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 substrate 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 you have them either alone or together with non-porous, abrasion-resistant cover layers and / or Unterlagestoffen introduced in products of the aforementioned kind Such a film of synthetic foam gives the product depending on the Schaumstoffart various desirable properties such as high elasticity and good feel.

The embossing of the synthetic resin films is usually carried out by means of an embossing roll or plate whose surface has previously been given the desired high-level pattern by engraving or other treatment. The film and / or embossing surface is then heated and the pattern is pressed into the heat-softened film.

It has also been proposed various methods for the production of Schaurßjtofferzeugnissen 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

Jo methods known as a strong improvement has been disclosed in US-PS 32 93 094 and 32 93 108. In this procedure, the decomposition temperature of a chemical blowing agent dispersed in a polymer resin composition is controlled by

J5 one applies to the mass surface an inhibitor. In the subsequent heat treatment, the blowing agent is then 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.

Although most of these known abrasion resistant 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 into the depressions of the chemically embossed products at such a thickness adjustment at the processing temperatures due to their fluidity and partially filled them up. 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 found that such calendered films have excessive dimensional stability.

they can not easily adapt to the coinage and sometimes bridge the distressed districts. To compensate for this excessive dimensional stability, one necessarily had to use thinner ones

h) Working and therefore drastically reducing the applicability of finished products for heavy duty applications where firmer and more resistant scuff layers are required

Higher levels of plasticizer, which sought to increase the flexibility and flowability of such abrasion-resistant layers, impaired both the feel of the finished product and the stain resistance of the protective layer. In addition, almost all plastisol approaches used as an abrasion-resistant layer were transparent, whereby the print pattern under the surface of the protective layer becomes visible and the embossing blur somewhat compensates. By reinforcing the printed appearance, however, the transparent areas almost completely suppress the uniform natural geometric appearance that the finished product should have.

The invention has for its object to provide a process improved in terms of the processing of the above-mentioned cover films or abrasion protective 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, wherein the mixture - based on their weight - 25 to 60% of a translucent or translucent filler added, η and calendering at a temperature lower than the resinous mixture melt temperature, the preformed abrasion protection layer is applied to this layer prior to heating the foamable, propellant-containing layer of resin material and imparting the required flowability to the abrasion-resistant layer during heating.

The inventively embodied abrasion protection layer * characterized by an exceptional performance and decorative appearance and at the same time avoids all previously mentioned UnvoUkommenheiten the previous abrasion protection layer

Thus, according to the invention, a multilayer, embossed, porous foam product is obtained by first forming a layer of a resin material containing a blowing agent, bringing portions of this layer into contact with a substance raising or lowering the blowing agent decomposition temperature, 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-layered foam product and the formation of the abrasion resistant layer with the desired abrasion resistance are a result of the final heating, whereby the inhibiting reaction is effected, due to which the blowing agent is selectively decomposed and the abrasion protection layer is ultimately formed in the desired manner, in particular the optimum adjustment is achieved.

It can be seen that the product obtainable by the process according to the invention combines the typical advantages of the chemical embossing technique with the unique performance of the described abrasion protection layers. 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

oderο or pressure and without regard to shape or outline of the surface 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 floor, wall, table and body coverings and the like and in fact wherever 2s on synthetic resin films or compounds with abrasion-resistant surface arrives. 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

■ »5 shows

Fig. 1 is a flow diagram of a typical embodiment of the erfiidungsgemäßen method 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 base all deformable to films, thermoplastic or elastomeric synthetic resin materials with any plasticizer or filler content, including typically

Fe ° 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, which made in this way reusable

fe5 can be.

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 seasoning layer acts which acts as a brake layer and prevents the felt-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 may consist of water, an organic solvent as organosol or a plasticizer as plastisol. The best results were 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. Piastisols are therefore preferred because, in contrast to latex or organosol, they do not require a large amount of carrier volume to be removed. However, the resin material may also consist of a dry mixture of resin particles with superficially absorbed plasticizer, stabilizer, pigments, and the like, together with propellant, which is applied in a smooth layer to 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. With porous design of the film penetration of the inhibitor is of course facilitated. Such films are normally subsequently heated and subjected to compression for densification.

