Digital ink-jet glass printer

DESCRIPTION

Ink for ceramic surfaces.

Field of the Invention

The present invention relates to an ink for printing on ceramic surfaces, especially glass, after printing, the surface is subjected to calcination (cooking) at temperatures above 600 ° C. 5

Background of the invention

Ceramic materials are hard, fragile, heat and corrosion resistant substrates shaping and then heating a nonmetallic mineral such as clay at an elevated temperature. Enamels, porcelain and bricks are examples of materials that are produced by molding or shaping minerals and cooking them at high temperatures.

Glass products are typically produced by melting silicates with boric oxide, aluminum oxide or phosphorus pentoxide at elevated temperatures. They have very variable mechanical and optical properties and solidify the molten state without crystallization in a transparent or translucent form. As glass objects in general are hard and fragile, their lack of crystalline structure places them in the class of amorphous solids. Glass objects that may require printed graphics include windows, mirrors, kitchen utensils, bottles, containers, etc.

From a printing point of view, several procedures for decorating glass and ceramics 15 with high quality images are available. The printing processes used to print glass and ceramics have a variety of ink systems. Contrary to sublimation inks, most inks belong to one of two families: organic and inorganic.

Organic inks are typically used in screen printing, inkjet printing and pad printing and consist of organic pigments and resins along with other chemicals that heal over time and depend on temperature or any other form of energy to create a bond With the substrate. The most effective organic inks are produced as two-component or two-part systems. These inks generally contain resins capable of polymerization that are mixed with catalysts to initiate polymerization. Heating the products to a temperature of approximately 200 ° C after printing can accelerate the curing process and improve adhesion. In addition, this exposure to heat will typically improve the mechanical and chemical resistance of the print. After printing, organic ink films will require at least 48 hours to polymerize, unless heat is applied.

Inorganic inks use pigments based on minerals and materials that, once printed, must be heated and melted at elevated temperatures to combine with the surface of the substrate and form a permanent bond. 30

Ceramic colors, as they are called ceramic inorganic inks, are a mixture of pigments (oxides and metal salts) and finely ground glass particles, called fried. These materials melt into the substrate by calcining them ("cooking" them) at temperatures between 600-1450 ° C. Cooking temperatures will vary according to the color structure, the nature of the substrate and other application criteria, but in all cases, temperatures must be carefully controlled to achieve specific colors after cooking. 35

These high cooking temperatures are used because ceramic colored components need to melt, so that they can melt on the ceramic surface on which they are printed. While these inks are typically referred to as "inorganic," they can also contain small amounts of organic material. Organic components are the materials in which the pigment and the frit are suspended to create a printing ink. These organic materials, which are oily by nature, are designed to burn quickly during cooking, without affecting print quality and final color.

Inorganic inks come in various forms. They include color formulations for screen printing and pad printing, thermoplastic varieties and total transfer inks. Both the screen printing system and the total transfer are known as "cold colors" inks, which means that they do not need to be heated to be printable, while thermoplastic inks must be heated before they can be applied to the substrate. Four. Five

Thermoplastic ink systems are waxy at room temperature and must be heated for printing. For pad printing, the inkwell, the plate and occasionally the pad are kept at a temperature of approximately (60 ° C). When the pad that carries the ink comes into contact with the cold object to be printed, the ink cools and sticks to the object.

When screen printing with thermoplastic inks, the mesh is made of stainless steel and an electric current 50 is passed. This heats the mesh and melts the ink, which then flows through the mesh and solidifies when it comes into contact with cold ceramics or glass. Current flow control is critical because too much will overheat the color and burn the mesh.

While printing on ceramic surfaces with organic inks can be obtained by mechanical screen printing, pad printing or digital printing, commercial ceramic inks are difficult to use in inkjet printing, because they typically have a viscosity greater than that required for printing. ink jet (approximately 20–40 cps) and the glass frit contained therein, which is in the micrometer size range, it tends to settle and also clogs the nozzles on the perforated plate from which the ink is ejected for 5 inkjet printing.

It would be highly desirable to use inkjet printing on ceramic surfaces with ceramic pigments, instead of the commonly used methods of mechanical screen printing or pad printing. The conversion to digital printing can have the following advantages: reduction of costs involved in the storage of screen printing or transfer devices due to digital storage of the desired patterns instead of physical storage; cost reduction for low value printing that can be prohibitive in screen printing; greater ease and versatility of change from one design to another, ability to use edge to edge printing.

