TRANSFER MATERIAL AND METHOD OF COLORING THE SURFACE OF AN OBJECT

Abstract: A transfer material comprising a substrate, a first layer of thermoplastic wax-like material formed on said substrate, a second layer of thermoplastic material formed on said first layer, and a design layer formed on said second layer. The materials of said first and second layers are heat-sensitive and have such a characteristic that they are not tacky at room temperature but activatable upon heating to become tacky and remain so for a predetermined period of time after said heating is terminated and solidify to effect complete adhe­ sion upon lapse of said predetermined period of time. The materials are decomposable when heated above the temper­ ature at which they are activated, and the material of the first layer has a higher degree of adhesivity to an object to be transfer-printed than that of the material of the second layer to a transfer head used in the process of transfer printing.

Description: Background of the Invention This invention relates to transfer printing and more particularly to a transfer material for use in coloring ceramic ware by transfer printing. Transfer printing has been in uide use for coloring ceramic ware on a mass production basis. The technique of transfer printing employs a transfer material, which typically comprises a substrate or base, a design layer including a design to be transfer-printed and a layer interposed between the substrate and the design layer to enable separation of the design layer from the substrate and subsequent adhesion of the design layer to the surface of an article to be transfer-printed when transfer printing is conducted. There are known three methods of coloring ceramic ware by using such transfer material as mentioned above. One method (I) involves applying glaze on the surface of unglazed ceramic ware, firing the ware at about 13000G, transfer printing a colored design on the glazed surface-of the ware and again firing the ware at about 8000C to 12000C. Another method (II) involves transfer printing a colored design on the surface of unglazed ceramic ware, firing the transfer-printed ware at about 50000 to 700 C, applying glaze on the colored surface of the ware and then firing the ware at about 13000C. A third method (III) involves applying a mixture of glaze and synthetic resin on the surface of unglazed ceramic ware, transfer printing a colored design on the applied layer of the mixture, and then firing the ware at about 130000. Among known types of transfer material that can be used in the above-mentioned methods of transfer printing, there is a type such that the material is moistened and swollen with water to render the design layer separable from the substrate, and manually applied to the surface of an object to be transferprinted so that the design layer is transferred from the sub strate to the surface of the object. This type of transfer material, however, is not suitable for use in transfer printing on a mass production basis since it requires much manual labor. Moreover, this type of transfer material cannot be used in the above-mentioned methods (II) and (III) wherein the surface of the piece of ceramic ware is in such a condition as to sbsorb much water thereby to prevent transfer of the design layer from the substrate layer to the ceramic surface. A transfer material particularly intended for use in the above-mentioned methods (II) and (III) has been proposed, which comprises a sheet of Japanese paper as a substrate or base and a design layer formed thereon by the gravure process with ink for coloring ceramic ware, with a water-soluble resin used as a binder. When the transfer material is pressed against the surface of an object to be transfer-printed, the material is moistened with water applied to the reverse side of the base sheet of paper so that the design layer is separated from the base sheet and transferred to the surface of the ceramic ware0 This type of transfer material also requires much manual labor and it is quite difficult to effect complete transfer of the design layer and a considerable degree of skill is required if this type of transfer material is used on a curved surface. Another type of transfer material is disclosed in U.S. Patent No. 3967021, which comprises a design layer including the design to be transfer-printed, a pair of adhesive layers between which the design layer is laminated, and a substrate layer supporting the three laminated layers. The two adhesive layers are heat-sensitive and activatable within different temperature ranges. When the design is to be transferred to a transfer head, the transfer material is heated to a temperature within one of the two temperature ranges so that one of the adhesive layers is activated to cause the design layer to be transferred to the transfer pad, and when the design layer is to be transferred from the pad to an article to be transfer-printed, the temperature drops within the other of the temperature ranges so that the other of said adhesive layers is activated to cause the design layer to be transferred from the pad surface to the surface of the article To carry out the above method it is necessary