Processes for producing colored glass or glass-ceramic articles bearing a non-stick coating, compositions for carrying out said processes, and resultant colored articles

Abstract: The invention provides processes and composi­ tions to make non-stick glass and glass-ceramic ware having clear, vivid, brilliant, attractive colors and stable and durable decorating patterns. The invention consists in precoating the substrate surface with a polyimide resin containing colored pigment and, prefera­ bly, an organosilane. The good imperviousness of this pigmented precoating insures the durability of the aspect and of the performances of the finished ware coated with a fluorocarbon or silicone polymer. By comparison with articles of the prior art, the resulting non-stick glassware is more attractive and its aspect is not deteriorated by the action of detergents and fat.

Description: The present invention relates to a process for producing colored articles consisting of a transparent glass or glass-ceramic substrate and of at least one layer of a non-stick polymer, to said articles and to a composition for carrying out said process. Non-stick cooking utensiles having good release properties toward food are usually coated with fluorocarbon polymers (polytetrafluoroethylene, PTFE, fluorinated ethylene-propylene copolymer, FEP, etc.) or with polysiloxanes (silicones resins). A gritblasting of the articles to be coated is the usual surface treatment recommended for metallic substrates such as aluminium, cast iron, in order to develop a mechanical anchoring of the non-stick coating into the substrate roughness. For an identical purpose, CORNING GLASS WORKS (CGW) has proposed a more effective surface treatment for polyphased glasses and glass ceramics including a gritblasting and a selective chemical etching (U.S. Patent No. 4.683.168). Another way, described in our concurrently filed EP-A-0386379 for "Article provided with a non-stick coating with improved adhesion to the substrate and durability, its manufacturing process and composition used", consists in the deposit of a precoating layer composed of a polyimide resin and an amino- or polyamino-alkoxysilane. This precoating is bonded to the glass via a condensation reaction of the hydroxy functions of the hydrolyzed silane and of the glass surface. When a fluorocarbon non-stick coating containing a polyimide binder is applied on this precoating a continuous chemical linkage from the glass surface to the non-stick coating is obtained. The silane modified polyimide precoating was found also very efficient to promote the adhesion of fluorinated coatings containing a polyether sulphone binder and of silicone coatings. In this way, the gritblasting of the substrate is not necessary. Fluorocarbon (PTFE) coatings are generally porous and are in use prone to staining due to the penetration of fat or food in their porosity. Manufacturers of fluorinated polymer coatings make this staining less visible by supplying dark colored coating compositions (dark grey, black, brown). Nevertheless, transparent glass articles coated after gritblasting with a PTFE non-stick coating are subject to a supplementary staining phenomenon resulting from the diffusion of detergents, fat and the like through the non-stick coating to the glass surface. These aspect damages are visible, for example, from the external side of a PTFE coated PYREX® cookware after a few uses. Besides, due to the glass transparency, coating of PYREX® cookware with the non-stick compositions presently supplied by manufacturers (DU PONT DE NEMOURS AND C°, WHITFORD CORPORATION, etc) leads to articles exhibiting externally the color of the non-stick coating, that is, as mentioned above, usually dark and non-attractive. A solution for these problems can be a strong coloration of the glass substrate. Colored glass can be obtained for instance by adding oxydes of transition metals (V, Cr, Mn, Fe, Co, Ni, Cu) to the glass composition or by introducing reducible ions of noble metals (Cu, Au, Ag, Pt) (see for example J. ZARZYCKI, "Les verres et l'état vitreux", Masson, Paris, 1982). In this case, the bulk of the glass is entirely colored. These processes are not very versatile given that a particular color of the glass requires a particular glass composition. The present invention has for object to solve said problems by another approach comprising the application on the colorless glass or glass-ceramic of a first polymer layer (precoating) having good barrier properties towards detergents and fat and having a suitable coloration to give to the finished article, with its non-stick coating, commercially attractive and durable aspect. This colored precoating also displays a good adhesion ability toward the glass substrate and the non-stick coating. The application of multi-colored precoating being possible, elaborated decorating