U.S. patent number RE47,886 [Application Number 16/043,208] was granted by the patent office on 2020-03-03 for tire with improved grip on wet ground.
This patent grant is currently assigned to COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN, MICHELIN RECHERCHE ET TECNIQUE S.A.. The grantee listed for this patent is Compagnie Generale Des Etablissements Michelin, Michelin Recherche Et Technique S.A.. Invention is credited to Olivier Durel, Olivier Mathey.
United States Patent |
RE47,886 |
Mathey , et al. |
March 3, 2020 |
Tire with improved grip on wet ground
Abstract
A tire comprising at least a rubber composition based on at
least a blend of natural rubber, NR, or synthetic polyisoprene, and
a styrene-butadiene copolymer, SBR, the SBR having a content
greater than or equal to 20 parts per hundred parts of elastomer,
phr, a reinforcing filler comprising carbon black, characterized in
that the composition comprises a plasticizing resin having a glass
transition temperature, Tg, greater than or equal to 20.degree. C.
and that the SBR has a Tg greater than or equal to -65.degree.
C.
Inventors: |
Mathey; Olivier
(Clermont-Ferrand, FR), Durel; Olivier
(Clermont-Ferrand, FR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Compagnie Generale Des Etablissements Michelin
Michelin Recherche Et Technique S.A. |
Clermont-Ferranc
Granges-Paccot |
N/A
N/A |
FR
CH |
|
|
Assignee: |
COMPAGNIE GENERALE DES
ETABLISSEMENTS MICHELIN (Clermont-Ferrand, FR)
MICHELIN RECHERCHE ET TECNIQUE S.A. (Granges-Paccot,
CH)
|
Family
ID: |
1000004365526 |
Appl.
No.: |
16/043,208 |
Filed: |
July 24, 2018 |
PCT
Filed: |
July 24, 2013 |
PCT No.: |
PCT/EP2013/065626 |
371(c)(1),(2),(4) Date: |
January 23, 2015 |
PCT
Pub. No.: |
WO2014/016340 |
PCT
Pub. Date: |
January 30, 2014 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
14416776 |
Jul 24, 2013 |
9416259 |
Aug 16, 2016 |
|
|
Foreign Application Priority Data
|
|
|
|
|
Jul 25, 2012 [FR] |
|
|
12 57194 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L
9/06 (20130101); C08L 7/00 (20130101); B60C
1/0016 (20130101); C08L 9/06 (20130101); B60C
1/0016 (20130101); C08L 7/00 (20130101); C08L
7/00 (20130101); C08L 7/00 (20130101); C08L
9/06 (20130101); C08L 9/06 (20130101); C08L
9/06 (20130101); C08L 9/06 (20130101); C08L
7/00 (20130101); C08L 7/00 (20130101); C08L
2205/02 (20130101); C08K 5/0016 (20130101); C08L
2205/035 (20130101); C08K 5/0016 (20130101); C08L
2205/035 (20130101); C08L 2205/02 (20130101) |
Current International
Class: |
C08L
9/06 (20060101); B60C 1/00 (20060101); C08L
7/00 (20060101); C08K 5/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Int'l Search Report for PCT/EP2013/065626, dated Oct. 23, 2013.
cited by applicant.
|
Primary Examiner: Johnson; Jerry D
Attorney, Agent or Firm: Dickinson Wright PLLC
Claims
The invention claimed is:
1. A tire comprising at least a rubber composition based on at
least: a blend of natural rubber, NR, or synthetic
polyisoprene.Iadd., wherein the content of NR or synthetic
polyisoprene ranges from 30 phr to 80 phr.Iaddend., and a
styrene-butadiene copolymer, SBR, the SBR having a content greater
than or equal to 20 parts per hundred parts of elastomer, phr, a
reinforcing filler comprising carbon black, and a plasticizing
resin having a glass transition temperature, Tg, greater than or
equal to 20.degree. C., wherein the SBR has a Tg greater than .[.or
equal to .]. -65.degree. C.
2. The tire according to claim 1, wherein the SBR content ranges
from 20 phr to 80 phr.
3. The tire according to claim 2, wherein the SBR content ranges
from 20 to 60 phr.
4. The tire according to claim 1, wherein the composition is
further based on a polybutadiene, BR.
.[.5. The tire according to claim 1, wherein the content of NR or
synthetic polyisoprene ranges from 30 phr to 80 phr..].
6. The tire according to claim .[.5.]. .Iadd.1.Iaddend., wherein
the content of NR or synthetic polyisoprene is greater than or
equal to 40 phr.
7. The tire according to claim 6, wherein the content of NR or
synthetic polyisoprene is greater than or equal to 60 phr.
8. The tire according to claim 1, wherein the SBR has a Tg greater
than or equal to -50.degree. C.
9. The tire according to claim 1, wherein the carbon black has a
CTAB specific surface area of between 75 and 200 m.sup.2/g.
10. The tire according to claim 9, wherein the carbon black has a
CTAB specific surface area of between 100 and 150 m.sup.2/g.
11. The tire according to claim 1, wherein the plasticizing resin
has a Tg greater than or equal to 30.degree. C.
12. The tire according to claim 1, wherein the content of
plasticizing resin ranges from 1 to 20 phr.
13. The tire according to claim 12, wherein the content of
plasticizing resin is less than or equal to 10 phr.
14. The tire according to claim 1, wherein the content of
reinforcing filler ranges from 20 to 200 phr.
15. The tire according to claim 14, wherein the content of
reinforcing filler ranges from 40 to 70 phr.
16. The tire according to claim 1, wherein the reinforcing filler
comprises an inorganic filler.
