CA1055182A - Floor-tile compositions comprising plasticized vinyl chloride polymers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
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/propylene copolymer; chlorinated polyethylene polymer; low molecular weight vinyl chloride/vinyl C2-C4 alkanoate/C2-C4alkene random terpolymer or a mixture thereof and (ii) vinyl chloride/vinyl acetate/ethylene terpolymer. The inclusion of a thermoplastic oxyalkanoyl polymer, e.g., epsilon-caprolactone homopolymer, with/without an antioxidant, e.g., a hindered phenol, yields compositions having good processing characteristics as well as products exhibiting improved mechanical properties such as impact strength.

1.

Description

This invention relates to novel resinou~
compositions. In one aspect the lnvention relatès to asbestos-free resinous compositions for use in producing thin sheets having utility as surface coverings.
Resinous composition surface coverings comprising synthetic resinous binder, stabilizers, plasticizers, fillers, and color pigments have come to be widely used as coverings for floor, walls, and the like. A widely used resinous composition is a polymer of a vinyl chloride such as thermoplastic poly(vinyl chloride). Such resins have extremely high wear and stain resistance which makes them excellent for use a ~urface coverings. It is common - practice to add flllers to the composltlon to decrease ~-the over-all cost. The addltion o~ such Mllcrs ln relatlvdy large quantltlos 18 detrimental to the physical propertles of the composltlon. As one would ~ expect, therefore, the higher guallty products have ¦ 20 Yery llttle M ller, whereas the low co~t products ~or thc mass market contaln a hlgh proportlon of flller.
These latter products may contain fillers and pigments 3' ln total amounts as hlgh as 80 welght percent of the ~ composltion.
i So-called vinyl asbesto~ composition sheet, e g " tile, 1~ an outgrowth of a~phalt compoal~lon 3 ~hcet and, a~ a result, it ha~ bcen convcntionally ~ormulatcd ~l~h a~besto~ ~o that its proces~lng and ~ ~erfor~ancc propertle~ ~ould m~tch tho~e o~ theA - 2 -,, ,, , ,, ,, ~
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asphalt composition as closely as possible Initially, this was essential in order that vinyl agbestog compositions would handle properly on the asphalt composition equipment and production lines, thereby requiring a minimum of equipmont modification. With the passage of time processors have succeeded in producing decorative chip stocks and very special ba e stocks without the inclusion of asbestos.
However, most of today's base stock formulations contain asbestos filler to avoid dimensional stability problem and processing problems.
Vinyl composition sheets are prepared by a number of different methods including calendering, pressing, and molding. In a calendering systom where 1, the relativ¢ly thln vinyl composltlon sheet has to ¦ pas~ through a number of calender rolls and other operatlons, the strength of the sheet at the relatlvely high temperatures neccssary for processlng 18 of great lmportancc. Tho ability of the sheet to adhere to the calender roll~ is also a significant factor.
Fibrous fillers, e~pecially asbestos, greatly lncrease the hot ~trength of a vinyl composition ¦ above that which can be obtained with non-fibrous j fillers. It has, thorefore, becomo unlversal practice 1 to ukllize aabesto~ ~hen hot strength 1~ needed ln j vl~yl composltlons. Requlred hot strength or hot i tensllc ~trength, as u~ed ln thl~ art, 1~ that ~roperty of a hot vinyl compo~ltlon whlch cXhlb~t~ the prop r a~ount of vl~cou~ nOw and mclt S ~ 3 -, "~ , . . .
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, 1055~82 elasticity so that the composition may be sheeted, calendered, and transported ~ithout sporadic ripping, tearing, or excessive elongation during hot processing on the calendering line. Excessive viscous flow causes the vinyl composition to deform easily and to rupture, A
deficiency in viscous now causes it to become excessively dry and results in a tendency to crumble and not form sheets.
Excessive melt elasticity contributes boardiness to the vinyl composition causing it to become extremely stiff making normal processing difficult, if not impo~sible.
Recently, various medical researchers and government officials have ~uggested that exposure to asbestos products may po~e a serious health peril to the general public. In one study conducted in 1971, a~bestos was reputedly found in the lung~ of each of 28 randomly ~elected autopsies of New York City resident~. Such findings startledthe medical world since they showed that even the man on the street, not occupationally exposed, was inhaling asbestos. It is quite understandable that there is ~crious concern among the variouR governmental agencies to regulate and restrict the handling of asbestos i and its end use application. In fact, legislation to these ends is pending in many municipalities and cities of the United States. Manufacturers of vinyl asbestos co~posltlon have thu~ inten~lfied their efforts to f~nd way~ to pro*uce, on a commerclal scale, asbestos-free vinyl composltlons ~uch a~ tlle.

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Unfortunately, attempts to use a filler such as dry ground limestone as the sole filler in "vinyl asbestos-type compositions" have repeatedly ~een unsuccessful in producing commercial base stocks. Such a composition requires extremely careful handling of the sheet on the calender rolls necessitating relatively slow speeds to prevent any undue tension on the sheet which would cause it to collapse or break apart Also, it is necessary to convey the ; sheet when not in contact with the calender rolls. Moreover, such limestone-filled vinyl compositions exhibit excessive fluidity and lack required hot strength for proper calendering on the production lines. Shrinkage or lack of dimensional stability is also a severPly troublesome defect in such vinyl composition sheets.
It is a purpose of this invention to minimize the need for asbestos in vinyl compositions used in making floor coverings. The invention seeks to provide novel filled resinous compositions which are essentially free of asbestos and which are commercially useful as surface coverings. The invention further seeks to provide novel vinyl compositions which are essentially or completely free of asbestos and which have good strength at high temperature processing, good roll adhesion, very low water absorption, and improved light resistance, Alternatively the invention seeks to provide novel non-fibrous ~ 20 filled vinyl composition sheets which possess the desirable properties of ; fibrous-filled composition sheets such as good indentation resistance, impact strength, and flexibility while lacking many of its disadvantages. Additional-ly ~he inv~ntion seeks~to provide(novel processes for producing vinyl composi-tion sheets A plasticized solid composition comprising a plasticizer contain- -s ing a homogeneous mixture of: (a) normally solid thermoplastic polymeric binder selected from the group consisting of: (i) vinyl chloride/vinyl C2-C4 ; alkanoate polymer in which the polymerized vinyl chloride portion thereof ,f. co~pr~es at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate po~tlon thereof comprize~ up to about 30 weight porcent (ii) vinyl-idcnc chloride/vlnyl cbloride pslymor ln which the polymerized vinyl chloritc port~on th4reof comprl~44 at loa~t about 50 woi~ht porcent and tho poly erized ~ ~ 5 _ ~ ,~"",~

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vinylidene chloride portivn thereof comprises up to about 50 weight percent ciii) vinyl chloride/propylene polymer in which the polymerized vinyl chloride portion thereof comprises at least about 90 weight percent and the polymerized polypropylene portion thereof comprises from a~out 10 percent to about 4 per-cent 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 percent by weight ~v) vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent viscosity less than about 0.5 in which the polymerized vinyl chloride portion thereof comprises the major proportion by weight (vi) mixtures of said polymers (b~ normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/-C2-C4 alkene relatively high molecular weight random terpolymer having an in-herent 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 rel-atively high molecular weight terpolymer 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 poly-meric binder and said relatively high molecular weight terpolymer, : Thus, another aspect of the invention provides a process for produ-cing non-asbestos containing plasticized vinyl sheet using equipment adaptable for producing asbestos-containing sheet which comprises forming a homogeneous mixture at a temperature of from about 250F to about 375F which comprises: (a) normally solid thermoplastic polymeric binder selected from the group consist-ing of~ vinyl chloride/vinyl C2-C4 alkanoate polymer in which the polymer-ized vinyl chloride portion thereo comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent ~ vinylidene chloride/vinyl chlorito polymer in which the poly~4rized vinyl chiorlde portion thereof comprl~e~ at least about 50 weight perccnt and the poly~erlzet vlnylldone chlorlde portion ther~of co~pri~s up R ~ - 6 -,, , 1~5518Z
to about 50 ~eight percent (iii) vinyl chloride/propylene polymer in which the polymerized vinyl chloride portion thereof comprises at least about 90 weight percent and the polymerized polypropylene portion thereof comprises from about 10 percent to about 4 percent by weight (iv) chlorinated polyethylene polymer having not greater than 5 percent crystallinity, a molten viscosity of frasm about 10,000 to 30,000 poises at 190C and a chlorine content of at least 40 : percent by weight (v) vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent viscosity less than about 0.5 in which the poly-merized vinyl chloride portion thereof comprises the major proportion by weight (vi) mixtures of said polymers (b) normally-solid thermoplastic vinyl chlo-ride/vinyl C2-C4 alkanoate/C2-C4 alkene relatively high molecular weight terpo-lymer having an inherent viscosity of from about 0.5 to about 0.9 in which the polymerized vinyl chloride portion thereof comprises the major portion by weight; (c) a filler; and (d) a plasticizer; wherein the total combined weight of said polymeric binder and said relatively high molecular weight terpolymer is comprised o 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 Z0 relatively high molecular weight terpolymer, and thereafter milling and calen-dering said homogeneous mixture into fused plasticized vinyl sheets.
In the practice of this invention, it has been found, quite unexpect-edly, that vinyl compositions which are essentially free of asbestos can be conveniently processed on existing "asbestos tile" equipment and production lines. These novel compositions exhibit a combination of acceptable process-ing characteristics while the novel products, useful as surface coverings, are characterized by good indentation resistance, good flexibility, improved light resistance, and very low water sensitivity, In addition, novel vinyl compo-sition~ can be preparet containing as much as 85 weight percent, and higher, 0f pi~en~ ant illor, o,g " titanium dioxite ant mixtures of rolati~ely coar~e ant fine l~me5tone, Such h~ghly-f~llcd vlnyl cumpo~itlons po55e55 8n ~ - 6a -~, ~, lOSS18Z

