Note: Descriptions are shown in the official language in which they were submitted.
12a~37~3~7
24133-613
BACKGROUND ~F THE INVENTION
This invention is directed to polymeric winyl halide for~
mulations and more particularly to the use of very fine particle
size (less than about l~ avg.) hydrated alumina to form a synergis-
tic combination with impact modifiers or fillers in polymeric vinyl
halide formulations, preferably rigid formulations. The present ap-
plication is directed to combinations with fillers and a divisional
application has been filed~ divided out of the present application,
directed to combinations with impact modifiers.
Generally, the most commercially important polymeric vinyl
halide material is polyvinyl chloride (PVC) and this invention will
be described herein in terms of PVC. However, it is to be understood
that it is applicable to other polymeric vinyl halide materials, as
hereinafter defined.
Fillers are added to polymeric vinyl halide materials
primarily to reduce cost and, when used in low concentrations, to
provide a scrubbing action and reduce plateout. Generally, when
their concentration is high enough to affect physical properties,
they increase modulus, decrease tensile strength ana elongation, and
usually decrease impact strength. There are a few fillers, such as
fine particle size precipitated, hydratea silieas and ultra-fine,
precipitated, coated calcium carbonates that maintain, and even
enhance, impact strength in rigid PVC formulations [J. Radosta,
37th SP~ Annual Technical Conference Preprints, pg. 593 (1979)].
These fillers have not gained wide use in
-2~ 3797
exterior rigid PVC applications because of their adverse
effect on weatherability.
Hydrated alumina has been gaining acceptance as an
additive for use in plastic parts, its low cost along wi.h
5 its flame-retardant and smoke-suppressing characteristics
being most widely referred to in the l~terature (J. ~.
Keating, Plastics Compounding, pg. 23, July/August, 1980).
Most reported uses of hydrated alumina in PVC compounds have
be*n generally limited to plasticized compositions where
10 improved flame retardancy is obtained when used in
concentrations greater than about 10 parts per hundred of
polymex [A. W. Morgan, T. C. Mathis and J. D. Hirchen, 30th
SPE Annual ~echnical Conference Preprints, Chicago, pg. 475
(1972); R. W. Sprague, "Systematic Study of Firebrake ZB as
15 a Fire Retardant in PVC - Part IV Alumina Trihydrate as a
Synergist", April, 1973, January, 1975, U. S. Borax Research
Corporation, Anaheim, California; C. E. Hoke, SPE Journal,
29 pg. 36 (May, 1973)], but I. Sobolev and E. A. Woychesin,
SPE Annual Technical Conference Preprints, pgO 709 (1973)
20 report the use of a 40~ loading of hydrated alumina in a
rigid PVC formula as a smoke suppressant and show that the
filler did not reduce the impact strength. Further, it has
recently been suggested, for example, in U. S. Patent
3,957,723 to Lawson et al U.S. Patent 3,985,706 to Kay, U.S.
25 Patent 4,143,030 to Hartitz, and U.S. Patent 4,147,690 to
Rich, that improved flame retardancy and smoke suppression
can be achieved by a synergistic combination of alumina
trihydrate with zinc oxide, zinc borate or bizmuth
subcarbonate.
It has now been found that extremely fine particle size
(less than 1~) hydrated alumina can not only be used as an
~ 379~
-
24133-613
additive for PVC which does not reduce the impact strength of the
material, but unexpectedly shows a high degree of s~nergism with con-
ventional impact modifiers to give significant increases in impact
strength accompanied by improved processibility and weathering.
Hydrated alumina has of~en ~een called alumina hydrate or
alumina trihydrate. The empirical formula is sometimes written as
A1203.3H20 because at elevated temperature, it functions as a flame
retardant by decomposing to aluminum oxide and water. But this for-
mula is technically incorrect. The product is actually finely
divided crystalline aluminum hydroxide with the composition Al(OH)3.
SUMMARY OF THE INVENTIO~
Very fine particle size (less than about 1~ avg.) hydrated
alumina is useful as a filler material in polymeric vinyl halide
materials, and when used in combination with impact modifiers or
fillers, act synergistically to enhance the impact strength of the
PVC materials.
According to one aspect of the present invention there is
provided a polymeric vinyl halide composition having improved
weatherability and processing characteristics which consists essen-
tially of a polymeric vinyl halide material, a ~iller material andup to 24 phr of hydrated alumina having an average particle size
less than 1~.
