DE10328531A1 - UV-drying lustering preparation for decorating ceramic, porcelain or glass, especially for ceramic transfer decoration, contains metal-organic compound, cationically-polymerisable monomer and suitable initiator - Google Patents

Abstract

A UV-drying lustering preparation (I) based on (A) organic compound(s) of precious or non-precious metals, for decorating ceramic, porcelain and glass, also contains (B) cationically-polymerisable monomer(s) and (C) initiator(s) for cationic polymerisation. An independent claim is also included for a method for coating ceramic substrates by applying preparation (I) and hardening the coating with UV light.

Description

The The invention relates to UV-drying chandelier preparations and their use.

Decoration materials from the group of chandelier preparations, used to decorate ceramics, porcelain and glass, are in numerous publications described.

• – Einer Mischung organischer Edel- und/oder Unedelmetallverbindungen, die sich beim Einbrennen zu den jeweiligen Metalloxiden oder Metallen zersetzen und der je nach Zusammensetzung die verschiedensten Farbtöne aufweisen kann.
• – Organischen Lösungsmitteln als Träger für die gelösten Metallverbindungen.
• – Natur- und Kunstharzen zur Einstellung der optimalen Verarbeitungsviskosität bzw. Anpassung und Optimierung der Eigenschaften der Präparate an die jeweilige Applikationsmethode.

They consist essentially of the following components:

• - A mixture of organic precious and / or base metal compounds which decompose on baking to the respective metal oxides or metals and which may have a variety of shades depending on the composition.
• - Organic solvents as carriers for the dissolved metal compounds.
• - Natural and synthetic resins for setting the optimum processing viscosity or adaptation and optimization of the properties of the preparations to the respective application method.

One considerable proportion of chandelier preparations Decoration is over so-called ceramic decals consumed. For this purpose, a preparation in pasty Shape in the desired Design applied by screen printing on a special carrier paper. To the drying of the paste and optionally the printing of other colors a ceramic transfer varnish is overprinted. After drying of the decal, the motif can be soaked in water from the backing paper replaced, applied to the object to be decorated and baked. Thermal decomposition forms the decorative metal oxide film out.

One greater Disadvantage of the solvent-containing preparations is in this process that the drying time for evaporation the solvent several hours. In the meantime, it has succeeded in producing ceramic decals, using the usual decorative colors by means of UV-drying To process print media and thus the drying time during the production process severely shorten. Furthermore, this technology has the advantage that there are no solvent emissions comes. It was therefore very desirable also to provide chandelier preparations, for themselves this technology of making ceramic decals are suitable.

In the European patent specification EP 0 346 570 B1 already photopolymerizable luster preparations are described. These chandelier preparations consist essentially of the following components:
Representatives of the organic precious and non-precious metal compounds;
Isobornyl acrylate or dicyclopentadienyl acrylate and optionally further acrylic or methacrylic acid esters;
Acrylic acid or methacrylic acid oligomers;
metal resinates;
Photoinitiator;
Natural or synthetic resins or mixtures thereof.

The The basic principle of these compositions is based on the radical Photopolymerization. By irradiation with UV light of suitable wavelength the photoinitiator is split into radicals that react with the acrylic acid esters react under polymerization.

Preparations of these Species have proven to be very good for direct printing on glass or proven on ceramic. Unfortunately, they have disadvantages in the application for ceramic Decals such that in the application of the ceramic transfer varnish always easy to solve of the UV-dried preparation through the solvents takes place, which has the consequence that washed after the burn the preparation or discolored contours through liberated Constituents or cloudy burns out.

An attempt has been made to eliminate this disadvantage by increasing the pigment volume concentration ( EP 1 291 335 A1 ).

When Another disadvantage was that in the presence of Goldsulforesinaten or sulfur-containing resins, as is often the case for gloss improvement in the preparation contain a strong inhibition of UV drying, because the sulfur present acts as a radical scavenger. It will therefore be a extremely long drying time with UV light needed, which is unsuitable for the practice or there is no UV drying at all.

task It is the object of the present invention to at least partially overcome these disadvantages to eliminate and chandelier preparations for disposal to ask for suitable for use in the manufacture of ceramic decals are.