The preferred and most commonly used topcoat resinous resin materials are vinyl chloride polymers. These can be either simple

che, unmixed vinyl chloride homopolymers or copolymers or terpolymers or the like, whose important, consisting of polyvinyl chloride polymer structure 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. Evidently, despite this preference for polyvinyl resins, the resin materials can also be formed from any other resin that can be foamed by means of a blowing agent. Therefore, the invention is by no means limited to a resin or a resin group of certain kind, but also with many others, the. Professional common resin types and groups feasible. Thus, for example, it is also possible to work with 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 polymers. They are available in particle sizes of from 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. Dispersion type resins usually have a higher molecular weight than calendering type resins. Their particles have surfaces of hard horny nature. Particularly effective are such vinyl chloride polymers, their specific viscosity - according to ASTM D 1243-60 method, ie in 30⁰C. warm solution of 0.4 g of resin in 100 ml of nitrobenzene, measured above about 0.25 and preferably between 0.3C and 0.70. The specific viscosity is calculated from the flow time (Fh) of the resin solution and the (Fn) of the pure nitrobenzene according to the formula (Fh: Fn) - 1! and stated. It provides 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 Han is uniformly dispersed in a mass of flowable plasticizer. The plastisol fluidity depends in part on the nature of the specific resin unc of the selected plasticizer, but also on the ratio of both and decreases with decreasing softener resin ratio. The coating formulations used in this invention each contain 10 (parts of resin material, about 20 to about 150 and, exceptionally high performance, about 50 to about 80 parts of plasticizer.) Plastisol viscosity may also be reduced by addition of some volatile solvents, not more than about IC Reduce parts thereof to each 100 parts of resin material but the solvent may not exert any solvating influence on the resin material. AL diluents are, for example, benzene, toluene, methyl ethyl ketone, petroleum solvents such as VM and P naphtha (with boiling ranges between 88^C and 135 ° C) and the like.

The organosols useful in carrying out the process of this invention preferably contain from about 20 to about 55 parts, and most preferably from about 30 to about 40 parts plasticizer, to j <100 parts resin material, while with plastisols as mentioned

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 Esters of alcohol and acid, at least one of which is an ester component of an aromatic nature, are desirable in that they impart 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 proved 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, further 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 foamable formulations, the stabilizer may also have an influence on the blowing agent decomposition. Some stabilizers catalyze insofar as they lower the decomposition temperature.

Depending on the desired color shade, the coating formulations can also contain pigments of 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. One can easily foam densities of 192 to about 641 kg / m³ Achieve about 1 to 20 parts of blowing agent per 100 parts resin material With about 2 to 10 parts of blowing agent per 100 parts of resin material obtained in particular foam masses of such density, as they are particularly desirable for the production of foot coverings.

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 on heating, thereby giving off an inert gas and leaving residues which coalesce with the

vertrο resin tolerate. 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 = NH₁¹I

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

The most widely used propellants in use are those compounds which have the "N-N" or N = N 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 = N-b

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 other decomposition temperatures.

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

Table I

propellant

decomposition temperature

Azodicarbonamide OO

CNH₂CN = NC-NH

P, p'-oxybis (benzenesulfonyl hydrazide)

163-204

149-154

continuation

propellant

Zersetzungstcmpcratur

p, p'Oxybis (benzolsult-Nylsemi- 149-163

carbazide)

Azobisisobutyrnilri! 102-121

N, N'-dimethyl-N'-dinitrosotere-38-104

phthalamide

Diazoaminobenzene 101-130

Other noteworthy propellants include

Ν, Ν'--dinitrosopentamethylenetetramine,

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-1,5-disulfonylhydrazide and

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 93 ° C. Thus, for example, together with the preferred vinyl chloride polymers, one can use a blowing agent which decomposes between about 149 ° and about 232 ° C. The lowest initial decomposition temperature must be high enough that no gas evolution occurs during processing. Sometimes you can also use propellant mixtures with advantage.

