide (from the Santocure CBS of Flexsys).
All the components except vulcanization system is introduced in closed mixing tank, thereby prepared composition.Vulcanizing agent (sulphur and promotor) is introduced in the external mixer under low temperature (position roll of mixing tank is at about 30 DEG C).
The character recording before and after solidifying provides in as following table 2.In order to understand better and compare test, result provides with radix 100, is reduced to 100 value by the experimental value of contrast, and then the value of test provides according to this radix of 100 of contrast.
table 2
Composition number C-1 C-2
Mooney (in radix 100) 100 116
M100 (in radix 100) 100 106
Tan (δ) max (in radix 100) 100 88
Than reference composition C-1, to find according to the reduction of the hysteresis quality relevant to tan (δ) max index of composition C-2 of the present invention, this is accompanied by similarly other character.

Claims (27)

1. comprise the tire of rubber combination, reinforcing filler and cross-linking system that described rubber combination based at least one diene elastomer, is mainly made up of silicon-dioxide, described composition is containing guanidine derivative or comprise the guanidine derivative that is less than 0.5phr, and the hydroxylation diamines of contained (I) in addition:
Wherein R 1represent the straight or branched alkylidene group that comprises 1 to 18 carbon atom, R 2and R 3represent independently the straight or branched alkyl that comprises 1 to 18 carbon atom, the hydroxylation diamines that should understand formula (I) is being selected from R 1, R 2and R 3at least one carbon back chain on there are one or more hydroxyls.
2. tire according to claim 1, the composition that wherein comprises described hydroxylation diamines comprises and is less than 0.45phr, is preferably less than the guanidine derivative of 0.4phr.
3. according to tire in any one of the preceding claims wherein, wherein the content of hydroxylation diamines is 0.1 to 8phr, is preferably and exceedes 0.15phr to 7phr.
4. tire according to claim 3, wherein the content of hydroxylation diamines is 0.2 to 5phr, is preferably and exceedes 0.25phr to 4phr.
5. according to tire in any one of the preceding claims wherein, wherein R 1, R 2and R 3comprise 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.
6. according to tire in any one of the preceding claims wherein, wherein R 1, R 2and R 3represent straight chain carbon back chain.
7. according to tire in any one of the preceding claims wherein, the hydroxyl value that the hydroxylation diamines of its Chinese style (I) has is 1 to 4, more preferably 1,2 or 3.
8. according to tire in any one of the preceding claims wherein, wherein said one or more hydroxyls are preferably by R 2and R 3institute has.
9. according to tire in any one of the preceding claims wherein, wherein dioxide-containing silica is 30 to 150phr.
10. according to tire in any one of the preceding claims wherein, wherein said reinforcing filler comprises a small amount of carbon black.
11. tires according to claim 10, wherein the content of carbon black is 0.5 to 50phr.
12. according to tire in any one of the preceding claims wherein, and wherein said diene elastomer is selected from polyhutadiene, synthetic polyisoprenes, natural rubber, butadienecopolymer, isoprene copolymer and these elastomeric mixtures.
13. according to tire in any one of the preceding claims wherein, and wherein said diene elastomer is mainly made up of the diene elastomer of non-isoprene.
14. tires according to claim 13, wherein said diene elastomer is made up of the diene elastomer of the non-isoprene of 100phr.
15. according to the tire described in any one in claim 13 and 14, and the diene elastomer of wherein said non-isoprene is selected from polyhutadiene, butadienecopolymer, isoprene copolymer and these elastomeric mixtures.
16. according to tire in any one of the preceding claims wherein, and wherein said composition comprises softening agent in addition, and described softening agent is preferably selected from resin of plastification, extending oil and their mixture.
17. tires according to claim 16, wherein the content of softening agent is 5 to 100phr.
18. according to tire in any one of the preceding claims wherein, and wherein said composition is in addition containing zinc, or comprises and be less than 0.5phr, is preferably less than the zinc of 0.3phr.
19. according to tire in any one of the preceding claims wherein, and it comprises coupling agent in addition.
20. tires according to claim 19, wherein said coupling agent is the silicol polysulfide corresponding to general formula (III):
(HO) aR (3-a)Si-R'-S x-R'-SiR (3-b)(OH) b (III)
Wherein:
-R group is identical or different, and is the alkyl that preferably comprises 1 to 15 carbon atom;
-R' group is identical or different, and is the divalent linker that preferably comprises 1 to 18 carbon atom;
-a and b are identical or different, and equal 1 or 2;
-x is more than or equal to 2 number.
21. tires according to claim 20, wherein said coupling agent is monohydroxy silane, wherein a and b equal 1.
22. according to the tire described in any one in claim 20 and 21, and wherein said R group is selected from C 1-C 6alkyl, C 5-C 8cycloalkyl or phenyl; R' group is selected from C 1-C 18alkylidene group or C 6-C 12arylidene.
23. according to the tire described in any one in claim 20 to 22, and wherein R group is selected from C 1-C 6alkyl, and R ' group is selected from C 1-C 10alkylidene group.
24. according to the tire described in any one in claim 20 to 23, and wherein said silicol is the monohydroxy silane polysulfide of formula (IV):
Wherein R group is C 1-C 3alkyl, is preferably methyl; R' group is C 1-C 4alkylidene group, preferably methylene radical, ethylidene or propylidene; X is more than or equal to 2.
25. according to the tire described in any one in claim 20 to 24, and wherein said silicol is two (propyl-dimethyl silanol) polysulfides of concrete formula (IVa):
26. according to tire in any one of the preceding claims wherein, the composition that the composition that wherein comprises hydroxylation diamines is tire layer, and described tire layer is selected from all or part of, tire belt all or part of of tyre surface and their combination.
27. tires according to claim 26, all or part of composition that the composition that wherein comprises hydroxylation diamines is tyre surface.
CN201280062619.4A 2011-12-21 2012-12-17 Including the tire being substantially free of guanidine derivatives and the compositions that comprises hydroxylating diamidogen Expired - Fee Related CN103998508B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1162191 2011-12-21
FR1162191A FR2984899B1 (en) 2011-12-21 2011-12-21 PNEUMATIC COMPRISING A COMPOSITION ESSENTIALLY FREE OF GUANIDIC DERIVATIVE AND COMPRISING A HYDROXYLATED DIAMINE
PCT/EP2012/075857 WO2013092527A1 (en) 2011-12-21 2012-12-17 Tyre comprising a composition essentially free of guanidine derivative and comprising a hydroxylated diamine

