JPS5835873B2 - Manufacturing method of resinous polymer sheet material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to decorative sheet materials, and in particular to floor, wall and ceiling coverings; desk, table and countertops; leather, textiles, wood, paper, paper products; glass, metal,
Surface layer of plastic, etc.; Upholstery, hanging cloth, clothing, etc.
Clothing materials; interior fittings for automobiles, trucks, trains, aircraft, and other vehicles or means of transportation; coverings for books, periodicals, and other publications; boxes, transport cartons, containers, and other receptacles; The present invention relates to decorative resinous polymer sheet materials having controlled selective placement of surface decorative effects for use in maps, road signs and similar and similar articles.

More particularly, the invention provides a smooth, shiny or shiny surface in some areas; or a raised, matte or matte surface in other areas; or a raised, shiny or glossy surface in still other areas. surface: or even in other areas has a smooth, matte or matte surface, and all such areas sharply contrast with each other and such decorative sheet material has been printed on. The present invention relates to a resinous polymer decorative sheet material that perfectly matches a pattern or design.

Decorative sheet materials of resinous polymer compositions have been produced for many years and one of the most common means of creating or enhancing decorative effects is e.g. smooth, glossy or shiny surfaces: raised , dull or matte surface; raised glossy or glossy;
and the surface of such decorative sheet materials by different types of contrasting finishes or effects, such as smooth, dull or matte surfaces, all of which sharply contrast with each other, or by differences in surface luster or luster. The idea was to give carefully selected parts to the people.

Although many methods have been devised to provide surfaces with such sharp contrasts, including differential mechanical embossing, inlaying or chemical embossing, and other methods, such prior art All methods of technology always left something to be desired.

For example, differential mechanical embossing in combination with pattern or design printing has always caused alignment and related difficulties.

Inlaying and chemical embalming methods are usually expensive and require a lot of processing time.

The alignment problems and difficulties '6E are therefore completely eliminated and, using methods that are not expensive or time-intensive, can be achieved by adjusting the arrangement of different surface finishes, reliefs, or differences in surface gloss. sheet with a selective surface decorative effect, in which the smooth or raised glossy or glossy surface portions sharply contrast with each other with the smooth or raised matte or matte finished surfaces; It is a principal purpose and object of the present invention to provide a resinous polymer composition in the form of a substance.

Such principal aims and objectives, as well as other principal aims and objectives, which will become apparent upon further reading and understanding of this disclosure, include:
a base layer or support; a layer of a printing composition forming a pattern or design on said base layer or support; a reactive polymerizable and cross-linked material on said printing composition layer substantially homogeneously therein; a resinous polymer durable layer comprising a reactive monomeric material; and polymerizing the reactively polymerizable, cross-linking monomeric material to increase the melt viscosity of the resinous polymer durable layer; This is accomplished by providing a resinous polymer sheet material for use in making a product having a decorative effect on a surface that includes a polymerization initiator capable of initiating a polymerization and crosslinking reaction for crosslinking. It turned out that.

The present invention further comprises: underlying or forming a substrate or support; applying a layer of printing composition forming a pattern or design on the substrate or support; substantially homogeneously therein a reactive polymerizable composition; and applying a resinous polymer durable layer having a cross-linking monomeric material to said printing composition layer; polymerizing and cross-linking said reactively polymerizable, cross-linking monomeric material. a polymerization initiator capable of initiating polymerization and cross-linking reactions for the reaction of the reactive polymerizable and cross-linking monomeric material; Heating the surface of the resinous polymeric durable layer to cause the polymerization initiator to polymerize and cross-link in the area of the polymerization initiator, thereby causing the resinous durable layer in the area to A method of making a resinous polymer sheet material having a surface decoration effect comprising increasing the melt viscosity of a resinous polymer sheet material is provided.

Such heating for sufficient time and pressure, preferably with mechanical ejection, polymerizes and/or crosslinks the reactive, polymerizable monomeric materials and also reduces the melt viscosity of the durable layer. However, only in the area immediately above the polymerization initiator or catalyst.

As a result, in such areas, mechanically embossed, flat dull or matte finishes or textures may be susceptible to elevated temperatures during any subsequent melting and/or foaming or foaming operations. It is possible to better resist softening and melting effects so that such areas remain substantially as they were originally mechanically formed into such areas.

However, in other areas where polymerization and/or cross-linking of the reactive polymerizable monomeric material in the resinous durable layer did not occur and its melt viscosity did not substantially increase, mechanical The flat, matte or matte finish or texture embossed on the surface is subject to any subsequent melting and/or
or is unable to resist the softening and melting effects of elevated temperatures during a foaming or foaming operation and thus melts sufficiently to soften and coalesce to flow and form a smooth glossy or glossy finish. It contrasts sharply with the adjacent flat, dull or matte finished polymerized and/or cross-linked areas of higher melt viscosity.

The above simplified and abbreviated illustrative method is just one of many variations in which the resinous polymer sheet materials of this invention can be made; it is merely illustrative of the broader nature of the invention. and it should be appreciated that some customary and standard steps, such as heating, gelling, cooling, drying, etc., have been omitted for purposes of clarity and brevity.

In the following specification and accompanying drawings, preferred exemplary embodiments of the invention will be described and illustrated, but the invention is not intended to be construed as specifically disclosed and illustrated therein. The invention should not be construed as limited to these embodiments, but rather should be recognized as encompassing other similar and equivalent embodiments as determined by the scope and spirit of the appended claims.

Referring now to the accompanying drawings, FIG. 1 is a fragmentary, schematic front cross-sectional view of one embodiment of the present invention, showing the resinous polymer composition in its original form prior to heating and foaming. FIG. 2 is a partial, schematic plan view of the resinous polymer composition of FIG. 1, but in its final form after heating and foaming; FIG. 3 is an embodiment of the FIG. 1 embodiment; FIG. 2 is a fragmentary, schematic, front cross-sectional view of the same, also showing its final form after heating and foaming, the cross-sectional view being taken about line 3--3 in FIG. : FIG. 4 is a fragmentary, schematic front cross-sectional view of another embodiment of the invention, showing its structure before heating and melting; FIG. 4A is a fragmentary, schematic front cross-sectional view of the embodiment of FIG. 4; FIG. 5 is a fragmentary, schematic front cross-sectional view of yet another embodiment of the invention showing its structure after heating and foaming; FIG. FIG. 5A is a partial, schematic front sectional view of embodiment 4 of FIG. 5, showing its structure after heating and foaming and subsequent removal of the release paper; FIG. FIG. 6A is a fragmentary, schematic front cross-sectional view of yet another embodiment of the invention, showing its structure before heating and melting; FIG. 6A is a fragmentary, schematic front cross-sectional view of the embodiment of FIG. 6; Figure 7 is a fragmentary, schematic front cross-sectional view of yet another embodiment of the invention showing its structure after heating and foaming; FIG. 8 is a fragmentary, schematic front cross-sectional view of yet another embodiment of the invention, showing its structure after heating and melting the resin; FIG. FIG. 3 is a fragmentary, schematic front cross-sectional view showing the resinous polymer composition prior to heating and melting, or if the resinous polymer composition contains a blowing or foaming agent; Figure 10 is a fragmentary, schematic front cross-sectional view of the embodiment of Figure 9, showing the structure of the product either after heating and melting the resin if no curing agent was included; Figure 11 shows the structure after foaming or foaming in addition to heating and melting the resin when the foaming agent was included in the resinous polymer composition; Figure 11 shows a print with a foaming or foaming inhibitor applied 10 is a fragmentary, schematic front cross-sectional view of the embodiment of FIG. 10 after heating and melting as well as foaming or foaming of the resin when included in a portion or area comprising an ink composition; and FIG. The figure is a fragmentary, schematic front cross-sectional view of yet another embodiment of the invention, in which a free radical polymerization initiator, catalyst, or organic peroxide is included in a separate layer of the product. There is.

These drawings are not drawn to scale or precision.

Certain parts and areas therein have been drawn with somewhat larger dimensions, while other parts and dimensions therein have been drawn with somewhat smaller dimensions.

This is done simply to clarify some details of small parts, such as the thickness of the printing ink composition layer drawn at increased multiples in the drawing, and to emphasize some of the more important main points. It was done to.

1-3 The present invention will be generally described and illustrated with reference to FIGS. 1-3, but these figures are for illustrative purposes and do not reflect the broader scope of the inventive concept. It is not limited to.

In these figures, a resinous polymer sheet material 10 is illustrated, which is a relatively flat sheet backing material 12.
and a base layer or support 11 of a potentially foamable polymeric composition 13 which is relatively high after mechanical embossing at elevated temperatures and pressures and subsequent foaming or foaming at even higher temperatures. , a foamed or foamed, unrestrained cellular resinous polymer composition 14 and a relatively low, relatively unfoamed and unfoamed, restrained, relatively or substantially non-cellular resinous polymer. It has composition 16.

The term "substantially non-cellular" does not mean a complete VJ [cells in which the cells, if any, are of extremely small dimensions and are significantly fewer than the number of cells in the so-called cellular portion 14. Indicates that it is a number.

The printing ink composition 18 in the form of the desired pattern or design, usually containing a number of different colorants, is subjected to mechanical embossing under high temperature and pressure and latent foaming prior to subsequent foaming and foaming at higher temperatures. The resinous polymer composition 130 is applied onto the surface.

The pattern or design of the printing ink composition 18 has certain predetermined areas or colorants 20, which in this embodiment include foam modifiers such as inhibitors, and free radical polymerization agents such as organic peroxides. Contains an initiator or catalyst.

However, other predetermined areas or colorants 21 may also include any foam modifiers or any free radical polymerization initiators or catalysts for purposes which will become apparent from further reading and understanding of this specification. do not have.

The resinous polymer composition in the form of durable layer 229 is applied substantially uniformly over the printing ink composition 18 .

As specifically noted in FIG. 3, the foam modifier or inhibitor inhibits foaming or foaming of the potentially foamable resinous polymer composition 130 in zone A, which corresponds to zone 20 and is fully aligned.

At the same time, a zone 20 containing a foam modifier or inhibitor
The foaming or foaming and expansion of the potentially foamable resinous polymer composition 13 is not inhibited or prevented in areas B that are not located directly above the.

Up to this point, all this is conventional and generally standard.

The free radical polymerization initiator or catalyst, which is also present in zone 20, is embossed in the durable layer 220 surface area located immediately above zone 20 for reasons that will be explained in more detail below. causing a flat, matte or matte finish or texture, whereas areas 20
It must be specified that the other area B of the durable layer 22, located immediately above and containing no Q free radical polymerization initiator or catalyst, has a glossy or shiny finish.

The two finishing types contrast sharply with each other.

It is understood that zone 20 not only contains a free radical polymerization initiator or catalyst, but also a foam modifier or inhibitor, as well as a predetermined pigment or colorant of printing ink composition 18 according to a multicolor pattern or design. Should.

The resulting embossed, flat, dull or matte finish or texture in area A results in a relatively low, unfoamed or non-foamed portion 16 of the resinous polymer composition 13, as well as a predefined pattern or design. Compatible completely and satisfactorily with pigments or colorants.

And, at the same time, the smooth, glossy finish in area B is due to the relatively high foamed or foamed portion 14 of the resinous polymer composition 13, as well as another predetermined pigment or colorant of the pattern or design. Match perfectly and flawlessly.

Such structures and their nature of relief, and finish or texture, and foamed or foamed areas, and perfect alignment of their individual colorings, and methods and procedures for obtaining such structures. More specific details will be described in more detail below with reference to the subsequent preferred and exemplary embodiments of the invention.

The base layer or support 11 may be a relatively flat, fibrous backing sheet material 12 and/or a foamed or non-foamed resinous polymer composition and/or other comparatively Contains flat sheet material.

If desired or required, a base layer or support 1 may be substituted for the resinous polymer sheet material 100 of the present concept.
1 as a relatively flat backing web or sheet material 1
It is possible to use 2.

Such backing sheet material 12 may include overlapping intermixed fibers and/or strands of felted or matted fibrous sheets; or nonwoven, knitted, woven, or other woven structures. or sheets of resinous polymeric compositions; or of paper or paper products or similar equivalent structures and materials.

Felt-like fibrous sheet materials include inorganic fibers such as asbestos, organic fibers such as cellulose, cotton, jute, or rayon; or polyolefins, polyamides, acrylics, glass, etc., and are the most commonly used backings. Sheet materials, but many others are equally suitable and can be used in special situations.

Such backing sheet material is disclosed in U.S. Pat. No. 3,293,099.
Nos. 4; 3,293,108 and 3,660,187 are shown in many Q prior art patents.

The thickness of such relatively flat backing sheet material 12 will vary widely depending on the particular product being made and the particular subsequent intended use.

Typically, such thicknesses range from about 10 mils to about 90 mils, but other thicknesses, especially those greater than 90 mils, can be used in special and unique circumstances. .

The relatively flat backing sheet material 12 can be used by itself as a base layer or support, or can be used with other sheet materials, such as potentially foamable or non-foamable resinous polymer compositions. .

Alternatively, the relatively flat backing sheet material 12 can be omitted entirely and the foamable or non-foamable resinous polymer composition used by itself.

Such resinous polymer compositions can be made by well-known standard and customary methods and may be made of one or more synthetic resins such as vinyl chloride polymers or copolymers or other resins such as polyurethanes. It is possible to contain more than one as the main constituent resin.

Other components of such resinous polymer compositions include: a blowing or foaming agent, such as azodicarboxamide, if a blowing or foaming agent is required; dibasic phthalate; Various accelerators/stabilizers or catalysts such as lead acid, zinc octoate, zinc oxide, lead octoate, dibasic lead phosphite, etc.; various light and/or heat stabilizers, and metallic soaps; phthalates. Plasticizers such as dioctyl acid, benzyl butyl phthalate, dibutyl sebaceous acid, etc.; Colorants and pigments such as titanium dioxide; Solvents and diluents such as methyl ethyl ketone, mineral spirits, etc.; Fillers such as clay and limestone. agents: and many other customary and well-known additives and modifiers.

Although vinyl chloride polymers or copolymers in the form of plastisols are desirable and typical synthetic resins for incorporation into resinous polymer compositions, many other resins are also suitable, not just in the form of plastisols, but also in organosols,
It is equally applicable in latex or solvent Q form.

The specific resins and their individual usage forms, as used herein, are not relevant to the essence of the inventive concept and many other suitable resins are shown in the US patents listed in the preamble. There is.

Also, although azodicarbonamide has been included herein and particularly in the examples as a desirable and typical blowing or foaming agent when a blowing or foaming agent is desired or required, many other similar or similar equivalent blowing or foaming agents are also applicable within the contemplation of the present invention.

