US2772182A - Ceramic decoration method - Google Patents

Description

United States Patent CERAMIC nnconATIoN METHOD Christian C. Jessen, Perth Amhoy, N. J., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application May 13, 1950, Serial No. 161,903

9 Claims. (Cl. 117-40) This invention relates to the application of ceramic decorations to base objects and more particularly to the decoration of such objects with ceramic colors by a squeegee printing method involving the application of multiple prints.

The squeegee or screen stencil method of applying ceramic decorations, e. g., glass colors composed of inorganic pigments and finely ground glass, to ceramic (glass, china, porcelain, etc.) and metal objects has long been in use. This method of decorating glassware is now used ahnost universally throughout the beverage and milk bottle industry and to a considerable extent in the decoration of tumblers and the like objects. Present practice generally involves the use of a dispersion of the decorating enamel in an oily vehicle containing a volatile solvent to form the squeegee paint. This type of vehicle has been used successfully for years in the preparation of squeegee paints but when a multi-colored decoration is desired all prints except the last must be dried to remove the volatile solvent and set the print before the next print can be applied without smearing resulting. Following the printing operation, the object bearing the design is then fired to fuse the ceramic decoration to the object.

A recent modification of the squeegee method involves the use of a vehicle which is solid at normal temperatures but fluid at somewhat elevated temperature during squeegeeing. Certain vehicles of this type and their use in t; e application of glass colors constitutes the subject matter of my pending application Serial No. 79,301, filed March 2, 1949, now U. S. Patent No. 2,607,701. Use of such vehicles is advantageous in that the hot vehicle solid-ifies instantly upon contact with the cold ware and obviates the necessity of a drying operation between successive applications of prints. However, the use of such a hotmelt vehicle for all applications in multiple-print operations involves the possibility of damage to previous prints due to the heat from the succeeding hot application. The present invention is concerned with a method whereby this dificulty is completely eliminated or substantially minimized.

It is an object of the invention to provide an improved method for the ceramic decoration of base objects, particularly ceramic materials such as glassware. A further object is an improvement in the application of ceramic decorations by the squeegee or screen stencil method where more than one printing is involved and whereby the use of driers for the removal of solvent from a printed design in order to solidify the design prior to application of a succeeding print is entirely eliminated. Still other objects will be apparent from the following description.

The above objects are accomplished in accordance with the invention by applying to a base object, particularly a ceramic object such as glass, china, porcelain or the like ware, one or more prints of a ceramic decorating composition comprising a dispersion of a ceramic decoration in a vehicle of the type hereinafter defined which immediately upon contact with the object solidifies to a firm, solid, adherent coating; and, without inter-mediate drying or firing said print or prints, applying a final print of a ceramic decorating composition comprising a ceramic decoration dispersed in a vehicle which includes a volatile solvent; and thereafter firing the printed object to fuse the decoration to the ware.

The decorating composition or compositions em loyed in the application of all but the last coating or print are applied to the ware employing the well-known squeegee or screen stenc l technique. These compositions are dispersions of ceramic decorations, such as finely ground mixtures of inorganic pigments and glass, in a vehicle which comprises: (a) 30 to of a material which melts within the temperature range to 230 E, which material may be a wax, a mixture of waxes, or a mixture of a wax or waxes with a wax-like substance; (17) 1 to 10% of ethyl cellulose; (c) 14 to 68% of resin or a rosin derivative or mixture of such substances; (d) 0.5 to 10% of an organic phosphate material such as lecithin or phosphorated tall oil; and (e) 0 to 1% of pyrogallic acid. Finely ground ceramic decorations dispersed in such a vehicle in proportions of about 2 to 6 parts by weight of the decoration to 1 part of the vehicle produces decorating compositions which are solids at ordinary or normal temperatures, are substantially non-volatile and can be applied readily and successfully to the object to be decorated at a temperature within the range of 120 to ..30 F. through a stencil screen employing the squeegee technique. At such temperatures the compositions are pastes or paints and when applied to were which is at ordinary temperature they solidify almost instantly to provide firm, solid, adherent coatings which require no drying or firing before the application of a subsequent print. The temperature of the ware to which such a hot composition is applied need not be at room temperature but should be at least about 15 F. lower than the melting temperature of the composition being applied. In practice, however, the ware ordinarily will be at about room temperature.