Until now, attempts at printing ceramic colors with the inkjet process have failed and, thus, making the inkjet process available to decorate ceramic items such as glass, enamel and porcelain, due to the pronounced trend from specifically heavy and thick colored powders to form 15 sediments. The specific gravity of the glaze and glaze colors ranges from 3.5 to 6.0 kg / 1 and the average grain fineness of these products ranges from 3 to 5 μm. These products are sedimented with aqueous or alcoholic suspensions that have the viscosity of conventional inkjet processing in a period ranging from a few seconds to 50% in some cases. These suspensions would quickly lead to block printing nozzles and the entire inkjet printer. Liquid colored pastes having a substantially higher viscosity 20, for example, 5000 mPa · s, such as those used in screen printing to decorate glass, will not be suitable for inkjet printing because the viscosity is much higher for Inkjet printers present today.

US Patent No. 6,357,868, incorporated herein by reference, discloses a method for decorating ceramics by inkjet technology, using inorganic and glass frit pigments present in a thermoplastic medium having a melting point. at least 30 ° C (as wax). The medium, which is solid under storage conditions, eliminates sedimentation of inorganic pigments. The ink melts just before it is used by a heated inkjet printer head.

According to said patent, sedimentation is removed using a thermoplastic medium that solidifies immediately. 30

EP 1,223,201, incorporated herein by reference, discloses an ink for printing on heat-resistant substrates comprising pigment, fusible vitreous agents with particles smaller than 10 μ and a carrier. The carrier according to this patent is also thermoplastic with a high melting point for phase change of the ink. Such ink, which is solid at room temperature, needs to be heated before printing.

Ink that is solid at room temperature and that must be heated in the inkjet head before printing is uncomfortable to handle, load and requires special equipment for actual printing. If the ink is liquid at room temperature, the performance and maintenance of the printer will be much better.

WO 2005/013337 A2 provides nanoparticles having a surface region of metal oxide or semiconductor oxide and a region of metal core or semiconductor. The nanoparticles are formed by grinding a bulk material until reduced to dust and then the powder is chemically attacked in a solution to a desired nanoparticle dimension.

US 2003/026957 A1 refers to an image transfer element that is capable of forming a multicolored image on a variety of substrates by non-direct transfer printing.

FR2 735 461 A1 describes a compound of the formula A (M, Tb) O3, wherein A is one or more alkaline earth metals and M is Sn or Ti and where M and Tb are present in solid solution. The particles of the compound can be used as a color pigment especially in plastics, paints, lacquers, gums, paper, ink, cosmetic products, mineral binders and coatings in layers) and, when coated with a layer of transparent oxide (esp . of silica, alumina, zirconia, etc.), as a color pigment in ceramic enamels.

WO 94/22966 A1 refers to a composition that modifies the light comprising a color pigment and a light conditioning component, which is a gray pigment characterized by having the ability to absorb light and reflect at least part of the absorbed light.

EP 0 944 097 A1 provides a light-colored electroconductive pigment comprising a substrate with a conductive coating of phosphorus-doped tin oxide (P) and / or fluorine (F). The pigment can be used to pigment varnishes, printing inks, plastics and enamels for ceramic materials and glass with this pigment. 55

Summary of the invention

The present invention relates to an ink composition for printing on a ceramic substrate, to melt on the substrate after baking, the ink is characterized by the features set forth in the appended claims.

The "substrate that forms the binder composition" (see below) comprising silica nanoparticles can be printed to produce a "non-colored pattern", for example, to provide the glass with a rough pattern, an opaque "matte pattern" ”, Sometimes desired for aesthetic or functional purposes on glass (to avoid accidental collision of passengers with glass doors).

In a preferred embodiment, the ink of the invention also comprises pigments that maintain their optical properties (color, absorbance, etc.) even after baking, which produces a colored pattern 10 after printing.

Thus, in a preferred embodiment, the present invention provides an ink composition as defined in the claims for printing onto a ceramic substrate, to melt on the substrate after baking such, which comprises heat-resistant inorganic pigment particles that It has an average dimension less than 1.2 micrometers: 15

The term "ceramic substrate" refers to an inorganic non-metallic substrate processed or used at high temperature. This includes surfaces such as glass for building windows, cars, electrical appliances such as ovens, etc., ceramic surfaces such as those formed by clay minerals such as tiles, Proclaim, enamel and other ceramic materials.

