DE1629612B2 - PROCESS FOR THE PRODUCTION OF A DECORATIVE FLOOR OR WALL COVERING - Google Patents

Description

The invention relates to a method for producing a decorative floor or wall covering with a relief pattern by applying a polyvinyl chloride plastisol or organosol, which is a Propellants in the form of azodicarbonamide, N, N'-dinitrosopentamethylene tetramine or p-toluenesulfonylsemicarbazide as well as a catalyst which lowers the decomposition temperature of the propellant, on a flexible, in particular fibrous base, application of a foam-reducing substance Substance in pattern-forming parts of the surface and subsequent heating of the covering layer to decompose of the propellant. As a result, a foamed topping is obtained in which, when heated, the pattern-forming Surface parts are less foamed or expanded due to the action of the weakening agent are than the other parts of the surface of the surface. The products produced in this way are particularly suitable for resilient and resilient floor coverings.

A method for the production of floor and wall coverings with a relief pattern, in which a mixture of polyvinyl chloride, a propellant and possible additives, including a catalyst to lower the decomposition temperature of the propellant, an inhibitor for the propellant is printed in a certain pattern, is in in NL-PS 64 10 827. The catalysts and inhibitors proposed herein differ from the compounds used according to the invention. In DT-OS 16 69 771 a similar covering is proposed, which is made from resin mixtures which contain a chelating agent with a chelating constant of at least 1 · 10 ⁴ , a blowing agent and a metal catalyst. As a result, a very special reaction of the chelating agent with the metal catalyst, namely the formation of a chelate, is achieved, which is not achieved in the method according to the invention

ίο is the case.

The invention is based on the object to improve the previous method and soil or To create wall coverings that are not only elastic and porous in the desired manner, but also with Only slightly discolour with aging and are characterized by a high resistance to sulphide pickling.

This object is achieved in that, in the case of the method for production given at the beginning a decorative floor or wall covering with a relief pattern according to the invention polyvinyl chloride plastisols or -Organosols used which contain an organic zinc compound as a catalyst, and to weaken the effect of the catalyst in the pattern-forming surface parts as a weakening agent Bentotriazole or aminotriazole applies.

The method for producing a floor or wall covering thus consists in a known manner in that a foam layer is applied to a flexible base. The foamable layer contains a polyvinyl chloride resin, a blowing agent dispersed therein and a catalyst therefor. The propellant is at a heating, the z. B. is made to fuse the plastics, decomposed, and gaseous decomposition products are formed, which lead in a desired manner to the porosity or the foam-like state of the material.
Before the heating, which produces the porosity, a substance is applied to pattern-forming areas of the foamable material which contains a weakening agent which reduces the ability of the foamable material to become porous when heated in the surface parts which form a pattern. As a result, the floor or wall covering has raised surface parts and incisions therebetween, the raised surface parts being relatively porous, whereas the incisions are quite solid.

When carrying out the method according to the invention, interactions between the Foams and the attenuating agents that are applied to the foam in preselectable patterns are being used. Only those substances are used that enable the products will not be discolored with aging, even if they are exposed to harmful influences during use so that a large number of patterns, which can even be light, pastel or white. possible are. Any number of complicated patterns can be selected.

Further, with the present invention, when the method is carried out, the following becomes large Advantage achieved: Sufficient expansion or foaming takes place without excessive high temperatures must be applied. This contributes to the properties mentioned above of the products are achieved, namely the possibility

3 4

the ability to produce a light and pastel-colored nature of the zinc catalyst is the decomposition temperature Shades without discoloration. Discoloration can be reduced by around 28 ° C. The decomposition The azodicarbonamide is therefore found in a test product, especially when using light-colored earth or for products that have at least some temperature range that is optimal for fusing have bright spots in the pattern, is noticeable harmful to the foam, d. H. in an area above make cash. the temperature at which the melted

The invention is now also based on the drawing material loses its toughness and then the described in detail. It shows cell walls rupturing, but below that

Fig. 1 is a plan view of a temperature according to the invention at which the viscosity of the resin so manufactured product, e.g. B. a floor covering, io small that the foam cells become irregular

F i g. 2 shows a section through FIG. 1 along the den and merge into one another because the cell walls Line 2-2, coincide.

F i g. 3 to 5 cuts through products after the The organic zinc compound also serves as

F i g. 1 and 2 during various manufacturing stabilizers for the plastic, i.e. H. to the minimum steps, 15 tion caused by the influence of light or heat

F i g. 6 a device for exercising the effects,
driving according to the invention and after applying the liquid foam

F i g. 7 a modification of the exemplary embodiment, this layer is heated sufficiently so that it is so according to FIG. 6.. gelled far enough that it becomes sufficiently firm and without

The F i g. 1 and 2 show a product with tile breaking 20 which can be bent, although it cannot shaped pattern. The tiles are preserved until they are fused to their utmost strength. flat surface parts 8 represented by a network. The heating stage takes place at a temperature are separated by incisions 9, which are not sufficient between the joints, the propellant even in the case of opposites resemble real tiles. According to FIG. 2 waiting for the zinc-containing catalyst to disintegrate expose the raised surface parts 8 from far.

