Photoinitiator systems with anthracene-based electron donors for curing cationically polymerizable resins
View Patent ↗The invention features a photopolymerizable composition that comprises a cationically polymerizable resin, and a photoinitiator system comprising an iodonium salt, a visible light sensitizer, and one or more anthracene-based compounds as electron donors. Electron donor combinations used in the invention include multiple substituted anthracene compounds or a combination of at least one substituted anthracene compound with unsubstituted anthracene.
1. A photoinitiator system comprising:
(a) an iodonium salt;
(b) a visible light sensitizer selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof;
(c) a first anthracene that has a light absorption maximum less than about 400 nanometers; and
(d) a second anthracene having the following structure
wherein each of R 1 to R 10 is independently selected from H, or alkyl, phenyl or alkoxy groups, provided that at least one of R 1 to R 10 is not H.
2. A photopolymerizable composition comprising:
(a) a cationically polymerizable resin; and
(b) a photoinitiator system for the cationically polymerizable resin, the photoinitiator system comprising:
(i) an iodonium salt;
(ii) a visible light sensitizer selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof;
(iii) a first anthracene that has a light absorption maximum less than about 400 nanometers; and
(iv) a second anthracene having the following structure
wherein each of R 1 to R 10 is independently selected from H, alkyl, phenyl or alkoxy groups, provided that at least one of R 1 to R 10 is not H.
3. The photopolymerizable composition according to claim 2 , wherein the cationically polymerizable resin is selected from the group consisting of epoxy, oxetane, vinyl ether and spiro-orthocarbonate resins, and combinations thereof.
4. The photopolymerizable composition according to claim 3 , wherein the cationically polymerizable resin comprises an epoxy resin.
5. The photopolymerizable composition according to claim 4 , wherein the cationically polymerizable resin comprises a silicon-containing epoxy resin.
6. The photopolymerizable composition according to claim 3 , wherein the cationically polymerizable resin comprises a blend of a silicon-containing epoxy resin and an epoxy resin that does not contain silicon.
7. The photopolymerizable composition according to claim 2 , wherein the iodonium salt is selected from the group consisting of diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, 4-octyloxyphenyl phenyliodonium hexafluoroantimonate, 4-(2-hydroxytetradecyloxyphenyl)phenyliodonium hexafluoroantimonate, 4-(1-methylethyl)phenyl 4-methylphenyliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.
8. The photopolymerizable composition according to claim 2 , wherein the visible light sensitizer is an alpha-diketone.
9. The photopolymerizable composition according to claim 8 , wherein said alpha-diketone is camphorquinone.
10. The photopolymerizable composition according to claim 2 , wherein the first anthracene is unsubstituted anthracene.
11. The photopolymerizable composition according to claim 2 , wherein the second anthracene is selected from 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 1,4-dimethoxyanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, and 9,10-diphenyl-2,6-di-tert-butylanthracene.
12. The photopolymerizable composition according to claim 2 , wherein the second anthracene is 2-ethyl-9,10-dimethoxyanthracene.
13. The photopolymerizable composition according to claim 2 , wherein the second anthracene is 9,10-dimethylanthracene.
14. The photopolymerizable composition according to claim 2 , wherein the second anthracene is 9,10-diethoxyanthracene.
15. The photopolymerizable composition according to claim 2 , wherein the second anthracene is 1,4-dimethoxyanthracene.
16. The photopolymerizable composition according to claim 2 , wherein the second anthracene is 9-methylanthracene.
17. The photopolymerizable composition according to claim 2 , wherein the second anthracene is 2-ethylanthracene.
18. The photopolymerizable composition according to claim 2 , wherein at least one of R 1 to R 10 is tert-butyl.
19. The photopolymerizable composition according to claim 2 , wherein the second anthracene is 2,6-di-tert-butylanthracene.
20. The photopolymerizable composition according to claim 2 , further comprising a free-radically polymerizable resin.
21. The photopolymerizable composition according to claim 2 , further comprising a hydroxyl-containing material.
22. The photopolymerizable composition according to claim 2 , wherein the photopolymerizable composition is a photopolymerizable adhesive.
23. A photoinitiator system comprising:
(a) an iodonium salt;
(b) a visible light sensitizer selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof;
(c) an electron donor comprising an alkoxy substituted anthracene; and
(d) a second electron donor compound having the following formula:
wherein each of R 1 to R 10 is independently selected from H, alkyl, phenyl or alkoxy groups.
24. A photopolymerizable composition comprising:
(a) a cationically polymerizable resin; and
(b) a photoinitiator system for the cationically polymerizable resin, the photoinitiator system comprising:
(i) an iodonium salt;
(ii) a visible light sensitizer selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof;
(iii) an electron donor comprising an alkoxy substituted anthracene; and
(iv) a second electron donor having the following formula:
wherein each of R 1 to R 10 is independently selected from H, alkyl, phenyl or alkoxy groups.
25. The photopolymerizable composition according to claim 24 , wherein the cationically polymerizable resin is selected from the group consisting of epoxy, oxetane, vinyl ether and spiro-orthocarbonate resins, and combinations thereof.
26. The photopolymerizable composition according to claim 25 , wherein the cationically polymerizable resin comprises an epoxy resin.
27. The photopolymerizable composition according to claim 26 , wherein the cationically polymerizable resin comprises a silicon-containing epoxy resin.
28. The photopolymerizable composition according to claim 25 , wherein the cationically polymerizable resin comprises a blend of a silicon-containing epoxy resin and an epoxy resin that does not contain silicon.
