DE3024919A1 - DECORATIVE LAMINATE AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

HOFFMANN · EITLE & PARTNER

PATENT LAWYERS 3 0 2 A 9 1

DR. ING. E. HOFFMANN (1930-197ί). Dl PL.-I NG. W.EITLE DR. RER. NAT. K. HOFFMANN. Dl PL.-ING. W. LEHN

DIPL.-ING. K. FOCHSLE DR. RER. NAT. B. HANSEN ARABELLASTRASSE 4 (STAR HOUSE). D-8000 MÖNCHEN 81 TELEPHONE (089) 911087 TELEX 05-29619 (PATHE)

. .33 .68.7 o / wa

TOPPAN PRINTING CO., LTD., TOKYO / JAPAN

Decorative laminate and its method
Manufacturing

The invention relates to decorative laminates using thermosetting resins and a method for the same Manufacturing.

Decorative laminates can be produced in different surface shapes, colors, luster and volumes and then resemble wood, enamel, ceramic, brick, natural stone
etc., and they are widely used as materials for making furniture or as building materials.
This type of decorative laminate is made by printing a printed decorative sheet with one

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Wood patterns or a printed enamel pattern soaked with a thermosetting resin, the printed decorative Sheets are laminated with a core paper, a coating paper or the like, and then the laminated body hot-pressed using an engraving plate with a predetermined embossing.

There are methods for producing three-dimensional patterns or a roughened surface with reduced gloss has been suggested, e.g., embossing using an etched or sandblown metal press plate. That However, a method for producing such metal press plates is difficult and the metal press plates produced are extremely expensive. Therefore, in practice, one works in such a way that a resin press plate is placed underneath Using a metal press plate as the original and then the resin press plate for the actual embossing used. However, a resin press plate made of, for example, a phenolic resin or an epoxy resin has the disadvantage that a release sheet must be used to prevent the panel from sticking to the decorative laminate. In addition, the durability is not satisfactory either. It is also used for various decorative laminates made of thermosetting resins, a printed decorative sheet with a printed pattern or an abstract pattern, a wood texture, stone grain, brick or ceramic-like pattern, or a number of others Inspect. Even if the print is very fine, a decorative laminate cannot be obtained in a satisfactory manner when the resin layer on the surface of the decorative laminate does not have or has a three-dimensional surface Has gloss suitable for printing. In particular

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In the case of decorative laminates with a wood grain, it is very difficult to completely remove the part of the printed decorative To align the sheet, which the xylem vessels, hereinafter referred to as the tracheal part) in the depressions formed during the embossing. For the production of this type of decorative laminates, a so-called wiping process is known in which a decorative Laminate using a press plate with a three-dimensional pattern made by etching the Surface of a metal plate such as stainless steel has been embossed. Then the indentations colored in the obtained decorative laminate with ink for coloring the tracheal parts. Even after this procedure it is extremely difficult to choose an ink which adheres very well to the surface of the decorative laminate and which also meets the other requirements is equivalent to. Even if you have a transparent resin over the ink layer to protect the ink layer coated, it is very difficult to preserve the original surface conditions and properties of the decorative Obtain laminate from a thermosetting resin. In addition, one is made by etching or sandblowing Metal press plate sharpens the slopes of the peaks and valleys, with the protruding parts generally smooth and the recessed parts rough. Decorative laminates made using such metal pressed sheets Are made in the reproduction of the surface of enamel or natural materials faulty. The main object of the invention is to provide a laminated thermosetting decorative sheet with to provide an improved design. Another object of the invention is to provide a method for

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Manufacture of a laminated, thermosetting, decorative Sheet to show, using a press plate, the improved release properties and high durability and which is cheap.

According to the invention, a decorative laminate with a soft three-dimensional pattern is shown, which preferably has a different surface gloss or a gloss pattern due to the formation of rough parts.

According to a preferred embodiment of the invention a decorative laminate is shown that consists of alternating protruding and recessed parts in continuous curves Divide is formed.

According to a further preferred embodiment of the invention, a decorative laminate is shown in which the protruding parts on the surface are glossy, the shoulders of the protruding parts are smooth and curvy and the floors in the depressions are rough and can be used as a decorative laminate with a brick pattern can. According to a further preferred embodiment, a decorative laminate is shown in which the floors of the Depressions on the surface are roughened and colored. This decorative laminate is available as a decorative laminate with suitable for a wood grain, the aforementioned depressions acting as tracheal parts or also for laminates suitable with brick patterns.

A decorative laminate according to the invention can be in a simple Way to be made using a press plate with an enamel layer on a metal substrate,

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this enamel layer having a three-dimensional pattern or a rough surface.

The invention is explained in more detail with reference to the accompanying drawings.

Fig. 1 is a schematic cross section of a

usual decorative laminate.

Fig. 2 is a schematic cross section of a

decorative laminate according to one embodiment of the invention.

Fig. 3 is a schematic cross section of a

embossed press plate with an enamel layer, as according to the invention is used.

Fig. 4 shows schematically an embodiment

the production of an embossed press plate with an enamel layer.

Figures 5 and 6 show embodiments of embossed

Press plates with an enamel layer.

Fig. 7 is a schematic cross section and

shows a method for hot-pressing decorative laminate elements with a press plate shown in FIG. 3.

Figures 8, 9 and 10 are cross sections showing further embodiments of the embossed press plates with an enamel layer.

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11 and 12 are cross-sectional views showing embodiments of the embossed press plates having a Enamel layer with rough protruding parts.

Figure 13 is a cross section of a decorative lami

nats, which was produced with an embossed press plate according to FIG.

Fig. 14 is a cross section of an embodiment

form of an embossed press plate with an enamel layer on the roughened one Surface.

Fig. 15 is a cross section of a decorative

Laminate made with an embossed press plate according to FIG became.

Figures 16 and 17 are schematic cross sections and show

Method for hot-pressing a decorative laminate element with an embossed Press plate with an enamel layer.

Figures 18, 19 and 20 are schematic cross sections and show Method of adhering a dye to the roughened protruding parts a layer of enamel.

Fig. 21 is a cross section of a decorative La

minats, in which the pits are roughened and colored.

