UV hardening glass printing ink and uv hardening glass printing lacquer and method for printing a glass substrate

Description

The present invention relates to UV-curable printing inks and varnishes as defined in claim 1, the use of UV curable printing inks and varnishes for printing glass objects as defined in claim 19, and a method of printing glass items. such inks according to claims 21 and 22.

[0002] UV-curable organic glass inks that require a subsequent heat treatment after curing have been used in recent years to replace the ceramic (inorganic) inks previously used. Such a solution enables the elimination of the need to use heavy metals, a larger palette of colors (standard and complex shades), and an increase in the brightness [purity of color] and gloss. A further advantage is that the shade [of the printout] can be assessed directly after the curing with UV radiation; unlike inorganic inks, for which evaluation is only possible after firing [of the printed object]. Organic paints also offer opportunities for more favorable process performance due to faster annealing (e.g. 20 minutes instead of 90 minutes [for inorganic paints]) and lower annealing temperatures (e.g. 160 ° C instead of 500-700 ° C); this allows lower process costs compared to processes using inorganic paints. Organic inks, however, are more expensive than ordinary inorganic inks for printing glass.

[0003] The milder conditions of the printing process with the use of organic inks eliminate the negative impact [of the printing process] on the internal pressure resistance of the bottles. However, organic glass inks cannot be used to print glass products that need to undergo post-treatment at high temperatures, such as molded glass for cars or glass with high gloss gold printing.

[0004] The organic glass inks that are available today can pose problems in areas such as mechanical resistance, hiding power and water resistance; it is particularly difficult to obtain sufficient scratch resistance.

[0005] Organic glass printing inks are used, for articles pretreated e.g. by flame, in a two-component printing method of adding an adhesion promoter to the printing ink and printing the glass post-annealed at a temperature of, for example, 140 ° C. - 200 ° C for a certain period of time.

[0006] A solution would be expected to simplify this printing process and thus reduce its costs. One option to simplify the process would be to eliminate the need for an adhesion promoter in the two-component process; a further possibility [to reduce costs] is the elimination of post-stress relief operations.

[0007] World patent WO 90/06336 discloses a method for printing glass in which an epoxy ink based on bisphenol A is printed on a glass substrate and then cured by radiation; the use of an adhesion promoter is envisaged if necessary.

[0008] According to the inventor [the author of the present patent], the above-described glass printing ink and the method of its application do not, however, provide - without further measures - sufficient scratch resistance, sufficient adhesion of the ink to the glass, and sufficient water resistance. Moreover, in all of the examples mentioned in WO 99/06336, an adhesive is used and the products are post-stress relieved at temperatures from 150 ° C to 200 ° C. United States Patent No. 5,656,336 A discloses a similar method, but with the same disadvantages.

[0009] United States patent AP US 2004/00668027 A1 discloses the composition of a UV-curable powder composition comprising the reaction product of a bisphenol A-based epoxy resin with acrylic acid. The known composition does not contain any monomer that is curable by UV radiation.

[0010] World patent WO 2005/040055 A1 discloses a colored composition [printing ink] in which a bisphenol A-based epoxy resin is dissolved in a UV-curable monomer.

[0011] US patent US 3,419,412 describes a composition in which the epoxy resin is cross-linked by adding a cross-linking agent. The described composition does not contain a monomer or a photoinitiator, but does contain a wax.

[0012] The object of the invention is to propose an ink and a varnish for printing glass which allow - without post-stress relief - to obtain sufficient scratch resistance and sufficient adhesion. The invention also relates to the use of glass ink and varnish in the printing process and the printing process used for this purpose.

[0013] The object of the invention may be achieved by using the glass printing ink and varnish according to claim 1, their use according to claim 19 in a printing process according to claims 21 and 22.

[0014] A significant advantage of the invention, apart from the [good] mechanical properties of the hardened paint or varnish layer, is the preservation of the possibility of simplifying the process as the expected mechanical properties are achievable - without post-stress relief - in both one- and two-component systems. In most cases, good resistance to [imprints] against moisture and water is maintained.

[0015] The terms glass printing ink and glass printing varnish should be understood to mean printing ink or varnish suitable for printing glass or vitreous surfaces such as ceramics and ceramic tiles.

