• 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 generally relates to a culinary article whose outer face is provided at the bottom of a hybrid coating, which is compatible with use on a glass-ceramic or induction plate. The present invention also relates to a method for making an article.
    公开号:FR3014890A1
    申请号:FR1362522
    申请日:2013-12-12
    公开日:2015-06-19
    发明作者:Aurelien Berrux
    申请人:SEB SA；
    IPC主号:
    专利说明:

    [0001] The present invention relates generally to a culinary article whose outer face is provided at the bottom with a hybrid sol-gel coating, which is compatible with the use of the invention. on a ceramic hob or induction hob. The present invention also relates to a method for making an article.
    [0002] For the purposes of the present invention, sol-gel coating is understood to mean a sol-gel synthesized coating from a solution based on precursors in the liquid phase, which is converted into a solid by a series of chemical reactions (hydrolysis). and condensation) at low temperature. The coating thus obtained can be either organo-mineral or entirely mineral. For the purposes of the present invention, the term "hybrid coating" means a coating incorporating a silicone resin used alone or as a mixture, a polyester silicone resin used alone or as a mixture or a mixture of a silicone resin (polysiloxane) and a silicone resin. a silane (or metal alkoxide), or the mixture of a polyester silicone resin and a silane (or metal alkoxide). The sol-gel coating compositions are known to be particularly fluid and therefore unsuitable for screen printing application. Such compositions also do not allow the suspension of a dense charge (for example of metallic type) in the formulation.
    [0003] To remedy these problems, the Applicant has developed a method for manufacturing a hybrid coating on a support, wherein the nature of the hybrid composition is adapted to allow its application to the support by screen printing. A known solution to allow the application by screen printing of a sol-gel composition based on metal alkoxide precursors, consists in modifying the rheology. Thus, the European patent application EP 2505619 describes a method of manufacturing a sol-gel coating in which the step of applying the sol-gel composition can be performed by screen printing by adding a cellulose in the composition of the coating and the replacement of the alcohol generated during the hydrolysis-condensation phase of the metal alkoxide precursor (s) of the composition with a heavier solvent such as a glycol. The viscosity of the sol-gel composition is therefore modified during its synthesis. This change in the viscosity of the sol-gel composition also makes it possible to incorporate dense beads (such as metal balls) into the composition, allowing them to remain in suspension and to slow down or even stop sedimentation. beads in the composition.
    [0004] However, the method of manufacturing a sol-gel coating as described in the European patent application EP 2505619 is complex (and therefore expensive) and difficult to integrate into a production flow. Indeed, it requires an additional solvent exchange step. In addition, such a coating requires, for use as an outer coating of cookware, the introduction of metal balls protruding from the sol-gel coating being distributed homogeneously on its surface. Indeed, it is known to those skilled in the art that sol-gel coatings, and in particular those developed alkaline, have a high hardness, which is a major disadvantage when using hobs in vitroceramic: the friction of the sol-gel coating on the plate is a glass-on-glass type friction, leading to the appearance of scratches very detrimental not only to the aesthetics, but also and especially to the proper operation of the hob . The present invention therefore aims at providing the consumer with an article, in particular a culinary item, whose outer face is provided with a hybrid coating, which is both compatible with use on a glass-ceramic plate and does not require the introduction of balls. , and can be achieved through a simple, inexpensive and easily integrable process into a workflow. More particularly, the present invention relates to an article comprising a support having two opposite faces, at least one of which is provided with a sol-gel coating layer in the form of a continuous film of a material. sol-gel comprising a matrix of at least one metal polyalkoxylate, characterized in that the article according to the invention further comprises a hybrid coating comprising at least a first screen-printing layer completely or partially covering said coating layer 30- gel, said first screen printing layer being made of a hybrid material comprising a matrix formed from a silicone resin, and preferably a polyester silicone resin. The hybrid coating according to the invention has the advantage of not scratching the vitroceramic hotplates, without requiring the presence of beads while having a glossy and smooth visual appearance, and good heat resistance, which makes it particularly attractive. adapted to decorate the outer surface of the bottom of the cookware.
    [0005] As a silicone resin that may be used in the context of the present invention, mention may be made especially of the resin marketed by the company Wacker under the trade name SILRES® 610. As a polyester-silicone resin that can be used in the context of the present invention, it is possible to mention mention in particular the resin sold by the company TEGO under the brand SILIKOFTAL®. Advantageously, the first screen-printing layer is partially covered by a second discontinuous screen-printing layer, which is also constituted by a hybrid material comprising a matrix formed from a silicone resin (preferably made of polyester-silicone resin) as defined above. Advantageously, the matrix of the hybrid material of the screen printing layer (or, where appropriate, the screen printing layers) is also formed from at least one metal alkoxide or silane, in addition to said silicone resin or said polyester silicone resin. . Preferably, it is a metal alkoxide, preferably prehydrolysed, or a silane, preferably prehydrolysed.
