Document 15vwnrn6vQQnMJbkV5Ymd9Epj

FILE NAME: Flooring (FLR) DATE: 1975 Sept 9 DOC#: FLR016 DOCUMENT DESCRIPTION: Patent - Braddicks, Union Carbide - Novel Floor-Tile Compositions Comprising Plasticized Vinyl Chloride Polymers United States Patent n*] Braddicks [ii] 3,904,579 [45] Sept. 9, 1975 [54] NOVEL FLOOR-TILE COMPOSITIONS COMPRISING PLASTICIZED VINYL CHLORIDE POLYMERS [75] Inventor: Robert P. Braddicks, Ml.Vernon, N.Y. [73] Assignee: Union Carbide Corporation, New York, N.Y. [22] Filed: Aug. 14, 1974 [21] Appl. No.: 497,254 Related U.S. Application Data [63] Continuation-in-part of Ser. No. 399,931, Sept. 24, 1973, abandoned, which is a continuation-in-part of Ser. No. 276,908, Aug. 1, 1972, abandoned. [52] U.S. Cl.... 260/42.46; 260/30.6 R; 260/31.8 M; 260/42.49; 260/897 C; 260/899; 260/998.15 [51] Int. Cl......................... C08f 45/42; C08f 45/40 [58] Field of Search........ 260/42.46, 42.49, 998.15, 260/897 C, 899 [56] 3.091.597 References Cited UNITED STATES PATENTS 6/1962 Henriques..................... 260/899 X 3,358,054 3,401,129 3,435,098 3,592,877 12/1967 9/1968 3/1969 7/1971 Hardt....................... 260/897 C X McGinley..................... 260/899 X Watanabe..................... 260/899 X Mullins......................... 260/899 X Primary Examiner--Lewis T. Jacobs Attorney, Agent, or Firm--R. C. Brown [57] ABSTRACT Filled vinyl compositions, useful as surface covering, comprising a well-defined mixture of at least two normally-solid thermoplastic vinyl chloride polymers, e g., (i) vinyl chloride/vinyl acetate copolymer; vinylidene chloride/vinyl chloride copolymer; vinyl chloride/propyiene copolymer; chlorinated polyethylene polymer; low molecular weight vinyl chloride/vinyl Co-C, alkanoate/C2-C 4alkene ramdon terpolymer or a mixture thereof and (ii) vinyl chloride/vinyl acetate/ethylene terpolymer. The inclusion of a thermoplastic oxyalkanoyl polymer, e.g., epsilon-caprolactone homopoly mer, with/without an antioxidant, e.g., a hindered phe nol, yields compositions having good processing char acteristics as well as products exhibiting improved me chanical properties such as impact strength. 73 Claims, No Drawings 3 ,904,579 1 2 come excessively dry and results in a tendency to crum NOVEL FLOOR-TILE COMPOSITIONS ble and not form sheets. Excessive melt elasticity con COMPRISING PLASTICIZED VINYL CHLORIDE tributes boardiness to the vinyl composition causing it POLYMERS to become extremely stiff making normal processing 5 difficult, if not impossible. This application is a continuation-in-part of applica Recently, various medical researchers and govern tion 399,931 filed Sept. 24, 1973, now abandoned, ment officials have suggested that exposure to asbestos which was a continuation-in-part of application products may pose a serious health peril to the general 276,908 filed Aug. 1, 1972, now abandoned. public. In one study conducted in 1971, asbestos was This invention relates to novel resinous composi 10 reputedly found in the lungs of each of 28 randomly se tions. In one aspect the invention relates to asbestos- lected autopsies on New York City residents. Such free resinous compositions for use in producing thin findings startled the medical worid since they showed sheets having utility as surface coverings. that even the man on the street, not occupationally ex Resinous composition surface coverings comprising posed, was inhaling asbestos. It is quite understandable synthetic resinous binder, stabilizers, plasticizers, fill 15 that there is serious concern among the various govern ers, and color pigments have come to be widely used as mental agencies to regulate and restrict the handling of coverings for floor, walls, and the like. A widely used asbestos and its end use application. In fact, legislation resinous composition is a polymer of a vinyl chloride to to these ends is pending in many municipalities and such as thermoplastic poly(vinyl chloride). Such resins cities of the United States. Manufacture of vinyl asbes have extremely high wear and stain resistance which 20 tos composition have thus intensified their efforts to makes them excellent for use as surface coverings. It is find ways to produce, on a commercial scale, asbestos- common practice to add fillers to the composition to free vinyl compositions such as tile. decrease the over-all cost. The addition of such fillers Unfortunately, attempts to use a filler such as dry- in relatively large quantities is detrimental to the physi ground limestone as the sole filler in "vinyl asbestos- cal properties of the composition. As one would ex 25 type compositions" have repeatedly been unsuccessful pect, therefore, the higher quality products have very in producing commercial base stocks. Such a composi little filler, whereas the low cost products for the mass tion requires extremely careful handling of the sheet on market contain a high proportion of filler. These latter the calender rolls necessitating relatively slow speeds to pamrooduuncttss ams ahyighcoansta8i0n wfeiilglehrts paenrdcenptigomf ethnetscoinmptootsail 30 cpareuvseenitt taonycoullnadpusee oternbsrieoank oanpatrhte. Ashlseoe,titwihsinchecewsosaurldy tion. to convey the sheet when not in contact with the calen So-called vinyl asbestos composition sheet, e.g., tile, der rolls. Moreover, such limestone-filled vinyl compo is an outgrowth of asphalt composition sheet and, as a sitions exhibit excessive fluidity and lack required hot result, it has been conventionally formulated with as 35 strength for proper calendering on the production lines. Shrinkage or lack of dimensional stability is also bestos so that its processing and performance proper a severely troublesome defect in such vinyl composi ties would match those of the asphalt composition as tion sheets. closely as possible. Initially, this was essential in order Accordingly, one or more of the following objects that vinyl asbestos compositions would handle properly will be achieved by the practice of the invention. It is a on the asphalt composition equipment and production 40 purpose of this invention to minimize the need for as lines, thereby requiring a minimum of equipment modi bestos in vinyl compositions used in making floor cov fication. With the passage of time processors have suc erings. It is an object of the invention to provide novel ceeded in producing decorative chip stocks and very filled resinous compositions which are essentially free special base stocks without the inclusion of asbestos. of asbestos and which are commercially useful as sur However, most of today's base stock formulations con 45 face coverings. It is another object of the invention to tain asbestos filler to avoid dimensional stability prob provide novel vinyl compositions which are essentially lems and processing problems. or completely free of asbestos and which have good Vinyl composition sheets are prepared by a number strength at high temperature processing, good roll ad of different methods including calendering, pressing, hesion, very low water absorption, and improved light and molding. In a calendering system where the rela 50 resistance. A further object of the invention is to pro tively thin vinyl composition sheet has to pass through vide novel non-fibrous filled vinyl compositions sheets a number of calender rolls and other operations, the which possess the desirable properties of fibrous-fillcd strength of the sheet at the relatively high temperatures composition sheets such as good indentation resis necessary for processing is of great importance. The tance, impact strength, and flexibility while lacking ability of the sheet to adhere to the calender rolls is also 55 many of its disadvantages. A yet further object of this a significant factor, Fibrous fillers, especially asbestos, invention is to provide novel processes for producing greatly increase the hot strength of a vinyl composition vinyl composition sheets. These and other objects will above that which can be obtained with non-fibrous fill become apparent to one skilled in the art from a con ers. It has. therefore, become universal practice to uti sideration of this specification. lize asbestos when hot strength is needed in vinyl com 60 In the practice of this invention, it has been found, p o s itio n s . R e q u i r e d hot s t r e n g t h o r h o t te n s ile s t r e n g t h , quite unexpectedly, that vinyl compositions which are as used in this art, is that property of a hot vinyl compo essentially free of asbestos can be conveniently pro sition which exhibits the proper amount of viscous flow cessed on existing " asbestos tile" equipment and pro and melt elasticity so that the composition may be duction linees. These novel compositions exhibit a sheeted, calendered, and transported without sporadic 65 combination of acceptable processing characteristics ripping, tearing, or excessive elongation during hot pro while the novel products, useful as surface coverings, cessing on the calendering line. Excessive viscous flow arc characterized by good indentation resistance, good 3 ,904,579 3 4 can be prepared containing as much as 85 weight per weight percent and the propylene portion upwards cent, and higher, of pigment and filler, e.g., titanium from about 4 weight percent to about 10 weight per dioxide and mixtures of relatively coarse and fine lime cent. Preferably the copolymer is comprised of from stone. Such highly-filled vinyl compositions possess an about 90 to about 96 weight percent polymerized vinyl obvious economic advantage over conventional vinyl 5 chloride and from about 4 to about 10 percent poly compositions which heretofore have been generally merized propylene. Preferred are polymers having an f i l l e d with asbestos and pigments to amounts not ex inherent viscosity ranging from about 0.4 to about 0.7. ceeding about 80 weight percent of the composition. Illustrative of the chlorinated polyethylene polymers The excellent processing and mechanical properties useful in the practice of this invention are those in of the novel vinyl compositions are attributable to a 10 which chlorine accounts for at least about 40 percent well-defined mixture of a normally-solid thermoplastic of the polymer weight. Polymer crystallinity should not polymer, namely, (i) vinyl chloride/vinyl Cr-C4alkano- exceed about 5 percent. Preferred are polymers having ale copolymer; vinylidene chloride/vinyl chloride co 0 percent crystallinity. The preferred chlorinated poly polymer; vinyl chloridc/propylene copolymer; chlori ethylene polymers are also those having a molten vis nated polyethylene polymer; low molecular weight 15 cosity of from about 10,000 to about 30,000 poises at vinyl chloride/vinyl C./-C4 alkanoatc/C2~C4alkene ran a temperature of 190C. dom terpolymer or a mixture thereof and (ii) a unique Typical of the normally-solid thermoplastic vinyl terpolymeric composition, namely vinyl chloride/vinyl chloride/vinyl C2-C 4alkanoate/C2-C4alkene terpoly- C2-C 4alkanoate/C2-C 4alkcne terpolymer. The term mers which are useful in the invention include, by way " normally-solid thermoplastic polymers" in reference 20 of illustration, vinyl chloride/vinyl acelate/cthyiene ter to the above described polymers, copolymers and ter- polymer, vinyl chloride/vinyl acetatc/propylene ter polymers is intended to describe those polymers which polymer, vinyl chloride/vinyl ucetate/butylene terpoly are normally-solid and thermoplastic at room tempera mer, vinyl chloride/vinyl propionatc/ethylenc terpoly ture and which can be processed on existing equipment 25 mer, vinyl chloride/vinyl propionate/propylenc terpoly and production lines for producing conventional asbe mer, vinyl chloride/vinyl propionatc/butylcne terpoly stos-filled vinyl sheets. Such equipment is generally op mer, vinyl chloride/vinyl butyrate/ethylenc terpolymer, erated at temperatures in the range of from about 150 vinyl chloride/vinyl butyrate/propylene terpolymer, to about 300F. and vinyl chloride/vinyl butyratc/butylenc terpolymer. The terms "non-asbestos" and " essentially free of as 30 The polymerized vinyl chloride portion of the terpoly bestos" are intended to describe compositions contain mer comprises the major portion by weight and, in gen ing from essentially O'# up to an amount which does not eral, desirably comprises at least about 75 weight per significantly influence the physical properties of the cent of the terpolymer. The polymerized vinyl C..