obvious economic advantage over conventional vinyl compositions which here-tofore have been generally filled with asbestos and pigments to am~unts not exceeding about 80 weight percent of the composition, The excellent processing and mechanical properties of the novel vinyl compositions are attributable to a well-defined mixture of a normally-solid thermoplastic - 6b -,' ~
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polymer, namely, (i) vinyl chloride/vinyl C2-C4alkanoate copolymer; vinylidene chloride/rinyl chloride/copolymer;
vinyl chloride/propylene copolymer; chlorinated polyethylene polymer, low molecular weight vinyl chloride/vinyl C2-C4 alkanoate/C2-C4alkene random terpolymer or a mixture thereof and (ii) a unique terpolymeric composition, namely vinyl chloride/vinyl C2-C4alkanoate/C2-C4alkene terpolymer. The term "normally-solid thermoplastic polymers" in reference to the above described polymers, copolymers and terpolymers is intended to describe those polymers which are normally-solid and thermoplastic at room temperature and which can be processed on existing equipment and production lines for producing conventional asbestos-filled vinyl sheets. Such equipment is generally operated at temperatures in the range of from about 150F. to about 300F.
The terms '3non-asbestocll and "essentially free of asbestos" are intended to de~cribe compo~itions contalning from es~entially 0% up to an amount which doe~ not sig~ificantly in nuence the physical properties of the final product.
Illustrative normally-~olid thermopla~tic vinyl chloride/vinyl C2-C4alkanoate copolymers include vinyl chloride/vinyl acetate copolymer, vlnyl chlorlde/vinyl propionate copolymer, and vinyl chloride/vinyl butyrate copoly~er The polymerized vinyl chloride portion of the copolymer compri~es at lea~t about 70 weight percent and the pol~merized vinyl C2-C4alka~oate portion upward~ to about 30 3 weight percent, ba~ed on the total weight of the copoly~3er. Preferably, the copolymer comprises at 14a~t about 80 to about 95 w d ght percent polymcrized f 30 ~inyl chlorldc ~na from about 5 to about 20 wclght pcrcc~t ~oly~crlzcd Ylnyl C2-C4alkanoatc ~he pre~erred f 1~5518Z
copolymer is vi~yl chlorlde/vinyl acetate. Particularly useful copolymers are those which have inherent vi~cosity value~ in the range of from about 0.35 to about o.65, preferably fro~
about 0.4 to o.6. Unless indicated to the contrary the inherent viscosity values were determined in accordance with ASTM Method D-1243-66 using 0,2 gram of polymer in 100 milliliters of cyclohexanone at 30C.
Illustrative normally-solid thermoplastic vinylidene chloride/vinyl chloride copolymers are those in which the polymerized vinyl chloride portion of the copolymer comprises at least about 50 weight percent and the vinylidene chloride portion upwards to about 50 weight percent, based on the total weight of the copolymer. Preferably, the copolymer is compri~e~
of frsm about 50 to about 90 weight percent polymerized vinyl chloride and from about 10 to about 50 weight percent polymer-ized vinylidene chloride. Suitable are copolymer~ having an inherent viscosity ranging from about .35 to about .9.
Preferred however are those hav~ng an inherent vi~cosity of from about .4 to about ,6, , 20 Illustrative of the vinyl chloride/propylene - copolymers are thGse in which the polymerized vinyl chloride - portion of the copolymer comprises at least about 90 weight percent and the propylene portion upwards from about 4 weight percent to a~out 10 weight percent, Preferably the copolymer 1~ compri~ed of fr~m about 90 to about 96 weight percent polymerized vinyl chloride and from about 4 to about 10 per-cent polymerized propylene, Preferred are polymer~ having an Snhercnt vi~cozlty rangin8 from about ,4 to ab~ut .7, Illu~tratlve of ~he chlorlnated polyethylene poly~ers u~eful ln the pr~ctlce of thl~ lnvcntion are tho~e ln whlch chlorlno ~ccount~ ~or at lo~Dt about 40 percent o~

,, the polymer weight Polymer cry~tallinity should not exceed about 5 percent. Preferred are polymer~ having 0 percent cry~tallinity. The preferred chlorinated polyethylene polymers are also those having a molten viscosity of from ~f~ about 1~00to about 3900~poises at a temperature of 190C
/ Typical of the normally-solid thermopla~tic vinyl chloride/vinyl C2-C4alkanoate/C2-C4alkene terpolymer~ which are useful in the invention include, by way of illustration, vinyl chloride/vinyl acetate/ethylene terpolymer, vinyl chloride/vinyl acetate/propylene terpolymer, vinyl chloride/vinyl acetate/butylene terpolymer, vinyl chloride/vinyl propionate/ethylene terpolymer, vinyl chloride/vinyl propionate/propylene terpolymer, vinyl chloride/vinyl propionate/butylene terpolymer, vinyl chloride/vinyl butyrate/ethylene terpolymer, vinyl chloride/vinyl butyrate/propylene terpolymer, and vinyl chloride/vinyl butyrate/butylene terpolymer, The polymerized vinyl chloride portion of the terpolymer comprises the ma~or portion by weight and, in general, desirably comprises at least about 75 weight percent of the terpolymer. The polymerized vinyl C2-C4alkanoate portion of the terpolymer normally contains less than about 24.5 weight percent whereas the polymerized alkene portion contains at least about 0.5 weight percent.
Polymerized ~inyl C2-C4alkanoate represents the ma~or component with respect to the polymerized alkene portion.
Highly suitable terpolymers comprise, polymerized therein, from about 80 to about 90 weight perc~nt chloride, from about 9 to about 17 weight percent vinyl C2-C4alkanoate, lOSS1~2 and from about 1 to about 3 welght percent ethylene, The preferred terpolymer 18 vinyl chloride/vinyl acetate/ethylene, The terpoly~ers useful in this invention are tho3e which have inherent vigcosity values ranging from about 0.4 to about 0.9, The terpolymers characterized as relatively high molecular weight terpolymers which are es~entlal ingredients in this invention are those having an inherent viscosity of least ,5 and preferably from about ,5 to about ,ô, These are to be distinguished from the lower molecular weight terpolymers having an inherent viscosity o~ less than about ,5, pre~erably about ,4 to about .5 which are optional ingredients, The terpolymers useful ln the practice of this invention are those prepared by the simultaneous polymeriza- -tion o~ the three monomeric ingredients, as distinguished from graft polymers, The expre~slon "terpolymers" a~ used herein therefore de~cribes polymeric materials produced by tho simultaneous reaction of all three monomers to produce a material whlch includes at least ~ome o~ all o~ the mono-meric moleties in the polymer backbone in what i~ believed to bc a random distribution.
The pre~brred compositions of thls lnvention are those lncluding vinyl chloride/vinyl alkanoate copolymer and relatively hlgh molecular weight terpolymer elther alone or ln comW nation with one or more of the specl~ied optional polymer W nder materials, Thi~ combinatlon af~ord~ a very ~ati~factory product in term~ o~ physical propertie~ and can bc produced on conventional equipment, Optional re~in~ can bc added to thc~e bafllc lngredlent~ Sf dcalred to modl~y phy~lcal pro~ertS-~ of the tlle pro~uct or to mo~lfy manu~acturinR
condltSons, Co~osltlons ~hlch do not lnclud~ ~lnyl _ 10 --/

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~055182 chloride/vinyl alkanoate copolymer provide useful products but generally require more difficult manufacturing conditions -In one aspect of the invention, novel non-asbestos filled vinyl compositions can be prepared which exhibit good processing characteristics such as required hot strength and good roll adhesion. Moreover, novel sheet products from such compositions exhlbit good impact resistance as well as the aforementioned desirable mechanical and physical properites.
These and other re~ults are achieved by incorporatlng lnto the novel vinyl compositions a minor amount of a normally-solld thermoplastic oxyalkanoyl polymer. The oxyalkanoyl polymer~
¦- which are suitable possess a reduced vlscosity value of at 1 least about 0.1. In various desirable embodlments, the thermo-,,~,' , plastic oxyalkanoyl polymers have a reduced visco~ity value ! of at least about 0.2. The upper value can be hlgh a~ 10, and ,~ greater, but no particular advantage ls apparent uslng thermo-plastic oxyalkanoyl polymers which have a reduced viscosity ~5 valu~ greater than about 3 The oxyalkanoyl polymers are further characterized ln that they contain at least about 50 ~eight percent of the oxyalkanoyl unlts, - otCH2~X- C - , -; , ~' , ,, , ~: -, , ,.. .

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recurring therein, wherein x is an integer having a value of 2, 3 and 5-7, preferably 5. In the practice of highly suitable embodiments of the invention, the thermoplastic oxyalkanoyl polymer~ contain at least about 60 weight percent, and preferably at least about - 80 weight percent, and upwards to about 100 weight percent of the oxycaproyl unit, i.e., - O(CH2)5C - , recurring therein.
The aforesaid recurring unit is inter-connected through the oxy group (-0-) of one unit with a carbonyl group (-C-) of a second unit. In other words, the interconnection of such units does not involve the direct bonding of two carbonyl group8, -~-~-. When the thermoplastic oxyalkanoyl polymer is a homopolymer or essentially a homo-polymer, the polymer chain thereof consists essentially of interconnected recurring oxyalkanoyl units. In addition to the recurrinK oxyalkanoyl unit, the ther7Qoplastic oxyalkanoyl polymer may comprise other moieties or groups therein especially ; those which irtersperse or terminate the polymeric chain thereof as illustrated by the oxyaIkylene F oup, 0 ~ H - ~ ; thc ~Rl~OR20 F~P;

the -~R2~y group; the ~ BrUP; the _ ~,z _ l()S518~

- dRlC 6roup; the urethane group, - ~H~O ; the - OR30~ -group; the -NH~HN -group; the biuret group, - NH ~NH- ; the -R2- ~ -R2 group; the divalent mono-; and polyaromatic rings including fused and bridged rings; lower alkyl substituted oxyalkanoyl groups;