expanded foam with a suitable thickness in relation to After gel formation in the foam layer

on the incisions 9. In addition, the product follows the printing of a substance containing a pigment applied to a flexible base 10, which contain at- or another suitable colorant for example, of organic felt or asbestos felt, but which in particular contains a means that can stand. 30 with the foam layer in a very specific

The tile-like pattern that reacts in a way. This in the following as »swabbing F i g. 1 and 2 is shown only as an example. There could also be flowers, pebbles or the zinc compound has an analytical effect on the any other pattern or pure phantasy foam. According to the invention, the wash-off pattern to get voted. 35 use benzotriazole or aminotriazole

Before the method of manufacture and the det. The effect of the catalyst is on those Properties of the floor or wall coverings in all places where the attenuating agent is applied will be described in the following will wear, very much less or completely suppressed, briefly on the features of the invention at the her- so that a higher temperature is necessary to Position of floor or wall coverings with relief 40 to achieve a decomposition of the propellant. the samples received. Floor or wall coverings with the decomposition temperature of the propellant are therefore on As is well known, relief patterns are those that make these areas larger than those for melting the surface Porous surface parts of greater thickness and the temperature used for this, so that the Incisions of smaller thickness, but in places where there is little or no foam of greater strength. 45 formation can be observed, while the remaining

For example, when floor coverings are made, parts expand and become porous. These will should, then a flexible pad, z. B. kung is surprising because in the absence of one a layer of felt, with a layer of liquid zinc containing catalyst, the printing with Foam covered, which is a polyvinyl chloride - the same weakening agent in the subsequent dispersion contains. In addition, apart from 5 ° ßenden heating, there is increased foam formation possibly desirable plasticizers or the azodicarbonamide or the others mentioned Pigments, two other ingredients, and propellant lead.

although a propellant in the form of azodicarbonamide, after the printing with the

Ν, Ν'-dinitrosopentamethylenetetramine or p-toluene weakening agent and before heating to versulfonyl semicarbazide, However, preferably azodi- 55 of the resins, the foam layer can be carbonamide, and an organic zinc compound, and the imprint is completely transparent, for example Zinc naphthenate. In the case of a foamed cover made of polyvinyl chloride resin, the material is covered This composition is used by the organic den, which acts as a wear layer for the product Zinc compound can serve as a catalyst for decomposition. The product is then of the propellant, which has the decomposition temperature 60 - regardless of whether such a layer is applied lowers. As a result of its presence, the leavening may or may not be heated to a temperature at medium are decomposed at lower temperatures, which fuse the existing resins and the same as if it is missing. The decomposition of the propellant early decomposes the propellant, whereby the Zerkann At comparatively medium temperatures, settlement in the unprinted areas, d. H. at be carried out within a range in the places where the catalytic converter does not work which the resin is easily fused. is weakened by the attenuator,

If, for example, azodicarbonamide is particularly pronounced as a driving force. The resulting product medium is used, then can by presen- ting a relief pattern that matches the imprinted

Pattern matches. The unprinted areas are raised areas, and the printed areas are incisions, such as B. in F i g. 1 and 2 is shown.

The F i g. 1 and 2 and also FIGS. 3 to 5, however, are not to scale the dimensions of the individual layers again, but they only serve to clarify the invention. The flexible pad the felt layer 10 can, for example, have a thickness of 1 mm.

An apparatus for carrying out the method according to the invention will now be described below:

According to FIG. 6, a suitable felt tape W is unwound from a supply roll 11. From there, the felt pad is fed to an application device which contains a container 12 in which there is a coating compound. An application roller 13 and a guide roller 14, around which the felt belt is guided, are moved into contact with the application roller. Since application devices of this type are known, details need not be mentioned here. The application device is used to apply a primary layer. Depending on the type of flexible base, two or more of these layers can be applied, or the primary layer can be omitted entirely. After being released from the roller 14, the strip is guided through one or more heating stations 15, which can either be radiant heating elements or hot air heaters. The applied coating mass is dried in the heating stations.

After passing through an accumulator of known construction, the band is replaced by another Out application device, which here is a known co-rotating roller application machine is. It contains a guide roller 16 covered with rubber, an application roller 17 and a further application roller 18. The two last-mentioned rollers are provided with wings or guides 19 or the like, which form a container 20 for the coating mass which is transferred from the applicator roller 17 to the belt will. As in FIG. 6 is shown, the roller application machine is used to apply the foamable PVC mass on the tape, which is then heated by suitable heating devices, e.g. B. a Oven 21, is performed so that the applied layer gels. The heating here is not so strong that that Propellant is decomposed, but it is sufficient to solidify the layer and thereby the printing or to otherwise allow a catalyst attenuator to be applied.

After exiting the furnace 21, the tape is passed through two printing devices which, for. B. work by engraving. The first printing device includes a container 22 for a printing medium. A pressure roller 23 with an etched or otherwise patterned surface takes the printing means from the container 22, and the excess is wiped off by a doctor blade. The rest arrives at the belt, which is guided by a guide roller 25. A heater 26 is used for partial up complete drying of the imprint material before the tape reaches the second imprint stage.

