• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a glass-ceramic article, in particular for use with at least one light source and / or at least one heating element, said article comprising at least one substrate, such as a plate, made of glass-ceramic, and having at least one light zone, said substrate being coated opposite said zone with a paint consisting of at least one silicone resin and pigment (s), the level of pigment (s) being greater than or equal to 1% and less at 10% by weight of the paint. The present invention also relates to a process for obtaining said article.
    公开号:FR3063723A1
    申请号:FR1752034
    申请日:2017-03-13
    公开日:2018-09-14
    发明作者:Clement Sieutat；Pablo Vilato；Adrien Beffa
    申请人:Eurokera SNC；
    IPC主号:
    专利说明:

    ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number: 3,063,723 (to be used only for reproduction orders) (© National registration number: 17 52034
    COURBEVOIE © Int Cl 8 : C 03 C 17/30 (2017.01), C 09 D 183/04, C 08 K 3/22
    A1 PATENT APPLICATION
    Date of filing: 13.03.17. © Applicant (s): EUFtOKEFtA S.N.C. - FR. © Priority : @ Date of availability of the request: 14.09.18 Bulletin 18/37. @ Inventor (s): SIEUTAT CLEMENT, VILATO PABLO and BEFFA ADRIEN. (56) List of documents cited in the preliminary search report: See the end of this brochure References to other related national documents: ® Holder (s): EUROKERA S.N.C .. o Extension request (s): © Agent (s): SAINT GOBAIN RECHERCHE Société anonyme.
    VITROCERAMIC ARTICLE WITH LIGHT DISPLAY.
    FR 3,063,723 - A1 (6 /) The present invention relates to a glass-ceramic article, intended in particular to be used with at least one light source and / or at least one heating element, said article comprising at least one substrate, such as that a plate, made of glass ceramic, and having at least one light zone, said substrate being coated facing said zone with a paint formed from at least one silicone resin and of pigment (s), the level of pigment (s ) being greater than or equal to 1% and less than 10% by weight of the paint.
    The present invention also relates to a method for obtaining said article.
    VITROCERAMIC ARTICLE WITH LIGHT DISPLAY
    The present invention relates to the field of glass-ceramics. More specifically, it relates to an article (or product) made of glass ceramic, intended in particular to cover or receive heating elements (such as a cooking plate), said article being provided with at least one zone capable of being lit ( so-called bright area). The term “ceramic glass article” means an article based on a substrate made of a ceramic material (such as a ceramic plate), said substrate possibly being provided with accessories or additional elements (decorative or functional). required for its final use, the article being able to designate both the substrate alone and that provided with additional equipment (for example a cooking plate provided with its control panel, its heating elements, etc.). The present invention also relates to a method for obtaining said article.
    There are several glass ceramic products in common use, in particular ceramic glass cooktops which have been very successful with housekeepers, appliance manufacturers and users. This success can be explained in particular by the attractive appearance of these plates and by their ease of cleaning.
    A glass-ceramic is originally a glass, called precursor glass (or mother glass or green-glass), whose specific chemical composition allows controlled crystallization to produce, by means of suitable heat treatments, called ceramization. This specific, partly crystallized structure gives the ceramic glass unique properties.
    There are currently different types of ceramic glass plates, each variant being the result of significant studies and numerous tests, given that it is very difficult to make modifications to these plates and / or to the process for obtaining them without risking an unfavorable effect on the desired properties: in particular, in order to be able to be used as a cooking plate, a glass-ceramic plate must generally have a transmission in the wavelengths of the visible range which is sufficiently low to mask at least some of the heating elements underlying at rest and sufficiently high so that, depending on the case (radiant heating, induction heating, etc.), the user can visually detect the heating elements in working order for safety purposes; it must also have a high transmission in the wavelengths of the infrared range in the case in particular of plates with radiant foci. The ceramic hobs must also have sufficient mechanical strength as required in their field of use. In particular, in order to be able to be used as a cooking plate in the household appliance sector, a glass-ceramic plate must have good resistance (as defined for example according to standard EN 60335-2-6) to pressure, to shocks ( support and falling utensils, etc.), etc.
    The most common ceramic hobs are dark in color, especially black or brown or orange-brown in color. With a low transmission coefficient below 600 nm, these plates above all allow the visibility of red elements such as heating elements brought to high temperature or even light displays based on red monochromatic light emitting diodes. Clearer and / or transparent glass-ceramic plates (such as KeraVision or KeraResin glass-ceramics, sold by the company EuroKera), associated, where appropriate, with opacifying coatings, or with filters or layers with a filtering effect (such as Keraspectrum glass-ceramics) also exist, allowing the display of other colors.
    The light sources used with the ceramic hobs generally make it possible to signal orders or heating zones, to display data, to create or highlight decorations, etc. The light sources used are generally installed under the plate, so as to be able to illuminate patterns (for example a pictogram or a symbol indicating that the heating zones are on, etc.). These sources can for example be formed of one or more light-emitting diodes (LED or LED) attached under the plate on a support or housing. To allow the lighting of the patterns, one or more savings can be provided, for example in one or more opacifying layers covering the plate, and / or on the system (such as a housing) making it possible to bring the light sources. As the intensity of the sources can be significant, it is known to insert an intermediate diffusing element (in the form for example of a disc or a pellet), traditionally made of polymer or ceramic, between the source and the plate at the level of the patterns or areas that can be illuminated to avoid dazzling the user. The production of these elements, from the electronic industry, is done in large series and hardly allows the realization of particular shapes, especially for small series, the mounting and fixing of these elements can also prove to be complex and expensive. . In addition, certain materials (in particular polymers) cannot be used in certain zones subjected to high temperature, such as the zones of heating.
    In addition to not dazzling the user, it is also desirable to obtain light patterns having homogeneous lighting over their entire surface, just as it is desirable that these patterns, especially those of small size, appear with sufficient sharpness and contrast and can be easily located. It is also desirable that the light does not diffuse over the contours of the pattern which in this case may not appear sharp, and in the case for example of the use of a plate having spikes on the underside, it is advisable to avoid these spikes being visible at the level of the patterns by transparency and can induce an optical distortion of the light of the light source.
    The present invention has therefore sought a solution which is simple to implement, resistant and durable over time, economical, effective, and flexible enough to allow adjustments, in particular according to the dimensions and the shape of the areas to be lit and / or the if necessary certain optical adjustments (transmission, etc.), in order to obtain patterns or light displays on ceramic glass articles in any desired zone (including possible heating zones), this solution also making it possible to preserve the sharpness of the contours of the light patterns appearing on the upper face of the glass-ceramic when they are lit by one or more light sources located in particular on the lower face of the glass-ceramic, and to obtain uniform lighting over the entire surface of the patterns, while avoiding the glare of the user and the visibility of elements located on the underside of the glass ceramic or any distortion effect n induced by these elements.