The particular blowing or foaming agent used is not essential to the invention and many other suitable and acceptable blowing or foaming agents are shown in the above-mentioned US patents.

All that is required is that the blowing or foaming agent has a sufficiently high decomposition temperature and is not activated or prematurely decomposed during the early stage operations of heating, gelling, and mechanical embossing described below. This means that it will not occur.

Special blowing or foaming agents and their Q decomposition temperatures at which they violently outgas include: Azodicarboxamide (390'F); N-N/-dimethyl-
N-N'-dinitrosoterephthalamide (220〒):
Azobisisobutyronitrile (240'F);p-p'
-oxybis(benzenesulfonylhydrazide) (32
o'F); dinitroso-pentamethylenetetramine (8
0%) (below 370); p-p'-oxybis(barium benzenesulfonyl semicarbazide (480"F or higher)) and many others.

Such decomposition temperature values are related to the violent evolution of gas in dioctyl phthalate.

In a similar manner are many other accelerators, initiators, catalysts, viscosity modifiers, light and heat stabilizers, UV absorbers, dyes, pigments, plasticizers, antioxidants, fillers, bacteriostatic agents, disinfectants. agents, and many other additives can be included in the resinous polymer composition.

The specific properties and individual physical and chemical properties and characteristics of the various components of the resinous polymer composition are not relevant to the essence of the inventive concept and the further specific precision of such additives is not essential. Believed to be necessary and not required.

All of these ingredients are well known and conventional in the industry, and many are described in the above-referenced US patents.

Desirably, the resinous polymer composition is also a dispersion of a synthetic resin in a liquid medium.

The dispersion medium may be a plasticizer in the case of plastisols, or water in the case of aqueous latexes, or an organic solvent in the case of organosols.

Good results have been obtained with dispersions of synthetic resins in plastisolized plasticizers, and such forms are desirable and typical for the application of the present invention.

Some desirable typical plasticizers useful in forming such plastisols are dibutyl sebacate, dioctyl sebacate, dioctyl adipate, didecyl adipate, dioctyl azelate, dibutyl phthalate,
Cicapryl phthalate, dioctyl phthalate, dibutoxyethyl phthalate, tricresyl phosphate, octyl diphenyl phosphate, dipropylene glycol dibenzoate, butyl benzyl sebacate, dibenzyl sebacate, dibenzyl phthalate, butyl benzyl phthalate. .

Although plastisols are used to further describe the invention, it should be appreciated that this is not intended to exclude the use of organosols or aqueous latexes, which can also be used.

Latently Effervescent Plastisol Compositions Some desirable and typical potentially effervescent plastisol compositions are as follows: The letters located at the far right of each half of the chart facilitate the reading and understanding of each portion of the chart. It was used only to help.

They have no other meaning. All plastisol compositions shown in the preceding table are foamable resinous polymer compositions insofar as azodicarboxamide is included in all formulations.

Such blowing agents would be omitted if a non-foaming resinous polymer composition is desired or required.

If a backing sheet such as a felt or matte fibrous wafer is not used, the plastisol may be knife-coated with a doctor blade, or rolled, poured, or cast, or otherwise peeled. Possible supports can be applied, such as steel belts, rubber belts, release paper, or felt or other fibrous materials with a release coating thereon and subsequent release therefrom.

However, if a backing sheet material is used and remains part of the final product, the plastisol may be knife coated with a doctor blade or roll coated.
or by pouring or casting or otherwise applying and adhering a relatively uniform thin coating to the support sheet material in a substantially uniform manner by procedures well known in the art.

The thickness of such plastisol coatings, as applied and still wet, as a foamable resinous polymer composition, if so desired or required, ranges from about 5 mils to about 50 mils. or thicker.

After the plastisol has been applied to the supporting backing sheet material, it is then heated in an oven or other suitable heating device under relatively mild or moderate heat for about 1 minute to about 4 minutes.
Heating at elevated temperatures of from about 240° C. to about 470° C., but more commonly commercially from about 290° C. to about 350° C., for a period of minutes, whereby the plus sol solidifies and gels, so that it remains easier to handle. Then, processing becomes possible.

The relationship between temperature and time is interdependent and the higher the temperature, the shorter the time required and vice versa.

However, the elevated temperatures are not sufficiently high to activate or decompose any individual foaming or foaming agents that may be present to cause foaming or foaming of the resinous polymer composition.

The gelled hard resinous polymer composition is then cooled and printed or applied with a suitable printing ink composition into the desired or required pattern or design, which may have many colors.

The particular pattern or design used is not relevant to the essence of the invention, and any suitable pattern or design can be chosen.

Printing procedures are conventional and need no further description insofar as such procedures are well known in the industry and are described in many prior art patents.

If it is desired to obtain foaming or foaming effects of different height levels, predetermined or specific portions of the pattern or design printed on one side of the resinous polymer composition may be desired. Foam modifiers or inhibitors may be included in different amounts, concentrations, types, etc. to vary differential foaming or foaming effects.

Such differential effects are well described in the above-referenced US patents and therefore need no further explanation or description.

Of course, if no differential effect is desired as a result of the foaming or foaming process, foam modifiers or inhibitors will not be included in the printing ink composition and the level and extent of the foaming or foaming effect will generally be uniform. Become.

Some typical and well known conventional printing ink compositions are described in the above-referenced US patents.

Additionally, certain predetermined portions or specific portions of the pattern or design that are selected and printed are also described more fully hereinafter with reference to the reactive polymerizable monomers which are to be more fully described hereinafter. A polymerization initiator or catalyst is included for that purpose.

The concentration of Q free radical polymerization initiator or catalyst in the printing ink composition varies and is from about 1% to about 35 or 40% by weight, based on the total weight of the printing ink composition, and desirably from about 1 to about 1% by weight. It will be in the range of 10% by weight.

These free-radical polymerization initiators or catalysts, as they are often referred to in the industry, are perhaps more correctly identified as organic peroxides, or peru compounds, which have thermal properties in their structure. It has strong chemical characteristics due to the presence of an unstable oxygen-oxygen configuration (ie, 0-0-, peroxy group).

Such groups usually decompose when heated to some high temperature to form free radicals and initiate the polymerization reaction.

The particular free radical initiator or catalyst selected for a particular polymerization or reaction will depend on the temperature at which the particular reaction or polymerization occurs, the rate of decomposition of the free radical initiator or organic peroxide, and the Depending on the rate of generation, the presence of metal ions or the diluent solvent when the organic peroxide is supplied commercially, the % peroxide and % oxygen in the analysis
According to the activation energy (Kca11 mol),
Determined by etc.

Upon further reading and understanding of this disclosure, it will become apparent that dicumyl peroxide is a desirable and typical organic peroxide or free radical polymerization initiator or catalyst for use with most polymerizable active monomers. Will.

Such preference is fundamentally due to the normal gelling temperature of the plastisol used, to the normal melting temperature of the resinous polymer composition used, and to the normal decomposition temperature of the blowing or foaming agent used. This is based on the fact that dicumyl peroxide is highly desirable in relation to its one-minute half-life temperature.

However, it goes without saying that many other organic peroxides or free radical polymerization initiators or catalysts are suitable and suitable for applying the gist of the inventive concept.

For example, dibutyltin dilaurate would be a desirable and typical crosslinking catalyst if different resinous polymer compositions such as polyurethanes are used.

Other desirable and typical organic peroxides and Peruvian compounds include: di-tert-butyl peroxide 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane 2. 5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3 ditertiary amyl peroxide tert-butyl peroxide-2-hydroxyethyl a・a/-bis(tert-butylperoxy) diisopropylbenzene peroxide Benzoyl peroxide diisobutyryl peroxide 2,4-dichlorobenzoyl peroxide diisononanoyl peroxide decanoyl peroxide lauroyl peroxide acetyl peroxide succinic acid peroxide his-p-chlorobenzoyl 2,5-dihydroperoxy-2,5-dimethylhexane Cumene hydroperoxide Tert-butyl hydroperoxide p-menthane hydroperoxide Diisoprobyl benzene hydroperoxide 1-1 ・
3,3-Tetramethylbutylhydroperoxide di(n-propyl)peroxydicarbonate diisopropylperoxydicarbonate di(nibutyl)beroxydicarbonate di(2-ethylhexyl)beroxydicarbonate dicyclohexylperoxydicarbonate Cetyl peroxydicarbonate bis(4-tert-butylcyclohexyl)beroxydicarbonate tert-butylperoxyisopropyl monocarbonate 2,2'-azobis(isobutyronitrile) l-bis(tert-butylperoxy) )-3・3・5-)IJ Methylcyclohexane tert-butyl peroxyacetate tert-butyl peroxyisobutyrate tert-butyl peroxy-2-ethylhexanoate tert-butyl peroxypivalate peroxyneodecanoate tert-butyl peroxymaleic acid ditert-butyl diberoxyphthalate 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane 2,3-dimethyl-2,5-bis(octanoylperoxy)hexane tert-butylperoctanoate Tributyl perbenzoic acid Acetyl peroxide cyclohexylsulfonyl peroxide Acetyl sec-butylsulfonyl 2-tert-butylazo-2-cyano-4-methoxy-4-
Methylpentane 2-tert-butylazo-2-cyano-4-methylpentane 2-tert-butylazo-2-cyanopropane peroxide Methyl ethyl ketone peroxide 2,4-pentanedione peroxide cyclohexanone Compounds include several types of peroxides and cover a very wide range, all of which, under selected conditions, individually affect the gelling temperature of plastisols, the melting temperature of plastisol and resinous polymer compositions, and the foaming and foaming temperatures. Although used in reference, they are typically commercially available at about 300 below, 350 below, and 3
It should be noted that the range is 95'F.

For certain purposes of the present invention, preferred peroxide ranges have one-minute half-lives of from about 272 degrees to less than about 376 degrees, with a particularly preferred commercial range having one-minute half-lives of from about 305 degrees to about 345 degrees. It attracts attention as having.

The desired 1 minute half-life range of from about 272 and below to about 376 and below is suitable for use after plastisol gelling operations and primarily during mechanical embossing operations, or possibly foaming and foaming operations, as discussed in more detail below. will most easily allow satisfactory and sufficient cross-linking of the reactive polymerizable monomers in the upper durable layer even during the early portions of the process.

In this way, mechanical embossing takes place after the gelling operation and is maintained throughout the expansion and foaming cycle in those areas where cross-linking of the polymerizable reactive monomers occurs.

If cross-linking of the reactive polymerizable monomers occurs too early in the overall operation, such as during the initial plastisol gelling operation or earlier, the desired mechanical relief may become difficult or impossible to achieve. It might even be possible.

Similarly, if the cross-linking of the polymerizable active monomers occurs too late, such as during later stages of the foaming or foaming operation, it may be because some embossed areas of the coating layer are mechanically embossed. It will be too late to hold the engraving.

The concentrations of the remaining components of printing ink compositions, including resins, pigments and dyes, solvents and diluents, foam modifiers and inhibitors, plasticizers, etc., are customary and in accordance with prior art patents such as the previously mentioned U.S. patents. It is within the scope described in the technology.

With respect to individual foam modifiers or inhibitors, the preferred and typical examples of such Three examples are trimellitic anhydride, fumaric acid and benzotriazole.

Some desirable typical printing ink compositions are: The printed and gelled latent expandable plastisol is then dried and a durable layer in the form of a resinous polymer composition or plastisol is applied thereon. Apply.

Such durable layers include resins (desirably and typically medium or low molecular weight polyvinyl chloride), plasticizers, stabilizers, pigments or dyes (in rare cases), solvents and diluents, viscosity modifiers and Contains customary or standard ingredients such as regulators and similar additives and substances.

Concentrations of such ingredients are conventional and standard and are within the ranges set forth in the above-mentioned US patents.

However, in addition to this, the durable layer composition also contains further components comprising one or more reactive polymerizable monomeric substances, the polymerization and/or cross-linking of which is as described above. It can be initiated by polymerization initiators or organic peroxides.

Such a polymerization initiator is conveniently placed at a predetermined portion of the pattern or design of the printing ink composition, whereby a predetermined portion of the reactive polymerizable monomer located immediately above it is polymerized and or some other predetermined portion of the pattern or design of the printing ink composition that is cross-linked, but does not contain any polymerization initiator therein, or the colorant is located on the reactive polymerizable Monomers are not polymerized and/or cross-linked.

The intrinsic viscosity of the polyvinyl chloride resin used in such durable layer compositions is determined by A.I. before the mechanical embossing procedure. S. T,M.
As measured and defined by D-1243-66, approximately 0
．． 6 to about 1.2, but depending on conditions and circumstances, about 1.

Heights up to 6 are also possible and this will be described more fully later.

The reactive polymerizable monomer is substantially homogeneously contained in the durable layer and contains at least two sites of olefinic unsaturation within its molecule.

Such monomers must be capable of polymerization at the desired high temperature, usually above the gelation temperature of the plastisol but below the blowing agent decomposition temperature.

Such polymerization occurs in selected portions of the printing ink composition or in all areas of the durable layer immediately above the free radical polymerization initiator or organic peroxide disposed in the colorant.

Desirable and typical cut flower polymerizable monomers include: fumaric acid diallyl maleate diallyl itaconate diallylphthalic acid diallyl dimethacrylate ethylene glycol diacrylate ethylene glycol dimethacrylate diethylene glycol diacrylate diethylene glycol dimethacrylate Acid triethylene glycol diacrylic acid triethylene glycol dimethacrylic acid tetraethylene glycol diacrylic acid tetraethylene glycol dimethacrylic acid polyethylene glycol diacrylic acid polyethylene glycol dimethacrylic acid 1,3-butylene glycol dimethacrylic acid 1,4-butylene Glycol diacrylic acid 1,3-
Butylene glycol diacrylic acid l/4-Butylene glycol diacrylic acid l/4-butanediol dimethacrylic acid l/6-hexanediol diacrylic acid l/6-hexanediol methacrylic acid allyl acrylic acid allyl diacrylate neopentyl glycol Neopentyl glycol dimethacrylate Bisphenol A (ethoxylated) divinylbenzene divinyl toluenyl methacrylate trimethylol propane triacrylate trimethylol propane triacrylate pentaerythritol trimethacrylate glyceryl cyanuric acid triallyl tetraacrylate pentaerythritol Pentaerythritol Tetramethacrylate 1.4-Butanediol Dimethacrylate Such monomers are polyfunctional and include difunctional, trifunctional and tetrafunctional monomers.

However, if desired, it is possible to include an amount of monofunctional monomers in the durable layer mixed with the polyfunctional monomers.

Such combinations often have unique and highly desirable characteristics and properties.

