DE2310891A1 - PROCESS FOR PRODUCING HIGH-GLOSS PLASTIC COVERINGS ON SUBSTRATE WEB - Google Patents

Description

STAR PAPER LIMITED, Feniscowles, Blackburn, Lancashire, UK

Process for the production of high-gloss plastic coatings on substrate webs

Substrate webs, especially paper and cardboard, can be made using a process known as cast coating is treated to give them a surface that is exceptionally flat and smoothness and has a mirror-like gloss. The coating compound, which is used for such working methods usually contains over 70 percent by weight of a mineral Pigment made with a mixture of a synthetic polymer and a film-forming substance animal or vegetable origin is bound. The high fisnish of these products makes them in Ideally suited for applications that emphasize prestige or the customer in particular highly appealing presentation arrives, e.g.

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as book covers or show packs. However, they have the disadvantage that the surface during use easily scratched and worn and also easily soiled or stained. There is therefore a technical one The need for a coating that has the finish of the known cast-coated products, but through superiority in terms of scratchability or wearability and staining is excellent.

Polymer coatings are those that are mainly made of a synthetic polymer material exist, can be designed so that they have improved resistance to scratching and Staining, but conventional methods of applying the polymeric coatings are used on paper and cardboard unable to give the products the gloss and smoothness of the cast-coated ones To lend products. For example, in a process in which a melt on the Suostrat is applied by extrusion and solidified thereon, the roughness and unevenness of the polymer underlying substrate. Similar results are obtained when using the paper or cardboard a solvent solution of a polymer coated will. A dire consequence occurs when aqueous dispersions or emulsions of the polymer are applied as the water causes the cellulose fibers in the substrate to swell, causing extreme roughness. Calendering the dried, rough product is not enough to achieve a technically satisfactory improvement to achieve.

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By applying a polymeric film to a cast-coated one by means of polymer coating or lamination Substrate one comes close to the original finish of the cast-coated product, but this is it double operations are costly, and the resulting product is often deficient due to the small size Dust particles or air bubbles or an uneven application of the coating or adhesive.

There are working methods known in which an aqueous dispersion or emulsion of a polymeric material a substrate is applied and the coated substrate is then processed in a manner similar to that which is used to apply mineral-based masses by pouring coating. However these methods, too, are either extraordinarily tedious to carry out in practice or they are damaged most, if not all, of the cellulosic substrates.

A typical example of such a method is the method described in U.S. Patent 5113888 to cite. According to this method, the substrate is coated with an aqueous mass, and it is - while it is still damp - in contact with a large, polished cylinder heated to a temperature of 80 to 99 ° C and the coating is applied to the polished surface without application of external pressure and without relative Movement between coating and surface kept in contact as long as the drum, for example, on a Line that makes up three quarters of its circumference rotates.

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This method corresponds to that between the moist coating on the substrate and the heated one The gap formed by the cylinder is usually a set nip, but it is essential that no noticeable one Pressure is applied at this point, otherwise the aqueous emulsion will be squeezed from the substrate would.

While the heated cylinder and the substrate move slowly together, the coating is deformed into a film and - provided the substrate is permeable - dries. A rate-regulating factor in this process is the fact that the substrate and the cylinder must be kept in contact for a long time in order for the polymeric material to have an opportunity to deform into a film, the film assuming the configuration of the polished surface and allow adequate drying to take place. In a typical embodiment of the process, the optimum speed of movement of the substrate is 25 m per minute and the diameter of the cylinder 3.7 m. The method could theoretically be carried out even faster if the roller were ^{heated to a temperature above 100 °} C., but it is this is not possible because, when the temperature approaches this range, there is a risk of bubbles forming in the coating due to the boiling of the water, or vapor bubbles could build up between the coating and the cylinder and surface parts would remain uncoated as a result.

