CN104884521B - Tyre comprising a rubber composition comprising an epoxy resin and a polyacid - Google Patents
Tyre comprising a rubber composition comprising an epoxy resin and a polyacid Download PDFInfo
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- CN104884521B CN104884521B CN201380066026.XA CN201380066026A CN104884521B CN 104884521 B CN104884521 B CN 104884521B CN 201380066026 A CN201380066026 A CN 201380066026A CN 104884521 B CN104884521 B CN 104884521B
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- 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
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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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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)
Abstract
The present invention relates to a tyre comprising a rubber composition based on at least one diene elastomer, a reinforcing filler, a crosslinking system, an epoxy resin, at a content included in a range of from 1 to 20 phr, a polycarboxylic acid of general formula (I) in which A is a covalent bond or a hydrocarbon-based group comprising at least one carbon atom, which is optionally substituted and optionally interrupted with one or more heteroatoms, and an imidazole of general formula (II) in which R1 is a hydrocarbon-based group or a hydrogen atom, R2 is a hydrocarbon-based group, R3 and R4 are, independently of one another, a hydrogen atom or a hydrocarbon-based group, or else R3 and R4 together form, with the carbon atoms of the imidazole ring to which they are attached, a ring.
Description
Technical field
The present invention relates to the tire prepared by rubber composition, the particularly rubber composition with high rigidity.
Background technology
Some parts of tire using in tire small strain when have high rigidity rubber composition be it is known (referring to
WO 02/10269).One of property having required for the stress that anti-small strain is tire to be born in response to it.
The acquisition of the reinforcing effect can be by improving reinforced filling in the composition rubber composition of the tire part
Content or introduce specific reinforced resin and realize.
However, in known manner, the rigidity of the rubber composition increased by improving filer content can damage delayed
Property, and therefore damage tire rolling resistance property.In fact, for economy and the purpose of environment, reducing the tire
Rolling resistance is a lasting target so as to reduce fuel consumption.
Traditionally, the rigid reinforcement is obtained by introducing the reinforced resin for being based on methylene acceptor/donor systems
's.Term " methylene acceptor " and " methylene donor " be it is well-known to those skilled in the art and be widely used in expression can one
On the one hand and the reinforced filling/bullet with reaction, the compound of three-dimensionally reinforced resin is produced by condensation, the three-dimensionally reinforced resin
Elastomer networks superposition and IPN, are on the other hand superimposed and IPN with elastomer/sulphur (if crosslinking agent is sulphur) network.Above-mentioned Asia
Acceptors are combined with the curing agent that can be crosslinked or solidify it, and the curing agent is commonly known as " methylene donor ".Subsequently exist
In the rubber mass solidification process, by the carbon atom at the ortho position and/or contraposition of resin and the phenol core of methylene donor it
Between formed methylene (- CH2-) bridging and there is the crosslinking of the resin, so as to produce three-dimensional resinous network.
The methylene donor for being generally used for rubber composition for tyre is hexa (abbreviation HMT) or hexakis-methoxy methyl
Melamine (abbreviation HMMM or H3M) or six ethoxymethyl melamines.
Nonetheless, it is intended that finding the substitute of traditional reinforced resin.
Previously, applicant company had been found that common reinforced resin can advantageously to diamines in their research
Replace as the epoxy resin of curing agent.This is used to cause to obtain firm with bigger low strain dynamic to epoxy resin and diamine reactant thing
Property rubber composition and significantly do not damage it is delayed be possibly realized, as described in file FR 2 951 182.
In the research that they continue, applicant company is it has now been discovered that two amine hardeners of the epoxy resin can have
Sharp ground is replaced in the presence of imidazoles with polyacid curing agent, and the polyacid curing agent includes several carboxylic-acid functional groups.This
It is because astoundingly having with the composition obtained from the reinforced resin based on epoxy resin and polyacid curing agent
The working properties and rigidity of improvement are suitable or more preferable than them with those compositions comprising prior art reinforced resin.
The content of the invention
Therefore, first topic of the invention is the tire containing rubber composition, and the rubber composition is based at least one
Plant the polyacid of diene elastomer, reinforced filling, cross-linking system, the epoxy resin that content is 1 to 20phr and logical formula (I)：
Wherein A represents covalent bond or the alkyl containing at least one carbon atom, and it is optionally substituted and optionally by one or many
Individual hetero atom is mixed with,
With the imidazoles of logical formula (II)：
Wherein：
-R1Alkyl or hydrogen atom are represented,
-R2Represent alkyl,
-R3And R4Independently represent hydrogen atom or alkyl,
Or R3And R4Ring is formed with the carbon atom of the imidazole ring being connected with them.
The present invention also preferably relates to tire as defined above, and wherein A represents covalent bond or comprising 1 to 1800 carbon atom
It is preferred that the bivalent hydrocarbon radical of 2 to 300 carbon atoms.More preferably A is represented comprising 2 to 100 carbon atoms and preferably 2 to 50 carbon originals
The bivalent hydrocarbon radical of son.Even more preferably from A represents the bivalent hydrocarbon radical comprising 4 to 30 carbon atoms and preferably 10 to 40 carbon atoms.
More preferably the invention further relates to upper tire as defined above, wherein A is divalent aliphatic or aromatics type divalent group,
Or the group comprising at least aliphatic part and aromatic fractions.It is preferred that A is aliphatic divalent radical, or comprising at least aliphatic part and virtue
The group of race part.More preferably A is saturation or undersaturated aliphatic type divalent group.It is alkylidene even more preferably from A.Further preferably A
It is mixed with by the hetero atom that at least one is selected from oxygen, nitrogen and sulphur, preferred oxygen.It is preferred that A is selected from alkyl, cycloalkyl alkane by least one
The free radical of base, aryl, aralkyl, hydroxyl, alkoxyl, amido and carbonyl replaces.More preferably A is by one or more carboxylic-acid functionals
Group and/or one or more selected from itself replaced by one or more carboxylic acid functionals alkyl, cycloalkyl, cycloalkyl-alkyl,
Aryl or aralkyl replaces.Also, it is preferred that A does not include other carboxylic-acid functional groups.
More preferably the invention further relates to tire as defined above, wherein the content of polyacid is relative to the epoxy resin
Middle epoxy-functional be 0.2 to 4 molar equivalent, preferably 0.3 to 3 molar equivalent.It is preferred that the content of the polyacid is relative to institute
It is 0.5 to 2 molar equivalent to state in epoxy resin epoxy-functional, preferably 0.5 to 1.5 molar equivalent.
It is preferred that the invention further relates to tire as defined above, wherein：
-R1Represent hydrogen atom or the alkyl with 1 to 20 carbon atom, the cycloalkyl with 5 to 24 carbon atoms, have
The aryl of 6 to 30 carbon atoms or the aralkyl with 7 to 25 carbon atoms, it optionally can be by between one or more hetero atoms
It is miscellaneous and/or substituted,
-R2Represent there is 1 to 20 carbon atom alkyl, the cycloalkyl with 5 to 24 carbon atoms, with 6 to 30
The aryl of carbon atom or the aralkyl with 7 to 25 carbon atoms, its optionally can be mixed with by one or more hetero atoms and/or
It is substituted,
-R3And R4Identical or different group is independently represented, it is selected from hydrogen or the alkyl with 1 to 20 carbon atom, tool
There are cycloalkyl, the aryl with 6 to 30 carbon atoms or the aralkyl with 7 to 25 carbon atoms of 5 to 24 carbon atoms, its
Optionally can be mixed with by hetero atom and/or be replaced, or R3And R4Choosing is formed together with carbon atom on the imidazole ring being connected with them
Ring in self-contained 5 to 12 carbon atoms, the preferably aromatics of 5 or 6 carbon atoms, fragrant miscellaneous or aliphatic ring.
It is preferred that the invention further relates to tire as defined above, wherein R1Represent selected from the alkane with 2 to 12 carbon atoms
Group in base or the aralkyl with 7 to 13 carbon atoms, these groups can optionally be substituted.
Further preferably the present invention relates to tire as defined above, wherein R1Represent and optionally substituted there are 7 to 13 carbon originals
The aromatic alkyl group and R of son2Represent the alkyl with 1 to 12 carbon atom.
It is preferred that the invention further relates to tire as defined above, wherein R1Represent and optionally substituted there are 7 to 9 carbon atoms
Aromatic alkyl group and R2Represent the alkyl with 1 to 4 carbon atom.
Further preferably the invention further relates to tire as defined above, wherein R3And R4Independently represent identical or different base
Group, selected from hydrogen or the alkyl with 1 to 12 carbon atom, the cycloalkyl with 5 to 8 carbon atoms, with 6 to 24 carbon originals
The aryl or the aralkyl with 7 to 13 carbon atoms of son, it can optionally be substituted.Or, preferred R3And R4Be connected with them
Imidazole ring on carbon atom form phenyl ring, cyclohexene ring or cyclopentene ring together.
It is preferred that the invention further relates to tire as defined above, wherein the imidazole content is relative to being present in the formula
(I) carboxylic acid functional on polyacid is 0.01 to 2 molar equivalent and preferably 0.01 to 1.2 molar equivalent.More preferably described miaow
Azoles content is 0.01 to 0.8 molar equivalent and preferably relative to the carboxylic acid functional being present on the logical formula (I) polyacid
0.01 to 0.5 molar equivalent.