    This object is achieved by the glass ceramic article (or product) according to the invention, intended in particular to be used with (in particular to cover or receive) at least one light source and / or at least one heating element, said article comprising at least one glass-ceramic substrate, such as a plate, and having at least one luminous (vocation) zone, said substrate being coated facing said zone with a paint formed of at least one silicone resin and of pigment (s), the level of pigment (s) being greater than or equal to 1% and less than 10% by weight of the paint.
    By light zone (or lighting zone) is meant a zone with a luminous vocation (in particular a display zone), that is to say a zone intended to be illuminated upon activation, for example, of a light source and / or a heating element, even if this activation is occasional, this zone can in particular be an information display zone (for example a zone indicating by a symbol or pictogram, or by terms, etc. the operating state or not of one or more heating zones). This zone comprises for example at least one light pattern, said pattern and / or said zone being in particular delimited (or intended to be delimited) by one or more savings, practiced for example in a coating of the substrate or in an element to be attached to the substrate (for example on a box carrying the light source or sources provided for lighting this area).
    If it is already known to coat ceramic plates with paint-type layers, they are generally opacifying layers with low transmission rate intended to obscure the underlying elements placed under the ceramic, most paints do not being furthermore not suitable for coating areas facing heating zones (normally due to their lower temperature resistance compared to enamel coatings). Note that the terms under, above, upper side, lower side, etc. qualify the positioning with respect to the glass-ceramic substrate considered in its position of use (the upper face in the case of a hob being that seen by the user, the lower or inner face being the opposite face, usually not seen by user and turned towards the heating zones).
    The paint used in the present invention combines an advantageous silicone resin and an unusually low level of pigments, for the coating of areas facing bright areas, the composition developed according to the invention can be used in any area of the glass-ceramic substrate, even when these zones are subjected to high temperatures and / or to strong lighting, and makes it possible to obtain at the same time and in an unusual and unexpected way a sufficient and homogeneous light transmission on the zone concerned, at the same time as a strong diffusion preventing the user from being dazzled, these two properties being generally contradictory (strong diffusion being generally associated with weak transmission and vice versa). The light transmission rate obtained for the paint coating according to the invention is in particular greater than 30% and its diffusion rate is simultaneously greater than 90%, as specified later.
    There is also a good adhesion of the paint to the substrate or to any adjacent layer, if any, present on the substrate (in particular a layer of opacifying paint having sparks forming the patterns to be illuminated), this paint also having good scratch resistance. .
    The solution according to the present invention makes it possible to obtain in a simple and economical manner, without complex operation (the paint layer being notably advantageously and simply deposited by screen printing), in a durable manner and with great flexibility, patterns or luminous displays on vitroceramic articles in any desired area, with bright patterns of clear contours, with homogeneous lighting over their entire surface, without risk of dazzling of the user nor disturbing visibility or distortion effect due to underlying elements.
    The article according to the invention can be a hob or any glass-ceramic article having a display or at least one light zone of a functional or decorative nature, such as a glass-ceramic worktop, or even perhaps a system with main display vocation (decorative and / or functional). In its most common application, the article according to the invention is intended to serve as a cooking plate, this plate generally being intended to be integrated into a hob or stove also comprising heating elements, for example radiant stoves or halogen or induction heating elements. In another advantageous application, the article according to the invention is a work plan with different displays, and without necessarily cooking zones.
    The article according to the invention comprises, or is formed from, at least one glass-ceramic substrate. Preferably, this substrate (or the article itself if it is formed only from the substrate) is a plate, intended in particular to cover or receive at least one light source and / or a heating element. This substrate (or respectively this plate) is generally of geometric shape, in particular rectangular, even square, even circular or oval, etc., and generally has an upper or external face (visible face or turned towards the user) in the position of use, another lower or internal face (generally hidden, for example in a chassis or cabinet of furniture) in the position of use, and a slice (or edge or thickness). The upper face is generally flat and smooth but may also have at least one raised area and / or at least one hollow area and / or at least one opening and / or beveled edges (these shapes having been added during manufacture of the substrate, for example by rolling or collapsing or pressing, etc., or having been added in recovery), etc., these variations in shape advantageously constituting continuous variations of the plate (without change of materials or fittings). The underside is preferably flat and smooth according to the present invention but could if necessary also have structures.
    The thickness of the glass-ceramic substrate is generally at least 2 mm, in particular at least 2.5 mm, and is advantageously less than 15 mm, in particular is of the order of 3 to 15 mm, in particular from 3 to 6 mm . The substrate is preferably a flat or almost flat plate (in particular with an arrow less than 0.1% of the diagonal of the plate, and preferably of the order of zero).
    The substrate can be based on any glass ceramic, this substrate advantageously having a zero or almost zero CTE, in particular less (in absolute value) at 30.10 ' 7 K' 1 between 20 and 300 ° C, in particular less than 15.10 ' 7 K ' 1 , or even less than 5.10' 7 K ' 1 between 20 and 300 ° C.
    Preferably, a dark appearance substrate is used, which is weakly transmissive and not very diffusing, in particular based on any glass ceramic having, intrinsically, a light transmission ranging from 0.8% to 40%, in particular from 0.8 to 5%, in particular from 0.8 to 2%, and an optical transmission (determined in a known manner by making the ratio between the transmitted intensity and the incident intensity at a given wavelength) of at least 2.5% for a wavelength of 625 nm included in the visible range. By "intrinsically" is meant that the plate has such a transmission in itself, without the presence of any coating. In particular, a substrate of black or brown appearance is used, making it possible, in combination with light sources placed below, to display light zones or decorations, while masking any underlying elements. In particular, it may be based on a black glass ceramic comprising crystals of β-quartz structure within a residual glass phase, the absolute value of its coefficient of expansion being advantageously less than or equal to 15.10 ' 7 K' 1 , or even 5.10 ' 7 K' 1 , such as the glass ceramic plates sold under the name Kerablack + by the company Eurokera. In particular, it may be a glass ceramic refined with arsenic of composition as described in patent application EP0437228 or US5070045 or FR2657079, or a glass ceramic refined in tin, having an oxide content of arsenic less than 0.2%, for example of composition as described in patent application WO 2012/156444, or further refined with (s) sulfide (s) as described in patent application WO2008053110.