The second imprint device contains the parts 22 a, 23 a, 24 a, 25 a and 26 a in a similar manner. The composition of the printing media used in the two printing stages will be discussed later described. However, at least one of the two imprinting means contains the attenuating agent for the catalyst that catalyzes the decomposition of the propellant.

After the band has left the second imprinting device, it becomes a further one in the same direction running roller printing machine supplied, which has a guide roller 27, an applicator roller 28 and a further application roller 29 contains. Furthermore, suitable wings or guides 30 are provided which form a container 31 for a coating mass. With this roller application machine, the A coating is applied to the printed product, which preferably consists of a transparent wear layer consists.

The tape provided with the various layers is then passed through an oven 32 in which is heated so much that the propellant decomposes and the polyvinyl chloride is fused. Through this the layers receive their final physical properties, i. h., a for Use finished product. The product can after suitable cooling and after passage through an accumulator of known construction can be wound onto a supply roll 33.

Suitable cooling can also be carried out between the said stations, e.g. B. between the furnace 21 and the printing device.
Not all procedural steps, as shown in FIG. 6 can be performed continuously. For example, the intermediate product obtained after heating in the oven 21 or the intermediate product obtained after printing could be wound up and stored. In a similar way, it is not necessary that the later with reference to FIG. 7 are carried out continuously. The device according to FIG. 6 can be used for the production of floor and wall coverings shown in FIGS. Layer 34 in FIGS. 2, 3, 4 and 5 is then the primary layer which is used in the first application device of FIG. 6 is applied. The thicknesses shown in FIGS. 2-5 are not drawn to scale. When using a felt tape, the primary layer can be largely absorbed by the surface of the felt.

According to FIG. 6 is a layer of foamable by the roller application machine 16 to 20 PVC mass (35 in F i g. 4 and 5) applied, which a certain blowing agent and as a catalyst for the propellant contains a zinc-containing compound.

The coating mass 36 in FIGS. 2, 4 and 5 represents the incisions or joints 9 of the in FIG. 1 shown pattern is corresponding to the print by means of a suitably etched pressure roller 23 of the printing device 22 to 26 can be applied. The imprint means contains the attenuating agent for the catalyst for the propellant in the foam.

The imprint 37 in FIGS. 2, 4 and 5 can by the second imprint device 22 a to 26 « be applied. In particular, it can contain any desired color with the first imprint is related so that the raised surface parts 8 of the pattern according to FIG. 1, d. H. the the Tiles representing surface parts that have the correct color tint. The one in this pressure device

7 8

The coating compound used does not contain the attenuating agent, although the attenuating agent for the catalyst

weakening agent for the catalyst so that the Sator according to FIG. 6 and the following described

catalytic effect of the catalyst, d. H. of heirs F i g. 7 is applied by means of pressure rollers,

mentioned zinc compound, in these areas of the apply for the type of application of the wash-down

Pattern is not weakened. 5 no strict regulations. It is only

The coating 38 in FIGS. 2 and 5 is any apparatus or method for transparent wear layer used e.g. B. by wearing the attenuating agent in a preselection roller coater 27 to 31 according to FIG. 6 patterns are necessary so that the is applied in every case. desired relief effect is created. With the nature of the

After passing through the oven 32, by applying the attenuating agent can also that the propellant in the areas of the pattern, the type of printing agent can be changed. That According to FIG. 1, which represent the tiles, the imprinting medium can only be decomposed according to the invention and the polyvinyl chloride is fused takes away the attenuating agent alone. In many the cross-section of the products shown in FIG. In 2 cases, however, it is more appropriate and practical to shown shape. The products have an excellent effect on the use of the attenuating agent as well embossed relief pattern between the areas that provide a binder, e.g. B. a binder are covered by the coating mass 36, and the polyvinyl chloride base. In addition, it is often leftover Split areas. moderate and practical, for the attenuator

If necessary, the device can be used after any printing process and an associated

F i g. 6 can be changed depending on the desired effect.

the. For example, it may be desirable to include only one sequence. The following is a description of FIG

printing device is to be provided, even if a production some parts identical or similar corresponding parts

nis according to the fig. 1 is to be produced. In this len the fig. 6 and are therefore only briefly described

Case can be the foamable layer 35, which by the. A supply roll 39 for a tape W delivers

Rolls on the carrying machine 16 to 20 is applied, 25 the tape in an application device, which is the one in the

consist in a coating composition that contains a pigment for F i g. 6 corresponds. From there the tape will go through

Achieving the desired color in the raised an accumulator to a roller assembly for