When the polyfunctional monomers include monofunctional monomers, they are present in an amount of about 5 to about 50 weight percent, based on the total weight of all monomers in the resinous durable layer formulation.

The total monomer weight in the durable layer is from about 5 to about 40 parts by weight per ioo parts resin (phr) in the durable layer formulation, or desirably 100 parts by weight in the resinous durable layer formulation.
from about 15 to about 35 parts by weight per part resin (phr).

The particular reactive polymerizable monomer or monomers selected for a particular use must, of course, be compatible with or dispersible in the resin that represents the major component in the resinous durable layer formulation. Must be.

It is usually contained in polyvinyl chloride copolymers, polymers or homopolymers.

That is, the active polymerizable monomer must be miscible or dispersible with the base resin in substantially all proportions and must be able to separate into separate, distinct layers or portions or be present in the resinous durable layer composition. It must be easily and intimately dissolved or dispersed therein without occupying separate separate parts or phases.

And, of course, the reactive polymerizable monomer must also be relatively inert at low temperatures and non-reactive with respect to the other components of the resinous durable layer composition.

The thickness of such resinous durable layer compositions, when applied to an originally printed pattern or design and still wet, ranges from about 2 mils to about 30 mils, or depending on special circumstances, requirements. , or thicker if conditions so require.

Desirable and typical formulations for the durable layer are described in the above-identified US patents, except that no reactive polymerizable monomers or monomers are included therein.

After the durable layer containing the reactive polymerizable monomer is applied to and adheres to the printed pattern or design of the printing ink composition, it is heated in an oven or other suitable equipment under gentle heat for about 1 minute to 10 minutes. About 240 below or about 4 for about 4 minutes
It is heated at an elevated temperature below 70°C, whereby it hardens or tightens and gels so that it can be easily handled in subsequent operations.

Temperature and time are interrelated and interdependent and the higher the temperature the shorter the time of heat application and vice versa.

However, the elevated temperature must not be so high as to activate or decompose the blowing or foaming agent normally present therein.

Also, the temperature and time must be too high to cause polymerization of the reactive polymerizable monomer in the durable layer.

As will become apparent upon further reading and understanding this disclosure, polymerization and cross-linking of the monomers in the durable layer occurs during the subsequent embossing step, which occurs under approximately the same temperature as the preceding gelation step. However, it is usually contemplated that this occurs under applied pressure so that the surface relief of the durable layer and the polymerization of the reactive polymerizable monomer occur during the same operation.

As previously mentioned, such a temperature is, of course, below the temperature at which the blowing or foaming agent in the plastisol becomes activated or decomposes and violently releases its gas.

Some desirable and typical durable layer compositions are as follows: It is emphasized that in the following mechanical embossing procedure, a flat, dull matte finish or texture is obtained, which is free from roughened surfaces. Without waves, with contours, with humps,
Wrinkles are applied or something similar is done.

Such may be prepared by applying a suitable pressure plate or similar tool, or by making the surface of the durable layer smooth, smooth, such as a fibrous paper surface, uneven or roughened metal surface, fibers or any other rough or granular material. This is accomplished by pressing against a roughened or preferably corrugated or contoured surface, such as a matte or glossy surface.

The depth of mechanical embossing can be as small as a fraction of a mil or at most about 15 mils, but is dependent on the type, thickness, and nature of the durable layer to be so mechanically embossed, desired or required. From about 1 mil to about 4 mils depending on the decorative effect being done, the type and form of mechanical embossing, etc.

When the mechanical embossing procedure is completed, the entire surface of the durable layer is embossed to temporarily give it the desired flat, dull matte finish or texture throughout.

Such a finish or texture is substantially completely devoid of shine, shine, luster or shine.

Its surface is regularly or irregularly, predetermined or randomly roughened, corrugated, unroughened,
Numerous tiny bumps, protrusions, bumps, which may be wrinkled or knobbed and give it the desired flat, dull matte appearance.
It will have points, nodules.

Mechanical embossing can take the form of very large numbers of very fine lines, which are straight and parallel, or spiral curves, about 60 or 80 lines per inch.
books or 100 or more, or it presses paper, woven material or woven, knitted or non-woven fabric against the surface of the durable layer to create the desired finish or texture on the surface. It is also a result of this.

Mechanical embossing to produce the desired flat, matte finish or texture or other finish is about 2 pounds per square inch depending on the local temperature, which ranges from about 240'F to about 4701-4000F. From the low pressure of about 30
Performed under pressure up to 0 pounds.

If pressure is applied in a surface plate, the pressure is approximately 1
It will be maintained for a period of time from 0 seconds to at most about 4 minutes.

If the pressure is applied by the heated embossing roll method, the temperature and pressure will be in the higher part of the range, but the time of applying the pressure will be correspondingly relatively short. It will be like this.

However, threading or wrapping a resinous polymer sheet material around a portion of the outer periphery of a heated embossing roll can be used to extend the time of heat application.

However, the applied pressure must be sufficient to achieve good adhesion between the heated die surface and the resinous polymeric material being embossed.

The temperatures and pressures achieved during the embossing procedure are usually sufficient to activate or decompose the free radical polymerization catalyst or organic peroxide within a predetermined portion of the IJ ink composition; This will result in polymerization or cross-linking of reactive polymerizable monomers located on such predetermined moieties.

As a result, such portions of the durable layer will have an increased melt viscosity therein and a harder, more resistant surface which will resist any softening or softening during subsequent heating involved during the foaming or foaming procedure. It can also resist the tendency to melt.

In this way, such parts can retain their flat, matte relief surface finish or texture through higher heating during foaming and foaming operations.

However, on the other hand, the predetermined portions of the durable layer that are located above the portions of the printing ink composition that do not contain any free radical polymerization initiators or organic peroxides do not substantially polymerize or cross-link, resulting in increased melting. have no viscosity and do not possess a harder, more resistant surface, and as a result they are subject to some softening or melting tendency that occurs when they are exposed to the higher heat of foaming or foaming operations. It resists softening, melting and flowing to coalesce into a glossy finish with relatively high gloss and shine.

Such a glossy surface is extremely smooth and flat and reflects any light incident upon it extremely well, which is in sharp contrast to a flat, matte finish, which is smooth and flat. It is neither bright nor reflective to any light incident upon it.

The contrast produced by the finishes or textures of these two types is striking.

The final product in one of its forms bears a striking resemblance to ceramic tile flooring, such as that commonly found in bathrooms for both floors and walls.

The smooth, glossy or glossy finish is very similar to burnished or fired ceramic tiles;
In contrast, flat matte surfaces closely resemble grout or cementitious materials placed between glazed ceramic tiles.

Such unusual and contrasting finishes and textures are produced during and as a result of the higher temperatures common in foaming and foaming operations.

The multilayer assemblage also includes: a backing sheet material and/or a potentially foamable (or non-foamable) plastisol; a printed pattern or design of the printing ink composition, portions thereof or coloration. the agent contains a modifier or inhibitor and a free radical polymerization initiator or organic peroxide; the other parts thereof or the coloring agent do not contain a modifier or inhibitor or a free radical polymerization initiator or organic peroxide;
and an upper durable layer containing a reactive polymerizable monomer substantially uniformly therein, which is mechanically embossed over its entire surface and then heated to a sufficiently high temperature to form a resinous polymer composition. It is possible to melt the greaseproofing agent in the material and also to activate or decompose the foaming or foaming agent in the potentially foamable plastisol to cause intense foaming or foaming therein. .

Furthermore, the surface of the durable layer is raised to a higher temperature whereby these areas of those which possess no higher melt viscosity or polymerized or cross-linked monomers soften, melt and flow resulting in a smooth, glossy, glossy surface. form.

And of course other areas possessing higher melt viscosities and polymerized or cross-linked monomers will withstand higher temperatures and will not soften, melt or flow and will have those flat, dull matte surfaces. Retains surface finish and texture.

The temperature of the entire assembly must reach the melting temperature of the resin to obtain the desired maximum strength.

The melting rate is usually around 300 ml depending on the particular polymeric product used
Obtained at temperatures from below 25°C to about 470°C.

Such temperature must also be sufficient to activate and decompose the individual blowing or foaming agents present in the plastisol.

It was again observed that the foaming and foaming temperatures, as well as the melting and gelling temperatures, are the temperature of the ambient air and not the temperature of the product being exposed to such ambient air temperature.

Reference to the drawings, and in particular to FIGS. 2 and 3, will clarify the effects that occur during such expansion and foaming.

Plastisols or inherently foamable resinous polymers initially contain a foaming or foaming agent, such as azodicarboxamide, which is substantially homogeneously dispersed therein.

However, those portions of the printing ink composition 18 located in the A-band additionally contain foaming or foaming control agents such as inhibitors, and therefore those portions of the resinous polymer composition located below the A-band is relatively non-foaming or foaming due to the inhibitory action of the foaming or foaming inhibitor.

On the other hand, the printing ink composition 18 located in the B band
These portions of the resinous polymer composition did not contain foaming or foaming control agents such as inhibitors and therefore those portions of the resinous polymer composition located below the B zone were relatively foamed or substantially completely foamed. form.

Such action is well described in the above-referenced US patents.

Moreover, these portions of the printing ink composition 18 in the A-band also contained free radical polymerization initiators or organic peroxides that could be activated or decomposed during the embossing operation to form the durable layer 22.
The reactive polymerizable monomers therein were polymerized and/or cross-linked and the melt viscosity of such portions increased.

As a result, such parts retained their flat, matte finish or texture through foaming or foaming operations.

However, on the other hand, these portions of the printing ink composition 18 in the B zone do not contain any free radical polymerization initiators or organic peroxides and therefore the polymerizable monomers in the durable layer do not undergo polymerization or cross-linking and The melt viscosity of such parts also did not increase.

As a result, such parts can withstand the high temperatures of the foaming or foaming cycle, and they melt, soften and flow in such zones to form a smooth, glossy and glossy surface. .

Available in smooth, glossy or glossy finishes,
When referenced in comparison to maintaining a flat or dull matte finish, the following numerical relative gloss levels and ranges may exist for satisfactory application of the principles of the inventive concept.

Smooth, glossy or glossy finish area is approximately 15
flat, matte finish areas should have a gloss level ranging from about 70 down to about 3, or less; The difference in gloss level between two contrasting finishes should be in the range of at least about 10 at gloss levels below 50 and at least about 20 at gloss levels equal to or greater than 50.

The gloss level values according to such numbers are A, S, T, M, 5.
23-67 (1972) at an angle of 600.

A smooth glossy or glossy finish compared to a flat, dull or matte finish.

The references should be viewed as merely exemplary or preferred embodiments of the invention.

These terms or terms are comparative or relative terms or terms and are used solely or primarily to indicate differences in gloss levels.

For example, the gist of the inventive concept is to obtain a smooth, glossy or glossy finish on some selected areas, and to obtain a smooth, glossy or glossy finish on other selected areas. Equally applicable is again keeping the difference in gloss level values greater than about 20 as long as the gloss levels included in such embodiments are greater than about 50.

Such a contrast between smooth and extremely smooth eliminates the mechanical embossing step with a rough surface and thus replaces it with plate pressing or pressure-roll operation with an extremely smooth, highly polished surface, thereby improving the resin quality. It is possible to obtain by giving the entire surface of the durable layer an extremely smooth, smooth, shiny, glossy or glossy finish.

As previously described in connection with the foaming and foaming stages, high temperatures and pressures are subsequently used as well, thereby cross-linking printing inks during heated platen pressing or pressure roll operations. The multifunctional reactive polymerizable and crosslinking monomers in the durable layer that overlies the polymerization and crosslinking initiators in the composition effectively resist such heat and pressure and these individual It is possible to "freeze" the areas so that they retain their extremely smooth, shiny, glossy or glossy finish through such subsequent foaming or foaming operations.

However, other areas containing monomeric materials that are not located above any polymerization or cross-linking initiator or organic peroxide still contain such monomeric materials in an unpolymerized or uncross-linked state. containing, thus softening, melting and flowing and thus losing some of their super smooth, shiny, glossy or glossy finish but super smooth, shiny, glossy or glossy. fully develop or retain their previous extremely smooth, shiny, glossy or glossy finish at least 20 units less in gloss level than the gloss level of the glossy finish.

Referring to Figures 1 to 3 for purposes of comparison only, the use of the alternative procedure described in the previous sections is therefore Area I.
BJ can be smooth, shiny or shiny, but area "A" will indicate that it is more smooth, shiny or shiny.

In some cases, the foaming or foaming action of a potentially foamable plastisol can cause gases generated or liberated by the foaming or foaming agent to escape upwardly from the heated plastisol and penetrate into the durable layer. Areas that undesirably affect the smoothness and flatness of the durable layer and have a particularly low melt viscosity, or monomers therein that are not substantially polymerized and/or cross-linked, or smooth, shiny or It was found to be strong (and violent in nature) enough to affect shiny surfaces.

Such would be destructive to the smoothness of their surfaces and undesirable from an aesthetic point of view.

Moreover, such influences a strong contrast between a smooth, glossy or glossy surface and an adjacent textured, flat, matte or matte surface.

This undesirable effect is only about 6 mils or less, and a relatively thin barrier coating or layer having a thickness as low as about 1 or 2 mils may be applied before the printed pattern or design is applied. This can be avoided by overlaying the foamable plastisol or alternatively by applying such a barrier coating over the printed pattern or design before application of the durable layer.

Such a barrier coating or film effectively prevents gas from escaping upwardly from the expanded or foamed plastisol and penetrating into the durable layer.

The barrier layer can be applied as a film, but is usually applied as a thin layer of a resin such as a vinyl chloride polymer or copolymer having a relatively very high molecular weight as a plastisol resinous polymer composition.

Gelation of such plastisol barrier layers is naturally carried out at elevated temperatures below the activation or decomposition temperature of the foaming or foaming agent and the polymerization initiator or organic peroxide.

The thickness of the barrier coating or layer is determined by the fact that the foam control agent or inhibitor exerts its foam control or suppression effect downwardly through the barrier layer into the plastisol during the foaming operation or polymerization and/or cross-linking of reactive polymerizable monomers. It should not be so large that it prevents the polymerization initiator from exerting its effect upwards.

Some desirable and typical barrier coating formulations are: BC-IBC-2 Polyvinyl chloride, high molecular weight, 89-90 dispersion grade, intrinsic viscosity 1.4 Polyvinyl chloride, high molecular weight, 11-10 formulation Resin, intrinsic viscosity 0.9 Dioctyl phthalate 6 Epoxidized soybean oil 55 2,2,4-trimethylto3-bentanediol diisobutyrate Butylbenzyl phthalate Polydodecylbenzene Ba-Zn phosphite Stabilizer Ultraviolet absorber Organic pigment 6.9 9 8.5 7.25 0.32 0.01 8.8 19.6 5.5 0.32 0.01 (Parts by weight based on 100 parts by weight of resin, phr >? Rie is ethoxyl 1 Hinonylphenol, MiIJl
Other additives and agents can also be used, such as plasticizers or other plasticizers and stabilizers, solvents or diluents, fillers, and the like.

