DE1236995C2 - HOT APPLICABLE CERAMIC DECAL - Google Patents

Description

_{is fast according to the} invention by means of a w roittels.

on warmed substrates hot ^{by W SOndem rCh}

rvoenstand der nruuuuug is a bite-applicable I ₀ SSSSr decal to be applied using kerarmscnes Λ «preheated sub-

SchneeUaufcnder Mjctanen a ^^ ^. ^

strate by denroigcu ^^ _waxundurCQ .

15th

The invention relates to a hot-applied ceramic decal for application by means of a high-speed transfer Machines on preheated substrates for decorating ceramic objects, for example China porcelain, glass, earthenware and porcelain.

For many years, the ceramics industry has been used to decorate glassware, porcelain or the like. Decals made with certain vitrifiable paints or ceramic paints. Most which are determined for this purpose / ι decals from a paper carrier or a paper backing on which the desired image can be glazed Color or in several vitrifiable colors is printed. This paper pad can be with Peel off water.

In one type of decal, the paper backing carries a thin layer of a water-soluble one Glue or rubber, and the glass image is printed on the rubberized surface so that it is after above points. Another type of decal, called a duplex, has one layer off thin tissue paper is available, which is supported by a thicker paper base and from this can be replaced. The thin tissue paper has a water-soluble rubber spread, and the The glass image layer is printed with the surface side down on the rubber spread.

The water-removable ceramic decals have major disadvantages. So let yourself be For example, do not apply fully automatically with high-speed machines, they can only be applied to cooled Substrates are applied, otherwise the water evaporates too quickly and tensions themselves if the substrate is only slightly heated by contact with the water and crystallization and brittleness can occur. When applied to unglazed porcelain ware, the porous surface absorbed excessive water, so that a special additional drying is required. In addition, there is a risk that the goods will be as a result of being contained in the water Components such as B. iron, discolored.

The object of the invention is therefore to provide a hot on-6s portable ceramic decal for application using high-speed machines on preheated Indicate substrates that the HaranMemls described above,

consists of the combinations of these V <· «Etael features selbs, w" d

S de, Earthing.suitable,

^ Sn known method adherent

Priority substrate can be applied.

^ The invention is explained in more detail below with reference to the drawings. It shows

Fiß 1 fchematischen a cross-section on a greatly enlarged scale, of a particular embodiment of the ceramic decal OF INVENTION ^dU F ⁸ i _'E 2 a similar cross section as Fig. 1, of another embodiment of the ceramic decal to the invention. .

Fi λ 3 a similar cross section as FIGS. 1 and 2 through a further embodiment of the ceramic transfer of the invention and

FU 4 has a similar cross section to FIG. 1 through 3 by a further embodiment of the ceramic decal of the invention.

Dta to Fig. 1 illustrated embodiment of the glass-like The decal can be purposely provided by a corrective measure Printing processes, e.g. by screen printing, SSdk translating or letterpress printing

has a picture

Se consists of the auxiliary paper carrier 1 m Interference layer 2, which is one side of the paper less S and ün essentially impermeable to wax

power. Above this is the separating layer 3 made of a polyethylene glycol of high molecular weight. One Synthetic resin film 4 lies over the separating layer 3 and serves as a carrier for the subsequently applied glass-like image 5, which lies directly on the clear sheet 4. Figure 5 consists in the usual way from a composite layer, which contains several different ceramic color races, the so are arranged to give the desired image or text. Over the outside of the vitreous image S is a layer 6 of a suitable thermoplastic or through Heat caking adhesive that acts as a temporary binder to attach the image to the to attach the decorative object. The bottom or opposite side of the sheet of paper 1 may have a wax spread or the like (not shown) that allows the stacking of allows individual decals without sticking or sticking together, so that on this way the use of special slip sheets when stacking a series of decals is prevented.