[0016] Both the ink and the printing varnish described in the invention contain wax. The inventor [the author of the present patent] found that the use of wax leads to a significant - in relation to known paints or varnishes - an increase in scratch resistance, and thus mechanical resistance [overprints] with inks or varnishes for printing according to the invention.

[0017] Waxes useful for the above-mentioned purpose are commercially available. In particular, the waxes listed below are involved;

for example, for each [type] of wax their trade names are given, while the sources of purchase are given in parentheses.

Polyethylene waxes:

Ceraflour 990 (Byk-Cera; Danzigweg 23; 7418 EN Deventer, The Netherlands)

Ceraflour 991 (Byk-Cera; Danzigweg 23; 7418 EN Deventer, The Netherlands)

Printwax ME 0825 (DEUREX Micro-Technologies GmbH; Dr. Bergius

Strasse 18/20 - 06729 Tróglitz, Germany)

Modified polyethylene waxes:

Ceraflour 961 (Byk-Cera; Danzigweg 23; 7418 EN Deventer, The Netherlands)

Everglide UV 961 25% (Krahn-Chemie GmbH; Grimm 10; 20457 Hamburg, Germany)

HD (high density) polyethylene waxes

Ceraflour 950 (Taurus-Cera; Danzigweg 23; 7418 EN Deventer. The Netherlands)

Composite of polymers with silicic acid

Deuteron MM 659 (Deuteron GmbH; in den Ellern 2; 28832 Achim, Germany)

Micronized polyolefin waxes

Micro Wax DM (Finma-Chemie GmbH; Theodor-Heuss-StraBe 5; 61191

Rosbach, Germany)

Micro Wax HTDM (Finma-Chemie GmbH; Theodor-Heuss-StraBe 5; 61191

Rosbach Germany)

Fischer-Tropsch waxes

Ceraflour 940 (Taurus-Cera; Danzigweg 23; 7418 EN Deventer. The Netherlands)

Micronized polytetrafluoroethylene waxes

Ceraflour 980 (Byk-Cera; Danzigweg 23; 7418 EN Deventer, The Netherlands)

Ultraglide UV 701 (Krahn-Chemie GmbH; Grimm 10; 20457 Hamburg,

Germany)

Shamrock SST-3 (Shamrock; Heesterveldweg 21; 3700 Tongeren, Belgium)

Micronized polytetrafluoroethylene / polyethylene waxes

Ceraflour 968 (Byk-Cera; Danzigweg 23; 7418 EN Deventer, The Netherlands)

Ceraflour 996 (Byk-Cera; Danzigweg23; 7418 EN Deventer, The Netherlands)

Amide waxes

Ceraflour 994 (Byk-Cera; Danzigweg 23; 7418 EN Deventer The Netherlands)

Deurex MA 7020 ((DEUREX Micro-Technologies GmbH; Dr. Bergius

Strasse 18/20 06729 Tróglitz, Germany)

Carnauba waxes

Ceraflour 4RC 1165 (Byk-Cera; Danzigweg 23; 7418 EN Deventer,

Netherlands)

Everglide UV 636 25% (Krahn-Chemie GmbH; Grimm 10; 20457

Hamburg, Germany)

Montana wax

Deurex MM 8120 ((DEUREX Micro-Technologies GmbH; Dr. Bergius

Strasse 18/20 06729 Tróglitz, Germany)

Deurex MM 8200 (DEUREX Micro-Technologies GmbH; Dr. Bergius

Strasse 18/20 06729 Tróglitz, Germany)

Micronized ester waxes with groups reactive to UV radiation

Ceridust TP5091 (Clariant GmbH; Am Unisyspark 1; 65843 Sulzbach, Germany)

Paraffin waxes

Polysperse HP (Eastman Chemical Deutschland GmbH; CharlottenstraBe 61; 51149 Cologne, Germany)

Polypropylene waxes

Crayvallack WN-1135 (Lubrizol Coating Additives GmbH; Max-Planck StraBe 6; 27721 Ritterhude, Germany)

Spray micronized polyolefin waxes

Printwax ΜΧΡ 9510 D ((DEUREX Micro-Technologies GmbH; Dr. Bergius Strasse 18/20 06729 Tróglitz, Germany)

Printwax MX 9815 (DEUREX Micro-Technologies GmbH; Dr. Bergius Strasse 18/20 06729 Tróglitz, Germany)

The preferred percentage of wax in the glass printing ink or varnish is 0.1% to 10% by weight, a more preferred range is 0.5% to 5.0% by weight, and the most preferred range is 1.0%. % to 3% by weight.

