Patent Grant
9507320
This application is the National Stage of PCT/DE2008/000273 filed on Feb. 14, 2008, which claims priority under 35 U.S.C. §119 of German Application No. 10 2007 008 073.7 filed on Feb. 15, 2007 and German Application No. 10 2007 019 866.5 filed on Apr. 25, 2007. The international application under PCT article 21(2) was not published in English.
The invention concerns a method for transferring surface textures, such as interference layers, holograms and other highly refractive optical microstructures onto substrates.
Possible substrates are in particular glass, ceramic and metal surfaces.
The use of transfer sheets for transferring patterns onto various backgrounds, whereby the pattern can also be burned in over or under a glaze, is for example known from U.S. Pat. No. 6,766,734, U.S. Pat. No. 6,694,885 and U.S. Pat. No. 6,854,386.
The application of hologram decals on paper or plastic backgrounds is also quite common, as can be seen for example in U.S. Pat. No. 5,702,805 and U.S. Pat. No. 5,318,816.
From KR 2002/024286 A, a hologram decal and its manufacturing processes are known which are, however, not suitable for glass or ceramic surfaces. JP 2004/358925 A describes a hologram decal, but it is not burnable nor is the transfer sheet carrying a hologram and described in JP 2003/280498 A suitable for glass or ceramic surfaces, which is also the case with the object of U.S. Pat. No. 5,702,805 A.
From WO 98/22648 A2, a composite material is known which is characterized by a substrate and a nanocomposite being in functional contact with it, which can be obtained by modifying the surface of
a) colloidal inorganic particles with
b) one or more silanes of the general formula
Rx—Si-A4-x
where the radicals A are identical or different and represent hydroxyl groups or groups that can be removed hydrolytically, except methoxy, where the radicals R are identical or different and represent groups that cannot be removed hydrolytically and x has the value 0, 1, 2 or 3, with x≧1 in at least 50 mol % of the silanes;
under the conditions of the sol-gel process with an under-stoichiometric amount of water, based on the hydrolysable groups which are present, with formation of a nanocomposite sol, and further hydrolysis and condensation of the nanocomposite sol, if desired, before being brought into contact with the substrate and following curing, said substrate not being a glass or mineral fiber or vegetable material.
The purpose of the invention is therefore to come up with a method for transferring interference layers, holograms and other highly refractive optical microstructures onto a substrate, which can also be used in the high temperature range.
This purpose of the invention is achieved by a method for transferring surface textures, such as interference layers, holograms and other highly refractive optical microstructures, onto a substrate, which includes the following process steps:
a) A flexible covercoat is applied to a carrier sheet as a release coating,
b) A stamping sol is applied to this covercoat and provided with surface texture,
c) Making a stack, consisting of a bonding agent coating and the surface texture, whereby the bonding agent is applied directly to the surface texture and this stack is then transferred to the substrate,
d) Removal of the carrier sheet,
e) Thermal treatment of the workpiece.
In this way a flexible covercoat is applied to the carrier sheet as a release coating.
The stamping sol, which should have a sufficiently different refractive index from the adhesive, is applied to this covercoat and provided with a surface texture, e.g. a hologram or another optical microstructure.
Subsequently, a stack is formed of a bonding agent coating and the surface texture.
Then the carrier sheet is removed.
The purpose of the invention is also achieved by a method for transferring surface textures, such as interference layers, holograms and other highly refractive optical microstructures, onto a substrate, which involves the following process steps:
a) A self-supporting printable sheet is given a surface texture,
b) Making a stack consisting of a bonding agent coating and the surface texture, whereby the bonding agent is applied directly to the surface texture and this stack is then transferred to the substrate,
c) Thermal treatment of the workpiece.
In this variant of the invention a self-supporting flexible, printable sheet is used directly with the flexible covercoat instead of the carrier sheet. In this case the latter is given a surface texture and covered with a highly refractive coating. In this process the stamping procedure can, however, also take place directly on it after the application of the highly refractive coating.
Finally the workpiece is treated thermally, so that in the end only the structured highly refractive coating adheres to the substrate surface by means of the bonding agent coating.
With such a transfer sheet one can transfer an interference layer, a hologram or another optical microstructure onto a substrate, whereby the transferred coatings are preserved in the transfer process so that an additional drying and oven baking process in the high temperature range are possible.
