[1]@Uni'ted States Patent Office 3,5479767 3,547,767 FLEXIBLF, HEAT AND PRESSURE CONSOLIDATED DECORAIIVE LAMINATE COMPRISING A NITRITE RUBBER LATEX IMPREGNATED BASE AND A SUPERIMPOSED TRANSPARENT ICHER. 5 MOPLASITC FILM Ronald James Keeling and Alfred Thomas Guertin, Cincinnati, Ohio, assignors to Forniica Corporation, Cincinnati, Ohio, a corporation of Delaware No Drawing. Filed June 27, 1967, Ser. No. 649,130 Int. Cl. D06n 7106, B32b 15108, 27108 10 U.S. Cl. 161-217 5 Claims ABSTRACT OF THE DISCLOSURE4 15 A decorative laminate comprising a heat and pressure consolidated assembly comprising in superimposed relationship at least one dried paper base sheet impregnated with a nitrile rubber latex surfaced with a transparent thermoplastic film back-printed with a desi.-n 20 thereby rendering the Mm translucent. BACKGROUND OF THE INVENTION Decorative laminates have been produced for a substqn- 25 tial plurality of years for use as surface materials for the application to tables, vanitories, vertical wall coverings, door coverings and the like. Ordinarily, these decorative laminates are prepared by assembling in superimposed relationship a plurality of kraft paper core sheets which 30 have been impregnated with a thermosettin-- phonolformaldehyde resin. Superimposed above these core sheets which may ntimber between I and 9 core sheets there is positioned a decorative sheet that is impregnated with a thermosetting resin which does not 1-indergo any notice- 35 able deterioration in color, such as darkeding, upon the subsequently applied lamiiiating conditions. Typical resins that meet this description are the melamineformaldehyde resins, the epoxy resins, the unsaturated polyester resins, the urea resins, and the like. The decorative sheet 40 may be a solid color a-,cellulose paper sheet which has been dyed or pigmented to a selected color such as white, pink, yellow, and the like, or the decorative sheet may be a print sheet in which some design such as a geometric design or a floral design or a wood print is iniparted to 45 the decorative side of the decorative sheet before or after impregnation with the color stable thermosetting resin. Frequently, there is superimposed above the decorative sheet an overlay sheet which is a sheet of fine quality paper such as a-cellulose paper sheet unpigmented, but im- 50 pregnated a.@ain with a color stable thermosetting resin, which overlay sheet is superimposed above the decorative sheet, and then the entire assembly is heat and pressure consolidated under conventional conditions of pressure and teinperature to produce a unitary laminated 55 product. The overlay is used primarily when the decorative sheet is a print sheet so as to provide a barrier to avert abrasion of the printed part of the print sheet and thus preserve its printed characteristics in tact for prolonged periods of time. More recently, a structure such as that 60 described hereinabove has had the overlay replaced with certain selected thermoplastic films produced from vinyl polymers such as films of poly(methyl methacrylate), blends of poly(methyl methacrylate) with polyvinylidene -fluoride, polyvinyl fluoride, and the like. 65 FIELD OF THE INVFNTION The concept of the present invention is in the field of making laminated plastic articles and, more particularly, decorative, flexible, laminated plastic articles which 7,0 laminated articles provide better solvent resistance, improved impact resistance, better glueability, more body, Patented Dec. 15, 1970 2 less telegraphing of substrate defects, greater flexibility, aiid improved handleability, and when used in combination with an aluminum foil positioned immediately beneath the decorative sheet to proiiide a surface with imProved heat dissipation and, finally, absence of blooming. DESCRIPTION OF THE PRIOR ART The known prior art is to be found in the United States Pats. 2,563,111, 2,729,585, 2,759,866 and 3,231,457. SUMMA@RY OF THE INVENTION This invention relates to a decorative laminate which has at least two layers, which layers are arranged in superimposed relationship and then heat and pressure consolidated to a unitary structure. The lower layer of this two-component laminate is sometimes hereinafter referred to as the base member and comprises at least one sheet of paper and, preferably, unbleached creped kraft paper, which has been impregnated with a nitrile rubber latex. Upon completion of the impregnation of the paper web, which can be impregnated contintiously, the aqueous portion of the latex or einulsion is then flashed off by passing the impregnated wet web throu.