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As can be seen from Fig. 1, shows the surface of a decorative laminate 1, which by means of a conventional Metal or resin press plate was made, the sharp protrusions and depressions of the press plate used and a smooth pattern of the protruding and recessed parts cannot be obtained. On the other hand, in FIG. 2 a decorative laminate 2 according to the invention is shown, with a smoother surface than a usual decorative Laminate. Therefore, the inventive decorative Laminates are advantageous because the three-dimensional surface is smooth and suitable for the reproduction of three-dimensional Patterns that match enamel, earthenware, brick, natural stone, and the like.

The inventive, decorative laminate is by means of a Press plate or an embossed plate made with an enamel layer 6 on a metal substrate 5 Steel, cast iron, copper, aluminum, stainless steel and the like as shown in FIG. The enamel layer 6 is produced by coating the substrate with a glaze and then firing. One to manufacture A press plate suitable for a decorative laminate with different patterns can be obtained by using a three-dimensional pattern or a glossy pattern, i.e. roughened parts on the surface of the enamel layer. A press plate with an enamel layer has proven advantageous in the manufacture of laminated thermosetting, decorative leaves highlighted in terms of the following features:

(1) Sufficient releasability is obtained with thermosetting resins such as melamine-formaldehyde resins because

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the surface of the enamel layer is very hard and fine.

(2) The formation of protruding parts on the surface of the enamel layer can be relatively easily achieved, e.g. by performing a screen print with a frit ink.

{(3) Roughening the protruding parts can be easily performed, for example, by mixing in a Matting agent in the fritting ink.

(4) The bottom surface of the depressions in the enamel layer is very smooth, so a dye like Ink does not adhere to a lot and can be easily removed. This ensures that the dye adheres takes place predominantly on the roughened surface of the protruding parts.

(5) A decorative laminate with a colored pattern that completely follows the three-dimensional pattern of the Plate is obtained because the dye adhering to the roughened surface is completely absorbed into the Depressions of the decorative laminate is transferred if you have an enamelled press plate with roughened and colored bumps are used.

(6) The dye transferred to the decorative laminate becomes due to the melting of the thermosetting Decorative laminate resin bonded.

Although the press plate is described here as being plate-shaped, it can also be roller-shaped.

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The following is the procedure for forming the indentations and bumps in the enamel layer of the press plate described. To form smooth depressions and elevations in the enamel layer of the substrate a method according to FIG. 4 can be used by applying a glaze 8 with a spray gun 9 to the surface of a substrate 7 and then forming a surface 10 with an arbitrary three-dimensional Pattern burns. Alternatively, as shown in FIG. 5, after uniformly applying a Glaze on the three-dimensional pattern of a substrate 11 a three-dimensionally patterned surface 12 by firing achieve. According to the procedure described in FIG. 6, glazes of different types can be made with different glazes Apply melting points to the surface of a substrate 13 in the form of a pattern or arbitrarily. A three-dimensional one Pattern is then formed at a firing temperature at which the glaze 14 has an increased melting temperature is fired and by melting the glaze or glazes 15 with a lower melting temperature. the Surface of the decorative laminate covered with a press plate embossed that was manufactured by one of these processes has a smooth three-dimensional pattern, as shown in FIG.

A decorative laminate with a continuously curved surface created by alternating indentations and Elevations is formed, is a preferred embodiment for a decorative laminate that is with a Press plate was made, which has an enamel layer with a soft, three-dimensional pattern.

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The press plate used for this embodiment can be produced by appropriately pretreating a metal substrate, for example degreasing; Using a spray gun to coat the substrate with a slurry obtained by adding a grinding aid and water to a glass frit, and kneading the mixture in a ball mill, followed by baking the coated substrate. The frit used can be a conventional one and can contain, for example, SiO ₃ , Al ₃ O ₃ , B ₃ O ₃ , Na ₃ O, K ₃ O, CaO, ZnO, MgO and the like as main components. The grinding aid can be a suspending material such as clay, an emulsifying material such as tin oxide, a coloring agent such as borax, or an electrolytic material such as magnesium carbide. The firing is carried out at a temperature which is higher than the melting temperature of the frit, and is generally in the range of 500 to 900 ⁰ C. The melted frit is in the form of a viscous liquid, so that the surface becomes as small as possible due to the surface tension. This, together with the flowability of the molten frit, has the effect that the sharpness of the depressions and elevations in the shape are rounded and depressions and elevations are obtained in a rounded shape. The most suitable flowability and the same degree of rounding at the depressions and elevations can be achieved by appropriately choosing the composition of the frit and the temperature conditions. In this way an enamel layer can be obtained which softly reproduces the surface of the metal substrate and which has depressions and elevations of similar dimensions. Although the three-dimensional pattern of the enamel layer of the press plate and the three-dimensional pattern of the under

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The laminate obtained using this press plate is opposed to it, but they have a similar appearance. Therefore, the three-dimensional pattern of the enamel layer does not necessarily have to be the reverse of the three-dimensional pattern of the decorative laminate to be produced. It is thus possible to manufacture a press plate that has a sinusoidal surface with alternating

! Depressions and elevations, i.e. with a horizontal I symmetrical curvature.

A laminated thermosetting decorative sheet is obtained in a conventional manner by means of a press plate. This here thermosetting resin used may be a melamine-formaldehyde resin, a diallyl phthalate resin, a polyester resin Be guanamine resin or the like. As shown in FIG is, a decorative laminate member made of a resin impregnated core paper 16, a printed decorative sheet 17 on which the desired pattern is printed and which is impregnated with the resin, and a Overcoat paper 18 impregnated with the resin is laminated. A press plate 19 is located above so that their enamel layer with a three-dimensional Pattern in contact with the overcoat paper 18 is. Instead of the core paper, you can also use plywood. A decorative laminate with a smooth three-dimensional Patterns and a gloss corresponding to the enamel are then obtained by hot pressing. This decorative laminate does not have sharp angles in the three-dimensional Pattern so that it does not look unnatural and no dust remains in the depressions to make cleaning easier.