29. The photopolymerizable composition according to claim 24 , wherein the iodonium salt is selected from the group consisting of diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, 4-octyloxyphenyl phenyliodonium hexafluoroantimonate, 4-(2-hydroxytetradecyloxyphenyl) phenyliodonium hexafluoroantimonate, 4-(1-methylethyl)phenyl 4-methylphenyliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.
30. The photopolymerizable composition according to claim 24 , wherein the visible light sensitizer is an alpha-diketone.
31. The photopolymerizable composition according to claim 30 , wherein the alpha-diketone is camphorquinone.
32. The photopolymerizable composition according to claim 24 , wherein the alkoxy substituted anthracene is selected from 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 1,4-dimethoxyanthracene.
33. A photoinitiator system comprising:
(a) an iodonium salt;
(b) a visible light sensitizer selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof;
(c) a first anthracene and a second anthracene both having the following structure:
wherein for said first anthracene each of R 1 to R 10 is independently selected from H, alkyl, phenyl, or alkoxy groups, provided that at least one of R 1 to R 10 is alkoxy, and
wherein for said second anthracene each of R 1 to R 10 is independently selected from H, alkyl, phenyl or alkoxy groups.
34. A photopolymerizable composition comprising:
(a) a cationically polymerizable resin; and
(b) a photoinitiator system for the cationically polymerizable resin, the photoinitiator system comprising:
(i) an iodonium salt;
(ii) a visible light sensitizer selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof;
(iii) a first anthracene and a second anthracene both having the following structure:
wherein for said first anthracene each of R 1 to R 10 is independently selected from H, alkyl, phenyl or alkoxy groups, provided that at least one of R 1 to R 10 is alkoxy, and
wherein for said second anthracene each of R 1 to R 10 is independently selected from H, alkyl, phenyl or alkoxy groups.
35. The photopolymerizable composition according to claim 34 , wherein the cationically polymerizable resin is selected from the group consisting of epoxy, oxetane, vinyl ether and spiro-orthocarbonate resins, and combinations thereof.
36. The photopolymerizable composition according to claim 35 , wherein the cationically polymerizable resin comprises an epoxy resin.
37. The photopolymerizable composition according to claim 36 , wherein the cationically polymerizable resin comprises a silicon-containing epoxy resin.
38. The photopolymerizable composition according to claim 35 , wherein the cationically polymerizable resin comprises a blend of a silicon-containing epoxy resin and an epoxy resin that does not contain silicon.
39. The photopolymerizable composition according to claim 34 , wherein the iodonium salt is selected from the group consisting of diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium tetrakis(pentafluorophenyl)borate, 4-octyloxyphenyl phenyliodonium hexafluoroantimonate, 4-(2-hydroxytetradecyloxyphenyl) phenyliodonium hexafluoroantimonate, 4-(1-methylethyl)phenyl 4-methylphenyliodonium tetrakis(pentafluorophenyl)borate, and combinations thereof.
40. The photopolymerizable composition according to claim 34 , wherein the visible light sensitizer is an alpha-diketone.
41. The photopolymerizable composition according to claim 40 , wherein said alpha-diketone is camphorquinone.
42. The photopolymerizable composition according to claim 34 , wherein first anthracene is selected from 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 1,4-dimethoxyanthracene.
43. A photopolymerizable composition according to claim 34 , wherein second anthracene is selected from 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 1,4-dimethoxyanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, and 9,10-diphenyl-2,6-di-tert-butylanthracene.
44. A photopolymerizable dental material comprising the photopolymerizable composition of claim 2 , 24 or 34 .
45. The photopolymerizable dental material of claim 44 further comprising at least one filler.
46. The photopolymerizable dental material of claim 45 , wherein said filler is selected from quartz, submicron silica, and non-vitreous microparticles.
47. The photopolymerizable dental material of claim 44 , further comprising at least one adjuvant.
48. The photopolymerization dental material of claim 47 , wherein said adjuvant is selected from accelerators, inhibitors, absorbers, stabilizers, pigments, dyes, viscosity modifiers, surface tension depressants and wetting aids, antioxidants.
49. A method for preparing a dental restorative or prosthesis, said method comprising:
(a) providing the photopolymerizable dental material of claim 44 ; and
(b) polymerizing the dental material by exposing it to light of an appropriate wavelength to provide said dental restorative or prosthesis.
50. The method of claim 49 , further comprising the step of disposing said material into the mouth of a patient before or after step (b).
51. The method of claim 49 , wherein said dental material is irradiated with light for a period of time less than 120 seconds.
52. A photoinitiator system comprising:
(a) an iodonium salt;
(b) a visible light sensitizer selected from the group consisting of ketones, coumarin dyes, xanthene dyes, fluorone dyes, fluorescein dyes, aminoketone dyes, p-substituted aminostyryl ketone compounds, and combinations thereof; and
(c) an electron donor selected from the group consisting of (i) the combination of a first anthracene that has a light absorption maximum less than about 400 nanometers and a second anthracene having the following structure
wherein each of R 1 to R 10 is independently selected from H, or alkyl, phenyl or alkoxy groups, provided that at least one of R 1 to R 10 is not H; and (ii) the combination of a first anthracene and a second anthracene both having the following structure:
wherein for said first anthracene each of R 1 to R 10 is independently selected from H, alkyl, phenyl, or alkoxy groups, provided that at least one of R 1 to R 10 is alkoxy, and wherein for said second anthracene each of R 1 to R 10 is independently selected from H, alkyl, phenyl or alkoxy groups.
53. The photoinitiator system of claim 52 , further comprising:
a cationically polymerizable resin so as to form a photopolymerizable composition.
54. The photopolymerizable composition of claim 53 , further comprising:
a filler.