In accordance with the invention of the divisional appli-
cation there is provided a method for increasing the impact resis-
tanGe of a polymeric vinyl halide material which comprises incorpo-
rating in a polymeric vinyl halide material an amount of an impact
modifier and of hydrated alumina having an average particle size
- 3 -
~ 3~79~
24133-613
less than about 1~ which forms a synergistic combination for in-
creasing the impact resistance o-f said polyvinyl halide material.
In accordance with the present invention there is also
provided polymeric vinyl halide compositions having improved weather-
ability and processing characteristics, comprising a polyvinyl chlo-
ride polymer or copolymer, a filler material and hydrated alumina
having an average particle size less than 1~. Preferably, said com-
positions also contain an impact modifier in an amount sufficient to
form a synergistic combination of impact modifier with said hydrated
alumina which substantially enhances the impact stren~th thereof.
Also provided in accordance ~ith the present invention is
a method for improving the weatherability of filled polymeric vinyl
halide material which comprises incorporating in a polymeric vinyl
halide material containing a reinforcing filler, a hydrated alumina
having an average particle size less than about 1~.
There is also provided, in accordance with the invention
of the divisional application, a composition which is suitable for
improving the impact resistance of polymeric vinyl halide material
which comprises an impact modifier and hydrated alumina having an
average particle size of less than about 1~ in the relative propor-
tions of said impact modifier and hydrated alumina that is suffi-
cient to form a synergistic combination.
DETAILED DESCRIPTION OF THE INVENTION
Very fine particle size (less than about 1~ avg,) hydrated
alumina compounded into impact modified rigid PVC formulations gives
compositions that surprisingly and unexpectedly exhibit a signifi-
cant synergistic increase in impact strength. The effect has been
~, - 4
~2gL379~
- 4a - 24133-613
demonstrated with a wide variety of impact modifiers generally used
in rigid PVC applications.
Torque rheometer and extrusion tests on rigid PVC formu-
lations containing such very fine particle size
- 4a -
~2~3~97
--5--
hydrated alumina show that motor amperage and toryues
decrease as hydrated alumina concentration increases.
Concurrently, an increase in dynamic heat stability was
observed.
Another benefit derived from the use of the very fine
particle size hydrated alumina in exterior PVC formulations
is improved weatherability with the potential for reducing
the amount of titanium dioxide or other fillers that are
conventionally used for particular applications.
lO Formulations compounded with various levels of the very fine
particle size hydrated alumina in accordance ~ith the
invention outperformed those with titanium dioxide alone
when exposed to both outdoor and accelerated weathering
environments. In addition, formulations using reduced
15 levels of titanium dioxide in conjunction with said hydrated
alumina weathered as well as compounds using higher levels
of titanium dioxide alone.
As used herein, very fine particle size hydrated
alumina means hydrated alumina having an average particle
20 size of less than about l~l and preferably about 0.5~ (0.4 to
0.6~) or less. Generally, if the average particle size of
the hydrated alumina is greater than the above limit there
will be a deleterious e~fect on the Izod impact strength of
the material.
It is preferred that the particle size distribution of
the hydrated alumina be such that there is no substantial
percentage of particles which have a particle size greater
than about 1~.
The term "Impact Strength" means the Izod Impact
30 Strength as determined in accordance with the procedures o~
ASTM D-256. Generally, this test i~ conducted by preparing
-6~ 37~7
samples measuring 2-1/2 x 1/2 x ./8 or 1/4 inch in
dimension, notching the speciments as specified, and
impacting the specimens vertically supported in the
cantilever beam impact test ~ith a pendulum hammer. The
5 energy absorbed in the width of the sample is trans~itted to
a range scale which re~isters the ~orce in pounds from which
is calculated the impact strength in foot pounds/inch of
notch.
The term "polymeric vinyl halide" means homopolymers
10 and copolymers derived from a vinyl halide as well as
polymer blends containing said homopolymer or copolymer as a
component. The homopolymers, copolymers and polymer blends
containin~ a vinyl halide useful in the practice of this
invention include for example, (13 polyvinyl chloride,
15 polyvinylidene chloride, polyvinyl bromide, polyvinyl
fluoride and polyvinylidene fluoride, (2) copolymers of
vinyl chloride with one or more copolymerizable
ethylenically unsaturated monomers such as vinylidene
chloride, vinyl acetate, vinyl butyrate, vinyl benzoate,
20 diethyl fumarate, diethyl maleate, other alkyl fumarates and
maleates, vinyl propionate, acrylic acid, methyl acrylate,
2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate and
other alkyl acrylates, methacrylic acid, methyl
- methacrylate, ethyl methacrylate, butyl methacrylate,
25 hydroxyethyl methacrylate and other alkyl methacrylates,
methyl alpha chloroacrylate, styrene, vinyl ethers such as
vinyl ethyl ether, vinyl chloroethyl ether and vinyl phenyl
ether, vinyl ketones such as vinyl methyl ketone and vinyl
phenyl ketone, 1-fluoro, -l-chloroethylene, acrylonitrile,
30 chloroacrylonitrile, allylidene diacetate, chloroallylidene
diacetate, olefins such as ethylene and propylene, and (3)
-7-
polymer blends such as blends of polyvinyl chloride and
polye~hylene, polyvinyl chloride and polymethyl
methacrylate, polyvinyl chloride and polybut~1 chloride and
acrylonitrile-butadiene-styrene terpolymers and ternary
5 mixtures such as those containing polyvinyl chloride,
polyethylene methacrylate.