The barrier layer 2 can consist of a surface sizing or a closable spread, z. B. made of starch, casein, glue, alkali metal silicate, water glass, etc., either with or without clay filler, exist. A very satisfactory barrier layer 2 consists of water glass or some other alkali metal silicate with dispersed talc, clay or similar filler. The presence of the barrier layer 2 on the paper 1 prevents the excessive Penetration and absorption of the polyethylene glycol, which softens and melts under the heat of detachment 3. The material chosen for the barrier layer 2 must be stable and should be supported by the heat dissipation of the decal is relatively unaffected stay. The presence of the barrier layer 2 closing the pores of the paper also obviously gives 4 " a more uniform and smoother separating layer 3, so that it is possible to apply this without impairment the clarity of printing images that have relatively fine and delicate details.

The separating layer 3 consists of a solid polyethylene glycol of high molecular weight, preferably of at least 1000. Such substances are wax-like solids and are available, for example, from Carbide & Carbon Chemicals Corporation sold under the trade name "Carbowachs".

The substances known as Carbowax 4000 and 6000 are particularly advantageous for use as a separating layer 3. They are particularly well suited for the purposes of the invention because of their excellent burning properties, with which combustion takes place without excessive soot deposition. At the same time, such, usually solid, polyethylene glycols have softening points between 55 and 62 ° C., so that they have the desired heat-releasing properties under many practical working conditions. Preferably, a polyethylene glycol polymer is used, the softening point of which is in the lower section of the temperature range mentioned, tim the desired softening effect and heat dissolving effect as possible when using the transfer! to obtain. This is important for the machine or automatic application of the decals. A particularly important advantage of using polyethylene glycols as the separating layer 3 is the relative insolubility of such substances in the solvents that are used in the production of the ceramic dyes used for the glass-like image screen 5. Under these conditions there is no tendency for the layer 3 to shift or deteriorate if the glass or ceramic colors are applied as a liquid during the production of the decal. The dry glass image 5 can therefore be applied to the separating layer 3 in an easily detachable position.

As a result of the detachable separating layer 3, the transfer image, consisting of the layers 4, 5 and 6, can be detached from the layer 3 as a unit. The layer 4, which forms a basis or a carrier for the glass image 5, is an unpigmented clear synthetic resin film or a synthetic resin film, which preferably consists of the same organic substance that forms the main part ν, ι different colored layers or prints in the glass image 5. Fiim 4 or sheet 4 consists of a plasticized acrylic resin layer, e.g. B. polymerized acrylic resin or a polymethyl methacrylic resin. The acrylic resin layer can be molded over the release liner 3 of the base using a liquid solution of the acrylic resin in a solvent which does not have a substantial dissolving effect on the release liner 3 for the reasons already described. The acrylic resin solution can also contain a suitable plasticizer, e.g. B. chlorodiphenyl included. The solvent for the acrylic resin solution consists of a petroleum hydrocarbon. As an example, a typical composition of a substance that can be used to produce a clear acrylic resin layer 4 is given:

1 part by weight of acrylic resin (Du Pont L-46), 1.3 part by weight aromatic petroleum hydrocarbon solvent, 1 part by weight chlorinated diphenyl plasticizer (Monsanto Chemical Company, Aroclor 1262).

This composition has good sieving properties and is therefore particularly suitable for Application of the layer 4 by means of the screen printing process. The relative amounts of acrylic resin, solvent however, and plasticizers may vary depending on the type of acrylic resin used or the printing properties desired can be changed in the formula.

As already mentioned, the image 5 usually consists of a composite layer or a Composite layer made by successively printing several ceramic colors on the Clear coat 4 is obtained.

The printing pastes or inks consist firstly of a vitrifiable material or a vitrifiable flux containing an appropriate pigment or dye and secondly of a flowable carrier or binder in which the pigmented flux is dispersed. Pigmented flux is known in the field of glass and porcelain decorating and is supplied by the color works as a finished glass color, which is then dispersed by hand with the carrier depending on the requirements of the respective goods to be produced.

