• 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 decoration process, in which a decoration using thermostable particulate inks is flexographically applied to a non-stick coating based on fluorocarbon resin (s), the decoration possibly consisting of colored hyperrealistic patterns.
    公开号:FR3014014A1
    申请号:FR1362044
    申请日:2013-12-03
    公开日:2015-06-05
    发明作者:Bris Stephanie Le；Laurent Caillier
    申请人:SEB SA；
    IPC主号:
    专利说明:

    [0001] BACKGROUND OF THE INVENTION The present invention relates generally to a method of decorating an article, in particular a culinary article. More particularly, the present invention relates to a method of decorating, in which a decor using thermostable particulate inks is flexographically applied to a non-stick coating based on fluorocarbon resin (s), the decor possibly consisting of hyperrealistic patterns. colored. The flexographic process is a known method of relief printing, direct transfer, which allows in particular to print colorful hyperrealistic patterns. It appeared around 1860 in the United States then in England, and in France in 1905 in Alsace. This was the aniline labeling process, which was called flexography in 1952. This process implements a device generally referred to as flexographic printing group 10, which is illustrated in FIG. The flexographic printing unit 10 of FIG. 1 consists of an inking unit 11 (inkwell 110 + spraying roller 111 + inking roller 112), a platen roller 12 and a counter-roller. The inking unit 11 controls and regulates the ink supply on the plate. It generally consists of a bubbler roll 111, a cylinder (or roll) inking 111 called anilox and a squeegee (not shown in Figure 1). The operating principle of the flexographic printing unit 10 is as follows: the ink 14 is transferred from the ink fountain 110 to the anilox roll (inking roll) 112 via the bubbler 111; the screened anilox cylinder 112 ink the embossed plate, which transfers the ink onto the support 2 to be printed (generally cardboard, as illustrated in FIG. 1) by virtue of a slight pressure applied by the counter-pressure cylinder 13. This printing process is mainly used in the field of packaging, and in particular of cardboard packaging. It is also known to use flexography for the decoration of lacquered kitchenware, as is the case, for example, with culinary articles marketed by the Tramontina company. However these articles have a lack of durability to use due especially to the poor thermal resistance of the lacquers themselves and inks used in the decor. These are coatings based on a polyester silicone binder and organic pigments. To overcome these drawbacks, the applicant has developed a method of decorating an article support, allowing the flexographic printing of pigmented decor composition (s) (or ink (s)) particulate (s) with good thermal resistance, preferably of inorganic nature, on a thermostable coating based on fluorocarbon resin known for its chemical and mechanical resistance at high temperature. For the purposes of the invention, the term "particulate composition" is intended to mean a composition comprising at least one organic or inorganic binder, filler or pigment in the form of a discrete solid or of a particle in suspension or in dispersion in a liquid. For the purposes of the invention, the term "particulate layer" means a layer obtained after natural or forced drying of the particulate composition. The particle size characterized by d50 is typically between 20 nm and 5 μm. For the purposes of the present invention, the term "pigmented decorative composition with good thermal resistance" means a composition comprising a pigment with good thermal resistance.
    [0002] The term "pigment with good thermal resistance" means a pigment whose delta E color evolution, measured at ambient temperature, is less than 1 after a heat treatment of 10 minutes at 410 ° C. +/- 30 ° C.
    [0003] By charge with good thermal resistance is meant a charge whose evolution in mass, after a thermal treatment of 10 minutes at 410 ° C. ± 30 ° C., does not exceed 5%. As pigments with good heat resistance used in the particulate sub-layer thermostable coating or in the pigmented composition, mention may be made inorganic pigments such as titanium dioxide, spinels, iron oxides, nickel titanate , carbon black, coated mica flakes, metallic flakes such as aluminum flakes, or organic pigments such as perylene reds. It is known to those skilled in the art that articles having anti-adhesion properties are very generally composed of a fluoropolymer-based coating. In particular, it is known that culinary articles provided with a coating based on polytetrafluoroethylene (PTFE) allow cooking that does not require the addition of fat for cooking food, while allowing easy cleaning of the food. article. It is also widely recognized that fluorocarbon resins, and more particularly polytetrafluoroethylene (PTFE) are the most appropriate compounds to obtain a coating having exceptional anti-adhesion properties. Conventional techniques for decorating such coatings such as pad printing or screen printing do not make it possible to obtain hyperrealistic decorations because of a too limited definition. The present invention therefore aims at providing a method for manufacturing an article, in particular a culinary article, provided with a thermostable non-stick coating and decorated with colored patterns that can be hyperrealistic, and which has an improved service life (high chemical and mechanical resistance). temperature, ie greater than 200 ° C.) More particularly, the present invention relates to a method of decorating an article comprising the following steps: a) providing a support comprising two opposite faces; then b) applying a thermally stable particulate coating composition on one of the faces of the support to form a particulate underlayer, the particulate composition comprising at least one fluorocarbon resin, alone or with a heat-stable bonding resin, and or at least one filler with good thermal resistance and / or a pigment with good thermal resistance, said application of the particulate composition being followed by a natural or forced drying; c) flexographic printing of a first pigmented decor composition on said particulate sub-layer to form a decor having a first discontinuous decor layer, said first decor composition comprising at least one pigment with good thermal resistance; d) solidification heat treatment of said particulate sub-layer and said first discontinuous decor layer; said method furthermore having at least one of the following alternative characteristics: the decor composition further comprises a fluorocarbon resin whose melting or crosslinking temperature is equal to or less than that of the fluorocarbon resin contained in the underlayer; and / or said method further comprises, between step c) of application of the decor composition and step d) solidification heat treatment, a step of application, on the decor, of a colorless finish composition comprising at least one fluorocarbon resin to form a colorless topcoat, and / or the particulate underlayer is a high absorption underlayer.