It is preferred that the invention further relates to tire as defined above, wherein the diene elastomer is selected from natural rubber, synthesis
The mixture of polyisoprene, polybutadiene, butadiene copolymer, isoprene copolymer and these elastomers.
It is preferred that the invention further relates to tire as defined above, the content of its epoxy resin is 3 to 20phr.More preferably
The content of the epoxy resin is 5 to 18phr.
It is preferred that the invention further relates to tire as defined above, wherein the reinforced filling include carbon black, silica or
The mixture of carbon black and silica.It is preferred that the amount of reinforced filling is 20 to 200phr.
The invention further relates to the method for preparing rubber composition as defined above, including following stages：
- in the first stage in (" nonproductive " stage), reinforced filling is introduced in diene elastomer, by all the components heat engine
Tool is kneaded until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequent in second stage (" production " stage), introducing crosslinked system；
- kneading all the components, to the maximum temperature less than 110 DEG C；
In the method, in the first stage and/or in second stage independently of each other and similarly, also added 1-
The epoxy resin of 20phr, logical formula (I) polyacid as defined above and logical formula (II) imidazoles as defined above.
According to the first embodiment, the invention further relates to method as defined above, it includes following stages：
- in the first stage in (" nonproductive " stage), reinforced filling, the epoxy of 1-20phr are introduced in diene elastomer
Resin, logical formula (I) polyacid as defined above and logical formula (II) imidazoles as defined above, all the components are thermomechanically kneaded
Until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequent in second stage (" production " stage), introducing crosslinked system；
- kneading all the components, the maximum temperature less than 110 DEG C.
According to the second embodiment, the invention further relates to method as defined above, it includes following stages：
- in the first stage in (" nonproductive " stage), reinforced filling is introduced in diene elastomer, by all the components heat engine
Tool is kneaded until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage (" production " stage), introducing crosslinked system, the epoxy resin of 1-20phr, limit as described above
Fixed logical formula (I) polyacid and logical formula (II) imidazoles as defined above；
- kneading all the components, the maximum temperature less than 110 DEG C.
According to the 3rd embodiment, the invention further relates to method as defined above, it includes following stages：
- in the first stage in (" nonproductive " stage), the epoxy of reinforced filling and 1-20phr is introduced in diene elastomer
Resin, all the components are thermomechanically kneaded until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequent in second stage (" production " stage), introducing crosslinked system, logical formula (I) polyacid as defined above
With logical formula (II) imidazoles as defined above；
- kneading all the components, the maximum temperature less than 110 DEG C.
According to the 4th embodiment, the invention further relates to method as defined above, it includes following stages：
- in the first stage in (" nonproductive " stage), reinforced filling, as defined above logical is introduced in diene elastomer
Formula (I) polyacid and logical formula (II) imidazoles as defined above, all the components are thermomechanically kneaded until reach 110-190 DEG C it
Between maximum temperature；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequent in second stage (" production " stage), the epoxy resin of introducing crosslinked system and 1-20phr；
- kneading all the components, the maximum temperature less than 110 DEG C.
According to the 5th embodiment, the invention further relates to method as defined above, it includes following stages：
- in the first stage in (" nonproductive " stage), reinforced filling, the epoxy of 1-20phr are introduced in diene elastomer
Resin and logical formula (II) imidazoles as defined above, all the components are thermomechanically kneaded until reaching between 110-190 DEG C most
Big temperature；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequent in second stage (" production " stage), introducing crosslinked system and logical formula (I) as defined above are polynary
Acid；
- kneading all the components are to the maximum temperature less than 110 DEG C.
According to the 6th embodiment, the invention further relates to method as defined above, it includes following stages：
- in the first stage in (" nonproductive " stage), reinforced filling and as defined above is introduced in diene elastomer
Logical formula (I) polyacid, all the components are thermomechanically kneaded until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage (" production " stage), introducing crosslinked system, the epoxy resin of 1-20phr and as described above
The logical formula (II) imidazoles for limiting；
- kneading all the components, the maximum temperature less than 110 DEG C.
According to the 7th embodiment, the invention further relates to method as defined above, it includes following stages：
- in the first stage in (" nonproductive " stage), reinforced filling, the epoxy of 1-20phr are introduced in diene elastomer
Resin and logical formula (I) polyacid as defined above, all the components are thermomechanically kneaded until reaching between 110-190 DEG C most
Big temperature；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage (" production " stage), introducing crosslinked system and logical formula (II) imidazoles as defined above；
- kneading all the components, the maximum temperature less than 110 DEG C.
According to the 8th embodiment, the invention further relates to method as defined above, it includes following stages：
- in the first stage in (" nonproductive " stage), reinforced filling and as defined above is introduced in diene elastomer
Logical formula (II) imidazoles, all the components are thermomechanically kneaded until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage (" production " stage), introducing crosslinked system, the epoxy resin of 1-20phr and as described above
The logical formula (I) polyacid for limiting；
- kneading all the components, the maximum temperature less than 110 DEG C.
The tire of the present invention is used in particular for passenger stock, also sulky vehicle (motor, bicycle), selected from motor van
It is the subway of industrial vehicle, " heavy type " vehicle-i.e., bus, heavy road transport vehicle (lorry, tractor, trailer), cross-country
Vehicle is loaded and unloaded in car, heavy agricultural vehicle or earthmoving equipment, aircraft and other transports.
Specific embodiment
The present invention and its advantage can easily understand that according to the description below and embodiment.
I.Test
Characterize as described below to rubber composition before curing and afterwards.
I.1. Mooney viscosity (or mooney plasticity)
As described in French Standard NF T 43-005 (1991), using concussion viscosimeter.Mooney is measured according to following principle
Plasticity：By composition in a state of nature (before solidifying), injection molding is heated to 100 DEG C in cylindrical groove.In one point of preheating
After clock, make rotor and rotated in the sample with 2 turns/min, and keep the work of the rotation to turn round measurement afterwards in 4 minutes is rotated
Square.Mooney plasticity (ML 1+4) with " mooney unit " (MU, 1MU=0.83 newton. rice) represent.
I.2. dynamic characteristic
Dynamic characteristic G* (10%) and tan (δ) the max basis on viscosity analyser (Metravib VA4000) at 40 DEG C
Standard ASTM D 5992-96 are measured.Vulcanising composition sample (cylinder is recorded according to standard ASTM D 1349-99
Shape sample, thickness 4mm, cross-sectional area 400mm2) in the case where simple AC sine shear stress is carried out, under 10Hz frequencies, in mark
Under quasi- temperature conditionss (23 DEG C), it is also possible to response at different temperatures.Strain amplitude scanning (is followed outward by 0.1% to 50%
Ring), then carry out from 50% to 1% (reciprocation cycle).The result for using is complexity dynamic shear modulus G* and fissipation factor
tan(δ).Maximum tan (δ) that reciprocation cycle is observed at 40 DEG C is shown, the strains of tan (δ) max and 10% are expressed as
Under complicated dynamic shear modulus G* (10%).
It is to be recalled that as known to those skilled in the art, 40 DEG C of tan (δ) max represents the delayed of material, because
And being rolling resistance, i.e., 40 DEG C of tan (δ) max is lower, and rolling resistance declines bigger.
II.The condition that the present invention is implemented
It based at least one diene elastomer, reinforced filling, cross-linking system, content is 1- that the rubber composition of the present invention is
The imidazoles of the polyacid and logical formula (II) of the epoxy resin of 20phr and logical formula (I).
Statement composition " being based on " is interpreted as the reaction product that composition contains mixture and/or Multiple components used
Thing, some basic ingredients especially can enter in its crosslinking or in vulcanizing in multiple stages of composition production with another kind
Row reacts or for reacting.
Statement " molar equivalent ", is known to the ordinarily skilled artisan, it is thus understood that have the molal quantity of related compounds with
The business of the molal quantity of reference compound.Thus, when representing using 1mol compound A relative to the 2 equivalents of compound B of compound A
The compound B of 2mol is used.
When " main " compound is mentioned, it is thus understood that in the present invention, compound same type in the composition
In compound in the highest flight, i.e., its weight in the compound of same type is maximum.Thus, for example main elastic body surface
Show the elastomer of the maximum weight of the gross weight for accounting for composition elastomer.Equally, main filler is represented and accounts for filling out for composition
The filler of the maximum weight of material.For example, only including in a kind of system of elastomer, the latter accounts for mainly in present invention definition
Position, and in the system comprising two kinds of elastomers, main elastomer represents the elastomer weight accounted for more than half.
Conversely, " minority " compound is the compound that maximum weight is not accounted in same type compound.
In this manual, unless otherwise indicated, shown percentage (%) is weight percentage (%).Additionally, passing through
Any interval that statement is represented " between a-b " is represented more than a to the scope (i.e. the excluded ranges of a and b) less than b, and is passed through
Any interval that statement " a to b " is represented is referred to by a up to scopes of b (i.e. including the scope for limiting a and b).
II.1. diene elastomer
The rubber composition of the present invention includes diene elastomer.
" diene " elastomer or rubber should be interpreted as at least part of (i.e. homopolymers or copolymer) by two in a known way
(one or more) elastomer obtained from alkene monomer (monomer with two conjugation or non-conjugated carbon-carbon double bond).