Preferably, the ceramic substrate is glass. twenty

The ink of the invention is of the type to melt in the substrate after baking, so that it becomes an integral part of the substrate, especially glass. The integration may be for the purpose of creating a "non-colored pattern" (opaque or rough pattern) or a "colored pattern".

The integration of ink into the substrate (glass) to provide a colored pattern may be required, for example, in windshields of vehicles and windows that have a thin painted frame around their upper parts that protects the tail that holds the window to the UV irradiation auto and decorates the windshield. This ink must be heat resistant, scratch resistant, so that it has become an integral part of the glass.

In architecture, many times, the window for internal and external use must have heat-resistant properties for safety reasons and the decorative patterns present in it must be an integral part of the window, so as to be durable. 30

Various electrical appliances, such as microwave oven windows, ovens and refrigerators, often have decorative or functional designs that need to demonstrate durability at high temperatures, typically resistance to temperatures above 600 ° C. Again, such windows need to have a design fused with the glass.

The integration of pigment-free ink into a surface to provide an uncolored pattern can be used especially in architecture to provide coarse, opaque or "matte" designs or surfaces on glass windows or doors both for aesthetic reasons and to avoid accidental collisions

Finally, other glass designs need to show resistance to stringent conditions such as heat, imbibition resistance in hot sulfuric acid, sodium hydroxide solutions, etc. and designs present there contain a pigment fused to glass and integrate with it. 40

The ink of the present invention is intended for these purposes.

Ink is defined by various characteristics. It has a viscosity that allows it to be printed by means of inkjet printing, typically a viscosity at jet temperature (the temperature present in the ink printhead during printing) printing below 20 cps, more preferably, at less than 15 cps, most preferably, between 10 and 13 cps. Four. Five

The term "jet temperature" refers to the temperature of the ink in the print head and is typically 30–60 ° C, preferably 35–45 ° C.

The viscosity in the inks described in this invention is measured by means of a Brookfield DV-II + viscometer, with a small sample adapter, while using an S18 spindle, at 80 rpm.

When the ink also comprises pigment particles to provide a color design, the ink should maintain its optical properties after exposure to temperatures greater than 500 °, preferably after exposures to temperatures greater than 580 °, most preferably, after to expose to a temperature

greater than 600 °. The "optical properties" that should be maintained are selected from color, optical density, UV blocking, brightness, etc. This means that the pigments used in accordance with these embodiments do not lose their optical properties after cooking.

The ink of the present invention becomes an integral part of the substrate when the substrate and the ink are exposed to temperatures greater than 500 °, preferably greater than 550 °, most preferably, greater than 600 °. Preferably, the ink of the present invention can be integrated with the substrate at a temperature below 700 °, as will be explained hereinafter.

The expression "becomes an integral part" means that the ink sinters, melts or melts to become inseparable from the top surface of the ceramic-glass substrate, so that it cannot be scratched after conventional physical or chemical abrasion tests , do not separate from the surface after heating or exposure to substances such as strong acid solutions.

Next, when the particle sizes are mentioned, the number refers to the average particle size.

The ink composition according to the "pigment-containing" aspect (to produce a color design) of the present invention essentially comprises submicron particles of heat-resistant inorganic pigment. Preferably, the average size of the inorganic pigments is less than 1.2 μ, preferably less than 0.9 μ, more preferably, less than 0.7 μ, most preferably, the average size of the inorganic pigment is less than 550 nanometers (0.55 μ). Preferably, when the color of the pigment is white, the average pigment size is between 0.17 and 0.25 μ.

The term "inorganic pigment" refers to a pigment that is at least partially inorganic. In a preferred embodiment, the inorganic pigments are metal oxides that are present a priori in an appropriate manner to provide the desired optical properties and do not need to oxidize in situ on the substrate during cooking to provide these properties. However, in other options, the pigments can be organometallic which, after cooking their organic parts, are burned and the metal constituents are oxidized to form metal oxides. Organic pigments can also be produced using other compounds that comprise metal elements that, after burning, oxidize to form colored metal oxide.