-h a heating chamber or oven or it may be passed through a plurality of heated rolls whereby the temperature is sufficient to evaporate the water from the web thereby leaving the nitrile rlibber present on and in the dried web. The dried web thus produced is ready to be cut into the desired s@@zes a@id positioned in the assembly preparatory to makin.@ the laminate. The nitrile rubbers may be acquired from a plurality of corni-nercially available sources and are copolymers of either acrylonitrile and/or metbacrylonitrile with a copolymerizable rubber latex forn-iing mononier Such as one or more of the butadienes. If desired, one may use a terpolymer of the type of rubber latex which is prepared by interpolymerizing acrylonitrile and/or methacrylonitrile with one or more of the butadienes and one or more of the polymerizable styrenes such as styrene per se c)r the rin.--substituted alkyl styrenes such as o-, m-, p-methyl styrene, and/or the ringsubstituted halostyrenes such as the chloro and bromo ringsubstituted styrenes and the like. It is preferred to make use of a nitrile rubber latex which is prepared by copolymerizing butadiene and acrylonitrile in a conventional latex or emulsion polymerization technique in which the copolymer contains between about 20 and 50 parts by weight of acrylonitrite and, correspondingly, between 80 and 50 parts of butadiene and, preferably, between about 25 and 35 parts, by,weight, of acrylonitrile and, correspondingly, from about 75 to about 65 parts, by weight, of butadiene. As used, the nitrile rubber latex in the aqueous dispersion may contain between about 35% aiid 55%, by weight, of solids based on the total weight of the latex and, preferably, botween about 45% and 50%, by weight, solids same basis. As a furthcr preferred embodimeiit, c,ne may blend with the nitrile rubber latex up to 75 parts, by weight, of a polyvinyl halide latex such as a po.lyvinyl chloride latex. These polyvinyl halide latices can be prepared by homopolymerizing a vinyl halide or by copolymerizing it with another compatible and copolymerizable monomer in an emulsion or latex emulsion system. The term viiiyl halide is deemed to be of sufficient scope to encompass the vinylidene halides as well which can be used as homopolymers or compolymers with one or more compatible monomers cop6lymerizable therewith in an emulsion or latex polymerization system. Among the vinyl halides which may be used to form this polyvinyl halide latex are vinyl chloride, vinyl fluoride, vinyl bromide, vinyl iodide, vinylidene chloride, vinylidene fluoride, vinylidei-ie bromide, vinylidene iodide, and the Ike. Afnong the
[2]3,547,767 3 polymerizable monomers which may be used to form copolymers, terpolymers, and the like with the vinyl halide are such polymerizable monomers as vinyl acetate, styrene, the ring-substituted halo and alkyl substituted styrenes, such as o-, m-, p-cbloro styrene, o-, m-, p-bromo styrene, and the like, or the 2,4-dichloro styrene, 2,5-dichloro styrene, 3,4- dibromo st@,rene, and the like. Additionally, oiie could use the o-, m-, p-methyl styrei-ic, o, ni-, p-ethyl styrene, and the like or the 2,4 - dimethyl styrene, the 2,5-diethyl styrene, and the lik-@. One n-iay Lise additionally such polyn-ierizable monomers as acrylic acid, methacrylic acid and their esters such as the methyl, ethyl, isopropyl, butyl methacrylates or ethacrylates. It is ordinarily desired that there be used a predetermined amount of the vinyl halide in the copolymer such as about 75 parts of the vinyl halide and, correspondingly, about 25 parts of the corresponding copolymerizable monomers. A particularly useful polyvinyl halide copolymer latex is one prepared by emulsifying 95 parts of vinyl chloride with 5 parts of ethyl acrylate, which copolymer contains no conventional nonpolymeric plasticizers. This vinyl latex may be present in an amount varying between 0% and 75%, whereas the nitrile rubber latex may be present correspondingly in an amount varying between 100% and 25%, by weight, based on the total wei.-ht of solids constituents in the latex. It is preferi-ed to use in the blend from about 40% to about 60%, by wei.-ht, of the vinyl latex and, correspondingly, fron-i about 60% to about 40%, by wei,-bt, of the nitrile i-ubber latex, samc basis as before. It will be apparent that when percentages, by weight, in the blend are @iven in corresponcting terms, it is obvious that the total amount of the separate components ai-e additively 100%. The filler paper used in the base member wiil be a conventional type of abcorbe.