[0019] The preferred method of incorporating the wax into the glass ink or varnish is to use a stirrer, dissolver, or a three-roll or bead mill; the above list does not preclude other approaches.

[0020] The glass printing ink or varnish according to the invention comprises, as a resin component, a bisphenol A based epoxy resin; a preferred range of molecular weight for the resin is in the range (weight average) of

700 to 1500. Resins of this type are commercially available. Particularly preferred examples of such resins are R0tapox - Harz 0194 from Bakelite AG; ARALDITE® from Vantico AG, K-401.1.32, CH-4002 Basel and Epikote 1055 from Brenntag.

The resin according to the invention is dissolved in the monomer which is curable by the action of UV radiation, for example due to the presence of polymerizable acrylic groups. Of the monomers mentioned above, mono-, diacrylates or higher equivalents thereof are preferable; for example, these may be monomers such as isobornyl acrylate; 2-phenylethyl acrylate; 2- (2-ethoxyethoxy) ethyl acrylate (EOEOEA); Hexanediol 1,6 acrylate (HDDA); dipropylene glycol acrylate (DPGDA); neopentylglycol diacrylate; pentaerythritohexyl diacrylate (DPHA); glycerin triacrylate ethoxylated with propylene oxide (GPTA); tripropylene glycol acrylate (TPGDA); dipentaerythritol pentyl [glycol] acrylate (DiPEPA); pentaerythritol [glycol] triacrylate (PETIA); ethoxylated trimethylpropionic acrylate (TMPEOTA); [glycol] triacrylate (DPHA); [glycol] diacrylate tricyclodecanedimethanol (TCDDMDA) and hydroxypropyl methacrylate. A particularly preferred solution is the use of 1,6 hexanediol diacrylate.

[0022] The preferred concentration of epoxy resin in the monomer is, based on the [mass] of the mixture, from 10 to 90% by weight, more preferably from 30% to 70% and most preferably 50% resin.

[0023] The concentration of epoxy in the glass printing ink or varnish according to the invention is generally in the range from 1% to 90% by dry weight, based on the total weight of the ink or varnish. Preferred epoxy content in paint or varnish is in the range from 5% to 20%; a particularly preferred range is from 11% to 14% by weight, based on dry weight.

[0024] The ink or varnish for printing the glass according to the invention may also contain, as an option, a resin with free functional groups such as amino, hydroxyl, epoxy, acid groups, acid anhydride groups and / or acrylic groups. The use of melamine-acrylic resins (for example NANOCRYL XP 21/0793 with silicon dioxide from Hansa Chemie GmbH, Charlotteburgerstrasse 9, D-21502 Geesthacht, Germany) or the multifunctional melamine acrylic resins ACTILANE 890 from Akzo Nobel Resins BV, Sales Office is particularly advantageous. Germany, Industńestrasse 8, PO Box 100265, D-46422 Emmerich,

Germany) or Viaktin VTE 5967 resin from Cytec Surface Specialties, Anderlechtstr. 33, B-1620 Drogenbos, Belgium), acid-modified polyester acrylate (e.g. GENOMER * 7154 from Rahn, Dórflistrasse 120, ZOńch, Switzerland; Ebecryl 770 from Cytec Surface Specialities). Further resins useful in these combinations are certain polyester resins (e.g. Roskydal UA XP 2416 from Bayer; Ebecryl 524 from Cytec Surface Specialties) and epoxyacrylates (e.g. Inchemrez UV 93IB50 by In Chem Corp. Ρ.Ο.Βοχ 69, CH 1170 Aubonne, Switzerland).

[0025] The content of the resins with the functional groups described above in the glass printing ink or varnish may vary over a wide range. In general, the content of these resins is in the range of 5 to 90% by weight, based on dry weight, based on the total weight of the paint or varnish. The preferred range for the resins is 5 to 40% by weight; a range of from 10 to 30% by weight is particularly preferred. The role of resins with functional groups is to reduce brittleness, and thus improve the flexibility of paint or varnish, in order to increase the adhesion and resistance to scratching of the finished prints.