catalyst residue; the carbonate group, O O - ; and others. With reference to the aforesaid groups or moieties, the variables R, Rl, R2, R3, and y can be illustrated as follows: R repre~ents hydrogen or lower alkyl; Rl represents a divalent hydrocarbon group; R2 represent~ a divalent aliphatic hydro-' carbon group or a divalent aliphatic oxa-hydrocarbon group; R3 roprosents a divalent aliphatic hydro-carbon group; and y represonts an integer whlch r ha~ a value of at least one, The term "lower alkyl", as used hereln, represents a monovalent aliphatic hydrocarbon gr4up having 1 to 4 carbon atoms, e.g " methyl, ethyl, propyl, ~ isopropyl, _-butyl, etc.- The term "divalent hydrocarbon 1 20 group", as used herein, includes radicals such as Cl-C12alkylene, C2-C12alkylidene, and C6-C12arylene, i e.g" methylene, propylene, butylene, hexamethylene, hepta~e*hylene, cyclohexylene, phenylene, naphthylene, propylido~e, butylidene, etc, ~he term "dlvalent i aliphatlc hydrocarbon group", as w ed hereln, includes ~, /
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C~-C12alkylene and C2-C12alkylidene, The term "divalent aliphatic oxa-hydrocarbon group", as u~ed herein, can be repre~ented by the empirlcal formula~
- C2- C12alkylene(oxyC2- C12alkylene t y ~he variable y, as used herein, represents an integer having a value of at least one.
As previously noted, the thermoplas*ic oxycaproyl polymers which are suitable in the practice of the invention are expressed in terms of their re-duced viscosity values. As is well known in the art, reduced viscosity value is a measure or indication of the molecular weight of polymers. ~he expression "reduced viscosity" is a value obtained by dividing the specific viscosity by the concentration of polymer in the ~olution, the concentration being mea~ured in grams of polymer per 100 milliliters of solvont.
~he ~pcciflc viscosity i8 obtained by divldlng the difference between the vi~co~ity of the ~olutlon and tho vi~coalty of the solvent by the viscosity of the ~olvent. Unles~ otherwise noted, the reduced viscosity values herein referred to are measured at a concentration of 0.2 grams of polymer in 100 millll$ter~ of benzene (benzene i~ preferred although cyclohexanone, chloroform, toluene or s other common organlc solvent for the polymer may be u~ed) at 30C
The thermoplastic oxyalkanoyl polymers can bc prepared by variou~ methods A general procedure lnvolves reactlng a largc molar excesa of the appropriate lactone, e.g., epsilon-eapro-lactone, zeta-enantholactone, and/or eta-caprylo-lactone with an organic initiator whieh contains two active hydrogen groups, e.g., hydroxyl, carboxyl, primary amino, secondary amino, and mixtures thereof, such groups being capable of opening the lactone ring whereby it adds as a linear chain (of recurring o~y-alkanoyl units) to the site of the active hydrogen-containing group, at an elevated temperature, preferably in the presence of a catalyst, and for a period of time sufficient to produce the desired polymers. By carefully controlling the purity and molar ratio of lactone reaetant to organie initiator, there can be produced "initiated" poly~oxyalkanoyl) polymer~ whose number average moleeular weight ean range from several hundred to above 100,000. Organie initiators whleh ean be employed inelude prlmary dlamines, seeondary diamines, mixed primary-~eeondary diamines, aminoaleohol~, diols, diearboxylie aeid~, hydroxyearboxylie aeids, aminoearboxylic acids, ete.
~ueh organie initiators are voluminously illustrated in the literature, e.g., United States Patent ~08.
3,169,945 and 3,427,346. Catalysts which can be employod inelude, for in~tanee, stannous octanoate, tetrabutyltitanate, dibutyltin dilaurate, and the like, A temperature in *he range of from about 150C
to about 250 & for periods r&nging upward~ to about Z4 hour~, and longcr, are ~uitable, /
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, Thermoplastic oxycaproyl polymers can al50 be prepared by reacting the cyclic ester, e.g., epsilon-caprolactone, and/or the correspondlng hydroxy-acid, e.g., 6-hydroxycaproic acid, and/or their oligomer~, with a mixture comprising diol and dicarboxylic acid, using a molar excess of diol with relation to the dicarboxylic acid, or alternatively, using a molar excess of dicarboxylic acid with relation to the diol.
It is highly desirable that free diol or free dicarboxylic acid not be present at the termination of the polyesterification reaction. The water of esterification which results during the reaction can be removed via conventional téchniques. The diols and dicarboxylic acids which are particularly suit-able include those illustrated by the formulae HO--~ R20 ~ H and HOOCRlCOOH such as ethylene glycol, propylene glycol, diethylone glycol, dlpropylene glycol, 1,4-butanediol, 1,5-pentanodiol, 1,6-hexane-, diol, l,10-dccanediol, 1,4-cyclohexanediol, succinlcf 20 acid, glutaric acid, adlpic acid, pimelic acid, suberic acid, azelaic acid, ~ebacic acid, phthalic acid, and the like.
In the absence of added organic initiator, the thermoplastic oxyalkanoyl polymers can be pre-pared by polymerizing a lactone reactant, e.g., beta-f propiolactonc, delta-valerolactone, epsllon-capro-lactone, etc., ln the presence of anionic cataly~t~
ç suc~ as di- -butylzlnc, tri-n-butylalumlnum, dietbyl-~ ~agne~lum, alumdnum trlisopropoxldo n-butyllithlum,'A 3 dlm~thylcadmlu~, and tho llke- The roactlon 18 ",, - 16 -"

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desirably conducted at an elevated temperature, e.g , 100C to 250 C, for periods of time ranging from minutes to several hours, e.g., from about 10 minutes to about 24 hours. The reaction mixture can comprise, in addition to the lactone reactant, minor quantities of other polymerizable cyclic monomers such as tetra-methylene carbonate, methyl-epsilon-caprolactone, keto-dioxane, etc. The number average molecular weight of the resulting polymeric product~ which are produced by this exemplified "non-initiated" method are, in general, quite high. For example, products which have number average moleçular weights ranging from about 10,000 to several hundred thousands can j be prepared. The patent literature, e,g , United States Patent Nos. 3,021,309 to 3,021,317, discus~e~
ln detail the preparation of these polymers.
Thcrmoplastlc oxy~lkanoyl polymer~ can ~ also be prepared by polymerlzlng an admixture of j C7-C91actone, a viclnal epoxy compound, e.g., ethylene oxide, propylene oxlde, butylene oxide, cyclohexene oxide, etc., and an interfacial agent such as a ~olid, relatively high molecular weight poly(vinyl 3 stearatc) or lauryl methacrylate/vinyl chloride copolymer (reduced vlscoslty ln cyclohexanone of ~rom about 0.3 to about 1.0), ln the prosence of an lnert normally-llqula saturat~d allphatlc hydro-carbon vchlcle ~uch a~ hsptane, using pho~phorus pentafluorldo a~ thc cat~v~* thoreforc,and ln the ab~cnco o~ an actlvo hydrog~n-contalnlng organlc , , . .
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initiator, at an elevated temperature, e.g., sbout 80C, and for a period of time sufficient to produce such polymers.
m ermoplastic oxyalkanoyl polymers can also be prepared by reacting a molar excess of a lactone with a polyoxyalkylene diol which has a molecular weight ranging from about 400 to about 20,000 under conditions discussed supra with - --reference to the "initiated" poly(oxyalkanoyl) polymers. Illustrative of the polyoxyalkylene diols dhich are contemplated include the poly(oxyethylene) diols, the poly(oxypropylene) diols, and the poly(oxyethyleneoxypropylene) diols. The resulting i polymers can be consldered, in effect, to be ABA
block polymers in dhich the A portions represent a polyoxyalkanoyl segment or block and in which the B
portion represent~ a polyo~yalkylene se~Qent or block The number average molecular weight of these ABA
block polymers can range updards to 50,000, and hl~her, depending on the molecular weight of the polyoxyalkylene diol reactant and the molar ratio of the lactonc reactant to polyoxyalkylene diol reactant e~ployed and consumed in the proce~s. By using mono end-blocked polyalkylene diols such a the monoaIkyl ether of polyoxyalkylene diol, the ab~ve discussed preparation rc~ults ln polymer~ having ~n AB block conflguratlon, ~yalkan~yl polymers whlch can be con~ld~red to be "gra~t" poly~erff can bo prepared by thc addltlon of C6-Cglactone at the active hydrogen sites, e g , hydroxyl or amino, which are pendant along the poly-meric chain of so-called vinyl polymers. Such vinyl polymers may, for example, be obtained by the co-polymerization of ethylene and vinyl acetate, followed by subsequent saponification of the acetate groups to yield polymers which are characterized by a plurality of pendant hydroxyl groups along the polymeric chain thereof. A wide host of ethylenically unsaturated monomers can be employed to prepare the vinyl polymers and include, for example, 2-hydroxyethyl acrylate,

2-hydroxy methacrylate, styrene, acrylonitrile, propylene, vinyl chloride, and the like. The choice of the ethylenically unsaturated monomers are ~uch that the resulting polymer contains a plurality of pendant hydroxyl groups, or groups which can be converted to hydroxyl groups. The addition of the C6-Cglactone at tho active hydrogon site wlll produce "graft" polymers of number average ~wlecular weights upward~ to approximately 100,000, and higher.
The oxyalkanoyl polymcrs which have numbcr average molecular weights of, for example, less than 25,000 are characterized by functional end groups.
Por i wtance, hydro~yl-terminated polymers can be prepared from a diol initiator and epsilon-caprolactone using molar ratios o~ lactone to initiator upwards to about 100:1 If de~ired, the~e polymers may be reac~od with a diisocyanate, o,g " 1,6-hexa-~ethyl~ne ~ilsocy~nat~, 2,4- and/or 2,6-tol~l~ne - lg-,, "

diisocyanate, bis(4-l~ocyanatophenyl)methane, bis(4-isocyanatocyclohexyl)methane, etc., to extend the polymerlc chain, or such hydroxyl-terminated polymers as well as their polyurethane extension products can be reacted with so-called "chain stoppers" such as a monocarboxylic acid or anhydride. As indicated previously, the thermoplastic oxy-aIkanoyl polymers which are suitable in the practice of the invention have, as its lower limit a reduced viscosity value of at least about 0.1.
The amounts of normally-solid thermoplastic polymers which comprise the total polymer binder in the novel composition are quite important. Desirable results are achieved by using from about 25 to about 65 weight percent c binder resin and from about 35 to about 75 weight percent relatively high molecular weight vinyl chloride terpolymer, based on the weight of total polymer binder. Enhanced processing and mechanical propcrtles in the novol compo3itlon~
are achieved by lncorporating lnto tho recipe ~rom about 0.5 to about 15 weight percent thermoplastic oxyalkanoyl polymer, based on the welght of total polymer binderf In the practice of preferred embodiments of the invention the total polymer blnder comprises from about 30 to about 60 weight percent bi~der resin, from about ~O to about 70 weight percent relatively high molecular weight vinyl chloride terpolymer, ana ~rom about one ko about 10 weight percent thermoplastic oxyalkanoyl polymer.
j A wlde range o~ pla~tlclzers ~or incorporatlon lnto the novel non-a~be~tos compositlons can be omployed.
~he par~lcular pla~tlclzer of cholce wlll be ln~luenced, to a ~lgnl~lcant exten~, on lt~

/

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,. . .