The advantages of the invention essentially are that a transfer sheet stable under high temperatures is created which can be applied to hot materials or materials that are heated later, and that is durable. This means also that the transferred interference layers, holograms and other optical microstructures cannot be removed or damaged by later thermal treatment. Besides, the transfer sheet can be produced on a sheet coating system with an attached stamping station in the form of film roles and is therefore suitable for mass production.
It is thus, for example, possible to transfer a hologram on substrates that are still hot or also a hologram to a substrate that is heated during use in the high temperature range, e.g. an engine mount or a vehicle catalyst. This opens up new possibilities to provide even such parts with safety characteristics, for example a verifiable hologram, in order to make sure that they are not fakes.
The optically effective principle of the invention is based on a sufficiently large difference in the refractive index between the optical microstructure and the bonding agent coating. This aspect makes a special variability possible since the hologram and/or the optical coating in combination with the bonding agent can be used for controlling the optical effects. Thus, for example, it becomes possible to manufacture coating stacks that are stable in high temperatures which work collectively like a reflection or antireflection coating, and/or like a hologram. In this process it is possible, for example, to provide only the surface of the relief hologram (or the optical coating) with a coating that has an adequate refractive index or the hologram (and/or the optical coating) can be made entirely of a material with the desired refractive index. In this connection it is of interest that the refractive index of the bonding agent can be adjusted by using highly refractive nanoparticles instead of SiO2 nanoparticles.
It is also within the perimeter of the invention that relief holograms are textured via simple or thixotropic stamping.
A thixotropically structured material is, for example known from EP 1 248 685 B1. Also disclosed is a stamping sol which is an organically modified inorganic polycondensate or precursors thereof.
An embodiment of the invention consists in that in step c) a bonding agent coating is applied to the substrate and dried, and that the surface texture is afterwards transferred onto the bonding agent coating.
It is within the perimeter of the invention that the bonding agent consists of a nanocomposite which can be obtained by modifying the surface of
In the method according to the invention it is also useful if the substrate is a glass surface, ceramic surface or metal surface.
It is also advantageous if the carrier sheet is a polyethylene sheet or a polyimide sheet.
It is advantageous if the covercoat is a sheet on a polyvinyl alcohol basis.
It is also within the perimeter of the invention that the self-supporting printable sheet is a sheet on a polyvinyl alcohol basis.
The invention also includes that in step e) the thermal treatment takes place at temperatures up to 800° C., preferably at temperatures up to 450° C.
Finally, the invention also provides that in the second alternative concerning step c) transfer to a hot substrate takes place in step e), whereby the substrate temperature is about 80° C. to 800° C., preferably 100° C. to 600° C., with particular preference for the range from 150° C. to 450° C.
As follows, the invention is described using illustrations and an example of an embodiment.
The illustrations show the following:
As
On this carrier sheet 1 a covercoat 2 (or release coating) containing in particular polyvinyl alcohol (PVA) and possibly additives, in particular fluoridated additives (e.g. zonyl) or additives with similar effects, is applied with a coating thickness of approx. 40 μm as shown in step 10 in
A hologram structure is imprinted on the highly refractive coating 3 as is also shown in step 12 in
Via the inorganic bonding agent 4, as is used for the production of a composite material in WO 98/22648 A2, the transfer sheet is applied onto a substrate 5 which preferably has a glass, ceramic or metal surface, with the highly refractive coating turned to the substrate 5 as shown in step 14 in
In this process the transferred structures with a periodicity of approx. 4 μm are preserved during the transfer process on an area of 1 cm2, allowing for an additional drying and oven-baking process at temperatures of 450° C. and in individual cases also up to 800° C.
In the second method of the invention for transferring a surface texture onto a substrate, as shown in
1 Production of the Sol
1.1 Adhesive Sol
142 g of silica sol Levasil 300/30 and 4 ml of a 37% HCl solution are added to the present 327.5 g methyltriethoxysilane and 95.5 g tetraethyl orthosilicate and stirred. After cooling the solution by about 15° C., a mixture of 327.5 g methyltriethoxysilane and 95.5 g tetraethyl orthosilicate of the reaction solution is admixed.