Contains surface parts of the finished product. The application of a smoothing layer on the tape

print 36 can then result in a contrasting coloration. The smoothing layer may be desirable

and in a single imprint if certain types of felt are used as a base

will wear. that are pretty rough. The smoothing layer

The coating mass 36 does not necessarily have to contain a container 40 with the smoothing mass entPigment, although for most samples, the composition of which is still described, the coating masses preferably contain pigments. The smoothing compound will be used by an application that will contain a weakening agent for 35 roller 41, which is covered with a rubber-covered guide to the catalyst. When the coating mass roller42 works together, added. The belt does not contain any pigment or any other coloring agent, runs through the gap between these two rollers, then a product can be produced which, although through and from there via the guide roller 42 in which also has raised surface parts and incisions, roller gap between this and a heated one However, both are the same color. In sol- 40 tion roller 43. The direction of rotation in these roller cases is the pattern effect or the structure arrangement is different than in the case of a product in the same direction due to the relief-like run-out roller application machine,
seeing the products conditionally. In this roller application machine, the roller has

With the device according to FIG. 6, an etched surface can also preferably be made to

another type of pattern can be made. 45 take up application compound from the container 40 and

This is achieved by using two printing devices. after working with a squeegee 44 on the

In one of the imprinting devices, a through-band is placed in the roller gap between the application roller 41

visible imprint applied, which and the rubber-coated guide roller 42 to

Contains attenuating agents, and transferred in the other. The etchings (or other markings

An imprinting device is applied to the imprinting device on the application roller 41 for applying the

which is not a weakening agent but a coating compound are preferably uniform over

Contains pigment. Here, products are distributed over the surface of the roller and can be

the raised surface parts and incisions take up sufficient volume so that a sufficient

and in which at least a part of the surface amount of the coating mass is on the tape.

chenteile has a color that is worn with the color 55 and a bead or reservoir from the over-

the incisions or with the coloring of other parts of the tensile mass in the nip between the rollers 42

the surface parts or with the coloring of both con and 43 is formed, as indicated at 45.

haunted. If the reservoir 45 is opened in this way

The printing can be made in a variety of patterns, then is done by a process called star. Instead of a simple rectangle similar to "film casting", a uniform and or tile pattern shown in FIG. 1 is shown, a smooth layer is applied to the tape, whereby intricate patterns can be applied, irregularities on the surface of the flexible e.g. B. Patterns that are reminiscent of sand or stones or a surface before the foam was applied from flowers. Those parts of the print that will be matched. The smoothing roller 43 is preferably the weakening agent for the catalytic converter, or a chrome-plated metal roller that holds from the inside, i.e. the incisions of the pattern, can be heated here in order to make the applied layer lie between raised areas that are exposed.
To represent stones or flowers. From the roller application machine described

the tape is led to another, similar roller application machine, whose designated 40 a to 45 a Parts work in the same way and over the smoothing layer the layer of foamable Apply PVC compound to the tape. In this facility, the temperature of the roller 43 a can be controlled in such a way that the polyvinyl chloride gels, but does not decompose the propellant will.

The tape is then fed to an imprinting stage which contains a container 46 for the imprinting medium, an etched imprint roller 47, a doctor blade 48 and a guide roller 49 covered with rubber. In the printing step, a solution is printed in a preselectable pattern which contains the attenuating agent for the catalyst for the foam which is previously applied together with the foamable mass. Following the imprint stage heating, at 50, he can -follow ¹ about the stickiness to remove. The tape is then passed through a roller application machine 27a, 28a, 30a and 31a running in the same direction, which is based on the process shown in FIG. 6 corresponds to the roller application machine described and is used to apply a transparent coating mass. The finished tape then runs through an oven 32 α, which corresponds to the oven 32 of FIG. 6 and is wound on a take-up reel 51 after passing through an accumulator.

It may be necessary or desirable to remove the tape before entering the last accumulator or also to cool between other of the stations described, for example between the roller application machines, with which the smoothing layer and the foam layer are applied, or between the roller application machine for the foamable mass and the printing device.

There are some differences between the devices according to FIGS. 6 and 7, which are immediately visible are, but it should be emphasized that the roller application machine for applying the foamable Layer according to FIG. 7 is particularly suitable for the production of relatively thin layers, for example have a thickness of 0.08-0.25 mm prior to foaming. For thicker layers that are also sometimes desired, e.g. B. Layers of about 0.6 mm prior to foaming are preferred with rollers running in the same direction, application machines according to FIGS. 16 to 20 according to FIG. 6 applied.

In the device according to FIG. 7 it is assumed that the smoothing layer produced by the roller coater 40 to 45 is applied, contains a polyvinyl chloride resin and that neither azodicarbonamide other propellants are also present.

After the description of the products and the devices that can be used for their manufacture follows now a brief indication of possible embodiments. The proportions are included, if not otherwise mentioned, given in parts by weight.

document

Any flexible layer can be used as the backing or substrate, preferably one Felt when it comes to flooring. In particular, an impregnated asbestos felt or is suitable cellulose impregnated with resin or other organic felts. With suitable sealing compounds can a felt saturated with asphalt can also be used. Finally, layers of paper are sometimes also suitable, Cloths and metal foils, especially when they are wall coverings or upholstery acts.

Primary layer

A sealing layer (primary layer) is not always necessary. As a primary layer, for. B. ίο a latex, which is an acrylic polymer and possibly Contains pigments or fillers. An example is the following:

Example A.