Not all vehicles which melt within the range 120 to 230 F. are suitable for use in applying the first decorating prints, i. e., all but the last print. In order for a vehicle to be suitable for this purpose it must give a squeegee paste or paint which is workable at about 120 to 230 F, i. e., it must not thicken or gel during long periods at the temperature of application; its viscosity should not change substantially at such temperature; it should not clog the screen; and it should have proper flow and leveling characteristics. This means that the vehicle should be substantially non-volatile at the working temperature, yet it should volatilize fast enough during firing to prevent running or slipping of the print. Furthermore, the vehicle must be one which solidifies instantly on application to the cold ware to" form a firm, smooth, tough, adherent coatin which is resistant to normal abrasion and shock and which is low in carbonaceous residue upon being fired. The vehicle also must be sufiiciently tacky to adhere the print to the ware, but it must not be so tacky as to cause pickup of a previous print on the underside of a later color screen, e. g., during superimposition of color prints. The vehicle should produce prints that are neither too hard nor too soft: if too hard, they fracture readily on handling; if too soft, they become marred, blurred and distorted readily. It has been discovered that to meet these requirements a vehicle must contain certain ingredients or types of ingredients which, furthermore, must be present in certain proportion ranges, as specified above.

The final application of ceramic decoration is made in accordance with the invention employing a dispersion of a ceramic decoration in a vehicle which is non-solid,

i. e., pasty or liquid, at ordinary temperatures. Such a vehicle may be of the type heretofore usually employed in the application of ceramic decorations. They are hereinafter referred to as air-dry vehicles and when they contain a dispersed ceramic decoration the resulting compositions are referred to as air-dry decorating compositions, as distinguished from the hot-melt type vehicle or decorating compositions described above, since they are solidified by the removal of solvent, i. e., by drying in the air, in a drier or in the furnace.

The final coating of ceramic decoration dispersed in an air-dry vehicle may be applied by various methods including spraying or brushing but is preferably applied by the squeegee method. Air-dry vehicles suitable for use in decorating compositions for the final print by squeegee application usually contain bonding, viscosify ing and dispersing agents in addition to a volatile solvent. Vehicles of the type described in Deyrup Patent 2,379,507 aresuitable and illustrative. However, air-dry vehicles of the following composition are preferred: (a) 50 to 80% of a volatile solvent, generally of the terpene or petroleum type such as terpene ethers, terpene alcohol and the aromatic and parafiin hydrocarbon solvents; (b) 15 to 35% of rosin or a rosin derivative or mixtures of such substances, which serve as binders; (c) 0.5 to 7% of ethyl cellulose which serves as a viscosifier and hardener; and (d) 0.5 to 10% of an organic phosphate material such as lecithin or phosphorated tall oil, which serve as wetting agents. The most effective amounts of such wetting agents are about 4 to 10% for lecithin and 0.5 to 7% for phosphorated tall oil. Of these two substances the latter is preferred. Still other substances may be present in minor amounts.

The following Table 1 shows the compositions of five preferred vehicles of the hot-melt type which are especially well-suited for use in the application of all but the last coating decoration, while Table 2 shows the compositions of six preferred air-dry vehicles for use in the squeegee application of the final coating decoration.

TABLE 1.HOT-MELT VEHICLES Composition Pyrogallic acid .i:

TABLE 2.AIR-DRY VEHICLES Composition F G H I i .T l K Polymerized abietic acid 7. 98 15. .1 10. 03 10. Hydrogenated rosin 13. 60 6.58 20. 1O 21. 11 11.03 11.10 Ethyl cellulose 2. 28 2. 28 3. 30 2. 39 3. 21 0.86 Diethyl oxalate 3. 28 3. 28 3. 50 3. 66 3.67 3. 70 dl-Malic aoid O. 0. 18 0. 20 0. 18 0. 18 0. 18 Terposol #3 12. 98 12.98 48. 44 Pine 0 a 30. 00 31. 23 16.11 73. 31 Petroleum solvent 51. 96 51. 96 35. 60 Boric acid 0. 40 0.37 10% Solution of 85% ortho pilimSphOfiC acid in pine o Diesel fuel Lecithin The Terposol #3 in some of the above compositions is a commercial terpene solvent described as a terpene ether obtained by the reaction of a terpene hydrocarbon with methanol. The Petroleum solvent in some of the compositions Was either Solvesso #150" or Arosol #12, which are commercial solvents of the aromatic hydrocarbon type. i

