DE4103153C1 - Decorating glass vessels - by applying coloured lacquers and curing - Google Patents

Abstract

Process for decorating glass vessels comprises application of one or more coloured lacquers to produce a pattern or image; then curing the lacquers with a stream of warm air. The lacquer is a mixt. of pigments, epoxy resin, liquid aliphatic or cycloaliphatic polyamine and polyamidoamine hardener, and opt. inert or reactive diluents (e.g. polyols, glycidyl esters and ethers, etc.). The glass vessels may be rotated about an axis during the application of coloured lacquer and during curing. USE - The prods. are decorated wine glasses, drinking glasses, beakers, containers, etc. (10pp Dwg.No.6d/7)

Description

The invention relates to a method for producing with a decor equipped glass bodies by applying glass paints containing liquid colorants on the Vitreous body, with the addition of Thinner glass lacquer set very thin Basis of a cold-curing two-component reaction lacquer is used.

It is common to apply colored decorations on vitreous bodies a color varnish with a brush or by spraying the To produce colored lacquer using a spray gun. That too Applying colored decors using the printing process Vitreous is applied. In all of these cases the Color or the color application immediately in the desired Decor, d. H. in the desired configuration.

DE 37 34 464 A1 describes a method for gloss polishing a transparent, at least on part of its surface frosted glass body described, the glass surface with a lacquer, especially a chemically curable 2-component paint, to improve its optical and mechanical properties glass pigments and color additives can be added, is coated.

DE-AS 21 02 091 describes a process for the production  decorative pigmented surface layers on solid Carriers known, being a fresh, still flowing lacquer or lacquer-like plastic layer a thin, if necessary liquid enriched with finely dispersed pigments, whose surface tension changes as a result of the addition surface-active substances from the coated surface distinguishes, is dripped on.

From DD 2 55 725 A1 is a process for the production of colored known transparent or opaque decors on glass objects, a mixture of colors on the object to be decorated Air or oven drying screen printing ink, epoxy resin and one organic solvent is sprayed on and the treated Object is then annealed.

DD-PS 22 288 describes a decoration process by Glass objects described with colored chandeliers, being on with diluted luster paints or paint thinners for Glass-colored painted glass object with a fine brush Diluents, such as benzene, gasoline or nitro thinner, dabbed or sprayed on.

DE-GM 19 77 351 discloses cold-curing synthetic resins, in particular on the basis of epoxy resins, polyurethane and unsaturated polyesters of different colors or Color tones to use for decorating glass objects.

The invention has for its object a method for Manufacture decorations on vitreous bodies to create with it it is possible to use variable decorations according to a given technique using the same principle. In particular, the method should not only be at the level Glass body surfaces can be used, but preferably also for curved surfaces, for example spherical surfaces, Cylindrical surfaces, conical surfaces.

To solve the task of decorating According to the invention, vitreous bodies are proposed  that the color application as a stripe and / or as Small areas covering the core area of a decor is applied to the vitreous and the color application by means of a compressed air jet on the surface of the Vitreous body is distributed starting from the core areas and then hardens. Due to the explosive distribution of the Paint applications create flame-like structures.

Varnishes are simply paints that as a binder a film former, for example art and Natural resin and, if applicable, auxiliaries, as well as usually Solvents are volatile components that make up the binder dissolve and convert into a workable consistency. However, there are already binders that are themselves liquid are, so that solvents for liquefaction are not essential required are. The paints are different Characterized criteria. One can paint according to the contained Binder z. B. as epoxy resin paints, nitro paints, Describe alkyd resin paints etc. or also according to Art their drying, for example, as stoving enamels or cold-curing paints or also according to your paint object Example as car paint, glass paint. The film formation can by Evaporation of the solvent contained in the paint occur physically or through the formation of cross-linked Polymers in chemical drying. Here, between oxidative drying, for example with drying oils modified alkyd resins, cold curing, for example Two-component reaction paints and oven-drying, for Example of so-called stove enamels. The The invention is particularly concerned with use cold-curing two-component reaction lacquers based Epoxy resin or polyurethane. Here are such cold-curing reaction lacquers used for the Paint objects made of glass are suitable.