Typical vinyl halide copolymers useable in this
invention include vinyl chloride-vinyl acetate, vinyl
chloride-vinylidene chloride, vinyl chloride-diethyl-
lO fumarate, vinyl chloride-trichloroethylene and vinyl
chloride-2-ethylhexyl acrylate. The polymer blends useable
in the practice of this invention comprise physical blends
of at least two or more distinct polymeric species and
typically contain from 25 to 95 weight percent of vinyl
15 halide homopolymer or vinyl halide copolymer. The vinyl
halide copolymers useable in the practice of this invention
typically contain from about 25 to about 9S mole percent
vinyl halide units.
In preferred embodiments of the present composition,
20 the polymer is a homopolymer or copolymer of vinyl chloride.
This preference is based on the lower cost and commercial
availability of vinyl chloride relative to other ~inyl
halides.
While the very fine particle size hydrated alumina
25 herein described may be used as a filler material in both
rigid and flexible polymeric vinyl halide formulations, the
surprisingly superior impact strength that can be achieved
is of particular commercial significance in rigid
formulations (those having less than 10% plasticizer).
The parameters surrounding and the effect of the use of
a very fine particle size hydrated alumina in accordance
~37~
~ith.the practice of the invention will now~ be discussed seriatum,
with reference to t~le accompan~ing drawings:, în which:
Figure 1 is a graphical illustration of the effect of
hydrated alumina concentration on the Izod impact strength of a
polymeric vinyl halide formulation;
Figure 2 is a graphical illustration of the effect of
hydrated alumina on extrusion, measured as head pressure, and
torque, measured as motor amperage, for a second polymeric vinyl
halide ~ormulation; and
Figure 3 is a graphical illustration of the effect oE
hydrated alum.ina and calci~m carbonate on weathering of a rigid
PVC formulation.
A. Impact Synergism
When calcium carbonate fillers with.an average particle
size over 1.0~ are used in rigid PVC formulations, they generally
have an adverse effect on impact strength. When the average
particle size is less than 1.0~, there is no loss in impact strength
and, occasionally a slight improvement in impact strength will
occur. In ormulations: containing both impact modifiers and
calcium carbonate fillers, there are only slight im~rovements in
impact strength over that obtained with the impact modifier itself.
In non-impact modifier containing PVC formulations the
very fine-particle size hydrated alumina us.ed in accordance with
this invantion also gives small increases in impact strength.
However, in PVC formulations containing impact modifiers, hydrated
alumina having a very f;ne particle size (less than about 1~2 as
herein described behaves dramatically different than calcium
-- 8 --
'.~,
3'797
carbonate and acts synergis.tically ~i.th the impact modifier to
give a significant and unexpecte~d increase in impact strength.
Thes-e results- are shown in Table 1~
The surprising and unexpected increase in impact
strength that is achieved is independent of the type of impact
modifier used in the formulation. Impact modifiers generally
are rubbery materials which are either partially or completely
incompatible with the polymeric vinyl halide and are present
as a separate discrete phase. This is in contrast to
plasticizers which.are completely compati~le ~ith.the
polymeric vinyl halide. Further, impact modifiers
- 8a
.~
~Z~37~7
g
24133-613
improve impact strength without significantly reducing the heat dis-
tortion temperature or impairing other desirable mechanical and
physical properties. Representative impact modifiers that are
suitable include but are not limited to ch:Lorinated polyethylene,
modified acrylic, all~acrylic, A~S and MBS modifiers. It is be-
lieved that any conventional impact modifier can be used in the
formulations and that the very fine particle size hydrated alumina
will continue to show these synergistic effects. For example, the
addition of 6 parts per hundred parts resin of very fine particle
size hydrated alumina to rigid PVC formulations containing 5 phr of
a conventional impact modifier gave increases in Izod impact strength
from almost twice to over ten times the impact strength obtained
without the addition of hydrated alumina. The data in Table 2 de-
monstrated that increases in Izod impact from 5-20 ft.-lbs./in.
notch can be obtained.
