CA2102478A1 - Polyvinyl halide compounds having improved surfaces and articles therefrom - Google Patents
Polyvinyl halide compounds having improved surfaces and articles therefromInfo
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- CA2102478A1 CA2102478A1 CA 2102478 CA2102478A CA2102478A1 CA 2102478 A1 CA2102478 A1 CA 2102478A1 CA 2102478 CA2102478 CA 2102478 CA 2102478 A CA2102478 A CA 2102478A CA 2102478 A1 CA2102478 A1 CA 2102478A1
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Abstract
ABSTRACT
The rigid polyvinyl halide compounds disclose have improved surfaces and are made from polyvinyl halide, 0.01 to 10 phr each of: alkyl polyol ester, carboxylic salt, mineral oil, a carboxylic acid and optionally epoxidized oil provide high gloss, gloss retention, processability and physical properties. The most preferred lubricant system comprises a C16 - C18 carboxylic acid, a mono C12 - C22 ester of glycerol, mineral oil, a calcium salt of a carboxylic acid and epoxidized soy oil . The compounds disclosed exhibit an improved combination of heat distortion temperature, dynamic thermal stability, impact strength especially low temperature impact strength and gloss. The compounds are made into articles including sheeting for thermoforming of shower stalls, wall panels, bathtubs, tub enclosures, refrigerator panels, cabinetry and the like, sporting equipment, appliance components, componentr for boats, automotive components, and business machine housings.
The rigid polyvinyl halide compounds disclose have improved surfaces and are made from polyvinyl halide, 0.01 to 10 phr each of: alkyl polyol ester, carboxylic salt, mineral oil, a carboxylic acid and optionally epoxidized oil provide high gloss, gloss retention, processability and physical properties. The most preferred lubricant system comprises a C16 - C18 carboxylic acid, a mono C12 - C22 ester of glycerol, mineral oil, a calcium salt of a carboxylic acid and epoxidized soy oil . The compounds disclosed exhibit an improved combination of heat distortion temperature, dynamic thermal stability, impact strength especially low temperature impact strength and gloss. The compounds are made into articles including sheeting for thermoforming of shower stalls, wall panels, bathtubs, tub enclosures, refrigerator panels, cabinetry and the like, sporting equipment, appliance components, componentr for boats, automotive components, and business machine housings.
Description
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POLYVINY~ ~A$ID~ COMPOUND~ EAVING I~PROV~D ~URFACEB
AND ARTICLE~ T~EREF~OM
FI~LD OF ~HE INVENTION
S This disclosure pertains to the field of a lubricant systems for polyvinyl halide resin. In particular, the invention pertains to impact modified polyvinyl chloride compounds, and lubricant systems incorporated therein for improved low temperature impact, high surface gloss and gloss retention after thermoforming. The invention also pertains to rigid or semi-rigid extruded, molded or thermoformed articles including appearance layers in a multi-layer article having layers of similar or dissimilar polymer matrices.
AC~GRO~ND OF TH~ INV~NTION
¦ A variety of compounding additives for polyvinyl halide are well established in the art. Particularly, lubricants for rigid polyvinyl halide are essential for processing of rigid PVC and are characterized for their inter-particle activity as in the case of external lubricants or their intra-particle activity as in the case of internal lubricants. The term particles herein specifically pertain to the micron sized primary particles resulting from the breakdown of agglomerates of polyvinyl halide undergoing fusion and flow in a melt-process stream.
The term "melt" is not technically precise, as polyvinyl halide polymers lack sufficient crystallinity to undergo a sharp melt transition. Processing of PVC i6 in some instances achieved in a temperature range and work load such that less than the entire volume matrix is in a true ' - 2 - ~ J ~ 7~
melt state and some of the material passes through the processing zone as partially fused primary particle flow units. A detailed treatise on the behavior of PVC
undergoing fusion in the melt process is found in Summers, J. W., A Review Of PolYvinvl Chloride Mor~holoav And Fusion, SPE RETEC- Chicago Section, 1986.
Often a balance is sought in incorporation of internal and external lubrication because several end-product physical properties are adversely affected by over- or under lubrication. It is generally understood that under-lubrication of polyvinyl halide results in shortened time until degradation ensues, beginning with premature fusion and rapid viscosity rise followed by degradation and discoloration. Over-lubrication is often associated with less than optimal fusion and work level imparted to the mass, thus resulting in poor tensile and impact strength, under these circumstances. ~
:, :;::
An extensive art for lubrication of PVC has been previously published. U.S. Patent No. 4,824,583, for ;~
example teaches the lubrication of rigid PVC with a combination of saponified triglyceride, and oxidized polyolefin. The desired effects are seen in the comparison of the extent of discoloration after time at -~
190C melt processing. Absent is a teaching to the effect of this lubricant system on surface gloss or resulting physical properties of the compound. Optimization of these properties takes on greater importance assuming that -~
processing conditions do not entail discoloration by over~
1 30 working the compound. That is, within a reasonable processing window for any given compound, it is important to determine the effect of the lubrication system on ~, - 3 ~
physical properties. The extent of extended work capability is only one aspect evidencing the safety margin to be expected in processing a given compound.
U.S. patent No. 4,481,324 is a detailed teaching on the nature of polyglycerol structure on lubrication of PVC.
The focus is on processing stability and gloss effects imparted by adjusting the internal/external lubricating mechanism via the degree of polymeriæation (Dp), the degree of esterification (n) and carbon chain length (Cx) of the ester group. External lubricants (higher Dp, "n", and Cx) are characterized by migration to the metal-polymer interface in processing, generally yielding surface gloss while delaying fusion according to amount used. ~his is contrasted with internal, more polymer soluble lubricants, for example glycerol monostearate. According to the empirical data of U.S '324, glycerol monostearate exhibits a relatively short fusion time of 6 minutes under the controlled Brabender fusion test, and would not contribute to surface gloss enhancement. Moreover, fusion time is not affected by an increase in amount of glycerol monostearate used. The inventive lubricants of U.S. '324 are those exhibiting higher dynamic stability time (DTS) and higher gloss, that is, di-glycerol- mono, di and tri ester of C12 I to C20 acid.
The study of lubrication per se in simple compounds of polyvinyl halide does not reveal a complete picture additionally because commercial compounds must contain a variety of other ingredients. Each ingredient imparts first order and second order effects. Process aids, impact modifiers and pigments have a drastic effect on overall properties, and lubrication with these components present -must be adapted, there being no predictable rules or extrapolations available for the practitioner. Moreover, stabilizers, lubricant systems, pigments and impact modifiers often create interferences with each other in attaining an acceptable balance of the critical properties in modified PVC compounds. Thus, one impact, lubricant or stabilizer system individually optimized does not suggest the best combination nor is predictive of successful utilization in a PVC compound. The best balance in all three critical performance attributes- processibility, gloss and physical properties are desired. In as much as high surface gloss, high processibility and good physical properties in the best balance are desired, extensive studies aimed at this objective have been undertaken with the result that particular preferred lubricant, impact and pigmentation systems have been found which impart a superior balance of gloss, processing stability, impact strength, and HDT.
~UMMARY OF T~E INVENTION
¦ 20 In one aspect, this invention is directed to high gloss polyvinyl halide compounds. The object of the invention is the maximization of surface gloss, impact strength and processing stability for extruded or molded compounds by the incorporation of additive systems disclosed hereinbelow. These aspects are generally achieved for a polyvinyl chloride compound comprising from 0.01 to 10 phr ~ ~;
,~
7 ~ J ~
each of: glycerol monostearate, fatty salt, hydrocarbon, and a fatty acid in specified amounts to provide high gloss, gloss retention, processibility and physical properties. The preferred embodiments are further limited by: the amount of impact modifier, optional rutile titanium dioxide, an absence of mineral wax lubricant, epoxidized material and less than about 2 parts each per hundred parts polyvinyl halide (phr) of carboxylic salt, and monoester of glycerol. The compounds of this invention are rigid and exhibit an HDT under a 66 psi load of at least 60C and exhibit an improved balance of variable height impact strength (VHIT), room temperature Izod, -40C Izod impact strength and dynamic process stability (DTS).
DE~TAII.ED DESCRIPTION
In general, the components of the compounds of the present invention are polyvinyl halide, stabilizer, impact modifier, a lubricant system and optional ingredients such as pi~nent, filler, and colorant, etc., each specified herein. In particular, the preferred embodiment of the invention comprises in a specified amount polyvinyl chloride homopolymer, an acrylic impact modifier, an MBS
impact modifier, a tin stabilizer, epoxidized vegetable oil, mineral oil, a long chain carboxylic acid, a metal salt of a long chain carboxylic acid, and an alkyl ester of an alkyl polyol, preferably a mono -C16 to C18- ester of glycerol. Preferred optional components are coated titanium dioxide, and polymeric acrylic processing aid.
Rigid compounds of this invention are distinguished from non-rigid compounds. Rigid compounds of this - 30 invention conform to the definition of ASTM-D883 for rigid -::
plastics that have a modulus of elasticity, either in flexure or in tension, greater than 700 Mpa (100,000 psi) at 23C and 50% relative humidity when tested in accordance with either ASTM Method D747 - Test for Stiffness of -Plastics by Means of a Cantilever Beam, ASTM Method D790 -Test for Flexural Properties of Plastics and Electrical Insulating Materials, ASTM Method D638 - Test for Tensile Properties of Plastics, or ASTM Method D882 - Test for Tensile Properties of Thin Plastic Sheeting tlg83).
The term polyvinyl halide used herein means polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride halogenated derivatives thereof and mixtures. These are homopolymers or copolymers, and well known and commercially available worldwide. Polyvinyl chloride polymers conte~plated for use in the present invention include those prepared in a variety of ways. PVC polymers can be prepared by polymerization methods including: mass, suspension, dispersion, and emulsion processes. A mass process is described in U.S. Patent No. 3,522,227. A phase inversion process may also be used and is disclosed in U.S.
Patent No. 3,706,722. A useful skinless, suspension PVC
resin is taught in U.S. Patent No. 4,711,908, in particular example 4 in that disclosure. The preparation of porous, skinless, crosslinked PVC resin can be prepared with the 25 direction of U.S. Patent No. 4,755,699, with particular reference to example 1 of that disclosure. PVC resins used herein are preferably those made by suspension or mass processes. Suspension or mass PVC resins used herein are - particulate homopolymer or rigid copolymer resin having a 30 particle size average ranging from ~bout 70 microns to 250 micron~.
Suitable comonomers that vinyl fluoride and polyvinylidene chloride may be included in minor amounts in the vinyl chloride polymer(s) are the olefins, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, ~-cyanoacrylic acid, and the like; esters of acrylic acid, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyanoethyl acrylate, hydroxethyl acrylate and the like; vinyl esters such as vinyl acetate and vinyl propionate; esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, and the like; nitriles, such as acrylonitrile and methacrylonitrile; acrylamides, such as methyl acrylamide, N-methylol acrylamide, N-butoxy 1 15 methacrylamide, and the like; halogen containing vinyl I monomers such as vinyl fluoride, vinylidene chloride, 1,2 -dichoroethylene, vinylidene fluoride, vinylidene and vinyl bromide; vinyl ethers such as ethylvinyl ether, chloroethyl vinyl ether and the like; the vinyl ketones, styrene and styrene derivatives including ~-methyl styrene, vinyl toluene, chlorostyrene; vinyl naphthalene; cross-linking monomers such as diallyl phthalate, trimethylol propane triacrylate, allyl methacrylate and the like; allyl and vinyl chloroacetate, vinyl pyridine, and methyl vinyl ketone; and any copolymerizable monomers or mixtures of monomers having suitable reactivity ratios with vinyl chloride and known to those skilled in the art.
