Embossed multi-layered resinous assembly and a method for its production

The invention relates to a process for producing a multilayer, embossed, porous foam product in which a layer of a resin material containing a blowing agent is formed, portions of this layer are brought into contact with a substance raising or lowering the blowing agent decomposition temperature, the layer is heated to decompose the blowing agent and to foam differently the differently treated portions after the application of an anti-abrasion layer.

Films made of synthetic resin materials are widely used as decorative and abrasion-resistant cover layers for many different products. They are used, for example, to the largest extent as wall, floor and table coverings, book covers, decorative containers and as a material for upholstery, clothing and automotive interiors and the like. In many cases, such films are applied to a base made of, for example, tissue, paper, felt, metal, glass, or the like, or shaped on it. These documents serve various purposes, in particular increasing strength and improving usability. Typically, such films are surface embossed to make them more decorative and, in many cases, more usable. Typical imprints of this type imitate leather or fabric, e.g. B. Linen structure after. In many cases, the embossed districts are filled with pigment according to a method called "ink printing"

color out.

Since the appearance of Kunstschaummassen they have also introduced either alone or together with non-porous, abrasion-resistant cover layers and / or padding materials in products of the aforementioned type Such a film of synthetic foam gives the product depending on the Schaumstoffart different desirable properties such as high elasticity and good feel.

The embossing of Kunstharzfoüen is usually done by means of embossing roll or plate whose surface has been previously given by engraving or other treatment, the desired high relief pattern. Then the film and / or embossing surface is heated and presses the pattern in the heat-softened film.

It has also been proposed various methods for the production of foam products with a textured or embossed surface without the use of embossing rollers. In fact, embossing rolls are expensive to manufacture and difficult to control in conjunction with a cold-drawing process. Sometimes you want to print a pattern and then make the embossing in register with the pattern. But you need very complicated facilities.

In addition, the embossing of curved or irregular surfaces causes very great difficulties.

An embossing technique known as "chemical imprinting", which has changed from that until then

As disclosed in US Pat. Nos. 3,393,094 and 3,293,108, this method of operation controls the decomposition temperature of a chemical blowing agent dispersed in a polymer resin composition by:

In the subsequent heat treatment, then the blowing agent is selectively decomposed, and obtained at the points where the inhibitor is applied in the final product either elevated or recessed districts.

In many cases, the embossed products have been coated with a transparent protective layer which is said to give them resistance to abrasion, attack by household chemicals and staining and elasticity.

While most of these known anti-abrasion coatings were satisfactorily effective, they had some imperfections in their use when more than 0.356 mm thick. Thus, for example, the typical coating layers penetrated

Thus, such thickness adjustment at the processing temperatures due to their fluidity in the wells of the chemically embossed products and partially filled them. This resulted in a significant reduction in fluidity and embossing depth.

One might expect that one would overcome this difficulty with filler-containing, calendered outer layers which can be rolled together with the foamable gel; However, it has been shown that such calendered films have excessive dimensional stability or "goodness" and therefore are not easily adapted to the embossings and sometimes bridge over the embossed districts. To compensate for this excessive dimensional stability, one necessarily had to use thinner ones

Tn coatings therefore drastically reduce the applicability of finished products for high load applications requiring stronger and more resistant anti-wear coatings

Higher levels of plasticizer, which sought to increase the flexibility and flowability of such abrasion resistant layers, affected both the feel of the finished product and the stain resistance of the protective layer. In addition, almost all the plastisol approaches used as an antisoure layer were translucent, thereby revealing the print pattern underlying the protective layer surface and the embossing blur something compensates. By this reinforcement of the printed appearance, however, the transparent districts suppress almost all the uniform natural geometric appearance that the finished product is supposed to have.

The object of the invention is to provide a process which is improved with respect to the processing of the above-mentioned cover films or abrasion protection layers, in whose process products the abrasion protection layer is optimally adapted to the embossed surface.

According to the invention this object is achieved in that the abrasion protection layer is obtained by calendering a mixture of about 25 to 50% of a resin material and about 75 to 50% thermoplastic decorative chips to a film of a minimum thickness of about 0.356 mm 2, wherein the mixture - based on its weight - 25-60% of a transparent or translucent filler have been mixed and the calendering carried out at a temperature below the melting temperature of the resinous mixture temperature, the preformed Abriebschutzschi ht before heating the foamable, a propellant-containing layer of the resin material is applied to this layer and the anti-abrasion layer is imparted the required flowability during heating.

The inventively embodied abrasion protection layer is characterized by an exceptional performance and decorative appearance and at the same time avoids all previously mentioned genann- to th imperfections of the previous abrasion protection layer.

According to the invention, therefore, a multilayer, embossed, porous foam product is obtained by first forming a layer of a propellant-containing resin material, bringing portions of this layer into contact with a propellant decomposition temperature-raising or lowering substance, e.g. B. with an inhibitor capable of penetrating the first layer and altering the decomposition temperature of the propellant, and applying as described an antisoiling layer forming the upper surface of the multilayer embossed porous foam product, the particular nature of this product being: the abrasion-resistant layer has a minimum thickness of 0.356 mm and the composition described above. The formed multi-ply foam product and the formation of the abrasion-resistant layer with the desired Abheebfestigkeit are a consequence of the <> o final E^rheat, whereby the inhibiting reaction is effected, due to which the blowing agent is selectively decomposed and the abrasion-resistant layer is ultimately formed in the desired WeiNe, in particular the optimal adjustment is achieved. ^b5

It can be seen that the product obtainable by the method according to the invention combines the typical advantages of the chemical embossing technique with the unique performance of the abrasion protection layers described. The invention thus enables the creation of a product with embossed surfaces, which can stand in a complete paßlage with a print pattern. In addition, the invention allows the use of all types of printing apparatus as a stamping tool, which eliminates the need for embossing rollers and associated facilities Furthermore, the expression of a surface or pressure application and regardless of shape or outline of the surface is possible.

The unique abrasion-resistant layers formed by the process of the present invention exhibit improved resistance to wear, household chemical attack and staining, and higher elasticity. Furthermore, it is highly significant that these abrasion-resistant layers are sufficiently fluid at the blowing agent decomposition temperatures and can thus easily be adapted to the embossings which will be produced later. As a result, such abrasion protection layers can be applied in a greater thickness than the previously known Plastisolschutzschichten and give in applications with high stress additional protection. In comparison with conventional products, they give a more pronounced presentation of comparable thickness of the protective layer. Because of the low plasticizer content of their starting formulations, they feel better and are more stain resistant. Being translucent, they also suppress the printed appearance of the embossed product without compromising its desired, textured appearance. Finally, you can achieve many different decorative effects with them.

The number of products that can be produced according to the invention is unlimited. They can be used as flooring, wall, table and body coverings and the like and in fact wherever resin-based foils or compounds with an abrasion-resistant surface are important. Many other applications for the invention will be readily apparent to those skilled in the art.

