Method of producing dressed film having structure or pores corresponding to printed images

© Beginning of patent period: 1978 10 15

Longest possible duration:

© Issued on: 1979 05 10 © inventor: ^fc © dependence:

ΛΛΟΩΟβ LV © References that have been considered to distinguish from the state of the art:

DE-AS1261B67

No. 350077

The invention relates to a method for producing a so-called finished effect film having spatial pores or structures corresponding to the printed image,

Finished effect films are printed with a decor, in particular wood decor, and impregnated with resin and coated carrier webs, for example made of paper, in which the resins are cured without pressure. These active-effect films are then applied to wood-based panel surfaces under the action of a low compression pressure of approximately 50 N / cm² like wood veneers glued on. The sizing may also be done by the resin or additional gluing films at higher pressure on the ribs of the final film.

So far, it has been customary, for example, in a finished effect film with wood decor, to press the pores into the not or virtually no longer flowing resin by means of a stamping calender. The disadvantage of this method is the mechanical stress of the web and in particular that surface structure and printed image do not generally match, because it is not possible for economic reasons to have available for each Druefcbild an associated calender roll and make the calendering according to the printing. It is also disadvantageous that a special work gear is required for calendering.

In recent years, various attempts have been made to arrive at structured films which do not have these disadvantages.

Thus, DE-PS No. 1942780 already discloses a process in which the paper is seen at the points where it is to have pores with a polymerization inhibitor for the coating resin. This can be done by a printing process. The hardening of the curing of the polymerization resin is prevented or delayed at these points, the curing of the resin, so that either the still liquid, uncured polymerization resin can flow away laterally or into the ground and from it to the points where the inhibitor was, a depletion of the Surface on cured resin results, creating an artificial pore is formed. Bringing now to the points of a wood decoration, which should have 25 pores, by a special printing process, the polymerization inhibitor, you get print-friendly pores. The disadvantage of this method is, inter alia, that it is initially limited to the use of a polyester resin, which must be cured on the paper web by organic monomeric compounds such as styrene, polymerizing. These monomers are partially volatile under curing conditions, and special precautions are required because of the flammability of these volatile components, with the monomers also being physiologically unobjectionable. In addition, the method is cumbersome and difficult to implement in practice, as is apparent from the description in the journal Japan Plastics Industrial Annual, 1975, page 64. Further description of the method is found in Published Japanese Patent Application 28262/74. It is particularly disadvantageous that the products 35 obtained using paper according to this method are not crack-resistant, so that with appropriate mechanical stress a slight separation of the surface from the substrate is possible.

From DE-AS 1277721 a chemical embossing method is known, in which on a foamable plastic layer, a foaming preventing or retarding agent is printed according to the pattern, so that different thickness surface areas arise.

Another method of making resin-impregnated wood surfaces is described in U.S. Patent No. 3,811,915. According to this method, the paper web is first provided with a coating on which, after drying, a printing ink causing the pore is printed, which contains 0.1 to 3% by weight of a liquid silicone. Then, this carrier web is coated with a conventional Harzbeschlchtung. This method takes advantage of the effect that the silicone-containing ink leads to wetting disturbances for the final coating, so that at the points where silicone-containing paint is present, the surface of resin is depleted and a physical build-up is produced ,

A particular disadvantage of this method is that the carrier sheet printed with the silicone-containing ink must be cured within a maximum of 20 hours, since the effect is no longer observed after this time.

The invention has for its object to produce a method for producing a printed image corresponding to the spatial pores or structures having finished effect film, in which these disadvantages are overcome and without additional process steps a requirements of all required finished effect film is produced.

According to the invention, this is achieved by printing the carrier tap at the locations which are to have spatial pores or structures in the finished effect film with substances which prevent or delay the penetration of the liquid phase of the aqueous resin preparation into the carrier web.

Underwater resin preparations are to be understood as meaning formulations in which the resin in Was3

No. 350077 is dispersed or dissolved. The polymerisate resins are used in the form of a dispersion, wherein the solids content of the dispersion should be about 30 to 60% by weight. The condensation resins are usually used in the form of their aqueous solutions and contain about 40 to

% By weight of solid resin.

Suitable substances for printing the carrier webs at the locations which are to have spatial pores or structures in the finished effect film are printing inks, especially those based on polymerization resins, condensation resins, addition resins and alkali metalates, the latter in particular in the form of waterglass solutions.

As polymerization resins, for example, polyacrylates, polymethorates, chloroprene rubbers, optionally partially saponified polyvinyl acetates and polyvinyl alcohols can be used.