    [0004] The method according to the invention makes it possible to achieve the objective sought by the present invention, in particular thanks to the coupled use of ink (s) resistant (s) at high temperatures and a heat-stable particulate sub-layer based on fluorocarbon resin, which makes it possible to obtain a good optimal adhesion between the underlayer and the layer or layers of decor printed by flexography. To allow the ink (or inks) to be anchored flexographically on the particulate underlayer while retaining good non-stick properties for the decor thus formed, the process according to the invention requires the production of at least one of the three abovementioned alternative characteristics, which are described below and in more detail in the examples. The various steps of the process according to the invention, as well as their preferred embodiments, will be described below. With regard to the first step a) of providing a support, this may be of any kind as long as it can withstand the temperatures required for the solidification of the fluorocarbon resins. If the support does not have the desired final shape for the article and is in the form of a preform such as a disc, the method according to the invention will advantageously comprise a step e) of shaping the preform until to obtain the shape of the desired article which is produced after step d) solidification heat treatment. If the support has the desired final shape for the article or, which amounts to the same, is in the form of a preform whose shaping is performed before all the other steps of the process, flexographic printing of the decor is then performed only on the flat part of the face provided with the decor.
    [0005] The article which is decorated according to the method according to the invention can be in particular a culinary article comprising a metal support having an inner face that can receive food and an outer face intended to be disposed towards the heat source.
    [0006] In the case of a culinary article, the support may advantageously be: a monolayer structure made of anodized or non-anodized aluminum, or polished, brushed or microblasted aluminum, sandblasted, chemically treated, or cast aluminum, or stainless steel polished, brushed or micro-blasted, or cast iron, or hammered or polished copper; or a multilayer structure, in part or in whole, comprising from outside to inside the following layers stainless steel / aluminum / stainless steel or stainless steel / aluminum / copper / aluminum / stainless steel, or a cap of aluminum foundry, aluminum or aluminum alloys lined with a stainless steel outer bottom. The face of the support to be coated can be surface treated to increase its surface area. For an aluminum substrate, this surface treatment may advantageously consist of anodization (creation of a tubular structure of alumina), or chemical etching, or sandblasting, microbilling, brushing, emerying. Other metal substrates may in particular The method according to the invention comprises, following step a) of supplying the substrate (and, if appropriate, its shaping and / or its possible surface treatment). ), a step of applying at least one thermostable coating particulate underlayer composition to the surface of the support to be provided with the decor, resulting in the formation of a particulate heat-stable coating underlayer. The particulate heat-stable coating composition can be conventionally applied by spraying, curtain, screen printing, roller printing, pad printing, ink jet printing, etc. The particulate composition comprises at least one fluorocarbon resin, alone or with a thermostable bonding resin, and / or at least one filler with good thermal resistance and / or a pigment with good thermal resistance. As the fluorocarbon resin which can be used in the particulate composition according to the invention, polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoropropylvinyl ether (PFA), the copolymer of tetrafluoroethylene and hexafluoropropylene (FEP ) and their mixtures. As thermostable bonding resin that may be used in the thermostable coating particulate composition according to the invention, polyamide imides (PAI), polyetherimides (PEI), polyimides (PI) and polyetherketones (PEK) may especially be mentioned. ), polyetheretherketones (PEEK), polyethersulfides (PES) and polyphenylene sulfides (PPS). As pigments with good heat resistance used in the particulate thermostable coating composition according to the invention, there may be mentioned inorganic pigments such as titanium dioxide, spinels, iron oxides, nickel titanate, black carbon, mica flakes or organic pigments such as perylene reds. The pigments of this particulate composition are preferably chosen to obtain a light color. As charges of good thermal resistance light colored fillers such as silica, talc, kaolin, barite and wollastonite will be used. The particulate underlayer thus formed must be dry prior to flexographic printing of the first decorative layer, which drying may be natural or forced by infrared radiation, convection of hot air. The wettability of the dried particulate sub-layer may further be improved by use of a cold plasma or corona treatment which promotes the spread of the pigmented decor layer on the underlayer. Then, at least the first pigmented decoration composition (or first ink) is flexographically printed on the particulate underlayer to form a first, discontinuous, decorative layer. If the decorative layer is not discontinuous and forms a total solid surface completely covering the decorative undercoat, then there is no decor, since it is obtained by the visible contrast of color between the coating layer. pigmented background and the particulate underlayer. The decor composition comprises at least one pigment with good thermal resistance, preferably of mineral nature. As pigments which can be used in the decorative layer according to the invention and which have good thermal resistance, mention may be made in particular of mineral pigments such as titanium dioxide, spinels, iron oxides, nickel titanate, carbon black, coated mica flakes, metallic flakes such as aluminum flakes or organic pigments such as perylene reds. According to the first alternative of the process according to the invention, use will be made of one or more inks (or composition (s) of decoration) comprising, in addition to the pigment with good thermal resistance, a fluorocarbon resin whose melting temperature or The crosslinking is equal to or less than that of the fluorocarbon resin contained in the particulate heat-stable coating sub-layer.