The modified base or support layer 11 of FIGS. 4 and 4A includes only a fibrous backing sheet material and other layers such as non-foaming or potentially foamable resinous polymeric compositions or other sheet materials. As mentioned earlier, it is possible to omit it.

Such modifications are illustrated in FIGS. 4 and 4A, which depict, respectively, the resinous polymer sheet material before and after completion of the embossing and subsequent heating steps in its manufacture.

In these drawings there is shown a relatively flat backing sheet material 32 of a fibrous nature, such as asbestos felt, on which the desired pattern or design is printed, usually in multiple colors, with a printing ink composition 38. A resinous polymer sheet material 30 is shown comprising.

If the asbestos felt 320 surface is too uneven, hairy, fibrous, or irregular, it may be smoothed or leveled, such as with an acrylic paint, if necessary, before printing the printing ink composition 38 thereon. A resinous polymer coating may be applied to the asbestos felt 32.

No foam modifiers or suppressants are included in any part of the pigment of the printed pattern or design.

However, while a free radical initiator or organic peroxide is included in portion 40 of the printed pattern or design, no free radical initiator or organic peroxide is included in portion 41.

A durable layer 42 is then applied in the conventional manner to the surface of the printed pattern or design and substantially homogeneously contains the polymerizable reactive monomer therein.

Durable layer 42 is then embossed throughout at sufficient pressure and at a sufficiently elevated temperature for a sufficient period of time to provide a desired finish or texture on its surface, such as a flat, matte or matte finish or texture. cause

During such mechanical embossing, the reactive polymerizable monomers in the durable layer 42 polymerize and/or cross-link and the melt viscosity increases, but it does not interfere with the free radical polymerization initiators or Only in those parts located directly above the organic peroxide.

All other areas that are not located on any free radical polymerization initiators or organic peroxides do not contain any polymerizing and/or crosslinking monomers in the durable layer and the melt viscosity of such areas is also Substantially unchanged.

The result is a durable layer that also has a relatively high melt viscosity when the mechanically embossed sheet material is raised to higher temperatures, somewhat similar to those that would exist under foaming or foaming conditions. The polymerized and/or cross-linked portions are able to withstand the softening and melting effects of such heating and retain their mechanical relief and remain flat, dull or matte in appearance. .

However, other areas that do not polymerize and/or cross-link and possess a relatively higher melt viscosity soften, melt and flow together to form a smooth, glossy and shiny appearance. .

A relatively flat, dull or matte finish or texture is indicated by the reference letter A in FIG. 4A and such areas are areas 40 containing free radical polymerization initiators or organic peroxides. and the printed patterns or designs of the individual colors containing such materials are specifically and precisely matched.

Also, a relatively smooth, glossy or glossy surface is indicated by the reference letter B and is present on areas of the printing ink composition that are free of free radical polymerization initiators or organic peroxides. and thus perfectly and precisely match such areas containing printed patterns or designs of different colors.

Note the small bumps in the durable layer 420 surface in the A-band.

These will be discussed in more detail later in this article.

Variations on Figures 5 and 5A As already mentioned, the base layer or support 11 simply comprises a resinous composition and other layers such as relatively flat, fibrous sheet material, or sheet material Can be omitted.

Such changes are illustrated in Figures 5 and 5A, which depict the resinous polymer sheet material before and after completion of the mechanical embossing step and the foaming or foaming procedure, respectively.

In these figures, a resinous polymeric sheet material 50 is shown including a relatively flat and relatively thin sheet of release paper 55 of a conventional commercially available nature.

On top of such release paper 55 is deposited or laid a layer of a potentially foamable resinous polymer composition 530 containing a conventional foaming or foaming agent such as azodicarbonamide.

The surface of the potentially expandable plastisol 53 is gelled and printed with printing ink set #! containing a free radical polymerization initiator or organic peroxide and individual pigments or colorants. 75B in 60 areas, whereas another area 61 contains no free radical polymerization initiators or organic peroxides, but contains different pigments or colorants.

No portion of printing ink composition 58 includes foam modifiers or suppressants.

Durable layer 62 is then applied to the surface of printing ink composition 58 and substantially homogeneously includes therein an amount of reactive polymerizable monomer.

The durable layer is then machined under sufficient pressure and at a sufficient temperature and for a sufficient length of time to create the desired flat, matte finish or texture on the durable layer in an all-over relief pattern. during which time the reactive polymerizable monomers usually polymerize and cross-link.

A conventional foaming or foaming operation is then carried out at a higher temperature whereby the foaming or foaming agent causes expansion of the resinous polymer composition.

Such expansion is well illustrated in Figure 5A.

At the same time, the highly polymerized or cross-linked monomers in zones 60, which also have high melt viscosities, resist softening or melting effects during foaming and foaming operations, and such zones 60 provide the desired flat, glossy remains with no or matte finish or texture.

However, the areas 61 that are not located on any part of the printing ink composition 58 that contain any free radical polymerization initiators or organic peroxides do not polymerize or cross-link and do not have a high melt viscosity and It is not possible to withstand the softening or melting tendencies that occur during the heating of the foaming and foaming cycle, so that such areas melt and flow together to form a smooth, glossy or glossy surface. This forms a sharp contrast to the flat, matte finish or texture of area 60.

Area A is again flat and matte, while area B is smooth and glossy or glossy.

As long as there are no foam modifiers or inhibitors in the printing ink composition, foaming or foaming is uniform and no chemical relief effect is realized on the surface of the durable layer.

Small ridges are shown on the durable layer 620 surface in zone A.

These will be discussed in more detail later in the text.

Following the foaming or foaming cycle, a relatively flat and relatively thin sheet of release paper is removed from the bottom of the resinous polymer composition.

However, if the resinous polymer composition, the printing ink composition, and the durable layer have sufficient strength to allow their handling, or if therefore another support is provided, foaming and the release paper may be removed prior to the forming operation.

Moreover, the resinous durable layer 62 is a polymerization initiator or organic peroxide that can be activated or decomposed at a temperature much higher than the decomposition or activation temperature of the polymerization initiator or organic peroxide in the printing ink composition 58. It is possible to have the substances substantially evenly incorporated therein.

Therefore, after the polymerization and/or cross-linking of the reactive polymerizable monomers in Zone A is substantially complete, it is possible to raise the temperature of the ambient air to obtain the following results.

Zone A, which contains polymerized and/or cross-linked monomers and has a high melt viscosity, retains its appearance and its prominence.

Zone B develops its smooth, glossy or glossy appearance as before.

So far, only the polymerization initiator in zone A has been activated and/or decomposed.

Polymerization initiators or organic peroxides in the durable layer are still not activated or decomposed due to their higher activation temperature.

However, if the temperature is raised high enough to cause foaming or foaming, then the polymerization initiator or organic peroxide in the durable layer becomes activated or decomposed, thereby eliminating any reactive polymerization in the durable layer. Monomers, including zone B, polymerize and/or cross-link.

As a result, the durable layer 620 surface in zone A is embossed;
The durable layer 620 surface in zone B has a flat, matte or matte textured finish, whereas the durable layer 620 surface in zone B has a smooth, glossy or glossy finish, but both zones A and B The composition contains reactive polymerizable monomers that are polymerized and cross-linked and that the fraction possesses a relatively high melt viscosity.

Variation of FIGS. 6 and 6A A further variation of the gist of the inventive concept is illustrated in FIGS. 6 and 6A.

What is shown therein is a conventional base layer or support comprising a relatively flat, fibrous backing sheet material 72, such as asbestos felt, upon which printing ink is applied in the form of a desired multicolored pattern or design. Composition 78 is applied, with predetermined components or colorants 80 comprising a free radical polymerization initiator or organic peroxide and an individual pigment or colorant.

The predetermined separate printed portions 81 of the printing ink composition 78 on the surface of the fibrous backing sheet material 72 do not contain any free radical polymerization initiators or organic peroxides, but contain different pigments or colorants. include.

There is no need for foaming or foaming modifiers or inhibitors in printing ink composition 78 or any portion thereof unless potentially foamable plastisols are present.

A top durable layer 82 comprising a resinous polymer composition is then applied to the surface of the printing ink composition 78 and substantially uniformly contains the reactive polymerizable monomer state therein.

Durable layer 82 is then heated to a relatively low temperature to gel and harden or tighten its surface and facilitate its subsequent handling and processing.

The durable layer 820 surface is not mechanically embossed of any type, and differs in this respect from the variant previously discussed with reference to FIGS. 4 and 4A.

Application of sufficient heat to raise the temperature of the resinous polymer homogeneous sufficiently to activate or decompose the free radical polymerization initiator or organic peroxide will result in polymerization and cross-polymerization of the reactive polymerizable monomeric materials in the durable layer. Bonding occurs, with a corresponding increase in the melt viscosity of the zone 83 immediately above the free radical polymerization initiator or organic peroxide in the printing ink composition 78.

However, in zone 81 it is not located on any free radical polymerization or cross-linking of the reactive polymerizable monomeric material in durable layer 82 and therefore there is no concomitant melt viscosity in zone 81. There has been no apparent increase in the number of cases.

Additionally, with respect to zone 83 where polymerization and/or cross-linking occurs with an increase in melt viscosity, an unusual and distinct relief effect occurs there which increases the surface of durable layer 82 by about 5 mils or more. will be raised or raised to a higher standard.

Such a raised or enhanced effect is achieved in area 81
There is no discernible difference and the combined relief effect of the raised sections in zone A is aesthetically superior when compared to the normal sections in zone B.

Such raised ridges, which are also observed in other embodiments of the invention, may be as small as about 1 or 2 mils, but suitably pronounced.

The exact reasons for such anomalous effects are not fully or fully understood, but it is believed to be due to differences in polymerization and/or cross-linking and melt viscosity in the two zones.

In any case, even the smallest bumps can be felt on the fingers and observed with the naked eye.

Modification of FIG. 7 FIG. 7 illustrates a further embodiment of the gist of the inventive concept.

A resinous polymer sheet material 90 is shown including a conventional, relatively flat, fibrous sheet material 92 such as asbestos felt.

Applied to a fibrous backing sheet material 92 is a layer of resinous polymeric composition 94 which is shown in a foamed state due to the pre-inclusion of a customary foaming or foaming agent such as azodicarbonamide, the latter being sufficiently enhanced. activated and decomposed by exposure to heat for a sufficient period of time at temperature.

A barrier coating or layer 95 is placed on top of the foamed cellular resinous polymer composition 94 and serves to prevent the escape of gases generated and liberated during the foaming and foaming operations.

Printing ink composition 98 is applied onto the barrier coating 950 surface in the form of a multicolored pattern or design.

Portions of the printed pattern or design contained free radical initiators or organic peroxides in areas 93, but other areas comprised no free radical initiators or organic peroxides.

No foam modifiers or inhibitors were included in any part of the printing ink composition 98 so that the foaming or foaming was uniform and the surface of the durable layer 91 applied on top of the printing ink composition 98 contained no foam modifier or inhibitor. There were no chemical reliefs of any kind.

The entire surface of the durable layer 91 has previously been mechanically embossed, but such embossment has disappeared in zone B, but is only evident in zone A.

As previously discussed, the ridges are again visible in zone A and can be easily felt with the fingers and observed with the naked eye, especially when multicolored patterns or designs are used.

Such a difference in appearance is, of course, due to the fact that the free radical polymerization initiator or organic peroxide in zone A causes polymerization and/or cross-linking of the reactive polymerizable monomeric materials in durable layer 91; This is caused by the fact that there is an increase in melt viscosity there, whereby the mechanical relief in such zones survives heating at the high temperatures of the foaming and foaming cycles.

However, in zone B, where no free radical polymerization initiator or organic peroxide is present in the printing ink composition 98, there is therefore no polymerization and/or cross-linking of the reactive polymerizable monomeric material in the durable layer 91. And there was no such increase in melt viscosity in Zone B.

As a result, such areas could not withstand the softening, melting and flow tendencies caused by elevated temperatures during foaming and foaming cycles.

Such areas B are no longer mechanically embossed and they no longer have a flat, matte or matte finish or texture but a smooth, glossy and glossy appearance.

The net effect is similar to that achieved with the products of Figures 1-3, with the major exception being that the resinous polymer composition in Figure 7 does not have any foam modification in the printing ink composition. Or, the foaming or foaming effect was not modified or inhibited by the presence of the inhibitor, but instead allowed to foam and form and expand evenly and uniformly.

In Figures 1-3, the foam modifying or suppressing agent provided the relief effect of the chemical relief process.

Variation of FIG. 8 In FIG. 8, another variation of the basic idea of the inventive concept is illustrated.

There is a resinous polymer sheet material 100 including a customary relatively flat, fibrous sheet material such as asbestos felt.
shows.

Applied to the fibrous backing sheet material 102 is a layer of resinous polymer composition 1040 which is in an unfoamed or unfoamed state since no foaming or foaming agents were originally included in the plastisol composition. It is indicated by.

In the absence of blowing or foaming agents, the resinous polymer composition is non-cellular in the final product.

Such modifications do not use barrier coatings and are not necessary unless there is any gas evolution or liberation in the plastisol during the hot melt operation at high temperatures.

Printing ink composition 108 is applied to the surface of resinous polymer composition 104 in a multicolored pattern or design.

Portions of the printing ink composition 108, such as zone 103, contain a free radical polymerization initiator or organic peroxide, whereas other portions of the printing ink composition 108, such as zone 106, do not undergo any free radical polymerization. Contains no initiators or organic peroxides.

Since there are no blowing or foaming agents in the resinous polymer composition, the final height of the resinous polymer sheet material 100 is significantly lower than that of FIG. 1, although the latter, as previously noted, A blowing or foaming agent such as azodicarboxamide is included in the resinous polymer composition 94.

As a result of the heated melting operation, zone 103 (zone A)
The mechanically embossed matte or dull texture is still retained, whereas zone 106 (zone B) has its flat, dull or matte texture smooth. It became shiny and glossy.

Such a difference in appearance is due to the fact that the free radical polymerization initiator or organic peroxide in Zone A causes polymerization and/or cross-linking of the reactive polymerizable monomeric materials in durable layer 101, thereby causing This is due to the fact that increasing the melt viscosity, such that the mechanical relief in zone A remained upon heating at the elevated temperature of the melt cycle.