    The substrate forming the article according to the invention is provided (or provided or coated), facing the area to be lit, with a paint (or a paint coating or with a layer or layers of paint), the paint being formed (or based) of at least one silicone resin and a low level of pigment (s) according to the invention. The silicone resins (or polysiloxanes) used (in particular in the form of polymer (s), monomer (s) and / or oligomer (s), optionally crosslinkable) can be chosen in particular from silicone resins modified with incorporation of at least one radical chosen by the following radicals: alkyl (which may optionally include an aromatic ring), phenyl (or other radicals from the aryl family), alkenyl, vinyl, allyl, alkynyl. Advantageously, the silicone resin or resins of the paint are resins not functionalized with (or devoid of) at least the following functional groups or groups: halogen, epoxy, polyester. The silicone resin (s) used for the paint can in particular be one or more polysiloxane or silsesquioxane resins chosen from polymethylsiloxanes, polydimethylsiloxanes, polyphenylmethylsiloxanes, polydiphenylsiloxanes, dimethylsiloxane-diphenylsiloxane copolymers, etc.
    Preferably, the proportion of silicone resin (s) in the paint composition used according to the invention is at least 25% by weight of the paint (total paint composition as deposited, possibly including a solvent, an inorganic filler, additives, etc.), and generally at least 30 to 43% by weight of the paint, its rate relative to the dry extract of the paint being at least 40% by weight.
    As indicated above, the paint used according to the invention is also formed of pigment (s), the level of pigment (s) being greater than or equal to 1% and less than 10% by weight of the paint (total paint composition such as deposited, possibly including also a solvent, an inorganic filler, additives, etc.), and preferably being from 2 to 6% by weight of the paint, in particular from 2 to 4% by weight of the paint.
    The pigments used for painting are preferably inorganic pigments. They are in particular chosen from pigments based on metal oxides, such as titanium oxides, chromium oxides, copper oxides, iron oxides, cobalt oxides, nickel oxides, oxides of zinc, manganese oxides, cerium oxides, etc. Preferably, as pigments, in particular as the only pigments, white pigments are used, in particular and advantageously pigments based on titanium oxides T1O2 (such as those sold by the company Kemira under the reference Kemira 300 or those sold by the Chemours company under the reference TiPure R900, etc). The pigments chosen in the present invention preferably exclude the so-called effect pigments, that is to say provided with coating (s) with effects, in particular with a reflective effect, the effect pigments can adversely affect the optical properties. wanted.
    The pigments are in particular dissolved or dispersed in the aforementioned silicone resin (s) (acting as a binder, the terms silicone binder can also be used to denote silicone resins) and / or in an added medium (such as specified later). Pigments are usually in powder form before being suspended or dispersed in a binder or medium. The pigments are preferably chosen in the present invention so that at least 50%, and preferably at least 75%, or even at least 90%, of the particles of (or forming these) pigments have a dimension or size ranging from 0.1 to 10 pm, whatever the shape of these particles.
    The size of a particle is called its equivalent diameter, that is to say the diameter of the sphere which would behave identically during the particle size analysis of the particles (or of the powder formed from said particles) forming the pigments considered. , the particle size distribution (set of particle sizes) being measured in particular by laser particle size. Advantageously, at least 50% (by number), and preferably at least 75%, or even at least 90%, of the (particles of) pigments present in the ink used in the present invention have a size ranging from 0.1 to 10 μm , in particular ranging from 0.1 to 1 μm (in particular for white pigments based on ΠΟ2).
    The aforementioned silicone resin (s) in particular coat the pigment powder in the paint and allow mass agglomeration of the particles after drying to form the solid paint layer. Where appropriate, the paint, in particular in its ready-to-deposit form, also contains, in addition to the silicone resin or resins binding the pigments, at least one (other) medium or solvent (or if necessary diluent), forming part of (or added with) the silicone resin as added to the paint composition and / or forming part of (or added to) the paint, this solvent allowing the desired viscosity to be applied for application to the substrate and allowing the prior bonding of painting with the substrate. As the solvent, it is possible to use, for example, white spirit (or heavy naphtha), xylene, turpentine, etc. The level of solvent in the paint during deposition is generally of the order of 20 to 40% by weight of the paint, the solvent then being removed to obtain the final layer (this elimination being done mainly during drying).
    Advantageously, the paint used according to the invention is devoid of water or of aqueous solvent for better implementation in particular.
    The paint also comprises in most cases one or more inorganic or mineral fillers (other than pigments and not melting in particular during cooking), advantageously insoluble, having in particular a role of reinforcement or also participating in the thermal behavior of the '' together (these fillers, unlike pigments, providing only low opacity), for example one or fillers formed of calcium and / or magnesium carbonates, and / or barium sulfate, silica or silicates, in particular of kaolin, talc, etc., at rates generally of at least 20% by weight and preferably not exceeding 40% by weight of the paint, to ensure its cohesion or its mechanical reinforcement, and preferably at rates ranging from 20 to 35% by weight of the paint. Preferably, the paint comprises in particular talc as mineral fillers for a good thermal resistance of the paint in particular.
    The paint can also optionally include other types of components, such as one or more additives (in particular wetting agents, stabilizing agent (s), dispersing agent (s), surfactant (s), pH or viscosity adjuster (s), biocide (s), defoamer (s), antioxidant (s), siccative, etc.).
    Unlike an enamel composition, the paint composition according to the invention is devoid of glass frit or of components capable of forming together a glassy matrix. The paint composition according to the invention is present in the form of a dispersion and is also advantageously devoid of silica gel or colloidal silica for better use of the composition (unlike a hydrolyzate or a sol-gel , it is notably easier to train and use).
    In a preferred embodiment according to the invention, the paint according to the invention has the following composition (or comprises the following constituents within the limits defined below, limits included), the proportions being expressed in percentages by weight (percentages by weight , or percentages by mass, relative to the total weight of the paint composition ready for deposition):
    - silicone resin (s)
    - pigment (s) (especially white)
    - filler (s) (in particular talc)
    - solvent (s)
    - 45%, preferably 30-45% 1 -10% preferably 2-6%
    - 40% preferably 20-35% 20 - 40% preferably 20-35%
    Once solid paint coating is formed mainly of the silicone resin (s), fillers and pigments mentioned above. The paint composition is mainly inorganic / mineral, that is to say that it comprises at least 50% by weight of inorganic components relative to the dry extract of the paint.
    The paint before deposition is generally in the form of a stable liquid-solid mixture and of pasty consistency, the viscosity on deposition of the paint being preferably between 1500 and 3000, in particular between 1600 and 2100 mPa.s.