Particularly preferred are non-crosslinked polyvinyl chloride homopolymer resins substantially free of gel particles.
The inherent viscosity (I.V.) (ASTM D-1243) of polyvinyl chloride used in this invention generally ranges `~
' - 8 ~
from about 0.2 to about 4.0, with a preferred I.V. range of from about 0.35 to about 1.2 and a more preferred I.V.
range of from about 0.5 to about 0.95. A combination of ~ -PVC polymers each having a different average molecular weight should be avoided to the extent that gloss is significantly reduced. The more preferred I.V. range is from 0.5 to 0.95, with the most preferred range from 0.52 to 0.80.
HDT modifiers may also be employed. These can be copolymers comprising a monomer of the formula:
Rl--C = CH2 ~ R2 (I) [R3]X
wherein X is 0, or 1, the non-substituted ring carbons are bonded to hydrogen, R1 is hydrogen, C1-C22 alkyl or halo Cl-C22 alkyl; R2 and R3 are independently hydrogen, Cl-C22 alkyl, halo (Cl-C22) alkyl, or C1-C22 substituted alkyl.
The term copolymer refers generally to a polymer containing two or more than two monomers, one of which is defined by (I). Copolymers comprise (I) copolymerized with other comonomers. Other comonomers include acrylates, methacrylates, like methylmethacrylate (II), acrylonitrile (III), methacrylonitrile, ~-chloroacrylonitrile, ethacrylonitrile, anhydrides such as maleic anhydride, N- :
substituted maleimide and styrene (IV). A combination of more than one species of I can be combined to comprise the monomer composition of the HDT modifier. Specific examples include a copolymer selected from the group consisting of I/II, I/III, I/IV, I/II/III, I/II/IV, I/III/IV, I/II/III/IV, and graft copolymers of either I/II, I/II/III, ~ .
I/II/IV, I/III, I/IV, I/III/IV graft polymerized on a rubbery polydiene, polyacrylate; alpha olefin copolymer, EPDM rubber, or butyl rubber or mixture thereof. Preferred are copolymers containing from about 50% by weight to about 95% by weight of (I).
Polyimide HD~ modifiers for use herein include polyimides, copolymers of vinyl aromatic and imide derivatives of an ethylenic unsaturated dicarboxylic acid such as a copolymer of alpha methyl styrene-styrene-N-cyclohexyl maleimide, also included are imidized polymethylmethacrylate, imidized styrene-maleic anhydride copolymer, acrylic-imide copolymer, polyglutarimide, polyitaconamide, and the like. Polyimide HDT modifiers also include copolymers derived from a comonomer of N-substituted maleimide expressed by the general formula:
1l CH C
N -R
CH- C
~ 20 0 ¦ wherein R is hydrogen, a non-substituted or substituted hydrocarbon group, cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group, any of these having from 4 to 20 carbon atoms. Examples of R include t-butyl, cyclohexyl, phenyl, 2-chlorophenyl, benzyl, 2-methyl phenyl, 2-ethyl phenyl, 2,6-dichlorophenyl, 2,6-diethyl phenyl, and the like. The most preferred imide HDT
modifiers are imidized polymethylmethacrylate. Examples of the preparation o polyimides are described by Kopchik, U.S. Patent No. 4,246,374, and Schroder, et al. U.S.
Patent No. 3,284,425. Imidized PMMA is commercially av~ilable from the Rohm and ~aas Company under the trade . .- ~,, ' ~
names of Paraloid~ HT-510, Paraloid~ EXL-4151, Paraloid~
EXL-4171, Paraloid~ EXL-4241 and Paraloid~ EXL-4261. In general, the degree of imidization can rànge from about 10 to 80 percent, preferably from 20 to about 60 percent.
Other heat distortion modifiers useful herein include post chlorinated polyvinyl chloride, polycarbonate, halogenated polycarbonate, polysulfones, polyesters, and polyacrylates.
Generally, the PVC compounds herein will contain a thermal stabilizer. The preferred thermal stabilizer system emplcyed herewith is a combination of tin compound and a co-stabilizer. The organotins are preferred tin compounds and include dimethyl tin-bis isooctylthioglycolate (methyltin), di-butyltin-bis-isooctylthioglycolate (butyltin), octyltin-bis isooctylthioglycolate, dialkyl tin di-carboxylates, methyltin mercaptides, butyltin mercaptides, dialkyl tin bis(alkyl mercaptocarboxylate) including di-n-octyltin-S,S'-bis(isooctyl mercaptoacetate), and butylthiostannoic acid, and mixtures thereof. Any alkylated tin having features such as low toxicity e.g. higher alkyl types, FDA
approval, USP class 6 approval, good color, clarity and compatibility, low plate-out on equipment, and non-staining properties are desirable and preferred for use in this invention. The more preferred stabilizer system of a tin compound and epoxide co-stabilizer can contain any other stabilizers such as derivatives of barium, cadmium, zinc, antimony or lead containing heat stabilizers.
Co-stabilizers may be employed for example, phosphite stabilizers, polymeric phosphites, thioesters such as dilauryl thiodipropionate, beta-diketones and epoxy derivatives. Co-stabilizer may be present at from 0.1 to lo weight parts, preferably from 0.3 to about 5 phr, and most preferably from 1.0 to 4.0 weight parts per 100 weight parts combined of PVC and HDT modifier (phr). The preferable costabilizer is an epoxy material.
Antioxidants are optionally present and include the various hindered alkylated phenolics such as 2,6-di-t-butyl-4-methyl phenol also referred to as butylated hydroxy toluene, bis-phenols such as 2,2'-methylenebis(4-methyl-6-t-butylphenol~, thio-phenols such as 4,4'-dihydroxydiphenyl sulfide, otherwise referred to as thiodiphenol, and di-phenyl ethers such as 4,4'-dihydroxydiphenyl ether, and mixtures thereof. When used, antioxidants are generally present in an amount from about 0.05 to 5 parts per hundred weight parts PVC and pre~erably at from 0.1 to 1.0 phr.
Preferred antioxidants are those having acceptability under applicable FDA regulations.
Polymeric impact modifiers may be present. Post-chlorinated polyethylene is an exemplary po~ymeric impact modifier. CPE is obtained from the chlorination of polyethylene having a density (ASTM-D1505-57T) of from about 0.91 to about 0.98 gram/cc. at 25C., a melting point usually in the range of from about ~OO~C to 130C., and melt index (according to ASTM-D1238-57T) above about 0.05, more preferably in the range from about 0.05 to about 20.
A method of preparing such a CPE material is more fully described in U.S. Patent 3,299,182. Suitable embodiments are commercially available from Dow Chemical Inc., or E.I.
DuPont deNemours, Inc. CPE materials generally contain from about 5% to about 50% wt. of combined chlorine. Those containing from about 25% to about 40% wt. of combined chlorine are preferred with PVC, and those containing from about 32% to about 38% chlorine are most preferred.
The preferred impact modifier comprises an MBS type optionally with an acrylic type. The principal embodiments of MBS types are copolymers of methylmethacrylate, butadiene, and styrene. Acrylonitrile may also be present (MABS). Preferred impact modifiers generally contain a rubbery core component, the particulars of this core being beyond the scope of the invention. Various preferred core embodiments include polymers derived from 1,3-butadiene, isoprene, acrylates, olefins, styrene, or mixtures so long as the core polymer exhibits a Tq of less than zero.
Preferably the Tg of the rubbery core polymer is below -30C. The rubbery rore polymer is preferably present inthe polymerization of the shell comprising styrene and ! methyl methacrylate. Commercial embodiments of MBS include Paraloid~ XM-653 and BTA-733 from Rohm and Haas, Inc., and Kane-Ace~ B-56 and B-22 available from Kanegafuchi, Inc. A
combination of two acrylic impact modifiers, the minor proportion being one containing a diene component and the major proportion being one without a diene component is most preferred. Both MBS and acrylic type polymeric impact modifiers can also referred to as multi-stage polymers. A
commercially available diene containing acrylic is ~ Durastrength~ 200 from Atochem North America, Inc. Non-!1' diene containing versions are Paraloid~ KM-330 or KM-334 from Rohm and Haas, Inc. The total amount of impact modifier present is from 0 to 30 weight parts preferably from 5 to less than 25 phr, and most preferably from lO to about 20 phr. Total MBS and acrylic impact modifier are -~ each present at ., ..
, ;, "A
';,~, - 13 - ~ . J L~ ~ ~
preferably 0 to 15 phr, more preferably 4 to 12 phr, and most preferably 5 to 10 phr.
The essential lubricants used in the present invention comprise a long chain carboxylic acid, a metal salt of a long chain carboxylic acid, an alkyl ester of an alkyl polyol, and a hydrocarbon. The carboxylic acids include C6-C24 carboxylic acids like undecylic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, behenic acid, chlorocaproic acid, hydroxy capric acid, hydroxy stearic acids and the like. Preferred are Cl6-Cl8 carboxylic acids like stearic acid.
The long chain carboxylic acids are employed at from 0.01 phr to about 10 phr, preferably the carboxylic acids are employed at from 0.1 phr to about 5 phr, more preferably from 0.2 to 2 phr and most preferably from 0.5 phr to about 1.1 phr.
The metal salts of long chain aliphatic carboxylic acids are sometimes referred to as metal carboxylate soaps. ~ -~
Metal carboxylate soaps include calcium, lithium, magnesium and zinc salts of C8 to C30 carboxylic acids. The calcium salts are preferred, with calcium salts of Cl6 to C18 carboxylic acids more preferred such as calcium stearate.
A metal carboxylate salt is preferably employed at from 0.01 to about 10 phr, preferably from 0.2 to 5 phr, more preferably 0.5 to 2.5 phr, and most preferably from 1.0 to 2.0 phr.
The alkyl esters of alkyl polyols include glycol esters and glycerol esters like ethylene glycol ester and - 30 propylene glycol ester. Also included are oligomeric 3 ~ 3 glycol esters or oligo-glycerol esters. Specific examples include glycerol mono 2-ethylhexanoate, diglycerol monostearate, triglycerol mono stearate, a polyglycerol ester of a C8 to C22 carboxylic acid such as hexaglycerol 5 mono stearate, hexaglycerol distearate, or any of the glycerol, diglycerol, triglycerol or polyglycerol partial esters of oleic acid. Preferred are the esters derived from the reaction of glycerol and a C16 to C18 carboxylic acid, with more preferred versions being mono-C16 to C18 10 esters of glycerol such as glycerol monostearate (GMS).
The esters of alkyl polyols are available commercially from Henkel Int., Inc. The alkyl polyol esters are employed at from 0.1 phr to 10 phr generally, preferably from 0.2 to 5, more preferably from 0.3 to 2.0 phr and most preferably 15 from 0.5 to 1.3 phr.
The hydrocarbon or derivative of hydrocarbon used herein in combination with other components include paraffins such as paraffin oils and mineral oils, microcrystalline wax, paraffin wax, and low molecular 20 weight polyolefin such as polyethylene wax, either in liquid, powder or flakes. These are commercially available from Sonneborn Division of Witco Chem. Co., Inc., Penreco Inc., Union Oil Co., Inc., and Frank B. Cross, Co., Inc Mineral oil is the preferred hydrocarbon. The hydrocarbon 25 is employed at from 0.1 to 10 phr, preferably 0.2 to 5 phr, more preferably from 0.5 to 3 phr and most preferably from 1.0 to 2.0 phr.
