DE2828004A1 - ORNAMENTAL LAMINATES - Google Patents

Description

PFENNING MAAS

MEINIQ - LEMKE- Mockery

SCHLEISSHEtMERSTR. 299

βΟΟΟ MUNICH 40 QZ ö Z ö UU

Gases 26 866

Formica Corporation Cincinnatij Ohio / USA

Decorative laminates

809884/0736

PFENNINQ MAAS

MEINIQ - LEMKE - SPOTT _r

SCHLEISSHEIMERSTR. 299 ^ Z8 28013

βΟΟΟ MUNICH 40 *

Produced under high pressure decorative laminates of paper laminate are usually of a core of a row (3 to 7) ^m it phenol / formaldehyde resin impregnated kraft paper sheets, a high quality printed or simply colored sheet with a thermosetting resin such as a melamine / formaldehyde Resin impregnated, and if desired an alpha-cellulose topsheet impregnated with a thermosetting resin, usually a melamine / formaldehyde resin.

Laminates produced under high pressure are also known for decorative purposes which have a metallic appearance over all or part of their surface. In one embodiment, these laminates consist of (A) a core practically the same as that used for paper laminates, (B) a thick one on the core adhering metal layer, usually of copper or aluminum, of about 0.1 mm or greater thickness and usually (C) an abrasion-resistant layer of a clear coating applied to the metal surface of the laminate is applied after its solidification by heat and pressure to form a uniform structure.

These known metallic laminates have certain disadvantages:

Ca) The metal foil is only used to create the desired appearance, but because of the handling difficulties associated with thin foils the foils are thicker than necessary to produce the metallic effect, which is economically inexpedient.

(b) The edge of the foil is sharp and can, if the foil is exposed, what happens if the foil is off the core is lifted off, causing injuries to people who have to do with the laminate.

(c) Because of the relatively high tensile strength of the thick metal foil, it can be peeled from the core.

(d) Because of the thickness of the film, fine textures cannot easily be applied to the surface of the laminate.

(e) Applying the abrasion-resistant coating to the metal surface after production of the individual laminates is ineffective.

(f) The laminates bend easily.

It has now been found that produced under high pressure Decorative films with a metallic appearance, in which these disadvantages are practically overcome, in an economical manner using thin metal foils, if desired can be provided with a transparent, abrasion-resistant layer and which are held by a paper substrate and cling to it, can be produced.

The invention relates to a laminate which consists of the following layers arranged one above the other:

(1) a core layer of one or more with a thermosetting one Resin impregnated paper sheets and

(2) a surface layer of a paper backing attached to a thin metal foil

is glued, the paper carrier adjoining the core layer.

In a preferred embodiment of the invention Laminate is firmly adhering, abrasion-resistant, transparent to the metal foil on the side facing away from the paper carrier Resin layer applied.

The invention also relates to a method for production of the decorative laminates according to the invention with metallic

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Appearance, which is characterized by the fact that the individual Components of the laminate solidified into a uniform structure with the aid of heat and pressure.

The thermosetting resin used to provide the thermosetting Resin impregnated paper core sheets can be any suitable thermosetting resin, which is known for such uses. Examples are polyester resins, epoxy resins, melamine resins and Phenol / formaldehyde resins. Preference is given to using thermosetting phenol / formaldehyde resins and, in particular, those those for use in the manufacture of conventional Plastic decorative laminates are known.

The core layer suitably comprises such thermosetting phenol / formaldehyde resin impregnated paper sheets which are known to be suitable for use in the manufacture of conventional decorative laminates. These become common manufactured by impregnating a Kraft paper web of the desired basis weight with a varnish, which in one containing dissolved resin in a suitable solvent, the web dries to a desired volatile content and cutting the dried web into sheets of the desired size. The impregnation is preferably carried out in such a way that that a resin content of about 25 to about 35 wt. JS in the dried impregnated sheet is obtained.

If the core consists of a number of sheets of paper impregnated with thermosetting resin, these sheets can be the same or different. For example, the core layer or middle layer can consist of a sheet of paper or a There are stacks of multiple sheets of paper, each impregnated with a first thermosetting resin, as well as one Sheet or sheets, which are impregnated with a second thermosetting resin and then to the first or the arranged on the first leaves or as an outermost leaf above one

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or both of the major surfaces of the stack of sheets of paper, impregnated with the first thermosetting resin are arranged.