[0026] The ink or varnish for printing the glass according to the invention may additionally contain - if necessary - additional resins to further improve their properties. These resins can be selected from a wide range of products, including for example methyl methacrylate copolymers (e.g. Paraloid B-48N, Paraloid B60, Paraloid B-82 from Rohm & Haas Deutschland GmbH, In der Krone 4, D-60439, Frankfurt (Main); Neocryl B-810 from Neoresins, Lurgiallee, D-60439, Frankfurt (Main); Ethyl methacrylate [polymers] (e.g. Paraloid B-72 by Rohm & Haas); butyl methacrylate copolymers (e.g. Degalan LP 65/12, Degalan LP 68/04 from Rohm & Haas GmbH & Co. KG, Kirschenallee, D-64239 Darmstadt); liquid epoxy resins (e.g. Polypox E 064 from LIPPC GmbH, R0tapox-Harz 0164 from Bakelite AG, Araldite GY 250 from Vantico); unsaturated polyester resins (e.g. Haftharz LTH from Degussa Chemiepark Marl, Paul-BaumannStr. 1, D-45764 Marl); saturated polyester resins (Dynapol L912, Dynapol L952 from Degussa).

[0027] Additional resins of this type may be used, for example, in amounts of from 1 to 50% by weight based on the dry weight and based on the total weight of the glass printing ink or varnish; a preferred range is from 3 to 10% by weight.

[0028] The ink or varnish for printing the glass according to the invention comprises at least one photoinitiator; two or even, if possible, three photoinitiators are usually used to initiate the surface and deep curing (cross-linking) of the glass printing ink by the action of UV (ultraviolet) radiation. Photoinitiators can be selected from a range of photoinitiators commonly used in UV curable printing inks; for example, products such as hydroxycyclohexylacetophenone (Irgacure® 184 from Ciba Spezialitaten-Chemie AG; Klybeckstrasse 141, Postfach, CH-4002 Basel, Switzerland), 2-methyl-1- [methylthiophenyl) -2-morpholinopropane] -1-one (Irgacure® 907 from Ciba), 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) butane -1-one (Irgacure® 369 from Ciba), phosphine bis (2,4,6 trimethylbenzoyl) phenyl oxide (Irgacure® 819 from Ciba), 2-hydroxy-2-methyl-1-phenyl-1-propanone (Darocur ® 1173 by Ciba), isopropylthioxanthone (ΙΤΧ by Lambson), 2-chlorothioxanthone (CTX from Lambson), phosphine-2,4,6 trimethylbenzyldiphenyl oxide (TPO from BASF) and methyl benzyl formate (MBF from Lambson). The total content of photoinitiators is generally from 1 to 12% by weight, based on the total weight of the glass printing ink or varnish; a preferred range is from 3 to 7 wt%.

[0029] The paints / varnishes may additionally contain co-initiators such as amines (e.g. MDEA from BASF Aktiengesellschaft, Carl Bosch-Strasse 38,

D-67056 Ludwigshafen, Germany), or amine modified acrylates (e.g. Ebecryl P115, Ebecryl 7100 from Cytec Surface Specialties, Actilane 705, Actilane 755 from Akzo Nobel Resins BV, Sales Office Germany, Industriestrasse 8, PO Box 100265, D-46422 Emmerich, Laromer PO 94F, Laromer LR 8869 from BASF, Craynor 503, Craynor 550 from Sartomer, Immeuble le Diamant B, F-92970 Paris, la Defense; Photomer 4775F from Cognis), at concentrations of 1 to 5% by weight based on the total weight of the glass printing ink or varnish.

The glass printing inks according to the invention may contain any pigments, for example titanium dioxide, zinc sulfide, pigment carbon black, azodiaryl yellow, isoindole yellow, diaryl orange, quinoacridine magenta, copper phthalocyanine blue, red diketopyrrole, copper phthalocyanine green, dioxazine violet and dicetometal oxide. A relatively comprehensive presentation of further pigments that may be used herein can be found in Color Index International, Fourth Edition Online, 2001, published by the Society of Dyers and Colourists [W. Kingdom] together with the American Association of Textile Chemists and Colorists. Pigments that give the desired effects, such as mica coated with metal oxides or metallic pigments, can also be used.

[0031] The color pigments are used in amounts ranging from 2 to 50% by weight of the total weight of the glass printing ink, depending on the type of pigment and the hiding power expected; preferred amounts are in the range 10-35 wt%. White pigments are usually used in amounts of from 20 to 50% by weight, preferably amounts in the range of 30-40% by weight.