Optional lubricating components include epoxide materials like epoxidized oils, epoxidized linseed oil, 30 epoxidized tall oil, epoxidized soy oil, and epoxy derivatives of bisphenol A, for example, the reaction 3 . .:
product of epichlorohydrin and bisphenol-A. Generally as liquids or meltable solids, epoxy materials include dig~lycidylether of bisphenol A, having molecular weight above about 370. A variety of commercial sources for epoxy containing materials is listed in Chemical Week Buyers' Guide, October, 1990. Epoxy resins are availablP
under the Epon~ trademark of Shell Chemical Co., Inc. The most preferred epoxide containing materials are the epoxidized oils like epoxidized soybean oil (ESO) and epoxidized linseed oil. The epoxy materials are used at from O.1 to 10 phr, more preferably at 1 to 6 phr and most preferably at from 1 to 4 phr.
The chemically modified waxes and mineral waxes are most preferably avoided. These include montan wax, and montan ester waxes which may be mixtures of long chain acids, long chain esters and resinous portions. Reference i5 made to Kirk-Othmer Encvclopedia of Chemical TechnolooY, Wiley Interscience, Vol. 23, 1978, Pg. 471. Montan ester wax is available from Hoechst-Celanese Inc.
. ~
The above specified ranges of amounts of each component in the invention is expressed in terms of weight parts of the component per 100 weight parts of PVC (phr).
The range of optional lubricant components is the same as specified above.
There is an optimal total amount of lubricant beyond which there are negative effects on HDT and impact strength. Generally the lubricant system compri6es a total ~ of about 1 to 10 phr of the above components, preferably ??1 from 3 to about 8 phr total and more preferably from about ~ 30 3.5 up to 7 phr and most preferably from about 3.5 to about ~? : .
" ' '~
?,,ijG . ., ~
J ~
6.2 phr. The precise total amount of lubricant desired will depend on *he I.V. of the PVC present. Generally, a lesser total amount of lubricant is required when lubricating a PVC having an I.Y. less than about 0.6.
Whereas, when lubricating a PVC of I.V. 0.6 or higher, relatively higher amounts of lubricating ingredients are suggested. Several combinations are suggested herein within practical ranges. Optimization of particular individual formulations is beyond the scope of the present invention, and can be achieved by one skilled in the art after reasonable trial and error.
At least one optional plasticizer may be included in a minor amount ranging from 0.1 t~ about 10 phr, preferably from 1 to 5 phr, the upper limit otherwise controlled by not allowing the flexural modulus to drop below 100,000 psi. Specific examples of plasticizers include carboxylic acid esters such as the various esters of adipic acid, azelaic acid, phthalic acid, benzoic acid, citric acid, isobutyric acid, isophthalic acid, sebacic acid, isosebacic acid, stearic acid, tartaric acid, oleic acid, succinic acid, phosphori~ acid, terephthalic acid, trimellitic acid, and mixtures. Other plasticizers include for example, partial esters of the above carboxylic acids, ethers, glycol and pentaerythritol derivatives, glycolates and glycerol derivatives. These are set forth in The Technoloav of Plasticizers, by Sears and Darby, pages 893-1085, John Wiley & Sons, New York, 1982. Preferred plasticizers are C4 and higher alkyl diesters of phthalic acid, such as di-2-ethylhexyl phthalate, and di-3C isodecylphthalate bisphthalates, C8 and higher alkyltriesters of trimellitic acid such as tri-octyltrimellitate (TOTM). Various polymeric plasticizers can also be utilized such as the polyesters, polyolefins, polyepichlorohydrins, polya¢rylates, ethylene copolymers, and copolymers prepared from di- and monoolefins.
Polyester plasticizers are generally made from a dicarboxylic acid having from about 3 to about 12 carbon atoms and from a diol having from about 2 to about lOOO ~-carbon atoms with propylene glycol being preferred.
Examples of suitable polyesters include various esters made from adipic acid such as a polyester having a molecular weight of 6,000, e.g., Paraplex0 G-40, a polyester made from adipic acid having a molecular weight of about 2,200, Paraplex0 G-50, a polyester made from adipic acid having a molecular weight of about 3,300, Paraplex0 G-54, a polyester made from azelaic acid having a molecular weight of about 2,200, Plastolein0 975, a polyester made from sebacic acid such as Paraplex0 G-25, a polyester made from glutaric acid, a polycaprolactone polyester, and the like.
Paraplex is a trademark of C.P. Hall Co. and Plastolein i8 -a trademark of Emery Industries, Inc. Plasticizer is preferably avoided to achieve higher HDT. For semi-rigid -~
compound a small a~ount is preferred.
:' ~
The PVC compounds disclosed herein will typically contain optional additives such as: pigments, blowing agents, coupling agents, processing aids, fillers, antistatic agents, anti-fogging agents, flame retardants, smoke suppressants, colorants all of which are commercially available and partially listed in Modern Plastics ~ -;
EncycloDedia 1988 published by McGraw Hill Co. ~-Exemplary antistats are commercially available under the Glycolube0 trademark of Lonza Corp. An exemplary ~:
::
- 18 ~
antifogging agent includes the alkyl phenol ethoxylates as for example those commercially available under the Surfonic trademark of Texaco, Inc~
Adjustment of melt viscosity can be achieved as well as increasing melt strength by employing process aids such as those containing polyacrylates. It has been found that these do not interfere with gloss at useful levels.
Exemplary processing aids are copolymers of polymethylmethacrylate. Paraloid~ X-120ND, K-120N, K-175 from Rohm and Haas, Inc. are a few examples. Reference to others is found in The Plastics and Rubber Institute:
International Conference on PVC PrQcessin~, April 26-28 (1983), Paper No. 17.
Fillers are optional and include clay, barytes, calcium carbonate, talc, mica, silica, aluminum trihydrate, dolomite and fiber reinforcement such as carbon, glass and boron fibers. Where used, calcium carbonate which has a particle sizes average of from 0.02 to 1.0 micron, preferably 0.02 to 1.0 micron and is treated with from ~ about 1% to 5% by weight of fatty acid is preferred. The ¦ precipitated calcium carbonates having these features are available from Pfizer Minerals, Inc. under the Ultraflex~
trademark. Preferable levels of fillers are 0 to 10 phr, more preferably 0 to 5 phr, and most preferably zero.
Exemplary opacifying pigments include titanium dioxide, preferably rutile grades. Rutile grades can be - surface coated with ingredients such as silica, zirconia, alumina, or other minerals, including combinations of these. The extent of coating is in a range of fro~ about 2% to about 99% surface ~rea coverage. Zinc co~ted ~iO2 ,~ ~
~;
should be avoided as it induces degradation with PVC. An -example of uncoated Tio2 is designated R-100 from E.I.
DuPont de Nemours. An example of lightly coated Tio2 is Tioxide~ RFC-6 from Tioxide of Canada Ltd. and contains a combination of zirconia and silica coatings. More preferred Tio2 grades are coated, for example, with from 90 % to 99.99 % of the surface covered with silica may also be used. Commercial versions include Tipure0R-960 from E.I.
DuPont de Nemours, Inc., and Zopaque0 RCL-6 from SCM
Corporation.
The impact performance levels preferred are a room temperature notched IZOD of at least above about 2 ft.-lbs/in. (of notch) and more preferably at least 4 ft.-lbs./in. The Preferred notched Izod impact properties at -40 achieved were greater than 1.0 ft.-lbs./in. and more preferred embodiments greater than 2 ft.-lbs./in. The most preferred embodiments achieved a notched Izod at -40~C
of greater than 4 ft.-lbs./in. of notched, with some examples below having greater than 6 ft.-lbs./in. of notch.
The preferred compositions exhibited a Brabender dynamic -thermal stability time at 200C and 50 rpm with a No. 5 mixing head of at least 20 minutes with the more preferred embodiments exhibiting a DTS time of 25 or more minutes and the most preferred embodiments achieved a DTS time of 30 minutes or more. Compounds of the present invention in the fused state exhibit an HDT at 66 psi of at least 58C, more preferably 60C and most preferably at least 64C. It is possible with the compositions to include an amount of heat distortion modifier to raise the HDT preferably at least 3C higher. Useful HDT modifiers including the aforementioned copolymers of alpha methyl styrene, styrene-acrylonitrile copolymers, imidized acrylic polymer, polycarbonate, halogenated polycarbonate, styrene maleic r~
~ 20 ~
anhydride copolymers, and the like may be employed to raise HDT.
The invention will be better appreciated by the following examples in which comparisons are made between examples not a subject of this invention with those which exemplify the improvements of this invention. All amounts of ingredients are shown in weight parts. The following ASTM test procedures were used in evaluation the performan¢e parameters measured.
Pro~erty Test Notched IZOD Impact Strength ASTM-D256 Heat Distortion ~emp.* ASTM-D648 Inherent Viscosity ASTM-D1243 Dynamic Thermal Stability Brabender Plasticorder~
(DTS) Gloss at 60 Glossgard0 II glossmeter A~ 66 F6i on unanncalcd compre~sion molded plaques : ' The compounds of the present invention can be utilized in melt forming processes such as, for example, injection molding, extrusion, co-extrusion, thermoforming, lamination, compression molding, calendering, and the like, including uses for a capping layer in a co-extr~sion or lamination of sheet or profile such as a capping layer on a substrate in the form of a layer of the compound in the fused state in intimate contact with a substrate selected from the group consisting of metal, wood, a thermoset article, and a thermoplastic article.
Specific articles derived from the invention include sheeting for thermoforming of shower stalls, wall panels, bathtubs, tub enclosures, refrigerator panels cabinetry and '.,, '~ 8 the like, doors, vertical and horizontal blinds, sporting equipment, automotive components, appliance components, components used in molded parts for boats, housewares, plumbing ware, signs and business machine housings. Thus, the present invention has extended the useful range of applications for polyvinyl halide-based thermoplastic articles where the improved combination of properties are needed and where it is desirable to combine the compo~nd with a substrate for improved asthetics and economy.
The DTS test measures the time-torque relationship at selected temperatures using an instrument such as the Brabender Plasticorder0. Model EPL-V30Z is a suitable model. The test value generally reported and u.sed for comparison is the 'IDTS time". DTS time is defined as the -time elapsed from the time the rotors are turned on in the presence of the sample, including the time the instrument torque falls to its minimum value, up to the point where torque has risen about 50 to lO0 meter-grams from the minimum. This time is limited by the stability limits of the composition under shear. DTS time is dependent on inherent polymer properties, but also on temperature, sample ~ize, compound formulation, instrument operating conditions, degree of instrument maintenance, and other conditions. In the examples below, DTS was run using a no.
5 mixing head, with a bowl temperature of 400F, other conditions controlled to provide for accurate comparisons.
The preferred compounds of this invention surprisingly gave a DTS time at 400F (204 C) of at least 20 minutes, more preferred embodiments gave 25 minutes or higher. This was achieved while at the same time, the preferred compounds exhibited excellent impact strength. The occurrence of a - boost in both gloss and impact strength properties was - ~.
',3 unexpected and defied the expected trend based on the conventional understanding of lubrication interferences with impact strength achievement.
VARIABLE HEIGHT IMPACT STRENGTH
Variable Height Impact Test. A weight (typically 8 lbs.) is placed in a cylindrical tube and a conical dart (typically with a 1/8" diameter tip) is attached to the bottom of the weight. The sample is placed below the cylinder and the weight with dart attached is dropped, while contained by the cylinder, onto the sample. The height of the weight is increased until the dart puncture area show a failure ttypically when a crack appears in the impacted area and light can be clearly seen through the crack). The height of the weight is then lowered incrementally until the impacted points pass the test (when no crack through which light can be seen is made). The height is then increased again until a failure occurs and I then decreased until a pass occurs. Typically 9 to 16 ¦ impacts are made per test. The height (of the dart above the sample) at which 50% of the time a pass occurs is taken as the value to be used to calculate the average impact strength. This value is the weight times the height and is usually reported in inch-pounds. The inch-pounds are then divided by the average thickness of the sample (here approximately 20 mils. a mil = 0.001 inch~ and the final value is reported as inch-pounds per mil.