However, in zone B there printing ink composition 1
08 does not have any free radical polymerization initiators or organic peroxides, so there is no polymerization and/or cross-linking of reactive polymerizable monomeric materials in durable layer 101, and no such zone B had no increase in melt viscosity.

70 As a result, such zones 106 were unable to resist the softening, melting and flow tendencies created by the elevated temperatures during melting of the resin.

Such zone B is no longer mechanically embossed and is no longer a flat, matte finish, but a smooth, glossy one.

The net effect was achieved with the products of Figure 7 with the main exception that the products of Figure 7 were foamed and foamed, whereas the products of Figure 8 were not foamed or foamed. somewhat generally similar to that given.

However, although the surface of the durable layer is very similar in both FIGS. 7 and 8, the chemical relief is slightly different.

In zone A, the raised or elevated protuberances as before were again visible.

Thus far in this disclosure, when a free radical polymerization initiator and a foam modifying or suppressing agent are used in the production of resinous polymer sheet material products, both are used in the same printed pattern or design of the printing ink composition. The main emphasis was placed on blending in the printed parts.

This is not necessarily always the case. If desired, the free radical polymerization initiator may be incorporated at one location in the printed pattern or design and the foam modifying or suppressing agent may be incorporated at another location in the print or design.

A desirable and typical printing ink composition for such a modification is as follows: Part solution edge vinyl chloride (90 parts) and vinegar Copolymer of vinyl 15ate (10 parts) Methyl ethyl ketone 83 Dicumyl peroxide Polymerization Initiator 2 pigments or coloring substances, as desired or required vinyl chloride (9 parts) and vinyl acetate 14 (10 parts)
Solvent edge copolymer with methyl ethyl ketone 66 trimellitic anhydride inhibitor 20 pigments or coloring substances, as desired or required, one desirable and typical end product is eventually obtained and illustrated in Figures 2 and 3 of the drawings. structurally similar to the final product.

Thus, if the trimellitic anhydride inhibitor
When incorporated, the lower surface of the overlying durable layer does not retain any mechanical relief imprinted thereon and is smooth, shiny, as shown in Figures 2 and 3. Has luster.

If Zone B is formulated with a dicumyl peroxide polymerization initiator, the higher surface of the overlying durable layer will be exposed to the machine stamped thereon, as shown in Figures 2 and 3. It retains the relief and is flat, matte.

Thus, the final product is visually different from the final product obtained in FIGS. 2 and 3.

The structure of the product of this embodiment is similar to that of the product illustrated in FIGS. 2 and 3, except for the reversal of the smooth, glossy or glossy finish area and the flat, dull matte texture area. would be equal to the structure.

Again, the portion of the durable layer overlying the polymerization initiator is relatively highly polymerized and cross-linked and has a relatively high melt viscosity, whereas the portion of the durable layer overlying the foam modifying or suppressing agent is The moiety is a monomer with relatively low polymerization or cross-linking and has a relatively low melt viscosity.

Such a reversal of the visual effect of the surface is often undesirable in pseudo-ceramic tile patterns or designs, where the higher areas are smooth, glossy or shiny and the lower mortar joints The areas are flat, dull or matte, but this may be desirable in other patterns or designs where a greater variety of visual effects is desired or required.

the predetermined portion of the printed pattern or design or the colorant containing the desired or required concentration of polymerization initiator or organic peroxide and any other predetermined portion of the printed pattern or design; Alternatively, it is not essential that the colorant does not contain any polymerization initiator or organic peroxide.

The polymerization initiator or organic peroxide can be included in several different parts of the printed pattern or design or in several different concentrations in the colorant.

By correct selection of the desired varying density it is possible to obtain several varying shades of surface finish or texture.

Although the sharpness of the individual contrasts may be limited to a certain extent, large changes in effects, partitions and organization can be obtained in this way.

Such changes and gradations in surface finish and texture can be achieved by the use of several different polymerization initiators or organic peroxides with several different levels of activity or different activation or decomposition temperatures. can also be obtained.

Polymerization initiators or organic peroxides with greater activity will cause the reactive polymerizable monomer to polymerize to a greater extent and increase the melt viscosity of the corresponding portion of the durable layer, thereby causing foaming. and creating greater resistance to melting, softening and flow effects during the forming cycle.

Therefore, placing a highly active polymerization initiator or organic peroxide in one area of the pattern or design to be printed will help maintain the flat, dull or matte finish of the relief applied during the embossing process. whereas, placing a low-activity polymerization initiator or organic peroxide in another area of the pattern or design to be printed will partially obliterate the raised flat dull or matte finish or texture. to obtain a different texture and/or to obtain a different gloss level or degree for a smooth, glossy or glossy finish.

In this way it is possible to obtain a large number of mattes and glosses and a large number of finishes and texture levels.

In addition to the use of multiple polymerization initiators or organic peroxides in multiple different parts of the printed pattern or design of the printing ink composition or in the colorants, additions with relatively high activation and decomposition temperatures Additional benefits are obtained by including the organic polymerization initiator or organic peroxide in a substantially homogeneous manner in the durable layer.

Thus, several different polymerization initiators or organic peroxides can be arranged to be activated or decomposed at several different process steps, thereby obtaining several different finishes or textures.

Then, at later stages, such as during the foaming and foaming cycle, the high temperature polymerization initiator or organic peroxide polymerizes and/or cross-reacts the reactive polymerizable monomers in the overall resinous durable layer. will be activated to bind.

The overall effect is thus to increase the melt viscosity of all the different areas of the resinous durable layer.

An alternative "tipped" procedure for making the resinous polymer sheet material of the present invention is as follows: a resinous durable layer as previously described with release properties and characteristics imparted thereon. Roughly textured parchment-type release paper or other roughened, uneven, wrinkled, ridged, or uneven surface, or any similar or ridge-like or variation Cast or otherwise shaped onto a suitable textured or embossed surface, such as a textured or embossed surface.

The resinous durable layer is fluid enough to flow into and completely fill all the recesses and crevices, nooks and crannies of the textured or embossed surface and thus to make the surface make and characteristics substantially equal to them.

Such a surface is highly variable and is not flat, pebbly or granular, so that it does not reflect the light rays properly but rather scatters them to some extent, resulting in a flat, dull or matte texture or floating surface. Gives a carved appearance to the eye,
If the release surface is then removed, anyone can see the shaped surface of the resinous durable layer composition.

over a resinous durable layer composition cast with a printing ink composition as previously described, or with a number of such compositions;
Apply it after gelling or adhering in the customary and standard manner.

The desired design or pattern is thus applied and, as previously described, a polymerization initiator or organic peroxide and, if desired, are added to the predetermined areas of the pattern or design to be printed. A foaming or foaming modifier or inhibitor is included, but other predetermined areas of the pattern or design to be printed are (1) free of any polymerization initiator or organic peroxide, or (2) identical to (3) different concentrations of polymerization initiators or organic peroxides; or (3) different polymerization initiators or organic peroxides having different levels or degrees of activity or different activation or decomposition temperatures.

The printing ink composition is then allowed to dry.

A resinous durable layer as previously described in the text is then applied over the dry printed pattern or design of the printing ink composition and allowed to adhere.

Heating of the printing ink composition, the polymerization initiator or organic peroxide contained therein, and the resinous durable layer to a sufficiently elevated temperature occurs, at which time polymerization of the reactive polymerizable monomer in the resinous durable layer and /or cross-linking occurs at selected predetermined portions thereof located below the polymerization initiator or organic peroxide.

However, in those portions of the resinous durable layer that are not located beneath any polymerization initiator or organic peroxide, no polymerization and/or cross-linking of any reactive polymerizable monomers occurs.

And, at the same time, the polymerized and/or cross-linked portions of the resinous durable layer develop an increased high melt viscosity.

Moreover, gelling of the resinous plastisol occurs, which facilitates further handling and processing.

A base layer or support, preferably comprising a relatively flat fibrous backing sheet of asbestos fibers as previously described, a potentially expandable resinous polymeric composition such as polyvinyl chloride plastisol, also as previously described. The objects are then laminated or bonded to the surface of the cutoff strain, preferably under pressure and elevated temperature, to form a single overall structure.

The removable textured release surface on which the durable resinous layer was initially cast or shaped is then removed and the resinous material precisely corresponds to the textured or embossed surface of the release material. Has a suitable texture on the durable layer or presents a embossed surface.

Heating to higher temperatures in a melting or foaming furnace has several effects.

Such portions of the resinous durable layer that do not contain any polymerized and/or cross-linked reactive polymerizable monomers and do not possess a relatively high melt viscosity will soften and melt and flow at such temperatures. Other resinous durable layers that form a smooth, glossy or glossy surface or finish, but have reactive polymerizable monomers polymerized and/or cross-linked thereto and have a relatively high melt viscosity. The parts resist the tendency to soften and melt at such elevated temperatures and maintain their original textured or embossed, flat, matte surface without flowing.

At the same time, foaming or foaming of the potentially foamable resinous polymer composition of the base layer or support, if any, occurs, such as foaming or foaming agents such as azodicarbonamide.

And if a foam modifier or inhibitor is included in the printed pattern or design of the printing ink composition, the foaming or foaming effect will be modified or suppressed accordingly.

The final product, of course, has the process advantage of being substantially similar to the final product obtained in the previously described method, but without requiring a separate mechanical embossing step.

In this alternative "tipped" procedure, the printing ink composition and the polymerization initiator therein and the resinous durable layer and the reactive polymerization therein are combined to effect the polymerization and/or cross-linking of the reactive polymerizable monomers. Care should be taken to apply the resinous cutoff strain to the dry printed pattern or design of the printing ink composition before heating the monomer.

This is simply the preferred or typical method.

The resinous break strain may be omitted altogether or, if desired, may be applied or adhered to the resinous durable layer prior to application of the printed pattern or design.

An important feature to be understood is that the polymerization initiator in the printing ink composition is capable of effecting polymerization and/or cross-linking of reactive polymerizable monomers and that the potentially foamable resinous polymer composition is subsequently foamed. If necessary, a barrier coating is present in case the gases formed and formed are released.

Special attention is believed to be in order with respect to the references to temperatures and temperature ranges in this disclosure.

Whenever a material is heated by passing it through a heated furnace or other heating device and the temperature of the so heated furnace is maintained at the desired temperature, especially if the material is exposed to such a heated environment. It should be recognized that the material will not reach that temperature if only exposed for a very short time.

The temperature of the material is typically lower than the temperature of the surrounding heated environment.

Such conditions normally exist during gelation of plastisols when the plastisol is passed through a heated environment containing hot air.

On the other hand, material is heated whenever it is pressed against a heated surface, such as a heated surface plate or other pressing device, and a very intimate contact is established between the heating element and the material being heated. The temperature of the material being heated will substantially approach the temperature of the heat source.

Such conditions normally exist during mechanical embossing operations where a heated platen or other embossed heated surface is pressed into very intimate contact with the material to be mechanically embossed.

This is true if a heated platen or die is pressed against the surface of the material to be heated and stamped under applied pressure, which in the present case ranges up to 200 pounds per square inch. Especially true.

Variations of Figures 9-12 So far the invention has been applied to surface parts comprising a durable layer with a flat, dull matte finish, such as produced by mechanical embossing, and in a heated oven. Emphasis has been placed on the concept of providing another surface area consisting of a durable layer with another contrasting texture or effect, such as a smooth, glossy or glossy finish.

In some cases, it may be desirable for substantially the entire surface portion of the durable layer to retain the textured finish created by the mechanical stamping operation.

Such an overall effect may be achieved in several ways, as illustrated in Figures 9-12 of the drawings.

In FIG. 9, a typical, relatively flat backing web or sheet material 112, similar to the backing sheet material 12 previously described, is illustrated.

Comparative flat, substantially uniform potentially foamable (or non-foamable) resinous polymer composition material similar to the previously described potentially foamable (or non-foamable) resinous polymer composition layer 13 113 is formed or applied over the backing sheet material 112.

Such resinous polymer composition 113 is then subjected to, for example, heating, gelling and solidifying, and cooling operations, as previously described, and 118a.

Processing includes printing or coating with a suitable printing ink composition 118 having the desired pattern or design of various colorants such as 118b, 118c, 118d, and 118e.

However, in previous embodiments of the invention, some of these printed and colored parts or areas contain amounts of polymerization initiators, catalysts, or organic peroxides, and other printed and colored parts or areas contain amounts of polymerization initiators, catalysts, or organic peroxides. All colorants, portions, or areas of the printed pattern or design of Figure 9 are similar, although the areas may contain different amounts or no initiator, catalyst, or organic peroxide. of the same polymerization initiator, catalyst, or organic peroxide in amounts and equivalent concentrations.

If desired, a relatively thin barrier coat or layer 115, such as the barrier coats or layers previously described, is subsequently applied, such as when a foaming or forming operation is used, before applying the printed pattern or design 118 thereto. Alternatively, as shown in FIG. 9, a printed pattern or design can be applied to the resinous polymer composition 113 and then placed over the potentially expandable resinous polymer composition 113.

The purpose of such barrier coatings or layers has been described above.

A relatively uniform thin durable layer 122 containing one or more reactive polymerizable monomeric materials, such as durable layer 22 previously described, is printed, gelled, and cooled into a latent foamable material. It is applied to the resinous polymer composition 113.

Gelification and solidification of the durable layer 122 occurs as previously described, followed by an overall mechanical embossing operation also as previously described.

As long as the entire surface of durable layer 122 is located over the polymerization initiator, catalyst, or organic peroxide in printing ink composition 118, polymerization and cross-linking of the reactive polymerizable monomeric material is substantially prevented. The melt viscosity increased during mechanical embossing is uniformly passed through the durable layer 122.
It is produced uniformly through 2.

Heating and melting, and foaming or foaming (if a foaming or foaming agent was originally included in the resinous polymer composition 113) occurs as previously described.

The mechanical relief on the durable layer 1220 surface remains substantially uniform even after such manipulation.

FIG. 10 shows a relatively flat, resinous polymer sheet material 120, which includes: a fibrous backing layer 11;
2; printing ink composition 118 homogeneously containing a polymerization initiator, catalyst, or organic peroxide; barrier coating or layer 1;
15; and durable layer 122, and all are substantially as previously described with individual reference to FIG.

Resinous polymer composition containing foaming or foaming agent 1
23 is used.

The steps of heating, gelling and solidifying the resinous polymer composition 123 and durable layer 122 as previously described, followed by general mechanical embossing of the surface of the gelled durable layer 122, and other previously described steps. and the customary heating and melting and foaming or foaming follow in the melting furnace.

FIG. 10 illustrates a foamed resinous polymer sheet material 123 following heating, melting and foaming.