17. The tire according to claim 16, wherein the inorganic filler
constitutes at least 10% by weight of the total reinforcing
filler.
18. The tire according to claim 16, wherein the inorganic filler
constitutes at most 50% by weight of the total reinforcing
filler.
19. The tire according to claim 16, wherein the inorganic filler
comprises silica.
20. The tire according to claim 19, wherein the inorganic filler
consists of silica.
21. The tire comprising a tread having a rubber composition
according to claim 1.
Description
This application is a 371 national phase entry of
PCT/EP2013/065626, filed 24 Jul. 2013, which claims benefit of
French Patent Application No. 1257194, filed 25 Jul. 2012, the
entire contents of which are incorporated herein by reference for
all purposes.
BACKGROUND
1. Field
The disclosure relates to a rubber composition, especially for a
tire tread, and more particularly for a tire intended to be fitted
onto vehicles carrying heavy loads and running at a sustained
speed, such as, for example, lorries, tractors, trailers or buses,
aircraft, etc.
2. Description of Related Art
Certain current "road" tires are designed to run at high speed for
ever longer distances, because of the improvement in the road
network and the expansion of motorway networks throughout the
world. However, since fuel savings and the need to protect the
environment have become a priority, it has proved necessary to
produce tires that have a reduced rolling resistance while
continuing to improve the wet grip performance.
Thus it is known to use, in the elastomeric matrix of such tires,
as a blend with natural rubber, styrene-butadiene copolymers (SBR)
having a high Tg (greater than or equal to -65.degree. C.), however
the use of such elastomers increases the hysteresis losses and
therefore degrades the rolling resistance of these tires.
SUMMARY
The Applicant companies have surprisingly discovered that the
combination within a rubber composition, of a high Tg SBR and a
high Tg (Tg greater than or equal to 20.degree. C.) plasticizing
resin made it possible to improve the wet grip of tires, the tread
of which has such a composition. while retaining a very similar
roiling resistance.
One subject of the invention is therefore a tire comprising at
least a rubber composition based on at least a blend of natural
rubber, NR, or synthetic polyisoprene, and a styrene-butadiene
copolymer, SBR, the SBR having a content greater than or equal to
20 parts per hundred parts of elastomer, phr, a reinforcing filler
comprising carbon black, characterized in that the composition
comprises a plasticizing resin having a glass transition
temperature, Tg, greater than or equal to 20.degree. C., preferably
greater than or equal to 30.degree. C., and that the SBR has a Tg
greater than or equal to -65.degree. C.
The invention also relates, in an embodiment to a tire comprising a
tread having a rubber composition based on at least a blend of
natural rubber, NR, or synthetic polyisoprene, and of a
styrene-butadiene copolymer, SBR, the SBR having a content greater
than or equal to 20 parts per hundred parts of elastomer, phr, a
reinforcing filler comprising carbon black, characterized in that
the composition comprises a plasticizing resin having a glass
transition temperature, Tg, greater than or equal to 20.degree. C.,
and that the SBR has a Tg greater than or equal to -65.degree.
C.
I. MEASUREMENTS AND TESTS USED
The rubber compositions are characterized, after curing, as
indicated below.
Dynamic Properties
The dynamic properties tan(.delta.).sub.max and
tan(.delta.).sub.-20.degree. C., are measured on a viscosity
analyser (Metravib VA4000), according, to the standard ASTM D
5992-96. The response of a sample of vulcanized composition
(cylindrical test specimen with a thickness of 4 mm and with a
cross section 400 mm.sup.2), subjected to a simple alternating
sinusoidal shear stress, at a frequency of 10 Hz, is recorded. For
the measurement of tan(.delta.).sub.max, a strain amplitude sweep
from 0.1% to 100% (forward cycle), then from 100% to 1% (return
cycle) is carried out at 60.degree. C. The results made use of are
the loss factor (tan .delta.). For the return cycle, the maximum
value of tan .delta. observed (tan (.delta.).sub.max), between the
values at 0.1% and at 100% strain (Payne effect), is indicated.
An arbitrary value of 100 is given for the control composition, a
result greater than 100 indicating an increase in the value of
tan(.delta.).sub.max, corresponding to a degradation of the rolling
resistance. For the measurement of tan(.delta.).sub.-20.degree. C.,
a temperature sweep is carried out, under a stress of 0.7 MPa, and
the value of tan observed at -20.degree. C. is recorded.
It should be remembered that, in a manner well known to a person
skilled in the art, the value is representative of the wet grip
potential: the higher the value of tan(.delta.).sub.-20.degree. C.,
the better the grip.
All arbitrary value of 100 is given for the control composition, a
result greater than 100 indicating an increase in the value of
tan(.delta.).sub.-20.degree. C., corresponding therefore to an
improvement in the wet grip performance.
II. DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS OF THE
INVENTION
The rubber composition according to an embodiment of the invention,
which can be used for the manufacture of tire tread, comprises at
least a blend of natural rubber or synthetic polyisoprene, and a
styrene-butadiene copolymer (SBR) having a high Tg (greater than or
equal to -65.degree. C.) and having a content greater than or equal
to 20 parts per hundred parts of elastomer, phr, a reinforcing
filler comprising carbon black and a plasticizing resin having a
glass transition temperature, Tg, greater than or equal to
20.degree. C.
Unless expressly indicated otherwise, the percentages indicated in
the present application are % by weight.
In the present description, unless expressly indicated otherwise,
all the percentages (%) indicated are % by weight. Moreover, any
range of values denoted by the expression "between a and b"
represents the field of values ranging from more than a to less
than b (that is to say limits a and b excluded) whereas any range
of values denoted by the expression "from a to b" means the field
of values ranging from a up to b (that is to say including, the
strict limits a and b).
