NO790276L - PROCEDURE FOR PREPARING A SHEET-SHAPED PLASTIC MATERIAL WITH PATTERNED SURFACE - Google Patents

Description

Method for producing a sheet-shaped plastic material with a patterned surface.

The present invention relates to decorative sheet materials, and more particularly decorative sheet materials of resin polymers with regulated selective placement of surface decorations for use as floor, wall and ceiling coverings; desk, table and counter surfaces; surface layer on leather, textiles, wood, paper, paper products, glass, metals, plastics, etc.; upholstery, drapery, upholstery and costume materials; interiors of cars, trucks, trains, planes and other vehicles or means of transport; covers for books, periodicals and other publications; boxes, cartons and containers; maps, road markers and similar articles. Even more particularly, the present invention relates to decorative sheet materials of resin polymers with smooth, glossy or shiny surfaces in some areas; or embossed glossy or shiny surfaces in other areas; or embossed, dead or dull. matt surfaces in still other areas; or smooth, dead or dull dull surfaces in still other areas; all such surfaces being in sharp contrast to each other and in perfect agreement with a pattern or design printed on such decorative sheet materials"

Decorative sheet materials of a resin polymer mixture

have been produced for many years, and one of the most common means of creating or enhancing the decorative effects has been to give selected parts of the surface of such decorative sheet materials different types of contrasting finishes or effects, or differences in surface gloss or shine, e.g. .ex. with smooth, glossy or shiny surfaces; embossed, dead or dull matte surfaces; embossed glossy or shiny surfaces; and smooth, dead or dull matte surfaces, all in stark contrast to each other.

Many methods, including various forms of mechanical embossing, inlaying or chemical etching, and other methods, have been proposed to obtain such sharply contrasting surfaces, but all such known methods have always left something to be desired. Different forms of mechanical embossing combined with pattern-

and design printing, for example, has always created registration problems and related difficulties. Implantation and chemical etchants have normally been expensive and time-consuming.

It is therefore the main purpose and object of the present invention to provide resin polymer mixtures in sheet material form with selective, surface decorative effects created by regulated placement of several different surface finishes, embossing or surface gloss differences in which smooth or embossed, glossy or shiny surface areas stand in sharp contrast to each other

and with smooth or embossed, dead or dull matte finish surfaces, using methods where registration problems and difficulties are essentially eliminated and which methods are neither expensive nor time-consuming. •

It has been found that such main purposes and objects,

and other main purposes and objects, which will become apparent upon further reading and . understanding of this description, can be carried out by. providing a resin polymer sheet material for use in the manufacture of a product having surface decorative effects comprising a base layer or substrate; a print compound layer forming a pattern or design on said base layer or substrate; a wear layer of resin polymer on said pressure mix layer comprising reactive, polymerizable and crosslinkable, monomeric materials substantially uniformly distributed therein; and a polymerization initiator capable of initiating a. polymerization and crosslinking reaction to crosslink and polymerize said reactive, polymerizable and crosslinkable, monomeric materials to increase the melt viscosity of said wear layer of resin polymer„

The invention further provides a method for the production of a sheet material of resin polymer with surface decorative effects which comprises laying down or forming a base layer or

- substrate; applying a print compound layer forming a pattern or design to said base layer or substrate; applying to said pressure mixture layer a wear layer of resin polymer with reactive, polymerizable and crosslinkable, monomeric materials substantially uniformly distributed therein; to interfere in areas of said sheet-

material of resin polymer a polymerization initiator capable of initiating a polymerization or cross-linking reaction to polymerize and cross-link said reactive, polymerizable and cross-linkable, monomeric materials; and heating the surface of said resin polymer wear layer to cause said polymerization initiator to start a reaction that polymerizes and crosslinks said reactive, polymerizable and crosslinkable, monomeric materials in the areas where said polymerization initiator occurs, whereby the melt viscosity of said resin polymer wear layer is increased in said areas"

It has been found that such heating to a sufficiently high temperature, preferably followed by mechanical embossing, for a sufficiently long time and the accompanying pressure, polymerizes and/or crosslinks the reactive, polymerizable, monomeric materials and also increases the melt viscosity in the wear layer, but only in the areas just above the polymerization initiator or catalyst. As a result, the mechanically embossed, dead or dull matte finish or texture in such areas is better able to resist softening and melting effects resulting from the elevated temperatures during any subsequent melting and/or blowing or foaming operations. operations and therefore such areas remain essentially as

they were originally mechanically formed in such areas.

But in the other areas where no polymerization and/or cross-linking of the reactive, polymerizable, monomers took place. materials in the resin wear layer, and where its melt viscosity did not increase significantly, the mechanically embossed, flat, dead or dull matte finish or texture will not be able to withstand the softening and melting effects of the elevated temperatures during any subsequent melting and/or or blowing or foaming operations, and it therefore softens and melts sufficiently to flow together and form a smooth, glossy, or lustrous finish which contrasts sharply with the adjacent flat, dead, or glossless matte finish in the polymerized and /or cross-linked areas with higher slurry viscosities.

It is to be understood that the above simplified and abbreviated illustrative method is only one of many variations for making resin polymer sheet materials according to the invention;

that it is merely illustrative of the broader aspects of the present invention; and that several conventional and standard steps, such as heating, gelation, cooling, drying etc. are omitted for reasons of clarity and brevity.

In the following description and accompanying, self-explanatory drawings, preferred and typical embodiments of the present invention are described and illustrated, but it should be understood that the present invention is not to be considered limited to such preferred and typical embodiments as are specifically described and illustrated here, but shall include other similar and equivalent embodiments, as determined by the scope and spirit of the accompanying claims.

Reference is made to the accompanying, self-explanatory drawings, where

fig. 1 is a fragmentary diagrammatic elevational cross-sectional view of an embodiment of the invention, showing the resin-polymer composition in its original form prior to heating and blowing.; '

fig. 2 is a fragmentary, diagrammatic plan view of the resin polymer composition of FIG. 1, but shown in its final form after heating and blowing;

fig. 3 is a fragmentary, diagrammatic view in elevation cross-section of the embodiment from fig. 1, also shown in its final form after heating and blowing, the cross-section being taken along the line 3 — 3 in fig'» 2;

fig. 4 is a fragmentary diagrammatic elevational cross-sectional view of another embodiment of the invention, showing its structure prior to heating and melting;

fig. 4A is a fragmentary, diagrammatic, elevational cross-sectional view of the embodiment of FIG. 4, showing the structure after heating and melting;

Fig. 5 is a fragmentary diagrammatic elevational view of yet another embodiment of the invention, showing its structure prior to heating and blowing;

fig. 5A is a fragmentary, diagrammatic, elevational cross-sectional view of the embodiment of FIG. 5A, showing its structure after heating and blowing and the subsequent removal of release paper;

fig. 6 is a fragmentary diagrammatic elevational cross-sectional view of a further embodiment of the present invention showing its structure prior to heating and melting;

fig. 6A is a fragmentary, diagrammatic, elevational cross-sectional view of the embodiment of FIG. 6, showing the structure after heating and melting;

fig. 7 is a fragmentary diagrammatic picture in elevation

cross-section of a further embodiment of the invention, showing its structure after heating and melting;

Fig. 8 is a fragmentary diagrammatic view in elevation cross-section of a further embodiment of the invention, showing its structure after heating and melting the resin;

fig. 9 is a fragmentary diagrammatic image in elevation cross-section of a further embodiment of the invention, showing the structure of the product, either before heating and melting the resin, if a foaming agent or blowing agent was mixed in the resin mixture, or after heating and melting, if no blowing - or foaming agent is mixed into the resin polymer mixture;

fig. 10 is a fragmentary, diagrammatic view in elevation cross-section of the embodiment in fig. 9, after heating and melting the resin, plus blowing and foaming if a blowing or foaming agent was included in the resin polymer mixture;

fig. 11 is a fragmentary, diagrammatic view of an embodiment in elevation cross-section, after heating and melting the resin, plus blowing and foaming if a blowing or foaming inhibitor was incorporated into certain portions or areas of the applied ink mixture; and

fig. 12 is a fragmentary, diagrammatic picture in elevation cross-section of a further embodiment of the invention, in which the free-radical polymerization initiator, catalyst or organic peroxide is contained in a separate layer in the product.

These figures are not drawn exactly to scale. Some parts and some dimensions are drawn on a slightly larger scale, while certain other parts and dimensions are drawn on a slightly smaller scale. This is done only to show more clearly some of the details of the smaller parts and to accentuate some of the most important features and aspects of the invention, such as, for example, the thickness of the printing ink layer which is drawn several times enlarged in the figures.

Figures 1-3.

The present invention shall be described and illustrated in general, primarily with reference to figures 1-3 which are illustrative, but not limiting/for^the scope of the invention. In these figures, a sheet material 10 of resin polymer is illustrated comprising a base layer or substrate 11 on a relatively flat sheet backing material 12 and a potentially foamable polymer mixture 13 which, after mechanical embossing at elevated temperature and under pressure and after subsequent blowing and foaming at an even higher temperature results in a relatively high, blown or foamed, uninhibited vellular resin polymer composition 14 and a relatively low, relatively unblown or unfoamed, inhibited, relative or substantially non-cellular resin polymer composition 16 . The phrase "substantially non-cellular" does not mean completely non-cellular, but indicates that the cells therein, if any, are of much smaller size and are much fewer in number than the cells of the so-called cellular parts"14. A 'printing ink mixture 18, in the form of a desired pattern or design usually containing many different colors, is applied to the surface of the potentially foamable resin polymer mixture 13, before mechanical embossing at the elevated temperature and pressure and the subsequent blowing and foaming at an even higher temperature.

The pattern or design in the printing ink mixture 18 has certain predetermined areas or colors 20, which in this embodiment contain a blow modifier, such as e.g. an inhibitor, and a free-radical polymerization initiator or catalyst, such as organic peroxides. However, other predetermined areas or colors 21 do not contain any blow modifier or any free-radical polymerization initiator or catalyst, for purposes that will become clearer by further reading and understanding of the present description. A resin polymer mixture in the form of a wear layer 22 is applied essentially evenly over the pressure ink mixture .18.

As is particularly noted in fig. 3, the blow modifier or inhibitor limits the blowing or foaming of the potentially foamable resin polymer mixture 13 in the areas A corresponding to and in perfect agreement with the areas 20.

At the same time, blowing or foaming and expansion of the potentially foamable resin polymer mixture 13 is not restricted or hindered in the areas B which do not lie directly above the areas 20 containing the blowing modifier or inhibitor. Up until now, all this is conventional and general standard.

It should also be noted that the free radical polymerization initiator or catalyst, which is also present in the areas 20 for reasons to be described in more detail later, causes the surface areas of the wear layer 22 directly above the areas 20 to have an embossed, flat , dead or lackluster matte finish or texture, while the other areas B of wear layer 22 not directly overlying areas 20 and containing no free-radical polymerization initiator or catalyst have a smooth, glossy or shiny finish" The two types finishes are in sharp contrast to each other.

It should also be understood that the regions 20. not only contain the free-radical polymerization initiator or catalyst, but also contain blow modifiers or inhibitor,

as well as a predetermined pigment or color of the printing ink composition 18, consistent with the multi-color pattern or design. As a result, the embossed flat, dead or dull matte finish or texture in the areas A is in complete and perfect agreement with the relatively low, uninflated or unfoamed portions 16 of the resin polymer mixture 13, as well as the predetermined pigment or color of the pattern or design. And at the same time, the smooth, glossy or shiny finish in the areas B is in complete and perfect agreement with the relatively high, inflated or foamed parts 14 of the resin polymer mixture 13, as well as the other predetermined colors or pigments in the pattern or design.

More specific details of such constructions and their properties in terms of perfect conformity for embossing, and finish and texture, and inflated or op<p>foamed areas, and their respective colorings, as well as methods and procedures for obtaining such constructions will be described in more detail later with reference to the following preferred and typical embodiments of the invention.

The base layer or substrate 11 may comprise a relatively flat, fibrous backing sheet material 12 and/or an inflated or unexpanded resin polymer mixture with a chemically embossed or non-embossed surface and/or another relatively flat sheet material.

A relatively flat backing fabric or sheet material 12 can be used, if desired or required, as a base layer or substrate 11 for the resin polymer sheet material 10 of the present invention.

Such backing sheet material 12 may comprise fibrous sheets of felt or mats with overlapping, intermingled fibers and/or filaments; or a non-woven, knitted, woven or otherwise manufactured textile construction; or a sheet of resin polymer blends; or paper or a paper product or similar or similar equivalent constructions and materials. A felt-like, fibrous sheet material comprised inorganic fibres, such as e.g. asbestos; or organic fibers such as e.g. cellulose, cotton, jute or rayon; or synthetic fibers and/or filaments, such as polyolefins, polyamides, acrylic polymers, glass, etc., are the most commonly used backing sheet materials, but many others are equally suitable and can be used in special situations. Such backing sheet materials are disclosed in many patents in the field, such as U.S. Patent Nos. 3,293,094, 3,293,108 and 3,660,187.

The thickness of such a relatively flat backing sheet material 12 will largely depend on the particular product to be made and the particular subsequent application it is. thought of. Normally, such thicknesses are in the range from approx. 10 to approx. 90 miles,

but other thicknesses, especially those greater than 90 mils, may be used in special and special circumstances,

The relatively flat backing sheet material 12 can be used as a base layer or substrate alone, or can be used together with other sheet materials such as e.g. a layer of potentially foamable or non-foamable resin-polymer mixture. Or the relatively flat backing sheet material 12 may be dispensed with entirely and the foamable or non-foamable resin polymer mixture may be used alone.

Such resin polymer mixtures can be prepared using known standard and conventional methods and can contain one or more synthetic resins, such as e.g. a polymer or copolymer of vinyl chloride, or other resins such as e.g. polyurethanes, as the main component resin.