Various metal oxides such as chromium oxide, copper oxide, mixed oxides of CuCr2O3 oxide (for black color), titanium dioxide (for white color), red iron oxide (red pigment 101), rutile can be used nickel yellow, antimony and titanium (yellow pigment 53), cobalt aluminate blue spinel (blue pigment 28), etc. 30

The term "heat resistant" in the context of the inorganic pigment refers to the fact that the pigment does not burn completely during the firing process of the substrate (although part of it can be burned as in the organometallic composition) and some of Its optical properties as described previously (color, optical density, UV absorbance, brightness, etc.) are maintained after cooking.

The liquid vehicle at room temperature of 15-28 ° C is composed of at least one water-based solution. 35

Finally, the ink also comprises submicron particles of a compound that is called "binder composition", where this term refers to a composition (may comprise a mixture of various different compounds) which, after cooking, sinters and melts with the ceramic substrate (glass), becoming an integral part.

The binder composition comprises silica nanoparticles. Typically, in the final ink formulation, the concentration (w / w) of the solid components (inorganic pigments together with the binder composition {silica particles} to the liquid carrier (based on water) is 10 to 60%, preferably 25 to 50%, most preferably, about 45%.

Typically, the concentration (w / w), in the solid content of the ink (without the carrier), of the inorganic pigment heat resistant to the binder composition (silica nanoparticles) is 1 to 3, preferably 1 to 2.5 , with maximum preference, from 1 to 2. This ratio depends on the required properties of the cooked substrate, such as optical density.

Preferably, the ink also comprises at least one dispersing agent and / or wetting agent, such as Bykumen (solution of a low molecular weight unsaturated acid polycarboxylic acid polyester and White spirit / isobutanol = 2/1), Disperbyk-166 ( solution of a high molecular weight block copolymer with related groups of pigment and methoxypropyl acetate / butyl acetate = 1/4), Disperbyk – 164 (solution of a high molecular weight block copolymer with related groups of pigment and butyl acetate), Disperbyk – 130 (polyamine amide solution of unsaturated polycarboxylic acids and alkylbenzene / butyl glycol = 5/1), Disperbyk – 182 ( solution of a high molecular weight block copolymer with related pigment groups and methoxypropyl / methoxypropoxypropanol / butyl acetate = 4/4/4), Disperbyk-163 (high molecular weight block copolymer solution 55 with related pigment groups, in xylene / butyl acetate / methoxypropyl acetate 3/1/1); Disperbyk – 161 (solution

of a high molecular weight block copolymer with related groups of pigment and methoxypropyl acetate / butyl acetate = 6/1), Disperbyk-101 (solution of a long chain polyamine amide salt, polar acid esters and mineral alcohol / butylglycol = 8/1), Disperbyk – 160 (solution of a high molecular weight block copolymer with related pigment and xylene / butyl acetate groups = 6/1), BYK – P – 104 (solution of a low molecular weight unsaturated polycarboxylic acid polymer and xylene / diisobutyl ketone = 9/1), BYK – P – 104 S 5 (solution of a low molecular weight unsaturated polycarboxylic acid polymer with a polysiloxane and xylene / diisobutyl ketone copolymer = 9/1), Disperbyk-180 (alkylammonium salt of a block copolymer with acidic groups), Disperbyk-110 (solution of a copolymer with acidic groups and methoxypropyl / alkylbenzene acetate = 1 / 1), BYK – 348 (polyether-modified poly-dimethyl-siloxane), BYK-346 (solution of a polyester-modified poly-dimethyl-siloxane in dipropylene glycol monomethyl ether), BYK – 381 (solution of a polyacrylic copolymer and dipropylene glycol monomethyl ether) (Chemie – BYK , Germany), BYK-306 (solution of a poly-dimethyl-siloxane modified with polyether and xylene / monophenylglycol + 7/2), BYK-358N (polyacrylate and alkylbenzene copolymer solution), BYK-333 (poly-dimethyl- polyether modified siloxane), Tego Dispers 650 (special modified polyether with related pigment groups), Tego Dispers 652 (concentrate of a fatty acid derivative), Tego Dispers 710 (solution of a basic urethane copolymer) (TegoChemie Service, Germany), Solsperse 43000 15 ( 50% polymeric dispersant in water), Solsperse 40000 (84% polymeric dispersant in water with diethanolamine) (Avecia, United Kingdom). As regards these dispersants, they are suitable for water-based inkjet formulations.