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lOS518Z
compatibility with the system, and the properties desired in the pla~ticized produet Illugtrative plasticizers include esterg of aliphatic hydrlc compound~ and aliphatic carboxyl compounds such as dibutyl sebacate, dioctyl sebaeate, dioctyl sdipate, didecyl adipate, dioctyl azelate, triethylene glycol di(2-ethylhexanoate), diethylene glycol dipelargonate, triethylene glycol dicaprylate, and the likej esters of aliphatic alcohols and aromatic acids, or aromatic alcohols and aliphatic acids, or aromatic alcohols and aromatic acids, including dibutyl phthalate, dicapryl phthalate, dioctyl phthalate, dipropylene glycol dibenzoate, butyl benzyl sebacate, butyl benzyl phthalate, dibenzyl sebacate, dibenzyl phthalate, and the like. Other types of plasticizers sueh as esters of inorganie aeids, ineluding trieresyl phosphate, oetyl diphenyl phosphate, and the like, alkyd deriratives of rosln;
ehlorinated paraffine, hlgh moleeular weight hydro-earbon eondensates; and the llke, ean also be w ed The plastieizer should preferably have a low vapor pressure at the temperatures required to fuse the resin. A vapor pressure of 2 millimeters of mereury or less at ~00F i~ usually eonsidered ~atis~aetory.
The plastieizer is employed in a plastieizing amount whieh is suffieient to provide the meehanieal properties whieh are desired in the end use applieatlon. Nor~ally a ~atl~factory range of plastlcizer, including mixture~
thereof, a~ fro~ about Z5 part~ by weight, ~nd lower, to about ~5 partz by welght, and hlgher, per 100 p~rt~ by welght Of total polymer blnd r, "

: ' 105518~

Small amount~ of stabillzers which are incorporated to reduce the effectg of degradation ~y light and heat are usually pre~ent in the novel composition. Suitable light stabilizers include epoxidized soya bean oil, epoxidized tallates, ~ood rosin, phosphites, resorcinol disalicylate, resorcinol dibenzoate, phenyl phthalate, phenyl benzoate, o-tolyl benzoate, eugenol, guaiacol, o-nitrophenol, o-nitraniline, - triethylene glycol salicylate, and organic phosphates and other complexes of such metals as barium, cadmium, strontium, lead, tin and the like. Suitable heat stabilizers include barium-cadium soaps, barium-cadmium-zinc-soaps, epoxide~, sulfldes and ~ulfites of silver, calcium, cadmium, magnesium, cerium, ~odium strontium and the like, glycerine, leucine, alanine, o- and p-amino benzoic and sulfanillc acid~, hexa-methylene tetramine, weak acid radicals including oleates, recinolea~es, abletatos, salicylates and the like Normally, the novel composition contain~ from about 0.5 to about 5 parts by weight of stabilizer per s 100 parts by weight of total polymer binder. If de~ired, small amounts of anti~xidant~ such as the i hindered phenol~, e.g., di-t-butyl-~-cresol, and lubricants such as stearlc acid, waxes, etc., may be incorporated into the novel compo~ition~ thereby obtainl~g further lmproved milling and calendering characteri~tlc~, A ~lde varlety of f~ller~ can be incorporated f lnto th~ nov~l co~o~itloD~ ~uch flll~rs caD b~ o~

,, /
,, lOSS18Z
the fibrous and non-fibrou~ type ag illustrated by limegtone, whiting, clay, pumice, talc, silica, wood flour, mlxtures thereof, and the like. Siliclc mineral type fillers, though contemplated and within the scope of the inventlon, do not -~ represent highly desirable fillers. In the practice of suit-able embodiments, non-fibrous type fillers are particularly use-ful. Limestone represents a preferred filler, especially lime-stone which comprises a wide spectrum of relatively coarse to fine particle sizes, e.g., those having average particle sizes ranging from about 15 microns to about 275 microns. The amounts of filler in the novel compo~itions can vary quite widely. The norel composition will normally contain from about 200, and lower, to about 750, and higher, parts by weight of total filler per 100 parts by weight of total polymer binder, and generally, from about 250 to about 500 parts by weight of total per 100 parts by weight of total polymer binder. The proper sclectlon of filler, combination of fillers, and/or the particle slze ranges thereo~, will depend, to a significant degree, on its composite oll absorption Variovs pigments can be used Puch as titaniu~ dioxide, iron oxldes, phthalocyanines, benzidines, and the like.
Although a principal obJectlve of this invention is to achieve an asbestos-free ~loor tile composition it will be s appreciated that minor amounts of asbestos, on the order of 1 to 5%, may be added i~ dezired, Even higher amcunt~ can be used i~ dcslred however an increase in asbestos content ~il7 ~ormally rcquire a proportlonate lncrease ln resin content whlch mu~ not bc dcslrable for economic rcasons Prc~erred aspects of thc lnvontlon includo novel non~a~bes~o~ cc~posltlon~ comprl~ln~ an antloxldan~ lncorpo-ra~e4 th~reln, Nov~l vinyl compo~ltlons com~rl~ot o~ ono or ~," , ,, ,, i, , 1055~8Z

more of the aforesaid ther~oplast~c blnder reslns, relatively high molecular weight terpolymer and oxyalkanoyl polymer and an antioxidant exhibit processing characteristics at least as good as those obtained under existing and con~entional produc-tion lines using asbestos-containing recipes. 2~oreover, the sheeted product, such as floor tile, posses3es a combination of useful and outstanding properties as illustrated previously in this specification. These processing advantages and improved mechanical and physical properties of the novel non-asbestos compositions heretofore have not been attainable under existing ; "asbestos tile" equipment.
Illustrative antioxidants include the sterically hindered phenols, the arylamines, the thloureas, the -~ thlocarbamates, the thioether esters, and the phosphites or mixtures or adducts~thereof. Specific examples are j tetrakisL~ethylene-3-3',5'-di-tert-butyl-4'-hydroxyphenyl)-7 propionati7methane, stearyl 3-(3',5'-di-tert-butyl-4'-hydroxy-phenyl)propionate, distearyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphite, 1,1,3-tris(5'-tert-butyl-4'-hydroxy-2'-methylphenyl)-butane, 4-methyl-1,-6-di(2'-hydroxy-3'-tert-butyl-5'-methyl-~ bcnzyl)phenol, 2,4-di(3'-5'-di-tert-butyl-4'-hydroxyphenoxy)-- triazine, 2,2'-thiobis(4'-methyl-6'-tert-butylphenol), 4-4'-thiobis(3-methyl-6-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxy- ani~ole, 2,6,-di-tert-butyl-p-cresol, N-phenyl-beta-naphthylamine, N,N'-diphenyl-p-phenylenediamine, 2-cthylhexyldiphenylamine, N,N'-di-beta-naphthyl-p-phcnylenediamine, N,N'-di-(2-octyl)-p-phenylenediamine, H,~'-dl-3(5-mo*hylhoptyl)-p-phcnylenedlaminc, ,.. .
"

4,4'-dioctyldiphenylamlne, 4-octylaiphenylamlne, 4-t-butoxydiphenylamine, trimethylthlourea, 1,3-diethylthiourea, ethylene thiourea, ~odium dibutyldithiocarbamate, dilauryl thiodipropionate, distearyl thiodipropionate,the mono-, di- and tri-nonylphenyl phosphites, and the like. Other anti-oxidants include p-cresol-formaldehyde resins; para-tertiary-alkylphenol formaldehyde resins in admixture with amino aithioformates; aliphatic polyepoxides;
para-tertiary alkylphenol formaldehyde resins in admixture with mercapto compounds; carboxylic acids such as succinic acid, and the like; substituted oxamides such as oxanalide and the like; amino acids ~uch as glycine and the like; aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylonetriaminepentaacetic acid, hydroxyethyl-ethylenediaminetriacetic acid, nitrilotrlacetic acld, hydroxyethyllminodlacetic acld, dlaminocyclohexane-tetraacetic acld, dlaminoethyl ether tetraacetic acid;
~ 20 pentaerythrltol; ~orbitol; resorclnol; and the like.
: Small amounts of antioxidants are employed; for example, from about 0.002, and lower, to about 2 wcight percent, and higher, of antioxidant, based on the weight of the total reclpe. Small amounts of lubricants such as stearic acld, waxes, etc., may also be incorporated lnto the novel compo~itlons thereby obtalnlng further improved milllng and calenderlng characteri~tic~, ,, ''', '' ', ', ' , ' ' ' '' . .