These diene elastomers can be divided into two classes：" substantially unsaturated " or " being substantially saturated ".Typically, " substantially not
Saturation " is interpreted as at least partly diene elastomer by obtained from conjugate diene monomer, wherein the diene of the diene monomers
Unit (conjugated diene) content is more than 15% (mol%)；Therefore, the such as diene of butyl rubber or EPDM types and-alkene are total to
Polymers is not belonging to above-mentioned definition, and (diene units content is relatively low can be especially defined as the diene elastomer of " being substantially saturated "
Or it is very low, typically smaller than 15%).In the classification of " substantially unsaturated " diene elastomer, " height is unsaturated " diene elastomer
Body should be especially appreciated that the content to refer to diene units (conjugated diene) is more than 50%.
According to these definition, more specifically, the diene elastomer that can be used for the present composition is understood to refer to：
- by any homopolymers obtained from the polymerization of the conjugate diene monomer with 4 to 12 carbon atoms；
- by one or more conjugated diene each other copolymerization or with the second one or more with 8 to 20 carbon atoms
The copolymerization of alkenyl aromatic compound and any copolymer for obtaining；
- by ethene and the alpha-olefin with 3 to 6 carbon atoms and the non-conjugated diene list with 6 to 12 carbon atoms
The copolymerization of body and the terpolymer that obtains, such as it is especially all by the non-conjugated diene monomers of ethene and propylene and the above-mentioned type
Such as Isosorbide-5-Nitrae-hexadiene, elastomer obtained from ENB or dicyclopentadiene；
The copolymer (butyl rubber) of-isobutene and isoprene, and the halides of the analog copolymer, in particular chloro
Or bromo-derivative.
Although any kind of diene elastomer is suitable for, the those of skill in the art of tire art should be understood that the present invention preferably makes
With the basic unsaturated diene elastomer of in particular above type (a) or (b).
Below it is particularly useful as conjugated diene：1,3-butadiene, 2- methyl isophthalic acids, 3- butadiene, such as 2,3- dimethyl-
1,3-butadiene, 2,3- diethyl -1,3-butadiene, 2- methyl -3- ethyls -1,3-butadiene or 2- methyl -3- isopropyl -1,
2,3- bis- (C1-C5 the alkyl) -1,3-butadiene of 3- butadiene, aryl -1,3-butadiene, 1,3-pentadiene or 2,4- oneself two
Alkene.Hereinafter vinyl aromatic compounds are for example suitable for：Styrene, o-, m- or p- methyl styrene, " vinyltoluene "
Commercial mixture, p- (tert-butyl group) styrene, methoxy styrene, chlorostyrene, 2,4,6- trimethyl styrenes, two
Vinyl benzene or vinyl naphthalene.
The copolymer can include the diene units of 99-20 weight % and the vinyl aromatic compounds of 1-80 weight %
Unit.The elastomer can have any micro-structural, and this depends on polymerizing condition used, particularly depend on presence or do not deposit
In modifying agent and/or the amount of randomizer and modifying agent used and/or randomizer.The elastomer such as can be embedding
The elastomer of section, statistics, order or micro- order, and can be prepared in dispersion liquid or solution；They can be with coupling
Agent and/or star-branched dose or functionalized agent are coupled and/or star-branched or functionalization.For the coupling with carbon black,
For example it can be mentioned that the functional group comprising C-Sn keys or ammonification functional group, such as benzophenone；For for and such as silica
Reinforcing inorganic filler coupling, such as it can be mentioned that silanol functional group or polysiloxanes with silanol end group are (such as such as FR
Described in 2 740 778 or US 6 013 718), alkoxysilane group is (such as such as FR 2 765 882 or the institutes of US 5 977 238
State), carboxyl (such as described in WO 01/92402 or US 6 815 473, WO 2004/096865 or US 2006/0089445)
Or polyether-based (such as described in EP 1 127 909 or US 6 503 973).For the example of other functions elastomer,
For example it can be mentioned that the elastomer (such as SBR, BR, NR or IR) of epoxidation type.
The following is suitable elastomer：The content (mol%) of polybutadiene, especially 1,2- units is those of 4-80%
Or those of the content (mol%) of cis -1,4- units more than 80%；Polyisoprene；Butadiene/styrene copolymers,
Especially Tg (glass transition temperature is measured according to ASTM D3418) is 0--70 DEG C and more particularly -10--60 DEG C, and benzene
Ethylene contents are 5-60 weight % and more particularly 20-50 weight %, and the content (mol%) of 1, the 2- keys of butadiene fraction is 4-
75% and anti-form-1, the content (mol%) of 4- keys for 10-80% those；Butadiene/isoprene copolymer, and especially
It is isoprene content for those that 5-90 weight % and Tg are -40 to -80 DEG C；Or isoprene/styrol copolymer,
And especially styrene-content is those that 5-50 weight % and Tg are -25--50 DEG C.In Butadiene/Styrene/isoamyl two
In the case of alkene copolymer, especially suitable is styrene-content for 5-50 weight % and more particularly 10-40 weight %, isoamyl
Diene content is 15-60 weight % and more particularly 20-50 weight %, and butadiene content is 5-50 weight % and more particularly
20-40 weight %, 1,2- unit contents (mol%) of butadiene fraction is 4-85%, anti-form-1, the content of 4- units
(mol%) it is 6-80%, 1, the 2- units of isoprene are 5-70% and isoprene plus the content (mol%) of 3,4- units
Anti-form-1, the content (mol%) of 4- units for 10-50% those, and more generally Tg is -20--70 DEG C any
Butadiene/Styrene/isoprene copolymer.
For summary, the diene elastomer composition of the present invention is preferably selected from polybutadiene (referred to as " BRs "), synthesizes different
The height of pentadiene (IRs), natural rubber (NR), butadiene copolymer, isoprene copolymer and these elastomer blends
Unsaturated diene elastomer.The copolymer more preferably butadiene/styrene copolymers (SBRs), isoprene/butadiene is common
Polymers (BIRs), isoprene/styrol copolymer (SIRs) and isoprene/butadiene/styrol copolymer (SBIRs).
According to specific embodiment, the diene elastomer main (i.e. more than 50phr) is SBR, or to make in emulsion
Standby SBR (" ESBR ") or the SBR (" SSBR "), SBR/BR, SBR/NR (or SBR/IR) that prepare in the solution, BR/NR
(either BR/IR) either SBR/BR/NR (or SBR/BR/IR) blend (mixture).In the situation of SBR (ESBR or SSBR)
Under, especially using with medium styrene-content, such as 20-35 weight %, high styrenic percentage, such as 35-45%, butadiene
Partial vinyl bond content is 15-70%, and the content (mol%) of trans-1,4- key is 15-75% and Tg is -10--55 DEG C
SBR；The SBR can be advantageously used for the mixture with BR, wherein the BR preferably has greater than the cis-1 of 90% (mol%),
4- keys.
" isoprene " elastomer should in a known way be interpreted as the homopolymers or copolymer of isoprene, in other words select
Can be plasticizing or colloidization from natural rubber (NR), synthetic polyisoprenes (IRs), various isoprene copolymers with
And the diene elastomer of the mixture of these elastomers.Especially it can be mentioned that isobutene/(butyl rubber in isoprene copolymer
Glue-IIR), isoprene/styrene (SIR), isoprene/butadiene (BIR) or isoprene/butadiene/styrene
(SBIR) copolymer.The preferred natural rubber of the isoprene elastomer or the cis -1,4- polyisoprene of synthesis；In these conjunctions
Cis-1 is preferably used in polyisoprene, the content (mol%) of 4- keys is more than 90%, more preferably greater than 98% poly- isoamyl
Diene.According to the present invention, the elastomer is preferably selected from above-mentioned isoprene elastomer, and the present composition is more preferably mainly wrapped
Containing natural rubber (NR), individually or as the blend with one or more other diene elastomer.
Another preferred embodiment of the invention, the rubber composition includes " (one kind that Tg is -70-0 DEG C
Or various) high Tg " diene elastomer and Tg be -110--80 DEG C, more preferably -105--90 DEG C of (one or more) " low Tg " two
The blend of alkene elastomer.The preferred S-SBRs of the high Tg elastomers, E-SBRs, natural rubber, synthetic polyisoprenes (cis-
Isosorbide-5-Nitrae-bonded content (mol%) is preferably greater than 95%), the mixture of BIRs, SIRs, SBIRs and these elastomers.It is described low
Tg elastomers preferably comprise butadiene unit of the content (mol%) at least equal to 70%, the bonded content of preferred cis-1,4-
(mol%) polybutadiene (BR) more than 90%.
Another specific embodiment of the invention, the rubber composition for example includes 30 to 100phr, especially
It is the blend of the low Tg elastomers of the high Tg elastomers and 0 to 70phr, especially 0 to 50phr of 50 to 100phr, according to another
One embodiment, it includes one or more SBRs for preparing in the solution for being total up to 100phr.
Another specific embodiment of the invention, the diene elastomer of the present composition is included has cis-1,
BR (as low Tg elastomer) and one or more S-SBRs or E-SBRs of the 4- bonded content (mol%) more than 90% (makees
For high Tg elastomers) blend.
The present composition can a kind of only mixture comprising diene elastomer or several diene elastomers, described two
Alkene elastomer or elastomer can be used for and except the composition of the external any kind of synthetic elastomer of diene elastomer in, or even
In the composition except the external polymer of elasticity, wherein the polymer such as thermoplastic polymer.
II.2. reinforced filling
Any kind of reinforced filling for making rubber composition reinforcement that can be used in tire production can be used, for example such as
The inorganic filler of the organic filler of carbon black, such as silica, and the blend of this two classes filler, especially carbon black and dioxy
The blend of SiClx.