Diene Elastomer
What is meant by a "diene" elastomer (or interchangeably rubber)
whether it is natural or synthetic, is, in a known manner, an
elastomer consisting at least in part (i.e., a homopolymer or a
copolymer) of diene monomer units (monomers bearing two conjugated
or non-conjugated carbon-carbon double bonds).
The elastomeric matrix of the composition in accordance with an
embodiment of the invention comprises at least: natural rubber, NR,
or synthetic polyisoprene, with a content ranging preferably from
30 phr to 80 phr, more preferably greater than or equal to 40 phr,
more preferably still greater than or equal to 60 phr; an SBR
having a Tg (Tg, measured according to ASTM D3418) greater than or
equal to -65.degree. C., with a content greater than or equal to 20
phr, preferably with a content ranging from 20 to 80 phr, more
preferably from 20 to 60 phr, and more preferably still from 20 to
40 phr. More preferably still, the SBR has a Tg greater than or
equal to -50.degree. C.
Advantageously, the elastomeric matrix may comprise a
polybutadiene, BR, preferably in a content ranging from 5 to 40
phr, and more preferably from 10 to 30 phr.
The aforementioned elastomers may have any microstructure which
depends on the polymerization conditions used, in particular on the
presence or absence of a modifying and/or randomizing agent and on
the amounts of modifying and/or randomizing agent employed. The
elastomers can, for example, be block, statistical, sequential or
microsequential elastomers and can be prepared in dispersion or in
solution; they can be coupled and/or star-branched or else
functionalized with a coupling and/or star-branching or
functionalization agent. Mention may be made, for example, for
coupling to carbon black, of functional groups comprising a C--Sn
bond or aminated functional groups, such as aminobenzophenone, for
example; mention may be made, for example, for coupling, to a
reinforcing inorganic filler, such as silica, of silanol or
polysiloxane functional groups having a silanol end (such as
described, for example, in FR 2 740 778, U.S. Pat. No. 6,013,718
and WO 2008/141702), alkoxysilane groups (such as described, for
example, in FR 2 765 882 or U.S. Pat. No. 5,977,238), carboxyl
groups (such as described, for example, in WO 01/92402 or U.S. Pat.
No. 6,815,473, WO 2004/096865 or US 2006/0089445) or else polyether
groups (such as described, for example, in EP 1 127 909, U.S. Pat.
No. 6,503,973, WO 2009/000750 and WO 2009/000752).
Mention may also be made, as functional elastomers, of those
prepared by the use of a functional initiator, especially those
bearing an amine or tin function (see for example WO
2010072761).
Mention may also be made, as other examples of functionalized
elastomers, of elastomers (such as SBR, BR, NR or IR) of the
epoxidized type.
It should be noted that the SBR may be prepared in emulsion
("ESBR") or in solution ("SSBR").
Whether it is an ESBR or SSBR, use is made in particular of an SBR
having a moderate styrene content, for example of between 10% and
35% by weight, or a high styrene content, for example from 35% to
55%, a content of vinyl bonds of the butadiene part of between 15%
and 70%, a content (mol %) of trans-1,4-bonds of between 15% and
75% and a Tg of between -10.degree. C. and -65.degree. C.,
preferably greater than or equal to -50.degree. C.
As BR, those BRS having a content (mol %) of cis-1,4-linkages of
greater than 90% are suitable.
The composition according to an embodiment of the invention may
contain another diene elastomer. It being possible for the diene
elastomers of the composition to be used in combination with any
type of synthetic elastomer other than a diene elastomer, or even
with polymers other than elastomers, for example thermoplastic
polymers.
Reinforcing Filler, Coupling Agent and Covering Agent
In the present account, the BET specific surface area is determined
in a known manner by gas adsorption using the
Brunauer-Emmett-Teller method described in "The journal of the
American Chemical Society", Vol. 60, page 309, February 1938, more
specifically according to the French standard NF ISO 9277 of
December 1996 (multipoint (5 points) volumetric method--gas:
nitrogen--degassing: 1 hour at 160.degree. C.--relative pressure
range p/po: 0.05 to 0.17). The CTAB specific surface area is the
external surface area determined according to the French standard
NF T 45-007 of November 1987 (method B).
The composition of an embodiment of the invention comprises any
type of reinforcing filler known for its abilities to reinforce a
rubber composition that can be used for the manufacture of tires,
for example an organic filler such as carbon black, a reinforcing
inorganic filler such as silica, combined with which is, in a known
manner, a coupling, agent, or else a mixture of these two types of
filler.
Suitable as carbon blacks are all carbon blacks, especially the
blacks conventionally used in tires or the treads thereof
(tire-grade blacks). Among the latter, mention will more
particularly be made of the reinforcing blacks of the 100, 200 or
300 series, or the blacks of 500, 600 or 700 series (ASTM grades),
such as for example the N115, N134, N234, N326, N330, N339, N347,
N375, N550, N683 and N772 blacks. These carbon blacks may be used
in the isolated state, as available commercially, or in any other
form, for example as a support for some of the rubber additives
used. The carbon blacks might, for example, be already incorporated
into the diene elastomer, in particular isoprene elastomer in the
form of a masterbatch (see, for example, applications WO 97/36724
or WO 99/16600). Also suitable as carbon blacks are the carbon
blacks partially or completely covered with silica via a
post-treatment, or the carbon blacks modified in situ by silica
such as, non-limitingly, the fillers sold by Cabot Corporation
under the name Ecoblack.TM. "CRX 2000" or "CRX4000".
The carbon blacks having a CTAB specific surface area of between 75
and 200 m.sup.2/g, and more particularly the carbon blacks having a
CTAB specific surface area of between 100 and 150 m.sup.2/g, such
as the carbon blacks of 100 or 200 series, are suitable.