1.2 Stamping Sol
22.43 g isopropanol is to be added to 4.46 g titan isopropylate quickly under constant stirring (part of 1). Then 0.68 g of a 16.9% HCl solution is added to 22.43 g of 1-butanol and stirred (Part 2). Part 2 is to be added to Part 1 and stirred.
1.3 Release Sol
4.22 g isopropanol and a mixture consisting of 1.083 g distilled water with 0.007 g Tween 80 is admixed to 36.50 g of approx. 8 percent polyvinyl alcohol (PVA, Poval 235) dissolved in water. A mixture of 0.16 g diethylene glycol, 0.08 g Zonyl FS-300 and 1.09 g is added to an aliquot of 38.56 g of the aforementioned PVA solution and stirred.
2 Making the Coating stack: Release, Printable Coating and Texturing of the Printable Coating
2.1 Making the Release Coating
The release sol described under point 1.3 is applied onto a PET carrier sheet using a 400 μm coating knife and dried at 150° C. for 20 min.
2.2 Making the Printable Coating
The stamping sol described under point 1.2 is applied to the release coating by flooding.
2.3 Texturing the Printable Coating
A relief hologram is etched into the wet film using a silicone rubber stamp. The stamp must be applied with a pressure of approx. 1 kg per square centimeter for approx. 1 second. After a rest period of 30 minutes the solvent is diffused into the silicone rubber so that the dried printable coating has sufficient firmness and the silicone rubber stamp can be removed.
3 Transfer of the hologram onto a substrate
3.1 Transfer of the hologram onto glass
The glass substrate must be coated with the adhesive by dip coating at 1 mm/s. After evaporation of the solvent at RT [room temperature] for approx. 1 h, the textured coating stack described under point 2 can be laminated onto the glass substrate. The glass substrate must then be heated for 8 h at 80° C., and within 4 h to 450° C. The temperature of 450° C. must be held for 1 h; then the workpiece must be cooled within 4 h to 20° C. 3.2 Transfer of the Hologram onto Ceramic
The ceramic substrate must be coated with the adhesive (dip coating 1 mm/s). After evaporation of the solvent at RT for approx. 1 h, the textured coating stack described under point 2 can be laminated onto the ceramic. The ceramic substrate must then be heated for 8 h at 80° C., and within 4 h to 450° C. The temperature of 450° C. must be held for 1 h; then the workpiece must be cooled within 4 h to 20° C.
3.3 Transfer of the Hologram onto High-Grade Steel
The high-grade steel substrate must be coated with the adhesive (dip coating 1 mm/s). After evaporation of the solvent at RT for approx. 1 h, the textured coating stack described under point 2 can be laminated onto the high-grade steel. The high-grade steel substrate must then be heated for 8 h at 80° C., and within 4 h to 450° C. The temperature of 450° C. must be held for 1 h; then the workpiece must be cooled within 4 h to 20° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2007 008 073 | Feb 2007 | DE | national |
| 10 2007 019 866 | Apr 2007 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/DE2008/000273 | 2/14/2008 | WO | 00 | 9/23/2009 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2008/098567 | 8/21/2008 | WO | A |
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| Number | Date | Country |
|---|---|---|
| 41 30 550 | Mar 1993 | DE |
| 44 17 405 | Nov 1995 | DE |
| 196 33 675 | Feb 1998 | DE |
| 196 47 368 | May 1998 | DE |
| 100 01 135 | Jul 2001 | DE |
| 1 248 685 | Oct 2002 | EP |
| 1 614 664 | Jan 2006 | EP |
| 1 632 362 | Mar 2006 | EP |
| 2003-280498 | Oct 2003 | JP |
| 2004-358925 | Dec 2004 | JP |
| 2002-024286 | Mar 2002 | KR |
| WO 9316888 | Sep 1993 | WO |
| WO 9822648 | May 1998 | WO |
| WO 02097537 | Dec 2002 | WO |
| Entry |
|---|
| English translation of WO98/22648 by Schmidt et al. May 1998. |
| English translation of description and claims of WO98/22648; May 1998. |
| International Search Report. |
| Leibniz-Institut fur Neue Materialien: Jahresbericht 2005, Saarbruecken, pp. 6-20. (With English Abstracts of each section and English Abstracts of each drawing) (German Exam. Report). |
| Number | Date | Country | |
|---|---|---|---|
| 20100032083 A1 | Feb 2010 | US |
