EP0699138A1

EP0699138A1 - Method of production and surface treatment

Info

Publication number: EP0699138A1
Application number: EP94915599A
Authority: EP
Inventors: Eric Besancenot
Original assignee: Individual
Current assignee: Individual
Priority date: 1993-05-10
Filing date: 1994-05-09
Publication date: 1996-03-06
Anticipated expiration: 2014-05-09
Also published as: ATE168076T1; CA2162584A1; DE69411561D1; FR2705063B1; WO1994026538A1; EP0699138B1; FR2705063A1

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

Manufacturing and surface treatment technique

The present invention relates to an improvement to the preparation process described in patent FR 2,658,756 so as to allow the popularization of an artisanal manufacturing process and its application to the mass production of supports having a flat surface or not but preferably in the form sheets or plates that the consumer can format or have formatted at his request and according to his tastes and needs to the dimensions he wishes.

The process of patent Fr 2,658756 which constitutes the closest prior art is characterized by the preparation of a decorative article obtained from a support made of metal, ceramic or plastic on which is applied according to contours and / or determined surfaces a partitioning projecting from the support, then in the meshes thereof, colors offering good adhesion to said surface and poor adhesion to the partitioning material.

This improvement differs from FR 2.658756 in that the process successively uses the screen printing technique and then electroplating, or chemical metallization, the concept being to first color the support and then mesh it, whereas in the patent here- above the coloring, intervening 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 just as well allows the mass production and surface treatment of translucent, transparent or opaque supports, of thermoplastics, plastics, polymers, glasses, etc., as the mass production of stained glass . Whatever the product envisaged, the invention reproduces on a support, with a flat surface or not, a graphic document the printing of which is done by the serigraphic route. To achieve the desired industrial result, the preparation of the supports requires several successive operations.

The first of the joint operations consists in the preparation of colored inks and conductive ink. For all the colors chosen, whether transparent or opaque, it is imperative to use colored inks whose constituent base is compatible or of the same chemical nature as the material of the support to be printed, a necessary and sufficient condition to offer a very high resistance and resistance over time illustrated by the presence of two asterisks in Table A. The conductive ink must have the double property of soldering perfectly to the colored support or not and of hanging the copper during the electroplating or chemical metallization phase.

This ink contains from 50 to 80% of silver or any other metal with high conductivity and for the rest a compatible binder or of the same chemical nature as the support material and the constituent base of the colored inks. Table B indicates the nature of the binder according to the various possible supports.

These tables are not limiting because the state of the art has established that in general to any support made of any material may correspond a color ink whose base is of the same nature as this support and an ink conductive whose binder is also made of this material.

To better understand the technical characteristics and advantages of the present invention, we will describe some embodiments, it being understood that these are not limiting as to their mode of implementation and the applications that can be made of them. .

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 frames, or window, or other applications such as floors, walls, ceilings, furniture, bottles, flasks, containers, preferably chosen according to the desired size of sheets or plates of <5 mm> thickness which are carefully cleaned in a first time.

Colored inks, transparent or opaque, can be acrylic. They are applied according to the screen printing principle and having taken care to leave free spaces between each colored area C1 and C2

(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 the colors, this making it possible to obtain, with translucent or transparent supports, a stained glass product with a single printed face whose conductive ink is used on the back of the frame delimiting the colors.

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

Phase 2:

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. 5.

- If we consider the successive phase of metallization by chemical means, the printing of the conductive ink can be done according to any scheme and without using nurses or any preparation.

- After printing the conductive ink, we oven and then clean the conductive mesh with a solution SO4H2 acid diluted to 5-10% or any other product used by those skilled in the art.

An alternative solution to printing nurse trays, envisaged in the case of electroplating, consists of the use of electrodes (1) preferably made of stainless steel called contact nuts as described in FIG. 4 and fixed to the cathode. by screws made of insulating material (2). As for the nurse vessels, these electrodes are only necessary and usable during the phases of metallization by electroplating, chemical metallization making no use of them. Each method of metallization envisaged by electroplating or by chemical metallization corresponds to a specific preparation of the support printed with conductive ink.

