Cycloolefin polymer container with a scratch resistant and anti-static coating
Cycloolefin polymer (COP) containers, including vials or syringes, having a scratch-resistant and anti-static coating on the external wall results in a reduction or prevention of static charge on the articles. The combination of an anti-scratch and anti-static coating results in the reduction of the attraction of charged particles to the container, leading to decreased particulate contamination while providing scratch resistance.
1. A container comprising:
a wall made of a cycloolefin polymer having an internal surface enclosing a lumen and an contact surface, and
an external anti-static and anti-scratch coating on the contact surface,
wherein the external anti-static and anti-scratch coating is optionally an inorganic-organic hybrid polymer coating comprising an anti-scratch agent and an anti-static agent.
2. A container as in claim 1 where the external anti-static and anti-scratch coating is sufficiently electrically conductive to substantially discharge a static charge.
3. A container as in claim 1 , where the static load is less than 0.5 kV, preferably a static load of essentially 0 kV, most preferably a static load of 0 kV, after being subjected to an electrostatic charge and held for 60 minutes.
4. The container of claim 1 , wherein the cycloolefin polymer consists essentially of COP resin.
5. The container of claim 1 , wherein the container is an injection blow molded vial, syringe, blood tube, screw-closure container, or ampoule.
6. The container of claim 1 wherein the container is filled with a pharmaceutical preparation and closed with a closure.
7. The container of claim 1 where the anti-static additive is selected from the group of materials consisting of ethoxylated alkylamines, ethoxylated alkyl amides, glycerol stearates, fatty acid esters, esters or ethers of polyols, sodium alkyl sulfonates, cationic polyacrylates, quaternary ammonium compounds, alkylphosphates, and a combination of two or more of these.
8. The container of claim 1 where the anti-static additive is blended into the inorganic-organic hybrid polymer at about 0.1 to 3 weight percent.
9. The container of claim 1 which first undergoes an atmospheric pressure corona air-type plasma pre-treatment before the external anti-static and anti-scratch coating is applied.
10. The container of claim 1 where the external anti-static and anti-scratch coating is cured or hardened by UV or IR radiation or heat treatment at from 60 to 150° C.
11. The container of claim 1 , wherein the external anti-static and anti-scratch coating is an inorganic-organic hybrid polymer comprising the reaction product of:
(i) a hydrolytic condensate, prepared from a metal compound and a silane of the formula R m SiX 4-m , wherein R is a crosslinkable organic radical; X is a hydrolyzable and condensable group; m is 1, 2, or 3; and
(ii) a prepolymer that is crosslinked with the radical R of the silane of the hydrolytic condensate.
12. The container of claim 11 , wherein R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl and alkynylaryl.
13. The container of claim 11 , wherein each R is independently an unsubstituted radical or a radical substituted by one or more substituents selected from the group consisting of halogen, unsubstituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, isocyano, cyanato, isocyanato, hydroxy, alkoxy, alkoxycarbonyl, sulfonic acid, phosphoric acid, acrylic, acryloxy, methacrylic, methacryloxy, glycidyl, glycidyloxy, epoxy and vinyl groups.
14. The container of claim 11 , wherein m is 2 or 3, and each R is independently an alkoxy, aryloxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, hydroxy, halogen, hydrogen, or substituted or unsubstituted amino group.
15. The container of claim 11 , wherein the prepolymer carries a reactive group, wherein the reactive group is an unsubstituted radical or a radical substituted by one or more substituents selected from the group consisting of halogen, unsubstituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, isocyano, cyanato, isocyanato, hydroxy, alkoxy, alkoxycarbonyl, sulfonic acid, phosphoric acid, acrylic, acryloxy, methacrylic, methacryloxy, glycidyl, glycidyloxy, epoxy and vinyl groups.
16. The container of claim 11 , wherein the prepolymer carries a reactive group, and wherein the reactive group is the same as R of the silane of the hydrolytic condensate.