Particularly advantageous curing resins such as crosslinkable acrylic resins or alkyd resins have proven. A vemetzhares silicone resin, such as a by atmospheric moisture at room temperature or by UV radiation curing Slllconharz, Is suitable.

The curable polymerization resin can be formed in situ by using peroxide-crosslinking acrylate monomers, polyole diacrylate, pentaerythritol di-or tri-methacrylate.

Also suitable are the condensation resins, such as the amino resins, which can be cured by the action of heat, addition resins, such as polyesters or polyacrylates, which contain reactive Settengruppen and can be crosslinked, for example, with polyisocyanate or Polyglycidylveiblndungen. Among the inorganic compounds, the alkali silicates, especially the form of water glass, have proven useful, which can be condensed into insoluble products by the action of heat, especially in the presence of acid.

Further suitable are protein-based binders, such as casein, or zein, starch-based, dextrin, methylcellulose, salts and esters of natural resin acids from the class of diterpene compounds, for example rosin esters, which may be phenol-resin modified, or metal resi nates, eg Zn or Ca resinate ,

These suits are part of the binder of printing inks or are used directly as binders. They cover the carrier web or penetrate it, whereby they can additionally be fixed by hardening and reduce the suction effect of the carrier web.

The viscosity of the printing inks is adjusted via the Festköipergehalt so that on the one hand not too high course occurs during printing, the boundary lines of the printed surfaces versohwlm30 men, on the other hand sufficient ink is applied to create a flawless print image.

Printing on the carrier web with the aforementioned substances causes the carrier cock to swell more when the aqueous resin admixtures are applied at the points adjacent to the pore pressure, so that a thickness change of the carrier web occurs. This change in the thickness of the carrier web, possibly in conjunction with a different destabilization of the aqueous resin zipper, causes the local formation of pores or structures corresponding to the printing sheet.

It has been found that the inventive method is best carried out when the

Penetration rate of the aqueous resin preparations at the printed locations is reduced to half to about the tenth part of the value that has the carrier web at the non-printed locations. The quotient of the penetration rate at the printed to the non-printed locations is thus 0.5 to 0.1.

The rate of penetration can be determined in a simple catfish by applying a drop of the aqueous resin formulation to the carrier web and measuring the time in seconds which elapses until at the rear the penetration of water through the carrier web can be observed.

In contrast to the process of US Pat. No. 3,811,915 cited in the prior art, in which liquid silicones are used, in the process according to the invention the effect is not primarily based on the water-repellent property of the Sillcon compound, but on the fact that it hampers penetration the liquid phase of the dispersion into the paper, eg by solidification (ter paper fibers or by closing the paper pores, eg a hardened silicone resin makes destabilization and dehydration difficult. As a result, the swelling of the paper is prevented at this point and, in addition, the dispersion is sucked into the better absorbent areas of the areas surrounding the desired pores. Another difference is that in the method according to the invention, the resin or Binder is applied directly to the Papieibahn to cause the solidification of the cellulose fibers, while in the method of US-PSNr. 3,811,915 the silicone compounds are applied as part of the printing ink on a resin base layer and there einwlрken on the paper.

If the ink contains a pigment, it is important that the content of the pigment in the ink is not above the critical pigment volume concentration, since in this case no closed barrier layer preventing penetration of the liquid phase of the dispersion is obtained.

A particularly preferred embodiment of the method according to the invention is that the aqueous resin preparation is first applied to the printed upper side of the carrier web and ge4

No. 350077, if appropriate, after a drying of the interleaf, impregnates the backing web on the back and, if appropriate, coats it.

By this procedure, the carrier web is given the opportunity to swell before the backside impregnation and before the optionally following coating and the aqueous Züberei5 tion at the sites that are to have pores later, depleted. Both effects together then lead to the formation of the desired surface structure in the finished process product.

Particularly preferred is a process procedure which is characterized (if the printed upper side of the carrier web is first coated with the aqueous dispersion of a polymerization resin and, if appropriate, after intermediate drying, the carrier web is impregnated with the aqueous solution of a condensation resin and impregnated with this solution or after intermediate drying, coated with the dispersion of a polymerization resin. The Rückseltenbeschlchtung the finished effect films are self-adhesive.

The polymerization resins which can be used in the process according to the invention are the customary prior art polymerization resins. The resins may be thermoplastic, wherein the softening temperatures of the thermoplastic resins must be so high that the pore or surface structure is retained in the subsequent gluing of the finished effect films. Examples of such resins are acrylic resins, vinyl chloride homo- or copolymers, polyester resins, alkyd resins, vinyl acetate and vinyl alcohol copolymers.

