Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
  • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
  • B44C1/20—Applying plastic materials and superficially modelling the surface of these materials
  • B44C1/205—Applying plastic materials and superficially modelling the surface of these materials chemical modelling
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44F—SPECIAL DESIGNS OR PICTURES
  • B44F1/00—Designs or pictures characterised by special or unusual light effects
  • B44F1/02—Designs or pictures characterised by special or unusual light effects produced by reflected light, e.g. matt surfaces, lustrous surfaces
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
  • D06N7/0005—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface
  • D06N7/0028—Floor covering on textile basis comprising a fibrous substrate being coated with at least one layer of a polymer on the top surface characterised by colour effects, e.g. craquelé, reducing gloss

Definitions

• the present invention relates to decorative sheet materials, and more particularly to multi-layered, resinous, decorative sheet materials having surface portions having differential gloss effects, and to methods of making such differential gloss, decorative sheet materials. Even more particularly, the present invention relates to differential gloss, decorative sheet materials having raised, embossed or textured surface areas in substantially perfect registry with the surface areas having the surface differential gloss effects Such decorative sheet materials having differential gloss are of use as: floor, wall or ceiling coverings; desk, table or counter tops; and a host of other commercial, industrial and household applications.
• Decorative sheet materials of a resinous polymer composition have been made for many years and one of the commonest ways of creating or enhancing the surfache decorative effects has been to provide selected portions of the surface of such decorative sheet materials with different types of contrasting finishes or effects, or surface gloss or luster differentials, for example, with smooth, glossy or lustrous surfaces; raised, embossed dead or dull mat surfaces, raised, embossed glossy or lustrous surfaces; smooth, dead or dull mat surfaces; etc., all sharply contrasting with one another to create differential gloss products.
• differential mechanical embossing inlaying, or chemical embossing or etching
• many other methods have been devised to provide sharply contrasting surface areas but all of such prior art methods or combinations thereof have always left something to be desired.
• differential mechanical embossing procedures combined with pattern or design printing procedures has always created registration problems and related difficulties.
• Inlaying procedures and chemical etching methods have normally been more costly and more process-time consuming.
• the result is the direct retention of the mechanical embossing in the areas where the monomer has been polymerized and its loss where polyvinyl chloride had been fused.
• the resulting product has dull surface areas corresponding to where the peroxide was applied and gloss areas in the other portions of the surface.
• a method of making a differential gloss product which comprises: forming a potentially foamable base resinous plastisol on a supporting structure, such as a fibrous backing sheet, heating and gelling the potentially foamable base resinous plastisol; applying to the surface of the gelled plastisol a printing ink composition in a predetermined pattern or design, some portions of which contain, a urethane polymerization catalyst and either the same or other portions of which contain a blowing or foaming inhibitor; applying to the surface of the printed, gelled base resinous plastisol a resinous plastisol wear layer; heating and gelling the resinous plastisol wear layer and blowing or foaming the potentially foamable base resinous plastisol at elevated temperatures and fusing the base resinous plastisol and the resinous wear layer; applying to the surface of the fused resinous wear layer a urethane
• FIGURE I is a fragmentary, diagrammatic, elevational, crosssectional view of one embodiment of the present invention, subsequent to the heating and fusing of the resinous materials, plus blowing or foaming if a blowing or foaming agent was originally included in the base resinous plastisol material composition and if a blowing or foaming inhibitor was originally included in some portions of the printing ink composition; and
• FIGURE II is a fragmentary, diagrammatic, elevational, cross-sectional view of another embodiment of the present invention under process conditions similar to those of Figure I .
• Figure II may represent a different product than that illustrated in Figure I or it may represent a different portion of the product illustrated in Figure L.
• FIG. I there is illustrated a relatively flat, fibrous backing sheet material 10 upon which is deposited or formed a conventional, potentially foamable, base resinous plastisol composition 12, or, if desired or required, a conventional, non-foamable, base resinous plastisol composition which does not contain any blowing or foaming agent.
• a relatively flat, backing web or sheet material 10 may be used, if desired or required, as the base layer or supporting substrate for the base resinous polymer compositions of the present inventive concept.