HAF in all carbon blacks, especially common medicine tire, ISAF or SAF types (" tire level " is black) are suitable for carbon black.
Among the latter, it is particularly possible to refer to the hard carbon black (ASTM levels) of 100,200 or 300 series, such as N115, N134, N234,
N326, N330, N339, N347 or N375 are black, or black (such as N660, the N683 of higher series are referred to according to purpose application
Or N772).For example the carbon black can be mixed in isoprene elastomer in the form of masterbatch (for example, see application WO
97/36724 or WO 99/16600).
The example of the organic filler in addition to carbon black can be mentioned that the polyethylene organic filler of functionalization, such as applied
Described in WO-A-2006/069792, WO-A-2006/069793, WO-A-2008/003434 and WO-A-2008/003435.
In the present invention, the definition of " reinforcing inorganic filler " be any inorganic or mineral filler (no matter its color, source,
It is naturally occurring or synthetic), also referred to as " white filler " " colourless filler " or it is contrary with carbon black be even referred to as " non-black fillers ", it can be with
Individually to carrying out reinforcement for the rubber composition that produces tire, and without the need for the help in addition to middle coupling agent, in other words, can
Conventional tire-grade carbon black is substituted with the effect with reinforcement, generally, the filler is characterised by a known way on its surface
There is hydroxyl (- OH).
Physical state at the reinforcing inorganic filler, if in powder, microballoon, particle, it is spherical or it is any its
His suitable densified form is unimportant.Certainly, reinforcing inorganic filler is it can be appreciated that refer to the mixing of different inorganic fillers
Thing, be especially discussed further below can high degree of dispersion silicon and/or Al filler.
The mineral filler of the silicon-type, especially silica (SiO2) or especially alundum (Al2O3) (Al2O3)
The mineral filler of aluminum type is especially fitted and can be used as reinforcing inorganic filler.Silica used can be any this area knack
Reinforcing silica known to personnel, especially any BET specific surface area and CTAB specific surface areas are respectively less than 450m2/ g, preferably
30 to 400m2The precipitation or aerosil of/g.As can high degree of dispersion precipitated silica (" HDSs "), for example can be with
Ultrasil 7000 and Ultrasil 7005 silica from Evonik or Degussa is referred to, from Rhodia's
Zeosil 1165MP, 1135MP and 1115MP silica, from the Hi-Sil EZ150G silica of PPG, from Huber
Zeopol 8715,8745 and 8755 silica, or as described in applying for WO 03/16837 with high-specific surface area
Silica.
Reinforcing inorganic filler used, if especially silica, preferably with 45-400m2/ g, more preferably 60-300m2/
The specific surface area of g.
It is preferred that, the content of total reinforced filling (carbon black and/or reinforcing inorganic filler, such as silica) is 20-200phr,
More preferably 30-150phr is preferably different according to specific purposes application in a known way：For example, for bicycle tyre
Reinforcement level certainly less than the level needed for the tire that can be run up with continuous fashion, wherein the tire such as motorcycle
Tire, passenger tyre, or the tire of the MPV of such as heavy-duty car.
Preferred embodiment of the invention, using including 30-150phr, more preferably 50-120phr especially carbon blacks
Organic filler reinforced filling, and optionally silica；If if having silica, preferable amount is less than 20phr, more
Preferably smaller than 10phr (such as 0.1-10phr).The preferred embodiment is isoprene rubber in the main elastomer of composition
It is particularly suitable during glue, more preferably natural rubber.
Another preferred embodiment of the invention, or using comprising 30-150phr, more preferably 50-120phr
The especially reinforced filling of the inorganic filler of silica, and optionally carbon black；If if having carbon black, preferable amount is less than
20phr, more preferably less than 10phr (such as 0.1-10phr).The preferred embodiment is in rubber composition comprising (a kind of or many
Kind) blend of " high Tg " diene elastomer and (one or more) " low Tg " diene elastomer when be particularly suitable, wherein described
The Tg of " high Tg " diene elastomer is -70-0 DEG C, and the Tg of " low Tg " diene elastomer is -110--80 DEG C.
In order to reinforcing inorganic filler is coupled to into diene elastomer, in a known way can be using in inorganic filler
(its particle surface) provides at least dual functional coupling of gratifying chemistry and/or physical connection and diene elastomer between
Agent (or bridging agent), especially bifunctional organosilan or polysiloxane.
Especially using for example such as application WO 03/002648 (or US 2005/016651) and (or the US of WO 03/002649
2005/016650) silane polysulfides described in, are referred to as " symmetrical " or " asymmetric " depending on its concrete structure.
What is be particularly suitable is the silane polysulfides for being referred to as " symmetrical " of below formula (I), but to being defined as below not
Limit：:
(I)Z-A-Sx- A-Z, wherein
- x is 2 to 8 integer (preferably 2 to 5)；
- A is bivalent hydrocarbon radical (preferred C1-C18Alkylidene or C6-C12Arlydene, more particularly C1-C10Alkylidene, especially
It is C1-C4Alkylidene, particularly propylidene)；
- Z is corresponding to one of following formula：
Wherein：
- group R1, replace or unsubstituted and be same to each other or different to each other, represent C1-C18Alkyl, C5-C18Cycloalkyl or C6-C18
Aryl (preferred C1-C6Alkyl, cyclohexyl or phenyl, especially C1-C4Alkyl, more particularly methyl and/or ethyl)；
- group R2Replace or unsubstituted and be same to each other or different to each other, represent C1-C18Alkoxyl or C5-C18Cycloalkyloxy is (excellent
Choosing is selected from C1-C8Alkoxyl and C5-C8Cycloalkyloxy, is more preferably selected from C1-C4Alkoxyl, especially methoxyl group and ethyoxyl).
In the case of the mixture of the alkoxy silane polysulfide of upper formula (I), especially commercially available mixture,
The mean value of " x " is preferably the fraction of 2-5, and more preferably from about 4.However, the present invention advantageously can also for example use alkoxyl
Silane polysulfides (x=2) and carry out..
As the example of silane polysulfides, two ((C are more specifically referred to1-C4) alkoxyl (C1-C4) alkyl tin groups, alkyl silane groups (C1-
C4) alkyl) polysulfide (especially disulphide, trisulfide or tetrasulfide), for example, two (3- trimethoxy silane bases
Propyl group) or two (3- Ethoxysilane base propyl group) polysulfides.It is [(C especially using formula in these compounds2H5O)3Si
(CH2)3S2]2Two (3- Ethoxysilane base propyl group) tetrasulfides, referred to as TESPT or formula are [(C2H5O)3Si(CH2)3S]2Two (tri-ethoxy silylpropyl) disulphide, referred to as TESPD.As preferred embodiment, two (one can also be referred to
(C1-C4) (the C of alkoxyl two1-C4) alkyl tin groups, alkyl silane groups propyl group) polysulfide (especially disulphide, trisulfide or four sulfurations
Thing), a two (ethyoxyls two being more particularly for example described in patent application WO02/083782 (or US 2004/132880)
Methyl-monosilane base propyl group) tetrasulfide.
As the coupling agent in addition to alkoxy silane polysulfide, it is particularly possible to refer to such as patent application WO 02/
Dual functional POSs described in 30939 (either US 6 774 255) and WO 02/31041 (or US 2004/051210)
(polysiloxane) or silicol polysulfide (in formula I above R2=OH), or such as patent application WO 2006/
The silane with azo dicarbapentaborane functional group described in 125532, WO 2006/125533 and WO 2006/125534 or
POSs。
In the rubber composition of the present invention, the preferred 4-12phr of content of coupling agent, more preferably 4-8phr.
Those skilled in the art should be understood that as filling out with the reinforcing inorganic filler identical for describing in this section
Material, can with using other properties reinforced filling, especially organic filler, as long as the reinforced filling by inorganic layer cover or
Including on its surface needs that bonded functional site is formed between filler and elastomer using coupling agent, especially hydroxyl position
Point, wherein the inorganic layer such as silica.
II.3. epoxy resin
Epoxy resin for the present invention includes all of polyepoxides, such as aromatic epoxide, aliphatic ring
Oxide and aliphatic epoxide.Specifically, in aromatic epoxide, preferred epoxy phenolics, 2,2- bis- [4- (contractings
Water glycerin ether epoxide) phenyl] propane, poly- [(o- toluene glycidol ethers)-copolymerization-formaldehyde] and these have the mixing of compound
Thing.For example it can be mentioned that Huntsman sale " ECN1273 ", " ECN1280 ", " ECN1299 " and " ECN 9511 " resin or
Person Dow Chemicals " DER 332 ", " DER 354 ", " DER 383 ", " DEN 425 ", " DEN 431 ", " DEN 438 " and
" DEN 439 " resin.
The epoxidation degree represented by the resin mean mol (EEW=epoxide equivalents) of each epoxy-functional can be with
Difference, such as 50-1000g/equivalent.For the requirement of the present invention, preferred epoxidation degree is 100-600g/ equivalents, excellent
Select 150-300g/ equivalents.
The amount of epoxy resin is 1 to 20phr；Less than shown minimum of a value, technique influence is not notable, and shown in being more than most
Big value, then excessively increase the risk with delayed excess destruction with hardness.For these reasons, preferred 3-20phr, more preferably 5-
The amount of 18phr.