As examples of organic fillers other than carbon blacks, mention
may be made of functionalized polyvinyl organic fillers as
described in applications WO-A-2006/069792, WO-A-2006/069793,
WO-A-2008/003434 and WO-A-2008/003435.
The expression "reinforcing inorganic filler" should be understood
here to mean any inorganic or mineral filler, whatever its colour
and its origin (natural or synthetic), also known as "white
filler", "clear filler" or even "non-black filler", in contrast to
carbon black, capable of reinforcing by itself alone, without means
other than an intermediate coupling agent, a rubber composition
intended for the manufacture of pneumatic tires, in other words
capable of replacing, in its reinforcing role, a conventional
tire-grade carbon black; such a filler is generally characterized,
in a known manner, by the presence of hydroxyl (--OH) groups at its
surface.
Mineral fillers of the siliceous type, preferably silica
(SiC.sub.2), are suitable in particular as reinforcing inorganic
fillers. The silica used may be any reinforcing silica known to a
person skilled in the art. In particular any precipitated or fumed
silica having a BET surface area and also a CTAB specific surface
area that are both less than 450 m.sup.2/g, preferably from 30 to
400 m.sup.2/g, in particular between 60 and 300 m.sup.2/g. Mention
will be made, as highly dispersible precipitated silicas ("HDSs"),
for example, of the "Ultrasil" 7000 and "Ultrasil" 7005 silicas
from Degussa, the "Zeosil" 1165MP, 1135MP and 1115MP silicas from
Rhodia, the "Hi-Sil" EZ150G silica from PPG, the "Zeopol" 8715,
8745 and 8755 silicas from Huber or the silicas with a high
specific surface area as described in application WO 03/016387.
As reinforcing inorganic filler, mention may also be made of the
mineral fillers of the aluminous type, in particular alumina
(Al.sub.2O.sub.3) or aluminium (oxide)hydroxides, or else
reinforcing, titanium oxides, for example described in U.S. Pat.
Nos. 6,610,261 and 6,747,087.
The physical state in which the reinforcing inorganic filler is
present is not important, whether it is in the form of a powder, of
micropearls, of granules, or else of beads. Of course, the
expression "reinforcing inorganic filler" is also understood to
mean mixtures of various reinforcing inorganic fillers, in
particular of highly dispersible silicas as described, above.
A person skilled in the art will understand that, as filler
equivalent to the reinforcing inorganic filler described in the
present section, a reinforcing :tiller of another nature, in
particular organic nature such as carbon black, could be used
provided that this reinforcing filler is covered with an inorganic
layer such as silica, or else comprises functional sites, in
particular hydroxyl sites, at its surface that require the use of a
coupling agent in order to form the bond between the filler and the
elastomer. By way of example, mention may be made, for example, of
tire-grade carbon blacks as described, for example, in patent
documents WO 96/37547 and WO 99/28380.
For the compositions in accordance with an embodiment of the
invention, the content of total reinforcing filler (carbon black
and/or reinforcing inorganic filler such as silica, etc.) is
preferably between 20 and 200 phr, more preferably between 30 and
150 phr. More preferably still, the content of reinforcing filler
ranges from 40 to 70 phr, in particular from 45 to 65 phr.
According to one embodiment of the invention, the composition
comprises, besides the carbon black, an inorganic reinforcing
filler with a preferential content of at least 10% of the total
reinforcing filler and more preferably of at most 50% of the total
reinforcing filler.
According to one embodiment variant of the invention, the inorganic
filler comprises silica and preferably it consists preferably of
silica.
In order to couple the reinforcing inorganic filler to the diene
elastomer, use is made, in a well-known manner, of an at least
bifunctional coupling agent (or bonding agent) intended to provide
a satisfactory connection, of chemical and/or physical nature,
between the inorganic filler (surface of its particles) and the
diene elastomer. Use is made, in particular, of at least
bifunctional organosilanes or polyorganosiloxanes.
The content of coupling agent is advantageously less than 20 phr,
it being understood that it is in general desirable to use the
least amount possible thereof. Typically the content of coupling
agent represents from 0.5% to 15% by weight relative to the amount
of inorganic filler. Its content is preferably between 0.5 and 12
phr, more preferably within a range extending from 3 to 10 phr.
This content is easily adjusted by a person skilled in the art
according to the content of inorganic filler used in the
composition.
The rubber compositions may also contain coupling activators when a
coupling agent is used, agents for covering the inorganic filler
when an inorganic filler is used, or more generally processing aids
capable, in a known manner, by virtue of an improvement in the
dispersion of the filler in the rubber matrix and of a lowering of
the viscosity of the compositions, of improving their ability to be
processed in the uncured state. These covering, agents are well
known (see for example patent applications WO 2006/125533, WO
2007/017060 and WO 2007/003408), mention will be made, for example,
of hydroxysilanes or hydrolysable silanes, such as hydroxysilanes
(see for example WO 2009/062733), alkylalkoxysilanes, in particular
alkyltriethoxysilanes such as for example 1-octyltriethoxysilane,
polyols (for example diols or triols), polyethers (for example
polyethylene glycols), primary, secondary or tertiary amines (for
example trialkanolamines), hydroxylated or hydrolysable
polyorganosiloxanes (for example
.alpha.,.omega.-dihydroxypolyorganosilanes (in particular
.alpha.,.omega.-dihydroxypolydimethylsiloxanes) (see for example EP
0 784 072) and fatty acids such as for example stearic acid.