    The paint can be formed directly by mixing these constituents in the required proportions, the viscosity being adjusted if necessary by the addition of the solvent, or else can be formed from an existing opacifying paint composition, by diluting said paint. using a transparent paint based on the same constituents, with the exception of pigments. The paint used according to the invention is preferably white, but can be colored if necessary (by the choice of colored pigments instead of white), in particular to change the color of the lighting perceived.
    The paint is preferably applied (in one or more layers, preferably one layer), quickly and simply, by screen printing (in particular in the form of a flat surface) on the glass-ceramic substrate (this deposit being made after the ceramization possible of the substrate), already partially coated or not (as specified later), advantageously on the underside of said substrate, in the appropriate zones (opposite the light zone or zones), delimited in particular by savings as indicated below, and over the entire surface delimited by each of said savings or over the entire surface facing said light areas, the deposition by screen printing making it possible in particular to obtain variable and precise patterns.
    Preferably, the screen printing canvas (or screen) used, composed for example of polyester or polyamide yarn fabrics, is chosen so as to have a number of threads per cm of between 43 and 120 threads per cm, thus allowing to obtain a particularly appropriate thickness and definition of the paint coating.
    The thickness of the final paint coating is thus preferably less than 25 μm, in particular between 2 and 20 μm, in particular between 4 and 15 μm, or even between 6 and 15 μm.
    The paint once deposited is dried and / or left to harden or baked, baking can be done with the other possible layers of paint present. The paint can in particular be cured (resumed) on the ceramic substrate, at temperatures of the order of 350 to 500 ° C., the coating of final paint obtained after drying and / or hardening and / or firing forming a base layer of polymers.
    It can be observed that the selected paint has good adhesion to the glass-ceramic material (without requiring prior treatment of the support and / or the use of an adhesion promoter, a bonding layer or a primer) and does not mechanically weaken the glass-ceramic substrate (unlike in particular an enamel).
    It can cover areas of varied shape while respecting the constraints, in particular thermal and mechanical, specific to the preferred application targeted (decorated plates subjected to high temperatures such as cooking plates) and this in an economical, simple and effective manner, the coating developed having good resistance (in particular mechanical, thermal and / or abrasion) and good durability.
    The coated article has in particular good thermal resistance compatible with the use of various types of heating, does not pose maintenance problems, scratches or abrasion.
    The paint advantageously resists high temperatures. In particular, it has a degradation temperature greater than 350 ° C, in particular between 350 ° C and 700 ° C,
    The paint as selected, combined with glass ceramic, also makes it possible to sufficiently mask the underlying elements without, however, preventing their visual detection in working condition, and without the risk of dazzling the user while allowing sufficient and homogeneous lighting of the bright areas.
    The paint, or the paint coating, as deposited, both semi-transparent and diffusing, has in particular a light transmission TL greater than 30%, preferably greater than 38%, in particular greater than 40%, and which can go up to 60%, and its diffusion rate is simultaneously greater than 90%, in particular greater than or equal to 99%, this rate being able to go up to 100%.
    The optical measurements of the paint are made according to standard EN 410 by taking a substrate coated with said paint, the optical characteristics of which must be determined, preferably a transparent or translucent substrate provided with said paint, by calibrating the spectrophotometer with the bare substrate ( without the paint layer, the paint layer being removed or the substrate being considered in an uncoated area of said layer, or the same substrate without paint coating being used), then by carrying out the measurement on the paint coated substrate , by placing the paint on the incident side of the light beam, the spectrum thus obtained being the spectrum of the coating alone.
    The light transmission T L (of paint, or other coatings, measured in the same way as for the paint layer, or of the substrate, or of the coated substrate) is measured according to standard EN 410 using the illuminant D65. , and is the total transmission (in particular integrated in the visible domain and weighted by the sensitivity curve of the human eye), taking into account both direct transmission and possible diffuse transmission, the measurement being made by example using a spectrophotometer provided with an integrating sphere (in particular with the spectrophotometer sold by the company Perkin Elmer under the reference Lambda 950).
    The light scattering rate is defined, in the context of the invention, as being the ratio of the diffuse transmission to the total transmission using the illuminant D65, this rate being evaluated for example using the spectrophotometer provided with an integral sphere used for light transmission measurements.
    As indicated previously, the paint chosen according to the invention covers the zone or zones opposite the luminous zone or zones, these zones being generally delimited by savings.
    In particular, the glass-ceramic substrate may comprise at least one opacifying coating (for example enamel, in particular on the upper face, or in painting, in particular on the underside) (or occulting coating or opacifying layer), in particular of transmission luminous TL less than 0.5%, covering the substrate and within which at least one saving is made in the form of the pattern or the light zone to be produced, the paint being deposited at the places of the saving (s) before and / or after deposit of said opacifying coating.
    The saving (s) are for example carried out by masking the zone (s) concerned during the deposition of the opacifying coating using a mask which is removed after the deposition, or by closing, for example, the meshes of the screen of screen printing used for depositing the opacifying coating in the zone or zones concerned, or by precisely targeting the zones to be coated with the opacifying coating, etc. The savings may have in particular the form of motif (s), letter (s), symbol (s), image (s), photo (s), pictography (s), geometric figure (s), drawing (s), etc.
    Alternatively, the light zone or zones can be delimited by savings made in a device or mask added after deposition of the paint on the glass-ceramic substrate (for example in a box allowing the light sources to be brought back).
    The paint according to the invention is applied opposite each saving, the light emitted by the light source or sources passing through this diffusing zone before passing through the glass-ceramic substrate, giving a light pattern, the paint preferably being on the underside of the glass-ceramic , between the zone or zones to be illuminated and the respective light source or sources which should illuminate the said zone or zones, the paint making it possible in particular to extract the radiation emitted by the source or sources towards the desired lighting zone. The paint coating, applied in each zone or savings concerned, is in particular of the same shape and / or dimension (or approximately the same shape and / or dimension) as the savings in which it is applied without being however necessary to perfectly align the two areas, and / or overflows on the opacifying coating (for example covers a few millimeters of said coating around the savings), the light emitted by the light source, concentrated at the level of the pattern, diffusing only in the savings and the contours of the pattern obtained being particularly clear without making perceptible the elements located under the pattern.
    In an advantageous embodiment according to the invention, the substrate according to the invention can comprise two opacifying coatings, or opacifying layers, in particular two layers of opacifying paint (s), one of the opacifying coatings, deposited under the underside of the glass-ceramic substrate, having one or more sparks delimiting one or more areas to be lighted, the paint according to the invention being applied in the said sparse (s), and the second coating covering the edges of the diffusing paint according to the invention, the paint according to the invention being in a way sandwiched between the two opacifying coatings, this mode notably making it possible to have better opacity of the areas around the savings.