    [0007] As fluorocarbon resins that may be used in the decor composition according to the invention, the same may be advantageously used as those that may be used in the particulate underlayer according to the invention. Of the same chemical nature, the ink (or inks) and the substrate (particulate underlayer) then have a high mutual affinity, ensuring good cohesion and after firing, the decoration has the characteristic non-stick properties of fluorocarbon coatings . According to the second alternative of the process according to the invention, the method according to the invention further comprises, between step c) of application of the first decor composition and step d) of solidification heat treatment, a the step of applying a colorless finishing composition comprising at least one fluorocarbon resin to the decor and, if appropriate, to said particulate sub-layer (the decor being discontinuous), to form a colorless topcoat. This colorless topcoat serves to protect the decor, and to bind it to the particulate underlayer, while contributing to the improvement of the non-stick properties of the coating. This colorless topcoat may, in the same way as the pigmented undercoat and, where appropriate, the colorless undercoat, be conventionally spray-coated, screen-printed, roller-screened, pad-printed, jet-printed The fluorocarbon resins used in the finishing composition according to the invention may advantageously be used as those which may be used in the pigmented underlayer according to the invention. According to the third alternative of the process according to the invention, a substrate (particulate underlayer) for the first decorative layer (in other words pigmented underlayer) is used, a substrate having good 'absorption. For the purposes of the present application, the term "substrate" or "particulate sub-layer having good absorption properties" means a porous underlayer or containing intrinsically porous or porosity-generating charges by their association at the time of drying, for allow the absorption of color and / or liquid phase from the decor layer. The sub-layer having good absorption properties has a degree of vacuum of at least 10% relative to the total volume of the material. As intrinsically porous or porosity-generating fillers, preferably particles of colloidal silica or colloidal alumina, porous silica particles, or zeolite particles. Advantageously, the method according to the invention may further comprise, between the steps c) of flexographic printing of the first decor composition (41) and the solidification heat treatment step d): phase of natural or forced drying of the first layer of decoration; then c ") printing by flexography of at least one second pigmented decor composition comprising a second pigment with good thermal resistance (which may be identical or different from that of the first decorative layer) to form a second decorative layer, said second decorative layer being arranged in superposition and / or in juxtaposition with the one or more previously printed pigmented layers, this step e) being repeated as many times as necessary in order to ensure the number of desired hues. It can also have more than two layers of decoration.If it has four layers of decor of different colors, the decoration is said quadrichrome.If it has six, it is said hexachrome.The combination of all these layers of colors. The solidification of the moist decorative layer is achieved in the method of decoration according to the invention. ion by a solidification heat treatment of the deposited layers and printed layers. For the purposes of the present invention, the term "solidification heat treatment" means the application by any suitable means of a thermal flux intended to remove solvents and / or volatile materials from the deposited or printed layers, and to melt and allow the coalescence of the resins contained in these layers and also to crosslink these resins on themselves or between them if necessary. Advantageously, the solidification heat treatment d) may consist of a firing that can be carried out (for example in a conventional oven) at a temperature between 380 ° C and 430 ° C. The face of the support which is not flexographically decorated may also be coated with a fluorocarbon resin release coating. The order of coating the faces does not matter. If the face opposite to that provided with a decoration is coated with such a non-stick coating second (that is to say after coating the decor, the method according to the invention will comprise: a precooking step of the particulate underlayer and the posterior decor layer or layers c) by flexography of the pigmented decor composition (s), - an application step f) a layer of non-stick coating on the face of the substrate opposite to that provided with the decorative layer or layers, this step f) being performed between said precooking step and the heat treatment step e). If the face opposite to that provided with a decoration is coated with such a non-stick coating first (i.e., before coating the particulate undercoat, then decorative layers, the process according to The invention will comprise: - the application before all the other steps of a layer of non-stick coating on the face of the substrate opposite to that provided with the decorative layer or layers, and then - pre-baking the non-stick coating layer covering the face of the substrate opposite to that provided with the decorative layer or layers, prior to step b) of coating the particulate sub-layer. The process according to the invention has the following advantages: it is possible to produce a non-stick decoration which can comprise very complex and / or hyperrealistic motifs (photos, textures, imitation stone, wood, marble, fabrics, etc.); - With a definition much greater than that which one would obtain with screen printing or pad printing, - while having properties of antiadhesiveness and thermal stability significantly strengthened, compared to those lacquers, generally used as support in flexography; - It is already possible to achieve a decor with very complex patterns from only four inks, 5 which is of undeniable interest in terms of formulation and also storage; - With a flexographic print of the decor, the Print Speed is compatible with a high rate of article manufacture; Finally, it is possible to use existing flexographic groups for printing lacquers without major modification of this apparatus. Other advantages and features of the present invention will result from the description which follows, given by way of non-limiting example and with reference to the appended figures and corresponding examples: FIG. 1 represents a schematic view of a known flexographic printing group used in the field of packaging; 2 represents a diagrammatic sectional view of a culinary article holder obtained according to a first variant of the method of the invention (see example 1), FIG. an exemplary culinary article obtained according to a second variant of the method of the invention (see Example 2), - Figure 4 shows a schematic sectional view of a food item holder according to the according to a third alternative embodiment of the method of the invention (see example 3), - Figure 5 shows a schematic sectional view of a culinary article holder obtained according to a fourth embodiment of the method of the invention. 4, FIG. 6 is a diagrammatic cross-sectional view of a culinary article holder obtained according to a fifth variant embodiment of the method of the invention (see example 5). FIG. 7 represents a view sc Hematological sectional of a culinary article holder obtained according to a sixth embodiment variant of the method of the invention (cf. EXAMPLE 10 6) FIG. 8 is a diagrammatic cross-sectional view of a culinary article holder obtained according to a seventh variant embodiment of the process of the invention (see Example 7); FIG. schematic sectional view of a culinary article holder obtained according to an eighth variant embodiment of the method of the invention (see Example 8), - Figure 10 shows a schematic sectional view of an article support. Culinary obtained by a process not in accordance with the invention (see Comparative Example 1). The identical elements shown in FIGS. 2 to 9 are identified by identical reference numerals. The different embodiments illustrated in FIGS. 2 to 10 are commented on in the examples below. In these examples, unless otherwise indicated, all percentages and parts are by weight.