The paper these sheets are made of is suitably of the type and basis weight as they are for use in the manufacture of conventional High pressure plastic laminates can be used. Papers for use in manufacture are preferred of core and border sheets impregnated with thermosetting resin for the production of conventional letterpress art fabric laminates are known.

The paper backing, which makes up the surface layer to which the metal foil is adhered, must face delamination resistant as well as permeable to both the thermosetting resin or the thermosetting resins used for impregnation the core sheets are used, as well as the adhesive that bonds the paper to the metal foil it's his; it must also have a smooth surface texture, so that a pushing through of the paper fiber through the metal foil is reduced to a minimum. Appropriately, the paper should have a basis weight of about 30 to about 100 g / m2. Suitable papers are of the type commonly referred to as "glazed glassine papers" (glazed imitation parchment papers) with a basis weight in the range of about 30 to about 50 g / m2.

The adhesive used to bond the paper support to the metal foil can be any suitable one Adhesive that is unrelated to the hot press used to consolidate the laminate or the conditions under which the laminate produced is likely to be used is affected. Such adhesive

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agents are, for example, adhesives based on organic solvents, such as acrylonitrile / Butadiene / styrene resins, polyvinyl chloride and copolymers thereof, epoxy resins, phenol resins and rubber-modified thermosetting resins such as modified with nitrile rubber Phenolic resins; Water-based swelling agents such as polyvinyl acetate, starch and dextrins; as well as in the form of hot Melt adhesives such as ethylene vinyl acetate, polyethylene and polyurethanes.

The amount of adhesive used is expediently determined by preliminary tests, the paper carrier and the Foil to be bonded together can be used and the method selected for applying the resin as well as its composition must be taken into account.

The adhesive can be applied to the paper backing, the metal foil, or both by any suitable method will. It can be applied to the paper carrier and / or the film, for example by spray coating, with the aid of a Wire bar, applied by gravure printing, by anil printing, with the help of a doctor blade, by extrusion or roller coating will. Regardless of the coating method used it must be designed in such a way that there is a uniform bond strength between the metal foil and the paper carrier, which forms the surface layer, guaranteed. The paper backing and the film are attached after the adhesive has been applied one or the other or both and, if desired, after a heat treatment to accelerate the Curing of the resin and / or to remove any volatile solvent present or to reduce its content connected to one another by means of pressure and, if desired, heat, expediently by passing through a nip, the method used in detail is determined by the nature and composition of the adhesive used to join the paper backing and the film

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is used.

The metal foil used can be any ductile metal foil, aluminum or copper foils being preferred because they are commercially available in a wide variety of widths, finishes, and thicknesses. In particular Metal foils with a thickness of no more than 0.05 mm and preferably about 0.01 mm are preferred. from the commercially available aluminum foils are particularly suitable for the process according to the invention with a thickness of 0.01 mm and a glossy and a matt surface. According to one embodiment of the invention In the process, the metal foil is applied to the sheet facing away from the paper carrier sheet before the laminate stack is produced The surface is provided with a layer of a firmly adhering, abrasion-resistant, translucent polymer. This layer can be applied to the metal foil before or after its plague sticking or during plague sticking on the paper backing, however, it is preferably applied immediately after the gluing process.

If an abrasion-resistant, clear polymer layer is used it can contain any polymer that adheres firmly to the metal foil and after the solidification of the laminate stack A firmly adhering, abrasion-resistant, transparent polymer layer to form a uniform laminate through heat and pressure results.

The abrasion-resistant polymer layer can either be a preformed polymer film which is glued onto the metal foil will, or it can be a plastic coating, which is applied to the metal foil in liquid form and converted into the solid state on this.

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A suitable preformed polymer film is, for example a polyester film. Polyester films are commercially available in a large number of colors and thicknesses, and clear adhesives that are used to bond the film with the metal surface are also known.

