Ceramic toner for electro-photographic printing
View Patent ↗A ceramic toner which is transferable to a high-temperature resistant glass, glass ceramic or ceramic substrate by electrophotographic printing and which can be fired in a subsequent temperature process, containing color pigment particles in addition to special glass flow particles. According to this invention, the ceramic toner has a thermoplastic synthetic matrix which melts in a homogeneous manner on the substrate within a temperature range of 100° C.–400° C. and which, within the temperature range of 300° C.–500° C., vaporizes in an almost residue-free manner and/or decomposes in order to obtain a toner which can be transferred especially in a direct printing mode and which has almost no synthetic matrix residue after firing.
1. A ceramic toner which can be transferred by an electro-photographic printing to a glass, a glass-ceramic or a ceramic substrate having a high temperature resistance and which can be baked on during a subsequent temperature process, and which contains color pigment particles, in addition to glass flux particles, wherein the ceramic toner has:
>30 to 80 weight-%, of a special glass frit,
and 0 to <20 weight-% of inorganic pigments, and 20 to 60 weight-% of a plastic matrix, the ceramic toner comprising:
a glass flux having a composition composed from a list of compositions 1–12, the compositions 1–12 being:
Glass
Glass
Glass
Composition 1
Composition 2
Composition 3
Gew.- %
Gew.- %
Gew.- %
Li 2 O
0 . . . 6.0
0 . . . 5.0
2.0 . . . 4.0
Na 2 O
0 . . . 5.0
0 . . . 5.0
5.0 . . . 9.5
K 2 O
0 . . . 2.0
0 . . . 2.5
1.5 . . . 4.0
MgO
0 . . . 4.0
0 . . . 3.0
0 . . . 0.5
CaO
0 . . . 4.0
0 . . . 4.0
0.0 . . . 0.1
SrO
0 . . . 4.0
0 . . . 4.0
BaO
0 . . . 1.0
0 . . . 4.0
ZnO
0 . . . 4.0
0 . . . 4.0
B 2 O 3
13.0 . . . 23.0
15.0 . . . 27.0
13.0 . . . 20.0
Al 2 O 3
3.0 . . . 10.0
7.0 . . . 20.0
5.0 . . . 10.0
Bi 2 O 3
0 . . . 2.5
0 . . . 2.5
La 2 O 3
0 . . . 3
0 . . . 0.9
SiO 2
50.0 . . . 65.0
43.0 . . . 58.0
41.0 . . . 59.0
TiO 2
0 . . . 4.0
0 . . . 3.0
ZrO 2
0 . . . 4.0
0 . . . 4.0
2.0 . . . 5.5
SnO 2
0 . . . 2.0
0 . . . 2.0
P 2 O 5
0 . . . 1.5
0 . . . 2.5
Sb 2 O 3
0 . . . 2.0
0 . . . 2.5
F
0 . . . 4.0
0 . . . 3.0
0 . . . 4.0
SO 3
Fe 2 O 3
Y 2 O 3
CeO 2
PbO
Further
Rare
Earth
Metal
Oxides
CdO
T g (° C.)
400 . . . 650
450 . . . 650
E w (° C.)
580 . . . 830
600 . . . 850
V A
840 . . . 1100
880 . . . 1150
(° C.)
α 20–700° C.
α 20–700° C.
(10− 6 K) < 2.0
(10− 6 K)
α 20–300° C.
3.5–7.0
(10− 6 K)
3.5–8.0
Glass
Glass
Glass
Composition 4
Composition 5
Composition 6
Gew.- %
Gew.- %
Gew.- %
Li 2 O
0 . . . 2.0
0 . . . 3.0
0.1 . . . 1.5
Na 2 O
0 . . . 5.0
0 . . . 2.5
7.0 . . . 13.0
K 2 O
0 . . . 5.0
0 . . . 8.0
0 . . . 1.5
MgO
0 . . . 0.5
0 . . . 8.5
CaO
0 . . . 1.0
0.5 . . . 4.0
SrO
BaO
0 . . . 28.0
2.0 . . . 4.0
ZnO
0 . . . 10.0
1.0 . . . 15.0
B 2 O 3
1.0 . . . 10.0
4.0 . . . 26.0
17.0 . . . 22.0
Al 2 O 3
0.5 . . . 10.0
2.5 . . . 18.0
4.0 . . . 8.0
Bi 2 O 3
La 2 O 3
SiO 2
20.0 . . . 45.0
40.0 . . . 62.0
55.0 . . . 65.0
TiO 2
0 . . . 0.5
0 . . . 2.0
ZrO 2
0 . . . 1.0
0 . . . 2.5
SnO 2
0 . . . 3.0
P 2 O 5
Sb 2 O 3
F
0 . . . 3.5
SO 3
Fe 2 O 3
Y 2 O 3
CeO 2
0 . . . 10.0
PbO
20.0 . . . 60.0
Further
Rare
Earth
Metal
Oxides
CdO
0 . . . 1.5
T g (° C.)
