Switchable polymer printing plates with carbon bearing ionic and steric stabilizing groups

1. An imageable member comprising a support and an imageable layer on the support, the imageable layer being rendered more hydrophobic or oleophilic upon thermal imaging, is capable of providing an image without wet processing, and comprises:

a) a heat-sensitive ionomer having a net positive or negative charge; and

b) a photothermal conversion material comprising carbonaceous particles having thereon both

i) an organic moiety having a molecular weight in the range of about 120 Da to about 1000 Da and including an ionic or ionizable substituent having like charge as the ionomer, and

ii) a group represented by the formula

—X-[NIon] p -R terminal

wherein X represents an aromatic group or an alkyl group,

NIon represents a non-ionic, non-ionizable group,

R terminal represents hydrogen, an aromatic group, an alkoxy group, or an alkyl group, and

p is an integer from 1 to about 500.

2. The imageable member of claim 1 , wherein the ionomer is a macromolecular polyelectrolyte.

3. The imageable member of claim 1 , wherein the ionomer is a copolymer derived from a polymerizable acrylate monomer.

4. The imageable member of claim 1 , wherein the ionomer is an anionic polymer having a backbone including constitutional units having carboxylate groups linked directly or indirectly to the polymer backbone.

5. The imageable member of claim 4 , wherein the ionomer is represented by the structure:

wherein A 1 represents constitutional units derived from ethylenically unsaturated polymerizable monomers;

X 1 represents a divalent linking group;

Z + represents a cation;

B 1 represents non-carboxylated constitutional units;

p is 0 or 1;

m 1 is 0 to 75 mol-%; and

n 1 is from 25 to 100 mol-%.

6. The imageable member of claim 4 , further comprising a quaternary ammonium counterion for the ionomer.

7. The imageable member of claim 6 , wherein the quaternary ammonium counterion includes at least one unsubstituted or substituted phenyl moiety bonded directly or via a (C 1 -C 3 ) alkylene to a quaternary nitrogen.

8. The imageable member of claim 1 , wherein the ionomer is a crosslinked vinyl polymer having in at least 15 mol-% of its constitutional units a positively charged, pendant N-alkylated aromatic heterocyclic group.

9. The imageable member of claim 8 , wherein the N-alkylated aromatic heterocyclic group is an imidazolium or pyridinium group.

10. The imageable member of claim 8 , wherein the ionomer is represented by the structure:

wherein R 1 represents an alkyl group;

R 2 represents an alkyl group, an alkoxy group, an aryl group, an alkenyl group, halo, a cycloalkyl group, or a heterocyclic group having 5 to 8 atoms in the ring;

Z″ represents carbon, nitrogen, oxygen, or sulfur atoms necessary to complete an aromatic N-heterocyclic ring having 5 to 10 atoms in the ring;

n is 0 to 6; and

W − represents an anion.

11. The imageable member of claim 8 , wherein the ionomer is represented by the structure:

wherein HET + represents a positively charged, pendant N-alkylated aromatic heterocyclic group;

X represents constitutional units having attached HET + groups;

Y represents constitutional units derived from ethylenically unsaturated polymerizable monomers that provide crosslinking sites;

Z represents constitutional units derived from additional ethylenically unsaturated polymerizable monomers;

x is from 15 to 100 mol-%;

y is from 0 to 20 mol-%;

z is from 0 to 85 mol-%; and

W − represents an anion.

12. The imageable member of claim 1 , wherein the ionomer is a crosslinked vinyl polymer having in at least 15 mol-% of its constitutional units a positively charged, pendant organoonium group.

13. The imageable member of claim 12 , wherein the ionomer is represented by one of the following structures:

wherein R represents an alkylene, arylene, or cycloalkylene group or a combination of two or more such groups;

R 3 , R 4 and R 5 independently represent substituted or unsubstituted alkyl, aryl or cycloalkyl groups, or any two of R 3 , R 4 and R 5 can be combined to form a heterocyclic ring with the charged phosphorus, nitrogen or sulfur atom; and

W − represents an anion.

14. The imageable member of claim 1 , wherein the ionomer is represented by the structure:

wherein ORG + represents an organoonium group;

X′ represents constitutional units having attached ORG + groups;

Y′ represents constitutional units derived from ethylenically unsaturated polymerizable monomers that provide crosslinking sites;

Z′ represents constitutional units derived from additional ethylenically unsaturated polymerizable monomers;

W − represents an anion;

x′ is from 15 to 99 mol-%;

y′ is from 1 to 20 mol-%; and

z′ is from 0 to 84 mol-%.