- I.V. - INHERENT VISCOSITY (ASTM-D1243) The inherent viscosity is measured for PVC using cyclohexanone as the solvent. The polymer is dissolved in ~ ' ' :
~j ~1 .
2 ~
the solvent at a concentration of 0.2 gram per 100 mls. of cyclohexanone at 90C for 90 minutes and then measured with a viscometer in a water bath at 30C.
S The compounds listed in table A below were prepared by hand mixing the components in a Henschel high intensity powder mixer to form a uniform powder blend. The powder blend was banded on a heated r~ll mill until well fused.
The temperature of the material on the mill was approximately 379F. Sheets were removed from the mill and compression molded into plaques used for physical testing.
A portion of the sheets taken from the mill were also cubed ~ and cubes were used for measurement of DTS. The cubes were ¦ extruded on a laboratory sized Brabender extruder using a 4 " X 0.020 " strip die to prepare samples for 60 gloss measurement and VHIT testing. In each compound 100 weight parts of polyvinyl chloride homopolymer having an I.V. of 0.68 was used. Two weight parts of tin stabilizer and -eight parts acrylic impact modifier stabilizer (2 parts of one containing a diene component and 6 parts of one absent a diene component) was included in each example except for ~ example 22 which contained only two parts of acrylic impact 3 modifier. The remaining components in each example are listed in table A on the basis of weight parts. Table B
illustrates the properties obtained from the compression ~ molded plaques made from the milled sheets. A least two c gloss measurements were obtained from each extruded 4" wide strip and averaged if different. Gloss measurements were ;~ obtained at 60 using a Gardner Glossgard II gloss meter supplied from Pacific Scientific, Inc. The gloss readings using this method and taken directly from the extruded ., . . .
';`
. j; . .
~la~
compounds with out further polishing yield preferably a gloss of at least 40%, more preferably 50% and most preferably greater than 55~ for the compounds of the invention.
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It can be seen from table A the effect on gloss of the lubricant system. Example 1 contains a combination of acrylic and MBS impact modifier and a preferred lubricant system containing ES0, Ca stearate, GMS, mineral oil and stearic acid. The gloss is high at 58.6. Example 6 confirms the high glo55 using this system. Example 1 was extruded on a sheet extrusion device. The sheet was measured for initial gloss before thermoforming. The draw ratio of initial to drawn thickness was 2:1. There was ~ -~
lo surprisingly no loss in gloss measured at the region which was drawn at the 2:1 ratio.
In commercial practices of sheet forming, typically a polishing stack is used and gloss is enhanced to a level of greater than 70 and preferably qreater than 80. The lS preferred embodiments of the invention can be polished in this manner and will typically exhibit a gloss of 80 or I higher and will lose less than 10% of the initial polished ¦ gloss when drawn at least 2:1 during thermofor~ing. It is recognized in the art that one can expect at least a 20%
gloss reduction after thermoforming. In one thermoforming run the compound in sheet form was polished to a gloss of 85. A 145 mil sheet was drawn by thermofor~ing. Quite unexpectedly, the gloss measured at a point having thickness of 70-75 mils, correspondinq to a 2:1 draw ratio, was 85.
Example 2 illustrates the loss of some gloss by ~ eliminating ES0; example 3 shows reduction in gloss on 3 elimination of mineral oil; example 4 shows reduction in 3 gloss on elimination of Ca stearate; example 5 with GMS
(ester of polyol) eliminated, a likewise reduction; example 7 is absent carboxylic acid and gloss is reduced; example 8 ., ~
':
' -:
,;, ib ~ L;~
is absent both ESO and mineral oil, however noting in table B that DTS is reduced to 21 minutes and gloss was lower than example one. Higher DTS is preferred. Example 9 illustrates a gain in DTS on addition of ESO.
Gloss is reduced on elimination of GMS and mineral oil as example 10 illustrates. Elimination of both ES0 and GMS
in example 11 shows reduced gloss and significantly lower DTS (19 min.). Elimination of mineral oil and stearic acid caused reduced gloss and reduced -40c Izod as shown in example 12. Gloss ranged from about 36 to about 44 for examples 13-16 wherein calcium stearate and at least one other preferred lubricant was eliminated. The use of ES0 shows in examples 13 and 15 versus 14 and 16 a recovery in DTS, however, low temperature impact is not as good without carboxylate salt. Gloss is also reduced in example 17 when GMS and mineral oil are absent.
Example 23 illustrates that high gloss can be obtained (64.5) with the elimination of MBS impact modifier, however it is noted the drastic lowering of -40C Izod impact.
3 . ~
Example 22 illustrates the elimination of the six parts of acrylic impact modifier and is comparable to example 1 which contains eight parts of acrylic impact modifier. The same lubrication system is used however, example 22 has lower gloss and significantly lower -40C
impact.
Examples 19, 20 and 21 have no polyol ester, no carboxylate salt and no ESO. Examples 20 and 21 have only one component of lubricant system, namely, mineral oil, and stearic acid, respectively. The gloss is reduced and -40C
impact is low. Examples 19-21 have unacceptable DTS times of 13, 14 and 9.5 minutes.
Examples 24 - 28 illustrate poor DTS time when at ¦ least one lubricant of the invention is missing, as well as ~ 15 the negative effects on gloss and -40C Izod.
I
Example 30 is comparable to example 1 to show the significant loss in gloss with the use of montan wax which is a mineral wax. Example 30 had a 37.4 gloss rating with the use of 1.0 phr montan wax, but the gloss rating ~ 20 increased when montan wax was eliminated and stearic acid ¦ was used in a preferred amount.
The data of example 31 shows that there is obtained, good gloss with the use of a relatively higher level of GMS
and carboxylic acid, however this leads to reduced -40C
impact strength.
.-:
Example 29 is comparable with example 1 except for the use of 10 phr CaCO3 filler. The data shows that DTS, glo~s ','~'~ '-; :
. "~
~:
,,:
C~
and notched Izod impact strength are reduced with the use of filler.
POLYVINY~ ~A$ID~ COMPOUND~ EAVING I~PROV~D ~URFACEB
AND ARTICLE~ T~EREF~OM
FI~LD OF ~HE INVENTION
S This disclosure pertains to the field of a lubricant systems for polyvinyl halide resin. In particular, the invention pertains to impact modified polyvinyl chloride compounds, and lubricant systems incorporated therein for improved low temperature impact, high surface gloss and gloss retention after thermoforming. The invention also pertains to rigid or semi-rigid extruded, molded or thermoformed articles including appearance layers in a multi-layer article having layers of similar or dissimilar polymer matrices.
AC~GRO~ND OF TH~ INV~NTION
¦ A variety of compounding additives for polyvinyl halide are well established in the art. Particularly, lubricants for rigid polyvinyl halide are essential for processing of rigid PVC and are characterized for their inter-particle activity as in the case of external lubricants or their intra-particle activity as in the case of internal lubricants. The term particles herein specifically pertain to the micron sized primary particles resulting from the breakdown of agglomerates of polyvinyl halide undergoing fusion and flow in a melt-process stream.
The term "melt" is not technically precise, as polyvinyl halide polymers lack sufficient crystallinity to undergo a sharp melt transition. Processing of PVC i6 in some instances achieved in a temperature range and work load such that less than the entire volume matrix is in a true ' - 2 - ~ J ~ 7~
melt state and some of the material passes through the processing zone as partially fused primary particle flow units. A detailed treatise on the behavior of PVC
undergoing fusion in the melt process is found in Summers, J. W., A Review Of PolYvinvl Chloride Mor~holoav And Fusion, SPE RETEC- Chicago Section, 1986.
Often a balance is sought in incorporation of internal and external lubrication because several end-product physical properties are adversely affected by over- or under lubrication. It is generally understood that under-lubrication of polyvinyl halide results in shortened time until degradation ensues, beginning with premature fusion and rapid viscosity rise followed by degradation and discoloration. Over-lubrication is often associated with less than optimal fusion and work level imparted to the mass, thus resulting in poor tensile and impact strength, under these circumstances. ~
:, :;::
An extensive art for lubrication of PVC has been previously published. U.S. Patent No. 4,824,583, for ;~
example teaches the lubrication of rigid PVC with a combination of saponified triglyceride, and oxidized polyolefin. The desired effects are seen in the comparison of the extent of discoloration after time at -~
190C melt processing. Absent is a teaching to the effect of this lubricant system on surface gloss or resulting physical properties of the compound. Optimization of these properties takes on greater importance assuming that -~
processing conditions do not entail discoloration by over~
1 30 working the compound. That is, within a reasonable processing window for any given compound, it is important to determine the effect of the lubrication system on ~, - 3 ~
physical properties. The extent of extended work capability is only one aspect evidencing the safety margin to be expected in processing a given compound.
U.S. patent No. 4,481,324 is a detailed teaching on the nature of polyglycerol structure on lubrication of PVC.
The focus is on processing stability and gloss effects imparted by adjusting the internal/external lubricating mechanism via the degree of polymeriæation (Dp), the degree of esterification (n) and carbon chain length (Cx) of the ester group. External lubricants (higher Dp, "n", and Cx) are characterized by migration to the metal-polymer interface in processing, generally yielding surface gloss while delaying fusion according to amount used. ~his is contrasted with internal, more polymer soluble lubricants, for example glycerol monostearate. According to the empirical data of U.S '324, glycerol monostearate exhibits a relatively short fusion time of 6 minutes under the controlled Brabender fusion test, and would not contribute to surface gloss enhancement. Moreover, fusion time is not affected by an increase in amount of glycerol monostearate used. The inventive lubricants of U.S. '324 are those exhibiting higher dynamic stability time (DTS) and higher gloss, that is, di-glycerol- mono, di and tri ester of C12 I to C20 acid.
The study of lubrication per se in simple compounds of polyvinyl halide does not reveal a complete picture additionally because commercial compounds must contain a variety of other ingredients. Each ingredient imparts first order and second order effects. Process aids, impact modifiers and pigments have a drastic effect on overall properties, and lubrication with these components present -must be adapted, there being no predictable rules or extrapolations available for the practitioner. Moreover, stabilizers, lubricant systems, pigments and impact modifiers often create interferences with each other in attaining an acceptable balance of the critical properties in modified PVC compounds. Thus, one impact, lubricant or stabilizer system individually optimized does not suggest the best combination nor is predictive of successful utilization in a PVC compound. The best balance in all three critical performance attributes- processibility, gloss and physical properties are desired. In as much as high surface gloss, high processibility and good physical properties in the best balance are desired, extensive studies aimed at this objective have been undertaken with the result that particular preferred lubricant, impact and pigmentation systems have been found which impart a superior balance of gloss, processing stability, impact strength, and HDT.