    [0006] By metal alkoxide is meant a material of the type RiMX (n_i) with M metal or transition metal for example Al Ce Zr Ti, Sn, V, Nb, Hf, Mg or Ln (Lanthanides) n valence of the metal X hydrolyzable group Xi identical or different R alkyl, phenyl or organofunctional R 1 identical or different n-1 By silane is meant a material of the type RiSiX (4_i) with X hydrolyzable group Xi identical or different R alkyl group, phenyl or organofunctional Ri identical or different i = 0 , 1,2,3. The pre-hydrolysed silanes make it possible to increase the silicon content in the hybrid coating.
    [0007] The higher this ratio, the higher the mechanical properties and the flame resistance. Advantageously, the hybrid material of the coating according to the invention may further comprise at least one pigment filler and / or a reinforcing filler. As pigment fillers that may be used in the context of the present invention, mention may be made especially of mica coated or not, titanium dioxide, mixed oxides (spinels), aluminosilicates, iron oxides, carbon black, and the like. carbon, perylene red, metallic flakes, pigments and thermochromic organic dyes, and mixtures thereof.
    [0008] These fillers have the main effect of bringing color, and furthermore to improve the diffusion of heat, to avoid hot spots and to have lubricating properties.
    [0009] For the purposes of the present invention, the term "reinforcing fillers" means fillers which are used to further improve the scratch resistance of the coating during its friction on the glass-ceramic or induction plates.
    [0010] The reinforcing filler of the hybrid sol-gel coating may furthermore advantageously comprise metal balls, a portion of which protrudes from the coating and is homogeneously distributed over its surface.
    [0011] Ball means for the purposes of the present invention rounded charges having substantially the shape of a sphere. The balls flush with the surface of the hybrid coating according to the invention have the effect of limiting the contact with the glass-ceramic or induction plate by creating a "ball-bearing" type effect. Thus, the surface density of the metal balls which protrude from said coating may advantageously be between 50 and 300 charges / mm 2 to obtain such an effect. (cf above) Below a surface density of 50 charges / mm 2, the weight distribution of the coating according to the invention can not be uniform. Above a surface density of 300 charges / mm 2, there is a decrease in thermal shock resistance and a loss of gloss.
    [0012] Preferably, the surface density of the balls which protrude from said outer coating, sol-gel will be between 100 and 250 charges / mm 2. This range makes it possible to maintain a good ease of application and a maximum "ball-bearing" type effect. The beads constituting the reinforcing filler may be of different types, for example glass or metal (or metal alloy). Advantageously, in the context of the present invention, stainless steel balls such as those marketed by the company HOGANAS under the trade name 316 HIC 15 pm. When "reinforcing" beads are present in the sol-gel coating, their quantity and granulometry are crucial because they must be flush with the surface of the coating without distorting its appearance and while maintaining homogeneity. As regards the quantity of beads in a screen printing layer, this may advantageously comprise between 0.01% and 5% by weight of beads. Below 0.01%, the effect of the beads on the properties of the hybrid sol-gel coating while above 5%, the cohesion between the beads and the hybrid coating according to the invention is impaired. As regards the particle size of the balls, their diameter is preferably between 5 and 30 μm, their mean diameter being between 15 and 20 μm, while the screen printing thickness is between 5 and 20 μm, so that a portion of the beads are flush with the surface of the coating layers. All the balls engaged to a depth that is at least equal to their diameter, are perfectly anchored in the hybrid coating. The article of the invention may advantageously be a culinary article having a support with an inner face adapted to receive food and an outer face intended to be disposed on the side of a heat source, the outer face being successively coated with the layer of sol-gel coating and the one or more hybrid coating layer (s).
    [0013] The support used in the context of the present invention may advantageously be made of a material selected from metals, glass, plastics and ceramics. As metallic supports that can be used in the context of the present invention, mention may advantageously be made of monolayer supports made of aluminum or aluminum alloy, of cast aluminum, of stainless steel, of cast iron or of copper, or the multilayer supports comprising, from the outside to the inside, the following layers ferritic stainless steel / aluminum / austenitic stainless steel or even stainless steel / aluminum / copper / aluminum / austenitic stainless steel, or a blanket of aluminum for casting, aluminum or aluminum alloys lined with a stainless steel outer bottom. The present invention further relates to a method for producing an article as defined in any one of claims 1 to 13, said method comprising the following steps: a) a step of providing a support having at least two faces opposite; b) a step b1) of preparing an aqueous sol-gel composition comprising at least one sol-gel precursor of metal alkoxide type, followed by a step b2) of hydrolysis of said sol-gel precursor by introduction of water and an acidic or basic catalyst, and finally followed by a condensation reaction (b3) causing the formation of an alcohol to obtain a sol-gel composition; c) a step of preparation cl) of a hybrid composition comprising in solvent medium at least one silicone resin which is preferably a polyester silicone resin, to obtain a hybrid composition (the step cl being possibly followed by a step c2 ) condensation when the hybrid composition further comprises a silane); d) applying on one of the faces of the support a layer of the sol-gel composition to form a sol-gel coating layer in the form of a continuous film; and optionally drying the sol-gel coating layer (for example, infrared radiation drying at a temperature of between 50 ° C and 100 ° C) e) applying by screen printing to said sol-gel coating layer at least one Hybrid composition layer, followed by optional drying (e.g. infrared radiation drying at a temperature between 50 ° C and 100 ° C); and f) firing said layer at a temperature between 200 ° C and 300 ° C. The method according to the invention is simple and easily integrable into the production flow. The support on which the hybrid composition according to the invention is produced can be: either a support having the final shape of a culinary article, with an inner face capable of receiving food and an outer face intended to be disposed on the side; 