U.S. patent application number 14/749205 was filed with the patent office on 2015-10-15 for tire composition using elastomer composite blends.
The applicant listed for this patent is COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN, MICHELIN RECHERCHE ET TECHNIQUE S.A.. Invention is credited to Michael D. Morris, Ting Wang, Xuan ZHANG.
Application Number | 20150291780 14/749205 |
Document ID | / |
Family ID | 43759218 |
Filed Date | 2015-10-15 |
United States Patent
Application |
20150291780 |
Kind Code |
A1 |
ZHANG; Xuan ; et
al. |
October 15, 2015 |
Tire Composition Using Elastomer Composite Blends
Abstract
A process for preparing a tire comprising a rubber composition
based on at least an elastomer composite, wherein the elastomer
composite is prepared by a method comprising: feeding a continuous
flow of a first fluid comprising a first elastomer latex to a
mixing zone of a coagulum reactor; feeding a continuous flow of a
second fluid comprising a second elastomer latex to the mixing
zone; feeding a continuous flow of a third fluid comprising a
particulate filler slurry to the mixing zone; allowing the first
elastomer latex and the second elastomer latex to coagulate with
the particulate filler; and discharging a flow of elastomer
composite from a discharge end of the coagulum reactor, wherein the
first elastomer latex and the second elastomer latex are
incompatible.
Inventors: |
ZHANG; Xuan; (Acton, MA)
; Wang; Ting; (Lexington, MA) ; Morris; Michael
D.; (Nashua, NH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN
MICHELIN RECHERCHE ET TECHNIQUE S.A. |
Clermont-Ferrand
Granges-Paccot |
|
FR
CH |
|
|
Family ID: |
43759218 |
Appl. No.: |
14/749205 |
Filed: |
June 24, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13497026 |
Jul 23, 2012 |
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PCT/US10/02514 |
Sep 16, 2010 |
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14749205 |
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61276842 |
Sep 17, 2009 |
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Current U.S.
Class: |
524/526 |
Current CPC
Class: |
B60C 1/00 20130101; C08L
7/02 20130101; C08L 9/06 20130101; B29C 48/29 20190201; C08L
2201/52 20130101; C08J 5/00 20130101; B60C 1/0016 20130101; C08J
2409/08 20130101; B29B 7/325 20130101; B01F 5/0646 20130101; B29B
7/7495 20130101; C08L 2666/08 20130101; B01F 5/0653 20130101; C08L
7/02 20130101; B29B 7/90 20130101; C08C 1/14 20130101; B29C 48/287
20190201; C08J 2307/02 20130101 |
International
Class: |
C08L 7/02 20060101
C08L007/02; C08C 1/14 20060101 C08C001/14 |
Claims
1. A process for preparing a tire comprising a rubber composition
based on at least an elastomer composite, wherein the elastomer
composite is prepared by a method comprising: feeding a continuous
flow of a first fluid comprising a first elastomer latex to a
mixing zone of a coagulum reactor; feeding a continuous flow of a
second fluid comprising a second elastomer latex to the mixing
zone; feeding a continuous flow of a third fluid comprising a
particulate filler slurry to the mixing zone; allowing the first
elastomer latex and the second elastomer latex to coagulate with
the particulate filler; and discharging a flow of elastomer
composite from a discharge end of the coagulum reactor, wherein the
first elastomer latex and the second elastomer latex are
incompatible.
2. The process according to claim 1, wherein the first fluid and
the second fluid combine with the third fluid to form a mixture,
and wherein the first fluid and the second fluid combine with the
third fluid substantially simultaneously.
3. The process according to claim 1, wherein the first fluid and
the third fluid combine to form a mixture, and wherein the second
fluid combines with the mixture.
4. The process according to claim 1, wherein the first elastomer
latex comprises a natural rubber latex.
5. The process according to claim 1, wherein the second elastomer
latex comprises a synthetic elastomer latex.
6. The process according to claim 1, wherein the particulate filler
comprises carbon black.
7. The process according to claim 4, wherein the second elastomer
latex comprises a synthetic elastomer latex, and wherein the
elastomer composite includes natural rubber and about 1 to about 36
wt % styrene-butadiene rubber with respect to the total rubber
content.
8. The process according to claim 7, wherein the elastomer
composite includes natural rubber and about 20 to about 36 wt %
styrene-butadiene rubber with respect to the total rubber
content.
9. The process according to claim 1, wherein the elastomer
composite exhibits a macrodispersion of less than 0.1% undispersed
area.
10. A process for preparing a tire tread having a rubber
composition based on at least an elastomer composite, wherein the
elastomer composite is prepared by a method comprising: feeding a
continuous flow of a first fluid comprising a first elastomer latex
to a mixing zone of a coagulum reactor; feeding a continuous flow
of a second fluid comprising a second elastomer latex to the mixing
zone; feeding a continuous flow of a third fluid comprising a
particulate filler slurry to the mixing zone; and allowing the
first elastomer latex and the second elastomer latex to coagulate
with the particulate filler; and discharging a flow of elastomer
composite from a discharge end of the coagulum reactor, wherein the
first elastomer latex and the second elastomer latex are
incompatible.
11. The process according to claim 10, wherein the first fluid and
the second fluid combine with the third fluid to form a mixture,
and wherein the first fluid and the second fluid combine with the
third fluid substantially simultaneously.
12. The process according claim 10, wherein the first fluid and the
third fluid combine to form a mixture, and wherein the second fluid
combines with the mixture.
13. The process according to claim 10, wherein the first elastomer
latex comprises a natural rubber latex.
14. The process according to claim 10, wherein the second elastomer
latex comprises a synthetic elastomer latex.
15. The process according to claim 10, wherein the particulate
filler comprises carbon black.
Description
RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 13/497,026 filed Jul. 23, 2012 which claims
priority under 35 USC .sctn.371 of PCT application No.
PCT/US10/002514, filed on Sep. 16, 2010. Priority is also claimed
of U.S. Provisional application No. 61/276,842 filed Sep. 17, 2009,
the entire content of which is hereby incorporated by reference
FIELD OF THE INVENTION
[0002] This invention pertains to elastomer composites including a
blend of elastomers, and methods of making such composites. More
particularly, this invention concerns a process for making a tire
comprising rubber compositions based on such elastomer
composites.
DESCRIPTION OF THE RELATED ART
[0003] In order to obtain the optimum reinforcement properties
imparted by a filler in a tire tread and thus high wear resistance,
it is known that this filler should generally be present in the
elastomeric matrix in a final form which is both as finely divided
as possible and distributed as homogeneously as possible. Now, such
conditions can only be obtained insofar as this filler has a very
good ability firstly to be incorporated into the matrix during
mixing with the elastomer and to be disagglomerated, and secondly
to be dispersed homogeneously in this matrix.
[0004] Since fuel economies and the need to protect the environment
have become priorities, it has proved necessary to produce tires
having reduced rolling resistance, without adversely affecting
their wear resistance. To improve the dispersion of filler into the
elastomeric matrix, numerous solutions have been proposed, some of
them proposing the use of masterbatches including elastomer and
filler.