II.4. polyacid and imidazole system
Above-mentioned resin is mixed with the logical formula (I) polybasic carboxylic acid and logical formula (II) imidazoles that can make its crosslinking or solidify.
During rubber substrate solidifies, the crosslinking of resin by the activation by logical formula (II) imidazoles in resin and
Covalent bond is formed between the acid functional group of logical formula (I) polybasic carboxylic acid and carried out, wherein the polybasic carboxylic acid also becomes curing agent.
The polyacid and imidazole system thus polybasic carboxylic acid and (at least one) comprising (at least one) logical formula (I) are logical
The imidazoles of formula (II).
II.4.a. polyacid
For the polybasic carboxylic acid that polyacid of the invention is logical formula (I)：
Wherein A represents covalent bond or the alkyl containing at least one carbon atom, optionally substituted and optionally by one or more
Hetero atom is mixed with.
It is preferred that in logical formula (I) polyacid, A represents covalent bond or comprising 1 to 1800 carbon atom and preferably 2 to 300
Carbon atom, more preferably 2- to 100 carbon atoms and highly preferred 2 to 50 carbon atoms bivalent hydrocarbon radical.More than 1800 carbon originals
Many carboxylics of son are the relatively low crosslinking agents of effect.Therefore, the preferred representatives of A includes 3 to 50 carbon atoms, preferably 4 to 30 carbon atoms
And the bivalent hydrocarbon radical of more preferably 4 to 20 carbon atoms.
It is preferred that, in many carboxylics of logical formula (I), A can be aliphatic series or aromatics type divalent group, or comprising at least aliphatic part and
The group of aromatic fractions.It is preferred that A is aliphatic type divalent group, or the group comprising at least aliphatic part and aromatic fractions.Or
It is preferred that, A can be saturation or undersaturated aliphatic type divalent group, such as alkylidene.
The A of logical formula (I) polyacid can be mixed with, preferred oxygen by least one selected from the hetero atom of oxygen, nitrogen and sulphur.
And, leading to the A of formula (I) polyacid can be selected from alkyl, cycloalkyl-alkyl, aryl, aralkyl, hydroxyl by least one
The free radical of base, alkoxyl, amido and carbonyl replaces.
Logical formula (I) polyacid can include more than two carboxylic acid functional；Now, A groups are by one or more carboxylic acids
Functional group and/or one or more selected from alkyl, cycloalkyl, cycloalkyl-alkyl, the alkyl of aryl or aralkyl and replace, they
Itself replaced by one or more carboxylic acid functionals.
According to preferred version, the A free radicals do not include another carboxylic acid functional；Thus the polyacid is diacid.
The content of polyacid is 0.2 to 4 molar equivalent relative to the epoxy-functional being present on epoxy resin, preferably
0.3 to 3 molar equivalent.It is preferred that, the content is 0.5 to 2 molar equivalent relative to the epoxy-functional being present on epoxy resin,
It is preferred that 0.5 to 1.5 molar equivalent.Less than the polyacid of 0.2 molar equivalent, then cross-linking effect is not notable, and is more than 4 moles and works as
The polyacid of amount, with lower content contrast extra benefit is not found.
Polyacid for application claims or for commercially available, or those skilled in the art can be according to knowing
Technology and easily prepare, wherein described in the reference for example quoted such as file US 7 534 917 and this document of the technology
Chemistry route, or biological approach, such as fermentation as described in file US 3 843 466.
As polyacids commercially available and for application claims, such as it can be mentioned that oxalic acid, butanedioic acid, adipic acid, the last of the ten Heavenly stems
Diacid, dodecanedioic acid, terephthalic acid (TPA) or polyacid such as benzenetricarboxylic acid or 3,4- bis- (carboxymethyl) cyclopentane-carboxylic acid.
II.4.b. imidazoles
For the imidazoles that the imidazoles in the cross-linking system of tire of the present invention is logical formula (II)：
Wherein：
-R1Alkyl or hydrogen atom are represented,
-R2Represent alkyl,
-R3And R4Independently represent hydrogen atom or alkyl,
- or R3And R4Ring is formed with the carbon atom on the imidazole ring being connected with them.
Preferred formula (II) imidazoles has following group：
-R1Represent hydrogen atom or the alkyl with 1 to 20 carbon atom, the cycloalkyl with 5 to 24 carbon atoms, have
The aryl of 6 to 30 carbon atoms or the aralkyl with 7 to 25 carbon atoms, it optionally can be by between one or more hetero atoms
It is miscellaneous and/or substituted,
-R2Represent there is 1 to 20 carbon atom alkyl, the cycloalkyl with 5 to 24 carbon atoms, with 6 to 30
The aryl of carbon atom or the aralkyl with 7 to 25 carbon atoms, its optionally can be mixed with by one or more hetero atoms and/or
It is substituted,
-R3And R4Identical or different group is independently represented, it is selected from hydrogen or the alkyl with 1 to 20 carbon atom, tool
There are cycloalkyl, the aryl with 6 to 30 carbon atoms or the aralkyl with 7 to 25 carbon atoms of 5 to 24 carbon atoms, its
Optionally can be mixed with by hetero atom and/or be replaced, or R3And R4Choosing is formed together with carbon atom on the imidazole ring being connected with them
Ring in self-contained 5 to 12 carbon atoms, the preferably aromatics of 5 or 6 carbon atoms, fragrant miscellaneous or aliphatic ring.
It is preferred that, R1Represent the base selected from the alkyl or the aralkyl with 7 to 13 carbon atoms with 2 to 12 carbon atoms
Group, these groups optionally can be substituted.It is further preferred that R1The optionally substituted aralkyl with 7 to 13 carbon atoms is represented, and
And R2Represent the alkyl with 1 to 12 carbon atom.It is further preferred that R1Represent the optionally substituted aralkyl with 7 to 9 carbon atoms
Base and R2Represent the alkyl with 1-4 carbon atom.
It is preferred that, R3And R4Independently represent identical or different group, selected from hydrogen or the alkyl with 1 to 12 carbon atom,
Cycloalkyl with 5 to 8 carbon atoms, the aryl with 6 to 24 carbon atoms or the aralkyl with 7 to 13 carbon atoms,
It optionally can be substituted.Or, preferred R3And R4Phenyl ring, ring are formed together with the carbon atom on the imidazole ring being connected with them
Hexene ring or cyclopentene ring.
For the excellent operation of the present invention, it is preferable that the content of the imidazoles is relative to carboxylic present on logical formula (I) polyacid
Acid functional group is 0.01 to 2 molar equivalent and preferably 0.01 to 1.2 molar equivalent.Less than 0.01 molar equivalent, then with individually make
Contrasted with polyacid situation and do not found the effect of imidazoles coagent, and be more than the value of 1.2 molar equivalents, with lower content
Contrast does not find extra benefit.Thus, imidazole content relative to carboxylic acid functional present on logical formula (I) polyacid, more
Preferably 0.01 to 0.8 molar equivalent and preferably 0.01 to 0.5 molar equivalent.
Imidazoles for application claims or for commercially available, or those skilled in the art can be according to knowing skill
Art and easily prepare, wherein the technology is for example such as file JP2012211122 and JP2007269658 or in Science of
Synthesis, described in 2002,12,325-528.
For example as application claims and commercially available imidazoles is used for, it can be mentioned that 1,2- methylimidazole, 1- decyl -2-
Methylimidazole or 1 benzyl 2 methyl imidazole.
II.4.c. polyacid and imidazoles
It is clear that according to the statement " being based on " of the present invention, based on above-mentioned logical formula (I) polyacid and logical formula (II) imidazoles
Composition can be that wherein described polyacid and the imidazoles react to each other in advance with one or more sour senses of polyacid
The composition of forming salt between group and one or more imidazole nucleus respectively.
II.5. cross-linking system
The cross-linking system can be vulcanizing system；It is preferably based on sulphur or sulfur donor and main vulcanization accelerator is (excellent
Select the primary accelerator of 0.5 to 10.0phr).In addition to the vulcanizing system, optionally various known vulcanization accelerators or sulfuration are activated
Agent, such as zinc oxide (preferably 0.5 to 10.0phr), stearic acid, guanidine derivatives (especially diphenylguanidine) or other are (preferably every
It is 0.5 to 5.0phr to plant).When the present invention is for tire tread, the preferred content of sulphur is 0.5-10phr, more preferably 0.5-
5.0phr, such as 0.5-3.0phr.
As (main or secondary) accelerator, it is possible to use can be in the presence of sulphur as diene elastomer vulcanization accelerator
Any compound, the especially accelerator and thiuram type accelerator and two thiocarbamate zinc-type of thiazole type and its derivative
Accelerator.These accelerator are preferably selected from 2-mercaptobenzothiazole based bisulfide (referred to as " MBTS "), N- cyclohexyl -2- benzene
And thiazole sulphamide (referred to as " CBS "), N, N- dicyclohexyl -2-[4-morpholinodithio sulphamide (referred to as " DCBS "), N- (tertiary fourths
Base) -2-[4-morpholinodithio sulphamide (referred to as " TBBS "), N- (tert-butyl group) -2-[4-morpholinodithio sulphamide (referred to as " TBSI "),
The mixture of benzyl disulfide zinc formate (referred to as " ZBEC ") and these compounds.Preferably use the main rush of sulfonyl amine type
Enter agent.