The ink, according to the invention, may comprise additional components typically selected from crosslinking agents, dispersing agents, defoamers, humectants, rheological control agents, organic polymers such as binders and fixing agents that provide "green force" (such as polyacrylates) or polyvinylpyrrolidone, PVP), anticorrosive agents, coalescing agents, pH control agents and biocides.

According to the invention, the vehicle is water with various additives, which are used for the preparation of water-based inkjet formulations, such as humidifying agents, humectants, polymers, cosolvents and / or preservatives. 25

According to one aspect of the present invention, the vehicle is water, and the binder compositions are silica nanoparticles, together with at least one organic binder such as an organic polymer. The purpose of the organic polymer is to cause the initial bonding of the ink with the substrate, thereby keeping the ink in place before cooking (when the organic polymer is burned). Appropriate organic polymers are those that have good water solubility or that are dispersed in water or submicron particles, and that maintain the viscosity in the appropriate range, and lead to the initial bonding of the pattern printed on the glass substrate.

Such polymers may be PVP (polyvinylpyrrolidone) (Sigma, USA), Joncryl-95 (colloidal acrylic dispersion), Joncryl-142 Joncryl SCX-661 (acrylic polymer emulsions), Joncryl-8003 (Hard Copolymer Emulsion), Joncryl SCX- 8082 (30% solution of hard acrylic resin in ammonia), Joncryl-8087 (50% solution of low molecular weight acrylic resin in ammonia and isopropanol), Joncryl-89 (emulsion of styrene acrylic copolymers) (SC Johnson Polymer, the Netherlands).

The term "silica nanoparticles" refers to commercial types of colloidal silica particles dispersed in an aqueous medium (for example Ludox dispersions (DuPont Company, United States).

While silica nanoparticles and organic binders are sufficient for the formation of ink that can be melted with the substrate after cooking, the actual temperatures necessary for such fusion are high. In order to reduce the temperatures necessary to sinter "melt" or "melt" silica nanoparticles, inorganic water-soluble additives are added to the ink so that sintering can be carried out at temperatures below 700 ° C. These additives are compounds that allow an optimal binding selected from boric acid (May and Baker, England), Sodium Perborate (Aldrich, United States), Sodium Tetraborate (BDH, England) or Disodium Tetrahydrate Octaborate (Borax, U.S).

It should be noted that the ink can be used without a pigment to provide a non-colored design (coarse or opaque / matte design) or it can be used together with a pigment to provide a color design.

In order to understand the invention and see how it is carried out in practice, a preferred embodiment will now be described, only by way of non-limiting examples. fifty

Detailed description of the invention

Pigments

When the ink of the present invention is designed to produce a colored design, it contains heat-resistant inorganic pigments having an average size of less than 1.2 micrometers. Although, in this invention, we describe a black ink, the invention can be easily applied to pigments having another 55 colors. These inorganic pigments can be metal oxides such as chromium oxide, copper oxide or mixed CuCr2O3 oxides (for the black color), titanium dioxide (for the white color), red iron oxide (for the

red color), yellow nickel, antimony and titanium rutile (for the yellow color), cobalt blue and aluminum spinel (for the blue color), etc. An important characteristic of pigments, in order to be suitable for inkjet printing, is the requirement of a very small pigment size. Conventional ceramic pigments, which are currently used for screen printing or pad printing, are in the micrometer size range (such as those mentioned in EP 1,223,201 which are 10 μ), which is unacceptable for inkjet printing. Consequently, the average required pigment size of less than about one micrometer (more precisely, less than about 1.2 microns), preferably less than 0.9 μ, more preferably, less than 0.7 μ, most preferably , less than 0.55 μ, can be obtained by grinding and crushing the micron size pigments (by means of appropriate instruments such as ball mill, pearl flour, jet mill, etc.) or synthesizing the pigment in conditions that give submicron particles (such as solution precipitation, forced hydrolysis, from metal alkoxides, gas phase reaction, etc.). It should be emphasized that, in all types of inkjet ink for glass inks described in this invention, the pigment should provide, after printing and baking at high temperature, appropriate optical properties such as optical density, UV blocking, brightness, etc. .