~UMMARY OF T~E INVENTION
¦ 20 In one aspect, this invention is directed to high gloss polyvinyl halide compounds. The object of the invention is the maximization of surface gloss, impact strength and processing stability for extruded or molded compounds by the incorporation of additive systems disclosed hereinbelow. These aspects are generally achieved for a polyvinyl chloride compound comprising from 0.01 to 10 phr ~ ~;
,~
7 ~ J ~
each of: glycerol monostearate, fatty salt, hydrocarbon, and a fatty acid in specified amounts to provide high gloss, gloss retention, processibility and physical properties. The preferred embodiments are further limited by: the amount of impact modifier, optional rutile titanium dioxide, an absence of mineral wax lubricant, epoxidized material and less than about 2 parts each per hundred parts polyvinyl halide (phr) of carboxylic salt, and monoester of glycerol. The compounds of this invention are rigid and exhibit an HDT under a 66 psi load of at least 60C and exhibit an improved balance of variable height impact strength (VHIT), room temperature Izod, -40C Izod impact strength and dynamic process stability (DTS).
DE~TAII.ED DESCRIPTION
In general, the components of the compounds of the present invention are polyvinyl halide, stabilizer, impact modifier, a lubricant system and optional ingredients such as pi~nent, filler, and colorant, etc., each specified herein. In particular, the preferred embodiment of the invention comprises in a specified amount polyvinyl chloride homopolymer, an acrylic impact modifier, an MBS
impact modifier, a tin stabilizer, epoxidized vegetable oil, mineral oil, a long chain carboxylic acid, a metal salt of a long chain carboxylic acid, and an alkyl ester of an alkyl polyol, preferably a mono -C16 to C18- ester of glycerol. Preferred optional components are coated titanium dioxide, and polymeric acrylic processing aid.
Rigid compounds of this invention are distinguished from non-rigid compounds. Rigid compounds of this - 30 invention conform to the definition of ASTM-D883 for rigid -::
plastics that have a modulus of elasticity, either in flexure or in tension, greater than 700 Mpa (100,000 psi) at 23C and 50% relative humidity when tested in accordance with either ASTM Method D747 - Test for Stiffness of -Plastics by Means of a Cantilever Beam, ASTM Method D790 -Test for Flexural Properties of Plastics and Electrical Insulating Materials, ASTM Method D638 - Test for Tensile Properties of Plastics, or ASTM Method D882 - Test for Tensile Properties of Thin Plastic Sheeting tlg83).
The term polyvinyl halide used herein means polyvinyl fluoride, polyvinyl chloride, polyvinylidene chloride halogenated derivatives thereof and mixtures. These are homopolymers or copolymers, and well known and commercially available worldwide. Polyvinyl chloride polymers conte~plated for use in the present invention include those prepared in a variety of ways. PVC polymers can be prepared by polymerization methods including: mass, suspension, dispersion, and emulsion processes. A mass process is described in U.S. Patent No. 3,522,227. A phase inversion process may also be used and is disclosed in U.S.
Patent No. 3,706,722. A useful skinless, suspension PVC
resin is taught in U.S. Patent No. 4,711,908, in particular example 4 in that disclosure. The preparation of porous, skinless, crosslinked PVC resin can be prepared with the 25 direction of U.S. Patent No. 4,755,699, with particular reference to example 1 of that disclosure. PVC resins used herein are preferably those made by suspension or mass processes. Suspension or mass PVC resins used herein are - particulate homopolymer or rigid copolymer resin having a 30 particle size average ranging from ~bout 70 microns to 250 micron~.
Suitable comonomers that vinyl fluoride and polyvinylidene chloride may be included in minor amounts in the vinyl chloride polymer(s) are the olefins, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, ~-cyanoacrylic acid, and the like; esters of acrylic acid, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyanoethyl acrylate, hydroxethyl acrylate and the like; vinyl esters such as vinyl acetate and vinyl propionate; esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, and the like; nitriles, such as acrylonitrile and methacrylonitrile; acrylamides, such as methyl acrylamide, N-methylol acrylamide, N-butoxy 1 15 methacrylamide, and the like; halogen containing vinyl I monomers such as vinyl fluoride, vinylidene chloride, 1,2 -dichoroethylene, vinylidene fluoride, vinylidene and vinyl bromide; vinyl ethers such as ethylvinyl ether, chloroethyl vinyl ether and the like; the vinyl ketones, styrene and styrene derivatives including ~-methyl styrene, vinyl toluene, chlorostyrene; vinyl naphthalene; cross-linking monomers such as diallyl phthalate, trimethylol propane triacrylate, allyl methacrylate and the like; allyl and vinyl chloroacetate, vinyl pyridine, and methyl vinyl ketone; and any copolymerizable monomers or mixtures of monomers having suitable reactivity ratios with vinyl chloride and known to those skilled in the art.
Particularly preferred are non-crosslinked polyvinyl chloride homopolymer resins substantially free of gel particles.
The inherent viscosity (I.V.) (ASTM D-1243) of polyvinyl chloride used in this invention generally ranges `~
' - 8 ~
from about 0.2 to about 4.0, with a preferred I.V. range of from about 0.35 to about 1.2 and a more preferred I.V.
range of from about 0.5 to about 0.95. A combination of ~ -PVC polymers each having a different average molecular weight should be avoided to the extent that gloss is significantly reduced. The more preferred I.V. range is from 0.5 to 0.95, with the most preferred range from 0.52 to 0.80.
HDT modifiers may also be employed. These can be copolymers comprising a monomer of the formula:
Rl--C = CH2 ~ R2 (I) [R3]X
wherein X is 0, or 1, the non-substituted ring carbons are bonded to hydrogen, R1 is hydrogen, C1-C22 alkyl or halo Cl-C22 alkyl; R2 and R3 are independently hydrogen, Cl-C22 alkyl, halo (Cl-C22) alkyl, or C1-C22 substituted alkyl.
The term copolymer refers generally to a polymer containing two or more than two monomers, one of which is defined by (I). Copolymers comprise (I) copolymerized with other comonomers. Other comonomers include acrylates, methacrylates, like methylmethacrylate (II), acrylonitrile (III), methacrylonitrile, ~-chloroacrylonitrile, ethacrylonitrile, anhydrides such as maleic anhydride, N- :
substituted maleimide and styrene (IV). A combination of more than one species of I can be combined to comprise the monomer composition of the HDT modifier. Specific examples include a copolymer selected from the group consisting of I/II, I/III, I/IV, I/II/III, I/II/IV, I/III/IV, I/II/III/IV, and graft copolymers of either I/II, I/II/III, ~ .
I/II/IV, I/III, I/IV, I/III/IV graft polymerized on a rubbery polydiene, polyacrylate; alpha olefin copolymer, EPDM rubber, or butyl rubber or mixture thereof. Preferred are copolymers containing from about 50% by weight to about 95% by weight of (I).
Polyimide HD~ modifiers for use herein include polyimides, copolymers of vinyl aromatic and imide derivatives of an ethylenic unsaturated dicarboxylic acid such as a copolymer of alpha methyl styrene-styrene-N-cyclohexyl maleimide, also included are imidized polymethylmethacrylate, imidized styrene-maleic anhydride copolymer, acrylic-imide copolymer, polyglutarimide, polyitaconamide, and the like. Polyimide HDT modifiers also include copolymers derived from a comonomer of N-substituted maleimide expressed by the general formula:
1l CH C
N -R
CH- C
~ 20 0 ¦ wherein R is hydrogen, a non-substituted or substituted hydrocarbon group, cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group, any of these having from 4 to 20 carbon atoms. Examples of R include t-butyl, cyclohexyl, phenyl, 2-chlorophenyl, benzyl, 2-methyl phenyl, 2-ethyl phenyl, 2,6-dichlorophenyl, 2,6-diethyl phenyl, and the like. The most preferred imide HDT
modifiers are imidized polymethylmethacrylate. Examples of the preparation o polyimides are described by Kopchik, U.S. Patent No. 4,246,374, and Schroder, et al. U.S.
Patent No. 3,284,425. Imidized PMMA is commercially av~ilable from the Rohm and ~aas Company under the trade . .- ~,, ' ~
names of Paraloid~ HT-510, Paraloid~ EXL-4151, Paraloid~
EXL-4171, Paraloid~ EXL-4241 and Paraloid~ EXL-4261. In general, the degree of imidization can rànge from about 10 to 80 percent, preferably from 20 to about 60 percent.
Other heat distortion modifiers useful herein include post chlorinated polyvinyl chloride, polycarbonate, halogenated polycarbonate, polysulfones, polyesters, and polyacrylates.
Generally, the PVC compounds herein will contain a thermal stabilizer. The preferred thermal stabilizer system emplcyed herewith is a combination of tin compound and a co-stabilizer. The organotins are preferred tin compounds and include dimethyl tin-bis isooctylthioglycolate (methyltin), di-butyltin-bis-isooctylthioglycolate (butyltin), octyltin-bis isooctylthioglycolate, dialkyl tin di-carboxylates, methyltin mercaptides, butyltin mercaptides, dialkyl tin bis(alkyl mercaptocarboxylate) including di-n-octyltin-S,S'-bis(isooctyl mercaptoacetate), and butylthiostannoic acid, and mixtures thereof. Any alkylated tin having features such as low toxicity e.g. higher alkyl types, FDA
approval, USP class 6 approval, good color, clarity and compatibility, low plate-out on equipment, and non-staining properties are desirable and preferred for use in this invention. The more preferred stabilizer system of a tin compound and epoxide co-stabilizer can contain any other stabilizers such as derivatives of barium, cadmium, zinc, antimony or lead containing heat stabilizers.
Co-stabilizers may be employed for example, phosphite stabilizers, polymeric phosphites, thioesters such as dilauryl thiodipropionate, beta-diketones and epoxy derivatives. Co-stabilizer may be present at from 0.1 to lo weight parts, preferably from 0.3 to about 5 phr, and most preferably from 1.0 to 4.0 weight parts per 100 weight parts combined of PVC and HDT modifier (phr). The preferable costabilizer is an epoxy material.
Antioxidants are optionally present and include the various hindered alkylated phenolics such as 2,6-di-t-butyl-4-methyl phenol also referred to as butylated hydroxy toluene, bis-phenols such as 2,2'-methylenebis(4-methyl-6-t-butylphenol~, thio-phenols such as 4,4'-dihydroxydiphenyl sulfide, otherwise referred to as thiodiphenol, and di-phenyl ethers such as 4,4'-dihydroxydiphenyl ether, and mixtures thereof. When used, antioxidants are generally present in an amount from about 0.05 to 5 parts per hundred weight parts PVC and pre~erably at from 0.1 to 1.0 phr.
Preferred antioxidants are those having acceptability under applicable FDA regulations.
Polymeric impact modifiers may be present. Post-chlorinated polyethylene is an exemplary po~ymeric impact modifier. CPE is obtained from the chlorination of polyethylene having a density (ASTM-D1505-57T) of from about 0.91 to about 0.98 gram/cc. at 25C., a melting point usually in the range of from about ~OO~C to 130C., and melt index (according to ASTM-D1238-57T) above about 0.05, more preferably in the range from about 0.05 to about 20.
A method of preparing such a CPE material is more fully described in U.S. Patent 3,299,182. Suitable embodiments are commercially available from Dow Chemical Inc., or E.I.
DuPont deNemours, Inc. CPE materials generally contain from about 5% to about 50% wt. of combined chlorine. Those containing from about 25% to about 40% wt. of combined chlorine are preferred with PVC, and those containing from about 32% to about 38% chlorine are most preferred.
The preferred impact modifier comprises an MBS type optionally with an acrylic type. The principal embodiments of MBS types are copolymers of methylmethacrylate, butadiene, and styrene. Acrylonitrile may also be present (MABS). Preferred impact modifiers generally contain a rubbery core component, the particulars of this core being beyond the scope of the invention. Various preferred core embodiments include polymers derived from 1,3-butadiene, isoprene, acrylates, olefins, styrene, or mixtures so long as the core polymer exhibits a Tq of less than zero.