Hydrated Alumina Particle Size
While the use of small particle size hydrated alumina
(average size of 1~) is not detrimental to the impact strength of
PVC formulations and the use of larger particle size hydrated alu-
mina will reduce the impact strength of the PVC composition, thevery substantial increase in impact strength that is achieved with a
synergistic combination of a conventional impact modifier and the
very fine particle size (less than 1~) hydrated alumina as herein
described is totally unexpected and surprising.
Table 3 shows that impact synergism is specific to
hydrated alumina with an average particle size below about
_ g _
-10-
1~. Tests with an average particle size of 1~ show no
effect on impact while larger particle size materials are
detrimental to impact strength.
C. ~ydrated Alumina Concentration
We have determined that maximum increase in impact
strength appears to occur at a ratio of very fine particle
size hydrated alumina to impact modifier of about 2-4:1, but
significant increases in impact strength are obtained even
at a 1:1 ratio and some useful effect is noticed as low as a
1:2 ratio. Even lower ratios may be used with some effect
but generally commercially significant results necessitate
at least the 1:2 ratio.
For example, with a formulation containing 3 phr
modified acrylic modifier, maximum impact was obtained at at
a ratio of 2:1 hydrated alumina to impact modifier. When
the concentration of hydrated alumina was increased to an
8:1 ratio of hydrated alumina to impact modifier, impact
strength equivalent to 3 phr impact modifier without
hydrated alumina was obtained (Figure 1).
Impact modifiers are generally utilized in the range of
about 1 phr to about 15 phr, and preferably in the range of
about 2 phr to about 10 phr. The particular level will
depend on the end use of the material. For example,
injection molded PVC generally has an impact modifier lvel
of about 2-3 phr while rigid PVC used for building siding
has a usual level of about 4-8 phr. The use of very small
particle size hydrated alumina in accordance with this
invention will allow the use of somewhat lower levels of
impact modifier. Inasmuch as high levels of impact modifier
tend to reduce tensile strength and heat distortion
37~
temperature, the reduced level of impact modifier can
provide polymeric vinyl halide materials which exhibit
somewhat superior physical properties.
Optimum concentration of impact modifier and hydrated
alumina will depend upon the formulation and desired
performance characteristics of the compound. For example,
if an Izod impact of ~.0 is sufficient for an outdoor
weathering compound, then the data shown in Fi~ure 1
illustrates that a formulation with 3 phr impact modifier
can contain as much as 24 phr hydrated alumina and still
maintain the same impact strength while taking advantage of
the surprising improvement in weathering and processing
characteristics also described herein and shown in Tables 6
and 7 and Figure 2~ If improved impact is also desired, the
hydrated alumina concentration can be reduced somewhat to
obtain the desired impact properties while still obtaining
advantageous weathering.
While as described above, the ratio of hydrated alumina
to impact modifier can be as high as 8:1, it is preferred
that the concentratlon of hydrated alumina ~e no higher than
a~out 50 phr. If the level is greater than 50 phr, the
processing characteristics may deteriorate and it may be
difficult to distribute the hydrated alumina uniformly
throughout the polymeric material.
D. Processibility
The addition of very fine particle size hydrated
alumina to rigid PVC formulations as herein described
results in improved processing characteristics as evidenced
by reduced torques, stoc~ temperatures and pressures, as
30 well as increased dynamic processing stability.
-12~ 37~7
A standard siding formulation containing, for example,
10 phr of said very fine particle size hydrated alumina,
maintained an equilibrlum torque of 1525 meter-grams and a
stock temperature of 206C compared to 1650 meter-grams and
208C for the same formulation without hydrated alumina. In
the same torque rheometer study, the compcund wlth 10 phr
hydrated alumina showed a 13~ increase in heat stability
with a stability time of 22.2 minutes compared to 19.6
minutes for the control. The same compound with 6 phr of
said hydrated alumina gave a 9% increase in heat stability
over the control ~Table 4).
In addition to the torque rheometer studies, the same
compounds we~e processed under controlled conditions on a
Kraus-Maffei 25 mm conical twin screw laboratory extruder
equipped with a 2-1/2", 40 mil strip die. The use of very
fine particle size hydrated alumina resulted in reduced
tor~ues (lower motor amperage) and pressures. The data ls
shown in Figure 2.