[0005] It is common to produce a masterbatch, that is, a premixture
of filler, elastomer and various optional additives, such as
extender oil. Carbon black masterbatch, for example, is prepared
with different grades of commercially available carbon black which
vary both in surface area per unit weight and in structure, which
describes the size and complexity of aggregates of carbon black
formed by the fusion of primary carbon black particles to one
another.
[0006] There are a variety of methods for producing masterbatch. In
one method, disclosed in U.S. Pat. No. 6,048,923, the contents of
which are incorporated by reference herein, a continuous flow of a
first fluid including an elastomer latex is fed to the mixing zone
of a coagulum reactor. A continuous flow of a second fluid
including a carbon black slurry is fed under pressure to the mixing
zone to form a mixture with the elastomer latex. The mixing of the
two fluids is sufficiently energetic to substantially completely
coagulate the elastomer latex with the carbon black prior to a
discharge end of the coagulum reactor. As disclosed in U.S. Pat.
No. 6,929,783, the coagulum may then be fed to a dewatering
extruder.
[0007] For some applications, it is desirable to employ blends of
elastomers to optimize the mechanical properties of the masterbatch
and/or a vulcanized rubber composition including such masterbatch.
Blends of elastomers may be produced by dry-mixing two polymers
together. Alternatively, blends may be produced by co-coagulating a
mixture of elastomer latices (see, e.g., U.S. Pat. No. 4,271,213)
or by recovering a polymer blend from a mixture of an elastomer
latex and a solution containing a second polymer (see, e.g., U.S.
Pat. No. 5,753,742). However, none of these references disclose a
wet masterbatch method of combining a filler with two or more
elastomers. Rather, the polymer blends produced by these methods
may be dry mixed with filler to form a masterbatch. However, dry
mixing can reduce polymer molecular weight and degrade polymer
properties.
[0008] U.S. Pat. No. 6,521,691 discloses a wet masterbatch method
in which two polymer emulsions and a filler slurry may be combined
and then coagulated to form a masterbatch. Similarly, U.S. Pat. No.
6,800,126 discloses that carbon black aggregates may be blended
with an oil and a low-molecular weight elastomer latex to form a
pre-blend, which preblend may be combined with an emulsion of a
diene-based elastomer. A composite of the elastomer and the carbon
black is then recovered from the mixture. U.S. Pat. No. 4,578,411
discloses a method in which an elastomer latex, an elastomer
solution, and a filler are combined, following which a composite of
the two elastomers with the filler is recovered. However, all of
these references disclose the combination of the filler with the
elastomer and the coagulation of the latex as separate processing
steps. Between these two process stages, the filler can flocculate
in the emulsion to the detriment of its even distribution in the
final composite.
[0009] U.S. Pat. No. 6,048,923 discloses a wet masterbatch method
in which coagulation ensues upon introduction of a filler slurry to
an elastomer latex, resulting in superior dispersion of filler
within the elastomer composite. No coagulant is required to form
this "wet mix" elastomer composite. The '923 patent discloses that
blends of elastomer latices may be combined with the filler slurry
to form a coagulum. However, because natural rubber latex is
essentially a biological material, it contains a number of
dissolved substances such as magnesium, potassium, phosphate, and
sulfate ions, fatty acids, amino acids, carbohydrates, peptides,
etc. The high ionic strength of the aqueous carrier can cause
synthetic latices with which natural rubber latex is combined to
coagulate before the filler slurry is introduced to the elastomer
latex blend. Such synthetic latices are said to be incompatible
with natural rubber latex. While it is possible to render the two
latices compatible by adding surfactant to either the synthetic or
the natural latex, the additional surfactant makes the latex more
difficult to coagulate and increases the concentration of
surfactant in the final rubber product. Thus, it is desirable to
have a method of producing elastomer composite masterbatches
incorporating a blend of materials that is not susceptible to the
problem of early coagulation but which still results in a
homogeneous dispersion of filler within the elastomer.
SUMMARY OF THE INVENTION
[0010] One aspect of the present invention is directed to a process
for preparing a tire comprising a rubber composition based on at
least an elastomer composite, wherein the elastomer composite is
prepared by a method comprising: feeding a continuous flow of a
first fluid comprising a first elastomer latex to a mixing zone of
a coagulum reactor; feeding a continuous flow of a second fluid
comprising a second elastomer latex to the mixing zone; feeding a
continuous flow of a third fluid comprising a particulate filler
slurry to the mixing zone; allowing the first elastomer latex and
the second elastomer latex to coagulate with the particulate
filler; and discharging a flow of elastomer composite from a
discharge end of the coagulum reactor, wherein the first elastomer
latex and the second elastomer latex are incompatible.
[0011] The first elastomer latex may include natural rubber latex,
and the second elastomer latex may include a synthetic elastomer
latex. The particulate filler may include carbon black. The first
fluid and the second fluid may combine with the third fluid to form
a mixture, and the first fluid and the second fluid may combine
with the third fluid substantially simultaneously. Alternatively,
the first fluid and the third fluid may combine to form a mixture,
and the second fluid may combine with the mixture. The first
elastomer latex and the second elastomer latex may be
incompatible.
[0012] The elastomer composite used for said tire composition, may
include natural rubber and about 1 to about 36 wt %
styrene-butadiene rubber, for example about 20 to about 36 wt %
styrene-butadiene rubber with respect to the total rubber content.
The elastomer composite may exhibit a macrodispersion of less than
0.1% undispersed area.
[0013] Another aspect of the present invention is directed to a
process for preparing a tire tread having a rubber composition
based on at least an elastomer composite, wherein the elastomer
composite is prepared by a method comprising: feeding a continuous
flow of a first fluid comprising a first elastomer latex to a
mixing zone of a coagulum reactor; feeding a continuous flow of a
second fluid comprising a second elastomer latex to the mixing
zone; feeding a continuous flow of a third fluid comprising a
particulate filler slurry to the mixing zone; allowing the first
elastomer latex and the second elastomer latex to coagulate with
the particulate filler; and discharging a flow of elastomer
composite from a discharge end of the coagulum reactor; wherein the
first elastomer latex and the second elastomer latex are
incompatible.
[0014] It is to be understood that both the foregoing general
description and the following detailed description are exemplary
and explanatory only and are intended to provide further
explanation of the present invention, as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The invention is described with reference to the several
drawings, in which,
[0016] FIG. 1 is a schematic diagram of an apparatus for producing
elastomer composite blends according to an exemplary embodiment of
the invention.
[0017] FIGS. 2A and 2B are schematic diagrams of apparatus for
injection of a second elastomer latex into a coagulum according to
an exemplary embodiment of the invention.
[0018] FIG. 3 is a schematic diagram of a top view of the apparatus
depicted in FIGS. 2A and 2B.
[0019] FIG. 4 is a schematic diagram illustrating the configuration
of samples for electrical resistivity testing.
[0020] FIG. 5 is a graph of the natural log of resistivity with
respect to loading levels of N234 carbon black comparing vulcanized
elastomer composite blends produced according to an exemplary
embodiment of the invention (triangles, numbers indicate the
proportion of styrene-butadiene rubber by weight with respect to
total rubber) to vulcanized elastomer composites produced from
natural rubber latex via a wet masterbatch method (diamonds),
vulcanized elastomer composite blends produced from natural rubber
and styrene-butadiene rubber via a dry mixing method (stars), and
vulcanized elastomer composites produced from natural rubber latex
via a dry mixing method (squares).