    In another advantageous embodiment according to the invention (alternative or cumulative to the previous mode), the substrate according to the invention comprises at least one layer or a colored filter on (between the paint and the opposite light source) or under (between the paint and the glass-ceramic substrate) the coating of diffusing paint according to the invention, and / or said paint is colored. Preferably, the layer or the colored filter (e) is on the coating of paint according to the invention, or even between the layer of paint and the light source facing it (in other words, the paint according to the invention is coated with at least one layer or colored filter.
    Where appropriate, the substrate may include one or more additional coatings, in particular localized (for example an enamel on the upper face to form simple patterns or logos).
    The article according to the invention also comprises at least one or more light sources and / or one or more heating elements (or heating elements, such as one or more radiant or halogen elements and / or one or more atmospheric gas burners and / or one or more means of induction heating) causing in particular, upon activation, the lighting of the light zones provided, and placed (s) on the underside of the substrate, so as in particular to illuminate the corresponding light zones. The source (s) can be integrated into / coupled to one or more display type structures (for example with light-emitting diodes called "7-segment"), to an electronic control panel with sensitive keys and digital display , etc. The light sources are advantageously formed by light-emitting diodes, more or less spaced apart, possibly associated with one or more optical guides. The diodes are advantageous in the present invention in terms in particular of space, efficiency, durability and resistance to the surrounding conditions (heat ...).
    The diodes can be carried by a support or strip or base, this base can have a surface (flat or inclined) treated and / or made reflective for better light efficiency.
    The assembly of the source (s) (to the plate or to another constituent of the article such as for example the control panel) can be done by welding, clipping, gluing, etc., if necessary by means of another element; for example, diodes can be mounted, welded to a support itself housed at the bottom of a metal profile, by clipping or gluing the profile. The positioning of the source (s) (relative to the plate in particular) is adapted to allow display through the glass ceramic.
    The sources, as well as their power supply and actuation, can be dissociated or not so as to allow simultaneous or separate lighting of the desired lighting zones as required.
    The light source (s) can be triggered by any control system, for example by electromechanical button (s) or by sensitive keys, in particular the light source (s) can be actuated according to a capacitive mechanism by the positioning of a finger on the glass ceramic at the location of (or on) the appropriate activation zone, this activation zone being indicated on the surface of the glass ceramic and corresponding in particular to a light zone according to the invention. The touch of the finger (electrical conductor) changes the capacity, electric charges being transferred to it, the change in capacity being detected by measurement systems, the latter notably triggering the activation of the associated light source or sources.
    Preferably, the article according to the invention comprises at least one luminous zone intended to highlight the operating state or not of at least one heating zone (zone called ON / OFF zone, the savings drawing the pattern to be illuminated in said area being for example in the form of a pictogram symbolizing the start-up). The article according to the invention thus preferably comprises an opacifying coating (such as an enamel deposited for example on the upper face in said zone or a paint, deposited for example on the lower face of the substrate), this coating being located (for example under disc shape) or on most of the relevant face of the substrate, and a saving being made in this opacifying coating according to the chosen pattern (such as the aforementioned ON / OFF pattern). This pattern indicates for example that it is the ON / OFF control key, located for example on the control panel, the activation of this key being done for example according to a capacitive mechanism by the positioning of a finger on the glass ceramic on said button. Activation of this activates an LED emitting a light (for example red in color). The light emitted by this LED is diffused by means of the paint according to the invention situated under the glass ceramic above the light source, the coating of paint in this area being for example of cylindrical shape (or circular or disc shape) , the diameter corresponding for example to that of the sparing), the red light appearing (from above the glass-ceramic substrate) at the spared area.
    The article may possibly comprise, in combination with the light sources at least one waveguide intended to propagate light from one part to another of the article (in particular by total internal reflection or by metallic reflection), the source or sources cooperating with the guide or guides and emitting / being coupled for example by the edge or the edge of the associated guide or guides. The guide (s) are advantageously clear or transparent, and are generally attached (assembled after having been designed separately) on the underside of the substrate. They can be organic and / or plastic (for example polycarbonate or polymethyl methacrylate PMMA), or mineral, in particular glass. They can be secured to the substrate, or to a support on which the article is mounted, by gluing and / or clipping, or by encapsulation, etc. The waveguide allows, among other things, to better conduct light to the desired lighting areas, in particular when the substrate is dark in color. If necessary, the geometry and roughness of the edge of a waveguide can also be worked to allow local and controlled extraction of light.
    The article according to the invention may optionally include, in addition to the substrate provided with the aforementioned coatings, other elements and / or layers. For example, in the case of a module or a baking sheet, the article can be provided with (or associated with) functional element (s) or additional decoration (frame, connector (s), cable (s), control element (s), etc. It can comprise various functional and / or decorative coatings, based on enamel, paint, etc. (for example, one of the faces of the substrate can comprise a layer of at least one enamel, for example of decoration, or of masking, etc.). The substrate or article can also be mounted on an apparatus inside which one or more heating elements are arranged. The invention thus relates to all apparatuses (or devices) for cooking and / or keeping at high temperature comprising at least one article according to the invention (in the form for example of a plate), for example cookers, built-in hobs , etc, the article can include different types of heating elements (gas, radiant, induction, etc.). In addition, the invention is not limited to the manufacture of hobs for cookers or hobs. The articles according to the invention can also be, as specified above, other articles (worktop, consoles, central island, etc.).
    As already mentioned, the present invention also relates to the method for manufacturing the articles according to the invention, in which the glass-ceramic substrate is coated facing at least one light zone with a paint formed from at least one silicone resin and pigment (s), the level of pigment (s) being greater than or equal to 1% and less than 10% by weight of the paint. As already indicated above, the paint is applied to the glass-ceramic substrate obtained beforehand by ceramization.
    For the record, the manufacture of ceramic glass plates is generally carried out as follows: in a melting furnace, the glass of composition chosen is melted to form the glass ceramic, then the molten glass is laminated into a standard ribbon or sheet by passing the glass melted between rolling rolls and the glass ribbon is cut to the desired dimensions. The plates thus cut are then ceramized in a manner known per se, ceramization consisting in baking the plates according to the thermal profile chosen to transform the glass into the polycrystalline material called "vitroceramic" whose coefficient of expansion is zero or almost zero and which withstands thermal shock of up to 700 ° C. Ceramization generally includes a step of gradual rise in temperature to the nucleation domain, generally located in the vicinity of the glass transformation domain, a step of crossing the nucleation interval over several minutes, a further gradual rise of the temperature up to the temperature of the ceramisation stage, the maintenance of the temperature of the ceramisation stage for several minutes then a rapid cooling down to room temperature.