[0032] Generally, the glass printing varnish is pigment-free.

[0033] A further reactive diluent is added to the ink or glass printing varnish - independently of the UV-curable monomer in which the bisphenol A epoxy resin is dissolved. The reactive diluents, also UV curable, may be the UV curable monomers mentioned above in connection with the polyester solutions. Further compounds with a single ethylenically unsaturated moiety can also be used, such as, for example, n-vinylpyrrolidone (NVP) and vinylcaprolactam. The amounts of additional reactive diluents used are - generally - from 0 to 60% by weight, more preferably from 3% to 20%, and most preferably from 4 to 8% by weight, e.g. 6 to 7% by weight, based on total weight of glass printing ink.

The glass printing inks and varnishes according to the invention may contain one or more fillers; the properties of these substances are not very critical. Fillers may be selected from products commonly used in printing inks such as, for example, China clay, barium sulfate (in the precipitated form known as blanc fixe), calcium carbonate, zinc sulfide, silica, talc, aluminum silicate, aluminum hydroxide and / or silicic acid; the above listing is not exclusive [other substances]. The amounts of fillers used are generally in the range of 0 to 50% by weight, preferably 10 to 30% by weight, e.g. 20% by weight, based on the total weight of the glass printing ink or varnish.

[0035] The glass printing inks and varnishes according to the invention may also contain thickeners selected from products normally used for this purpose in paints / varnishes; this group includes - without excluding other products - eg pyrogenic silicic acid, layered silicates and castor oil derivatives. The amounts of thickeners used are - generally from 0 to 10% by weight, a range of 1% to 5% is more preferred, and a range of 1.5 to 3% by weight is most preferred, based on the total weight of the glass printing ink and depending on type of pigment, or depending on the type of glass printing varnish.

[0036] The glass printing inks and varnishes according to the invention contain antifoams and / or paint / varnish flow-aid.

The amounts of these agents used are - generally - from 0.5 to 2.5% by weight, more preferably from 0.5% to 1.5% and most preferably a content of al% by weight, based on the total weight of the paint or glass printing varnish. The antifoams can be selected from the group of modified acrylates or modified acrylate copolymers, but silicone-based products are preferred. The paint / varnish flow improvers may, for example, be from the group of polyacrylates and polysiloxanes.

[0037] Preferred as stabilizers are Genorad 16 from Rahn and Fluorstab UV2 from Kromachem, Park Industrial Center, Tolpits Lane, Watford, Hertfordshire WD1 8SP, UK.

[0038] The glass printing inks and varnishes may be provided with - immediately prior to the printing process - adhesion promoters [paint / varnish on glass]; the amounts used are from 1 to 20% by weight, more preferably a range from 1% to 10%, based on the total weight of the glass printing ink or varnish. Possible here are isocyanate adhesion promoters, for example aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate (TMHDI), cycloaliphatic polyisocyanates such as isophorodiodiisocyanate (IPDI) or hydrogen diisocyanate diisocyanate (IPDI) or hydrogen dihydrogen diisocyanate (IPDI). Aromatic polyisocyanates such as toluyl diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI) or diphenylmethane diisocyanate (MDI) are also possible. Commercially available products are e.g. Desmodur E41 or Desmodur N 75 from Bayer. Further products that can be used for this purpose are polymides such as polyethyleneimide or polycarboimides.

Preferred paint / varnish adhesion agents, however, are silanes such as alkylsilanes, vinylsilanes, methacryloxy silanes, epoxy silanes, aminosilanes, urea silane derivatives, chlorosilanes and isocyanosilanes. The use of aminosilanes such as gammaaminopropyl-triethoxysilane, gamma-aminopropyl-trimethoxy-silane, n-beta (aminoethyl) -ga (77 / 7α-aminopropyl-trimethoxy-silane), bis (gamma-trimethoxysilylpropyl) amine has shown particularly advantageous results; N-phenyl-gamma-aminopropyl-trimethoxysilane or N-beta (aminoethyl-gamma-aminopropyl-methyl-dimethoxy-silane. Also possible is isocyanatosilanes such as gamma-isocyanato-propyl-triethoxysilane.

[0039] The group of articles that can be printed in accordance with the invention includes glass, ceramics, ceramic tiles and the like, in which at least the surface is glass. Accordingly, the invention also relates to the use of an ink or varnish for printing glass, ceramics, ceramic tiles and the like, the surface of which at least has the nature of glass.