The colorants are preferred to the paints in liquid form, e.g. B. in suitable solvents or liquid binders dissolved organic dyes added. However, it is also possible to use as colorant pigments, which are also in  Liquids are distributed, possibly both dissolved Dyes and pigments in order to achieve appropriate color effects in the To achieve decor.

It is essential for the method according to the invention Meaning that the color application from the reaction resin, hardener, Colorant is set to be very thin to the after following the application of the paint on the glass body Processing with compressed air as fine a distribution as possible to be able to achieve. In principle it must be stated that the Paint application compared to normal on a glass, for example a colored glass varnish to be applied with a lower viscosity should have. The aim here is that the viscosity η the color application for the implementation of the invention Process should preferably be below 5000 mPa · s 25 ° C.

The cold-curing glass lacquers which can be used according to the invention then contain at least one liquid reaction resin, liquid hardener and liquid colorant. The paint application will on the vitreous in core areas as islands or applied in strips and is then subsequently by means of Compressed air extracted, d. H. the paint application is from the core area driven away, frayed in the respective flow directions of the compressed air jet. With the method according to the invention feather-like structural images can be achieved, provided that a is very low viscosity glass lacquer, which by means of Compressed air jet extendable and in predefinable directions is distributable. The compressed air jet is used, for example an air gun achieved, preferably with pressures in Range of 2 to 4 bar and relatively little air, i.e. H. with a very small nozzle. It is preferred with the Nozzle, d. H. the nozzle outlet, very close to the surface of the Glass body and the paint application approach, preferably up to a few millimeters to about 2 cm distance between the surface of the Vitreous and nozzle. After spreading the paint job on the surface of the vitreous, with relatively little Amounts of paint application a very fine even over larger areas  distributing fibrous structures can be achieved, and the color application does not run after distribution is to be feared more, the hardening of the Color application and thus the final fixation.

As already mentioned, are for the color application Carrying out the method according to the invention in particular Two-component reaction lacquers based on epoxy resins or Polyurethanes can be used. A glass lacquer based is preferred a cold-curing two-component reaction lacquer based Epoxy resin as a binder in liquid form and a hardener used. Solvent-free, thin liquids are preferred Reaction resins with a viscosity at 25 ° C below 7000 mPa · s used. Of the general usable Polyepoxide compounds are the most bisphenol A resins best known, however their viscosity η is 25 ° C between 9,000 to 15,000 mPa · s with epoxy numbers (Aeg / kg) of 5.1 to 5.4 and an epoxy equivalent (g) 185 to 196. Because of their high viscosity they are mostly only with the addition of Solvents or thinners as two-component paint used to a corresponding light liquid to reach. However, bisphenol F resins are advantageous as Two-component reactive resins without the addition of Solvent can be used because it is much lower Have viscosity at 25 ° C of about 3500 to 6500 mPa · s. In the manufacture of bisphenol F resins, phenol and Out of formaldehyde. The bisphenol-F resins have one Epoxy number (Aeg / kg) from 5.8 to 6.1 and an epoxy equivalent (g) from 164 to 172.

