COATED GLASS OR GLASS CERAMIC ARTICLE
20170247289 · 2017-08-31
Assignee
Inventors
Cpc classification
F21Y2115/30
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
C03C1/04
CHEMISTRY; METALLURGY
B23K26/361
PERFORMING OPERATIONS; TRANSPORTING
C03C10/00
CHEMISTRY; METALLURGY
B23K26/18
PERFORMING OPERATIONS; TRANSPORTING
H05B3/74
ELECTRICITY
F21Y2115/10
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B23K26/0006
PERFORMING OPERATIONS; TRANSPORTING
B23K26/57
PERFORMING OPERATIONS; TRANSPORTING
B23K26/0624
PERFORMING OPERATIONS; TRANSPORTING
F21W2131/30
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F21V3/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B23K26/0853
PERFORMING OPERATIONS; TRANSPORTING
B23K26/082
PERFORMING OPERATIONS; TRANSPORTING
B41M5/24
PERFORMING OPERATIONS; TRANSPORTING
G02B6/001
PHYSICS
International classification
F21V3/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
C03C10/00
CHEMISTRY; METALLURGY
H05B3/74
ELECTRICITY
Abstract
A method is provided for producing a glass or glass ceramic article that includes: providing a sheet-like glass or glass ceramic substrate having two opposite faces, which in the visible spectral range from 380 nm to 780 nm exhibits light transmittance of at least 1% for visible light that passes from one face to the opposite face; providing an opaque coating on one face where the coating exhibits light transmittance of not more than 5% in the visible spectral range from 380 nm to 780 nm; and directing a pulsed laser beam onto the opaque coating and locally removing the coating by ablation down to the surface of the glass or glass ceramic article, repeatedly at different locations, thereby producing a pattern of a multitude of openings defining a perforated area in the opaque coating, so that the opaque coating becomes semi-transparent in the area.
Claims
1. A method for producing a glass or glass ceramic article, comprising the steps of: providing a sheet-like glass or glass ceramic substrate having two opposite faces, the substrate exhibiting light transmittance in the visible spectral range from 380 nm to 780 nm of at least 1% for visible light that passes across the substrate from one face to the opposite face; providing an opaque coating on one face of the substrate, the opaque coating exhibiting light transmittance of not more than 5% in the visible spectral range; directing a pulsed laser beam onto the opaque coating to locally remove the opaque coating by ablation down to the face of the substrate, repeatedly at different locations, thereby producing a pattern of a multitude of openings defining a perforated core area in the opaque coating so that the opaque coating becomes semi-transparent in the perforated core area; and directing a pulsed laser beam onto the opaque coating to locally remove the opaque coating by ablation down to the face of the substrate, repeatedly at different locations, thereby producing another pattern of a multitude of openings defining a transition area along a periphery of the perforated core area in the opaque coating, the transition area having an ablated percentage surface area that is lower on average within the transition area than within the core area, the ablated percentage surface area being defined by a ratio of ablated surface area to non-processed surface area.
2. The method as claimed in claim 1, wherein the openings are arranged at different spacings to each other and/or have different sizes.
3. The method as claimed in claim 2, wherein the spacings and/or the size of the openings vary stochastically according to a random distribution.
4. The method as claimed in claim 1, wherein the openings have a shape of circular dots.
5. The method as claimed in claim 1, wherein the openings are spaced from each other by less than 200 μm.
6. The method as claimed in claim 1, wherein the openings have a size of less than 30 μm.
7. The method as claimed in claim 1, wherein the ablated percentage surface area of the core area is greater than 0.5%.
8. The method as claimed in claim 1, wherein the ablated percentage surface area is reduced by less than 2% per mm in the transition area.
9. The method as claimed in claim 1, further comprising cleaning the substrate after directing a pulsed laser beam onto the opaque coating.
10. The method as claimed in claim 9, wherein the cleaning comprises using an adhesive roller to clean the substrate.
11. The method as claimed in claim 9, further comprising, after the cleaning step, providing the core and/or transition area with a transparent coating or a transparent sealing layer.
12. The method as claimed in claim 1, wherein the substrate comprises a material that has an ablation threshold that is higher than an ablation threshold of the opaque coating for a wavelength of more than 532 nm.
