Document Qk3aJ3EYrkX8B0pEE5YyaEMRk

FILE NAME: Flooring (FLR) DATE: 1978 A p r i l DOC#: FLR017 DOCUMENT DESCRIPTION: Patent - Harris, Armstrong Cork Co. Decorative Non-Vinyl Surface Covering Composition United States Patent ?] Harris____________ / _ [54] DECORATIVE NON-VINYL SURFACE COVERING COMPOSITION [75] Inventor: Thomas G. Harris, Lancaster, Pa. [73] Assignee: Armstrong Cork Company, Lancaster, Pa. [21] Appl. No.: 789,297 [22] Filed: Apr. 20, 1977 [511 I n t CL*..........................C08K 3/00; C08K 3/26 [52] U A a ........................... 260/18 PF; 260/17.4 R; 260/30.6 R; 26/31.6; 260/31.8 M; 260/42.46; 260/897 C; 260/998.15; 260/DIG. 3! [58] Field of Search....... 260/42.46. 897 C, DIG. 31, 260/998.15,17.4 R, 31.6, 31.8 M. 30.6 R, 18 PF [uj 4.083.821 [45] Apr. 11, 1978 [56] References Cited U.S. PATENT DOCUMENTS 3,536,788 10/1970 Hurwitz et aL ................ 260/897 C 3,814,740 6/1974 Miller et aL ................. 260/897 C primary Examiner--la m a H. Dcrrington [57] ABSTRACT A decorative non-vinyl flooring composition is de scribed which comprises a mineral filler distributed substantially uniformly throughout a binder comprising a blend of a copoly(C, to C alkyl acryIate/C6 to C 12 cycloalkyl acrylate) and a chlorinated polyethylene. 9 Claims, No Drawings 4,083,821 vinyl chloride/vinyl C3-C, aikanoate/Cj-C alkene and DECORATIVE NON-VINYL SURFACE COVERING filler. While the composition contains no asbestos, the COMPOSITION terpolymer comprises at least 75% to 80% of the com BACKGROUND OF THE INVENTION position, such containing vinyl chloride. Chlorinated polyethylene is disclosed to be of use in place of. or 1. Field o f the Invention along with, poly(vinyl chloride) in this formulation. This invention relites to a non-vinyl composition However, the esc of such docs little to eliminate the use useful as a surface covering material. More particularly, of vinyl chloride in the compounded composition. Fur it relates to a floor tile composition comprising a min- ther, chloropolycthylcnc-containing compositions have era! filler and a binder that is a blend of a copolyfalkyl 10 been noted as difficult to process on low-intensity acrylate) and chloropolyethylene. equipment and lack clarity and hardness. 2. Description of the Prior Art Most acrylates have high affinity for absorbing mois A widely used resinous binder material having partic ture and are poor flooring materials in this respect. ular unility in surface coverings is based on those poly They also have high Tg's and, if plasticizer used to mers of vinyl chloride, such as the thermoplastic poly(- IS adjust, such become mushy. vinyl chloride). When properly compounded wiJt an assortment of plasticizers, heat and light stabilizers, SUMMARY OF THE INVENTION fillers and pigments, the resultant vinyl composition It is, therefore, an object of this invention to provide displays satisfactory physical, traffic ab'uion and stain an improved flooring composition that is non-vinyl. resistance properties, such finding particular use as 20 It is a further object of this invention to provide a flooring materials. The economics of formulations em non-vinyl flooring composition that has good process ploying these vinyl polymers particularly favors high ing properties. filler loadings. However, the cavalier addition of filler It is an additional object of the present invention to materials to the vinyl resin binder is disadvantageous to provide a non-viny* flooring composition substantially those commercially important physical properties men- 25 free of asbestos and having good melt strength and ease tioned above. For example, one of the least expensive Of processing. filler materials commonly used in vinyl compositions is It is an additional object of the present invention to calcium carbonate. Its sole use in vinyl formulations is provide a non-vinyl, non-flbrous flooring composition generally detrimental to the compounding operation, possessing the desirable properties of fibrous flooring requiring careful handling at slow speeds on sheet or 30 compositions, such as good tensile strength, low mois- calender rolls. Fluid>'y of the resultant molten mass