DETAILED DESCRIPTION OF THE DRAWINGS
[0021] In one embodiment, an tire comprises a rubber composition
which is based on an elastomer composite which is prepared by
feeding a continuous flow of a first fluid comprising a first
elastomer latex to a mixing zone of a coagulum reactor, feeding a
continuous flow of a second fluid comprising a second elastomer
latex to the mixing zone, feeding a continuous flow of a third
fluid comprising a particulate filler slurry to the mixing zone,
allowing the first elastomer latex and the second elastomer latex
to coagulate with the particulate filler, and discharging a flow of
elastomer composite from a discharge end of the coagulum reactor.
We have found that this method allows the production of elastomer
composite blends, for example, blends of natural rubber latex and
styrene-butadiene copolymers, from incompatible polymer
emulsions.
[0022] Accordingly, said rubber composition may be used for the
tread portion, sidewalls, wire skim and/or carcass.
Characterization of Particle Distribution in Filled
Vulcanizates
[0023] Improvements in rubber reinforcement are reflected in the
ratio of the stresses at different elongations. For carbon
black-filled vulcanizates, stresses at given elongations reflect,
among other things, the effect of filler morphology (particle size
and structure) and surface activity, which determines
filler-polymer and aggregate-aggregate interaction. The ratio of
the stress at 300% elongation to that at 100% elongation,
T300/T100, provides a useful approach for quantifying the degree of
polymer-filler interaction because the factors governing the
stresses at different elongations are different. Structure affects
the occlusion of rubber in the filler aggregates. Increased
occlusion increases the effective filler volume fraction, a
description of the extent to which filler actually interacts with
the rubber matrix and influences the properties of the rubber
matrix composite, and thus the stresses at given elongations for
the filled vulcanizate. For two compounds prepared with the same
polymer and filled with the same carbon black at the same loading
level or volume fraction, the effects of structure and surface area
on stress should be the same. As a result, any difference in
stresses at different strains can be attributed to the crosslinking
density of the polymer matrix, polymer-filler interaction, and
aggregate-aggregate interaction, the last of which leads to filler
agglomeration. At low strain, the agglomerates are not broken down,
and the rubber trapped in the agglomerates can be treated as
filler. This increases the effective volume of the fillers, thus
increasing the stress at a given elongation (i.e., strain). The
filler agglomerates gradually break with increasing strain so that
the effect of filler agglomeration on stress at given elongation
will decrease and finally disappear at about 100% elongation. On
the other hand, at higher elongation, e.g., at 300% elongation, a
different mechanism is involved. In the absence of interaggregate
association, the interaction between the polymer and filler has a
greater influence on the stress. Where the interaction between the
polymer and the filler is weak, high strain leads to slippage and
deattachment (dewetting) of rubber molecules on the black surface,
reducing stress for a given strain. The effect of cross-link
density on stress is the about the same at both 100% and 300%
strain. As a result, the ratio T300/T100 provides a measure of the
in-rubber polymer-filler interaction (S. Wolff and M.-J. Wang,
Rubber Chem. Technol., 65, 329 (1992)).
[0024] We have also found that improvements to the filled rubber
are reflected in the microstructure of the composite. As described
in U.S. Pat. No. 6,048,923, rubber composites produced by the
method disclosed therein exhibit improved macrodispersion of filler
with respect to dry mixed rubbers. Macrodispersion, as indicated by
percent undispersed area D(%), describes the dispersion of filler
within a composite at length scales of 10 microns or greater.
Without being bound by any particular theory, it is believed that
good macrodispersion results from the breakup of filler pellets and
the uniform distribution of the resulting material within the
elastomer matrix. We have found that improvements in the
distribution of filler with respect to shorter length scales are
correlated with improvements in the mechanical properties of the
bulk product. This feature of the composite microstructure is
termed microdispersion. Without being bound by any particular
theory, it is believed that improvements in microdispersion result
from better separation of individual filler aggregates and/or small
clusters of aggregates (i.e., agglomerates) within the
composite.
[0025] As used herein, the term "aggregate" refers to the smallest
dispersible unit of the filler. For example, carbon black
aggregates are made up of primary particles of carbon black and
generally cannot be broken into smaller pieces by mechanical
forces. As used herein, the term "agglomerate" refers to a
plurality of aggregates in physical contact with one another and
held together by physical forces. These agglomerates may be broken
by mechanical forces into smaller units or particles; the smaller
units may be aggregates, smaller agglomerates, or both.
[0026] The difference in conductivity between carbon black and
rubber may be exploited to characterize microdispersion in carbon
black--rubber composites. The conductivity of such composites
depends primarily on the concentration and morphology (e.g.,
surface area, particle size, and structure) of the carbon black. In
addition, the conductivity of these composites is influenced by the
state of dispersion of the carbon black in the rubber matrix. The
conductivity of a carbon black--rubber composite first increases,
then decreases as the carbon black becomes more dispersed in the
matrix (A. I. Medalia, "Electrical Conduction in Carbon Black
Composites," Rubber Chemistry and Technology, 1986, Vol. 59, p.
432). The initial increase is attributed to the increasing
distribution and dispersion of larger carbon black agglomerates,
thereby decreasing the average distance between particles in the
composite. Further improvements in dispersion lead to a decrease in
conductivity. As noted above, this is attributed to the separation
of small groups of individual carbon black aggregates within the
system (Medalia, 1986).
[0027] In certain embodiments, a wet mix elastomer composite is
prepared from natural rubber and carbon black. When the elastomer
composite is processed using a standardized method, CTV Method 1
(defined below), the resulting vulcanized wet mix elastomer
composite exhibits a resistivity satisfying
ln(resistivity).gtoreq.-0.1(loading)+x, where x is 14.
Alternatively or in addition, the resistivity may also satisfy
ln(resistivity).gtoreq.-0.1(loading)+x, where x is 14.5. In
addition, the resistivity may satisfy
ln(resistivity).ltoreq.-0.1(loading)+y, where y is 17.
Alternatively or in addition, y may be 16. Alternatively or in
addition, the vulcanized wet mix elastomer composite exhibits a
resistivity that is at least about 2.9 times higher, for example,
at least about 3.5 times higher, at least about 4 times higher, at
least about 4.5 times higher, or at least about 5 times higher than
the resistivity of a vulcanized dry mix elastomer composite having
the same composition and prepared using a comparative method, CTV
Comparative Method 1 (defined below). For example, the resistivity
may be from about 3 times to about 6 times higher, from about 4
times to about 5 times higher, from about 2 times to about 5.5
times higher, or from about 2.5 times to about 4.5 times higher for
the vulcanized wet mix composite than for the vulcanized dry mix
composite. In any of these embodiments, the wet mix elastomer
composition may include less than 2 phr of surfactant, for example,
less than 1.5 phr of surfactant, less than 1 phr of surfactant,
less than 0.75 phr of surfactant, less than 0.5 phr of surfactant,
or from 0.25 to 2 phr of surfactant.