Hydrocarbon Plasticizing Resin
The rubber compositions of an embodiment of the invention use a
hydrocarbon plasticizing resin, the Tg, glass transition
temperature, of which is above 20.degree. C. and the softening
point of which is below 170.degree. C., as explained in detail
below.
In a manner known to a person skilled in the art, the term
"plasticizing resin" is reserved in the present application, by
definition, for a compound that is, on the one hand, solid at
ambient temperature (23.degree. C.) (in contrast to a liquid
plasticizing compound such as an oil), and, on the other hand,
compatible (that is to say, miscible at the level used, typically
greater than 5 phr) with the rubber composition for which it is
intended, so as to act as a true diluent.
Hydrocarbon resins are polymers well known to a person skilled in
the art, which are therefore miscible by nature in the elastomer
compositions when they are additionally described as
"plasticizing".
They have been widely described in the patents or patent
applications cited in the introduction of the present document, and
also for example in the work entitled "Hydrocarbon Resins" by R.
Mildenberg, M. Zander and G. Collin (New York, VCH, 1997, ISBN
3-527-28617-9) chapter 5 of which is devoted to the applications
thereof, especially in the tire rubber field (5.5. "Rubber Tires
and Mechanical Goods").
They may be aliphatic, naphthenic, aromatic or else of
aliphatic/naphthenic/aromatic type, that is to say based on
aliphatic and/or naphthenic and/or aromatic monomers, They may be
natural or synthetic, and may or may not be petroleum-based (if
such is the case, also known under the name of petroleum resins).
They are preferably exclusively hydrocarbon-based, that is to say
that they comprise only carbon and hydrogen atoms.
Preferably, the hydrocarbon plasticizing resin has at least one,
more preferably all, of the following characteristics: a
number-average molecular weight (Mn) of between 400 and 2000 g/mol;
a polydispersity index (Ip) of less than 3 (reminder: Ip=Mw/Mn with
Mw being the weight-average molecular weight).
More preferably, this hydrocarbon plasticizing resin has at least
one, more preferably still all, of the following characteristics: a
Tg above 30.degree. C.; an Mn weight of between 500 and 1500 g/mol;
an Ip index of less than 2.
The glass transition temperature Tg is measured in a known manner
by DSC (Differential Scanning Calorimetry), according to the
standard ASTM D3418 (1999), and the softening point is measured
according to the standard ASTM E-28.
The macrostructure (Mw, Mn and Ip) of the hydrocarbon resin is
determined by size exclusion chromatography (SEC): solvent
tetrahydrofuran; temperature 35.degree. C.; concentration 1 g/l;
flow rate 1 ml/min; solution filtered through a filter with a
porosity of 0.45 .mu.m before injection; Moore calibration with
polystyrene standards; set of 3 "WATERS" columns in series
("STYRAGEL" HR4E, HR1 and HR0.5); detection by differential
refractometer ("WATERS 2410") and its associated operating software
("WATERS EMPOWER").
According to one particularly preferred embodiment, the hydrocarbon
plasticizing resin is selected from the group consisting of
cyclopentadiene (abbreviated to CPD) or dicyclopentadiene
(abbreviated to DCPD) homopolymer or copolymer resins, terpene
homopolymer or copolymer resins, C.sub.5-cut homopolymer or
copolymer resins and the mixtures of these resins.
Among the above copolymer resins, use is preferably made of those
selected from the group consisting of (D)CPD/vinylaromatic
copolymer resins, (D)CPD/terpene copolymer resins,
(D)CPD/C.sub.5-cut copolymer resins, terpene/vinylaromatic
copolymer resins, C.sub.5-cut/vinylaromatic copolymer resins, and
the mixtures of these resins.
The term "terpene" encompasses here, in a known manner,
.alpha.-pinene, .beta.-pinene and limonene monomers; use is
preferably made of a limonene monomer, which compound exists, in a
known manner, in the form of three possible isomers: L-limonene
(laevorotatory enantiomer), D-limonene (dextrorotatory enantiomer),
or else dipentene, racemate of the dextrorotatory and laevorotatory
enantiomers.
Suitable vinylaromatic monomers are, for example, styrene,
.alpha.-methylstyrene, ortho-, meta- and para-methylstyrene,
vinyltoluene, para-tert-butylstyrene, methoxystyrenes,
chlorostyrenes, vinylmesitylene, divinylbenzene, vinylnaphthalene,
any vinylaromatic monomer derived from a C.sub.9-cut (or more
generally from a C.sub.8- to C.sub.10-cut). Preferably, the
vinylaromatic compound is styrene or a vinylaromatic monomer
derived from a C.sub.9-cut (or more generally from a C.sub.8- to
C.sub.10-cut). Preferably, the vinylaromatic compound is the
minority monomer, expressed as a mole fraction, in the copolymer in
question.
According to one more particularly preferred embodiment, the
hydrocarbon plasticizing resin is selected from the group
consisting of (D)CPD homopolymer resins, (D)CPD/styrene copolymer
resins, polylimonene resins, limonene/styrene copolymer resins,
limonene/D(CPD) copolymer resins, C.sub.5-cut/styrene copolymer
resins, C.sub.5-cut/C.sub.9-cut copolymer resins, and the mixtures
of these resins.
