Container having improved ease of discharge product residue, and method for the production thereof
In order to improve the emptying of residual contents from containers, such as pharmaceutical packaging, the invention provides corresponding substrates with a hydrophobic coating. Provided for this purpose is a composite material which comprises a substrate and a coating deposited on it, which forms at least a part of the surface of the coated substrate, with the coating having a compound containing the elements C, O, and H, with further elements, apart from Si, C, H, having a content of less than 10 at %, preferably less than 5 at %, characterized in that this compound has a composition SiO x C y H z , in which x is at most 1.2.
1. A composite material comprising:
a substrate; and
a hydrophobic coating deposited on at least a part of the surface of the substrate, the coating having a compound comprising Si, C, O, and H along with further elements, the further elements having a content of less than 10 at %, said compound having a composition SiO x C y H z , in which
x lies in the range of 0.6 to 0.9,
y lies in the range of 1.2 to 3.3, and
z lies in the range of 0.0 to 6.0.
2. The composite material according to claim 1 , wherein the coating is fluorine-free.
3. The composite material according to claim 1 , wherein the coating comprises a polymerizate.
4. The composite material according to claim 1 , further comprising an inorganic layer is embedded between the coating and the substrate.
5. The composite material according to claim 1 , wherein the substrate comprises a hollow body and the coating is deposited on an inner side of the hollow body.
6. The composite material according to claim 5 , wherein the coating improves the emptying of residual contents of the hollow body in comparison to the uncoated hollow body.
7. The composite material according to claim 1 , wherein the substrate comprises a glass hollow body or a polymer hollow body.
8. The composite material according to claim 1 , wherein the substrate is a pharmaceutical packaging selected from the group consisting of a vial, a syringe, and a carpule.
9. The composite material according to claim 1 , wherein the coating has a contact angle for water of greater than or equal to 90°, or an outflow or draining angle of less than 90°, for a water droplet having a volume of 26 μL.
10. The composite material according to claim 9 , wherein, when a sterilization test selected from the group consisting of an autoclave test at 121° C., 30 minutes, a depyrogenation test at 300° C., 20 minutes, gamma sterilization test with 25 kGy, an electron-beam sterilization test with 25 kGy, and an ethylene oxide sterilization test was conducted, the contact angle is changed by less than 4° or the outflow or draining angle is changed by less than 30°.
11. The composite material according to claim 10 , wherein the contact angle is changed by less than 1°.
12. The composite material according to claim 10 , wherein the outflow or draining angle is changed by less than 10°.
13. The composite material according to claim 9 , wherein, after a storage test of the composite material with an aqueous liquid in contact with the coated substrate, after a storage time of 2 weeks at 60° C., the contact angle is changed by less than 4, or the outflow or draining angle is changed by less than 30°, or the coating still exhibits the outflow or draining angle of less than 90°, or the coating has the contact angle of greater than or equal to 90°.
14. The composite material according to claim 1 , wherein the content of the further elements is less than 5 at %.
15. The composite material according to claim 1 , wherein x lies in the range of 0.7 to 0.8.
16. The composite material according to claim 1 , wherein y lies in the range of 1.5 to 2.5.
17. The composite material according to claim 1 , wherein the coating comprises a cross-linked polymerizate.
18. The composite material according to claim 1 , wherein the substrate is a component for a pharmaceutical packaging selected from the group consisting of a needle and a stopper.
19. The composite material according to claim 1 , wherein the coating has a contact angle for water of greater than or equal to 100° or an outflow or draining angle of less than 50°, for a water droplet having a volume of 26 μL.
20. The composite material according to claim 1 , wherein the coating an outflow or draining angle of less than 30° for a water droplet having a volume of 26 μL.
21. A method for producing a composite material, comprising:
depositing a coating on a substrate by plasma-assisted chemical vapor deposition in which, for deposition, a process gas having a silicon-containing gas component, as well as carbon and oxygen as further gas components, is admitted into a reaction chamber, which is bounded at least in part by the substrate, and
igniting a plasma in the reaction chamber by pulsed irradiation of electromagnetic energy, resulting in the formation of reaction products in the plasma, which are deposited as a layer on the substrate, wherein the pulsed irradiation of electromagnetic energy comprises a pulsed plasma having a pulse duration in the range of 0.1 μs to 100 μs.
22. The method according to claim 21 , wherein said layer has a composition of the form SiO x C y H z , wherein x lies in the range of 0.6 to 0.9, y lies in the range of 1.2 to 3.3, and z lies in the range of 0.0 to 6.0, and wherein said composition comprises other elements, apart from Si, O, C, and H, that have a content of less than 10 at %.
23. The method according to claim 22 , wherein igniting said plasma comprises using a plasma process with an average energy input per mass ε M in a range of 10 −1 J/kg to 10 9 J/kg with the average energy input per mass ε M being defined by
ɛ
M
=
W
_
∑
1
i
F
i
·
M
~
i
,
with
the
mean
power
W
_
=
Δ
t
pd
Δ
t
pd
+
Δ
t
pp
·
W
p
,
where W represents the mean microwave power, F i the flow of the component i of the process gas mixture having the components O 2 , precursor, and, if appropriate, a carrier gas, {tilde over (M)} i the molecular weight of the component i, Δt pd the pulse duration, Δt pp the pulse pause, and W p the pulse power.
24. The method according to claim 21 , comprising continually passing a constant pulse pause without energy input between the pulses, the pulse pause being greater than the pulse duration.
25. The method according to claim 24 , further comprising a ratio of pulse pauses to pulse durations is at least 5:1.
26. The method according to claim 21 , wherein the coating by plasma deposition is produced with a process gas comprising an organosilicon starting compound.
27. The method according to claim 26 , further comprising using a process gas composition, in which a fraction of the organosilicon starting compound is greater than 10% for the deposition of the layer.
28. The method according to claim 21 , wherein the pulsed irradiation of electromagnetic energy comprises a pulsed plasma having a pulse duration in the range of 0.5 μs to 100 μs.
29. The method according to claim 21 , wherein the pulsed irradiation of electromagnetic energy comprises a pulsed plasma having a pulse duration in the range of 1 μs to 50 μs.
30. A method for producing a composite material, comprising:
depositing a coating on a substrate by plasma-assisted chemical vapor deposition in which, for deposition, a process gas having a silicon-containing gas component, as well as carbon and oxygen as further gas components, is admitted into a reaction chamber, which is bounded at least in part by the substrate;
igniting a plasma in the reaction chamber by pulsed irradiation of electromagnetic energy, resulting in the formation of reaction products in the plasma, which are deposited as a layer on the substrate, wherein the pulsed irradiation of electromagnetic energy comprises a pulsed plasma having a pulse duration in the range of 0.1 μs to 500 μs; and
prior to the deposition of the layer, heating the substrate to a temperature between 40° C. and 300° C.
31. The method according to claim 30 , wherein heating the substrate comprises heating with a plasma process by using a gas selected from the group consisting of a noble gas, an inert gas, an oxygen-containing gas, and a nitrogen-containing gas.
32. The method according to claim 30 , wherein heating the substrate comprises heating the substrate outside of the coating reactor with an infrared radiator.
33. The method according to claim 32 , wherein the pulsed irradiation of electromagnetic energy during the deposition of the coating, averaged over time, is less by a factor of at least 10 than the light emission of the infrared radiator, averaged over time.
34. The method according to claim 30 , further comprising a gas exchange time between the heating and the coating process of less than 60 seconds.
35. The method according to claim 30 , wherein the mean power used for the heating process is higher than for the coating process.
36. The method according to claim 30 , wherein the temperature is between 60° C. and 200° C.