    The application of the paint can be carried out by any suitable and rapid technique making it possible in particular to make flat areas, such as deposit with a brush, with a squeegee, by spraying, electrostatic deposit, soaking, deposit with a curtain, deposit by screen printing, spray, etc., the application preferably being carried out by screen printing, this application being followed if necessary by drying (in the open air or by heat treatment), for example by infrared or in an oven, in particular between 100 and 250 ° C, so as to evaporate at least part of the solvent present, if necessary, fix the coating and allow the article to be handled, the substrate coated with paint then generally being heat treated in order to effect the curing / crosslinking paint and, if necessary, the removal of any remaining solvents. The cooking of the substrate provided with the coating of paint being carried out separately from the operation of ceramization of the substrate (one then speaks of a process with annealing or cooking in recovery), this cooking can in particular be carried out at a temperature suitable for cooking the paint. , this range of temperatures being in particular between 80 and 500 ° C. for the present invention.
    Where appropriate, the method also includes a cutting operation (generally before ceramization), for example by water jet, mechanical tracing with a wheel, etc. followed by a shaping operation (grinding, beveling, ...).
    The present invention and its advantages will be better understood on reading the example which follows, given only by way of illustration and not limitation.
    In this example, the article produced is a flat cooking module comprising a translucent black glass-ceramic plate (substrate), sold under the reference KeraBlack + or KeraVision by the company
    Eurokera, this plate having a smooth upper face and a smooth lower face, the article further comprising a light source fixed under the plate against the latter, this light source being a light-emitting diode (LED). In addition, an opacifying paint composed of 33% by weight of silicone binder, 26% by weight of talc, 26% by weight of a solvent based on xylene and white spirit is deposited by screen printing on the underside of the plate. 15% by weight of black pigments based on graphite and smoke black, the thickness of the deposited layer being of the order of 15 μm. This deposit is made in the form of a flat and a savings in the form of a pictogram indicating activation is practiced in this deposit using corresponding masks in the screen printing screen used for the deposit. The pattern created indicates that it is a control zone (ON / OFF zone), the activation of this zone being carried out using a capacitive mechanism. The deposited layer is then dried at around 220 ° C.
    At the same time, a diffusing paint composition is made from an opaque white paint composition composed of 30% by weight of silicone binder (half formed of silicone resin sold under the reference 249 by the company Dow Corning and half of silicone resin sold under the reference P850 by the company Bayer, 25% by weight of talc, 25% by weight of a solvent based on xylene and white spirit sold under the reference Solvesso 100 by the company ExxonMobile and 20% by weight of white pigments based on TiO 2 marketed by the company Kern will go under the reference Kern will go 300, this composition of opaque white paint then being diluted with a second paint, this time transparent and composed of the same elements as the white paint opaque except pigments, i.e. 37.5% by weight of silicone binder, 31.25% by weight of talc, 31.25% by weight of solvent, in propo 20 parts by weight of opacifying paint for 80 parts by weight of transparent paint. A paint is obtained having the following composition: 36% by weight of silicone binder, 30% by weight of talc, 30% by weight of solvent and 4% by weight of white pigments based on T1O2, these pigments having a size included ( for at least 90% of the particles of these pigments) between 0.1 and 1 pm. The two paints are mixed and the viscosity is adjusted if necessary to be between 1600 and 2100 mPa.s (the viscosity being measured using a Brookfield DV-II + Pro reference device sold by the company Brookfield), by adding, if necessary, the Solvesso 100 reference solvent if the viscosity is too high, or a filler or thickener in the form of Aerosil reference silica sold by the company Evonik if the viscosity is too low.
    The paint obtained is then applied by screen printing in the savings made under the ceramic hob and then dried at 205 ° C, all the layers of paint being then fired at around 450 ° C. The deposition is carried out using a screen printing fabric 90, that is to say having 90 threads per cm, the deposition made using a fabric 32 being comparatively too coarse and that made using a fabric 43 being too thick and too opaque. The deposit is made by overflowing from 2 to 5 cm on the savings left in the layer of opacifying paint where the lighting will be located in the final assembly.
    The thickness of the layer of diffusing paint after curing is 10 μm. Its light transmission is also measured by coating (in the same way as above) a glass-ceramic substrate, this time transparent as indicated previously in the method of measuring the light transmission of the paint. The light transmission obtained for the diffusing paint layer is 46.2%, that for the black substrate of the present example coated with said paint layer being 1.4%. The light diffusion rate for the layer of diffusing paint (on transparent substrate) is at the same time 99%.
    These values are close to those obtained (instead of diffusing paint) with a polymer diffusing pellet (for example made of polyvinyl chloride (PVC)) from 0.2 to 0.60 mm thick, which is bonded under the glass ceramic. or on the light source (this source possibly being encapsulated in PVC), the mounting of this patch being however more complex and the lighting obtained being less homogeneous than with the paint according to the invention, a peak of intensity being observed in particular with this patch above the hot spot or light beam of the LED located below.
    Also comparatively, the light transmission obtained for the opacifying paint layer (undiluted, with a pigment content of 20% by weight) is 19.9%, that for the black substrate of the present example coated with said opacifying paint layer being its share of the order of 0%, these light transmissions (as well as that obtained for the same paint diluted so as to have a rate of pigments of 10% by weight) proving insufficient to obtain, in combination with the rate of diffusion obtained (of the order of 95% in these two cases), sufficient and uniform lighting without dazzling the user.
    An aging and thermal resistance test simulating an accidental situation of forgetting a pan on an induction heating zone was also carried out (the temperatures reached varying between 450 ° C and 600 ° C for a few minutes to a few tens of minutes ), no coloration or degradation being observed on the diffusing paint according to the invention, in contrast to the opacifying paint which undergoes discoloration when the plate is observed on its underside, the discoloration being however not visible on the upper face of the substrate, even when lit.
    The deposited diffusing paint therefore has both good thermal resistance allowing this paint to be used in all areas of the induction hob, from cold areas (control panel) to hot areas (inside the cooking area) , an appropriate combination of maximum light transmission and scattering, ease of implementation and adjustment of characteristics, and moderate cost.