is lure absorpiio.? yyLbih dimensional stability. These generally so high that the melt strength is negligible and and other objects will become apparent to one skilled in proper calendering is all but impossible. Lack of dimen the art from the consideration of the specification. sional stability, as exhibited by sheet shrinkage upon removal from the calender (nerve), is a further problem 3J in these formulations. Of course, many difficulties with DESCRIPTION OF THE PREFERRED EMBODIMENTS the calcium carbonate-only filled compositions can In accordance with the present invention, a decora readily be resolved by the use of fibrous fillers, espe tive non-vinyl surface covering is formed by the admix cially asbestos. Compositions containing such filler ma ture of a mineral filler, such being substantially uni- terial display good melt strength, exhibiting the proper 40 formly distributed throughout a binder"that is a blend of degree of viscous flow and melt elasticity, so that they a chlorinated polyethylene and t copoly(alkyl can be readily sheeted, calendered and/or tiansported acrylate/cydoalkyl acrylate), without excessive tearing or elongation in the manufac- The mineral fillers of preference herein are those of a turing process. However, the use of asbestos has re- non-fibrous nature such as limestone, whiting, clay, talc, cently found a great deal of disfavor since various medi- 45 silica, pumice, wood floor, and mixtures thereof. As cal researchers and government officials have suggested disclosed earlier, while fibrous fillers are within the that exposure to asbestos fiber-containing products may scope of the present invention, such do not represent pose a serious health peril to the general public. At the highly desirable fillers. In the preparation of the compo- present time, many states and municipalities are contem- silions of the various embodiments herein, filler mix plating or have preliminarily passed legislation to end 50 tures of reduced fiber content are preferred. Non- the use of asbestos in the confines of their jurisdiction. fibrous type filler compositions are particularly useful The manufacturing of compositions have reduced levels and limestone rcpiescnts the most preferred filler, espe- or completely free of asbestos has, therefore, become a daily limestone comprising very coarse to very fine prime goal in the flooring industry. particle sizes, such having average particle sizes ranging Additionally, vinyl chloride resins themselves have 55 from about 40 to about 340 mesh (Tyler). The amount become subject to health hazard study. The monomer, of filler to be blended with the surface treating composi vinyl chloride, is a noted carcinogen. This, in concert tion described below can vary widely and will normally with the recent scarcity of the monomer-forming start be in the range of from about 60 to about 85 weight ing materials, suggests the importance of discovering percent. non-vinyl, e.g. non-vinyl chloride-containing, resin 60 As an essential ingredient, chloropolyethylene forms binders. one component of this mineral-filled surface covering In this respect, various surface covering materials composition. have been compounded using such non-vinyl chloride- The chlorinated polyethylene of use in accordance containing resin binders, one of the most successful with the present invention is produced from high den- being the chlorinated polyolefin binders, For example, 65 sity polyethylene by a slurry phase chlorination pro in U.S. Pat. No. 3.904.579, a novel flooring composition cess, as disclosed in U.S. Pat. No. 3,401,129, incorpo- is disclosed that comprises a plasticized vinyl chloride rated herein by reference. The chlorinated polyethylene polymer compounded with a terpoiymer comprising of particular use herein lias a chlorine content of be- 4,083,821 3 4 tween 35 weight percent and 48 weight percent, prefer about 15 weight percent based on the total binder com ably 42% to 45% by weight, a crystallinity of 0% to position. 