E w (° C.)
V A
(° C.)
Glass
Glass
Glass
Composition 7
Composition 8
Composition 9
Gew.- %
Gew.- %
Gew.- %
Li 2 O
2.0 . . . 5.0
0 . . . 7.0
2.0 . . . 5.0
Na 2 O
1.0 . . . 2.5
2.0 . . . 8.0
5.0 . . . 10.0
K 2 O
1.0 . . . 3.0
0 . . . 5.0
MgO
0 . . . 1.5
0 . . . 2.0
CaO
0 . . . 3.0
1.0 . . . 7.0
SrO
0 . . . 3.0
0 . . . 2.0
BaO
0 . . . 4.0
ZnO
0 . . . 1.0
2.0 . . . 10.0
7.0 . . . 13.0
B 2 O 3
10.0 . . . 20.0
20.0 . . . 32.0
14.0 . . . 26.0
Al 2 O 3
5.0 . . . 10.0
1.0 . . . 15.0
4.0 . . . 16.0
Bi 2 O 3
0 . . . 10.0
La 2 O 3
SiO 2
60.0 . . . 70.0
24.0 . . . 40.0
30.0 . . . 50.0
TiO 2
0 . . . 2.0
0 . . . 4.0
ZrO 2
0 . . . 2.0
0 . . . 3.0
SnO 2
P 2 O 5
Sb 2 O 3
F
0 . . . 3.0
SO 3
Fe 2 O 3
Y 2 O 3
CeO 2
PbO
Further
Rare
Earth
Metal
Oxides
CdO
T g (° C.)
E w (° C.)
V A
(° C.)
Glass
Glass
Glass
Composition
Composition
Composition
10
11
12
Gew.- %
Gew.- %
Gew.- %
Li 2 O
2.5 . . . 4
0.9 . . . 7.4
Na 2 O
3.0 . . . 10.0
2.7 . . . 7.4
1.6 . . . 8.2
K 2 O
2.9 . . . 8.0
0.5 . . . 6.1
MgO
0 . . . 2.0
0 . . . 0.5
0 . . . 4.0
CaO
2.0 . . . 5.0
0 . . . 0.5
0.4 . . . 4.5
SrO
0 . . . 4.0
BaO
0.5 . . . 3.0
0 . . . 0.5
ZnO
6.0 . . . 13.0
0 . . . 1.5
0.4 . . . 3.8
B 2 O 3
20.0 . . . 40.0
14.5 . . . 18.5
11.0 . . . 36.4
Al 2 O 3
3.0 . . . 5.0
2.0 . . . 14.6
Bi 2 O 3
La 2 O 3
0 . . . 3.0
SiO 2
45.0 . . . 70.0
53.0 . . . 70.0
28.0 . . . 69.0
TiO 2
0 . . . 20
0 . . . 0.5
0 . . . 6.0
ZrO 2
5.5 . . . 13.5
1.3 . . . 20.6
SnO 2
P 2 O 5
0 . . . 0.5
0 . . . 10.0
Sb 2 O 3
0 . . . 0.5
F
0 . . . 4.0
0 . . . 8.0
SO 3
0 . . . 0.5
Fe 2 O 3
0 . . . 0.5
Y 2 O 3
0 . . . 0.5
0 . . . 1.0
CeO 2
0 . . . 0.5
PbO
0 . . . 2.0
0 . . . 1.5
Further
0 . . . 1.0
Rare
Earth
Metal
Oxides
CdO
T g (° C.)
470 . . . 610
E w (° C.)
V A
(° C.)
α 20–300° C.
(10− 6 K)
5.0 . . . 8.0.
2. The ceramic toner in accordance with claim 1 , wherein the ceramic toner has a thermoplastic matrix which melts homogeneously onto a substrate in a temperature range between 100° C. and 400° C., and in a second temperature range starting at 300° C. to 500° C. at least one of evaporates and is burned off with almost no residue.
3. The ceramic toner in accordance with claim 2 , wherein the thermoplastic matrix has toner resins on an acrylate basis, including styrene acrylate and polymethylmethacrylate.
4. The ceramic toner in accordance with claim 3 , wherein the thermoplastic matrix contains polymers, including at least one of polyvinyl alcohol, polyoximethylene, styrene copolymers, polyvinylidene fluoride, polyvinylbutyral, polyester including unsaturated and saturated and mixtures thereof, polycarbonate, polyvinyl pyrrolidone, vinyl imidazole copolymers and polyether.