effects can also be obtained. More precisely, the present invention relates to a process for producing colored article consisting of a transparent glass or glass-ceramic substrate and of at least one layer of a non-stick polymer covering at least partially said substrate, characterized by (A) gritblasting the portion of the substrate surface to be coated ; (B) applying on that portion a layer of a pigmented polyimide resin ; (C) drying and heating said pigmented polyimide resin at a temperature sufficiently high to convert said pigmented resin into a pigmented solid film ; and then (D) applying said non-stick layer. The present invention relates also to a composition for carrying out the process defined in claim 1, which comprises (1) a polyimide resin, and (2) a pigment. According to a preferred embodiment of the process of the invention, the pigmented polyimide resin applied in step (B) contains further an organosilane having two types of functional groups, one of them reacting, after hydrolysis, with -OH groups of the substrate surface, the other being reactive with the polyimide resin. The invention relates also to a composition useful for carrying out said preferred process, characterized in that it consists of (1) a polyimide resin ; (2) a pigment; and (3) an organosilane with two types of functionnal groups, one of them being reactive, after hydrolysis, with -OH groups of the substrate surface and the other being reactive with said polyimide. The present invention relates finally to an article consisting of a transparent glass or glass-ceramic substrate, and of at least one layer of a non-stick polymer covering at least partially said substrate, characterized by the fact that it contains also, applied between said substrate and said non-stick polymer, a pigmented polyimide layer, said layer being applied on a gritblasted surface of said substrate ; as well as to such an article wherein said pigmented polyimide layer further comprises an organosilane chemically bound to -OH groups of the substrate surface and to said polyimide layer. The present invention permits to produce glass cookware articles coated with a non-stick coating and exhibiting externally clear, vivid, brilliant, attractive colors and durable decorations non-sensitive to staining. It consists in the application of a colored precoating on a transparent glass or glass ceramic cookware before the application of the non-stick coating. The role of this precoating is multiple, preventing the diffusion of detergents and fat toward the inside cookware surface, ensuring the adhesion of the non-stick coating, and determining colors or the decoration of the finished non-stick article. The polyimide resin used in the present invention can be any polyimide resin. Preferred classes of polyimide resin are, however, the polyamide-imides 1 (PAI-1) and 2 (PAI-2) defined in the Recommendation LI of the Bundesgesundheitsamt (issued as communication 160 in the Bundesgesundheitsblatt, Vol. 26, n° 7, Juillet 1983, pages 219-221) which teaches appropriate polymeric coating systems for frying, boiling and baking utensils. PAI-1 is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diisocyanatodiphenylmethane with trimellitic anhydride.PAI-2 is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diaminodiphenylmethane with benzoyl chloride-3,4-dicarboxylic acid anhydride. These polyamide-imides are prefered because of their food-contact approval by the administrations of most countries. It should be noted that these polyamide-imides 1 and 2 are described in tee above-referred Recommendation as bonding resins to be used in admixture with homopolymers or copolymers of tetrafluoroethylene. Said recommendation does not suggest that these polyamide-imides can be used for forming a colored pre-coating to be overcoated with a non-stick coating. Polyamide-imide resins (PAI-1, PAI-2) are currently supplied by WHITFORD CORPORATION (Box 507, West Chester, Pa 19381, USA), WHITFORD PLASTICS Ltd (Brindley 86, Astmoor, Runcorn, Cheshire, WA7 1PF, GB), AMOCO CHEMICALS CORPORATION (200 East Rodolphe Drive, Chicago, Illinois, 60 601, USA), among others. An example of unpigmented polyamide-imide resin is supplied by WHITFORD PLASTICS Ltd under the reference XYLAN® 8470-0170-3320 Clear Resin (PAI-1). The coloration of a clear PAI resin is achieved by adding pigments giving the desired color. As examples of clear colored pigments, one can use the IRIODIN® pearl lustre pigments (E. MERCK, Postfach 4119, D-6100 Darmstadt 1, WG), the ET 1024 aluminium pigment (SILBERLINE Ltd, Banbeath Industrial Estate, Leven, Fife, Scotland, KY8 5 HD, GB), etc... A darkening of the color is also possible, for example, with SPEZIALSCHWARZ carbon black pigments (DEGUSSA AG, GB AC, D-6000, Frankfurt 1, WG). All the pigments cited are physiologically safe and thermally stable. Examples of typical colors