As a carrier for the ceramic color, the Invention uses a resin material whose Ef *

softening point is not below 165 ° C, so that the Decal transfer at relatively high release temperatures can be used without that there is a disturbance in the proper detachment of the image. The resin material should also be at Burning decomposes quickly and should not go through a liquid or "fast flowing" state. Finally, the resin material of the ceramic ink carrier should completely evaporate or burn off before the keep that from 62.8 ° / o of lead or litharge, 17.8 ° / o boron oxide, 14.1 ⁰ Zo silica and 5.3 · / · cadmium oxide is, all in weight percent. 16 percent by weight of titanium dioxide is added to this composition as a covering agent.

2. A red layer of paint can contain: 56.0% lead oxide or black lead, 29.8% / · silicon oxide, 3.2% Boron oxide, 2.1% lithium oxide, 4.1% cadmium oxide, 3.0% titanium dioxide and 1.8% sodium oxide, all in

vitrifiable "constituents of the ceramic paint to erio weight percent. This flux formula are

soften or begin to melt, e.g. B. below 480 ° C. Experience has shown that acrylic resins meet these requirements are very satisfactory and are therefore the preferred materials or substances for the Purposes of the invention. For example, the acrylic resin "Lucite" manufactured by Du Pont has one Softening point of about 165 to 175 ° C, decomposed and will not evaporate completely before the vitrifiable components begin to soften liquid or "fast flowing" when burning, so that all difficulties from smudging and draining of the applied decal can be avoided during the firing process.

The ratio of pigmented flux to carrier or organic matter in the glass color as or glass paste, which is necessary to obtain satisfactory color values, burning properties and service life, depends largely on the Density and other properties of the particular pigmented flux or ceramic paint. For example, in many cases a useful paste can be made by grinding about 2 parts by weight of the pigmented flux or the ceramic paint with about 1 part by weight of the organic substance 9 weight percent red pigment, e.g. B. cadmium sulfoselenide and cadmium oxide, admixed.

3. A black colored layer of the flux can contain: 78.0% lead oxide or black lead, 10.3% Boron oxide and 11.7% silicon oxide, all in percent by weight. With this composition will be about 16 weight percent black pigment bonded, e.g. B. a mixture of cobalt, chromium and iron oxides.

All pigment fluxes mentioned are ground in an organic substance, preferably in an acrylic resin carrier of the type described, the Amount of organic matter and its softener content are regulated so that the desired coloring, retention and burning properties are obtained in the finished decal will. The above-described clear acrylic resin composition for layer 4 is very satisfactory Substance for use in the above ceramic paint compositions. The mixing ratio consists of 2 parts by weight of Kera micro-dye to 1 part by weight of clear acrylic resin carrier.

The thermoplastic or heat adhesive

can be obtained. The organic substance has an adhesive layer 6 which is becoming 35 and which has the temporary binding-sufficient amount of softening agent, thus means for temporarily adhering the glass image 5 that the printed film has the right flexibility for both objects to be decorated, can result retains, even if large amounts of the pigmented, any suitable resin adhesive, e.g. B. Flux have been applied to the film. In a maleinmodified resin or maleate resin, other cases, e.g. B. if a paint application of less than 40 an acrylic resin, a vinyl resin, polyvinyl methyl starch is desired, the relative amount of ether, etc., can exist. Good results come with one pigmented flux are reduced by obtaining modified ethyl cellulose lacquer residue, about 2 parts by weight of the pigmented flux which is an appropriate plasticizer, e.g. B. diphenyl chlorinated with about 3 parts by weight of the organic substance, and an ester gum, e.g. B. be mixed. In this case, the soft glyceryl, methyl or ethyl ester of resin acids, making agent content of organic matter such as contains. Experience has shown that it is in many cases Usually, for certain applications it is advantageous to put a small amount in the adhesive layer 6 The vitreous transfer described here can contain a clear, non-pigmented flux or improved burning properties and can include upper vitreous material. The inclusion The flux supports the adhesion or the fact that the corresponding color layers of the glass support the glass image 5 on the one below Fig. 5 arranged the object in an orbestmten order when burning and also prevents that be net, so that the occurrence of holes or the like lying on the clear coat in the final fired Color printing the hardest or most difficult to image. The flux can consist of a mixture of melting layer forms while the following 55 non-pigmented organic oxides of the above Layers of color are always softer or consist more and more easily described and is preferably a