In the following, detailed description and drawings, the invention will be explained in more detail. It shows

Fig. 1 is a flow diagram of a typical embodiment of the method according to the invention and

F i g. 2 is a diagrammatic partial cross section through the foam product obtainable according to the invention on an enlarged scale.

What is used as a base material largely depends on the type of finished product. If the pad is to remain as a component, it may consist of synthetic resin composition, felt web, fabric, knitted or the like. For the purposes of the invention are suitable as a support all deformable to films, thermoplastic or elastomeric synthetic resin materials with optional plasticizer or filler content, including typically butadiene-styrene copolymers, polymerized chloroprene, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers and the like. Also suitable are sometimes also waste or degraded resin masses that can be made useful in this way.

Furthermore, as already mentioned, wovens made of cotton, wool, asbestos and many plastic fibers are suitable as underlay. If you are loosely woven

Material like ζ. B. packing canvas used, one can prevent the passage of the resin material through the fabric meshes by either providing the fabric with customary in textile technology finish or applying high-viscosity resin materials. It is also possible to quickly dry or harden the coating before it passes through the fabric.

Sometimes, and especially with a felt, prior to the creation of the first-mentioned layer, a finish layer acts which acts as a brake layer and prevents the film-impregnating agent from migrating into the applied layer. This seasoning layer is preferably applied as an aqueous emulsion of a suitable resin, but possibly also as a plastisol or the like. Acrylic resins and vinyl chloride polymers proved particularly suitable for this purpose.

If the pad is to be removed from the finished product again, it is preferable to use peel-off paper, which usually has a surface finish which allows the layer of resin material to be easily peeled from the paper. Such a coating typically consists of clay, silicone composition, polyvinyl alcohol, and similar specialty approaches well known in the art.

According to the invention, a foamable polymeric resin material is applied to the substrate. This resin material is preferably of such a nature that it coagulates or melts into a coherent film by the action of heat, thus providing a good printable area by gelling the composition. By the term "melted" is meant that state which is achieved in a resin material in the transition from a randomly dispersed dispersion or suspension of discrete resin particles in the plasticizer to such a homogeneous consistency, uniform viscosity and rheological behavior.

The foamable batch furthermore preferably consists of a dispersion of resin material in a liquid medium, which in the case of an aqueous latex can consist of water, an organic solvent as organosol or a plasticizer as plastisol. The best results have been achieved with a resin material dispersion commonly referred to as "plastisol" in a plasticizer. Such a plastisol is noticeably fluid at normal room temperatures, but can be converted by heat into a molten, flexible and tough thermoplastic mass. Plastisols are therefore preferred because, unlike latex or organosol, they do not require a large amount of carrier to be removed. The Harzmateriai can also consist of a dry mixture of resin particles with superficially absorbed plasticizer, stabilizer, pigments and the like, together with blowing agent, which is applied in a smooth layer on a substrate. This layer is then heated to either form a porous film or partially or completely fuse into a solid film. The layer thus formed is then placed in some suitable manner. When the film is porous, penetration of the inhibitor is of course facilitated. Such films are normally subsequently heated and subjected to compression for compression.

The preferred and most commonly used topcoat resinous resin materials are vinyl chloride polymers. These can be either simple, unmixed vinyl chloride homopolymers or copolymers or terpolymers or the like, whose important polymer structure consisting of polyvinyl chloride is interspersed intermittently with the copolymerized residues of other ethylenically unsaturated compounds. This polyvinyl chloride polymer structure retains its essential property as long as not more than about 40% of foreign monomer is copolymerized. Despite this preference for polyvinyl-

It can be seen that the resin materials can also be formed from any other resin which can be foamed by means of blowing agent. Therefore, the invention is by no means limited to a resin or a resin group of a certain kind, but also many

i) other resin types and groups familiar to the person skilled in the art. For example, it is also possible to use polyethylene, polypropylene, methacrylates, synthetic rubber such as neoprene, silicone, SBR or nitrile rubber, polyurethanes, polyamides, polystyrene, phenolic resins, urea-formaldehyde condensation products, cellulose esters, epoxy compounds or silicones.

The resin materials suitable for vinyl plastisol approaches are commonly referred to as dispersion type

resins. They are available in particle sizes of about 0.02 to about 2 microns, and thus differ from so-called calender-type vinyl resins, which are available in particle sizes up to about 200 microns. Have dispersion type resins

Their particles have surfaces of a hard, horny nature, especially vinyl chloride polymers whose specific viscosity is - according to ASTM D 1243-60 method, & h⁰C warm solution of 0.4 g of resin in 100 ml of nitrobenzene, measured above about 0.25 and preferably between 030 and 0.70. The specific viscosity is determined from the flow time (Fh) of the resin solution and the (Fn) of the pure nitrobenzene calculated and specified according to the formula (Fh: Fn) -1. It is a good measure of the relative molecular weight of the polymer and its value increases with increasing molecular weight.

When preparing the Plastisolmassen useful for the purposes of the invention, the finely divided resin is evenly dispersed in a mass of flowable plasticizer The plastisol flow depends in part on the nature of the specific resin and the selected plasticizer, but also the ratio of both and decreases with sinking

so softener resin ratio from. The coating formulations used according to the invention contain about 20 to about 150 per 100 parts of resin material and preferably about 50 to about 80 parts of plasticizer for particular performance. The plastisol viscosity can also be reduced by adding a little volatile solvent of not more than about 10 parts thereof per 100 parts of the resin material, but the solvent is not allowed to exert a solvating influence on the resin material. For example, benzene, toluene, methyl ethylacetone, petroleum solvents such as

VM and P naphtha (with boiling ranges between 88 ° and 135 ° C) and the like.

The organosols which can be used in carrying out the process according to the invention preferably contain from about 20 to about 55 parts per 100 parts of resin material and most preferably from about 30 to about 40 parts of plasticizer, while in the case of plastisol.

usually the amount ratio is about 1: 0.45 to 1: 1.5. How much solvent is used depends largely on the coating viscosity with which the used application apparatus works most favorably. ■>

It depends on the correct choice of the plasticizer insofar as it determines the strength and flexibility of the coating of the resin material, furthermore the batch viscosity and its constancy and finally also the foaming behavior of the foamable batch. Esters of straight or branched chain alcohols with aliphatic acids give low viscosity and good viscosity stability. Plasticizer of aromatic type on the other hand, ie Alcohol and acid esters, at least one of which is an ester component of an aromatic nature, are desirable in that they provide good foaming properties to a plastisol; however, the utility of highly aromatic plasticizers is limited by their tendency to yield high viscosity plastisols. But you can also with other plasticizer types, eg. B. Esters of inorganic acids, alkyd derivatives of gum, chlorinated paraffins, high molecular weight hydrocarbon condensates, and the like. The plasticizer or plasticizer mixture is then selected to obtain a formulation of desired viscosity and / or slurry properties. In addition, the plasticizer should preferably have a low vapor pressure at the temperatures required to melt the resin material. Such a maximum of 2 mm Hg column at 204 ° C has been found to be particularly satisfactory.