According to another working method, which is described in US Pat. No. 2,555,662, an aqueous emul-

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sion is selected in its composition in such a way that it does not have a continuous film on the substrate when it dries forms. The emulsion is applied, the coating dried and then melted to make a continuous Form a film through the application of heat, and the whole thing then undergoes a compression set operation in the heat subjected, which ultimately gives a smooth and shiny finish. In this working method, the melting stage has an almost complete removal of the water from the substrate. In a typical example, a coating in an amount of 5 g per m, on dry weight related, dried and then heated to 148 ° C for 45 seconds before deformation. Such a strong one Heat treatment of cellulose substrates can cause permanent embrittlement of the paper or cardboard. It also causes the product to develop an objectionable curl tendency, since the moisture is again absorbed by the substrate after processing. The heat treatment does that Moreover, the process is lengthy and costly. In addition, coating weights are generally low required, and these are unsuitable for ensuring the required high-gloss finish or for evoking the desired protective effect of the polymer coating.

It is an object of the present invention to provide a working method for forming a smooth, shaped To make polymer coating available on a substrate in web form, which is carried out much faster can be considered as the known methods available for this purpose, and those due to an appropriate one Able to choose polymeric materials

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is to deliver very smooth coatings and high-gloss coatings, such as those obtained with cast coating, but which do not have the disadvantage of coatings applied by cast coating.

According to the teaching of the invention, an aqueous coating composition consisting of an aqueous emulsion or dispersion of a polymeric material is applied to the substrate, a continuous film of the polymeric material is formed in the presence of water, and then at least some of the water is evaporated, and Although durcn heating the aqueous coating without the application of pressure to a temperature which is higher than the film forming temperature of the polymeric material, and the film is then formed by reacting presses it under high pressure against a Formfiäche at a temperature of about 10O ⁰ C.

Thus, according to the teaching of the invention, the aqueous coating is heated to form the continuous film and to evaporate at least part of the water before any shaping takes place, and it is then possible to mold at high pressure and high temperature to achieve a surface effect that is as good and mostly is much better than the surface effect that could previously be achieved. As a result of the application of the high Temperature and the high pressure, the molding and thus the entire process can be carried out much faster than was previously possible. So, in the typical case, the substrate at a speed of 70 m per Minute (while in a typical prior art method only 25 meters per minute can be achieved). Furthermore, in the case where the deformation surface is a roller, this roller can do a great deal

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be smaller than was considered necessary in the previously known methods; their diameter can for example, to a third of the diameter of a roller, as used in the known method will amount to. This means an enormous saving in economic terms, because the chrome-plated or in another way mirror-polished forra surfaces can only be manufactured and maintained at an excessively high cost.

Another advantage of using a combination of high temperature and pressure is that there are no pin-sized Holes that occur as a result of imperfections in the coating, such as tiny bubbles of foam, can be eliminated by the shaping, and so a completely continuous coating is achieved. It should also be noted that the process can be carried out in a pressure range that is too low is than having stiffness and other properties desirable for packaging use Could noticeably affect cellulosic substrates in any way.

The process according to the invention is best carried out continuously in such a way that the coating compound is applied continuously to the substrate, the substrate provided with the coating is continuously passed through a drying zone and the shaping is then effected by calendering, ie by passing the coated substrate through the spaxt _A pressure roller and a forming roller, the film being held in contact with the forming roller.

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Such a device is shown schematically in the accompanying drawing. In this drawing is a substrate web 1 is removed from a delivery roller 2 and via an application roller 3, which is fed into a trough 4 dips, which is filled with the aqueous emulsion or dispersion to be applied, performed. The thickness of the applied Coating is regulated by an air knife 5. The one provided with the wet coating The substrate then runs around a guide roller 6 into a heating zone in which it is heated by the heating elements 7 will. During the passage through this zone, the coating is heated to a temperature which is above the film formation temperature, so that the polymer forms a film, and after the film formation is in general, more water evaporates.

After the substrate is passed around a guide roller 8, passes this substrate that now carries a continuous film of the polymeric material in the gap 9 between a polished roller 10 which serves as a mold surface and is heated to a temperature of about 100 ⁰ C, and a press roll 11. Finally, the coated substrate web is wound onto the take-up roll 12 or it can be fed directly to a cutting device to cut the web into sheets or plates for later practical use.