of non-stick PYREX® articles prepared from several pigmented precoating compositions are given in the table A. Type of pigment External color of non-stick PYREX® article IRIODIN® 504 Brilliant red IRIODIN® 530 Brilliant bronze IRIODIN® 502 Brilliant red-brown IRIODIN® 235 Clear green (interference color) IRIODIN® 225 Blue (Interference color) ET 1024 aluminium Sparkle grey IRIODIN® 153 + FW6 carbon black Sparkle dark grey The amount of pigments added to the clear PAI resin is a function of the desired coloring effect, of the type of pigment, of the particle size, etc... Typical formulations will be proposed in the examples of the present invention. By using masks and silkscreen printing, decorating patterns of several colors (stars, flowers,....) can be designed from differently pigmented procoating compositions. Dried thicknesses of the colored precoating between 10 to 20 µm are usually satisfactory to obtain the desired coloring effect and good barrier properties towards detergents and fat ; but, of course, thicker precoatings would be also useful. Gritblasting of the glass cookware provides a suitable mechanical anchoring of the colored precoating onto the inside cookware surface. Roughness profile with an arithmetic mean (Ra) value of a few µm, for example of the order of 5 µm has been found satisfactory. Nevertheless, the preferred process consists in adding to the precoating compositions a small amount of an amino- or polyamino-alkoxysilane (1 to 10% by weight of the colored polyimide resin composition), for achieving a chemical bonding at the precoating/glass interface. Among the amino- or polyamino-alkoxysilanes which are well-known compounds, gamma-aminopropyltriethoxysilane (A-1100, UNION CARBIDE ; 73000 SILBIONE, RHONE-POULENC, etc.) is preferred, due to its relatively low price and its approval for food contact. In addition, silane release measurements, in food simulants (water, oil, alcohol, acetic acid), from coated articles have been found below 1 mg per liter (< 1 ppm). The used non-stick layer or layers can be of any type. The most currently used are produced from compositions based on polymers or copolymers of tetrafluoroethylene or on silicones. Such compositions are commercially available from various sources and their mode of application is well-known. It appears, thus unnecessary to disclose them further. The invention will be further illustrated by the following non-limiting examples. In these examples, the performance and durability of glass coated with non-stick coatings, with or without a precoating according to the present invention, were evaluated by using adhesion tests, thermal aging test, and experiments of permeability to detergents and fat. Adhesion tests : Adhesion is evaluated with the cross-hatch and the thumb nail tests after submerging the non-stick articles in boiling water for 15 minutes. After the boiling water treatment, the samples are dried and cooled to room temperature. Cross-hatch test (CHT): The materials used are a scalpel or a razor blade, 3M's Scotch Brand 898 adhesive tape and a template having eleven parallel grooves (distance between two grooves: 2 mm). Using the template, eleven cuts are scribed through the coating, and eventually through the precoating, to the glass substrate. This procedure is repeated at right angle to produce a grid of 100 squares. Over the scribed area, a strip of adhesive tape is pressed, the tape running parallel to one set of scribed lines. The tape is firmly rubbed with the fingernail to obtain maximum contact. Then, the tape is firmly and rapidly pulled off at a 90° angle. This last step is repeated with a fresh piece of tape after having rotated the area of 90°. Adhesion is good if no scribed square is peeled off. Thumb nail test (TNT): This scratch test involves the use of the thumbnail to chip or peel away the coating, and eventually the precoating, from the edge of a deliberate scalpel scratch in the non-stick coating (and in the precoating). The scalpel scratch is made down to the bare glass. After the coating (and the precoating) is (are) firmly pulled away from the scratch at a 90° angle, the length of the nail track is measured. Adhesion is considered as good if the length of the track is smaller than 6 millimetres. Thermal aging : The thermal aging is evaluated by heating the coated samples, with or without precoating in a stove at 250°C for 6 days and submitting them to the adhesion tests. Detergent permeability The samples are submerged in a 3 percent sodium carbonate solution (80 g of Na₂CO₃, 10 H₂O for one liter of deionized water) at 95°C for one hour. After rinsing with cold water and drying, the coating inside of the samples and the coating or precoating/glass interface are observed. Presence of blisters, pops, delamination, permeation, staining and the like is noticed. Fat permeability The samples are filled