[0028] As used herein, CTV Method 1 means compounding a masterbatch
in a 1.6 L Banbury mixer using the formulation in Table 1 and the
procedure in Table 2. After each Banbury mixing stage, compounds
are sheeted on a 2-roll mill operated at ambient temperature and
about 40 rpm with a nip gap of about 2 mm using 4 cross-cuts and 2
end-rolls, with a rest time between stage 1 and stage 2 mixing from
4-6 hours. Compounds are then cured in a press at 150.degree. C.
using a mold with a 2 mm thick spacer for a time determined by a
conventional rubber rheometer (i.e., T90+10% of T90).
TABLE-US-00001 TABLE 1 Ingredient Phr Rubber 100 ZnO 4 Stearic acid
2 6PPD* (antioxidant) 1.5 TBBS** (accelerator) 0.8 Sulfur 1.2
*N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine
**N-tert-butyl-2-benzothiazolesulphenamide
TABLE-US-00002 TABLE 2 Time (min) Operation Stage 1 Farrel BR
Banbury mixer (1600 cc), 75% fill factor, 80 rpm, 60.degree. C. 0
Add rubber-carbon black masterbatch 1 Add zinc oxide, stearic acid
and 6PPD 1.5 Sweep 2.5 Dump Roll mill using 4 cross-cuts and 2 end
rolls Stage 2 Farrel BR Banbury mixer (1600 cc), 65% fill factor,
60 rpm, 50.degree. C. 0 Add stage 1 compound, sulfur and
accelerator 1 Dump Roll mill using 4 cross-cuts and 2 end rolls
[0029] As used herein, CTV Comparative Method 1 means preparing a
vulcanized elastomer composite in a 1.6 L Banbury mixer using the
formulation in Table 1 and the procedure in Table 3. After each
Banbury mixing stage, compounds are sheeted on a 2-roll mill
operated at ambient temperature and about 40 rpm with a nip gap of
about 2 mm using 4 cross-cuts and 2 end-rolls, with a rest time
between stage 1 and stage 2 mixing from 4-6 hours. Compounds are
then cured in a press at 150.degree. C. using a mold with a 2 mm
thick spacer for a time determined by a conventional rubber
rheometer (i.e., T90+10% of T90).
TABLE-US-00003 TABLE 3 Stage 1 Fill factor (%) 75 Rotor speed (rpm)
80 Start temperature (.degree. C.) 60 Time NR addition (s) 0 Time
CB addition (s) 30 Time smalls addition (s) 150 Time for sweep (s)
60, 180 Dump time (s) 240 Stage 2 Fill factor (%) 65 Rotor speed
(rpm) 60 Start temperature (.degree. C.) 50 Time masterbatch and
curatives (s) 0 Dump time (s) 60
[0030] Handling of the vulcanized compounds can affect resistivity.
To avoid skewing test results, the compounds should not be stored
under conditions of high humidity or high temperature (e.g.,
greater than about 30 or 40.degree. C.) for extended periods of
time, nor should they be significantly mechanically deformed.
[0031] Wet mix elastomer composite blends prepared according to
certain embodiments of the invention exhibit a ratio of T300 to
T100 that is at least about 18% greater than the same ratio for a
vulcanized dry mix elastomer composite blend having the same
composition. For example, the ratio T300/T100 may be at least about
20% greater, at least about 25% greater, at least about 30%
greater, or at least about 35% greater for a vulcanized wet mix
elastomer blend than for a dry mix elastomer composite blend.
Alternatively or in addition, the ratio T300/T100 may be from about
20% to about 30% greater, from about 25% to about 35% greater, from
about 30% to about 40% greater, or from about 35% to about 45%
greater for a wet mix elastomer composite blend than for a dry mix
elastomer composite blend. In any of these embodiments, the wet mix
elastomer composition may include less than 2 phr of surfactant,
for example, less than 1.5 phr of surfactant, less than 1 phr of
surfactant, less than 0.75 phr of surfactant, less than 0.5 phr of
surfactant, or from 0.25 to 2 phr of surfactant.
[0032] As used herein, the term "wet mix elastomer composite blend"
refers to an elastomer composite blend which has been prepared by a
wet masterbatch process. In contrast, the term "dry mix elastomer
composite blend" refers to an elastomer composite blend which has
been prepared by combining two dry elastomers (e.g., less than 1%
water) and particulate filler in powder form or by combining dry
elastomer with an elastomer masterbatch.
Preparation of Elastomer Composite Blends
[0033] As shown in FIG. 1, a particulate filler slurry is fed into
a mixing portion 10 of a coagulum reactor 11 via a filler feed line
12. A first elastomer latex is fed into mixing portion 10 via first
latex feed line 14. A second elastomer latex is fed into mixing
portion 10 via second latex feed line 16. The two latices coagulate
in the mixing portion 10, and the coagulum, including both
elastomers and particulate filler, proceeds through a diffuser
portion 17 of coagulum reactor 11. As shown in FIG. 1, the diffuser
portion 17 has a series of sections 18a-18d, each one having
progressively higher diameter than the previous section 18.
Preferably, transition regions 20a-c provide a gradual increase in
diameter from one section 18 to the next. One of skill in the art
will recognize that the diffuser portion may have greater or fewer
sections 18 than shown in the figure. The elastomer composite
coagulum emerges from diffuser portion 17 as "masterbatch
crumb".
[0034] In one embodiment, the masterbatch crumb is passed from
coagulum reactor 11 to a de-watering extruder via a simple gravity
drop or other suitable apparatus known to those of skill in the
art. The dewatering extruder may bring the elastomer composite
from, e.g., approximately 70-85% water content, to a desired water
content, e.g., approximately 1% to 20% water content. The optimal
water content may vary with the elastomer employed, the type of
filler, and the desired downstream processing procedure. Suitable
de-watering extruders are well known and commercially available
from, for example, the French Oil Mill Machinery Co. (Piqua, Ohio,
USA).
[0035] After de-watering, the resulting dewatered coagulum may be
dried. In certain embodiments, the dewatered coagulum is simply
thermally dried. Preferably, the dewatered coagulum is mechanically
masticated while drying. For example, the dewatered coagulum may be
mechanically worked with one or more of a continuous mixer, an
internal mixer, a twin screw extruder, a single screw extruder, or
a roll mill. Suitable masticating devices are well known and
commercially available, including for example, a Unimix Continuous
Mixer and MVX (Mixing, Venting, eXtruding) Machine from Farrel
Corporation of Ansonia, Conn., a long continuous mixer from Pomini,
Inc., a Pomini Continuous Mixer, twin rotor corotating intermeshing
extruders, twin rotor counterrotating non-intermeshing extruders,
Banbury mixers, Brabender mixers, intermeshing-type internal
mixers, kneading-type internal mixers, continuous compounding
extruders, the biaxial milling extruder produced by Kobe Steel,
Ltd., and a Kobe Continuous Mixer. Alternative masticating
apparatus suitable for use with various embodiments of the
invention will be familiar to those of skill in the art. Exemplary
methods for mechanically masticating dewatered composite are
disclosed in U.S. Pat. Nos. 6,929,783 and 6,841,606, and PCT
Application No. U.S. Ser. No. 09/000,732, the contents of all of
which are incorporated herein by reference.