-@t filler paper, of which a plurality are available conlmercially such as the up@bleached creped kraft paper (Mosinee R-3-B) havin@ an apparent density of 0.327 g./cc. The base paper is treated with the nitrile rubber or resin blend using typical paper saturating techniques to a resin pick-up within the range of from about 45 to about 75%, by weight, based on the total weight of the impregnated dried paper and, preferably, between about 50% and 68%, by weight, of the resin solids based on the total weight of the impregnated dried paper. The base paper thus treated and dried provides a stable, tackfree sheet. The base sheet is then surfaced with a transparent thermoplastic film back-printed with a design thereby rendering the film translucent. The expression "backprinted" means printed on its back or underside which side will contact the base sheet. The thernioplastic transparent film used as the surface layer may be any transparent colorless thermoplastic film containing no plasticizer or plasticized very lightly with a non-migratory polymeric plasticizer, including such plasticizers as rubbery polymers and copolymers. The essential feature of this thermoplastic film is to impart to the laminate surface a good stain and solveiit resistance. Any film containing a plasticizer which impairs this resistance is therefore not acceptable. Additionally, any thermoplastic film which is solubl-@ in common solvents to any si,-nificant extent such as alcohols, acetates, carbon tetrachloride, and the like, are unacceptable. The thickness of the surface film is not critical, but economics and commercial availability tend to dictate that the film be selected from those having a thickness between about 0.5 and 6 mils and, preferably, between about 2 and 4 mils. Illustrative of the type of thermoplastic transparent films which may be used for the surface layer of the laminates of the present invention are polyvinyl chloride films, either plasticized lightly or unplasticized films of polyacrylonitrile, films of nylon, films of chlorinated polyetbers ' films of polyesters, films of polycarbonates, films of poly@ (methyl methacrylate), films of blends of poly(methyl methacrylate) with polyvinylidene fluoride and films of polyionomers of DuPont Surlyn A, which is a com4 mercially available copolymer of ethylene copolymerized with a monomer containin.@ carboxyl groups to provide an ionically reactive site. One of the preferred vinyl films which may be used to surface the laminate of the present invention is polyvinyl chloride which may be used as a hamopolymer or as a copolymer prepared by copolymerizing vinyl chloride with minor amounts such as 15% or less of the acrylates such as methyl acrylate, ethyl acrylate, propyl'acrylates, butyl acrylates, methyl meth10 acrylate, ethyl methacrylate, r@iethyletbacrylate, ethyl ethacrylate, vinyl acetate, vinyl propionate, and the like. In addition, the polyvinyl chloride homopolymer may be blended with minor amounts such as 15% of a polymeric processing aid such as polymers or copolymers of the 15 acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, methyl ethacrylate, vinyl acrylate, etc. These surfacing films may contain, if desired, small quantities of plasticizer in an amount of 5% or less such as com20 merically available epoxy ester metal salts, urethane extended epoxies and other conventional plasticizers such as dibutyl phthalate, dioctyl phthalate, and the like. In producing the decorative laminates of the present invention, a variety of press cycles may be used such as 2,3 by varyin.- the pressure between about 200 and 1400 p.s.i. with temperatures between about 135' C. and 260' C. and press times froni about five seconds to about 30 minutes. Ordinarily, the time factor diminishes as the temperatures and pressures are increased and vice-versa. If @,( a fully flexible laminate is desired, the core sheets should be eliminated altogether or kept to a minimum such as between about I and 4 core sheets as hereinabove defined or sheets similar to the base sheet hereinabove defined. Laminates prepared by increasing the number of core 35 sheets from I to 4 all gave satisfactory products but with slightly increased stiffness with the increased number of core sheets. If ffexibility of the laminate is less important than rigidity, a plurality of core sheets even in excess of 4 can be used up to about 8 or 9, but beyond that, noth40 ing of significance is to be gained by increasing the total number of core sheets. In