5. The ceramic toner in accordance with claim 4 , wherein as an additive the ceramic toner contains at least one of charge-control materials and oxidation agents, and auxiliary flow materials, including aerosils.
6. The ceramic toner in accordance with claim 5 , wherein the ceramic toner is coated with the auxiliary flow materials.
7. The ceramic toner in accordance with claim 6 , wherein the additives and the auxiliary materials are added in amounts respectively between 0 and 1.0 weight-%.
8. The ceramic toner in accordance with claim 7 , wherein a particle size of the glass flux and the pigments lies in the range of 0.5 to 25 μm (D5O vol.).
9. The ceramic toner in accordance with claim 8 , wherein toner particles have an irregular shape and are partially encased by the plastic matrix.
10. The ceramic toner in accordance with claim 9 , wherein the ceramic toner contains at least one of peroxides and azo compounds for decomposition of polymers at a decomposition temperature >150° C.
11. The ceramic toner in accordance with claim 10 , wherein the ceramic toner is applied to a transfer medium.
12. The ceramic toner in accordance with claim 11 , wherein the transfer medium is a carrier, including one of a paper and a foil coated with gum arabic.
13. The ceramic toner in accordance with claim 1 , wherein the plastic matrix has toner resins on an acrylate basis, including styrene acrylate and polymethylmethacrylate.
14. The ceramic toner in accordance with claim 1 , wherein the plastic matrix contains polymers, including at least one of polyvinyl alcohol, polyoximethylene, styrene copolymers, polyvinylidene fluoride, polyvinylbutyral, polyester including unsaturated and saturated and mixtures thereof, polycarbonate, polyvinyl pyrrolidone, vinyl imidazole copolymers and polyether.
15. The ceramic toner in accordance with claim 1 , wherein as an additive the ceramic toner contains at least one of charge-control materials and oxidation agents, and auxiliary flow materials, including aerosils.
16. The ceramic toner in accordance with claim 1 , wherein the ceramic toner is coated with auxiliary flow materials.
17. The ceramic toner in accordance with claim 1 , wherein additives and auxiliary materials are added in amounts respectively between 0 and 1.0 weight-%.
18. The ceramic toner in accordance with claim 6 , wherein a particle size of the glass flux and the pigments lies in the range of 0.5 to 25 μm (D5O vol.).
19. The ceramic toner in accordance with claim 1 , wherein toner particles have an irregular shape and are partially encased by the plastic matrix.
20. The ceramic toner in accordance with claim 1 , wherein the ceramic toner contains at least one of peroxides and azo compounds for decomposition of polymers at a decomposition temperature >150° C.
21. The ceramic toner in accordance with claim 1 , wherein the ceramic toner is applied to a transfer medium.
22. The ceramic toner in accordance with claim 21 , wherein the transfer medium is a carrier, including one of a paper and a foil coated with gum arabic.
23. A ceramic toner which can be transferred by an electro-photographic printing to a glass, a glass-ceramic or a ceramic substrate having a high temperature resistance and which can be baked on during a subsequent temperature process, and which contains color pigment particles, in addition to glass flux particles, wherein the ceramic toner has:
45 to 60 weight-%, of a special glass frit,