[0040] The articles mentioned above may have any form or shape, such as containers, plates, ceramic tiles, figurines, etc. In a preferred embodiment, the article is glass used in packaging (beverage bottles, cosmetic packaging) or industrial glass.

[0041] The expression glass, as used in the description of the invention, should be understood to denote glass, ceramics, ceramic tiles and similar glass-like materials.

[0042] Glass is typically pretreated prior to printing; it is a flame treatment, the pre-treatment can be omitted for the appropriate type of glass.

[0043] The UVitro method from Isimat, Ringelbacherstrasse 38-40, D-73479 Ellwangen (Germany) is considered to be a particularly efficient pretreatment process. This process is fully described in German patent DE 100 19 926 A1 and in United States patent AP US 6 513 435 B2. The first step in this process is to treat the glass surface with an oxidizing flame (ie with excess oxygen), usually within 3-4 seconds; the second step is to treat with a silicizing flame (i.e. flame into which a silicon compound is introduced, e.g. tetramethoxysilane), also for 3-4 seconds.

[0044] The printing process is carried out [immediately] after the pretreatment. As the printing method, it is possible to use, for example, silk-screen, pad printing, offset printing, flexographic or gravure printing; screen printing is preferred.

[0045] The curing [cross-linking] of the glass printing ink / varnish provides for exposure [of the printout] to UV [ultraviolet] radiation in the wavelength range of 200 to 400 nm; the exposure time is determined in the range ensuring full curing [of the applied paint / varnish]. Alternatively, the glass printing ink / varnish can be cured, also without photoinitiators, by electron beam [radiation],

[0046] It is possible to print the full range of colors [colors]. In the screen printing process, it is preferable to use a template fabric with [thread density] 100-40 to 180-27; preferably between 140-34, applied paint thickness from 5 to 10 µm. Standard mercury, medium-pressure lamps are used for hardening the printouts, depending on the printing machine and the nature of the print; alternatives are lamps doped with gallium or iron. The radiant energy of such lamps is in the range of 80 to 400 W / cm, the preferred range is 120 to 200 W / cm; lamp radiation is generally focused [on print], Exposure time depends on printing speed; this is due to the coupling of the printing process with the exposure process. The printing speed of the bottles is typically between 40 and 120 prints / minute.

[0047] After the UV-curing, an annealing step may be applied - if desired - for example at a temperature of 130 to 200 ° C, more preferably in the range of 130 to 170 ° C, preferably at a temperature of 160 ° C, for example from 20 to 40 minutes, optimally in 20 minutes.

[0048] The glass printing ink or varnish has good interlayer adhesion and may be [decorated] with hot stamping foil.

[0049] The following examples explain the [essence] of the invention.

EXAMPLES

Example 1

[0050] The glass bottles were pretreated by UVitro (arcogas FTS 401 flame treatment device (Arcogas GmbH, Rotweg 25, D-71297 Mannheim, Germany):

Burner: MB3 100 degree degree treatment time flame pre-treatment (air 300 l / min; propane butane 11 l / min)

Uvitro; air 200 l / min; propane / butane 7.5 l / min

3-4 seconds each step

[0051] The bottles were then cooled to 35 ° - 40 ° C.

[0052] The glass printing ink with the composition given below was prepared by dispersing [ingredients] using a three-roll mill or a bead mill.

<td>Ingredient</td><td>trade name</td><td>Amount (wt%)</td>

<td>1,6-hexanediol acrylate</td><td>LAROMER * HDDA</td><td> 6,6</td>

<td>Polysiloxane based antifoam</td><td>Tym Airex 920 *** Tego Rad 2500 **** 0.5</td><td> 0,5 0,5</td>

<td>Photoinitiator 1</td><td>DAROCURE 1173 / 1173C</td><td> 1</td>

<td>Photoinitiator 2</td><td>Lucirin TPO</td><td> 4,9</td>

<td>Kooinitiator</td><td>EBECRYL7100 *****</td><td> 4</td>

<td>Pigment</td><td>TiO₂</td><td> 27,5</td>

<td>Micronized wax based on poly-tetrafluoroethylene</td><td>Lanco TF 1778 ******</td><td> 3</td>