According to the present Invention can These disadvantages are avoided when the precious metal preparations by Cationic photopolymerization are cured.

• A mindestens eine organische Edel- oder Unedelmetallverbindung;
• B mindestens ein kationisch polymerisierbares Monomer; und
• C mindestens einen Initiator für die kationische Polymerisation.

The invention thus relates to a chandelier preparation for decorating ceramics, porcelain and glass containing

• A is at least one organic precious or base metal compound;
• B at least one cationically polymerizable monomer; and
• C at least one initiator for the cationic polymerization.

By the cationic photopolymerization on the one hand, the inhibition drying by sulfur mostly be avoided, on the other hand, it is possible to avoid that when overpainting the hardened preparations a "solving" by the paint and thus a discolored Contour after firing arises.

The The principle of cationic photopolymerization is that suitable photoinitiators in the UV irradiation produce protic acids. These protic acids can react with different types of monomers that are cationic Polymerization accessible are.

• 1. Ionische Photoinitiatoren 1a. „Onium" Salze Typische Beispiele sind z.B. Aryldiazonium-Salze, Diaryliodonium-Salze, Triarylsulfonium-Salze, Triarylselenium-Salze, Dialkylphenacylsulfonium-Salze, Triarylsulfoxonium-Salze usw., wobei die Anionen Tetrafluoroborate, Hexafluorophosphate, Hexafluoroantimonate und Hexafluoroarsenate sind. 1b. Organometall-Salze Typische Beispiele sind z.B. Eisen-Aren Komplexe, wie etwa Irgacure 261 [(eta⁶-Isopropylbenzol)(eta⁵ cyclopentadienyl)eisen]hexafluorophosphat.
• 2. Nicht-ionische Photoinitiatoren 2a. Organosilane 2b. Latente Sulfonsäuren 2c. Verschiedene sonstige nichtionische Verbindungen

The cationic photoinitiators can be divided into the following groups:

• 1. Ionic photoinitiators 1a. "Onium" salts Typical examples are, for example, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triarylselenium salts, dialkylphenacylsulfonium salts, triarylsulfoxonium salts, etc., where the anions are tetrafluoroborates, hexafluorophosphates, hexafluoroantimonates and hexafluoroarsenates. Salts Typical examples are, for example, iron-arene complexes such as Irgacure 261 [(eta ^6- isopropylbenzene) (eta ⁵ cyclopentadienyl) iron] hexafluorophosphate.
• 2. Nonionic photoinitiators 2a. Organosilane 2b. Latent sulfonic acids 2c. Various other nonionic compounds

Further Examples can be found in the monograph S.P. Pappas (ed), Radiation Curing: Science and Technology (1992).

Commercially In use, however, are essentially only the diaryliodonium and Triarylsulfonium salts with hexafluorophosphate and antimonate anions.

When reactive Monomers are especially suitable cationically polymerizable monomers such as cyclic ethers, epoxides, lactones, cyclic sulfides, acetates and siloxanes or vinyl ethers. Especially suitable and most common are the epoxides.

In addition to the low molecular weight monofunctional and difunctional epoxy monomers, epoxy prepolymers and higher oligomers can also be used. Among the epoxy resins, essentially three major types are used in the formulation of cationic curable systems:
Cycloaliphatic epoxy resins,
Glycidyl ether resins, eg, bisphenol A dicyclodyl ether, and
Epoxidized oils, eg epoxidized soybean oil.

The generated during the photolysis of the cationic photoinitiators Lewis or Bronsted acids react with above Monomers, oligomers and resins under cationic polymerization. The Bronsted acid protonates first the epoxide group. The protonated epoxide forms a carbonium ion with ring opening, which reacts further with another epoxide molecule with chain formation.