10 of a heat source, - or a disc (therefore substantially planar) which is previously coated by the hybrid composition according to the invention, shaped, for example by cold stamping to obtain a cap, and then cut . According to an advantageous embodiment of the method according to the invention the face of the support, intended to be coated by the hybrid coating according to the invention, may be previously subjected to a surface treatment. It is preferably a cold plasma surface treatment which makes it possible to improve the adhesion of the hybrid sol-gel coating to the surface on which it is deposited (article support or coating layer). conventional gel based on metal polyalkoxylate 25 deposited on the support by spraying, called adhesion layer: see examples). The cold plasma surface treatment can be advantageously carried out by working for example with ammonia in the plasma. Another possibility for improving the adhesion of the sol-gel coating to the surface on which it is deposited is to create -N groups on the surface with a N2H2 plasma to establish silazane bonds (Si-N) between the support or the intermediate coating layer and screen printing. Finally, to improve the adhesion of the sol-gel coating to the surface on which it is deposited (either the support or the adhesion layer), it is still possible to use a coupling agent, for example an aminosilane such as 3 aminopropyl-triethoxysilane (APTES), which can either be incorporated directly into the polyester silicone resin (to be grafted to the polyester of the resin, the silane part then being able to react by condensation with the surface hydroxyls). sol-gel coating), or - deposit on the sol-gel coating in the presence of anhydrous toluene. Step b) of producing the sol-gel composition is carried out in a conventional manner, for example as described in the French patent application FR 2973390. For the preparation of the aqueous sol-gel composition, it will preferably be used as a precursor a metal alkoxide selected from - the precursors having the general formula M1 (OR1) 25 the precursors corresponding to the general formula M2 (OR2) (n-1) R2 and the precursors corresponding to the general formula M3 (OR3) ( n-2) R3'2, with: R1, R2, R3 or R3 'denoting an alkyl group, R2' denoting an alkyl or phenyl group, n being an integer corresponding to the maximum valence of the metals M1, M2 or M3 , M1 M2 or M3 denoting a metal, a transition metal or a non-metal selected from Si, Zr, Ti, Sn, Al, Ce, V, Nb, Hf, Mg or Ln (Lanthanides), Advantageously, the metal alkoxide Solution 5 SG is an alkoxysilane. As alkoxysilanes that may be used in the SG solution of the process of the invention, mention may especially be made of methyltrimethoxysilane (MTMS), tetraethoxysilane (TEOS), methyltriethoxysilane (MYES), dimethyldimethoxysilane, and mixtures thereof. Preferably, the alkoxysilanes MIES and TEOS will be used because they have the advantage of not containing methoxy groups. In fact, the hydrolysis of methoxy leads to the formation of methanol in the sol-gel formulation, which, in view of its toxic classification, requires additional precautions during application. In contrast, the hydrolysis of the ethoxy groups only generates ethanol having a more favorable classification and therefore less restrictive use requirements for the sol-gel coating. Embodiment c) of the hybrid composition comprises the preparation cl) of a hybrid composition comprising in solvent medium at least one silicone resin (which is preferably a polyester silicone resin) to obtain a hybrid composition, the step cl being able to be optionally followed by a condensation step c2) when the hybrid composition further comprises a silane. The silicone resin, and optionally the polyester silicone resin, are as defined above. The solvent medium may advantageously comprise [at least one light organic solvent as a diluent and at least one heavy organic solvent as a humectant. These solvents (both heavy and light solvents) allow the hybrid composition (also called "screen printing ink") not to dry in the mesh of the screen screen (thanks to the action of the heavy solvent) and to obtain a faster drying of the composition at the surface to produce multilayer screen printing (thanks to the rapid evaporation of the light solvent).
    [0014] The heavy solvents used in the hybrid composition according to the present invention can advantageously be chosen from polyols (in particular diols, ester-diols, ether-diols or polyphenols) and terpene derivatives (for example terpineol). The heavy organic solvents according to the invention typically have a high molecular weight (equal to or greater than 100 g / mol) and a high boiling point (especially equal to or greater than 150 ° C). The light solvents used in the composition The sol-gel hybrid according to the invention may advantageously be chosen from polar solvents having a boiling point of less than or equal to 150 ° C. The light solvent used is preferably xylene since it is already present in the polyester silicone resin. This is also soluble in esters, ketones and glycol ethers. Step c1) of preparing the hybrid composition may advantageously comprise the addition of one or more silanes, which are preferably previously hydrolysed or hydrolysed in situ. The silanes are as defined above. The addition of pre-hydrolysed silanes makes it possible to increase the silicon content in the hybrid coating according to the invention. The process according to the invention may advantageously comprise a step b ') of adjusting the viscosity of the hybrid composition to a value of between 0.2 Pa s and 5 Pa s (between 2 and 50 Poises), and preferably at a value between 0.5 Pa s and 2 Pa s (between 5 and 20 Poises). For this purpose, the hydride composition may advantageously be thickened using a modified or unmodified cellulose, and preferably an ethylcellulose (for example that marketed under the Dow Ethocel STD300® trademark) in order to increase it. viscosity and facilitate deposition by screen printing. The addition of other organic thickeners of a different nature, such as xanthan gum, or clays (for example that marketed under the trademark Bentone SD2) or thixotropic rheological additives of modified urea type, may also be used. envisaged to adjust the rheology of the desired screen printing ink. It is also possible to add a pigment charge and / or a reinforcing filler to the hybrid composition just after step c). The pigmentary (s) and / or reinforcing fillers (s) are as defined above. The aqueous sol-gel composition may be applied in monolayer or multilayer, on the support (by condensation hydrolysis of metal alkoxide precursors). The hybrid composition may be applied in monolayer or multilayer, on the sol-gel coating layer based on metal polyalkoxylate (by hydrolysis condensation of metal alkoxide precursors) previously applied by spraying, and optionally dried.