[0036] In certain embodiments, additives can be combined with the
dewatered coagulum in the mechanical mixer. Specifically, additives
such as filler (which may be the same as, or different from, the
filler used in the coagulum reactor; exemplary fillers include
silica and zinc oxide, with zinc oxide also acting as a curing
agent), other elastomers, other or additional masterbatch,
antioxidants, antiozonants, plasticizers, processing aids (e.g.,
stearic acid, which can also be used as a curing agent, liquid
polymers, oils, waxes, and the like), resins, flame-retardants,
extender oils, lubricants, and a mixture of any of them, can be
added in the mechanical mixer. In certain other embodiments,
additional elastomers can be combined with the dewatered coagulum
to produce elastomer blends. Exemplary elastomers include, but are
not limited to, rubbers, polymers (e.g., homopolymers, copolymers
and/or terpolymers) of 1,3-butadiene, styrene, isoprene,
isobutylene, 2,3-dialkyl-1,3-butadiene, where alkyl may be methyl,
ethyl, propyl, etc., acrylonitrile, ethylene, and propylene and the
like. Methods of producing masterbatch blends are disclosed in our
commonly owned U.S. Pat. Nos. 7,105,595, 6,365,663, and 6,075,084.
Alternatively or in addition, traditional compounding techniques
may be used to combine vulcanization agents and other additives
known in the art with the dewatered coagulum or, where a
masticating apparatus is used to dry the material, the resulting
masticated masterbatch, depending on the desired use.
[0037] The mixing portion 10 of the coagulum reactor 11 may be
configured in several ways. FIG. 2A shows an exemplary
configuration in which materials emerging from filler feed line
212, first latex feed line 214, and second latex feed line 216 all
combine with one another substantially simultaneously. The angle
beta between first latex feed line 214 and filler feed line 212 and
the angle beta' between second latex feed line 216 and filler feed
line 212 may be varied independently. Either of these angles may
vary from greater than 0.degree. to less than 180.degree..
Preferably, beta and beta' are varied independently from 30.degree.
to 90.degree.. The optimal angle may be determined in part by the
relative flow rates of the three fluids and their compositions.
[0038] The angle alpha between the two latex feed lines may also be
varied from greater than 0.degree. to less than 180.degree. (FIG.
3). Alternatively or in addition, a plurality of latex feed lines
may be used for either or both of the first and second elastomer
latex streams.
[0039] Alternatively or in addition, the injection points of the
two latices may be staggered with respect to the injection of the
filler slurry (FIG. 2B). For example, the outlet of first latex
feed line 214 and second latex feed line 216 may be spaced by a
distance x.
[0040] Preferably, the first elastomer latex is prepared from a
natural rubber latex.
[0041] The term "diene" elastomer or "diene" rubber (elastomer and
rubber are well known to be synonymous terms) should be understood
as meaning, in a known way, an (one or more are understood)
elastomer resulting at least in part (i.e., a homopolymer or a
copolymer) from diene monomers (monomers carrying two carbon-carbon
double bonds which may or may not be conjugated).
[0042] These diene elastomers can be classified into two
categories: "essentially unsaturated" or "essentially saturated".
The term "essentially unsaturated" is understood to mean generally
a diene elastomer resulting at least in part from conjugated diene
monomers having a level of units of diene origin (conjugated
dienes) which is greater than 15% (mol %); thus it is that diene
elastomers such as butyl rubbers or copolymers of dienes and of
.alpha.-olefins of EPDM type do not come within the preceding
definition and can in particular be described as "essentially
saturated" diene elastomers (low or very low level of units of
diene origin, always less than 15%). In the category of
"essentially unsaturated" diene elastomers, the term "highly
unsaturated" diene elastomer is understood to mean in particular a
diene elastomer having a level of units of diene origin (conjugated
dienes) which is greater than 50%.
[0043] Thus natural rubber belongs to the category of "highly
unsaturated" diene elastomer. Exemplary natural rubber latices
include but are not limited to field latex, latex concentrate
(produced, for example, by evaporation, centrifugation or
creaming), skim latex (a by-product of the centrifugation of
natural rubber latex) and blends of any two or three of these in
any proportion. The latex should be appropriate for the intended
purpose or application of the final rubber product. The latex is
provided typically in an aqueous carrier liquid. Selection of a
suitable latex or blend of latices will be well within the ability
of those skilled in the art given the benefit of the present
disclosure and the knowledge of selection criteria generally well
recognized in the industry.
[0044] The natural rubber latex may also be chemically modified in
some manner. For example, it may be treated to chemically modify or
reduce various non-rubber components, or the rubber molecules
themselves may be modified with various monomers or other chemical
groups such as chlorine. Exemplary methods of chemically modifying
natural rubber latex are disclosed in European Patent Publications
Nos. 1489102, 1816144, and 1834980, Japanese Patent Publications
Nos. 2006152211, 2006152212, 2006169483, 2006183036, 2006213878,
2006213879, 2007154089, and 2007154095, U.S. Pat. Nos. 6,841,606
and 7,312,271, and U.S. Patent Publication No. 2005-0148723. Other
methods known to those of skill in the art may be employed as well.
Preferably, the second elastomer latex is prepared using synthetic
latex. Synthetic diene elastomer of the composition in accordance
with the invention is preferably chosen from the group of the
highly unsaturated diene elastomers consisting of polybutadienes
(abbreviated to "BR"), synthetic polyisoprenes (IR), butadiene
copolymers, isoprene copolymers and the mixtures of these
elastomers. Such copolymers are more preferably chosen from the
group consisting of butadiene/styrene copolymers (SBR),
isoprene/butadiene copolymers (BIR), isoprene/styrene copolymers
(SIR) and isoprene/butadiene/styrene copolymers (SBIR).
[0045] The elastomers can, for example, be block, random,
sequential or microsequential elastomers and can be prepared in
dispersion or in solution; they can be coupled and/or star-branched
or also functionalized with a coupling and/or star-branching or
functionalization agent. For coupling with carbon black, mention
may be made, for example, of functional groups comprising a C--Sn
bond or of aminated functional groups, such as benzophenone, for
example; for coupling with a reinforcing inorganic filler, such as
silica, mention may be made, for example, of silanol functional
groups or polysiloxane functional groups having a silanol end (such
as described, for example, in U.S. Pat. No. 6,013,718), of
alkoxysilane groups (such as described, for example, in U.S. Pat.
No. 5,977,238), of carboxyl groups (such as described, for example,
in U.S. Pat. No. 6,815,473 or US 2006/0089445) or of polyether
groups (such as described, for example, in U.S. Pat. No.
6,503,973). Mention may also be made, as other examples of such
functionalized elastomers, of elastomers (such as SBR, BR, NR or
IR) of the epoxidized type.
[0046] The following are preferably suitable: polybutadienes, in
particular those having a content of 1,2-units of between 4% and
80% or those having a content of cis-1,4-units of greater than 80%,
polyisoprenes, butadiene/styrene copolymers in particular those
having a styrene content of between 5% and 50% by weight and more
particularly between 20% and 40%, a content of 1,2-bonds of the
butadiene part of between 4% and 65% and a content of
trans-1,4-bonds of between 20% and 80%, butadiene/isoprene
copolymers, in particular those having an isoprene content of
between 5% and 90% by weight and a glass transition temperature
("Tg"--measured according to ASTM D 3418-82) of -40.degree. C. to
-80.degree. C., or isoprene/styrene copolymers, in particular those
having a styrene content of between 5% and 50% by weight and a Tg
of between -25.degree. C. and -50.degree. C.