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example 1

A steel plate 1.6 mm thick is pretreated by degreasing. A slip was prepared from a frit, the main components of which were SiO ₂ , ^B 2 ° 3 ' ^A1 2 ° 3' ^Na 2 ° and the like, water and a suspension material such as GAIROME clay (calcined clay) and other additives. The slip was applied to the surface of the steel plate with a spray gun and formed an arbitrary three-dimensional pattern thereon. After firing for 3 minutes at 850 ° C., an embossed press plate with an enamel layer on the surface was obtained. This embossed plate was used to make a decorative laminate from a melamine-formaldehyde resin. In this way, a melamine-formaldehyde resin decorative laminate having a smooth three-dimensional pattern and improved gloss could be obtained. After more than 100 repeated embossings, no defects were found on the embossed press plate, regardless of the fact that the hot pressing was carried out at a temperature of '
was leading.

temperature of 140 C and a pressure of 80 kg / cm.

Another method for producing a three-dimensional pattern on a press plate is described below.

An enamel layer is produced in the usual way on a metal substrate, with peaks and valleys form. For example, it is possible to apply a raised pattern to the surface of the enamel layer by a screen printing process is used and an ink is used

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with a glass content of over 10%, i.e. a frit ink, applies and then burns. It is also possible to have an adhesive with a desired pattern on the surface to apply the enamel layer and to distribute glass powder on it and after removing the frit on the not to burn the parts forming the pattern. It is also possible to have a raised pattern on the surface of the Form an enamel layer using a transfer sheet with a pattern that is on a sheet such as a sheet of paper or a plastic film, through an ink containing a pigment and frit, and then Burning was formed.

The method for producing elevations or depressions in the enamel layer is described in detail below on a press plate.

In one embodiment shown in FIG. 8, a basecoat layer 22 is applied to both surfaces Metal substrate 21 is formed. The formation of these layers is preferred because it allows both the adhesion between the top enamel coating to the metal substrate as well as the durability of the press plate can be improved. It is also advantageous to apply a base coat of the back surface of the metal substrate to prevent warping and corrosion of the press plate to avoid. A so-called black base containing cobalt oxide can be used to produce the base coats. use. After the basecoat layer 22 has been completely baked and the substrate has cooled, an overcoat Enamel layer 23 formed over the base layer 22. For the covering enamel coating you can use a

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Use slip, i.e. a glaze that is obtained by adding grinding aids to a commercially available one Enamel frit and by grinding the mixture in a ball mill. Any coating process can be used to get voted. In general, however, the coating is carried out by spraying when the press plate is a has a large dimension. As in the case of the base coat layer 22, a covering enamel layer 23 is preferably applied to both surfaces of the substrate 21.

The conditions for the surface treatment of the covering Amailles layer can be varied by appropriate selection of the type of frit and the grinding aids, the Viscosity of the applied slip, the coating method, the baking temperature and the like. The desired Surface conditions can be chosen so that the surface is either smooth or very weak and soft is chosen. The aforementioned methods can be used to form a three-dimensional pattern. That The simplest method for this is to increase the viscosity of the slip, to reduce the degree of leveling or to enlarge the surface of the droplets of the slip by increasing the air pressure of the spray gun reduced. In this case there must be variations in the level of the pattern in the final enamel coating be kept within a certain range because excessive fluctuations result in irregular ink transfer in the Layer in screen printing or in the transfer process would cause. With regard to the gloss on the surface of the uppermost enamel layer, this gloss can be used choose arbitrarily by looking at the terms accordingly

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changed so that the gloss can vary from a mirror finish to a completely smooth surface. A matting the surface of the top enamel layer can be simple be done by adding a matting agent to the glaze or by lowering the firing temperature. The surface finish of the enamel coating can also be changed by using glazes of different particle sizes in a suitable manner or with different melting points. In both cases, the enamel layer should not be too thick and preferably below 500 µm. If this layer is too thick, it can occur during hot pressing Pressure break.

Method for producing the elevations 24 on the surface of the fired enamel layer 23 using screen printing or a transfer process as in Fig. 8 are shown below.

First, the screen printing method will be described. The pressure screen can be a screen with 150 to 200 mesh or, preferred in the present process, a thicker sieve with 60 to 70 meshes (60 meshes = clear mesh size 0.250 mm, 70 meshes = clear mesh size 0.210 mm, 200 meshes = mesh size 0.074 mm, 150 meshes = clear mesh size 0.105 mm). In the latter case, the decorative laminate has due to the thickness of the ink layer a very nice three-dimensional look. The meshes, the wire diameter, the thickness of the screen and the ones used Sieve materials and the like depend on the desired Effect, e.g. the desired degree of fineness of the pattern, but a sieve with 30 to 250 meshes (0.500

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up to 0.063 now clear mesh size) using Monofilament threads or multifilament threads made of nylon or Polyester is generally used. Commercially available frying ink can be used as the screen ink, i.e. a commercially available glass frit that finely grinds and was kneaded with a sieve oil.

The transfer procedure is described below. A A predetermined pattern of a fritting ink is applied to the surface of a base material such as a sheet of paper or a film, applied in a suitable printing method, e.g. by screen printing or by photo-engraving printing. screen printing enables thick patterns to be printed, while photo-engraving enables fine patterns to be printed. The transmission method can be selected in any way from the usual methods, e.g. a method for the production of lacquer transfer layers on the surface of enamel layers and transfer by pressing or can be a process for the production of lacquer transfer layers on the surface of a transfer paper, this is then transferred directly to the surface of the top layer of enamel. That Transfer method is advantageous because you use the transfer paper beforehand and the actual transfer can be done easily by a water transfer method or can be done with a simple device. However, the thickness of the formed ink layer is limited and the height of the raised ink layer is slightly inferior compared to a direct screen printing process .

Modified embodiments for making a

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three-dimensional pattern by screen printing or by transfer are described below. In the case of the in Fig. 9 is a pattern by screen printing or by transferring to a top layer of enamel 25 using a fritted ink with a higher specific gravity than the upper enamel layer 25. During firing, the temperature is increased to a point at which the top enamel layer 25 melts. I Then the frying ink particles sink into the upper enamel layer 25 and form the recessed parts 26. Different shaped surfaces can also be obtained by the screen printing process is combined with the transfer process. Either of these two methods can be repeated for better effects. For example, you can have more than one printing screen, each with a different one Use thicknesses to change the height of the protruding parts in different stages. Of the Gloss can also be changed by changing the ink composition. When making a press plate This type of ink layer transfer and firing can be repeated, or the firing will be repeated after several Transfers of the ink layer performed. 1 shows an embodiment of this method of manufacture of low protruding parts 28 and high protruding parts 29 on the uppermost enamel layer 27. Such a press plate can be used to produce a decorative laminate with indentations of different depths Has.