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 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, oxyde, stearate, carbonate, 2-ethylhexanoate, di-n-octoate or similar zinc salts, cadmium octoate, -oxyd, -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 foamable batch 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 "gelling" 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

Temperature is limited so that premature blowing agent decomposition in the batch is avoided. When using the preferred polyvinyl chloride approach increases the approach temperature to about 116 ° to about 135 ° C, of ​​course, the furnace temperature must be set slightly higher. 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 Aufschäumausmaß a typical Plastisolansatzes depending on the blowing agent content is shown in Table II below.

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

For the preferred polyvinyl chloride resin, Table III below presents the most favorable heating conditions in temperature and duration for the various film states. The film tested was, in its initial state, a 0.356 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="3"><tbody><row><entry>Table II</entry><entry>ratio of</entry><entry>Density in kg / m³</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>

Table III

film state

Temp, of the oven air resin material Temp.

duration of treatment

(Sec.)

elastomer point

Melted Foamed

116-149 121-204

171-191 171-204

177-232 177-232

10-200

60-240 60-240

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.

<p><tgroup cols="3"><tbody><row><entry>Table IV</entry><entry>Film thickness (in mm)</entry><entry>Duration of treatment (sec) at 149 C</entry></row><row><entry>document</entry><entry>0,203 0,356 0,356</entry><entry>45 69 90</entry></row><row><entry> \ AB</entry><entry></entry></row><row><entry></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 like a printing ink. It usually contains a carrier for the pigment, for. 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. First and foremost, 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 attempt. 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 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 a difference of at least 11⁰C should exist. 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 variety of chemical blowing agent compositions, the type of compound used as the inhibitor also varies. As has been shown above, one can determine the usefulness of a particular compound by a simple experiment. As effective, that is, the decomposition temperature-changing inhibitors for propellant - N = N or&gt; N - N &lt;bonds, the following compound groups have been found:

1) organic acids and especially including maleic, fumaric, adipic, malic, citric, salicylic, trimellitic, pyromellitic, malonic, 1,2-phthalic, anthranilic, oxalic, formic, Furancarbon, benzoic, 2,6-dihydroxybenzoic, sorbic, levulin, stearic, myristic, trimesin, olein, octanoic, o-nitrobenzoic, isosebainic and glutaric acid, trans-1-diaminocyclohexane -tetraessigsäureinonohydrat,

4-methoxybenzoic, dihydroxy, o-aminobenzoic, m-aminobenzoic, p-aminobenzoic, 1-naphthoic, terephthalic, ^D Di-almond, azelaic, nitrilotriacetate, trichloroacetic,

Barbituric, 2-pyridinecarbon, 2,3-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 -Chloride 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, pheniacetyl chloride, acetylbromide, n-butyryl chloride, propionyl chloride, isovaleryl chloride, n-butyl Valeryl chloride, 2-bromopropionyl bromide, dichloroacetyl chloride, oxalyl chloride, lattroyl chloride, Myristoyl chloride, palmitoyl chloride, succinyl chloride, hexanoyl chloride,

