EP0699138B1 - Method of production and surface treatment - Google Patents

Abstract

Method of mass production and surface treatment of supports with a plane or non-plane, translucent, transparent or opaque surface for glass roofs, composite glazing, doors, windows, floors, walls, ceilings or other applications such as furniture, bottles, phials, containers. The method is characterized by screen printing a pattern in colour and then a grid using conductive inks containing from 50 to 80 % of silver or any other highly conductive metal. The supports are then successively dipped in a first electrolytic or chemical copper bath, then in a second electrolytic or chemical nickel bath or any other metal resistant to corrosion and suitable for these metallizing methods. The invention also concerns the products obtained.

Description

The present invention relates to an improvement in preparation process described in patent FR 2,658,756 likely to popularize a process of handcrafted and its application to production in series of supports having a flat surface or not but preferably in the form of sheets or plates that the consumer can format or have formatted at his demand and according to their tastes and needs to the dimensions he wants.

The process of patent Fr 2,658,756 which constitutes art nearest anterior is characterized by the preparation of a decorative article obtained from a support made of metal, ceramic or plastic material on which applies according to defined contours and / or surfaces a projecting partitioning on the support, then in the meshes of it, colors providing good adhesion to said surface and poor adhesion to partitioning material.

This improvement differs from FR 2,658,756 in that the method successively uses the screen printing technique and then electroplating, or chemical metallization, the concept being to color first the support and then mesh it, while in the above patent the coloring, occurring after the mesh, did not allow the industrialization of the process because it required the manual skill of the craftsman to avoid overflows and burrs.

By reversing the operations, the technique presently described also allows the manufacture and series surface treatment of supports translucent, transparent or opaque, in thermoplastics, plastics, polymers, glasses etc ..., than mass production of stained glass. Regardless envisaged product, the invention reproduced on a support, flat surface or not, a graphic document whose the printing is done according to the serigraphic way.

To achieve the desired industrial result, the preparation of supports requires several operations successive.

This technique combining screen printing and electrolytic or chemical metallizations allows essentially to achieve in series partitions of metal, on various materials. These partitions are directly obtained on the surface of these supports in metallizing the conductive ink of the printed mesh. That is made possible by the fact that the conductive ink must have a compatible or similar binder chemical as the support material and the base constituent of colored inks in the case of supports previously printed with colored inks, condition necessary and sufficient to provide a very large resistance and resistance over time illustrated by presence of two asterisks in the attached Table A.

This ink contains 50 to 80% silver or all other high conductivity metal. Table B shows the nature of the binder according to the various possible supports.

These tables are not limiting because the state of the technique has established that generally speaking at all support made of any material can match a color ink whose base is same nature as this support and a conductive ink of which the binder is also made up of this material.

To better understand the technical characteristics and the advantages of the present invention, we will describe exemplary embodiments with the understanding that these are not limiting as to their mode of placing and the applications that can be made of it.

Example 1 Phase 1 :

For the preparation of supports in acrylic or polyacrylic resins for canopies, composite glasses or intended to be inserted in door or window frames, or other applications such as floors, walls, ceilings, furniture, bottles, flasks, containers, preferably choose according to the desired size of sheets or plates ≤ 5 mm> thick which should be cleaned carefully at first.

Colored inks, transparent or opaque, can be acrylic. They are applied according to the screen printing principle and having taken care to leave between each colored zone C1 and C2 free spaces (Figure 1) just less than the width of the line composing the mesh (Figure 2), which will then be printed on the conductive ink in marking on the colors, it allows obtaining, with translucent or transparent materials, a product window to a single printed side of which the conductive ink is used to frame of back delimiting colors.

It is possible to print color by color and to steam each time, or to print all the colors and to steam once.