The air-dry vehicles of Table 2 may be prepared by heating a mixture of the ingredients, other than the pine oil solution of phosphoric acid and the lecithin or phosphorated tall oil, at a moderately elevated temperature, e. g. about 194 F., until the mixture is homogeneous. The mixture is then cooled somewhat, e. g. to about 106 F., and the remaining ingredients are added and the entire batch stirred until homogeneous. Squeegee paints using such vehicles are made by mixing 2 to 6 parts of glass enamel with 1 part of vehicle and then passing .the resulting mixture through a roll mill, or other type of equipment commonly used to disperse ceramic pigments in vehicles, to obtain a uniform paint. j

The hot-melt vehicles of Table 1 may be prepared by heating a mixture of the ingredients, other than the lecithin, phosphorated tall oil and pyrogallic acid, at an elevated temperature, e. g. about 266 F., until the mixture is homogeneous. The remaining ingredients are then added and the entire batch is agitated at about the same temperature until homogeneous. Squeegee paints or pastes using these vehicles are made by mixing 2 to 6 parts of glass enamel with 1 part of the vehicle, then passing the resulting mixture through a roll mill or the like to obtain a uniform composition. ,The mixture will usually be kept at a temperature of about 176 to 230 F. during such processing. The paste or paint may then be used directly or run into a shallow pan, allowed to solidify and then broken up into lumps for shipment or storage.

The following examples illustrate the use of various of the above vehicles in the application of ceramic decorations to glassware in accordance with the invention. In

all cases the decorating paints were prepared using 2 to' 6 parts of glass color per part of vehicle.

Example 1 room temperature until the paint was maintained at 120 to 230 F. during the operation. A second print decoration, not superimposed over the first, was applied by the squeegee method using a glass color paint prepared with air-dry vehicle F of Table 2. In the second printing both the ware and the paint were at room temperature. The printed ware Was then fired in the usual manner at a temperature necessary to fuse the decoration to the glass. No difliculty was encountered in applying the second print and an excellent final decoration resulted.

Example 2 The procedure of Example 1 was repeated except that the second print was superimposed over the first print and the paint used in the second printing was prepared with air-dry vehicle I of Table 2. An excellent decoration resulted and no damage to the first print resulted upon application of the second print. Similar results were obtained when the paint for the second or superimposed print was prepared employing air-dry vehicles .H, I or K of Table 2.

Example 3 The general procedure of Example 1 was repeated except that three printings of decoration were applied to the ware. Hot-melt vehicle B was used in preparing the paint for the first two prints, the second of which was superimposed over the first. in preparing the paint for the final print which was superimposed over the first two prints. No damage to any of the prints resulted from the application of succeeding prints and an excellent final decoration resulted upon firing the printed ware to fuse the decoration to the glass. The same results were obtained when air-dry vehicle I was used in preparing the paint for the final print.

Example 4 Example 1 was repeated except that the decorating Air-dry vehicle G was used paint for the first print was made using hot-melt vehicle A and the paint for the second print, which was superimposed over the first, was made using air-dry vehicle G. An excellent final decoration resulted upon firing the printed ware to fuse the decoration to the glass. Substantially the same results were obtained when hot-melt vehicle C was used in preparing the paint for the first print.

The ceramic decorating compositions, referred to in the examples as paints will generally be prepared by suspending or dispersing the ceramic decoration, such as a finely ground mixture of an inorganic pigment and glass, in either the hot-melt or air-dry vehicle in proportions of about 2 to 6 parts by weight of the decoration for each part of vehicle, the most usual proportions being about 4 to l.

The wax, mixture of waxes, or mixture of a wax with a wax-like material, used in the hot-melt vehicle should melt at a temperature within the range of 120 to 230 F. and constitute from 30 to 80%, preferably 40 to 60%, of the vehicle. Examples of suitable waxes and wax-like materials which may be used either alone, in the case of certain waxes, or as mixtures to provide material melting Within the required temperature range are: parafiin, carnauba wax, spermaceti, beeswax, canawax, microcrystalline wax, palmitic acid, stearic acid and solid soaps.