    [0015] After application of the various layers of sol-gel composition based on precursor (where appropriate) and hybrid sol-gel composition according to the invention, a co-firing phase of the various layers of sol gel coating may be carried out in an oven conventional convection 10 in a conventional atmosphere, inert or oxidizing. This cooking should be carried out at a cooking temperature of between 200 ° C and 300 ° C. Other advantages and features of the present invention will result from the description which follows, given by way of nonlimiting example and with reference to the examples and corresponding appended figures: FIG. 1 represents a diagrammatic sectional view of a culinary article according to the prior art provided with a completely sol-gel coating, as described in the French patent application FR 2973390 belonging to the applicant. - Figure 2 shows a schematic sectional view of a culinary article holder according to the invention according to a second embodiment. - Figure 3 shows a schematic sectional view of a culinary article holder according to the invention according to a third embodiment. The identical elements shown in FIGS. 1 to 3 are identified by identical reference numerals.
    [0016] In these examples, unless otherwise indicated, all percentages and parts are by weight. In Figures la and lb appended, there are shown two portions of cookware 1 each comprising a support 2 of aluminum or stainless steel, having two opposite faces 21 (inner side) and 22 (outer face). The outer face 22 is covered with a continuous film 4 of sol-gel coating, according to the teaching of the patent application FR 2973390. In the variant illustrated in the figure the annexed (corresponding to the conditions of the comparative example 1), the sol-gel coating does not comprise metal balls, whereas in the variant illustrated in FIG. 1b annexed, the sol-gel coating comprises metal balls (corresponding to the conditions of Comparative Example 2), with a first sol-gel layer 4 without beads and a second layer 41 applied by screen printing and comprising metal balls. The article illustrated in the appended FIG. 2 is an article according to the invention, which is different from the article of FIG. 1 in that a hybrid coating film 32 is deposited on a continuous film 31 of soil coating. gel based on metal polyalkoxylate (also called adhesion layer). The culinary articles obtained by the process of the invention with the experimental conditions (compositions) of Examples 1, 2, 4 and 5 are illustrated in Figure 2. In the variant illustrated in Figure 3 attached, the film 32 of hybrid coating comprises metal balls 31, 311, some of which 411 protrude from the surface of this layer 32. The cookware obtained by the method of the invention with the experimental conditions of Examples 3 and 6 are illustrated in Figure 2. Figures 1 to 3 also show that the inner surface 21 of the support 2 of the culinary article can be coated with a release layer 5 (eg sol-gel-ceramic or PTFE.) Advantageously, the adhesive layer 31 covers the entire outer face 22 of the cap 2 (not shown in the figures), while the hybrid coating layer according to the invention is applied only in the area of the bottom 2 of the article 1. The adhesion layer 31 in the sol-gel coating (likewise the sol-gel coating 4 according to the prior art) can be applied by spraying, immersion dipping ("dip coating") or by spin coating; while the silkscreen sol-gel coating layer 32 is applied by screen printing. When screen printing the hybrid composition for forming the screen printing layer 32, it is pushed through the meshes of a screen by means of a doctor blade which deposits the balls 41, 411 in the screen. sol-gel layer 32. The sol-gel coating layer 31 (or adhesion layer) and the hybrid layer according to the invention 32 are fired simultaneously at a temperature of the order of 150 ° C. to 350 ° C. . EXAMPLES Aluminum or stainless steel support products; sol-gel precursors; resin sold by the company WACKER under the trademark SILRES® 610. polyester silicone resin that can be used in the context of the present invention, mention may be made in particular of the resin marketed by the company TEGO under the trade name SILIKOFTAL®. prehydrolysed silanes (TEOS MIES, stainless steel balls marketed by the company HOGANAS under the trade name 316 HIC 15} Tests Flame resistance: The coating is subjected to the action of the flame of a Bünsen nozzle for 20 seconds It is cooled by quenching with cold water, after which the flaming of the coating is evaluated, the overall appearance of the coating is evaluated, in particular the presence of traces of oxidation (generally white / brown) or carbonization (usually black) Adhesion test (from the EN 10209 test) This is in fact the Erichsen EN 10209 test for enamels and applied to sol-gel coatings. shock using a warhead by potential energy.After the test, the residual cohesion of the coating is analyzed on its metal support.