Other ingredients in such resin polymer mixtures include: a blowing or foaming agent such as azodicarbonamide, if a blowing or foaming agent is required; various accelerators/stabilizers or catalysts such as dibasic lead phthalate, zinc octate, zinc oxide, lead octate, dibasic lead phosphite, etc.; various light and/or heat stabilizers, and metal soaps; softeners such as e.g. dioctyl phthalate, butyl benzyl phthalate, dibutyl sebacate, etc.; dyes and pigments such as titanium dioxide; solvents and diluents such as e.g. methyl ethyl ketone, mineral spirits, etc.; fillers such as clay and limestone; and many other conventional and well-known additives and improvers.

Although a polymer or copolymer of vinyl chloride in the form of a plastisol is the preferred and typical synthetic resin for incorporation into the resin polymer composition, many other resins can be used equally well, not only in piastisol form but also in organosol latex or solvent form. The particular resin and the particular form used are not of importance here to the scope of the invention and many other suitable resins are disclosed in the aforementioned U.S. Pat. patents.

Although azodicarbonamide is indicated herein and particularly in the examples as the preferred and typical blowing or foaming agent for incorporation into the resin polymer-plastisol mixture, when desired or required, many other similar or equivalent blowing or foaming agents may also be used in the invention. The particular blowing or foaming agent used does not relate to the main idea of the invention, and many other suitable and acceptable blowing and foaming agents are found in the previously mentioned U.S. patents. Everything that

required is that the blowing or foaming agent has a sufficiently high reid decomposition temperature so that it is not activated or decomposed too early during the earlier heating and gelling processes and the mechanical embossing which will be described - later.

Specific blowing or foaming agents and therefore decomposition temperatures at which lively gas evolution takes place include: azodicarbonamide (199°C), N,N<1->dimethyl-N,N'-dinitrosoterephthalamide (104°C), azobisisobutyronitrile (116°C), p,p'-oxybis(benzenesulfonylhydrazide) (160°C), dinitrospentamethylenetetramine (80%)

(188°C), p,p1-oxybis(benzenesulfonylsemicarbazide) (219°C), barium azodicarboxylate (above 250°C) and many others. Such decomposition temperature values apply to the lively release of gas in dioctyl phthalate.

Similarly, many other accelerators, initiators, catalysts, viscosity improvers, light and heat stabilizers, UV absorbents, dyes, pigments, thickeners, antioxidants, fillers, bacteriostatic and bactericidal agents and many other additives can be incorporated into the resin polymer mixture. The specific nature and the special physical and chemical properties of the various components in the resin polymer mixture do not relate to the main idea of the invention and further special description of such additives is considered unnecessary and not required. All of these components are well known and conventional in the industry and many are discussed in the previously mentioned U.S. patents.

The resin polymer mixture is also preferably a dispersion of a synthetic resin in a liquid medium. The dispersing agent can be a plasticizer in the case of a plastisol, or water in the case of an aqueous latex, or it can be an organic solvent in the case of an organosol. Excellent results have been obtained with a dispersion of a synthetic resin in a plasticizer such as a plastisol and such a form is the preferred and typical form in the application of the present invention.

A few preferred and typical plasticizers useful in the formation of such pastisols are dibutyl sebacate, dioctyl sebacate, dioctyl adipate, didecyl apidate, dioctyl azelate, dibutyl phthalate, dicapryl phthalate, dioctyl phthalate, dibutoxyethyl phthalate, tricresyl phosphate, octyldiphenyl phosphate, dipropylene glycol dibenzoate, butyl benzyl sebacate, dibenzyl sebacate, divenzyl phthalate, butyl benzyl phthalate.

It should be understood that although plastisols will be used

in the further description of the present invention, it is not intended to exclude the use of organosols or aqueous latexes, • which are also applicable.

The potentially foamable plastisol mixture. •

A few preferred and typical potentially foamable plastisol compositions are as follows:

The letters palsied on the right side of each part

of the preceding table is used only to facilitate the reading and understanding of each part of the table. They have no other meaning.

All plastisol mixtures listed in the preceding table are foamable. resin polymer mixtures, provided that azodicarbonamide is present in all mixtures. Such a blowing agent would be precluded if a non-foamable resin polymer composition was desired or required.

If backing sheet material is not to be used, e.g.

a fibrous tissue in the form of felt or mat, the plastisol may be applied with a doctor blade, or roller coated, or poured, or cast, or otherwise applied to a peelable support which may be a steel belt, a rubber belt, tear paper, or a felt or another substance or material that has a peelable coating on it and which is then peeled off.

If, however, a backing material is to be used which is to remain as part of the final product, then the plastisol can be applied with a doctor blade, or wax coated, or poured, or cast, or otherwise applied and adhered to the carrier sheet material in a substantially uniform manner in a relatively even, thin coating using methods known to the person skilled in the art. The thickness of such a plastisol coating as a foamable resin polymer composition, when applied while still wet, is in the range of from about 5 to approx. 50 mil., or possibly more if desired or required.

After the plastisol has been applied to the supporting backing sheet material, it is heated under relatively low or moderate heat in an oven or other suitable heating device for a period of from approx. 1 min. to approx. 4 min. at an elevated temperature of from approx. 116 to approx. 243°C; but more normally commercial from approx. 143 to approx. 177°C, whereby the plastisol sets and gels so that it can be handled and processed afterwards more easily. The temperature and time conditions are mutually dependent and the higher the temperature, the shorter the necessary time, and vice versa. However, the elevated temperature is not sufficiently high to activate or degrade the particular blowing or foaming agent that may be present to cause swelling or foaming of the resin polymer mixture.

The gelled, solid resin polymer mixture is then cooled and printed or coated with a suitable printing ink mixture in the desired or required pattern or design which may have many colors. The particular pattern or design used does not apply to the main features of the invention, and any desired pattern or design may be selected

The printing method is conventional and should not require further description, provided that such methods are well known in the industry and are described in many previous patents in the field.

If it is desired that different height levels of the blowing or foaming effects be achieved, predetermined portions or portions of the pattern or design printed on the surface of the resin polymer composition contain a blowing modifier or inhibitor in different amounts, concentrations or types, etc., depending on the type of different blowing or foaming effects desired. Such different effects are well described in the previously mentioned U.S. Pat. patents and should not need further explanation or description.

If no different effects are desired as a result of the blowing or foaming process, naturally no modifiers or inhibitors are mixed into the printing ink mixture, and the level and degree of blowing or foaming effect is generally uniform. Some typical and well-known conventional printing ink compositions are disclosed in the aforementioned U.S. Pat. patents.

In addition, there is incorporated into certain predetermined portions or portions of the selected printed pattern or design a polymerization initiator or catalyst for a purpose to be described more fully hereinafter, with reference to certain reactive polymerizable monomers also to be described more fully hereinafter .

The concentration of the free-radical polymerization initiator or catalyst in the printing ink mixture will vary and will lie in the range from approx. 1 to approx. 35 or 40% by weight, and preferably from approx. 1 to approx. 10% by weight, based on the total weight of the printing ink mixture.

These free-radical polymerization initiators or catalysts, as they are often referred to in industry, are perhaps more correctly identified as organic peroxides, or per-compounds, which materials are mainly characterized chemically by the presence of thermally unstable oxygen-oxygen groups (ie - 0-0-, a peroxy group) in its structure. Such a group is usually broken down by heating to a certain elevated temperature, to form free radicals which initiate the polymerization ion reaction. The specific free-radical polymerization initiator or catalyst selected for a particular polymerization or reaction depends on the temperature at which the specific reaction or polymerization takes place, on the rate of decomposition of the free-radical polymerization initiator or organic peroxide,

of the rate of generation of free radicals, of the presence of metal ions or of solvents or diluents in which the organic

IN

Peroxides are often marketed commercially, by percentage of peroxide

and percentage of oxygen in the sample, of the activation energy (kcal per mol), etc.

Upon further reading and understanding of this description

it will be apparent that dicumyl peroxide is the preferred and typical organic peroxide or free radical polymerization initiator or catalyst used with the majority of polymerizable reactive monomers. Such preference is based essentially on the fact that dicumyl peroxide is very well matched in terms of its one-minute half-tic temperature to the normal gelation temperature of the plastisol used, to the normal melting temperature of the resin polymer mixture used, and to the normal decomposition temperature of the blowing or foaming agent used (azodicarbonamide). However, it should be understood that many other organic peroxides or free-radical polymerization initiators or catalysts are suitable and satisfactory for use in the present invention. For example, dibutyltin dilaurate' would be a preferred and typical cross-linking catalyst, if another resin polymer mixture was used, such as e.g. a polyurethane. Other preferred and typical organic peroxides and per-compounds include:

Di-t-butyl peroxide

2,5-dimethyl-2,5-bis(t-butylperoxy)hexane

2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3

. di-t-amyl peroxide

t-butyl-2-hydroxyethyl peroxide α,α'-bis(t-butylperoxy)-diisopropyl-benzene

benzoyl peroxide

diisobutyryl peroxide

2.4-dichlorobenzoyl peroxide

diisononanoyl peroxide

decanoyl peroxide

lauroyl peroxide

acetyl peroxide

succinic acid peroxide

bis-p-chlorobenzoyl peroxide

2.5-dihydroperoxy-2,5-dimethyl-hexane

cumene hydroperoxide

t-butyl hydroperoxide

p-menthane hydroperoxide

diisopropylbenzene hydroperoxide

1,1,3,3-tetramethyl 1-butyl hydroperoxide

dl (n-propyl) peroxydicarbonate

diisopropyl peroxydicarbonate

di(sec-butyl)-peroxydicarbonate

di(2-ethylhexyl)-peroxydicarbonate

dicyclohexyl peroxydicarbonate

dicetyl peroxydicarbonate

bis(4-t-butylcyclohexyl)-peroxydicarbonate

t-butyl peroxyisopropyl monocarbonate

2,2'-azobis(isobutyronitrile)

1,1-bis(.t-butylperoxy)-3,3,5-trimethyl-cyclohexane

t-butyl peroxyacetate

t-butyl peroxyisobutyrate

t-butyl-peroxy-2-ethylhexanoate

t-butyl peroxyperivalate

t-butyl peroxide decanoate

t-butyl-peroxymaleic acid

di-t-butyl-diperoxyphthalate

2,5-diethyl-2,5-bis(benzoylperoxy)hexane

2.3-dimethyl-2,5-bis(octanoylperoxy)hexane

t-butyl peroctoate

t-butyl perbenzoate

acetyl cyclohexyl sulfonyl peroxide

acety1-sec-heptyl-sulfonyl peroxide

2^t-butylazo-2-cyano-4-methoxy-4-methyl-pentane

2-t-butylazo-2-cyano-4-methyl-pentane

2-t-butylazo-2-cyanopropane

methyl ethyl ketone peroxide

2.4- pentanedione peroxide

cyclohexanone peroxide

It should be noted that the compounds cover several classes of peroxides and include a very wide spectrum, all of which are nevertheless useful under selected conditions, with particular reference to the plastisol gelation temperature, the melting temperatures of the plastisol and the resin-polymer mixture, and blowing and the foaming temperatures, which when it comes to the preferred arbide conditions in the present invention are normally commercial in the range of from approx. 149, 177 and 202°C respectively. For specific purposes according to the invention, it is to

note a preferred range of peroxides that have half-times on

one minute at from approx. 133 to approx. 191°C, with particularly preferred commercial ranges of one minute half-time of from approx. 152 to approx. 174°C.

The preferred ranges of one-minute-and-a-half times from approx.

133 to approx. 191°C, as will be discussed in more detail later, will most readily provide satisfactory and sufficient cross-linking of the reactive, polymerizable monomer in the upper carrier layer after the plastisol gelation operation, or perhaps even during the mechanical embossing operation, or perhaps even in the early part of the blowing and foaming process. In this way, the mechanical embossing takes place after the gelation operation and is then retained throughout the blowing and foaming cycle in the areas where cross-linking of the polymerizable, reactive monomer has taken place. If cross-linking of the reactive, polymerisable monomer were to take place too early in the overall process, such as before or during the original plastisol gelling operation, the desired mechanical embossing would be difficult or even impossible to achieve. In the same way, if cross-linking of the polymerisable, reactive monomer were to take place too late, such as e.g. during the last part of the blowing or foaming process, maybe too. late for certain embossed areas of the wear layer to

retain their mechanical character.

The concentration of the remaining components of the printing ink mixtures comprising resins, pigments and. dyes, solvents and diluents, blow modifiers and blow inhibitors, softeners, etc., are conventional and are within the ranges indicated in the prior art, such as e.g. in the aforementioned U.S. patents. With special reference to the blow modifiers and blow inhibitors, it can be stated, although essentially all of the substances mentioned in these U.S. patents are applicable within the broader aspects of the present invention, that three preferred and typical examples of such are trimellitic anhydride, fumaric acid and ben-zotriazpl.

A few preferred and typical printing ink mixtures are as follows:

The printed, gelled, potentially foamable plastisol is then allowed to dry, and a wear layer in the form of a resin polymer blend or plastisol is then applied to it. Such a wear layer contains conventional or standard components, such as e.g. resins (preferred and typically medium to low molecular weight polyvinyl chloride), plasticizers, stabilizers, pigments or dyes (rarely), solvents and diluents, viscosity improvers and regulators, and similar additives and materials. The concentrations of such constituents are conventional and standard and are in the ranges indicated in the previously mentioned U.S. patents.

In addition, however, a further component is also mixed into the wear layer, comprising one or more reactive, polymerisable, monomeric materials whose polymerization and/or cross-linking can be initiated by means of the previously described polymerization initiators or organic peroxides. Such polymerization initiators locate: advantageously in certain predetermined portions or colors of pattern or design in the printing ink composition, whereby certain predetermined portions of the reactive, polymerizable monomers directly above are polymerized and/or cross-linked, while certain other predetermined portions or colors of pattern or design in the printing ink composition which contain no polymerization initiator, do not polymerize and/or crosslink the reactive, polymerizable monomers overlying them.