• a backing sheet material 10 may comprise a felted or matted fibrous sheet of overlapping, intermingled fibers and/or filaments; or a nonwoven, knitted, woven, or otherwise fabricated textile construction; or a sheet of resinous polymer composition; or paper or a paper product; or similar or like materials and constructions.
• a felted fibrous sheet material comprising inorganic fibers, such as asbestos; or organic fibres, such as cellulose, cotton, jute or rayon; or synthetic or manmade fibers and/or filaments, such as polyolefins, polyamides, acrylics, polyesters, glass, etc., are the most commonly used backing sheet materials but others are equally suitable and are utilizable in special situations, Such backing sheet materials are well set forth in many prior art patents, such as United States Patents 3,293,094, 3,293,108, 3,660,187 and 4,187,131.
• the thickness of such a relatively flat, fibrous backing sheet material 10 will depend to a large extent upon the particular product to be made and the particular subsequent use for which it is intended. Normally, such a thickness is in the range of from about 10 mils to about 90 mils, but other thicknesses, especially those greater than 90 mils, may be used in particular and special circumstances.
• the relatively flat, backing sheet material 10 may be omitted completely and the foamable or non-foamable resinous polymer composition 12 may be used by itself.
• resinous polymer composition 12 may be made by well-known standard and conventional methods and may contain one or more synthetic resins, such as a polymer or co-polymer of vinyl chloride, or other resins such as polyurethane, an elastomer such as natural or synthetic rubber, and the like, as the main constituent resin.
• a blowing or foaming agent such as azodicarbonamide, if a blowing or foaming agent is desired or required
• various accelerator/stabilizers or catalysts such as dibasic lead phthalate, zinc octoate, lead octoate, dibasic lead phosphite, etc.
• various light and/or heat stabilizers such as metallic soaps
• one or more plasticizers such as dioctyl phthalate, butyl benzyl phthalate, dibutyl sebacate, etc.
• coloring agents and pigments such as titanium dioxide
• solvents and diluents such as methyl ethyl ketone, mineral spirits, etc.
• fillers such as clay and limestone
• many other conventional and well-known additives and improvement agents such as azodicarbonamide, if a blowing or foaming agent is desired or required
• various accelerator/stabilizers or catalysts such as dibasic lead phthalate, zinc octoate, lead oc
• the base resinous composition may be doctored by a doctor blade, or roll coated, or poured, or cast, or otherwise applied or formed on a strippable supporting carrier which may be a steel belt, a rubber belt, release paper, or felt or other fabric or material having a release surface or coating thereon and subsequently stripped or removed therefrom.
• the base resinous composition 12 may be doctered by a doctor blade, or roll coated, or poured, or cast, or otherwise applied or formed and adhered to the carrying sheet material, such as the fibrous backing sheet material 10, in a substantially uniform manner in a relatively uniform thin coating by procedures well-known in the art.
• the thickness of such a base resinous composition 12 as a foamable material, as applied and still wet, is in the range of from 5 mils to about 50 mils, or even more, if so desired or required by its subsequent use.
• the base resinous plastisol composition 12 After the base resinous plastisol composition 12 has been applied or formed on the carrying backing sheet material, it is then heated under moderately gentle heat for a period of time of from about 1 ⁇ 2 minute to about 4 minutes at an elevated temperature of from about 240o F. to about 400o F., but more normally commercially from about 290o F. to about 350°F., whereby the plastisol gels and firms so that it can be more easily handled and processed in subsequent operations.
• the elevated temperature is not that sufficiently high as to activate or to decompose the particular blowing or foaming agent which may be present as to cause blowing or foaming of the base resinous polymer composition.
• the gelled, firm base resinous composition 12 is then cooled and is printed or coated with a suitable printing ink composition or compositions 14 in the desired or required pattern or design which may posses many colors.
• a suitable printing ink composition or compositions 14 in the desired or required pattern or design which may posses many colors.
• the particular pattern or design which is used does not relate to the essence of the invention and any suitable pattern or design may be selected.
• the printing procedure, in general, is conventional and should require no further description, inasmuch as such procedures are well known in the industry and are described in many publications and patents.