    [0008] EXAMPLES Flexographic decoration device The device illustrated in FIG. 1, usually intended for the printing of a cardboard support, is used as a printing device. Supports: Aluminum discs 31 cm in diameter and 2.4 mm thick. Aluminum caps with a diameter of 26 cm and a thickness of 2.9 mm. Inks and particulate compositions: Products - inorganic pigments: temperature-stable inorganic pigments such as titanium dioxide, spinels, iron oxides, and nickel titanate; antifoam agent: product sold under the trade name Dehydran G by the company Cognis, - wetting agent: product of alkylphenol ethoxylated type sold under the trade name Triton X100 by Dow or equivalent - solvent: propylene glycol - thickening acrylic resin sold under the trade name SD15 by the company Synthomer 30 [ PTFE dispersion with 60% dry extract marketed under the trade name 5035Z by the company Dyneon - PFA dispersion containing 50% of dry extract marketed under the trade name 6900GZ by the company Dyneon 15 colloidal silica: product marketed by Clariant under the trade name Klebosol 47V50. porous silica: product marketed by AGC under the trade name Sunlovely. Formulation The inks used for flexographic printing in the process of the invention are aqueous formulations suitable for flexographic printing as known to those skilled in the art. These formulations contain inorganic pigments allowing good color temperature stability, water as main carrier with at least one co-solvent (propylene glycol) These aqueous formulations are prepared from a pigment paste, as follows: Preparation of a pigment paste A pigment paste (PP) of a given color (including a white color) is prepared in the first place and is a dispersion whose composition is indicated below in the table. 1: Table 1: Composition of the pigment paste (PP) produced Quantity (% by weight) Inorganic pigment 49.6 Water 41.6 Antifoaming agent 0.8 Wetting agent 5 NH 4 OH 0.6 Solvent 2 Total 100 This dispersion is prepared in a grinding mill (for example the ball mill) making it possible to reduce the particle size of the pigment particles so that their D50 is less than 5 μm 2 / Preparation of a fluorinated aqueous ink (ink 1 or compound 1) From the pigment paste PP, a first pigmented decoration composition (fluorinated ink 1) is prepared as follows: 120 parts by weight of pigment paste, 22.5 parts by weight of solvent, - 0.75 parts by weight of antifoaming agent, - 1.5 parts by weight of NH4OH, 15 - 1.88 parts by weight of acrylic thickening resin, and - 180 parts by weight of PTFE dispersion This formula has physical properties (viscosity, dry speed) similar to those of a traditional ink used in flexography (viscosity 26 cp according to the AFNOR4 density standard of 1.5 g / cm3). 3 / Preparation of a non-fluorinated aqueous ink (ink 2 or non-fluorinated pigmented decor composition 2) From the pigment paste PP, a second non-fluorinated pigmented decor composition 2 (ink 2) is prepared, as follows : - 120 parts by weight of pigment paste - 22.5 parts by weight of solvent, 30 - 180 parts of water - 0.75 parts by weight of antifoam, - 1.5 parts by weight of NH4OH, - 1 , 88 part by weight of acrylic thickening resin, This formula has physical properties (viscosity, dry speed) similar to those of a traditional ink used in flexography (viscosity 26 cp according to the standard AFNOR 4 density of 1.5 g / cm 3) 4a / Preparation of a pigmented thermostable coating sublayer (SC1) particulate composition Starting from a white PP pigment paste, as prepared in point 1 with titanium dioxide as inorganic pigment, is prepared a fluorinated particulate composition of underlayer, as shown in Table 2 below: Table 2: white undercoating composition for screen printing application (SC1) Product Quantity (% by weight) PP (TiO 2) 20 PTFE dispersion 50 colloidal silica 1 Solvent 10 Water Antifoaming agent 1 thickening acrylic resin 2 NH 4 OH 1 TOTAL 100 This formula has standard physical properties (viscosity, dry speed) for screen printing application (viscosity equal to 10,000 mPa.s at room temperature). of a particulate composition of high-absorption thermostable coating undercoat (SC2) From a white PP pigment paste, as described prepared in point 1, with titanium dioxide as inorganic pigment, is prepared a fluorinated particulate composition of high absorption underlayer, as shown in Table 3 below: Table 3: High absorption white undercoat composition for serum application aphie (SC2) Product Quantity (wt.%) PP (TiO2) 10 PTFE dispersion 50 colloidal silica 1 porous silica 10 Solvent 10 Water antifoaming agent 1 thickening acrylic resin 2 NH4OH 1 TOTAL 100 This formula has physical properties (viscosity standard dry speed) for screen printing application (viscosity of 10,000 mPa.s at room temperature). 4c / Preparation of a Colorless Undercoat (SC3 and SC4) Particle Composition A colorless undercoat was prepared as described in Tables 4 (SC3) and 5 (SC4) below: TABLE 4 : Colorless undercoat composition for screen and roller application (SC3) Product Quantity (% by weight) PTFE dispersion 75 Solvent 15 Water 5 Antifoaming agent 2 Thickening acrylic resin 2 NH4OH 1 TOTAL 100 This formula has physical properties (viscosity standard dry speed) for screen printing application (viscosity of 10,000 mPa.s at room temperature) Table 5: Colorless undercoat composition for spray application (SC4) product Quantity (% by weight) PTFE dispersion 80 PFA dispersion Acrylic water-soluble 0.5 spreading agent Non-charged type 2 surfactant alkylphenolethoxylate Water 12.5 Total 100 5 / Preparation of a colorless topcoat composition (C F 1 and CF 2) A fluorinated particulate composition of a colorless topcoat is prepared as shown in Tables 6 (CF 1) and 7 (CF 2) hereinafter: Table 6: Finishing composition for screen printing application and roller (CF 1) product Quantity (% by weight) PTFE dispersion 75 solvent 15 water 5 defoamer 2 thickening acrylic resin 2 NH4OH 1 TOTAL 100 This formula has standard physical properties (viscosity, dry speed) for a screen printing application (viscosity equal to 10 000 mPa.s at room temperature) Table 7: Colorless topcoat composition for spray application (CF 2) product Quantity (% by weight) PTFE dispersion 80 PFA dispersion 5 Alumina mica flakes 1 Acrylic water-soluble 0.5 spreading agent Non-charged type 2 surfactant alkylphenolethoxylate Water 11.5 Total 100 Test: withstand and transfer test (cohesion) This test uses the NF D 21-511 standard. Grids (dimensions 1 cm x 1 cm) of 100 tiles are drawn with a razor blade on the decoration. The application of an adhesive tape and its tearing allows: 1. to evaluate the cohesion of the decoration by the observation of possible phenomena of lifting, delamination or cleavage after tearing of the adhesive; 2. by examining the adhesive side of the adhesive, after the test, to detect a possible color transfer from the decoration to the adhesive. EXAMPLE 1: Printing of a fluorinated pigmented heat-stable ink (ink 1) on a PTFE-based pigmented underlayer Embodiment a i. The aluminum disc 2 is prepared by chemical treatment to give it good adhesion properties; ii. one of the faces 21 of the disk 2 is applied to the SC1 heat-treated screen-printing particulate composition to form a particulate sub-layer 3, dried by infrared radiation; iii. then, the fluorinated pigmented ink (ink 1) is printed by flexography on this particulate sub-layer 3 forming a layer 41 of decoration iv. the disc thus coated is precooked at a temperature of 350 ° C for 8 minutes; v. then applying to the opposite face 22 of the disc 2 the non-stick coating composition by screen printing forming a layer 7 of non-stick coating; vi. the disc thus coated is fired at a temperature of 430 ° C for a period of 8 minutes; vii. before being shaped by stamping to obtain the desired shape of item 1. The disc thus coated and decorated corresponds to that illustrated in FIG.