The intrinsic viscosity of the polyvinyl chloride resins used •

in such wear layer mixtures are in the range of from approx. 0.6 to approx. 1,: but can, depending on conditions and circumstances, be as high as approx. 1.6, measured and determined according to A.S.T.M. D-1243-66, before initiating the mechanical embossing process, which will be described more fully later.

The reactive, polymerisable monomers are mainly mixed evenly in the wear layer and are multi-functional and contain at least two olefinically unsaturated positions in their molecules. Such monomers must be able to polymerize at desired, elevated temperatures which are usually higher than the plastisol gelation temperature, but lower than the decomposition temperature of the blowing agent. Such polymerization takes place in all areas of the wear layer that lie directly above the free-radical polymerization ion initiator or where organic peroxides are localized to certain selected parts or colors of the printing ink mixture.

Preferred and typical reactive polymerizable monomers include:

Diallyl fumarate

Diallyl maleate

Diallyl itaconate

Diallyl phthalate

Ethylene glycol dimethacrylate

Ethylene glycol diacrylate

Diethylene glycol methacrylate

Diethylene glycol diacrylate

Triethylene glycol dimethacrylate

Triethylene glycol diacrylate

Tetraethylene glycol dimethacrylate

Tetraethylene glycol diacrylate

Polyethylene glycol dimethacrylate

Polyethylene glycol diacrylate

1-3-butylene glycol dimethacrylate 1,4-butylene glycol dimethacrylate

1.3-butylene glycol diacrylate

1.4-butylene glycol diacrylate

1,4-butanediol diacrylate

1,6-hexanediol dimethacrylate

1,6-hexanediol diacrylate

Allyl methacrylate

Neopentyl glycol diacrylate

■ Neopentyl glycol^dimethacrylate

Bisphenol A dimethacrylate (ethoxylated) Divinylbenzene

Divinyl toluene

Trimethylolpropane trimethacrylate

Trimethylolpropane triacrylate

Pentaerythritol triacrylate

Glyceryl trimethacrylate Trially1 cyanurate

Pentaerythritol tetraacrylate

Pentaerythritol tetramethacrylate

1,4-butanediol dimethacrylate

It should be noted that such monomers are polyfunctional and include di-, tri- and tetra-functional monomers. However, if desired, a certain amount of monofunctional monomers can be mixed into the wear layer in a mixture with the polyfunctional monomers. Such combinations often have unique and highly desirable characteristics and properties.

When monofunctional monomers are mixed together with the polyfunctional monomers, they are present in amounts of from approx. 5 to approx. 50% by weight based on the total weight of all monomers in the resin wear layer formulation. The total weight of all monomers in the wear layer is in the range of from approx. 5 to approx. 40 parts by weight, based on 100 parts by weight of resin (phr) in the wear layer formulation, or preferably from approx. 15 to approx. 35 parts by weight based on 100 parts herpix (phr) in the resin wear layer formulation.

The particular reactive polymerizable monomer or monomers selected for a particular application must, of course, be compatible with or dispersible in the resin which forms the main component of the resin wear layer formulation. It is usually contained in a copolymer, polymer or homopolymer of polyvinyl chloride. That is to say, the reactive, polymerizable monomer must be miscible or dispersible in essentially all conditions with the main resin and must be easily and intimately able to dissolve or disperse therein without separating into separate, distinct layers or parts, or occupying separate, small parts or phases in the resin wear layer mixture. The reactive, polymerizable monomer must also of course be relatively inert at low temperatures and non-reactive with the other components in the resin wear layer mixture.

The thickness of such a resin-wear layer mixture, as it is first applied to the printed pattern or design and still moist, is in the range of from approx. 2 to 30 mil, or thicker if required in special circumstances, requirements and conditions. ■

Preferred and typical compositions of the wear layer are indicated in the previously cited US patents, except that the reactive(s),. polymerizable monomer(s) are not included therein.

After the wear layer containing the reactive, polymerizable monomers is applied and attached to the printed pattern or design of the printing ink mixture, it is heated under moderate, low heat in an oven or other suitable heating device for a period of from approx.

1 min. to approx. 4 min. at an elevated temperature of from approx. 116 to approx. 243°C,' whereupon it hardens or sets and gels so that it can be easily handled during further processing. Temperature and time have such a mutual relationship that they are dependent on each other, and the higher the temperature, the shorter the time for application of heat and vice versa. However, the elevated temperature must not be so high that the blowing or foaming agent that is • normally present is activated or broken down. The temperature and time must also not be of such a magnitude that it leads to polymerization of the reactive, polymerisable monomer in the wear layer.

As will become apparent upon further reading and understanding of the present description, it is normally assumed that polymerization and cross-linking of the monomers in the wear layer takes place during the embossing process which follows and which takes place under approximately the same temperature as in the preceding gelation process, but under additional pressure whereby the embossing of the surface of the wear layer and polymerization of the reactive, polymerizable monomers take place in the same operation.

As mentioned earlier, such temperatures are naturally lower than the temperature at which the blowing or foaming agent in the plastisol mixture will activate or break down to give off gases in a lively manner.

A few preferred and typical wear layer mixtures are as follows:

(Parts by weight, based on 100 parts resin, phr)

In the following description of the mechanical embossing method, emphasis will be placed on achieving a flat, dead or gloss-less matte finish or texture that is roughened, corrugated, contoured, fluted, aligned or the like". treatment can be achieved with a suitable pressure stamp or similar tool, or by pressing the surface of the wear layer against a roughened or desirable corrugated or contoured surface, such as a fibrous paper surface,

an uneven or rough metal surface, a fabric, or any rough, grainy surface that is not smooth, shiny, shiny, or lustrous.

The depth of the mechanical embossing can be as small as a fraction of a mile or it can be as deep as approx. 15 miles, but preferably it is from approx. 1 to approx. 4 mil, depending on the type, thickness and nature of the wear layer that is mechanically embossed in such a way, on the decorative effect that is desired or required, on the type and form of the mechanical embossing, etc.

At the end of the mechanical embossing process, the entire surface of the wear layer is embossed so that it temporarily acquires the desired flat, dead or dull matte finish or texture over the whole. Such a finish or texture essentially lacks gloss and shine. The surface may be roughened, corrugated, roughened, aligned or fluted in a regular or irregular, predetermined or random manner and may have many small knobs, protrusions, ridges, points or swellings to give it the desired flat, dead or dull-matte appearance. The mechanical embossing can also take the form of very many, very fine lines which are straight and parallel, swirling curves>as many as approx. 60 or 80 to even 100 or more lines per 2.54 cm, or it may be the result of pressing paper, textured materials or fabrics, woven, knitted or non-woven, against the surface of the wear layer to create a finish or texture on the layer.

The mechanical embossing to achieve the desired flat, dead or dull matte finish or texture or other finishes can take place under pressures which can be as low as approx. 0.35 to approx* 21 kg/cm 2 depending on the existing temperature in the area approx. 116 to approx. 243°C. If the pressure is applied in a press plate,

the pressure can be maintained for a period of from approx. 10 sec. to as much as approx. 4 min. If the pressure is applied by means of a heated embossing roll, the temperatures and pressures will be in the higher parts of those before

mentioned areas, while the time for applying the pressure will be correspondingly short. However, guiding or wrapping the resinous polymer sheet material around a portion of the periphery of the heated embossing roll can be used to extend the duration of application of heat. However, the pressures applied must be sufficient to establish good, intimate contact between the heated embossing surface and the resin polymer material being embossed.

The temperatures and pressures used during the embossing process are normally sufficient to activate or degrade the free radical polymerization catalyst or the organic peroxide in the predetermined portions of the printing ink mixture, which will bring about a polymerization or cross-linking of the overlying reactive polymerizable monomers such parts.. As a result, these parts of the wear layer get an increased melt viscosity there, and a harder, more resistant surface that can resist any softening or melting tendencies during the subsequent heating involved in the blowing or foaming process. In this way, such parts are able to retain their flat, dead or dull matte, embossed overfiat finishes or textures through the high heating during the blowing and foaming operations.

The predetermined parts of the wear layer which lie above the parts of the printing ink mixture which do not contain any free-radical polymerization initiator or any organic peroxide are, on the other hand, not significantly polymerized or cross-linked, have not increased melt viscosity and do not acquire a harder and more resistant surface, and as a result they will not be able to resist softening or melting tendencies, which are created when exposed to the more intense heat during the blowing or foaming operation, and they will melt and soften and flow so that they melt into a glossy, shiny finish with a relatively high gloss and sheen. Such a glossy, shiny surface is very smooth and very flat and highly reflective of all light shining on it, in sharp contrast to the flat, dead or dull matte finish which is not smooth and not so reflective when illuminated by it. The contrast created by these two types

of finishes or textures is striking.

The final resulting product is very similar in one of its forms to a ceramic floor tile, as it is commonly found in bathrooms, both as floor and wall surfaces. The smooth, glossy finish resembles the surface of a glazed or hardened tile, while the flat, dead or dull matte surface closely resembles the plaster or cementitious material placed between the glazed ceramic tiles.

Such unusual and highly contrasting finishes and textures are produced during and as a result of the elevated temperatures that occur during the blowing and foaming operation.

The multi-layer composition comprises: backing sheet materials and/or the potentially foamable (or non-foamable) plastisol;

the printed pattern or design of the printing ink composition, parts or colors of which contain modifiers or inhibitors and free radical polymerization initiators or organic peroxides, or parts or colors of which do not contain modifiers or inhibitors or free radical polymerization initiators or organic peroxides; and the upper wearing layer containing, in all substantially evenly distributed therein, the reactive, polymerisable monomers,

which, after having been mechanically impressed over its entire surface, is heated to a sufficiently elevated temperature which causes a melting of the resins in the resinous polymer mixture and which is also capable of activating or breaking down blowing or foaming agents in the potentially foamable plastisols to cause violent blowing or foaming therein. Furthermore, the surface in the wear layer is raised to higher temperatures, whereby the areas thereof, which do not have higher melt viscosities or polymerized or cross-linked monomers, soften, melt and flow more to form smooth and glossy surfaces. And of course they resist other areas that have higher melt viscosities and polymerized

or cross-linked monomers higher temperatures and does not soften, melt or flow, but retains its flat, dead or dull matte finish or texture. The temperature of the entire composition must reach the melting temperature of the resins in order for it to achieve the desired maximum strength. Melting is normally achieved at a temperature of from approx. 163 to approx. 243°C, depending on the particular polymeric product used. Such temperatures must also be sufficient to activate or break down the special blowing or foaming agent present in the plastisol. It must also be observed that the blowing and foaming temperatures, as well as the melting and gelling temperatures, are ambient air temperatures and not temperatures in the product to which it is exposed

such ambient air temperatures.

Reference to the drawings, and in particular to fig. 2 and 3, will clarify the operations that take place during such blowing and foaming procedures. The plastisol or the original potentially foamable resin polymer mixture originally contained a blowing or foaming agent, which e.g. azodicarbonamide, which was substantially uniformly distributed. The parts of the printing ink mixture 18 which are in the zones A

however, contains a blowing or foam modifying agent,

like for example. an inhibitor, and therefore the portions of the resin polymer mixture underlying it in zones A become relatively unblown or unfoamed due to the inhibitory effect of the blowing or foaming inhibitor. On the other hand, the parts of the printing ink mixture 18 which are in the zones B do not contain any blowing or foaming modifier, such as e.g. an inhibitor, and therefore those portions of the resin polymer mixture which lie below in the zones B become relatively fully inflated or foamed. Such effects are well described in the previously mentioned US patents.

In addition, the parts of the ink mixture 18 in the zones A also contained a free radical polymerization initiator or an organic peroxide which was activated or degraded during the embossing operation to polymerize and/or crosslink the reactive, polymerizable monomer in the wear layer 22 and to increase the melt viscosities of such parts. As a result, such parts retained their flat, dead or dull matte finish or texture throughout the blowing or foaming operation. On the other hand, the parts of the printing ink mixture contained 18 which were

in the zones B, however, no free radical polymerization initiator or organic peroxide, and there was no polymerization or cross-linking of the polymerizable monomer in the wear layer above and the melt viscosities of such parts did not increase. As a result, such parts were unable to withstand the elevated temperatures of the blowing and foaming cycle and melted, softened and flowed to form smooth and shiny surfaces in such parts of Zone B.

With further reference to the development of the smooth and shiny finish, compared to the retention of the flat, dead finish, the following numerical comparative gloss levels and ranges are available for satisfactory application of the principles of the present invention.

The areas with a smooth or shiny finish should have gloss levels in the range of from approx. 15 to approx. 90, or even higher; those with a flat, dead or lackluster.matt finish should have gloss levels in the range of from approx. 70 down to approx. 3, or even less; as the difference in gloss levels between the two contrasting finishes must be at least approx. 10 in gloss level areas below 50 and at least approx. 20 in gloss level ranges equal to or above 50. Such numerical gloss level values are determined using the method described in A.S.T.M. 523-67 (1972) at an angle of 60°.

It should also be observed that reference to smooth, glossy or lustrous finishes, as compared to flat, dead or matte finishes, is only a typical or preferred mode of expression used in the invention. These expressions or phrases are comparative or relative expressions or phrases, ie they are used only or primarily to indicate differences in gloss levels.

The principles according to the invention can for example be used to achieve a smooth, glossy or shiny finish in some selected areas and to achieve even smoother, more glossy or shiny finishes in certain other selected areas, the differences in gloss level values still being kept greater than approx. . 20, provided that the gloss levels in question in such an embodiment will be greater than approx. 50.