Specific embodiment of the invention, the present composition does not contain guanidine derivatives, or comprising less than 0.5phr
Guanidine derivatives.It is preferred that, the composition or the compound is entirely free of, or comprising less than 0.45phr, preferably smaller than
The guanidine derivatives of 0.4phr, more preferably less than 0.3phr, preferably smaller than 0.2phr and highly preferably less than 0.1phr.Term " guanidine
Derivative " is understood to refer to the organic compound with guanidine functional group as main functional group, such as in tire composition
It is known those, especially as vulcanization accelerator, such as diphenylguanidine (DPG) or two (o- tolyl) guanidines (DOTG).
Another specific embodiment of the invention, in the tire of the present invention, the epoxy comprising application claims
The composition of resin also without zinc or, comprising less than 0.5phr, preferred 0.3phr, more preferably less than 0.2phr and very preferably
Zinc less than 0.1phr.
II.6. multiple additives
The tread rubber composition of the present invention is also comprising all or portion being usually used in the elastic composition of production tyre surface
The protective agent of point additive, such as such as pigment, ozone-resistant wax, chemical antiozonant or antioxidant, age resistor, except it is above-mentioned that
Crosslinking agent beyond a little, reinforced resin or plasticiser.It is preferred that, the plasticiser is solid-state hydrocarbon resin (or plasticizing resin), and chain is oily
The mixture of (or plasticizing oil) or both.
In addition to the coupling agent, these compositions can also include coupling activator, for covering the examination of inorganic filler
Agent, or more generally, comprising dispersion in a known way by improvement filler in rubber substrate and reduction composition
Viscosity and the processing aid of its ecosystem processability can be improved, for example hydrolyzable silane of these reagents, such as alkyl alkane
TMOS, polyol, polyethers, primary amine, secondary amine or tertiary amine, or hydroxylating or hydrolyzable polysiloxane.
II.7. the production of rubber composition
Composition for tyre surface of the present invention can be in suitable mixer, using known to the ordinarily skilled artisan
Two continuous preparatory phases and produced, the first rank of thermomechanical work under high temperature or kneading (" nonproductive " stage)
Section, up to 110-190 DEG C of the temperature, preferred 130-180 DEG C of maximum temperature, followed by it is down to the machine work of lower temperature
The second stage of (" production "), wherein the lower temperature is typically smaller than 110 DEG C, such as 40-100 DEG C, wherein there is introducing crosslinked
System completes the stage.
Method for preparing said composition for example includes following stages：
- in the first stage in (" nonproductive " stage), reinforced filling is introduced in diene elastomer, all the components are carried out
Thermomechanically knead until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequent in second stage (" production " stage), introducing crosslinked system；
- kneading all the components are to the maximum temperature less than 110 DEG C；
It should be understood that in the first stage and/or in second stage, independently of each other and similarly, also added above-mentioned
The logical formula (I) polyacid for limiting and the logical formula (II) imidazoles and the epoxy resin of 1-20phr of above-mentioned restriction.
For example, non-productive stage is carried out in the single thermomechanical stage, wherein, in a first step, by all need
During the basis (diene elastomer increases filler and other compositions) wanted adds suitable mixer, for example Standard internal is mixed
In conjunction machine, then in second step, for example, other additives are added after kneading one to two minute, optionally in addition to cross-linking system
Other reagents or other processing aids for covering filler.The preferred 1-15min of total kneading process of non-productive stage.At this
In stage, epoxy resin, curing agent and activator can be optionally added, or only add epoxy resin.If in this stage not
Epoxy resin and polyacid and imidazole system are added, then must be added them in the following stage, so that application claims
Epoxy resin and polyacid and imidazole system be present in final composition.
Will because obtained from mixture cooling after, then keep (such as 40-100 DEG C) at low temperature to add cross-linking system
In entering internal mixer, such as in mill.Then blended product is mixed into (production phase) several minutes, such as 2-15min.
In this stage, epoxy resin and polyacid and imidazole system can be optionally added, if adding epoxy in non-productive stage
Resin, then only add polyacid and imidazole system.
Then by thus the final composition of gained rolled, such as in the form of sheets or tabular, to be particularly useful for laboratory
Characterize, it is also possible to extruded, such as with formation for the rubber profiled piece in tire production of the present invention.
The present invention relates to the tire and above-mentioned use of ecosystem (before solidifying) and cure states (after being crosslinked or vulcanizing)
In tire semi-finished product, rubber parts.
II.8. tire of the invention
The rubber composition of the present invention can be used for the different parts of tire, especially top, bead area, lateral side regions and
Tyre surface (especially in tread base).
Preferred embodiment of the invention, above-mentioned rubber composition can be as hard elastomer layer in tire
At least one part in in tire.
Elastomer " layer " is interpreted as any by the manufacture of rubber (or " elastomer ", both regard synonym as) composition
Three-dimensional micromodule with any shape and thickness, wherein the shape especially sheet, strip, or other have it is any transversal
The component in face, such as rectangle or triangle.
First, the elastomer layer can be used in positioned at tyre surface (being used for the part contacted with road surface in operation) and make
The tread base in tire summit between the band of the top reinforcement.The thickness of the elastomer layer preferably 0.5 to 10mm, especially
It is 1 to 5mm.
Another preferred embodiment of the invention, the rubber composition of the present invention can be used for being formed positioned at tire
Elastomer layer in bead area, it is radially between carcass ply, bead and carcass ply turned up portion.
Equally, the present composition can be used for layer top (tire belt) or the region between layer top and carcass ply.
Another preferred embodiment of the present invention can be formed positioned at tyre side regions using the present composition
In elastomer layer.
Or, the present composition may be advantageously used with tire tread.
III. the embodiment of the present invention
III.1. the preparation of the composition
Tested as follows as follows：By diene elastomer, reinforcing fiber and epoxy resin and vulcanisation system
Outer various other compositions, curing agent and activator order add (final charging degree in internal mixer：About 70 bodies
Product %), about 60 DEG C of initial vessel temp.Then thermomechanically operated (non-productive stage) in a single stage, it is altogether
Last about 3-4 minutes, until it reaches 180 DEG C maximum of " decline " temperature.
Reclaim thus gained mixture, and cool down, then at 30 DEG C by sulphur, sulfonyl amine type accelerator, and polynary
Acid and imidazole system are added in blender (uniform collator), by every kind of composition mixing (production phase) reasonable time (for example
5-12min)。
By thus the composition of gained rolled, either plate-like (2 to 3mm is thick) or in rubber sheet shape measuring
Its physics or engineering properties, or it is extruded as profiled piece.
III.2. the test of rubber composition
The test shows the rubber composition that can be particularly useful for tire bottom or bottom section, wherein the area requirement
Higher low strain dynamic hardness.These compositions are shown than conventional rubber composition (comprising phenolic resin and HMT as methylene
Base donor) bigger hardness, and remain similar and acceptable level delayed；Additionally, the processability of the present composition and
Scorch safety is significantly improved, with regard to the composition comprising epoxy resin and polyacid and imidazole system.
For this purpose, by as above rubber composition is prepared, composition C1 and C2 are Comparative composition, and composition C3 to C6 is
The present composition (referring to table 1).
The property of composition C1 to C6 measured as described above and as a result it is shown in Table 2.
It should be noted that passing through epoxy resin, polybasic carboxylic acid and imidazoles in C3 to C6 compositions of the present invention and fortified phenol/first
Urea formaldehyde HMT pair and composition can be made to obtain the processability that significantly improves, this is represented by lower Mooney point.Additionally,
The complicated dynamic shear modulus G* (10%) at 40 DEG C is noticed equal to or more than Comparative composition, this represents the present composition
Low strain dynamic hardness be improved, and while limit the raising of fissipation factor at 40 DEG C, that is, keep delayed in acceptable level.
For summary, these test results show to use epoxy resin and polybasic carboxylic acid curing agent in the compositions of the present invention
Can obtain having and improve the rubber of processability and low strain dynamic hardness equal to or more than conventional composition (here is Comparative composition)
Glue composition, that is, improve pavement properties, and maintain it is acceptable delayed, especially in some regions of tire, particularly
Bottom section and bottom.
Table 1
| C1 | C2 | C3 | C4 | C5 | C6 | |
| NR(1) | 100 | 100 | 100 | 100 | 100 | 100 |
| Carbon black (2) | 70 | 70 | 70 | 70 | 70 | 70 |
| ZnO(3) | 3 | 3 | 3 | 3 | 3 | 3 |
| Stearic acid (4) | 2 | 2 | 2 | 2 | 2 | 2 |
| 6PPD(5) | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| Sulphur (6) | 3 | 3 | 3 | 3 | 3 | 3 |
| Accelerator (7) | 2 | 2 | 2 | 2 | 2 | 2 |
| Resin 1 (8) | 12 | - | - | - | - | |
| Resin 2 (9) | - | 12 | 12 | - | - | - |
| Resin 3 (10) | - | - | 12 | 12 | 12 | |
| Curing agent 1 (11) | 4 | |||||
| Curing agent 2 (12) | 4 | - | - | - | - | |
| Curing agent 3 (13) | - | 4 | 4 | - | - | |
| Curing agent 4 (14) | - | - | - | 4 | 6 | |
| Imidazoles (15) | - | 0.3 | 1 | 1 | 1 |
(1) natural rubber；
(2) carbon black N326 (being named according to standard ASTM D-1765)；
(3) zinc oxide (technical grade, Umicore)；
(4) Stearin (from the Pristerene 4931 of Uniqema)；
(5) N- (1,3- dimethylbutyls)-N- phenyl-p-phenylenediamines are (from the Santoflex 6- of Flexsys
PPD)；
(6) 80% insoluble sulphur；
(7) accelerator：N- cyclohexyl -2-[4-morpholinodithio sulphamide (from the Santocure CBS of Flexsys)；
(8) resin 1：Phenol/formaldehyde novolac resin (from the Peracit 4536K of Perstorp)；
(9) resin 2：From the epoxy resin " DEN 439 " of Dow Chemical Co.；
(10) resin 3：From the epoxy resin " ECN 1273 " of Huntsman；
(11) curing agent 1：P- xylylene diamines (from Sigma-Aldrich)；
(12) curing agent 2：Hexa (from Degussa)；
(13) curing agent 3：Succinic acid (CAS 124-04-9), from Sigma-Aldrich；
(14) curing agent 4：Terephthalic acid (TPA) (CAS 100-21-0), from Sigma-Aldrich；
(15) 1 benzyl 2 methyl imidazole (CAS 13750-62-4), from Sigma-Aldrich.