21%, preferably 0% to 3% as provided by differential Small amounts o f stabilizers may be incorporated to thermal analysis, a 100% modulus of at least about 250 reduce the efTects of degradation of heat and light. to about 500, preferably 350-450, and an ultimate tensile 5 Suitable light stabilizers include epoxidized soya bean strength of 1000 to 3500 psi. The glass transition tem oil. epoxidized tallates. wood rosin, phosphites, resorci perature (Tg) of --25' C. to +25* C., preferably --15* nol disalicylate, resorcinol dibenzoatc, phenyl phthal C. to +10* C., is demonstrated by the chlorinated poly- ate, phenyl benzoate, ortho-tolyl benzoate, eugenol, and ethylenes of use in accordance with the present inven organic phosphates and other complexes of such metals tion. 1 as barium, cadmium, strontium, lead, tin and the like. As a second ingredient to be used herein, it has been Suitable beat stabilizers include barium-cadmium ascertained that when 30 weight percent to 70 weight soaps, barium-cadmium-zinc soaps, epoxides, sulfides percent of certain random alkyl acrylate copolymers and sulfites of the metals silver, calcium, cadmium, are blended with the above chlorinated polyethylene, magnesium, cerium, sodium, strontium and the like. surprising processing, physical and end use properties Normally, the novel compositions in accordance with are imbued to suiface covering compositions using the piesent invention contain from about 2.5 to 7.5 these components as binders. weight percent of the above heat and light stabilizers These acrylates, employed in accordance with this based on total amount of binder. If desired, small embodiment of the present invention, are those random amounts of antioxidants such as the hindered phenols, copolymer acrylates having molecular weights (Slw) 20 e.g. di-t-butyl-p-crcsol, and lubricants such as stearic greater than about 500,000. The upper limit of such acid, waxes, and so forth, may be incorporated to obtain molecular weight is not in itself critical, but conven further improved calendering and compounding char tional techniques do not readily produce these copoly acteristics. mers in molecular weights greater than about 2 million For roost purposes, the compositions of this invention These copolyacrylates have secondary transition tem are prepared with a pigment. Examples of suitable pig peratures (Tg) in the 45*--85* C. range. The preferred ments are titanium dioxide, phthalocyanine blue, phtha- copolymers are the linear or branched C| to Ct alkyl locyaninc green, chrome yellow, chrome orange, red acrytate/C4to Cu cycloalkylacrylate. Most preferred iron oxide, carbon black, lamp black, chrome oxide are the copolymers of linear or branched C| to C4alkyl green, and the like. The proportion of pigment in the acrylate/cyclohexyl acrylate or isobomy! acrylate and composition varies depending on the type of pigment are set in U.S. Pat. No. 2,117,321, incorporated herein and may be as low as 0.5% by weight and up to about by reference. 5.0% by weight total composition. Inert and extender The above-disclosed copolymeric acrylate and chlo* pigments, such as silica aerogels, talcs, and diatoma- ropolyethylene are mixed with the mineral filler in the 35 ceous silica, commonly used in organic coatings arc ratios of 8-32:32-8:60 to 3-12:12-3:85, preferably from suitable Tor controlling the gloss of the composition, if 26-14:3-12:60 to 9.75-5.25:3-12:85, most preferably desired. 4-16:80. Mixing can be by any conventional technique The compositions in accordance with the present utilized for blending filler with resinous materials. invention have tensile strength of from 1000 psi to 4000 These techniques include the fusing of the composition 43 psi, displaying superior product durability than vinyl in a Baker Perkins mixer and sheeting through hot cal counterparts. They also show higher Olsen stiffness ender rolls. (from greater than 2.4 to about 6.0) and advantageously In addition to the copolymeric acrylate and chlo- lower moisture absorption than the typical all vinyl ropolyethylenc binder blend in accordance with the chloride systems. present invention, a wide range of organic plasticizers 4; The surface covering compositions of this invention can also be incorporated in these compositions. Illustra are of particular use in the calendering and