15. The imageable member of claim 1 , wherein the ionomer is a charged polymer having in at least 15 mol-% of its constitutional units a negatively-charged, pendant thiosulfate group.

16. The imageable member of claim 15 , wherein the ionomer is represented by the structure:

wherein A represents a polymeric backbone;

R 6 represents a divalent linking group; and

Y 1 represents a hydrogen or a cation.

17. The imageable member of claim 1 , wherein the organic moiety has a molecular weight in the range of about 120 Da to about 200 Da.

18. The imageable member of claim 1 , wherein the organic moiety includes an ionic substituent having like charge as the ionomer.

19. The imageable member of claim 18 , wherein the organic moiety is a phenyl or naphthyl group including the ionic substituent.

20. The imageable member of claim 18 , wherein the ionic substituent is a sulfonate, carboxylate, or phosphate group.

21. The imageable member of claim 18 , wherein the ionic substituent is an ammonium or phosphonium group.

22. The imageable member of claim 18 , wherein the ionic substituent is a quaternary ammonium group.

23. The imageable member of claim 1 , wherein X is covalently bound to the carbonaceous particle.

24. The imageable member of claim 1 , wherein X represents a phenylene group.

25. The imageable member of claim 1 wherein X represents a benzoate group represented by

-[Ph-C(═O)—O—],

wherein Ph represents a phenylene group.

26. The imageable member of claim 1 , wherein NIon represents an alkylene oxide group comprising from 1 to about 12 carbons.

27. The imageable member of claim 1 , wherein NIon represents a straight or branched alkylene oxide group comprising 1 to 3 carbons.

28. The imageable member of claim 1 , wherein NIon represents a —(CH 2 ) 2 —O—) group.

29. The imageable member of claim 1 , wherein R terminal represents hydrogen or an aliphatic alkyl group.

30. The imageable member of claim 1 , wherein p is an integer from about 5 to about 100.

31. The imageable member of claim 1 , wherein:

X represents a benzoate group represented by -[Ph-C(═O)—O—], wherein Ph represents a phenylene group;

NIon represents a straight or branched alkylene oxide group comprising 1 to 3 carbons;

R terminal represents hydrogen or an aliphatic alkyl group; and

p is an integer from about 5 to about 100.

32. An imageable member comprising a support and an imageable layer on the support, the imageable layer being rendered more hydrophobic or oleophilic upon thermal imaging, is capable of providing an image without wet processing, and consists essentially of:

a) a hydrophilic heat-sensitive polymeric salt having:

i) an anionic polymer having a backbone including repeating units having carboxylate groups linked directly or indirectly to the polymer backbone; and

ii) a quaternary ammonium counterion having at least one quaternary nitrogen; and

b) a photothermal conversion material comprising carbonaceous particles having thereon both

i) an organic moiety having a molecular weight in the range of about 120 Da to about 1000 Da including an anionic substituent, and

ii) an aromatic or alkyl group substituted with at least one poly(alkylene oxide) group, wherein each alkylene oxide unit of the poly(alkylene oxide) group comprises from 1 to about 12 carbons.

33. The imageable member of claim 32 , wherein the anionic polymer is a copolymer derived from a polymerizable acrylate monomer.

34. The imageable member of claim 32 , wherein the quaternary ammonium counterion includes at least one unsubstituted or substituted phenyl or benzyl moiety bonded directly or via a (C 1 -C 3 ) alkylene to the quaternary nitrogen.

35. The imageable member of claim 34 , wherein the substituted phenyl or benzyl moiety includes at least one substituent selected from halo, methyl, ethyl, methoxy, and 2-ethoxy.

36. The imageable member of claim 32 , wherein at least one (C 1 -C 3 ) hydroxyalkyl group is bonded to the quaternary nitrogen.

37. The imageable member of claim 32 , wherein at least one hydroxyethyl group is bonded to the quaternary nitrogen.

38. The imageable member of claim 32 , wherein the quaternary ammonium counterion is multi-cationic and includes at least two quaternary nitrogens.

39. The imageable member of claim 32 , wherein the quaternary nitrogen is a member of a 5- to 14-atom heterocyclic ring.

40. The imageable member of claim 39 , wherein the quaternary nitrogen is at the vertex of two intersecting heterocyclic rings.

41. The imageable member of claim 32 , wherein the organic moiety has a molecular weight in the range of about 120 Da to about 200 Da.

42. The imageable member of claim 32 , wherein the organic moiety is an aromatic group.

43. The imageable member of claim 32 , wherein the organic moiety is a phenyl or naphthyl group including the anionic substituent.