    [0009] Embodiment b i. The aluminum disc 2 is prepared by chemical treatment, viii. one of the faces 22 of the disc 2 is applied to the non-stick coating composition by screen printing to form a layer 7 (decorated or not) of non-stick coating; ii. the disc thus coated is precooked at a temperature of 350 ° C. for 8 minutes; ix. then, on the opposite face 21 of the disk 2, the SC thermostable coating particle composition SC 1 is applied to form a particulate sub-layer 3 which is dried (infrared radiation) iii. the fluorinated pigmented ink (ink 1) is flexographically printed on this layer 3, forming a decorative layer 41; iv. the disc thus coated is fired at a temperature of 430 ° C for a period of 8 minutes; v. before being shaped by stamping. The disk thus coated and decorated also corresponds to that illustrated in FIG.
    [0010] For both embodiments, the cohesion of the fluorinated decoration layer with the fluorinated particulate sub-layer was evaluated using the check and transfer test by grids: 0% of tearing is obtained and no transfer EXAMPLE 2: Printing a fluorinated pigmented heat-stable ink (ink 1) on a PTFE-based colorless undercoat Embodiment a i. The aluminum disc 2 is chemically treated to give it good grip properties; x. one of the faces 21 of the disk 2 is applied to the white pigmented particulate composition SC1 by screen printing to form a wet particulate sub-layer; ii. the underlayer 3 is dried; iii. a colorless undercoat SC3 is applied to the particulate underlayer 3 by screen printing to form a colorless underlayer 6 which is dried (infrared radiation); iv. the fluorinated pigmented ink (ink 1) is flexographically printed on this colorless sub-layer 6 to form a decorative layer 41; v. the disc is then precooked at a temperature of 350 ° C for a period of 8 minutes; vi. on the opposite face 22 of the disk 2 is applied a nonstick coating composition by screen printing, of non-stick coating, which may or may not be decorated; vii. the thus coated disc is baked at a temperature of 430 ° C for a time of 8 minutes; viii. before being shaped by stamping.
    [0011] The disk thus coated and decorated corresponds to that illustrated in FIG.
    [0012] Embodiment b. i. The aluminum disc 2 is chemically treated to give it good grip properties; xi. one of the faces 22 of the disc 2 is applied to the non-stick screen-printing composition forming a layer 7 of non-stick coating; ii. the disc thus coated is precooked at a temperature of 350 ° C for a time of 8 minutes; xii. then, on the opposite face 21 is applied the SC1 pigmented particulate sublayer composition by screen printing, to form a particulate sub-layer 3; iii. the underlayer 3 is then dried; iv. then, the SC3 colorless undercoat composition is applied to the particulate underlayer 3 by screen printing to form a colorless underlayer 6 which is dried (infrared radiation); v. the fluorinated pigmented ink (ink 1) is then printed by flexography on this colorless sub-layer 6, to form a decorative layer 41; vi. the disc thus coated is fired at a temperature of 430 ° C for a period of 8 min; vii. before being shaped by stamping.
    [0013] The disk thus coated and decorated also corresponds to that illustrated in FIG. 3. For both embodiments, the cohesion of the fluorinated decoration layer on the colorless fluorinated PTFE-based sub-layer was evaluated using the test of holding and transfer by grids: 0% of tearing is obtained and no color transfer on the adhesive tape.
    [0014] EXAMPLE 3: Printing a non-fluorinated pigmented heat-stable ink (ink 2) on a pigmented PTFE-based undercoat and protected by a fluorinated colorless topcoat Embodiment a i. The aluminum disc 2 is chemically treated in order to ii. give it good grip properties; one of the faces 21 of the disk 2 is applied to the SC1 particulate underlayer composition by screen printing to obtain a pigmented underlayer 3 which is dried (infrared radiation) iii. the non-fluorinated pigmented ink (ink 2) is printed flexographically on the underlayer, to form the decorative layer 41; iv. then, the decor layer 41 is applied to the fluorinated CF1 topcoat composition by screen printing to form the topcoat 5; v. the disc thus coated is precooked at a temperature of 350 ° C for a period of 8 minutes; vi. then, on the second face 22 of the disc 2, a non-stick coating composition is applied by screen, roll, inkjet, curtain or spray coating to form a non-stick coating layer; vii. the disc thus coated is fired at a temperature of 430 ° C for a period of 8 minutes; viii. before being shaped by stamping.
    [0015] The disk thus coated and decorated corresponds to that illustrated in FIG.
    [0016] Embodiment b. i. The aluminum disc 2 is chemically treated to give it good grip properties; ii. one of the faces 22 of the disc 2 is applied to the non-stick coating composition by screen printing to form a layer 7 of non-stick coating; iii. the disc thus coated is precooked at a temperature of 350 ° C for a period of 8 minutes; iv. the disk 2 receives on its second face 21 a particulate underlayer 3 which is obtained by applying the SC1 particulate underlayer composition by screen printing which is dried (infrared radiation) v. The unscented pigmented ink (ink 2) is flexographically printed on the pigmented underlayer 3 vi. then, applying to the decor layer 41 the fluorinated CF1 topcoat composition applied by screen printing to form the topcoat 5; vii. the disc is baked at a temperature of 430 ° C for a period of 8 minutes; viii. before being shaped by stamping. The disk thus coated and decorated also corresponds to that illustrated in FIG.