<td>50% bisphenol A epoxy resin solution in Laromer HDDA</td><td>ARALDITE 7072 50% in Laromer HDDA 52</td><td> 52</td>

<td></td><td></td><td> 100</td>

<td colspan="3">* Laromer is a product of BA SF * ** Tego Airex 920 antifoam from Tego Chemie Service GmbH, GoldschmidtstraBe 11. D-45127 Essen * *** Tego Rad 2500 is a paint flow aid from the Tego company * **** Eb_ecry | 7ioo with an amine modified acrylate from Surface Specialty UCB * ***** | __anco yf i77g j_esf with a PTFE-based wax from Noveon</td>

The mixture with the composition given in the table above was mixed with 4% by weight of a diaminosilane (e.g. N-beta (aminoethyl] -gammaaminopropyl-trimethoxy-silane, bis (gamma-trimethoxy-silylpropyl) amine) or with 10.% by weight of gamma-silane. isocyanato-propyl-triethoxy-silane After mixing, the ink was screen-printed on an ISIMAT 1000 P printer using a 120-34 template to print, at 60 prints / min, pre-treated glass bottles.

[0054] The printing process was correct.

[0055] The UV curing was performed in a UV dryer with a radiation density of 600 mJ / cm³ (as measured by a UV MAP meter from EIT, Inc., 108 Carpenter Drive, Sterling, VA20164, USA).

[0056] A paint firing was not performed.

[0057] A very good scratch resistance and a good adhesion of the undamaged color film were obtained. The scratch resistance was determined using an Erichsen model 318 hardness rod, with a value of not less than 5 N; in most cases the obtained value was not less than 7 N.

Example 2

[0058]

<td>Ingredient</td><td>trade name</td><td>Amount (wt%)</td>

<td>1,6-hexanediol acrylate</td><td>LAROMER * HDDA</td><td> 6</td>

<td>Stabilizer</td><td>FLORSTAB UV-2 **</td><td> 1</td>

<td>Polysiloxane based antifoam</td><td>Tym Airex 920 *** Tego Rad 2500 **** 0.5</td><td> 0,5 0,5</td>

<td>Photoinitiator 1</td><td>DAROCURE 1173 / 1173C</td><td> 1</td>

<td>Photoinitiator 2</td><td>Lucirin TPO</td><td> 4,9</td>

<td>Kooinitiator</td><td>EBECRYL7100 *****</td><td> 4</td>

<td>Pigment</td><td>TiO₂</td><td> 27,5</td>

<td>Micronized wax based on polytetrafluoroethylene</td><td>Lanco TF 1778 ******</td><td> 3,1</td>

<td>50% bisphenol A epoxy resin solution in Laromer HDDA</td><td>ARALDITE 7072 50% in Laromer HDDA 52</td><td> 23</td>

<td>Silicon nano-dioxide in melamine acrylate</td><td>NANOCRYLXP 21/0793</td><td> 10</td>

<td>35% MMA copolymer solution in Laromer HDDA</td><td>PARALOID B60 35% in HDDA</td><td> 18,5</td>

<td></td><td></td><td> 100</td>

<td colspan="3">(Indexes * *** **** and ***** see example 1) ** FLORSTAB UV-2 is a stabilizer from Kromachem</td>

The mixture with the composition given in the table above was mixed with 4% by weight of a diaminosilane (e.g. N-beta (aminoethyl] -gammaaminopropyl-trimethoxy-silane, bis (gamma-trimethoxy-silylpropyl) amine) or with 10.% by weight of gamma - isocyanato-propyl-triethoxy-silane After mixing, the ink was screen-printed on an ISIMAT 1000 P printer using a 120-34 template to print, at 60 prints / min, pre-treated glass bottles.

[0060] The printing process was correct.

[0061] The UV curing was performed in a UV dryer with a radiation density of 600 mJ / cm² (see example 1).

[0062] A paint firing was not performed.

[0063] A very good scratch resistance and good adhesion of the undamaged color film was achieved. The scratch resistance was determined using an Erichsen model 318 hardness test rod with a value not less than 5 N; in most cases the obtained value was not less than 7 N.

The dishwashing resistance test was carried out with over 1,000 cycles in a Winterhalter industrial dishwasher and over 150 cycles in a Miele domestic dishwasher; in both tests, no changes in the quality and appearance of the bottle imprint were found.