    [0017] Abrasion test (from the NFD 21-511 standard test) The abrasion resistance of a sol-gel coating formed (hybrid according to the invention or conventional sol-gel according to the prior art) is evaluated in subjecting it to the action of a SCOTCH BRITE abrasive pad (trademark) green. The abrasion resistance of the coating is qualitatively estimated as a function of the number of buffer passes necessary to create the first scratch (corresponding to the appearance of the metal constituting the support).
    [0018] EXAMPLES CARRIED OUT (compositions and experimental conditions With regard to Examples 1 to 6 according to the invention and Comparative Examples 1 and 2, a sol-gel composition SG1 based on metal alkoxide precursors, the composition of which is indicated in FIG. Table 1 below This composition forms, after coating on the support, the sol-gel adhesion layer 31 under the hybrid coating 3 according to the invention (for the examples according to the invention 1 to 6) or in a conventional sol-gel coating obtained from metal alkoxide precusors (Comparative Examples 1 and 2). Table 1: Components Percentage (%) Precursor 80 to 97% of the general formula M2 (OR2) (n-1) R2 T Precursor answering the 0 to 20% general formula M3 (OR3) (n-2) R3 T 2 acid or basic catalyst 0.1 to 5% water 1 to 10% Chelating agent 0 to 10% (for example an alcohol) EXAMPLE 1 With regard to Example 1 according to the invention, Hybrid bumper SGH1 composition according to the invention, the silicone resin containing SILRES® 610 from Wacker, or Plain bearing silanes, whose composition is shown in Table 2 below. This composition forms, after application to the sol-gel layer 31 by screen printing, a screen printing layer 31 of hybrid coating. Example 1 is illustrated in Figure 2.
    [0019] Table 2: Components Percentage (%) SILRES® 610 40 to 70% Solvents: 5 to 20% Xylene, butyl acetate (80/20) Charge: alumina 5 to 20% Black mineral pigments: 5 to 20% Iron oxide Example 2 With reference to Example 2 according to the invention, a hybrid SGH2 composition according to the invention containing silicone resin SILRES® 610 from Wacker, without beads, is prepared. but with silanes, the composition of which is indicated in Table 3 below. This composition forms, after application on the sol-gel layer 31 by screen printing, a screen printing layer 31 of hybrid coating (the thickness of which is typically of the order of 10 microns after firing). Example 2 is also illustrated in Figure 2.
    [0020] Table 3: Components Percentage (%) SILRES® 610 40 to 70% Silane: 5 to 20% aminopropylsilane Solvents: 5 to 20% Xylene, butyl acetate (80/20) Charge: alumina 5 to 20% Black mineral pigments: 5 to 20% Iron oxide, FeCrCu oxide Rheological additive 0 to 5 cellulose% EXAMPLE 3 With regard to Example 3 according to the invention, a hybrid SGH3 composition according to the invention, containing SILRES silicone resin, is prepared. ® 610 from Wacker, with beads and silanes, the composition of which is shown in Table 4 below. This composition forms, after application to the sol-gel layer 31 by screen printing, a screen printing layer 31 of hybrid coating. Example 3 is illustrated in FIG.
    [0021] Table 4: Components Percentage (%) SILRES® 610 40 to 70% Silane: 5 to 20% aminopropylsilane Solvent: 5 to 20% Xylene butyl acetate Loads: 5 to 20% alumina Black mineral pigments: 5 to 20% iron, FeCrCu oxide Stainless steel balls 2 to 15% Rheological additive 0 to 5% cellulose EXAMPLE 4 With regard to Example 4 according to the invention, a hybrid sol-gel SGH4 composition according to the invention is prepared, containing SILKOFTAL® Silicone Silicone Resin from TEGO without beads and without silanes, the composition of which is shown in Table 5 below. This composition forms, after application to the sol-gel layer 31 by screen printing, a screen printing layer 31 of hybrid coating. Example 4 is also illustrated in Figure 2. Table 5: Components Percentage (%) SILIKOFTAL® 40 to 70% Solvents: 5 to 20% Xylene, Butyl acetate 80/20 Charge: 5 to 20% Alumina Mineral Pigments blacks: 5 to 20% Iron oxide, FeCrCu oxide Rheological additive 0 to 5% cellulose EXAMPLE 5 With regard to Example 5 according to the invention, a hybrid sol-gel SGH5 composition according to the invention, containing SILKOFTAL® polyester silicone resin from TEGO without beads but with silanes, the composition of which is indicated in Table 6 below. This composition forms, after application to the sol-gel layer 31 by screen printing, a screen printing layer 31 of hybrid coating. Example 5 is also illustrated in FIG. 2. Table 6: Components Percentage by weight (%) SILIKOFTAL® 40 to 70% Silane: aminopropylsilane 5 to 20% Solvents: 5 to 20% Xylene, butyl acetate 80/20 Charge: 5 to 20% Alumina Black mineral pigments: 5 to 20% Iron oxide, FeCrCu oxide Rheological additive 0 to 5% cellulose EXAMPLE 6 With regard to Example 6 according to the invention, a sol-gel composition is prepared