-C- final product. ,alkanoate portion of the terpolymer normally contains Illustrative normally-solid thermoplastic vinyl chlori- 35 less than about 24.5 weight percent whereas the poly dc/vinyl C^Cfalkanoate copolymers include vinyl merized alkene portion contains at least about 0.5 chloride/vinyl acetate copolymer, vinyl chloride/vinyl weight percent. Polymerized vinyl C2-C 4alkanoate rep propionate copolymer, and vinyl chloride/vinyl buty resents the major component with respect to the poly rate copolymer. The polymerized vinyl chloride por merized alkene portion. Highly suitable terpolymers tion of the copolymer comprises at least about 70 40 comprise, polymerized therein, from about 80 to about weight percent and the polymerized vinyl C2-C 4alkano- 90 weight percent chloride, from about 9 to about 17 atc portion upwards to about 30 weight percent, based weight percent vinyl C2-C 4alkanoate, and from about 1 on the total weight of the copolymer. Preferably, the to about 3 weight percent ethylene. The preferred ter copolymer comprises at least about 80 to about 95 polymer is vinyl chloride/vinyl acetate/ethylene. weight percent polymerized vinyl chloride and from 45 The terpolymers useful in this invention are those about 5 to about 20 weight percent polymerized vinyl which have inherent viscosity values ranging from C2-C 4alkanoate. The preferred copolymer is vinyl chlo about 0.4 to about 0.9. The terpolymers characterized ride/vinyl acetate. Particularly useful copolymers are is relatively higli molecular weight terpolymers which those which have inherent viscosity values in the range are essential ingredients in this invention are those hav of from about 0.35 to about 0.65, preferably from 50 ing ah inherent viscosity of least 0.5 and preferably about 0.4 to 0 .6. Unless indicated to the contrary the from about 0.5 to about 0.8. These are to be distin inherent viscosity values were determined in accor guished from the lower molecular weight terpolymers dance with ASTM Method D-1243-66 using 0.2 gram having an inherent viscosity of loss than about 0.5. pref of polymer in 1.00 milliliters of cyclohexanone at 30C. erably about 0.4 to about 0.5 which are optional ingre Illustrative normally-solid thermoplastic vinylidene 55 dients. chloride/vinyl chloride copolymers are those in which The terpolymers useful in the practice of this inven the polymerized vinyl chloride portion of the copoly tion are those prepared by the simultaneous polymeri mer comprises at least about 50 weight percent and the zation of the three monomeric ingredients, as distin vinylidene chloride portion upwards to about 50 weight guished from graft polymers. The expression " terpoly percent, based on the total weight of the copolymer. 60 mers" as used herein therefore describes polymeric Preferably, the copolymer is comprised of from about materials produced by the simultaneous reaction of all 50 to about 90 weight percent polymerized vinyl chlo three monomers to produce a material which includes ride and from about 10 to about 50 weight percent po at least some of all of the monomeric moieties in the lymerized vinylidene chloride. Suitable are copolymers polymer backbone in what is believed to be a random having an inherent viscosity ranging from about 0.35 to 65 distribution. .ihraii r><j Preferred however are those having an in The preferred compositions of this invention are 3 ,904,579 5 6 bination affords a very satisfactory product in terms of physical properties and can be produced on conven tional equipment. Optional resins can be added to these basic ingredients if desired to modify physical properties of the tile product or to modify manufacturing con ditions. Compositions which do not include vinyl chloride/vinyl alkanoate copolymer provide useful products but generally require more difficult manufacturing con ditions. of a second unit. In other words, the interconnection of such units does not involve the direct bonding of two carbonyl groups. In one aspect of the invention, novel non-asbestos When the thermoplastic oxyalkanoyl polymer is a ho filled vinyl compositions can be prepared which exhibit mopolymer or essentially a homopolymer, the polymer good processing characteristics such as required hot chain thereof consists essentially of interconnected re strength and good roll adhesion. Moreover, novel sheet curring oxyalkanoyl units. In addition to the recurring products from such compositions exhibit good impact 15 oxyalkanoyl unit, the thermoplastic oxyalkanoyl poly resistance as well as the aforementioned desirable me mer may comprise other moieties or groups therein es chanical and physical properties. These and other re pecially those which intersperse or terminate the poly sults are achieved by incorporating into the novel vinyl meric chain thereof as illustrated by the oxyalkylene group,the-Mo^O-sroup; th e --0 {R^o)-y g ro u p ; t h e --] i{ ri i group; the 0 -- CR-^C--g ro u p ; the u r e th a n e g r o u p , --NHCO-- ; the 0 0 --OR^OC- g ro u p ; th e -NHCHN--group ; the b i u r e t g ro u p , 9 o ii | -- NHCNCNH-- ; t h e -- R -N--R^-- g ro u p ; th e d i v a l e n t mono- H compositions a minor amount of a normally-solid ther 40 and polyaromatic rings including fused and bridged moplastic oxyalkanoyl polymer. The oxyalkanoyl poly rings; lower alkyl substituted oxyalkanoyl groups; cata mers which are suitable possess a reduced viscosity lyst residue; the carbonate group, value of at least about 0.1. In various desirable embodi ments, the thermoplastic oxyalkanoyl polymers have a reduced viscosity value of at least about 0.2. The upper 45 value can be high as 10, and greater, but no particular - 0C0 - ; advantage is apparent using thermoplastic oxyalkanoyl and others. With reference to the aforesaid groups or polymers which have a reduced viscosity value greater moieties, the variables R, R,, R.2, R;l, and y can be illus than about 3. The oxyalkanoyl polymers are further trated as follows: R' represents hydrogen or lower al characterized in that they contain at least about 50 50 kyl; R, represents a divalent hydrocarbon group; R.2 weight percent of the oxyalkanoyl units represents a divalent aliphatic hydrocarbon group or a 0 II 0 (CH2)- divalent aliphatic oxa-hydrocarbon group: R:, repre sents a divalent aliphatic hydrocarbon group; and v represents an integer which has a value of at least 1. 55 The term " lower alkyl", as used herein, represents a monovalent aliphatic hydrocarbon group having 1 to 4 recurring therein, wherein x is an integer having a value carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, n- of 2,4 and 5-7, preferably 5. In the practice of highly butyl, etc. The term "divalent hydrocarbon group", as suitable embodiments of the invention, the thermoplas used herein, includes radicals such as C^-C^alkylcne, tic oxyalkanoyl polymers contain at least about 60 60 C2-C |2alkylidenc, and Cir-Cl2arylcne, e.g., methylene, weight p e r c e n t , a n d p r e f e r a b l y a t l e a s t about BO w e ig h t propylene, butylene, hcxumethylcnc, hcptamethylcne. percent, and upwards to about 100 weight percent of cyclohexylenc, phenylenc, napthylenc, propylidene, the oxycaproyl unit, i.c.. butylidenc, etc. The term " divalent aliphatic hydrocar -- 0 ( ch2) 5 bon group", as used herein, includes C2-C,,alkylcne 65 and Ca-Cijalkylidene. The term "divalent aliphatic ox- a-hydrocarbon group", as used herein, can be repre recurring therein. sented by the empirical formula. --C..--C.,alk- 3 ,904,579 7 As previously noted, the thermoplastic oxycaproyl 8 beric acid, azelaic acid, sebacic acid, phthalic acid, and polymers which are suitable in the practice of the in the like. vention are expressed in terms of their reduced viscos In the absence of added organic initiator, the thermo ity values. As is well known in the art, reduced viscosity plastic oxyalkanoyl polymers can be prepared by poly value is a measure Or indication of the molecular 5 merizing a lactone reactant, e.g., betapropiolactone, weight of polymers. The expression " reduced viscos ity" is a value obtained by dividing the specific viscosity by the concentration of polymer in the solution, the delta-valcrolactone, epsilon-caprolactone, etc., in the presence of anionic catalysts such as di-n-butylzinc, trin-butylaluminum, diethylmagncsium, aluminum triiso- concentration being measured in grams of polymer per propoxide n-butyllithium, dimcthylcadmiurri, and the 100 milliliters of solvent. The specific viscosity is ob 10 like. The reaction is desirably conducted at an elevated tained by dividing the difference between the viscosity temperature, e g., 100 to 250C, for periods of time of the solution and the viscosity of the solvent by the ranging from minutes to several hours, e.g.', from about viscosity of the solvent. Unless otherwise noted, the re 10 minutes to about 24 hours. The reaction mixture duced viscosity values herein referred to are measured can comprise in addition to the lactone reactant, minor at a concentration of 0.2 gram of polymer in 100 milli 15 quantities of other polymerizable cyclic monomers liters of benzene (benzene is.preferred although cyclo such as tetramethylene carbonate, methyl-epsilon- hexanone, chloroform, toluene or other common or caprolactone, keto-dioxane, etc. The number average ganic solvent for the polymer may be used) at SO'C. molecular weight of the resulting polymeric products The thermoplastic oxyalkanoyl polymers can be pre which are produced by this exemplified "non-initiated" pared by various methods. A general procedure in 20 method are, in general, quite high. For example, prod volves reacting a large molar excess of the appropriate ucts which have number average molecular weights lactone, e.g., epsilon-caprolactone, zeta-enantho.lac- ranging from about 10,000 to several hundred thou tone, and/or eta-caprylolactone with an organic initia sands can be prepared. The patent literature, e.g., U.S. tor which contains two active hydrogen groups, e.g., 25 Pat. Nos. 3,021,309 to 3,021,317, the preparation of these polymers. discusses in detail hydroxyl, carboxyl, primary amino, secondary amino, and mixtures thereof, such groups being capable of Thermoplastic oxyalkanoyl polymers can also be pre opening the lactone ring whereby it adds as a linear pared by polymerizing an admixture of Cr-C,, lactone, chain (of recurring oxyalkanoyl units) to the site of the a vicinal epoxy compound, e.g., ethylene oxide, propy active hydrogen-containing group, at an elevated tem 30 lene oxide, butylene oxide, cyclohexene oxide, and an interfacial agent such as a solid, relatively etc., high perature, preferably in the presence of a catalyst, and molecular weight poly(vinyl) stearate) or lauryl metha- for a period of time sufficient to produce the desired crylate/vinyl chloride copolymer (reduced viscosity in polymers. By carefully controlling the purity and molar cyclohexanone of from about 0.3 to about 1.0), in the ratio of lactone reactant to organic initiator, there can presence of an inert normally-liquid saturated aliphatic be produced " initiated" poly(oxyalkanoyl) polymers 35 hydrocarbon vehicle such as heptane, using phospho whose number average molecular weight can range rus pentafluoride as the catalyst therefor, and in the ab from several hundred to above 100,000. Organic initia sence of an active hydrogen-containing organic initia tors which can be employed include primary diamines, tor, at an elevated temperature, e.g., about 80C, and secondary diamines, mixed primary-secondary di for a period of time sufficient to produce such poly amines, aminoalcohols, diols, dicarboxylic acids, hy- 40 mers. droxycarboxylic acids, aminocarboxylic acids, etc. Thermoplastic