Such smooth and very smooth contrasts can be achieved by omitting the mechanical embossing method with a roughened surface and by replacing it with a plate-press or roller-press operation with a very smooth, highly polished surface, whereby the entire surface of resin - the wear layer is given a very smooth, shiny or glossy surface.

High temperatures and pressure are also then used, as previously described in connection with the blowing and foaming step, whereby the polyfunctional, reactive, polymerizable and crosslinkable monomers in the wear layer, which lie above the polymerization and crosslinking initiators in the printing ink mixture, which are crosslinked below the plate-press or roll-press operation, effectively resists such heating and pressure, and "freezes" these particular areas, whereby they are able to retain their extremely smooth, shiny or glossy finish during such subsequent blowing or foam operation.

However, the other areas containing monomeric materials that do not overlie any polymerization or crosslinking initiators or organic peroxides still contain such monomeric RNA materials in an unpolymerized and uncrosslinked state and therefore melt, soften and flow and thus lose some of their smooth, shiny and glossy finish, but develop or retain sufficient of their previous extra smooth, shiny or glossy finish at least on

about. 20 units in gloss level, less than the gloss level of an extreme

smooth, shiny or glossy finish.

Reference to fig. 1 - 3 of the drawings for comparison purposes would therefore only indicate that using ab the alternative methods described in the preceding few paragraphs would give areas "B" a smooth, shiny or glossy finish, while areas "A" would be even more smooth, shiny or glossy.

In some cases it has been found that the blowing or foaming action of the potentially foamable plastisol is of such a strong and vigorous nature that the gases evolved or released by the blowing or foaming agent tend to escape upwards from the heated the plastisol and tends to enter the wear layer so that the smoothness and evenness of the wear layer's surface is adversely affected, and this particularly applies to those areas thereof that have a low melt viscosity or essentially do not have polymerized and/or cross-linked monomers or smooth, shiny or glossy surfaces. This would be destructive to the evenness of such surfaces and would be undesirable from

an aesthetic point of view. This would also affect the strong contrast between the smooth, shiny or glossy surfaces and the embossed, flat, dead or dull surfaces that are close to them.

This undesirable effect can be avoided by placing a relatively thin barrier coating or layer with a thickness of only approx. 6 miles or less, down to approx. 1-2 mil, on top of the potentially foamable plastisol before the printed pattern or design is applied thereon, or alternatively such a barrier coating is applied over the printed pattern or design before applying the wear layer. Such a barrier coating or such a barrier film effectively prevents the gases escaping upwards from the blowing or foaming plastisol and entering the wear layer. The barrier layer can be applied as a film, but is normally applied as a resin polymer mixture plastisol in a thin layer of a resin such as e.g. a vinyl chloride polymer or copolymer with a relatively high molecular weight. Gelation of such a plastisol barrier layer follows naturally at an elevated temperature below the activation or decomposition temperature of the blowing or foaming agent and the polymerization initiator or the organic peroxide.

The thickness of the barrier coating or layer must not be so great as to prevent the blow modifier or inhibitor from exerting its blow modifying or inhibitory effects down through the barrier layer into the plastisol during the blowing operation, or the polymerization initiator from exerting their effects upwards during the polymerization and/or the crosslinking of the reactive, polymerisable monomers.

A few preferred and typical barrier coating compositions are as follows:

(Parts by weight, based on 100 parts by weight resin, phr)

Other additives, such as ethoxylated nonylphenol, a viscosity reducing agent, or other plasticizers and stabilizers, solvents or diluents, fillers, etc. may be used.

The modification in fig. 4 and 4A.

It has previously been established here that the base layer or substrate 11 can simply comprise a fibrous backing sheet material and that other layers, such as e.g. non-foamable or potentially foamable resin polymer blends or plastisols or other sheet materials may be omitted.

Such a modification is illustrated in fig. 4 and 4A depicting resin polymer sheet materials before and after completion of embossing and subsequent wafer steps in its manufacture, respectively. IN

these figures, there is shown a resin polymer sheet material 30 comprising a relatively flat backing sheet material 32 of a fibrous nature, such as e.g. an asbestos felt on which is usually printed a printing ink mixture 38 in the form of a desired pattern or design in several colours. If necessary, a leveling or leveling coating of resin polymer can be applied,

like for example. an acrylic coating, on the asbestos felt 32, if its surface is too uneven, - hairy, fibrous or irregular before printing the printing ink mixture on it. No blow modifiers or inhibitors in-

mixed in any part or color in the printed pattern or design.

However, a free-radical polymerization initiator or an organic peroxide is incorporated into the portions 40 of the printed pattern or design, while that. no free-radical polymerization initiator or organic peroxide is mixed into part 41. A wear layer 42 is then applied to the surface of the printed pattern or design in the usual way and this contains essentially uniformly distributed polymerizable, reactive monomers. The wear layer 42 is then embossed all over under sufficient pressure and at a sufficiently elevated temperature for a sufficiently long time so that the desired finish or texture is formed on the surface, such as e.g. a flat, dead or dull matte finish or texture.

During such mechanical embossing, the reactive, polymerizable monomers in the wear layer 42 are polymerized and/or cross-linked, and the melt viscosity is increased, but only in the parts thereof that lie directly above the free radical polymerization initiator or the organic peroxide in the printing ink mixture. All other areas that do not lie above any free radical polymerization initiator or any organic peroxide have no polymerized and/or cross-linked monomers in the wear layer and the melt viscosity in such areas is also essentially unchanged.

As a result, when the temperature of the mechanically embossed sheet material is raised to an even higher temperature, similar to that which would occur under blowing or foaming conditions, the polymerized and/or cross-linked parts of the wear layer which also have relatively higher melt viscosities , capable of withstanding the softening and melting effects of such heating and retaining its mechanical character and remaining flat, dead, and dull in appearance. The other areas which are not polymerized and/or cross-linked and do not have relatively higher melt viscosities, soften, melt and flow together to give a smooth, shiny and glossy appearance.

The relatively flat, dead eåås dull matte finish or texture is denoted by the reference letter A in fig. 4A, and it should be noted that such areas are in complete and precise agreement with the areas 40 containing the free radical polymerization initiator or organic peroxide and with the particular color of the printed pattern or design containing such material. The relatively smooth shiny and glossy surfaces are denoted by the letter B and lie over areas of the printing ink mixture that do not contain free radical polymerization ion initiator or organic peroxide and are thus in complete agreement with such areas that contain different colors in printed patterns or designs. Small outgrowths are visible in the surface of the wear layer 42 in the zones A. These will be discussed in more detail later.

The modification in fig. 5 and 5A.

It is also established herein that the base layer or substrate 11 can comprise only a resin polymer mixture and that other layers, such as e.g. a relatively flat, fibrous sheet material, or other sheet materials may be omitted. Such a modification is shown in fig. 5 and 5A respectively depict the resin polymer materials before and after the mechanical embossing step and the blowing and foaming process are completed.

In these figures, a resin polymer material 50 is shown comprising a relatively flat and relatively thin sheet of tear paper 55 of a conventional, commercially available grade. Upstairs. on such a tear-off paper 55, a layer of a potentially foamable resin polymer mixture 53 containing a conventional blowing or foaming agent such as e.g. azodicarbonamide. The surface of it

. potentially foamable plastisol 53 is gelled and then a pressure ink mixture 58 containing a free-radical polymerization initiator or an organic peroxide and a special pigment, or a color in the areas 60 while other areas 61 do not contain a free-radical polymerization initiator or organic peroxide, but contains.a different pigment or dye. No blow modifiers or inhibitors are incorporated into any part of the printing ink mixture 58.

A wear layer 62 is then applied to the surface of the printing ink mixture 58, and this wear layer contains substantially evenly distributed amounts of a reactive, polymerizable monomer. The wear layer is then mechanically embossed under sufficient pressure and at a sufficiently high temperature and for a sufficient time to provide a desired flat, dead or dull matte finish or texture in an overall embossing pattern, during which time the reactive polymerizable monomer is normally polymerized or cross-linked.

A conventional blowing or foaming operation then follows at an even higher temperature, whereby the blowing or foaming agent causes expansion of the resin polymer mixture. Such an expansion is well shown in fig.' 5A. At the same time, the highly polymerized or cross-linked monomers in the regions 60, which regions also have higher melt viscosities, resist the softening or melting effects of the heat during blowing.

and the foaming operation and such areas 60 remain as desired with a flat, dead or dull matte finish or texture. Areas 61,

which does not lie above any parts of the printing ink mixture 58 which contain

holds free radical polymerization initiator or organic peroxide, however, does not polymerize or crosslink, and does not have higher melt viscosities and is therefore unable to resist the softening and melting tendencies that occur during the heating in the blowing and foaming cycle, and therefore melts and similar areas flow together to form a smooth, shiny, or glossy surface, which is in sharp contrast to the flat, dead, or dull matte finish or texture in areas 60. Thus, areas A are flat, dead, and dull matte, while areas B are smooth, shiny or glossy.

Provided that no blowing or foaming modifiers or inhibitors were present in the ink mixture, the blowing or foaming is uniform and no chemical embossing occurs on the surface of the wear layer. Small growths can be seen in the surface of the wear layer 62 in zones A. These will be discussed in more detail later. The relatively flat and relatively thin sheet of tear paper is removed from the bottom surface of the resinous polymer mixture after the blowing or foaming cycle. If, however, the resin polymer mixture, the printing ink mixture and the wear layer have sufficient strength to allow their handling, or if another carrier is supplied for it, the release paper can be removed before the blowing or foaming operation.

In addition, a polymerization initiator or an organic peroxide that can be activated or decomposed at an even higher temperature than the decomposition or activation temperature for the polymerization initiator or the organic peroxide in the printing ink mixture 58 can be mixed in substantially evenly distributed in the wear layer 62.

Thus, after the polymerization and/or cross-linking of the reactive, polymerizable monomer in the zones A is essentially complete, the temperature of the surrounding air can be raised to achieve the following •results. The zones A which contain polymerized and/or cross-linked monomers and have higher melt viscosities retain their appearance and growths. The B zones develop their smooth, shiny or glossy appearance as before. So far, only the polymerization initiator in zones A has been activated and/or degraded. The polymerization initiator or the organic peroxide in the wear layer has not been activated or degraded until further notice because it has a higher activation temperature. But when the temperature is raised sufficiently so that blowing or foaming can be carried out, the polymerization initiator or the organic peroxide in the wear layer is activated or broken down, whereby all reactive, polymerisable monomers in the wear layer, including the zones B, are polymerized and/or cross-linked.

The result is that the surface of wear layer 62 in zones Å has an embossed, flat, dead or dull matte finish, while the surface of wear layer 62 in zones B has a smooth, shiny or glossy finish, but both zones A and B contain high concentrations of polymerized and/or cross-linked reactive, polymerizable monomers and both have relatively high melt viscosities.

The modification in fig. 6 and 6A.

In Figures 6 and 6A, yet another modification of the principles according to the invention is illustrated. A conventional base layer or substrate is shown comprising a relatively flat fibrous backing sheet material 72, such as asbestos felt, on which is applied a printing ink mixture 78 in the form of a desired multi-colored pattern or design in which certain predetermined parts or colors 80 contain a free radical polymerization ion initiator or an organic peroxide and a special pigment or dye. Other predetermined printed portions 81 of the ink composition 78 on the surface of the fibrous backing sheet material 72 do not contain free radical polymerization initiator or

organic peroxide, but contains another pigment or dye.

As long as no potentially foamable plastisol is included, there is no need for a blow or foam modifier or inhibitor in the ink composition 78 or in any portion thereof.

An upper wear layer 82 comprising a resin polymer mixture is then applied to the surface of the printing ink mixture 78 and the layer contains substantially uniformly distributed reactive, polymerizable monomeric material. The wear layer 82 is then heated to a relatively low temperature to gel and harden or set its surface and facilitate its subsequent handling and processing. No mechanical embossing of any kind takes place on the surface of wear layer 82, and in this respect the experiment differs from the modification referred to in the discussion of Figures 4 and 4A.

Upon application of sufficient heat to raise the temperature of the resin polymer material sufficiently to activate or degrade the free radical polymerization initiator or organic peroxide, polymerization and cross-linking of the reactive, polymerizable, monomeric materials in the wear layer occurs, with a corresponding increase in melt viscosity in those areas 83 which is located just above the free-radical polymerization initiator or the organic peroxide in the printing ink mixture 78. In the areas 81 which do not lie above any free-radical polymerization initiator, no polymerization or cross-linking of the reactive, polymerizable, monomeric materials in the wear layer 82 takes place, and there is no simultaneous increase in the melt viscosity in the areas 81.

With respect to the areas 83 where polymerization and/or cross-linking occurs along with increased melt viscosity, there is furthermore created an unusual and distinct, marked effect which causes the surface of the wear layer 82 to be raised or elevated, to a higher level as much as about. 5 miles or even more. Such raised or raised effects cannot be felt at all in the areas 81, and the combined embossed effect of the raised portions in zones A as opposed to the normal portions in zones B is aesthetically excellent. Such raised or elevated outgrowths, which can also be noted in other embodiments of the invention, can be as small as approx. 1 or 2 miles, but are very noticeable. The exact reason for such an unusual effect is not fully or completely understood, but it is believed to be caused by the differences in polymerization and/or cross-linking and melt viscosities in the two zones. In all cases, even the smallest growths can be felt with the fingers and observed with the naked eye.

The modification in fig. 7.

In fig. 7, a further modification of the principles according to the invention is illustrated. A resin polymer sheet material 90 is shown comprising a conventional, relatively flat, fibrous sheet material 92, such as, e.g. an asbestos felt. Applied to the fibrous backsheet material 92 is a layer of a resin polymer composition 94, which appears in an inflated state due to the premixed conventional blowing or foaming agent, such as azodicarbonamide, which was activated and degraded by exposure to heat at a sufficiently high temperature for a sufficiently long time.