Hybrid SGH6 according to the invention, containing SILIKOFTAL® polyester silicone resin from TEGO, with beads and silanes, the composition of which is indicated in Table 7 below. This composition forms, after application to the sol-gel layer 31 by serigraphy, a screen printing layer 31 of hybrid coating. Example 6 is illustrated in FIG. 3. Table 7: Components Percentage by weight (%) SILIKOFTAL® 40 to 70% Silane: aminopropylsilane 5 to 20% Solvents: 5 to 20% Xylene, butyl acetate 80/20 Charge: 5 at 20% Alumina Black mineral pigments: 5 to 20% Iron oxide, FeCrCu oxide Stainless steel balls 2 to 15% Rheological additive 0 to 5% cellulose COMPARATIVE EXAMPLE 1 A sol gel composition SGC1 based on 5 metal alkoxide precursors and not containing metal beads, the composition of which is indicated in US Pat. No. 6,863,923 to Example 3. COMPARATIVE EXAMPLE 2 A sol-gel coating SGC1 based on metal alkoxide precursors and comprising stainless steel, in accordance with the teaching of FR 2973390, the composition of which is indicated in Table 8 below. Table 8: Components Percentage mass (%) Resin derivatives or 20 to 50% terpene 30 to 50% modified sol gel composition Mineral pigments 0 to 10% Spherical fillers 5 to 30% Stainless steel 20 The modified sol-gel composition for the paste Screen printing is obtained as follows: as for the sol-gel adhesion composition, starting from an initial sol-gel composition based on a metal alkoxide precursor as defined above; this metal alkoxide is then hydrolysed in a reactor in the presence of water and an acid or a base (preferably hydroxide of Na, K alkali and alkaline earth and there is formation of alcohol by a reaction of condensation, o filtration of the sol-gel composition thus obtained may be necessary if grains have been formed (for example generation of agglomerates formed in situ during the condensation hydrolysis of the metal alkoxide precursors, especially if it is carried out alkaline ) during the condensation hydrolysis reaction; the alcohol thus generated during the hydrolysis-condensation reaction is removed from the sol-gel composition by evaporation / distillation (improved by vacuum drawing) and is then replaced; by a glycol or a terpene derivative (terpineol) to form a modified sol-gel composition, the modified sol-gel composition is then mixed with a cellulose (Dow Ethocel STD 20C) in order to form a modified sol-gel composition; n increase the viscosity and facilitate application by screen printing. A target viscosity of 0.5 to 5 Pa.s. (between 5 and 50 poles) is targeted. The addition of other organic CMC-type binders, xanthan gum may be useful for adjusting the desired rheology of screen printing paste; In a final step, the metal fillers (for example Hoganas 316 HIC15} gym) are added by dispersion and the charged screen printing paste is obtained.
    [0022] Results of Tests Performed The substrates coated with each of Examples 1 to 6 according to the invention and Comparative Examples 1 and 2 are subjected to the tests of resistance to flame, adhesion and abrasion. The results for these different tests are shown in Table 10 below.
    [0023] Table 10 (Results) Examples Screen Printing Ability Flame Adhesion Abrasion 1 acceptable acceptable. Good Good SG1 + SGH2 (Fig. 2) 2 acceptable acceptable. Good Very good SG1 + SGH2 (Fig. 2) 3 acceptable acceptable. Good Very good SG1 + SGH3 (Fig. 3) 4 Excellent Good Good Good SG1 + SGH4 (Fig. 2) Excellent Very good Good Very good SG1 + SGH6 (Fig. 2) 6 Excellent Very good Good Good SG1 + SGH6 (Fig. 3) Comparative 1 Excellent Excellent Excellent Not good SG1 + SGC1 (Fig. La) Comparative 2 Excellent Excellent Excellent SG1 + SGC2 scratch (Fig. Lb) The results in Table 10 show that the hybrid coatings according to the invention (Examples 1 to 6) can be applied by screen printing, and overall have acceptable adhesion to the underlying sol-gel coating. Their flame resistance properties are also good. On the other hand, unlike conventional sol-gel coatings based on metal alkoxide precursors (Comparative Examples 1 and 2), they resist abrasion and can therefore be used on glass-ceramic plates, without necessarily adding metal beads (cf. Examples 1, 2, 4 and 5). Comparison of Examples 1 and 2 (single silicone resin) on the one hand and 4 and 5 (polyester silicone resin) on the other hand shows that the addition of silane in the hybrid coating composition improves the abrasion resistance. Comparison of Examples 2 and 3 (Silicone Resin with Silanes) on the one hand and 4 and 5 (Silicone Silicone Resin with Silane) on the other hand shows that the addition of beads in the sol-gel hybrid coating composition containing already silanes further improves the abrasion resistance. Comparison of Examples 1 (single silicone resin) and 3 (polyester silicone resin) on the other hand shows that the passage of a single silicone resin to a polyester silicone resin makes it possible to further improve the screen printing ability.