oxyalkanoyl polymers can also be pre Such organic initiators are voluminously illustrated in pared by reacting a molar excess of a lactone with a the literature, e.g., U.S. Pat. Nos. 3,169,945 and polyoxyalkylene diol which has a molecular weight 3,427,346. Catalysts which can be employed include, ranging from about 400 to about 20,000 under condi for instance, stannous octanoate, tetrabutyltitanate, di- 45 tions discussed supra with reference to the initiated butyltin dilauratc, and the like. A temperature in the range of from about 150C to about 250'C for periods poly(oxylalkanoyl) polymers. Illustrative of the poly oxyalkylene diols which are contemplated include the ranging upwards to about 24 hours, and longer, are poly(oxyethylene) diols, the poly(oxypropylene) diols, suitable. and the poly(oxyethyleneoxypropylene) diols. The re Thermoplastic oxycaproyl polymers can also be pre 50 sulting polymers can be considered, in effect, to be pared by reacting the cyclic ester, e.g., epsilonca- ABA block polymers in which the A portions represent prolactone, and/or the corresponding hydroxy-acid, a polyoxyalkanoyl segment or block and in which the B e.g., 6-hydroxycaproic acid, and/or their oligomers, portion represents a polyoxyalkylene segment or block. with a mixture comprising diol and dicarboxylic acid, The number average molecular weight of these ABA using a molar excess of diol with relation to the dicar 55 block polymers can range upwards to 50,000, and boxylic acid, or alternatively, using a molar excess of higher, depending on the molecular weight of the poly dicarboxylic acid with relation to the diol. It is highly oxyalkylene diol reactant and the molar ratio of the lac desirable that free diol or free dicarboxylic acid not be tone reactant to polyoxyalkylene diol reactant em present at the termination of the polyesterification re ployed and consumed in the process. By using mono action. The water of esterification which results during 60 e n d - b l o c k c d p o l y a l k y l e n e d i o l s s u c h as t h e m o n o a l k y l the reaction can be removed via conventional tech ether of polyoxyalkylene d io l, the above discussed niques. The diols and dicarboxylic acids which are par preparation results in polymers having an AB block ticularly suitable include those illustrated by the formu configuration. lae H 0 fR 204jH and HOOCRiCOOH such as ethylene Oxyalkanoyl polymers can be considered to be glycol, propylene glycol, diethylcne glycol, dipropylene 65 " graft" polymers can be prepared by the addition of glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hex- Cn-C,,: lactone at the active hydrogen sites, e.g., hv- c. ^ m r w x tttU in V i ' r o n n n r l ' i n t n ln r ir r f h n n r v l V _ 3 ,904,579 9 ymers may, for example, be obtained by the copoly 10 matic acids, including dibutyl phthalate, dicapryl merization of ethylene and vinyl acetate, followed by phthalate, dioctyl phthalate, dipropylene glycol diben- subsequent saponification of the acetate groups to yield zoale, butyl benzyl sebacatc, butyl benzyl phthalate, polymers which are characterized by a plurality of pen dibenzyl sebacate, dibenzyl phthalate, and the like. dant hydroxyl groups along the polymeric chain 5 Other types of plasticizers such as esters of inorganic thereof. A wide host of ethylenically unsaturated mon acids, including tricresyl phosphate, octyl diphenyl omers can be employed to prepare the vinyl polymers phosphate, and the like; alkyd derivatives of rosin; and include, for example, 2-hydroxyethyl acrylate, 2- chlorinated paraffine; high molecular weight hydrocar hydroxy methacrylate, styrene, acrylonitrile, propy bon condensates; and the like; can also be used. The lene, vinyl chloride, and the like. The choice of the eth 10 plasticizer should preferably have a low vapor pressure ylenically unsaturated monomers are such that the re at the temperatures required to fuse the resin. A vapor sulting polymer contains a plurality of pendant hy pressure of 2 millimeters of mercury or less at 400F is droxyl groups, or groups which can be converted to hy usually considered satisfactory. The plasticizer is em droxyl groups. The addition of the Cir-C^actone at the ployed in a plasticizing amount which is sufficient to active hydrogen site will produce graft polymers of 15 provide the mechanical properties which are desired in number average molecular weights upwards to approxi the end use application. Normally a satisfactory range mately 100,000, and higher. of plasticizer, including mixtures thereof, is from about The oxyalkanoyl polymers which have number aver 25 parts by weight, and lower, to about 45 parts by age molecular weights of, for example, less than 25,000 weight, and higher, per 100 parts by weight of total pol are characterized by functional end groups. For in 20 ymer binder. stance, hydroxyl-terminated polymers can be prepared Small amounts of stabilizers which are incorporated from a diol initiator and epsiloncaprolactone using to reduce the effects of degradation by light and heat molar ratios of lactone to initiator upwards to about are usually present in the novel composition. Suitable 100: 1. If desired, these polymers may be reacted with a light stabilizers include epoxidized soya bean oil, epoxidiisocyanate, e.g., 1,6-hexamethylene diisocyanate, 25 dized tallates, wood rosin, phosphites, resorcinol disali 2,4- and/or 2,6-tolylene diisocyanate, bis(- cylate, resorcinol dibenzoate, phenyl phthalate, phenyl 4( isocyanatophenyl Jmethane, bis( 4- benzoate, o-tolyl benzoate, eugenol, guaiacol, o-nitro- isocyanatocyalohexyl)methane, etc., to extend the pol phenol, o-nitraniline, tricthylene glycol salicylate, and ymeric chain, or such hydroxyl-terminated polymers as organic phosphates and other complexes of such metals well as their polyurethane extension products can be 30 as barium, cadmium, strontium, lead, tin and the like. reacted with so-called "chain stoppers" such as a Suitable heat stabilizers includes barium-cadmium monocarboxylic acid or anhydride. As indicated previ soaps, barium-cadmium-zinc-soaps, epoxides, sulfides ously, the thermoplastic oxyalkanoyl polymers which and sulfites of silver, calcium, cadmium, magnesium, are suitable in the practice of the invention have, as its cerium, sodium strontium and the like, glycerine, leu lower limit a reduced viscosity value of at least about 35 cine, alanine, o- and p-amino benzoic and sulfanilic 0 .1. acids, hexamethylene tetramine, weak acid radicals in The amounts of normally-solid thermoplastic poly cluding oleates, recinoleates, abietates, salicylates and mers which comprise the total polymer binder in the the like. Normally, the novel composition contains novel composition are quite important. Desirable re from about 0.5 to about 5 parts by weight of stabilizer sults arc achieved by using from about 25 to about 65 40 per 100 parts by weight of total polymer binder. If de weight percent binder resin and from about 35 to about sired, small amounts of antioxidants such as the hin 75 weight percent relatively high molecular weight dered phenols, e.g., di-t-buty!-p-cresol, and lubricants vinyl chloride terpolymer, based on the weight of the such as stearic acid, waxes, etc., may be incorporated total polymer binder. Enhanced processing and me into the novel compositions thereby obtaining further chanical properties in the novel compositions are 45 improved milling and calendering characteristics. achieved by incorporating into the recipe from about A wide variety of fillers can be incorporated into the 0.5 to about 15 weight percent thermoplastic oxyalkan novel compositions. Such fillers can be of the fibrous oyl polymer, based on the weight of total polymer and non-fibrous type as illustrated by limestone, whit binder. In the practice of preferred embodiments of the ing, clay, pumice, talc, silica, wood flour, mixtures invention the total polymer binder comprises from 50 thereof, and the like. Silicic mineral type fillers, though about 30 to about 60 weight percent binder resin, from contemplated and within the scope of the invention, do about 40 to about 70 weight percent relatively high mo not represent highly desirable fillers. In the practice of lecular weight vinyl chloride terpolymer, and from suitable embodiments, non-fibrous type fillers are par about one to about 10 weight percent thermoplastic ticularly useful. Limestone represents a preferred filler, ojiyalkanoyl polymer. 55 especially limestone which comprises a wide spectrum A wide range of plasticizers for incorporation into of relatively coarse to fine particle sizes, e.g., those hav the novel non-asbestos compositions can be employed. ing average particle sizes ranging from about 15 mi The particular plasticizer of choice will be influenced, crons to about 275 microns. The amounts of filler in to a significant extent, on its compatibility with the sys the novel compositions- can vary quite widely. The tem. and the properties desired in the plasticized prod 60 novel composition will normally contain from about uct. Illustrative plasticizers i n c l u d e e s t e r s ol aliphatic 2 0 0 , a n d lo w e r , t o a b o u t 7 5 0 , a n d h i g h e r , p a r t s by- hydric compounds and aliphatic carboxyl compounds weight of total filler per 100 parts by weight of total such as dibutyl sebacatc, dioctyl sebacate. dioctyl adi polymer binder, and generally, from about 250 to pate, didecyl adipate, dioctyl azelate, tricthylene glycol about 500 parts by weight of total per 100 parts bydi( 2-elhylhexanoate), dicthylenc glycol dipelargonatc, 65 weight of total polymer hinder. The proper selection of triethylene glycol dicaprylate, and the like; esters of ali filler, combination of fillers, and/or the particle size phatic alcohols and aromatic acids, or aromatic alco- ranges thereof, will depend, to a significant degree, on 3 ,904,579 11 used such as titanium dioxide, iron oxides, phthalocya- 12 acid, waxes, etc., may also be incorporated into the nines, benzidines, and the like. novel compositions thereby obtaining further improved Although a principal objective of this invention is to milling and calendering characteristics. achieve an asbestos-free floor tile composition it will be The novel vinyl compositions are conventionally pre appreciated that minor amounts of asbestos, on the 5 pared by mixing the normally-solid thermoplastic poly order of 1 to 5%, may be added if desired. Even higher mers (total polymer binder), plasticizer, filler, pig amounts can be used if desired however an increase in ments and stabilizer together at temperatures above the asbestos content will normally require a proportionate softening point of said polymers which is usually be increase in resin content which may not be desirable tween about 250 and about 375F. This mixing opera for economic reasons. 