with a thick layer of sunflower oil and placed in a stove at 200°C for one hour. After this cooking, the samples are cooled, cleaned out and the coating or precoating/glass interface is examined. One notices the possible presence of staining or greasy spots due to the diffusion of fat down to the glass surface. EXAMPLES The efficiency of the proposed invention in comparison with the processes of the prior art is proved by the following examples. Exemple 1 : In this example, we compare the performance and the aspect of PYREX® articles coated with two layers of PTFE compositions supplied by E.I. DU PONT DE NEMOURS AND C° after the usual gritblasting, and the performance and the aspect of PYREX® articles precoated according to the invention, then coated with the PTFE layers. The precoating composition was prepared by adding 6 parts by weight of IRIODIN® 504 to 100 parts of XYLAN® 8470-0170-3320 clear polyamide-imide resin (PAI-1 from WHITFORD). Viscosity adjustment was made by adding ethanol and water. For mechanical adhesion of the precoating, the PYREX® article is gritblasted to an arithmetic mean roughness (Ra) of about 5 µm. For chemical adhesion of the precoating,1.25 part of gamma-aminopropyltriethoxysilane was added to 100 parts of the colored precoating. This precoating was directly applied after ethanol cleaning of the ware. The different layers were applied by gun spraying in order to have a total dried PTFE film thickness of about 20 µm and a precoating thickness of about 10 µm. Precoating, drying and PTFE curing schedules are given in Table 1. The results of the adhesion evaluation by means of the cross-hatch test (CHT) and the thumb nail test (TNT) performed before and after thermal aging and the results of the experiments of permeability toward detergents and fat are summarized also in Table 1. From these results it can be concluded that the PTFE coatings are very permeable to detergents and fat. On the contrary, the colored polyamide-imide precoating has very good barrier properties and good adhesion ability toward glass and PTFE coating. PYREX® were treatments of type C and D show that the colored precoating/glass adhesion can be either mechanical or chemical in nature. It appears also clearly that non-stick PYREX® ware precoated according to the invention exhibit a brilliant and attractive red color quite different from the dark color of the PTFE non-stick coatings supplied by E.I. DU PONT DE NEMOURS AND C°. This vivid color is not effected by staining and is not altered by the thermal aging. Example II : As in example I, we compare the performance and the aspect of PYREX® samples coated with two layers of PTFE compositions supplied by E.I. DU PONT DE NEMOURS AND C° under the reference 459 Z 67303 and 456 Z 67302 after the usual gritblasting, and the performance and the aspect of PYREX® articles precoated according to the invention, then coated with the PTFE layers. The precoating composition was obtained by mixing 6 parts by weight of IRIODIN® 225 with 100 parts of XYLAN® 8470-0170-3320 clear polyamide-imide resin (PAI-1 from WHITFORD). An arithmetic mean roughness (Ra) of 5 µm was created by gritblasting to promote the glass/precoating mechanical adhesion. An alternative chemical adhesion has been obtained by adding 1.5 part of gamma-aminopropyltriethoxysilane to 100 parts of the colored precoating composition. The total thickness of the PTFE layers was of 20 µm and, for the PYREX® items coated according to the invention, the precoating thickness was of 10 µm. Three different samples were considered corresponding to the B, C and D samples of Table 1 for the drying conditions of the precoating and for the PTFE curing. All the results concerning the adhesion evaluted with the cross-hatch test and the permeability are collected in Table 2. The external aspect of non-stick PYREX® articles is also compared. As mentioned in example I, it can be concluded that precoated items have good adhesion properties and a good impermeability toward detergent and fat. Blue to blue-green nuances of the precoating can be obtained by adjusting the precoating thickness (interference color). PYREX® ware treatment ADHESION PERMEABILITY EXTERNAL COLOR BEFORE THERMAL AFTER AGING Detergents Fat - Gritblasting (Ra=5µm) good good complete permeation blisters complete permeation Dark grey - Gritblasting (Ra=5µm) good good no defect no defect Blue - Colored precoating (according to the invention) - Silylated colored precoating (according to the invention) good good no defect no defect Blue Example III : A non-stick PYREX® dish having externally a brilliant red aspect was obtained by adding 4 parts by weight of IRIODIN® 504 to 100 parts of XYLAN® 8470-0170-3320 clear resin. The mixing of 4.3 parts of gamma-aminopropyltriethoxysilane with 100 parts of the colored composition provided the adhesion of this precoating to