melt so that the outermost or topmost coat of paint of the decal is the softest coat of paint or is the easiest-melting layer of paint. In general, the degree of hardness or the melting temperature of the ceramic colors in question will pass Regulation of the amount and composition of the fluid content of the paint can be easily regulated. For purposes of explanation, but not for purposes of limitation, some summary Pieces for typical ceramic colors for glass picture 5

1. A white layer of paint can be a flux that has a slightly lower melting point has the pigmented flux shown in Figure 5. This gives a ratio of 1 part by weight Flux to 15 parts by weight adhesive gives good results.

When decorating a ceramic object, e.g. B. a porcelain or glass object with the As described in the decal, the ceramic object is first preheated and then the outer thermoplastic layer 6 of the decal! applied to the preheated object.

7 8

Bringing heat results in two active agents or varnish 9 in the desired outline in a single step. Above all, the thermoplastic is activated or made adhesive by means of a known technique, preferably by means of layer 6 , so that the glass image applied by a flat printing process or the like is temporarily attached to the ceramic surface. Binding agents or varnishes of this type are stapled or glued. At the same time, the known technology and consists, for example, of the action of heat on the transfer of the linseed oil with a suitable plasticizing image of the same, a melting and softening agent. After the application of the layer 9 and in the footing layer 3, so that the still wet or sticky state of this layer 9 covered with a barrier layer paper auxiliary carrier 1 is the desired ceramic color or glass color is removed automatically. The clear layer 4 naturally detached as 10 in powdered or finely divided form on the one unit with the image 5 and is on the preformed image layer 9 dusted or widened outwards when the image 5 is sprayed on. The particles of vitrifiable paint 10 are located in the ceramic object. Then the th is only on the sticky spread surfaces, wäh ceramic object at high temperature in the rend the dry, non-sticky protective layer 8 burned in the usual way, so that the glass image S 15 adhering of the glass particles to the wax spread 3 melted and permanently in the ceramic guard . After the layer 9 has dried, the surface can be melted down. The clear layer 4, the loose glass or ceramic color particles easily organic components of the glass image 5 and that are removed. Then the external temporary binders 6 are completely thermoplastic layer 6 consumed during firing in the same way, so that only the pigmented flux as previously described is applied. To the club component of the glass image S remains. The panning is shown in FIG. 3 only a single layer 9, written technique can of course be dusted on glazed items with ceramic color particles 10, items and unglazed items on. However, any number can be used in the glass image. Unglazed objects, so-called superimposed layers, are present, whereby biscuit objects are preheated and the waste from each layer is formed and dried by means of the same deposition and drawing pattern in the manner described above. Then the biscuit is heated with the image that has been stuck on before the next layer is applied, followed by the organic one.

To drive off components of the image, and then in the case of FIG. 4 shown special

the glass-like image is formed by dipping or spraying a liquid glass guide of the invention

sur upset. After the first drying it will be made of a metallic colored ornament or

The goods are then burned, which then have a very permanent font, e.g. B. gold, silver, platinum, palladium or the like.