Table 2
| C1 | C2 | C3 | C4 | C5 | C6 | |
| Mooney | 77 | 140 | 70 | 71 | 67 | 69 |
| (10%) 40 DEG C of G* | 6.5 | 7.8 | 8.8 | 6 | 7.5 | 7 |
| Tan(δ)max 40℃ | 0.23 | 0.33 | 0.31 | 0.31 | 0.30 | 0.29 |
Claims (46)
1. a kind of tire comprising rubber composition, the rubber composition based at least one diene elastomer, reinforced filling,
Cross-linking system, content are the epoxy resin of 1 to 20phr, and logical formula (I) polybasic carboxylic acid：
Wherein A represents covalent bond or the alkyl containing at least one carbon atom, and it is optionally substituted and optionally miscellaneous by one or more
Atom is mixed with,
With the imidazoles of logical formula (II)：
Wherein：
-R1Alkyl or hydrogen atom are represented,
-R2Represent alkyl,
-R3And R4Independently represent hydrogen atom or alkyl,
- or R3And R4Ring is formed together with the carbon atom on the imidazole ring being connected with them.
2. the tire comprising rubber composition of claim 1, wherein A represents covalent bond or comprising 1 to 1800 carbon atom
Bivalent hydrocarbon radical.
3. the tire comprising rubber composition of claim 1, wherein A represents covalent bond or comprising 2 to 300 carbon atoms
Bivalent hydrocarbon radical.
4. the tire comprising rubber composition of claim 1 and one of 2, wherein A represents comprising 2 to 100 carbon atoms two
Valency alkyl.
5. the tire comprising rubber composition of claim 1 and one of 2, wherein A represents the divalence comprising 2 to 50 carbon atoms
Alkyl.
6. in claim 1-2 any one the tire comprising rubber composition, wherein A represent include 3 to 50 carbon atoms
Bivalent hydrocarbon radical.
7. in claim 1-2 any one the tire comprising rubber composition, wherein A represent include 4 to 30 carbon atoms
Bivalent hydrocarbon radical.
8. in claim 1-2 any one the tire comprising rubber composition, wherein A represent include 10 to 40 carbon atoms
Bivalent hydrocarbon radical.
9. in claim 1-2 any one the tire comprising rubber composition, wherein A represents aliphatic type or aromatics type divalence
Group or the group comprising at least aliphatic part and aromatic fractions.
10. in claim 1-2 any one the tire comprising rubber composition, wherein A is aliphatic type divalent group or bag
Group containing at least aliphatic part and aromatic fractions.
The tire comprising rubber composition of any one in 11. claims 1-2, wherein A is saturation or unsaturated aliphatic type
Divalent group.
The tire comprising rubber composition of any one in 12. claims 1-2, wherein A is alkylidene.
The tire comprising rubber composition of any one in 13. claims 1-2, wherein A by least one selected from oxygen, nitrogen and
The hetero atom of sulphur is mixed with.
The tire comprising rubber composition of 14. claims 13, wherein the hetero atom is oxygen.
The tire comprising rubber composition of any one in 15. claims 1-2, wherein A is selected from alkyl, ring by least one
The substituent group of alkyl-alkyl, aryl, aralkyl, hydroxyl, alkoxyl, amino and carbonyl.
The tire comprising rubber composition of any one in 16. claims 1-2, wherein A is by one or more carboxylic-acid functionals
Roll into a ball and/or replaced selected from alkyl, cycloalkyl, cycloalkyl-alkyl, aryl or aralkyl by one or more, the alkyl, cycloalkanes
Base, cycloalkyl-alkyl, aryl or aralkyl itself is replaced by one or more carboxylic acid functionals.
The tire comprising rubber composition of any one in 17. claims 1-2, wherein A does not include another carboxylic-acid functional
Group.
The tire comprising rubber composition of any one in 18. claims 1-2, wherein relative to being present on epoxy resin
Epoxy-functional, the content of polybasic carboxylic acid is 0.2 to 4 molar equivalent.
The tire comprising rubber composition of any one in 19. claims 1-2, wherein relative to being present on epoxy resin
Epoxy-functional, the content of polybasic carboxylic acid is 0.3 to 3 molar equivalent.
The tire comprising rubber composition of any one in 20. claims 1-2, wherein relative to being present on epoxy resin
Epoxy-functional, the content of polybasic carboxylic acid is 0.5 to 2 molar equivalent.
The tire comprising rubber composition of any one in 21. claims 1-2, wherein relative to being present on epoxy resin
Epoxy-functional, the content of polybasic carboxylic acid is 0.5 to 1.5 molar equivalent.
The tire comprising rubber composition of any one in 22. claims 1-2, wherein：
-R1Represent hydrogen atom or the alkyl with 1 to 20 carbon atom, the cycloalkyl with 5 to 24 carbon atoms, with 6 to 30
The aryl of individual carbon atom or the aralkyl with 7 to 25 carbon atoms, the group optionally can be by one or more hetero atoms
It is mixed with and/or is substituted,
-R2Represent there is 1 to 20 carbon atom alkyl, the cycloalkyl with 5 to 24 carbon atoms, with 6 to 30 carbon atoms
Aryl or the aralkyl with 7 to 25 carbon atoms, the group optionally can be mixed with by one or more hetero atoms and/or
It is substituted,
-R3And R4Identical or different group is independently represented, it is selected from hydrogen or the alkyl with 1 to 20 carbon atom, with 5
Cycloalkyl, the aryl with 6 to 30 carbon atoms or the aralkyl with 7 to 25 carbon atoms to 24 carbon atoms, it is described
Group optionally can be mixed with by hetero atom and/or is substituted, or R3And R4Together with carbon atom on the imidazole ring being connected with them
Form the ring in the aromatic ring comprising 5 to 12 carbon atoms, hetero-aromatic ring or aliphatic ring.
The tire comprising rubber composition of 23. claims 22, wherein R3And R4With carbon atom on the imidazole ring being connected with them
The ring in the aromatic ring comprising 5 or 6 carbon atoms, hetero-aromatic ring or aliphatic ring is formed together.
The tire comprising rubber composition of any one, wherein R in 24. claims 1-21Represent selected from 2 to 12 carbon
The group of the alkyl of atom or the aralkyl with 7 to 13 carbon atoms, the group optionally can be substituted.
The tire comprising rubber composition of any one, wherein R in 25. claims 1-21Represent and there are 7 to 13 carbon atoms
Optionally substituted aralkyl, and R2Represent the alkyl with 1 to 12 carbon atom.
The tire comprising rubber composition of any one, wherein R in 26. claims 1-21Represent and there are 7 to 9 carbon atoms
Optionally substituted aralkyl, and R2Represent the alkyl with 1 to 4 carbon atom.
The tire comprising rubber composition of any one, wherein R in 27. claims 1-23And R4Independently represent it is identical or
Different groups, its be selected from hydrogen or the alkyl with 1 to 12 carbon atom, the cycloalkyl with 5 to 8 carbon atoms, with 6 to
The aryl of 24 carbon atoms or the aralkyl with 7 to 13 carbon atoms, the group optionally can be substituted.
The tire comprising rubber composition of any one, wherein R in 28. claims 1-23And R4With the miaow being connected with them
Carbon atom forms together phenyl ring, cyclohexene ring or cyclopentene ring on azoles ring.
The tire comprising rubber composition of any one in 29. claims 1-2, wherein relative to logical formula (I) polybasic carboxylic acid
Present on carboxylic acid functional, the content of the imidazoles is 0.01 to 2 molar equivalent.
The tire comprising rubber composition of any one in 30. claims 1-2, wherein relative to logical formula (I) polybasic carboxylic acid
Present on carboxylic acid functional, the content of the imidazoles is 0.01 to 1.2 molar equivalent.
The tire comprising rubber composition of any one in 31. claims 1-2, wherein relative to logical formula (I) polybasic carboxylic acid
Present on carboxylic acid functional, the content of the imidazoles is 0.01 to 0.8 molar equivalent.
The tire comprising rubber composition of any one in 32. claims 1-2, wherein relative to logical formula (I) polybasic carboxylic acid
Present on carboxylic acid functional, the content of the imidazoles is 0.01 to 0.5 molar equivalent.
The tire comprising rubber composition of any one in 33. claims 1-2, wherein the diene elastomer is selected from natural
The mixing of rubber, synthetic polyisoprenes, polybutadiene, butadiene copolymer, isoprene copolymer and these elastomers
Thing.