Liquid polymer coating compositions for producing transparent coatings on metals are also known. For example, coatings, polyurethanes, nitrocellulose resins, alkyd resins contain _s alkylated melamine resins or epoxy resins are used for producing the abrasion-resistant layer on the metal foil because they yield transparent coatings when cured that protect the metal foil against scratches and abrasion damage. They can be applied by any suitable method, such as, for example, such methods as have been described above for the preparation of the adhesive layer.

A liquid resin compound is preferably applied to the film, to create the abrasion-resistant layer. It does not matter whether a preformed film or a liquid coating is used is, the application to the metal foil takes place before the foil is arranged in the laminate stack and this is consolidated into a uniform laminate by heat and pressure.

The thickness of the clear, abrasion-resistant layer must be sufficient to provide the desired level of abrasion resistance in the laminate produced. As a result of the different Abrasion properties of the resins that can be used to make the layer will be the appropriate thickness of the Layer expediently determined by preliminary tests, the selected polymer film or coating being applied to the metal film with different thicknesses and the

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Abrasion resistance of the laminate produced is determined by suitable tests. For economic reasons it is it is preferred to provide the film and thus also the finished laminate with the thinnest abrasion-resistant layer that is acceptable Imparts abrasion and scuff resistance.

The laminates according to the invention can, if necessary, be provided with a contoured and / or textured surface will. For example, the laminate can - if desired with the aid of separating films - with the printing plate, which lies against the surface layer and has contours that are required in the laminate produced Contours are complementary to be pressed. Contoured press plates are known and can be made from engraved or etched metal, sculpted, calcined clay or the like, or from fiber-reinforced laminates of thermosetting Plastics ^ exist, if desired with a surface made of a metal sheet or a metal foil are provided.

Alternatively or additionally, the appearance of the laminate can be changed by changing the surface texture of the used Metal foil varies. For example, as mentioned above, metal foils are available in which one surface has more gloss than the other; if the surface layer of the laminate stack contains a film, its glossier side is outwardly, the laminate made therefrom will have a different appearance than a laminate made using the same press plates with surface layers in which the same film, but with the less shiny side out, is used.

In addition, the metal foil can, before the eventual application of an abrasion-resistant, transparent layer, the necessary-

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if it can be colored, anodically or otherwise oxidized and / or with a desired lettering or graphic representation or a pattern can be printed.

Further, the transparent, abrasion-resistant layer may be colored in such a way that the appearance of the laminate, both the colored _s wear-resistant resin layer is determined by the metal foil as well. For example, an aluminum foil can be coated with a resin composition containing an orange-brown colorant to produce a laminate having an appearance like a metallic copper foil.

Alternatively or additionally, by suitable modification of the composition of the transparent, abrasion-resistant resin layer a laminate can be produced having a desired level of surface gloss. For example, the Abrasion-resistant layer can be formulated so that the laminate produced has a strong, matt or semi-matt surface gloss having.

By means of these means, used individually or in combination, laminates can be produced from any individual metal foils which have a very different decorative metallic appearance.

The stacked laminate layers become useful solidified by hot pressing into a unitary laminate, using such conditions and such methods, devices and equipment conventionally used in the manufacture of high pressure laminates made of thermosetting plastics can be used.

For example, the laminate stack can reach pressures from 42 to 14O at (600 up to 2000 psi) and at temperatures from 120 to 160 ° C during

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15 to 45 minutes. Appropriately is solidification at a pressure of about 10 5 at (1500 psi) and a temperature of 125 to 155 C for 15 to 35 minutes, and the laminate produced is in the Press partially cooled before removal.

The following examples illustrate the invention without it to restrict.

example 1

A decorative laminate with a shiny silver metallic appearance is made as follows:

A sheet of 0.02 mm thick, soft-rolled aluminum foil with a glossy and a matte surface was made on the matte side using the wire bar technique with a layer of a rubber-modified one Phenolic resin adhesive provided.

The adhesive used is a commercially available organic solvent based adhesive and was made in a Amount applied that a coating weight of 24g / qm was achieved.

A sheet of glazed glassine paper with a basis weight of 100 g / m² was then placed on the surface coated with the adhesive and the whole thing passed between a gap of unheated rollers in order to ensure that the paper adhered to the coated film. The composite was then heated to 65 ° C to remove volatile solvent.