the glass. After application of this composition and drying for 10 minutes at 100°C (dried thickness: 15 µm), the two coat non-stick coating, code 459 Z 67303 and 456 Z 67302, from E.I. DU PONT DE NEMOURS AND C°, was sprayed on the precoated substrate. The thickness of these two layers was respectively 12 and 8 µm. The curing of the coating was achieved after 10 minutes at 400°C. Adhesion at interfaces evaluated by using CHT and TNT was found very good and durable after thermal aging. The brilliant red color was stable after thermal aging and was not sensitive to detergent or greasy staining. Example IV : A non-stick PYREX® bakeware, externally brilliant red was prepared as described in example III, by adding 8 parts of IRIODIN® 504 to 100 parts of XYLAN® 8470-0170-3320 clear resin. Example V : With the same procedure as that of Example III, a brilliant bronze colored non-stick PYREX® bakeware was obtained by adding 8 parts of IRIODIN® 530 to 100 parts of XYLAN® 8470 clear resin. Example VI : An externally brilliant red-brown non-stick PYREX® bakeware was prepared as described in example III, by adding 8 parts in weight of IRIODIN® 502 to 100 parts of XYLAN® 8470 polyamide-imide clear resin. Example VII : Similarly to example V and VI, externally brilliant bronze or red-brown non-stick PYREX® articles were prepared by adding respectively 6 parts by weight of IRIODIN® 530 or IRIODIN® 502 to 100 parts of XYLAN® 8470 polyamide-imide clear resin. Example VIII : An externally clear green, non-stick PYREX® bakeware was prepared as described in example III, by adding 6 parts by weight of IRIODIN® 235 to 100 parts of XYLAN® 8470 polyamide-imide clear resin (interference color). Example IX : A non-stick PYREX® bakeware colored in sparkle dark grey was prepared by adding carbon black and silver white IRIODIN® 153 to a polyamide-imide resin of type 2 (PAI-2) from WHITFORD PLASTICS Ltd, modified with gamma-aminopropyltriethoxysilane (4.3 parts for 100 parts of colored resin). The non-stick coating was applied as described in example III. Example X : A non-stick VISION® frypan having a sparkle metallized grey external aspect was prepared by adding 10 parts by weight of ET 1024 SILBERLINE® aluminium pigment to 100 parts of the clear polyamide-imide resin (PAI-I) from WHITFORD PLASTICS Ltd. In this mixture was also added 4,3 parts by weight of gamma-aminopropyltriethoxysilane per 100 parts of colored resin. After spraying and drying of this precoating, the fluorinated non-stick coating was applied as in example III. Example XI : By using masks and silkscreen printing, decorating patterns of several colors (stars, flowers, ...) were obtained with a silane-modified polyamide-imide layer differently pigmented. The non-stick coating was then applied on the multicolored precoating as described in example III. Example XII : A bakeware was coated with a silicone resin obtained by mixing 10 parts by weight of 6-2230 resin in 100 parts of Q1-2531 resin (resins supplied by Dow Corning C°). Aluminium pigment (sparkle silver 5000 AR, SILBERLINE) and carbon black were added to color in grey the non-stick coating. This coating was applied on a brilliant red precoated bakeware, the precoating being composed of XYLAN® 8470 clear resin (PAI-1) containing 7.1% by weight of IRIODIN® 534 and 3.8% by weight of gamma-aminopropyltriethoxysilane. Drying of the precoating and curing of the non-stick coating were achieved at 150°C and 250°C, respectively. The aspect of the finished non-stick bakeware was thus grey inside and brilliant red outside. Precoating and non-stick coating adhesion was found very good and durable after the thermal aging. The aspect of this item was stable, durable and not sensitive to the action of detergents and fat. The above examples clearly demonstrate that the present invention provides means to produce non-stick glass and glass ceramic ware having clear, vivid, brilliant, attractive colors and stable and durable decorating patterns. For transparent substrates, an infinite number of color nuances and of decorating possibilities can be created. The decorating effects and colors are not sensitive to detergents and fat staining given the perfect imperviousness of the pigmented polyimide precoating. Besides, the precoating compositions have a good adhesion ability toward the glass and glass ceramic substrates and toward non-stick coatings. Thus, the precoating properties insure a good durability of the aspect and of the performances of the non-stick glass ware made according to the present invention. Moreover, the compositions and the processes disclosed are particularly suitable for application to an industrial scale. Obviously, the procedures described above are only examples, and they could be modified, in particular by substitution of technical equivalents without departing from the scope of the present invention.