Preferably the Tg of the rubbery core polymer is below -30C. The rubbery rore polymer is preferably present inthe polymerization of the shell comprising styrene and ! methyl methacrylate. Commercial embodiments of MBS include Paraloid~ XM-653 and BTA-733 from Rohm and Haas, Inc., and Kane-Ace~ B-56 and B-22 available from Kanegafuchi, Inc. A
combination of two acrylic impact modifiers, the minor proportion being one containing a diene component and the major proportion being one without a diene component is most preferred. Both MBS and acrylic type polymeric impact modifiers can also referred to as multi-stage polymers. A
commercially available diene containing acrylic is ~ Durastrength~ 200 from Atochem North America, Inc. Non-!1' diene containing versions are Paraloid~ KM-330 or KM-334 from Rohm and Haas, Inc. The total amount of impact modifier present is from 0 to 30 weight parts preferably from 5 to less than 25 phr, and most preferably from lO to about 20 phr. Total MBS and acrylic impact modifier are -~ each present at ., ..
, ;, "A
';,~, - 13 - ~ . J L~ ~ ~
preferably 0 to 15 phr, more preferably 4 to 12 phr, and most preferably 5 to 10 phr.
The essential lubricants used in the present invention comprise a long chain carboxylic acid, a metal salt of a long chain carboxylic acid, an alkyl ester of an alkyl polyol, and a hydrocarbon. The carboxylic acids include C6-C24 carboxylic acids like undecylic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, behenic acid, chlorocaproic acid, hydroxy capric acid, hydroxy stearic acids and the like. Preferred are Cl6-Cl8 carboxylic acids like stearic acid.
The long chain carboxylic acids are employed at from 0.01 phr to about 10 phr, preferably the carboxylic acids are employed at from 0.1 phr to about 5 phr, more preferably from 0.2 to 2 phr and most preferably from 0.5 phr to about 1.1 phr.
The metal salts of long chain aliphatic carboxylic acids are sometimes referred to as metal carboxylate soaps. ~ -~
Metal carboxylate soaps include calcium, lithium, magnesium and zinc salts of C8 to C30 carboxylic acids. The calcium salts are preferred, with calcium salts of Cl6 to C18 carboxylic acids more preferred such as calcium stearate.
A metal carboxylate salt is preferably employed at from 0.01 to about 10 phr, preferably from 0.2 to 5 phr, more preferably 0.5 to 2.5 phr, and most preferably from 1.0 to 2.0 phr.
The alkyl esters of alkyl polyols include glycol esters and glycerol esters like ethylene glycol ester and - 30 propylene glycol ester. Also included are oligomeric 3 ~ 3 glycol esters or oligo-glycerol esters. Specific examples include glycerol mono 2-ethylhexanoate, diglycerol monostearate, triglycerol mono stearate, a polyglycerol ester of a C8 to C22 carboxylic acid such as hexaglycerol 5 mono stearate, hexaglycerol distearate, or any of the glycerol, diglycerol, triglycerol or polyglycerol partial esters of oleic acid. Preferred are the esters derived from the reaction of glycerol and a C16 to C18 carboxylic acid, with more preferred versions being mono-C16 to C18 10 esters of glycerol such as glycerol monostearate (GMS).
The esters of alkyl polyols are available commercially from Henkel Int., Inc. The alkyl polyol esters are employed at from 0.1 phr to 10 phr generally, preferably from 0.2 to 5, more preferably from 0.3 to 2.0 phr and most preferably 15 from 0.5 to 1.3 phr.
The hydrocarbon or derivative of hydrocarbon used herein in combination with other components include paraffins such as paraffin oils and mineral oils, microcrystalline wax, paraffin wax, and low molecular 20 weight polyolefin such as polyethylene wax, either in liquid, powder or flakes. These are commercially available from Sonneborn Division of Witco Chem. Co., Inc., Penreco Inc., Union Oil Co., Inc., and Frank B. Cross, Co., Inc Mineral oil is the preferred hydrocarbon. The hydrocarbon 25 is employed at from 0.1 to 10 phr, preferably 0.2 to 5 phr, more preferably from 0.5 to 3 phr and most preferably from 1.0 to 2.0 phr.
Optional lubricating components include epoxide materials like epoxidized oils, epoxidized linseed oil, 30 epoxidized tall oil, epoxidized soy oil, and epoxy derivatives of bisphenol A, for example, the reaction 3 . .:
product of epichlorohydrin and bisphenol-A. Generally as liquids or meltable solids, epoxy materials include dig~lycidylether of bisphenol A, having molecular weight above about 370. A variety of commercial sources for epoxy containing materials is listed in Chemical Week Buyers' Guide, October, 1990. Epoxy resins are availablP
under the Epon~ trademark of Shell Chemical Co., Inc. The most preferred epoxide containing materials are the epoxidized oils like epoxidized soybean oil (ESO) and epoxidized linseed oil. The epoxy materials are used at from O.1 to 10 phr, more preferably at 1 to 6 phr and most preferably at from 1 to 4 phr.
The chemically modified waxes and mineral waxes are most preferably avoided. These include montan wax, and montan ester waxes which may be mixtures of long chain acids, long chain esters and resinous portions. Reference i5 made to Kirk-Othmer Encvclopedia of Chemical TechnolooY, Wiley Interscience, Vol. 23, 1978, Pg. 471. Montan ester wax is available from Hoechst-Celanese Inc.
. ~
The above specified ranges of amounts of each component in the invention is expressed in terms of weight parts of the component per 100 weight parts of PVC (phr).
The range of optional lubricant components is the same as specified above.
There is an optimal total amount of lubricant beyond which there are negative effects on HDT and impact strength. Generally the lubricant system compri6es a total ~ of about 1 to 10 phr of the above components, preferably ??1 from 3 to about 8 phr total and more preferably from about ~ 30 3.5 up to 7 phr and most preferably from about 3.5 to about ~? : .
" ' '~
?,,ijG . ., ~
J ~
6.2 phr. The precise total amount of lubricant desired will depend on *he I.V. of the PVC present. Generally, a lesser total amount of lubricant is required when lubricating a PVC having an I.Y. less than about 0.6.
Whereas, when lubricating a PVC of I.V. 0.6 or higher, relatively higher amounts of lubricating ingredients are suggested. Several combinations are suggested herein within practical ranges. Optimization of particular individual formulations is beyond the scope of the present invention, and can be achieved by one skilled in the art after reasonable trial and error.
At least one optional plasticizer may be included in a minor amount ranging from 0.1 t~ about 10 phr, preferably from 1 to 5 phr, the upper limit otherwise controlled by not allowing the flexural modulus to drop below 100,000 psi. Specific examples of plasticizers include carboxylic acid esters such as the various esters of adipic acid, azelaic acid, phthalic acid, benzoic acid, citric acid, isobutyric acid, isophthalic acid, sebacic acid, isosebacic acid, stearic acid, tartaric acid, oleic acid, succinic acid, phosphori~ acid, terephthalic acid, trimellitic acid, and mixtures. Other plasticizers include for example, partial esters of the above carboxylic acids, ethers, glycol and pentaerythritol derivatives, glycolates and glycerol derivatives. These are set forth in The Technoloav of Plasticizers, by Sears and Darby, pages 893-1085, John Wiley & Sons, New York, 1982. Preferred plasticizers are C4 and higher alkyl diesters of phthalic acid, such as di-2-ethylhexyl phthalate, and di-3C isodecylphthalate bisphthalates, C8 and higher alkyltriesters of trimellitic acid such as tri-octyltrimellitate (TOTM). Various polymeric plasticizers can also be utilized such as the polyesters, polyolefins, polyepichlorohydrins, polya¢rylates, ethylene copolymers, and copolymers prepared from di- and monoolefins.
Polyester plasticizers are generally made from a dicarboxylic acid having from about 3 to about 12 carbon atoms and from a diol having from about 2 to about lOOO ~-carbon atoms with propylene glycol being preferred.
Examples of suitable polyesters include various esters made from adipic acid such as a polyester having a molecular weight of 6,000, e.g., Paraplex0 G-40, a polyester made from adipic acid having a molecular weight of about 2,200, Paraplex0 G-50, a polyester made from adipic acid having a molecular weight of about 3,300, Paraplex0 G-54, a polyester made from azelaic acid having a molecular weight of about 2,200, Plastolein0 975, a polyester made from sebacic acid such as Paraplex0 G-25, a polyester made from glutaric acid, a polycaprolactone polyester, and the like.
Paraplex is a trademark of C.P. Hall Co. and Plastolein i8 -a trademark of Emery Industries, Inc. Plasticizer is preferably avoided to achieve higher HDT. For semi-rigid -~
compound a small a~ount is preferred.
:' ~
The PVC compounds disclosed herein will typically contain optional additives such as: pigments, blowing agents, coupling agents, processing aids, fillers, antistatic agents, anti-fogging agents, flame retardants, smoke suppressants, colorants all of which are commercially available and partially listed in Modern Plastics ~ -;
EncycloDedia 1988 published by McGraw Hill Co. ~-Exemplary antistats are commercially available under the Glycolube0 trademark of Lonza Corp. An exemplary ~:
::
- 18 ~
antifogging agent includes the alkyl phenol ethoxylates as for example those commercially available under the Surfonic trademark of Texaco, Inc~
Adjustment of melt viscosity can be achieved as well as increasing melt strength by employing process aids such as those containing polyacrylates. It has been found that these do not interfere with gloss at useful levels.
Exemplary processing aids are copolymers of polymethylmethacrylate. Paraloid~ X-120ND, K-120N, K-175 from Rohm and Haas, Inc. are a few examples. Reference to others is found in The Plastics and Rubber Institute:
International Conference on PVC PrQcessin~, April 26-28 (1983), Paper No. 17.
Fillers are optional and include clay, barytes, calcium carbonate, talc, mica, silica, aluminum trihydrate, dolomite and fiber reinforcement such as carbon, glass and boron fibers. Where used, calcium carbonate which has a particle sizes average of from 0.02 to 1.0 micron, preferably 0.02 to 1.0 micron and is treated with from ~ about 1% to 5% by weight of fatty acid is preferred. The ¦ precipitated calcium carbonates having these features are available from Pfizer Minerals, Inc. under the Ultraflex~
trademark. Preferable levels of fillers are 0 to 10 phr, more preferably 0 to 5 phr, and most preferably zero.
Exemplary opacifying pigments include titanium dioxide, preferably rutile grades. Rutile grades can be - surface coated with ingredients such as silica, zirconia, alumina, or other minerals, including combinations of these. The extent of coating is in a range of fro~ about 2% to about 99% surface ~rea coverage. Zinc co~ted ~iO2 ,~ ~
~;
should be avoided as it induces degradation with PVC. An -example of uncoated Tio2 is designated R-100 from E.I.
DuPont de Nemours. An example of lightly coated Tio2 is Tioxide~ RFC-6 from Tioxide of Canada Ltd. and contains a combination of zirconia and silica coatings. More preferred Tio2 grades are coated, for example, with from 90 % to 99.99 % of the surface covered with silica may also be used. Commercial versions include Tipure0R-960 from E.I.
DuPont de Nemours, Inc., and Zopaque0 RCL-6 from SCM
Corporation.
The impact performance levels preferred are a room temperature notched IZOD of at least above about 2 ft.-lbs/in. (of notch) and more preferably at least 4 ft.-lbs./in. The Preferred notched Izod impact properties at -40 achieved were greater than 1.0 ft.-lbs./in. and more preferred embodiments greater than 2 ft.-lbs./in. The most preferred embodiments achieved a notched Izod at -40~C
of greater than 4 ft.-lbs./in. of notched, with some examples below having greater than 6 ft.-lbs./in. of notch.