A barrier coating or layer 95 is located on top of the inflated cellular resin polymer mixture 9'4 and serves to prevent any of the gases developed and released during the Inflation and Foaming operation from escaping. A printing ink composition 98 is applied to the surface of the barrier coating 95 in the form of a multi-colored pattern or design. Portions of the printed pattern or design contained a free radical polymerization initiator or an organic peroxide in Areas 93, while certain other areas did not contain a free radical polymerization initiator or organic peroxide.

No blow modifier or inhibitor is incorporated into any part of the ink composition 98, and therefore the inflation or foaming is uniform and there is no chemical embossing of the top surface of the wear layer 91 applied to the ink composition 98. The entire wear layer surface 91 was previously mechanically embossed. , but this embossing has disappeared from zones B and is visible only in areas A. Growths, as discussed earlier, are again noted in zones A and can be easily felt with the finger and observed by the naked eye, especially when multi-colored patterns or designs are used.

Such differences in appearance are naturally caused by the fact that the free radical polymerization initiator or the organic peroxide in the zones A caused a polymerization and/or cross-linking of the reactive, polymerizable, monomeric material in the wear layer 91, together with an increase in the melt viscosity there, whereby the mechanical embossing in such zones survived the heating to higher temperatures in the blowing and foaming cycle. In the zones B where, however, there was no free radical polymerization initiator or organic peroxide in the printing ink mixture 98, there was no corresponding polymerization and/or cross-linking of the reactive, polymerizable, monomeric material in the wear layer 91, and there was no increase in the melt viscosity in such zones B As a result, such areas were unable to resist the softening-melting and flow tendencies that occurred due to the high temperatures during the blowing and foaming cycle. Such areas B are no longer mechanically embossed and they no longer have a flat, dead or dull matte finish or texture, but have become smooth, shiny and glossy in appearance.

The net effect is roughly similar to that achieved in the products in fig. 1-3, with the main difference that the resin polymer mixture in fig.7 does not have its blowing and foaming effect modified or inhibited by the presence of a blowing modifier or inhibitor in the ink mixture, but is allowed to swell and foam so that the expansion takes place evenly and uniformly. In fig. 1-3, the blowing modifier or blowing inhibitor produced the embossed effect by the chemical embossing method.

The modification in fig. 8.

In fig. 8, a further modification of the main principles according to the invention is illustrated. There is shown a resin polymer sheet material 100 comprising a conventional, relatively flat, fibrous sheet material, such as e.g. an asbestos felt. Applied to the fibrous backing sheet material 102 is a layer of a resin polymer composition 104 which is shown in an unblown or unfoamed state, provided that no blowing or foaming agent was originally included in the plastisol mixture. In the absence of blowing or foaming, the resin polymer mixture is non-cellular in the final product.

No barrier coating is used in such a modification and there is no need for such, of course. as no gas evolution or release occurs in the plastisol during the heated melting operation at elevated temperature. A printing ink composition 108 is applied to the surface of the resin polymer composition 104 in the form of a multi-colored pattern or design. Parts of the printing ink mixture contain a free radical polymerization initiator or an organic peroxide,

like for example. in areas 10 3, while other parts of the pressure ink mixture 108 do not contain any free radical polymerization initiator or organic ■ peroxide, as in areas 106.

As long as there is no blowing or foaming agent in the resin polymer composition, the final height of resin polymer sheet materials 100 is significantly less than that of FIG. 7, which, as previously noted, did not contain a blowing or foaming agent, such as e.g. azodicarbonamide, in its resin polymer blend 94. The mechanically embossed, dead or dull, flat, matte texture in areas 103 (zones A) is nevertheless retained, while areas 106 (zones B) have lost their flat, dead or dull matte texture and have become smooth , shiny and glossy as a result of the heated melting operation.

Such a difference in appearance is caused by the free radical polymerization ion initiator or the organic peroxide in zones A causing a polymerization and/or crosslinking of the reactive, polymerizable, monomeric material in the wear layer 101, together with an increase in the melt viscosity there, whereby the mechanical embossing in such zones A survived the heating at the elevated temperatures of the melting cycle.

In zones B where there was no free radical polymerization initiator, or organic peroxide in the printing ink mixture 108, there was, however, correspondingly no polymerization and/or cross-linking of the reactive, polymerizable, monomeric materials in the wear layer 101, and there was no increase in the melt viscosity in such zones B. As a result, such areas 10 6 were unable to resist the softening, melting and flow tendencies created by the elevated temperatures during melting of the resins. Such areas B are no longer mechanically embossed, and they no longer have a flat, dead or dull matte finish, but have become smooth, shiny and glossy.

The net effect is generally something similar to that achieved in the product in fig. 7, with the main difference that the product in fig. 7 is inflated and foamed, while the product in fig. 8 is not inflated or foamed. The surface of the wear layer is, however, very similar in both fig. 7 and 8, only the chemical embossing is different. Raised or elevated outgrowths are again observed in zones A as before.

So far in the description, emphasis has been placed on mixing free radical polymerization initiator and blow modifier or blow inhibitor into the same printed part of the printed pattern or design of the printing ink mixture, when both are to be used in the production of the resin polymer sheet material product. This is not always necessarily the case. If desired, a free radical polymerization initiator may be incorporated into one portion of the printed pattern or design and a blow modifier or blow inhibitor incorporated into another portion of the print or design.

Preferred and typical printing ink compositions for such modifications are as follows:

A preferred and typical end product is obtained, and this

is structurally similar. the final product illustrated in Fig. 2 and 3 i

the drawings. If trimellitic anhydride as an inhibitor is thus mixed into zones A, the lower surface of the wear layer above it retains, as shown in fig. 2 and 3, not the mechanical embossing which is applied and becomes smooth, shiny and glossy. And if dicumyl peroxide is mixed in as a polymerization initiator in zones B, the upper surface of the wear layer above, as shown in fig. 2 and 3, retain the mechanical embossing applied thereon which is flat, dead and dull dull. Thus, the final product is visually different from

final product that is obtained in figures 2 and 3.

The structure of the product in this embodiment would be identical to the structure of the product illustrated in fig. 2

and apart from the interchange of the areas of smooth, shiny and glossy finish and areas of flat, dead' and lackluster matte texture. Again, the parts of the wear layer that lie above the polymerization initiator are relatively highly polymerized and cross-linked and have relatively high melt viscosities, while the parts of the wear layer that lie above the blow inhibitor or modifier are relatively poor in polymerized and cross-linked monomers and have relatively low melt viscosities.

Such an exchange of surface visual effects is in most cases not desirable in simulated patterns and designs on ceramic tiles where it is normally desirable to have a smooth/shiny or glossy finish on the higher areas, while the lower mortar areas should be flat, dead or matte, but is desirable in other patterns or designs where a greater difference in visual effects is desirable

It is not essential that certain predetermined portions or colors of the printed pattern or design contain desired or required concentrations of the polymerization initiator or organic peroxide and that certain other predetermined portions or colors of the printed pattern or design contain absolutely no concentrations of polymerization initiator or organic peroxide. The polymerization initiator or organic peroxide can be contained in many different parts or colors of the printed pattern or design in many different concentrations. With the right choice of desired, varying concentrations, many gradations of surface finishes or textures can be achieved. The sharpness of the individual contrast can be reduced to some extent, but there is thus a much greater possibility of variation when it comes to effects, finishes and textures.

Such variations and gradations of surface finishes and textures can also be achieved by using many different polymerization initiators or organic peroxides with many different activity levels or degrees or many different activation or decomposition temperatures. Polymerization initiators or organic . peroxides that have greater activity tend to polymerize the reactive, polymerisable monomers to a greater extent and to increase the melt viscosity of the corresponding parts of the wear layer to a greater extent, thereby creating a greater resistance to melting, softening and flow - the effects during the blowing and foaming cycle. Thus, placing a polymerization ion initiator or a high activity organic peroxide in an area of the printed pattern or desig will tend to retain the embossed flat, dead, or dull matte finish that was applied during the embossing process, while placing a polymerization initiator or a low activity organic peroxide in another area of the printed pattern or design will tend to allow the embossed flat, dead or dull finish or texture to partially disappear to provide a different and different textural and/or gloss level or degree of the smooth, shiny or lustrous finish. Thus, it is possible to achieve different mattness and gloss and different finish and texture levels.

In addition to using a number of polymerization initiators or organic peroxides in a plurality of different parts or colors in the printed pattern or design in the printing ink mixture, a further effect can be achieved by mixing in an additional polymerization initiator or an organic peroxide with a relatively high activation or breakdown temperature in the wear layer in a substantially uniform manner.

It can be arranged so that the different polymerization initiators or organic peroxides are activated or broken down at many different steps in the process, whereby many different finishes or textures can be achieved. At a much later stage, such as during the blowing or foaming cycle, the high temperature polymerization initiator or organic peroxide can then be activated to polymerize and/or crosslink the reactive, polymerizable monomers throughout the resin wear layer. Such a treatment would increase melt viscosities in all different areas of the resin. - the wear layer as a total effect.

An alternative "upside-down" method of making the resin polymer sheet materials. according to the invention are as follows: et

resin wear layer, as described earlier, is cast or otherwise

formed on a suitably textured or embossed surface, such as a coarsely textured, parchment-type tear paper, or other raised, roughened, uneven, rippled, wrinkled, or dented surface, or any similar or similarly irregular surface with protrusions that has release properties.

The mixture in the resin wear layer is sufficiently fluid that it flows into and completely fills all nooks and crannies, depressions and niches in the textured or embossed surface and assumes

thus essentially identical surface properties and features.

Such a surface, which is so irregular, uneven or grainy that it

does not reflect light in a regular manner, but more or less scatters it, would present a flat, dead or dull matte, textured or embossed appearance, if the release surface were to be removed therefrom so that the shaped surface of the resin wear layer mixture could be seen.

An ink composition, or several such compositions, as previously described herein, is applied or otherwise deposited on the surface of the cast resin wear layer after it has gelled by standard and conventional methods. A desired design or pattern is thus applied, and as described earlier herein, certain predetermined areas of the printed pattern or design contain a polymerization initiator or an organic peroxide, and if desired also a blow or foam modifier or inhibitor, while other predetermined areas of the printed pattern or design contains either 1) no polymerization initiator or organic peroxide in it at all, or 2) a different concentration of the same polymerization initiator or organic peroxide, or 3) a different polymerization initiator or organic peroxide with a different activity degree or level or other activation or decomposition temperature. The ink mixture is then dried.

A resin barrier coating, as described hereinbefore, may then be applied to or otherwise deposited on the dried printed pattern or design of the printing ink composition.

Heating the printing ink mixture and the polymerization initiator or the organic peroxide in the mixture and resin wear layer

to a sufficiently high temperature then takes place, whereupon the polymerization and/or cross-linking of the reactive, polymerizable monomer in the resin wear layer takes place in selected, predetermined parts thereof which lie below the polymerization initiator or the organic peroxide. However, no polymerization and/or cross-linking of the reactive, polymerizable monomer takes place in the parts of the resin wear layer that are not under any polymerization initiator or organic peroxide. And at the same time, the polymerized and/or cross-linked parts of the resin wear layer develop higher melt viscosities.

In addition, gelation of the resin plastisols takes place, whereby further handling and further processing is made easier.

A base layer or substrate, preferably comprising a relatively flat, fibrous backing sheet of asbestos fibres, such as described earlier herein, and a potentially foamable resin polymer mixture, such as e.g. a polyvinyl chloride plastisol, also as described hereinbefore, is laminated or otherwise attached to the surface of the barrier coating, preferably under pressure and at elevated temperatures in a laminator to form a uniform, integrated structure.

The tearable, coarsely textured tear-off surface on which the resin wear layer originally formed. molded or shaped., is then removed and reveals a suitable textured or embossed surface on the resin wear layer, exactly corresponding to the textured or embossed surface of the tear-off material.

Heating to an even higher temperature in a melting, or . blowing or foaming furnace atmosphere causes a number of effects. The parts of the herpik wear layer that do not. contain some polymerized and/or cross-linked reactive polymerizable monomers and which do not have relatively high melt viscosities, soften and melt at such temperatures and flow so as to form a smooth, shiny or glossy surface or finish, while the other parts of the resin wear layer containing polymerized and/or cross-linked reactive polymerizable monomers and having relatively higher melt viscosities, are able to resist the softening and melting tendencies at such high temperatures and do not flow but retain their original, textured or embossed, flat, dead or matte surfaces.

At the same time, if a blowing or foaming agent, such as e.g. azodicarbonamide, is present in the potentially foamable resin polymer mixture in the base layer or substrate, a swelling or foaming thereof takes place. And, if a blowing modifier or inhibitor is also mixed into the printed pattern or design of the printing ink mixture, the blowing or foaming effect will be correspondingly modified or inhibited.

The end product is of course essentially similar to the end product that was obtained in the previously described methods, but has the advantage that no separate mechanical embossing step is necessary in the method.

In this alternative "upside-down" method, it is noted that the resin barrier coating is applied to the printed pattern or design of the ink composition prior to the heating of the ink composition and the polymerization initiator therein and the resin wear layer and the reactive polymerizable monomer therein to effect polymerization and/or crosslinking of the reactive, polymerizable monomer. This is only a preferred or typical method. The resin barrier coating can be left out completely or, if desired, applied to or otherwise attached to the resin wear layer prior to application of the printed pattern or design. The important function to be implemented is that the polymerization initiator in the ink mixture must be capable of polymerization and/or cross-linking of the reactive, polymerizable monomer and that the barrier coating is present, if necessary, when the potentially foamable resin polymer mixture is subsequently inflated or foamed and the produced gases are released^

It is considered recommendable to pay particular attention to indications of temperatures and temperature ranges in the present description. Whenever a material is heated by being passed through a heated oven or other heating device, and the temperature in such a heated oven is maintained at a desired temperature, it shall be understood that the material does not reach this temperature, especially if it is in such a heated environment in only a very short time. The temperature of the material is usually a few degrees lower than the temperature of the heated surroundings. Such a situation exists during a gelation operation of the plastisol, when the plastisol is passed through a heated environment containing heated air.