Per 100 parts by weight of an acrylic polymer (here an acrylic emulsion polymer of 35 to 40% Ethyl acrylate and 60 to 65% methyl methacrylate) are added to 80 parts by weight of water and 80 parts by weight Tone used. Such a primary layer is characterized by a good bond with the fibers the base, also allows smoothing with a hot roller to iron out the protruding ones Fibers and continues to give surfaces to which vinyl compounds are subsequently applied will adhere well. However, the exact composition of the primary layer is not intended here will be discussed in more detail.

Polymers for the layers

For most of the other applied layers, i. H. the smoothing layer, if one is used (e.g. in Fig. 7), the foam layer and the clear cover and sometimes also the attenuating agent uses polyvinyl chloride plastisols or organosols. Different these substances are generally (because of their use) as paste-like or suspension-like polyvinyl chlorides designated.

The polyvinyl chlorides useful herein can be used over a fairly wide range of molecular weights vary, with a polyvinyl chloride having a lower molecular weight for the foam layer is used, while for the other layers, e.g. B. the smoothing layer or the upper wear coating, polyvinyl chloride with higher molecular weight can be applied. For the foam layer is suitable e.g. B. a polyvinyl chloride, whose molecular weight to a relative Viscosity of 2.05, which is measured in a manner to be described.

For the upper coating, however, is suitable for. B. a polyvinyl chloride with a relative viscosity of 2.65.

The relative viscosities result in the following way: A 1% solution of the polyvinyl chloride in cyclohexanone is passed through an Ostwaldtsches viscometer (1 mm capillary), and the flow time is compared with that of the pure cyclohexanone. The comparison takes place in one Instead of a water bath of 25 ° C. The relative viscosity is then the ratio of the flow time of the 1% solution at the flow time of the pure cyclohexanone at 25 ° C.

The imprint media should preferably be more soluble vinyl resins than the paste or dispersion type Be polyvinyl chloride. You should preferably use small amounts of copolymer components, ζ. Β.

Vinyl acetate. The resins used for this could be called "dissolved" resins.

Smoothing layer

If necessary, the following material can be used as a smoothing layer:

Example B.

For every 100 parts by weight of a homopolymeric dispersion PVC of high molecular weight, its relative viscosity is 2.65, the following substances are used:

Butyl benzyl phthalate 50.00

Turpentine oil substitute with high

Boiling point 0.60

Epoxidized soybean oil 5.00

Barium-Cadmium Stabilizer 5.00

Wetting agent for viscosity reduction 0.50

Titanium dioxide 30.00

The smoothing layer will not be discussed in any more detail here either.

Foam layer

A paste-like or dispersion-like polyvinyl chloride is preferably used as the foam. A liquid solution is produced from this, which is used for application by means of a running in the same direction Roller application machine according to FIG. 6 or by means of a device according to FIG. 7 is suitable. The exact Composition is e.g. B. the following:

Example C

For every 100 parts by weight of a homopolymer Dispersion PVC with a relatively low molecular weight and a relative viscosity of 2.05 used:

a) Butyl benzyl phthalate (plasticizer) .. 56.00

b) Turpentine oil substitute 4.15

c) Epoxidized Soybean Oil 6.40

d) titanium dioxide (pigment) 7.40

e) azodicarbonamide 2.50

f) zinc octoate (8 ° / o zinc) 2.225

The components c), d) and e) are preferably first ground to a paste, which is then a Mixture of the other ingredients is added, which also contain the polyvinyl chloride itself and are mixed together.

Various other plasticizers can also be used in place of or together with butyl benzyl phthalate be e.g. B. dioctyl phthalate.

The pigment d) can either be omitted entirely, or other pigments or colorants can be used be used, e.g. B. printer's ink, although in most cases lighter shades or a white backgrounds for the patterns are desired, as caused by titanium oxide.

The amount of the individual substances in the foam layer can vary. The amount of Plasticizer a) can, for. B. between 30 and 80 parts by weight per 100 parts by weight of polyvinyl chloride vary, and a number of different plasticizers can be known in conjunction with the used here. The turpentine oil substitute b) does not necessarily have to be added, however, its amount can vary depending on the viscosity required for the particular layer chosen 10 and 15 parts by weight vary. Said epoxidized soybean oil can be added as a stabilizer the amount of which varies between 2 and 8 or 9 parts by weight per 100 parts by weight of PVC can. This component serves to stabilize the polyvinyl chloride against discoloration when heated.

Azodicarbonamide is preferably added as a blowing agent, but such. B. also N, N'-dinitrosopentamethylenetetramine or p-toluenesulfonyl semicarbazide. Have the mentioned propellants the following decomposition temperatures:

20th

Azodicarbonamide 193-202 ° C

Ν, Ν'-Dinitrosopentamethylene

tetramine 179 to 191 ° C

p-Toluenesulfonyl semicarbazide 212-221 ° C

These blowing agents with decomposition temperatures between about 177 and 221 ° C are obtained when using the organic zinc compounds are catalyzed, decomposition temperatures in a range which is convenient for fusing the polyvinyl chlorides.