Phase 2 :

• Si l'on envisage la phase successive de métallisation de l'encre conductrice par voie électrolytique, l'impression de cette encre doit se faire impérativement selon un schéma permettant la continuité de la conduction électrique au cours de la phase de galvanoplastie. A cet effet, on imprime en même temps que le maillage conducteur et de façon solidaire au dessin quatre languettes dites nourrices selon l'exemple de disposition en quatre points apparaissant sur la figure 5.
• Si l'on envisage la phase successive de métallisation par voie chimique, l'impression de l'encre conductrice peut se faire selon n'importe quel schéma et sans recourir à des nourrices ni à une quelconque préparation.
• Après impression de l'encre conductrice, on étuve puis on nettoie le maillage conducteur avec, une solution acide de SO₄H₂ diluée à 5-10% ou tout autre produit utilisé par l'homme de l'Art.

The printing of the mesh is carried out on the front of the sheet according to the screen printing principle described in phase 1 and in reference to the other colors (Figure 3). But in this phase, the printing is done using a conductive ink composed of 50 to 80% silver or any other metal with high conductivity and for the rest of an acrylic binder or a solvent acrylic and polyacrylic resins such as, for example, carbitol acetate.

• If we consider the successive phase of metallization of the conductive ink by electrolytic means, the printing of this ink must imperatively be done according to a diagram allowing the continuity of the electrical conduction during the electroplating phase. To this end, we print at the same time as the conductive mesh and in solidarity with the drawing, four so-called nurse tongues according to the example of arrangement in four points appearing in FIG.
• If we consider the successive phase of metallization chemically, the printing of the conductive ink can be done according to any scheme and without resorting to nurses or any preparation.
• After printing the conductive ink, we oven and then clean the conductive mesh with an acid solution of SO ₄ H ₂ diluted to 5-10% or any other product used by those skilled in the art.

An alternative solution to printing nipples, considered in the case of electroplating is constituted by the use of electrodes (1) preferably made of stainless steel called contact nuts such as described in figure 4 and fixed to the cathode by screws made of insulating material (2). As for nipples, these electrodes are only necessary and usable only during the metallization phases by electroplating, chemical metallization not doing appeal. For each metallization mode envisaged by electroplating or by chemical metallization corresponds special preparation of the support printed in ink conductive.

Phase 3 :

The prepared support is placed to undergo electroplating treatment in a first copper electrolytic bath. After the conductive ink has risen in copper, it can be rinsed with water and then, depending on the type of electrolytic bath that has been used, acid or alkaline, and the type of copper used at the anode, it can be rinsed in a second bath. containing, for example, either from 5 to 10% of SO ₄ H ₂ , or 10% of HCl, or from 10 to 20% of sodium persulfate or ammonium persulfate or any other product used by man of art.

Or we place the prepared support to follow a chemical treatment in a first chemical bath of copper. It is a chemical metallization obtained conventionally by ion reduction based on redox reactions at the metal interface. To the end of the copper plating operations, we will repeat the processes of rinses described above.

Phase 4 :

You can place the support reassembled in copper by electroplating or by chemical metallization in a second electrolytic bath of nickel or any other metal suitable for electrolytic deposits and resistant to corrosion. At the end of the electroplating operations, we can eliminate the nurses either by cutting the plate at flush with printing, either by removing only nannies (Figure 6), or in the event that contact nuts have been used, we will unscrew them.

You can also place the reassembled copper support by electroplating or by chemical metallization in a second chemical bath of nickel or any other metal suitable for chemical metallization resistant to corrosion. It is a chemical metallization based on the same principles as those described in phase 3 for chemical copper plating. We can also provide for this same final stage partitioning made of another metal.

If we proceed to the metallization phase with the nickel, whatever the type of metallization envisaged, electroplating or chemical, we can apply at the end of either nickel plating operation a cover chemical gold.

Example 2

We print on a translucent, transparent or opaque acrylic or polyacrylic resin ink conductor described in phase 2 of Example 1 from a silkscreen screen silhouetting the chosen motif. Yes we are considering the successive metallization phase of conductive mesh by electroplating, printing is will do according to a diagram allowing the continuity of the electrical conduction. We print simultaneously nannies, usually four in number (Figure 5) and one proceeds according to claim 4 of the FR patent 2,658,756. We can alternatively use the technique contact nuts. If we consider the successive phase metallization of the conductive mesh by chemical means, the printing will be done according to any scheme and without use nurses or any other preparation. After printing, we will repeat the steaming process and of cleaning of phase 2 of example 1.