Claims: Claims for the following Contracting States : ES, FR, IT Process for producing colored article consisting of a transparent glass or glass-ceramic substrate and of at least one layer of a non-stick polymer covering at least partially said substrate, characterized by (A) gritblasting the portion of the substrate surface to be coated ; (B) applying on that portion a layer of a pigmented polyimide resin ; (C) drying and heating said pigmented polyimide resin at a temperature sufficiently high to convert said pigmented resin into a pigmented solid film ; and then (D) applying said non-stick layer. Process according to claim 1, characterized in that the pigmented polyimide resin applied in step (B) contains further an organosilane having two types of functional groups, one of them reacting, after hydrolysis, with -OH groups of the substrate surface, the other being reactive with the polyimide resin. Process according to claim 1 or 2, characterized by the fact that the polyimide resin is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diisocyanatodiphenylmethane with trimellitic anhydride. Process according to claim 1 or 2, characterized by the fact that the polyimide resin is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diaminodiphenylmethane with benzoyl chloride-3,4-dicarboxylic acid anhydride. Process according to claim 2, characterized by the fact that the organosilane is an amino or polyaminoalkoxysilane. Process according to claim 5, characterized by the fact that the amino-alkoxysilane is gamma-aminopropyltriethoxysilane. Process according to claim 6, characterized by the fact that the proportion of organosilane is between 1 to 10 percent by weight of the mixture applied in step (B). Process according to claim 7, characterized by the fact that the proportion of organosilane is between 1 to 5 percent by weight of the mixture applied in step (B). Process according to any one of claims 1 to 8, characterized by the fact that said non-stick coating is comprised of either a fluorocarbon or a silicone polymer. Article consisting of a transparent glass or glass-ceramic substrate, and of at least one layer of a non-stick polymer covering at least partially said substrate, characterized by the fact that it contains also, applied between said substrate and said non-stick polymer, a pigmented polyimide layer, said layer being applied on a gritblasted surface of said substrate. Article according to claim 10, characterized in that said pigmented polyimide layer further comprises an organosilane chemically bound to -OH groups of the substrate surface and to said polyimide layer. Article according to claim 10 or 11, characterized in that said polyimide derives from poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diisocyanatodiphenylmethane with trimellitic anhydride. Article according to claim 10 or 11, characterized in that said polyimide derives from poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diaminodiphenylmethane with benzoyl chloride-3,4-dicarboxylic acid anhydride. Article according to any one of claims 10 to 13, characterized in that said non-stick polymer is a fluorocarbon or a silicone polymer. Article according to any one of claims 10 to 14, characterized in that it is cookware. Composition for carrying out the process defined in claim 1, which comprises (1) a polyimide resin, and (2) a pigment. Composition for carrying out the process defined in claim 2, which comprises (1) a polyimide resin ; (2) a pigment and (3) an organosilane with two types of functional groups, one of them being reactive, after hydrolysis, with -OH groups of the substrate surface and the other being reactive with said polyimide. Composition according to claims 16 or 17, characterized in that said polyimide resin is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diisocyanatodiphenylmethane with trimellitic anhydride. Composition according to claims 16 or 17, characterized in that said polyimide resin is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diaminodiphenylmethane with benzoyl chloride-3,4-dicarboxylic acid anhydride. Composition according to claim 7, characterized in that said organosilane is an amino- or polyaminoalkoxysilane. Composition according to claim 20, characterized in that said amino-alkoxysilane is