In order to suppress the decomposition of the coating approaches by light and heat, they are usually added to small amounts of stabilizers. Suitable substances of this type are phenyl phthalate, phenyl benzoate, o-tolyl benzoate, o-nitrophenol and organic phosphates and other metal complex salts such. Barium, cadmium, calcium, zinc, strontium, lead, tin and the like. Among the useful heat stabilizers include the sulfides and sulfites of aluminum, silver, calcium, cadmium, magnesium, cerium, sodium, strontium and the like, furthermore leucine, alanine, o- and p-aminobenzoic acid and weak acid radicals including ricinoleates and abietates and the like. Normally, about 0.5 to about 5.0 parts of stabilizer are added per 100 parts of resin material. In the case of foamable mixtures, the stabilizer can also have an effect on the blowing agent decomposition. Some stabilizers catalyze insofar as they lower the decomposition temperature.

Depending on the color shade desired, the topcoat formulations can also contain pigments of an inorganic or organic nature, as are customary in plastics technology. Normally, about 0.5 to about 5.0 parts of pigment are added per 100 parts of resin.

As a further additive, the foamable formulations still contain an effective amount of propellant. The more that is used within practical limits, the greater the foam mass expansion. It is readily possible to achieve foam mass densities of 192 to about 641 kg / ms by adding about 1 to 20 parts of blowing agent per 100 TeOe resin material. With about 2 to 10 parts blowing agent per 100 parts resin material, in particular, foaming masses of the same density are obtained For the production of floor coverings are particularly desirable.

Propellants are substances known per se, and their selection in the individual case depends only on aspects such as price, type of resin material and desired foam mass density. While there are many compounds that give off gas in the decomposition, only a few of them are commercially available in quantities. It is preferable to use complex organic compounds which decompose upon heating, thereby giving off an inert gas and leaving behind residues which are compatible with the resin. Such materials have the property that they decompose within a narrow temperature range, which is particularly suitable for achieving a good foam composition.

Noteworthy types of propellants include substituted nitroso compounds

R -N-R '

NO

substituted hydrazides (RSO₂NHNHR '), substituted azo compounds (RN = N-R'), acid azides (R-CON2), guanyl compounds

/ NH = C =

and the like, wherein R and R 'represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

The most widespread propellants in use are those compounds which have the "N-NO" or "-NsN" bond and decompose at a higher temperature with the release of a nitrogen-rich gas having the general structural formula

bd

N = N or a-N = Nb

ac

in which a, b, c and d are hydrocarbon radicals having preferably 1 to 10 carbon atoms or a hydrogen atom together with at least one hydrocarbon radical. Many of these hydrocarbon radicals contain additional nitrogen radicals such as hydrazide, amido, nitro, nitrile, and the like. The presence of such residues is also desirable because they readily react with the inhibitor to form derivatives having different decomposition temperatures.

In the table below are some typical blowing agents together with their decomposition temperature range

Table I

propellant

decomposition temperature

Azodicarbonamide OO

CNH

2

CN = NC-NH,

p, p'-oxybis (benzenesulfonyl hydrazide)

163-204

149-154

continuation

<p><tgroup cols="3"><tbody><row><entry> I. </entry><entry>propellant</entry><entry>Decomposition temperature C</entry></row><row><entry></entry><entry>p, p'Oxybis (benzenesulfonylsemicarbazide)</entry><entry>149-163</entry></row><row><entry>[</entry><entry>azobisisobutyronitrile</entry><entry>102-121</entry></row><row><entry>}:</entry><entry>N, N'-dimethyl-N, N'-dinitrosoterephthalamide</entry><entry>38-104</entry></row><row><entry></entry><entry>diazoaminobenzene</entry><entry>101-130</entry></row><row><entry></entry><entry>Other notable blowing agents include Ν, Ν'-dinitrosopentamethylenetetramine,</entry></row></tbody></tgroup></p>

aminoguanidine,

p, p'-thiobis (benzolsulphonhydrazid)

ρ, ρ'-Diphenylmethandisulphonhydrazid,

Benzene-m-disulphonhydrazid,

Benzolsulphonhydrazid.Terephthalazid,

Benzazide, p-tert-butylbenzide,

Phthalazide, isophthalazide,

1.3 Diphenyltriazen,

Azohexahydrobenznitril,

Diethyl azodicarboxylate,

Naphthalene-l, 5-disulfonylhydrazidund

Biuret.

Blowing agents used in the present invention must decompose to an effective extent at a temperature below the decomposition temperature of the resin material. Preferred blowing agents include those which decompose above the elastomeric point of the resin material formulation, as this allows at least partial gelation of the foamable formulation and thus easy printing of its surface. Propellants of this type usually decompose above 93⁰C. For example, together with the preferred vinyl chloride polymers, one may use a blowing agent which decomposes between about 149 "and about 232 ° C. The lowest initial decomposition temperature must be so high that no gas evolution occurs during processing. Sometimes propellant mixtures may also be used to advantage use.

Usually, the approaches are also added to accelerators or catalysts to accelerate the propellant decomposition, to lower the decomposition temperature and / or to narrow the decomposition temperature range. For this purpose, one usually uses various types of metal salts, such as. B. dibasic lead phosphite-stearate phthalate or acetate, basic lead acetate, lead stearate, acetate or oxide, tribasic lead maleate, tetrabasic lead naphthenate, lead fumarate, lead 2-ethylhexanoate or similar lead salts, zinc laurate, oxide, stearate, carbonate, 2-ethylhexanoate, di-n-octoate or similar zinc salts, cadmium octoate, oxide, acetate, naphthenate or stearate, barium, calcium, nickel, aluminum, magnesium and tin stearate, dibutyltin maleate and oxide , These compounds also act as stabilizers for the approach. The term "propellant" is intended here to include not only the propellant or the chemical itself but also the combination of a propellant with an accelerator.

The paintable formulation is first formed into a film of the desired thickness and then gelled by heating to provide a well printable surface for the deposition of the inhibitor. The term "gelation" is intended to encompass both the partial (at least the elastomer point) and the complete solvation of the resin material or mixture of resin materials in the plasticizer (fusing). The heating is in terms of duration and

limited in temperature so that premature Treibmittelzersetzung is avoided in the approach. When using the preferred polyvinyl chloride approach, the batch temperature is increased to about 116 ° to about 135 ° C, of ​​course, the furnace temperature slightly higher

ι&gt; must be set. If the foamable batch is to be formed into a self-supporting film, the temperature would usually be high enough to melt the batch.

The foaming extent of a typical plastisol

2 »depending on the blowing agent content is shown in Table II below.