Surprisingly, it is possible by dissolving the metal compounds suitable for chandelier preparations in suitable epoxy monomers to prepare solutions which undergo cationic polymerization can be thrown. On the one hand, these monomers must have good solubility for the suitable noble metal compounds, but on the other hand should not interfere with the formation of a high-gloss metal film during thermal decomposition. The preparations according to the invention are thus preferably free from customary organic solvents.

When epoxy monomers have proven particularly suitable which differ from Derive terpene hydrocarbon structures. Examples are alpha and beta-pinene oxide, limonene monoxide and dioxide, terpinolene dioxide, Mycene dioxide, dicyclopentadiene dioxide, terpenol oxide, myrcene monoxide etc.

Further Suitable mono- and difunctional epoxides are derived from epoxycyclohexyl compounds from.

Farther it is surprising that usually Onium salts used as cationic photoinitiators during baking the formation of the shiny Oxide film does not always affect negatively. Triarylsulfonium hexafluoroantimonate, hexafluorophosphates and tetrafluoroborates as photoinitiators proved to be quite suitable and lead to high gloss Metal films after baking.

The Amounts of monomers are usually about 20 - 60% im Preparation. In addition to the monomers can the formulations also a share of epoxy resins but also of non-reactive resins as they usually do in bright precious metal preparations to be used. Examples include asphalt, rosin rosin-derived resins, phenolic resins, maleate resins, Alkyd resins, sulfurized natural resins and mixtures of these resins. The amounts of these additional components are preferably from 0 to about 20%.

The Formulations can a big Number of organic metal compounds included, to achieve of the desired Shades needed are. Examples are the resinates, sulforesinates or carboxylates of Elements B, Al, Cr, Cu, Fe, Co, Mn, Ni, Bi, V, Rh, Si, Rh, Pd, Pt, Ru, Ir, Ti, Zr, Ag, etc., and mixtures thereof. The metal compounds are preferably individually from 1 to 20% by weight and together about 5 up to 30% by weight in the UV-drying preparations.

The preparations according to this Invention can printed on a ceramic decal paper and with a commercial High-pressure mercury lamp to be dried in 1 - 2 sec. After transferring on porcelain and baking at 820 ° C, a high-gloss, crack-free movie in the for Chandelier typical Appearance.

The following examples illustrate the invention in more detail, without limiting it: Example of a UV-drying Luster Preparation: limonene 52.5 g rosin 40 g tetraisobutylorthotitanate 4 g Triarylsulfonium hexafluoroantimonate (50% solution) 3 g defoamers 0.5 g total 100 g

The Components are solved and screen-printed with a 130 mesh / cm polyester fabric on a conventional printed ceramic decals paper.

The UV drying is done with a standard High pressure mercury lamp at a belt speed of 15 m / min. in 1 - 2 Second

Subsequently, will with a usual ceramic screen printing varnish overcoated (Heraeus L 406).

To drying is the decal by soaking in water from backing paper superseded and as usual at 800 ° C baked.

It forms a shiny, iridescent mirror of titanium oxide.

Claims (7)

UV-drying luster preparation for decorating ceramics, Porcelain and glass, containing A at least one organic Precious or base metal compound; B at least one cationic polymerizable monomer; and C at least one initiator for the cationic polymerization. Luster preparation after Claim 1, containing as component B one or more epoxy monomers. Luster preparation after Claim 2, characterized in that the metal compounds) dissolved in the / the epoxy monomers are. Luster preparation after one of the claims 2 or 3, characterized in that the epoxy monomers differ from Terpene hydrocarbon structures or epoxycyclohexyl compounds derived. Luster preparation after one of the claims 1 to 4, characterized in that the initiator of the group of Belongs to onium salts. Process for coating ceramic substrates by applying a chandelier preparation one of the claims 1 to 5 and subsequent hardening with UV light. Use of chandelier preparations according to one of the claims 1 to 5 for the decoration of ceramic substrates.