As shown in Fig. 11, it is possible to use a matt Surface 33 on the bumps 32 that are on the enamel layer 31 of the press plate are formed to produce. The matting

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the top surface of the protruding parts can easily be done using a matting ink, which is obtained by mixing a matting agent with a fritting ink and which is then applied to the enamel layer or transferring the top layer of enamel by screen printing or transfer. Alternatively, you can do this can also be achieved by mixing coarse particles with a higher melting point, such as aluminum oxide or Zirconia. In this case, the firing must be carried out at a temperature at which aluminum oxide or Do not melt zirconia. To particularly emphasize the matt surface on the protruding parts and to increase the decorative effect, the top layer of enamel 31, which forms the depressions, preferably smooth. The composition of the slip and the firing conditions must be chosen so that the The surface of the pits is as smooth as a mirror surface or over 50% of the mirror reflection in one Angle of incidence of 60. However, the surface of the upper enamel layer does not have to be uniform and can have soft waves and hills. A decorative laminate formed with a press smoothness according to FIG. 11 has a smooth surface on the bottoms of the wells and a smooth surface on the ridges and is therefore particularly advantageous. With a conventional etched metal press plate, the wells and the Elevations in the decorative laminate formed are consequently also matt, whereas the depressions are soft. It is difficult with this type of press board to produce a decorative laminate, as is obtained according to the invention, to manufacture.

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Below are some embodiments of a decorative Laminate described with such a matte surface. According to a first embodiment shown in FIG. 12, a raised ink layer is applied to the surface of the uppermost enamel layer 34 with a thick screen using a fritting ink containing a matting agent. Run away at a suitable temperature, the sides 36 of the elevations 35 melt and connect with the upper one Enamel layer 34 with the formation of a glossy surface. Only the top surfaces 3 7 are matted. A decorative laminate made with such a press plate is shown in Fig. 13 and has rounded shoulders 39 and shiny protruding parts 3 8 and matte surfaces at the bottom of the recesses 40. After this procedure you can make a decorative laminate with a brick pattern very well. Such a decorative laminate can one made with a press plate, which was created by printing part of the the joints between the Bricks corresponds, using a frit ink containing a matting agent and subsequent firing. This decorative laminate looks very similar to real bricks and the parts that make up the shoulders of the bricks are rounded and the joint parts are matted.

A second embodiment is shown in Figs. As shown in Fig. 14, it is possible to use an ink layer 42 that has the same level as the covering one Amailles layer 41, to form and which is on the surface is matted by the specific gravity of a fritted ink containing a matting agent, or the firing temperature adjusts. One with such a press plate

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The decorative laminate produced is shown in FIG. The surface is essentially smooth, but has to Part matted parts 43 and glossy parts 44. This is very suitable for a decorative laminate with the appearance of natural stone.

The method of making a laminated thermosetting decorative sheet with a press plate with a matted surface obtained in the manner described above is not fundamentally different from the previously described procedures. The manufacturing method is explained with reference to FIG. 16, Using a decorative laminate made from a melamine-formaldehyde resin. over an enamel layer of a press plate 45 are applied in the order shown: an overcoat paper 46 that is coated with a melamine-formaldehyde resin is impregnated, a printed decorative sheet 47, which is similarly impregnated with a melamine-formaldehyde resin is impregnated, a barrier paper 48, which, if necessary, also with a melamine-formaldehyde resin is impregnated, a desired number of core materials 49 impregnated with a phenol resin, and a anti-warping sheet 50. A plurality of such combinations are stacked and combined into one Hot press given for hot pressing. The rear surface of the press plate is in contact with the rear surface of the decorative laminate to be produced. So if there is a layer of enamel on the rear surface of the press plate is formed, it is advantageous because a special release paper or a separating film is not required, as the enamel layer itself has separability. The pressing conditions

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can be the same as in the usual procedure for the production of decorative laminates from melamine-formaldehyde resin, so that you don't have to take any special measures here. The preferred temperature is maximum at 140 to 160 ° C and the pressure at 50 to 120 kg / cm and the heating time is 15 to 30 minutes and the cooling time is 15 to 30 minutes.

Protruding parts of an ink layer can be formed on the enamel layer on the back of the press plate, so that both surfaces of the press plate can be used for the production of decorative laminates. Since decorative laminate elements can be placed on both sides of the press board, the required Halve the number of pressing plates 51 so that only half the number is required for the number of the corresponding elements will. Due to this measure, one can reduce the number of decorative laminate elements that are pressed at the same time can increase. If so, two arrangements of decorative laminate elements, such as the Overcoat paper, the printed decorative sheet, the core material sheets and the like are placed between the press plates 51 and the press plates 52. Between A release paper 53 is to be placed in each of these arrangements.

Example 2

A cold rolled steel plate 1.6 mm thick was made for the production of an enamel layer on predetermined

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Dimensions cut, degreased, stripped and washed with water. On both surfaces of this steel plate a black base coat of the following composition would be sprayed on evenly. After this Drying, the plate was baked at a maximum temperature of 870 C for 3 minutes.

Parts by weight

Base coat frit 100 GAIROME clay 7

Feldspar 3

Borax 0.75

Magnesium carbonate 0.25

Water 40

White enamel of the composition shown below was evenly applied over both surfaces of the steel plate, which was already provided with the base coat, coated. After drying, the firing was done so that the maximum temperature of 850 ° C. was maintained for 2 minutes.

Parts by weight

Enamel coating frit 100

GAIROME tone 5

Tin oxide 8

Magnesium carbonate 1

Water 50

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The surface of the enamel coating obtained showed excellent gloss and very good smoothness. Parts corresponding to the joints of hexagonal bricks were printed on this enamel layer using a 70 mesh screen. The ink was prepared by kneading sieve oil with a commercially available pressure frit (already ground) to which a matting agent had been added. The firing ι was carried out under such conditions that a maximum temperature of '75O ⁰ C was maintained for 2 minutes. The edges of the ink parts were glossy and rounded by melting, and the tips of the ink parts were matted. The ink layer formed bumps that were integrated with the top enamel layer. A decorative laminate made of melamine-formaldehyde resin was pressed using this press plate. As a printed decorative sheet, a titanium paper sheet with a brick pattern printed thereon was prepared in advance. The hot pressing was carried out in the usual way. The pressing conditions were as follows: 14 5 ° C maximum temperature, 20 minutes heating, 80 kg / cm ² pressure and 20 minutes cooling. A release sheet was not used. The decorative laminate thus obtained had a smooth, smooth, enamel-like surface with a printed pattern on the protruding parts and frosted parts corresponding to the joints between the bricks, these parts being very similar to the real joints of brick walls. This decorative laminated sheet of melamine-formaldehyde resin was, on the whole, extremely similar in external appearance to the real surface of brick. The press plate could be used repeatedly for pressing more than 100 times.