order that the present invention may be more compl@-tely tinderstood, the following examples are set forth in which all parts are parts by weight unless otherwise indicated. These examples are set forth primarily for the 4 @@3 purpose of illustration and any specific enumeration of detail contained therein should not be interpreted as alimitation on the case except as is indicated in the appended claims. Example I 50 A laminate is prepared by using 2 mil thick transparent rigid unplasticized polyvinyl chloride film backprinted with a wood-grain printed design over a base sheet of 31 lbs. (basis weight) of unbleached, absorbant 55 creped kraft paper treated to a resin level of 50% with a polyblend resin of 55 parts of a polyvinyl chloride latex and 45 parts of an acrylonitrile-butadiene rubber latex (35165 A:B, respectively), and laminated together at a maximum temperature of 136' C., 1000 p.s.i. for 17 60 minutes in a veneer pack in a flat bed press. A plurality of these laminates 'were pressed simultaneously in the press and were separated from one another with suitable release sheets. One of the laminates produced hereinabove was subjected to a plurality of tests and displayed 65 the following properties: NEMA impact (LDI-2.15) ----- >116". 70 Minimum radius (room temp.) -- 0". CS abrasion ------------------ 9200 cycles. Stains ------------------------ No NEMA stains on short contact. Peel strength (vinyl base sheet) -- 4.2 lbs./lineal inch. Thickness -------------------- -007". 73
[3]3,547,767 5 Example 2 Example I is repeated in aH essential details ex,ept that the base sheet is replaced with an uncreped, unbleached kraft of 43 lb. basis weight. The properties of this laminate are favorably comparable to those produced in Example 1 except that the thickness is increased to 0.009". -Example 3 The procedure of Example I is repeated in all essential details except that the base sheet is replaced with a creped, unbleached kraft paper sheet of 50 lb. basis weight. The properties of this laminate are similar to those of Example I extept that the thickness is .010". Example 4 Example I is repeated in all essential details except that the base sheet contains 68% of the resin blend based on the total weight of the dried base sheet and resin. T'he properties of this laminate are the same as those of Example 1 except that the thickness is .008". Example 5 Example I is repeated in all essential details except that the filler is treated to a 68% pick-up with a nitrile rubber latex containing 28 parts of acrylonitrile and 72 parts of butadiene. The properties of this laminate are the same as those of Example 1. Example 6 Example I is repeated in all essential details except that the base is treated to a 68% resin pick-up with a 25/75 blend of polyvinyl chloride latex with the same nitrile rubber latex. The properties of this laminate are essentially the same as those described in Example 1. Example 7 The process of Example I is repeated in all essential details except that instead of using a flat press the layers are compressed together into a uniform product using a continuous laminating process by passing the assembly through heated nip rolls. The properties of this laminate are the same as in Example 1. Example 8 -Example I is repeated in all essential details except that in the place of the 2 mil polyvinyl chloride fflm there is substituted a 2 mil transparent film of nylon backprinted with a floral design. A further difference resided in the fact that the laminate was processed in a continuous laminating operation using the apparatus shown in the U.S. Pat. 3,159,526. The final laminate has superior scratch and stain resistance. Example 9 Example 1 is repeated in all essential details except that the polyvinyl chloride surface film is replaced with a clear nylon film back-printed with a wood grain design and the entire assembly is heat and pressure consolidated into a unitary structure by the process of Example 1. The properties of this laminate are essentially the same as those of Example I except for superior scratch and solvent resistance. Example 10 Example 9 is repeated in all essential details except that the clear nylon film is replaced with a clear film of polyacrylonitrile back-printed with a geometrical design. The properties of the laminate thus produced are favorably comparable of those of Example I except for excellent stain resistance. Example I I ,Example 9 is repeated in all essential details except that the nylon film is replaced by a commercially available clear film of a ohlorinated polyether of the same thickness backprinted with a wood grain design. The 6 properties are similar to those of the laminate described in Example I except for improved stain resistance. Example 12 Example 9 is repeated in all essential details except that the clear nylon film is replaced by a back-printed clear film of unplasticized polyvinylidene chloride of the same thickness. The properties of this laminate are comparable to those described in Example 1. 