The support is initially placed in a copper electrolytic or chemical bath as described in example 1, phase 3, then in a second step, in an electrolytic or chemical bath of nickel or any other metal suitable for these metallization modes and resistant to corrosion as described in Example 1, phase 4. We thus obtain at the final stage and after elimination of nurses or removal of contact nuts in the case of electroplating, as described in Example 1, a translucent or opaque support provided with a nickel partitioning ≤ or> 10/10 mm thick on the front of this support. On the nickel used, we can still apply a layer of gold chemically. Can also provide, at the same final stage, for a partitioning made up another corrosion-resistant metal.

Example 3

When the specifications imply the use of supports in transparent acrylic or polyacrylic resin or translucent with a thickness> 5 mm, it is preferable, to avoid the phenomenon of refraction of light and optical deformation of the mesh, to print the back of the stained glass, the front having been treated according to example 1 or 2.

On the back of the support, we can print the same colors by turning over the films. For printing the mesh, we can use an acrylic white mixed with black to mimic the effect of lead. This impression is done by screen printing in reference to the other colors (figure 1). We repeat in this option the operation of drying described for printing the front in the example 1 phase 1.

For the printing of the mesh on the back, you can also, reversing the films, proceed as in Example 1, phases 2-3-4.

Example 4 Phase 1 :

For the preparation of polycarbonate supports for canopies, composite glass or glass intended to be inserted in door or window frames or the like applications such as floors, walls, ceilings, furniture, bottles, flasks, containers, we choose preferably according to the desired size of the sheets or plates of ≤ 5 mm> thick which should be cleaned carefully in first time.

Colored, transparent or opaque inks are preferably vinyl. They are applied according to the screen printing principle and having taken care to leave between each colored area free spaces (Figure 1) just less than the width of the line composing the mesh (Figure 2) which will then be printed with conductive ink as a reference. on colors; this allowing the production of a window produced in the case of transparent or translucent substrate to one face printed with the conductive ink is used for the back frame defining colors.

It is possible to print color by color and to steam each time or to print all the colors and to steam in one go.

Phase 2 :

The printing of the mesh is carried out on the front of the support according to the screen printing principle described in the phase 1 and in reference to the other colors (Figure 3). But in this phase, the printing is done using a conductive ink composed of 50 to 80% silver or any other high conductivity metal and the rest a vinyl binder or solvent for polycarbonates such as example ethylene chloride.

The printing is done according to a diagram allowing or not the continuity of the electrical conduction according to the metallization mode envisaged in the successive phase by proceeding as in phase 2 of Example 1. After printing of the conductive ink, we repeat the steaming and cleaning processes of the conductive mesh in an acidic solution of SO ₄ H ₂ diluted to 5-10% or any other product used by a person skilled in the art, as described in phase 2 of example 1. In this phase, we can also follow the alternative solution of example 1 phase 2 if we consider electroplating as a metallization mode.

Phases 3 and 4 :

They are identical to those followed in the example 1.

Example 5

We proceed as in Example 2 starting from a translucent, transparent or opaque support in polycarbonate, printed in conductive ink described in phase 2 of Example 4. After printing, the steaming and cleaning process described in phase 2 of example 1. We then proceed to the operations of metallization described in Example 2.

Example 6

The procedure is as in Example 3, the supports being in transparent or translucent polycarbonate, their front having been treated according to example 4 or 5. The colors in this case being vinyl inks.

The printing of the mesh on the back can be made with a vinyl white mixed with black then dried as in phase 1 of Example 4, or carried out as in example 4 phases 2-3-4 by reversing the films.