13. The method as claimed in claim 1, wherein the opaque coating comprises a matrix of an oxidic network with decorative pigments embedded therein.
14. The method as claimed in claim 1, wherein the opaque coating comprises a color with an L value in the L*a*b color space of at least 20.
15. A glass or glass ceramic article, comprising: a glass or glass ceramic substrate having two opposite faces; an opaque coating on one of the two opposite faces, wherein the opaque coating exhibiting a light transmittance of not more than 5% in the visible spectral range from 380 nm to 780 nm, wherein the opaque coating comprises an area that is provided with a pattern of openings defining a perforated core area, which openings allow light that is incident onto the opaque coating to pass through the opaque coating and the substrate so that the perforated core area appears semi-transparent, the openings being spaced by less than 200 μm; and wherein the opaque coating comprises a transition area along a periphery of the perforated core area, which includes further ablated openings in a manner so that the ablated percentage surface area defined by a ratio of ablated surface area to non-processed surface area is lower on average within the transition area than within the core area.
16. The glass or glass ceramic article as claimed in claim 15, further comprising at least one light-emitting element that is arranged so that light emitted from the light-emitting element is incident onto the substrate at the openings and is able to pass through the opaque coating and the substrate.
17. The glass or glass ceramic article as claimed in claim 15, wherein the openings are arranged at different spacings to each other and/or have different sizes.
18. The glass or glass ceramic article as claimed in claim 15, wherein the light-emitting element comprises at least one light-emitting diode or laser diode.
19. The glass or glass ceramic article as claimed in claim 18, further comprising a diffusing element for distributing the light emitted by the light-emitting element throughout the openings.
20. The glass or glass ceramic article as claimed in claim 18, further comprising a side-emitting light guide for distributing the light emitted by the light-emitting element throughout the openings.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0045] The invention will now be described in more detail with reference to the accompanying figures. In the figures, the same reference numerals designate the same or equivalent elements. In the drawings:
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DETAILED DESCRIPTION
[0056] For producing a glass or glass ceramic article according to the invention, initially a planar or sheet-like glass or glass ceramic substrate 2 is provided. Accordingly, the glass or glass ceramic substrate 2 has two opposite faces 20, 21. One of the faces is provided with an opaque or lightproof layer 5, in the example shown in
[0057] Particularly preferred coatings 5 include inorganic and/or inorganically-organically modified sol-gel coatings. The oxidic network may preferably consist of SiO.sub.2, TiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3 components. The network may moreover include organic residues.
[0058] Pigments that may be added in particular include color-imparting pigments in the form of metal oxides, in particular cobalt oxides/spinels, cobalt-aluminum spinels, cobalt-aluminum-zinc oxides, cobalt-aluminum-silicon oxides, cobalt-titanium spinels, cobalt-chromium spinels, cobalt-aluminum-chromium oxides, cobalt-nickel-manganese-iron-chromium oxides/spinels, cobalt-nickel-zinc-titanium-aluminum oxides/spinels, chromium-iron-nickel-manganese oxides/spinels, cobalt-iron-chromium oxides/spinels, nickel-iron-chromium oxides/spinels, iron-manganese oxide/spinels, iron oxides, iron-chromium oxides, iron-chromium-tin-titanium oxide, copper-chromium spinels, nickel-chromium-antimony-titanium oxides, titanium oxides, zirconium-silicon-iron oxides/spinels.
[0059] Preferred pigments are absorption pigments, platelet- or rod-shaped pigments, coated effect pigments e.g. based on mica. Also suitable are pigments such as carbon blacks, graphite, and dyes.
[0060] Also, the layers (decorative/sealing layers) may include further constituents such as fillers, preferably nanoscale fillers. Suitable fillers are in particular, SiO.sub.x particles, aluminum oxide particles, fumed silica, lime-soda particles, alkali aluminosilicate particles, polysiloxane spheres, borosilicate glass spheres, and/or hollow glass spheres.