<p><tgroup cols="3"><tbody><row><entry>20 1 13 </entry><entry>2</entry><entry>124 14 </entry></row><row><entry>Hydrocinnamoyl chloride, adipyl chloride,</entry><entry></entry><entry>Alizarin, Purpurin, Morin,</entry></row><row><entry>Isobutyryl ^ methyl-n-valeryl,</entry><entry></entry><entry>o-HydroxybenzylalkohoLa-nitroso - ^ - naphthol</entry></row><row><entry>Crotonyl ^ -Chlorpropionylchlorid,</entry><entry></entry><entry>and nitrobenzene azo-naphthol.</entry></row><row><entry>2-Phenoxypropionylchlorid, PhenoxyacetylchloΓid,</entry><entry></entry><entry>Useful aliphatic alcohols preferably contain</entry></row><row><entry>Propionyl bromide, isobutyryl bromide,</entry><entry> 5 </entry><entry>at least 2 hydroxy radicals. Belong to them</entry></row><row><entry>n-Valerylbromid,</entry><entry></entry><entry>Mannitol, sorbitol, glycerin,</entry></row><row><entry>2-BΓom-2-methylpΓopionylbΓomid, sebacyl chloride,</entry><entry></entry><entry>Ethylene glycol and diethylene glycol.</entry></row><row><entry>Cyclohexanecarbonyl, ÄthyIoxalylchlorid,</entry><entry></entry><entry></entry></row><row><entry>1O-undecenoyl chloride, undecanoyl chloride,</entry><entry></entry><entry>5) carbohydrates, such as. B.</entry></row><row><entry>Benzoyl bromide, m-bromobenzoyl bromide,</entry><entry> 10 </entry><entry>d-maltose, d-galactose, d-glucose and</entry></row><row><entry>o-Chlorbenzoylchlorid.Anisoylchlorid,</entry><entry></entry><entry>Fructose.</entry></row><row><entry>2-furoyl chloride, 2-naphthoyl,</entry><entry></entry><entry></entry></row><row><entry>m-bromobenzoyl ^ -Dichlorbenzoylchlorid,</entry><entry></entry><entry>6) Nitrogen-containing compounds, such as amines, amides,</entry></row><row><entry>p-phenylazobenzoyl chloride and</entry><entry></entry><entry>Oximes and the like, among others</entry></row><row><entry>l-nitro ^ -anthrachinoncarboxylchlorid.</entry><entry> 15 </entry><entry>Ethanolamine, cyclohexylamine, benzylamine,</entry></row><row><entry></entry><entry></entry><entry>Piperazine, p-nitroaniline, acetoacetanilide,</entry></row><row><entry>3) Organic acid anhydrides preferably having 2 to</entry><entry></entry><entry>Ν, Ν'-disalicylidene l ^ propanediamine,</entry></row><row><entry>20 Carbon atoms, such as. B.</entry><entry></entry><entry>Ethylenediamine, triethylenediamine,</entry></row><row><entry>Maleic, phthalic, succinic,</entry><entry></entry><entry>NN-Diäthylanilin.oc-benzoinoxime,</entry></row><row><entry>Pyromellitic dianhydride, citraconic acid,</entry><entry> 20 </entry><entry>Dimethylglyoxime, «furfil dioxime,</entry></row><row><entry>Brenoic Acid, Dodecenyl Succinic Acid,</entry><entry></entry><entry>Diphenylcarbazone, salicylaldoxime,</entry></row><row><entry>Trimellitic acid, tetrahydrophthalic acids</entry><entry></entry><entry>Guanidine carbonate, triethylenetetramine,</entry></row><row><entry>Tetrachlorophthalic acid, hexahydrophthalic acids</entry><entry></entry><entry>N-chlorosuccinimide, piperazine,</entry></row><row><entry>Endo-bis-cyclo [2,2,1] hept-5-end</entry><entry></entry><entry>3,3'-imino-b spropylamine, p-phenylenediamine,</entry></row><row><entry>2,3-dicarboxylic acid anhydride,</entry><entry> 25 </entry><entry>Nicotine, quinine, quinidine, 8-hydroxyquinoline,</entry></row><row><entry>S.B '^^' - Benzophenontetracarbonsäure-</entry><entry></entry><entry>Piperazine, 13-dichloro-5,5-dimethylhydantoin,</entry></row><row><entry>dianhydride,</entry><entry></entry><entry>Imidazole, 1,10-phenanthroline monohydrate,</entry></row><row><entry>l ^^ - cyclopentanetetracarboxylic</entry><entry></entry><entry>p-nitrobenzene-azo-a-naphthol,</entry></row><row><entry>dianhydride,</entry><entry></entry><entry>1 - (2-pyridylazo) 2-naphthol, phthalic acid hydrazide,</entry></row><row><entry>chlorendic,</entry><entry> 30 </entry><entry>Hydrazobenzene, p-toluenesulfonhydrazide,</entry></row><row><entry>Dichloromaleic anhydride, acetic anhydride,</entry><entry></entry><entry>Maleic hydrazide, as well</entry></row><row><entry>Benzoic anhydride, chloroacetic anhydride,</entry><entry></entry><entry>Hexadecyltrimethylammoniumstearat,</entry></row><row><entry>Propionic anhydride, n-butyric anhydride,</entry><entry></entry><entry>hexadecyl,</entry></row><row><entry>Isobutyric anhydride, n-valeric anhydride,</entry><entry></entry><entry>1 -Äthylchinaldiniumiodid.