A common problem among weatherable rigid PVC processors
ls screw and barrel wear caused by the abrasiveness of
titanium dioxide ~Moh hardness about 6.5). Unlike alumina,
which is very hard (Moh hardness about 9), hydrated alumina
~ is relatively soft and similar to calcium carbonate with a
: Moh hardness of about 3. The potential for reduced ti.tani.um
25 dioxide levels when formulating with the very fine particle
size hydrated alumina could lead to reduced barrel and screw
wear.
E. Weatherability
Another surprising and unexpected benefit derived from
the use of the very fine particle size hydrated alumina as
~rqde tn~
-13- ~ 24379~
herein described in rigid PVC formulatlons is improved
weatherability with the potential for reducing Tio2
levels. For example, a standard siding formulation was
compounded with various levels of very fine particle size
hydrated alumina and extruded on the KM-25~1aboratory
extruder. Accelerated light stability testing of extruded
samples in a ~luorescent Sunlamp/Black Light (FSBL) light
source showed that the addition of hydrated alumina improved
light stability (Table 5).
Another series was similarly extruded and tested in a
QUV machine. It also showed that addition of very small
particle size hydrated alumina improved light stability. In
this series, a formulation containin~ 10 phr Tio2 and 6
phr of ~uch hydrated alumina appeared to be at least
equivalent in light stability to the contr~l ormulation
containing 12 phr Tio2 and no hydrated alumina (Table 6).
Long term outdoor weathering tests have been conducted
with hydrated alumina formulations for 12 months. White
compound extruded strips were weathered 45 south in Arizona
and green compound extruded strips were weathered 45 south
in Florida. The results as shown in Tables 7 and 8 show
this improvement.
Arizona weathering tests conducted on rigid PVC
formulations containing very small particle size hydrated
alumina and calcium carbonate show that the compound
containing calcium carbonate was more susceptible to
yellowing and subsequent chalking than either the control or
the formulation containing hydrated alumina. This
characteristic of calcium carbonate is the reason this
filler is not widely used in exterior compounds, especially
,~
t Yade ~arlc
~37~7
14 - 24133-613
colored formulations where chalking is especially detrimental
(Figure 3).
Variable height impact tests (VHIT) were run on the green
extruded strips prepared for Florida weathering tests. Impact re-
sults on the extruded samples containing hydrated alumina in accor-
dance with the invention were equivalent to the control (Table 8).
In addition to the very fine particle size hydrated alu-
mina and impact modifiers herein described J the polymeric vinyl
halide compositions may contain the usual compounding ingredients
such as stabilizers and fillers and optional additives such as pig-
ments, lubricants, dyes, ultraviolet light absorbing agents,
plasticizers and the like.
Generally, the very fine particle size hydrated alumina
may be introduced into the polymeric vinyl halide formulation in any
conventional manner, such as by preblending the selected hydrated
alumina and impact modifier before blending with the polymeric
resin, or alternatively, the components are blended individually in
-the resin. It is of course necessary that it be dispersed substan-
tially uniformly throughout the mixture. In extruded formulations
incorporation of hydrated alumina tends to reduce back pressure,
so one should ~e careful that sufficient shear exists for thorough
dispersion.
Conventional processing temperatures and conditions may be
utilized so long as the processing temperature remains ~elow about
230C. If the processing temperature is higher than that value,
there may be some decomposition of the hydra-ted alumina due to loss
o~ water.
14 -
-15- ~2~3797
EXAMPLE 1
~ ._
Izod impact specimens were prepared using 35~40 mil
sheet, milled at 325F for five minutes after banding. The
milled sheet was then cut into four 6" x 6" sheets and
5 plied, alternating the oriented sheets. The samples were
compression molded into 1j8" plaques at 375F for ten
mlnutes at 3000 PSI. Izod impact strength was determined
according to AST~I D~256. Physical properties were
determined according to the procedures described in ASTM
D-1784.
Torque rheometer dyn~.~ic processing sta~ility was
obtained using a ~rabender*Plasti-Corder (C. W. ~rabender,
HacXensack, N. J.t electrically heated torque rheometer
equipped with a No. 6 bowl according to the conditions
identified in the ta~les.
Accelerated and outdoor weathering and variable height
impact test ~VHIT) were all determined on extruded strips
obtained from compounds blended in a high intensity mixer
and extruded under the same conditions on a KM-25 laboratory
extruder equipped with a 2-1/2", 40 mil strip die.
Extrusion conditions were Zones ~ 2 and ~3, 320F, 295F,
325F, respectively, and 380F on the die at 20 rpm screw
speed.