The ethyl cellulose content of the hot-melt vehicle should be not less than about 1% nor greater than about and is preferably 1 to 5%. Its content in the preferred air-dry vehicles should be about 0.5 to about 7%. The ethyl cellulose functions as a viscosifier or thickener and also as a hardening agent. In either type of vehicle low, medium or high viscosity ethyl cellulose may be used but the medium viscosity grade is generally preferred.

The amount of rosin or rosin derivative in the hotmelt vehicle should be 14 to 68% and preferably 35 to 55%, Whereas the amount for the preferred air-dry vehicle is 15 to These materials serve in either type of vehicle as hardeners and facilitate adherence of the decoration print to the ware. They also aid in rendering the ethyl cellulose miscible with the wax constituent of the hot-melt vehicle. Examples of these materials are: rosin and abietic acid; rosin esters and esters of abietic acid, such as methyl abietate; polymerized rosin and polymerized abietic acid; hydrogenated rosin and hydrogenated abietic acid; and the metal salts of rosin and of abietic acid, e. g., the zinc, titanium and calcium salts. The most preferred of these materials is hydrogenated rosin.

The hot-melt vehicle must contain from 0.5 to 10% of an organic phosphate material such as soya lecithin, heat-treated or cooked lecithin and phosphorated tall oil. One or both of these phosphate materials, which function as wetting agents, will also be present in the preferred air-dry vehicles, the amount being 0.5 to 10%. The preferred amount of lecithin in either type of vehicle is 4 to 10% whereas the preferred amount of phosphorated tall oil is 0.5 to 7.0%. The use of phosphorated tall oil is preferred.

Pyrogallic acid is not an essential ingredient of the hotmelt vehicle. However, its presence, e. g., in concentrations of 0.01 to 1%, appears desirable in some instances to inhibit undesired thickening of the hot vehicle or paint. Also, in the case of the preferred air-dry vehicle, it is frequently desirable, although not essential, that other substances be present in minor amounts as is indicated by the compositions shown in Table 2. Examples of such other substances whose presence may be desirable to prevent the squeegee paints from gelling during preparation or storage, and the concentrations in which they generally will be present when used, are: diethyl oxalate, 1 to 5%; dl-malic acid, 0.1 to 1%; boric acid, 0.4 to 0.6%; and 10% solution of 85% ortho phosphoric acid in pine oil, 1 to 10%.

The present method of employing a hot-melt vehicle in the application of all but the last print decoration and of using an air-dry vehicle in applying the last print, is

unique and results in definite and important advantages over methods using either type of vehicle in the application of all prints. One important advantage is that the use of driers, conventionally employed in all air-dry multiple-print methods, is entirely eliminated. Another important advantage is that the method permits anchoring the ware firmly in an automatic decorating machine for all color applications thereby simplifying the problem of registration of multi-color designs and eliminating the necessity of molding a registration nib on the bottle as is now common practice. The present method further eliminates the necessity for maintaining the stencil screen and paint for the final print at an elevated temperature as would be necessary if all prints were applied using hotmelt compositions. Also, the amount of carbonaceous material which must be burned off in the lehr is reduced as compared to all hot-prints. Finally, there is less chance of damage to preceding prints when the final print is applied at room temperature instead of at an elevated temperature. Where only two prints are to be applied the present method eliminates entirely the possibility of damage to the first print from the application of a succeeding hot composition.

Throughout the specification and in the appended claims the percentage values given are, unless otherwise specified, percentages by weight based upon the total weight of the vehicle or decorating composition.

i claim:

1. A method of decorating a ceramic object comprising applying to said object by the squeegee method at least one print of a hot-melt ceramic decorating composition while maintaining said composition at a temperature within the range 120 to 230 F. and while said object is at about room temperature, said composition being nonvolatile and solid at room temperature and nonsolid at said temperature within the range 120 to 230 F., and said print being solidified instantly upon contact with said object, then superimposing on said print an airdry ceramic decorating composition containing a volatile solvent and firing said object to fuse the decorations thereto, all of said decorating compositions containing 2 to 6 parts by weight of a ceramic decoration dispersed in one part of a vehicle, and said air-dry composition being one which is non-solid at normal temperature and which solidifies upon the removal of the volatile solvent therefrom by drying.