Any convenient system for applying the emulsion can be used. Instead of e.g. the coating, After it has been applied, the layer thickness can be adjusted (using an air knife), the coating can can be adjusted in their thickness from the start,

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for example by providing a double roller application system by means of which a metered amount of the coating compound is applied to roller 3. The applied mass generally has a solids content of 40 to 60 % and the absorption by the substrate is generally 5 to 50 g, for example 10 to

2
25 g per m, calculated as dry weights.

In the heating zone, the coating can be heated by any suitable heating system, e.g. by infrared radiators or hot air heating. Air can also be circulated through part of the heating zone or through the entire heating zone to increase the rate of evaporation.

The Pormoberflache should be a surface that the has the desired configuration for the molded cover. In general, it is the shaping surface smooth, so that the finished coating is also smooth. If desired, however, it can also have embossed patterns. Generally it is made of polished chrome, usually it is chrome plated, but it can also be, for example are made of polished nickel or have a silicone coating.

The mold roll is heated by any suitable means, for example superheated steam, to a temperature of about 100 ⁰ C, for example at least 105 ° C. The maximum temperature which the roller 10 can reach is usually determined by the difficulties which arise in practical operation, but it is generally not advantageous to work at temperatures above 150 ^° C.

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The preferred temperature range is usually between 110 ° and 125 ° C. Of course the temperature must be can also be selected taking into account the materials in the film to be formed.

The press roll can be any roll capable of pressing the substrate against the forming roll. she can consist of a substantially non-elastic material such as steel, or it can be made of an elastic Material, for example a steel roller provided with a coating such as rubber or felt. It must be able to exert significant pressure. While belonging to the state of the art Deformation process at a negligible pressure, e.g. normally less than 1 kg / cm, is being worked, the pressure at the invention

o If the method is always at least 5 kg / cm, and for some

homely at least 10 kg / cm. The best results are generally obtained at pressures above 25 kg / cm. The maximum pressure to be used in any particular process is determined primarily by practical considerations. Are the elasticity of the gap (nip) and the substrate thickness - as will generally be the case - such that the gap has a width of 2 to 1 cm, for example, then it is usually unnecessary

To apply pressures of more than 50 kg / cm, but if the substrate is thinner or the gap is less elastic, so that the pressure is applied over e.g. 2 mm, then higher pressures, e.g. those up to 100 kg / cm, be advantageous. In this way a smaller width becomes a lower one Dwell time in the gap compensated for by a higher pressure.

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Numerous different types of substrates can be coated using the method of the present invention including paper and cardboard and foils, usually metal foils such as aluminum foils. The minimum weight of the

Coated paper is about 40 g per m and the maximum weight of the cardboard is usually about

400 g per m. For example, one can assume that Papers have a weight of 40 to 200 g per square meter and cardboard

ρ have a weight of 200 to 400 g per m. A for the purposes of the invention preferred in question granular

mendes weight is between 8o and 400 g per m. The paper or the cardboard is preferably made of cellulose fibers, but it can also be made of synthetic fibers or mixtures consist of synthetic fibers and cellulose fibers. If synthetic fibers are used, so you have to outlaw it as a rule that they consist of a material that during the shaping operation does not melt. The substrate may have undergone a pre-coating before being coated with the polymer, and such precoatings are those commonly used in papermaking, and they can contain pigments or be pigment-free. These pre-coatings are applied when required is to mitigate the roughness of the fiber substrate or the extent to which water is removed from the polymer emulsion or dispersion is lost prior to the formation of a continuous film.