<p><tgroup cols="3"><tbody><row><entry>Table 11</entry><entry>ratio of</entry><entry>Density in kg / m¹</entry></row><row><entry>Parts Azodicar</entry><entry>Foam mass thickness</entry><entry></entry></row><row><entry>bonamid on each</entry><entry>to initial thickness</entry><entry></entry></row><row><entry>100 Parts resin</entry><entry></entry><entry></entry></row><row><entry>material</entry><entry>1: 1</entry><entry>1281</entry></row><row><entry>0,0</entry><entry>1,33 : 1</entry><entry>961</entry></row><row><entry>0,1</entry><entry>2:1</entry><entry>641</entry></row><row><entry>0,5</entry><entry>3:1</entry><entry>432</entry></row><row><entry>1,0</entry><entry>4,5:1</entry><entry>280</entry></row><row><entry>2,0</entry><entry>6,5:1</entry><entry>197</entry></row><row><entry>3,0</entry><entry>9,3:1</entry><entry>138</entry></row><row><entry>5,0</entry><entry></entry></row><row><entry></entry></row></tbody></tgroup></p>

Experience has shown densities of about 160 to 481 kg / m³ the most useful products.

For the preferred polyvinyl chloride resin, Table IH below presents the most favorable heating conditions in temperature and duration for the various film states.

The film tested was, in the initial state, a 0356 mm thick plastisol layer on 6.35 mm thick cellulose felt backing impregnated with 9% vinyl acetate and 30% petroleum hydrocarbon. In the convection oven, the sample lay on a wire mesh.

<p><tgroup cols="6"><tbody><row><entry>Table H!</entry><entry> 55 </entry><entry>elastomer</entry><entry>Temp, of</entry><entry>Ofenluft-</entry><entry>treatment</entry></row><row><entry>film state</entry><entry></entry><entry>⁶⁰ Point</entry><entry>resin material</entry><entry>Temp.</entry><entry>duration</entry></row><row><entry>molten</entry><entry>(C)</entry><entry>(C)</entry><entry>(Sec.)</entry></row><row><entry>up</entry><entry>116-149</entry><entry>121-204</entry><entry>10-200</entry></row><row><entry>foamed</entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry>171-191</entry><entry>177-232</entry><entry>60-240</entry></row><row><entry>171-204</entry><entry>177-232</entry><entry>60-240</entry></row><row><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry></row></tbody></tgroup></p>

The further Table IV shows the partial dependence of the treatment time of the film at 149 ° C on the film thickness and the special pad.

Backing A consisted of a 0.635 mm thick cellulose felt impregnated with 25% vinyl acetate homopolymer.

Backing B, on the other hand, consisted of a 1.09 mm thick cellulose felt containing 5% hardened urea-formaldehyde resin and 25% butadiene-acrylonitrile polymer.

Table IV

document

Film thickness (in mm)

Duration of treatment (sec) at 149 C

<p><tgroup cols="3"><tbody><row><entry>A</entry><entry>0,203</entry><entry>45</entry></row><row><entry>A</entry><entry>0,356</entry><entry>69</entry></row><row><entry>B</entry><entry>0,356</entry><entry>90</entry></row></tbody></tgroup></p>

Although the foamable batch has been described above as a layer applied to a pad, it can of course also be laminated as a preformed film or, depending on the intended use of the finished product by casting, extrusion molding, calendering or other deformation in any desired shape.

The propellant inhibitor is applied to one side of the polymeric resin material in any desired pattern. This is preferably done with the aid of a liquid carrier medium, since then you can better control the applied amount of inhibitor. If the inhibitor does not dissolve in the carrier medium, it can be finely dispersed in the carrier medium by conventional staining technique. One of the simplest methods of applying the inhibitor-containing approach is to utilize any conventional printing technique, such as screen, offset, or direct gravure gravure. As already mentioned, the inhibitor mixture can be transparent or pigmented. It is usually formulated as an ink. It usually contains a carrier for the pigment, e.g. A vinyl resin, and sometimes a plasticizer for the resin for better adhesion to the printing surface. The blowing agent inhibitor is effective to change the decomposition temperature of the blowing agent in the region of the foamable batch above or below which it is located. By varying the concentration of inhibitor, thickness of the order or its degree of penetration (solubility or diffusibility) in the foamable approach, the extent of suppression or acceleration of blowing agent decomposition can be adjusted to foam layers of different height or Thickness produce. Unusual pattern effects can be achieved by printing the foamable batch with a multicolor pattern, the inks containing partially different inhibitor levels and, secondly, no inhibitor at all.

The choice of inhibitor for a propellant depends on several factors. Primarily, it depends on the particular type of blowing agent, stabilizer and plasticizer used in the system, as well as the fusion and decomposition temperature of the resin. Since every single factor plays a role, one must verify the suitability of any particular system by a simple Versach. For this purpose, the testable, foamable approach is applied in any way to a substrate and, as far as possible without Treibmittelzersetzung, gelled or partially cured by heat. On the surface of the thus gelled approach you bring then at a parallel distance strokes of test inks, which are characterized by different inhibitor content of z. B. 5.20 and 50% differ. Thereafter, the sample is heated thoroughly to melt the batch and the blowing agent in the

zο decompose desired districts. The interaction of a specific inhibitor with the selected formulation and the treatment conditions can then be easily observed on a sample cross-section. As a general rule, that between the two

r&gt; decomposition temperatures of unaffected or inhibited blowing agent should be a difference of at least 11 ° C. When using a propellant which decomposes below the batch gelling temperature, this can first be applied to the substrate and above this the foamable batch. Instead, the inhibitor may also be applied to the surface of the viscous, foamable coating prior to its heating.

Because of the diversity of the chemical propellant

The composition of the compound used as inhibitor also varies. As has been shown above, one can determine the usefulness of a particular compound by a simple experiment. As effective, ie the decomposition temperature-changing inhibitors for propellant -N = N or&gt; N-N bonds, the following compound groups have been found:

1) organic acids and including in particular maleic, fumaric, adipic, malic, citric, salicylic,

³Trimellitic, pyromellitic, malonic, 1,2-phthalic, anthranilic, oxalic, formic, furanecarbonic, benzoic, 2,6-dihydroxybenzoic, sorbic, levulinic, stearic, myristic , Trimesin, olein, octanoic, o-nitrobenzoic, isosebainic and glutaric acid, trans-1-diamino-cyclohexane-tetraacetic acid monohydrate,

4-methoxybenzoic, dihydroxy, o-aminobenzoic, m-aminobenzoic, p-aminobenzoic, 1-naphthoic, terephthalic,

Di ° almond, azelaic, nitrilotriacetic, trichloroacetic, barbituric, 2-pyridinecarbon, 23-pyridinedicarboxylic, ascorbic and abietic acids.

In general, the most useful acids are those having at least two carboxyl groups or at least one carboxyl group and from 2 to 12 carbon atoms.

2) Organic acid halides and in particular chlorides having 2 to 20 carbon atoms, such as. B.