[0047] In the case of butadiene/styrene/isoprene copolymers, those
having a styrene content of between 5% and 50% by weight and more
particularly of between 10% and 40%, an isoprene content of between
15% and 60% by weight and more particularly between 20% and 50%, a
butadiene content of between 5% and 50% by weight and more
particularly of between 20% and 40%, a content of 1,2-units of the
butadiene part of between 4% and 85%, a content of trans-1,4-units
of the butadiene part of between 6% and 80%, a content of 1,2-plus
3,4-units of the isoprene part of between 5% and 70% and a content
of trans-1,4-units of the isoprene part of between 10% and 50%, and
more generally any butadiene/styrene/isoprene copolymer having a Tg
of between -20.degree. C. and -70.degree. C., are suitable in
particular.
[0048] While it is expected that random copolymers will be more
commonly exploited, emulsions of block copolymers are also suitable
for use according to the teachings herein. In some embodiments, it
may be desirable to inject a coagulant, for example, a salt or acid
solution, along with the latex stream, to promote coagulation of
the elastomer.
[0049] The particulate filler fluid may be a carbon black slurry or
any other suitable filler in a suitable carrier fluid. Selection of
the carrier fluid will depend largely upon the choice of
particulate filler and upon system parameters. Both aqueous and
non-aqueous liquids may be used, with water being preferred in many
embodiments in view of its cost, availability and suitability of
use in the production of carbon black and certain other filler
slurries. Small amounts of water-miscible organic solvents may also
be included in aqueous carrier fluids.
[0050] Selection of the particulate filler or mixture of
particulate fillers will depend largely upon the intended use of
the elastomer masterbatch product. As used here, particulate filler
can include any material which is appropriate for use in the
masterbatch process. Suitable particulate fillers include, for
example, conductive fillers, reinforcing fillers, fillers
comprising short fibers (typically having an L/D aspect ratio less
than 40), flakes, etc. In addition to carbon black and silica-type
fillers, discussed in more detail below, fillers can be formed of
clay, glass, polymer, such as aramid fiber, etc. It is expected
that any filler suitable for use in elastomer compositions may be
incorporated into elastomer composites according to various
embodiments of the invention. Of course, blends of the various
particulate fillers discussed herein may also be used.
[0051] When a carbon black filler is used, selection of the carbon
black will depend largely upon the intended use of the elastomer
masterbatch product. Optionally, the carbon black filler can
include also any material which can be slurried and combined with a
latex. Exemplary particulate fillers include but are not limited to
carbon black, fumed silica, precipitated silica, coated carbon
black, chemically functionalized carbon blacks, such as those
having attached organic groups, and silicon-treated carbon black,
either alone or in combination with each other. Exemplary carbon
blacks include ASTM N100 series--N900 series carbon blacks, for
example N100 series carbon blacks, N200 series carbon blacks, N300
series carbon blacks, N700 series carbon blacks, N800 series carbon
blacks, or N900 series carbon blacks. Carbon blacks sold under the
Regal.RTM., Black Pearls.RTM., Spheron.RTM., Sterling.RTM., and
Vulcan.RTM. trademarks available from Cabot Corporation, the
Raven.RTM., Statex.RTM., Furnex.RTM., and Neotex.RTM. trademarks
and the CD and HV lines available from Columbian Chemicals, and the
Corax.RTM., Durax.RTM., Ecorax.RTM., and Purex.RTM. trademarks and
the CK line available from Evonik (Degussa) Industries, and other
fillers suitable for use in rubber or tire applications, may also
be exploited for use with various embodiments. Suitable chemically
functionalized carbon blacks include those disclosed in
International Application No. PCT/US95/16194 (WO 96/18688), the
disclosure of which is hereby incorporated by reference.
[0052] Both silicon-coated and silicon-treated carbon blacks may be
employed in various embodiments. In silicon-treated carbon black, a
silicon containing species such as an oxide or carbide of silicon
is distributed through at least a portion of the carbon black
aggregate as an intrinsic part of the carbon black. Conventional
carbon blacks exist in the form of aggregates, with each aggregate
consisting of a single phase, which is carbon. This phase may exist
in the form of a graphitic crystallite and/or amorphous carbon, and
is usually a mixture of the two forms. Carbon black aggregates may
be modified by depositing silicon-containing species, such as
silica, on at least a portion of the surface of the carbon black
aggregates. The result may be described as silicon-coated carbon
blacks.
[0053] The materials described herein as silicon-treated carbon
blacks are not carbon black aggregates which have been coated or
otherwise modified, but actually represent a different kind of
aggregate having two phases. One phase is carbon, which will still
be present as graphitic crystallite and/or amorphous carbon, while
the second phase is silica (and possibly other silicon-containing
species). Thus, the silicon-containing species phase of the
silicon-treated carbon black is an intrinsic part of the aggregate;
it is distributed throughout at least a portion of the aggregate. A
variety of silicon-treated blacks are available from Cabot
Corporation under the name Ecoblack.TM.. It will be appreciated
that the multiphase aggregates are quite different from the
silica-coated carbon blacks mentioned above, which consist of
pre-formed, single phase carbon black aggregates having
silicon-containing species deposited on their surface. Such carbon
blacks may be surface-treated in order to place a silica
functionality on the surface of the carbon black aggregate as
described in, e.g., U.S. Pat. No. 6,929,783.
[0054] One or more additives also may be pre-mixed, if suitable,
with the particulate slurry or with either the first or second
elastomer latex fluids or may be combined with the mixture of these
during coagulation. Additives also can be mixed into the coagulum.
Numerous additives are well known to those skilled in the art and
include, for example, antioxidants, antiozonants, plasticizers,
processing aids (e.g., liquid polymers, oils and the like), resins,
flame-retardants, extender oils, lubricants, and a mixture of any
of them. Exemplary additives include but are not limited to zinc
oxide and stearic acid. The general use and selection of such
additives is well known to those skilled in the art.
[0055] The ratio of the dry rubber contents of the first and second
elastomers (i.e., the amount of rubber contributed to the coagulum
by the first and second elastomer latices) may be adjusted by
adjusting the relative flow rates of the two elastomers, by
diluting one of the two elastomer latices, e.g., with water and/or
skim latex, or both. Other variables that may be manipulated to
optimize the filler loading include the absolute flow rate of the
elastomer latex streams and filler slurry (e.g., the production
rate) and the relative flow rate of the elastomer latex streams and
filler slurry (e.g., the filler loading).
[0056] The amount of filler in the elastomer composite may be any
amount of filler that is used to make elastomer composites. For
example, rubbers may be produced with at least 30 parts per hundred
of rubber (phr), at least 40 phr, at least 50 phr, at least 55 phr,
at least 60 phr, at least 65 phr at least 70 phr, at least 75 phr,
at least 80 phr, at least 85 phr, at least 90 phr, at least 95 phr,
or at least 100 phr of filler.