Publications (2)

Publication Number Publication Date
CN103998508A true CN103998508A (en) 2014-08-20
CN103998508B CN103998508B (en) 2016-09-21

Family

ID=47557046

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280062619.4A Expired - Fee Related CN103998508B (en) 2011-12-21 2012-12-17 Including the tire being substantially free of guanidine derivatives and the compositions that comprises hydroxylating diamidogen

Country Status (3)

Country Link
CN (1) CN103998508B (en)
FR (1) FR2984899B1 (en)
WO (1) WO2013092527A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108699187A (en) * 2015-12-08 2018-10-23 米其林集团总公司 The simple function or distant pawl copolymer of 1,3- butadiene and ethylene

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1196745A (en) * 1996-06-26 1998-10-21 株式会社普利司通 Rubber composition and preumatic tire
CN1478125A (en) * 2000-10-13 2004-02-25 �����ּ�����˾ Rubber composition comprising as coupling agent polyfunctional organosilane
CN101080452A (en) * 2004-12-16 2007-11-28 兰科瑟斯有限公司 Silica-filled elastomeric compounds

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2673187B1 (en) 1991-02-25 1994-07-01 Michelin & Cie RUBBER COMPOSITION AND TIRE COVERS BASED ON SAID COMPOSITION.
FR2732351B1 (en) 1995-03-29 1998-08-21 Michelin & Cie RUBBER COMPOSITION FOR A TIRE ENCLOSURE CONTAINING ALUMINUM DOPED SILICA AS A REINFORCING FILLER
FR2740778A1 (en) 1995-11-07 1997-05-09 Michelin & Cie SILICA-BASED RUBBER COMPOSITION AND FUNCTIONALIZED DIENE POLYMER HAVING TERMINAL SILANOL FUNCTION
BR9708412A (en) 1996-04-01 2000-10-24 Cabot Corp New elastomer apparatus, method and compounds
FR2749313A1 (en) 1996-05-28 1997-12-05 Michelin & Cie DIENE RUBBER COMPOSITION BASED ON ALUMINA AS A REINFORCING FILLER AND ITS USE FOR THE MANUFACTURE OF TIRE COVERS
FR2765882B1 (en) 1997-07-11 1999-09-03 Michelin & Cie CARBON BLACK-BASED RUBBER COMPOSITION HAVING SILICA ATTACHED TO ITS SURFACE AND ALCOXYSILANE FUNCTIONALIZED DIENE POLYMER
EP1019228B1 (en) 1997-09-30 2004-12-01 Cabot Corporation Elastomer composite blends and methods for producing them
ATE226229T1 (en) 1998-07-22 2002-11-15 Michelin Soc Tech ADHESIVE COMPOSITION (WHITE FILLER/DIENRUBBER) CONTAINING AN ALKOXYSILANE POLYSULFIDE, A ZINC DITHIOPHOSPHATE AND A GUANIDINE DERIVATIVE
CA2338152A1 (en) 1998-07-22 2000-02-03 Societe De Technologie Michelin Coupling system (white filler/diene elastomer) based on polysulphide alkoxysilane, enamine and guanidine derivative
EP1127909B1 (en) 2000-02-24 2005-03-09 Société de Technologie Michelin Composition of curable rubber, suitable to produce a tire and tire containing this composition
EP1204702B1 (en) 2000-05-26 2012-04-25 Société de Technologie Michelin Rubber composition for use as tyre running tread
JP4252304B2 (en) 2000-10-13 2009-04-08 ソシエテ ド テクノロジー ミシュラン Polyfunctional organosilane that can be used as a coupling agent and method for producing the same
DE60218446T2 (en) 2001-03-12 2007-11-29 Société de Technologie Michelin RUBBER COMPOSITION FOR TIRES