Thereafter, the composite was on the exposed metal surface the slide with a layer of a clear, practical

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colorless coating compound made of alkyd resin. The coating compound was commercially available and was mixed with a catalyst according to the manufacturer's instructions before use mixed. It was applied to the film using the wire bar technique and a layer with a weight was obtained from 4.4g / sqm. The coated composite was then Heated to 115 ° C for two hours to cure the resin coating and give the surface layer a glossy appearance to achieve the composite body.

The surface composite layer produced in this way, which consists of a consisted of a sheet of paper glued to a thin metal foil, with the metal foil on the sheet facing away from the sheet of paper Surface had a firmly adhering layer of abrasion-resistant, transparent alkyd resin, was then coated with the Metal foil surface facing up as the top layer on a stack of five with thermosetting phenol / formaldehyde resin impregnated sheets of kraft paper, each of the five sheets being cut from a sheet that was approximately 305? Resin based on the weight of the impregnated sheet contained.

The whole was then sandwiched between polypropylene release sheets and solidified into a unitary structure between the plates of a hydraulic press using polished pressure plates by heating under pressure Maintained pressure and a temperature of 135 ° C. The laminate was cooled in the press at about 8O ⁰ C, and then removed, after which the release films were removed and there was obtained a decorative laminate, which had a strong silvery, metallic appearance and satisfactory results zeitigte when subjecting it attempts

282800A

traditionally used to determine the durability of decorative laminates.

Example 2

An aluminum foil about 0.01 mm thick was coated with a commercially available polyurethane adhesive based on organic solvents with the aid of a roller, the adhesive being catalyzed according to the manufacturer's invasions and dissolved in methyl ethyl ketone. The coating compound made up 25% by weight , based on pesticides, and was applied in such an amount that a coating with a weight of 12 g / m 2 was obtained on the film after drying at 85 ° C.

The film coated with the adhesive was glued to a sheet of glassine paper with a basis weight of about 40 g / m 2 by hot pressing and the composite body thus obtained was then printed with a flower pattern by the anil printing process using black printing ink. The printed composite body was then coated with a commercially available polyurethane resin composition which, according to the manufacturer's instructions, was mixed with a catalyst and dissolved in ethyl acetate to form a 35% solution, a roller coating method being used, after which a coating weight of after drying at 85 ^° C. 4.2 g / m2 was obtained.

The glossy surface layer produced in this way was used to manufacture a decorative laminate, as in FIG Example 1 described. The laminate obtained had a black floral pattern on a shiny silver metallic Background and was similar to that of Example 1 in all other respects.

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282800A

Example 3

According to the procedure of Example 2, a composite body made of paper and aluminum foil is produced and then coated with a colored acrylic resin compound.

The acrylic resin composition was in methyl ethyl ketone together with an orange-brown dye to form a 45 $ solution, based on Solids, dissolved. It was applied to the film by the wire bar method and a coating weight was obtained after drying at 120 C of about 5 g / qm-.

The surface layer produced in this way was used to produce a laminate as described in Example 1, and the laminate produced had a shiny, metallic appearance similar to that of copper. All other properties were the same as those of the laminate according to Example 1.

Example 4

A sheet of soft aluminum foil 0.1 mm thick was placed on an equally dimensioned sheet of machine-glazed, bleached kraft paper of 44 g / m² basis weight using an extrusion coating method as well of low density polyethylene and a coating weight of 10 to 12 g / m2.

It was then applied to the exposed surface of the metal foil a nitro cellulose lacquer based on organic solvents is applied and the coated film is then applied heated to remove the solvent. After the solvent has been removed, the lacquer provides a firmly adhering, transparent, abrasion-resistant resin layer on the surface of the film with a weight of 1 to 2 g / sqm.

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The surface composite layer produced in this way, which consists of a The carrier sheet consisted of Kraft paper and a thin metal foil bonded to it, the metal foil on the The surface that was not bonded to the paper had a firmly adhering, transparent, abrasion-resistant nitrocellulose resin layer, was with the nitrocellulose coated metal foil facing up as the top layer on a stack of five with thermosetting phenol / formaldehyde resin impregnated Kraft paper sheets, each of the five sheets of one Web was cut that was about $ 30 based on that resin Weight of the impregnated sheet.

