Printing Substance For Coating Glass Surfaces

Abstract

The present invention relates to a printing substance for coating glass surfaces by way of an ink jet printing method, the printing substance comprising A) at least one monomer having at least one C—C double bond; B) at least one cationically curable monomer comprising epoxy groups; C) at least one cationically curable monomer comprising oxetane groups; D) at least one adhesion agent. In addition, the present invention describes a method for producing the printing substance and the use thereof.

Claims

1-22. (canceled)

23. A printing substance for coating surfaces, comprising A) at least one monomer having at least one C—C double bond; B) at least one cationically curable monomer comprising epoxy groups; C) at least one cationically curable monomer comprising oxetane groups; D) at least one adhesion agent.

24. The printing substance according to claim 23, wherein the monomer having at least one C—C double bond comprises a (meth)acrylate.

25. The printing substance according to claim 23, wherein the monomer having at least one C—C double bond comprises at least one vinyl ether monomer.

26. The printing substance according to claim 23, wherein the monomer having at least one C—C double bond represents a mixture comprising at least one (meth)acrylate and at least one vinyl ether monomer.

27. The printing substance according to claim 23, wherein the monomer having at least one C—C bond comprises at least one crosslinking monomer.

28. The printing substance according to claim 23, wherein the adhesion agent comprises at least one silane compound.

29. The printing substance according to claim 23, wherein the printing substance comprises at least 5% by weight of adhesion agent.

30. The printing substance according to claim 23, wherein the cationically curable monomer comprising epoxy groups contains at least one monomer having two epoxy groups.

31. The printing substance according to claim 23, wherein the cationically curable monomer comprising oxetane groups comprises at least one monomer having at least two oxetane groups.

32. The printing substance according to claim 23, wherein the molar ratio of monomer comprising epoxy groups to monomer comprising oxetane groups is in the range from 40:1 to 1:15.

33. The printing substance according to claim 23, wherein the molar ratio of monomer having at least one C—C double bond to cationically curable monomer having an epoxy and/or oxetane group is in the range from 20:1 to 1:5.

34. The printing substance according to claim 23, wherein the proportion of water in the printing substance is at most 4% by weight.

35. The printing substance according to claim 23, wherein the proportion of organic solvent in the printing substance is at most 4% by weight.

36. The printing substance according to claim 23, wherein the adhesion agent comprises a curable group.

37. The printing substance according to claim 23, wherein the printing substance comprises at least 60% by weight of components A), B), C), and D).

38. The printing substance according to claim 23, wherein the printing substance further comprises at least one initiator.

39. The printing substance according to claim 37, wherein the at least one initiator comprises at least one photoinitiator

40. A method for producing the printing substance according to claim 23, comprising mixing components A), B), C), and D).

41. An object at least partially coated with the printing substance according to claim 23, wherein the object comprises at least one surface comprising at least one of glass, ceramic, metal, wood, or plastic.

42. The object of claim 41, wherein the at least one surface comprises glass, and wherein the printing substance is applied to said glass by inkjet printing.

Description

EMBODIMENT EXAMPLES 1 AND 2 AND COMPARISON EXAMPLES 1 AND 2

[0143] The printing substances presented in the following table are prepared by mixing,

[0144] Preliminary treatment of the plate glass (air side and also bath side): cleaning first with ethanol, then with ethyl acetate.

[0145] Application with doctor blade: 8 μm spiral doctor blade from the company BYK

[0146] Wet film thickness per layer 8-12 μm. Measured with the wet film thickness measuring device Erichsen model: 234 R/I

[0147] Lamp: Company Höhnle UV Technology (LED-Powerline PLD), water-cooled, wavelength: 385 nm

[0148] The dose is 380-420 mJ/cm.sup.2, measured with PUK (company Kühnast Strahlungstechnik) UV integrator.

TABLE-US-00001 Comparison Comparison Example 1 Example 1 Example 2 Example 2 Color White White Cyan Cyan Components % by weight % by weight % by weight % by weight Cycloaliphatic epoxide 6.87 7.77 8.80 9.96 Aliphatic epoxide, 6.38 7.19 5.28 5.99 glycidyl ether having two epoxy groups Aliphatic epoxide, 7.56 8.34 6.65 7.53 glycidyl ether having three epoxy groups Oxetane having two 6.87 7.78 8.81 10.01 oxetane groups Vinyl ether having one 3.93 4.47 5.28 6.02 vinyl group Vinyl ether having two 14.48 15.56 18.59 21.06 vinyl groups Cyclic acrylate 14.74 16.65 19.56 22.34 (non-crosslinking) Polyvinylbutyral 1.96 3.37 Cationic initiator; 5.89 6.66 3.67 4.14 diaryliodonium salt Sensitizer; UV radical 1.97 2.22 1.22 1.39 initiator Thioxanthone Silicone-based leveling agent 0.39 0.46 0.39 0.44 Rheology additive 1.0 1.15 Epoxysilanes 9.84 9.79 White pigment dispersed 20.07 21.76 in acrylates Cyan pigment dispersed in 10.00 7.75 acrylates Total 100.00 100.00 100.00 100.00

[0149] The coatings obtained on a glass plate are tested by the cross cut test and the double rub ethanol test, wherein the results presented in the following table are achieved:

TABLE-US-00002 Com- Com- Com- Ex- Ex- parison parison Ex- parison ample ample Example Example ample Example 1 1 1 1 2 2 Side of the Air Bath Air Bath Air Air plate glass side side side side side side Cross cut 0 0 2-3 5 0-1 3 after curing Double rub >50 >50 30 22 >50 25 ethanol 24 h after curing

[0150] The examples show that, by the addition of adhesion agents, surprising increases in the solvent resistance can be achieved.