The proportion of propellant can be between V2 and about 20, preferably 1 to 5, parts by weight 100 parts by weight of the polyvinyl chloride vary. In addition, the amount added changes a little depending on the type of propellant used. If azodicarbonamide is used, then about V2 to 4 or 5 parts by weight per 100 parts by weight of PVC can be used. Below however, from 3.5 parts by weight the porosity is only slightly increased.

The component f) serves to solve two tasks. First, it serves as a catalyst for the Decomposition of the azodicarbonamide or one of the other propellants and thereby enables the Foaming at lower temperatures than without its addition. Second, it acts as a stabilizer to suppress the changes caused by light and heat on the polyvinyl chloride can be.

A number of organic zinc compounds can be used. Are common here the salts of organic acids, especially fatty acids, e.g. B. zinc stearate, zinc palmitate, zinc laurate, or salts of other organic acids, e.g. B. zinc resinate and especially zinc naphthenate and zinc octoate, the latter two are preferable. They can also be used individually or mixed together will.

The proportion of zinc catalysts can be between 1 and 4 or 5 parts by weight per 100 parts by weight Polyvinyl chloride lie, but below 3 parts by weight the catalysis is very pronounced.

The foam is also preferably composed such that selected ingredients, e.g. B. certain stabilizers, are not present. For example, the presence of organic barium

or cadmium compounds prevent the catalysis of the organic zinc compound on the propellant.

The heating of the foamable layer after its application is preferably just sufficient to to gel the polyvinyl chloride, but it is so small that the propellant is not decomposed. It Temperatures between 121 ° C for 2 to 4 minutes and 177 ° C for shorter times are suitable for this. At the higher temperatures, the heating must be limited to very short periods of time.

Attenuators

The attenuating agent can vary widely depending on many parameters, in particular but depend on the method by which they are applied. When printing, a preferred one Method for this purpose, the imprint material can either be in the form of a solution or in In the form of a dispersion.

A suitable dispersion can be prepared on the basis of a paste-like polyvinyl chloride as follows will:

Example D

For every 100 parts by weight of a homopolymeric dispersion PVC with high molecular weight and a relative viscosity of 2.65 are used:

Dioctyl adipate 96.00

Polyethylene glycol monolaurate 1.80

Benzotriazole 25.00

The specified composition does not contain any colorant or pigment, but this is, as described above, unnecessary. If necessary, a pigment can also have the specified composition be admitted.

The imprint "pigment" is to be understood here in a broad sense, as different colorants and even Dyes can be used. The special color additives will not be discussed further here will.

The proportion of 25 parts by weight of benzotriazole in the specified composition ensures a adequate suppression or attenuation of the effect of the zinc catalyst on the propellant, which is used in conjunction with the foamable composition described above. In most Cases, however, an even more pronounced suppression of the catalytic effect is desirable to the To emphasize the relief effect of the product. This is achieved by changing the amount of attenuator increased in the imprint. Based on the plastic binder used in the imprint For example, the benzotriazole can be used at 40 to 150 parts by weight, the most favorable range being between about 70 and 100 parts by weight lies. Penetrate within this range using a normal overprint process effective amounts of benzotriazole in the foamable layer and act on the catalyst or suppress its effect.

A suitable solution is an imprint material made from almost equal parts by weight of two polymer components, one of which is a copolymer of vinyl chloride and vinyl acetate with 10% vinyl acetate and the other a tertiary polymer of 86% vinyl chloride, 13% vinyl acetate and 1% maleic acid contains.

Example E.

For every 100 parts by weight of polymer are used:

Dioctyl phthalate 12.00

Xylene 192.00

Methyl isobutyl ketone 65.00

Methyl ethyl ketone 433.00

Titanium oxide 240.00

Benzotriazole 80.00

The solvent type printing medium dries by evaporation of the solvent components and requires less heat than the dispersion type imprint medium. However, both can be used in conjunction with a suitable drying process (after printing) can be used.

The following example shows the use of aminotriazole. It will be the same plastic mixture as used in the previous example:

Example F
30th

For every 100 parts by weight of polymer are used:

Methyl ethyl ketone 280.00

Xylene 152.00

Methyl isobutyl ketone 45.00

Aminotriazole 95.00

In the last two examples, the polymer composition can be changed, e.g. B. the ratio of the two components can be changed from 3: 1 to about 1: 3.

If aminotriazole is used, then the amount added can be over the same range as fluctuate with benzotriazole. The attenuating property of aminotriazole is that of benzotriazole similar.

Various effects can be obtained by using either of the two attenuating agents will. While benzotriazole is soluble in the solvents that are used to make the imprint media are used, aminotriazole is insoluble in these solvents. Benzotriazole has a softening effect on the imprint material and thus makes it sticky, especially when it is large Quantities is used. On the other hand, the aminotriazole must, since it is used in the printing medium Solvent is insoluble, like a pigment can be ground to something. In addition, the imprint can be provided with a larger proportion of aminotriazole, which is sometimes desirable is, especially if a strong suppression of the catalysis is to be achieved.