10 Example 13 Example 9 is repeated in all essential details except that the nylon film surface layer is replaced by a commercially available clear film of polycarbonate back15 printed with a wood grain design.. The properties of the laminate are similar to Example I except for reduced stain resistance. Example 14 Example 9 is repeated in all essential details except 20 that the clear nylon film is replaced by a clear film of a commercially available polyester @resin back-printed with a wood grain design. The properties of this laminate are similar to those described in Example 1. 25 Example 15 Example I is repeated in all essential details except that a bondable aiuminum foil is positioned between the decorative film and the base layer. The properties of the laminate thus produced are comparable to those of Ex30 ample I except for the greatly enhanced thermal properties, namely, heat and cigarette burn resistance. Example 16 Example 1 is repeated in all e;ssential details except 35 that three core sheets are incorporated between the decorative film and the base sheet. The core sheets had been preimpregnated with a conventional thermosetting phenolformaldehyde resin. The properties 6f the laminate thus produced are favorably comparable to those of Example 40 1 except for the increased thickness, body and rigidity. Example 17 Example I is repeated in all essential details except that the layers are formed into a uniform product by exerting a pressure of 300 p.s.i. The properties of this 45 laminate are favorably comparable to those of Example 1. Example 18 Example 9 is repeated in all essential details except 50 that the nylon surface film is replaced by a clear backprinted film comprising a blend of i6O parts of poly (methyl methacrylate) and 4G parts of polyvinylidene fluoride of the same thickness. The properties of this laminate are comparable to those produced in Example I except 55 for the improved outdoor weatherability. Example 19 Example I is repeated in all essential details except that under the base sheet there is positioned a rigid 60 wooden board and the, lamination is accomplished in one step with the use of a continuous laminating press comparable to that used in Example 8. Example 20 Example I is repeated in all essential details except 65 that the polyvinyl chloride film is replaced by a backprinted clear film of a commercially available homopolymer blend or copolymer of a 80/20 methyl methacrylate/ ethylacrylate, respectively,- back-printed with a wood grain 70 design. Example 21 Example 9 is repeated in all essential details except that the clear nylon film is replaced by a clear film of a commercial bondable polyolefin such as polypropylene 7-5 made bondable by copolymerization with small quanti-
[4]7 ties of acrylic acid (less than 15 parts) which is back@ printed with a wood grain or other design. Properties of this laminate are siniilar to those described in Example I except for improved stain resistance. In the foregoing examples, when reference is made to a clear film which has been back-printed, it should be understood that the film before printing is clear, but that after the back-printing has been accomplished, the film is converted from a transparent state to a translucent one. Although the back-printed film is converted during the backprinting operation from a transparent to a translucent one, it is desired to approach opacity and in order to accomplish this, the translucent back-printed film can be given a "ground coat" optionally, which ground coating is accomplished by applying a layer of a conventional printitig ink on the top of the back-print in a thickness varying between about 0.1 niil and I.Oi mil and, prefera-bly, between .3 and .5 mil. This ground coat is applied directly to the printed side of the film and the color of the ink used in the ground coat is generally selected from those which are compatible color-wise with the color of the back-printed film. When a brownish wood grain is used to print the design on the transparent film, a brownish ink may readily be used as the ground coat. We