Example 7 Phase 1 :

For the preparation of glass supports for canopies, composite glass or glass intended to be inserted in door or window frames or the like applications such as furniture, floors, walls, ceilings, bottles, flasks, containers, we choose preferably, depending on the desired size, sheets or plates of ≤ 5 mm> thick which should be cleaned carefully in first time. Most often, these are glasses architectural. Transparent color inks or opaque can be glass enamels. Enamels for glass are mixtures of various fluxes such as glass powders and mineral dyes. Regardless of the screen printing method envisaged, cold or hot, the glass enamels are applied according to the principle screen printing and taking care to spare between each colored area of the free spaces (Figure 1) just less than the width of the line making up the mesh (Figure 2) which will then be printed with enamel conductor marked on the colors; this allowing obtaining, with transparent or translucent glasses, of a stained glass product with a single printed face, conductive enamel can be used on the back side delimiting the colors.

Two types of screen printing can be used: cold screen printing and hot screen printing.

In cold screen printing, once the colors printed in enamel for glass we will dry before cooking.

In hot screen printing, drying before baking will no longer be necessary. We then use enamels hot-melt in the form of thermoplastic pastes of which the job requires a metallic screen heated by effect Joule or by infrared lamps.

There is an immediate solidification of the enamel layer on the cold glass to be printed. The interest of these enamels is to be able to produce overprints or juxtapositions of enamels without intermediate drying between each pass.

Regardless of the screen printing method used for applying the colors, we will do a final baking of enamel at a temperature suitable for the types of enamel and glasses used.

During cooking, the organic constituents of the medium are burnt and the enamel melts on the surface of the glass to form the vitrified coating.

Phase 2 :

The printing of the mesh is carried out on the front of the support according to the screen printing principle described in the first phase and as a benchmark on the other colors.

Printing is done using conductive ink which is here a conductive metallic enamel which can be a mixture composed of 50 to 80% silver or any other high conductivity metal and transparent enamel for glass. Depending on whether you use cold screen printing or hot, this glass enamel will be an oily paste or a hot-melt enamel that will be mixed hot with silver or any other high conductivity metal suitable for conditions for the firing temperature of this enamel. The printing of the conductive enamel is done according to a scheme whether or not allowing continuity of conduction electric according to the metallization mode envisaged in proceeding as in phase 2 of Example 1.

After printing, and depending on the type of screen printing used, it is dried and cooked as in phase 1. After cooling, the conductive mesh is cleaned with an acid solution of SO ₄ H ₂ diluted to 5-10% or any other product used by those skilled in the art. In this phase we can also follow the alternative solution of Example 1 phase 2 if we consider electroplating as a metallization mode.

Phases 3 and 4 :

They take place as in Example 1.

Example 8

For the preparation of glass support, a variant of the screen printing technique used in example 7 allows by the use of paper to transfer decal as a manufacturing intermediary, to significantly reduce the cost price of the product by lower storage costs, speed and flexibility of the process and a single cooking.

In this example, we print with enamels for glass all colors and the conductive enamel part. Colors and conductive enamel can air dry free. After drying the paper backing, a varnish-transfer. At this point it should be emphasized that we can store in low volume and at the lowest cost. This varnish-transfer, after immersion in water will allow slide or drag the decal onto the glass. We then bakes the enamels in one operation at a time colored for glass and conductive mesh.

After cooling we clean the mesh conductor as in example 7 phase 2 and we proceed metallization operations described in phases 3 and 4 of Example 1.

Example 9

We proceed as in Example 2 starting from a translucent, transparent or opaque glass support. The printing of the conductive enamel is done according to the phase 2 of Example 7 and / or according to the method described in Example 8. After printing, the process of repeating cooking and cleaning described in phase 2 of the example 7. The metallization operations are then carried out described in Example 2.

Example 10

The procedure is as in Example 3. The supports being transparent or translucent glasses, their front side is treated according to examples 7, 8 or 9, the colors are glass enamels, the impression of the mesh is made using a white enamel for glass mixed with a black enamel then undergoes firing as described in phase 1 of Example 7 or carried out as in example 7 phases 2, 3, 4 by inverting the films or again carried out by the method of Example 8.