[0061] Such coatings are highly durable and temperature resistant and can be produced in an almost unlimited variety of visual appearances, depending on the choice of the decorative pigments. However, the patterning of such coatings is a problem, especially if they contain a high proportion of pigments, or if the individual pigment particles are rather large. The latter is for instance the case when platelet-shaped decorative pigments are used to produce metallic or glitter effects. The inventive method even permits to sever the individual pigment particles and to cut them exactly when the openings or holes are created.
[0062] The decorative pigments and their content in the coating composition are selected so that with the intended layer thickness of the coating 5 the latter has a transmittance in the visible spectral range of less than 5%. Optionally, such a low transmittance may as well be achieved by a multi-layered coating.
[0063] Suitable coating compositions and coatings prepared therefrom are known, inter alia, from DE 10 2008 031 426 A1, and from DE 10 2008 031 428 A1, and the contents disclosed therein concerning such coating compositions and coatings is hereby fully incorporated into the subject matter of the present application. Accordingly, in one embodiment of the invention an opaque coating 5 can be produced by preparing the decorative layer by a sol-gel process in a first step, the layer being applied on the glass or glass ceramic substrate and cured by baking, and in a second step the decorative layer is covered by a sealing layer which is also produced by a sol-gel process, in which inorganic decorative pigments and fillers are mixed with a sol, wherein the inorganic decorative pigments comprise platelet-shaped pigment particles and inorganic solid lubricant particles which are added in a ratio ranging from 10:1 to 1:1 wt %, preferably from 5:1 to 1:1 wt %, and more preferably from 3:1 to 1.5:1 wt %, and wherein the prepared mixture is applied to the glass ceramic substrate provided with the cured decorative layer and is then cured at elevated temperatures. The cured sealing layer may have the same composition as the cured decorative layer, with the difference that in terms of the number of organic residues the metal oxide network of the sealing layer has more organic residues than the metal oxide network of the decorative layer, preferably at least 5% more organic residues. Metal oxide network herein also refers to an oxidic network including elements which are semiconducting in elemental form (i.e. in particular the SiO.sub.2 network already mentioned, inter alia).
[0064] Unlike described before, other sealing layers may likewise be used. In addition to the sol-gel sealing layers described above, silicone layers or silicone-based layers are for instance suitable as well to seal an underlying coating. Sealing layers based on organic polymers such as polyurethanes, polyacrylates etc. are also possible. The sealing layers may be pigmented.
[0065] The sealing layers may be transparent, dyed transparent, translucent, or opaque. Pigmented sealing layers are preferred.
[0066] Ceramic inks that are specifically adapted to the requirements of a ceramic lower surface coating may as well be used on the face. A preferred embodiment of this invention are hybrid layers such as described in DE 10 2012 103 507 A1.
[0067] Once the coating 5 has been produced, an apparatus for laser ablation is then used to create a multitude of openings or holes 9, which together define a perforated area 10. An example of such an apparatus 11 is shown in
[0068] The apparatus for laser ablation 11 comprises a laser 71 and a device for guiding the laser beam 7 produced by the laser 71 over the surface 20 of the glass or glass ceramic substrate 2 coated with a coating 5. For example a galvanometer scanner 15 can be employed as the device for guiding the laser beam 7 over the surface.
[0069] For some applications it is desired, in addition to perforation, to produce cutouts having the shape of long straight lines, for example in cooktop panels where such lines are intended to delineate a cooking area or to mark a cooking zone. For long straight lines it is advantageous to use a polygon scanner, because when stitching long lines a small offset might quickly be produced. Due to the offset the line would become wider at the crossing point and therefore would appear much brighter at this point when backlit.
[0070] As illustrated in
[0071] The openings or holes preferably have the shape of circular dots. However, the openings may as well have the shape of elongated ovals. Other geometries are also conceivable, e.g. parallel lines.
[0072] In the case of dot-shaped openings, these dots form a dot pattern as a whole. The spacing between the individual openings or dots should be less than 200 μm, preferably less than 150 μm, more preferably less than 100 μm. The openings or dots have a size of less than 30 μm, preferably less than 20 μm.
[0073] In order to ensure consistent high accuracies, it is also possible to use a synchronized scanning and displacing apparatus. In this case, the movement of table 16 or another means for displacing the substrate 2 is synchronized with the deflection of the scanner, e.g. galvanometer scanner 15.