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 else place the prepared support to follow a chemical treatment in a first copper chemical bath. It is a chemical metallization obtained conventionally by reduction of ions based on redox reactions at the metal interface. At the end of the copper plating operations, the rinsing processes described above will be repeated.

Phase 4:

The support reassembled in copper can be placed 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, the nurses can be eliminated either by cutting the plate with when printing is done, either by removing only the nurses (Figure 6), or even if contact nuts have been used, we will unscrew them.

It is also possible to place the support reassembled in copper 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 at this same final stage a partition made of another metal.

If the metallization phase is carried out with nickel, whatever the type of metallization envisaged, galvanoplastic or chemical, it is possible to apply at the end of one or the other nickel-plating operation a cover of chemical gold .

Example 2

The conductive ink described in phase 2 of Example 1 is printed on a translucent, transparent or opaque support in acrylic or polyacrylic resin from a screen printing screen silhouetting the chosen pattern. If one considers the successive phase of metallization of the conductive mesh by electroplating, the printing will be done according to a diagram allowing the continuity of the electrical conduction. Feeders are printed simultaneously, generally four in number (Figure 5) and the procedure is as claimed in claim 4 of patent FR 2,658,756. Alternatively, the contact nut technique can be used. If we consider the successive phase of metallization of the conductive mesh by chemical means, the printing will be done according to any scheme and without using nurses or any preparation. After printing, the steaming and cleaning processes of phase 2 of Example 1 will be repeated.

The support is first placed in an electrolytic or chemical copper 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 modes. metallization and resistant to corrosion as described in example 1, phase 4. In the final stage and after removal of the nurse plates or removal of the contact nuts in the case of electroplating, as described in example 1, a translucent or opaque support is thus obtained fitted with a nickel partition <or>

10/10 mm thick on the front of this support. A layer of gold can still be applied chemically to the nickel used. One can also provide, at this same final stage, a partition consisting of another metal resistant to corrosion.

Example 3

When the specifications involve the use of transparent or translucent acrylic or polyacrylic resin supports with a thickness> 5 mm, it is preferable, to avoid the phenomenon of light refraction 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, you can print the same colors by turning over the films. For the printing of the mesh, one can use a white acrylic mixed with black to imitate the effect of lead. This printing is done by screen printing as a benchmark on the other colors (Figure 1). In this option, the drying operation described for the printing of the front in example 1 phase 1 is repeated.

For the printing of the mesh on the back, you can also, by inverting 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 intended to be inserted in door or window frames or other applications such as floors, walls, ceilings, furniture, bottles, flasks, containers, it is preferable to choose according to the desired size of sheets or sheets <5 mm> thick which should be cleaned carefully at first. 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 making it possible to obtain a stained glass product in the case of transparent or translucent supports with a single printed face, the conductive ink of which serves as the backdrop for the frame delimiting the colors.

It is possible to print color by color and bake each time or to print all colors and bake at one time.

Phase 2:

The printing of the mesh is carried out on the front of the support according to the screen printing principle described in phase 1 and in reference to the other colors (Figure 3). But in this phase, 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 a vinyl binder or solvent for polycarbonates such for 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 SO4H2 diluted to 5-10% or any other product used by a person skilled in the art, as described in phase 2 of the 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 Example 1. Example 5

The procedure is as in Example 2, starting from a translucent, transparent or opaque polycarbonate support, printed with conductive ink described in phase 2 of Example 4. After printing, the steaming processes are repeated and cleaning described in phase 2 of example 1. The metallization operations described in example 2 are then carried out.

Example 6

The procedure is as in Example 3, the supports being made of 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 carried out using a vinyl white mixed with black and then dried as in phase 1 of example 4, or carried out by proceeding as in example 4 phases 2-3 -4 by inverting the films.