The preferred compositions exhibited a Brabender dynamic -thermal stability time at 200C and 50 rpm with a No. 5 mixing head of at least 20 minutes with the more preferred embodiments exhibiting a DTS time of 25 or more minutes and the most preferred embodiments achieved a DTS time of 30 minutes or more. Compounds of the present invention in the fused state exhibit an HDT at 66 psi of at least 58C, more preferably 60C and most preferably at least 64C. It is possible with the compositions to include an amount of heat distortion modifier to raise the HDT preferably at least 3C higher. Useful HDT modifiers including the aforementioned copolymers of alpha methyl styrene, styrene-acrylonitrile copolymers, imidized acrylic polymer, polycarbonate, halogenated polycarbonate, styrene maleic r~
~ 20 ~
anhydride copolymers, and the like may be employed to raise HDT.
The invention will be better appreciated by the following examples in which comparisons are made between examples not a subject of this invention with those which exemplify the improvements of this invention. All amounts of ingredients are shown in weight parts. The following ASTM test procedures were used in evaluation the performan¢e parameters measured.
Pro~erty Test Notched IZOD Impact Strength ASTM-D256 Heat Distortion ~emp.* ASTM-D648 Inherent Viscosity ASTM-D1243 Dynamic Thermal Stability Brabender Plasticorder~
(DTS) Gloss at 60 Glossgard0 II glossmeter A~ 66 F6i on unanncalcd compre~sion molded plaques : ' The compounds of the present invention can be utilized in melt forming processes such as, for example, injection molding, extrusion, co-extrusion, thermoforming, lamination, compression molding, calendering, and the like, including uses for a capping layer in a co-extr~sion or lamination of sheet or profile such as a capping layer on a substrate in the form of a layer of the compound in the fused state in intimate contact with a substrate selected from the group consisting of metal, wood, a thermoset article, and a thermoplastic article.
Specific articles derived from the invention include sheeting for thermoforming of shower stalls, wall panels, bathtubs, tub enclosures, refrigerator panels cabinetry and '.,, '~ 8 the like, doors, vertical and horizontal blinds, sporting equipment, automotive components, appliance components, components used in molded parts for boats, housewares, plumbing ware, signs and business machine housings. Thus, the present invention has extended the useful range of applications for polyvinyl halide-based thermoplastic articles where the improved combination of properties are needed and where it is desirable to combine the compo~nd with a substrate for improved asthetics and economy.
The DTS test measures the time-torque relationship at selected temperatures using an instrument such as the Brabender Plasticorder0. Model EPL-V30Z is a suitable model. The test value generally reported and u.sed for comparison is the 'IDTS time". DTS time is defined as the -time elapsed from the time the rotors are turned on in the presence of the sample, including the time the instrument torque falls to its minimum value, up to the point where torque has risen about 50 to lO0 meter-grams from the minimum. This time is limited by the stability limits of the composition under shear. DTS time is dependent on inherent polymer properties, but also on temperature, sample ~ize, compound formulation, instrument operating conditions, degree of instrument maintenance, and other conditions. In the examples below, DTS was run using a no.
5 mixing head, with a bowl temperature of 400F, other conditions controlled to provide for accurate comparisons.
The preferred compounds of this invention surprisingly gave a DTS time at 400F (204 C) of at least 20 minutes, more preferred embodiments gave 25 minutes or higher. This was achieved while at the same time, the preferred compounds exhibited excellent impact strength. The occurrence of a - boost in both gloss and impact strength properties was - ~.
',3 unexpected and defied the expected trend based on the conventional understanding of lubrication interferences with impact strength achievement.
VARIABLE HEIGHT IMPACT STRENGTH
Variable Height Impact Test. A weight (typically 8 lbs.) is placed in a cylindrical tube and a conical dart (typically with a 1/8" diameter tip) is attached to the bottom of the weight. The sample is placed below the cylinder and the weight with dart attached is dropped, while contained by the cylinder, onto the sample. The height of the weight is increased until the dart puncture area show a failure ttypically when a crack appears in the impacted area and light can be clearly seen through the crack). The height of the weight is then lowered incrementally until the impacted points pass the test (when no crack through which light can be seen is made). The height is then increased again until a failure occurs and I then decreased until a pass occurs. Typically 9 to 16 ¦ impacts are made per test. The height (of the dart above the sample) at which 50% of the time a pass occurs is taken as the value to be used to calculate the average impact strength. This value is the weight times the height and is usually reported in inch-pounds. The inch-pounds are then divided by the average thickness of the sample (here approximately 20 mils. a mil = 0.001 inch~ and the final value is reported as inch-pounds per mil.
- I.V. - INHERENT VISCOSITY (ASTM-D1243) The inherent viscosity is measured for PVC using cyclohexanone as the solvent. The polymer is dissolved in ~ ' ' :
~j ~1 .
2 ~
the solvent at a concentration of 0.2 gram per 100 mls. of cyclohexanone at 90C for 90 minutes and then measured with a viscometer in a water bath at 30C.
S The compounds listed in table A below were prepared by hand mixing the components in a Henschel high intensity powder mixer to form a uniform powder blend. The powder blend was banded on a heated r~ll mill until well fused.
The temperature of the material on the mill was approximately 379F. Sheets were removed from the mill and compression molded into plaques used for physical testing.
A portion of the sheets taken from the mill were also cubed ~ and cubes were used for measurement of DTS. The cubes were ¦ extruded on a laboratory sized Brabender extruder using a 4 " X 0.020 " strip die to prepare samples for 60 gloss measurement and VHIT testing. In each compound 100 weight parts of polyvinyl chloride homopolymer having an I.V. of 0.68 was used. Two weight parts of tin stabilizer and -eight parts acrylic impact modifier stabilizer (2 parts of one containing a diene component and 6 parts of one absent a diene component) was included in each example except for ~ example 22 which contained only two parts of acrylic impact 3 modifier. The remaining components in each example are listed in table A on the basis of weight parts. Table B
illustrates the properties obtained from the compression ~ molded plaques made from the milled sheets. A least two c gloss measurements were obtained from each extruded 4" wide strip and averaged if different. Gloss measurements were ;~ obtained at 60 using a Gardner Glossgard II gloss meter supplied from Pacific Scientific, Inc. The gloss readings using this method and taken directly from the extruded ., . . .
';`
. j; . .
~la~
compounds with out further polishing yield preferably a gloss of at least 40%, more preferably 50% and most preferably greater than 55~ for the compounds of the invention.
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It can be seen from table A the effect on gloss of the lubricant system. Example 1 contains a combination of acrylic and MBS impact modifier and a preferred lubricant system containing ES0, Ca stearate, GMS, mineral oil and stearic acid. The gloss is high at 58.6. Example 6 confirms the high glo55 using this system. Example 1 was extruded on a sheet extrusion device. The sheet was measured for initial gloss before thermoforming. The draw ratio of initial to drawn thickness was 2:1. There was ~ -~
lo surprisingly no loss in gloss measured at the region which was drawn at the 2:1 ratio.
In commercial practices of sheet forming, typically a polishing stack is used and gloss is enhanced to a level of greater than 70 and preferably qreater than 80. The lS preferred embodiments of the invention can be polished in this manner and will typically exhibit a gloss of 80 or I higher and will lose less than 10% of the initial polished ¦ gloss when drawn at least 2:1 during thermofor~ing. It is recognized in the art that one can expect at least a 20%
gloss reduction after thermoforming. In one thermoforming run the compound in sheet form was polished to a gloss of 85. A 145 mil sheet was drawn by thermofor~ing. Quite unexpectedly, the gloss measured at a point having thickness of 70-75 mils, correspondinq to a 2:1 draw ratio, was 85.
Example 2 illustrates the loss of some gloss by ~ eliminating ES0; example 3 shows reduction in gloss on 3 elimination of mineral oil; example 4 shows reduction in 3 gloss on elimination of Ca stearate; example 5 with GMS
(ester of polyol) eliminated, a likewise reduction; example 7 is absent carboxylic acid and gloss is reduced; example 8 ., ~
':
' -:
,;, ib ~ L;~
is absent both ESO and mineral oil, however noting in table B that DTS is reduced to 21 minutes and gloss was lower than example one. Higher DTS is preferred. Example 9 illustrates a gain in DTS on addition of ESO.
Gloss is reduced on elimination of GMS and mineral oil as example 10 illustrates. Elimination of both ES0 and GMS
in example 11 shows reduced gloss and significantly lower DTS (19 min.). Elimination of mineral oil and stearic acid caused reduced gloss and reduced -40c Izod as shown in example 12. Gloss ranged from about 36 to about 44 for examples 13-16 wherein calcium stearate and at least one other preferred lubricant was eliminated. The use of ES0 shows in examples 13 and 15 versus 14 and 16 a recovery in DTS, however, low temperature impact is not as good without carboxylate salt. Gloss is also reduced in example 17 when GMS and mineral oil are absent.
Example 23 illustrates that high gloss can be obtained (64.5) with the elimination of MBS impact modifier, however it is noted the drastic lowering of -40C Izod impact.
3 . ~
Example 22 illustrates the elimination of the six parts of acrylic impact modifier and is comparable to example 1 which contains eight parts of acrylic impact modifier. The same lubrication system is used however, example 22 has lower gloss and significantly lower -40C
impact.
Examples 19, 20 and 21 have no polyol ester, no carboxylate salt and no ESO. Examples 20 and 21 have only one component of lubricant system, namely, mineral oil, and stearic acid, respectively. The gloss is reduced and -40C
impact is low. Examples 19-21 have unacceptable DTS times of 13, 14 and 9.5 minutes.
Examples 24 - 28 illustrate poor DTS time when at ¦ least one lubricant of the invention is missing, as well as ~ 15 the negative effects on gloss and -40C Izod.
I
Example 30 is comparable to example 1 to show the significant loss in gloss with the use of montan wax which is a mineral wax. Example 30 had a 37.4 gloss rating with the use of 1.0 phr montan wax, but the gloss rating ~ 20 increased when montan wax was eliminated and stearic acid ¦ was used in a preferred amount.
The data of example 31 shows that there is obtained, good gloss with the use of a relatively higher level of GMS
and carboxylic acid, however this leads to reduced -40C
impact strength.
.-:
Example 29 is comparable with example 1 except for the use of 10 phr CaCO3 filler. The data shows that DTS, glo~s ','~'~ '-; :
. "~
~:
,,:
C~
and notched Izod impact strength are reduced with the use of filler.
5~, . : , , . , '''' :,,: ,~,' ': '' '' , : ', ' B~amples 32- 7 The examples below illustrate the effect on gloss of various Tio2 embodiments. These compounds listed in table C were prepared similarly to the previous examples except for hand mixing of the powder compound. The following base compound is included in Examples 32-37:
PVC (I.V. 0.68)100 Acrylic Process aid 2 Acrylic Impact Modifier 2 *
Stabilizer 2 Ca Stearate 1.5 GMS
Mineral Oil 1.5 Stearic Acid 0.8 * DurastrengthR 200, ex. Atochemie , ., In addition to the above weight parts of ingredients, Examples 32-37 contain the following:
EXANPL~
~BLE C ~ 9 I
Acrylic Impact Mod~ - 6 Acrylic Impact Mod2 6 6 6 6 6 , MBS Impact Mod. (A)3 8 8 ~ 8 8 8 il MBS Impact Mod.(B)4 - - 8 Tio2 (A) 5 4.5 - 4.5 _ _ 4.5 Tio2 (B) 6 - 4.5 - - - - ~
Tio2 (C) 7 - - - 4.5 Tio2 (D) 8 - _ _ _ 4.5 1 RM-334 ex. Rohm and Haas, Inc.