[0074] For focusing the laser beam 7 on the surface in order to achieve the highest possible intensity, appropriate focusing optics 19 may be provided. In the example shown in
[0075] For locally removing the coating 5 to create an opening 9 which extends through coating 5, the device for guiding the laser beam moves the laser beam 7 over the surface, and the laser 7 is adjusted so that the ablation threshold of the material of coating 5 is exceeded and thus the coating is removed at the point of impingement. However, the output power of the laser is adjusted so that the ablation threshold of the substrate material, that is the material of the glass or glass ceramic of substrate 2, is not reached so that only the coating is removed. The glass ceramics marketed under the tradenames ROBAX and CERAN CLEARTRANS may be mentioned as an example here. For these glass ceramics the ablation threshold for a laser wavelength of 1064 nm is approximately 5.2*10.sup.17 W/m.sup.2.
[0076] More broadly, without being limited to the specific exemplary embodiment discussed above, it is therefore advantageous if the materials of the glass or glass ceramic material and of the opaque coating are selected so that the ablation threshold of the material of the glass or glass ceramic substrate 2 is higher than the ablation threshold of the opaque coating 5, in particular in the infrared spectral range, more particularly at a wavelength of 1064 nm.
[0077] Furthermore, it is generally advantageous if the layer thickness of the opaque coating is not too large. This facilitates the removal by laser ablation on the one hand. On the other hand, this is advantageous for light transmission through the openings 9 in the area 10 of the coating. If the coating is too thick, the walls of the openings 9 will have a corresponding length and will swallow an unnecessary amount of light. Therefore, it is generally preferred for the opaque coating 5 to have a layer thickness of not more than 300 μm, more preferably not more than 160 μm, most preferably not more than 50 μm.
[0078] On the other hand, however, coatings that are too thin are also unfavorable, in particular in view of ensuring a sufficient degree of light blocking. Preference is given to layer thicknesses of more than 3 μm, preferably at least 5 μm. The minimum and maximum thicknesses given above are mean values of layer thickness.
[0079] The laser beam guiding device is controlled by a control device 13 which may for instance execute a program that translates the shape and location of the pattern feature into control signals by means of which the laser beam 7 is moved over the surface by the laser beam guiding device. Preferably, the control device also controls the laser 7, in particular with regard to switching on and off and laser intensity.
[0080] According to one exemplary embodiment, a pulsed laser 71 was selected which can be sufficiently well focused to ablate dots of the dimensions mentioned before. This was achieved with a neodymium-YAG laser with a wavelength of 1064 nm and a pulse length of 10 ps. A scanner with optics having a focal length of 255 mm was employed. The M2 factor is less than 1.4, preferably less than 1.2. The tubular beam had a diameter of 12 mm. Average output power W50 at 200 kHz was reduced to about 4 W. Other lasers may also be used. In particular a laser with a wavelength of 532 nm and a pulse length of more than 1 ns is advantageous, since the smaller wavelength allows for better focusing and due to the longer pulse length the material will not become stained which is disadvantageous in case of light colors. Furthermore, lasers in the ns range have a distinct cost advantage over lasers in the short ps range. In any case it is advantageous for the ablated features to have a width of less than 0.025 mm.
[0081]
[0082] In the example shown on the left in
[0083] According to yet another embodiment, with the preferred layer thicknesses and the maximum width 91 of the opening at the substrate according to the invention, a condition is generally met according to which the width 91 of opening 9 is smaller than the layer thickness of the opaque coating 5.
[0084] As a result of both the smaller width of the opening compared to the layer thickness and the slight angle, if any, of the wall 92 relative to the vertical, the visual axis will not extend through the opening 9 but will end at the wall 92 already when viewing the opening 9 slightly obliquely. This in conjunction with the small width 91 of the opening results in the fact that the opening remains invisible to a viewer. It can only be perceived when light from a light source on the side of the glass or glass ceramic article 1 that is hidden to the viewer due to the light blocking layer 5 passes through the opening.