10 tion is conventionally carried out in a Banbury mixer or Preferred aspects of the invention include novel non Baker-Perkins type mixer. The mixed composition is asbestos compositions comprising an antioxidant incor then fed to a two-roll mill which converts the resulting porated therein. Novel vinyl compositions comprised fused mixture into a flat sheet suitable for feeding the of one or more of the aforesaid thermoplastic binder calenders. The two-roll mill is operated to maintain the resins, relatively high molecular weight terpolymer and 15 temperature of the fused stock. It is conventional prac oxyalkanoyl polymer and an antioxidant exhibit pro tice to maintain a temperature differential between the cessing characteristics at least as good as those ob rolls to cause the sheet to adhere or to follow one of the tained under existing and conventional production rolls, e.g., the front roll is normally operated at, for ex lines using asbestos-containing recipes. Moreover, the ample, about 170 to about 200F whereas the back roll sheeted product, such as floor tile, possesses a combi 20 is normally maintained at about 275 to about 325F. nation of useful and outstanding properties as illus The milled sheet can be subjected to further various trated previously in this specification. These processing calendering operations to reduce its gauge and to advantages and improved mechanical and physical smooth its surface, or the sheet can be converted into properties of the novel non-asbestos compositions regular or irregular granules which can then be mixed heretofore have not been attainable under existing as 25 with similar granules of contrasting coloration and bestos tile equipment. molded into a sheet. Typical calendering operations for Illustrative antioxidants include the sterically hin forming vinyl sheets are well-documented in the art; dered phenols, the arylamines, the thioureas, the thi- note, for example, U.S. Pat. No. 2.917,781. The sheet ocarbamatcs, the thioethcr esters, and the phosphites produced can be laminated to a backing sheet of resin or mixtures or adducts thereof. Specific examples arc 30 impregnated felt, fabric or a resinous sheet and can also tetrakis[methylcne-3-3 ',5 '-di-tert-butyl-4 '-hydroxy- be cut into tiles or other appropriate shape, depending phenyl )-propionate]methane, stearyl 3-( 3',5 '-di-tert- upon the particular use to which the product is to be butyl-4'-hydroxyphcnyl)propionate, distearyl 3,5-di- put. tert-butyl-4-hydroxybenzyl phosphite, l,l,3-tris(5'- The following Examples are illustrative. tert-butyl-4'-hydroxy-2'-methylphenyl)butanc, 4- 35 In the illustrative Examples hereinafter disclosed, nu methyl-1,-6-di( 2 '-hydroxy-3 '-tert-butyl-5 '-methylbcn- merical notations following the copolymer or terpoly zyl Jphenol, 2,4-di( 3'-5 '-di-tert-butyl-4'-hydroxy- mer designations indicate parts by weight. For exam phenoxy )-triazine, 2,2'-thiobis(4'-methyl-6'-lert-butyl- ple, 86 vinyl chloride/14 vinyl acetate refers to a co phenol), 4-4'-thiobis(3-methyl-6-lert-butylphenol), polymer containing 86 parts by weight of vinyl chloride 3,5-di-tert-butyl-4-hydroxy- anisole, 2,6,-di-tcrt-butyl- 40 and 14 parts by weight of vinyl acetate chemically com p-crcsol, N-phenylbeta-naphthylamine, N,N'-diphcnyl- bined therein. p-phenylenediamine, 2-ethylhexyldiphcnylamine, N. N'-di-bcta-naphthyl-p-phenylenediaminc, N,N'-di- EXAMPLES 1-2 (2-octyl )-p-phenylenediamine, N,N'-di-3(5-methyl- Examples 1-2 illustrate the processing and mechani heptyl)-p-phenylcnediamine, 4,4'-dioctyldiphenyia- 45 cal properties of two comparable recipes. The first rec mine, 4-octyldiphenylamine, 4-t-butoxydiphenylaminc, ipe, designated for convenience as NAT (non-asbestos trimethylthiourea, 1,3-diethylthiourea, ethylene thio tile), used limestone as the sole filler and the unique urea, sodium dibutyldithiocarbamatc, dilauryl thiodi- combination of thermoplastic polymers as the poly propionate, distearyl thiodiproionate, the mono-, di- meric binder, i.c., (i) 86 vinyl chloride/14 vinyl acetate and tri-nonylphenyl phosphites, and the like. Other an 50 copolymer, inherent viscosity of 0.4, (ii) 88 vinyl chlo- ti-oxidants include p-cresol-formaldehyde resins; para- ridc/10.5 vinyl acetate/!.5 ethylene terpolymer, inher tertiary-alkylphcnol formaldehyde resins in admixture ent viscosity of 0.7, and (iii) epsilon-caprolactone ho with amino dithioformates; aliphatic polyepoxides; mopolymer, reduced viscosity 0.7; the second recipe para-tertiary alkylphcnol formaldehyde resins in ad designated for convenience as VAT (vinyl asbestos mixture with mercapto compounds; carboxylic acids 55 tile), employed asbestos as one of the fillers and used such as succinic acid, and the like; substituted oxa- the aforesaid 86 vinyl chloride/14 vinyl acetate copoly midcs such as oxanalide and the like; amino acids such mer as the polymeric binder. The recipes were blended as glycine and the like; aminopolycarboxylic acids such in a Hobart mixer and then mixed and fused in a Ban as ethylcnediaminctctraacetic acid, dicthylcnetri- bury mixer at 350F until fused and homogeneous. The a m m c p e n t a a c e t i c a c i d , h y d r o x y e t h y l c t h y l e n e d l a m i n c - 60 fused stocks were then banded on an 8 inch two roll triacetic acid, nitrilotriacctic acid, hydroxye- mill set at I 10 and 140C on the front and back rolls, thyliminodiacctic acid, diaminocyclohexanetctraacetic respectively. A sheet gauge of approximately 190 mils acid, diaminoethyl ether telraacctic acid; pentaerythri- was removed from the mill and calendered to 125 mils tol; sorbitol; resorcinol; and the like. Small amounts of gauge with two successive passes through the calender. antioxidants are employed; for example, from about 65 Specimens were cut and conditioned at 25C and 50c/r O. 002, and lower, to about 2 weight percent, and relative humidity prior to testing. Methods provided in r a - h o r n f untioviH iint h a s e d o n the weicht o f the total Federal Test Method Standard No. 501 A were used to 3 ,9 0 4 ,5 7 9 13 pact resistances, and volatilities, In addition, mill rat ings and Brabendcr Plasticorder molten flow data were determined. The Brabender employed a No. 6 roller head using a sample charge of 100 grams; bowl temper ature was set for 150C and rpm's at 60. Water absorp 5 tion and water expansion data were also derived. Val ues were obtained for both tests after water exposures 14 TABLE Il-continued PERFORMANCE PROPERTIES (WIH INCH GAUGE) NAT RECIPE VAT RECIPE 1 min., 77F 10 min.. 77K Max. Allowed V4 m in ., 1 1 5 F 8.4 12.2 13.0 23.8 7.2 9.5 11.5 27.6 of 1,3 and 7 days at room temperature. The absorption values represent weight percent gain after the desig Water Absorption (Weight Gain) nated exposures. Expansions are in terms of mils per 8 10 inch measured across machine direction. 1 D;iy 3 Days 7 Days The recipes are set out in Table I infra, performance properties of Vfe-inch gauge sheet are recorded in Table Water Expansion (Mils/X inch) II infra, and tensile data (ASTM Method D-412) are 1 Diiy recorded in Table III infra. 15 3 Da>s 7 Days 0.83 1.59 2.08 None 5 5 1.46 2.11 2.63 5 IU 30 TABLE I FORMULATION; WT. 7, l.ight Stability"' (Fadcomelcr Hrs.) >192 112 7R Asbestos 40 Mesh Limestone "Atomito" (fine limestone) Copolymer*11 Terpolynter'2' Wood Rosin " Amoco" 1H*:" Ba*Cd Stabilizer DOP'M Butyl Benzyl Phthalatc EPO" * White Pigment Stearic Acid " Mark" 140MSI PCI.'1' Total NAT RECIPE -- 55.G 24.7 5.7 5.3 0.19 0.98 0.35 2.20 -- 0.52 3.7b -- -- 0.70 too VAT RECIPE 20 57 -- 12.0 -- 0.2 0.7 0.3 _ 4.30 0.62 4.0 0.08 O.KO -- 100 ' Tile Density 20 (lhs./ft.:l) 2,18 2.12 " T h e s e are mill processing properties reflecting roll adhesion, toughness and sheeting qualities. '-'N o. 6 roller head. 60 PPM . 100 gm specim en. 15i '"D ata o b tained m 1/ 1r>th gauge tile: T'ed em i Test Metbi ui Standard No. 5u 1A. average o f 3 experiments, " 'D eterm ined in acco rd an ce with ASTM M ethod F.-42-M 30 7H"F T A B L E III TENSILE DATA NAT RECIPE VAT RECIPE '"Sh Vinyl chloride/14 vinyl acetate copolym er, inherent viscosity o f about 0.4. *-'HK Vinvi chlnrklo/10'5 vinyl aeeta lc /1 .5 ethylene lerp o K in cr. inherent viscosity of about 0.7. Modulus rA Elongation 'I ensile Strength 6100 14 795 5300 11 950 ,:,'Polv(alph;i*mclhilKtvrcnc), a v erag e m olecular weight o f ab o u t H00--1000. >nD il2 -c th y lh c \y ij phthalate. ,riir.l>oxhliyeil soya bean oil. '"'Nitrogenous hasctl vinyl asbestos tile stabilizer tdicyundiam idc). `"L'psUon-enprotoetone hom opolym er. rcdttccd viscosity o f about 0.7. HKIF 35 Modulus ck Elongation 1 ensile Strength 4060 21.5 400 3725 22 372 TABLE II 40 PERFORMANCE PROPERTIES OATH INCH GAUGE) NAT RECIPE VAT RECIPE Milling Properties"' Hot Strength Tack Plasticity Good Fair Acceptable Good Good Normal I25F Modulus Elongation 1 ensile Strength 150F Modulus rA Elongation Tensile Strength 2020 33 200 540 46 88 1760 38 160 700 42 74 Brhender Data1"1 Peak 'Torque (m-gni) Equilibrium Torque (m-gm) Max. Temperature Impact Resistance*11' Average Range MeBurnev indentation 4900 2550 I70C 10.7 9-13 4900 2100 167C 6.7 4-9 EXAMPLES 3-8 Six all limestone, non-asbestos filled recipes were 50 prepared, blended, fused, sheeted, and tested as de scribed in Examples 1-2 supra. The data are recorded in Tables IV and V infra. TABLE IV Example* FORMULATIONS. WT. 9f 3 4 5 6 7 8 Copolvmer"' Tcrpolymcr*2' PCI.13' PVC"' DOP" 5.7 5.7 _ 1 1.0 _ 5.7 5.3 5.3 -- -- 1 1.0 -- 0.7 -- 0_18 0.7 1 1.0 0_.7 0_.7 0.7 5.3 2.2 2.62 2,2 2.2 2.2 2.2 " `Kfi Vinyl ch lo rid e/14 vim I acetate copolym er, inherent mscosUao f uktout tl 4 ,3'HX Vinyl chloride/ 10.5 vinyl a c e ta te /1 .5 ethylene te rp o L m c r. inherent viscosity n f a h o u i 0.7 ,:,,Epsilon-caprolaetone hnrnopol) nter, reduced viscosity ol :iK>ut 0.7. '"PnlW vinyl ch lo rid e), inherent viscosity ol about 0.5. "\U t 2-cthvlbcsyl )phthidatc. E x cep t fo r m onom eric plastiei/vr (IX )P>, all o th er ingredients (filler, pigm ent, processing aids, etc are used in the sam e am ounts show n for the all lim estone, noivasK 'slos filled NAT recipe of Examples 1-2 supra EXAMPLES Milling Properties Hoi Strength Tack Plasticity 3 ,9 0 4 ,5 7 9 15 16 TABLE V PERFORMANCE PROPERTIES 3 4 5 6 7 8 Good Fair Acceptable Good Good Good -- Bud (No Sheet) Poor Good Excessive Good Poor Very Boardy Gtxid Poor Slightly Boardy McBurney Hardness 1 minute at 77F 8.4 9.3 8.9 8.9 8.3 Brabender Molten Flow Peak Torque (m-gm) u* Equilibrium Torque (m-gm) Mux. Tem perature C 4900 2550 170 5200 2200 164 4600 2450 170 3400 1850 161 4900 2550 170 6000 2250 168 Impact Resistance <2' (number of impacts required for failure) 8,1 10 7, K -- 1. 2 23, 28 3, 4 ,0 Mutcr-grcim. ,3) V alues d e te rm in e d for du p licate test sp ecim en s With reference to Table V, the data therein reveals ond recipe designated for convenience as VAT (vinyl tchoaptorleycmipeers(cEoxnatmaipnlieng8a)l,l aPlVl Crel(aEtixvaemlyplheig5h),mPoVlCecpulluasr 25 afislbleersstoasndtilues)e,demthpeloafyoerdesaasibde8st6osviannydl clhimloersitdoen/e14asvinthyel weight terpolymer (Example 7), and all copolymer acetate copolymer as the polymeric binder. The recipes (Example 6 ) showed sufficient deficiencies to be re were blended in a Hobart mixer and then mixed and jected. The all PVC recipe (No. 5) exhibited very poor fused in a Banbury mixer at 350F untile fused and ho milling properties due to poor roll adhesion and board mogeneous. The fused stocks were then banded on an y characteristics which caused considerable difficulty 30 8 inch two roll mill set at 110 and l40C on the front in forming a mill blanket. The all terpolymer recipe and back rolls, respectively. A sheet gauge of approxi (No. 7) gave exceptionally good impact resistance but mately 190 mils were removed from the mill and calen again poor milling properties due to inferior roll adhe dered to 125 mils gauge with two successive passes sion (tack) causing the stock to wander from the front 35 through the calender. Specimens were cut and condi to rear mill rolls. The recipe employing all copolymer tioned at 25C and 50% relative humidity prior to test (No. 6 ) was excessively plastic and lacked hot strength. ing. Methods provided in Federal Test Method Stan Recipe (No. 8 ) utilizing copolymer and homopolymer dard No. 501A were used to obtain McBurney hard had inferior processing properties due to poor roll ad ness values at 77 and 115F, impact resistances, and hPeCsLioninancodmitbsibnoaatirodnywchitahrathcteercisotpico.lyLmowereranadmoteurnptosloyf 40 vPolalasttiilciotiredse. r Inmoaldtednitifolnow, mdialtla rwateinregsdeatnedrmBinreadb.enTdheer mer, as illustrated in recipes (No. 3 and No. 4) exhib Brabender employed a No. 6 roller head using a sample ited good processing and performance properties. charge of 100 grams; bowl temperature was set for 150C and rpm's at 60. Water absorption and water ex EXAMPLES 9-10 pansion data were also derived. Values were obtained Examples 9-10 illustrate the processing and mechan 45 for both tests after water exposures of 1, 3 and 7 days ical properties of two comparable recipes. The first rec at room temperature. The absorption values represent ipe, designated for convenience as NAT (non-asbestos weight percent gain after the designated exposures. Ex tile), used limestone