If the substrate that is to be provided with the coating is impenetrable, e.g. consists of a metal foil, so it is recommended that the coated

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The substrate at the time it enters the mold gap 9 is essentially dry, for example contains less than 2 % water, based on the weight of the substrate. However, particularly good results are obtained with the aid of the method according to the invention when the substrate is permeable, for example made of paper or cardboard, and when it is still moist when it enters the gap 9 immediately before the deformation. Due to the fact that the substrate is moist, this substrate is also more elastic and thus enables better adaptation to the mold surface 10. It is therefore generally recommended that the coated substrate still has at least 8 percent by weight, preferably 12 percent by weight of water, based on the Substrate weight when it enters gap 9. However, the substrate should not contain too much water either, since otherwise the vapor pressure that is built up in the gap can be so great that it damages the substrate or the film. As a rule, the coated substrate should therefore not contain more than 18 percent by weight, preferably not more than 15 percent by weight, of water, based on the weight of the substrate.

The majority of at least the moisture in the coated substrate evaporates when it enters the gap 9 and reaches out of the substrate as quickly as it can after it has left the gap. Is the substrate permeable, it therefore evaporates through the back of the substrate. There should preferably be no relative movement will take place between the coated surface and the mold surface, and the best results will be if the coated surface is in contact

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cycle with the forming roller while this evaporation takes place until the coated product has dried to a stable moisture content, for example while the roller rotates from 45 to 270 °. For example, cellulosic substrates normally have 5 to 8 % moisture and the coated surface is preferably kept in contact with the mold surface until such a moisture level is reached.

A wide variety of polymeric materials can be provided with the coating according to the teaching of the invention, but in practice these must meet two criteria. The first and most important criterion is that the material be able to form a continuous film in the presence of water solely by heating the aqueous coating in the heating zone. This, again, means that the film forming temperature must be well below 100 ⁰ C. However, film formation is a dependent process in the sense that if the water is removed quickly, as is the case with porous substrates, the temperature of film formation is effectively increased. The film formation temperature therefore depends on the particular process in which the film is formed. An absolute value that can be used to denote the temperature at which a film is formed is the second order transition temperature. As a rule, the polymeric material used for the purposes of the present invention must have a glass temperature below 40 ° C. in order to be of practical use. However, if the substrate is impermeable, for example a metal foil, then satisfactory results can also be achieved with higher values, for example up to 70 ° C.

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The second criterion which the polymeric material must meet is that it is at the applied Mold temperature by pressing against the mold surface is deformable. In order for the film to flow and conform closely to the surface, it must therefore be made of one material exist that to a certain extent wets the surface, but when it does the surface too if it is heavily wetted, it will stick to the surface with potentially devastating consequences. It is therefore inevitable to create a balance with the polymeric material that sticks to the surface and adapts to this surface inappropriately. In general, the best results are obtained when that polymeric material has a viscosity of 40 to 80 units, preferably 50 to 70 units, for example 60 units, determined with the aid of a Mooney viscometer, at mold temperature.

The polymeric materials used in the invention can be made from a variety of materials can be selected, e.g. consist of polyvinyl acetate, polyvinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polystyrene copolymers, polyurethanes, polyacrylates, polymethacrylates, polyacrylonitriles, Polyamides and polyethylenes. Generally speaking, however, it is best when the polymeric material consists of such a material which is produced by an emulsion or dispersion polymerization reaction has been won because it has been found that there are often too many surfactants in branded articles representative emulsions or dispersions of materials such as polyamide and polyethylene which have been prepared by some other polymerization method and then dispersed in water.

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While an advantage of the method of the invention is that it can use commercially available aqueous emulsions or dispersions, it has been found that for best results, and particularly for producing a surface finish that is as good as the finish produced by a cast coating of a mineral-containing coating compound, most commercially available materials do not meet the requirements required for the shaping stage, which means that exactly the right degree of adhesion to the heated mold surface is achieved in the sense that the coating is tightly against this surface hugs and takes on their high shine. Usually these materials are too sticky at mold temperature and a modifier must be added to reduce this effect. It is therefore very generally particularly advisable to add a small amount, for example less than 50%, based on the dry weight of the main polymer, of a tackiness-reducing agent to the emulsion or dispersion. The optimal amount will depend on the particular anti-tack agent and polymeric material being used. For example, sodium carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol and polyvinylpyrrolidone can be used in amounts up to 10 % based on the weight of the main polymer, while sodium alginate can be used in amounts up to 2 % based on the weight of the main polymer. Other materials that can be used include emulsions of wax, polyethylene, and stearates.

