D1479 STABLE LIQUID BAP PHOTOINITIATOR AND ITS USE IN RADIATION CURABLE COMPOSITIONS

• US 20130237626A1
• Filed: 03/13/2013
• Published: 09/12/2013
• Est. Priority Date: 06/30/2010
• Status: Active Grant

• Current Assignee: Covestro NV (Covertro Deutschland AG)
• Original Assignee: DSM IP Assets BV (DSM-Firmenich AG)
• Inventors: Murphy, Edward Joseph, Southwell, John Edmond, Sarmah, Satyendra, Lee, TaiYeon, BISHOP, Timothy Edward
• Granted Patent: US 9,062,083 B2
• Time in Patent Office: Days
• US Class Current: 522/28
• CPC Class Codes: C03C 25/106 Single coatings
• CPC Class Codes: C03C 25/25 Non-macromolecular compounds
• CPC Class Codes: C04B 28/02 containing hydraulic cements other than calcium sulfates
• CPC Class Codes: C04B 41/0045 Irradiation; Radiation, e.g. with UV or IR C04B41/0036 takes precedence
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/483 Polyacrylates
• CPC Class Codes: C04B 41/63 Macromolecular compounds
• CPC Class Codes: C07F 9/5036 Phosphines containing the structure -C(=X)-P or NC-P
• CPC Class Codes: C07F 9/5337 Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
• CPC Class Codes: C08F 2/40 using retarding agents
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: C08F 222/1025 of aromatic dialcohols
• CPC Class Codes: C08K 5/50 Phosphorus bound to carbon only
• CPC Class Codes: C09D 133/08 Homopolymers or copolymers of acrylic acid esters

Abstract

The invention relates to radiation curable compositions comprising a liquid 0/s(acyl)phosphine photo initiators of formula (I): wherein each of Ar¹, Ar² and Ar³ is independently a substituted or unsubstituted aryl group. The invention also relates to stabilized forms of liquid bis(acyl)phosphines of formula (I) and radiation curable composition comprising said stabilized photoinitiators. The radiation curable compositions are selected from the group consisting of an optical fiber coating composition and a coating composition capable of radiation cure on concrete and a coating composition capable of radiation cure on metal.

Claims

1-14. -14. (canceled)

15. A radiation curable composition selected from the group consisting of an optical fiber coating composition and a coating composition capable of radiation cure on concrete and a coating composition capable of radiation cure on metal comprising at least one free-radical polymerizable component and a combination of at least two photoinitiators wherein at least one photoinitiator is liquid bis(2,4,6-trimethylbenzoyl)phenylphosphine and at least one photoinitiator is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

16. The radiation curable composition of claim 15, wherein the combination of bis(acyl)phosphine and bis(acyl)phosphine oxide are liquid at a temperature of about 15°

C. or greater.

17. The radiation curable composition of claim 16, wherein liquid bis(2,4,6-trimethylbenzoyl)phenylphosphine and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide are present in a ratio of about 1:

1 as measured by HPLC.

18-19. -19. (canceled)

20. A liquid bis(acyl)phosphine of formula (I):

21. A liquid bis(acyl)phosphine of formula (I):

22. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid photoinitiator selected from the group consisting of 2,4,6-(trimethylbenzoyl ethoxy, phenyl phosphine) oxide, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, methyl phenylglyoxylate and acrylated benzophenone.

23. The stabilized liquid bis(acyl)phosphine of claim 22 comprising about 25 wt. % to about 75 wt. % of bis(acyl)phosphine.

24. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the bis(acyl)phosphine is stabilized a mixture with at least one solid photoinitiator selected from the group consisting of 4-methyl benzophenone, p-phenyl benzophenone, 4,4′

-bis(dimethylamino)benzophenone, 4-benzoyl-4′

-methyl diphenylsulphide, 4,4′

-(tetraethyldiamino)benzophenone, 4,4′

-(tetraethyldiamino)benzophenone, benzophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 4-(2-hydroxyethoxy)phenyl-(2-propyl)ketone, camphorquinone and 2,4,6-trimethylbenzophenone.

25. The stabilized liquid bis(acyl)phosphine of claim 24 comprising about 25 wt. % to about 75 wt. % of bis(acyl)phosphine.

26. The stabilized liquid bis(acyl)phosphine of claim 24, wherein the mixture is an eutectic mixture.

27. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid or solid phosphite of formula (III):

28. The stabilized liquid bis(acyl)phosphine of claim 27, wherein each of R¹, R² and R³ is independently an alkylphenyl group.