    [0017] For both embodiments, the cohesion of the decor layer (whether or not fluorinated) protected by a fluoridated colorless topcoat layer on the fluorinated particulate sub-layer was evaluated using the withstand test and Grid transfer: 0% tearing is obtained and no color transfer on the adhesive tape.
    [0018] EXAMPLE 4 Printing of a non-fluorinated pigmented thermostable ink (ink 2) on a colorless undercoat based on PTFE unpigmented and protected by a colored topcoat.
    [0019] Embodiment a i. The aluminum disc 2 is chemically treated to give it good grip properties; ix. one of the faces 21 of the disk 2 is applied to the SC1 particulate underlayer composition by screen printing to obtain a wet particulate sub-layer 3; ii. the underlayer 3 is dried; x. then, on the underlayer 3, the colorless undercoat SC3 is applied by screen printing to form a colorless underlayer 6; xi. the pigmented ink (ink 2) is flexographically printed on this colorless sub-layer 6 to form a decorative layer 41; xii. then applying to the decor layer 4 the CF1 topcoat composition by screen printing to form a topcoat 5; iii. the disc is precooked at a temperature of 350 ° C for a period of 8 minutes; xiii. the second face 22 of the disc 2 receives a non-stick coating 7 decorated or not by screen printing iv. the disc is baked at a temperature of 430 ° C for a longer period of 8 minutes; v. before being shaped by stamping. The disc thus coated and decorated corresponds to that illustrated in FIG.
    [0020] Embodiment b. i. The aluminum disc 2 is chemically treated to give it good grip properties; ii. a PTFE release coating is applied to the first face 22 of the disc 2 by means of screen printing to obtain a heat-stable coating layer 7; iii. the disc is precooked at a temperature of 350 ° C for a period of 8 minutes; iv. the disk receives on its second face 21 a particulate underlayer 3 by screen printing of the particulate underlayer composition SC1; v. the pigmented sub-layer 3 is dried; vi. the SC3 screen-printed colorless undercoat composition is applied to the particulate underlayer 3 to obtain a colorless underlayer 6 which is dried; vii. the pigmented ink (ink 2) is flexographically printed on this colorless sub-layer 6 to obtain a decorative layer 41; viii. the silkscreened CF1 finish coat composition CF1 is applied to the decor layer 41 to form the protective topcoat 5; ix. the disc is baked at a temperature of 430 ° C for a period of 8 minutes; x. before being shaped by stamping. The disc thus coated and decorated also corresponds to that illustrated in FIG.
    [0021] For both embodiments, the cohesion of the decorative layer, protected by a colored topcoat, on a PTFE-based colorless undercoat was evaluated using the check and transfer test using grids: 0% of tearing is obtained and no color transfer on the adhesive tape.
    [0022] EXAMPLE 5 Printing of a non-fluorinated pigmented heat-stable ink (ink 2) on a PTFE-based high absorption particulate underlayer Embodiment a i. The aluminum disc 2 is chemically treated to give it good grip properties; ii. one of the faces 21 of the disc 2 is applied iii. SC2 high absorption particulate underlayer composition applied by screen printing to obtain a particulate underlayer 3 which is dried (infrared radiation); the pigmented ink 2 is printed by flexography on this pigmented sub-layer 3 to obtain a decorative layer 41; iv. the disc thus coated is precooked at a temperature of 350 ° C for a period of 8 minutes; v. then, the second face 22 of the disc 2 is applied to the non-stick coating composition decorated or not by screen printing to obtain a non-stick coating layer 7; vi. the disc thus coated is fired at a temperature of 430 ° C for a period of 8 minutes; vii. before being shaped by stamping. The disk thus coated and decorated corresponds to that illustrated in FIG.
    [0023] Embodiment b. i. The aluminum disc 2 is chemically treated to give it good grip properties ii. applying the non-stick coating composition by screen printing to a face 22 of the disc 2 to obtain a non-stick coating layer 7; iii. the disc thus coated is precooked at a temperature of 350 ° C for a period of 8 minutes; iv. the disk receives on its second face 21 a high absorption particulate sub-layer 3 applied by screen printing of the particulate high-absorption sub-layer composition SC2; v. the pigmented ink 2 is printed by flexography on this particulate sub-layer 3 which is dried by infrared radiation, to obtain a decorative layer 41; vi. the disc thus coated is fired at a temperature of 430 ° C for a period of 8 minutes; vii. before being shaped by stamping. The disc thus coated and decorated also corresponds to that illustrated in FIG. 6. For both embodiments, the cohesion of the decorative layer on a particulate sub-layer with high absorption was evaluated using the holding test. and transfer by grids: 0% tearing and no color transfer on the adhesive tape. EXAMPLE 6: Hexachromic printing on the bottom of a workpiece in the form of six heat-stable inks pigmented on an undercoat particulate non-pigmented and protected by a fluorless colorless finish coat i. For the printing of the decoration, yellow, cyan, magenta, green, orange and black inks are made by using the respective pigments in a type 2 formulation ink; ii. The aluminum disc 2 is shaped by stamping iii. The shaped article is subjected to a mechanical treatment (shot blasting with stainless steel ball) to give it good grip properties; iv. The non-stick coating 7, which is dried by infrared radiation, is applied to the inner face 22 of the article; v. on the outer surface 21 of the article (skirt 20 and flat bottom) shaped the unpigmented particulate SC4 composition of thermostable spray coating to form a particulate sub-layer 3, dried by infrared radiation; vi. then, a first pigmented ink is flexographically printed on the planar portion of this particulate sub-layer 3 forming a first pigment layer 41; vii. A second pigment ink is flexographically printed on the first pigment layer 41, forming the second pigment layer 42; viii. A third fluorinated pigmented ink is printed by second pigment layer flexography 42, forming the third pigment layer 43; ix. A fourth fluorinated pigmented ink is flexographically printed on the third pigment layer 43, forming the fourth pigment layer 44; x. A fifth pigmented ink is flexographically printed on the fourth pigment layer 44, forming the fifth pigment layer 45; xi. A sixth pigmented ink is flexographically printed on the fifth pigment layer 45, forming the sixth pigment layer 46; xii. The fluorinated topcoat 5 is applied over the entire outer face 21 thus decorated of the shaped article from the finishing composition CF2; xiii. The article thus coated on both sides is fired at a temperature of 430 ° C for a period of 8 minutes; The disc thus coated and decorated corresponds to that illustrated