US 3489587 A
Description (OCR text may contain errors)
Jan. l3, 1970 s. WEINGRAD 3,489,587
CERAMIC DECALCOMANIAS Filed Sept. 13, 1965 ATTORNEY United States Patent 3,489,587 CERAMIC DECALCOMANIAS Saul Weingrad, Hillsdale, NJ., assignor to Commercial Decal, Inc., Mount Vernon, N.Y., a corporation of New York Filed Sept. 13, 1965, Ser. No. 486,953 Int. Cl. 341m 3/12 U.S. Cl. 117-3.6 7 Claims ABSTRACT OF THE DISCLOSURE 'A vitreous decalcomania is formed from a contiguous design layer and film layer on a backing material support. The design layer contains vitriliable oxide colorants in a resinous vehicle and the' iilm layer contains oxide materials in a resinous vehicle. The resinous vehicles of each layer are of substantially different polarity.
This invention relates to decalcomanias and more particularly to a novel decalcomania for use in connection with ceramic ware.
In providing a decoration or insignia for ceramic ware, it has heretofore been customary to use a water mount or slide olf decalcomania. This type of decalcomania usually comprises a paper backing, an imprinted design or insignia layer, and a so-called lacquer layer. When this decalcomania is applied to the ware, the paper backing is removed by the' application of water. The provision of a lacquer layer is essential in order that the integrity of the design be maintained while removing the paper backing after the decalcomania has been applied to the ware. The lacquer layer maintains the design or insignia intact while transferring the decalcomania from the paper backing to the ware itself. In addition the lacquer layer performs the additional function of protecting the design layer during transport and storage of the decalcomania and prevents deterioration or damage of the design or insignia.
After being initially formed to the desired shape, the ceramic ware is covered with a glaze either before or after the application of the decalcomania thereto. In the majority of instances, an underglaze decalcomania is provided in which the glaze is applied after the decalcomania is placed on the ware. This method is widely used because the glaze thereafter acts as a protective coating over the decalcomania adding to the longevity and preventing deterioration of the decalcomania. However, the glaze material is incompatible with the essential ingredients of the lacquer layer of the ceramic decalcomania and could not be applied thereover. Therefore it has heretofore been necessary when providing underglaze decalcomanias to conduct at least two firing operations in order to iirst remove the lacquer layer and thereafter to apply the glaze to the ware. This method was expensive and time and labor consuming.
The lacquer layer comprises noxious materials and in those few instances Where the decalcomania is applied as an overglaze decalcomania, that is, over the glaze previously applied to the ware, these materials have a deleterious effect on certain colors of the pigment or design layer and on the decoration or insignia provided thereby when the ware is fired to harden on the decalcomania. Furthermore, the lacquer layer when red is odiferous, permeating the surrounding areas with undesirable odors and detracting from the working conditions.
It has been suggested that a decalcomania be used whose paper backing is released by the presence of heat. This decalcomania, however, is quite expensive to produce and is not completely eicient. In addition, in applying this decalcomania to the ware, it is necessary to provide an additional coating in order to be able to secure the decalcomania for the reason that the release media and the glaze are incompatible. This additional step is also expensive and time and labor consuming.
There is a decalcomania whose paper backing is removable by the use of a release media which softens in the presence of a chemical solvent. This solvent release type of decalcomania is seldom used in connection with many types of ceramic ware for it is not at all adaptable for mass application to ware. It is difficult, tedious and time consuming to apply, and in many instances two firing operations are required to apply the glaze and to harden on the decalcomania.
It is therefore an object of the present invention to provide a novel ceramic decalcomania which eliminates the necessity for more than one firing in applying both the underglaze decalcomania and the glaze itself to the ware while nevertheless permitting the transfer of the decalcomania to the ware without any damage to the design.