• predetermined portions or parts 14A of the particular pattern or design printed on the surface of the base resinous polymer compositions 12 contain a blow modifier or inhibitor in different amounts, concentrations, or types, and so forth, depending upon the variety of differential blowing or foaming effects desired.
• Such differential blowing effects are well described in the previously mentioned United States Patents and should need no further explanation or description.
• blowing or foaming inhibitors are normally included in the particular printing ink composition in amount of from about 1% to about 35% by weight, based on the total weight of the printing ink composition.
• Many typical blowing and foaming inhibitors are mentioned in the previously described United States Patents, among the more popular are: trimellitic aanhydride fumaric acid benzotriazole
• trimellitic aanhydride fumaric acid benzotriazole are mentioned in the previously described United States Patents, among the more popular are: trimellitic aanhydride fumaric acid benzotriazole
• urethane polymerization catalyst in predetermined parts or portions 14B of the predetermined pattern or design, which parts or portions 14B are shown in different places of the predetermined pattern or design in Figure I, but which may be the same places and, as a matter of fact, there may even be places where is neither blowing or foaming inhibitor nor urethane polymerization catalyst, there is included a urethane polymerization catalyst in an amount of from about 1 ⁇ 4% to about 20% by weight, based on the total weight of the printing ink composition in which it is included.
• Preferred and typical examples of such urethane polymerization catalysts are:
• N-methyl diethanolamine N-methyl diethanolamine
• a relatively small amount, say, from about 1 ⁇ 4% to about 2% by weight, a low concentration, of the urethane polymerization catalyst may also be included in the portions or parts 14A, in order to modify, adjust, or control the relative degree of tackiness of the superjacent surfaces of the wear layer lying directly thereover, such as in the surface areas 18A.
• a resinous wear layer 16 in the form of a resinous polymer composition or plastisol is then applied thereto substantially uniformly.
• a wear layer 16 contains conventional and standard constituents, such as synthetic resins, preferred and typical being polymers or co polymers of vinyl chloride, medium to low molecular weight, and plasticizers, stabilizers, pigments or dyes on rare occasions, solvents and diluents, viscosity improvement and controlling agents, and like additives and materials.
• concentrations of such added constituents are conventional and standard and are in the ranges and concentrations set forth in the previously mentioned United States Patents.
• the realtively flat, resinous wear layer 16 has an average thickness of from about 0.002 inch to about 0.025 inch and is applied substantially uniformly to the surface of the printed, gelled and firmed base resinous polymer composition 12.
• the wear layer 16, in normal practice, is usually a clear, unpigmented resinous polymer composition and its basic purpose in usually to give to the final product improved wearing properties and qualities.
• the wear layer 16 After the wear layer 16 has been applied to the printed, gelled base resinous composition 12, it may be desired to gel and firm its surface in a separate operation. If it is, then the wear layer is heated under moderately gentle heat in an oven or other heating device for a period of from about 1 ⁇ 2 minute to about 4 minutes at an elevated temperature of from about 240oF. to about 400oF., whereby it hardens or firms and gels so that it can be handled more easily in subsequent operations. Again, the elevated temperatures must not be that high as to activate or to decompose the blowing or foaming agent which is normally present in the base resinous composition 12, if blowing or foaming is desired in the final product but not desired at this particular time in the manufacturing process.
• blowing and foaming, as well as fusion of the resinous materials take place in the same procedure at elevated temperature along with the gelling of the wear layer, such may be easily accomplished by heating in an oven or other suitable heating device to an elevated temperature which is higher than the previously stated temperatures for gelling.
• elevated temperatures are in the range of from about 325°F. to about 470°F. for a period of time of from about 1 minute to about 4 minutes.
• heating procedures are standard and conventional and are described in the previously cited United States Patents.
• a urethane top coating coating composition 18 is then applied or formed substantially uniformly on the blown or foamed and fused surface of the resinous wear layer 16 to a depth or thickness of from about 0.0005 inch to about 0.015 inch.