2 KM-330 ex. Rohm and Haa~, Inc.
3 KM-653 ex. Rolun and ~3aas, Irlc.
4 BTA-733 ex. Rohm and Haa~, Inc.
5 uncoated TiO : ~-100, ex. DuPont 6 non-chalking, coated TiO : R-FC-6, ex. Tioxide of Canada 7 non-chalking, coated Tio: R-960 ex. DuPont 8 non-chalking, coated TiO : 2CL-6 ex. SCM Chemical The above compou~ds were measured for 60 gloss with the following results:
~xample 32 33 . 34 35 36 37 60 gloss 79.9 80.6 80.1 87. 3 86.1 82.1 DTS (Min) 33.5 36.5 34.5 35 33 32 ~' :~
,~
2 ~
The above examples 32-37 also exhibited an HDT at 66 psi of at least 66C, and room temperature notched Izod impact strength of at least 16 ft.-lbs./in.
Noting the above gloss measurements, it can now be appreciated that the above compounds have a good balance of desirable properties. Especially good gloss was obtained with the use of heavily coated Tio2 and is preferred.
PVC (I.V. 0.68)100 Acrylic Process aid 2 Acrylic Impact Modifier 2 *
Stabilizer 2 Ca Stearate 1.5 GMS
Mineral Oil 1.5 Stearic Acid 0.8 * DurastrengthR 200, ex. Atochemie , ., In addition to the above weight parts of ingredients, Examples 32-37 contain the following:
EXANPL~
~BLE C ~ 9 I
Acrylic Impact Mod~ - 6 Acrylic Impact Mod2 6 6 6 6 6 , MBS Impact Mod. (A)3 8 8 ~ 8 8 8 il MBS Impact Mod.(B)4 - - 8 Tio2 (A) 5 4.5 - 4.5 _ _ 4.5 Tio2 (B) 6 - 4.5 - - - - ~
Tio2 (C) 7 - - - 4.5 Tio2 (D) 8 - _ _ _ 4.5 1 RM-334 ex. Rohm and Haas, Inc.
2 KM-330 ex. Rohm and Haa~, Inc.
3 KM-653 ex. Rolun and ~3aas, Irlc.
4 BTA-733 ex. Rohm and Haa~, Inc.
5 uncoated TiO : ~-100, ex. DuPont 6 non-chalking, coated TiO : R-FC-6, ex. Tioxide of Canada 7 non-chalking, coated Tio: R-960 ex. DuPont 8 non-chalking, coated TiO : 2CL-6 ex. SCM Chemical The above compou~ds were measured for 60 gloss with the following results:
~xample 32 33 . 34 35 36 37 60 gloss 79.9 80.6 80.1 87. 3 86.1 82.1 DTS (Min) 33.5 36.5 34.5 35 33 32 ~' :~
,~
2 ~
The above examples 32-37 also exhibited an HDT at 66 psi of at least 66C, and room temperature notched Izod impact strength of at least 16 ft.-lbs./in.
Noting the above gloss measurements, it can now be appreciated that the above compounds have a good balance of desirable properties. Especially good gloss was obtained with the use of heavily coated Tio2 and is preferred.
Claims (36)
1. A compound comprising 100 weight parts polyvinyl halide, and a lubricant system comprising from 0.01 to 10 parts weight per 100 weight parts of said polyvinyl halide (phr) each of: a carboxylic acid, a carboxylic acid salt, a hydrocarbon and an alkyl ester of a polyol, said compound is rigid and exhibits from an extrudate of said compound a 60° Gardner gloss of at least 40%.
2. The compound of claim 1 wherein said alkyl ester of a polyol is a C8 - C22 mono ester of glycerol and said carboxylic acid is a C6-C24 carboxylic acid.
3. The compound of claim 2 wherein said C6-C24 carboxylic acid is present at from 0.1 to 5 weight parts per 100 parts of said polyvinyl halide, said hydrocarbon is mineral oil and is present at from 0.2 to 5 phr, said C8 - C22 mono ester of glycerol is present at from 0.2 to 5 phr, and said carboxylic acid salt is present at from 0.2 to 5 phr.
4. The compound of claim 3 wherein said carboxylic acid is selected from the group consisting of undecylic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, behenic acid, chlorocaproic acid, and hydroxy capric acid.
5. The compound of claim 1 wherein said polyvinyl halide is polyvinyl chloride having an inherent viscosity of from 0.35 to 1.2.
6. The compound of claim 5 wherein said polyvinyl chloride has an inherent viscosity of from 0.5 to 0.95.
7. The compound of claim 1 wherein said polyvinyl halide is a polyvinyl chloride homopolymer, said carboxylic acid is stearic acid, said carboxylic acid salt is calcium stearate, said alkyl ester of a polyol is a monoester of glycerol, and said hydrocarbon is mineral oil.
8. The compound of claim 1 further comprising a stabilizer, impact modifier and rutile titanium dioxide.
9. The compound of claim 1 further comprising an epoxide material selected from the group consisting of epoxidized soy oil, epoxidized linseed oil, epoxidized tall oil, epoxy derivative of bisphenol A and an epoxy resin.
10. The compound of claim 8 wherein said impact modifier is selected from at least one of the group consisting of MBS, and polyacrylate impact modifiers.
11. The compound of claim 10 wherein said at least one impact modifier is present at from 5 to 10 phr each.
12. The compound of claim 1 in the form of an extruded sheet extruded through a die having a width of at least 10 inches.
13. The compound of claim 1 in the form of an extruded sheet extruded through a die having a width of at least 40 inches.
14. The compound of claim 1 in the form of a thermoformed article.
15. The compound of claim 8 wherein said rutile titanium dioxide is coated and is non-chalking.
16. The compound of claim 9 wherein said epoxide material is present at from 1 to 6 phr.
17. The compound of claim 16 wherein said epoxide material is present at from 1 to 4 phr.
18. The compound of claim 1 wherein said alkyl ester of a polyol is selected from the group consisting of oligoglycerol esters, oligoglycol esters, esters of ethylene glycol, esters of propylene glycol and esters of glycerol.
19. The compound of claim 1 wherein said carboxylic acid is present at from 0.2 to 2 phr, said carboxylic acid salt is present at from 0.5 to 2.5 phr, said hydrocarbon is present at from 0.5 to 3 phr, and said alkyl ester of a polyol is present at from 0.3 to 2 phr.
20. The compound or claim 19 further comprising an epoxy material present at from 1 to 6 phr.
21. The compound of claim 1 wherein said carboxylic acid is present at from 0.5 to 1.1 phr, said carboxylic acid salt is present at from 1 to 2 phr, said hydrocarbon is present at from 0.5 to 1.3 phr, and said alkyl ester of a polyol is present at from 0.5 to 1.3.
22. The compound of claim 8 wherein said at least one impact modifier is present at from 4 to 12 phr each.
23. The compound of claim 22 wherein said at least one impact modifier is present at from 5 to 10 phr each.
24. The compound of claim 1 wherein said lubricant system is present at from 3 to 8 phr.
25. The compound of claim 24 wherein said lubricant system is present at from 3.5 to 7 phr.
26. An article comprising 100 weight parts polyvinyl halide, and a lubricant system comprising from 0.01 to 10 parts weight per 100 weight parts of said polyvinyl halide (phr) each of: a carboxylic acid, a carboxylic acid salt, a hydrocarbon and an alkyl ester of a polyol, said article is rigid and in the form of an extrudate, exhibits a 60° Gardner gloss of at least 40%.
27. The article of claim 26 wherein said alkyl ester of a polyol is a C8 - C22 mono ester of glycerol and said carboxylic acid is a C6-C24 carboxylic acid.
28. The article of claim 28 wherein said C6-C24 carboxylic acid is present at from 0.1 to 5 weight parts per 100 parts of said polyvinyl halide, said hydrocarbon is mineral oil and is present at from 0.2 to 5 phr, said C8 - C22 mono ester of glycerol is present at from 0.2 to 5 phr, and said carboxylic acid salt is present at from 0.2 to 5 phr.
29. The article of claim 26 further comprising an epoxide material selected from the group consisting of epoxidized soy oil, epoxidized linseed oil, epoxidized tall oil, epoxy derivative of bisphenol A and an epoxy resin.
30. The article of claim 26 further comprising an impact modifier which is selected from at least one of the group consisting of MBS, and polyacrylate impact modifiers.
31. The article of claim 30 wherein said at least one impact modifier is present at from 5 to 10 phr each.
32. The article of claim 26 in the form of a shower stall, a wall panel, a bathtub, a tub enclosure, a refrigerator panel, cabinetry, a door, a vertical blind, a horizontal blind, sporting equipment, an automotive component, an appliance component, a boat component, a houseware article, a plumbing ware article, a sign and a business machine housing.
33. The article of claim 26 wherein said article is in the form of a layer in intimate contact with a substrate selected from the group consisting of a metal article, wood, a thermoset article, and a thermoplastic article.
34. The article of claim 26 which is laminated to a substrate selected from the group consisting of metal, wood, a thermoset article, and a thermoplastic article.
35. A process for producing an article comprising:
combining 100 weight parts polyvinyl halide, and a lubricant system comprising from 0.01 to 10 parts weight per 100 weight parts of said polyvinyl halide (phr) each of: a carboxylic acid, a carboxylic acid salt, a hydrocarbon and an alkyl ester of a polyol to form a compound, and extruding said compound to form an article wherein said article exhibits a 60° Gardner gloss of at least 40%.
combining 100 weight parts polyvinyl halide, and a lubricant system comprising from 0.01 to 10 parts weight per 100 weight parts of said polyvinyl halide (phr) each of: a carboxylic acid, a carboxylic acid salt, a hydrocarbon and an alkyl ester of a polyol to form a compound, and extruding said compound to form an article wherein said article exhibits a 60° Gardner gloss of at least 40%.
36. The process of claim 35 further comprising the step of extruding another thermoplastic compound simultaneously with said compound in a coextrusion step.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US97884592A | 1992-11-19 | 1992-11-19 | |
| US07/978,845 | 1992-11-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2102478A1 true CA2102478A1 (en) | 1994-05-20 |
Family
ID=25526445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2102478 Abandoned CA2102478A1 (en) | 1992-11-19 | 1993-11-04 | Polyvinyl halide compounds having improved surfaces and articles therefrom |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2102478A1 (en) |
| MX (1) | MX9307223A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6730734B1 (en) | 1998-12-08 | 2004-05-04 | Rohm And Haas Company | Impact modifier compositions which enhance the impact strength properties and lower the viscosity of melt processed plastics resins and methods of making said compositions |
| SG109414A1 (en) * | 1998-12-08 | 2005-03-30 | Rohm & Haas | Impact modifier compositions which enhance the impact strength properties and lower the viscosity of melt processed plastics resins, and methods of making said compositions |
-
1993
- 1993-11-04 CA CA 2102478 patent/CA2102478A1/en not_active Abandoned
- 1993-11-18 MX MX9307223A patent/MX9307223A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6730734B1 (en) | 1998-12-08 | 2004-05-04 | Rohm And Haas Company | Impact modifier compositions which enhance the impact strength properties and lower the viscosity of melt processed plastics resins and methods of making said compositions |
| SG109414A1 (en) * | 1998-12-08 | 2005-03-30 | Rohm & Haas | Impact modifier compositions which enhance the impact strength properties and lower the viscosity of melt processed plastics resins, and methods of making said compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9307223A (en) | 1994-07-29 |
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