The pigment can also be an organometallic material, where, after cooking, the organic constituent 15 burns and the metal constituent oxidizes to form metal oxides. Alternatively, colors can be produced using compounds containing metallic elements that, after burning, oxidize to form colored metal oxides. The resulting ink can be any color, preferably black, cyano, magenta, yellow or white, or a variation of the foregoing.

Proper selection of the relationship between the concentration of the pigment and the substrate that forms the pigment binder composition 20 in the ink and the particle size distribution of the ink can achieve these optical properties.

Inkjet ink for water-based glass

1.- General 25

This type of ink contains mainly water as a liquid vehicle, and as a binder composition a mixture of glass-forming material and an organic polymer. The glass-forming material described in this invention is based on silica nanoparticles (dimension less than 60 nanometers), water-soluble materials that cause a reduction in the sintering temperature of silica nanoparticles, and optional organic binders that lead to the bond Initial with the glass substrate. These compositions cause a significant reduction in the sintering temperature of the silica, thus allowing good adhesion and formation of glass by the silica particles, at a temperature not exceeding 580 ° C. It should be noted that the melting point of large silica particles is approximately 1,700 ° C, a temperature that does not allow its use as a binder in glass substrates, because the glass will not be solid at that temperature. Therefore there is a need to use silica in the form of nanoparticles, which in the presence of appropriate additives can sinter and bind to the glass, at a temperature below 1700 ° C. The possible use of silica nanoparticles solves the need to grind the frit to obtain the required size of the glass forming materials. The present invention thus provides a simple process and compositions for preparing inks for low viscosity glass, heat-resistant and chemical resistant, having only water-soluble materials together with nanoparticles and organic polymers. This type of inks is especially suitable for inkjet printing due to the low viscosity and the reduced particle size.

2.- Preparation procedure - General

The procedure for preparing water-based ink is very simple: it is only necessary to mix the components to obtain stable homogeneous inks. Four. Five

More specifically, the glass-forming binder is based on commercially available silica dispersions, such as le Ludox ™, produced by Du Pont. Ludox is the trademark of silica nanoparticles dispersed in an aqueous medium (Du Pont, United States). Ludox dispersions contain 30-50% silica nanoparticles with a size between 22 nm. There are anionic or cationic silica particles, modified or unmodified with or without polymeric stabilizers. fifty

In general, it was found that by applying the LudoxTM dispersions on glass, followed by cooking at temperatures below 650 ° C, all the LudoxTM dispersions that were tested did not form a vitreous film on the glass substrate, and there was no adhesion to the glass substrate and they could be easily peeled although integration at a higher sintering temperature was likely. Therefore it was clear that the sintering temperature of the silica nanoparticles should be reduced. 55

According to the invention, it has been found that it is possible to dissolve in the dispersion LudroxTM electrolytes

specific, that in the presence of organic polymers, could be strongly bound to a glass surface, providing a chemical resistance to acids and bases.

Organic polymers (water-soluble or colloidal system) such as PVP (polyvinylpyrrolidone, PM = 10,000, Sigma, United States), or various types of styrene or acrylic latex, Johnson Polymers, The Netherlands) and water-soluble inorganic additives should be selected with careful, to obtain optimum performance of glass binder 5. The compounds that allow for optimal binding are compounds containing boron (B), phosphates, sodium silicates, etc. More specifically, it has been found that sodium perborate, sodium perborate without boric acid, aluminum phosphate, disodium tetrahydrate octaborate ("polybo", Borax, United States) are capable of reducing the sintering temperature of silica nanoparticles and improve its adhesion and fusion with the glass substrate. All these compositions produce low viscosity liquids, without gel formation or phase separation for a long time. These findings make the compositions containing them very suitable for use as new binders for glass jet ink for glass. Therefore, such compositions could be used as the binding component in water-based glass inkjet ink.