Example 11 Phase 1 :

For the preparation of ceramic plates intended treatment of floors, walls, ceilings, doors, we choose according to the desired size of the plates which we clean carefully at first. The colored, transparent or opaque inks can be ceramic enamels. Ceramic enamels are mixtures of various fluxes, colorless enamels transparent or covered, and metallic oxides.

The ceramic enamels are applied according to the principle screen printing and taking care to spare between each colored area of the free spaces (Figure 1) just less than the width of the line making up the mesh (Figure 2) which will then be printed with enamel conductor in reference on the other colors. Once these colors printed in ceramic enamel, we will dry then we will cook the enamel.

Phase 2 :

The printing of the mesh is carried out on the front of the plate according to the screen printing principle described in the first phase and mark it on the other colors.

Printing is done using conductive ink which is here a conductive metallic enamel which can be composed of 50 to 80% silver or any other metal to high conductivity. The impression of the conductive enamel is made according to a diagram allowing or not the continuity of the electrical conduction according to the metallization mode envisaged in the successive phase by proceeding as in the phase 2 of example 1.

After printing the conductive enamel, dry and bake as for example in phase 1. After cooling, clean the conductive mesh with an acid solution of SO ₄ H ₂ diluted to 5-10% or any other product used by those skilled in the art. In this phase we can also follow the alternative solution of Example 1 phase 2 if we consider electroplating as a method of metallization.

Phases 3 and 4 :

They take place as in Example 1.

Example 12

For the preparation of ceramic plates we can also use the same method as described in Example 8 for glass supports, i.e. the use of transfer decal papers, but using ceramic enamels. We then proceed as in example 8 and we end the operations with a unique firing of colored enamels for ceramics and conductive mesh.

After cooling, we clean the mesh conductor as in example 11 phase 2 and we proceed then to the metallization operations described in the phases 3 and 4 of example 1.

Example 13

We proceed as in Example 2, starting from ceramic plates. The impression of the conductive enamel is done according to phase 2 of Example 11 and / or according to the method described in example 12.

After printing, the cooking processes are repeated and cleaning described in phase 2 of Example 11. We then proceeds to the metallization operations described in example 2.

Example 14 Phase 1 :

For the preparation of glass or ceramics, we proceed as in Example 1, phase 1, but colored inks, transparent or opaque, are epoxy.

Phase 2 :

We proceed as in Example 1 but the impression is done using a conductive ink composed of 50 to 80% silver or any other metal with high conductivity and for the rest, an epoxy binder.

Phases 3 and 4 :

They take place as in Example 1.

Example 15

We proceed as in Example 14 starting from a support in translucent, transparent or opaque glass or of a ceramic support but only phases 2, 3 and 4 are carried out.

Example 16

For the preparation of polyethylene supports translucent, transparent or opaque, we proceed as in Example 1 but the color inks, transparent or opaque, are preferably epoxy.

Phases 1 and 2 take place as in the example 14, phases 3 and 4 taking place according to them Example 1.

E xample 17

We proceed as in Example 16, starting from a translucent, transparent or opaque polyethylene support; only phases 2 of Example 14 and 3 and 4 of Example 1 are carried out.

Claims (36)