It is also possible to use the known curable polymerization resins, examples of such resins being described in DE-PS No. 1961452 and DE-PS No. 2212928.

As condensation resins, which are intended to substantially solidify the Fertigeffekfcfilms inside and its adhesion to the substrate, the amino resins also known from the prior art, in particular urea and / or melamine-formaldehyde condensation resins can be used. As the adhesion-promoting resins, dispersions of vinyl acetate homo-25 or copolymers can also be used.

This procedure is in contrast to the usual in practice Beharzung of carrier webs. Here, the Trägeibahn is first durchträrikt and then coated. However, the preferred method claimed here is precisely characterized in that first the surface coating is carried out with the dispersion of an optionally curable polymerization resin. The dispersion penetrates the carrier web at different speeds, and the destabilization of the dispersion at the unprinted areas will be faster. Destabilization takes place more slowly on the printed areas, so that the dispersion can be sucked out of the pressure area. Subsequently, the support web is impregnated with condensation resins, for example customary amino resins, such as melamine and / or urea-formaldehyde resins, and optionally coated. It may also be carried out after impregnation Be35 coating with Polymerisattonsharzen if it is gewünsoht that the finished effect film has self-adhesive properties.

The version of the method according to the invention is thus in particular that the pore-generating substance during printing in the form of binder of Druckfaibe or at least a portion of the binder of the Druckfaibe, so when printing without additional operation, is applied and the 40 pretreated Trägeibahnen in a conventional manner can be coated and soaked in the usual resins which can be used for this purpose. There are no Porduktionsumstellungen necessary if on the same system successively finished films with and without surface structure to be produced. In principle, the selection of the substances influencing the swelling paths of the carrier webs which are used as binders of the printing fibers or as additives of these binders is sufficient. The Verfahrens45 products are mechanically durable and can be stored indefinitely.

The process according to the invention will be explained in more detail with reference to the following examples:

EXAMPLE 1 15 parts by weight of a pigment mixture are poured out in a ball mill for a period of 15 minutes

5.60 parts by weight of iron oxide yellow

0.07 parts by weight of flame soot

1.05 parts by weight of titanium dioxide 0.98 parts by weight of iron oxide red 3.85 parts by weight of chrome yellow in a mixture of 82.5 parts by weight of a binder based on a methoxy end-terminated

Methyl phenyl siloxane Ha rzes and 0.25 parts by weight of n-butyl titanate dispersed.

On the top of a suitable filled decorative paper with a basis weight of 80 g / m² a wood reproduction is printed with a three-ply gravure printing machine, whereby in the first and second

No. 350077

Printing unit, the structure is printed with a printing ink, which leads in the later coating not to spatial pores, but to a two-dimensional, two-tone wood decor and third printing unit, a printing cylinder is used, which prints a pore structure corresponding to the printed image using the above-prepared ink, the in the later coating forms concave structures. The curing of the silicone binder necessary for the subsequent discrete formation of the pore structure is accelerated by the admission of water vapor and subsequent infrared irradiation.

For the formation of the concave pores, a decor paper is used by which the liquid phase of the coating dispersion is formed at the position of printing with the silicone ink after about 180 seconds and at the position with the ink through which a two-dimensional printed image is formed after coating. penetrated after about 20 s.

The printed decor paper is coated with an aqueous acrylate dispersion according to DE-PS No. 2212928 using a wire doctor and impregnated after an indwelling tent of about 15 s with intermediate drying with an IR radiator back with an aqueous urea resin solution and then to a Darrwert of 2.0 % dried. The application amount of acrylic resin is 45 g / m², The introduced amount of urea resin 52 g / m²,

The resulting film shows a three-dimensional representation of the pore print image. The depth of the pores measured with a roughness depth meter is 20 to 45 μ and after pressing on a chipboard with liquid urea resin at a temperature of 135 ° C and a pressure of about 50 N / em²for 60 s 18 to 40 μ. The film proves to be pressed as gap-proof.

Example 2: The procedure is as in Example except that instead of the aqueous acrylate dispersion the aqueous solution of a thiourea modified urea-formaldehyde condensation product with a DIN-Beoher Viskosltät (nozzle 4mm) of 30 s for the coating and aqueous solution of a melamine-formaldehyde condensation product is used for the back impregnation.