Example 7

Phase 1 :

For the preparation of glass supports for canopies, composite glasses or intended to be inserted in door or window frames or other applications such as furniture, floors, walls, ceilings, bottles, flasks, containers, it is preferable to choose according to the desired size, sheets or plates <5 mm> thick which should be cleaned carefully at first. Most often, these are architectural glasses. Transparent or opaque color inks can be glass enamels. Glass enamels are mixtures of various fluxes such as glass powders and mineral dyes. Whatever the screen printing method envisaged, cold or hot, the glass enamels 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 component line the mesh (Figure 2) which will then be printed on the conductive enamel as a reference on the colors; this making it possible to obtain, with transparent or translucent glasses, a stained glass product with a single printed face whose conductive enamel can be used for. weft back 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 have been printed in glass enamel, they will be dried before baking.

In hot screen printing, drying before cooking will no longer be necessary. Hot-melt enamels are then used in the form of thermoplastic pastes, the use of which requires a metal screen heated by Joule effect or by infrared lamps.

The enamel layer immediately solidifies on the cold glass to be printed. The advantage of these hot-melt enamels is that they can be used to overlay or juxtapose enamels without intermediate drying between each pass.

Whatever the screen printing method used for applying the colors, the final enamel will be fired at a temperature suitable for the types of enamel and glass used.

During baking, 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 in reference to the other colors.

The printing is done using a conductive ink which is here a conductive metallic enamel which can be a mixture composed of 50 to 80% of silver or any other metal with high conductivity and a transparent enamel for glass. Depending on whether cold or hot screen printing is used, 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 temperature conditions of cooking this enamel. The printing of the conductive enamel is done according to a scheme whether or not allowing continuity of electrical conduction according to the metallization mode envisaged by 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 SO4H2 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 makes it possible, by the use of transfer decal paper as a manufacturing intermediary, to significantly reduce the cost price of the product by lowering the storage costs, speed and flexibility of the process and a single cooking.

In this example, we print with glass enamels all colors and the conductive enamel part. Colors and conductive enamel can dry in the open air. After the paper support has dried, a transfer varnish is coated. At this stage it should be emphasized that it can be stored in low volume and at the lowest cost. This transfer varnish, after immersion in water, will make it possible to slide or slide the decal on the glass. The colored glass enamels and the conductive mesh are then baked in a single operation.

After cooling, the conductive mesh is cleaned as in Example 7 phase 2 and the metallization operations described in phases 3 and 4 of Example 1 are carried out.

Example 9

The procedure is as in Example 2, starting from a support in translucent, transparent or opaque glass. The printing of the conductive enamel is done according to phase 2 of Example 7 and / or according to the method described in Example 8. After printing, the processes are repeated. cooking and cleaning described in phase 2 of the example

7. The metallization operations described in example 2 are then carried out.

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 printing of the mesh is carried out by '' 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 by proceeding 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 for the treatment of grounds, walls, ceilings, doors, one chooses according to the desired dimension of the plates which one cleans carefully at first. Colored, transparent or opaque inks can be ceramic enamels. Ceramic enamels are mixtures of various fluxes, transparent or covered colorless enamels, and metal oxides.

The ceramic enamels 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 on the conductive enamel in reference on the other colors. Once these colors have been printed in ceramic enamel, we will dry them and then proceed to firing the enamel.

Phase 2:

The printing of the mesh is carried out on the front of the plate according to the serigraphic principle described in the first phase and in reference to the other colors. The printing is done using a conductive ink which is here a conductive metallic enamel which can be composed of 50 to 80% silver or any other high metal. conductivity. The printing of the conductive enamel is done according to a diagram allowing or not the continuity of the electric conduction according to the metallization mode envisaged in the successive phase by proceeding as in 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 SO4H2 diluted to 5-10% or any other product used by l man of 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, the same method can also be used as that described in Example 8 for glass supports, that is to say the use of transfer transfer papers, but using enamels. ceramics. The procedure is then as in Example 8 and the operations are terminated by a single firing of the colored enamels for ceramic and of the conductive mesh.