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Example 3

On the surface of the top enamel coating, which is in in the same manner as in Example 2 was obtained. screen prints were applied.

No mesh pattern ink

1 0.105 glossy grained stone engraving

2 0.250 modified brick joint, matt

After printing No. 1 was carried out, the ink layer was dried by heating at 100 ° C. After drying Print No. 2 was carried out. This was followed by firing in order to combine the layer of ink with the upper layer of enamel. The releasing conditions were the same as in Example 2. The surface of the printing plate thus obtained was shiny and slightly protruding on the parts that corresponded to a grainy stone texture; she was even more sublime and matted on the parts that corresponded to the brick joints and were the shoulders of the raised layer of ink rounded and shiny. This enamelled press plate was used under the same conditions as in Example 2 a decorative laminate molded from a melamine-formaldehyde resin. The decorative laminate produced had parts which looked exactly the same as brick joints and had a fine grained stone structure on the parts that form the surface of bricks corresponded. The overall appearance was even more reminiscent of real bricks than in the case of example 2.

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Example 4

A diallyl phthalate impregnated paper was placed over a sheet of plywood 4 mm thick. The hot pressing was with a press plate produced according to Example 2 at a temperature of 130 C and a pressure of 10 kg / cm carried out for 10 minutes. The press plate separated without using a release sheet. The diallyl phthalate decorative laminate had the same Appearance like the decorative laminate produced according to Example 2.

Example 5

To produce the press plate of Example 3, the granular stone texture was previously applied to a sheet of transfer paper manufactured. The printed pattern was transferred to the surface of the top layer of enamel. Through this transfer process a printing process was omitted. The press plate produced in this way had the same surface structure as in the case of example 3.

Example 6

A black base coat (SG-Q, manufactured by Nihon Frit Company Ltd.) was uniformly applied to both surfaces applied to a pretreated steel plate 1.6 mm thick,

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It was then fired in such a way that a maximum temperature of 870 ° C. was maintained for 3 minutes. A half-matt, White enamel top coat (manufactured by Nihon Frit Co., Ltd.) was applied to both surfaces of the plate applied. Firing was carried out again under such conditions that a maximum temperature of 750 ° C. during the 2nd Minutes was maintained. Then parts that corresponded to a wood grain on the tracheal parts were printed on, using a matting ink and applying a 200 mesh screen to the surface the top enamel coating. It was then fired again at a maximum temperature of 730 ° C., the Was maintained for 2 minutes. The enamel plate obtained in this way was semi-matted on the surface of the enamel coating and on the parts that form the tracheal parts of a Wood grain matched, completely matted. The shoulders of the ink layer were not rounded, but rather spicy. The enamel plate thus used was used as a press plate. The hot pressing became more common Way using a printed decorative sheet with a printed pattern of Japanese oak made with melamine-formaldehyde resin was impregnated. The thus obtained decorative laminate made of a melamine-formaldehyde resin had depressions that corresponded to the tracheal parts. These tracheal parts were matted and made a decorative one Laminate with an excellent design.

According to the invention it is possible to produce decorative laminates, in which a dye is fixed in the wells by using a press plate, which holds the dye in the frosted parts of the bumps formed on the enamel layer of the press plate.

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The dye to be used can be arbitrarily selected, but it must be mixed with the melted thermosetting resin be compatible with the deformation process. The dye can be a single pigment. There were a number of Investigations into the durability of decorative laminates made in this way. As a result of these investigations it has been found that the colored parts in the decorative laminate produced are stable when one a dye used which, in addition to the color component, such as a pigment, contains a resin as a binder, the Resin is the same thermoplastic resin used for the decorative laminate or a thermosetting one Resin which is compatible with the thermosetting resin of the decorative laminate and which has a lower curing temperature than the thermosetting resin of the decorative Laminate. The result of a study on the adhesion of various dyes after the aforementioned Way to the decorative laminate made of a melamine-formaldehyde resin is shown in Table 1. The rating shows the degree of fading after getting the wiped colored parts of the decorative laminate 100 times with a cloth dampened with lacquer thinner.

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- 33 Table 1

dye binder Art Shelf life of the
decorative la
minats Ink A for
decorative
Laminate Harz on Zellu
loose base fluid
(soluble
in oil) bad Ink B for
decorative
Laminate Harz on Zellu
loose or
Acrylic base fluid
(soluble
in water) quite
Well Screen ink A Alkyd resin fluid
(soluble
in oil) quite
Well Screen ink B Alkyd resin,
Melamine resin fluid
(soluble
in oil) Well sample
Ink A Melamine resin fluid
(soluble
in water) Well sample
Ink B Epoxy resin fluid
(soluble
in oil) Well Pigment A
Pigment B none
Vinyl resin powder
powder bad
bad powder
Color a Polyamide resin powder bad powder
Color B Polyester resin powder quite
Well sample
toner Melamine resin powder Well

030064/0862

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The table shows that the resistance of a decorative laminate made of a melamine-formaldehyde resin the colored parts will be better than the thinner if you use colors as a binder a binder containing a thermosetting resin such as a melamine-formaldehyde resin or an epoxy resin. In the case of Powder Color B in Table 1, although the binder was thermosetting, it was sufficiently hardened not achieved because the curing temperature was higher than the pressing temperature of the decorative laminate made of melamine-formaldehyde resin. The relationship between the resin of the decorative Laminate and the binder also applies to decorative laminates made from other thermosetting resins, such as Diallyl phthalate or polyester resin too. The dye containing the coloring components with a binder can be used in be in liquid form or in powder form. The powder form is preferred because it is simpler than the smooth ones Parts of the press plate can be removed.