as the sole filler and, as the poly pansions are in terms of mils per 8 inch measured dmee/r1ic4 bviinnydlerasc, eatatceomcobpinoalytimonero, fin(hi)er8en6t vvinisycloscihtyloroif 50 acTrohses rmecaicpheisneardeirseecttioount. in Tabic VI infra and perfor 0.4, and (ii) 88 vinyl chloride/10.5 vinyl acetate/1.5 mance properties of '/s-inch gauge sheet are recorded ethylene terpolymer, inherent viscosity of 0.7; the sec- in Table VII infra. TABLE VI 7R Asbestos 40 Mesh Umcsionc " Atomitc" (true limestone) Copolymer" ' Terpolymer*"1 Wood Rosin " Amoco" IH,:" Ba-Cd Stabilizer DOP1" Butyl Benzyl Phthalate EPO'"" White Pigment Stearic Acid FORMULATION; WT. rh NAT RECIPE (No PCL) _ 55.6 24.8 5.7 5.3 0.19 1.0 0.35 --2.80 0.50 3.76 _ _ VAT RECIPE (N o PCL) 20 57 _ p .n _ (1.2 0.7 _0,3 4.30 0.62 4.0 0,08 n un 3 ,904,579 17 18 TABLE VI-continued FORMULATION; WT. NAT RECIPE (No PCD VAT RECIPF. (Nu PCL.) Total UX) 100 "*H6 Vinyl chlc>Tidc/l4 v itn l sicctatc copolym er, inherent viscosity o t'a lm u l 0.4. ,a,KH Vinyl e h lo n d e /)0 .5 vinyl a c e ta te /1.5 ethylene turpolyntcr. in h eren t viscosity o f ab o u t 0.7. "'PolyO ilphu-m othylstyrcne). average m olecular weight o f ab o u t KtxMOOO. ,4,Di| 2-ethylhuxy!) phthalate. `a,Epo*idi^c<l soya bean oil. ""Nitrogenous based vinyl asbestos tile stahili/er (dicyandiam ide). TABLE VI PERFORMANCE PROPERTIES % INCH GAUGE NAT RECIPE VAT RECIPE (NO PC D (NO PCI.) Milling Properties"1 Hot Strength Tack Plasticity Satisfactory Good Acceptable Good Good Normal Brhender Daly'-' Peak Torque (m-gm) Equilibrium Torque (m-gm) Max. Temperature 3400 ISSO ih re 4900 2100 ih re Impact Resistance"*' Average 5 8 McBurney Indentation 1 min.. 77F 8.5 7.2 1U min.. 77F 12.y 9.5 Vi min.,' 115F 21.4 27.0 Water Absorption (Weight rA Gain) 1 Day 3 Da vs 7 Davs 0.8 1.5 1.5 2.1 I.K 2.0 Water Expansion (Mils/8 inch) 1 Dav 5 5 3 Days 5 10 7 Days 5 30 Light Stability"' (Fadcometcr Hrs. ) 192 112 " T h e s e are mill processing properties reflecting roll adhesion, toughness and sheeting qualities. '?,No. 6 Roller head. GO RPM , IlH) gm specim en. I50*C`. '"'Data o b tain ed tin l/IG th gauge tile-. Federal T est M ethod S tandard No. 501 A. average o f 3 experiments. " 'Determ ined in accordance with ASTM M ethod E-4264. exhibited torque values which did not equilibriate in a 15 normal fashion but whose torque continued to increase with time. The Brabender data was consistent with the observed milling characteristics of the recipes. The non-asbestos NAT recipe (with antioxidant) exhibited no boardiness and generally good milling qualities com2Q parable to the asbestos-containing VAT recipe. Table VIII below records both recipes. TABLE VIII EORMU1 .ATION; WT. f/< NAT RECIPE 25 EXAMPLE 1 1 7R Asbestos 40 Mesh Limestone " Atomhc" (fine limestone) Copolvmer Tcrpoivm er,-1 30 Wood Rosin " Amoco" !K,;u Ba-Cd Stabilizer HOP"' Hulvl Bcn/yl Phthalate EPO ,r" White Pigment 35 Stearic Acid " Mark" 140 PCI. lonol _ 55.6 24.1 5.7 5.3 0.19 0.98 0.35 _2.20 0.52 3.76 _n.i 0.70 0.50 Total 100 VAT RECIPE 12 20 5--7 12.0 -- 0.2 0.7 _0.3 4.30 0.62 4.0 0.08 _0.80 -- 100 1.1 KG Vinyl chloride/14 vinyl a cetate copolym er, inherent viscosit\ of about (1.4 4 0 '* KK Vinyl ehloridc/10.5 vinyl ac eta te /I .5 ethylene tcrpolym er. inherent viscosity o r about 0.7. ,;m l'oly(alpha-m ethyl.st\renc). average m olecular weight o f about 8U0-K J0U. Di(2*cth\lhcvyl) phthalate Epoxidi/eil soya bean oil. N itrogenous bast'll vinyl asbestos tile s ta h ili/e r <(iieyandiantide ). 1.1 E psilon-eaprolaelim e hum npolym er. red u ced viscosity v>f aGout 0.7. 4 5 "l' 2.G-Di-t*hulyl*p-cresol. EXAMPLES 11-12 Two recipes were prepared and processed in the EXAMPLES 13-16 identical manner as set forth in Examples 1-2 supra. Four recipes were prepared (see Table IX) and pro- The non-asbestos NAT recipe (Example 11) is practi 50 cessed as described in Examples 1 and 2 for compari cally the same as the NAT recipe of Examples 1-2 with son purposes. Example 13 is a typical and preferred the exception that 0.1 weight percent stearic acid and composition according to this invention. Example 14 is 0.5 weight percent Ionol (2,6-di-t-butyl-p-cresol) arc essentially identical to Example I 3 except that it docs incorporated therein. The asbestos-containing VAT not include the preferred normally-solid oxyalkanoyl recipe (Example 12) is the same as the VAT recipe of 55 polymer. Examples 1-2. Example 15 illustrates the use of conventional vinyl The milling properties of both recipes are rated as resin comprised of a blend of two copolymeric resins in follows: non-asbestos NAT recipe (Example II) --g- the formulation of non-asbestos tile. Example 16 illus oood hot strength, good tack, and normal plasticity; as trates the use of a blend of a copolymeric vinyl resin bestos-containing VAT recipe (Example 12)--good w) and a terpolymeric vinyl resin of the type used in the hot strength, good ta c k , a n d normal p la s tic ity . The B ra - present invention, but without solid oxyalkanoyl poly bender Plasticorder molten flow data of the nonasbe mer. stos NAT recipe revealed that the resulting torque-time The test results set forth in Table X clearly show that molten flow curve became normal in that the equilib the incorporation of a minor amount of oxyalkanoyl rium torque value was achieved within a time span gen 65 polymer (Example 13) affords a substantial improve erally considered to be within the optimum range for ment in hot strength which is shown by improved ten asbestos-containing VAT recipes. Without the 2,6-di-t- sile strength and milling qualities of Example 13 as butvl-D-crcsol antioxidant, the nonasbestos-tile recine cnm nttnd tn F v ^ m n lp 14. H n t fam -iln c tro rm tk ...< 3 ,904,579 19 creased by approximately 16% along with a substantial increase in Brabendcr equilibrium tongue. 20 EXAMPLES 17-30 The drastically reduced Brabendcr equilibrium Fourteen limestone filled, non-asbestos recipes in tongue values and extremely poor milling properties for corporating varying amounts of: vinylidene chloride/vi- Examples 15 and 16 demonstrate the total unsuitability 5 nyl chloride copolymer; vinyl chloride/propylene co of these formulations for floor tile use. The substantial polymer; chlorinated polyethylene polymer; or low mo increase in stress relaxation time also precludes the use lecular weight vinyl chloride/vinyl C2-C 4 alkanoate/C- of these compositions in non-asbestos tile applications 2-C4 alkene random terpolymer were prepared, due to a serious lack in dimensional stability. It is con blended, fused, sheeted and tested as described in Ex sidered important to note that the substitution of ter- 10 amples 1-2 supra. In examples 19, 22 24 and 27 rela polymer in Example 16 for one of the copplymers of tively high molecular weight terpolymer was omitted Example 15 produced a dramatic increase in Bra- from the recipe to confirm the criticality of this ingredi bender equilibrium torque and in hot tensile strength ent to better indicate the contribution of the binder even though the terpolymer included only l .5% ethyl resin to the properties of the final product and to pro ene. cessing conditions. Data obtained is recorded in Tables TABLE IX FORMULATIONS; PARTS BY WEIGHT EXAMPLE 13 14 15 u> Raw Materials 40 Mesh Limestone " Atomile" (fine limestone) Copolymer Terpolymer Copolvmcr C opolvm er111 PCI.-700 Wood Rosin " Amoco" 18 "i* Ha-Cd Stuhilt/cr lonolm DOP "" F.PO While Pigment TOa "B onw fV x" yXX Stearic Acid TOTAL 2780 1235 285 265 0 0 35 9.5 49 17.5 12.5 110 26.5 1XX 0 0 5013 278U 235 285 265 0 0 0 9.5 47 17.5 12.5 145 26.5 188 0 0 5013 0 2388 0 575 825 0 0 0 100 0 0 0 5(H) 600 12.5 5000.5 2388 0 575 0 825 0 0 0 UK) 0 0 0 5(H) 600 12.5 5000.5 Ul Kf> vinyl c h lo rid e /U vinyl aconite copolym er, in h eren t viscosity o f dtout (1.4 1:1 HH vinyl chloride/IO .5 vinyl e th y len e, terpolym er. in h eren t viscosity o f ab o u t 0.7 n ' Xb vinyl ch lo rid e/1 4 v in jl a c e ta te copolym er, in h eren t viscosity o f al*>ut 0.5 NX vinyl chloride/1 2 vinyl a c e ta te copolym er, inherent viscosity o f ab o u t 0,7 0> F psilon-caprolnclonc h o m o polym er, re d u c e d viscosity o f ab o u t 0,7 *** Epsilon-caprolnetone h b m o polynter, red u c e d viscosity o f ab o u t 0 7. P o M a lp h a -m e th y lsty re n e ). av erag e m olecular weight o f about HOO-lOtm *5` 2.<>-l)i-i-huiyl-p-ercsol Di< 2-elhylhe.vyl) phthalate, (*po\idi/ed soya I'can oil Dipnpylene glycol iliben/oate TABLE X Example TILE PERFORMANCE PROPERTIES 13 14 15 Milling Properties m Hot Strength Tack Plasticity Nerve Good Good Normal Minor Fair Good Normal Minor Too plastic to rate Poor Excessive Excessive Brabendcr Melt Flow Data Equil. Torque (m-gms) Max. Stock Temp. CC.) 2650 2100 9(K> IK0 169 151 McBurncy Hardness t;" I min. at 77T' 7.6 8,0 23.3 Impact Resistance ,A> Average Range 8.6 7,3 30 8-10 7-8 -- Relaxation Tinte (sees.) ,M 38 38 UK) Tensile Strength at I80PF 44 38 51 rA Elongation at I80F 31 32 189 mill processing p ro p erties rellec tin g roll adltcsion. toughness ami sltc d iu g validities * No. 6 R oller h a u l. Ml RPM . ]0 0 gm Specim en. I5<J*C*. F ederal Spec. Test M eth o d No. 501 A M eth o d No. 321 J V alues show n are average results from six replicates. 16 Too plastic to rate Poor Excessive Excessive 1 125 55 23.0 30 -- UK) 82 I7U 3 ,904,579 21 XI and Xll below. In Table XI a dash signifies omission dicates that the test was no2t2preformed on the data was of the indicated ingredient while in Table Xll a dash in- not recorded. TABLE XI Example Raw Materials 40 Mesh l,,imesione Fine Limestone Binder Resin m Binder Resin 1,1 Binder Resin <2'1 Binder Resin ,!M Binder Resin 141 Binder Resin <a* Terpolymer ,m " Amoco" IK 1,1 Bu*Cd Stabilizer Di( 2-ethylhexyl )phthalate Wood Rosin White Pigment (TiO*) EPO PCL-7UO " 17 IK 50 1300 221 140 -- -- -- 199 47.6 11 112 X 50 26.2 35.2 Formulation; Parts by Weight IX 19 20 21 2850 13(H) 147 2X1) -- -- -- -- 133 47.6 1 1 112 X 50 26.2 35.2 2600 1 I8X -- 512 -- -- -- -- -- 43.5 10 102.4 7.3 45.7 24 32.2 2850 13(H) 2_21 -- 140 _ -- 199 47.6 11 112 X 50 26.2 35.2 2850 1300 147 __ -- 280 -- _ 133 47.6 1 1 112 X 50 26.2 35.2 22 2850 1300 __ __ -- 560 __ -- -- 47.6 1 1 112 8 50 26.2 35.2 23 2850 1300 146.5 __ __ _ 146.5 _ 267 47.6 1 1 112 8 50 26.2 35.2 24 25 2ft 2850 1300 293 -- _ _ 267 _ __ 47.6 II l 12 8 50 26.2 35.2 2850 1300 221 __ _ _ 14(1 199 47.6 1 1 1 12 8 50 26.2 35,2 2X50 1300 147 _ _ 280 133 47..6 1 1 1 12 X 50 26.2 35.2 Example 27 2X 29 30 Raw Materials 40 Mesh Limestone Fine Limestone Binder Resin *" Binder Resin Wl Binder Resin 120 Binder Resin 1:11 Binder Resin Binder Resin lT,i Terpolymer Hi> " A m o c o " 1X 171 Bn-Cd Stabilizer Di( 2-ethylhexy! )phlhulate Wood Rosin White Pigment (TiO*.) EPO P C I.-700 MM 2X50 1300 -- -- -- -- -- 560 -- 47.6 1 I 112 X 50 26.2 35.2 2850 1300 iy y -- 140 -- -- -- 199 47.6 I 1 1 12 X 50 26.2 35.2 2X50 1300 133 _ 2X0 _ _ -- 133 47.6 1 1 1 12 X 50 26.2 35.2 2X50 1300 __ --_ __ 293 -- 267 47.6 II 1 12 X 50 26.2 35.2 Nows; *" X( vinyl chlnride/M vinyl a c e ta te copolym er, in h eren t viscosity o f ab o u t 0.4 '-1 vinylitjenc chlnridu/40 vinyl chloride; inherent viscosity .39-.40 *'9.3-97 v im lid cn c c h lo rid c/3 -7 vinyl chloride; inherent viscosity .8 3 -.H6 9 6 vinyl chloride/4 propylene; inherent viscosity .57-.fi3 **' Dow C hem ical MX 2243.35 c h lo rin ated polyethylene; J.S'/f chlorine; i)rA relative crystallinity; m olten IS> K7.2 vinyl c h lo rid e/1 1.7 vinyl acetate/1 .1 ethylene, terpolym ur. in h eren t viscosity ab o u t 0.5 " KK vinyl ch lo rid e/1 0.5 vinyl a e e ta tc /l .5 ethylene, terp n ly m er. inherent viscosity o f about 0,7 ,ri Poly ( iilpha-mclh> Istyrene av erag e m olecular weight o f ab o u t KtK>--t (HM> '" Epoxidt/.cd soya beau oil ,w Epsilun-cuprolaetune hom opolym er, reduced viscosity o f ab o u t 0.7. viscosity 2200 poises at I9()C. Example Banbury Mix Time (mins.) Kilowatts (Peak) Drop Temperature Mill Hot Strength Brhender Min. Torque (m-gms) Temperature C ATorque (m-gms)11' Shear Relaxation l2> l/e (sees.) McBurncv 1 min. Indent (mils) Average Impacts Hot Tensile Relaxation (secs. ) Example Banbury Mix Time (mins.) tfilouniHu / Pon I TABLE Xll Experimental Results . 