17. The container of claim 11 , wherein the R is interrupted one or more times by one or more of an O, S, N or NH group, “interrupted” meaning that the radical R optionally has the structure R a —Y—R b — in which R a —R b — meets the definition of R in the silane formula and Y is a linking or interrupting group, here —O—, —S—, —N<, and/or —NH—.
18. The container of claim 11 , wherein the R has a terminal OH, SH or NH 2 group.
19. The container of claim 11 , wherein the inorganic-organic hybrid polymer comprises one or more non-crosslinkable organofunctional silanes.
20. The container of claim 19 , wherein the non-crosslinkable organofunctional silane has the formula R′ m SiX 4-m , wherein R′ is a non-crosslinkable organic radical; X is a hydrolyzable and condensable group; and m is 1, 2, or 3.
21. The container of claim 20 , wherein R′ is selected from the group consisting of alkyl, cycloalkyl, aryl, arylalkyl and alkylaryl.
22. The container of claim 20 , wherein and each R′ is independently an unsubstituted radical or a radical substituted by one or more substituents selected from the group consisting of halogen atoms, unsubstituted amide, aldehyde, keto, alkylcarbonyl, carboxy, cyano, alkoxy, alkoxycarbonyl groups.
23. The container of claim 20 , wherein m is 1 or 2, and each X is independently an alkoxy, aryloxy, alkylcarbonyl, alkoxycarbonyl, hydroxy, halogen, hydrogen or substituted or unsubstituted amino group.
24. The container of claim 20 , wherein R′ is interrupted one or more times by one or more of an O, S, N, or NH group.
25. The container of claim 20 , wherein R′ has a terminal OH, SH or NH 2 group.
26. The container of claim 11 , wherein the external anti-static and anti-scratch coating further comprises a low-volatility oxide.
27. The container of claim 26 , wherein the low-volatility oxide comprises an element from
(i) main group Ia, IIa, IIIa, IVa or Va; or
(ii) sub-group IIb, IIIb, Vb, VIIb, VIIb or VIIIb, wherein the element is not aluminum.
28. The container of claim 26 , wherein the low-volatility oxide comprises an element from
a. main group Ia, IIa, IIIa, IVa and Va; or
b. sub-group IIb, IIIb, Vb, VIb, VIIb and VIIIb, wherein the element is not aluminum.
29. The container of claim 11 , wherein the prepolymer carries a reactive group, wherein the reactive group is alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl and alkynylaryl.
30. The container of claim 29 , wherein the reactive group is interrupted one or more times by one or more of an O, S, N or NH group.
31. The container of claim 29 , wherein the reactive group has a terminal OH, SH or NH 2 group.
32. The container of claim 1 , wherein the external anti-static and anti-scratch coating is an inorganic-organic hybrid polymer in which:
(i) the silane has an epoxy group or epoxy groups, and the prepolymer is epoxy resin; or
(ii) the silane has a vinyl radical and the prepolymer has crosslinkable double bonds; or
(iii) the silane has polymerizable double bonds and the prepolymer has cross-linkable double bonds; or
(iv) the silane has a mercapto group and the prepolymer has crosslinkable double bonds; or
(v) the silane has a isocyanate group and the prepolymer is a polyol; or
(vi) the silane has a hydroxyl group and the prepolymer is isocyanate; or
(vii) the silane has an amino group and the prepolymer is epoxy resin.
33. The container of claim 32 , wherein the hydrolytic condensate is a silane with an acrylic group and the prepolymer is acrylate.
34. The container of claim 1 where the internal surface comprises a PECVD tie coating or layer, a barrier coating or layer, and a pH protective coating or layer or one of the individual coatings or layers.
35. The container in claim 34 where the tie coating or layer is SiO x C y H z or SiN x C y H z in which x is from about 0.5 to about 2.4 as measured by X-ray photoelectron spectroscopy (XPS), y is from about 0.6 to about 3 as measured by XPS, and z is from about 2 to about 9 as measured by Rutherford backscattering spectrometry (RBS) or hydrogen forward scattering (HFS).
36. The container in claim 34 where the tie coating or layer has an outer surface facing the internal surface and the tie coating or layer has an interior surface.