</entry></row><row><entry>Hexanoic anhydride, n-heptanoic anhydride,</entry><entry> 35 </entry><entry></entry></row><row><entry>citraconic,</entry><entry></entry><entry>The amine is preferably a primary or</entry></row><row><entry>Bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid</entry><entry></entry><entry>secondary, aliphatic mono- or polyamine. Of the</entry></row><row><entry>anhydride, '</entry><entry></entry><entry>Aliphatic portion may be an aromatic or</entry></row><row><entry>cis-4-cyclohexene-1,2-dicarboxylic anhydride,</entry><entry></entry><entry>contain cyclic moiety and saturated or</entry></row><row><entry>7-oxabicyclo (2,2, l) heptane-2,3-dicarboxylic acid</entry><entry> 40 </entry><entry>be unsaturated. Cyclic compounds can</entry></row><row><entry>anhydride.</entry><entry></entry><entry>for example, a 6- to 10-membered ring and 3 to 12</entry></row><row><entry>Malco pimarsäureanhydrid,</entry><entry></entry><entry>Contain carbon atoms. Certain aliphatic</entry></row><row><entry>Trifluoroacetic anhydride, glutaric,</entry><entry></entry><entry>Tiamines are also useful.</entry></row><row><entry>Dichloroacetic anhydride, itaconic anhydride,</entry><entry></entry><entry></entry></row><row><entry>4-methyl-2-cyclohexane-l, 2-dicarboxylic acid</entry><entry> 4) </entry><entry>7) Sulfur containing compounds such as thiols</entry></row><row><entry>anhydride,</entry><entry></entry><entry>or mercaptans, sulfides, sulfones, sulfoxides, sulfone</entry></row><row><entry>tetrabromophthalicanhydride,</entry><entry></entry><entry>acids, sulfonyl chloride, sulfonamides, sulfimides, and</entry></row><row><entry>3-nitrophthalic anhydride,</entry><entry></entry><entry>like. Including z. B.</entry></row><row><entry>Tetrajodphthalsäureanhydrid,</entry><entry></entry><entry>2-MercaptobenzthiazoI, 'A'-dimercapto-p-xylene,</entry></row><row><entry>naphthalic,</entry><entry> 50 </entry><entry>Mercaptosuccinic acid, 1 -dodecanethiol,</entry></row><row><entry>5-norbornene-2,3-dicarboxylic anhydride,</entry><entry></entry><entry>Methanthiolbleisalz,</entry></row><row><entry>3-chlorophthalic anhydride,</entry><entry></entry><entry>Trimethylolpropane-tris- (3-mercaptopropionate),</entry></row><row><entry>4-chlorophthalic anhydride,</entry><entry></entry><entry>Benzothiazyl, tetraethylthiuram disulfide,</entry></row><row><entry>4-methylphthalic anhydride,</entry><entry></entry><entry>Butadiene sulfone, glycol dimercaptoacetate,</entry></row><row><entry>Pyromellitic.</entry><entry> 55 </entry><entry>oc-monothioglycerol,</entry></row><row><entry></entry><entry></entry><entry>tetramethylthiuram,</entry></row><row><entry>4) Polyhydric alcohols and as a special need</entry><entry></entry><entry>Carboxymethylmercaptosuccinic acid,</entry></row><row><entry>bare subclass of which are the aromatic alcohols</entry><entry></entry><entry>Thiodiglycolsäure.Tetramethylthiuramdisulfid,</entry></row><row><entry>preferably two functional groups and 2 to 20</entry><entry></entry><entry>Ethylene thiourea, thiourea,</entry></row><row><entry>Carbon atoms, such as</entry><entry> 60 </entry><entry>Diphenylthiocarbazone, 1-cysteine,</entry></row><row><entry>p-aminophenol, catechin, resorcinol, hydroquinone,</entry><entry></entry><entry>o-benzoic,</entry></row><row><entry>Pyrogallol, phloroglucin,</entry><entry></entry><entry>sym-diphenyl thiourea,</entry></row><row><entry>4-tert-butylcatechol,</entry><entry></entry><entry>a-naphthalenesulfonic acid,</entry></row><row><entry>2,5-di-tert-butylhydroquinone, p-benzoquinone,</entry><entry></entry><entry>4,4'-diphenyldisulphonic,</entry></row><row><entry>1,8-dihydroxyanthraquinone, 2,3-naphthalenediol,</entry><entry> b^r&gt; </entry><entry>2-naphthalenesulfonic acid, 1-butanesulfonic acid,</entry></row><row><entry>2,5-dichloro-3,6-dihydroxy-p-benzoquinone,</entry><entry></entry><entry>m-Benzoldisulfonsäure.Thioacetamid,</entry></row><row><entry>2,7-naphthalenediol, 1,3-naphthalenediol,</entry><entry></entry><entry>p-toluenesulfon,</entry></row><row><entry>1,5-naphthaliridiol, monotert.-butylhydroquinone,</entry><entry></entry><entry>l-ethyl-2-phenyl-2-thiourea,</entry></row></tbody></tgroup></p>