17- 18 19 20 21 22 23 24 25 5 4.5 7 5 5 4 6 8.6 X.7 7.1 7.8 7.9 X.X X.3 X.X 7.6 315 310 270 328 331 330 345 340 325 Good Fair Poor Good Good Good Poor Poor Good 2700 2470 1500 -- 178 174 59 -- 6XO - 730 - 48 -- 30 -- 2920 -- 177 -- - - -- 3370 3110 _ 182 1X1 -- 640 540 - 54 54 _ 8.5 10.4 23.5 7.2 7.1 6.7 10.0 14.0 7.6 Too 2.3 3.ft Soft 2.3 3 1.6 30 27 4 -- 9.7 -- _ 27 -- 32 12 _ 26 27 28 29 30 5 4.5 7 H.S 4 7 U 7 7 U6 un un Example Drop Temperature 3 ,904,579 23 24 TABLE XII-continued Experimental Results 17 IX 19 20 21 22 23 24 25 320 310 345 345 345 Mill Hot Strength Fair Poor Good Poor Fair BruH endcr Min. Torque (m-gms) Tem perature `C T orque (m-gms) 111 Shear Relaxation l/e (sees.) McBurncy 1 min. indent (mils) Average impacts Hot Tensile Relaxation i:tl (sees.) 2740 182 _ - - --_ 7.6 K.6 4.6 3.6 IV.2 -- _ 3620 175 3670 182 - - 630 -- -- 42 7.2 7.8 15-15.5 11.3 7 >50 -- - 4 0 18 Notes: A T orquo. im m ediate to rq u e in crease caused by allow ing specim en to rem ain a t rest o n e m inute followed by co n tin u e d shearing; used Ixring lo rote senstivity o f stock to Hetn^ w orked. Decay rate o f A torque, also used as measure o f com position's sensitivity to worked. Tim e for (ensile stress at IHOT to decay to l/c of initial value ( ) . used ns a measure of tile dimensional stability. The data recorded above demonstrates the impor tance of including relatively high molecular weight ter- polymer in the recipe as all of the Examples ( 19, 22, 24 and 27) in which it was totally excluded resulted in a product which was unacceptable and could be pro 30 duced only by resorting to processing conditions which are equally unacceptable. The remaining recipes yielded products which are acceptable from the stand point of both product characteristics and processing conditions but which do not appear as desirable on bal 35 ance as those achieved with recipes employed in the earlier examples. Examples 17-19 reveal the important contribution of the vinylidene chloride/vinyl chloride copolymer to product dimensional stability while Ex amples 23, 24 and 30 reveal the remarkable contribu 49 tion of chlorinated polyethylene to impact stability. These data provide the skilled worker in the field with the means to tailor the recipes of this invention by add ing varying amounts of binder ingredients to achieve a compromise in product physical properties and in pro 45 cessing conditions best suited to the requirements of a particular application. I claim: 1. A plasticized solid composition comprising a plas ticizer containing a homogeneous mixture of: 50 a. normally solid thermoplastic polymeric binder se lected from the group consisting of: i. vinyl chloride/vinyl Cr-C^ alkanoate polymer in which the polymerized vinyt chloride portion thereof comprises at least about 70 weight per 55 cent and the polymerized vinyl C2-C 4 alkanoate portion thereof comprises up to about 30 weight percent ii. vinylidene chloride/vinyl chloride polymer in which the polymerized vinyl chloride portion 60 thereof comprises at least about 50 weight per cent and the polymerized vinlylidene chloride portion thereof comprises up to about 50 weight percent iii. vinyl chloride/propylene polymer in which the 65 polymerized vinyl chloride portion thereof com prises at least about 90 weight percent and the prises from about 10 to about 4 percent by weight iv. chlorinated polyethylene polymer having not greater than 5 percent crystallinity; a molten viscosity of from about 10,000 to 30,000 poises at 190C and a chlorine content of at least 40 per cent by weight v. vinyl chloride/vinyl C2-C 4 alkanoate/C2-C 4 alkene random terpolymer having an inherent viscosity less than about 0.5 in which the polymer ized vinyl chloride portion thereof comprises the major proportion by weight vi. mixtures of said polymers b. normally-solid thermoplastic vinyl chloride/vinyl C2-C 4 alkanoate/C2-C 4 alkene relatively high mo lecular weight random terpolymer having an inher ent viscosity of from about 0.5 to about 0.9 in which the polymerized vinyl chloride portion thereof comprises the major portion by weight; and c. a filler; wherein the total combined weight of said polymeric binder and said relatively high molecular weight ter polymer is comprised of from about 25 to about 65 weight percent polymeric binder and from about 75 to about 35 weight percent of said terpolymer; and wherein said filler is present in amounts ranging from about 200 to about 750 parts by weight per 100 parts by weight of said polymeric binder and said relatively high molecular weight terpolymer. 2. The composition of claim 1 wherein said terpoly mer is vinyl chloride/vinyl acetate/ethylene terpolymer. 3. The composition of claim 1 wherein said poly meric binder is vinyl chloride/vinyl C^-C, alkanoate co polymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C 4 alkanoate portion thereof comprises up to about 30 weight percent. 4. The composition of claim 1 wherein said poly meric binder is vinylidene chloride/vinyl chloride polymer in which the polymerized vinyl chloride portion thereof comprises at least about 50 weight percent and the polymerized vinylidene chloride portion thereof 3 ,904,579 5. The composition of 2cl5ai.m 1 wherein said poly 26 to about 5 weight percent polymerized vinyl acetate; meric binder is vinyl chloride/propylenc polymer in wherein said terpolymer comprises at least about 75 which the polymerized vinyl chloride portion thereof weight percent polymerized vinyl chloride, less than comprises at least about 90 weight percent and the po about 24.5 weight percent polymerized vinyl acetate, lymerized polypropylene portion thereof comprises 5 and at least about 0.5 weight percent polymerized eth from about 10 percent to about 4 percent by weight. ylene. 6. The composition of claim 1 wherein said poly 15. The composition of claim 14 wherein said poly meric binder is chlorinated polyethylene polymer hav meric binder comprises from about 30 to about 60 ing not greater than 5 percent crystallinity, a molten weight percent of said copolymer, from about 40 to viscosity of from about 1000 to 3000 poises at 1 9 0 ^ 10 about 70 weight percent of said terpolymer, and from and a chlorine content of at least 40 percent by weight. about one to about 10 weight percent of said thermo 7. The composition of claim 3 wherein said copoly plastic oxyalkanoyl polymer. mer comprises from about 80 to about 95 weight per 16. The composition of claim 1 wherein said filler is cent polymerized vinyl chloride and from about 20 to a non-fibrous filler. about 5 weight percent polymerized vinyl acetate; and 15 17. The composition of claim 16 wherein said filler is wherein said relatively high molecular weight terpoly- limestone. mer comprises at least about 75 weight percent poly 18. The composition of claim 1 wherein said homo merized vinyl chloride, less than about 24.5 weight per geneous mixture also comprises a small amount of an cent polymerized vinyl acetate, and at least about 0.5 antioxidant. weight percent polymerized ethylene. 20 19. The composition of claim 18 wherein said antiox 8. The composition of claim 7 wherein said tcrpoly- idant is 2,6-di-t-butyl-p-cresol. mer comprises from about 80 to about 90 weight per 20. The composition of claim 1 wherein said vinyli- cent polymerized vinyl chloride, from about 9 to about dene chloride/vinyl chloride polymer is one in which 17 weight percent polymerized vinyl acetate, and from the polymerized vinyl chloride portion thereof com about 1 to about 3 weight percent polymerized ethyl 25 prises from about 50 to about 90 weight percent and ene. the polymerized vinylidene chloride portion thereof 9. The composition of claim 1 wherein said poly comprises from about 50 to about 10 weight percent, meric binder also contains from about 0.5 to about 15 having an inherent viscosity of from about 0.35 to weight percent of a normally-solid thermoplastic oxyal- about 0.60. kanoyl polymer having a reduced viscosity value of at 30 21. The composition of claim 1 wherein said vinyl least about 0.1 and which is further characterized in chloride/propylene polymer has an inherent viscosity that at least about 50 weight percent of said thermo of from about 0.4 to about 0.7 and the polymerized plastic oxyalkanoyl polymer is attributable to recurring vinyl chloride portion thereof comprises from about 90 oxyalkanoyl units of the formula to 96 weight percent and the polymerized polypropyl 35 ene portion thereof comprises from about 10 to about 0 4 weight percent. 22. A plasticized solid composition comprising a --- 0---- (CH^----- C ---- , 4 X plasticizer containing a homogeneous mixture of: a. a mixture of normally solid vinyl chloride/vinyl 40 CVC.) alkanoate copolymer in which the polymer wherein .v is an integer having a value of 2 to 7, with the ized vinyl chloride portion thereof comprises at proviso that .v does not equal 3. least about 70 weight percent and the polymerized 10. The composition of claim 9 wherein said recur vinyl C.,-C.i alkanoate portion thereof comprises up ring oxyalkanoyl units have the formula to about 30 weight percent and one or more nor 45 mally solid thermoplastic polymeric binder resins 0 II ------ 0 ----------(ch2^ -------- C--------- . selected from among: i. vinylidene- chloride/vinyl chloride polymer in which the polymerized, vinyl chloride portion thereof comprises at least about 50 weight per 50 cent and the polymerized vinylidene chloride 11. The composition of claim 9 wherein said thermo portion thereof comprises up to about 50 weight plastic oxyalkanoyl polymer has a reduced viscosity percent value of at least about 0.2 to about 3 and is further ii. vinyl chloride/propylene polymer in which the characterized in that at least about 60 weight percent of said polymer is attributable to the recurring oxyal 55 polymerized vinyl chloride portion thereof com prises at least about 90 weight percent and the kanoyl unit shown therein. polymerized polypropylene portion thereof com 12. The composition of claim 11 wherein at least prises from about 10 percent to about 4 percent ubout 80 to about 100 weight percent of said thermo by weight plastic oxyalkanoyl polymer is attributable to recurring oxycaprovl units. 60 iii. chlorinated polyethylene polymer having not greater than 5 percent crystallinity a molten vis 13. The composition of claim 12 wherein said poly cosity of from about 1000 to 3000 poises at meric binder is vinyl chloride/vinyl acetate copolymer, 190C and a chlorine content of at least 40 per wherein said terpolymer is vinyl chloride/vinyl acetate- cent by weight and /ethylcne terpolymer. and wherein said thermoplastic oxyalkanoyl polymer is poly(epsilon-caprolactone). 65 iv. vinyl chloride/vinyl C2-C4 alkanoate/Cj-C., alkene random terpolymer having an inherent vis 14. The composition of claim 13 wherein said co cosity less than about 0.5 in which the polymer polymer comprises from about 80 to about 95 weight _______* ___i_____ :___t ..:__ i ..L i__ : . i _ __ i r --------,.i-------. n o ized vinyl chloride portion thereof comprises the 3 ,9 0 4 ,5 7 9 27 28 b. normally-solid thermoplastic vinyl chloride/vinyl 30. The composition of claim 29 wherein said recur C2-C.,alkanoate/C2-C.|Ulkene relatively high mo ring oxyalkanoyl units have the formula lecular weight random terpolymer having an inher ent viscosity of from about 0.5 to about 0.9 in which the polymerized vinyl chloride portion 5 thereof comprises the major portion by weight; and -------0 ----------- ( C H ^ ---------- C ---------- . c. a filler; wherein the total combined weight of said polymeric binder and said relatively high molecular weight ter 31. The composition of claim 29 wherein said ther polymer is comprised of from about 25 to about 65 10 moplastic oxyalkanoyl polymer has a reduced viscosity weight percent polymeric binder and from about 75 to value of at least about 0.2 to about 3 and is further about 35 weight percent of said terpolymer; and characterized in that at least about 60 weight percent wherein said filler is present in amounts ranging from of said polymer is attributable to the recurring oxyal about 200 to about 750 parts by weight per 100 parts kanoyl unit shown therein. by weight of said polymeric binder and said relatively 15 32. The composition of claim 31 wherein at least high molecular weight terpolymer. about 80 to about 100 weight percent of said thermo 23. The composition of claim 22 wherein said ter plastic oxyalkanoyl polymer is attributable to recurring polymer is vinyl chloride/vinyl acetate/ethylenc ter oxycaproyl units. polymer. 