One method of holding the dye on only the frosted portions of the enamel layer of the press plate is as follows explained. The so-called wiping method is the easiest and is therefore preferred. As shown in FIG is, a dye 62 is applied to the entire surface of the enamel layer 61 of a press plate 60 and the surface is wiped with a cloth or a sheet of paper. The dye on the smooth parts 64 will be removed. Wiping is easier if the cloth or sheet of paper has been cleaned with a solvent is moistened for the dye used. While the dye on the smooth parts 64 of the enamel layer can be easily wiped away, it can only be

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030064/0862

very difficult to wipe off the matted parts 65 because the dye is in the fine depressions of the surface holds on. In practice, of course, the wiping of the press plate cannot usually be done manually Carry out wiping because the press plate can be very large. In this case, a mopping machine is preferred as shown in FIG. 19. In Fig. 19, a dye 68 is applied to the entire surface of a Press plate 67 applied by means of a coating roller 66. He is by means of a wiping roller 69, which opposes the movement of the pressing plate 67 rotates, wiped. If the dye is liquid, a rubber wiping roller can be used be used. If the dye is a powder, a soft material, such as a cotton roller, will be used for the Mopping roller used. With this procedure one can wipe the entire surface of the press plate over effect a large area in a uniform manner and the dye is only retained on the matted parts. Alternatively, a screen printing process can also be used will. As shown in Fig. 20, a mesh plate for making the frosted parts 73 is on the surface the enamel layer 71 attached to the enamel layer 71 so that the line drawing parts of the printing screen 70 and the Matted parts 73 of the enamel layer 71 are aligned with one another. A dye 72 is screen printed applied so that only the matted parts 73 are colored. The special printing screen for the formation of the Matted parts is not required; a separate printing screen with the same positive pattern can be used as an alternative use. Especially if you have a printing screen for the production of matted parts with a small mesh size and thicker is used, a printing screen is not

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030064/0862

preferred because too much dye is applied. In this case, better results will be obtained with a separate printing screen of a lesser thickness of about 0.074 open mesh (200 mesh). If that continues Positive is not used to make the frosted parts, but a corrected positive with slightly narrower ones Lines used to make a printing screen, processability is improved because the dye does not run out of the frosted parts of the enamel layer.

It is also possible to apply more than one color, by dividing the matted parts between more than one printing screen and the matted parts with dyes different shades of color. A preserved one decorative laminate is then colored with more than one color and has an improved ornament.

In all of the aforementioned processes for applying a dye or dyes to the matted parts by the wiping method or by the screen printing method, water or a volatile material such as a solvent, in the dye that adheres to the matted parts of the enamel layer, removed by thorough drying, if a liquid dye is used. If too much of such a material remains, it will evaporate it during the press production of the decorative laminate and then surface irregularities or Bubbles remain on the decorative laminate. However, such considerations do not have to be made if one a powdered dye is used.

It is possible in this way, the depressions in the

03006A / 0862 -37-

to matt and color decorative laminate of a thermosetting resin by using a press plate, the holds a dye or dyes only on the frosted parts. The pressing process for the decorative laminate is not different from that with reference to Figs. 7, 16 and 17 described. The thermosetting resin forms after it is hot-pressed during the decorative laminate melted, recessed frosted parts from where

the protruding frosted parts of the enamel layer are the press plate and at the same time it is combined with the dye applied to the protruding matted parts in the enamelled layer of the press plate is. By curing the thermosetting resin, the dye will stick to the recessed matted parts of the decorative Laminate is bound and does not stay on the enamel layer of the press plate. In this way the press plate can be used again immediately so that a dye can be applied for the next pressing process. A decorative laminate thus obtained is shown in FIG. This decorative laminate has smooth raised parts 75 and the bases of the depressions 76 are matted and colored in the desired manner by means of a dye 77 been. The decorative laminate thus obtained shows a particularly beautiful design. If you have a printed decorative Sheet with a brick or stone pattern together with the frosted parts of an enamel layer with an adapted If you use a grain of sand or brick joint pattern (embossed pattern), you get a decorative laminate that is very similar to real bricks or ceramic coatings and has a very nice design. Preferably a printed decorative sheet with a wood grain together with matted tails of an enamel layer one

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03006A / 0862

Press plate, in which a tracheal pattern is applied, is used and a decorative laminate is then obtained, the recessed parts of which are colored in the color of the tracheal part. In a thus obtained decorative laminate · j with the wood grain Trachealteile in the \ wells and the colored portions are aligned with each other completely, in contrast to the usual comparison. ι drives in which the color of the tracheal parts is printed on a printed decorative sheet. Such a decorative laminate with wood grain is extremely good in design and reproduces the natural wood grain very well. j

Example 7

A very low carbon steel plate and a thickness of 1.6 mm for making the enamel layer was cut to the predetermined size and then degreased, descaled and washed with water. A black base coat was on both of them Surfaces of the steel plate sprayed. After drying, at a maximum temperature of 87O ° C, which during 3 Minutes was held, burned. White enamel coating was applied to both surfaces in a similar manner. After drying, it was fired again, the maximum temperature of 850 ° C. being maintained for 2 minutes became. This gives a surface of the surface enamel layer which is glossy and smooth. Parts that the Joints of hexagonal bricks were made on the surface of the enamel layer using one

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030064/0862 j

OMGINAL INSPECTED

Printing screen with 70 mesh (70 mesh) printed on. The ink was made by pulverizing sieve oil together with a commercially available pressure frit and an added, already ground matting agent. Afterward was fired at a maximum temperature of 750 ° C. which was held for 2 minutes. the Edges on the inked parts rounded and became translucent. The tips of the with ink treated parts were matted. The ink-treated parts protruded from the enamel layer and were integrally connected with this.

A dye of the composition shown in Table 2 was applied to the surface of a press plate produced after the aforementioned method was applied. The dye was moistened with a moistened with water Cloth wiped so that it remained only in the frosted parts.