[0057] The invention also concerns the use of resulting elastomer
composite blend accordingly to any of the mentioned embodiments for
the fabrication of tires, in particular for the compositions of
tire treads, tire sidewalls, wire-skim for tires, carcass and
cushion gum for retread tires.
[0058] The rubber compositions of the invention also comprise all
or a portion of the usual additives generally used in the elastomer
compositions intended for the manufacture of treads for tyres, in
particular for winter tyres, such as, for example, protection
agents, such as antiozone waxes, chemical antiozonants,
antioxidants, reinforcing resins, methylene acceptors (for example
phenolic novolak resin) or methylene donors (for example HMT or
H3M), a crosslinking system based either on sulphur or on donors of
sulphur and/or peroxide and/or bismaleimides, vulcanization
accelerators, or vulcanization activators.
[0059] These compositions can also comprise coupling activators
when a coupling agent is used, agents for covering the inorganic
filler or more generally processing aids capable, in a known way,
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 property of processing in the raw
state; these agents are, for example, hydrolysable silanes, such as
alkylalkoxysilanes, polyols, polyethers, amines, or hydroxylated or
hydrolysable polyorganosiloxanes.
[0060] The rubber compositions of the invention are further
processed in appropriate mixers using two successive preparation
phases according to a general procedure well known to a person
skilled in the art: a first phase of thermomechanical working or
kneading (sometimes described as "non-productive" phase) at high
temperature, up to a maximum temperature of between 130.degree. C.
and 200.degree. C., preferably between 145.degree. C. and
185.degree. C., followed by a second phase of mechanical working
(sometimes described as "productive" phase) at a lower temperature,
typically of less than 120.degree. C., for example between
60.degree. C. and 100.degree. C., finishing phase during which the
crosslinking or vulcanization system is incorporated.
[0061] The crosslinking system proper is preferably based on
sulphur and on a primary vulcanization accelerator, in particular
on an accelerator of sulphenamide type. Added to this vulcanization
system are various known secondary accelerators or vulcanization
activators, such as zinc oxide, stearic acid, guanidine derivatives
(in particular diphenylguanidine), and the like, incorporated
during the first non-productive phase and/or during the productive
phase. The level of sulphur is preferably between 0.5 and 12 phr,
preferably between 1 and 10 phr, and that of the primary
accelerator is preferably between 0.5 and 5.0 phr.
[0062] Use may be made, as accelerator (primary or secondary) of
any compound capable of acting as accelerator of the vulcanization
of diene elastomers in the presence of sulphur, in particular
accelerators of the thiazoles type and their derivatives,
accelerators of thiurams types, or zinc dithiocarbamates. These
accelerators are more preferably chosen from the group consisting
of 2-mercaptobenzothiazyl disulphide (abbreviated to "MBTS"),
N-cyclohexyl-2-benzothiazolesulphenamide (abbreviated to "CBS"),
N,N-dicyclohexyl-2-benzothiazolesulphenamide ("DCBS"),
N-tert-butyl-2-benzothiazolesulphenamide ("TBBS"),
N-tert-butyl-2-benzothiazolesulphenimide ("TBSI"), zinc
dibenzyldithiocarbamate ("ZBEC") and the mixtures of these
compounds.
[0063] The final composition thus obtained is subsequently
calendered, for example in the form of a sheet or of a plaque, in
particular for laboratory characterization, or else extruded in the
form of a rubber profiled element which can be used directly like
for example tire tread.
[0064] The vulcanization (or curing) is carried out in a known way
at a temperature generally of between 130.degree. C. and
200.degree. C. for a sufficient time which can vary, for example,
between 5 and 90 min depending in particular on the curing
temperature, the vulcanization system adopted and the vulcanization
kinetics of the composition under consideration.
[0065] The invention relates to the rubber compositions and to the
treads described above, both in the raw state (i.e., before curing)
and in the cured state (i.e., after crosslinking or
vulcanization).
[0066] The present invention will be further clarified by the
following examples which are intended to be only exemplary in
nature
Examples
Carbon Black Slurry Preparation
[0067] Dry N234 carbon black (Cabot Corporation, Boston, Mass.) was
mixed with water and ground to form a slurry having a concentration
of about 10-15%. The slurry was fed to a homogenizer at an
operating pressure of around 3000 psig such that the slurry was
introduced as a jet into the mixing zone to produce a finely ground
carbon black slurry. The carbon black flow rate was adjusted to
about 690-1160 kg/hr to modify final carbon black loading levels.
The actual carbon black loading levels were determined by nitrogen
pyrolysis or thermogravimetric analysis (TGA).
Natural Rubber Latex Delivery
[0068] Field latex having a dry rubber content of about 27-31% was
pumped to the mixing zone of the coagulum reactor. The latex flow
rate was adjusted between about 650-720 kg/h in order to modify
final carbon black loading levels and the relative proportions of
natural rubber and synthetic latex.
Synthetic Latex Delivery
[0069] Styrene-butadiene latex (Nipol LX112, Zeon Corporation,
Tokyo, Japan) was pumped to the mixing zone of the coagulum reactor
for injection simultaneously with the natural rubber latex. The
latex flow rate was adjusted between about 130-310 kg/h in order to
modify final carbon black loading levels and the relative
proportions of natural rubber and synthetic latex.
Carbon Black and Latex Mixing
[0070] The carbon black slurry, natural rubber latex, and synthetic
latex were mixed by entraining the two latex streams into the
carbon black slurry in a mixing portion of a coagulum reactor
similar to that shown in FIG. 1. During the entrainment process,
the carbon black was intimately mixed into the latex and the
mixture coagulated.
Dewatering
[0071] The masterbatch crumb discharged from the coagulum reactor
was dewatered to 10-20% moisture with a dewatering extruder (The
French Oil Machinery Company, Piqua, Ohio). In the extruder, the
masterbatch crumb was compressed, and water squeezed from the crumb
was ejected through a slotted barrel of the extruder.
Drying and Cooling
[0072] The dewatered coagulum was dropped into a continuous
compounder (Farrel Continuous Mixer (FCM), Farrel Corporation)
where it was masticated and mixed with antioxidant. The moisture
content of the masticated masterbatch exiting the FCM was around
1-2%. The product was further masticated and cooled on an open
mill.
Curing
[0073] The cooled elastomer composite was compounded according to
the formulation in Table 4 and the procedure outlined in Table
5.
TABLE-US-00004 TABLE 4 Ingredient Phr Rubber 100 ZnO 4 Stearic acid
2 6PPD* (antioxidant) 1.5 TBBS** (accelerator) 0.8 Sulfur 1.2
*N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine
**N-tert-butyl-2-benzothiazolesulphenamide
TABLE-US-00005 TABLE 5 Time (min) Operation Stage 1 Farrel BR
Banbury mixer (1600 cc), 75% fill factor, 80 rpm, 60.degree. C. 0
Add rubber-carbon black masterbatch 1 Add zinc oxide, stearic acid
and 6PPD 1.5 Sweep 2.5 Dump Roll mill using 4 cross-cuts and 2 end
rolls Stage 2 Farrel BR Banbury mixer (1600 cc), 65% fill factor,
60 rpm, 50.degree. C. 0 Add stage 1 compound, sulfur and
accelerator 1 Dump Roll mill using 4 cross-cuts and 2 end rolls
[0074] Vulcanization was carried out in a heated press set at
150.degree. C. for a time determined by a conventional rubber
rheometer (i.e., T90+10% of T90, where T90 is the time to achieve
90% vulcanization).