It is a further object of the present invention to provide a ceramic decalcomania which is composed so as to eliminate the dispersion of noxious materials or odors during its application to the ware while nevertheless being provided with a protective coating, preventing any damage or deterioration of the design during transport or storage of the decalcomania.
Still another object of the present invention is to provide a ceramic decalcomania which requires no additional coating for the ware but which is nevertheless positive and eicient in application.
Still a further object of the present invention is to provide a ceramic decalcomania which is economical to produce while nevertheless being capable of rapid application to ware in volume.
`Other objects and advantages, as well as the features of the present invention, are described in greater detail in the following specification taken in conjunction with the drawings in which:
FIG. 1 is a diagrammatic cross-sectional view representing an embodiment of a ceramic decalcomania of the present invention; and
FIG. 2 is a diagrammatic cross-sectional view of another embodiment of a ceramic decalcomania of the present invention.
Referring to the drawing of FIG. 1, the embodiment of the invention as illustrated therein comprises a ceramic decalcomania or transfer which may be produced by any suitable printing method, viz. lithography, silk screen printing, rotogravure or the like. This decalcomania has a backing which is to be' released when the decalcomania is applied to the ware. In the illustration this backing consists of a paper sheet 1. The paper sheet may be of the usual slide off type provided with a thin layer of water soluble gum or adhesive or it may be the so-called duplex paper. In either case it is removable when water is applied thereto. A lilm 2 is applied over the paper sheet, and imprinted over the lm is the design or insignia 3.
While the arrangement of the portions of the decalcomania and the functions of each layer may appear to be similar to those heretofore used in the preparation of underglaze decalcomanias, nevertheless the new and novel construction of the present invention comprises a combination of ingredients producing extremely beneficial results. For example, heretofore in applying underglaze decalcomanias after the paper was removed or stripped off, it has been essential to tire the ware before applying the glaze in order to burn off the previously used lacquer layer and harden on the decalcomania. Thereafter it was necessary to again re the ware to apply the glaze, Thus two separate and distinct expensive and time consuming firing operations were required. The use of the present invention, however, eliminates the necessity for the dual firing operation by the provision of a novel l-m layer 2 and design layer 3 arrangement. This invention provides a decalcomania whose iilm layer 2 is bonded suficiently to the design in order to protect the design during transport and storage. However, the structure is such that the iilm layer may be easily removed, manually or by air pressure or the like from the design layer after the decalcomania is applied to the ware and witho-ut any initial ring operation. Thus the initial tiring operation is eliminated with all of the consequent benefits attendant upon such elimination.
It has been discovered in accordance with the present invention that this new and extremely advantageous decalcomania is accomplished according to the present invention by providing solids of high polarity comprising the film when using solids of low polarity in the design pigment vehicle, or using solids of high polarity in the design pigment vehicle when solids of low polarity comprise the film. For example, when cellulose esters are used as the solids in the film, cellulose ethers are utilized as the solids in the pigment vehicle. Furthermore, when the acrylics comprise the solids in the pigment vehicle, cellulose ethers may be used to form the film cellulose esters or cellulose ethers may be utilized in the design pigment vehicle. With the use of these compositions, it is also possible to use a tremendous variety of colors for the design, and the brilliance of the colors themselves is enhanced.
In accordance with the present invention, various types and kinds of solvents may be used for the solids used in the lm and in the design pigment vehicle. The invention provides that where the design pigment vehicle comprises solids which are soluble in aromatic or aliphatic hydrocarbons, the solids contained in the lilm are to be soluble in esters and ketones. A decalcomania possessing the same advantages may be provided according to the present invention where the solids of the design pigment vehicle are soluble in aromatic or aliphatic hydrocarbons and the solids in the iilm are soluble in esters and ketones. Examples of the typical formulations which may be utilized in providing the decalco-mania of the present invention follow. Of course, the solvents are not limited to those specified in the examples as different ones Within the same class may be used. Furthermore, the solids are specilically defined merely for illustrative purposes and the amounts of the ingredients used are only illustrative.
