CA1243797A - Small particle size hydrated alumina as an impact synergist for impact modified vinyl halide polymers - Google Patents
Small particle size hydrated alumina as an impact synergist for impact modified vinyl halide polymersInfo
- Publication number
- CA1243797A CA1243797A CA000415883A CA415883A CA1243797A CA 1243797 A CA1243797 A CA 1243797A CA 000415883 A CA000415883 A CA 000415883A CA 415883 A CA415883 A CA 415883A CA 1243797 A CA1243797 A CA 1243797A
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- Prior art keywords
- hydrated alumina
- impact
- particle size
- vinyl halide
- phr
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
SMALL PARTICLE SIZE HYDRATED ALUMINA
AS AN IMPACT SYNERGIST FOR
IMPACT MODIFIED VINYL HALIDE POLYMERS
ABSTRACT OF THE DISCLOSURE
Very finely divided hydrated alumina is useful as a filler material for polymeric vinyl halide materials and acts synergistically with conventional impact modifiers to improve Izod impact strength.
-i-
AS AN IMPACT SYNERGIST FOR
IMPACT MODIFIED VINYL HALIDE POLYMERS
ABSTRACT OF THE DISCLOSURE
Very finely divided hydrated alumina is useful as a filler material for polymeric vinyl halide materials and acts synergistically with conventional impact modifiers to improve Izod impact strength.
-i-
Description
12a~37~3~7 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
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
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~
-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 ~ 3~79~
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 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) 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 '.~, 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 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 _ 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 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.
-15- ~2~3797 ~ ._ 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.
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.
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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 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 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~
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~
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 , . .. . . ~ .. . . . . . .. . . . .
:~Z~3'7~
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.
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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.
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-29- ~43~
QW ACCELEE~TEI:1 WEATHERING
_1 lowne s s Index Formul~ tions 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 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
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~
-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 ~ 3~79~
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 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) 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 '.~, 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 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 _ 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 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.
-15- ~2~3797 ~ ._ 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.
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.
. .
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11~ ~i ~rl~i f'i ~ri ~ri ~ ri ¦ (d S-i ~ ,~ Si f'i U; liV.'i O ~ ~) ~ f-i U~ ~i U~ S-i ~if~i O ~ f'i m ~ m N ~i O O -i m ~, m H '~ æ ~ #
~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 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 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~
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~
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 , . .. . . ~ .. . . . . . .. . . . .
:~Z~3'7~
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.
37~7 O O :~ O C ~'~ o~ ~ ~' t` 0 ~3 , O
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 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~
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., 11_ ~, ,~ ' 'I ~ , ~ J . ~;
._; ~ r;~
r~ rj ^' ,~ -~ y Lr~ ~- 3 ~_~ O O ~ .'-1 ~ r~ 1 o :!~ 3 '~ C
~ ~ ,p~
~LZ43'79~
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~
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O
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-29- ~43~
QW ACCELEE~TEI:1 WEATHERING
_1 lowne s s Index Formul~ tions 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 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
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A polymeric vinyl halide composition having improved weatherability and processing characteristics which consists essen-tially of a polymeric vinyl halide material, a filler material and up to 24 phr of hydrated alumina having an average particle size less than 1µ.
2. The composition of Claim 1 which includes an impact modi-fier in an amount sufficient to form a synergistic combination with said hydrated alumina which substantially enhances the impact strength of said composition.
3. The composition of Claim 2 wherein said impact modifier is present in an amount from about 1 phr to about 15 phr, and wherein said hydrated alumina is present in a weight ratio to said impact modifier of from about 1:2 to about 8:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000572255A CA1263793A (en) | 1982-11-03 | 1988-07-15 | Small particle size hydrated alumina as an impact synergist for impact modified vinyl halide polymers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US32314181A | 1981-11-19 | 1981-11-19 | |
| US323,141 | 1981-11-19 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000572255A Division CA1263793A (en) | 1982-11-03 | 1988-07-15 | Small particle size hydrated alumina as an impact synergist for impact modified vinyl halide polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1243797A true CA1243797A (en) | 1988-10-25 |
Family
ID=23257887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000415883A Expired CA1243797A (en) | 1981-11-19 | 1982-11-18 | Small particle size hydrated alumina as an impact synergist for impact modified vinyl halide polymers |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS58174430A (en) |
| KR (1) | KR890003260B1 (en) |
| BR (1) | BR8206683A (en) |
| CA (1) | CA1243797A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1080384A (en) * | 1977-01-17 | 1980-06-24 | General Tire And Rubber Company (The) | Low-smoke plastic |
| JPS6010540B2 (en) * | 1979-04-18 | 1985-03-18 | 信越化学工業株式会社 | Expandable vinyl chloride resin composition |
-
1982
- 1982-11-18 CA CA000415883A patent/CA1243797A/en not_active Expired
- 1982-11-18 BR BR8206683A patent/BR8206683A/en unknown
- 1982-11-19 KR KR8205235A patent/KR890003260B1/en active
- 1982-11-19 JP JP57202194A patent/JPS58174430A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BR8206683A (en) | 1983-10-04 |
| KR840002428A (en) | 1984-07-02 |
| JPS58174430A (en) | 1983-10-13 |
| KR890003260B1 (en) | 1989-08-30 |
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