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While all of these tack-reducing agents allow processing of the polymeric materials and give the product a smooth and shiny finish, it has been found that many at the same time Polymers that have a glass transition temperature below 40 ° C, are soft to the extent that they are unsatisfactory as a finish for practical use. It is therefore in most cases it is advisable to incorporate materials that both reduce tack as well as increasing the hardness of the molded polymer coating. As has been found, certain acrylic copolymers are useful as tack-reducing agents in a variety of polymeric materials, e.g. for butadiene / methyl methacrylate copolymers (e.g. materials under the name "Butakon" in Are sold) and styrene / acrylic copolymers (e.g. materials that are sold under the name "Revertex" in the trade), and therefore, because they both improve appearance and increase hardness. A suitable anti-tack agent Acrylic-based agent is sold under the name "Amberlac AI65" by Rohm and Haas U.K. Limited commercially distributed; it consists of an ammonium salt and is by nature not film-forming. Another suitable tack-reducing agent that is of particular use when the polymeric main material made from a styrene / acrylic copolymer is a styrene / maleic anhydride copolymer, e.g. the material sold by the Arco Chemical Company under the name "SMA Resin", which can be dissolved in ammonium hydroxide to form a solution which, when dried, gives a continuous film.

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In order to meet the requirement that the surface of the finished product is generally hard, the polyi
on.

polymeric material often has a glass temperature above -1O ° C

The method according to the invention has wide applicability in the manufacture of, for example, coated papers and foils. If you make an optimal selection of polymeric material, e.g. as described above, then it is possible to achieve a surface finish of extreme smoothness and extremely high gloss. Will be a matte surface is required, then it is generally produced according to the invention by being in the same Deformed like a high-gloss surface against an extremely smooth surface, but a polymeric one Mass used, which gives the optical illusion of a matt effect. If an embossed surface is desired, a smooth surface is usually created in the usual way and then afterwards provided with an embossed pattern.

The substrate can be a solid color substrate and the coating can be clear or a small amount of pigment included for decorative or functional purposes. However, the invention is of particular value when used for Applying a clear glossy coating to a printed surface is used, e.g. on paper or Cardboard with a print, for example a wood grain effect or a photograph. Thus, with the help of the invention, postcards can be viewed in the Way to be made that one prints the desired pictures on the card, then a clear glossy layer by means of

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applying the method according to the invention and cutting the substrate to the desired size.

Other additives can be incorporated into the coating mix be to the processing or functional Improve properties, and these include foam inhibitors, Viscosity modifiers, plasticizers, coalescing agents and release agents. The use of such materials results optimal manageability and end-use flexibility. The coating compositions can also contain a small amount of an inorganic pigment or an organic pigment Pigment, a dye, a metal pigment, a pigment producing mother-of-pearl effects, a matting agent, etc., or mixtures of such materials, to create a colorful variety of decorative To deliver plastic coatings. Similarly, materials that absorb ultraviolet light can be used in clear coatings can be incorporated to provide a product with excellent resistance to discoloration to result from exposure to sunlight.

In order to explain the invention in more detail, some examples are given below.

example 1

15 g (dry weight) per m of a mixture which consisted of an aqueous emulsion, the 100 (dry) parts one under the name "Butakon ML 501" on the market butadiene / methyl methacrylate copolymers sold with a glass transition temperature of -21 ° C and 180 parts Water and 20 (dry) parts of an ammonium salt

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an acrylic copolymer marketed under the name "Amberlac AI65" was applied to a substrate made of wood-free cardboard, 100 g / m 2. The provided with the coating substrate was 5 seconds passed through a drying zone in which the air temperature was 110 ⁰ C, and was then molded at 130 ⁰ C and by pressing under a pressure of 35 kg / cm against a highly polished chrome plated roll, the device shown in the drawing was used. The finished product had a smooth, high-gloss coating that was at least equal to that which had been produced by cast coating a mineral-containing coating compound.