Variable height impact tests were carried out according
to procedures described in ASTM D-3679.
Outdoor and accelerated weathering tests were carried
out as follows:
Outdoor Weathering - All samples were e~posed 45 south
with backing.
* Trade Mark
-16- ~4~79~
Fluorescent Sunlamp/Black Light (FSBL) ~ Samples were
exposed with a repeating cycle of 100 hours U.V.
exposure followed by 68 hours dark time.
QUV - Accelerated Weathering Test - Samples were
exposed with a repeating cycle of 2 hours U.V. at 50C
followed by 4 hours condensate at 50C using equipment
conforming to ASTM G-53 manufactured by the Q-Panel
Co., Cleveland, Ohio.
10 The following fonnulation materials were produced.
Formulation "A"
PVC (~65) 100.0
Tio2 (rutile) 2.0
Calcium Stearate 0.8
Paraffin Wax, 165F 1.2
Processing Aid 1.0
Butyltin Mercaptide Stabilizer 1.5
Formulation "B"
PVC (K=65) 100.0
Ti02 (rutile3 12.0
Modified Acrylic Modifier 5.0
Processing Aid 0.3
Calcium Stearate 2.0
Paraffin Wax, 165F 1.0
Butyltin Mercaptide Stabilizer 1.5
~rQI~
-17- ~243~7
Formulation "C"
PVC (K=65) 100.0
TiO2 (ruti].e) 6.0
Modified Acrylic Modifier 5.0
Processing Aid 1.0
Calcium Stearate 2.0
Paraffin Wax, 165F 1.
Butylti~ Mercaptide Stabilizer 1.5
Formulation "A: was used for the Izod impact studies,
the re~ults o which are summarized in Tables 1, 2 and 3;
and Formulation "B" was used for torque rheome~er stability
studies, extrusion, variable height impact testing and
: weathering studies, the results of which are summarized in
Tables 4, 5, 6, 7 and 8. Formulation "C" was used for a
weathering study in which hydrated alumina was compared to
calcium carbonate, the results of which are shown in Figure
3. For green siding compound, a non-chalking grade of
titanium dioxide was substituted for the chalking grade of
titanium dioxide used in the white siding compound. Unless
otherwise noted, hydrated alumina referred to in the tables
was prepared by a precipitation process and had an average
particle size of 0.5~u.
-18~ 3~7
The following tables illustrate the effects of
hydrated alumina on various properties of rigid PVC
materials.
TABLE 1
SYNERGISM OF HYDR~TED ALUMINA & I~PACT MODIFIER
Formulation "A"
Variable 1 _ 2 _ phr 6 7 ~ 9
Modi~ied Acrylic - 5 - 5 3 - 3 - 3
Hydrated Alumina - - 12 12 - 6 6
Calcium Carbonate(l~ 6 6
Izod Impact 0~8 14.3 1.8 18.3 2,1 1.6 8.1 1.0 2.2
(ft.-lbs./in.-~otch)
(1) Coated, average particle size 0.8u.
. .
~2~37~7
- 19 24133-613
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~2~7~7
-20~
TABLE _
EFFECT OF PARTICLE SIZE AND FILLER TYPE
(Formulation 'IA'')
_,
_ phr
Variable 1 2_ 3 _ 4 5 6
~odified
Acrylic 3.0 3.0 3.0 3.0 3.0 3.0
Hydrated
Alumina - 6.0 6.0 6.0
Alumina ~ 6.0
Hydrated
Silica - - - - - 6.0
A~erage
Particle
Size, u. - 0.5 1.0 8.0 1.0 0.12
Izod Impact 2.1 8.1 2,1 1.0 0.7 2.0
~ft.-lbs./
in.-notch)
...... .. .....
-21~ ~7
TABLE 4
EFFECT OF E~:Y5RATED ALUMINA
ON DYNAlMIC PROCESSING STABILITY(l~
Variable
Formulation A A B _ B
TiO2 2.0 2.0 12.0 12.012.0
Modified Acrylic 3.0 3.0 5.05.0 5.0
Hydrated Alumina - 6.0 - 6.0 10.0
Stability, .~in. 25.3 27.5 19.621.3 22.2
Equi 1 . Torque,
m-g. 22S0 2200 1650 16001525
(1) Torque Rheometer
Formulation "A: ~ 200C, 60~. charge 60 RPM
Formulation "B: - 200C, 65g, charge 75 RPM
,, .. , ..... ~ ... . . . . . . ... ..