1 1-diethyl-thiourea, 1-phenyl-2-thiourea, UAS-tetramethyl-thiourea, 2,5-dihydrothiophene-1,1-dioxide, p-toluenesulfonyl chloride, 2-naphthalenesulfonyl chloride, glyoxal sodium bisulfite, sodium dithionite, benzenethiol, 1 Butanethiol, p-toluene thiol, 2-naphthalene thiol, ethanethiol, a-toluene thiol benzylmercaptan X 3-methyl-1-butanethiol, 1-propanethiol, methanethiol, 2-propanethiol, 1-heptanethiol, 2-methylpropanethiol, mercaptoacetic acid thioglycolic acid), 1-pentanethiol, glutathione . o-toluene thiol, m-toluene thiol, 1,2-ethanedithiol, o-mercapto benzoic acid, methyl, propane, 2-mercapto-6-nitrobenzothiazole, o-amino-mercaptobenzothiazole,

2-mercaptoethanol, ethylmercaptoacetate, o-aminobenzo) thioj, toluene-3,4-dithiol,

1 Hexanethiol, 5-amino-2-benzimidazolethiol, 2-benzoxazolethiol, 3-mercaptopropionic acid, 1-podecanethiol, 2-mercaptoacetanilide,

2-ethyl-1-hexanethiol, p-chlorobenzenethiol,

Methylmercaptoacetate.W-quinoxalindithiol, 2-furanmethanethiol, 2-phenylethanethiol, p-tert-butylbenzenethiol, 1-octanethiol, 2- (phenylthiol) quinoline,

Ethyl-2-mercaptoäthylcarbonat,

4-mercaptobutyric acid, 2,3-dimecaptopropanol, 2,3-dihydroxy-1,4-dithiolbutane, isooctyl-S-mercaptopropionate, isooctylthioglycolate, 1-thioglycerol, thiomalic acid, methoxymethylthioglycolate,

Phenylmercaptoacetic acid. ^ -P-methanedithioI, / i-mercaptoethyl-S-mercaptocyclohexane, / J-mercaptoethyl-mercaptocyclohexane, 3-chloropropanethiol-1, pinanyl mercaptan, dithiol terephthalic acid, lauryl thioglycolate, stearyl thioglycolate, lauryl-jS-mercaptopropionate, stearyl-jS-mercaptopropionate, Hydroxyethyl thioglycolate, hydroxyethyl-jS-mercaptopropionate, ethylene-bis-mercaptoacetate, ethylene-bis-iJ-mercaptopropionate, trimethylolethane trismercaptoacetate, trimethylolpropane trismercaptoacetate, Pentaerythritol tetrakismercaptoacetate, pentaerythritol tetrakis-JJ-mercaptopropionate, 31-grganocinnine sulfur, dibutyltin mercaptopropionate, dibutyltin-bis (laurylmercaptide), alkyltin mercaptide and benzylthiouronium chloride.