Table 2

Parts by weight

Melamine resin 100

Soot 4

Iron oxide yellow pigment 16

Iron oxide red pigment 5

Water 100

Surfactant 2

Thickener 2

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03006A / 0862

A decorative melamine laminate was made using a Press plate molded with a layer of enamel, with a dye only adhering to the matted parts after the water content in the dye had been removed by drying. A titanium paper with a printed on it Brick pattern was used as the printed decorative sheet, and hot-pressing was carried out in the usual manner carried out. When deforming, the maximum tem-

i _o

temperature 145 C, the heating time 20 minutes, the pressure 80 kg / cm ² and the cooling time 20 minutes. No release sheet was used. The decorative laminate thus obtained had protrusions with a smooth surface with a gloss resembling that of enamel and a matching printed brick pattern, and the depressions had a matt surface and a firmly adhering colored pattern. The laminate obtained as a whole had a very nice design. The external appearance was very similar to that of a real brick pattern. In the dyed recessed parts, the dye was integrated with the melamine-formaldehyde resin and adhered very firmly there, so that no defects were found after the decorative laminate was wiped 100 times with a cloth moistened with a thinner. Furthermore, the dye was completely transferred to the decorative laminate in the molding process and no dye remained on the surface of the enamel layer after the mold was opened.

Example 8

As in Example 7, a sieve plate was used to apply the

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030064/0862

Dye on the enamel layer of a press plate used. The sieve plate was made from a nylon sieve with a mesh size of 0/074 mm (200 mesh) and A hexagonal brick pattern was used as a positive pattern, which had previously been used to produce the matted surface had been used on the press plate. The coloring of the matted surface of the decorative laminate was extremely easy by this method and enabled staining in higher concentrations.

Example 9

A decorative melamine laminate was made as in Example 7 produced with the exception that the dye of the composition according to Table 2 was dried and ground before it was then applied in powder form. Applying the dye was much easier and went a lot smoother than in the case of a liquid dye. The durability of the colored parts of the obtained decorative Laminate corresponded to the durability that was obtained in Example 7 with the laminates there.

Example 10

Screen prints in the combination shown in Table 3 were made with a frit ink on the surface of an enamel layer of a press plate according to that described in Example 7 Procedure applied.

030064/0862

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Table 3

No mesh screen pattern fritt-ink

1 150 mesh granular stone texture matting (0.105 mm)

2 60 mesh modified brick joint matting (0.25 mm)

After the screen printing, no. 1, the ink layer was dried by heating to 100 ⁰ C. Then, No. 2 screen printing was performed and baked to firmly adhere both ink layers to the enamel coating. The firing conditions were the same as in Example 7. In the surface of the enamel layer of the pressed plate thus obtained, the parts corresponding to the granular stone texture were frosted and protruded slightly, and the parts corresponding to the brick joint was frosted and protruded further than that Parts showing the stone grain and the shoulders of the ink layer were rounded and shiny.

Screen prints with 200 mesh were made with the positive patterns that used in the respective No. 1 and No. 2 prints above. Using each of these Printing screens, the matted surfaces of the enamel layer of the press plate were colored according to Table 4.

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03006A / 0862

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Tabel

Mesh screen pattern

dye

200 mesh granular stone texture light gray 200 mesh modified brick joint black

About the dye had the following composition:

Tabel

No. 1 dye (light gray)

Melamine formaldehyde resin (S-260) soot

Titanium dioxide

water

Surfactant thickener

Parts by weight

100

23 100

No. 2 'dye (black)

Melamine formaldehyde resin (S-260) soot

water

Surfactant thickener

100

100

After the dyes had dried, a decorative melamine laminate was produced with this press plate. The thus obtained decorative laminate made of melamine-formaldehyde resin was matte

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03006A / 0862

and colored black in the brick joint parts and was smooth with fine matted depressions and gray colored in the brick surface parts. Overall this showed decorative Laminate a very nice design and looked extremely similar to the surface of real bricks.

Example 11

The press plate used in Example 7 and the dye having the composition shown in Table 6 were used for coating of a dye is used on the matted surface of the press plate. A sheet of paper made with diallyl phthalate resin was impregnated, was applied to a plywood sheet of 4 mm thick and at 130 ° C by 10 kg / cm while Pressed for 15 minutes

Table 6

Parts by weight

Diallyl phthalate resin

Prepolymer 93

Diallyl phthalate resin

Monomer 7

Pigment 25

Solvent (acetone: MIBK 1: 1) 100

The shape was easy to open and without the use of a Separation film. The decorative DAP laminate thus obtained had an appearance quite similar to the melamine-formaldehyde decorative laminate obtained in Example 7 and the adhesion of the dye to the matted surface

030064/0862 -45-

was sufficiently firm in the depressions.

Example 12

A basecoat was applied to both surfaces of a steel plate 1.6 mm thick. Then became baked so that the base coat became smooth on both surfaces of the steel plate. Afterward a coating with enamel was applied to both base layers to form an enamel layer. It was then baked a second time, giving the enamel coating a smooth, semi-rough enamel coating revealed. The enamel layer consisted of 10 parts by weight of a matting agent and 100 parts by weight of a frit. It showed a mirror reflection of about 70%.

Using a 150 mesh (0.105 mesh) pressure screen and fritting ink to form a complete In the matted enamel layer, the tracheal pattern of a walnut grain was printed onto the enamel layer. Then it was fired a third time and a press plate with matt protruding parts of a thickness was obtained of about 5 µm. The press plate was then coated with charcoal ink on the enamel layer. This was with Wiped off a felt cloth, leaving the charcoal ink only in the matted surface of the protruding parts that matched the tracheal portions of the specimen. The charcoal ink consisted of alkyd resin, melamine resin, Dye and solvent.

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030064/0862

A decorative melamine laminate was then placed underneath Use of the press plate thus produced and a titanium paper on which a walnut core pattern was printed and which was impregnated with a melamine-formaldehyde resin. The laminate thus obtained showed in the depressions the tracheal parts that were stained with charcoal. The surface was extremely similar to one real walnut grain with a so-called open-pored coating.

Example 13

A press plate was obtained in the same way as in Example 12, with the exception that a pressure screen with 0.250 Mesh size was used to add elevation of about 100 µm thickness to the tracheal parts of an oak grain corresponded. The press plate was covered with charcoal ink on the enamel layer. This was then covered with a felt cloth rubbed off, the charcoal remaining only in the concave areas of the matted elevations, which the tracheal parts of the pattern. The charcoal ink was the same as Example 13.

Using a press plate and a titanium paper on which an oak tracheal pattern was printed and impregnated with melamine-formaldehyde resin was made a decorative melamine laminate. The laminate obtained in this way showed tracheal parts in the depressions Colored with charcoal and had a stereographic appearance

030064/0862

had. The surface was very similar to a real oak veneer with an antique finish.