~S518Z

The novel vinyl compo~itions are conventionally prepared by mixing the normally-solid thermoplastic polymers (total polymer binder), plasticizer, filler, pigments and stabilizer together at temperatures above the softening point of said polymers which is usually bet~een about 250F and about 375F. This mixing operation ls conventionally car~ied out in a Banbury* mixer or Baker-Perkins* type mixer. me mixed conposition is then fed to a two-roll mill which converts the resulting fused mixture into a flat sheet suitable for feeding the calenders. The twD-roll mill is operated to maintain the temperature of the fused stock. It is con-ventional practice to maintain a temperature differential beyween therolls to cause the sheet to adhere or to follow one of the rolls, e.g., the front roll is normally operated at, for example, about 170F to about 200P
whereas the back roll is normally maintained at about 275F to abou~ 32 ~ .
lhe milled sheet can be sub~ected to further various calendering ope.rations to reduce its gauge and to smooth its surface, o.r the sheet can be convçrted into rçgular o.r irregular granules which can then be mixed with similar granule~ of contrastlng coloratlon and molded into a sheçt. Typical ~ calendering operatlons ~or forming vinyl sheets are well-documented in the art; note, for example, United States Patent No. 2,917,781. The ~heet produced can be laminated to a backlng sheet of resin #~de l~s ~, ",~

105518~

impre~nated felt, fabric or a re~lnous sheet and can al~o be cut into tlles or other appropriate shape, depending upon the particular use to whlch the product 18 to be put.
j The following Examples are lllustrative.
In the illustratlve Examples herelnafter ,; :
disclosea, numerical notation~ followlng the copolymer or terpolymer deslgnatlons lndlcate parts by welght. For , -, example, ô6 vinyl chloride/14 vinyl acetate refer~ to a copolymer contalning 86 parts by weight of vinyl chloride and 14 parts by w d ght of vinyl acetate : chemically comblned thereln.

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Exarnples 1-2 illustrate the processing and rr.echanical prop-erties of two comparable recipes. The first reclpe, de~lgnated for conven-ience as NAT (non-asbestos tile), used limestone as the sole flller and the unique combination of therm~plastic polymers as the polymeric binder, i.e., (i) 86 vinyl chloride/14 vinyl acetate copolymer, inh~rent viscosity of 0.4, (ii) 88 vinyl chloride/10.5 vinyl acetate/1.5 ethylene terpolymer, inherent viscosity of 0.7, and (iii) epsilon-caprolactone hon~polymer, reduced viscosity 0.7; the second recipe designated for convenience as VAT (vinyl asbestos tile), employed asbestos as one of the fillers and used the aforesald 86 vinyl chloride/14 vinyl acetate copolymer as the polymerlc binder. The recipes were blended in a Hobart* rnixer and then mixed and fused in a Banbury* rnixer at 350F until fused and homogeneous.
The fused sto¢ks were then banded on an 8 in¢h two roll mill set at 110C
and 140& on the front and ba¢k rolls, respe¢tlvely. A sheet gauge of approxlmately 190 mlls was removed from the mill and calendered to 125 mil~
gauge with two su¢ce3slve passes through the calender. Specimens were ¢ut and condltloned at 25C and 50% relatlve humidlty prlor to testing. Methods provlded in Federal Test Method Standard #501A were used to obtaln M~Burney hardness values a~ 77F and 115F, impa¢t reslstances, and volatilltle~.
In additlon, mlll ratings and Brabender Plastlcorder* molten fl~w "

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lOS518Z

data were determined. The Brabender employed a #6 roller head using a sample charge of 100 grams; bowl temperature was set for 150C and rpm'~ at 60. Water ab~orptlon and water expansion data were also derived.
Values were obtained ~or both tests a~ter water exposure~ of 1, 3 and 7 day~ at roc~ temperature. The absorption values repre~ent weight percent gain a~ter the de~ignated exposure~. Expansion~ are ln terms o~
mils per 8 inch mea~ured acro3s machine direction.
The recipe~ are set out in Table I infra, performance properties of 1/8 inch gauge sheet are recorded i~ Table II in~ra, and tenslle data (A~TM Method D-~12) , are recorded ln Table III in~ra.

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TABLE II
PERFORMANCE PROPERTIE~ ~1/8TH INCH GAUGE) NAT RECIPE VAT RECIPE
Milling Properties(l) Hot Strength Good Good Tack Fair Good Plasticity Acceptable ~ormal Brabender Data( ) Peak Torque (m-gm) 4900 4900 Equilibrium Torque (m-gm) 25500 2100 Max. Temperature 170 C 167C

Impact Resistance(3) Average 10.7 6-7 Range 9-13 4-9 McBurney Indentation 1 min., 770F 8.4 7.2 10 min., 77 F 12.2 9.5 Max. Allowed 13.0 11.5 1/2 min., 115F 23.ô 27.6 ;

- Water Absorption ~Weight % Gain) 1 Day 0.83 1.46

3 Days 1-59 2 11 7 Days 2.08 2.63 Water Expansion (~ils/8 lnch) 1 Day ~one 5 3 Days 5 10 7 Days 5 30 Light ~tability(4) ~ 192 112 (~adeometer Hrs.) Tlle Dens~ty 2.18 2.12 (lbs./ft, ~
(1) The~e are mill procosslng propertie~ re~lecting roll adhesion, toughne~s and sheeting gualities.
(Z) ~6 roller head, 60 RPM, 100 gm ~pecimen, 150C.
(3) Data ob~alned on 1/16th gauge t~le; Federal Te~t Mo*hcd S~andard ~o, 501A, average o~ 3 experlment~.

(4) Dckermlnea ln a¢cordance with A~T~ ~otho4 E-42-64, , s , , " ~ , , , g o U~ o ~ O O ~ c~ ~D O O
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Six all limestone, non-asbestos ~illed recipes were prepared, blended, ~used ~heeted, and tested as described in Example~ 1-2 ~u~ra. The data are rscorded in Tables IY and V in~ra.

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With reference to Table V, the data therein reveals that recipes containing all PVC (Example 5~, PVC plus copolymer (Example 8), all relatively high molecular weight terpolymer (Example 7), and all copolymer (Example 6) showed sufficient deficiencies to be rejected, The all PVC recipe (#5) exhibited very poor milling properties due to poor roll adhesion and board y characteristics which caused considerable difficulty in forming a mill blanket. The all terpolymer recipe (#7) gave exceptionally good impact resistance but again poor milling properties due to inferior roll adhesion (tack) causing the ~tock to wander from the front to rèar mill rolls. me recipe employing all copolymer (#6) was excessively plastic and lacked hot strength. Recipe (#8) utilizing copolymer and homopolymer had inferior processing properties due to poor roll adhesion and its board y characteri~tic. Lower amounts of PCL in combination with the copolymer and terpolymer, a~ illustrated in recipes (#3 and ~4) exhibited good proce~sing and performance properties.

36, Examples 9-10 illu~trate the processing and mechanical properties of two comparable recipes The first recipe, designated for convenience as NAT
(non-asbestos tile), used limestone as the sole filler and, as the polymeric binders, a combination of (i) 86 vinyl chloride/14 vinyl acetate copolymer, inherent viscosity of 0.4, and (ii) 88 vinyl chloride/10.5 vinyl acetate/1.5 ethylene terpolymer, inherent viscosity of 0.7j the second recipe designated for convenience as VAT (vinyl asbestos tile), employed asbestos and limestone as the fillers and used the aforesaid 86 vinyl chloride/14 vinyl acetate copolymer as the polymeric binder. The recipes were blended in a Hobart mixer and then mixed and fused in a Banbury mixer at 350F until fu~ed and homogeneous. The fused stock~ were then banded on an 8 inch two roll mill set at 110C and 140C on the front and back rolls, respectively. A sheet gauge of approximatoly 190 miles was removed from the mill and calendered to 125 mils gauge with ~ two ~ucco~ive pa~ses through the calender. Specimens - were cut and conditioned at 25C and 50% relative humidity prior to testing. Methods provided in Federal Te~t Method Standard #501A were used to obtain McBurney hardne~ value~ at 77F and 115C, lmpact resi~tances, and volatllltles In addition, mlll ratlng~ and Brabonder Pla~tlcordor molton flow , ... .

, ,, 1~5518Z

data were determined. The Brabender employed a #6 roller head using a sample charge of 100 grams; bowl temperature was set for 150C and rpm'~ at 60. Water absorption and water expanslon data wers al~o deri~ed.
Value~ were obtained for both te~ts after water exposures of 1, 3 and 7 day~ at room temperature. ~he absorption value~ represent weight percent gain after the de~ignated expo~ure~. Expan~ion~ are in terms o~
mil~ per 8 inch mea~ured acro~ machine direction.
The reclpe~ are set out in Table VI infra and performa~ce properties of 1/8 inch gauge ~he~t are rec~rded 1~ Tab~e VII lnfra, ~ ~S3 _ ~vl ~w ~) ~o ~ ~ ~:1 ' Q ~ ~ ~0 0~ ~ O ~

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TABLE VII
PERFOR2~4NCE PROPERTIES 1/8 I~CH GAUGE
NAT RECIPE VAT RECIPE
(NO PCL~ ~O PCL) Milling Properties(l) Hot Strength Satis~actory Good Tack Good Good Plasticity Acceptable Normal Brabender Data( ) Peak Torque (m-gm) 3400 4900 Equilibrium Torque (m-gm) 1850 2100 Max. Temperature 161C 167C
Impact Resistance(3) Average 5 8 McBurney Indentation 1 min., 77F 8.5 7.2 10 min., 77F 12.9 9-5 1/2 min., 115F 21.4 27.6 Water Absorption (Weight % Gain) 1 Day 0.8 1.5 3 Days 1.5 2.1 7 Days 1.8 2.6 Water Expanslon ~Mils/8 lnch) 1 Day 5 5 3 Day~ 5 10 7 Days 5 30 Light Stability( ) (Fadeometer Hr~.) 192 112 " , are mill proce~ing properties re nectlng roll adheslon, toughne~s and ~heeting qualitie~.
(2) #6 Roller head, 60 RPM, 100 gm specimen, 150C.
(3) Data obtained on 1/16th gauge tile; Federal Test Method ~tandard No. 501A, average of 3 experiments.
(4) Determined in accordance with A~TM Method E-42-64.