When, on the other hand, a material is pressed against a heated surface, such as e.g. a heated plate or other pressing device, and a very intimate contact is established between the heating element and the material to be heated, the temperature of the material being heated will be very close to the temperature of the heat source. Such a situation normally exists during a mechanical embossing operation, in which a heated plate or another embossed, heated surface is pressed into very intimate contact with the material to be mechanically embossed. This is especially the case if the heated plate or stamp is pressed against the surface of the material that is heated and embossed under applied pressure, which in the present case can be in the range of up to 14.1 kg/cm 2.

The modifications in fig. 9-12.

So far, in the present invention, emphasis has been placed on giving certain surface parts in the wear layer a flat, dead or lackluster matte finish, as is formed by mechanical embossing, and giving certain other surface parts in the wear layer another contrasting texture or effect, such as e.g. . a smooth, shiny or lustrous finish, as formed in a heated melting furnace. In some cases, it may be desirable that substantially the entire surface of the wear layer retains the textured finish formed during the mechanical embossing operation. Such a total effect can be achieved by several methods, such as e.g. illustrated in Figures 9 - 12 in the drawings.

In fig. 9, there is illustrated a resin polymer sheet material 110 comprising a typical relatively flat backing web or sheet material 112,

similar to the backing sheet material 12, which has been described previously. A relatively flat, substantially uniform layer of a potentially foamable (or non-foamable) resin polymer mixture 113, similar to the previously described potentially foamable (or non-foamable) resin polymer mixture layer 13 is formed on, or applied, to the backsheet material 112.

Such a resin polymer mixture 113 is processed as described earlier herein, including for example a heating, gelling, fixing and cooling operation, and is printed or coated with a suitable printing ink mixture 118 with a desired pattern or design

.of different colours, such as 118a, 118b, 118c, 118d and 118e.

While in the previous embodiments of the invention some of these printed, colored parts or areas contained certain amounts of polymerization initiators, catalysts or organic peroxides,

and other printed, colored parts or areas contained different amounts or no polymerization initiators, catalysts or organic peroxides at all, all "colors, parts or areas of the printed pattern or design in Fig. 9 contain equal amounts and equal concentrations of the same polymerization initiators,

-catalysts or organic peroxides.

If desired, e.g. when a blowing or foaming operation is then used, a relatively thin barrier coating or layer 115 can be placed, which e.g. the previously described barrier coating or layer over the potentially foamable resin-polymer mixture 113, either before the printed pattern or design 118 is applied thereto, or as shown in fig. 9, after the printed pattern or design is applied to the resin polymer mixture 113. The purpose of such a barrier coating or layer has previously been described herein.

A relatively thin, uniform wear layer 122, containing a

or more reactive, polymerizable, monomers. materials, such as the wear layer 22 described earlier is then applied to the printed, gelled and cooled, potentially foamable resin polymer mixture 113. Gelling and fixing of the wear layer 122 takes place, as described earlier, followed by a total mechanical embossing process, also as described earlier.

As long as the entire surface of the wear layer 122 lies above any polymerization initiators, catalysts or organic peroxides in the printing ink mixture 118, polymerization takes place and

cross-linking of the reactive, polymerizable, monomeric materials,

substantially uniformly throughout the wear layer 122, together with increased melt viscosities which are also formed uniformly during the mechanical embossing throughout the wear layer 122.

Heating and melting, as well as blowing or foaming (if a blowing or foaming agent was originally incorporated into the resin polymer mixture 113), takes place as previously described.

The mechanical embossing of the surface of the wear layer 122 is maintained substantially evenly throughout, even after such treatments.

Fig. 10 shows a relatively flat resin polymer sheet material

120 comprising: a fibrous backing layer 122; a printing ink mixture 116 which uniformly contains a polymerization initiator, catalyst or organic peroxide; a barrier coating or layer; and a wear layer 122, all essentially as described earlier with particularity

reference to fig. 9. A resin polymer mixture 123 is used which contains a blowing or foaming agent. The previously described heating, gelling and fixing procedures for the resin polymer mixture 123 and the wear layer 122, simultaneously with the subsequent total mechanical embossing of the surface of the gelled wear layer 122, and the other previously described methods take place, followed by conventional heating< p>g melting, and swelling or foaming in a melting furnace. Fig. 10 illustrates the inflated resin polymer sheet material 123, after the heating, melting and blowing or foaming operations. The mechanical embossing on the surface of the wearing layer 122 is maintained substantially evenly throughout.

Fig. 11 shows a relatively flat resin polymer sheet material 130 comprising: a fibrous backing layer 112; a resin polymer composition 133 containing a blowing or foaming agent; a printing ink mixture 138 which substantially evenly distributed contains equal concentrations and amounts of a free radical polymerization initiator, catalyst or organic peroxide in all parts and areas thereof, as well as a blowing or foaming modifier or inhibitor which is contained only in certain selected portions or areas 138a of the ink mixture layer 138; a relatively thin barrier coating or layer 115; and a resin polymer wear layer 122 containing a substantially uniformly distributed reactive, polymerizable, monomeric material.

A blowing or foaming agent is uniformly mixed into the resin polymer mixture- 133 and it is heated and melted, blown, foamed,

as illustrated. Due to the presence of blowing or foaming modi-

tor or inhibitor in certain selected parts or areas 138a in the printing ink mixture 138, however, the blowing or foaming takes place selectively, as is well known in the field of chemical embossing, and the finished, embossed product is illustrated in fig. 11.

The intermediate operations of heating, gelling and fixing the resin polymer mixture 133, printing the ink mixture layer 138, applying and gelling, fixing and cooling the resin polymer wear layer 122, and heating, melting and inflating or foaming are standard and conventional operations and are described herein before and should require no further explanation or description.. It should be noted that the mechanical embossing of the surface of wear layer 122 is maintained substantially uniformly throughout.

In fig. 12, there is illustrated a resin-polymer sheet material 140 comprising: a typical, relatively flat backing web or sheet material 112; a resin polymer composition 143 which is potentially foamable or non-foamable, as desired or required; an essentially uniform resin-pic polymer coating such as e.g. a clear printing ink mixture 144 containing essentially evenly distributed from approx. 1 to approx. 35 or 40% by weight, and preferably from approx. 1 to approx. 10% by weight of a polymerization initiator, catalyst or an organic peroxide; a printing ink composition 148 containing no polymerization initiator, catalyst, or organic peroxide; a relatively thin barrier coating or layer 145, if a blowing or foaming agent is incorporated into the resin polymer blend layer 143; and a wear layer 142 which contains relatively evenly distributed one or more reactive, polymerisable, monomeric materials.

Standard and conventional operations, such as heating, gelling and setting of the resin polymer-plastisol mixture 143 and of the plastisol wear layer 142, as well as the mechanical embossing of the gelled and cooled surface of the wear layer, and the subsequent heating and melting, and blowing or foaming of the resin polymer mixture 143 (if any mixed with a blowing or foaming agent in it) follows in a well-known manner.

Fig. 12 illustrates the resin polymer sheet material 140, either just prior to heating and melting, and the blowing or foaming operation (if a blowing or foaming agent is present), or after the heating and melting operations, if not present blowing or foaming agent. The mechanical embossing on the entire surface of the wear layer 142 is maintained uniformly throughout all of these heat, melt, blow or foam operations.

If a blowing or foaming agent was originally mixed in the resin polymer mixture 143 in fig. 12, then. such a resin polymer composition 143 would be expanded and expanded so that it would generally resemble the inflated or foamed resin polymer composition 123 illustrated in FIG. 10.

Similarly, if a blow or foam modifier or inhibitor had originally been incorporated into certain selected, predetermined portions or areas of the ink mixture 148 in FIG. 12, such resin polymer composition 148 (and all layers above it) has been expanded and expanded so that it would generally resemble the inflated and chemically imprinted resin polymer composition 133 of FIG. 11.

A further embodiment according to the invention which leads to the maintenance of the total mechanical embossing on the surface of the wear layer through the heating and melting, and inflating or foaming operations can be described without the need for or the necessity of yet another figure in the drawings; Such an embodiment excludes the presence of any polymerization initiator, catalyst or organic peroxide from the ink composition, as in Figures 9-11, and also excludes the presence

of some polymerization initiator, catalyst or organic peroxide in a separate layer, as in fig. 12.

In this non-illustrated embodiment, the polymerization initiator, catalyst, or organic peroxide is mixed directly and uniformly into the wear layer containing the reactive, polymerizable, monomeric materials, usually in an amount of from about 0.5 to approx. 5% by weight and preferably from approx. 1 to approx. 2% by weight based on the weight of the reactive polymerizable,. the monomeric materials.

Alternatively, the polymerization initiator, catalyst or organic peroxide can be mixed into the barrier coating 115 in fig. 9 in a quantity of from approx. 0.08 to approx. 0.0% by weight and preferably from approx. 0.16 to approx. o.32% by weight based on the total weight of the barrier coating mixture.

Activation and polymerization and cross-linking of such reactive, polymerizable, monomeric materials takes place during the mechanical embossing process as usual. Retention of such mechanical imprinting effects is noted at the end of the heating and melting, and inflating or foaming operations.

The present invention will be described further with particular reference to the following specific examples, where preferred and typical embodiments of the invention are shown. However, it should be understood that such specific examples are primarily illustrative of the general principles of the invention and that the specific materials, chemicals, patterns, designs and other special aspects shall not be considered limiting of the wider scope of the invention idea, except as defined by scope and spirit of the accompanying requirements.

Example 1.

A resin polymer sheet material as illustrated in Figures 1-3 of the drawings is produced by the following methods: The base layer or substrate comprises a relatively flat, 0.1 cm thick fibrous sheet of asbestos fiber felt with a smooth acrylic coating. The asbestos felt fiber layer is coated essentially evenly to a wet thickness of approx. 0.04 cm with the following potentially foamable resin polymer-plastisol mixture:

Gelation and fixing of the potentially foamable plastisol is carried out in an oven at an elevated temperature of approx. 149°C for approx. 3 min. The temperature! is not sufficiently high to activate or degrade the azodicarbonamide.

The gelled, potentially foamable plastisol is then imprinted with a ceramic tile pattern or design as shown in fig. 2 and 3

in the drawings. Zones B are printed with a standard or conventional printing ink mixture containing a predetermined pigment but containing no blow modifier or inhibitor or any

free radical polymerization initiator or organic peroxide. Such a standard or conventional printing ink mixture contains:

Pigment or dye as desired or required

However, the following printing ink mixture containing another pigment or dye is printed on the zones A:

Pigment or dye as desired or required

The printed, gelled, potentially foamable plastisol is then allowed to dry and a wear layer is applied to it to a wet thickness of approx. 0.04 cm and with the following composition:

Gelation and fixing of the wearing layer plastisol is carried out by heating in an oven atmosphere with an elevated temperature of just below. 149°C for a time of approx. 3 min.

The gelled wear layer is then mechanically embossed with a fine overall pattern of a parchment paper-like texture in a "Watson-Stillman Press" for approx. 2 min. under a pressure of 9.8 kg/cm 2 and at an elevated temperature which is achieved in the wear layer at slightly above 149°C.

. The heated embossing takes place, together with the polymerization and/or cross-linking of the trimethylolpropane trimethacrylate in the wear layer, but only in the parts of it directly above the dicumyl peroxide, while there is essentially no polymerization and/or cross-linking

bonding to any significant or significant degree in other" areas of the wear layer that do not lie directly above the dicumyl peroxide. In addition, the melt viscosity of the wear layer parts that lie above the dicumyl peroxide is significantly increased, while the melt viscosity of the wear layer parts that do not lie directly above the dicumyl peroxide remains essentially unchanged .

The mechanically embossed material is then heated in a melting furnace which is kept at a temperature of approx. 20 2°C for approx. 2-3/4 min. Melting of the resins takes place, along with the swelling and foaming of the potentially foamable plastisol in the areas not directly below the trimellitic anhydride inhibitor in the ink mixture. There is very little swelling or foaming in the areas directly below the trimellitic anhydride. The difference effect of the chemical embossing is excellent.

In addition, they develop raised parts or land in the wear layer, as seen in fig. 3 in the drawings, a smooth, lustrous or glossy finish, with a high luster and sheen, while the lower or depressed parts or the mortar part retain the flat, dead or lusterless matte finish created in them by the mechanical embossing with " Watson Stillman Press". The appearance of materials, after the blowing or foaming cycle, is very similar to that of a glossy, high-skin glazed ceramic mica tile, surrounded by a flat, dead or dull matte finish that is given the appearance of mortar or other cementitious material between the ceramic tiles.

The different colors of the printed pattern or design in the ink mixture completely and perfectly match 1) the above described mechanical embossing effects on the contrasting smooth, shiny or glossy areas and the flat, dead or dull areas, as well as 2) the above , described the chemical imprint effect on the higher and lower areas on the surface of the wear layer.

Testing by means of solubility in tetrahydrofuran establishes that the trimethylolpropane trimethacrylate is not polymerized or cross-linked prior to the mechanical embossing; that it is polymerized and cross-linked during the mechanical embossing; and that it is still polymerized and cross-linked after the blowing and foaming cycle has ended, but only in the areas of the wear layer that lie directly above the dicumyl peroxide, which is present in the printing ink mixture, while in all other areas of the wear layer that do not lie directly above the dicumyl peroxide is not any significant polymerization or cross-linking of trimethylolpropane trimethacrylate.