[0065] Bottles with imprints were filled with fruit juice at the bottling line without damaging the color film [of the print].

Example 3 (reference)

[0066] The plate glass, which had not been pretreated, was printed - without the use of an adhesion promoter - with a printing ink of the following composition, by silk-screen printing technology using the template 140-34.

<td>Ingredient</td><td>trade name</td><td>Amount (wt%)</td>

<td>1,6-hexanediol acrylate</td><td>LAROMER * HDDA</td><td> 2</td>

<td>Stabilizer</td><td>FLORSTAB UV-2 **</td><td> 1</td>

<td>Polysiloxane based antifoam</td><td>Tym Airex 920 *** Tego Rad 2500 **** 0.5</td><td> 0,5 0,5</td>

<td>Photoinitiator 1</td><td>DAROCURE 1173 / 1173C</td><td> 1</td>

<td>Photoinitiator 2</td><td>Lucirin TPO</td><td> 4</td>

<td>Kooinitiator</td><td>EBECRYL7100 *****</td><td> 2,5</td>

<td>Pigment</td><td>TiO₂</td><td> 27,5</td>

<td>Micronized wax based on polytetrafluoroethylene</td><td>Lanco TF 1778 ******</td><td> 3,1</td>

<td>Acid modified polyester acrylate</td><td>GENOMER 7154</td><td> 57,9</td>

<td></td><td></td><td> 100</td>

<td colspan="3">(Indexes see examples 1 and 2)</td>

[0067] The UV curing was carried out using diameter mercury lamps with a power density of 2 x 120 W / cm.², at a speed of about 5 m / min. [0068] Good netting resistance was achieved without firing. The scratch resistance is very good, both for the undamaged film [without cuts] and for the damaged film [after cuts]. The resistance was determined using an Eńchsen model 318 hardness rod, with a value not less than 5 N.

Example 4

[0069] The untreated plate glass was printed with a printing ink having the composition given below - without the use of an adhesion promoter - by silk-screen printing with the template 140-34.

<td>Ingredient</td><td>trade name</td><td>Amount (wt%)</td>

<td>1,6-hexanediol acrylate</td><td>LAROMER * HDDA</td><td> 6,6</td>

<td>Polysiloxane based antifoam</td><td>Tym Airex 920 *** Tego Rad 2500 **** 0.5</td><td> 0,5 0,5</td>

<td>Photoinitiator 1</td><td>DAROCURE 1173 / 1173C</td><td> 1</td>

<td>Photoinitiator 2</td><td>Lucirin TPO</td><td> 4,9</td>

<td>Kooinitiator</td><td>EBECRYL7100 *****</td><td> 4</td>

<td>Pigment</td><td>TiO₂</td><td> 27,5</td>

<td>Micronized wax based on polytetrafluoroethylene</td><td>Lanco TF 1778 ******</td><td> 3</td>

<td>50% bisphenol A epoxy resin solution in Laromer HDDA</td><td>ARALDITE 7072 50% in Laromer HDDA</td><td> 23,5</td>

<td>Acid modified polyester acrylate</td><td>GENOMER 7154</td><td> 28,5</td>

<td></td><td></td><td> 100</td>

<td colspan="3">(Indexes * *** **** and ***** see examples 1 and 2)</td>

[0070] The UV curing was carried out using medium pressure mercury lamps with a power density of 2 x 120 W / cm², at a speed of about 5 m / min. [0071] Good netting resistance was obtained without firing. The scratch resistance is very good for both the undamaged film [without cuts] and the damaged film [after cuts]. The resistance was determined using an Erichsen hardness rod, model 318, obtaining a value not less than 5 N.

[0072] In another test, the paint was postfired for 20 minutes at 160 ° C.

[0073] Following this process [after firing], the glass printing ink scored GT 0 in the EN ISO 2409 mesh scoring test carried out immediately after the dew test (condensed water).

[0074] The glass printing inks as defined in examples 1 and 2 make it possible to obtain, in a two-component printing, without the need for baking, good or very good scratch resistance, and also good adhesion [glass ink]; the paints are also resistant to water. The glass printing inks defined in examples 3 and 4 allow one-component printing, without burnout, to obtain good scratch resistance as well as good adhesion [ink to glass]. The post-firing of the paint of example 4 additionally allows a good water resistance of the formed color film. This possibility means a simplification of the printing process as compared to the state of the art.