EMBODIMENT EXAMPLES 3 AND 4 AND COMPARISON EXAMPLE 3

[0151] The printing substances presented in the following table are prepared by mixing, applied by way of inkjet printing onto a glass substrate (plate glass) and cured as presented above:

TABLE-US-00003 Comparison Example 3 Example 4 Example 3 Color White White White Components % by weight % by weight % by weight Cycloaliphatic epoxide 9.50 7.03 9.35 Aliphatic epoxide, 5.50 6.58 8.75 glycidyl ether having two epoxy groups Aliphatic epoxide, 7.23 7.72 10.26 glycidyl ether having three epoxy groups Oxetane having two 9.49 7.03 0.00 oxetane groups Vinyl ether having one 5.51 4.08 4.08 vinyl group Vinyl ether having two 20.37 14.72 14.72 vinyl groups Cyclic acrylate 15.36 15.36 (non-crosslinking) Cationic initiator; 5.99 5.70 5.70 diaryliodonium salt Sensitizer, UV-radical 2.00 1.90 1.90 initiator thioxanthone Silicone-based leveling agent 0.41 0.38 0.38 Epoxy silanes; 10.02 9.5 9.5 White pigment dispersed 20.00 20.00 in acrylates White pigment dispersed in 23.97 cycloaliphatic epoxide and vinyl ether Total 100.00 100.00 100.00

[0152] The coatings obtained on a glass plate were tested by the cross cut test and the double rub ethanol test, wherein the results presented in the following table are achieved:

TABLE-US-00004 Ex- Ex- Ex- Ex- Com- Com- ample ample ample ample parison parison 3 3 4 4 Example 3 Example 3 Side of the Air Bath Air Bath Air Bath plate glass side side side side side side Cross cut 2-3 4 0-1 2-3 3-4 5 after curing Cross cut 2-3 5 0 0-1 5 5 after 30 minutes in water at 70° C. Double rub 50 40 ethanol 24 h after curing

[0153] The examples and the comparison example show that, by the use of cationically curable monomers having oxetane groups, substantially higher adhesion strengths can be achieved. Furthermore, printing substances having acrylates exhibit better adhesion strengths than printing substances without acrylates.

EMBODIMENT EXAMPLES 5 TO 9

[0154] The printing substances presented in the following table are prepared by mixing, applied by way of inkjet printing onto a glass substrate (plate glass), and cured as presented above:

TABLE-US-00005 Example 5 Example 6 Example 7 Example 8 Example 9 Ratio of epoxy to oxetane groups 1:0.33 1:1.79 1:0.6 1:0.14 1:2.13 with respect to % by weight Components % by weight % by weight % by weight % by weight % by weight Cycloaliphatic epoxide 6.23 1.33 4.67 7.79 0.85 Aliphatic epoxide, 5.83 1.25 4.37 7.29 0.80 glycidyl ether having two epoxy groups Aliphatic epoxide, 6.84 1.47 5.13 8.55 0.93 glycidyl ether having three epoxy groups Oxetane having two 9.46 24.31 14.19 4.73 25.78 oxetane groups Vinyl ether having one 4.08 4.08 4.08 4.08 4.08 vinyl group Vinyl ether having two 14.72 14.72 14.72 14.72 14.72 vinyl groups Cyclic acrylate 15.36 15.36 15.36 15.36 15.36 (non-crosslinking) Cationic initiator; 5.7 5.7 5.7 5.7 5.7 diaryliodonium salt Sensitizer; UV-radical 1.9 1.9 1.9 1.9 1.9 initiator thioxanthone Silicone-based leveling agent 0.38 0.38 0.38 0.38 0.38 Epoxysilanes; 9.5 9.5 9.5 9.5 9.5 White pigment dispersed 20.00 20.00 20.00 20.00 20.00 in acrylates Total 100.00 100.00 100.00 100.00 100.00

[0155] The coatings obtained on a glass plate are tested by the cross cut test, wherein the results presented in the following table are achieved:

TABLE-US-00006 Example 5 Example 6 Example 7 Example 8 Example 9 Side of the plate glass Bath side Bath side Bath side Bath side Bath side Cross cut after curing 5 5 5 5 5 Cross cut 24 hours after 0 1.5 0 0.5 0.5 curing Cross cut after 3 days in 2 5 4 3 5 cold water (7° C.)