The whole thing was enclosed between tear-off sheets made of polypropylene and placed between a pair of metal printing plates, the surface of the printing plate being that of the surface layer of the stack was adjacent, was provided with a relief-like pattern. The whole thing was subsequently between the printing plates, as described in Example 1, pressed, and after solidification and cooling, printing plates were made and peeled off release films, whereupon a decorative laminate was obtained which had a relief-like metallic surface which can be used as a support material for a vertical surface and which had all the properties required for recognized surface tests for decorative laminates to pass.

Example 5

The procedure according to Example 1 was repeated with the difference, that the colorless alkyd resin coating composition was omitted. It also became an attractive decorative laminate manufactured.

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Claims (20)

282SQQ4 - vs - P at ent claims 1. Laminate arrangement of the following arranged one above the other
Ingredients: (a) a printing plate, (b) a core layer of one or more sheets of paper impregnated with thermosetting resin and (c) a surface layer made of a paper carrier which is attached to a metal foil with a thickness of not more than 0.05 mm is glued, wherein the carrier sheet of paper is adjacent to the core layer. 2. Arrangement according to claim 1, characterized in that the Metal foil is anodically or otherwise oxidized or on the side facing away from the paper carrier sheet a printed Letteringj a printed pattern or a printed one Drawing bears. 3 · Arrangement according to claim 1, characterized in that the Metal foil on the side facing away from the paper carrier sheet a firmly adhering, abrasion-resistant, transparent plastic layer wears. 4. Arrangement according to claim 3j, characterized in that the firmly adhering j transparent, abrasion-resistant plastic layer
is a polyester film glued to the metal foil. 5. Arrangement according to claim 3> characterized in that the firmly adhering, practically transparent, abrasion-resistant plastic layer is applied as a coating to the metal foil, the coating being a polyurethane resin, a nitrocellulose resin, an alkyd resin, an alkylated melamine resin
or contains an epoxy resin. 809884/0736 -vs- 6. Arrangement according to claim J> _3, characterized in that the firmly adhering, abrasion-resistant, transparent plastic layer is colored. 7. Arrangement according to claim 1, characterized in that the paper carrier sheet has a basis weight of 30 to 100 g / m². 8. Arrangement according to claim 1, characterized in that the paper carrier sheet and the thin metal foil to each other with an adhesive based on an organic solvent are bound. 9 · Arrangement according to claim 8, characterized in that the Glue is polyethylene. 10. The arrangement according to claim 1, characterized in that the Printing plate has a contoured or textured surface on the side adjacent to the surface layer. 11. Decorative laminate, consisting of the following arranged one above the other Ingredients: (1) a core layer of one or more sheets of paper impregnated with thermosetting resin, and (2) a surface layer of a paper carrier sheet which is now on a metal foil with a thickness of not more than 0.05 is glued on, the paper carrier sheet being adjacent to the core layer. 12. Laminate according to claim 11, characterized in that the metal foil is anodically or otherwise oxidized or on on the side facing away from the paper carrier sheet, a printed lettering, a printed pattern or a printed one Drawing bears. 80988A / 0736 13. Laminate according to claim 11, characterized in that the metal foil is on the side facing away from the paper carrier sheet carries a firmly adhering, abrasion-resistant, transparent plastic layer. 14. Laminate according to claim 13, characterized in that the firmly adhering, transparent, abrasion-resistant plastic layer is a polyester film glued to the metal foil .. 15. Laminate according to claim 13, characterized in that the firmly adhering, practically transparent, abrasion-resistant plastic layer is applied as a coating to the metal foil, the coating being a polyurethane resin, a nitrocellulose resin, an alkyd resin, an alkylated melamine resin
or contains an epoxy resin. 16. Laminate according to claim 13, characterized in that the firmly adhering, abrasion-resistant, transparent plastic layer is colored. 17. Laminate according to claim 11, characterized in that the Paper carrier sheet has a basic weight of 30 to 100 g / m². 18. Laminate according to claim 11, characterized in that the Paper carrier sheet and the thin metal foil together with an adhesive based on an organic solvent are bound. 19. Laminate according to claim .18, characterized in that the Glue is polyethylene. 20. Laminate according to claim 11, characterized in that the Metal foil is contoured or textured. 809884/0736