' Where the lm comprises a cellulose ester as the solid, the design pigment vehicle contains a cellulose ether such as ethyl cellulose. An example of this composition is the following:
Film: Percent Cellulose acetate butyrate 20 Diacetone alcohol 8O Design pigment vehicle:
Ethyl cellulose (10 sec. visc.) 20 Plasticizer Butyl lactate 65 Following the invention, cellulose ethers may be used in the hlm provided that the solid of the design layer comprises acrylics as illustrated in the following example:
Film: Percent Ethyl cellulose sec. visc.) 15 Plasticizer 5 Solvesso 100 50 Diacetone alcohol Design pigment vehicle:
Isobutyl methacrylie 20 Plasticizer l0 Solvesso 150 30 Butyl lactate 40 Where vinyls are used in the lilm according to the present invention, cellulose esters may be used as the solid in the design pigment vehicle. An example of this is the following:
Film: Percent Vinyl chloride acetate copolymer 15 Plasticizer Diacetone alcohol 80 Design pigment vehicle:
Cellulose acetate butyrate 20 Plasticizer 15 Butyl lactate 65 Furthermore, where vinyls are used as solids in the film, it is possible to use cellulose ethers as, for example, ethyl cellulose in the design pigment vehicle. An example of this is as follows:
According to the present invention, where cellulose esters are used in the film, butadiene styrene may be used as the solid in the design pigment vehicle. An example of this is as follows:
Film: Percent Cellulose acetate butyrate 20 Diacetone alcohol 80 Design pigment vehicle:
Butadiene styrene copolymer 20 Plaisticizer 15 Solvesso l5() 65 Another illustration of the use of solids of high and low polarity respectively in the iilm and the design pigment vehicle is the combination of cellulose ethers, such as ethyl cellulose in the film and butadiene in the design pigment vehicle. An example follows:
Film: Percent Ethyl cellulose (20 sec. visc.) 15 lPlasticizer 5 Solvesso 100 50 Diacetone alcohol 30 Design pigment vehicle:
Butadiene styrene copolymer 20 Plasticizer 15 Solvesso 150 65 It has been found that an effective strip-off film may be produced by utilizing polystyrene in the design pigment vehicle and ethyl cellulose in the film. Exemplary of the formulae for these compositions is the following:
Film: Percent Ethyl cellulose (20 sec. visc.) l5 Plasticizer 5 Diacetone alcohol 80 Design pigment vehicle:
Polystyrene (low visc. grade) 30 Solvesso 150 70 Furthermore, the design pigment vehicle may comprise cellulose acetate butyrate in which the film would contain cellulose nitrate as disclosed in the following eX- ample:
Film: Percent Cellulose nitrate (5-6 sec. grade) 22 Plasticizer 4 Diacetone alcohol 74 Design pigment vehicle:
Cellulose acetate butyrate (1/2 sec. grade) 25 Plasticizer Butyl lactate 65 Film containing ethy=l cellulose may also be used according to the present invention when the design pigment vehicle is isobutyl methacrylic as follows:
It is also possible to use an oil modified alkyd in the design pigment vehicle where ethyl cellulose comprises the solid in the film as follows:
Film: Percent Ethyl cellulose Plasticizer 5 Diacetone alcohol 80 Design pigment vehicle:
Oil modified alkyd 50 Varsol 50 l The vehicle in this combination contains organometallic driers and would dry by solvent evaporation, polymerization and oxidation, thus, becoming insoluble in either subsequent coating operations or in solvents used to obtain adhesion of the film and pigment pattern to the ware.
It will be understood that all of the foregoing are detailed examples of various compositions which may be used to provide a very effective strip off film and are in no vway intended to be a limitation upon the broad concept of the invention disclosed herein.