In order to convert the epoxy resins into the thermoset state suitable crosslinking agents - hardeners - required, their reactive groups with the epoxy or hydroxyl groups react. When curing epoxy resins using amines the reaction takes place by opening the epoxy ring under Accumulation of the hardener, liquid aliphatic as hardener and cycloaliphatic polyamines and polyamidoamines are preferred be used. This also includes amine adducts and  Ketimine. The reactions with these hardeners proceed at room temperature. When using aliphatic, cycloaliphatic and aromatic amines as hardeners for As a rule, epoxy resins become active per epoxy group Hydrogen atom used. The calculation of the theoretical the minimum amount of polyamine required is known the epoxy number of the resin and the H + active equivalent weight of the amine used for curing, it takes place after the Equation: amount of polyamine / 1000 g epoxy resin = epoxy content H + active equivalent weight (molar mass of the amine divided by the number of moles of reactive hydrogen). As Harder are possible: Aromatic, cycloaliphatic, aliphatic, such as B. 4,4'-diaminodiphenylmethane, his o, o, -alkyl-substituted derivatives, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 2,4-diamino-3,5-diethyl-toluene, hydrogenated 4,4'-diaminodiphenylmethane, isophoronediamine, diethylenetriamine, Triethylenetetramine, polyaminoamides based on Diethylenetriamine or similar amines and fatty acids.

As already stated, the liquid reactive resins can Basis of epoxy resins and hardeners by adding Solvents or thinners reduced in their viscosity will. Aromatic solvents are preferred Hydrocarbons, such as alcohols, aromatics, ketones, are used. The colorants can also in such solvents or Solvent mixtures are dissolved or dispersed. The dissolved resin component is used shortly before use Hardener solution, polyamine, amine adduct, polyamidoamine etc. admitted. The amount of solvent can Viscosity of the paint application in the desired thin liquid can be set. However, the solvent must then Dry.

Therefore, they are more environmentally friendly and save energy solvent-free reaction lacquers based on epoxy resins. Instead of solvents, epoxy resins can be used both the bisphenol-F resins and the bisphenol-A resins  to reduce the viscosity of reactive thinners, in particular low-viscosity di- or monoepoxides, with a Viscosity η at 20 ° C less than 100 mPa · s can be added. A mixture can also be used for epoxy resins such as bisphenol A resins of solvents and reactive thinners are used to keep the solvent content small to get the desired one To achieve thin liquid of the paint application. At Bisphenol-F resins are able to produce the desired thin liquid the paint application also by adding reactive thinner to achieve alone. Examples of reactive thinners are: Butane-1,4-diol, neopentyl glycol, hexane-1,6-diol, 1,4-bis-hydroxymethylcyclohexane di-glycidyl ether, glycidyl ester Lauric acid and Versatic acids (branched Fatty acid derivatives), vinylcyclohexene dioxide and n-butyl, Isooctyl, dodecyl, tetrahydrofurfuryl, phenyl and Cresyl glycidyl ether. It is also possible to apply varnishes Epoxy resin based dyes in low molecular weight low viscosity epoxides such as those listed To dissolve and liquefy reactive thinners.

Bisphenol-F resins are preferred as solvent-free Reaction paints are used, which also means Reactive thinners to correspondingly low viscosities for set a suitable paint application according to the invention can be. All reaction paints come as hardeners Based on epoxy resins the aliphatic, cycloaliphatic or aromatic polyamines, polyamidoamines and ketimine in question.

The curing of the epoxy resins is also possible with polyisocyanates possible. This group of hardeners is used the hydroxyl groups of the resin instead of polyurethane formation. These curing reactions also take place at room temperature. For the calculation of the necessary for curing epoxy resins The amount of polyisocyanate is both the OH equivalent weight of the used resin as well as the isocyanate content of the polyisocyanates used important. When making a The resin is coated with epoxy / polyisocyanate  a solvent, ketones, esters, aromatics dissolved and that Isocyanate - the hardener - added before application. The Epoxy resins are cured more quickly with isocyanates than with Polyamines. Isocyanate-hardened paints have better cold and hot water resistance as well as higher solvent resistance as epoxy resins hardened with polyamines. By adding Solvents and optionally reactive thinners can also here the viscosity can be set accordingly low the light liquid of the paint application for the subsequent one Distribution by means of compressed air for decorating according to the invention of glass surfaces. A particularly quick hardening is reached at room temperature if Epoxy-polyisocyanate systems modified by di-alkanolamine will.