8) isocyanates, such as. B. 2,4-tolylene diisocyanate, ρ, ρ'-diphenylmethane diisocyanate, bitylene diisocyanate, methylene bis (4-phenyl isocyanate), dianisidine diisocyanate, phenyl isocyanate, 1-naphthyl isocyanate, p-tolyl isocyanate, p-nitrophenyl isocyanate, -naphthyl isocyanate, m-tolyl isocyanate. Tolyl isocyanate, p-ethoxyphenyl isocyanate, p-bromophenyl isocyanate, o-chlorophenyl isocyanate, m-chlorophenyl isocyanate, p-chlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, o-ethoxyphenyl isocyanate, o-nitrophenyl isocyanate, 2-biphenylyl isocyanate_&gt;mN-t-pentyl isocyanate, 4-biphenylyl isocyanate, o-methoxyphenyl isocyanate, p-methoxyphenyl isocyanate, tolylene W diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate,

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

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

13-diphenyl-1,3-propanedione, 1-phenyl-13-butanedione and glyoxal. Preferred compounds of this class, such 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-hexylchloroformate,

p-Nitrobenzylchlorformat.Dibutylzinnmaleat

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, azo group used, then 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 Λ, Λ'-dimercapto-p-xylene and

Mercaptosuccinic acid as well as the reducing sugars.

As already mentioned, some inhibitors cause the districts in contact with them to be raised beyond the remainder 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 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),

roan also uses maleic acid and trimellitic anhydride and, for the latter, fumaric acid and terephthaloyl chloride as inhibitor. Interestingly, inhibitors such as these catalyze the decomposition of Ν, Ν'-dinitrosopentamethylenetetramine and, therefore, cause, in their use, 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 z. Z. not yet known, but probably the inhibitor reacts with a functional group on the propellant or more and thus forms a compound or a complex having a decomposition temperature which is different from that of the propellant. This probably applies to 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 affect the effectiveness of the accelerator. For a propellant such as azobisformamide, the metallic accelerator probably causes hydrolysis of its amide group and formation of the corresponding salt, in which case the inhibitor may 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 chelating.

It is important that the decomposition temperature of the s&gt; o resin material approach in the regions covered by the inhibitor be sufficiently different from that of the other approaches to allow differential expansion. Therefore, the fusion temperature of the b5 polymer formulation determines the temperature range in which, in order to achieve this different decomposition, why the inhibitor prevents or accelerates propellant decomposition merely by application to the surface of the foamable formulation. 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 readily soluble inhibitors their amount and concentration have 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.

The anti-abrasion coating formulations furthermore contain fillers and pigment in accordance with the substrate dyeing desired in the finished product. Suitable as a 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. Scaly Tale is a particularly good filler of this kind.

The scuff-resistant layer is prepared by first forming the filler-containing resin material into chips, coating the particles with a plastisol, and finally rolling the mixture into a film without melting the plastisol. The necking particles are preferably multicolored. The simplest way to do this is to combine separate lots of different colored har / seed sets.

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. deformed by rolling or extrusion molding into films, and these films then finally get the desired geometric shape. Preferably, all chips get uniform thickness. Therefore, they cut most advantageous from films. Its thickness is preferably about one-third to about seven-quarters, and most preferably about one-half to about two-thirds the thickness of the decorative abrasion resistant layer to be made, which in turn may vary, but must be at least 0.356 nr.n, and generally not more than 1.27 mm should be. In addition, in order to obtain the desired decorative effect, the size of the pigmented seed chips zn, 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 production 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 method of preparation consists in first applying to the foamable layer an intermediate layer of a non-foamable, solid batch of polymeric! Apply Harzmate .- 'al and apply the inhibitor over it first. 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 relief 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 initially by heating particularly sticky and then let it come into contact with the abrasion protection layer.