• the specific and particular urethane top coating composition 18 which is employed does not relate to the essence of the present invention and normally comprises a substantially uniform mixture of unreacted polyols or polyhydroxy compounds and unreacted polyisocyanates, as originally applied to the surface of the resinous wear layer 16, along with additives, such as surfactants, or other constituents, as desired or required.
• such a top coating urethane coating composition 18 does not contain any urethane polymerization catalysts or any urethane polymerization initiators.
• the polyols and the polyisocyanates do not react with each other to any substantial degree at the time of the application to the blown or foamed and fused resinous wear layer.
• the polyols or polyhydroxy compounds may be selected from a very wide range of suitable diols, triols, tetrols, or various other polyols and polyhydroxy compounds, or mixtures thereof, from many various sources, including glycols, polyether glycols, polyester glycols, glycerols, trialkylol alkanes, alkane triols, polyether triols, polyester triols, erythritol, pentaerythritol, polyols having a functionality higher than four, caprolactone polyols poly (hydroxyalkyl) derivatives of such compounds as the alkylene polyamines, the various polyether polyols with amines, etc.
• One example of the latter-most groups is N,N,N' ,N '-tetrakis (2-hyddroxypropyl) ethylenediamine. Mixtures of polyols may be used.
• the polyisocyanates may be selected from a large group of aliphatic, aromatic, cycloaliphatic, and heterocyclic polyisocyanates, such as methylene-bis (4-cyclohexylisocyanate), isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethyl-cyclohexyl-isocyanate), 2 ,4,4-trimethyl-hexamethy-lene diisocyanate, etc. Mixtures of polyisocyanates may be used.
• the blown or foamed and fused resinous material with the applied urethane top coating composition 18 thereon is then exposed to elevated temperatures of from about 250°F. to about 425°F. and preferably from about 270°F. to about 420 F. for a period of time of from about 2 minutes to about 10 minutes in an oven or other suitable heating means, whereupon the polymerization reaction between the polyols and the polyisocyanates in the urethane top coating composition 18 is initiated.
• such polymerization reaction is initiated only in those portions or parts 18B of the urethane top coating composition 18 which lie directly over the predetermined parts or portions 14B of the printing ink composition 14 containing the urethane polymerization catalyst.
• such urethane polymerization catalyst has apparently migrated from the printing ink composition areas 14B to polymerize the areas 18B of the urethane top coating composition 18 to a hardened, cured high glossy condition.
• the other parts or portions 18A of the urethane top coating composition 18 which do not lie directly over any catalyst-containing area are substantially uncured and remain tacky and fluid or semifluid and remain in a very soft state, as contrasted to the parts or portions 18B of the urethane top coating composition 18 which are cured and polymerized to a firm, hardened, glossy or shiny condition which is substantially tack-free.
• the depth of the mechanical embossing may be as little as a fraction of a mil or it may be as much as about 15 mils, but preferably is from about 1 mil to about 4 mils, depending upon the type, thickness, and the nature of the wear layer being so embossed mechanically upon the decorative effect which is desired or required, upon the type and the form of the mechanical embossing, and so forth.
• the unpolymerized areas, tacky or slightly tacky become embossed.
• the cured areas remain glossy.
• Such a finish or texture is substantially completely lacking in brilliance, gloss, luster or sheen.
• the surface may be roughened, corrugated, coarse, lined or knurled in regular or irregular, predetermined or random fashion and may possess numerous very small knobs, projections, ridges, points, or protuberances to give it the desired flat, dead or dull matte appearance.
• the mechanical embossing may also take the form of very many, very fine lines which are straight and parallel or swirling curves, as many as about 60 or 80 or even 100 or more lines per inch, or it may be the result of pressing paper, textured materials or fabrics, woven, knitted or nonwoven against the surface of the wear layer to create thereon the desired finish or texture.
• the embossing material preferably has release characteristics, such as silicone rubber.
• the mechanical embossing to yield the desired flat, dead or dull matte finish or texture or other finishes may take place under pressures which may be as low as about 2 pounds per square inch gauge up to about 300 pounds per square inch gauge, depending upon the existing temperature which is in the range of from about 240oF. to about 470o F. If the pressure is applied in a press platen, the pressure may be maintained for a period of time of from about 10 seconds to as much as about 4 minutes. If the pressure is applied by means of a heated embossing roll, then the temperatures and the pressures will be in the higher portions of the aforementioned ranges, whereas the time of the application of the pressure will be correspondingly relatively short.