[0085] However, laser ablation may cause a dark discoloration of the coating. If the coating itself is dark, such discoloration and hence the opening 9 will remain invisible. However, this is different for coatings having a light color hue. In this case, the dark discoloration may be visible at the edges of the opening 9. This can be counteracted by adjusting the pulse frequency of the laser and the rate at which the laser beam is directed over the coating such that the points of incidence of the laser pulses do not overlap each other, which results in the desired dot pattern. According to this embodiment of the invention, it is thus even possible to produce openings that are invisible to a viewer in an opaque coating that has a color with an L value in the L*a*b color space of at least 20, preferably at least 40, more preferably at least 50. The L value of the color of the opaque coating may for example be determined using a spectrophotometer. The value relates to an exposed surface of the coating 5, that means it is not a color value measured across the glass or glass ceramic.
[0086] According to a refinement of the invention, a top-hat profile of the laser beam 7 is used in order to minimize the thermal impact in the peripheral area of the opening to be produced so as to avoid the staining effect. In this case, the edge regions of the initially Gaussian beam which have not enough energy for ablating the ink but yet have enough energy to heat the coating to an extent to cause discoloration thereof, are eliminated. Another advantage of a top-hat profile is better contour definition, since a Gaussian profile does not permit to remove multi-layered systems with sharp contours, although this effect causes blurring on a micrometer scale that is hardly visible or not visible at all to the eye.
[0087] The invention is most preferably implemented so that the coating is deposited on the surface 20 of the glass or glass ceramic substrate 2 that faces away from the user. Accordingly, the light from a light source will therefore first pass through the coating through opening 9, then through the glass or glass ceramic substrate and will then exit from the opposite face 21.
[0088] The invention can be employed in a variety of applications for backlit glass or glass ceramic articles of household appliances. The invention is particularly suitable for cooktops. A control panel, for example on a stove or oven, may also be implemented using a glass or glass ceramic article according to the invention. In case of a household appliance, the opaque coating serves to create a certain visual appearance on the one hand, on the other to hide the components of the household appliance.
[0089] Broadly, without being limited to the exemplary embodiments described below, the invention relates to a household appliance which has a control surface that is defined by the glass or glass ceramic article, and which comprises at least one light-emitting element arranged in the interior of the household appliance so that light emitted from the light-emitting element is incident onto the openings 9 of the area 10 in the opaque coating 5 and can pass through the openings 9 and the substrate 2.
[0090]
[0091] Regardless of the type of household appliance 3, the opaque coating 5 is preferably applied on the surface 20 of the glass or glass ceramic substrate 2 facing the interior. In the example of glass ceramic cooktop 30, the opaque coating 5 is accordingly provided on the lower surface of the substrate, which accordingly is a glass ceramic substrate 2 in this case. One or more heaters 23 are arranged below the glass ceramic substrate 2, for heating food to be cooked or cookware placed on the cooktop panel, or on face 21. The heaters 23 may comprise induction coils for an induction cooker, for example.
[0092] Without being limited to the illustrated exemplary embodiment, a light-emitting diode is used as the light-emitting element 18. Depending on the design of the opening, an array of a plurality of light-emitting diodes 18 may be used as well. The latter is favorable, for example, if the openings 9 are elongated and are to be illuminated the most uniformly possible. In order to allow much light to pass through the small opening, it is also possible according to yet another embodiment of the invention to use a laser diode as the light-emitting element.
[0093] Generally, without being limited to the illustrated example, it may moreover be favorable to arrange a diffusing element 17 in front of light-emitting element 18. Diffusing element 17 extends along a trench-shaped opening 9 and ensures that the light from light-emitting element 18 is distributed more evenly along trench-shaped opening 9. In this manner, a more uniform illumination of the linear display feature created with such a trench-shaped opening 9 is achieved.
[0094] The display feature created by the illuminated opening 9 may for instance serve to mark a cooking zone. Such marking is used to indicate which one of the cooking zones is currently enabled and heated. For this purpose, the trench-shaped opening 9 may for instance extend annularly around the area heated by heater 23.
[0095] Besides a diffusing element 17, a side-emitting light guide is suitable as well for distributing the light emitted by light-emitting element 18 along openings 9.