2. A method of decorating a ceramic object comprising applying at least one decorating print of a hot-melt type ceramic decorating composition by the squeegee method to said object while maintaining said composition at a temperature within the range 120 to 230 F. and while said object is at a temperature at least 15 F. below the melting temperature of said composition, said print solidifying instantly upon contacting said object, superimposing on said print; an air-dry type ceramic decorating composition and then filing the object to fuse the decoration thereto, said hot-melt composition being non-volatile and solid at normal temperature and comprising a dispersion of a ceramic decoration in a vehicle in the proportion of 2 to 6 parts by weight of said ceramic decoration per part of said vehicle, said vehicle containing: (a) 30 to of a material which melts within the temperature range to 230 F. and is from the group consisting of waxes, mixtures of waxes, and mixtures of a wax with a material from the group consisting of palmitic acid, stearic acid and solid soaps; (b) 14 to 68% of a material from the group consisting of rosin and abietic acid, rosin esters and esters of abietic acid, polymerized rosin and polymerized abietic acid, hydrogenated rosin and hydrogenated abietic acid, and metal salts of rosin and of abietic acid; (c) 1 to 10% of ethyl cellulose; (d) 0.5 to 10% of an organic phosphate material from the group consisting of lecithin and phosphorated tall oil; and (e) 0 to 1% of pyrogallic acid, said air-dry composition being non-solid at normal temperature and comprising a dispersion of a ceramic decoration in a vehicle which includes a volatile solvent, said air-dry composition being one which solidifies upon the removal of said volatile solvent therefrom by drying and which con tains 2 to 6 parts by weight of the ceramic decoration per part of the vehicle.

3. The method of claim 2 wherein the vehicle for the hot-melt composition contains: 40 to 60% of ingredient (a); 35 to 55% of ingredient (b); l to 5% of ingredient (c); 0.5 to 7% of ingredient (d), which is phosphorated tall oil; and to 1% of ingredient (e).

4. The method of claim 2 wherein the vehicle for the air-dry composition contains: (a) 50 to 80% of a volatile solvent; (b) 15 to 35% of a material from the group consisting of rosin and abietic acid, rosin esters and esters of abietic acid, polymerized rosin and polymerized abietic acid, hydrogenated rosin and hydrogenated abietic acid, and metal salts of rosin and of abietic acid; (c) 0.5 to 7% of ethyl cellulose; and (d) 0.5 to 10% of an organic phosphate material of the group consisting of lecithin and phosphorated tall oil.

5. The method of claim 2 wherein the vehicle for the hot-metal composition contains: (a) 40 to 60% of a material which melts within the temperature range 120 to 230 F. and is from the group consisting of waxes, mixtures of waxes, and mixtures of a wax with a material from the group consisting of palmitic acid, stearic acid and solid soaps; (b) 35 to 55% of hydrogenated rosin; (c) 1 to 5% of ethyl cellulose; (d) 0.5 to 7% of phosphorated tall oil and (e) O to 1% of pyrogallic acid, and the vehicle for the air-dry composition contains: (7) 50 to 80% of a volatile solvent; (g) 15 to 35 of a material from the group consisting of rosin and abietic acid, rosin esters and esters of abietic acid, polymerized rosin and polymerized abietic acid, hydrogenated rosin and hydrogenated abietic acid, and metal salts of rosin and of abietic acid; (h) 0.5 to 7% of ethyl cellulose; and (i) 0.5 to of a material of the group consisting of lecithin and phosphorated tall oil.

6. A method of decorating a ceramic object comprising applying a hot-melt type ceramic decorating composition by the squeegee method to said object while maintaining said composition at a temperature within the range 120 to 230 F. and while said object is at a temperature at least F. below the melting temperature of said composition, whereby a solid, firm print is formed instantly upon contact of said composition with said object, and, without intermediate drying, superimposing on said print an air-dry type ceramic decorating composition and then firing the object to fuse the decoration thereto, said hotmelt composition being non-volatile and solid at normal temperature and comprising a dispersion of a ceramic decoration in a vehicle in the proportion of 2 to 6 parts by weight of said ceramic decoration per part of said vehicle, said vehicle containing: (a) 40 to 60% of a material which melts within the temperature range 120 to 230 F. and is from the group consisting of waxes, mix tures of waxes, and mixtures of a wax with a material from the group consisting of palmitic acid, stearic acid and solid soaps; (b) 35 to 55 of a material from tht group consisting of rosin and abietic acid, rosin esters and esters of abietic acid, polymerized rosin and polymerized abietic acid, hydrogenated rosin and hydrogenated abi tic acid, and metal salts of rosin and of abietic acid; (c) l to 5% of ethyl cellulose; (d) 0.5 to 7% of phosphorated tall oil; and (e) 0 to 1% of pyrogallic acid, said air-dry composition being non-solid at ordinary temperature and containing a volatile solvent, the removal of which by drying causes the composition to solidify.