    The articles, in particular plates, according to the invention can in particular be used with advantage to produce a new range of hobs for cookers or hobs or a new range of work tables, consoles, central islands, etc.
    权利要求:
    Claims (20)
    [1" id="c-fr-0001]
    Claims
    1. Glass-ceramic article, intended in particular to be used with at least one light source and / or at least one heating element, said article comprising at least one substrate, such as a plate, made of glass-ceramic, and having at least one zone luminous, said substrate being coated facing said zone with a paint formed of at least one silicone resin and of pigment (s), the level of pigment (s) being greater than or equal to 1% and less than 10% in weight of paint.
    [2" id="c-fr-0002]
    2. Glass-ceramic article according to claim 1, characterized in that the pigments are white pigments, in particular are pigments based on titanium oxides ΠΟ2, the rate of this (these) pigment (s) being preferably from 2 to 6% by weight of the paint, effect pigments being excluded.
    [3" id="c-fr-0003]
    3. Glass-ceramic article according to one of claims 1 to 2, characterized in that at least 50%, preferably at least 75%, or even at least 90% of the pigment particles have a size ranging from 0.1 to 10 μm, in particular from 0.1 to 1 pm.
    [4" id="c-fr-0004]
    4. Glass-ceramic article according to one of claims 1 to 3, characterized in that the paint comprises one or more inorganic or mineral fillers, advantageously insoluble, for example formed from calcium and / or magnesium carbonates, and / or barium, silica or silicates, in particular kaolin and / or talc, at rates of at least 20% by weight and not exceeding 40% by weight of the paint, and preferably at rates ranging from 20 to 35% by weight of the paint.
    [5" id="c-fr-0005]
    5. Glass-ceramic article according to one of claims 1 to 4, characterized in that the silicone resin or resins of the paint are resins chosen from silicone resins modified by the incorporation of at least one radical chosen by the following radicals : alkyl, phenyl, alkenyl, vinyl, allyl, alkynyl and are advantageously non-functionalized by at least the following functional groups or groups: halogen, epoxy, polyester.
    [6" id="c-fr-0006]
    6. Glass-ceramic article according to one of claims 1 to 5, characterized in that the paint is devoid of water or aqueous solvent.
    [7" id="c-fr-0007]
    7. Glass-ceramic article according to one of claims 1 to 6, characterized in that the paint is devoid of glass frit or of components capable of forming together a glassy matrix.
    [8" id="c-fr-0008]
    8. Glass-ceramic article according to one of claims 1 to 7, characterized in that the paint is present on deposit in the form of a dispersion, and is in particular devoid of silica gel or colloidal silica
    [9" id="c-fr-0009]
    9. Glass-ceramic article according to one of claims 1 to 8, characterized in that the paint has the following composition, the proportions being expressed in percentages by weight:
    - silicone resin (s) 25 - 45%, preferably 30-45%
    - pigment (s) 1-10% preferably 2-6%
    - charge (s) 20 - 40% preferably 20-35%
    - solvent (s) 20 - 40% preferably 20-35%
    [10" id="c-fr-0010]
    10. Glass-ceramic article according to one of claims 1 to 9, characterized in that the viscosity on deposition of the paint is between 1500 and 3000 mPa.s.
    [11" id="c-fr-0011]
    11. Glass-ceramic article according to one of claims 1 to 10, characterized in that the thickness of the paint coating is less than 25 pm, in particular between 2 and 20 pm, in particular between 4 and 15 pm, the paint preferably being on the underside of the glass-ceramic substrate.
    [12" id="c-fr-0012]
    12. Glass-ceramic article according to one of claims 1 to 11, characterized in that the paint forms a layer based on polymers.
    [13" id="c-fr-0013]
    13. Glass-ceramic article according to one of claims 1 to 12, characterized in that the paint coating has a light transmission TL greater than 30%, preferably greater than 38%, in particular greater than 40%, and being able to go up to at 60%, and in that its diffusion rate is greater than 90%, in particular greater than or equal to 99%.
    [14" id="c-fr-0014]
    14. Glass-ceramic article according to one of claims 1 to 13, characterized in that the glass-ceramic substrate comprises at least one opacifying coating covering the substrate and within which at least a saving is made in the shape of the pattern or the area luminous to realize, the paint being deposited at the places of the savings.
    [15" id="c-fr-0015]
    15. Glass-ceramic article according to one of claims 1 to 14, characterized in that the substrate comprises two opacifying coatings, in particular two layers of opacifying paint (s), one of the opacifying coatings, deposited under the underside of the substrate vitroceramic, having one or more savings delimiting one or more areas to be lit, the paint according to the invention being applied in the said savings, and the second coating covering the edges of the diffusing paint according to the invention, the paint being taken sandwiched between the two opaque coatings.
    [16" id="c-fr-0016]
    16. Glass-ceramic article according to one of claims 1 to 15, characterized in that the substrate comprises at least one layer or a colored filter on or under the paint, the layer or the colored filter preferably being located on the paint, in particular between the paint and the opposite light source, and / or said paint is colored.
    [17" id="c-fr-0017]
    17. Glass-ceramic article according to one of claims 1 to 16, characterized in that the substrate is of dark appearance, in particular of black or brown appearance, this substrate having a light transmission ranging from 0.8% to 40%, preferably from 0.8% to 5%, in particular from 0.8 to 2%, and an optical transmission of at least 2.5% for a wavelength of 625 nm.
    [18" id="c-fr-0018]
    18. Glass-ceramic article according to one of claims 1 to 17, characterized in that said article or said substrate is a hob or a worktop.
    [19" id="c-fr-0019]
    19. A method of manufacturing a glass ceramic article according to one of claims 1 to 18, characterized in that the glass ceramic substrate is coated facing at least one light area with a paint formed of at least one resin silicone and pigment (s), the level of pigment (s) being greater than or equal to 1% and less than 10% by weight of the paint.
    [20" id="c-fr-0020]
    20. A method of manufacturing a glass ceramic article according to claim 19, characterized in that the paint is applied by screen printing on the glass ceramic substrate, already partially coated or not, advantageously on the underside of said substrate, facing the light zone (s), delimited in particular by savings and over the entire surface delimited by each of said savings or over the entire surface facing said light zones, the screen printing fabric used being chosen so as to have a number of threads per cm between 43 and 120 threads per cm.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP1958481B1|2019-06-19|Transparent or translucent glass ceramic plate and a method for the production thereof
    EP1492737B1|2018-07-11|Glass-ceramic plate
    EP2132490B1|2018-01-17|Glass ceramic plate and method for making same
    WO2018167413A1|2018-09-20|Glass ceramic item with light display
    FR2962192A1|2012-01-06|COOKING DEVICE COMPRISING A GLASS OR VITROCERAMIC PLATE OF THE TYPE HAVING AT LEAST ONE MEANS OF MASKING INTERNAL ELEMENTS COVERED BY THE PLATE
    FR2976683A1|2012-12-21|VITROCERAMIC ARTICLE WITH COLOR LUMINOUS DISPLAY.