3 Water based formulations

15

3.1.- Formulation with Joncryl-95 (5.1% SiO3 as solids) without pigment

<dl>&lt;dt /&gt;<dd> Solution weight, g Solid weight in solution, g </dd></dl>

<dl><dt> Ludox TMA </dt><dd> 1,00 0,34 </dd></dl>

<dl><dt> Solution. of sodium perborate tetrahydrate (1.6%)</dt><dd> 4,03 0,065 </dd></dl>

<dl><dt> Joncryl - 95 (complete) </dt><dd> 0,28 0,084 </dd></dl>

<dl><dt> Glycerol </dt><dd> 0,33 0,33 </dd></dl>

<dl><dt> Dowanol DB (complete) </dt><dd> 1,00 1,00 </dd></dl>

<dl><dt> BYK-384 (complete) </dt><dd> 0,0053 0,0053 </dd></dl>

3.2 PVP formulation (4.99% SiO2 as solids) without pigment

<dl>&lt;dt /&gt;<dd> Solution weight, g Solid weight in solution, g </dd></dl>

<dl><dt> Ludox TMA </dt><dd> 1,00 0,34 </dd></dl>

<dl><dt> Solution. of sodium perborate tetrahydrate (1.6%)</dt><dd> 3,62 0,058 </dd></dl>

<dl><dt> PVP solution (30%) </dt><dd> 0,83 0,25 </dd></dl>

<dl><dt> Glycerol </dt><dd> 0,34 0,34 </dd></dl>

<dl><dt> Dowanol DB </dt><dd> 1,02 1,02 </dd></dl>

<dl><dt> BYK-384 </dt><dd> 0,0068 0,0068 </dd></dl>

Preparation Procedure 20

Add Joncryl-95 (Johnson Polymer, The Netherlands) or PVP to a solution of sodium perborate and mix with a stirrer for 5 minutes. Then, add glycerol (JT Baker, United States), Dowanol DB and Ludox solution mixing for 5 minutes after each addition. The BYK-348 is added last and mixed again for 5 minutes.

25

3.3 Formulation with PVP and aluminum phosphate (9.2% SiO2 as solids) without pigment

<dl>&lt;dt /&gt;<dd> Solution weight, g Solid weight in solution, g </dd></dl>

<dl><dt> Ludox TMA </dt><dd> 1,00 0,34 </dd></dl>

<dl><dt> PVP solution (15.0%) </dt><dd> 1,67 0,25 </dd></dl>

<dl><dt> Aluminum phosphate solution </dt><dd> 0,30 0,15 </dd></dl>

<dl><dt> Glycerol </dt><dd> 0,37 0,37 </dd></dl>

<dl><dt> Dowanol DB </dt><dd> 0,37 0,37 </dd></dl>

<dl><dt> BYK-384 </dt><dd> 0,0037 0,0037 </dd></dl>

Preparation Procedure

Add Glycerol and Dowanol DB to the PVP solution and mix with the stirrer for 5 minutes after each material addition. Then add Ludox and mix again for 5 minutes. The aluminum phosphate solution (Johnson Matthey, The Netherlands) was added after the Ludox while stirring. The BYK-348 was added last and mixed again (5 minutes). It should be noted that these "pigment-free" formulations can be used to produce a colorless design (coarse, matt opaque).

3.4.- Formulation with Joncryl and boric acid (12.7% SiO2 as solids) without pigment

<dl>&lt;dt /&gt;<dd> Solution weight, g Solid weight in solution, g </dd></dl>

<dl><dt> Ludox TMA </dt><dd> 1,00 0,34 </dd></dl>

<dl><dt> Sodium tetrahydrate perborate solution (1.6%) </dt><dd> 1,00 0,016 </dd></dl>

<dl><dt> Boric acid </dt><dd> 0,24 0,024 </dd></dl>

<dl><dt> Joncryl-95 </dt><dd> 0,28 0,084 </dd></dl>

<dl><dt> Glycerol </dt><dd> 0,17 0,17 </dd></dl>

<dl><dt> Dowanol DB </dt><dd> 0,52 0,52 </dd></dl>

<dl><dt> BYK-384 </dt><dd> 0,0034 0,0034 </dd></dl>

10

3.5.- Formulation with Polybor (14.4% SiO2 as solids) without pigment

<dl>&lt;dt /&gt;<dd> Solution weight, g Solid weight in solution, g </dd></dl>

<dl><dt> Ludox AM 30 </dt><dd> 12 3,6 </dd></dl>

<dl><dt> Disodium tetraborate octaborate solution (15%) </dt><dd> 1,8 0,27 </dd></dl>

<dl><dt> Glycerol </dt><dd> 5 5 </dd></dl>

<dl><dt> 1 methyl 2-pyrrolidone </dt><dd> 1 1 </dd></dl>

Preparation Procedure

Add Glycerol to the solution of disodium tetraborate octaborate and mix with the stirrer for 5 minutes. Then add Ludox and mix again for 5 minutes, add 1 methyl 2 pyrrolidone (Aldrich, United States) and mix for 5 minutes.