Upper cover

After printing, a suitable wear layer can be applied, which is also on

the basis of a paste or dispersion-like polyvinyl chloride is prepared. The following example is particularly suitable:

Example G

For 100 parts by weight of a high polymer dispersion PVC having a high molecular weight and a relative viscosity of 2.65 are used:

Dioctyl phthalate 22.50

Epoxidized soybean oil 7.00

Polyethylene glycol monolaurate 0.80

Light stabilizer 5.00

Turpentine oil substitute with high

Boiling point 18.00

In most cases more dioctyl phthalate or plasticizer will be used than stated here. z. B. 30 to 50 parts by weight. The composition of the top coat can also be known in a known manner Way can be changed according to other points of view, but will not go into further detail here will.

The final heating of the product after application of the coating preferably takes place in an oven with an air temperature 171-204 ⁰ C. Higher temperatures, e.g. B. 218 ° C are also possible depending on the speed at which the strip W is fed through the oven.

The following examples serve to further clarify the invention.

example 1

An asbestos felt with a thickness of about 1 mm, which is impregnated with about 15% chloroprene rubber, is first coated with a primary layer which contains 40 ⁰ zo solid polyacrylic latex. The primary layer is dried in hot air at 93 ° C.

The foamable layer is then coated with a coating machine up to a thickness of 0.3 mm applied. The composition of this layer corresponds to that of Example C, but with 2,2,4-trimethylpentanediol isobutyrate benzoate as plasticizer a) is used in the same amount, while instead of 2.225 parts by weight now 2.5 parts by weight Zinc octoate are present.

The foamable layer is gelled by heating in an air oven operated at 121 ° C, wherein the heating time is 2.5 minutes.

After gel formation, the layer is printed with rollers in a pattern, the imprint being the Represents joints between small, irregular tiles. The imprint means corresponds to the example F, but small amounts of orange and black pigments are added to make the printed Places are tinted.

After the print has dried, a transparent coating of 0.17 mm applied. The composition of the coating is as follows:

On 100 parts by weight of a high polymer dispersion PVC High molecular weight with a relative viscosity of 2.65 are used:

2,2,4-trimethylpentanediol isobutyrate

benzoate 50.00

Light stabilizer 5.00

Turpentine oil substitute with high

Boiling point 6.00

Alkyl phenyl ethers of polyethylene

glycol 0.60

Epoxidized soybean oil 6.00

The material is placed in an oven for final heating so that the polymers melt together, the propellant decomposes and the foam develops in the non-printed areas of the pattern will. A hot air oven is used for this, in which the material is heated to elevated temperatures on both sides is held. The heating is carried out for 3.5 minutes at an air temperature of 179 ° C.

The product produced in this way has a good foam quality. The originally applied foamable layer is on the unprinted areas to about 250% in relation to the thickness of the heated printed areas expands. This results in a pronounced relief effect with a high Elasticity in the unprinted areas. The product also has good color quality and Color fastness and is resistant to staining, especially to the influence of sulphides.

Example 2

Another pavement is produced in almost the same way as in Example 1. The foamable layer however, instead of zinc octoate, it contains 2.5 parts by weight of zinc naphthenate (10% zinc).

The product has similar properties to the product according to Example 1. The foam formation or the expansion of the unprinted areas in the end product is somewhat greater. The thickness of the unprinted areas in the end product is approximately 275% of the thickness of the printed areas.

Example 3

Here, too, a product is produced essentially as in Example 1, but in the Foam layer uses the following two ingredients in place of the zinc octoate alone:

Zinc naphthenate (12% zinc) 1.5

Zinc octoate (8% zinc) 1.0

The end product has an expanded foam layer, the thickness of which is 350% of the thickness of the printed one Places is, so that higher projections or a more pronounced relief effect can be achieved.

Example4

In this example, a cellulose felt is used as the base used, which is impregnated with polyvinyl acetate and with other resin components. His. thickness is about 1.3 mm.

First, a primary layer is applied, which contains a polyacrylic latex (40% solids) and in an oven operating at a temperature of 121 ° C for 20 seconds.

609 514/451

17 18

A smoothing layer is then applied. The product is heated in a hot air oven, which is described in connection with FIG. 7, which is kept at 182.degree. The residence time bene procedure is applied. It takes about 5 minutes to put them together in the oven.
Settlement corresponds to that of Example B. The tape is expanded or foamed for 1.5 seconds by resting against the top 5, so that a noticeable area of the chrome-plated roller (43, in FIG. 7) heated, there is a relief effect in relation to the lower joints, which are kept at a temperature of around 143 ° C. The thickness of the heated and used. As a result, the smoothing layer gels, so that the melted foam layer can be applied to the foamable layer. foamed areas about 0.4 mm and in the

For the smoothing layer, 0.17 mm of material is needed for the joints.

applies that a thickness of about 0.6 mm and _R. .

results in a smooth surface on which the foam example 3

Layer of fabric is applied. A cellulose felt is used as a base here.

After cooling, the tape is passed through the front, the one with polyvinyl acetate and other resin direction for applying the foam layer is impregnated components and a thickness of leads, the z. B. has the roller application machine after about 1.3 mm.