~2~L37~7
-22-
TAELE
THE EFFECT OF HYDRATED ALUMINA ON
FSBL ~1) ACCELERATED_TNEATHERING
Variables 1 2 3 4 5 6
~odified Acrylic 3 3 3 4 4 4
~ydrated Alumina - 4.0 6.0 - 4.0 6.0
Hours _ _ Yellowness Inde~
Initial 4.6 4.9 4.9 4~4 4.6 4.7
500 9.6 9.2 8~5 8.4 7.8 8.1
1000 16.1 14.5 13.7 14.0 12.8 12.6
1500 18.6 16.3 16.1 16.4 15.6 14.5
(1) Fluorescent Sunlamp/Black Light
TAB~E 6
THE EFFECT OF HYDRATED ALUMINA ON
QUV ACCELERATED WEATHERING
(Formulation "B")
Hydrated Yellowness Inde~
TiO2,~ Alumina, phr Initial 2 Wks. 4 Wks. 1~ '~ks,
12 - 4.4 6.3 10.5 13.2
~2 6 3.2 5.3 8.3 11.2
12 10 3.2 5.7 8.5 10.7
6 3.2 5.~ 8.8 11.8
':
-23- -~2~3~
TABLE 7
THE EFFECT OF HYDRATED ALUMINA
ON WEATHERING (1
(Formulation "B")
Variables 1 _ 2 3
~; TiO2 1~ 12 12
i~odified Acrylic 5 5 5
; Hydrated Alumina - 3.0 6~0
Mo~ths Yellowness In~
O 3.0 3.0 3,l
3 9.4 8.4 6.4
6 10.0 9.1 ~.3
9 11.6 9.9 6.7
12 14.2 13.6 9.7
(1) Arizona
,... . .... ....... .. .
~;~43~
-24-
TABLE 8
TEIE EFFEC? OF HYD ATED A:LUMIMA ON
WE~THERING (1l~ 21
Variables 1 2 _3_ 4
TiO2 12 12 12 12
~odified Acrylic 5 5 3 3
Hydrated Alumina - 6 - 6
VHIT, In .-Lbs/
Mil, 23C 3.4 3.4 3. 6
Months E ( 3 )
_ _
3 03 .3 .a~ . 5
6 . 6 .2 .5 . 2
9 . 7 . 2 . 6 . 3
12 1.0 .7 .9 . 5
(2) Formulation "B", non-chalking TiO2, 1.5 phr chroms
oxide
( 3 ) ~STM D-2244
, . .. . . ~ .. . . . . . .. . . . .
-25-
:~Z~3'7~
EXAMPLE 2
A series of polyvinyl chloride formulations were
prepared using the proportion of ingredients listed in Table
9 to evaluate the effect of hydrated alumina on
weatherability of formulations prepared with or without
impact modifiers and/or plasticizers. Accelerated
weathering tests (FSBL and QUV) described in Example 1 were
used to evaluate eacn of the formulations and the results
are also summarized in Table 9.
Each of the formulations of this example were milled
for 5 minutes at 350F after bonding and test samples were
compression molded at 350F for 5 minutes into 125 mil
plaques. Yellowness index was obtained on a MACBET~R 150Q
colormeter.
It can be seen from the results reported in Table 9
that each of the formulations containing very fine particle
size hydrated alumina (O.Su avg~ exhibited improved
weatherability over those formulations which did not contain
said hydrated alumina. This improvement in weatherabi1iiy
can be seen for formulations which were prepared with or
without an impact modifier or plasticizer, and with
formulations containing both an impact modifier and
plasticizer. While the results show that the impact
modifier and plasticizer used in the foxmulations of this
example result in improved weatherability, ~he use of
hydrated alumina having an average particle size of 0.5u
further enhanced the weatherability of the formulation.
--26--
37~7
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O ~ ~ C~ L~J r~ ~ ~ r~! r~
O O Ou~ O O ~O L'J G~ r-. ri
O O ~ o : ~Jr~ 1 t3 L~ ~ ~3 cr ~ o r,r; cd
01
o Orr, o~) Ln O 00 e:~ ~ ~ L~ t~ ;O
G~ ~ O C~ ;) O L~' O ~i Ci r~! O ~1
r~
o O cr~ o o ~ o oo ~ o ~ 5` c~ ,~ O
r~4 O C~ O ~ ~1 ~1 ~ ~ O ~ r
~ O O 1~ 0 O t~ D ~ O ~n N
C- ~~ C~ O CJ r~ r-l ~ O ~ ri ~q ~- r~ ~ :~
^ ~ ~ ~1 0 00 ~.1 r~l r r- "~ ~ - .~1
C~ C C`~ O ~ ~1 ~ 3 L~ e' ~ o C7 0 ,
_~ r~
S~ O ~ ~ O ~ L~ O O O ~C ;- r~; O G` O -~
L~ g C~ O C~ ri .~ ~ r~ O ~ Lr~ Or.
o .~ ~ .