For solvent-free reaction varnishes based on epoxy resins are between 30 to 65 parts by weight of reactive diluent per 100 parts by weight of solvent-free reaction lacquer, added, to get a sufficiently low viscosity. The amount of liquid dyes depends on the desired Colours. An advantageous selection is the characteristic one Features of claim 7 can be removed. Here it is for Achieve fine patterns, i.e. H. fine fibers and veins, from Advantage, the viscosity of the paint application below 3000 mPa · s 25 ° C.

With the method according to the invention can also advantageously rotationally symmetrical bodies, such as glasses, containers, etc., be decorated. It is proposed that rotationally symmetrical vitreous bodies with rapid rotation around their Rotation axis with the paint application, so this stays in the core areas and not prematurely runs.

The one to distribute the paint job on the The compressed air jet required on the vitreous surface should be fine and with little air at pressures of 2 to 4 bar on the Surface. To distribute either Glass body can be moved relative to the compressed air jet  or vice versa or both against each other.

The inventive method for decorating surfaces of vitreous can be both on smooth clear vitreous as well also on matt surfaces of glass bodies that for example, are sandblasted.

It is also possible to apply several colors to the vitreous to apply one after the other, whereby the paint application first is distributed by means of a compressed air jet before the next color application is applied. That way structured multi-colored decorations can be achieved. It is also possible to apply several different types of paint on the Apply vitreous and distribute them at the same time by means of a compressed air jet, but an early one The colors run through by working quickly is to avoid.

The invention is illustrated in the drawing using exemplary embodiments explained. Show it

Fig. 1 and 2, a glass with paint application and finished with decorative;

FIGS. 3 and 4 a glass container with paint application and finished with decorative in perspective view;

FIG. 5a, b, c manufacturing a decoration to a glass in a perspective schematic representation;

FIGS. 6a-d, the method steps of manufacturing a decoration to a glass;

Fig. 7 various decorated glass bodies.

According to FIGS. 5a, b and c, a glass body 1 , for example a drinking glass, is to be provided in a rotationally symmetrical form with a rotation axis 4 with a decoration according to the method according to the invention. The paint application 2 is applied to the surface 10 of the glass 1 with a brush 3 or another application device as a band-shaped strip, the glass 1 being rotated. The color application 2 takes place in the desired core areas either as strips or as a small area or at intervals. Starting from the core areas that have been applied and covered with paint, this is distributed in a pattern over part of the glass surface by means of the compressed air jet 6 from the compressed air gun 5 . In this case, either the compressed air pistol can be directed to new places of the paint application while rotating the glass 1 about its axis of rotation in order to distribute it, for example by removing the compressed air pistol from the surface of the glass 1 and repeatedly bringing it up or vice versa by correspondingly removing and moving the Glases 1 . With this method, the effect of the compressed air jet creates spring-like decors 20 , as can be seen in FIG. 5c, which lead away from the thinned core areas 2 a of the paint application. The surface 10 of the glass body 1, starting from the core region 2a on both sides with spring-like or flame-like patterns in any desired distances from one another, depending on the point of application of the compressed air jet, can be provided. The resulting patterns run along the flow lines and turbulence and vortices that the compressed air jet passes through on the surface of the vitreous body and on which it takes the paint application from the core area and distributes it.

FIG. 1 shows a glass body 1 with an annular paint application 2 , which is drawn out by means of a compressed air jet to form a decor 20 , as is indicated schematically in FIG. 2.

In the Fig. 3 and 4 a larger container 1 is shown with handles 8, also made of glass, for example, receives only an island-shaped paint applicator 2, see Fig. 3, which is then directly shown in Fig. 4 by means of a compressed air jet for example, in Shape was distributed to a decor 20 and pulled out.

Advantageous is the nozzle outlet 5 a in the distribution of the color application, see Fig. 5b, only at a small distance of about 1 cm from the surface of the glass 1 and the application of paint 2 is removed to a very small and fine jet of compressed air 5 with 2 to 3 bar on the paint application to distribute it. The nozzle 5 a should also have a very small diameter in the range of 2 to 4 mm. This enables precise and targeted work. For the paint application 2 , for example, a two-component reaction lacquer is used, which air-dries and hardens at room temperature, which contains a liquid epoxy resin, an amine hardener, liquid color concentrate and a reactive thinner and, overall, has a viscosity corresponding to a liquid ink.