F i g. 7 is. In this case, the roller 43 has a α First, a primer layer is applied, the

larger diameter than the roller 43, and therefore contains a polyacrylic latex (40% solids) and

finds a slightly longer contact with the heated one in an oven operated at 121 ° C for 20 seconds

Roller instead. The contact time is about 2 seconds.

announce at a temperature of around 149 ° C. At this point, a foamable layer is created up to

at this temperature an excellent yellow color with a thickness of 0.3 mm is applied.

Formation of the foamable layer takes place, but the composition corresponds to that of Example 4. That

Azodicarbonamide does not decompose in the layer. Product is used to gel the foamable

The composition of the foamable layer 25 layer heated for 2V2 minutes at 121 ° C,
is the following: For every 100 parts by weight of a high The product is then printed with a polymeric dispersion PVC low molecular setting according to Example F, using a printing weight and a relative viscosity of about roller. The pressure roller contains 2.05 are used: pressure areas that line the joints between small target

30 gel stones correspond.

2,2,4-Trimethylpentanediol isobutyrate- A topcoat whose composition is the

benzoate corresponds to 54.7 in Example 4, is up to a thickness of

Epoxidized soybean oil 6.3 0.17 mm applied.

rj. ,,. ,. -, ς The final heating takes place about 3V2 minutes

Zinc catalyst ifi _{35 te}

_{35 th} nec} ^ J _{79 c gtaU}

Terpentine substitute 6.3 _The end product has a pronounced relief character

Titanium dioxide 25.0 ter, whereby the foam in the unprinted

Azodicarbonamide 2.5 range reaches a thickness that is 200% of the thickness in

the printed areas.

The applied amount creates a layer of 40.

0.12 mm thick before expanding. The e 1 s ρ 1 e

coated tape is covered with a red brick. The procedure is essentially as in Example 4.

Pattern printed while the joints turned gray, but the smoothing layer was omitted color received and only the imprint for this is sen. Also, in the foamable Add the catalyst attenuator 45 layer in place of 2.5 parts by weight of azodicarbonder Foam layer, namely benzotriazole, entamide now contains 12 parts by weight of p-toluenesulfonyl semi. The printing medium corresponds to example E, carbazid used.

only the colorant has been changed so that the gray As in example 4 corresponds to the composition

tinting of the joints is achieved. of the attenuating agent that of Example E, wherein

An upper coating is applied over the imprint - but instead of a gray pigmentation, a roller-dark brown pigmentation running in the same direction is created.
application machine is used. The thickness of this The fusing temperature at the end is

Coating is 0.38 mm. The coating does not contain 182 ° C, but 188 ° C, whereby the product the following: left in the hot air oven for 3 minutes.

For every 100 parts by weight of a high-polymer di- 55 The rest of the treatment is identical to that in the co-dispersion PVC high molecular weight and game 4.

a relative viscosity of 2.65 are used. The foam produced is of good quality,

turns: and the relief effect of the foamed areas leads

to a thickness about 225% of the thickness of the be-2,2,4-trimethylpentanediol ^{isobutyrate-6o} printed areas.

^{benzoate 42} > ⁰⁰ Example 7

Epoxidized soybean oil 6.00. ,,. ... ", .._, ..,.

T-u u'i · c nn Here, too, is essentially the same as in Example 4

Licntstabilizer 5, UO proceeded. However, the smoothing layer is removed

Turpentine substitute with high 65, and be left in the foamable layer

Boiling point 6.3 _in place of 2.5 parts by weight of azodicarbonamide

Alkylphenyl ethers of polyethylene - now 10 parts by weight of Ν, Ν'-dinitrosopentamethylene

glycol 0.6 tetramine is used.

The final heating to fuse the polyvinyl chloride is carried out in a hot air oven operated at 179 ° C. The residence time in the oven is 3 ¹ A minutes. Otherwise, proceed as in example 4.

The foam quality is good. The extension of the

However, foam is not as strong as in some other examples, but the expanded areas only achieve a thickness that is about 170% the thickness of those areas covered with the attenuating agent are provided.

For this purpose 3 sheets of drawings

Claims (3)

Patent claims: 1. Method of making a decorative Floor or wall covering with a relief pattern by applying a polyvinyl chloride plastisol or -Organosol, which is a propellant in the form of azodicarbonamide, Ν, Ν'-dinitrosopentamethylenetetramine or p-toluenesulfonyl semicarbazide as well contains a catalyst which lowers the decomposition temperature of the blowing agent, to a flexible, in particular fibrous, base, application of a foam-reducing substance Substance in pattern-forming parts of the surface and heating of the covering layer therein to decompose of the propellant, whereby a foamed topping is obtained in which, when heated, the Surface parts forming patterns are less foamed due to the action of the attenuating agent or are expanded than the remaining surface parts of the covering, characterized in that that one uses plastisols or organosols which are an organic zinc compound as a catalyst contained, and to weaken the effect of the catalyst in the pattern-forming Surface parts as a weakening agent benzotriazole or aminotriazole applies. 2. The method according to claim 1, characterized in that the attenuating agent in a carrier liquid introduced is printed on individual surface parts. 3. The method according to claim 2, characterized in that the carrier liquid also contains a pigment or colorant.