molding of tive plasticizers include esters of aliphatic glycols and floor tiles. Such molding can produce tiles of various aliphatic dicarboxylic acids such as dibutyl sebacatc, shapes and sizes including the usual 9 inch X 9 inch tile. dioctyl sebacate, dioctyl adipate, didecyl adipate, dioc The compositions can be molded into sheets and such tyl azelate, triethylene glycol di(2-ethylhexanoate), di- 50 used to cover large areas of floor surfaces. It is also ethylene glycol dipelargonate, triethylene glycol dicap- within the contemplation of the present invention to use rylale, and the like; esters of aliphatic alcohols and the molded sheets for other applications where non aromatic acids, or aromatic glycols and aliphatic acids, vinyl compositions of superior tensile strength and elon or aromatic alcohols and aromatic acids, including dibu gation are desired, for example, as covering tables, tyl phthalate, dicapryl phthalate, dioctyl phthalate, 55 counters and the like. dipropylene glycoi dibenzoate, butyl benzyl sebacate, butyl benzyl phthalate, dibenzyl sebacate, dibenzyl EXAMPLES phthalate, and the like, are useful herein. Other types of The chloropolyelhylene used in the illustrative exam plasticizers such as esters of inorganic acids, including ples is Cl % by weight 43.1, Tg 0* C., and 100% modu tricrcsyl phosphate, octyl diphenyl phosphate, and the 60 lus 432. like, Paraplex G-25 linear polyester or epoxidized soy The copoly(alkyl acrylate) is shown in these exam bean oil can also be used. These plasticizers should ples as acrylic copolymer and is the copoly(methylme- preferably have low vapor pressure at compounding thacrylatc/isobomyl acrylate 30/70) of Tg 61* C. and temperatures, i.e. 400* C, Tlicy arc employed in plasti Ktw 800,000. S tab ilizer I, dicyandiam idc-bascd, T en- cizing amounts sufficient to provide mechanical proper- 6J neco V5660; Stabilizer II, melamine-based, Tenneco ties which are desirable in the end use applications. V I762; asbestos, 7R grade. Normally, a satisfactory range of plasticizer, including In the illustrative examples, the following compo mixtures thereof, is from about 5 weight percent to nents were admixed in the ratios noted. 4,033,821 6 Chloropolyeihylwe Acrylic Cpolymer Subduer 1 Stabilizer II Asbestos Limettone 40M Titanium Dioxide Example 1 % b y wt. 15.36 3.S4 0.54 0.26 4.92 74. !0 0.98 (pin* binder) The above are mixed in the Baker Perkin* to 290? F. (20 minutes), The materia] is discharged unto a mill with the rolls set at 200* F./260* F. The flexible sheet is pressed polished and the physical properties measured 5 (Table I). Example 5 % by wi. (parts binder) 100.00 Chloropolyethylene 6.018 (80) Acrylic copolymer 1.500 (20) Coumerottc Indent retin 6.135 The above are mixed in the Baker Perkins io 290* F. (Hercules 6100) Butyl benzyl pnlhalale 1.3)0 (20 minutes). The material is discharged unto a mill with Subilizcr t 0.211 the rolls set at 220* F./270* F. The slightly rigid sheet is press polished and the physical properties measured Srabiliaer IF Abbott* Limestone SOM 0.136 5.170 77.S00 (Table I). Titanium Dioxide 1.030 Example 2 % by wt. Chloropolyethylene Acrylic copolymer Butyl benzyl phthaUlc Stabilizer I Stabilizer 11 A tb e tio t Limestone 46M Titanium Dioxide 13.056 3.264 1.000 0.450 0.230 5.043 75.948 1.009 (parti binder) (80) (20) The above are mixed in the Baker Perkins to 280* F. (10 minutes). The material is discharged unto a mill with the rolls set at 10* F./280* F. The flexible sheet is press 20 polished and the physical properties measured (Table I). _________ Example 6 % by wt. Chloropolyethylene 6.0 The above are mixed in the Baker Perkins to 290* F. ACocurryr*lZicTicVo)cpoirlnyimetetcr icMii (Kciculs! 