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,~;,, , ,~, , , T~o recipes were prepared and processed in the identical manner as set forth in Examples 1-2 supra. The non-asbestos NAT recipe (Example 11) is practically the same as the ~AT recipe of Examples 1-2 with the exception that 0.1 weight per-cent stearic acid and 0.5 weight percent Ionol (2,6-di-t-butyl-p-cre~ol) are incorporated thcrein. The asbestos-containing VAT recipe (Example 12) i8 the same as the VAT recipe of Examples 1-2.
The milling properties of both rec$pes are rated as follows: non-asbestos ~AT recipe (Example 11) --good hot strength, good tack, and normal plasticity;
asbestos-contalning VAT recipe (Example 12~--good hot strength, good tack, and normal plasticlty The Brabender Plasticorder molten flow da~a of the non-asbe~tos ~AT recipe revealed that the re~ulting torgue-time molten ~low curve became normal in that tho s equillbrium torgue value wa~ achieved withln a tlmè
~' 20 span generally consldered to be wlthln the optlmum range for asbestos-containing VAT rccipes. Wlthout the 2,6-ai-t-butyl-p-cresol antloxidant, the non-asbestos-tlle reclpe exhiblted torque values whlch did not equlllbriate ln a normal fashion but who~e --torque contlnucd to lncrease wlth tlme. The Brabender data was co~lstent wlth th~ obs~rved milling characterlstlc~ of the reclpe~, The non-a~besto~
HA~ rocl~e (wlth antloxldant~ ~xhlblted no boardlne~

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and generally good mllllng gualitle~ comparable to the a~bosto~-containing VAT reclpe. Table VIII
b-lo~ r-cord~ both recip-~.

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912~-2 EXAMPI~S 13-16 Four recipe~ were prepared (Qee Table IX) and processed a~ described in Examples 1 and 2 for comparison purposes. Example 13 i8 a typical and preferred compo~iti~n according to this invention. Example 14 i8 e~gentially identical to Example 13 except that it does not include the preferred normally-solid oxyalkanoyl polymer.
Example 15 illustrates the use of conventional vinyl resin comprised of a blend of two copolymeric resins in the formulation of non-asbestos tile. Example 16 illustrates the use of a blend of a copolymeric vinyl re~in and a terpolymeric vinyl resin of the type u~ed in the pre-sent invention, but without solid oxyalkanoyl polymer.
The test results set orth in Table X clearly sh~w that the incorporation of a minor amount of oxyalkanoyl ~; polymer (Example 13) affords a ~ubstantial i~provement in - hot 3trength which is shown by improved ten~ile strength and milling qualitiefi of ~xample 13 as compared to Example 14. Hot tensile strength was increased by approximately 16%
along with a ~ub~tantial increase in Brabender equilibrium tongue.
T~e dra~tically reduced Brabender equilibrium tongue value~ and extremely poor mllling propertie~ for Examples ~5 and 16 demon~trate the total un~uitability of the~e formula-tion~ for 100r tlle u~e. The ~ub~tantial lncrea~e in ~tre~ relaxatlon ti~æ al~o preclude~ the u~e of these compos~tlons in non-a~be~to~ tlle application~ due to a 44, lOS5182 seriou~ lack in dimen~ional ~tability, It i~ considered ~ important to note that the substitution of terpolymer in Ji Example 16 for one of the copoly~ers of Example 15 produced a dramatic increase in Brabender equilibrium torque and in ~ hot ten~ile strength even though the terpolymer included ç only 1.5% ethylene.
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~ U ~J ~3~ V ,~ ~J U ~ 0 Exampleg 17-30 Fourteen limestone filled, non-asbestos recipe~
incorporating varying amounts of: vinylidene chloride/vinyl chloride copolymer; vinyl chloride/propylene copolymer;
chlorinated polyethylene polymer; ~ low molecular weight vinyl chloride/vinyl C2-C4alkanoate/C2-C4alkene random terpolymer were prepared, blended, fused,sheeted and tested as described in Examples 1-2 supra. In examples 19, 22, 24 and 27 relatively high molecular weight terpolymer was omitted from the recipe to confirm the criticality of this ingredient to better indicate the contribution of the binder resin to the propertie~ of the final product and to proce~s-ing condition~. Data obtained i9 recorded in Table~ XI
and XII below In Table XI a dash signifies omission of the indicated ingredient while in Table XII a dash indicates that the test was not preormed on t~e data was not recorded.

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3 v ~ ~o a The dat,~ recorded above demonstrate~ the importance of in~luding relatively high molecular weight terpolymer in the recipe aR all of the Exampleq ~19, 22, 24 and 27) in which it was totally excluded resulted in a product which waR unacceptable and could be produced only by resorting to processing conditions which are equally unacceptable. The remaining recipes yielded products which are acceptable from the standpoint of both product characteristics and processing conditions but which do not appear as desirable on balance 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 3tability while Examples 23, 24 and 30 reveal ~he remarkable con-tribution of chlorinated polyethylene to impact stabllity, These data provite the skilled worker in the field with the means to tailor the recipes of this invention by adding varying amounts of binder ingredients to achieve a compromise in product physical properties and in processing conditions be~t suited to the requirements of a particular application.

Claims (73)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A plasticized solid composition comprising a plasticizer con-taining a homogeneous mixture of:
(a) normally solid thermoplastic polymeric binder selected from the group consisting of:
(i) vinyl chloride/vinyl C2-C4 alkanoate polymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent (ii) 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 cam-prises up to about 50 weight percent (iii) vinyl chloride/propylene polymer in which the polymer-ized vinyl chloride portion thereof comprises at least about 90 weight per-cent and the polymerized polypropylene portion thereof comprises from about 10 percent to about 4 percent by weight (iv) chlorinated polyethylene polymer having not greater than 5 percent crystallinity; a molten viscosity of from 10,000 to 30,000 poises at 190°C and a chlorine content of at least 40 percent by weight (v) vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent viscosity less than about 0.5 in which the polymerized vinyl chloride portion thereof comprises the major proportion by weight (vi) mixtures of said polymers (b) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene relatively high molecular weight random terpolymer having an inherent 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 relative-ly high molecular weight terpolymer 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. m e composition of claim 1 wherein said terpolymer is vinyl chloride/vinyl acetate/ethylene terpolymer.

3. me composition of claim 1 wherein said polymeric binder is vinyl chloride/vinyl C2-C4 alkanoate copolymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent.

4. me composition of claim 1 wherein said polymeric 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 comprises up to about 50 weight percent.

5. me composition of claim 1 wherein said polymeric binder is vinyl chloride/propylene polymer in which the polymerized vinyl chloride portion thereof comprises at least about 90 weight percent and the polymerized polypropylene portion thereof comprises from about 10 percent to about 4 percent by weight,

6. The composition of claim 1 wherein said polymeric binder is chlorinated polyethylene polymer having not greater than 5 percent crystal-linity, a molten viscosity of from about 10,000 to 30,000 poises at 190°C
and a chlorine content of at least 40 percent by weight.

7. The composition of claim 3 wherein said copolymer comprises from about 80 to about 95 weight percent polymerized vinyl chloride and from about 20 to about 5 weight percent polymerized vinyl acetate; and wherein said relatively high molecular weight terpolymer comprises at least about 75 weight percent polymerized vinyl chloride, less than about 24.5 weight percent polymerized vinyl acetate, and at least about 0.5 weight percent polymerized ethylene.

8. The composition of claim 7 wherein said terpolymer comprises from about 80 to about 90 weight percent polymerized vinyl chloride, from about 9 to about 17 weight percent polymerized vinyl acetate, and from about 1 to about 3 weight percent polymerized ethylene.

9. The composition of claim 1 wherein said polymeric binder also contains from about 0.5 to about 15 weight percent of a normally-solid thermoplastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units of the formula , wherein x is an integer having a value of 2 to 7, with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from ; -COR1-CO2R2O-; ; ; -COR1-CO-;
-NH-?-O-; -OR2OCO-; -NHCONH-; the biuret group; -R2-NR-R2-; divalent mono-and poly-aromatic rings, including fused and bridged rings; lower alkyl substituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O-, group; wherein R represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group; R3 represents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one.

10. The composition of claim 9 wherein said recurring oxyalkanoyl units having the formula .

11. The composition of claim 9 wherein said thermoplastic oxy-alkanoyl polymer has a reduced viscosity value of at least about 0.2 to about 3 and is further characterized in that at least about 60 weight percent of said polymer is attributable to the recurring oxyalkanoyl unit shown therein.

12. The composition of claim 11 wherein at least about 80 to about 100 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxycaproyl units.

13. The composition of claim 12 wherein said polymeric binder is vinyl chloride/vinyl acetate copolymer, wherein said terpolymer is vinyl chloride/vinyl acetate/ethylene terpolymer, and wherein said thermoplastic oxyalkanoyl polymer is poly(epsilon-caprolactone).

14. The composition of claim 13 wherein said copolymer comprises from about 80 to about 95 weight percent polymerized vinyl chloride and from about 20 to about 5 weight percent polymerized vinyl acetate; wherein said terpolymer comprises at least about 75 weight percent polymerized vinyl chloride, less than about 24.5 weight percent polymerized vinyl acetate, and at least about 0.5 weight percent polymerized ethylene.

15. The composition of claim 14 wherein said polymeric binder com-prises from about 30 to about 60 weight percent of said copolymer, from about 40 to about 70 weight percent of said terpolymer, and from about 1 to about 10 weight percent of said thermoplastic oxyalkanoyl polymer.

16. The composition of claim 1 wherein said filler is a non-fibrous filler.

17. The composition of claim 16 wherein said filler is limestone.

18. The composition of claim 1 wherein said homogeneous mixture also comprises a small amount of an antioxidant.

19. The composition of claim 18 wherein said antioxidant is 2,6-di-t-butyl-p-cresol.

20. The composition of claim 1 wherein said vinylidene chloride/-vinyl chloride polymer is one in which the polymerized vinyl chloride portion thereof comprises from about 50 to about 90 weight percent and the polymerized vinylidene chloride portion thereof comprises from about 50 to about 10 weight percent, having an inherent viscosity of from about .35 to about .60.