FR2823215B1 (en) 2001-04-10 2005-04-08 Michelin Soc Tech TIRE AND TIRE TREAD COMPRISING AS COUPLING AGENT A BIS-ALKOXYSILANE TETRASULFURE
EP1419195B1 (en) 2001-06-28 2010-04-21 Société de Technologie Michelin Tyre tread reinforced with silica having a low specific surface area
JP4536375B2 (en) 2001-06-28 2010-09-01 ソシエテ ド テクノロジー ミシュラン Tire tread reinforced with silica with extremely low specific surface area
SE519792C2 (en) 2001-08-17 2003-04-08 Volvo Lastvagnar Ab Method for estimating the mass of a vehicle which is carried on a road with a varying slope and method for estimating the slope of the road on which a vehicle is driven
FR2854404B1 (en) 2003-04-29 2005-07-01 Michelin Soc Tech METHOD OF OBTAINING GRAFT ELASTOMER WITH FUNCTIONAL GROUPS ALONG THE CHAIN AND RUBBER COMPOSITIONS
FR2880354B1 (en) 2004-12-31 2007-03-02 Michelin Soc Tech ELASTOMERIC COMPOSITION REINFORCED WITH A FUNCTIONALIZED POLYVINYLAROMATIC LOAD
FR2880349B1 (en) 2004-12-31 2009-03-06 Michelin Soc Tech FUNCTIONALIZED POLYVINYLAROMATIC NANOPARTICLES
FR2886304B1 (en) 2005-05-26 2007-08-10 Michelin Soc Tech RUBBER COMPOSITION FOR PNEUMATIC COMPRISING AN ORGANOSILICIC COUPLING SYSTEM
FR2886305B1 (en) 2005-05-26 2007-08-10 Michelin Soc Tech PNEUMATIC RUBBER COMPOSITION COMPRISING AN ORGANOSILICALLY COUPLED AGENT AND AN INORGANIC CHARGE RECOVERY AGENT
FR2886306B1 (en) 2005-05-26 2007-07-06 Michelin Soc Tech PNEUMATIC RUBBER COMPOSITION COMPRISING AN ORGANOSILOXANE COUPLING AGENT
FR2903416B1 (en) 2006-07-06 2008-09-05 Michelin Soc Tech ELASTOMERIC COMPOSITION REINFORCED WITH A FUNCTIONALIZED NON-AROMATIC VINYL POLYMER
FR2903411B1 (en) 2006-07-06 2012-11-02 Soc Tech Michelin NANOPARTICLES OF FUNCTIONALIZED VINYL POLYMER
FR2915202B1 (en) 2007-04-18 2009-07-17 Michelin Soc Tech MONOMODAL COUPLED DIENIC ELASTOMER HAVING CHAIN SILANOL FUNCTION, PROCESS FOR OBTAINING THE SAME, AND RUBBER COMPOSITION CONTAINING SAME.
FR2918064B1 (en) 2007-06-28 2010-11-05 Michelin Soc Tech PROCESS FOR THE PREPARATION OF POLYETHER BLOCK DIENE COPOLYMER, REINFORCED RUBBER COMPOSITION AND PNEUMATIC WRAPPING.
FR2918065B1 (en) 2007-06-28 2011-04-15 Michelin Soc Tech PROCESS FOR THE PREPARATION OF POLYETHER BLOCK DIENE COPOLYMER, REINFORCED RUBBER COMPOSITION AND PNEUMATIC WRAPPING.
FR2951178B1 (en) 2009-10-08 2012-08-17 Michelin Soc Tech FUNCTIONALIZED DIENIC ELASTOMER AND RUBBER COMPOSITION CONTAINING SAME.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1196745A (en) * 1996-06-26 1998-10-21 株式会社普利司通 Rubber composition and preumatic tire
CN1478125A (en) * 2000-10-13 2004-02-25 �����ּ�����˾ Rubber composition comprising as coupling agent polyfunctional organosilane
CN101080452A (en) * 2004-12-16 2007-11-28 兰科瑟斯有限公司 Silica-filled elastomeric compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108699187A (en) * 2015-12-08 2018-10-23 米其林集团总公司 The simple function or distant pawl copolymer of 1,3- butadiene and ethylene
CN108699187B (en) * 2015-12-08 2020-12-22 米其林集团总公司 Monofunctional or telechelic copolymers of 1, 3-butadiene and ethylene