Comparative Examples
Dry Mixing
[0075] Dry mix elastomer blends were prepared from coagulated
natural rubber and either SBR1500, a coagulated rubber available
from Polimeri Europa (Milan, Italy) or coagulated Nipol LX112 (Zeon
Corporation). Nipol LX112 was coagulated with 0.15 kg of aqueous
10% Ca(NO.sub.3).sub.2 per kilogram of latex after adjusting the pH
to 3 with 10% H.sub.2SO.sub.4. These materials were compounded
using the formulation in Table 4, above and the procedure in Table
6.
TABLE-US-00006 TABLE 6 Stage 1 Fill factor (%) 75 Rotor speed (rpm)
80 Start temperature (.degree. C.) 60 Time NR addition (s) 0 Time
CB addition (s) 30 Time smalls addition (s) 150 Time for sweep (s)
60, 180 Dump time (s) 240 Stage 2 Fill factor (%) 65 Rotor speed
(rpm) 60 Start temperature (.degree. C.) 50 Time masterbatch and
curatives (s) 0 Dump time (s) 60
Materials Characterization
[0076] The tensile stress of vulcanized samples (T300 and T100)
were measured according to ASTM standard D-412. Tan delta
60.degree. was determined using a dynamic strain sweep between
0.01% and 60% at 10 Hz and 60.degree. C. Tan .delta..sub.max was
taken as the maximum value of tan 8 within this range of strains.
Rebound was measured according to ASTM standard D7121.
[0077] Tan delta 30.degree. was measured according to the following
method: specimens were prepared by curing cylinders 16 mm in
diameter and 10 mm in length between parallel plates coated with a
Chemlok.TM. bonding agent. All test specimens were allowed to
equilibrate in the test laboratory for at least 24 hours prior to
testing, and all were allowed to warm-up for 15-20 minutes in the
rheometer at the test temperature (30.degree. C.). Samples were
first strained to 25% at 1 Hz and held at 20% steady strain for 30
s before a strain sweep from 0.1% to 30%.
[0078] Macrodispersion was determined using a disperGrader
available from Alpha Technologies (Akron, Ohio) according to the
manufacturer's instructions. Vulcanized rubber is cut using the
cutter available from Alpha Technologies. The freshly cut surface
is then analyzed for undispersed area using the pre-programmed
EXP_HISTOGRAM/30 Test. The average undispersed area is reported for
each sample using three scans across three different areas of the
sample.
[0079] Electrical resistivity measurements were performed on wet
masterbatch materials vulcanized according to CTV Method 1 and dry
mix materials vulcanized according to CTV Comparative Method 1.
After curing, the sheets produced from both wet masterbatch
materials and dry mixed materials were rested for at least 24
hours. FIG. 4 shows the configuration of samples for electrical
testing. Sheets 300 measuring 150 mm by 70 mm were measured at four
points close to the points 305 for electrical contact. Both
surfaces of the sample were cleaned by wiping with isopropyl
alcohol, following which the sample was only handled with gloves.
Silver paint was applied to both ends 310a of the sample and as two
strips 310b near the center of the sample. A template was used to
apply the center strips 310b of conductive paint. After the paint
dried, the template was removed. The prepared sample was placed on
a flat, non-conductive base, and current supply electrodes were
attached by metal bars at each end of the sheet. Gold electrodes
were lowered onto the center paint strips with their closest edges
spaced exactly 10 mm apart using a spring-loaded device that
applied constant load. These were used for voltage measurement. A
signal generator was used to apply pulses of 50 ms duration, with a
gap of 50 ms between pulses. The direction of the current was
reversed for each pulse. The current was increased for each
successive pulse and the voltage measured each time. The initial
current and size of the current increments were chosen such that at
least 50 data points were obtained over an output range of 0-10 V.
The results were first checked to ensure that voltage was
proportional to current. The resistance was then obtained from a
linear regression of a plot of voltage against current. The
measured resistance was converted to resistivity by multiplying it
by the average sample thickness and dividing the result by the
distance between the center electrodes (10 mm). All compounds were
tested in triplicate, and the average result was used.
Results
[0080] Table 7 shows the values of T300/T100, tan delta, and
macrodispersion for vulcanizates of wet masterbatch samples and dry
mixed samples prepared as described above.
TABLE-US-00007 TABLE 7 SBR tan tan Loading content T300/ delta
delta Undispersed Masterbatch (phr) (wt %) T100 (60.degree.)
(30.degree.) Rebound area (%) Wet 39 20 5.73 0.176 0.179 53.6 0.06
masterbatch 55 30 5.87 0.246 0.267 40.0 0.08 57 36 5.87 0.252 0.282
38.6 0.04 Dry mix (NR + 39 20 5.17 0.168 0.182 52.2 0.44 SBR1500 55
30 5.10 0.235 0.268 42.8 0.14 57 36 5.06 0.236 0.273 42.2 0.16 Dry
mix (NR + 39 20 4.83 0.168 0.189 49.5 1.21 Zeon SBR) 55 30 4.76
0.242 0.294 38.1 1.07 57 36 4.48 0.256 0.308 37.3 0.69
[0081] The wet masterbatch materials exhibit superior
microdispersion with respect to the dry mixed samples. This is
reflected in the values of T300/T100 for the wet masterbatch and
dry mixed samples. The superior performance of the wet masterbatch
samples reflects the superior interaction and dispersion of the
carbon black filler with respect to the elastomer.
[0082] FIG. 5 compares the resistivity of a number of samples,
including dry mixed and wet masterbatch materials produced with
only natural rubber latex, blends prepared by dry mixing SBR with a
wet masterbatch material produced with natural rubber latex, and
blends prepared by the wet masterbatch method described in the
Examples. The masterbatches including only natural rubber latex
were compounded using cyclohexyl benzothiazole sulfenamide (CBS) as
the accelerator rather than TBBS. The difference in resistivity
between these vulcanizates and vulcanizates prepared using TBBS as
the accelerator is expected to be small. The results show that the
resistivity of wet mix elastomer composite blends is higher than
that of dry mix elastomer composite blends. In addition, the
resistivity of both wet and dry mix elastomer composite blends is
greater than that of the corresponding composites produced with
only natural rubber latex.
[0083] The foregoing description of preferred embodiments of the
present invention has been presented for the purposes of
illustration and description. It is not intended to be exhaustive
or to limit the invention to the precise form disclosed.
Modifications and variations are possible in light of the above
teachings, or may be acquired from practice of the invention. The
embodiments were chosen and described in order to explain the
principles of the invention and its practical application to enable
one skilled in the art to utilize the invention in various
embodiments and with various modifications as are suited to the
particular use contemplated. It is intended that the scope of the
invention be defined by the claims appended hereto, and their
equivalents.
* * * * *