21. The composition of claim l wherein said vinyl chloride/propylene polymer has an inherent viscosity of from about .4 to about .7 and the poly-merized vinyl chloride portion thereof comprises from about 90 to 96 weight percent and the polymerized polypropylene portion thereof comprises from about 10 to about 4 weight percent.

22. A plasticized solid composition comprising a plasticizer con-taining a homogeneous mixture of:
(a) a mixture of normally solid vinyl chloride/vinyl C2-C4 alkanoate co-polymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprisees up to about 30 weight percent and one or more normally solid thermoplastic polymeric binder resins selected from among:
(i) 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 comprises up to about 50 weight percent (ii) vinyl chloride/propylene polymer in which the polymerized vinyl chloride portion thereof comprises at least about 90 weight percent and the polymerized polypropylene portion thereof comprises from about 10 percent to about 4 percent by weight (iii) chlorinated polyethylene polymer having not greater than 5 percent crystallinity, a molten viscosity of from about 10,000 to 30,000 poises at 190°C and a chlorine content of at least 40 percent by weight and (iv) vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent viscosity less than about 0.5 in which the polymerized vinyl chloride portion thereof comprises the major proportion by weight (b) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene relatively high molecular weight random terpolymer having an inherent 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 terpolymer 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.

23. The composition of claim 22 wherein said terpolymer is vinyl chloride/vinyl acetate/ethylene terpolymer.

24. The composition of claim 22 wherein said polymeric 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 comprises up to about 50 weight percent.

25. The composition of claim 22 wherein said polymeric binder is vinyl chloride/propylene polymer in which the polymerized vinyl chloride portion thereof comprises at least about 90 weight percent and the polymer-ized polypropylene portion thereof comprises from about 10 percent to about 4 percent by weight.

26. The composition of claim 22 wherein said polymeric binder is chlorinated polyethylene polymer having not greater than 5 percent crystal-linity, a molten viscosity of from about 10,000 to 30,000 poises at 190°C
and a chlorine content of at least 40 percent by weight.

27. The composition of claim 22 wherein said copolymer comprises from about 80 to about 95 weight percent polymerized vinyl chloride and from about 20 to about 5 weight percent polymerized vinyl acetate; and wherein said relatively high molecular weight terpolymer comprises at least about 75 weight percent polymerized vinyl chloride, less than about 24.5 weight percent polymerized vinyl acetate, and at least about 0.5 weight percent polymerized ethylene.

28. The composition of claim 27 wherein said terpolymer comprises from about 80 to about 90 weight percent polymerized vinyl chloride, from about 9 to about 17 weight percent polymerized vinyl acetate, and from about 1 to about 3 weight percent polymerized ethylene.

29. The composition of claim 22 wherein said polymeric binder also contains from about 0.5 to about 15 weight percent of a normally-solid thermo-plastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recur-ring oxyalkanoyl units of the formula -O-?CH2??CO-, wherein x is an integer having a value of 2 to 7, with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from -O?CHR-CHR??;
-COR1-CO2R2O-; -O-?R2O??; -NR-?R1NR?? ; -COR1-CO- ; -NH-?-O- ; -OR2OCO-;
-NHCONH- ; the biuret group; -R2-NR-R2-; divalent mono- and polyaromatic rings, including fused and bridged rings; lower alkyl substituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O- , group; wherein R
represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group; R3 represents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one.

30. The composition of claim 29 wherein said recurring oxyalkanoyl units have the formula -O-?CH2???-.

31. The composition of claim 29 wherein said thermoplastic oxy-alkanoyl polymer has a reduced viscosity value of at least about 0.2 to about 3 and is further characterized in that at least about 60 weight percent of said polymer is attributable to the recurring oxyalkanoyl unit shown therein.

32. The composition of claim 31 wherein at least about 80 to about 100 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxycaproyl units.

33. The composition of claim 22 wherein said filler is a non-fibrous filler.

34. The composition of claim 33 wherein said filler is limestone.

35. A plasticized solid composition comprising a plasticizer con-taining a homogeneous mixture of:
(a) polymeric binder comprising (i) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate copolymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent; and (ii) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent 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 (b) a filler;
(c) said polymeric binder comprising from about 25 to about 65 weight per-cent of said copolymer and from about 35 to about 75 weight percent of said terpolymer; and (d) said filler being employed in amounts ranging from about 200 to about 750 parts by weight per 100 parts by weight of said polymeric binder.

36. The composition of claim 35 wherein said terpolymer is vinyl chloride/vinyl acetate/ethylene terpolymer and wherein said copolymer is vinyl chloride/vinyl acetate.

37. The composition of claim 36 wherein said copolymer comprises from about 80 to about 95 weight percent polymerized vinyl chloride and from about 20 to about 5 weight percent polymerized vinyl acetate; and wherein said terpolymer comprises at least about 75 weight percent polymerized vinyl chloride, less than about 24.5 weight percent polymerized vinyl acetate, and at least about 0.5 weight percent polymerized ethylene

38. The composition of claim 37 wherein said terpolymer comprises from about 80 to about 90 weight percent polymerized vinyl chloride, from about 9 to about 17 weight percent polymerized vinyl acetate, and from about 1 to about 3 weight percent polymerized ethylene.

39. The composition of claim 35 wherein said polymeric binder also contains from about 0.5 to about 15 weight percent of a normally-solid thermoplastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units of the formula -O-?CH2??CO- , wherein x is an integer having a value of 2 to 7, with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from -O-?CHR-CHR?? ; -COR1-CO2R2O- ; -O-?R2O?? ; -NR?R1NR?? ; -COR1-CO- ;
NH-?-O- ; -OR2OCO- ; -NHCONH- ; the biuret group; -R2-NR-R2-; divalent mono-and poly-aromatic rings, including fused and bridged rings; lower alkyl substituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O-, group; wherein R represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group; R3 repre-sents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one.

40. The composition of claim 39 wherein said recurring oxyalkanoyl units have the formula -O-?CH2???- .

41. The composition of claim 39 wherein said thermoplastic oxy-alkanoyl polymer has a reduced viscosity value of at least about 0.2 to about 3 and is further characterized in that at least about 60 weight percent of said polymer is attributable to the recurring oxyalkanoyl unit shown therein.

42. The composition of claim 41 wherein at least about 80 to about 100 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxycaproyl units.

43. The composition of claim 42 wherein said copolymer is vinyl chloride/vinyl acetate copolymer, wherein said terpolymer is vinyl chlor-ide/vinyl acetate/ethylene terpolymer, and wherein said thermoplastic oxy-alkanoyl polymer is poly(epsilon-caprolactone).

44. The composition of claim 43 wherein said copolymer comprises from about 80 to about 95 weight percent polymerized vinyl chloride and from about 20 to about 5 weight percent polymerized vinyl acetate; wherein said terpolymer comprises at least about 75 weight percent polymerized vinyl chloride, less than about 24.5 weight percent polymerized vinyl acetate, and at least about 0.5 weight percent polymerized ethylene.

45. The composition of claim 44 wherein said polymeric binder comprises from about 30 to about 60 weight percent of said copolymer, from about 40 to about 70 weight percent of said terpolymer, and from about 1 to about 10 weight percent of said thermoplastic oxyalkanoyl polymer.

46. The composition of claim 35 wherein said filler is a non-fibrous filler.

47. The composition of claim 46 wherein said filler is limestone.

48. The composition of claim 37 wherein said filler is a non-fibrous filler.

49. The composition of claim 48 wherein said filler is limestone.

50. The composition of claim 35 wherein said homogeneous mixture also comprises a small amount of an antioxidant.

51. The composition of claim 50 wherein said antioxidant is 2,6-di-t-butyl-p-cresol.

52. The composition of claim 37 wherein said homogeneous mixture also comprises a small amount of an antioxidant.

53. The composition of claim 52 wherein said antioxidant is 2,6-di-t-butyl-p-cresol.

54. As an article of manufacture, plasticized floor tile having very low water absorption, good light resistance, and good identation re-sistance and which is manufactured from a processible mixture comprising a homogeneous mixture of:
(a) normally solid thermoplastic polymeric binder selected from the group consisting of:
(i) vinyl chloride/vinyl C2-C4 alkanoate polymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent (ii) 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 comprises up to about 50 weight percent (ill) vinyl chloride/propylene polymer in which the polymer-ized vinyl chloride portion thereof comprises at least about 90 weight per-cent and the polymerized polypropylene portion thereof comprises from about 10 percent 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 190°C and a chlorine content of at least 40 percent by weight (v) vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent viscosity less than about 0.5 in which the polymerized vinyl chloride portion thereof comprises the major proportion by weight (vi) mixtures of said polymers (b) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene relatively high molecular weight random terpolymer having an inherent 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 relative-ly high molecular weight terpolymer is comprised of from about 25 to about 65 weight percent polymeric binder and from about 75 to about 35 weight per-cent 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.

55. The article of manufacture of claim 54 wherein said homogeneous mixture also contains from about 0.5 to about 15 weight percent of a normally solid thermoplastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units of the formula -O-?CH2??CO- , wherein x is an integer having a value of 2 to 7, with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from -O-?CHR-CHR?? ; -COR1-CO2R2O- ; -O-?R2O?? ; -NR-?R1-NR?? ;
-COR1-CO- ; -NH-?-O-; -OR2OCO- ; -NHCONH- ; the biuret group; -R2-NR-R2-;
divalent mono- and poly-aromatic rings, including fused and bridged rings;
lower alkyl substituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O- , group, wherein R represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group;
R3 represents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one.