Trimellitic anhydride monoacid chloride, stearoyl chloride, phthaloyl chloride, benzoyl chloride, palmitoyl chloride, cinnamoyl chloride, fumaryl chloride, 1-naphthoyl chloride, terephthaloyl chloride, p-nitrobenzoyl chloride, 4-methoxybenzoyl chloride, isophthaloyl chloride, trichloroacetyl chloride, bromoacetyl bromide, chloroacetyl chloride, phenylacetyl chloride, acetylbromide, n-butyryl chloride, propionyl chloride, isovaleryl chloride, n-valeryl chloride, 2-bromopropionyl bromide, dichloroacetyl chloride, oxalyl chloride, lattroyl chloride, Myristoyl chloride, palmitoyl chloride, succinyl chloride, hexanoyl chloride,

Hydrocinnamoylchlorid.Adipylchlorid,

Isobutyryl ^ methyl-n-valeryl,

Crotonyl ^ -Chlorpropionylchlorid,

2-phenoxypropicyl chloride, phenoxyacetyl chloride,

Propionyl bromide, isobutyryl bromide,

n-Valerylbromid,

2-bromo-2-methyl pΓopiony! Bromide, Sebacylch ORID!,

CydohexancarbonyIchlorid, Äthyloxalylchlorid,

1O-undtcenoyl chloride, undecanoyl chloride,

Benzoylbromid.m-bromobenzoyl bromide,

o-chlorobenzoyl chloride.Anisoyl chloride, 2-furoyl chloride, 2-naphthoyl chloride, m-bromobenzoyl chloride ^^ - dichlorobenzoyl chloride, p-phenylazobenzoyl chloride and 1-nitro-2-anthraquinonecarboxyl chloride.

3) organic acid anhydrides preferably having 2 to carbon atoms, such as. B.

Maleic acid, phthalic acid, succinic acid, pyromellitic dianhydride, citraconic acid, tartaric acid, dodecenylsuccinic acid, trimellitic acid, tetrahydrophthalic acids, tetrachlorophthalic acid, hexahydrophthalic acid, endo-bis-cydo [2 l, l] hept-5-end

2,3-dicarboxylic anhydride, sweet '/ M'-benzophenone tetracarboxylic acid

dianhydride, 1 ^^ cyclopentanetetracarboxylic dianhydride,

Chlorendic anhydride, dichloromaleic anhydride, acetic anhydride, benzoic anhydride, chloroacetic anhydride, propionic anhydride, n-butyric anhydride, isobutyric anhydride, n-valeric anhydride, hexanoic anhydride, n-heptanoic anhydride, citraconic anhydride, bicyclo (2α) -5-heptene-2,3-dicarboxylic anhydride,

cis -cyclohexene-1-dicarboxylic anhydride, 7-oxabicyclo (2,2, l) heptane-2,3-dicarboxylic acid anhydride,

Malco-pimaric anhydride, trifluoroacetic anhydride, glutaric anhydride, dichloroacetic anhydride, itaconic anhydride, 4-methyl-2-cyclohexane-1,2-dicarboxylic anhydride,

Tetrabromophthalic anhydride, 3-nitrophthalic anhydride, tetraiodophthalic anhydride, naphthalenic anhydride, S-norbornene-β-dicarboxylic anhydride, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 4-methylphthalic anhydride, pyromellitic dianhydride.

4) Polyhydric alcohols and a particularly useful subclass thereof, the aromatic alcohols preferably having two functional groups and 2 to 20 carbon atoms, such as p-aminophenol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4-tert-butylpyrocatechol, 2.5 Di-tert-butylhydroquinone, p-benzoquinone, 1,8-dihydroxyanthraquinone, 2,3-naphthalenediol, 2,5-dichloro-3,6-dihydroxy-p-benzoquinone, 2,7-naphthalenediol, 1,3-naphthalenediol, 1,5-naphthalene, Monotert.-butylhydroquinone, Alizarin, Purpurin, Morin, o-Hydroxybenzylalcohol, «- Nitroso - ^ - naphthol and Nitrobenzene-azo-a-naphthoL Useful aliphatic alcohols preferably contain at least 2 hydroxy radicals. These include mannitol, sorbitol, glycerin, ethylene glycol and dietary glycine

5) carbohydrates, such as. As d-maltose, d-galactose, d-glucose and fructose.

6) Nitrogen-containing compounds, such as amines, amides, oximes and the like, among others

Ethanolamine, cyclohexylamine, benzylamine, piperazine, p-nitroaniline, acetoacetanilide, N, N'-disalicylidene-1'-propanediamine, ethylenediamine, triethylenediamine, Ν, Ν-diethylaniline, -B-benzoinoxime, dimethylglyoxime, -F -furildicxime, diphenylcarbazone, salicylaldoxime, Guanidine carbonate, triethylenetetramine, N-chlorosuccinimide, piperazine, Sβ'-imino-bis-propylamine .p-phenylenediamine, nicotine, chifini, quinidine, 8-hydroxyquinoline, piperazine, 1-dichloro-S, -dimethylhydantoin, imidazole, 1.10 -Phenanthrolinmonohydrat, p-nitrobenzene-azo-Ä-naphthol, 1- (2-pyridylazo) -2-naphthiol, phthalic hydrazide, hydrazobenzo-p-toluenesulfonhydrazide, maleic hydrazide, as well as hexadecyltrimethylammonium stearate, hexadecylpyridinium chloride, 1-ethyl-quinaldinium iodide.

The amine is preferably a primary or secondary aliphatic mono- or polyamine. The aliphatic moiety may contain an aromatic or cyclic moiety and be saturated or unsaturated. For example, cyclic compounds may contain a 6- to 10-membered ring and 3 to 12 carbon atoms. Certain aliphatic tertiary amines are also useful.

7) Sulfur-containing compounds such as thiols or mercaptans, sulfides, sulfones, sulfoxides, sulfonic acids, sulfonyl chloride, sulfonamides, sulfimides, and the like. Including z. Eg ·

2-mercaptobenzothiazole, m / x'-dimercapto-p-xylene, so mercaptosuccinic acid, 1-dodecanethiol,

Methanthiolbleisalz,

TrimethyloIpropan-tris- (3-mercaptopropionate),

Benzothiazyl, tetraethylthiuram disulfide,

Butadienesulfone.Glycoldimercaptoacetate, (X-monothioglycerol,

tetramethylthiuram,

Carboxymethylmercaptosuccinic acid,

Thiodiglycolsäure.Tetramethylthiuramdisulfid,

Ethylene thiourea, thiourea, fco diphenyl thiocarbazone, 1-cysteine, o-benzoic acid sulfimide,

sym-diphenyl thiourea,

(X-naphthalene sulfonic acid,

4,4'-diphenyldisulfonic acid, *&gt;^r&gt; 2-naphthalenesulfonic acid, 1-butanesulfonic acid, m-benzenedisulfonic acid, thioacetamide, p-toluenesulfone dichloroamide,