7. The method of claim 6 wherein the vehicle for the air-dry composition contains: (a) 50 to 80% of a volatile solvent; (b) 15 to 35% of a material from the group consisting of rosin and abietic acid, rosin esters and esters of abietic acid, polymerized rosin and polymerized abietic 8 acid, hydrogenated rosin and hydrogenated abietic acid, and metal salts of rosin and of abietic acid; (0) 0.5 to 7% of ethyl cellulose; (d) 0.5 to 10% of an organic phosphate material of the group consisting of'lecithin and phosphorated tall oil.

8. A method of decorating a ceramic object comprising applying to said object a squeegee print of a hot-melt type decorating composition while maintaining said composition at a temperature within the range 120 to 230 F. and while said object is at a temperature at least 15 F. below the melting temperature of said composition, whereby a solid, firm print is formed instantly upon contactof said composition with said object and' superimposing on said print a squeegee print of an air-dry type decorating composition, and then firing said object to fuse the decoration thereto, said hot-melt composition being nonvolatile and solid at normal temperature and comprising a dispersion of a ceramic decoration, in a vehicle in the proportion of 2 to 6 parts by weight of said ceramic decoration per part of said vehicle, said vehicle containing: (a) 30 to of a material which melts within the temperature range to 230 F. and is from the group consisting of waxes, mixtures of waxes, and mixtures of a wax with a material from the group consisting of palmitic acid, stearic acid and solid soaps; (b) 14 to 68% of a material from the group consisting of rosin and abietic acid, rosin esters and esters of abietic acid, polymerized rosin and polymerized abietic acid, hydrogenated rosin and hydrogenated abietic acid, and metal salts of rosin and of abietic acid; (0) 1 to 10% of ethyl celulose; (d) 0.5 to 10% of an organic phosphate material from the group consisting of lecithin and phosphorated tall oil; and (e) 0 to 1% of pyrogallic acid, said air-dry composition being non-solid at normal temperature and comprising a dispersion of a ceramic decoration in a vehicle in the proportion of 2 to 6 parts by weight of the ceramic decoration per part of the vehicle, the vehicle of said air-dry composition containing: (7) 50 to 80% of a volatile solvent the removal of which by drying causes said air-dry composition to solidify; (g) 15 to 35 of a material from the group consisting of rosin and abietic acid, rosin esters and esters of abietic acid, polymerized rosin and polymerized abietic acid, hydrogenated rosin and hydrogenated abietic acid, and metal salts of rosin and of abietic acid; (11) 0.5 to 7% of ethyl cellulose; and (i) 0.5 to 10% of an organic phosphate material of the group consisting of lecithin and phosphorated tall oil.

9. A method of decorating a ceramic object comprising applying to said object at least one squeegee print of a hot-melt decorating composition while maintaining said composition at a temperature .within the range 120 to 230 F. and while said object is at a temperature at least 15 F. below the melting temperature of said composition, whereby a solid, firm print is formed instantly upon contact of said composition with said object, superimposing on said print an air-dry ceramic decorating composition and then firing the object to fuse the decoration thereto, said hot-melt composition being non-volatile and solid at normal temperature and comprising a dispersion of a ceramic decoration in a vehicle which contains:

(a) 30 to 80% of a wax which melts within the range V 120 to 230 F.; (b) 14 to 68% of hydrogenated rosin; (c) 1 to 10% of ethyl cellulose; (cl) 0.5 to 10% of an organic phosphate material from the group consisting of lecithin and phosphorated tall oil; and (e) 0 to 1% of pyrogallic acid, said air-dry composition being non-solid at normal temperature and comprising a dispersion of a ceramic decoration in a vehicle which includes a volatile solvent whose removal by drying causes said air-dry composition to solidify, all of said decorating compositions containing 2 to 6 parts by weight of a ceramic decoration per part of the vehicle.