The preferred procedure, however, is that at the time of their formation, the abrasion-resistant layer is combined with the foamable resin batch to form a double layer. For this purpose, the viscous mass of pigmented chips and resin material batch is applied to a pair of calender rolls whose gap width is set to more than the instep thickness the rolling of the mass without ίο 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 foil will

: ό then connected 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 converted to Foiie. This is achieved, for example, by passing the preformed polyvinyl chloride batch through about 107 ° to 149 °⁰C hot rollers run through.

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, all of the base material on the pad must come to the resin melt temperature in order to achieve a product of the greatest possible strength and stain resistance. The preferred vinyl resin material achieves fusing in the temperature range of about 163 ° to about 191 ° C. 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 substantially below the melting temperature and also the lowest blowing agent decomposition temperature, as long as necessary at this removal

b5 lies. So, for example, if you work with a hydrocarbon solvent fraction (reaching up to 177 ° C reaching boiling), you can by heating for 5 minutes at 93 ° to 121 ° C so much of it

Remove that you get a good and bubble-free pore structure at the subsequent fusing and foaming at about 204 ° C, this Schliesshitzung can be done in a hot air oven or otherwise, for example, by passing the product to 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 of this, the finished product can also be blown with cold air, sprayed with water or passed through IC cooling rolls.

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 made according to the invention have excellent elasticity, which depends in part on the thickness of the foam layer. In addition, they are characterized by a pronounced three-dimensionally structured appearance, which, if desired, completely coincides with a printed pattern. A further advantage of the products obtainable according to the invention is their good thermal insulation properties owing to 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 dirt 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 for the products obtainable according to the invention.

a) Preparation of the foamable resin material approach

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

low molecular weight polyvinyl chloride

high molecular weight polyvinyl chloride

dibasic lead phosphate

azodicarbonamide

titanium dioxide

Butylbenzoylphthalat

dodecylbenzene

Parts 50 50

55 10

The applied layer was heated by heating for 2 '/ 2 minutes in a 204⁰C hot oven gelled.

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

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

The following plastisol formulation was prepared by thoroughly mixing the following ingredients

<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>1,3</entry></row></tbody></tgroup></p>

The translucent chips used in conjunction with this plastisol formulation for the production of the abrasion protection layer originated from the following approach

parts

Polyvinyl chloride 100

Tending talcum (as filler) 50

Dioctyl phthalate (as plasticizer) 32.5

Butylbenzoyl phthalate 4.5 Stabilizer 7.5 UV-light factor 0.4 Pigment 6.0

This approach was initially formed into a 0.381 mm thick film and this in turn comminuted into square chips of about 3.2 mm greatest extension.

The chips thus obtained were then introduced into the clear plastisol in a weight ratio of 65% (shavings) to 35% (plastisol), and the mixture at about 21 ° C was applied to two chrome plated calender rolls, of which the upper was 143 ° C and the was heated to 132 ° C and both left so much gap between them that a 0.762 mm thick film was formed. This film was held in contact with the lower roller to almost the entire circumference and then pulled off ersi at a flow 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 plastisol formulation by passing both films intactly over the protective layer to the printed batch side at a throughput rate of 9.14 m / minute through a laminating press and meanwhile at a drum temperature of Subjected to a roller pressure of 40.4 atm. Dabe they were united by the interaction of heat pressure and stickiness of the vinyl embossing color to a uniform, firmly adhering Verbundgebildf The so obtained composite web was sent dam

Again at 9.14 m / minute throughput speed through a furnace with four, each 9.14 m long and 149 °, 207 ° or 204⁰C 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, with the raised areas not containing the inhibitor

Embossed ink printed sections corresponded.

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

For this 1 sheet drawings