in FIG. 8. The cohesion of the fluorinated decor layers on the particulate sub-layer was evaluated using the holding and transfer test using grids: 0% is obtained. tear and no color transfer on the tape. EXAMPLE 7 Four-Color Printing of Four Fluorescent Pigmented Thermostable Inks on a Non-pigmented Particle Substrate i. For the printing of the decor, yellow, cyan, magenta and black inks of 30 colors are made by using the respective pigments in a type 1 formulation ink; ii. The aluminum disc 2 is prepared by mechanical treatment (fine brushing with abrasive rollers) to give it good grip properties; iii. one of the faces 21 of the disc 2 is applied to the unpigmented particulate SC3 composition of heat-stable roll coating to form a particulate sub-layer 3 dried by infrared radiation; iv. then, a first fluorinated pigmented ink is printed flexographically on the particulate sub-layer 3, forming a first pigment layer 41; v. A second fluorinated pigmented ink is flexographically printed on the first pigment layer 41, forming a second pigment layer 42; vi. A third fluorinated pigmented ink is flexographically printed on the second pigment layer 42, forming the third pigment layer 42; vii. A fourth fluorinated pigmented ink is flexographically printed on the third pigment layer 42, forming the fourth pigment layer 42; 20viii. the disc thus coated and decorated is precooked at a temperature of 350 ° C for 8 minutes; ix. then applying to the opposite face 22 of the disc 2 the non-stick coating composition per roll forming a layer 7 of non-stick coating; 25 x. the disc thus coated is fired at a temperature of 430 ° C for a period of 8 minutes; xi. before being shaped by stamping to obtain the desired shape of item 1. The disc thus coated and decorated corresponds to that illustrated in FIG. 9. The cohesion of the fluorinated decorative layers on the particulate sub-layer has has been evaluated using the check and transfer test grid: 0% of tearing and no color transfer on the adhesive tape.
    [0024] COMPARATIVE EXAMPLE 1: Printing a non-fluorinated pigmented heat-stable ink (ink 2) on a particulate PTFE-based underlayer i. The aluminum disc 2 is chemically treated to give it good grip properties; ii. the disc 2 receives on one of its faces 21 a particulate sub-layer 3 printed per roll of the composition SC1; iii. the underlayer 3 is dried; iv. the non-fluorinated pigmented ink 2 is flexographically printed on this colorless 3v underlayer. the disc thus coated is precooked at 380 ° C for 5 minutes; vi. the second face 22 of the disc 2 receives a non-stick coating 7 applied by roll; vii. the disc 2 thus obtained is baked at a temperature of 430 ° C for a period longer than 5 minutes; viii. before being shaped by stamping.
    [0025] The disk thus coated and decorated corresponds to that illustrated in Figure 10. The anti adherence of the decor is insufficient. The cohesion of the decorative layers on the particulate sub-layer was evaluated using the grid transfer test: a large color transfer is obtained on the adhesive tape.
    权利要求:
    Claims (17)
    [0001]
    REVENDICATIONS1. A method of decorating an article (1) comprising the following steps: a) providing a support (2) comprising two opposite faces (21, 22); then b) applying a heat-stable particulate coating composition to one (21) of said faces of the support (2) to form a particulate underlayer (3), said particulate composition comprising at least one fluorocarbon resin, alone or with a thermostable bonding resin, and / or and at least one filler with good thermal resistance and / or a pigment with good thermal resistance, said application of the particulate composition being followed by a natural or forced drying; c) flexographic printing of a first pigmented decor composition on said particulate sub-layer (3) to form a decor having a discontinuous first decor layer (41), said first decor composition comprising at least one well-held pigment thermal; d) solidification heat treatment of said particulate sub-layer (3) and said first discontinuous decor layer (41); said method being characterized in that the decor composition further comprises a fluorocarbon resin whose melting or crosslinking temperature is equal to or less than that of the fluorocarbon resin contained in the particulate sub-layer (3).
    [0002]
    2. A method of decorating an article (1) comprising the following steps: a) providing a support (2) comprising two opposite faces (21, 22); b) applying a heat-stable particulate coating composition to one (21) of said faces of the support (2) to form a particulate underlayer (3), said particulate composition comprising at least one fluorocarbon resin, alone or with a thermostable bonding resin, and / or and at least one filler with good thermal resistance and / or a pigment with good thermal resistance, said application of the particulate composition being followed by a natural or forced drying; c) flexographic printing of a first pigmented decor composition on said particulate sub-layer (3) to form a decor having a discontinuous first decor layer (41), said first decor composition comprising at least one well-held pigment thermal; d) solidification heat treatment of said particulate sub-layer (3) and said first discontinuous decor layer (41); said method being characterized in that it further comprises, between step c) of applying the decor composition and step d) solidification heat treatment, an application step on the decor of a colorless finish composition comprising at least one fluorocarbon resin to form a colorless topcoat (5). 25
    [0003]
    3. A method of decorating an article (1) comprising the following steps: a) providing a support (2) comprising two opposite faces (21, 22); then b) applying a thermally stable particulate coating composition to one (21) of said faces of the support (2) to form a particulate underlayer (3), said particulate composition comprising at least one fluorocarbon resin, alone or with a heat-stable tackifying resin, and / or and at least one filler with good thermal resistance and / or a pigment with good thermal resistance, said application of the particulate composition being followed by a natural or forced drying; c) flexographic printing of a first pigmented decor composition on said particulate sub-layer (3) to form a decor having a discontinuous first decor layer (41), said first decor composition comprising at least one well-held pigment thermal; d) solidification heat treatment of said particulate sub-layer (3) and said first discontinuous decor layer (41); said method being characterized in that the particulate sub-layer (3) is a high absorption underlayer.
    [0004]
    4. A method according to any one of claims 1 to 3, further comprising, prior to step b) of applying the particulate composition, a step a) of surface treatment of the face of the support (21). ) intended to be coated.