Also Published As

Publication number Publication date
CN103998508B (en) 2016-09-21
WO2013092527A1 (en) 2013-06-27
FR2984899A1 (en) 2013-06-28
FR2984899B1 (en) 2014-08-15

Similar Documents

Publication Publication Date Title
CN102869522B (en) Its tyre surface comprises the tire of the rubber composition containing polyvinylesters resin
CN107912044B (en) Rubber composition comprising a styrene-butadiene copolymer having a low glass transition temperature and a high content of fillers and plasticizers
CN102906178B (en) Tyre of which the tread comprises a thermoplastic vulcanizate (TPV) elastomer
CN102781683B (en) Tyre surface comprises the tire of thermoplastic elastomer
CN105658718B (en) Include the tire containing zinc acrylate resin derivative and the composition of peroxide
CN106414590B (en) Tire with low rolling resistance
CN103270100B (en) The tire that tyre surface comprises thermoplastic polyurethane block copolymer
CN102666706B (en) Tire having a crown area provided with a sublayer comprising a thermoplastic elastomer
CN107001704B (en) Include the tire of the composition containing polyfunctional acrylic ester derivative and peroxide
CN107001710B (en) Include the tire of the composition containing polyfunctional acrylic ester derivative and peroxide
CN108026329B (en) Rubber composition comprising hydrocarbon resin having low glass transition temperature
CN102770284A (en) Tire, the tread of which comprises a hydrogenated thermoplastic elastomer
CN103998252B (en) Including the tire being substantially free of guanidine derivatives the compositions that comprises alkali metal hydroxide or alkaline earth metal hydroxide
JP2014534283A (en) Tire with improved grip on wet ground
CN104011123B (en) Tyre comprising a composition essentially free of guanidine derivative and comprising a primary amine
US20180223082A1 (en) Rubber composition including a hydrocarbon resin with a low glass transition temperature
CN108136829B (en) Tire having a composition comprising an imidazole compound
US20130231417A1 (en) Rubber composition that can be used for manufacturing a tyre of which the composition comprises a starch and an aqueous or water-soluble plasticizer
CN106604958A (en) A rubber composition comprising silicone oil
CN104271361A (en) Tyre tread
US9522571B2 (en) Tire comprising a composition essentially free of guanidine derivative and comprising a hydroxyalkylpiperazine
US9260588B2 (en) Tire comprising a composition essentially devoid of guanidine derivative and comprising an amino ether alcohol
CN103998509A (en) Tyre comprising a composition essentially free of guanidine derivative and comprising a primary ether amine
CN103998508A (en) Tyre comprising a composition essentially free of guanidine derivative and comprising a hydroxylated diamine

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20171016

Address after: French Clermont Ferrand

Patentee after: Compagnie General Des Etablissements Michelin

Address before: French Clermont Ferrand

Co-patentee before: Michelin Research & Technology Co., Ltd.

Patentee before: Compagnie General Des Etablissements Michelin

TR01 Transfer of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160921

Termination date: 20181217

CF01 Termination of patent right due to non-payment of annual fee