33. The composition of claim 22 wherein said filler is 24. The composition of claim 22 wherein said poly 20 a non-fibrous filler. meric binder is vinylidene chloride/vinyl chloride poly 34. The composition of claim 33 wherein said filler is mer in which the polymerized vinyl chloride portion limestone. thereof comprises at least about 50 weight percent and 35. A plasticized solid composition comprising a cthoempproilsyems eurpizteod avbionuytli5d0enweecighhlot rpiderecepnot.rtion thereof 25 plaa.stipcoizleyrmceornictaibniinndgera hcoommporgiesinnegou(si)mnixotrumrealolyf:-solid 25. The composition of claim 22 wherein said poly thermoplastic vinyl chloridc/vinyl C2-Cj alkanoate meric binder is vinyl chloride/propylcne polymer in copolymer in which the polymerized vinyl chloride which the polymerized vinyl chloride portion thereof portion thereof comprises at least about 70 weight comprises at least about 90 weight percent and the po 30 percent and the polymerized vinyl C2-C 4alkanoate portion thereof comprises up to about 30 weight lymerized polypropylene portion thereof comprises percent; and (ii) normally-solid thermoplastic vinyl from about 10 percent to about 4 percent by weight. 26. The composition of claim 22 wherein said poly chloridc/vinyl C2-C , alkanoate/Q-C, alkene ran meric binder is chlorinated polyethylene polymer hav dom terpolymer in which the polymerized vinyl ing not greater than 5 percent crystallinity, a molten 35 chloride portion thereof comprises the major por tion by weight; and viscosity of from about 1000 to 3000 poises at 190C b. a filler; and a chlorine content of at least 40 percent by weight. c. said polymeric binder comprising from about 25 to 27. The composition of claim 22 wherein said co about 65 weight percent of said copolymer and polymer comprises from about 80 to about 95 weight from about 35 to about 75 weight percent of said percent polymerized vinyl chloride and from about 20 40 terpolymer; and to about 5 weight percent polymerized vinyl acetate; d. said filler being employed in amounts ranging from and wherein said relatively high molecular weight ter about 200 to about 750 parts by weight per 100 polymer comprises at least about 75 weight percent po parts by weight of said polymeric binder. lymerized vinyl chloride, less than about 24.5 weight 36. The composition of claim 35 wherein said ter percent polymerized vinyl acetate, and at least about 45 polymer is vinyl chloride/vinvl acetate/ethylenc ter 0.5 weight percent polymerized ethylene. polymer and wherein said copolymer is vinyl chloride/- 28. The composition of claim 27 wherein said ter vinyl acetate. polymer comprises from about 80 to about 90 weight 37. The composition of claim 36 wherein said co percent polymerized vinyl chloride, from about 9 to polymer comprises from about 80 to about 95 weight about 17 weight percent polymerized vinyl acetate, and 50 percent polymerized vinyl chloride and from about 20 from about 1 to about 3 weight percent polymerized to about 5 weight percent polymerized vinyl acetate; ethylene. and wherein said terpolymer comprises at least about 29. The composition of claim 22 wherein said poly 75 weight percent polymerized vinyl chloride, less than meric binder also contains from about 0.5 to about 15 about 24.5 weight percent polymerized vinyl acetate, weight percent of a normally-solid thermoplastic oxyal- 55 and at least about 0.5 weight percent polymerized eth kanoyl polymer having a reduced viscosity value of at ylene. least about 0.1 and which is further characterized in 38. The composition of claim 37 wherein said ter that at least about 50 weight percent of said thermo polymer comprises from about 80 to about 90 weight plastic oxyalkanoyl polymer is attributable to recurring percent polymerized vinyl chloride, from about 9 to oxyalkanoyl units of the formula 60 about 17 weight percent polymerized vinyl acetate, and from about 1 to about 3 weight percent polymerized 0 ethylene. -- -- II c ------------------ ------------------ 39. The composition of claim 35 wherein said poly meric binder also contains from about 0.5 to about 15 65 weight percent of a normally-solid thermoplastic oxyal kanoyl polymer having a reduced viscosity value of at wherein .v is an integer having a value o f 2 to 7, with the least about 0.1 and which is further characterized in u .* o u * m U . .* c n i..s - .:,.u * ________ . ,, r ,, ,, j + . . . . . . 3 ,9 0 4 ,5 7 9 29 plastic oxyalkanoyl polymer is attributable to recurring 30 and good dentation resistance and which is manufac oxyalkanoyl units of the formula tured from a processible mixture comprising a homoge neous mixture of: II0 ---- 0------(.CRy)------ C ----- , c x a. normally solid thermoplastic polymeric binder se 5 lected from the group consisting of: i. vinyl chloride/vinyl Cj-C, alkanoate polymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight per wherein x is an integer having a value of 2 to 7, with the cent and the polymeriz.ed vinyl C2-C Aalkanoate proviso that x does not equal 3. 10 portion thereof comprises up to about 30 weight 40. The composition of claim 39 wherein said recur percent. ring oxyalkanoyl units have the formula ii. vinylidene chloride/vinyl chloride polymer in which the polymerized vinyl chloride portion II0 thereof comprises at least about 50 weight per 15 cent and the polymerized vinylidene chloride ------- 0 ------- ch2^ -------- C ---------- . portion thereof comprises up to about 50 weight percent iii. vinyl chloride/propylene polymer in which the 41. The composition of claim 39 wherein said ther moplastic oxyalkanoyl polymer has a reduced viscosity 20 polymerized vinyl chloride portion thereof com prises at least about 90 weight percent and the value of at least about 0.2 to about 3 and is further polymerized polypropylene portion thereof com characterized in that at least about 60 weight percent prises from about 10 percent to about 4 percent of said polymer is attributable to the recurring oxyal by weight kanoyl unit shown therein. 42. The composition of claim 41 wherein at least 25 iv. chlorinated polyethylene polymer having not greater than 5 percent crystallinity a molten vis about 80 to about 100 weight percent of said thermo cosity of from about 1000 to 3000 poises at plastic oxyalkanoyl polymer is attributable to recurring 190C and a chlorine content of at least 40 per oxycaproyl units. cent by weight 43. The composition of claim 42 wherein said co polymer is vinyl chloride/vinyl acetate copolymer, 30 v. vinyl chloride/vinyl Cr C4 alkanoate/C-i-C^ alkcnc random terpolymer having an inherent vis wherein said terpolymer is vinyl chloride/vinyl acetate- cosity less than about 0.5 in which the polymer /ethylene terpolymer, and wherein said thermoplastic ized vinyl chloride portion thereof comprises the oxyalkanoyl polymer is poly(epsilon-caprolactone). major proportion by weight 44. The composition of claim 43 wherein said co vi. mixtures of said polymers polymer comprises from about 80 to about 95 weight 35 b. normally-solid thermoplastic vinyl chloride/vinyl percent polymerized vinyl chloride and from about 20 C2-C4alkanoate/C2-C.,alkene relatively high mo to about 5 weight percent polymerized vinyl acetate; lecular weight random terpolymer having an inher wherein said terpolymer comprises at least about 75 ent viscosity of from about 0.5 to about 0.9 in weight percent polymerized vinyl chloride, less than about 24.5 weight percent polymerized vinyl acetate, 40 which the polymerized vinyl chloride portion thereof comprises the major portion by weight; and and at least about 0.5 weight percent polymerized eth c. a filler; wherein the total combined weight of said ylene. polymeric binder and said relatively high molecular 45. The composition of claim 44 wherein said poly weight terpolymer is comprised of from about 25 to meric binder comprises from about 30 to about 60 weight percent of said copolymer, from about 40 to 45 about 65 weight percent polymeric binder and from about 75 to about 35 weight percent of said about 70 weight percent of said terpolymer, and from terpolymer; and wherein stud filler is present in about one to about 10 weight percent of said thermo amounts ranging from about 200 to about 750 plastic oxyalkanoyl polymer. parts by weight per 100 parts by weight of said pol 46. The composition of claim 35 wherein said filler is a non-fibrous filler. 50 ymeric binder and said relatively high molecular weight terpolymer. 47. The composition of claim 46 wherein said filler is 55. The article of manufacture of claim 54 wherein limestone. said homogeneous mixture also contains from about 48. The composition of claim 37 wherein said filler is 0.5 to about 15 weight percent of a normally solid ther a non-fibrous filler. moplastic oxyalkanoyl polymer having a reduced vis 49. The composition of claim 48 wherein said filler is 55 cosity value of at least about 0.1 and which is further limestone. characterized in that at least about 50 weight percent 50. The composition of claim 35 wherein said homo of said thermoplastic oxyalkanoyl polymer is attributa geneous mixture also comprises a small amount of an ble to recurring oxyalkanoyl units of the formula antioxidant. 51. The composition of claim 50 wherein said antiox 60 idant is 2,6-di-t-butyl-p-cresol. 52. The composition of claim 37 wherein said homo geneous mixture also comprises a small amount of an II0 ----------0 --------- (ch2^ --------- C------- , antioxidant. 53. The composition of claim 52 wherein said antiox 65 wherein x is an integer having a value of 2 to 7, with the idant is 2,6-di-t-butyl-p-cresol. proviso that x does not equal 3. 54. As an article of manufacture, plasticized floor tile having verv low water absorDtion. cood lieht resistance 56. The article of manufacture of claim 54 wherein Silift filln r ic n n n n .f ii,r /m c fill . 