The tire comprising rubber composition of any one in 34. claims 1-2, wherein the content of the epoxy resin is 3
To 20phr.
The tire comprising rubber composition of any one in 35. claims 1-2, wherein the content of the epoxy resin is 5
To 18phr.
The tire comprising rubber composition of any one in 36. claims 1-2, wherein the reinforced filling comprising carbon black,
The mixture of silica or carbon black and silica.
The tire comprising rubber composition of any one in 37. claims 1-2, wherein the amount of the reinforced filling is 20
And 200phr between.
38. methods for preparing the tire comprising rubber composition of any one in claim 1-37, it is characterised in that its bag
Containing with the next stage：
- in the first stage, i.e., in " nonproductive " stage, reinforced filling is introduced in diene elastomer, all the components are carried out into heat
Machinery kneading is until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " in the stage, introducing crosslinked system；
- kneading all the components are to the maximum temperature less than 110 DEG C；
It is characterized in that in the first stage and/or in second stage, independently of each other and similarly, also added 1-20phr's
Epoxy resin, limits in the logical formula (I) polybasic carboxylic acid limited in any one of claim 1-21 and such as any one of claim 22-32
Fixed logical formula (II) imidazoles.
The method of 39. claims 38, it is characterised in that it was included such as the next stage：
- in the first stage, i.e., in " nonproductive " stage, the epoxy between reinforced filling, 1-20phr is introduced in diene elastomer
The logical formula (I) polybasic carboxylic acid limited in resin, such as any one of claim 1-21 and such as restriction in any one of claim 22-32
Logical formula (II) imidazoles, all the components are carried out thermomechanically to knead until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " in the stage, introducing crosslinked system；
- kneading all the components are to the maximum temperature less than 110 DEG C.
The method of 40. claims 38, it is characterised in that it was included such as the next stage：
- in the first stage, i.e., in " nonproductive " stage, reinforced filling is introduced in diene elastomer, all the components are carried out into heat
Machinery kneading is until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " in the stage, epoxy resin between introducing crosslinked system, 1-20phr, such as right
Require the logical formula (I) polybasic carboxylic acid limited in any one of 1-21 and such as the logical formula (II) limited in any one of claim 22-32
Imidazoles；
- kneading all the components are to the maximum temperature less than 110 DEG C.
The method of 41. claims 38, it is characterised in that it was included such as the next stage：
- in the first stage, i.e., in " nonproductive " stage, the ring between reinforced filling and 1-20phr is introduced in diene elastomer
Oxygen tree fat, all the components are carried out thermomechanically to knead until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " in the stage, introducing crosslinked system, as limited in any one of claim 1-21
Logical formula (I) polybasic carboxylic acid and the logical formula (II) imidazoles such as the restriction of any one of claim 22-32；
- kneading all the components are to the maximum temperature less than 110 DEG C.
The method of 42. claims 38, it is characterised in that it was included such as the next stage：
- in the first stage, i.e., in " nonproductive " stage, reinforced filling, such as claim 1-21 are introduced in diene elastomer and is appointed
The logical formula (I) polybasic carboxylic acid limited in one and the logical formula (II) imidazoles such as restriction in any one of claim 22-32, will be all
Composition carries out thermomechanically kneading until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " epoxy resin in the stage, between introducing crosslinked system and 1-20phr；
- kneading all the components are to the maximum temperature less than 110 DEG C.
The method of 43. claims 38, it is characterised in that it was included such as the next stage：
- in the first stage, i.e., in " nonproductive " stage, the epoxy between reinforced filling, 1-20phr is introduced in diene elastomer
Resin and such as the logical formula (II) imidazoles limited in any one of claim 22-32, by all the components carry out thermomechanical kneading until
Reach the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " in the stage, introducing crosslinked system and such as restriction in any one of claim 1-21
Logical formula (I) polybasic carboxylic acid；
- kneading all the components are to the maximum temperature less than 110 DEG C.
The method of 44. claims 38, it is characterised in that it was included such as the next stage：
- in the first stage, i.e., in " nonproductive " stage, reinforced filling, such as claim 1-21 are introduced in diene elastomer and is appointed
The logical formula (I) polybasic carboxylic acid limited in one, all the components are carried out thermomechanically to knead until reaching between 110-190 DEG C most
Big temperature；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " in the stage, epoxy resin between introducing crosslinked system, 1-20phr and such as right
Require the logical formula (II) imidazoles limited in any one of 22-32；
- kneading all the components are to the maximum temperature less than 110 DEG C.
The method of 45. claims 38, it is characterised in that it was included such as the next stage：
- in the first stage, i.e., in " nonproductive " stage, the epoxy between reinforced filling, 1-20phr is introduced in diene elastomer
Resin and and such as the logical formula (I) polybasic carboxylic acid limited in any one of claim 1-21, all the components are thermomechanically kneaded
Until reaching the maximum temperature between 110-190 DEG C；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " in the stage, limit in introducing crosslinked system and such as any one of claim 22-32
Logical formula (II) imidazoles；
- kneading all the components are to the maximum temperature less than 110 DEG C.
The method of 46. claims 38, it is characterised in that it was included such as the next stage：
- in the first stage, i.e., in " nonproductive " stage, reinforced filling is introduced in diene elastomer and such as claim 22-32
The logical formula (II) imidazoles limited in any one, all the components are carried out thermomechanically to knead until reaching between 110-190 DEG C most
Big temperature；
The mixture that-cooling merges is to the temperature less than 100 DEG C；
- subsequently in second stage, i.e., " produce " in the stage, epoxy resin between introducing crosslinked system, 1-20phr and such as right
Require the logical formula (I) polybasic carboxylic acid limited in any one of 1-21；
- kneading all the components are to the maximum temperature less than 110 DEG C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1262165A FR2999582B1 (en) | 2012-12-17 | 2012-12-17 | PNEUMATIC COMPRISING A RUBBER COMPOSITION COMPRISING AN EPOXY RESIN AND A POLYACID |
| FR1262165 | 2012-12-17 | ||
| PCT/EP2013/076427 WO2014095588A1 (en) | 2012-12-17 | 2013-12-12 | Tyre comprising a rubber composition comprising an epoxy resin and a polyacid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104884521A CN104884521A (en) | 2015-09-02 |
| CN104884521B true CN104884521B (en) | 2017-04-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380066026.XA Active CN104884521B (en) | 2012-12-17 | 2013-12-12 | Tyre comprising a rubber composition comprising an epoxy resin and a polyacid |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN104884521B (en) |
| FR (1) | FR2999582B1 (en) |
| WO (1) | WO2014095588A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3024155B1 (en) * | 2014-07-22 | 2016-07-22 | Michelin & Cie | PNEUMATIC FOR AIRCRAFT |
| FR3053344B1 (en) * | 2016-06-30 | 2018-07-06 | Compagnie Generale Des Etablissements Michelin | RUBBER COMPOSITION COMPRISING AN EPOXY RESIN AND A SPECIFIC AMINE HARDENER |
| FR3074183B1 (en) * | 2017-11-30 | 2020-07-24 | Michelin & Cie | HIGH MODULUS RUBBER COMPOSITION INCLUDING AN EFFICIENT SULFUR CURLING SYSTEM |
| WO2019122587A1 (en) * | 2017-12-21 | 2019-06-27 | Compagnie Generale Des Etablissements Michelin | Diacid-crosslinked rubber composition comprising a phenolic compound |
| US11674035B2 (en) * | 2017-12-22 | 2023-06-13 | Compagnie Generale Des Etablissements Michelin | Epoxy-functionalized novolak resin composition |
| FR3083242B1 (en) * | 2018-07-02 | 2020-06-12 | Compagnie Generale Des Etablissements Michelin | RUBBER COMPOSITION BASED ON EPOXIDE RESIN AND AN AMINOBENZOATE DERIVATIVE |
| FR3085955B1 (en) | 2018-09-17 | 2020-09-11 | Michelin & Cie | COMPOSITION OF RUBBER BASED ON EPOXIDE RESIN, AN AMINE HARDENER AND AN IMIDAZOLE |
| FR3108118B1 (en) * | 2020-03-10 | 2022-07-15 | Michelin & Cie | RUBBER COMPOSITION BASED ON EPOXY RESIN AND A HIGH LATENCY HARDENER |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100419063B1 (en) * | 2000-06-10 | 2004-02-14 | 주식회사 엘지화학 | Epoxy resin composition and laminate using the same |
| JP2011057797A (en) * | 2009-09-08 | 2011-03-24 | Sumitomo Rubber Ind Ltd | Rubber composition for tire and pneumatic tire |
| FR2951182B1 (en) * | 2009-10-14 | 2012-09-21 | Michelin Soc Tech | RUBBER COMPOSITION COMPRISING AN EPOXY RESIN |
-
2012
- 2012-12-17 FR FR1262165A patent/FR2999582B1/en not_active Expired - Fee Related
-
2013
- 2013-12-12 WO PCT/EP2013/076427 patent/WO2014095588A1/en active Application Filing
- 2013-12-12 CN CN201380066026.XA patent/CN104884521B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104884521A (en) | 2015-09-02 |
| WO2014095588A1 (en) | 2014-06-26 |
| FR2999582A1 (en) | 2014-06-20 |
| FR2999582B1 (en) | 2015-02-13 |
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