1. A method of mass production and surface treatment of translucent, transparent or opaque substrates with a planar or non-planar surface, of glass, ceramic, thermoplastic, acrylic, polyacrylic, polycarbonate, polyethylene or polymeric material for glass roofs, composite glasses, doors, windows, floors, walls, ceiling or other uses such as furniture, bottles, phials or containers, characterized by screen-printing of a graphic document on one and/or the other face of said substrates with the aid of coloured inks with constituent bases compatible with or of the same chemical type as the substrate material; these coloured inks being applied by the screen printing principle, care having been taken to provide between each coloured zone free spaces, which will, after drying and/or firing, be printed with a mesh on one and/or the other face by means of an electrographic ink containing from 50 to 80 % of highly conductive metal bonded to a substance which is compatible with or of the same chemical type as the substrate material and the constituent base of the coloured inks, the substrates then having, after drying and/or firing, to be placed successively in a first electrolytic or chemical bath of copper and then in a second electrolytic or chemical bath of nickel, silver or any other corrosion-resistant metal suitable for these methods of metallisation, so as to obtain a screen.
2. A method according to claim 1, characterized in that the electrical conduction is effected by means of feeders during the stages of metallisation by galvanoplasty.
3. A method according to claim 1, characterized in that the electrical conduction is effected by means of electrodes known as contact studs during the stages of metallisation by galvanoplasty.
4. A method according to claim 1, characterized in that, since the substrate is more than 5 mm thick, printing of the mesh on the reverse is effected by turning over the films in the screen-printing stage to prevent the phenomenon of light refraction and that of optical deformation of the image, after which it is possible to proceed with the metallisation stages.
5. A method according to claims 1 and 4, characterized by the use for the mesh of a white, either with an acrylic base or a vinyl base or a white enamel for glass mixed respectively with a black ink compatible with or of the same chemical type as the material acting as a substrate to imitate the effect of lead.
6. A method according to any one of claims 1 to 3, according to which the nickel screen is of any thickness and may be either matt or shiny or gilded.
7. A method according to any one of claims 1 to 3, according to which the screen consists of any corrosion resistant metal and is of any thickness.
8. A method according to claim 1, according to which metallisation is effected chemically by oxidation-reduction at the metal interface.
9. A method according to claim 1 for the preparation of substrates of acrylic or polyacrylic resins wherein the coloured inks and electrographic ink are acrylic.
10. A method according to claim 1 for the preparation of substrates of polycarbonate wherein the coloured inks and the electrographic ink are preferably vinyl.
11. A method according to claim 1 for the preparation of substrates of glasses according to which the coloured inks and the electrographic ink are enamels for glass.
12. A method according to claim 1 wherein the screen-printing technique used is based on the use of decal transfer paper as glass substrate production intermediate.
13. A method according to claim 1 for the preparation of ceramic substrates according to which the coloured inks and the electrographic ink are of ceramic enamel.
14. A method according to claim 1 for the preparation of glass or ceramic substrates in which the coloured inks and the electrographic ink are epoxies.
15. A method according to claim 1 for the preparation of polyethylene substrates according to which the coloured inks and the electrographic ink are epoxies.
16. A translucent, transparent or opaque product of planar or non-planar surface of glass, ceramic, thermoplastic, plastic or polymeric material, the structure of which is characterized by:

    1°/ a substrate in the form of sheets, plates, phials, bottles or other containers, the constituent material of which is acrylic resin, polymethyl methacrylate, polycarbonate, glass, ceramic, cellulose acetobutyrate (C.A.B.), cellulose acetate, polystyrenes, acrylonitrile butadiene polystyrene (A.B.S), polyacetal, polyvinyl chloride (P.V.C.), polyvinylpyrrolidone (P.V.P.), polyvinyl butyral, polyester, polyamide, polyethylene, phenol formaldehyde (Bakelite), melanin formaldehyde (melanin), polyurethane, epoxide;

    2°/ screen-printing on the substrate of a conductive mesh by means of an electrographic ink containing from 50 to 80 % of silver or any other conductive metal and having the double property of welding perfectly to the coloured or non-coloured substrate and of attaching the copper in the first metallisation stage according to claim 1, this substrate being capable of prior coloration by screen-printing with the aid of coloured inks with a constituent base compatible with or of the same chemical type as the substrate material;