    权利要求:
    Claims (27)
    [0001]
    REVENDICATIONS1. Article (1) comprising a support (2) having two opposite faces (21, 22), at least one of which is provided with a layer (31) of sol-gel coating in the form of a continuous film a sol-gel material comprising a matrix of at least one metal polyalkoxylate, characterized in that said article (1) further comprises a hybrid coating (3) comprising at least one first (32) screen-printing layer completely covering or partially said sol-gel coating layer (31), said first screen printing layer (32) being made of a hybrid material comprising a matrix formed from a silicone resin.
    [0002]
    The article (1) according to claim 1, wherein the silicone resin is a polyester silicone resin.
    [0003]
    The article (1) according to claim 1 or 2, wherein said first screen printing layer (32) is partially covered by a discontinuous second screen layer (33), which is also made of a hybrid material comprising a matrix formed of from a silicone resin or, where appropriate, a polyester silicone resin. 30
    [0004]
    4. Article (1) according to any one of the preceding claims, wherein the matrix of the hybrid material of the one or more layers (32, 33) serigraphic is also formed from at least one silane and / or from minus a metal alkoxide, besides said silicone resin.
    [0005]
    5. Article (1) according to claim 4, wherein said silane and / or said metal alkoxide are prehydrolysed.
    [0006]
    6. Article (1) according to claim 4 or 5, wherein said matrix of the hybrid material of the one or more layers (32, 33) serigraphic further comprises at least one pigment filler and / or a reinforcing filler.
    [0007]
    7. Article (1) according to claim 6, wherein the pigment load is selected from coated mica or not, titanium dioxide, mixed oxides (spinels), aluminosilicates, iron oxides, carbon black, perylene red, metallic flakes, pigments and thermochromic organic dyes, and mixtures thereof.
    [0008]
    8. Article (1) according to claim 6 or 7, wherein the reinforcing filler comprises metal balls (41, 411, 42, 421), part of which (411, 421) protrudes from said hybrid sol-gel coating. (3) homogeneously distributed on its surface. 30
    [0009]
    9. Article (1) according to claim 8, wherein the surface density of the metal balls (41, 411, 42, 421) which protrude from said sol-gel hybrid coating (3) is between 50 and 300 charges / mm 2, and preferably between 100 and 250 charges / mm 2.
    [0010]
    10. Article (1) according to claim 8 or 9, wherein the diameter of the metal balls (41, 411, 42, 421) is between 5 and 30 pm, their average diameter being between 15 and 20 pm, and thickness of said coating (32, 33) being between 5 and 20 μm.
    [0011]
    11. Article (1) according to any one of claims 8 to 10, the quantity of metal balls (41, 411, 42, 421) in a screen printing layer (32, 33) is between 0.01% and 5%. % relative to the weight of said layer (32, 33).
    [0012]
    12. Article (1) according to any of the preceding claims, which constitutes a culinary article (1) having a support (2) with an inner face (21) adapted to receive food and an outer face (22) for to be disposed on the side of a heat source, said outer face (22) being successively coated with the layer (31) of sol-gel coating and the layer (s) (32, 33) serigraphic (s) ) of hybrid sol-gel coating.
    [0013]
    13. Article (1) according to any one of the preceding claims, wherein the support (2) 30 is a monolayer support of aluminum or aluminum alloy, cast aluminum, stainless steel, cast iron. steel or copper, or a multilayer support comprising from the outside to the inside the following layers ferritic stainless steel / aluminum / austenitic stainless steel or even stainless steel / aluminum / copper / aluminum / austenitic stainless steel, or a cap of aluminum foundry, aluminum or aluminum alloys lined with a stainless steel outer bottom.
    [0014]
    14. A method for producing an article as defined in any one of claims 1 to 13, said method comprising the following steps: a) a step of providing a support (2) having at least two opposite faces (21, 22); b) a step b1) of preparing an aqueous sol-gel composition comprising at least one sol-gel precursor of metal alkoxide type, followed by a step b2) of hydrolysis of said sol-gel precursor by introduction of water and an acidic or basic catalyst, and finally followed by a condensation reaction (b3) causing the formation of an alcohol to obtain a sol-gel composition; c) a step of preparing cl) a hybrid composition comprising at least one silicone resin in a solvent medium, to obtain a hybrid composition; d) applying on one of the faces (21, 22) of the support (2) a layer of the sol-gel composition to form a layer (31) of sol-gel coating in the form of a continuous film ; then drying of said layer (31) of sol-gel coating) application by screen printing on said layer (31) of sol-gel coating of at least one layer (32, 33) of hybrid composition, followed by a possible drying and f) firing said layer at a temperature between 200 ° C and 300 ° C.
    [0015]
    15. The method of claim 14, wherein the silicone resin is a polyester silicone resin.
    [0016]
    The process of claim 14 or 15, wherein the step of preparing cl) of the hybrid composition comprises adding a silane and / or a metal alkoxide.
    [0017]
    17. The method of claim 16, wherein the silane and / or the metal acoxide are previously hydrolysed. 20
    [0018]
    18. A process according to any one of claims 14 to 17 wherein the solvent medium of said hybrid composition comprises at least one light organic solvent as a diluent and at least one heavy organic solvent as a humectant.
    [0019]
    19. The process according to claim 18, wherein the light organic solvent of the hybrid composition is a polar solvent having a boiling point less than or equal to 150 ° C.