After cooling, the conductive mesh is cleaned as in example 11 phase 2 and then the metallization operations described in phases 3 and 4 of example 1 are carried out.

Example 13

The procedure is as in Example 2, starting from a ceramic plate. The printing 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 and cleaning processes described in phase 2 of Example 11 are repeated. then proceeds to the metallization operations described in Example 2.

Example 14

Phase 1 :

For the preparation of glass or ceramic supports, the procedure is as in Example 1, phase 1, but the colored inks, transparent or opaque, are epoxy.

Phase 2:

The procedure is as in Example 1, but 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, an epoxy binder.

Phases 3 and 4:

They take place as in Example 1.

Example 15

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

Example 16

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

Phases 1 and 2 take place as in Example 14, Phases 3 and 4 take place according to Example 1.

Example 17

The procedure is 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

1. Mass production and surface treatment technique for supports having a flat surface or not, translucent, transparent or opaque, in glasses, ceramics, thermoplastics, plastics, or polymers for canopies, composite glasses, doors, windows, floors, walls, ceilings, or other applications such as furniture, bottles, flasks, containers, characterized by the screen printing of a design on one and / or the other side of said supports using colored inks of compatible constituent bases or of the same chemical nature as the support material, then after drying and / or baking, printing a mesh using a conductive ink containing 50 to 80% silver or any another metal with high conductivity linked to a compatible substance or of the same chemical nature as the support material and the constituent base of the colored inks, the supports being then placed after drying and / or firing successively t in a first electrolytic or chemical bath of copper and then in a second electrolytic or chemical bath of nickel or any other corrosion-resistant metal suitable for these metallization modes.

2. Technique according to claim 1 characterized in that the electrical conduction is carried out using nurses during the metallization phases by electroplating.

3. Technique according to claim 1 characterized in that the electrical conduction is carried out using electrodes called contact nuts during the phases of metallization by electroplating.

4. Technique according to claim 1 characterized in that, the support having more than 5 mm of thickness, the printing of the mesh on the back is carried out by turning the films in the screen printing phase to avoid the phenomenon of light refraction and that of the optical deformation of the image after which we can proceed to the metallization phases.

5. Technique according to claims 1 and 4 characterized by the use for the mesh of a white either acrylic based or vinyl based or an enamel. white for glass mixed respectively with a compatible black ink or of the same chemical nature as the material serving as a support to imitate the effect of lead.

6. Technique according to any one of claims 1 to 3 according to which the nickel partitioning is <or> 10/10 mm thick and can be either matt or glossy or golden.

7. Technique according to any one of claims 1 to 3 according to which the partitioning consists of any metal resistant to corrosion and is <or> 10/10 mm thick.

8. Technique according to claim 1 according to which the metallization is carried out chemically by oxidation-reduction at the metal interface.

9. Technique according to claim 1 for the preparation of supports in acrylic or polyacrylic resins where the color inks and the conductive ink are acrylic.

10. The technique of claim 1 for the preparation of polycarbonate substrates where the color inks and the conductive ink are preferably vinyl.

11. The technique as claimed in claim 1 for the preparation of glass supports in which the color inks and the conductive ink are glass enamels.

12. The technique as claimed in claim 1, in which the screen printing technique used is based on the use of transfer transfer paper as an intermediate in the manufacture of glass supports.

13. Technique according to claim 1 and 12 for the preparation of ceramic supports in which the color inks and the conductive ink are made of ceramic enamel.

14. The technique as claimed in claim 1 for the preparation of glass or ceramic supports in which the colored inks and the conductive ink are epoxies.

15. The technique of claim 1 for the preparation of polyethylene supports in which the color inks and the conductive ink are epoxy.

16. Products obtained according to one of claims 1 to 15.