that the two steps should be conducted either in two different chambers the temperatures inside which are maintained within the abovementioned respective ranges, or separately at a certain time interval, that isi first at a first temperature within one of the two temperature ranges and after a time interval at a different temperature within the other of the temperature ranges. In either case, the process is time-consuming and not suitable for mass production. Accordingly, the primary object of the invention is to provide a transfer material which is suitable for use in transfer printing a colored design on articles made of various kinds of material. Another object of the invention is to provide a transfer material particularly suitable for use in transfer printing a colored design on pieces of ceramic ware of different contours and shapes on a mass production basis. Another object of the invention is to provide such a transfer material as aforesaid which enables simpler, easier and more delicate coloring of the surface of an object than if conventional types of transfer material are used. The invention will be described is detail with reference to the accompanying drawings. Brief Description of the Drawing Figs. 1 and 2 are schemstic cross-sectionsl views of different forms of the transfer material of the invention; and Figs. 3a through 3f are schemstic cross-sectional views for explanation of a transfer printing method which uses the transfer material shown in Fig. 1. Summary of the Invention Briefly stated, in accordance with the invention there is provided a transfer material which comprises a substrate, a first layer of thermoplastic uax-like material formed on the substrate, a second layer of thermoplastic material formed on the first layer, and a design layer formed on the second layer of thermoplastic material with an ink for coloring ceramic ways, The thermoplastic materials of both the first and second layers are not tacky at room temperature but thermally activatable to become tacky and remain so for a predetermined period of time and solidify to effect complete adhesion upon lapse af the predetermined period of time. The materials of the two layers have different softening points and different melting points and are decomposable when burned. The material of the first layer has a higher degree of adhesivity to an object to be transfer-printed than that of the material of the second layer to the pad of a transfer head used for transfer printing. Description of Preferred Embodiments Referring to Fig. 1, a transfer material 1 is schematically shown in cross section and comprises a substrate 2, a first or lower layer 3 of thermoplastic wax-like material formed on the substrate 2, a second or upper layer 4 of thermoplastic material formed on the first thermoplastic layer 3, and a design layer 5 formed on the second thermoplastic layer4. The substrate 2 can be a sheet of paper of suitable quality such as coated paper, kraft paper, or a film of a suitable resinous material such as polyethylene terephthalate or-the like resinous material. When a sheet of paper is used as the substrate, it may be thoroughly coated with a material that is both oilresistant and water-resistant and has no affinity for the thermoplastic wax-lEke material. Such coating is useful in preventing expansion and shrinkage of the paper and infiltration of the wax like material into the paper thereby to ensure proper and smooth separation of the layer 3 from the substrate 2. The materials of the two layers 3 and 4 are potentially adhesive and heat-activatable to a state of continuous tackiness. In other uords, these materials have such a characteristic that they are not tacky or adhesive at room temperature but activated by heating to a state of tackiness, which continues for a substantial period of time even after the application of heat is terminated, and solidify with a required degree of adhesion. The materials preferably are decomposable when they are fired or burned. The thermoplastic wax-like material of the first layer 3 is a mixture of thermoplastic hydrocarbon or rosin as a chief component and wax such as metalized synthesized wax, oxidized modified wax made from montan wax, paraffin wax, microcrystalline wax, animal wax and plant wax, and wax copolymerized with ethylene. Mineral oil, animal oil and/or plant oil may be added to the mixture in order to adjust the softening point, the melting point and the fluidity or viscosity of the mixture, as well as to make easy application of the above-mentioned mixture on the substrate 2 to form the first thermoplastic layer 3 and subsequent formation of the second thermoplastic layer 4 and the design layer 5 thereon and to improve the print- ing characteristic of the resulting transfer material. The softening point of the uax-like material of the first layer 3 is preferably between 55bC and 600G and the melting point thereof is preferably between 850C and 95 C although not restricted to the temperature ranges, with the difference between the softening and melting points being preferably between 2500 and 350C. The above-mentioned hydrocarbon resin suitable for use in the transfer material of the