Compositions: coating or plastic – Coating or plastic compositions – Marking
Reexamination Certificate
2000-01-07
2002-06-11
Koslow, C. Melissa (Department: 1755)
Compositions: coating or plastic
Coating or plastic compositions
Marking
C106S031620, C106S031750, C106S031860, C106S031870, C106S031880, C106S401000
Reexamination Certificate
active
06402823
ABSTRACT:
FIELD OF INVENTION
The present invention relates to individual inks and an ink set for use in the color ink jet printing of glazed articles that are to be subjected to high temperatures such as, for example, ceramic tiles, a method of decorating glazed articles using the inks of the ink set, and glazed articles having ink jet printed decorations formed thereon.
BACKGROUND OF THE INVENTION
Articles that are subjected to high temperatures during processing such as, for example, glazed ceramic tiles, are conventionally decorated by serigraphic screen printing or roller processes, which are well known. Articles are decorated in this manner by the sequential application of pastes that contain solid milled colored pigments and/or glasses suspended in a liquid carrier. After the pastes have been applied or transferred to the surface of the article, the article is heated to high temperatures, typically from about 500° C. to about 1,250° C., for several minutes to melt the glasses and incorporate the color-forming solids onto the surface of the ceramic article and to burn off the liquid carrier.
Serigraphic screen printing and roller processes are well suited for some applications such as, for example, single-color decoration of glazed ceramic tiles. However, such processes are not particularly well suited for generating complex multicolor decorations because separate pastes and separate screens are usually required for each color used in the decoration. While it is possible in some cases to generate intermediate colors using serigraphic screen printing or roller processes by combining by overprinting two or more pastes from a set of subtractive complementary color pastes, such intermediate colors tend to vary widely in color and quality from piece to piece because it is very difficult to consistently position sequential screens or patterns on an object and apply precise amounts of paste. Moreover, the overprinted combinations of different color pigments do not always produce satisfactory colors on glazed ceramic tiles and surfaces. Due to these limitations, intermediate colors are conventionally generated in serigraphic screen printing and roller processes by applying a paste of the desired color.
One of the printing processes that can be used to generate consistent high quality multicolor decorations is color ink jet printing. In the process of color ink jet printing, which is well known, intermediate colors are generated on the surface of articles that are to be exposed only to relatively low temperatures such as, for example, sheets of paper, by closely printing small dots of at least two inks from an ink set that commonly includes at least three inks for producing the standard subtractive complementary cyan (“C”), magenta (“M”), and yellow (“Y”) colors. Ink sets of this type are conventionally referred to as CMY ink sets. To the unaided human eye, the closely printed small dots of the subtractive complementary colored ink appear to be high quality intermediate colors such as red, green, blue, orange, and brown. However, when viewed under magnification, it is usually possible to identify discrete dots of the subtractive complementary colored inks which may or may not actually overlap.
Typically, ink sets for use with color ink jet printers for low temperature objects (such as paper) also include an ink for producing the color black (“K”) as opposed to generating black by combination of other inks of the ink sets. Ink sets of this type are conventionally referred to as CMYK ink sets. A black ink is included in these ink sets because black is usually the most frequently printed color on low temperature articles, such as sheets of paper, and including a black ink in the ink set avoids the necessity and expense of using the other inks of the ink set to form a black color. Furthermore, a better and more intense black color is usually obtained using a black ink than by combination of the other inks of the ink set.
It would be highly advantageous to be able to decorate high temperature articles, such as glazed ceramic tile and other glazed articles, using color ink jet printing technology. Color ink jet printing is a non-contact process that could significantly reduce loss due to breakage in production of decorated glazed ceramic tiles or articles, which would thus reduce the amount of waste generated during such processes. Another advantage of color ink jet printing is that instant design changes are possible by changing the software command signal that is sent to the print head, thus increasing the speed and efficiency of the process of developing new tile decoration designs. By contrast, with the currently used serigraphic screen printing decoration technology, new screens must be created and properly aligned and a new coloring paste prepared every time a design change is made. Thus, the changing of designs and colors with conventional screen printing and roller processes is costly and time consuming.
Inks conventionally used in the color ink jet printing of articles that are exposed only to low temperatures, such as sheets of paper, cannot be used on articles that are to be subjected to high temperatures, such as glazed ceramic tiles, because the organic color producing pigments in such conventional inks decompose when exposed to temperatures greater than 300° C. for more than a few minutes. Similarly, pastes conventionally used in the serigraphic screen printing of articles that are to be subjected to high temperatures, such as glazed ceramic tiles, cannot be used in ink jet printers because such pastes are too viscous and contain high loadings of suspended colorforming solids which tend to sediment.
Airey et al., U.S. Pat. No. 5,407,474, discloses inks containing solid inorganic pigments that can be applied to high temperature articles using an ink jet printer, but it has been found that it is difficult to precisely control the application of such inks. Inks which are based upon the suspension of inorganic solids in solution are not stable due to the large difference between the density of the inorganic solid and the solution in which they are suspended. Moreover, such inks also require a relatively high loading of inorganic color producing solids in order to achieve satisfactory color intensities, thus further complicating their use in ink jet printers. It is known that the size and size distribution of solids included in inks used in ink jet printing is critical, as the working lifetime of the ink jet print head is significantly reduced by clogging, especially if there are particles that are too large to pass through the nozzles. It is also known that even very small solid particles can agglomerate to form larger particles, again causing sedimentation of the ink and clogging of the nozzles of the print head. de Saint Romain, U.S. Pat. No. 5,273,575, discloses several ink compositions that can be applied using an ink jet printer to articles that are to be subjected to temperatures greater than 300° C. These ink compositions contain water soluble metallic salts which, after decomposition by heat, form colored oxides or colored combinations with the material of the article upon which they are deposited. Several ink compositions are disclosed in the examples in de Saint Romain that can be used to form the colors black, gray, green, blue, brown, and gray-blue on the surface of various ceramic surfaces, the color obtained being dependent upon the composition of the article and the firing temperature employed. Although de Saint Romain discloses several ink compositions that can be applied to high temperature articles using an ink jet printer, de Saint Romain does not teach or suggest that the ink compositions can be used on glazed surfaces. Moreover, de Saint Romain does not teach or suggest that the ink compositions can be used in combination to form a subtractive complementary color set capable of forming intermediate colors for decoration. Moreover, de Saint Romain does not disclose any ink compositions that can be used to form the colors magenta, yellow, or a high quality black on a
Benet Garcia Carlos
Fenollosa Romero Jose Luis
Garcia Sainz Javier
Querol Villalba Antonio Manuel
Secrest Patricia C.
Faison Veronica F.
Ferro Corporation
Koslow C. Melissa
Rankin, Hill Porter & Clark LLP
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