29. The stabilized liquid bis(acyl)phosphine of claim 27, wherein the liquid or solid phosphite is selected from the group consisting of tris(nonylphenyl)phosphite, tributyl phosphite, or mixtures thereof.

30. The stabilized liquid bis(acyl)phosphine of claim 27, wherein the mixture is about a 1:

1 mixture or less in phosphite.

31. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid or solid thiophosphinic acid of formula (IV):

32. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid or solid phosphine sulfide of formula (V):

33. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid or solid phosphine selenide of formula (VI):

34. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid or solid phosphine telluride of formula (VII):

35. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid or solid phosphine halogenide of formula (VIII):

36. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid or solid iminophosphorane of formula (IX):

37. The stabilized liquid bis(acyl)phosphine of claim 21, wherein the mixture comprises at least one liquid or solid dioxaphospholane of formula (X):

38. A liquid bis(acyl)phosphine of formula (I):

39. The stabilized liquid bis(acyl)phosphine of claim 38, wherein the metal is a transition metal.

40. The stabilized liquid bis(acyl)phosphine of claim 38, wherein the metal is selected from the group consisting of vanadium (V), iron (Fe), Indium (In), thorium (Th), mercury (Hg), copper (Cu), nickel (Ni), yttrium (Y), lead (Pb), zinc (Zn), cadmium (Cd), cobalt (Co), manganese (Mn), calcium (Ca), magnesium (Mg), strontium (Sr), barium (Ba), zirconium (Zr), titanium (Ti), chromium (Cr), rubidium (Rb), molybdenum (Mo), ruthenium (Ru), palladium (Pd), silver (Ag), cadmium (Cd), tin (Sn), antimony (Sb), barium (Ba), tungsten (W), platinum (Pt), gold (Au), bismuth (Bi) and beryllium (Be).

41. The stabilized liquid bis(acyl)phosphine of claim 38, having formula (XI) or formula (XII):

42. The stabilized liquid bis(acyl)phosphine of claim 38, wherein the Lewis acid is selected from the group consisting of supramolecular polymers, imidazole derivatives and guanidine derivatives.

43. The stabilized liquid bis(acyl)phosphine of claim 38 having formula (XIII) or formula (XIV):

44. The stabilized liquid bis(acyl)phosphine of claim 20, wherein each of Ar¹, Ar² and Ar³ is independently selected from the group consisting of a phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, trialkylphenyl group, isopropylphenyl group, tert-butyl phenyl group, methoxy phenyl group, dimethoxyphenyl group, ethoxy phenyl group, diethoxy phenyl group, isopropoxy phenyl group, thiomethoxy phenyl group, naphthyl group, thiophenyl group and pyridyl group.

45. The stabilized liquid bis(acyl)phosphine of claim 44, wherein the trialkylphenyl group is a trimethylphenyl group.

46. The stabilized liquid bis(acyl)phosphine of claim 45, wherein the trimethylphenyl group is a 2,4,6-trimethylphenyl group.

47. The stabilized liquid bis(acyl)phosphine of claim 44, wherein the stabilized phosphine is stabilized liquid bis(2,4,6-trimethylbenzoyl)phenylphosphine, wherein Ar¹ is a phenyl group and each of Ar² and Ar³ is a 2,4,6-trimethylphenyl group.

48. A radiation curable composition comprising the stabilized liquid bis(acyl)phosphine of claim 20 and at least one free-radical polymerizable component.

49. The radiation curable composition of claim 48, wherein said composition is selected from the group consisting of an optical fiber coating composition, and a coating composition capable of radiation cure on concrete and a coating composition capable of radiation cure on metal.

50. The radiation curable composition of claim 49, wherein said composition is an optical fiber coating composition.

51. The optical fiber coating composition of claim 50, wherein the optical fiber coating composition is selected from the group consisting of a primary coating, a secondary coating, an ink coating, an up-jacketing coating, a buffer coating and a matrix coating.

52. The radiation curable composition of claim 49, wherein said composition is a coating capable of radiation cure on concrete.

53. The radiation curable composition of claim 49, wherein said composition is a coating capable of radiation cure on metal.

54. The radiation curable composition of claim 48, wherein said composition is a liquid.

55. The radiation curable composition of claim 48, wherein the composition is curable by UV light generated by a conventional UV light source.

56. The radiation curable composition of claim 48, wherein the composition is curable by light generated by a LED light source.