[0096] Generally, a coating on a glass or glass ceramic substrate may not only serve to prevent transparency. In addition, a coating may also be advantageous for sealing the coated side of the substrate. In the region of openings 9, such a sealing layer would however be interrupted. If a transparent sealing layer is used, it may as well be applied after introducing the openings 9, according to one embodiment of the invention, so that the openings will be covered or closed. The light from the light-emitting element will still be able to pass through openings 9 across the transparent sealing layer.
[0097] Such a refinement of the invention, in which opening 9 is sealed by a transparent sealing layer 6 is shown in
[0098] A sealing layer as represented by layer 6 refers to a coating which protects the glass or glass ceramic material and/or the opaque coating 5 from environmental influences. Such environmental influences may for instance include condensation products. Therefore, the sealing layer should be impermeable to liquid- and oil-containing substances as included in food, for example. Should such substances penetrate into coating 5, this might cause visible, unattractive alterations in visual appearance.
[0099] Moreover, the opaque coating 5 itself may constitute a sealing layer for protecting the surface of the glass or glass ceramic covered by coating 5.
[0100] Besides lighting that is not visible in the off state, another application is to create an invisible mark which serves as an anti-counterfeit feature. If it is desired to identify whether a particular glass or glass ceramic article is a genuine product, this can then be easily verified by examining the article under back lighting. Therefore, according to one aspect of the invention, it is contemplated to use a mark in the form of a preferably linear opening 9 in the opaque coating 5 created according to the invention for labeling an origin of the glass or glass ceramic article.
[0101] As stated above, the ratio of ablated to the total treated surface area is a process parameter of the method according to the invention. If the ratio is too great this may cause a visual alteration of the processed areas. Therefore, a transition area may be created exhibiting a reduced ratio compared to that of the core area of the treated surface area. However, this measure will often be unsatisfactory for areas with very light and very dark decorative layers, since in these cases it will not always be possible to obtain a sufficient dead front effect.
[0102] According to a further embodiment of the invention, the dead front effect can be improved by dithering, that is a random distribution of the size and position of the openings 9, which is also referred to as a stochastic or irregular distribution. In this case, the spacing and the size of the openings 9 is not kept constant throughout the entire processed area, but is varied by subdividing a cutout into a multitude of smaller areas.
[0103]
[0104]
[0105]
[0106] A dot size of 20 μm can be very advantageous when dithering is used, since in this case even agglomerations, that is openings coincidentally located close to each other, will not be visually perceived as a difference in brightness.
[0107] Dithering permits to achieve overall improved display performance of the treated glass or glass ceramic substrate.
[0108] If some finer patterns are superimposed, for example in displays with regularly arranged picture elements (pixels), this may cause a visual impression of an overlapped coarser pattern. This moire effect can be reduced or often even avoided by the use of dithering.
[0109] For generating irregular patterns by dithering, pulsed lasers with ultrashort pulses with a pulse duration of a few picoseconds are preferably used as lasers which can be used for the method of the invention. The wavelengths of such pulsed lasers are either in the IR range or in the UV range.
[0110]
[0111]
[0112] In transition area 110, the openings 9 also form a regular pattern.
LIST OF REFERENCE NUMERALS
[0113] 1 Glass or glass ceramic article [0114] 2 Sheet-like glass or glass ceramic substrate [0115] 3 Household appliance [0116] 5 Opaque coating [0117] 7 Pulsed laser beam [0118] 9 Openings or holes in 5 [0119] 10 Perforated core area [0120] 11 Apparatus for laser ablation [0121] 13 Control device [0122] 15 Galvanometer scanner [0123] 16 X-Y table [0124] 17 diffusing element [0125] 18 Light-emitting element [0126] 10 focusing optics [0127] 20, 21 Faces of 2 [0128] 23 Heater [0129] 25 Side-emitting light guide [0130] 30 Glass ceramic cooktop [0131] 50 Surface of 5 [0132] 71 Laser [0133] 91 Width of 9 on substrate 2 [0134] 92 Wall of 9 [0135] 93 Angle of wall 92 relative to the surface normal of the substrate [0136] 94 Spacing [0137] 95 Width of opening 9 at surface 50 of 5 [0138] 96 Size of opening [0139] 110 Perforated transition area [0140] 210 Non-perforated area