Example 2

ρ
15 g dry weight per m of a mixture consisting of an aqueous emulsion, the 100 (dry) parts of a ^{styrene / acrylic copolymer marketed under the name "Revertex A309 11} " with a glass temperature of 28 ° C and 160 parts of water and 20 Containing (dry) parts of an ammoniacal solution of a ^{low molecular weight styrene / maleic anhydride mixed polymer sold under the name 11} SMA Resin 144OH "was applied to a substrate made of wood-free cardboard, 240 g / m 2. The substrate provided with the coating was then heated for 4 seconds in a heating zone in which the air had a temperature of 120 ° C and then un-

ter a pressure of 35 kg / cm and at a temperature of 105 ° C in the apparatus shown in the accompanying drawing. The finished product had a smooth, high-gloss surface.

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Example 3

The procedure of Example 1 was repeated with the modification that a harder butadiene / methyl methacrylate copolymer was used with a glass temperature of -11 ° C, which is sold under the name "Butakon ML577 / 1" is used and a mold temperature of 125 ° C was maintained. The finished product had a smooth, high-gloss coating on.

Example 4

The procedure of Example 2 was repeated with the modification that a harder styrene / acrylic copolymer with a glass transition temperature of 19 ° C, which is marketed under the name "Revertex AJ> 86" is used and molded at 110 ° C and a molding pressure of 40 kg / cm. A smooth one was obtained High gloss coating.

The products of Examples 1 and 3 gave a softer one Surface at room temperature than those of Examples 2 and 4, whereas the latter materials are very flowable at high temperature and require a low mold temperature. Mixtures can therefore also be used of copolymers can be used, as illustrated in Example 5.

Example 5

A combination of 70 (dry) parts of a butadiene / methyl methacrylate polymer emulsion, marketed under the name "Butakon ML577 / 1",

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30 (dry) parts of a styrene / acrylic copolymer emulsion, sold under the name "Revertex A386", 20 (dry) parts of an ammonium salt of an acrylic copolymer, sold under the name "Amberlac AI65", and water in an amount such that the final solids content is 40% - as in example 1 - shaped ge partially dried and calcined at 120 ⁰ C and a pressure of 40 kg / cm. The product had all the visual properties of conventional cast-coated products and the surface was hard and free from blocking tendencies.

Example 6

A mixture was prepared from 100 (dry) parts of a marketed by Farbenfabriken Bayer AG under the name "Polyurethane dispersion CA7524" in the trade aqueous emulsion, which is known, that it is able to form a film below 20 ⁰ C, and 180 Parts of water and 10 parts of a low molecular weight styrene / maleic anhydride copolymer formed. This

Mixture was at a strength of 12 g dry weight

2 applied per m on a substrate made of wood-free Paper with a square meter weight of 80 g existed and had a pigment-containing coating on each side with a thickness of 10 g / m 2. The coated with the coating composition substrate was performed 6 seconds through a drying zone in which the air temperature was 10O ⁰ C, and then by pressing under a pressure of 50 kg / cm molded against a highly polished chrome plated roll at 120 ⁰ C, the in the

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Drawing schematically shown apparatus was used. The smooth and high-gloss surface was also distinguished by good rub resistance.

Polystyrene has a glass temperature of over 100 ^° C. and therefore its emulsions do not form a film under the conditions of the present invention. However, the film-forming temperature can be lowered by incorporating a plasticizer, as explained in Example 7.

Example 7

A coating mass is formed from 100 (dry) parts of a under the name "Vinamul 7700" commercially available polystyrene emulsion, 20 parts of a dibutyl phthalate plasticizer and 10 (dry) Share one called "Amberlac AI65" in the Acrylic copolymers sold commercially. This coating compound can be applied using the amounts, temperatures and pressures given in Example 2, dried and molded, and a smooth, glossy product is obtained.