The above preferred resins are well known to a person skilled in
the art and are commercially available, for example sold, as
regards the: polylimonene resins: by DRT under the name "Dercolyte
L120" (Mn=625 g/mol; Mw=1010 g/mol; Ip=1.6; Tg=72.degree. C.) or by
ARIZONA under the name "Sylvagum TR7125C" (Mn=630 g/mol; Mw=950
g/mol; Ip=1.5; Tg=70.degree. C.); C.sub.5-cut/vinylaromatic
copolymer resins, especially C.sub.5-cut/styrene or
C.sub.5-cut/C.sub.9-cut copolymer resins: by Neville Chemical
Company under the names "Super Nevtac 78", "Super Nevtac 85" or
"Super Nevtac 99", by Goodyear Chemicals under the name "Wingtack
Extra", by Kolon under the names "Hikorez T1095" and "Hikorez
T1100", and by Exxon under the names "Escorez 2101" and "ECR 373";
limonene/styrene copolymer resins: by DRT under the name "Dercolyte
TS 105", and by ARIZONA Chemical Company under the names "ZT115LT"
and "ZT5100".
The content of hydrocarbon resin preferably ranges from 1 to 20
phr. The content of hydrocarbon resin is more preferably still less
than or equal to 10 phr.
Crosslinking System
The crosslinking system is preferably a vulcanization system, that
is to say a system based on sulphur (or on a sulphur donor) and on
a primary vulcanization accelerator. Added to this base
vulcanization system, incorporated during the first non-productive
phase and/or during the productive phase as described subsequently,
are various known secondary vulcanization accelerators or
vulcanization activators such as zinc oxide, stearic acid or
equivalent compounds, and guanidine derivatives (in particular
dipheny lguanidine).
The sulphur is used at a preferred content of between 0.5 and 10
phr, more preferably between 1 and 8 phr, in particular between 1
and 6 phr when the composition of the invention is intended,
according to a preferred embodiment of the invention, to constitute
an inner "liner" (or rubber composition) of a tire. The primary
vulcanization accelerator is used in a preferred content of between
0.5 and 10 phr, more preferably of between 0.5 and 5.0 phr.
Use may be made, as accelerator, of any compound capable of acting
as an accelerator of the vulcanization of diene elastomers in the
presence of sulphur, in particular accelerators of the thiazole
type and also derivatives thereof, and accelerators of thiuram and
zinc dithiocarbamate types. These primary accelerators are more
preferably selected from the group consisting of
2-mercaptobenzothiazyl disulphide (abbreviated to "MBTS"),
N-cyclohexyl-2-benzothiazyl sulphenamide (abbreviated to "CBS"),
N,N-dicyclohexyl-2-benzothiazyl sulphenamide (abbreviated to
"DCBS"), N-tert-butyl-2-benzothiazyl sulphenamide (abbreviated to
"TBBS"), N-tert-butyl-2-benzothiazyl sulphenimide (abbreviated to
"TBSI") and mixtures of these compounds.
Other Constituents
The rubber matrices of the composites in accordance with the
invention also comprise all or some of the additives customarily
used in the rubber compositions intended for the manufacture of
motor vehicle ground-contact systems, in particular tires, such as
for example anti-ageing agents, antioxidants, plasticizers or
extending oils, whether the latter are of aromatic or non-aromatic
nature, in particular oils that are very slightly aromatic or
non-aromatic (e.g. naphthenic or paraffinic oils, MES or TDAE
oils), agents that improve the processability of the compositions
in the uncured state, a crosslinking system based either on
sulphur, or on sulphur donors and/or peroxide, vulcanization
accelerators, activators or retarders, anti-reversion agents such
as for example sodium hexathiosulphonate or
N,N'-m-phenylene-biscitraconimide, methylene acceptors and donors
(for example resorcinol, HMT or H-3M) or other reinforcing resins,
bismaleimides, other systems for promoting adhesion with respect to
metallic reinforcers, especially brass reinforcers, such as for
example those of "RFS" (resorcinol-formaldehyde-silica) type, or
else other metal salts such as for example organic salts of cobalt
or nickel. A person skilled in the art will know how to adjust the
formulation of the composition depending on his specific
requirements.
Preparation of the Rubber Compositions
The compositions are manufactured in appropriate mixers, using two
successive preparation phases well known to a person skilled in the
art: a first phase of thermomechanical working or kneading
(referred to as a "non-productive" phase) at high temperature, up
to a maximum temperature of between 110.degree. C. and 190.degree.
C., preferably between 130.degree. C. and 180.degree. C., followed
by a second phase of mechanical working (referred to as a
"productive" phase) up to a lower temperature, typically below
110.degree. C., finishing phase during which the crosslinking
system is incorporated.
By way of example, the non-productive phase is carried out in a
single thermomechanical step of a few minutes (for example between
2 and 10 min) during which all the necessary base constituents and
other additives, with the exception of the crosslinking or
vulcanization system, are introduced into an appropriate mixer such
as a standard internal mixer. After cooling the mixture thus
obtained, the vulcanization system is then incorporated in an
external mixer such as an open mill, maintained at low temperature
(for example between 30.degree. C. and 100.degree. C.). Everything
is then mixed (productive phase) for a few minutes (for example
between 5 and 15 min).
The final composition thus obtained may then be calendered, for
example in the form of a sheet or a slab, or else extruded, for
example in order to form a robber profiled element used for the
manufacture of a composite or a semi-finished product, such as for
example plies, treads, sublayers, and other blocks of rubber
reinforced by metallic reinforcers, intended to form for example a
part of the structure of a tire.
The vulcanization (or curing) may then be carried out in a known
manner at a temperature generally between 130.degree. C. and
200.degree. C., preferably under pressure, for a sufficient time
that may vary for example between 5 and 90 min depending in
particular on the curing temperature, the vulcanization system used
and the vulcanization kinetics of the composition in question.
It will he noted that the invention relates to rubber compositions
previously described as both in the "uncured" state (i.e. before
curing) and in the "cured" or vulcanized state (i.e. after
vulcanization).
III--EXEMPLARY EMBODIMENTS OF THE INVENTION
The following examples make it possible to illustrate the
invention, the latter not however being limited to these examples
alone.