Has underglaze decoration. Metal colors, e.g. B. the so-called "sieve gold",

The type and composition of the one that takes place at high speeds differ completely from the Machine transfer of the decal is based on 35 common ceramic colors mentioned earlier. Under It is particularly important that the gold ceramic color from layers 4, S has a much deeper and 6 existing transfer section fast and feren melting point than the usual ceramic colors, perfectly detached from the temporary carrier. as a result, there is a tendency towards carbon particles

In the case of the in FIG. 2 shown modification of 40 between the applied gold color and the counter-described Decals are paper support 1, to be included, if there is one in between Barrier layer 2, separating layer 3 and clear layer 4 in the binder layer, for example those caused by heat essentially the same as mentioned adhesive layer 6 which becomes adhesive in the embodiment Fig. 1. The glass image 7, however, has been turned over. In other words: with the behaviorally integral Constituent part of a thermoplastic or slightly lower melting point of the gold fiber The adhesive component that becomes adhesive due to heat has the adhesive component that becomes adhesive due to heat on, which enables the in F i g. 1 illustrated rial 6 not always opportunity to fully vaporize specific To omit adhesive layer 6. If used or completely decomposed, before the GoIc tion, the layer 7 melts to the preheated, with the result that part of the adhesive ceramic article laid out, whereby the layer with such a substance or carbon residue during firing it a relatively low preheating temperature of the gold paint is included. The detainee so great a bond strength developed that the layer 7 speed of the gold color is consequently low, and di < Decorated goods sticks directly to the object and has an unsatisfactory stained

The modification shown in Fig. 3 is appearance.

the glass image by means of a different technique 55 metal colors also often show the undesirable

The auxiliary paper carrier 1 with the blocking tendency to shrink on firing when egg

Layer 2 and the separating layer 3 are de adhesive material between the paint and the surface in this case

the same layers as previously described. Goods are available. When shown in Fig. 4!

. A clear layer 8 is also applied over the separating layer 3, layers 1, 2, 3 and 4 are used

upset. However, while in the embodiment according to FIG. 60 the same as in the embodiment according to FIG. 1

Fig. 1 the clear layer 4 in the main as Immediately above the clear layer 4 is the durd

The carrier film for the glass image 5 is used, has a heat-sticking adhesive layer U at the beginning

in the case of the clear layer 8, in addition to this, the wich- over which the gold-colored or other metal

term purpose to protect the separating layer 3. Vorlische glass image 12 is placed. Make the gold picture

as a result, the clear layer 8 preferably has a 65, that is to say in this embodiment of the invention the one indicated

so great that it covers the separating layer 3 lying portion of the decal. So now di

completely covered there is certainty that at least one paragraph

Over the clear protective layer 8, a binder, the adhesive layer t which becomes adhesive due to heat, is placed

rests against the preheated object in order to To achieve temporary adhesion of the decal in this way prior to firing, it is important that the gold layer 12 is discontinuous, so that a number of openings or cracks 13 between the various Parts of the gold image are present. Then can *. the exposed, sticking through heat future adhesive 11, which is in the open spaces or in between the gold-colored Areas 12 existing cracks or crevices are located, apply directly to the surface of the heated object. This contact ^ - or contact surface sufficient to cause the necessary temporary adhesion of the transfer layer to the object achieve and secure. At the same time, the gold surfaces 12 are in direct contact with the Object brought so that there is no glue or other material during the subsequent firing is located between the gold color and the surface of the object. ao

Thus, in accordance with the invention, a hot-applied cosmetic decal is created "that very much." important and valuable advantages over the known decals previously used in this field Has. The use of water in applying the decal to the item is made completely switched off, so that there are no problems with staining or water deposits. Also the drying times necessary before firing, those that work with water Removal procedures are not required. The thermoplastic adhesive burns off completely, like this that the difficulties mentioned in connection with gum paints and varnishes avoided will. The very simple and easy application of the decals enables them to be used for the first time high-speed machines) that carry out the application, so that as a result worker spam achieved and the manufacturing cost can be reduced.

1 sheet of drawings

Claims (1)

Does not have disadvantages, Claim: Ceramic transfer, which can be applied hot, to be applied using high-speed machines on preheated substrates, characterized by the following structure: auxiliary paper carrier (1) with a wax-impermeable barrier layer (2), separating layer (3) made of a high polyethylene glycol Molecular weight, image layer (5) made of ceramic paint and a resin material in combination with a heat-activatable adhesive made of thermoplastic material, the softening point being the resin material is not below 165 ° C. Cons ve,