The mechanical relief on the durable layer 1220 surface remains substantially uniform throughout.

FIG. 11 shows a relatively flat, resinous sheet material 130, which includes: a fibrous backing layer 112: a resinous polymeric composition 133 containing a blowing or foaming agent.
a printing ink composition 138 substantially homogeneously comprising an equal concentration and amount of free polymerization initiator, catalyst, or organic peroxide in all portions of the area; and a selected one of the printing ink composition layers 138; portion or area 138a
A foaming or foaming modifier or inhibitor contained only in: a relatively thin barrier coating or layer 115; and a resinous polymeric durable layer 122 substantially uniformly containing reactive polymerizable monomeric material therein.゜The foaming or foaming agent is a resinous polymer composition 133
homogeneously contained therein and heated and melted and foamed or foamed as illustrated.

However, due to the presence of foaming or foaming modifiers or inhibitors present in selected portions or areas 138a of printing ink composition 138, foaming or foaming operations are well known in the chemical embossing art. The finished relief product is illustrated in FIG.

Intermediate operations of heating, gelling and solidifying the resinous polymer composition 133, printing the printing ink composition layer 138, applying and gelling, solidifying and cooling the resinous polymer durable layer 122, and heating, melting and foaming or Forming is standard and conventional and has been described previously, so there will be no need to further explain or describe it here.

Note that the mechanical relief on the durable layer 1220 surface is maintained throughout.

Illustrated in FIG. 12 is a resinous polymer sheet material 140 which includes: a typical, relatively flat backing web or sheet material 112; potentially foamable or Non-foaming resinous polymer composition 143: A substantially homogeneous resinous polymer coating, such as transparent printing ink composition 144, having substantially homogeneously contained therein from about 1% to 35 or 40% by weight. %,
and desirably from about 1 to about 10% by weight of a polymerization initiator, catalyst, or organic peroxide; printing ink composition 148 that does not contain any polymerization initiator, catalyst, or organic peroxide:
If resinous polymer composition layer 143 includes a foaming or foaming agent, a relatively thin barrier coating or layer 1
45: heating, gelling and solidifying of the resinous polymer plastisol 143 and the durable layer 142 substantially uniformly containing one or more reactive polymerizable monomeric monomers, and the plastisol durable layer 142; Mechanical embossing of the gelled and cooled surface of durable layer 142 and subsequent heating and melting and foaming or foaming of resinous polymer composition 1430 (if a foaming or foaming agent is included therein). Standard and customary operations such as ) follow well-known practices.

Figure 12 shows the resinous polymer immediately before heating and melting and foaming or foaming (if a foaming or foaming agent is present) or following the heating and melting operation if a foaming or foaming agent is not present. A sheet material 140 is illustrated.

The mechanical relief on the entire surface of durable layer 142 remains substantially uniform throughout these heating, melting, foaming, or foaming operations.

If a blowing or foaming agent is initially included in the resinous polymer composition 143 of FIG. 12, such resinous polymer composition 143 will swell and swell generally as shown in FIG. The foamed or foamed resinous polymer composition 123 illustrated in FIG.

Similarly, if foaming or foaming modifiers or inhibitors are initially included in selected, predetermined portions or areas of the printing ink composition 148 of FIG. Composition 148 (and all layers above it) expands and bulges to generally resemble the foamed and chemically embossed resinous polymer composition 133 of FIG.

Still further embodiments of the invention leading to the retention of general mechanical relief on the surface of the durable layer through heating and melting and foaming or foaming operations can be described without the need or need for yet further drawings.

Such embodiments eliminate the presence of any polymerization initiator, catalyst, or organic peroxide from the printing ink composition, as in Figures 9-11, and in the separating layer as in Figure 12. The presence of any polymerization initiators, catalysts, or organic peroxides present is also excluded.

In this non-illustrated embodiment, the polymerization initiator, catalyst, or organic peroxide is applied directly and uniformly into the durable layer containing the reactive polymerizable monomeric material, usually the reactive polymerizable monomeric material. from about 0.5 to about 5% by weight based on the weight of
The content is preferably about 1 to about 2% by weight.

Alternatively, the polymerization initiator, catalyst, or organic peroxide is present in the barrier coating 115 of FIG. 9 from about 0.08% to about 0% by weight, based on the total weight of the barrier coating composition. .8%
And desirably, it can be included in about 0.16% to about 0.32%.

Activation and polymerization and cross-linking of such reactive polymerizable monomeric materials conventionally occur during mechanical embossing.

Retention of such mechanical relief effects is achieved by heating and melting,
and at the end of the foaming or foaming operation.

The invention will now be described more particularly with respect to the following specific examples, in which preferred and exemplary embodiments of the invention are shown.

However, such specific embodiments are primarily general illustrations of the subject matter of the invention, and the specific materials, drugs, patterns, designs, and other individual aspects are intended to be within the scope and spirit of the appended claims. Nothing should be construed as limiting the broader scope of the inventive concept except as specified.

EXAMPLE ■ A resinous polymeric sheet material as illustrated in Figures 1-3 of the drawings is prepared according to the following procedure.The base or support is felted asbestos with a smooth leveled acrylic coating applied thereon. A relatively flat 0.040 inch thick fibrous sheet with

The asbestos felt fibrous sheet is substantially homogeneously coated with about 0.0 of the potentially expandable resinous polymer plastisol composition described below.
Apply to 15 inch wet thickness: parts by weight polyvinyl chloride, medium molecular weight, general purpose 30.2 dispersion resin, intrinsic viscosity 0.99 (ASTMD 1243-6
6) Polyvinyl chloride, medium molecular weight, dispersion buffer 8.2 fat,
Intrinsic viscosity 1.0 Polyvinyl chloride, medium molecular weight, blended resin, 17.1 Intrinsic viscosity 0.9 Anhydrous silicate alumina filler 6.9 parts by weight Benzyl butyl phthalate 15.4 Alkyl phthalate plasticizer Benzyl low boiling point 9 .3 Polydodecyl Benzene Azodicarbonamide Accelerator/Stabilizer Titanium Dioxide Dioctyl Phthalate Wetting Agent 7.4 1.1 0.4 2.5 1.5 0.0 Gelation and solidification of the potentially expandable plastisol occurs in the oven It took about 3 minutes at a high temperature of about 300'F.

The temperature did not rise enough to activate or decompose the azodicarbonamide.

The gelled, potentially expandable plastisol is then
Print on ceramic brick patterns or designs as shown in Figures and 3.

Zone B is printed with a standard or customary printing ink composition containing the predetermined pigments but without any foam modifiers or inhibitors or any free radical polymerization initiators or organic peroxides.

Such standard or customary printing ink compositions include: Part solution grade copolymer of vinyl chloride (90 parts) and vinyl acetate (1015 parts) Methyl ethyl ketone 5 Pigments or colorants, as desired or required. However, zone A is printed with the following printing ink composition containing different pigments or colorants: 1 part solution grade copolymer of vinyl chloride (90 parts) and vinyl acetate (10 parts) 2 parts methyl ethyl ketone peroxide Dicumyl 6 parts trimellitic anhydride 0 pigments or colorants as desired or required The printed, gelled, potentially foamable plastisol is then dried and coated with a durable layer having the following formulation: approx.
Apply to it at a wet thickness of inches: Part Polyvinyl Chloride, Dispersion Edge, Intrinsic Viscosity 0, 8 00 Trimethylolpropane Trimethacrylate (90 ppm Hydroquinone) 5 Butyl Phthalate Pendel Plasticizer 2,4,4-Trimethyl Pentyl - 3,5-diisobutyrate alkyl phthalate Benzyl, low boiling point plasticizer 3, 8 3, 3 4, 1 Ba-Zn phosphite, heat stabilizer epoxidation tall oil 6, 4 2, 4 Durable layer plastisol gel curing and solidification is exactly 300'
Heat for about 3 minutes in a furnace atmosphere with elevated temperature below F. to complete.

The gelled durable layer is then coated with a fine, parchment-like texture at elevated temperatures of just over 300'F, which is created in the durable layer under a pressure of about 140 psig in a Watson-Stellman press. Mechanically embossed with a target pattern.

Hot embossing is carried out with polymerization and/or cross-linking of trimethylolpropane trimethacrylate in the durable layer, but only in the part of it located immediately above the dicumyl peroxide, whereas In other areas of the durable layer not immediately above the dicumyl peroxide, substantially no polymerization and/or cross-linking occurs to any significant or practical degree.

Moreover, the melt viscosity of the portion of the durable layer overlying dicumyl peroxide increases significantly, whereas the melt viscosity of the portion of the durable layer not overlying dicumyl peroxide remains essentially unchanged.

The mechanically embossed material is then heated in a melting furnace held at an elevated temperature of about 395'F for about 2x minutes.

Melting of the resin occurs with foaming and foaming of the potentially expandable plastisol in areas not immediately below the trimellitic anhydride inhibitor in the printing ink composition.

Very little blowing or foaming agent is present in the area immediately below the trimellitic anhydride.

Chemical relief differential effect is excellent. Moreover, as can be seen in Figure 3 of the drawings, elevated areas or locations of the durable layer develop a smooth, glossy or glossy finish or texture with high shine and brilliance; The low or depressed portion or mortar retains the flat, dull or matte finish created therein by mechanical embossing in a Watson-Stillman press.

The appearance of the material after the foaming or foaming cycle closely resembles a high gloss glazed ceramic tile with a flat, dull or matte finish surrounded by a grout between ceramic tiles. or give the appearance of other cementitious substances.

The different colors of the printed pattern or design of the printing ink composition are completely and satisfactorily (1) mechanically embossed smooth, glossy or glossy areas as described above and flat, matte or Matching the contrasting effects of the matte areas and (2) the chemical relief effects of the high and low areas on the surface of the durable layer described above.

Testing by method of dissolution rate in tetrahydrofuran shows that trimethylolpropane trimethacrylate does not polymerize or cross-link before mechanical embossing; it polymerizes and cross-links during mechanical embossing: and foams. and after the completion of the forming cycle still polymerizes and cross-links, but only in the area of the durable layer immediately above the dicumyl peroxide present in the printing ink composition, whereas dicumyl peroxide It is established that in all other areas of the durable layer that are not located immediately above, substantially no polymerization and cross-linking of the trimethylolpropane trimethacrylate takes place.

Furthermore, with reference to melt viscosity measurements for relatively highly polymerized and cross-linked portions and relatively low polymerized and non-cross-linked portions of the resinous durable layer, the pursuit of a melt viscosity range is an application of the principles of the present concept. It has been proven that it is suitable for

Using the conditions described in Example 1 for Brabender measurements, the torque reading for the highly cross-linked portion of the durable layer is about 1000 to about 4000 US-grams and the torque reading for the relatively non-cross-linked portion. readings from about 300 to about 900, and the difference in torque readings for two contrasting parts of the same product is at least about 2
It would be 50 US-grams.

References in the foregoing and throughout this disclosure to cross-linked polymeric materials refer to multifunctional materials such as, for example, trimethylolpropane trimethacrylate in the resinous durable layer, which is of course cross-linked and heat cured. It will be noted that only reference has been made to the polymerization and cross-linking of reactive polymerizable monomeric materials.

It should also be appreciated that the primary resin in the durable layer, such as polyvinyl chloride, is substantially uniformly and homogeneously dispersed therein and in a molten and polymerized state.

However, it is not cross-linked compared to the cross-linked and heat-cured multifunctional polymeric materials in those parts of the durable layer that overlie the polymerized or cross-linked initiator or organic peroxide. And it is still in a thermoplastic state.

There is also a complete and perfect match: the flat, dull or matte textured parts of the durable layer; the corresponding colored parts of the pattern or design of the printing ink composition: and the resinous polymer. It should be noted that the relatively unfoamed or unfoamed portion of composition 16 lies between:

At the same time, there is a perfect and unimpeachable match: a smooth, glossy or glossy finished surface; a corresponding colored part of the pattern or design of the printing ink composition; and of the resinous polymer composition. It is present between the foamed and foamed 2'-3 parts.

Regarding the measurement of the melt phase of various parts of the resinous durable layer, it is relatively more complex.

1965 of Heint and Warnitsch Productions
The report on the C,W,-Lavender Plastograph, or "Plast I-der", described in the July issue, solves such measurements with ease and with great accuracy.

Information on procedures such as "-" can also be found in journals.
197 of Obcellular Plastics January/2
It can be found on pages 23 to 32 of the monthly issue.

Brabender measurements were performed on samples of highly polymerized parts of the resin durable layer and relatively unpolymerized parts of the resin durable layer at 150°C for 15 minutes at a shear rate of 30 revolutions per minute. A state of equilibrium is reached.

A type 6 roller mixer measuring head is used for measuring the melt rheology of durable layer plastisols.

The highly polymerized portion of the resinous durable layer provides a torque reading of 2510 US-grams, whereas the relatively unpolymerized portion provides a reading of only 650 US-grams.

EXAMPLE ■ A resinous polymer sheet material as illustrated in FIG. 7 is made as follows: Following the method described in Example I except that trimellitic anhydride is removed from the printing ink composition, the composition is The product contains the following ingredients: Part vinyl chloride (90 parts) and Vinyl acetate (IQ 15 parts)
A solution edge copolymer of methyl ethyl ketone dicumyl peroxide trimellitic anhydride 3 with a pigment or colorant, as desired or required, results obtained from this example are generally similar to those obtained in Example I, but The difference is that the resinous polymer sheet material of this example is not chemically embossed and the foaming or foaming operation is substantially uniform in its effect such that the surface of the durable layer is substantially horizontal. And they must be the same height.

Flat, matte or embossed matte finishes and smooth, glossy or glossy finishes lie substantially on the same level.

Regarding the concentration of polymerized or cross-linked trimethylolpropane trimethacrylate, it is relatively high in those areas located directly above dicumyl peroxide and relatively low in areas not located directly above dicumyl peroxide. .

The melt viscosity is again relatively higher and lower as shown in Example 1.

The ridges are visible as shown in the drawings and can be felt by "finger test".

Barrier method Be-1 is used to ensure that no gas is evolved and escapes into the durable layer during foaming or foaming.

EXAMPLE ■ A resinous polymer sheet material as illustrated in FIG. In addition to omitting the trimellitic anhydride foam modifier or inhibitor from the printing ink composition, the azodicarbondiamide foaming or foaming agent is omitted from the plastisol formulation.

The results obtained in this example are generally similar to those obtained in example The molten resin is heavier and is located below the portion of the printing ink composition that contains the foam modifier or inhibitor, as illustrated in Figure 3 of the drawings. It is very dissimilar to that part of .

Such parts are identified in FIG. 1 by the reference letter A.