Preparation of the Rubber Compositions
The tests which follow are carried out in the following manner:
introduced into an internal mixer, Which is 70% filled and has an
initial vessel temperature of approximately 50.degree. C., are the
mixed diene elastomers (NR, SBR and where appropriate BR), the
reinforcing filler (carbon black and, where appropriate, silica),
where appropriate the coupling agent (when the latter is present)
then, after kneading for one to two minutes, the various other
ingredients, with the exception of the vulcanization system, are
introduced. Thermomechanical working (non-productive phase) is then
carried out in one step (total kneading time equal to around 5
min), until a maximum "dropping" temperature of around 165.degree.
C. is reached. The mixture thus obtained is recovered and cooled
and then the vulcanization system (sulphur and sulphenamide
accelerator) is added on an external mixer (homofinisher) at
70.degree. C., all the ingredients being mixed (productive phase)
for around 5 to 6 min.
The compositions thus obtained are then calendered either in the
form of slabs (thickness of 2 to 3 mm) or thin sheets of rubber,
for the measurement of their physical or mechanical properties, or
in the form of profiled elements that can be used directly, after
cutting and/or assembling to the desired dimensions, for example as
semi-finished products for tires, in. particular as tire
treads.
III-3 Characterization of the Rubber Compositions
III-3.1 Test 1
The purpose of this test is to demonstrate the improved properties
of compositions in accordance with an embodiment of the invention
compared to control compositions conventionally used in road tire
treads.
For this, six compositions based ono 40/20/40 phr NR/BR/SBR blend
reinforced by carbon black were prepared.
These six compositions differ essentially by the following
technical features: the control composition C1 is a control
composition conventionally used comprising an SSBR with a Tg of
-65.degree. C. and without plasticizing resin, the control
composition C2 comprises an SSBR with a Tg, of -65.degree. C. and a
high Tg (44.degree. C.) plasticizing resin, the control composition
C3 comprises an SSBR with a Tg of -65.degree. C. and a high Tg
(72.degree. C.) plasticizing resin, the control composition C4
comprises a high Tg (-48.degree. C.) SSBR without plasticizing
resin, the composition in accordance with the invention C5
comprises a high Tg (-48.degree. C.) SSBR and a high Tg (44.degree.
C.) plasticizing resin, the composition in accordance with the
invention C6 comprises a high Tg (-48.degree. C.) SSBR and a high
Tg (72.degree. C.) plasticizing resin.
Tables 1 and 2 give, respectively, the formulation of the various
compositions (Table 1--content of the various products expressed in
phr) and the properties after curing (around 30 min at 140.degree.
C.).
It will be noted that the accelerator content of the various
compositions is adjusted with respect to the presence of resin as a
person skilled in the art knows how to do, so that these
compositions can be comparable with identical curing conditions
(time and temperature).
Examination of Table 2 shows that the addition of an aliphatic or
terpenic high Tg resin (compositions C2 and C3) to a conventional
control formulation (C1) makes it possible to obtain an improvement
in the wet grip properties (improved value of
tan(.delta.)-20.degree. with a slight increase in the roiling
resistance (value of tan(.delta.).sub.max). Similarly, composition
C4 (having a high Tg SBR but without high Tg plasticizing resin)
relative to the conventional control composition C1 also exhibits
an improvement in the wet grip properties (improved value of
tan(.delta.)-20.degree. with a slight increase in the roiling
resistance. But it is surprisingly observed that the compositions
C5 and C6 in accordance with the invention comprising both a high
Tg SBR and a high Tg resin, permit, with respect to the composition
C1, a very significant improvement in the wet grip properties
accompanied by a degradation of the rolling resistance performance,
but that remains small. These results for the compositions C5 and
C6 in accordance with the invention go well beyond a simple
additivity of the effect of the high Tg SBR and of the high Tg
resin (effect obtained for composition C2 or C3 added to the effect
obtained for composition C4) and demonstrate a true synergy between
these constituents in the compositions in accordance with the
invention.
III-3.2 Test 2
The purpose of this test is to demonstrate the improved properties
of compositions in accordance with the invention with formulations
different from those of test 1, compared to control compositions
conventionally used in road tire treads.
For this, six compositions were prepared, two compositions based on
a 60/20/20 NR/BR/SBR elastomeric blend reinforced by carbon black,
two compositions based on a 60/15/25 NR/BR/SBR elastomeric blend
reinforced by carbon black and silica and two compositions based on
an 80/20 NR/SBR elastomeric blend reinforced by carbon black.
These six compositions differ essentially by the following
technical features: the control compositions C7, C9 and C11 are
control compositions conventionally used comprising an SSBR with a
Tg, of -65.degree. C. and without plasticizing resin, the
compositions in accordance with the invention C8, C10 and C12
comprise a high Tg (-48.degree. C.) SSBR and a high Tg (44.degree.
C.) plasticizing resin.
Tables 3 and 4 give, respectively, the formulation of the various
compositions (Table 3--content of the various products expressed in
phr) and the properties after curing (around 30 minutes at
140.degree. C.).
As in the preceding test, the accelerator content of the various
compositions is adjusted with respect to the presence of resin as a
person skilled in the art knows how to do, so that these
compositions can be comparable with identical curing conditions
(time and temperature).
It is surprisingly observed that the compositions C8, C1.0 and C12
in accordance with an embodiment of the invention comprising both a
high Tg SBR and a high Tg resin, permit, with respect to the
control compositions C7, C9 and C11, respectively a very
significant improvement in the wet grip properties although
accompanied by a slight degradation of the rolling resistance
performance.