and 5 to >20 weight-% of inorganic pigments, >30 to 50 weight-% of a plastic matrix, the ceramic toner comprising:
a glass flux having a composition composed from a list of compositions 1–12, the compositions 1–12 being:
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Glass
Composition
Composition
Composition
Composition
Composition
Composition
Composition
Composition
Composition
Composition
Composition
Composition
1
2
3
4
5
6
7
8
9
10
11
12
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Gew.-%
Li 2 O
0 . . . 6.0
0 . . . 5.0
2.0 . . . 4.0
0 . . . 2.0
0 . . . 3.0
0.1 . . . 1.5
2.0 . . . 5.0
0 . . . 7.0
2.0 . . . 5.0
2.5 . . . 4
0.9 . . . 7.4
Na 2 O
0 . . . 5.0
0 . . . 5.0
5.0 . . . 9.5
0 . . . 5.0
0 . . . 2.5
7.0 . . . 13.0
1.0 . . . 2.5
2.0 . . . 8.0
5.0 . . . 10.0
3.0 . . . 10.0
2.7 . . . 7.4
1.6 . . . 8.2
K 2 O
0 . . . 2.0
0 . . . 2.5
1.5 . . . 4.0
0 . . . 5.0
0 . . . 8.0
0 . . . 1.5
1.0 . . . 3.0
0 . . . 5.0
2.9 . . . 8.0
0.5 . . . 6.1
MgO
0 . . . 4.0
0 . . . 3.0
0 . . . 0.5
0 . . . 0.5
0 . . . 8.5
0 . . . 1.5
0 . . . 2.0
0 . . . 2.0
0 . . . 0.5
0 . . . 4.0
CaO
0 . . . 4.0
0 . . . 4.0
0.0 . . . 0.1
0 . . . 1.0
0.5 . . . 4.0
0 . . . 3.0
1.0 . . . 7.0
2.0 . . . 5.0
0 . . . 0.5
0.4 . . . 4.5
SrO
0 . . . 4.0
0 . . . 4.0
0 . . . 3.0
0 . . . 2.0
0 . . . 4.0
BaO
0 . . . 1.0
0 . . . 4.0
0 . . . 28.0
2.0 . . . 4.0
0 . . . 4.0
0.5 . . . 3.0
0 . . . 0.5
ZnO
0 . . . 4.0
0 . . . 4.0
0 . . . 10.0
1.0 . . . 15.0
0 . . . 1.0
2.0 . . . 10.0
7.0 . . . 13.0
6.0 . . . 13.0
0 . . . 1.5
0.4 . . . 3.8
B 2 O 3
13.0 . . . 23.0
15.0 . . . 27.0
13.0 . . . 20.0
1.0 . . . 10.0
4.0 . . . 26.0
17.0 . . . 22.0
10.0 . . . 20.0
20.0 . . . 32.0
14.0 . . . 26.0
20.0 . . . 40.0
14.5 . . . 18.5
11.0 . . . 36.4
Al 2 O 3
3.0 . . . 10.0
7.0 . . . 20.0
5.0 . . . 10.0
0.5 . . . 10.0
2.5 . . . 18.0
4.0 . . . 8.0
5.0 . . . 10.0
1.0 . . . 15.0
4.0 . . . 16.0
3.0 . . . 5.0
2.0 . . . 14.6
Bi 2 O 3
0 . . . 2.5
0 . . . 2.5
0 . . . 10.0
La 2 O 3
0 . . . 3
0 . . . 0.9
0 . . . 3.0
SiO 2
50.0 . . . 65.0
43.0 . . . 58.0
41.0 . . . 59.0
20.0 . . . 45.0
40.0 . . . 62.0
55.0 . . . 65.0
60.0 . . . 70.0
24.0 . . . 40.0
30.0 . . . 50.0
45.0 . . . 70.0
53.0 . . . 70.0
28.0 . . . 69.0
TiO 2
0 . . . 4.0
0 . . . 3.0
0 . . . 0.5
0 . . . 2.0
0 . . . 2.0
0 . . . 4.0
0 . . . 20
0 . . . 0.5
0 . . . 6.0
ZrO 2
0 . . . 4.0
0 . . . 4.0
2.0 . . . 5.5
0 . . . 1.0
0 . . . 2.5
0 . . . 2.0
0 . . . 3.0
5.5 . . . 13.5
1.3 . . . 20.6
SnO 2
0 . . . 2.0
0 . . . 2.0
0 . . . 3.0
P 2 O 5
0 . . . 1.5
0 . . . 2.5
0 . . . 0.5
0 . . . 10.0
Sb 2 O 3
0 . . . 2.0
0 . . . 2.5
0 . . . 0.5
F
0 . . . 4.0
0 . . . 3.0
0 . . . 4.0
0 . . . 3.5
0 . . . 3.0
0 . . . 4.0
0 . . . 8.0
SO 3
0 . . . 0.5
Fe 2 O 3
0 . . . 0.5
Y 2 O 3
0 . . . 0.5
0 . . . 1.0
CeO 2
0 . . . 10.0
0 . . . 0.5
PbO
20.0 . . . 60.0
0 . . . 2.0
0 . . . 1.5
Further
0 . . . 1.0
Rare
Earth
Metal
Oxides
CdO
0 . . . 1.5
T g (*C)
400 . . . 650
450 . . . 650
470 . . . 610
E w (*C)
580 . . . 830
600 . . . 850
V A (*C)
840 . . . 1100
880 . . . 1150
α 20–700° C.
α 20–700° C.
α 20–300° C.
(10 − 6 K) < 2.0
(10 − 6 K)
(10 − 6 K)
α 20–300° C.
3.5–7.0
5.0 . . . 8.0
(10 − 6 K) 3.5–
8.0
24. The ceramic toner in accordance with claim 1 , wherein additives and auxiliary materials are added in amounts respectively between 0.2 and 0.5 weight-%.
25. The ceramic toner in accordance with claim 6 , wherein a particle size of the glass flux and the pigments lies in the range of between 1 and 10 μm.