6100) 61..86 (20 minutes). The material is discharged unto a mill with Butyl benzyl phlhalate 1.4 the rolls set at 220* F./280* F. The flexible sheet is press Stabilizer 1 0.2 polished and the physical properties measured (Tabic I). Subilizcr it Asbestos 0.2 5.2 Limestone SOM 77.6 Titanium diosidc 1.0 Example i Chloropolyethylene Acrylic copolymer Butyl benzyl phthalate Stabilizer I Stabilizer 11 Asbestos lim estone 40M Titanium Dioxide % by wt. 8.287 8.288 1000 0.280 0.145 5.04) 75.948 1.009 (parts binder) (50) (50) The above was charged to a Baker Perkins mixer and heated to 290* F. (15 minutes). The mix was quite wet at 35 discharge. It was sheeted on the rolls (175* F./270' F.) and calendered to i inch gauge. Physical properties were then determined (Table I). Example 7 % by wt. phr The above are mixed in the Baker Perkins to 320* F. Chloropolyeihylene (100% moTduglu~s =-31636,' C , 13.10 83 (20 minutes). The material is discharged unto a mill with a = 43.1%) the rolls set at 220' F./280* F. The rigid sheet is press polished and the physical properties measured (Table I). Acrylic copolymer Butyl benzyl phlhalate Stabilizer (dicyandiamkfc type) 3.30 20 1.00 0.40 Subilizcr (melamine type) 0.20 Limestone J25M 1.25 __________________Example 4 % by wi. (parti binder) Limestone 40M Tiunium dioxide 79.75 1.00 ChltTOpoiycihylene Acrylic copolymer Evtfyl benzyl jfivrtraUte Stabilizer I Stabilizer II Asbestos Limestone 40M Titanium Dioxide 12.67 J) y 17 (20) 1-50 0.44 0.22 S.04 75.95 t.0l The above materials are mixed on a Baker Perkins mixer for 15 minutes at 310* F. The large particles are discharged unto a mill with rolls set at 200V260* F. The flexible sheet obtained is press polished and physical properties measured (Table I). Table I Typical1 Vinyl Tile 1 2 3 4 5 6 7 Thickness (mils) Specific Gravity Tensile Strength (pst) Elongation (% ) Olsen Stiffness (in.-lb.) Bend Break Angle (degrees) Moisture Absorption (% W) Dimensional Stability (% L) 63 2.15 899 2.1 1.9 27 2.31 -0.12 71 2.17 2284 IS 48 15 0.81 -0.04 72 2.21 1633 5 1 3.3 37 0.97 -0.01 69 2.22 3345 0.7 5.1 6 0.83 -0.02 74 2.22 1092 6.0 2.5 42 1.20 -0.18 66 2.27 1820 0.6 3.6 7 0.72 -0.08 129 2.17 1277 2.2 1.03 72 2.22 1485 5.1 4.3 40 1.12 -.1 9 Via)I chloride/vuyl accuie copolymer Ww 41,(00,11% by wrighl blended with enum ero indent retin 2% by weithi. phihtltie plttbeUer 4.1% by wci(in, suM ieer I to d Subiliier II (l.l) 0.19% by w djbX asbestos 4.99% by weight. lim a lo (CM. 75.12% by weight end titanium diotide 100% by weigh'. What is claimed is: ,033,82 i 1. A nnn-viny! surface covering composition com 1 30% to 70% by welsht based on total binder cf prising a. a mineral filler distributed substantially uniformly throughout b. a binder comprising the components 1. chloropolyethylene of chlorine content 35% to 48% by weight, a 100% modulus of 250 to about 500 and a glass transition temperature of from -25* C. to 30* C.; and 10 chloropolyethylene of chlorine contest 35% to 48% by weight, a 100% modulus of 250 to about 500 and a gltas transition temperature of from -25* C to 30* C.; and 2. 70% to 30% by weight based on total binder of a copoiy(C| to C , alkyl acrylate/C to C u cycloalkyl acrylate) of molecular weight from about 500,000 to about 2 million. 5. The surface covering composition of claim 4 2. a copoly(C| to C, alkyl acrylate/C to C12cyclo wherein said non-fibrous filler is calcium carbonate, and alkyl acrylate) of molecular weight from about said component (2) is copo)y(C|to C4alkyl acrylate/cy- 500,000 to about 2 million where the ratio of clohexyl acrylate or Isobomyl acrylate). compc-rnt (l):component (2):mineral filler is 6. The surface covering composition of claim 4 addi from 8-32:32-8:60 to 3-12:12-3:85. 1* tionally containing 5-15% by weight of an organic 2. The composition o f claim 1 wherein said compo plastizicer. nent (2) is copoly(Ci to C4 alkyl acrylate/cyclobexyl 7. The surface covering composition of claim 5 acrylate or isobomyl acrylate). wherein said calcium carbonate Is of average particle 3. The composition of claim 1 wherein laid ratio is . . siz8e. fMroomldaebdofulot o3r2t5ilmesefsrhomto tahbeocuotm40pomsietsiohn(Tdeyflienre).d in from 26-14:3-12:60 to 9.75-5.25:3-12:85. claim 4 having a tensile strength greater than 1000 psi to 4. A non-vinyl surface covering composition com 4000 psi. prising 9. The molded floor tiles of claim 4 additionally con a. 60% to 85% by weight of a non-fibrous filler, taining asbestos and said component (2) is 20 to 65 b. 40% to 15% by weight of a binder comprising the u weight percent of said bine components 30 35 40 45 50 55 60 65