Substantially all of the melted plastisol in the product of FIG. 8 is similar.

Again, the flat, dull or matte texture of Zone A is retained after mechanical embossing and through melt heating at high temperatures.

However, the texture as in zone B is lost during melt heating at high temperatures and the final appearance in such zone B is smooth, glossy and shiny.

The raised or raised ridges shown in the drawings are discernible and can be felt with a "finger-test."

No blocking method is used unless blowing agents or inhibitors are included in this example.

EXAMPLE ■ The procedure described in Example ■ except that the proportions of the components of the printing ink composition containing both the free radical polymerization initiator or organic peroxide and the foam modifier or inhibitor were varied as follows. Comprising substantially as described in: Reducing clear X
Solution Edge Copolymer Plus Pigment of 90 Parts Vinyl Chloride and 10 Parts Vinyl Acetate in Methyl Ethyl Ketone 0 Anhydrous Trimeritic Oxidative Inhibitor 2040%
Dicumyl peroxide (active), precipitated carbonate 10 supported on lime The results of this example are generally similar to those of Example 2.

Again, the multifunctional reactive polymerizable monomeric material, namely trimethylolpropane trimethacrylate, polymerizes and cross-links only in the area of the durable layer located directly above the polymerization initiator, namely dicumyl peroxide. This is confirmed.

In other parts of the durable layer not immediately above the peroxide, the trimethylolpropane trimethacrylate does not effectively polymerize and cross-link.

EXAMPLE ■ The procedure generally described in Example I was followed substantially as described therein, with the following changes:
using a potentially foamable plastisol composition of p-1;
The wet thickness is approximately 18.7 mils and the thickness is approximately 300 mils.
Run 5 in a heated air atmosphere of 300' F for 3 minutes; a BC-1 barrier coating is used and its thickness is about 3 mils; it gels in a heated air atmosphere of about 300' F for 3 minutes. the printing ink composition is P-1 and contains dicumyl peroxide and trimellitic anhydride as a polymerization initiator or organic peroxide and a foam modifier or inhibitor, respectively; the inactive printing ink composition is a polymerization initiator; or organic peroxides or the like; the resinous durable layer is of W-1 composition and contains trimethylolpropane trimethacrylate as the reactive polymerizable monomer; it is approximately 12 mils thick. and gel in a heated air atmosphere for about 3 minutes at about 300°C; mechanical embossing is carried out at about 300°C for about 3 minutes against a textured parchment-type release paper with a pressure of 110 psig. Foaming and foaming takes place in a heated melting furnace for approximately 3
Run at high temperature of 95'F for approximately 2 minutes and 40 seconds.

The results obtained in this example are generally similar to those obtained in Example 2.

Areas of relatively low, relatively unfoamed mortar are embossed with a flat, matte or dull finish or texture, whereas areas of relatively elevated, relatively foamed platform. has a smooth, glossy or shiny surface.

The mortar zone has a relatively high concentration of polymerized and cross-linked monomers and has a high melt viscosity.

The platform zone has virtually no concentration of polymerized and cross-linked monomer and has a relatively low melt viscosity.

The product is commercially acceptable as a resilient floor covering.

EXAMPLES VI-XVI The procedure set forth in Example V is carried out substantially as described therein, except that the P1 printing ink composition used therein is prepared by adding 11 additional As an example, printing ink compositions P-7 to P-17 were substituted: The results of these examples are generally similar to those obtained in Example 2.

(1) Flat, matte or matte textured finishes and smooth, glossy or glossy areas and (
The relative differences between 2) the degree of polymerization and/or cross-linking of the reactive polymerizable monomers within these zones and (3) the degree of increase in melt viscosity of the polymerized and cross-linked zones are significant and notable. Worth it.

Examples ■ - The procedure described in Example V is carried out substantially as described therein, except that the peroxidized polymerization initiator in the printing ink composition is replaced by: Example X■ Tert-butyl penoxyacetate Example X■ 2,5-dimethyl-2,5-bis(bensoylperoxy)hexane Example X■ Tertiary-butyl peroxymaleate Example X
X Tert-butyl peroxymaleate Example XXI2.
5-Dimethyl-2.5-bis(2-ethylhexylperoxy)hexane The results of these examples are generally similar to those obtained in Example 2.

Examples X-XXV The procedure described in Example V is followed substantially with the following exceptions regarding the printing ink composition used therein, but
In which the printing ink compositions identified in the relevant tables from P-2 to P-5 are used: Example XX [(P-2) contains trimellitic anhydride but not dicumyl peroxide or It does not contain any other polymerization initiators or organic peroxides.

This results in the product shown structurally in Figures 2 and 3 of the drawings, but without any areas of raised, flat, matte, hollow texture, and with no areas of increased melt viscosity. do not have.

Example XXI [I(P-3) contains trimellitic anhydride and dicumyl peroxide.

This yields a product generally similar to that obtained in Example 2.

It has a difference in embossed, flat, matte textured areas and smooth, glossy or glossy finished areas and melt viscosity.

It is commercially acceptable as a resilient floor covering.

Example XXIV (P-4) contains trimellitic anhydride but no dicumyl peroxide or any other polymerization initiator or organic peroxide.

This results in the product shown structurally in Figures 2 and 3 of the drawings, but without any areas of raised, flat, matte, hollow texture, and with no areas of increased melt viscosity. do not have.

Example XXV (P-5) contains dicumyl peroxide but no trimellitic anhydride or other foam modifiers or inhibitors.

This yields a product structurally similar to that shown in Figure 7 of the drawings.

There are areas with embossed, flat, dull or dull textures, as well as areas with a smooth, glossy or glossy finish, and differences in melt viscosity, but the surface of the durable layer. There are no chemical reliefs other than small raised or raised ridges shown in Figure 7.

Examples XXVI-XXXI Durable layer compositions W-3, W-6, W-7, W-9, W- in which the durable layer composition W-1 used therein is listed in the related table
Following the procedure described in Example V except substituting W-10 and W-12.

The results of these examples are generally similar to those obtained in Example 2 with Durable Layer Composition W-1.

The contrast between embossed, flat, matte or textured areas and smooth, glossy or glossy smooth finished areas is striking.

The differences in polymerization and/or cross-linking of the reactive polymerizable monomers in each durable layer are significant and significant.

Differences in melt viscosity in different areas of the durable layer are also observed and are significant and significant.

The product is commercially acceptable as a resilient floor covering.

Example XXX [[-7 Glycol Example xxxm Tetraethylene glycol diacrylate Example xxxrv 1,6-hexanediol diacrylate Example xxxv Neopentyl glycol dimethacrylate Example XXXVI) Trimethylolpronone lyacrylate The results of these Examples generally The results are similar to those obtained in (2).

Polymerization and/or cross-linking and increase in melt viscosity
As described therein, with contrasting areas of flat, matte or dull texture and areas of smooth, glossy or shiny texture.

Example XXX ■ The procedure described in Example ■ was followed as is, except that the composition of the resinous durable layer was changed as follows: Part IJ vinyl chloride, dispersion edge, 0.850 intrinsic viscosity polyvinyl chloride, Compound edge, intrinsic viscosity 500.71 Trimethylolpropane trimethacrylate (90 ppm hydroquinone) 5 Butyl benzyl phthalate 3.8 2,4,4-trimethylpentyl 5-diisobutyrate 3.3 Alkyl benzyl phthalate 4.1 parts Ba-Zn Phosphite Thermal Stabilizer 6.4 Epoxidized Tall Oil (2.4 weight paper phr per 100 parts by weight resin) The results of this example are generally similar to those obtained in Example 2.

Polymerization and/or cross-linking Q differences and melt viscosity differences of the reactive polymerizable monomers in various parts of the durable layer can result in a flat, matte or matte texture and a smooth, smooth, glossy or glossy texture. It is notable for its contrasting surface finish.

The product is commercially acceptable as a resilient floor covering.

Similar to the product of Example ■, the flat, matte or matt finish areas of the durable layer are cross-linked and thermoset, whereas the smooth, smooth, glossy or glossy areas are crosslinked and heat cured. Portions of the durable layer in certain finishing areas are neither cross-linked nor thermoset, but are still thermoplastic.

Example XXX■ Example ■ except that the blocking method composition 'BC-1 used therein is replaced by the previously described blocking method composition BC-2.
Follow the steps exactly as described.

The results of this example are generally similar to those obtained in Example 2.

The thickness of the barrier coating is also 4.5 mils.

EXAMPLES XXXIX-XLI The procedure described in Example ■ was followed exactly, except that the barrier coating thickness was changed to 1.5 mils, 4 mils, and 5 mils instead of 0.45 mils as in Example ■. .

The results of these Examples are generally similar to those obtained in Example 2.

EXAMPLE XLn - XLIV 50 p3ig186 psig and 100 ps instead of the 110 psig pressurization used in Example V
The procedure described in Example 3 is followed except that the mechanical embossing is carried out under pressure in the ig.

The results of these Examples are generally similar to those obtained in Example 2.

Flat, matte or matte finished areas contain crosslinked and thermoset resins, while smooth, smooth, glossy or glossy finished areas contain uncrosslinked thermoplastic resins.

Example XLV Conditions for mechanical embossing of resin durable layer: 140p
sig, at 360'F for approximately 15 seconds.

The results of this example are generally similar to those obtained in Example V.

Example XLVI Conditions for mechanical embossing of resin durable layer: 86 p
sig, 315'F for approximately 2 minutes.

The results of this example are generally similar to those obtained in Example 2.

Example XL■ The method described in Example ■ is followed except that the mechanical embossing is modified as follows: Rough texture placed on the surface of a gelled resinous durable layer by the Watson-Stillman surface plate method. Instead of applying pressure and heat to a parchment-type release paper, approximately 330'F.
Pressure and heat are applied by rotating contact with a 24-inch rotating embossing roll having a temperature of .

The surface of the embossing roll has a rough, sandblasted finish.

The durable resin layer is guided around the heated embossing roll,
After passing through the pressure roll nip, it remains in intimate contact with the main portion of the heated periphery, thus creating an effective heating contact circumference of about 5 feet.

The results of this example are generally similar to those obtained in Example 2.

The polymerized and cross-linked thermoset portions of the resinous durable layer with a higher melt viscosity retain the surface characteristics and characteristics of a coarsely textured parchment-type release paper, whereas the uncrosslinked portions of the resinous durable layer have a higher melt viscosity. The thermoplastic part of the bond becomes smooth, smooth and glossy.

EXAMPLE XL■ A heated pressurized embossing roll is engraved with very fine parallel lines, 50 lines per inch, resulting in a flat, matte texture or finish, and a cross-linked thermoset resin. substantially as described in Example XL, except in contrast to smooth, smooth, glossy or shiny areas comprising an uncured thermoplastic resin. Follow the street.

The results of this example are generally similar to those of Example XL■.

EXAMPLES The ink composition, barrier coating composition, and durable layer composition are as described in Example V.

A resinous durable layer plastisol containing reactive polymerizable monomers and still being highly flowable is cast onto the surface of coarse textured, parchment-type release paper to a depth of about 15 mils.

The durable layer plastisol is fluid enough to flow and completely fill all irregularities in the release paper, thereby ensuring the surface qualities and characteristics of the release paper.

The durable layer is then gelled under 300°C.

Some contain both a dicumyl peroxide initiator and a trimellitic anhydride foam modifier and others contain no initiator or organic peroxide or any foam modifier or inhibitor. A printing ink composition is applied to various areas of the exposed surface of the gelled durable layer in a desired pattern or design.

The printing ink composition is then allowed to dry. A barrier layer of 3 mils is applied and adhered to the printing ink composition and approximately 320 mils of barrier layer is applied and adhered to the printing ink composition.
'F temperature for a sufficient period of time to not only gel the resinous coating but also to activate or decompose the dicumyl peroxide in the mana durable layer to form reactive polymers located in the same longitudinal zone. The monomers are polymerized and/or cross-linked and increase the melt viscosity of the resin in such vertical zones.

A base layer or support comprising a potentially foamable plastisol composition and an adhered fibrous sheet of felt fossil cotton fibers is then applied to the gelled barrier coating by passing through a lamination device under pressure and at elevated temperature. match.

The resulting laminated product is integral and structurally intact.

When the coarsely textured parchment-type release paper is then peeled away from the durable layer, the surface of that layer is exposed and has a correspondingly coarse texture and parchment-like appearance, with a flat, matte nips across its surface. found to be an organization.

This laminated product is then passed through a heated melting furnace at a temperature of about 395'F and the resin is melted along with the foaming and forming operations in which the foaming and foaming agents and foam modifiers or suppressors are removed. Achieve the chemical relief procedure previously described.

The resulting foamed product is generally similar and comparable to the product of Example II.

Those portions of the durable layer where the reactive polymerizable monomers are polymerized and/or cross-linked and also have a high melt viscosity retain their coarse-textured, parchment-type, flat, dull or matte structure and appearance.

In other parts of the layer, substantially no polymerization and/or cross-linking of reactive polymerizable monomers and where the melt viscosity is still relatively unchanged and relatively low, occurs during the foaming and foaming operations. The surface melts to form a smooth, smooth, glossy or lustrous finish.

The cross-linked portions are thermoset, whereas the non-cross-linked portions are thermoplastic.

Example L A polymerization initiator or organic peroxide, cumene hydroperoxide, which can be activated or decomposed only at relatively high temperatures, is additionally introduced substantially uniformly into the resinous durable layer.
The procedure described in Example V was followed except that it was included at a concentration of about 7 parts by weight based on 0.00 parts resin.

Cumene hydroperoxide does not activate or decompose during gelling or mechanical embossing operations, whereas dicumyl peroxide does at that point activate or decompose in the printing ink composition, thereby making it a durable layer of choice. The moieties become polymerized and/or cross-linked and develop relatively high melt viscosities, as described in more detail herein and in Example 1.

However, cumene hydroperoxide subsequently activates or decomposes at the higher temperatures present during higher melting, foaming or foaming cycles, thereby leaving behind a smooth, smooth, glossy or glossy finish area. The reactive polymerizable monomers are then polymerized and/or cross-linked, thereby increasing the melt viscosity in such smooth, smooth, glossy or shiny parts.

Obviously, softening, melting and flow in such areas promotes polymerization and/or cross-linking and increases melt viscosity in such areas.

There is no substantial change in the areas of flat, dull or dull texture that are polymerized and/or cross-linked and have a relatively high melt viscosity.

The entire surface is therefore polymerized and/or cross-linked and has a relatively high viscosity.

Example LI Durable layer surface of various polyvinyl chloride resin sheet materials (
Gloss level measurements are obtained for both the platform and the mortar area) using a manual, hand-adjusted laboratory procedure at 60° using a standardized Gardner laboratory gloss meter on a suitable gloss plate for 600 mm. done by.