• the passing or the wrapping of the resinous polymer sheet material around a portion of the periphery of the heated embossing roll can be used to extend the duration of the application of heat.
• the pressures which are exerted, however, must be sufficient as to establish a good intimate contact between the heated embossing surface and the resinous polymeric materials being embossed.
• the sleek, glossy or lustrous finish areas should have gloss levels in the range of from about 15 to about 90, or even higher; the flat, dead or dull mat finish areas should have gloss levels in the range of from about 70 down to about 3, or even less; with the differences in the gloss levels between the two contrasting finishes being in the range of at least about 10 in gloss level ranges below 50 and at least about 20 in gloss level ranges equal to or about 50.
• Such numerical gloss level values are determined by the procedures set forth in A.S.T.M. 523-67 (1972) at an angle of 60°.
• the principles of the present inventive concept are equally applicable to the obtaining of a sleek, glossy or lustrous finish in some certain selected areas and the obtaining of even more sleek, glossy or lustrous finishes in certain other selected areas, again keeping the differences in the gloss level values greater than about 20, inasmuch as the gloss level values greater than about 20, inasmuch as the gloss levels involved in such embodiment will be greater than about 50.
• the final resulting product in one form thereof, greatly resembles a ceramic title flooring such as in commonly found in bathrooms, both as floor and as wall surfaces.
• the sleek, glossy or lustrous finish greatly resembles the surface of a glazed or fired ceramic tile, whereas the flat, dead or dull matte surface greatly resembles the grout or cementitious materials which are placed between the glazed ceramic tile.
• urethane polymerization catalyst then is applied to the surface of the mechanically embossed product.
• the catalyst can be applied by any manner such as by spraying it on the surface or passing the sheet through a coating operation. Alternatively, the catalyst in dry powder form can be dusted on the surface of the product. Alternatively, the urethane polymerization catalyst can be applied to the entire surface of the urethane top coating before the mechanical embossing step. This sequence actually can improve the retention of the embossing pattern and the release of the embossing medium from the urethane coating. If desired, a release agent may be incorporated into the catalyst composition.
• the multi-layered resinous construction with the additional layer of urethane polymerization catalyst thereon is then exposed to elevated temperatures of from about 250°F. to about 425°F. and preferably from about 270°F. to about 420°F. for a period of time of from about 2 minutes to about 10 minutes in an oven or other suitable heating means, whereupon the polymerization reaction between the polyols and the polyisocyanates in the urethane top coating areas 18A is initiated.
• the urethane polymerization catalyst has migrated thereinto and has initiated such a polymerization reaction.
• the portions or the parts 18A although they harden and cure, do not achieve a high gloss or shiny appearance, due to the mechanical embossing which have created a roughened, somewhat pebbled surface having a very irregular surface texture, in share contrast to the smooth shiny, high gloss surface areas 18B.
• the roughened surface of the mechanical embossing is retained after polymerization in areas 18A whereas, in contrast thereto, the previously polymerized portions 18B, which had been temporarily roughened by the mechanical embossing, revert back to their original high gloss condition.
• the smooth, shiny, high gloss surface areas 18B are in substantially perfect registry with the catalyst-containing portions 14B of the printing ink composition and that the roughened, pebbled, dead, dull surface areas 18A are in substantially perfect registry with the inhibitor-containing portions 14A of the printing ink composition, as well as with the relatively raised, chemically embossed surface areas and the relatively depressed, chemically embossed surface areas of the resinous wear layer, as well as the urethane top coating.
• the resinous urethane top coating composition 20 is substantially completely cured or polymerized in all surface areas, that is, 18A and 18B, as a result of the two curing operations and is thus substantially monomer free.
• Figure II illustrates an application of the basic principles of the present invention in a slightly different manner in order to achieve a slightly different differential gloss effect, on a slightly different final product.