1-ethyl-2-phenyl-2-thiourea,

13-diethyl-2-thiourea, 1-phenyl-2-thiourea, 1.1Aa-tetramethyl-thiourea, 2p-dihydrothiophene-1,1-dioxide, p-toluenesulfonyl chloride, 2-naphthalenesulfonyl chloride,

Glyoxal sodium bisulphide, sodium thiourione,

Benzenethiol, 1-butanethiol, p-toluene thiol,

2-NaphthaIinthiol, Äthanthiol, flt-toluenethiol (benzyl), 3-methyl-l-butanethiol, 1-propanethiol, methanethiol, 2-propanethiol, 1 -Heptanthiol, 2-methylpropanethiol,

Mercaptoacetic acid (thioglycolic acid),

1 -Pentanthiol, glutathione, o-toluenethiol, m-toluenethiol, 1,2-ethanedithiol, o-mercaptobenzoic acid, 2-methyl-2-propanethiol, 2-mercapto-6-nitrobenzothiazole, 6-amino-2-mercaptobenzothiazole,

2-mercaptoethanol, ethylmercaptoacetate, o-aminobenzenethiol, toluene-3,4-dithiol, 1-hexanethiol, S -aninobenzimidazolethiol, 2-benzoxazothiol, 3-mercaptopropionic acid, 1-dodecanethiol, 2-mercaptoacetanilide, 2-ethyl 1-hexanethiol, p-chlorobenzenethiol,

Methyl mercaptoacetate, 2,3-Chinoxalindithiol,

2-furanmethanethiol, 2-phenylethanethiol, p-tert-butylbenzenethiol, 1-octanethiol, 2- (phenylthiol) quinoline,

Ethyl-2-mercaptoäthylcarbonat,

4-mercaptobutyric acid, 23-dimercaptopropanol, 23-dihydroxy-1,4-dithiolbutane,

Isooctyl-S-mercaptopropionate,

Isooctyltioglycolate, 1-thioglycerol

ThioäpfelsäurcMethoxymethylthioglycolat,

PhenyImercaptoessigsäure, 2,9-p-methanedithiol,

/ J-mercaptoethyl-3-mercaptocyclohexane, β-mercaptoethyl-4-inercaptocyclohexane, 3-chloropropanethiol-1, pinanylmercaptan,

DithiolterephthalsJiure, Laurylthioglycolate,

StearylthioglycoIat.Lauryl-beta-mercaptopropionate,

Stearyl-beta-mercaptopropionate,

Hydroxyäthylthioglycolat,

Hydroxyethyl - ^ - mercaptopropionate,

Ethylene-bis-mercaptoacetate,

Ethylene-bis - ^ - mercaptopropionate,

Trimethylolethane-trismercaptoacetat,

Trimethylolpropane trismercaptoacetat,

Pentaerythritol tetrakismercaptoacetat,

Pentaerythritol tetrakis-JJ-mercaptopropionate,

31 Organotin jars,

Dibutylzinnmercaptopropionat,

Dibutyltin bis (laurylmercaptid)

Alkyltin mercaptide and benzylthiouronium chloride.

8) isocyanates, such as. B. 2,4-tolylene diisocyanate, ρ, ρ'-diphenylmethane diisocyanate, bitylene diisocyanate, methylene-bis-phenyl isocyanate), dianisidinediisocyanato-phenyl isocyanate, 1-naphthyl isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, 2-naphthyl isocyanate, m-tolyl isocyanate, toyl isocyanate, p -Ethoxyphenyl isocyanate, p-bromophenyl isocyanate, o-chloroisocyanate, m-chlorophenyl isocyanate, p-chlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, o-ethoxyphenyl isocyanate, o-nitrophenyl isocyanate, 2-biphenylyl isocyanate, m-nitophenyl isocyanate, 4-biphenylyl isocyanate, o-methoxyphenyl isocyanate, p-methoxyphenyl isocyanate, tolylene-2,4-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate,

Methylene di-p-phenyl diisocyanate and p-phenylazophenyl isocyanate

9) ketones and aldehydes, such as. B. Cycloο cyclohexanone, acetylacetone,

13-diphenyl-13-propanedione,

1-phenyl-13-butanedione and glyoxal. Preferred compounds of this class, such as. As polyketones or polyaldehydes contain two functional groups.

10) phosphate and phosphite compounds, such as. Acidic n-butyl phosphate, diamylamyl phosphonate, trilauryl trithiophosphite and

Phenylneopentylphosphit

11) Other interesting compounds with inhibiting properties, such. B.

6,6-dimethylfulvene, hexachlorocyclopentadiene, 2,4-nitrophenol, n-hexyl chloroformate, p-nitrobenzyl chloroformate, dibutyltin maleate

and positive chlorine compounds, such as. B.

Dichloroisocyanuric acid, trichloroisocyanuric acid, potassium dichloroisocyanurate,

N-chloro-p-benzoquinone imine, dichloramine and halane.

Some of these last mentioned compounds belong to earlier groups.

When you use propellant with a reducible, so

for example, an azo group used, then is a

Reducing agent is a particularly effective inhibitor.

Such typical reducing agents are, for example,

hydroquinones,

Polyhydroxyaromatic compounds, phenylenediamines, hydrazobenzenes, alkali metal dithonite, mercaptans such as "A" -dimercapto-p-xylene _U.Nd

Mercaptosuccinic acid as well as the reducing sugars.

As already mentioned, some inhibitors cause the districts in contact with them to rise above the rest of the layer area, because there the propellant decomposition temperature is lowered. Sometimes, when the foam is heated to a higher temperature, this increased decomposition may also cause these districts to collapse due to overgrowth. Such a collapsed product may then look exactly as if the propellant decomposition had been prevented.

The inhibitors are not useful for certain types of blowing agents. For example, aminoguanidine bicarbonate is best prepared with anhydrides, e.g. As the malein or trimellitic acid inhibited. N, N'-dimethyl-N, N'-dinitrosoterephthalamide reacts to similar anhydrides as well as to chlorides such as terephthaloyl chloride, p, p-oxybis (benzenesulfonyl hydrazide) is particularly strongly inhibited by trimellitic anhydride, terephthaloyl chloride, fumaric acid and hydroquinone. For diazoaminobenzene and p, p'-oxybis (benzenesulfonylsemicarbazide),

One also uses maleic and trimellitic anhydride and for the latter also fumaric acid and terephthaloyl chloride as an inhibitor. Interestingly, inhibitors such as these catalyze the decomposition of Ν, Ν'-dinitrosopentamethylenetetramine and, therefore, in their use, cause an increase in the districts affected by them. It is therefore necessary to take care to obtain a desired product care in the inhibitor selection.