invention can be commercially obtained from Arakawa Chemical Cho., Osaka, Japan and the abovementioned metalized synthesized wax, oxidized modified wax and other waxes can be obtained from Hoechst Oorporation, West Germany, The material of the second thermoplastic layer 4 formed on the first thermoplastic layer 3 is a wax-like mixture ofuax, oil and synthetic resin. Examples of the wax are metalized synthesized wax, oxidized modified wax, paraffin wax, animal wax and plant uax, which may be used either individually or in mixture. Examples of the oil are mineral oil, animal oil and plant oil, which may be used either individually or in mixture. Examples of the resin are thermoplastic hydrocarbon resins and ethylene copolymers, which may also be used either individually or in mixture. The wax-like mixture may be used in the form of emulsion. Alternatively, the thermoplastic material of the second layer 4 may be composed of one or a mixture of two or more of thermoplastic latexes such as styrene-butadiene latex and nitrilbutadiene rubber latex; copolymer emulsions of thermoplastic resins such as alkyd emulsion, acrylic ester copolymer emulsion, ethylene-vinylacetate copolymer emulsion, acryl emulsion,- and vinylchloride copolymer emulsion; hydrocarbon resin emulsion; and rosin emulsion. The softening point of the material of the second thermoplastic layer 4 is preferably between 5000 and 550C and the melting point thereof is preferably between 750C and 8for, though not restricted to the temperature ranges, with the difference between the softening and melting points being preferably between 200C and 300G, The compositions of the materials of the first and second thermoplastic layers 3 and 4 are 80 selected that both the softening and melting points of the material of the second layer 4 are lower than those of the first layer 3. The difference in each of the softening and melting points between the materials of the first and second thermoplastic layers 3 and 4 is preferably between 50C and 15 C though not restricted thereto. The materials of the first and second thermoplastic layers 3 and 4 must be thermally decomposable when fired. The compositions of the materials of the first and second thermoplastic layers are also so selected that the material of the first thermoplastic layer 3 has a higher adhesivity to an article to be transfer-printed than that of the second thermoplastic layer 4 to the pad of a transfer head to be described later. The design layer 5 may be formed by offset, gravure, silk screen or any other suitable printing techniques with a suitable ink commonly used for printing and containing colorants, a binder, and other necessary component elements. If necessary, an additional layer 6 of an elastomeric material such as urethane resin may be formed on or beneath the design layer 5 as shown in Fig. 2 to prevent distortion of the design layer when transfer printing is conducted. If the design is delicate and complex, the protective layer 6 is psrticularly useful to maintain the original design in the course of transfer printing. Referring now to Figs. 3a to 3f, a transfer printing process in which the transfer material shown in Fig. 1 is used will now be explained. First, a sheet 1 of the transfer material as prepared in the above-mentioned manner is provided. The sheet is then heated to such a temperature that the thermoplastic layers 3 and 4 are softened and become tacky. The dual-layer arrangement with the material of the first or louer layer 3 having higher softening and melting points than those of the second or upper layer 4 enables uniform softening and activation of the materials of the two layers and subsequent smooth separation of the layer 3 from the substrate 2 and proper adhesive application thereof to the surface of an article to be transferprinted. Any suitable device may be used for heating the sheet. A table 7 provided with an electric heater 8 may advantageously be used for the purpose since the next step of the process can immediately be taken on the heated sheet 1 on the table 7. A transfer head 9 is provided with a pad 9a made of a suitable resiliently deformable material such as silicone rubber and so contoured as to have a convexly curved surface 9b. The head 9 is brought downwardly into contact with the upper surface of the heated sheet 1 of transfer material with a suitable pressure as shown in Fig. 3b, so that as the head 9 is raised, most of the thermoplastic layers 3 and 4 together with the design layer 5 and, if provided, the coating layer 6 are transferred to the surface 9b of the pad 9a as shown in Fig. 3c. Some of the thermoplastic material of the layer 3 is left on the substrate 2 as shown at 3'. At the next step, the transfer head 9 with the design an other layers on the surface of the pad 9a is brought into contact with the surface of a piece of ceramic ware 10 to be colored or transfer-printed with a suitable contact pressure as shown in Fig. 3d, so that as the head 9 is raised agai the design layer 5 and the thermoplastic layers 3 and 4 are tFanga ferred from the pad surface to the surface of the ceramic vare as shown in Fig. 3e with chiefly the adhesive wax-like mate rial 3 being