Polyvinylidene chloride and its copolymers usually have only low tack and do not adhere sufficiently to the heated mold surface. In this case it is necessary to have a material add, which is able to increase the adhesion to the mold surface so much that the coating has the high gloss finish as illustrated in Example 8.

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Example 8

A coating mass is formed from 100 (dry) parts of a polyvinylidene copolymer marketed by Solvay et Cie under the name "IXAN WA 50" and 10 (dry) parts of an acrylic copolymer dispersion, which is marketed under the name " Primal WS-24 "is available. This coating composition can be applied, dried and shaped using the amounts, temperatures and pressures set out in Example 2, and a smooth, glossy product is obtained.

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Claims (1)

Claims 1. A process for producing a shaped polymer coating on a substrate web, characterized in that a coating composition consisting of an aqueous emulsion or dispersion of a polymeric material is applied to the substrate, a continuous film of the polymeric material is formed in the presence of water and then by no pressure the aqueous coating to a temperature above the film-forming temperature of the polymeric material temperature is at least evaporated method practiced heating some of the water and the film formed by pressing of this film under high pressure against a mold surface at a temperature above 100 ⁰ C. 2. The method according to claim 1, characterized is that the aqueous coating composition applied continuously, the heating means of passing the coated substrate made by a drying zone and molding caused by press-molding the coated substrate at a temperature of 105-150 ⁰ C. 3. The method according to claims 1 or 2, characterized in that that the mold surface consists of a chrome-plated roller. k. A method according to any one of the preceding claims, characterized in that the molded polymer coating is a high gloss coating. 309838/0918 5. Method according to any of the preceding claims, characterized in that the substrate consists of a metal foil or of paper or cardboard. 6. The method according to any one of the preceding claims, characterized in that the polymeric material mainly from a butadiene / methyl methacrylate copolymer or a styrene / acrylic copolymer. 7- method according to any of the preceding claims, characterized in that the emulsion or dispersion contains a small amount of a tack-reducing agent Contains means. 8. The method according to claim 7 *, characterized in that that the tack-reducing agent consists of an acrylic copolymer. Process according to claim 7, characterized in that the polymeric material consists mainly of a styrene / acrylic copolymer and the tack-reducing agent consists of a styrene / maleic anhydride copolymer. 10. The method according to any one of claims 7 to 9 »thereby characterized in that the polymeric material has a glass transition temperature of below 40 ° C. 11. The method according to any of the preceding claims, characterized in that the substrate is permeable and the substrate provided with the coating 309838/0918 immediately before the shaping step has a water content of 8 to 18 %, based on the weight of the substrate. 12. The method according to any one of the preceding claims, characterized in that the substrate is impermeable and the coated substrate has a water content of less than 2 %, based on the substrate weight, immediately before the shaping step. 13. The method according to any of the preceding claims, characterized in that the molding pressure is at least 10 kg / cm. 14. The method according to claim 13 *, characterized in that 2 that the molding pressure is 25 to 50 kg / cm. 15 · Method according to any of the preceding claims, characterized in that the temperature during of molding is 110 to 125 ° C. 16. The method according to any one of the preceding claims, characterized in characterized in that the viscosity of the polymeric material at the mold temperature is 40 to 80 units, determined in the Mooney viscometer is. 17. The method according to any one of the preceding claims, characterized in that the coating weight of the 2 polymeric material is 10 to J50 g per m. 18. The method according to any one of the preceding claims, characterized in that the molding is carried out by 309838/0918 by passing the coated substrate through the gap between a press roller and a forming roller, the film being guided in contact with the forming roller and the film with it without any relative movement between the film and the forming roller
the forming roll remains in contact until the coated product has dried to a stable moisture content. 19. Provided with a coating substrate, characterized in that it by a method such as
as claimed in any one of the preceding claims. 309838/0918 Blank page