EMBODIMENT EXAMPLES 10 TO 15

[0156] The printing substances presented in the following table are prepared by mixing, applied by way of inkjet printing onto a glass substrate (plate glass), and cured as presented above:

TABLE-US-00007 Example 10 Example 11 Example 12 Ratio of epoxy to oxetane groups 1:0.29 1:0.33 1:1.81 with respect to % by weight Components % by weight % by weight % by weight Cycloaliphatic epoxide 9.0 8.55 1.83 Aliphatic epoxide, 5.4 5.13 1.10 glycidyl ether having two epoxy groups Aliphatic epoxide, 6.8 6.45 1.38 glycidyl ether having three epoxy groups Oxetane having two 9.0 10.07 25.89 oxetane groups Vinyl ether having one 5.4 5.4 5.4 vinyl group Vinyl ether having two 19.0 19.0 19.0 vinyl groups Cyclic acrylate 20.0 20.0 20.0 (non-crosslinking) Polyvinylbuteral 3.0 3.0 3.0 Cationic initiator; 3.8 3.8 3.8 diaryliodonium salt Sensitizer; UV-radial 1.3 1.3 1.3 initiator thioxanthone Silicone-based leveling agent 0.4 0.4 0.4 Epoxysilanes; 10.0 10.0 10.0 Cyan pigment dispersed in 7.0 7.0 7.0 acrylates Total 100.00 100.00 100.00 Example 13 Example 14 Example 15 Ratio of epoxy to oxetane groups 1:0.60 1:0.14 1:2.15 with respect to % by weight Components % by weight % by weight % by weight Cycloaliphatic epoxide 6.41 10.69 1.17 Aliphatic epoxide, 3.85 6.41 0.70 glycidyl ether having two epoxy groups Aliphatic epoxide, 4.84 8.07 0.88 glycidyl ether having three epoxy groups Oxetane having two 15.1 5.03 27.45 oxetane groups Vinyl ether having one 5.4 5.4 5.4 vinyl group Vinyl ether having two 19.0 19.0 19.0 vinyl groups Cyclic acrylate 20.0 20.0 020.0 (non-crosslinking) Polyvinylbutyral 3.0 3.0 3.0 Cationic initiator; 3.8 3.8 3.8 diaryliodonium salt Sensitizer; UV-radial 1.3 1.3 1.3 initiator thioxanthone Silicone-based leveling agent 0.4 0.4 0.4 Epoxysilanes; 10.0 10.0 10.0 Cyan pigment dispersed in 7.0 7.0 7.0 acrylates Total 100.00 100.00 100.00

[0157] The coatings obtained on a glass plate are tested by the cross cut test and the thumb rotation test, wherein the results presented in the following table are achieved:

TABLE-US-00008 Ex- Ex- Ex- Ex- Ex- Ex- ample ample ample ample ample ample 10 11 12 13 14 15 Side of the Bath Bath Bath Bath Bath Bath plate glass side side side side side side Cross cut 3 3 5 4 3.5 5 after curing Cross cut 0 0 0 0 0 0 24 hours after curing Cross cut 2 3 5 5 0 5 after 3 days in cold water (7° C.) Thumb 1 1 0 0 2 0 rotation test

EMBODIMENT EXAMPLES 16 AND 17

[0158] The printing substances presented in the following table are prepared by mixing, applied by way of inkjet printing onto a glass substrate (plate glass), and cured:

TABLE-US-00009 Example 16 Example 17 Components % by weight % by weight Cycloaliphatic epoxide 7.24 7.12 Aliphatic epoxide, glycidyl ether 6.73 6.61 having two epoxy groups Aliphatic epoxide, glycidyl ether 7.97 7.83 having three epoxy groups Oxetane having two oxetane groups 7.24 7.12 Vinyl ether having one vinyl group 4.14 4.07 Vinyl ether having two vinyl groups 14.90 14.65 Cyclic acrylate (non-crosslinking) 15.52 15.26 Cationic initiator; diaryliodonium salt 6.21 6.10 Sensitizer; UV-radial initiator thioxanthone 2.07 2.04 Silicone-based leveling agent 0.41 0.41 Rheology additive 0.66 0.71 Epoxysilanes 10.34 10.17 White pigment dispersed in acrylates 16.57 17.91 Total 100.00 100.00

[0159] The coating composition presented in Example 16 was cured at a relative air humidity above approximately 60% (room temperature), wherein it was cured over a relatively long time period, without an appropriate degree of curing being achieved. The substantially identical composition according to Example 17 was cured at a relative air humidity of approximately 32% (room temperature), wherein a satisfactory curing was achieved in a short time period. Due to the unsatisfactory curing, no tests were carried out with the coating obtained according to Example 16.

TABLE-US-00010 Example 17 Example 17 Side of the plate glass Air side Bath side Cross cut after curing 0 1 Cross cut after 30 minutes in water at 70° C. 0 0 Double rub ethanol 24 h after curing >100 >100

[0160] The examples show that the problems presented above are solved by the present invention, in particular the adhesion and the stability of a decoration obtained by the printing substance according to the invention can be surprisingly clearly increased, without other properties of the printing substance or of the decoration being disadvantageously influenced thereby.