The inhibitor causes different levels of soaking between the areas touched by it and the other areas, provided that the heating of the batch is adjusted so that this differential expansion is possible. It results from a reduction or increase in the decomposition of the contacted propellant. Those areas of the layer of the resin material to which the inhibitor is applied are either higher or lower because of this different propellant decomposition. What is going on chemically is currently unknown, but the inhibitor probably reacts with a functional group on the propellant or more, thus forming a compound or complex with a decomposition temperature different from that of the propellant the acids and acid anhydrides. When using a reducing agent, the azo group is reduced by hydrogen or a hydrocarbon radical. The inhibitor may also influence the effectiveness of the accelerator. Probably, the metallic accelerator in a propellant such as azobisformamide causes the hydrolysis of its amide group and the formation of the corresponding salt, and then the inhibitor can retard or arrest this hydrolysis. Instead, the inhibitor may act as a catalyst or activator even when changing the blowing agent decomposition temperature. Another procedure consists in using a mixture of propellant and inhibitor or a compound formed from them both as propellant in the resin batch.

Then, on the surface of such an approach, a second inhibitor is removed which removes the first inhibitor from the propellant and, as a result, causes it to assume its original decomposition temperature again. A typical example of such an approach would be the use of an acid as a first and a base as a second inhibitor. The inhibitor can form a compound with the existing accelerator, thereby reducing the ability of the blowing agent decomposition temperature to decrease. For example, using lead as an accelerator, one can add a chlorine ion donor, which then prevents the lead from accelerating by salt formation. It has also been found that certain chelating agents can remove metallic accelerators from the system by chelation.

It is important to give the batch of resin material in the regions covered by the inhibitor a decomposition temperature which is sufficiently different from that of the other batch areas to allow for differential expansion. Therefore, the fusion temperature of the polymer formulation determines the temperature range in which to work to achieve this differential decomposition.

Why the inhibitor by merely applying to the surface of the foamable approach, the propellant decomposition prevented or accelerated, z. Z. not yet completely clear. Certainly plays in this process, the existing at the decomposition temperature solubility or Eindiffundierbarkeit the inhibitor with respect to the foamable approach an essential role. When using slightly soluble inhibitors have their amount and concentration

κι a pronounced influence on the degree of inhibition. Insoluble or only slightly soluble inhibitors can be made more easily insoluble or diffusible at the working temperatures by giving them a fine pigment character

The proportion of material in the ink largely determines the extent of foaming inhibition. Particularly good results were achieved with 5 to about 75% inhibitor. The effectiveness of the system can be increased by covering the inhibitor with a barrier layer of, for example, acrylic resin and thereby preventing it from migrating to the non-foamable abrasion protection layer

The inventively formed Abriebsschutzschicht consists of a preformed, self-supporting film containing a thermoplastic material, ie either consists of only or even has a plasticizer.

For this scuff-resistant layer, one can use the same resins described above as suitable for the foamable resin material batch. Again, vinyl chloride polymers proved to be a particularly effective material. Furthermore, you can enforce the Abriebsschutzschichtansätzen also the previously mentioned heat and light stabilizers.

Fillers and Pigment Suitable as neutral filler are silica in both amorphous and crystalline form, whiting, talc, clay, pumice, limestone and the like. The pigments are selected according to the desired color. For example, if the substrate is to be white, titanium dioxide or zinc oxide is taken alone or extenders such as. B. Barium sulfate, magnesium carbonate, magnesium silicate or the like. For colored background one uses any known inorganic or organic color pigment

Experience has shown that the presence of filler is apparently important to the invention in order to avoid shrinkage and distortion of the abrasion protection layer. How much filler is required depends largely on its type; however, the desired results were achieved with at least 25% based on batch weight and no more than 60% filler. Since the inhibitor is preferably applied to the surface of the foamable batch with a print pattern to be visible through the scuff-resistant layer, it is important that the filler be transparent or translucent. Schup-

bo pentalkum is a particularly good filler of this type

The scuff-resistant layer is prepared by first forming the filler-containing resin material into chips, coating the particles with a plastisol, and finally, without the mixture

To melt h5 plastisol, to roll it into a foil. The starting particles are preferably multicolored. The easiest way to prepare them is to separate separate lots of differently colored resin mixtures.

mixes, then granules and the granule mixture mixed in the desired amount to obtain the desired color combination. The granule mixture is then suitably, e.g. B. by rolling or extrusion molding into films, and then these films finally get the desired geometric cut Preferably, all chips get uniform thickness. Therefore, they cut most advantageous from films. Their thickness is preferably about one third to about seven nights¹ and most preferably about one-half to about two-thirds of the thickness of the decorative abrasion-resistant layer to be made, which in turn may vary but be at least 0.356 mm and generally should not exceed 1.27 mm. In addition, in order to achieve the desired decorative effect, the size of the pigmented seed chips, whose front surface should be about 1.27 to about 12.7 mm in diameter, is particularly important.

The chips are then coated with a liquid resin batch. It was achieved with a mixture of about 25 to about 50% liquid approach and about 75 to about 50% chips the desired results. A mixture of about 30 to about 40% liquid approach and about 70 to about 60% chips proved to be particularly powerful.

According to one embodiment of the invention, it is possible to carry out the preliminary preparation of the foamable resin material batch in such a way that a substrate with a layer of propellant-containing approach of polymeric! Resin material, then the coating, without decomposing the propellant, in order to create a comparatively solid surface at least gel and finally on the surface of the gelled film imprints a hemmstoffhaltigen approach or otherwise applies, which is able to change the decomposition temperature of the propellant contained in this film.

According to a modified embodiment, it is possible first to apply the foaming inhibitor to a backing or otherwise, and then to apply the foamable formulation over it. In this case, if desired, the pad may be a release liner and the applied pattern a decal. Furthermore, you can also the foamable approach while avoiding propellant decomposition z. B. calendering to form a completely or partially melted film and then cover this on one side or the other with the inhibitor. Yet another preparation route consists in first applying to the foamable layer an intermediate layer of a non-foamable, solid batch of polymeric resin material and first applying the inhibitor over it. This then migrates through the blowing agent-free layer into the foamable layer during subsequent heating. In this case, however, it is necessary to work with a higher concentration of inhibitor than in the case of direct application in order to achieve the same rubbing effect.

The second step of the method according to the invention, namely the application of the abrasion protection layer, can be carried out in various ways. For example, the resin film can be applied directly to the inhibitor-containing batch with or without binder aid. Instead, you can make the printed, foamable layer even by heating particularly sticky and then only with the Abriebsschutz

layer into contact.

The preferred procedure, however, is that the abrasion protection layer at the time of their formation with the foamable resin mixture to double layer united For this purpose, bringing the viscous mass of pigmented chips and resin material approach on a pair of calender rolls, whose gap width is set to more than clamping thickness Thus the rolling of the mass without significant size and shape change of the chips are effected. The calender rolls are heated so that a partial solvation of the resin takes place and the liquid mass is converted into a chip-containing, solid, self-supporting film. In this respect, it depends in particular on how long the batch with the hot calender rolls in contact, as he must be able to absorb enough heat to pass from the liquid to the gelled solid state. The heated film is then bonded to the printed, foamable layer.