(References on iollowingpage) References Cited in the file of this patent UNITED STATES PATENTS Huber Jan. 6, 1942 Huber Jan. 6, 1942 5 Ellis et al. Mar. 3, 1942 Rummelsburg Dec. 15, 1942 10 2,318,124 Shurley May 4, 1943 2,390,123 Rietz et a1. Dec. 4, 1945 2,426,277 Miller Aug. 26, 1947 OTHER REFERENCES Printing Inks, Ellis Reinhold Publishing Corp., 1940, pages 206 and 333 relied upon.

Claims (1)

1. 8. A METHOD OF DECORATING A CERAMIC OBJECT COMPRISING APPLYING TO SAID OBJECT A SQUEEGEE PRINT OF A HOT-MELT TYPE DECORATING COMPOSITION WHILE MAINTAINING SAID COMPOSITION AT A TEMPERATURE WITHIN THE RANGE 120 TO 230* F. AND WHILE SAID OBJECT IS AT A TEMPERATURE AT LEAST 15* F. BELOW THE MELTING TEMPERATURE OF SAID COMPOSITION, WHEREBY A SOLID, FIRM PRING IS FORMED INSTANTLY UPON CONTACT OF SAID COMPOSITION WITH SAID OBJECT AND SUPERIMPOSING ON SAID PRINT A SQUEEGEE PRING OF AN AIR-DRY TYPE DECORATING COMPOSITION, AND THEN FIRING SAID OBJECT TO FUSE THE DECORATION THERETO, SAID HOT-MELT COMPOSITION BEING NONVOLATILE AND SOLID AT NORMAL TEMPERATURE AND COMPRISING A DISPERSIOIN OF A CERMAIC DECORATION, IN A VEHICLE IN THE PROPORTION OF 2 TO 6 PARTS BY WEIGHT OF SAID CERAMIC DECORATION PER PART OF SAID VEHICLE, SAID VEHICLE CONTAINING: (A) 30 TO 80% OF A MATERIAL WHICH MELTS WITHIN THE TEMPERATURE RANGE 120 TO 230* F. AND IS FROM THE GROUP CONSISTING OF WAXES, MIXTURES OF WAXES, AND MIXTURES OF A WAX WITH A MATERIAL FROM THE GROUP CONSISTING OF PALMITIC ACID, STEARIC ACID AND SOLID SOAPS; (B) 14 TO 68% OF A MATERIAL FROM THE GROUP CONSISTING OF ROSIN AND ABIETIC ACID ROSIN ESTERS AND ESTERS OF ABIETIC ACID, POLYMERIZED ROSIN AND POLYMERIZED ABIETIC ACID, HYDROGENATED ROSIN AND HYDROGENATED ABIETIC ACID, AND METAL SALTS OF ROSIN AND OF ABIETIC ACID; (C) 1 TO 10% OF EHTYL CELLULOSE; (D) 0.5 TO 10% OF AN ORGANIC PHOSPHATE MATERIAL FROM THE GROUP CONSISTING OF LECITHIN AND PHOSPHORATED TALL OIL; AND (E) 0 TO 1% OF PYROGALLIC ACID, SAID AIR-DRY COMPOSITION BEING NON-SOLID AT NORMAL TEMPERATURE AND COMPRISING A DISPERSION OF A CERAMIC DECORATION IN A VEHICLE IN THE PROPORTION OF 2 TO 6 PARTS BY WEIGHT OF THE CERAMIC DECORATION PER PART OF THE VEHICLE, THE VEHICLE OF SAID AIR-DRY COMPOSITION CONTAINING: (F) 50 TO 80% OF A VOLATILE SOLVENT THE REMOVAL OF WHICH BY DRYING CAUSES SAID AIR-DRY COMPOSITION TO SOLIDIFY; (G) 15 TO 35% OF A MATERIAL FROM THE GROUP CONSISTING OF ROSIN AND ABIETIC ACID, ROSIN ESTERS AND ESTERS OF ABIETIC ACID, POLYMERIZED ROSIN AND POLYMERIZED ABIETIC ACID, HYDROGENATED ROSIN AND HYDROGENATED ABIETIC ACID, AND METAL SALTS OF ROSIN AND OF ABIETIC ACID; (H) 0.5 TO 7% OF ETHYL CELLULOSE; AND (I) 0.5 TO 10% OF AN ORGANIC PHOSPHATE MATERIAL OF THE GROUP CONSISTING OF LECITHIN AND PHOSPHORATED TALL OIL.