44. The imageable member of claim 32 , wherein the anionic substituent is a sulfonate group.

45. The imageable member of claim 32 , wherein the aromatic or alkyl group is covalently bound to the carbonaceous particle.

46. The imageable member of claim 32 , wherein the aromatic group is a phenylene group.

47. The imageable member of claim 32 , wherein the aromatic group is a benzoate group represented by

-[Ph-C(═O)—O—],

wherein Ph represents a phenylene group.

48. The imageable member of claim 32 , wherein the poly(alkylene oxide) group is represented by

—[(CH 2 ) m —O—)] p R,

wherein m is an integer from 1 to 12;

p is an integer from 1 to 500; and

R represents hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aromatic group.

49. The imageable member of claim 32 , wherein the poly(alkylene oxide) group consists of straight or branched alkylene oxide units comprising 1 to 3 carbons.

50. The imageable member of claim 32 , wherein the poly(alkylene oxide) group consists of alkylene oxide units represented by —(CH 2 ) 2 —O—).

51. In an imageable member having an imageable layer being rendered more hydrophobic or oleophilic upon thermal imaging, is capable of providing an image without wet processing, and comprises:

a heat-switchable ionomer characterized by a net positive or negative charge; and

photothermal conversion material;

the improvement comprising:

as a photothermal conversion material, carbonaceous particles having thereon both

i) an organic moiety having a molecular weight in the range of about 120 Da to about 1000 Da and including an ionic substituent having like charge as the ionomer, and

ii) a group represented by the formula

—X-[NIon] p -R terminal

wherein X represents an aromatic group or an alkyl group,

NIon represents a non-ionic, non-ionizable group,

R terminal represents hydrogen, an aromatic group, an alkoxy group, or an alkyl group, and

p is an integer from 1 to about 500.

52. The imageable member of claim 51 , wherein the organic moiety has a molecular weight in the range of about 120 Da to about 200 Da.

53. The imageable member of claim 51 , wherein the organic moiety includes an ionic substituent having like charge as the ionomer.

54. The imageable member of claim 53 , wherein the organic moiety is a phenyl or naphthyl group including the ionic substituent.

55. The imageable member of claim 53 , wherein the ionic substituent is a sulfonate, carboxylate, or phosphonate group.

56. The imageable member of claim 53 , wherein the ionic substituent is an ammonium or phosphonium group.

57. The imageable member of claim 53 , wherein the ionic substituent is a quaternary ammonium group.

58. The imageable member of claim 51 , wherein X is covalently bound to the carbonaceous particle.

59. The imageable member of claim 51 , wherein X represents a phenylene group.

60. The imageable member of claim 51 , wherein X represents a benzoate group represented by

-[Ph-C(═O)—O—],

wherein Ph represents a phenylene group.

61. The imageable member of claim 51 , wherein NIon represents an alkylene oxide group comprising from 1 to about 12 carbons.

62. The imageable member of claim 51 , wherein NIon represents a straight or branched alkylene oxide group comprising 1 to 3 carbons.

63. The imageable member of claim 51 , wherein NIon represents a —(CH 2 ) 2 —O—) group.

64. The imageable member of claim 51 , wherein R terminal represents hydrogen or an aliphatic alkyl group.

65. The imageable member of claim 51 , wherein p is an integer from about 5 to about 100.

66. The imageable member of claim 51 , wherein:

X represents a benzoate group represented by -[Ph-C(═O)—O—], wherein Ph represents a phenylene group;

NIon represents a straight or branched alkylene oxide group comprising 1 to 3 carbons;

R terminal represents hydrogen or an aliphatic alkyl group; and

p is an integer from about 5 to about 100.

67. A method of providing a lithographic printing plate comprising imagewise exposing to thermal energy, an imageable member comprising a support and an imageable layer on the support, the imageable layer being rendered more hydrophobic or oleophilic upon thermal imaging, is capable of providing an image without wet processing, and comprises:

a) a heat-sensitive ionomer having a net positive or negative charge; and

b) a photothermal conversion material comprising carbonaceous particles having thereon both

i) an organic moiety having a molecular weight in the range of about 120 Da to about 1000 Da and including an ionic or ionizable substituent having like charge as the ionomer, and

ii) a group represented by the formula

—X-[NIon] p -R terminal

wherein X represents an aromatic group or an alkyl group, NIon represents a non-ionic, non-ionizable group,

R terminal represents hydrogen, an aromatic group, an alkoxy group, or an alkyl group, and

p is an integer from 1 to about 500,

to provide a printing surface comprised of exposed and non-exposed regions in the imageable layer without wet processing.

68. The imageable member of claim 1 wherein said imageable layer is the only heat-sensitive imageable layer on said support.