The characteristic of the abrasion-resistant layer of the resin material which is crucial for the purposes of the invention is that it must be fluid or viscous in the temperature range used for propellant decomposition. One meets this requirement in that it rolls out at a temperature below its melting temperature or otherwise converts to the film. This is achieved, for example, by passing the preformed polyvinyl chloride batch through hot rollers at about 107 ° to 149 ° C.

Subsequently, the multilayer structure of foamable resin material batch, inhibitor and translucent abrasion protection layer is then heated to such an extent that both resin mixtures melt as a result of complete resin solvation by the plasticizer and the blowing agent system is decomposed. In this case, the entire, located on the base batch mass must come to the resin melt temperature in order to achieve a Eikeugnis of the greatest possible strength and stain resistance. In the preferred vinyl resin material, the melting in the temperature range of about 163 ° to about 191 ° C is achieved. In addition, the foamable approach must be heated from the resin material in its total mass so high that the blowing agent is decomposed. When using the preferred high temperature propellant, foaming does not start until the batch of resin material has fused. However, the heating may only be so high that decomposes the propellant only in the desired districts. As a result of the heating, the abrasion-resistant layer also acquires the desired flowability, so that it can conform to the relief formed on the surface of the resin material.

If volatiles have been incorporated into the batches, care must be taken to ensure that they are virtually completely removed from it prior to fusing the film. This can be achieved, for example, by heating the batch to a temperature which is substantially lower than the melting temperature and also the lowest blowing agent decomposition temperature, as long as necessary for this removal. So, for example with a hydrocarbon solvent fraction (up to 177⁰C reaching a final boiling point), you can so much by heating for 5 minutes at 93 ° to 121 ° C.

remove that at the subsequent fusing and foaming at about 204⁰C receives a good and bubble-free pore structure, this Schlußhitzung can be done in a Heißurnluftofen or otherwise, for example, by passing the product by heat radiators or instead heated dielectrically.

After leaving the oven, the frothed and melted product is allowed to cool. This measure is particularly important because the product may coincide partially with premature, ie immediately after foaming handling and could suffer Gefü Damädigung. The cooling can be carried out in free circulating air, and for this purpose is controlled by the rate of flow of the support substrate through the treatment apparatus and the distance between the furnace and the end of the furnace so that the product can cool enough on her. Instead, the finished product can also be blown with cold air, sprayed with water or passed through cooling rollers.

After cooling, the product is removed from the apparatus and can then be used depending on the further use in the existing film form or divided into plates or otherwise designed blanks. Such products according to the invention have excellent elasticity, which depends in part on the thickness of the foam mass layer. Moreover, they are distinguished by a pronounced, three-dimensionally structured appearance, A further advantage of the products obtainable according to the invention is their good heat-insulating capacity as a result of the foam layer which makes them warmer in winter time compared to conventional resin cover layers

Finally, the products have excellent resistance to wear, chemical attack and contamination due to their complete and experience even all relief cracks filling surface cover with a transparent, decorative abrasion protection layer.

The following example, in which all parts, unless otherwise stated, relate to weight, the invention will be explained in more detail.

example

This example describes the preparation of an abrasion-resistant, relief-carrying resin material approach, as is typical of the products according to the invention

a) Preparation of the foamable resin material batch

A 0.89 mm thick asbestos web as a carrier underlay was coated in 0381 mm wet layer thickness with the following, foamable plastisol

The coated layer was gelled by heating for 2½ minutes in a 204 ° C oven.

Subsequently, the gelled layer was printed in sections by means of a rotary printer with the following embossing color:

parts

low molecular weight polyvinyl chloride 50

high molecular weight polyvinyl chloride 50

dibasic lead phosphate 1.5

Azodicarbonamide 23

Titanium dioxide 5

Butylbenzoyl phthalate 55

Dodecylbenzene 10

fumaric acid

Vinyl chloride-vinyl acetate copolymer

methyl ethyl ketone

titanium dioxide

parts

10

7,5

47,5

14,0

b) Preparation of the abrasion protection layer

π The following plastisol formulation was prepared by thoroughly mixing the following components

<p><tgroup cols="2"><tbody><row><entry></entry><entry>parts</entry></row><row><entry>Dioctyl phthalate (as plasticizer)</entry><entry>99</entry></row><row><entry>Butylbenzoylphthalat</entry><entry>16</entry></row><row><entry>stabilizer</entry><entry>19,2</entry></row><row><entry>Polyvinyl chloride and dioctyl</entry><entry></entry></row><row><entry>phthalate plastisol</entry><entry>48</entry></row><row><entry>Dispersion type polyvinyl chloride</entry><entry>320</entry></row><row><entry>Stearic acid (as lubricant)</entry><entry>13</entry></row></tbody></tgroup></p>

The translucent chips used together with this plastisol formulation for the production of the abrasion protection layer were produced from the following jo batch

parts

Polyvinyl chloride 100

Tending talcum (as filler) 50

Dioctyl phthalate (as plasticizer) 323

Butyl benzoyl phthalate 43

Stabilizer 73

UV light-absorbing device 0.4

Pigment 6.0

This batch was first formed into a 0381 mm thick film and this in turn comminuted into square chips of about 3.2 mm in size. The chips thus obtained were then introduced into the clear plastisol in a weight ratio of 65% (shavings) to 35% (plastisol). and the approximately 21 "C warm" mixture was applied to two chrome-plated calender rolls, of which the upper one was 143⁰C and the lower was heated to 132 ° C and both let so much gap between them that a 0.762 mm thick film was formed. This film was held with the bottom roll to almost full extent in Köiiiakl and then pulled off with a throughput rate of 5.79 m / minute.

- c) lamination and relief formation

The 0.762 mm thick, coated abrasion resistant film was then laminated to the foamable plasticisate batch by passing both films through the liner at a throughput rate of 9.14 m / min through a laminating press, and thereafter a drum temperature of 171 ° C ιπκ subjected to a roller pressure of 40.4 atü. Dabe they were united by the interaction of heat pressure and stickiness of the vinyl embossing color to a uniform, firmly together Verbundgebildi The composite web thus obtained you sent dam

again at 9.14 m / minute throughput speed through a furnace with four, each 9.14 m long and 149 ", 207 and 204 respectively⁰C hot zones through. During this heating process, the composite was melted and the propellant decomposed to form raised, porous sections on the product surface. The difference in thickness between the foamed and the original thickness remaining areas of the structured surface was 3: 1, the raised areas not with the hemnistoffhaltigen

Embossed ink printed sections corresponded.

In addition, the scuff-resistant layer perfectly conformed to the surface relief of the product, giving it an excellent resistance to wear, discoloration and chemical attack. In addition, because of the precise retention of the desired pattern of relief and the combination of abrasive and anti-pigmented flakes, the surface finish of the product was particularly uniform and pleasing.

For this 1 sheet drawings