    3°/ a metal screen obtained by successive metallisation of the conductive mesh printed by screen-printing on the substrate.
17. A product according to claim 16, in which the substrate is of acrylic resin such as poly methyl methacrylate, the binder of the electrographic ink being acrylic or an acrylic resin solvent such as carbitol acetate, and, if the substrate has been previously coloured by printing, the coloured inks are acrylic or vinyl.
18. A product according to claim 16, in which the substrate is of polyacrylic resin, the binder of the electrographic ink being acrylic or an acrylic resin solvent and, if the substrate has been previously coloured by printing, the coloured inks are acrylic or vinyl.
19. A product according to claim 16, in which the substrate is of polycarbonate, the binder of the electrographic ink being vinyl or a polycarbonate solvent, such as ethylene chloride and, if the substrate has been previously coloured by printing, the coloured inks are vinyl.
20. A product according to claim 16, in which the substrate is glass, the binder of the electrographic ink is an epoxide or an enamel for glass and, if the substrate has been previously coloured by printing, the coloured inks are epoxides or glycerophthalates or consisting of enamel for glass.
21. A product according to claim 16, in which the substrate is cellulose acetobutyrate (C.A.B), the binder of the electrographic ink being cellulose or a cellulose acetobutyrate solvent such as carbitol acetate, and, if the substrate has been previously coloured by printing, the coloured inks are cellulose.
22. A product according to claim 16, in which the substrate is of cellulose acetate, the binder of the electrographic ink being cellulose or a cellulose acetate solvent such as carbitol acetate, and, if the substrate has been previously coloured by printing, the coloured inks are cellulose.
23. A product according to claim 16, in which the substrate is of polystyrene, the binder of the electrographic ink being acrylic or a polystyrene solvent such as methylene chloride, and, if the substrate has been previously coloured by printing, the coloured inks are acrylic.
24. A product according to claim 16, in which the substrate is acrylonitrile butadiene polystyrene (ABS), the binder of the electrographic ink being acrylic or a solvent of ABS such as dichloroethylene, and, if the substrate has been previously coloured by printing, the coloured inks are acrylic.
25. A product according to claim 16, in which the substrate is of polyacetal, the binder of the electrographic ink being an epoxide and, if the substrate has been previously coloured by printing, the coloured inks are epoxides or polyurethanes.
26. A product according to claim 16, in which the substrate is of polyvinyl chloride (P.V.C.), the binder of the electrographic ink being vinyl or a polyvinyl chloride solvent such as ethyl acetate, and, if the substrate has been previously coloured by printing, the coloured inks are acrylic or vinyl.
27. A product according to claim 16, in which the substrate is of polyvinylidene fluoride (PVF), the binder of the electrographic ink being vinyl, and, if the substrate has been previously coloured by printing, the coloured inks are vinyl.
28. A product according to claim 16, in which the substrate is of polyvinyl butyral, the binder of the electrographic ink being vinyl or a polyvinyl butyral solvent such as diethyl triglycol acetate, and, if the substrate has been previously coloured by printing, the coloured inks are vinyl.
29. A product according to claim 16, in which the substrate is of polyester, the binder of the electrographic ink being a polyester or a polyamide or even a polyester solvent such as methylene chloride, and, if the substrate has been previously coloured by printing, the coloured inks are polyesters or polyamides.
30. A product according to claim 16, in which the substrate is of polyamide, the binder of the electrographic ink being a polyamide, and, if the substrate has been previously coloured by printing, the coloured inks are polyamides.
31. A product according to claim 16, in which the substrate is of polyethylene, the binder of the electrographic ink being an epoxide, and, if the substrate has previously been coloured by printing, the coloured inks are polyamides or epoxides.
32. A product according to claim 16, in which the substrate is a phenol formaldehyde such as bakelite, the binder of the electrographic ink being an epoxide, and, if the substrate has been previously coloured by printing, the coloured inks are glycerophthalates or epoxides.
33. A product according to claim 16, in which the substrate is of melamine formaldehyde such as melamine, the binder of the electrographic ink being an epoxide, and, if the substrate has been previously coloured by printing, the coloured inks are glycerophthalates or epoxides.
34. A product according to claim 16, in which the substrate is of polyurethane, the binder of the electrographic ink being a polyurethane, and, if the substrate has been previously coloured by printing, the coloured inks are polyurethanes.
35. A product according to claim 16, in which the substrate is an epoxide, the binder of the electrographic ink also being an epoxide, and, if the substrate has been previously coloured by printing, the coloured inks are likewise epoxides.
36. A product according to claim 16, in which the substrate is ceramic, the binder of the electrographic ink being an epoxide or an enamel for ceramics, and, if the substrate has been previously coloured by printing, the coloured inks are either epoxides, or glycerophthalates or an enamel for ceramics

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