gamma-aminopropyltriethoxysilane. Composition according to claim 21, characterized in that the organosilane proportion in the pigmented polyimide resin is between 1 to 10% by weight. Claims for the following Contracting States : DE, GB Process for producing colored article consisting of a transparent glass or glass-ceramic substrate and of at least one layer of a non-stick polymer covering at least partially said substrate, characterized by (A) gritblasting the portion of the substrate surface to be coated ; (B) applying on that portion a layer of a pigmented polyimide resin ; (C) drying and heating said pigmented polyimide resin at a temperature sufficiently high to convert said pigmented resin into a pigmented solid film ; and then (D) applying said non-stick layer. Process according to claim 1, characterized in that the pigmented polyimide resin applied in step (B) contains further an organosilane having two types of functional groups, one of them reacting, after hydrolysis, with -OH groups of the substrate surface, the other being reactive with the polyimide resin. Process according to claim 1 or 2, characterized by the fact that the polyimide resin is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diisocyanatodiphenylmethane with trimellitic anhydride. Process according to claim 1 or 2, characterized by the fact that the polyimide resin is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diaminodiphenylmethane with benzoyl chloride-3,4-dicarboxylic acid anhydride. Process according to claim 2, characterized by the fact that the organosilane is an amino or polyaminoalkoxysilane. Process according to claim 5, characterized by the fact that the amino-alkoxysilane is gamma-aminopropyltriethoxysilane. Process according to claim 6, characterized by the fact that the proportion of organosilane is between 1 to 10 percent by weight of the mixture applied in step (B). Process according to claim 7, characterized by the fact that the proportion of organosilane is between 1 to 5 percent by weight of the mixture applied in step (B). Process according to any one of claims 1 to 8, characterized by the fact that said non-stick coating is comprised of either a fluorocarbon or a silicone polymer. Article consisting of a transparent glass or glass-ceramic substrate, and of at least one layer of a non-stick polymer covering at least partially said substrate, characterized by the fact that it contains also, applied between said substrate and said non-stick polymer, a pigmented polyimide layer, said layer being applied on a gritblasted surface of said substrate. Article according to claim 10, characterized in that said pigmented polyimide layer further comprises an organosilane chemically bound to -OH groups of the substrate surface and to said polyimide layer. Article according to claim 10 or 11, characterized in that said polyimide derives from poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diisocyanatodiphenylmethane with trimellitic anhydride. Article according to claim 10 or 11, characterized in that said polyimide derives from poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diaminodiphenylmethane with benzoyl chloride-3,4-dicarboxylic acid anhydride. Article according to any one of claims 10 to 13, characterized in that said non-stick polymer is a fluorocarbon or a silicone polymer. Article according to any one of claims 10 to 14, characterized in that it is cookware. Composition for carrying out the process defined in claim 1, which comprises (1) a polyimide resin, and (2) a pigment, no organosilane being present in said composition. Composition according to claim 16, characterized in that said polyimide resin is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diisocyanatodiphenylmethane with trimellitic anhydride. Composition according to claims 16 or 17, characterized in that said polyimide resin is poly-N-(4,4'-diphenylmethane-trimellitamide-imide) prepared by reaction of 4,4'-diaminodiphenylmethane with benzoyl chloride-3,4-dicarboxylic acid anhydride.

Inventors: CARRE ALAIN ROBERT EMILE, ROGER FRANCOISE MARIE MICHELE, CARRE, ALAIN ROBERT EMILE, ROGER, FRANCOISE MARIE MICHELE, Roger, Françoise Marie Michèle
Applicants: CORNING INC, CORNING INCORPORATED
Application year: 1989
Main classification: C03C17
IPC codes: C03C17