The results of the invention are summarized below. The decorative laminates according to the invention have the following properties and advantages:

(a) The surface of the decorative laminates obtained has a soft gloss, very similar to that of earthenware and has a three-dimensional pattern on the surface that corresponds to the smooth surface of the enamel pattern, which was formed by firing an enamel layer on the press plate. The decorative laminate thus obtained looks extremely similar to natural stone or earthenware. A decorative laminate that one Enamel layer is similar and that has the luster and a three-dimensional pattern like an enamel layer will obtained when a single color is used as the dye.

(b) A decorative laminate can be obtained with peaks and valleys that are continuous sinusoidal have a curved surface. Since this decorative laminate has no sharp edges in the pattern, it is suitable as a decorative laminate that resembles enamel or earthenware. Furthermore, no dust collects on the surface of the laminate and can easily be removed from it in the event that it has accumulated there.

(c) A decorative laminate can be obtained with shiny protruding parts and matte recessed parts Share. This kind of a decorative laminated sheet

- 48 030064/0862

could not previously be obtained with a metal press plate formed by conventional etching processes or the like had been made. Such a decorative laminate is suitable for patterns with a brick or enamel design.

(d) Mam can have a decorative laminate with matted and colored depressions. This decorative Laminate is suitable for wood grain patterns with tracheal parts or for brick patterns.

The inventive manufacturing method for decorative Laminate has the following advantages;

(a) There is no need for a release sheet in making a decorative laminate because of its mold release properties the enamel layer on the surface of the press plate are very good compared to the resin.

(b) The press plate with a layer of enamel can be made very easily without complicated processes, such as Athens or sanding are required and this makes the process economical.

(c) When making a decorative melamine

2 laminates, pressures of 50 to 120 kg / cm and temperatures of up to 140 to 160 ° C. are generally required. Since the embossed plate according to the present invention was ^{fired at a temperature of 500 to 1000 °} C., it can easily withstand the aforementioned pressures and temperature. The life of this embossed plate is therefore practically infinite.

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030064/0862

(d) If an enamel layer is formed on both outer surfaces of the press plate, warping of the Enamel layer in the firing process for the formation of the enamel layer and in the pressing process for the decorative laminate should be avoided. Is a three-dimensional pattern on the enamel layer on both surfaces formed of the press plate, you can form a decorative laminate with both surfaces and thereby the manufacturing efficiency is improved.

(e) Because an enamel layer has better thermal conductivity has than the usual resin press plate, the manufacturing efficiency is improved.

(f) Because the three-dimensional pattern of the enamel layer has smooth curves, dust does not tend to be to collect there and can easily be removed by wiping in the event of an accumulation.

Q30064 / 0862

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Claims (1)

PAT K N TAN WALT E ^ DR. ING. E. HOFFMANN (1930-1976). DI PL.-IN GW EITLE · D R. R ER. NAT. K. HOF FMAN N DI PL.-IN GW LE HN DIPL.-ING. K. FDCHSLE ■ DR. RER. NAT. B. HANSEN ARABELLASTRASSE 4 (STERNHAUS) D-8000 MO N C H EN 81 TE LE FO N (089) 911087. TE LEX 05-29619 (PATH E) 33 687 o / wa TOPPAN PRINTING CO., LTD., TOKYO / JAPAN Decorative laminate and process for its manufacture PATENT CLAIMS Decorative laminate made from a thermosetting resin with a three-dimensional pattern on the surface consists of raised parts and recessed parts with smooth curves. 2. Decorative laminate according to claim 1, characterized ^^ indicates that the raised parts and the recessed parts (peaks and valleys) of the surface consist of continuous curves. 3. Decorative laminate according to claim 1, characterized _ 2 - 030064/0862 characterized in that it is made by means of a press plate which has an enamel layer on the surface has been made. 4. Decorative laminate according to claim 2, characterized characterized in that the depressions and elevations form horizontally symmetrical curves. 5. Decorative laminate according to claim 1, characterized marked having more than one indentation with different depths at the Surface are formed. 6. Decorative laminate according to claim 1 with a three-dimensional Pattern on the surface, characterized in that the ridges are smooth and that the bottoms of the wells are matted. 7. Decorative laminate according to claim 6, characterized in that the shoulder parts the bumps form smooth curves. 8. Decorative laminate according to claim 7, characterized indicated that the pattern is a brick or enamel design. 9. Decorative laminate according to claim 6, characterized characterized in that a dye adheres to the bottoms of the wells. 030064/0862 10. Decorative laminate according to claim 9, characterized characterized in that the pattern has wood grain. 11. Decorative laminate according to claim 9, characterized in that the depressions are all colored with a single dye. 12. Decorative laminate according to claim 9, characterized in that the depressions are colored with at least two dyes. 13. A method for producing a decorative laminate, in which decorative laminate elements using a press plate are hot-pressed, characterized in that the press plate is a Has a layer of enamel that adheres to the surface of the metal substrate used. 14. The method according to claim 13, characterized in that a smooth, three-dimensional Pattern is formed on the surface of the enamel layer. 15. The method according to claim 13, characterized in that the enamel layer is formed, by adding water and a grinding aid to a glass fr itte gives, kneaded the mixture, applied the mixture to a metal substrate and the coating layer burns. 03006A / 0862 -A- 16. The method according to claim 13, characterized in that a press plate is used, which was made by making raised parts by printing a pattern with a fritting ink containing it Glass and enamel, and subsequent firing. | 17th Method according to claim 16, characterized in that g e k e η η - • records that raised spots with at least two different heights can be formed. 18. The method according to claim 16, characterized in that a base coating and over it an enamel coating can be formed on a metal substrate and that the raised parts on the upper enamel layer are formed. 19. The method according to claims 16 or 17, characterized in that the raised parts Matting means that you can add a matting agent to the fritting ink to make the raised parts interferes. 20. The method according to claim 19, characterized in that the dye is only applied to the matted Place the raised parts of the press plate during the hot-pressing of a decorative laminate element is held so that the recessed parts of the decorative laminate are then matted and colored. 21. The method according to claim 20, characterized in that the dye is a color-forming 03006A / 0862 Component and as a binder a resin, the same Is resin that has been used for the decorative laminate or is a resin that is compatible with the resin and wherein the binder is cured at a temperature below the resin. 030064/0862