III-3.3 Test 3
The purpose of this test is to demonstrate the improved properties
of compositions in accordance with the invention with formulations
different from those of tests 1 and 2, compared to control
compositions conventionally used in road tire treads.
For this, two compositions based on a 60/10/30 phr NR/BR/SBR blend
reinforced by carbon black were prepared.
These four compositions differ essentially by the following
technical features: the control composition C13 is a control
composition conventionally used comprising an SSBR with a Tg of
-65.degree. C. and without plasticizing resin, the composition in
accordance with the invention C14 comprises a high Ig (-48.degree.
C.) SSBR and a high Tg (44.degree. C.) plasticizing resin.
Tables 5 and 6 give, respectively, the formulation of the various
compositions (Table 5--content of the various products expressed in
phr) and the properties after curing (around. 30 min at 140.degree.
C.).
The accelerator content of the various compositions is adjusted
with respect to the presence of resin as a person skilled in the
art knows how to do, so that these compositions can be comparable
with identical curing, conditions (time and temperature).
Examination of Table 6 surprisingly shows that the composition C16
in accordance with the invention comprising both a high Tg SBR and
a high Tg resin, permits, with respect to the control composition
C13, a very significant improvement in the wet grip properties
accompanied by a degradation of the rolling resistance performance,
but that remains small.
Thus, for compositions in accordance with the invention comprising
both high Tg SBRs and high Tg reinforcing resins, with various
elastomeric blends and various reinforcing fillers, a surprising
effect is observed on the wet grip properties without too great a
degradation of the rolling resistance properties.
TABLE-US-00001 TABLE 1 Composition No. C1 C2 C3 C4 C5 C6 NR (1) 40
40 40 40 40 40 BR (2) 20 20 20 20 20 20 SBR (3) 40 40 40 -- -- --
SBR (4) -- -- -- 40 40 40 Carbon black (5) 54 54 54 54 54 54 Resin
(6) -- 8 -- -- 8 -- Resin (7) -- -- 8 -- -- 8 Paraffin 1 1 1 1 1 1
Antioxidant (8) 2 2 2 2 2 2 ZnO (9) 2.4 2.4 2.4 2.4 2.4 2.4 Stearic
acid (10) 2 2 2 2 2 2 Sulphur 1.1 1.1 1.1 1.1 1.1 1.1 Accelerator
(11) 1.1 1.25 1.35 1.1 1.25 1.35 (1) Natural rubber (2) Neodymium
Polybutadiene 98% 1,4-Cis,Tg = -108.degree. C. (3) Non-extended,
tin-functionalized SBR solution with 24% 1,2-polybutadiene units,
15.5% styrene, Tg = -65.degree. C. (4) Non-extended,
tin-functionalized SBR solution with 24% 1,2-polybutadiene units,
26.5% styrene, Tg = -48.degree. C. (5) Carbon black N234 (6)
C.sub.5-cut/C.sub.9 -cut resin sold by Cray Valley under the name
"Resine THER 8644" (Tg = 44.degree. C.) (7) polylimonene resin sold
by DRT under the name "Dercolyte L120" (Tg = 72.degree. C.) (8)
N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine sold by Flexsys
under the name "Santoflex 6-PPD" (9) zinc oxide (industrial grade -
sold by Umicore) (10) stearin sold by Uniqema under the name
"Pristerene 4931" (11) N-cyclohexyl-2-benzothiazyl sulphenamide
sold by Flexsys under the name "Santocure CBS"
TABLE-US-00002 TABLE 2 Properties Composition No. after curing C1
C2 C3 C4 C5 C6 tan(.delta.).sub.max 100 103 103 105 112 108
tan(.delta.).sub.-20.degree. C. 100 108 117 126 151 152
TABLE-US-00003 TABLE 3 Composition No. C7 C8 C9 C10 C11 C12 NR (1)
60 60 60 60 80 80 BR (2) 20 20 15 15 -- -- SBR (3) 20 -- 25 -- 20
-- SBR (4) -- 20 -- 25 -- 20 Carbon black (5) 54 54 51 51 54 54
Silica (12) -- -- 7 7 -- -- Silane (13) -- -- 0.6 0.6 -- -- Resin
(6) -- 8 -- 8 -- 8 Paraffin 1 1 1 1 1 1 Antioxidant (8) 2 2 2 2 2 2
ZnO (9) 2.4 2.4 2.4 2.4 2.4 2.4 Stearic acid (10) 2 2 2 2 2 2
Sulphur 1.1 1.1 1.1 1.1 1.1 1.1 Accelerator (11) 1.1 1.25 1.25 1.45
1.1 1.25 (12) "ZEOSIL 1165 MP" silica from Rhodia in the form of
micropearls (BET and CTAB: around 150-160 m.sup.2/g); (13) TESPT
("SI69" from Evonik-Degussa).
TABLE-US-00004 TABLE 4 Properties Composition No. after curing C7
C8 C9 C10 C11 C12 tan(.delta.).sub.max 100 107 100 102 100 113
tan(.delta.).sub.-20.degree. C. 100 130 100 134 100 148
TABLE-US-00005 TABLE 5 Composition No. C13 C14 NR (1) 60 60 BR (2)
10 10 SBR (3) 30 -- SBR (4) -- 30 Carbon black (5) 62 62 Resin (6)
-- 8 Paraffin 1 1 Antioxidant (8) 2 2 ZnO (9) 2.4 2.4 Stearic acid
(10) 2 2 Sulphur 1 1 1.1 Accelerator (11) 1.1 1.25
TABLE-US-00006 TABLE 6 Composition No. Properties after curing C13
C14 tan(.delta.).sub.max 100 108 tan (.delta.).sub.-20.degree.C.
100 133
* * * * *