3.6.- Tests 5

All samples were applied on glass as a 5 µl drop and baked in an oven at 580-6050 ° C for 10 minutes. The resulting coating was scratch resistant, and resists soaking in an acid and a base, in a test procedure similar to solvent-based frit glass inks described for the ink compositions claimed in EP 1 658 342, in which the chemical resistance was tested by immersion in sulfuric acid solutions at 80 ° C, for 4 hours, and the NaOH solution overnight. 10

The sample was also filtered through a 0.45 µm filter, and then printed by a Lexmark z602 printer. The resulting saying had good adhesion to a glass slide, after heating at 580 ° C for 10 minutes.

4.- Adding pepper.

After having the aqueous glass binders, it was possible to prepare inkjet inks for glass, with simply mixing pigments or a pigment dispersion with the glass forming binder. It should be noted that the aqueous glass binder is composed, according to the present invention, of silica nanoparticles, water, inorganic additives that reduce the sintering temperature of silica nanoparticles, and optionally an organic binder that provides the initial binding at low temperature .

4.1.- Formulation (with 15% by weight of the formulation pigment) with Joncryl-95 (organic binder) (4.1% SiO2 as solids)

<dl>&lt;dt /&gt;<dd> Solution weight, g Solid weight in solution, g </dd></dl>

<dl><dt> Ludox TMA </dt><dd> 1,00 0,34 </dd></dl>

<dl><dt> Sodium tetrahydrate perborate solution (1.6%) </dt><dd> 4,03 0,065 </dd></dl>

<dl><dt> Joncryl-95 </dt><dd> 0,28 0,084 </dd></dl>

<dl><dt> Glycerol </dt><dd> 0,33 0,33 </dd></dl>

<dl><dt> Dowanol DB </dt><dd> 1,00 1,00 </dd></dl>

<dl><dt> BYK-384 </dt><dd> 0,0053 0,0053 </dd></dl>

<dl><dt> Pigment IJBLAC1J or Pigment IJBLAC2D or white pigment such as Kronos 2300 </dt><dd> 1,6 1,17 </dd></dl>

This formulation has a viscosity of less than 10 cps and a surface tension of less than 40 dynes / cm at room temperature, making them an excellent candidate for inkjet printing. A unique and surprising feature of this ink is its high chemical and scratch resistance, despite the fact that the glass / pigment ratio is much lower than conventional paint and ink systems (n 25 ink for conventional glass for printing this ratio is 3: 1, while in this ink the ratio is the opposite, 1: 3,6 Obviously, the pigment / silica ratio can be customized according to the requirements of the final printed design. In addition, silica nanoparticles are commercially available as economical dispersions, ready to use, without the need for a further reduction in their particle size. Currently, particles smaller than 300 nm are suitable for inkjet printers, and it is known that the smaller the particle size, the better the ink yield. The particles used in our invention are much smaller, in the dimension range of 7 to 22 nm.

4.2.- Formulation with Joncryl-95 and boric acid (with 15% by weight of the formulation pigment) (9.6% SiO2 as solids)

<dl>&lt;dt /&gt;<dd> Solution weight, g Solid weight in solution, g </dd></dl>

<dl><dt> Ludox TMA </dt><dd> 1,00 0,34 </dd></dl>

<dl><dt> Sodium tetrahydrate perborate solution (1.6%) </dt><dd> 1,00 0,016 </dd></dl>

<dl><dt> Boric acid </dt><dd> 0,024 0,024 </dd></dl>

<dl><dt> Joncryl-95 </dt><dd> 0,28 0,084 </dd></dl>

<dl><dt> Glycerol </dt><dd> 0,17 0,17 </dd></dl>

<dl><dt> Dowanol DB </dt><dd> 0,52 0,52 </dd></dl>

<dl><dt> BYK-384 </dt><dd> 0,0034 0,0034 </dd></dl>

<dl><dt> IJBLAC2D pigment </dt><dd> 0,83 0,6 </dd></dl>

4.3.- Water based ink forming porous glass

Based on our findings, it seems that it is also possible to combine Ludox-type systems with sodium silicate solutions and obtain interesting ink characteristics after cooking. 5