• a potentially foamable (or non-foamable) base resinous polymer composition 12' is applied or formed as a substantially uniform layer on the surface of a typical fibrous backing sheet material 10'.
• the gelling operation to firm the surface of the applied base resinous polymer composition 12' is identical to that previously described with reference to Figure I .
• a printing ink composition 14' is then applied to the surface of the gelled, firmed potentially foamable base resinous polymer composition 12' but, in this embodiment, both a blowing or foaming inhibitor and a urethane polymerization catalyst are included in the same parts or portions 14A' of the printing ink composition 14', whereas the parts or portions 14B' contain neither the blowing or foaming inhibitor nor the urethane polymerization catalyst.
• a relatively small amount or low concentration of the urethane polymerization catalyst may also be included in the parts or portions 14B' in order to modify, adjust, or control the degree of tack of the superjacent portions lying directly thereover, such as in the surfaces of the urethane top coating composition 18B', to be described hereinafter.
• the printed, gelled potentially foamable base resinous polymer composition 12' is then allowed to dry and a resinous wear layer plastisol composition 16' is substantially uniformly applied or formed thereon in the same fashion as previously described with reference to Figure 1. Gelling of the applied resinous wear layer plastisol composition 16' to firm its surface takes place as previously described. Blowing or foaming and fusion may take place simultaneously or successively with the gelling operation.
• a urethane top coating composition 18' is then applied or formed substantially uniformly on the surface of the blown or foamed and fused multi-layered product and contains a substantially uniform mixture of unreacted polyols and unreacted polyisocyanates, additives such as surfactants and other agents, but again there is no inclusion of any urethane polymerization catalysts.
• the polyols and polyisocyanates are as previously described herein.
• the thickness of the applied layer of urethane top coating composition 18' is again in the range of from about 0.005 inch to about 0.015 inch, although greater or lesser thickness may be employed for special conditions and circumstances.
• Such multi-layered product is then exposed to the elevated temperatures of the second curing operation, as described previously, whereby the portions 18B' of the urethane top coating compsition 18' are also cured or polymerized.
• the resinous urethane top coating composition 18' is substantially completely cured or polymerized in all surface areas 18A' and 18B' and is substantially completely monomer free.
• Such result is generally comparable to the results obtained in the embodiment of Figure I, although in sort of a reverse fashion.
• the raised, chemically embossed surface areas 18B' are dead and dull, have a pebbly, roughened appearance and a relatively low gloss effect.
• the relatively lower, chemically unembossed surface areas 18A' are shiny and glossy and create an excellent contrast to the dead and dull areas 18B'. It is also to be observed that there is substantially perfect registry with the corresponding portions 14A' and 14B' of the pattern or design of the printing ink composition 14'.
• the corresponding portion of the surface of the urethane top coating composition lying directly thereover will have a normal chemically unembossed height and will have a shiny, smooth, high gloss surface, such as noted in areas 18A' .
• a resinous polymer sheet material such as illustrated in Figure I of the drawings, is made as follows:
• the backing sheet material comprises a relatively flat, 0.030 inch thick fibrous sheet of felted asbestos fibers with an acrylic smoothing or leveling coating thereon.
• the asbestos fibrous backing sheet material is coated substantially uniformly to a wet thickness of about 0.012 inch with the following potentially foamable base resinous polymer composition: Parts Polyvinyl chloride, med. mol. wt., general purpose dispersion resin, inh. vis. 0.99 (ASTM D-I243-66) 30.2
• Polyvinyl chloride med. mol. wt., dispersion grade resin, inherent viscosity 1.0 8.2
• Gelling and firming of the potentially foamable base resinous polymer composition is accomplished in an oven atmosphere maintained at an elevated temperature of about 300oF. for a time of about 3 minutes. This temperature is not sufficiently high as to activate or decompose the blowing or foaming agent.