According to FIG. 6a, on the glass body 1 , a goblet-like glass, a color application 2 on a cold-hardening, diluted glass lacquer as an island, possibly in a geometric preform, for example a circle, oval, triangle, square, 3 -, 4-, 5- angular star, S-stripes or the like, applied with the brush 3 by hand. Subsequently, this paint application 2 , see Fig. 6b, by means of a compressed air jet 6 from the compressed air gun 5 , nit supply hose 7 for the compressed air on the surface of the glass body in a pattern. The resulting decor, see FIG. 6c in a schematic enlargement, contains feather-like, flame-like structures 2 b starting from the core area 2 a of the paint application. FIG. 6d shows a provided by the inventive method with decor 20 Glas 1.

Fig. 7 shows a variety of glass body 1 according to the invention with decors 20th

Claims (14)

1. A process for the production of glass bodies equipped with a decor by applying liquid colorants containing glass lacquers to the glass body, a glass lacquer adjusted by adding diluent on the basis of a cold-curing two-component reaction lacquer being used as a thin layer, characterized in that the color application as stripes and / or as islands covering small areas forming the core area of a decor is applied to the glass body and the paint application is distributed on the surface of the glass body by means of a compressed air jet starting from the core areas and then hardening. 2. The method according to claim 1, characterized in that a cold curing Two-component reaction lacquer based on epoxy resin Binder and a hardener is used. 3. The method according to claim 2, characterized in that hardener based on liquid aliphatic and cycloaliphatic polyamines and Polyamidoamines are used. 4. The method according to claim 2 or 3, characterized in that solvent-free thin Reaction resins with a viscosity η at 25 ° C below 7000 mPa · s can be used as glass lacquers. 5. The method according to any one of claims 1 to 4, characterized in that as a diluent  Reactive diluents, especially low-viscosity di- or Monoepoxides, with a viscosity η at 20 ° C less than 100 mPa · s can be used. 6. The method according to any one of claims 1 to 5, characterized in that the forming the glass lacquer solvent free liquid reaction resin or the in a reaction resin dissolved in solvent between 30 to 65 parts by weight of thinner, based on 100 parts by weight Glass lacquer, can be added. 7. The method according to claim 6, characterized in that on 100 parts by weight of glass varnish Based on an epoxy resin 20 to 40 parts by weight of liquid Dyes and a sufficient weight of hardener, based on the amount of epoxy resin used, and 25 to 40 wt .-% of a diluent, based on the Sum of the amounts by weight of glass lacquer and dye and Harder. 8. The method according to any one of claims 1 to 7, characterized in that rotationally symmetrical Vitreous body rotating rapidly around its axis of rotation with the paint application. 9. The method according to any one of claims 1 to 8, characterized in that for distributing the paint job working with compressed air in the range of 2 to 4 bar. 10. The method according to any one of claims 1 to 9, characterized in that the compressed air from a nozzle is blown onto the paint application that is a short distance away from a few millimeters to a maximum of 2 cm from the Vitreous surface and the paint application is is blown. 11. The method according to any one of claims 1 to 10, characterized in that for distributing the paint job  on the surface of the vitreous body opposite the vitreous body the incoming compressed air jet is moved back and forth. 12. The method according to any one of claims 1 to 11, characterized in that for distributing the paint job the compressed air jet on the surface of the vitreous is moved back and forth against the vitreous. 13. The method according to any one of claims 1 to 12, characterized in that the surface of the vitreous is matted before applying the paint, for example, is sandblasted. 14. The method according to any one of claims 1 to 13, characterized in that several paint jobs are successively applied to the vitreous, whereby the next color application after distributing the previous color application is applied.