56. The article of manufacture of claim 54 wherein said filler is a non-fibrous filler.

57. As an article of manufacture, plasticized floor tile having very low water absorption, good light resistance, and good indentation re-sistance and which is manufactured from a processible homogeneous mixture comprising:
(a) a mixture of normally solid vinyl chloride/vinyl C2-C4 alkanoate polymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent and one or more normally solid thermoplastic polymeric binder resins selected from among:
(i) 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 com-prises up to about 50 weight percent (ii) vinyl chloride/propylene polymer in which the polymerized vinyl chloride portion thereof comprises at least about 90 weight percent and the polymerized polypropylene portion thereof comprises from about 10 percent to about 4 percent by weight (iii) chlorinated polyethylene polymer having not greater than 5 percent crystallinity, a molten viscosity of from about 10,000 to 30,000 poises at 190°C and a chlorine content of at least 40 percent by weight and (iv) vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent viscosity less than about 0.5 in which the polymerized vinyl chloride portion thereof comprises the major proportion by weight (b) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene relatively high molecular weight random terpolymer having an inherent 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 relative-ly high molecular weight terpolymer is comprised of from about 25 to about 65 weight percent polymeric binder and from about 75 to about 35 weight per-cent 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.

58. The article of manufacture of claim 57 wherein said homogeneous mixture also contains from about 0.5 to about 15 weight percent of a normally solid thermoplastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units of the formula , wherein x is an integer having a value of 2 to 7, with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from ; -COR1-CO2R2O- ; ; ; -COR1-CO-;
-NH-?-O- ; -OR2OCO- ; -NHCONH- ; the biuret group; -R2-NR-R2- ; divalent mono- and poly-aromatic rings, including fused and bridged rings; lower alkyl substituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O-, group, wherein R represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group; R3 represents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one.

59. The article of manufacture of claim 57 wherein said filler is a non-fibrous filler.

60. As an article of manufacture, plasticized floor tile having very low water absorption, good light resistance, and good indentation re-sistance and which is manufactured from a processible mixture comprising:
(a) polymeric binder comprising (i) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate copolymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent; and (ii) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene terpolymer having an inherent 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 (b) a filler;
(c) said polymeric binder comprising from about 25 to about 65 weight per-cent of said copolymer, and from about 35 to about 75 weight percent of said terpolymer; and (d) said filler being employed in amounts ranging from about 200 to about 750 parts by weight per 100 parts by weight of said polymeric binder.

61. The article of manufacture of claim 60 wherein said polymeric binder also contains from about 0.5 to about 15 weight percent of a normally solid thermoplastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units of the formula , wherein x is an integer having a value of 2 to 7, with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from ; -COR1-CO2R2O- ; ; ; -COR1-CO-;
-NH-?-O-; -OR2OCO-; -NHCONH-; the biuret group; -R2-NR-R2; divalent mono-and poly-aromatic rings, including fused and bridged rings; lower alkyl sub-stituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O-, group; wherein R represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group; R3 represents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one,

62. The article of manufacture of claim 61 wherein said thermo-plastic oxyalkanoyl polymer has a reduced viscosity value of at least about 0.2 to about 3 and is further characterized in that at least about 60 weight percent of said polymer is attributable to recurring oxycaproyl units;
wherein said copolymer is vinyl chloride/vinyl acetate; and wherein said terpolymer is vinyl chloride/vinyl acetate/ethylene terpolymer.

63. The article of manufacture of claim 62 wherein said polymeric binder comprises from about 30 to about 60 weight percent of said copolymer, from about 40 to about 70 weight percent of said terpolymer, and from about 1 to about 10 weight percent of said thermoplastic oxyalkanoyl polymer.

64. The article of manufacture of claim 63 wherein said filler is a non-fibrous filler.

65. The article of manufacture of claim 63 wherein said mixture also comprises a small amount of an antioxidant.

66. The article of manufacture of claim 65 wherein said antioxidant is 2,6-di-t-butyl-p-cresol.

67. A process for producing non-asbestos containing plasticized vinyl sheet using equipment adaptable for producing asbestos-containing sheet which comprises forming a homogeneous mixture at a temperature of from about 250°F to about 375°F which comprises:
(a) normally solid thermoplastic polymeric binder selected from the group consisting of:
(i) vinyl chloride/vinyl C2-C4 alkanoate polymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent (ii) 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 comprises up to about 50 weight percent (iii) vinyl chloride/propylene polymer in which the polymer-ized vinyl chloride portion thereof comprises at least about 90 weight per-cent and the polymerized polypropylene portion thereof comprises from about 10 percent 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 35,000 poises at 190°C and a chlorine content of at least 40 percent by weight (v) vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent viscosity less than about 0.5 in which the polymerized vinyl chloride portion thereof comprises the major proportion by weight (vi) mixtures of said polymers (b) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene relatively high molecular weight terpolymer having an inherent vis-cosity of from about 0.5 to about 0.9 in which the polymerized vinyl chloride portion thereof comprises the major portion by weight;
(c) a filler; and (d) a plasticizer;
wherein the total combined weight of said polymeric binder and said relat-ively high molecular weight terpolymer is comprised of from about 25 to about 65 weight percent polymeric binder and from about 75 to about 35 weight per-cent 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, and thereafter milling and calendering said homogeneous mixture into fused plasticized vinyl sheets.

68. The process of claim 67 wherein said homogeneous mixture also contains from about 0.5 to about 15 weight percent of a normally-solid thermoplastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units. of the formula , wherein x is an integer having a value of 2 to 77 with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from ; -COR1-CO2R2O-; ; ; -COR1-CO- ;

-NH-?-O-; -OR2OCO- ; -NHCONH-; the biuret group; -R2-NR-R2-; divalent mono- and poly-aromatic rings, including fused and bridged rings; lower alkyl substituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O-, group; wherein R represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group; R3 represents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one.

69. A process for producing non-asbestos containing plasticized vinyl sheet using equipment adaptable for producing asbestos-containing sheet which comprises forming a homogeneous mixture at a temperature of from about 250°F to about 375°F which comprises:
(a) a mixture of normally solid vinyl chloride/vinyl C2-C4 alkanoate co polymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent and one or more normally solid thermoplastic polymeric binder resins selected from among:
(i) 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 comprises up to about 50 weight percent (ii) vinyl chloride/propylene polymer in which the polymerized vinyl chloride portion thereof comprises at least about 90 weight percent and the polymerized polypropylene portion thereof comprises from about 10 percent to about 4 percent by weight (iii) chlorinated polyethylene polymer having not greater than 5 percent crystallinity, a molten viscosity of from about 10,000 to 30,000 poises at 190°C and a chlorine content of at least 40 percent by weight and (iv) vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene random terpolymer having an inherent viscosity less than about 0 5 in which the polymerized vinyl chloride portion thereof comprises the major proportion by weight (b) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene relatively high molecular weight random terpolymer having an inherent viscosity of from about 0.5 to about 0.9 in which the polymerized vinyl chloride portion thereof comprises the major portion by weight;
(c) a filler; and (d) a plasticizer;
wherein the total combined weight of said polymeric binder and said relative-ly high molecular weight terpolymer is comprised of from about 25 to about 65 weight percent polymeric binder and from about 75 to about 35 weight per-cent 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, and thereafter milling and calendering said homogeneous mixture into fused plasticized vinyl sheets.

70. The process of claim 69 wherein said homogeneous mixture also contains from about 0.5 to about 15 weight percent of a normally-solid thermo-plastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units of the formula , wherein x is an integer having a value of 2 to 7, with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from COR1-CO2R2O-; ; ; -COR1-CO- ; -NH-?-O- ;
-OR2OCO ; -NHCONH-; the biuret group; -R2-NR-R2-; divalent mono- and poly-aromatic rings, including fused and bridged rings; lower alkyl substituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O-, group;
wherein R represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group; R3 represents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one.

71. A process for producing non-asbestos containing plasticized vinyl sheet using equipment adaptable for producing asbestos-containing sheet which comprises forming a homogeneous mixture comprising:
(a) polymeric binder comprising (i) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate copolymer in which the polymerized vinyl chloride portion thereof comprises at least about 70 weight percent and the polymerized vinyl C2-C4 alkanoate portion thereof comprises up to about 30 weight percent; and (ii) normally-solid thermoplastic vinyl chloride/vinyl C2-C4 alkanoate/C2-C4 alkene terpolymer having an inherent viscosity of from about 0.5 to about 0.9 in which the polymerized vinyl chloride portion thereof com-prises the major portion by weight;
(b) a filler; and (c) a plasticizer;
(d) said polymeric binder comprising from about 25 to about 65 weight per-cent of said copolymer, and from about 35 to about 75 weight percent of said terpolymer;
(e) said filler comprising from about 200 to about 750 parts by weight per 100 parts by weight of said polymeric binder;
(f) said homogeneous mixture being formed at a temperature of from about 250°F to about 375°F; and (g) thereafter milling and calendering said homogeneous mixture into fused plasticized vinyl sheets.

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 thermo-plastic oxyalkanoyl polymer having a reduced viscosity value of at least about 0.1 and which is further characterised in that at least about 50 weight percent of said thermoplastic oxyalkanoyl polymer is attributable to recurring oxyalkanoyl units of the formula , wherein x is an integer having a value of 2 to 7, with the proviso that x does not equal 3, together with, if desired at least one other moiety or group chosen from ; -COR1-CO2R2O- ; ; ; -COR1-CO- ;
-NH-?-O- ; -OR2OCO- ; -NHCONH- ; the biuret group; -R2-NR-R2-; divalent mono-and poly-aromatic rings, including fused and bridged rings; lower alkyl substituted oxyalkanoyl groups; catalyst residues, and the carbonate, -O?-O-, group; wherein R represents hydrogen or a lower alkyl group; R1 represents a divalent hydrocarbon group; R2 represents a divalent aliphatic hydrocarbon group or a divalent aliphatic oxa-hydrocarbon group; R3 repre-sents a divalent aliphatic hydrocarbon group and y represents an integer having a value of at least one.

73. The process of claim 72 wherein said mixture also contains from 0.002% to 2% of a hindered phenol.