• the gelled and firmed, potentially foamable base resinous polymer composition is then printed with a ceramic tile brick pattern, or design as shown in Figure 1, as follows:
• Areas 14A are printed with the following ink compositions: Parts Solution grade co-polymer of vinyl chloride (90 Parts ⁇ and vinyl acetate(10 Parts) 14
• the printed, gelled, potentially foamable base resinous polymer composition is then allowed to dry and a resinous wear layer composition is applied thereto to a wet thickness of about 0.010 inch and having the following composition:
• Gelling or firming, blowing or foaming, and fusion of the resins take place by heating in an oven atmosphere at an elevated temperature of about 430oF. for a period of about 1 minute and 40 seconds.
• the blown or foamed, fused, chemically embossed, resinous polymer sheet material is then coated with a urethane top coating composition to a substantially uniform thickness of about 11 ⁇ 2 mils and having the following formulation: Parts Methylene-bis (cyclohexylisocyanate), 31.8% minimum NCO-content 85.8
• Reactive silicone wetting agent hydroxyl number 47, molecular weight 2400 0.12
• Polymerization or curing of the applied urethane top coating composition takes place in an oven atmosphere having an elevated temperature of about 325oF. for about 5 minutes.
• the relatively lower mortar or grout areas 18A lying directly over the inhibitor containing areas 14A of the printing ink composition are uncured and are soft, fluid or semi-fluid.
• the relatively higher land areas 18B lying directly over the catalyst-containing areas 14B of the printing ink composition are cured, hardened or firmei and have a smooth, shiny, high gloss.
• the product upon cooling, is passed through the nip of a silicone rubber roll under pressure which results in a surface of reduced gloss.
• dibutyl tin dilaurate urethane polymerization catalyst is applied onto the product, such as by spraying a 1/4 to 1% solution of the catalyst in tertiary butyl alcohol.
• the differential gloss effect of the contrast of the raised, chemically embossed, shiny, high gloss areas 18B with the normal height, chemically unembossed, dull, dead, low gloss areas 18A is unusual and most interesting.
• Substantially perfect registry is noted between the areas of the ink composition, as well as with the substantially perfect registry of the areas 18B of the urethane top coating composition with the printed areas 14 B of the ink composition, with all areas in perfect registry with the chemically embossed relatively higher and lower portions.
• Substantially all the monomeric material originally in the top coating composition are polymerized or cured.
• the resinous polymer sheet material product finds exellent use as a resilient floor covering.
• the facts that the polyurethane top coating is polymerized and/or cross-linked in all portions, and is thermoset is highly advantageous, in that such surfaces are more resistant to changes under future conditions.
• Example II The procedures described in Example I are followed substantially as set forth therein, with the exception that the printing ink composition are changed, in order to prepare the resinous polymer sheet material product illustrated in Figure II.
• the printing ink composition which is applied to areas 14A' contains both a blowing or foaming inhibitor, as well as a urethane polymerization catalyst, as follows:
• the printing ink composition which is applied to areas 14B' contains neither a blowing or foaming agent nor a urethane polymerization catalyst, as follows:
• Example III The procedures described in Example I are followed substantially as set forth therein, with the exception that the methylene-bis-(cyclohexylisocyanate) is replaced by isophorone diisocyanate (3- isocyanatomethyl -3,5,5-trimethylcyclohexyl-isocyanate. The results of this Example are generally comparable to the results obtained in Example I.
• Example IV The procedures described in Example I are followed substantially as set forth therein, with the exception that the methylene-bis-(cyclohexylisocyanate) is replaced by 2,4,4-trimethyl-hexamethylene diisocyanate. The results of this Example are generally comparable to the results of Example I.
• the results of this Example are generally comparable to the results of the procedures of Example I, as more specifically described therein.
• the urethane top coating composition of the final resinous polymer sheet material is substantially cured or polymerized in all portions thereof and is substantially monomer free in all portions. All portions are thermoset and have relatively high melt viscosities.

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• 1982
  • 1982-11-12 CA CA000415404A patent/CA1195558A/en not_active Expired
• 1983
  • 1983-08-05 AU AU19454/83A patent/AU1945483A/en not_active Abandoned
  • 1983-08-05 EP EP19830902839 patent/EP0115534A1/de not_active Withdrawn
  • 1983-08-05 WO PCT/US1983/001204 patent/WO1984000719A1/en unknown

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