3,904,579 31 32 57. As an article of manufacture, plasticized floor tile 59. The article of manufacture of claim 57 wherein having very low water absorption, good light resistance, said filler is a non-fibrous filler. and good indentation resistance and which is manufac 60. As an article of manufacture, plasticized floor tile tured from a processible homogeneous mixture com having very low water absorption, good light resistance, prising: 5 and good indentation resistance and which is manufac a. a mixture of normally solid vinyl chloride/vinyl tured from a processible mixture comprising; Cz-C i alkanoate polymer in which the polymerized a. polymeric binder comprising (i) normally-solid vinyl chloride portion thereof comprises at least thermoplastic vinyl chloride/vinyl C2-C 4alkanoate about 70 weight percent and the polymerized vinyl Cj-C j alkanoate portion thereof comprises up to 10 copolymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight about 30 weight percent and one or more normally percent and the polymerized vinyl C2-C 4alkanoate solid thermoplastic polymeric binder resins se portion thereof comprises up to about 30 weight lected from among: percent; and (ii) normally-solid thermoplastic vinyl i. vinylidene chloridc/vinyl chloride polymer in which the polymerized vinyl chloride portion 15 chloride/vinyl C2-C 4alk.anoate/C2-C 4alkenc ter polymer in which the polymerized vinyl chloride thereof comprises at least about 50 weight per portion thereof comprises the major portion by cent and the polymerized vinylidene chloride weight; and portion thereof comprises up to about 50 weight b. a filler; percent 20 c. said polymeric binder comprising from about 25 to ii. vinyl chloride/propylenc polymer in which the about 65 weight percent of said copolymer, and polymerized vinyl chloride portion thereof com from about 35 to about 75 weight percent of said prises at least about 90 weight percent and the terpolymer; and polymerized polypropylene portion thereof com d. said filler being employed in amounts ranging from prises from about 10 percent to about 4 percent 25 by weight about 200 to about 750 parts by weight per 100 parts by weight of said polymeric binder. iii. chlorinated polyethylene polymer having not 61. The article of manufacture of claim 60 wherein greater than 5 percent crystallinity a molten vis said polymeric binder also contains from about 0.5 to cosity of from about 10,000 to 30,000 poises at about 15 weight percent of a normally solid thermo 190C and a chlorine content of at least 40 per 30 plastic oxyalkanoyl polymer having a reduced viscosity cent by weight and value of at least about 0.1 and which is further charac iv. vinyl chloride/vinyl C2-C 4 alkanoate/C2-C 4 al- terized in that at least about 50 weight percent of said kene random terpolymer having an inherent vis thermoplastic oxyalkanoyl polymer is attributable to cosity less than about 0.5 in which the polymer recurring oxyalkanoyl units of the formula ized vinyl chloride portion thereof comprises the 35 major proportion by weight b. normally-solid thermoplastic vinyl chloride/vinyl C2-C 4alkanoatc/C2-C 4alkene relatively high mo lecular weight random terpolymer having an inher 0 --------- 0------------ fCH2^ -------- cII---------, ent viscosity of from about 0.5 to about 0.9 in 40 which the polymerized vinyl chloride portion wherein a-is an integer having a value of 2 to 7, with the thereof comprises the major portion by weight; and proviso that .x does not equal 3. c. a filler; wherein the total combined weight of said 62. The article of manufacture of claim 61 wherein polymeric binder and said relatively high molecular said thermoplastic oxyalkanoyl polymer has a reduced weight terpolymer is comprised of from about 25 to 45 viscosity value of at least about 0.2 to about 3 and is about 65 weight percent polymeric binder and further characterized in that at least about 60 weight from about 75 to about 35 weight percent of said percent of said polymer is attributable to recurring ox- terpolymer; and wherein said filler is present in ycaproyl units; wherein said copolymer is vinyl chlori amounts ranging from about 200 to about 750 de/vinyl acetate; and wherein said terpolymer is vinyl parts by weight per 100 parts by weight of said pol 50 chloride/vinyl acetatc/ethylene terpolymer. ymeric binder and said relatively high molecular 63. The article of manufacture of claim 62 wherein weight terpolymer. said polymeric binder comprises from about 30 to 58. The article of manufacture of claim 57 wherein about 60 weight percent of said copolymer, from about said homogeneous mixture also contains from about 40 to about 70 weight percent of said terpolymer, and 0.5 to about 15 weight percent of a normally solid ther 55 from about one to about 10 weight percent of said ther moplastic oxyalkanoy! polymer having a reduced vis moplastic oxyalkanoyl polymer. cosity value of at least about 0.1 and which is further 64. The article of manufacture of claim 63 wherein characterized in that at least about 50 weight percent said filler is a non-fibrous filler. of said thermoplastic oxyalkanoy] polymer is attributa 65. The article of manufacture of claim 63 wherein ble to recurring oxyalkanoyl units of the formula 60 said mixture also comprises a small amount of an anti oxidant. il0 66. The article of manufacture of claim 65 wherein said antioxidant is 2,6-di-t-hutyl-p-cresol. ----------0---------(CH2^ --------- c---------- , 67. A process for producing non-asbestos containing 65 plasticized vinyl sheet using equipment adaptable for producing asbestos-containing sheet which comprises wherein -v is an integer having a value o f 2 to 7, with the forming a homogeneous mixture at a temperature of 3 ,904,579 33 a. normally solid thermoplastic polymeric binder se 34 producing asbestos-containing sheet which comprises lected from the group consisting of: forming a homogeneous mixture at a temperature of i. vinyl chloride/vinyl C^-C., alkanoate polymer in from about 250 to about 375F which comprises: which the polymerized vinyl chloride portion thereof comprises at least about 70 weight per 5 a. a mixture of normally solid vinyl chloride/vinyl C2-C 4 alkanoate copolymer in which the polymer cent and the polymerized vinyl Cj-C/, alkanoate portion thereof comprises up to about 30 weight ized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized percent vinyl C2~C4alkanoate portion thereof comprises up ii. vinylidene chloride/vinyl chloride polymer in to about 30 weight percent and one or more nor which the polymerized vinyl chloride portion 10 mally solid thermoplastic polymeric binder resins thereof comprises at least about 50 weight per selected from among: cent and the polymerized vinylidene chloride i. vinylidene chloride/vinyl chloride polymer in portion thereof comprises up to about 50 weight which the polymerized vinyl chloride portion percent iii. vinyl chloride/propylene polymer in which the 15 thereof comprises at least about 50 weight per cent and the polymerized vinylidene chloride polymerized vinyl chloride portion thereof com portion thereof comprises up to about 50 weight prises at least about 90 weight percent and the percent polymerized polypropylene portion thereof com ii. vinyl chloride/propylene polymer in which the prises from about 10 percent to about 4 percent by weight 20 polymerized vinyl chloride portion thereof com prises at least about 90 weight percent and the iv. chlorinated polyethylene polymer having not polymerized polypropylene portion thereof com greater than 5 percent crystallinity a molten vis prises from about 10 percent to about 4 percent cosity of from about 1000 to 3000 poises at by weight 190C and a chlorine content of at least 40 per cent by weight 25 iii. chlorinated polyethylene polymer having not greater than 5 percent crystallinity a molten vis v. vinyl chloride/vinyl C2-C4 alkanoate/C2-C 4 al- cosity of from about 10,000 to 30,000 poises at kene random terpolymer having an inherent vis 190C and a chlorine content of at least 40 per cosity less than about 0.5 in which the polymer cent by weight and ized vinyl chloride portion thereof comprises the major proportion by weight 30 iv. vinyl chloride/vinyl C2-C , alkanoate/C2-C_, alkene random terpolymer having an inherent vis vi. mixtures of said polymers cosity less than about 0.5 in which the polymer b. normally-solid thermoplastic vinyl chloride/vinyl ized vinyl chloride portion thereof comprises the C2-C.,alkunoate/C2-C.ialkene relatively high mo major proportion by weight lecular weight terpolymer having an inherent vis b. normally-solid thermoplastic vinyl chloride/vinyl cosity of from about 0.5 to about 0.9 in which the 35 C2-C.,alkanoate/C2~C4 alkene relatively high mo polymerized vinyl chloride portion thereof com lecular weight random terpolymer having an inher prises the major portion by weight; ent viscosity of from about 0.5 to about 0.9 in c. a filler; and which the polymerized vinyl chloride portion d. a plasticizer; thereof comprises the major portion by weight; wherein the total combined weight of said polymeric 40 c. a filler; and binder and said relatively high molecular weight ter d. a plasticizer; polymer is comprised of from about 25 to about 65 wherein the total combined weight of said polymeric weight percent polymeric binder and from about 75 to binder and said relatively high molecular weight ter about 35 weight percent of said terpolymer; and polymer is comprised of from about 25 to about 65 wherein said filler is present in amounts ranging from 45 weight percent polymeric binder and from about 75 to about 200 to about 750 parts by weight per 100 parts about 35 weight percent of said terpolymer; and by weight of said polymeric binder and said relatively wherein said filler is present in amounts ranging from high molecular weight terpolymer, and thereafter mill about 200 to about 750 parts by weight per 100 parts ing and calendering said homogeneous mixture into by Weight of said polymeric binder and said relatively fused plasticized vinyl sheets. 50 high molecular weight terpolymer, and thereafter mill 68. The process of claim 67 wherein said homogene ing and calendering said homogeneous mixture into ous mixture also contains from about 0.5 to about 15 fused plasticized vinyl sheets. weight percent of a normally-solid thermoplastic alkan- 70. The process of claim 69 wherein said homogene oyl polymer having a reduced viscosity value of at least ous mixture also contains from about 0.5 to about 15 about 0.1 and which is further characterized in that at 55 weight percent of a normally-solid thermoplastic alkan- least about 50 weight percent of said thermoplastic oyl polymer having a reduced viscosity value of at least oxyalkanoyl polymer is attributable to recurring oxyal- about 0.1 and which is further characterized in that at kanoyl units of the formula least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyal 60 kanoyl units of the formula ----------0--------- (CH2^ --------- c --------, 0 il wherein .v is an integer having a value of 2 to 7, with the 65 ------- 0 -------------------------- C ------- , proviso that x does not equal 3. 69. A process for producing non-asbestos containing wherein is an integer having a value o f 2 to 7, with the 3 ,9 0 4 ,5 7 9 35 36 71. A process for producing non-asbestos containing f. said homogeneous mixture being formed at a tem plasticized vinyl sheet using equipment adaptable for perature of from about 250 to about 375F; and producing asbestos-containing sheet which comprises g. thereafter milling and calendering said homogene forming a homogeneous mixture comprising: a. polymeric binder comprising (i) normally-solid thermoplastic vinyl chloride/vinyl C-^-Cj alkanoate copolymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl Cj-C., alkanoate portion thereof comprises up to about 30 weight percent; and (ii) normally-solid thermoplastic vinyl chloride/vinyl C2-C j alkanoate/C2-C., alkene terpolymer in which the polymerized vinyl chloride ous mixture into fused plasticized vinyl sheets. 5 72. The process of claim 71 wherein said polymeric binder also contains from about 0.5 to about 15 weight percent of a normally-solid thermoplastic alkanoyl pol ymer having a reduced viscosity value of at least about 10 0 .1 and which is further characterized in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units of the formula portion thereof comprises the major portion by weight; 15 0 b. a filler; and c. a plasticizer; II --------- 0 ------ -- ( ch2- ^ ------- C ------- , d. said polymeric binder comprising from about 25 to about 65 weight percent of said copolymer, and from about 35 to about 75 weight percent of said 20 wherein .vis an integer having a value of 2 to 7, with the terpolymer; proviso that x does not equal 3. e. said filler comprising from about 200 to about 750 73. The process of claim 72 wherein said mixture also parts by weight per 100 parts by weight of said pol comprises a small amount of a hindered phenol. ymeric binder; ***** 25 30 35 40 45 50 55 60 65 UNITED STATES PATENT OFFICE ?age 3 f 3 CERTIFICATE OF CORRECTION Patent No. 3.904.579_____________ Dated September 9. 1975 Inventor(s) Robert P. Braddicks______________________ It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: Column 22, subheading 26 of Table XI, "47..6" should read "47.6". Column 23 and 24 "17 18 19, 20 21 22 23 24 25" should read " 26 27 28 29 30". Column 30, line 1, "dentation" should read "indentation". (SEAL) Attest: RUTH C. MASON Attesting Officer Signed and Sealed this seventeenth J ) a y o f February 1976 C. MARSHALL DANN Commissioner o f Patents and Trademarks