in close contact with the surface of the ceraniic ware0 Although the border line between the layers 3 and 4 are shown clear and sharp in Figs. 3c to 3e, actually it is not so clear and sharp because the materials of the two layers are mixed st the border. In this connection, the substrate and the layers are shown exaggerated in thickness for simplicity and clarity of illustration in all the figures. As can be seen from the above, when the design layer 5 and the thermoplastic layers 3 and 4 of the transfer material are transferred from the substrate 2 thereof to the pad surface 9b of the transfer head 9, the layer 4 adheres more strongly to the pad surface 9b than the layer 3 adheres to the substrate 2, and when the layers are transferred from the pad surface to the surface of the ceramic ware 10, the layer 3 adheres more strongly to the surface of the ceramic ware than the layer 4 adheres to the pad surface. This is possible by proper selection of the materials of the substrate and the thermoplastic layers of the transfer msterial, and by the state of continuous tackiness of the activated thermoplastic or adhesive layers. At the next step of the process, the ceramic ware 10 with the transferred layers on the surface thereof lis fired to such a temperature as to securely fix the design layer to the surface of the ceramic ware while simultaneously decomposing the thermoplastic materials 3 and 4 and removing the burned remnants from the surface of the article, so that the surface becomes clean with the design clearly transfer-printed thereon as shown in Fig. 3f. Some preferred examples of the invention will now be given below for better understanding of the invention0 Example I Coated paper weighing 128 g per square meter is used as the substrate sheet, on which a first layer of thermoplastic wax- like material and a second layer of thermoplastic material are successively formed one upon the other with a mixture of the following compositions. Composition of the thermoplastic wax-like material of the first layer: Parts by weight Hydrocarbon resin (Arukon, product of 38 Arakava Chemical Co., Osaka, Japan) Metalized synthesized wax (Caw-20, 8 product of Hoechst Co.) Oxidized modified wax (KPE, 12 product of Hoechst Co.) Oxidized modified wax (R21 4 product of Hoechst Co.) Wax copolymerized with ethylene 8 Bees wax 4 Paraffin wax 16 White oil 10 Composition of the thermoplastic material of the second layer: : Hydrocarbon resin (Arukon) 16 Oxidized modified wax (KPE) 16 Wax copolymerized with ethylene 12 Castor wax 8 Bees wax 8 Paraffin wax 24 White oil 16 On the surface of the second thermoplastic layer thus formed a design layer is formed by the gravure process with sn ink commonly used for coloring ceramic ware and containing inorganic pigments as chief components to produce a sheet of transfer material. The sheet of transfer material is put on a heating plate heated to about 1300C, and a transfer head with a silicone rabber pad is pressed against the upper surface of the heated sheet of transfer material 80 that as the transfer head is removed therefrom the design layer and most of the thermoplastic layers are transferred to the pad surface of the transfer head. The head is then pressed against the unglazed surface of a piece of ceramic ware so that the design layer and the thermoplastic layers are transferred from the pad surface to the surface of the ceramic ware. After the ware is preliminarily fired at about 500 C, glaze is applied to the surface of the ceramic ware, which is then again fired at 13500C. The ware has now been glazed, with the design having been clearly and securely transfer-printed on the surface thereof. Example II A sheet of transfer material is prepared in the same manner as in Example I by forming on a substrate sheet similar to that in Example I a first and a second thermoplastic layer success sively one upon the other with a mixture of each of the follow¯ ing compositionsO Composition of the thermoplastic wax-like material of the first layer: Parts by weight Hydrocarbon resin (Arukon) 40 Metalized synthesized wax (Caw-20) 2 Oxidized modified wax (KPE) 12 Oxidized modified wax (R21) 5 Wax copolymerized with ethylene 14 Castor wax 2 Bees wax 3 Paraffin wax 14 White oil 8 Composition of the thermoplastic material of the second layer: : Hydrocarbon resin (Arukon) 12 Metalized synthesized wax (Caw-20) 8 Oxidized modified wax (KPE) 12 Wax copolymerized with ethylene 16 Castor wax 10 Bees wax g Paraffin wax 26 White oil 16 On the surface of the second thermoplastic layer thus formed a design layer having a delicate flower design is formed by screen printing with an ink commonly used for coloring ceramic ware and on the design layer there is formed a coating of elaa- tomeric acrylic resin. A piece of ceramic ware has its surface glazed and fire 1 and the sheet of transfer materials prepared in the abovementioned manner is applied to the glazed surface of the ceramic ware to transfer the design layer from the sheet of trnafer material to the surface of the ceramic ware, which is then fired at about 8000C so that the delicate flower design Fig now been transfer-printed on the glazed surface of the ceramic ware.