The application amount of coating resin is 42 g / m², the amount of impregnating resin introduced 48 g / m², the Darrwert 2.9%. The resulting film shows a three-dimensional representation of the pore print image. The depth of the pores measured with a Rauhtiefenmeßgerät is 20 to 30 μ and after compression on a chipboard with an aqueous urea resin solution at a temperature of 135 ° C and a pressure of about 40 N / cm² for 90 s 10 to 20 μ. The film proves to be after the compression as gap-resistant.

Example 3: In a heatable and coolable agitator, 20 parts by weight cornstarch adhesive; 16 parts by weight of water and 32 parts by weight of ethanol at 50 ° C until complete dissolution of the adhesive stirred, After cooling the solution 32 parts by weight of ethylene glycol and 6 parts by weight Elsenoxydrot stirred and then a mixture with 5 % sodium hydroxide solution adjusted to a pg value of 6.5. The viscosity of this solution is 33 s, measured in a DIN cup with a nozzle of 4 mm diameter.

The resulting ink is used in place of the siltcori-based ink as in Example 1; Otherwise, the procedure is as in this example.

The penetration time of the liquid phase of the coating dispersion used is 35 s at the location of the dispersion which has been printed with the abovementioned printing ink. The application rate of the 40 acrylate resin used for the coating is 55 g / m², the amount of urea resin used g / m²,

The resulting film shows a three-dimensional, concave reproduction of the pore print image. The depth of the pores measured with a Rauhtiefenmeßgerät is 20 to 42 μ and after the compression of the film on a chipboard at a temperature of 135 ° C and a pressure of about 50 N / cm² 17 to 38 μ.

The film proves to be a gap-proof after compression,

EXAMPLE 4 A printing ink is prepared which consists of 100 parts by weight of a 50% strength aqueous solution of a urea-formaldehyde resin with a DIN cup viscosity (4 mm nozzle diameter) of 20 s, 2 parts by weight ammonium chloroacetate and 5 parts by weight of a pigment preparation consisting of 4 parts by weight of a chromium yellow pigment and 1 part by weight of a hydrogenated Collophonlumesters.

The resulting ink is used in place of the silica-based ink as in Example 1, except that the printed paper is heated at 200 ° C for 60 seconds for complete condensation of the urea resin.

At the point of printing with the cured, pigmented urea resin, the decorative paper is penetrated by the liquid phase of the coating dispersion in 172 s and at the point with the printing ink, through which a two-dimensional printed image is coated after the coating, after 23 s.

The printed decorative paper thus obtained is coated with an aqueous dispersion based on a copolymerylate of vinylidene chloride and vinyl chloride using a wire doctor blade and after a residence time of about 15 s with intermediate drying with an IR radiator impregnated at the back with an aqueous urea resin solution and then to a Darrwert of 2 , 5% dried. The

No. 350077

- 6 application amount of VInylldenchlorid-VInylchlorid-Copolymerlsat is 52 g / m², the amount introduced

Urea resin 75 g / m²,

The resulting film shows a three-dimensional representation of the pore print image. The depth of the pores is 15 to 40 microns and after Veipressung on a particle board mltfliisslgemHammstoffbarz at one

Temperature of 135 ° C and a pressure of about 50 N / cm² for 60 s 12 to 35 μ. The film proves to be a gap after pressing.

Example 5: A printing ink is prepared by mixing

Wt. Zn Resinat 9 parts by weight Eisenoxydbiaun

60 Parts by weight of toluene

Parts by weight of ethyl glycol acetate and

Parts by weight Bentone in a ball mill for 15 min.

The printing ink used for the printing of the poreris is treated as in Example 1, the amount of coating resin applied is 49 g / m², the amount of impregnating resin introduced is 68 g / m², the Darrwert 3,6%.

The resulting film shows a three-dimensional representation of the pore print image. The depth of the pores is 30 to 48 microns and after pressing on a chipboard with an aqueous urea resin solution bet temperature of 140 ° C and a pressure of about 50 N / cm² for 70 s 25 to 42 μ. The film er20 shows after the compression as gap-fixed.

Example 6 In accordance with Example 1, the printing inks shown in the table below were used on a decorative paper having a basis weight of 80 g / m² Produced pore prints; the coating and impregnation takes place again with an aqueous acrylic resin dispersion or with an aqueous urea resin solution. The table shows what pigment content (iron oxide red) the ink binder has, how high the application rate of acrylic resin is, which takes time to penetrate the deco-paper, then the acrylic resin dispersion, when a side-folded paper sample floats on the dispersion and what pore depth is after the ink Film production and after Veipressung on a chipboard results. The amount of impregnating resin varies between 49 and 53 g / m², the unprinted paper shows a penetration time of 18 s compared to the acrylic resin dispersion.

No. 350077

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No. 350077