FIG. 2 illustrates a slide off type decalcomania in which the paper backing is slid from under the design and film layer rather than removed Ifrom over the design and film layer as is the case in FIG. l. Similar compositions to those above specified may be used for it has been discovered according to the present invention that the desired results may be accomplished when solids of low polarity are used in the film together with solids of high polarity in the design pigment vehicle. Furthermore, when solids of high polarity are used in the film, solids of low polarity are used in the design pigment vehicle. This arrangement which provides a film which Is readily strippable manually or automatically from the design layer after application to the Ware and without firing, nevertheless also provides a sufficient degree of adhesion between the design layer and the film to permit the decalcomania to be shipped and stored without damage to the design layer.
The preparation and application of the decalcomania to the ceramic ware are as follows: The slide off decalcornanias illustrated are printed on a standard sheet which has been coated with a water-soluble coating. The film 2 is applied over the color film 3. The ware to be decorated should be clean and dry. The decalcomania is then slid off the paper backing and applied to the ware. The decalcomania may then be squeegeed. Within la relatively short period of time after the decalcomania is transferred, the film may be removed off the Ware by air pressure or stripped by hand. Removal by air pressure can be Iaccomplished by using .an air hose with any type nozzle. After the film is removed, the ware is permitted to dry and the glazing process may begin. There is no firing necessary until the firing required to apply the glaze.
It is to be understood that while the invention has been described in great detail, and with many examples to illustrate a portion of the scope thereof, nevertheless these illustrations and the detailed description are not to be construed as limiting the scope `or spirit of the invention as it is defined in the appended claims.
What is claimed is:
1. A vitreous decalcomania comprising a backing sheet adapted to be removed prior to the application of the decalcomania to ceramic ware,
a printed design layer on said backing sheet consisting of ceramic oxide colorants in a resinous vehicle of one polarity,
a film layer consisting of a resinous vehicle of a polarity different from that of the design layer,
said design and film layers being disposed immediately adjacent to and in surface contact with each other, the resinous vehicle in one of said layers being of a high polarity and the resinous vehicle in the other said layer being of a low polarity,
said film layer adherent to the design layer but readily removable from the said design layer prior to firing the design layer directly on the ware,
whereby said design layer only is firmly adhered to the ware in one firing operation together with an overglaze.
2. A vitreous decalcomania in accordance with claim 1 wherein said film layer ycomprises ethyl cellulose as the resinous vehicle and said design layer comprises a polystyrene resin as the resinous vehicle.
3. A vitreous decalcomania in accordance with claim 2 wherein said lm layer comprises cellulose acetate butyrate as th-e resinous vehicle and said design layer comprises butadiene-styrene copolymer.
4. A vitreous decalcomania in accordance with claim 1 wherein said lm layer is formed with ethyl cellulose as the resinous vehicle and said design layer is formed with isobutyl methacryate as the resinous vehicle.
5. A vitreous decalcomania in accordance with claim 1 wherein said lm layer is formed with vinyl chloride acetate copolymer as the resinous vehicle and said design layer is formed with cellulose acetate butyrate as the resinous vehicle.
6. A vitreous decalcornania in accordance with claim 1 wherein said film layer is formed with vinyl chloride acetate copolymer as the resinous vehicle and said design layer is formed with ethyl cellulose as the resinous vehicle.
7. The vitreous decalcomania according to claim 1 wherein the said film layer is formed of cellulose acetate butyrate as the resinous vehicle and said design layer is formed with ethyl cellulose as the resinous vehicle.
References Cited UNITED STATES PATENTS 10/1930 Laws 1l7--3.6 l/ 1933 Mitchell et al 1l7-3.6 3/1938 McNutt 156-89 2/1953 Rathke 1l7-3 .6 2/1956 Karne 156-140 5/1956 Matthes 156--140 1/1961 Porth 156-89 11/1961 Akkeron 156-8 1/1962 Gobel 117-3.6
FOREIGN PATENTS 12/ 1959 Canada.
MURRAY KATZ, Primary Examiner U.S. C1. X.R.