Claims: Claims What we claim is: 1. A transfer material comprising a substrate, a first layer of thermoplastic wax-like material formed on said substrate, a second layer of thermoplastic material formed on said first layer, and a design layer formed on said second layer, said materials of said first and second layers being hest-sensitive and having such a characteristic that they are not tacky at room temperature but activatable upon heating to become tacky and remain so for a predetermined period of time after said heating is terminated and solidify to effect complete adhesion upon lapse of said predetermined period of time and that said materials are decomposable when heated above the temperature at which said materials are activated, and said material of said first layer having a higher degree of adhesivity to an object to be transfer-printed than that of said material of said second layer to a transfer head to be used for transfer printing. 2. The transfer material of claim 1, wherein said material of said first layer has a softening point between 550C and 600C and a melting point between 850C and 950C. 3. The transfer material of claim 2, wherein the difference between the softening and melting points of said material of said first layer is between 250C and 3500. 4. The transfer material of claim 1, wherein said material of said second layer has a softening point between 500C and 550C and a melting point between 75 C and 850G. 5. The transfer material of claim 4, wherein the difference between the softening and melting points of said material of said second layer is between 200C and 30 C. 6. The transfer material of claim 1, wherein the difference in the softening point between said materials of said first and second layers is between 50C and 150C. 7. The transfer material of claim 1, wherein the difference in the melting point between said materials of said first and second layers is between 50C and 150C1, 8. The transfer material of claim 1, wherein the material of said design layer includes an ink used for coloring ceramic ware. 9. The transfer material of claim 1, further including a layer of an elastomeric material coating said design layer. 10. The transfer material of claim 1, further including a layer of an elastomeric material underlying said design layer. 11. The transfer material of claim 1, wherein said substrate comprises a member selected from the group consisting of paper and synthetic resin. 12. The transfer material of claim 11, wherein said substrate comprises a sheet of paper thoroughly coated with a material which is oil-resistant and water-resistant and has no affinity for the material of said first layer. 13. The transfer material of claim 1, wherein said first layer comprises a mixture of thermoplastic resin, wax and oil. 14. The transfer material of claim 1, wherein said second layer comprises a mixture of thermoplastic resin, wax and oil. 15. The transfer material of claim 1, wherein said second layer comprises a member selected from the group consisting of thermoplastic latexes, copolymer emulsions of thermoplastic resins, hydrocarbon resin emulsion and rosin emulsion. 16. The transfer material of claim 1, wherein said second layer comprises a mixture of at least two members selected from the group consisting of thermoplastic latexes, copolymer emulsions of thermoplastic resins, hydrocarbon resin emulsion and rosin emulsion. 17. A method of coloring the surface of sn object, comprising a first step of providing a sheet of transfer material which comprises a substrate, a first layer of thermoplastic wax-like material formed on said substrate, a second layer of thermoplastic material formed on said first layer, and a design layer formed on said second layer, said materials of said first and second layers being heat-sensitive and having such a characteristic that they are not tacky at room temperature but activatable upon heating to become tacky and remain so for a predetermined period of time after said heating is terminated and solidify to effect complete adhesion upon lapse of said predetermined period of time and that said msterials are decomposable when heated above the temperature at which said materials are activated, and said material of said first layer having a higher degree of adhesivity to an object to be transfer-printed than that of said material of said second layer to a transfer pad to be used for transfer printing; a second step of heating said sheet to a temperature at which said first and second layers become tacky; and a third step of trsnsferring said design layer from said sheet to the surface of said object. 18. The method of claim 17, wherein said transferring step comprises pressing a transfer pad against said design layer so that said design layer and said first and second layers are transferred to the surface of said pad, and then pressing said pad surface with said transferred layers thereon against the surface of said object so that said design and thermoplastic layers are transferred from said pad surface to said surface of said object. 19. The method of claim 17, wherein said sheet of transfer material further include a a coating layer protecting said design layer from distortion or damage. 20. The method of claim l8, wherein said object is a piece of glazed ceramic ware and said design layer comprises ink used for coloring ceramic ware, and further including a fourth step of heating said object to a temperature at which said materials of said'first and second layers are decomposed, thereby to remove the burned remnants from the surface of said object. 21. The method of claim 18, wherein said object is a piece of unglazed ceramic ware and said design layer comprises ink used for coloring ceramic ware, and further including a fourth step of heating said object to a temperature at which said materials of said first and second layers are decomposed, thereby to remove the burned remnants from the surface of said obJect a fifth step of applying glaze to the surface of said ceramic ware with said design layer thereon and a sixth step of firing said ceramic ware. 22. The method of claim 17, wherein asaid second step of. heating is conducted by placing said sheet of transfer material on a heating member. 23. The method of claim 17, wherein said transfer pad is of a resiliently deformable material and said object has a curved surface, against which said pad with said design and thermoplss tic layers is pressed.

Inventors: NAKAMURA, YUZO, OOICHI, TOSHIO
Applicants: NIPPON KORES KABUSHIKI KAISHA, NISSHA PRINTING CO., LTD.
Application year: 1982
Main classification: B44C1
IPC codes: B44C1, B41M1