~1 t O O '.'~ O ~ L^ O O Lr~ o X~ L~ X
_ ~1 O C~ O ~1 ~ r-l C~ t5) 3 d C
~ r '!~
~ 1 o o ~ ~ o L~ o;~ o L~ O ~ ~ L
,_ "~ ~ _
O O c~ O O L~ O O~ X L~J ~ ~
C~ ~ Or~ ~J'J
O O r.~ O C~ L'~ r ~ r
1-~ ~ ~ U2
' '~
_ E
' CO ~ V
'Ero ~'~ O - ~ X ~ :~ ~ ~ r~ ,~
~t ~ ~ ,~ ,~ ;~
^~0 ~ 3 '~ ~:5 C ~ . ;.
Lr~ ~n ~ o ~ ~, ,C ,~
., 11_ ~, ,~ ' 'I ~ , ~ J . ~;
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r~ rj ^' ,~ -~ y Lr~ ~- 3
~_~ O O ~ .'-1 ~ r~ 1 o :!~ 3 '~ C
~ ~ ,p~
~LZ43'79~
EXAMPLE 3
A series of polyvlnyl chloride formulations were
prepared using the proportion of ingredients listed in Table
10 to evaluate the effect of hydrated alumina on
weatherability. Accelerated weathering tests ~PSBL and Q W)
described in Example 1 were used and the results obtained
are summarized in Ta~le 11.
Each of the formulations of this example were milled
for 5 minutes at 350F after bonding. Formulations 1 to 5
were prepared by individually adding each of the ingredients
and formulation 6 was prepared by preblending the impact
modifier, stabilizer, processing aid, TiO2 and hydrated
alumina were prepared by individually adding each of the
ingredients and formulation 6 was prepared by preblending
the impact modifier, stabilizer, processing aid, Tio2 and
hydrated alumina.
It can be seen from the results shown in Table 11 that
the addition of a hydrated alumina having an average
particle size of 0.5u and O.9u to polyvinyl chloride
formulations enhanced the weathering characteristics thereof
as compared to a formulation which did not contain the
hydrated alumina filler. It can also be seen from the
results that hydrated alumina having an average particle
size of 0.5u enhanced the weatherability of PVC formulations
which contained an impact modifier and these advantageous
results were obtained with the compounding ingredients being
added individually or as a preblended mixture.
~37~
--28--
0
~n
~1
o ~ o o o o o
..... . ., . 5~ ;,
O O ~1 ~ C~
C o o
CO
O 11~ 0 0 0 0 1~ ~ N a~
. . .1 . . I . . ~rl .rl
l~O O ~
O
'-- O ~ O O O O O ~ CQ ' C~ ~
h . . . . . I O - S 4 ~4
~ ~O O ~ 1 C) V
O ~ ~ ~ O
a~ . V c~
O U~ O O O ~ ~ O Z
¦o o ~ N I P ~ R
o 1~ 00 0 0 U~ I:c/ C) ,~ 0 ~ h
. . . .. I I ~ P~ 0 5~3 C~ ~( td a)
C~ O O ~ a N
O~
O C~
O LS~ O O C~ V
¦ ~C`J N ~ ~ o h
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a . P~
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5 `~ 'a^
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C~ lt) h Oh O ,~
O $~ ~ O ~1
h ~d c ~
P/ P~ qr~
-29- ~43~
TABLE 1 1
QW ACCELEE~TEI:1 WEATHERING
_1 lowne s s Index
Formul~ tions
2 3 4 5 6
Initial Y.I. 7.6 7.8 8.4 9.2 8.2 11.5
YoI~ 168 hrs. 5.4 3.8 3.8 2.0 4.0 3.1
336 hrs. 16.0 8.9 8.4 5.1 9.4 5.9
420 hrs. 19.0 10.9 10.8 5.8 10.9 6.1
FSBL ACCELERATED WEAT~ERING
Yello~mess Index
Formulations
2 3 4 5 6
Initial Y.I. 7.6 7.8 8.4 9.2 8.2 11.5
âY.I. 168 hrs.2.3 1.4 1.0 1.0 1,7 1.5
336 hrs. 4.1 1.8 2.3 l.O 3.0 1.4