    [0005]
    5. A process according to any one of the preceding claims, wherein the fluorocarbon resin of the thermostable coating particulate composition and optionally the fluorocarbon resin of the decor composition and / or the finishing composition are selected from the group consisting of polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoropropylvinyl ether (PFA), the copolymer of tetrafluoroethylene and hexafluoropropylene (FEP) and mixtures thereof.
    [0006]
    6. Process according to any one of the preceding claims, in which the thermostable coating composition comprises, in addition to the fluorocarbon resin, a thermostable bonding resin chosen from polyamide imides (PAI), polyetherimides (PEI) and polyimides. (PI), polyetherketones (PEK), polyetheretherketones (PEEK), polyethersulfides (PES) and polyphenylene sulfides (PPS).
    [0007]
    7. A process according to any one of the preceding claims, wherein the particulate sub-layer (3) is naturally dried, or forced by infrared radiation or convection of hot air.
    [0008]
    8. Method according to any one of the preceding claims, characterized in that the (or) pigment (s) with good thermal resistance of the decor composition and, where appropriate, the underlayer (3) of thermostable coating, is (are) chosen from inorganic pigments such as titanium dioxide, spinels, iron oxides, nickel titanate, carbon black, flakes of mica, or organic pigments such as perylene reds.
    [0009]
    9. A method according to any one of the preceding claims, further comprising between steps c) of flexographic printing of the first decor composition (41) and step d) of solidifying heat treatment: c ') a natural or forced drying phase of said first decorative layer (41); then c) flexographically printing at least one second pigmented decor composition comprising a second heat-stable pigment to form a second decor layer (42), said second decor layer (42) being superposition and / or juxtaposition of the previously printed pigment layer (s) (41), this step e) being repeated as many times as necessary to ensure the desired number of hues.
    [0010]
    10. Process according to any one of the preceding claims, characterized in that the solidification heat treatment d) is a firing carried out at a temperature between 380 ° C and 430 ° C.
    [0011]
    11. A method according to any one of the preceding claims, wherein the support (2) is in the form of a preform, and said method further comprises a step e) shaping the preform to obtain the form of the desired article.
    [0012]
    12. The method of claim 11, wherein the shaping step e) is carried out after step d) solidification heat treatment.
    [0013]
    13. The method of claim 11, wherein the substrate (2) is previously shaped before the step of applying the particulate sub-layer (3), the flexographic printing of the layer or layers of decor ( 41, 42) being then made only on the flat part of the face (21).
    [0014]
    The method of any one of the preceding claims, further comprising: - a precoating step of the particulate underlayer (3) and the at least one backing layer (41, 42) after printing (c) by flexography of the pigmented decorative composition (s), an application step f) a non-stick coating layer (7) on the one or more decorative layers (41, 42). ), this step f) being performed between said precooking step and the heat treatment step e).
    [0015]
    The method of any one of claims 1 to 13, further comprising: - applying before all the other steps a non-stick coating layer (7) on the face of the substrate (22) opposite to that (21) ) provided with one or more decorative layers (41, 42), and then - pre-baking the non-stick coating layer (7) covering the face of the substrate opposite to that provided with the decorative layer or layers (41, 42), prior to step b) of coating the particulate sub-layer (3).
    [0016]
    16. A method according to any one of the preceding claims, wherein the article (1) is a culinary article comprising a metal support (2) having an inner face (22) capable of receiving food and an outer face (21) for to be disposed towards the heat source.
    [0017]
    17. The method of claim 16, wherein the support (2) is: a monolayer structure of anodized aluminum or not, or polished aluminum, brushed or microblasted, sandblasted, chemically treated, or cast aluminum, or polished, brushed or micro-blasted stainless steel, or cast iron, or hammered or polished copper; or a multilayer structure, in part or in whole, comprising from outside to inside the following layers stainless steel / aluminum / stainless steel or stainless steel / aluminum / copper / aluminum / stainless steel, or a cap of aluminum foundry, aluminum or aluminum alloys lined with a stainless steel outer bottom 5.
    类似技术:
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    同族专利:
    公开号 | 公开日
    KR20160094392A|2016-08-09|
    CN105793054A|2016-07-20|
    EP3077210B1|2017-10-04|
    ES2645485T3|2017-12-05|
    FR3014014B1|2015-11-20|
    JP2017501778A|2017-01-19|
    EP3077210A1|2016-10-12|
    US20160368261A1|2016-12-22|
    WO2015082820A1|2015-06-11|
    CN105793054B|2018-09-11|
    KR102298956B1|2021-09-08|
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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 |
    2019-09-27| ST| Notification of lapse|Effective date: 20190906 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362044A|FR3014014B1|2013-12-03|2013-12-03|METHOD FOR DECORATING BY FLEXOGRAPHY AN ARTICLE COMPRISING A THERMOSTABLE COATING|FR1362044A| FR3014014B1|2013-12-03|2013-12-03|METHOD FOR DECORATING BY FLEXOGRAPHY AN ARTICLE COMPRISING A THERMOSTABLE COATING|
    ES14821766.4T| ES2645485T3|2013-12-03|2014-12-01|Flexography decoration procedure of an article comprising a thermostable coating|
    KR1020167017401A| KR102298956B1|2013-12-03|2014-12-01|Method for decorating an item including a heat-stable coating by flexography|
    JP2016536555A| JP2017501778A|2013-12-03|2014-12-01|Article decoration method by flexographic printing including a heat-stable coating|
    PCT/FR2014/053104| WO2015082820A1|2013-12-03|2014-12-01|Method for decorating an item including a heat-stable coating by flexography|
    CN201480066138.XA| CN105793054B|2013-12-03|2014-12-01|The trailing that the device including refractory coating is decorated by flexographic printing|
    US15/101,185| US20160368261A1|2013-12-03|2014-12-01|Method for Decorating an Item Including a Heat-Stable Coating by Flexography|
    EP14821766.4A| EP3077210B1|2013-12-03|2014-12-01|Process for decorating an article by flexography, said article comprising a heat-resistant coating|
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