With further reference to the melt viscosity determinations for the relatively highly polymerized and cross-linked parts and those. relatively charge-polymerized and non-crosslinked portions of the resin wear layer, it has been determined that the following melt viscosity ranges are appropriate for the application of the principles of the invention.

Using the conditions set out in Example 1 for the Brabender determinations, the torque readings for the highly cross-linked parts of the wear layer should be in the range of from approx. 1000 to .approx. 4000 meter-grams and the torque readings for the relatively non-t<y>err bound parts should be in the range of from approx. 30 0 to approx. 900', as the difference in the torque readings for the two contrasting parts in the same product is at least approx. 250 meter-grams.

It should be understood that the references in the preceding paragraph and elsewhere in this description to cross-linked polymeric materials refer only to the polymerization and cross-linking of the polyfunctional, reactive, polymerizable, monomeric materials, such as e.g. the trimethylolpropane trimethacrylate, for example in the resin wear layer, which is naturally cross-linked and heat-cured.

It should also be understood that the main resin in the wear layer, for example polyvinyl chloride, is essentially evenly and homogeneously distributed therein and is in a molten and polymerized state. However, it is not cross-linked and is still in a thermoplastic state, compared to the cross-linked and thermoset polyfunctional polymeric materials in the parts of the wear layer overlying the polymerization or cross-linking initiator or the organic peroxide.

It should also be noted that there is complete and perfect correspondence between: the flat, dead or dull, textured parts of the wear layer;

their corresponding colored parts of the pattern or design of the printing ink mixture; and the relatively unblown or unfoamed portions of the resin polymer composition 16. At the same time, there is complete and perfect correspondence between: the smooth, shiny or glossy finish surfaces;

their corresponding colored parts of pattern or design in the printing ink mixture; and the inflated and foamed portions of the resin polymer mixture.

With regard to the determination of the melt viscosities of the various parts of the resin wear layer, this is relatively a more complicated method. However, use of the "C.W. Brabender Plastograph" or "Plasticorder", as described in Paint and Vårnish Production, July, 1965, makes such determinations relatively simple and very accurate. Further information on such methods can also be found on pages 23 to 32 of the Journal of Cellular Plastics, January/February, 1971.

Brabender determinations are run on samples of the highly polymerized parts of the resin wear layer at 150°C, at a shear rate of 0 revolutions per minute. minute for 15 min. at which time the 53-gram samples are in equilibrium. A type 6 roller mixer measuring head is used to determine the melt rheology of the wear layer plastisol. The highly polymerized parts of the resin wear layer gave torque readings on

2510 meter-grams, while the relatively unpolymerized parts gave readings of only 6 50 meter-grams.

Example 2.

A resin polymer sheet material as illustrated in FIG. 7 on

the drawings, are made as follows:

The procedure described in example 1 is essentially followed as indicated there, with the exception that trimellitic anhydride is omitted from the printing ink mixture which comprises the following ingredients:

Pigment or question substance, as desired or required.

The results obtained in this example are generally comparable to the results obtained in Example 1, with the exception that the resin polymer sheet material in the present example is not chemically imprinted and that the blowing or foaming operation is substantially uniform in its action , whereby the surfaces in the wear layer are

essentially flat and of the same height. The flat, dead, or matte, embossed finish and the smooth, shiny, or glossy finish are essentially on the same level plane. With regard to the concentration of polymerized or cross-linked trimethylolpropane trimethacrylate, this is relatively high in the areas that lie above the dicumyl peroxide and relatively low in the areas that do not lie directly above the dicumyl peroxide. The melt viscosities are also relatively higher and lower, as indicated in example 1. Dumps shown in the drawings can be distinguished and felt by the "finger test". Barriére coating BC-1 is used to ensure that no gases developed during inflation or foaming escape into the wear layer.

Example 3.

A resin polymer sheet material as illustrated in FIG. 8 in the drawings, is produced as follows: The procedure described in example 2 is essentially followed as indicated there, with the exception that, in addition to the omission of trimellitic anhydride as blowing modifier or inhibitor, azodicarbonamide as blowing or foaming agent is also omitted from the plastisol composition.

The results obtained in this example are generally comparable to the results obtained in Example 2, with the exception that the resin polymer blend or plastisol is not chemically inflated or foamed at all and the result is a denser, non-cellular polymer sheet material in which the fused resins are heavier and are not very different from the portion of the fused resins illustrated in fig. 1 with the reference letter A. In the product in fig. 8, all parts of the molten plastisol are essentially the same.

Again, the flat, dead, dull matte texture is retained in zones A after mechanical embossing and after melt heating at high temperatures. However, such a texture is lost in the zones B during the melt heating at high temperatures and the final appearance of such zones B is smooth, shiny, and glossy. Raised or raised bulges shown in the drawings can be discerned and felt by the "finger test". As long as no blowing or foaming is included in this example, no barrier coating is used.

Example 4.

The procedures described in Example 1 are followed essentially as described there, with the exception that the amounts of the components in the printing ink mixture containing both free radical polymerization initiator or organic peroxide and blow modifier or inhibitor were changed as follows:

The results in this example are generally comparable to the results from example 1.

Again, it can be determined that the polyfunctional, reactive, polymerisable, monomeric material, namely trimethylolpropane trimethacrylate, is polymerized and crosslinked only in the areas of the wear layer that lie directly above the polymerization initiator, namely the dicumyl peroxide. In the other parts of the thin layer which do not lie directly above the dicumyl peroxide, the trimethylolpropane trimethacrylate is essentially unpolymerized and not cross-linked.

Example 5.

The methods that are generally described in example 1 are essentially followed as indicated there with the following variations: The potentially foamable plastisol mixture P-1 is used; the wet thickness is approx. 18.7 miles; gelation takes place in heated air at approx. 149°C for 3 min.; a BC-1 barrier coating with a thickness of approx. 3 miles; it gels in a heated air atmosphere at approx. 149° for approx. 3 min.; the printing ink mixture is P-1 and contains dicumyl peroxide and trimellitic anhydride as polymerization initiator or organic peroxide and blow modifier or inhibitor, respectively; the non-active printing ink composition does not contain polymerization initiator or organic peroxide or any equivalent material; the resin wear layer is a W-1 mixture and contains trimethylolpropane trimethacrylate as reactive, polymerizable monomer;

it is approx. 12 mil thick and gels in a heated air atmosphere at approx. 149°C for approx. 3 min.; mechanical embossing takes place at approx. 152°C under an applied pressure of 7.7 kg/cm 2 for 3 min. against a coarsely textured parchment-type tear-off paper; inflation and foaming take place in a heated melting furnace at an elevated temperature of approx. 202°C for approx. 2 min. and 40 sec.

The results obtained in this example are generally comparable to the results obtained in Example 1. The relatively low, relatively uninflated mortar areas have embossed, flat, dead or dull finishes or textures, while the relatively elevated, relatively inflated land areas have a smooth ,.shiny or glossy surface. The mortar areas have a relatively high concentration of polymerized, crosslinked monomer and have a high melt viscosity. The Landom councils have practically no concentration of polymerised, cross-linked monomer and have a relatively low melt viscosity. The product is commercially acceptable as a resilient floor covering.

Examples 6 - 16.

The procedures set forth in example 5 are followed substantially as described in i, with the exception that the P-1 printing ink mixture used there is replaced by the printing ink mixtures P-7 to P-17, as described earlier herein, as eleven additional examples.

The results obtained in these examples are comparable to the results obtained in Example 5. The relative differences between 1) the flat, dead or dull matte textured finishes and the smooth, shiny or glossy areas and 2) the degree of polymerization ion and/or crosslinking of the reactive, polymerisable monomer

in these areas and 3) the degree of increase in the melt viscosity of the polymerized and crosslinked. areas are significant and.noticeable.

Examples 17 - 21.

The methods described in example 5 are followed essentially as described there, with the exception that the dicumyl peroxide polymerization initiator in the printing ink mixture is replaced with:

The results from these examples are generally comparable to the results from example 5.

Examples 22 - 25.

The methods described in example 5 are followed

substantially as set forth therein, with the following exceptions as to the printing ink composition used and where the printing ink compositions identified as P-2 through P-5 in the applicable table are used: Example 22 (P-2) contains trimellitic anhydride but no dicumyl peroxide or any other polymerization initiator or no other organic peroxide. This gives a product which is structurally shown in fig. 2 and 3 endorsements, but without any embossed, flat, dead or dull, textured areas, and without any areas of increased melt viscosities. •

Example 23 (P-3) contains trimellitic anhydride and dicumyl peroxide. This gives a product that is generally comparable to the product obtained in Example 5. It has embossed, flat dead or dull, textured areas and smooth, shiny or glossy finish areas and differences in melt viscosities. It is commercially acceptable as a resilient floor covering.

Example 24 (P-4) contains trimellitic anhydride, but no dicumyl peroxide or any other polymerization initiator or any other organic peroxide. This gives a product which is structurally shown in fig. 2 and 3 in the drawings, but without any embossed, flat, dead or dull textured areas and without parts with increased melt viscosities.

Example 25 (P-5) contains dicumyl peroxide but no trimellitic anhydride or any other blow modifiers or inhibitors. This gives a product that is structurally similar to that shown in fig. 7 in the drawings. There are embossed, flat, dead, or matte textured areas, as well as smooth, shiny, or glossy finish areas, and differences in melt viscosities, but there is no chemical embossing in the surface of the wear layer, other than small, raised, or raised bumps as shown in fig. 7.

Examples 26 - 31.

The procedures described in Example 5 are essentially followed as indicated there, with the exception that the wear layer mixture W-1 used there is replaced with the wear layer mixtures W-3, W-6, W-7, W-9, W-10 and W -12, as described in the relevant table here. The results of these examples can generally be compared with the results obtained in example 5 with wear layer mixture W-1. The contrast between the embossed, flat, dead or matte textured areas and the smooth, shiny or glossy smooth finish areas is very clear. The differences in polymerization and/or cross-linking of the reactive, polymerizable monomers in the respective wearing layers are marked and significant. The differences in melt viscosities in the different areas of the wear layer are also observed and are marked and significant. The products are commercially acceptable as resilient floor coverings.

Examples 32 - 36.

The procedures described in example 5 are essentially followed as indicated there, with the exception that the reactive, polymerizable monomer trimethylolpropane trimethacrylate is replaced with:

The results of these examples are generally comparable to the results obtained in example 5'. Polymerisation and/or cross-linking and increase in melt viscosity are as described therein, together with the contrasting drooping, dead or dull textural areas and the smooth, shiny or glossy areas.

Example 37.

The procedures indicated in example 1 are essentially followed as described there, with the exception that the composition of the resin wear layer is changed to the following:

(Parts by weight based on 100 parts :resin,.phr)

The results of this example are generally comparable

with the results obtained in Example 1. The differences in polymerization and/or cross-linking of the reactive, polymerizable monomer and the difference in melt viscosities in the different parts of the wear layer are noted, together with the contrasting surfaces with a flat, dead or lackluster matte texture and a smooth, shiny or glossy finish. The product is commercially acceptable as a resilient floor covering. Similar to the product in Example 1, the part of the wear layer in the area of flat, dead or lackluster matte finish is cross-linked and heat-set, while the part of the wear layer in the areas of smooth, shiny, even or glossy finish is not cross-linked or heat-set, but is still thermoplastic .

Example 38.

The procedures described in example 5 are essentially followed as described there, with the exception that the barrier coating mixture BC-1 used there is replaced with the barrier coating mixture BC-2,

as previously described here. The results of this example are generally comparable to the results obtained in example 5. The thickness of the barrier coating is also 4.5 mils.

Example 39-41.

The procedures described in Example 5 are essentially followed as described there, with the exception that the thickness of the barrier coating is changed to 1.5, 4, and 5 mils instead of 4.5' mils which was the thickness in Example 5. The results of these examples are generally comparable to the results from example 5.

Examples 42 - 44.

The procedures described in Example 5 are essentially followed as indicated there, with the exception that the mechanical embossing takes place under applied pressures of 3.52, 6.05 and 7.0 kg/cm 2 instead of the 7.73 kg/cm 2 that was applied in Example 5. The results of these examples are generally comparable to those obtained in Example 5. The areas of flat, dead or dull matte finish contain cross-linked and heat-cured resin, while the areas of smooth, even, shiny or glossy finish contains non-crosslinked, thermoplastic resin.

Example 45.

The procedures described in example 5 are essentially followed as indicated there, with the exception that the conditions for the mechanical embossing of the resin wear layer are changed to: -9.84 kg/cm^ at 182°C

for a time period of approx..15 sec-

The results in this example are generally comparable to the results obtained in example 5.

Example 46.

The procedures described in example 5 are essentially followed as indicated there, with the exception that the conditions for the mechanical embossing are changed to: 6.05 kg/cm^ at 157°C for approx. 2 min.

The results from this example are generally comparable to the results obtained in example 5.

Example 47.

The procedures described in Example 1 are followed essentially as described there, with the exception that the mechanical embossing is changed as follows: In the set to apply pressure and heat to the coarsely textured parchment-type release paper placed on the surface of the gelled resin wear layer by means of a "Watson-Stillman Press" plate, pressure and heat are applied by roller contact with a 60 cm rotating embossing roller with a temperature of approx. 166°C and with a rotation speed of 2 revolutions per my. The surface of the embossing roller has a rough, sandblasted finish. The resin wear layer is directed towards the heated periphery of the embossing roller and is kept in close contact with it in the main part of the heated periphery, after passing through the pressure-applying roller clamp, thus creating an approx. 1.5 m useful heated contact periphery.

The results of this example are generally comparable to the results obtained in Example 1. The polymerized and cross-linked heat-cured portions of the resin wear layer having the highest melt viscosity retain the surface features and properties of the coarsely textured parchment tear paper -type, while the non-crosslinked parts of the resin wear layer become smooth, even, shiny and glossy.