Such laboratory procedures are not as complex or sophisticated as commercial factory manufacturing procedures and occasional blisters and irregularities cause lower than normal gloss readings.

Various polyvinyl chloride resinous sheet materials were obtained by the procedure generally described in Example I, and any changes made during such procedure are noted.

Gloss Measurement Changes from Molar Example ■ No change from Tal Example ■6 Inhibitor is 25% trimellitic anhydride8 Inhibitor is 25% trimellitic anhydride5 Inhibitor is 25% anhydride 3 The monomer is 1,6-hexanediol dimethacrylate at 28 phr 4 The monomer is 1,6-hexanediol dimethacrylate at 28 phr 9 The monomer is pentaerythritol triacrylate at 20 phr 0 The monomer is 20 phr pentaerythritol triacrylate 7 The inhibitor is 20% benzotriazole: dicumyl peroxide is increased to 10% 5 No peroxide (control experiment) Peroxide (control experiment) 0 2 Examples LI [60% for durable layer surfaces (both platform and mortar) of various polyvinyl chloride resinous sheet materials made by an automated, electronically controlled commercial manufacturing factory process. Gloss level measurements are made using a Gardner Laboratory Gloss Meter standardized to 60° on a suitable gloss plate at 60°.

Such commercial production factory processes are extremely complex and highly sophisticated and yield higher gloss level measurements than those obtained with laboratory procedures.

Various polyvinyl chloride resinous sheet materials are obtained by the procedure generally described in Example 3, any variations in such procedure being noted.

Gloss Measurement Molar Changes from Example ■ No changes from Tal Example I 7220 inhibitor is 25% trimelite anhydride) 78 Inhibitor that is 19 acid is 25% trimerite anhydride 79 Inhibitor is 18 acid 25% trimeric anhydride) 72 17 acid monomer is 28 phr dimethacrylic 8027 acid 1
・The monomer that is 6-hexanediol is 28 phr of dimethacrylic 7121 acid 1
The monomer which is 6-hexanediol is 20 phr triacrylic; the monomer which is pentaerythritol 6716 acid is 20 phr triacrylic; and the inhibitor is 20% benzotriacyl 6314: dicumyl peroxide. is increased to 10% Lm C, W, using Brabender "Plasticorder" 1
Jacket temperature of 50°C - equilibration within 15 minutes: 3/min
Hot melt viscosities are obtained for various polyvinyl chloride plastisols at a shear rate of 0 revolutions: and a sample weight of 53 f.

In the following diagrams, the reactive polymerizable monomeric materials and organic peroxides or free radical polymerization initiators are as indicated.

Monomer “A” is trimethylolpropane trimethacrylate; monomer IBj is dimethacrylic acid 1,6-
hexanediol; and monomer "C" is pentaerythritol triacrylate.

The organic peroxide or free radical polymerization initiator is 40% active dicumyl peroxide supported on precipitated calcium carbonate.

The resin for the first two control experiments was 100 parts Firestone polyvinyl chloride resin 605.

The resins for the second two control experiments are 89.5 parts of Zeon polyvinyl chloride resin 120X271 and 10.5 parts of Tenetko 501.

The resin marked ☆☆ in the second diagram is 100 parts Firestone PVC Resin 605.

A 53.3 phr resin plasticizer formulation is used for control experiments.

Control Experiments No Monomers No Monomers No Monomers No Monomers Hot Melt Viscosity - Grams 00 00 40 20 Examples LIV A barrier coat or layer was used as shown in Figure 9 and the desired pattern or design was gelled and cooled. All differently colored parts and areas of the printing ink composition used to apply the resinous polymer plastisol composition have the following formulation containing the same concentration and amount of dicumyl peroxide polymerization initiator or catalyst: The procedure set forth in Example I is followed substantially as described therein with the following exceptions: Part Solution Grade Copolymer of Vinyl Chloride (90 Parts) and Vinyl Acetate (1015 Parts) Methyl Ethyl Ketone 3 Dicumyl Peroxide Pigment or Colorant , the amount of heating and melting desired or required in the individual pattern or design, and the product immediately prior to the foaming or foaming operation is illustrated in FIG.

Azodicarbonamide blowing or foaming agent (1
, Part 1) provides a final unfoamed or unfoamed product as illustrated in FIG. is completely retained.

In the absence of such foaming or foaming, the barrier coating or layer is absent.

Azodicarbonamide blowing or foaming agent (11
Part) provides a foamed final product as illustrated in FIG. 10, where the mechanical relief is substantially completely retained throughout the heating and melting and foaming or foaming operations.

In such cases, a barrier coating or layer would be used.

A selected printing ink composition comprising a formulation as described above in this example without foaming or foaming modifiers or inhibitors therein was prepared using trimellitic anhydride as shown below in this example. Substitution with another selected printing ink composition having a formulation containing a foaming or foaming modifier or inhibitor provides a relief effect to the surface in the foamed or foamed final product.

Part Solvent grade copolymer of vinyl chloride (90 parts) and vinyl acetate (10 parts) 2 Methyl ethyl ketone Dicumyl peroxide trimellitic anhydride 60 Pigment or colorant, amount desired or required in the individual pattern or design Final A foamed or foamed chemically embossed product is illustrated in FIG.

The mechanical relief on the surface of the durable layer is substantially completely retained in this latter form of the embodiment, as well as in all other forms of the embodiment, through heating and melting, and foaming or foaming operations. .

Example LV The process described in Example ■ is followed substantially as described therein, except that the printing ink composition does not contain any polymerization initiators, catalysts, or organic peroxides and has the following formulation: : Solvent grade copolymer of vinyl chloride (90 parts) and vinyl acetate (1015 parts) Methyl ethyl ketone A separate layer or coating, such as a transparent printing ink composition comprising: is applied over the entire surface as shown in the structure of the product illustrated in FIG.

Such a transparent printing ink composition has the following formulation:
Solution grade copolymer of vinyl chloride (90 parts) and vinyl acetate (1015 parts) methyl ethyl ketone part dicumyl peroxide The structure of the product immediately before heating and melting and foaming or foaming is illustrated in FIG.

Although the structure of the product following any heating and melting and foaming or foaming operations is not illustrated, mechanical relief may be applied to the surface of the durable layer through heating and melting and foaming or foaming operations. substantially completely retained as shown in the figure.

EXAMPLE LVI The procedure described in Example ■ is substantially followed except that an LVI barrier coating or layer is used and neither printing ink composition contains any polymerization initiators, catalysts, or organic peroxides therein. Follow.

Such a printing ink composition has the following formulation: Part solvent number copolymer of vinyl chloride (90 parts) and vinyl acetate (1015 parts) Methyl ethyl ketone pigment or colorant, as desired or required by the individual pattern or design. In addition, a separate, overarching layer or application, such as a clear printing ink composition containing any polymerization initiator, catalyst, or organic peroxide, as used in Example LV, may affect the structure of the product. Not included.

However, such polymerization initiators, catalysts, or organic peroxides are included directly and uniformly in the durable layer having the following formulation: 1 part polyvinyl chloride, after dispersion, intrinsic viscosity 1000, 8 parts trimethylolpropane trimethacrylate. (90 ppm hydroquinone) 5 Butylbenzyl phthalate Plasticizer 13,8 2,4,4-trimethylpentyl-3,5-diisobutyrate 3 Part Alkylbenzyl phthalate Low boiling point plasticizer Ba-Zn phosphite Thermal stabilizer Epoxidized Tall Oil Dicumyl Peroxide Polymerization Initiator 4, 1 6, 4 2, 4 0, 3 The product immediately before heating and melting and foaming or foaming operations forms the product illustrated in Figure 1 of the drawings. Generally similar to things.

Subsequently, it is observed that the mechanical relief on the surface of the durable layer is virtually completely retained throughout the heating and melting and foaming or foaming operations.

Example L ■ The procedure described in Example I is substantially followed except that no barrier coat or layer is used and the printing ink composition does not contain therein any polymerization initiators, catalysts, or organic peroxides.

Such a printing ink composition has the formulation described in Example LVI.

Additionally, separate, full-length applications such as transparent printing ink compositions containing any polymerization initiators, catalysts, or organic peroxides as used in Example LV are not included in the structure of the product. There wasn't.

However, such polymerization initiators, catalysts, or organic peroxides may be incorporated directly and uniformly into a barrier coating having the following formulation: Part polyvinyl chloride, high molecular weight, dispersion edge, 89 intrinsic viscosity 1
．． 4 Polyvinyl chloride, high molecular weight, blended resin, intrinsic viscosity 0.9 Epoxidized soybean oil 2,2,4-trimethyl 1-1,3-bentanediol diimbutyrate butyl benzyl phthalate polydodecylbenzene Ba-Zn phosphite Stabilizer Ultraviolet absorber Organic pigment 6,9 9 8,5 7,25 0,32 0,01 part Dicumyl peroxide Polymerization initiator 0.5 The printing ink composition contains a polymerization initiator, catalyst, or organic peroxide. The product immediately prior to heating and melting and foaming or foaming operations is generally similar to the product illustrated in Figure 9 of the drawings, except that it does not contain any.

Subsequently, it is observed that the mechanical relief on the surface of the durable layer is substantially completely retained throughout the heating and melting and foaming or foaming operations.

Although the invention has been particularly particularly described in a number of the foregoing specific embodiments, in which preferred and exemplary embodiments of the inventive concept are illustrated, they are not intended to limit the broader aspects of the inventive concept. They should not be interpreted, but are merely examples.

The special materials, chemicals, patterns, designs and other special features of such embodiments are for illustrative purposes only and are limited and defined by the spirit and scope of the appended claims. It is not intended to limit the broader scope of the invention.

[Brief explanation of the drawing]

In the accompanying drawings, FIG. 1 is a fragmentary schematic front cross-sectional view of one embodiment of the present invention showing the original form of the resinous polymer composition prior to heating and foaming; FIG. 1 shows the final form after heating and foaming of the composition; FIG. 3 is taken along line 3-3 of FIG. 2;
FIG. 4 is a fragmentary schematic front cross-sectional view of another embodiment of the invention showing its structure before heating and melting; FIG.
Figure A shows the same structure as in Figure 4 after heating and melting; Figure 5 shows a fragmentary view of yet another embodiment of the invention;
Figure 5A is a schematic front cross-sectional view showing the structure before heating and foaming; Figure 5A shows the same structure as Figure 5 after heating and foaming and subsequent removal of the release paper;
FIG. 6 is a fragmentary schematic front cross-sectional view of yet another embodiment of the invention, showing its structure before heating and melting; FIG. 6A is the same as FIG. 6, except that the heating and melting FIG. 7 is a fragmentary schematic front sectional view of a further embodiment of the invention, showing its structure after heating and foaming; FIG. 8 is a further embodiment of the invention; FIG. 9 is a fragmentary schematic front sectional view of another embodiment showing its structure after heating and melting the resin; FIG. 9 is a fragmentary schematic front sectional view of yet another Q embodiment of the invention; Figure 10 shows the structure of the product, either before or after heating and melting the resin, with or without the presence or absence of a blowing or forming agent in the resinous polymer composition; Figure 11 shows the structure of the resin after heating, melting and foaming when a blowing agent or foaming agent is included in the polymer; 10 is a fragmentary schematic front view of the embodiment of FIG. 10 after heating the resin to foaming when the resin is heated; and FIG. 12 is a fragmentary schematic front cross-sectional view of yet another embodiment of the invention; where the free radical polymerization initiator, catalyst, or organic peroxide is included in a separate layer of the product.

Claims (1)

Claims: 1. A printing ink composition comprising a polymerization initiator for laying down or forming a base layer or support; a pattern or design on said base layer or support in a predetermined area of a resinous polymeric sheet material. applying a resinous durable layer substantially uniformly containing a reactive polymerizable monomer to the printed pattern or design; mechanically stamping the surface of the resinous durable layer to form a flat surface on the surface; The polymerization initiator is (1) directly above the polymerization initiator in the intended area of the printed pattern or design, with mechanical embossing being applied to the resin-like structure to provide a matte or matte structure. polymerizing and/or cross-linking said reactive polymerized monomers in said portion of the durable layer and (11) at an elevated temperature sufficient to increase the melt viscosity of said portion; or exposing the support and said resinous durable layer to an elevated temperature to cause softening and melt flow of said resinous durable layer to polymerize and/or cross-link reactive polymerizable monomers. including,
and the portion of the resinous durable layer excluding the portion where the melting viscosity has been increased is made glossy, smooth, glossy or shiny, and the excluded portion does not soften or melt and is flat;
A resinous polymer sheet with a selectively positioned surface decoration effect characterized in that it remains in a matte or matte structure and contrasts with said glossy, smooth glossy or glitter finish. Method of manufacturing the material. 2. The method according to item 1 above, wherein a polymerization initiator is included in a part of the pattern of the printing composition. 3. The method according to item 1 or 2 above, wherein the polymerization initiator is substantially uniformly contained in all parts of the pattern of the printing composition. 4. The method according to item 1 or 2 above, wherein a polymerization initiator is included throughout the separate printing composition layer. 5. The method according to item 1 or 2 above, wherein a polymerization initiator is included in the resinous durable layer. 6. The method of item 1 or 2 above, wherein the polymerization initiator is included in the barrier coating that is in contact with the printing composition layer. 7. The laying down or formation of a base layer or support consists of applying a resinous polymeric composition onto a relatively flat fibrous sheet material, whereby said base layer or support, said printed pattern or design, and said resinous durable 2. The method of claim 1, wherein the portion of the resinous durable layer immediately above the polymerization initiator is elevated when the layer is exposed to the elevated temperature. 8 Resinous Polymer Composition A potentially foamable resinous composition comprising a force-foaming agent, whereby said base layer or support, said printed pattern or design, and said resinous durable layer are heated to said elevated temperature. 8. The method of claim 7, wherein the potentially foamable resinous polymer composition is foamed upon exposure to. 9. Including a blowing or foaming modifier in selected areas of a printed pattern or design, whereby upon exposing said substrate or support to said elevated temperature said potentially foamable resinous polymeric composition. The foaming of the latent resinous polymer composition is carried out in such a way that a portion of the printed pattern or design that contains the foam modifier is not under the selected area of the printed pattern or design. 10. Impregnating selected areas of the printed pattern or design with a blown or foamed modifier and predetermined areas of the printed pattern or design. containing a polymerization initiator in a consistent manner,
9. The method of claim 8, whereby the flat, dull or matte structure of the resinous durable layer is matched with the modified blown or foamed portion of the potentially foamable resinous polymer composition.