    FR3018171A1|2015-09-11|WORK PLAN IN VITROCERAMIC
    WO2015136204A1|2015-09-17|Glass-ceramic worktop of large size
    WO2015136205A1|2015-09-17|Glass-ceramic worktop of large size
    WO2015055953A1|2015-04-23|Glass ceramic item and enamel for coating same
    EP2086899B1|2021-12-08|Manufacturing process for a glass-ceramic plate
    EP2935136B1|2017-06-28|Glass-ceramic article having a luminous display
    EP3755667A1|2020-12-30|Glass-ceramic article
    EP3346875A1|2018-07-18|Glass ceramic worktop
    WO2019158881A1|2019-08-22|Glass-ceramic article
    WO2020126534A1|2020-06-25|Glass-ceramic item
    WO2020127020A1|2020-06-25|Glass-ceramic article
    WO2020114958A1|2020-06-11|Surface-textured glass-ceramic article and process of manufacture
    FR3072958A1|2019-05-03|VITROCERAMIC ARTICLE WITH LAYER AND PROCESS FOR OBTAINING THE SAME
    同族专利:
    公开号 | 公开日
    DE202018003825U1|2018-11-15|
    KR20190124730A|2019-11-05|
    CN110382428A|2019-10-25|
    FR3063723B1|2019-03-22|
    WO2018167413A1|2018-09-20|
    JP2020514234A|2020-05-21|
    EP3596022A1|2020-01-22|
    US20200189969A1|2020-06-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20050214521A1|2004-03-26|2005-09-29|Florent Frederic H|Glass-ceramic and glass plates, heating plates, and preparation|
    WO2014027161A1|2012-08-14|2014-02-20|Eurokera S.N.C.|Glass ceramic item with coloured light display|
    FR3040768A1|2015-09-08|2017-03-10|Eurokera|WORK PLAN IN VITROCERAMIC|
    FR2657079B1|1990-01-12|1993-04-09|Corning France|VITROCERAMIC PRECURSOR GLASSES, PROCESS FOR CONVERTING THESE VERY LOW OR NULL DILATION VITROCERAMIC GLASSES AND VITROCERAMIC MATERIALS OBTAINED.|
    CN104691056A|2004-03-26|2015-06-10|欧罗克拉公司|Glass-ceramic and glass plates and heating plates and its manufacture|
    WO2005092811A2|2004-03-26|2005-10-06|Eurokera|Reinforcement of glass-ceramic or glass plates and reinforced plates|
    FR2868066B1|2004-03-26|2006-06-23|Snc Eurokera Soc En Nom Collec|VITROCERAMIC AND GLASS PLATES, HEATING PLATES, PREPARATION|
    JP4311417B2|2006-07-06|2009-08-12|鳴海製陶株式会社|Glass top plate for electromagnetic cooker and method for manufacturing the same|
    US8127571B2|2006-10-27|2012-03-06|Eurokera S.N.C.|Method of refining a lithium aluminosilicate glass and glass-ceramic obtained|
    JP2010021111A|2008-07-14|2010-01-28|Narumi China Corp|Glass top plate for heating cooker|
    DE102008058318B3|2008-11-21|2010-06-17|Schott Ag|Scratch-resistant silicone coating for cooking surfaces made of glass or glass ceramic|
    JP5338304B2|2008-12-25|2013-11-13|鳴海製陶株式会社|Glass top plate for heating cooker|
    FR2960233B1|2010-05-19|2012-08-10|Eurokera|PREPARATION OF AN ARTICLE IN A GLASS OR A VITROCERAMIC WITH IMPROVED COATING AND SAID ARTICLE|
    FR2967236B1|2010-11-04|2014-10-10|Eurokera|LUMINOUS VITROCERAMIC ARTICLE|
    FR2975391A1|2011-05-16|2012-11-23|Eurokera|QUARTZ-BETA VITROCERAMICS WITH CONTROLLED TRANSMISSION CURVE; ARTICLES IN VITROCERAMIC LENSES, PRECURSORIC GLASSES.|
    FR3000057B1|2012-12-21|2015-01-09|Eurokera|VITROCERAMIC ARTICLE WITH LUMINOUS DISPLAY|FR3090621A1|2018-12-20|2020-06-26|Eurokera S.N.C.|VITROCERAMIC ARTICLE|
    FR3090620B1|2018-12-20|2021-09-03|Eurokera|ARTICLE vitroceramic|
    DE102020201483A1|2020-02-06|2021-08-12|B. Braun Melsungen Aktiengesellschaft|Non-return valve, drip chamber, port for needle-free metering of a liquid, non-return valve, infusion or transfusion system and method for manufacturing a non-return valve|
    法律状态:
    2018-03-22| PLFP| Fee payment|Year of fee payment: 2 |
    2018-09-14| PLSC| Search report ready|Effective date: 20180914 |
    2020-03-25| PLFP| Fee payment|Year of fee payment: 4 |
    2021-03-31| PLFP| Fee payment|Year of fee payment: 5 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1752034|2017-03-13|
    FR1752034A|FR3063723B1|2017-03-13|2017-03-13|VITROCERAMIC ARTICLE WITH LUMINOUS DISPLAY|FR1752034A| FR3063723B1|2017-03-13|2017-03-13|VITROCERAMIC ARTICLE WITH LUMINOUS DISPLAY|
    KR1020197026535A| KR20190124730A|2017-03-13|2018-03-12|Glass ceramic articles with light display|
    EP18712993.7A| EP3596022A1|2017-03-13|2018-03-12|Glass ceramic item with light display|
    US16/492,794| US20200189969A1|2017-03-13|2018-03-12|Glass ceramic item with light display|
    CN201880018088.6A| CN110382428A|2017-03-13|2018-03-12|The glass and ceramic product shown with light|
    DE202018003825.3U| DE202018003825U1|2017-03-13|2018-03-12|Glass ceramic articles with illuminated display|
    JP2019550197A| JP2020514234A|2017-03-13|2018-03-12|Glass-ceramic article with optical display|
    PCT/FR2018/050567| WO2018167413A1|2017-03-13|2018-03-12|Glass ceramic item with light display|
    [返回顶部]