Example 48,

The procedures described in example 47 are essentially followed as indicated there, with the exception that the heated, pressure-applying embossing roller is engraved with very fine, parallel lines, 50 lines per 2.54 cm, which creates the flat, dead or dull matte texture or finish and contains cross-linked, thermoset resin, as opposed to the smooth, smooth, shiny or glossy parts that contain non-cross-linked, thermoplastic resin. The results from this example are generally comparable to the results from example 47.

Example 49..

The resin polymer sheet material illustrated in FIG. 2 and 3 are generally produced using the following, alternative "upside-down" method, in which the composition of the potentially foamable plastisol, the printing ink mixtures, the barrier coating mixtures and the wear layer mixtures is as described in example 5.

The resin wear layer plastisol containing the reactive, polymerizable monomer and still in a free-flowing form is cast onto the surface of a coarsely textured parchment-type tear paper in a. depth of approx. 15 ml. The wear layer plastisol is sufficiently fluid to flow into and completely fill all irregular recesses in the release paper and thereby assume the surface features and properties of the release paper. The wear layer then gels at 149°C.

The various printing ink mixtures, some containing both dicumyl peroxide as a polymerization initiator and trimellitic anhydride as a blow modifier and others containing neither polymerization initiators nor organic peroxides or blow modifiers or inhibitors, are applied to different areas of the exposed phase of the gelled wear layer in the desired pattern or design. The printing ink mixtures are then dried.

A barrier coating of 3 mil is applied and attached to the printing ink mixtures and heated at a temperature of approx. 160°C for a sufficiently long time not only to gel the resin barrier coating, but also to activate or break down the dicumyl peroxide in the wear layer so that the reactive, polymerizable monomers located in the same vertical zones are polymerized and/or cross-linked, and so that melt- • the properties of the resins in such vertical zones are increased.

A base layer or substrate comprising a potentially foamable plastisol mixture and an adhered fibrous sheet of asbestos fiber felt is then laminated to the gelled barrier coating by passing through a laminator under pressure and at elevated temperature. The resulting laminated product is smooth and integrated in structure.

The coarsely textured parchment-type tear paper is then torn off from the wear layer, the surface of which is thus exposed and found to be similarly coarsely textured and parchment paper-like in appearance,<p>g with a flat, dead or dull texture over the entire surface.

This - laminated product is then passed through a heated melting furnace at temperatures of approx. 202°C, and the resins are fused with the blowing and foaming operation, in which the blowing and foaming agent and blowing modifier or inhibitor perform their previously described embossing procedures.

The resulting inflated product is generally similar to and comparable to the product of Example 5. Those portions of the wear layer in which the reactive, polymerizable monomers are polymerized, and/or cross-linked, and also have a higher melt viscosity, retain their coarsely textured parchment-like, . dead, flat or lackluster matte texture and appearance. In other cases of the wear layer where there has been no significant polymerization and/or cross-linking of the reactive, polymerizable monomers, and where the melt viscosity remains relatively unchanged and is relatively low, the surfaces are melted to form smooth, even, shiny or glossy finishes , which occurs during the blowing and foaming operation. The cross-linked parts are heat-set, while the parts which are not cross-linked are thermoplastic.

Example 50.

The procedures described in example 5 are followed essentially as described there, with the exception that cumene hydroperoxide, which is a polymerization initiator or organic peroxide which can be activated or decomposed only at relatively high temperatures, is additionally mixed into the resin wear layer in an essentially uniform manner in a concentration of approx. 7 parts by weight - based on 100 parts resin, phr.

The cumene hydroperoxide is not activated or degraded during the gelling operations or during the mechanical embossing operations,

at which time the dicumyl peroxide is activated or broken down in the printing ink mixture, whereby certain selected parts of the wear layer are polymerized and/or cross-linked, and develop relatively high melt viscosities, as described in more detail in this description and in example 5.

However, the cumene hydroperoxide is then activated or degraded at the high temperatures that occur during the melt, blow, or foam cycle, whereby the reactive, polymerizable monomers in the remaining areas of smooth, smooth, shiny, or glossy finishes are polymerized and/or cross-linked at this time. , at the same time the increase in melt viscosities in these smooth, even, shiny or glossy parts. Visibly, the softening, melting and flying in such areas precede the polymerization and/or cross-linking and the increase in melt viscosities.

There is no significant change in the areas of flat, dead or matte texture, which are polymerized and/or cross-linked and have relatively high melt viscosities. Thus, the entire surface is polymerized and/or cross-linked and has relatively high viscosities.

Example 51.

Gloss level measurements are obtained for the wear layer surfaces (both land and mortar areas) of various polyvinyl chloride resin sheet materials, and these measurements are made by hand-operated, manually regulated laboratory procedures at 60°C, using a Gardner Laboratories gloss meter standardized against an appropriate gloss plate for 60° measurement. Such laboratory processes are not as advanced or as refined as commercial factory processes and random blisters and irregularities cause lower gloss readings than normal. The different sheet materials of polyvinyl chloride resin are obtained by means of the methods which are generally described in example 1, and any variations in these methods are noted.

Example- 52.

Gloss level measurements are obtained for wear layer surfaces (both land and mortar areas) for various sheet materials of polyvinyl chloride resin that are produced by means of automated, with elec-. tronics regulated, commercial factory manufacturing methods, at 60° using a Gardner Laboratories gloss meter standardized against a suitable gloss plate for 60° measurement. Such commercial manufactures in factories are very advanced and refined, and provide gloss level measurements that are higher than those obtained by laboratory methods. The various sheet materials of polyvinyl chloride resin are obtained by means of methods which are generally described in example 1,

as variations in the method are noted.

Example 5 3..

Hot melt viscosities for various lead vinyl chloride plastisols are obtained using C.W. Brabender "Plasticorder" with a jacket temperature of 150°C - to equilibrium in 15 min.; a cutting speed of 30 revolutions per my.; and a test weight of 53 grams.

In the following tables, the reactive, polymerizable monomeric materials and the organic peroxide or free radical polymerization initiator are as indicated. Monomer "A" is trimethylolpropane trimethacrylate; monomer "B" is 1,6-hexanediol dimethacrylate; and monomer "C" is penta-erythritol triacrylate. The organic peroxide or free radical polymerization initiator is 40% active dicumyl peroxide, with precipitated calcium carbonate as carrier. The resin for the first two controls is 100 parts "Firestone polyvinyl chloride resin 605". The resin in the other two controls is 89.5 parts "Geon polyvinyl chloride resin 120X271" and 10.5 parts "Tenneco 501". The resin in the second table is 100 parts "Firestone polyvinyl chloride resin 605". 53.3 parts per hundred resin-plasticizer mixtures are used in the controls.

Example 54.

The procedures indicated in example 1 are essentially followed as described there, with the exception that a barrier coating or layer is used, as shown in fig. 9, and all the various colored parts and areas of the ink composition used for applying the desired pattern or design to the gelled and cooled resin polymer-plastisol mixture have the following compositions containing the same concentrations and amounts of dicumyl peroxide as polymerization initiator or catalyst :

Pigments or dyes.as desired or

required in the particular pattern or design.

The product is shown in fig. 9 just before heating and melting, inflation and foaming.

Omission of the blowing or foaming agent azodicarbonamide (1.1 parts) from the composition of the resin polymer-plastisol mixture in Example 1 gives an unblown or unfoamed final product, such as illustrated in fig. 9, where the mechanical embossing is substantially completely retained during heating and melting, inflating or foaming. In such cases where inflation or foaming does not occur, the barrier coating or layer is eliminated.

Incorporation of the blowing or foaming agent azodicarbonamide (1.1 parts) into the composition of the resin polymer-plastisol mixture from example 1 enables the production of an inflated end product,

like for example. shown in fig. 10, while the mechanical embossing is substantially completely retained during heating and melting, inflation or

■foaming. In such a case, a barrier coating or layer can be used.

Substitution of certain selected ink compositions with compositions shown above in this example that do not contain blow or foam modifiers or inhibitors, with other selected ink compositions with compositions shown later in this example that contain the blow or foam modifier or

- the inhibitor trimellitic anhydride, enables the achievement of surface embossing effects in the inflated or foamed end product.

Pigments or dyes as desired or, required,

in the particular pattern or design.

The finished inflated or foamed, chemically surface-imprinted product is illustrated in fig. 11. The mechanical embossing on the surface of the wear layer is substantially completely retained during heating and melting, and inflation or foaming in this last form of the example, as well as in all other forms of this example Example 55.

The procedures indicated in example 1 are essentially followed as described there, with the exception that none of the printing ink mixtures contain any polymerization initiators, catalysts or organic peroxides and have the following compositions:

Pigments or dyes as desired

or required by the particular pattern

or design.

A separate layer or coating such as however, a clear printing ink mixture containing dicumyl peroxide as a polymerization initiator or catalyst is applied over the whole, as shown in the structure of the product illustrated in fig. 12. Such a clear printing ink mixture has the following composition:

The structure of the product just before heating and melting, swelling or foaming, is shown in fig. 12. The structure of the product after possible heating and melting, and inflating or foaming, is not shown, but the mechanical embossing is essentially completely retained on the surface of the wearing layer through heating and melting,• and inflating or foaming as shown in other figures in the drawings .

Example 56.

The procedures indicated in example 1 are essentially followed

just as described there, with the exceptions that a barrier coating or layer is used, and none of the printing ink compositions have any polymerization initiators, catalysts or organic peroxides. Such printing ink mixtures have the following compositions:

Pigments or dyes as desired or

required by the particular pattern or design.

In addition, no separate layer or coating is used over the whole, such as e.g. a clear printing ink composition containing polymerization initiators, catalysts or organic peroxides as used in Example 55, in the product structure.

However, such polymerization initiator, catalyst or organic peroxide is mixed directly and evenly into the wear layer, which has the following composition:

The product, just prior to heating and melting, and inflating or foaming, is generally similar to the product illustrated in Fig.1 of the drawings. It is then observed that the mechanical embossing of the surface of the wear layer is substantially completely maintained through heating and melting, and inflation or foaming.

Example 5 7 .

The procedures indicated in example 1 are essentially followed as described there, with the exceptions that a barrier coating or layer is used and that none of the printing ink mixtures have any polymerization initiators, catalysts or organic peroxides. Such printing ink mixtures have the compositions described in example 56.

In addition, no separate coating is used in the product structure at all, such as a clear printing ink mixture containing polymerization initiators, catalysts or organic peroxides that was used in example 55.

However, such a polymerization initiator, catalyst or organic peroxide is mixed directly and evenly into the barfére coating, which has the following composition:

The product, just prior to heating and melting, and blowing or foaming, is generally similar to the product illustrated in Fig. 9 of the drawings, except that the printing ink compositions contain no polymerization initiator, catalyst, or organic peroxide.

It is then observed that the mechanical embossing on the surface of the wear layer. is retained substantially completely through the heating and melting, and inflating or foaming operations.

Although the present invention is described very specifically in the many preceding examples where preferred and typical embodiments of the invention idea are shown, these examples should not be considered limiting for the broader aspects of the invention idea, but only as illustrative of it. The specific materials, chemicals, patterns, designs and other special aspects of such examples are illustrative only and do not limit the broad scope of the invention which is limited and defined by the scope and spirit of the appended claims.

Claims (11)

1. Process for producing a resin polymer sheet material with surface decorative effects, comprising laying down or forming a base layer or substrate, applying a layer of a printing ink mixture forming a pattern or design, to said base layer or substrate ; applying to said printing ink mixture a resin polymer wear layer with substantially evenly distributed reactive, polymerizable and crosslinkable, monomeric materials, characterized in that a polymerization initiator is mixed into areas of the resin polymer sheet material which can initiate a polymerization or crosslinking reaction to polymerize and crosslink the reactive polymerizable and crosslinkable monomeric materials; and that the surface of the resin polymer wear layer is heated to cause said polymerization ion initiator to start a polymerization and cross-linking of said reactive, polymerizable and cross-linkable, monomeric materials in the areas of said polymerization initiator, whereby the melt viscosity of said resin polymer layer is increased in said areas. 2. Method according to claim 1, characterized in that the surface of the wear layer is mechanically embossed at elevated temperature to carry out said polymerization and cross-linking of said reactive, polymerisable and cross-linkable materials. 3. Method according to claim 1 or 2, characterized in that the polymerization initiator is mixed into certain parts of the printing ink pattern. 4. Method according to claim 1 or 2, characterized in that the polymerization initiator is mixed substantially evenly into all parts of the printing ink pattern. 5. Method according to claim 1 or 2, k. a r a c t e r i'. - certed by mixing the polymerization initiator into a separate, total printing ink layer. 6. Method according to claim 1 or 2, characterized in that the polymerization initiator . is mixed into the resin polymer wear layer. 7. Method according to claim 1 or 2, characterized in that the polymerization initiator is mixed into a barrier recoating layer in contact with the printing ink layer. 8. Method according to one of the preceding claims, characterized in that the base layer or substrate contains a blowing agent, and that the resin polymer sheet material is exposed to elevated temperatures after the polymerization and cross-linking reaction in order to inflate or foam said base layer or substrate. 9. Method according to claim 8, characterized in that selected parts of the pattern of the printing ink mixture contain a blow modifier. 10. Method according to one of the preceding claims, characterized in that the polymerization initiator used is an organic peroxide. 11. Resin polymer sheet material for use in the method according to one of the preceding claims, comprising a base layer or - substrate; a printing ink compound layer forming a pattern or design on said base layer or substrate; and a resin polymer wear layer on said printing ink mixture layer comprising substantially uniformly distributed therein reactive, polymerizable and crosslinkable monomeric materials; characterized in that there is a polymerization initiator which can initiate a polymerization or crosslinking reaction to polymerize and crosslink said reactive, polymerizable and crosslinkable, monomeric materials and increase the melt viscosity in said resin polymer wear layer.