    [0020]
    20. The method of claim 18 or 19, wherein the heavy organic solvent of the hybrid composition is a polyol or terpene derivative.
    [0021]
    21. Process according to any one of claims 14 to 20, further comprising a step of adjusting the viscosity of the hybrid composition to a value of between 0.2 Pa s and 5 Pa s, and preferably at least one value between 0.5 Pa.s and 2 Pa.s.
    [0022]
    22. The method of claim 21, characterized in that the step of adjusting the viscosity of the hybrid composition is carried out by adding a cellulose, modified or not, and preferably ethyl cellulose.
    [0023]
    23. A method according to any one of claims 14 to 22, further comprising, just after step c2) hydrolysis-condensation of the hybrid composition a step of adding a pigment load and / or a reinforcing filler.
    [0024]
    24. The method of claim 23, wherein the pigment filler is selected from mica coated or uncoated, titanium dioxide, mixed oxides of copper-chromium-manganese (spinels), aluminosilicates, iron oxides. carbon black, perylene red, metal flakes, pigments and thermochromic organic dyes, and mixtures thereof.
    [0025]
    25. The method of claim 23 or 24 wherein the reinforcing filler (4) comprises metal balls.
    [0026]
    26. A method according to any one of claims 14 to 25, wherein the support (2) has the final shape of a culinary article, having an inner face (21) adapted to receive food and an outer face (22). intended to be disposed on the side of a heat source.
    [0027]
    27. A method according to any one of claims 14 to 25, further comprising a step of forming the support (2) before the step d) of application of the hybrid composition when the support is in the form of a disk .
    类似技术:
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    同族专利:
    公开号 | 公开日
    JP6581091B2|2019-09-25|
    CN105874021B|2019-04-16|
    JP2017501789A|2017-01-19|
    KR102342481B1|2021-12-24|
    WO2015086999A1|2015-06-18|
    KR20160096663A|2016-08-16|
    US10806296B2|2020-10-20|
    US20170020331A1|2017-01-26|
    FR3014890B1|2017-02-03|
    EP3080220A1|2016-10-19|
    CN105874021A|2016-08-17|
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    US20130266781A1|2010-07-21|2013-10-10|Schott Ag|Silicone coating as a sealing layer for a decoration layer|
    EP2412846A1|2010-07-26|2012-02-01|Seb Sa|Article comprised of a sol-gel coating with a functional decor, and method for manufacturing such an article|
    EP2505619A1|2011-04-01|2012-10-03|Seb S.A.|Scratch-proof culinary item and method for producing such an item|
    EP0729921A3|1995-03-02|1996-09-11|Bayer Ag|
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    DE102012111836A1|2012-12-05|2014-06-05|Schott Ag|Coating material and substrate with a semi-transparent coating|FR3052770B1|2016-06-17|2018-07-13|Eurokera S.N.C.|GLASS-CERAMIC GLASS-LIKE ARTICLE AND PROCESS FOR OBTAINING THE SAME|
    US10246594B2|2016-07-20|2019-04-02|The Boeing Company|Corrosion inhibitor-incorporated layered double hydroxide and sol-gel coating compositions and related processes|
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    US10421869B2|2017-01-09|2019-09-24|The Boeing Company|Sol-gel coating compositions including corrosion inhibitor-encapsulated layered metal phosphates and related processes|
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    法律状态:
    2015-12-31| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-29| PLFP| Fee payment|Year of fee payment: 4 |
    2017-06-23| CA| Change of address|Effective date: 20170518 |
    2018-01-02| PLFP| Fee payment|Year of fee payment: 5 |
    2018-12-31| PLFP| Fee payment|Year of fee payment: 6 |
    2019-12-30| PLFP| Fee payment|Year of fee payment: 7 |
    2020-12-28| PLFP| Fee payment|Year of fee payment: 8 |
    2021-12-30| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362522A|FR3014890B1|2013-12-12|2013-12-12|CULINARY ARTICLE HAVING A HYBRID COATING AND METHOD FOR REALIZING SUCH A ARTICLE|FR1362522A| FR3014890B1|2013-12-12|2013-12-12|CULINARY ARTICLE HAVING A HYBRID COATING AND METHOD FOR REALIZING SUCH A ARTICLE|
    KR1020167018251A| KR102342481B1|2013-12-12|2014-12-11|Culinary utensil provided with a hybrid coating and process for producing such a utensil|
    US15/102,668| US10806296B2|2013-12-12|2014-12-11|Culinary utensil provided with a hybrid coating and process for producing such a utensil|
    CN201480067561.1A| CN105874021B|2013-12-12|2014-12-11|It is provided with the cook utensil of mixed coating and the method for producing this apparatus|
    PCT/FR2014/053266| WO2015086999A1|2013-12-12|2014-12-11|Culinary utensil provided with a hybrid coating and process for producing such a utensil|
    EP14827495.4A| EP3080220A1|2013-12-12|2014-12-11|Culinary utensil provided with a hybrid coating and process for producing such a utensil|
    JP2016539208A| JP6581091B2|2013-12-12|2014-12-11|Cookware having a hybrid coating and method for manufacturing such an appliance|
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