Adhesion promoting ingredients for on-press developable lithographic printing plate precursors

1. An imageable element comprising:

(a) a substrate comprising a support; and

(b) an imageable layer over the substrate;

in which:

the support is aluminum or an aluminum alloy;

the imageable layer comprises a polymerizable compound and a polymeric binder;

the polymeric binder comprises K units and L units, and

the imageable element comprises one or more adhesion promoting ingredients selected from the group consisting of:

i) titanium chelates;

ii) co-polymers that comprise L units and M units; and

iii) mixtures thereof;

the K units are selected from —[CH 2 C(R 1 )R 2 ]—, —[CH 2 CR 1 (CO 2 R 3 )]—, —[CH 2 CR 1 (CONR 3 2 )]—, —[CH(CONR 6 CO)CH]—, and mixtures thereof;

the L units are —[CH 2 C(R 1 )(CO 2 (CH 2 CH 2 O) n T)]—;

the M units are —[CH(R 4 )CH(CO 2 H)]—;

each R 1 is independently hydrogen, methyl, or a mixture thereof;

R 2 is hydrogen, methyl, phenyl, substituted phenyl, halogen, cyano, alkoxy of one to four carbon atoms, acyl of one to five carbon atoms, acyloxy of one to five carbon atoms, allyl, or a mixture thereof;

R 3 is alkyl of one to six carbon atoms, phenyl, or a mixture thereof;

R 4 is hydrogen, methyl, CO 2 H, CO 2 R 5 , or a mixture thereof;

R 5 is an alkyl group of one to six carbon atoms or a mixture of alkyl groups of one to six carbon atoms;

R 6 is hydrogen, hydroxyl, phenyl, substituted phenyl, alkyl of one to six carbon atoms, cyclohexyl, benzyl, or a mixture thereof;

n is about 5 to about 400; and

T is hydrogen, alkyl of one to eight carbon atoms, phenyl, or a mixture thereof,

provided that when said adhesion promoting ingredient includes a titanium chelate, it is present in said imageable layer only.

2. The imageable element of claim 1 in which the element further comprises an additional layer between the substrate and the imageable layer, and the additional layer comprises one or more adhesion promoting ingredients comprising only the copolymers that comprise L units and M units.

3. The imageable element of claim 1 in which the imageable layer comprises the one or more adhesion promoting ingredients.

4. The imageable element of claim 1 in which the one or more adhesion promoting ingredients comprises one or more of the titanium chelates in said imageable layer.

5. The imageable element of claim 4 in which the one or more adhesion promoting ingredients comprises titanium(triethanolamineaminato)iso-propoxide.

6. The imageable element of claim 1 in which the one or more adhesion promoting ingredients comprises one or more co-polymers selected from the co-polymers that comprises L units and M units.

7. The imageable element of claim 6 in which each of the one or more co-polymers comprises about 5 wt % to about 70 wt % of the L units and about 95 wt % to about 30 wt % of the M units, and the L units and the M units together comprise about 100 wt % of each of the one or more co-polymers.

8. The imageable element of claim 7 in which R 3 is methyl; T is hydrogen, methyl, ethyl, n-butyl, or a mixture thereof; and n is about 10 to about 100.

9. The imageable element of claim 8 in which each of the one or more co-polymers comprises about 20 wt % to about 40 wt % of the L units and about 80 wt % to about 60 wt % of the M units.

10. The imageable element of claim 1 in which the K units are selected from —[CH 2 C(R 1 )R 2 ]—, —[CH 2 CR 1 (CO 2 R 3 )]—, and mixtures thereof; R 2 is phenyl, cyano, or a mixture thereof; and R 3 is methyl.

11. The imageable element of claim 10 in which imageable layer comprises the adhesion promoting ingredient or mixture of adhesion promoting ingredients.

12. The imageable element of claim 11 in which the one or more adhesion promoting ingredients comprises one of more titanium chelates.

13. The imageable element of claim 12 in which the one or more adhesion promoting ingredients comprises titanium(triethanolamineaminato)iso-propoxide.

14. The imageable element of claim 11 in which the one or more adhesion promoting ingredients comprises one or more co-polymers selected from the co-polymers that comprises L units and M units.

15. The imageable element of claim 14 in which each of the one or more co-polymers comprises about 5 wt % to about 70 wt % of the L units and about 95 wt % to about 30 wt % of the M units, and the L units and the M units together comprise about 100 wt % of each of the one or more co-polymers.

16. The imageable element of claim 15 in which R 3 is methyl; T is hydrogen, methyl, ethyl, n-butyl, or a mixture thereof; and n is about 10 to about 100.

17. The imageable element of claim 16 in which each of the one or more co-polymers comprises about 20 wt % to about 40 wt % of the L units and about 80 wt % to about 60 wt % of the M units.

18. The imageable element of claim 10 in which the adhesion promoting ingredient or mixture of adhesion promoting ingredients is in a separate layer between the substrate and the imageable layer.

19. The imageable element of claim 18 in which the adhesion promoting ingredient or mixture of adhesion promoting ingredients comprises one or more co-polymers selected from the co-polymers that comprises L units and M units.

20. The imageable element of claim 19 in which each of the one or more co-polymers comprises about 5 wt % to about 70 wt % of the L units and about 95 wt % to about 30 wt % of the M units, and the L units and the M units together comprise about 100 wt % of each of the one or more co-polymers.

21. The imageable element of claim 20 in which R 3 is methyl; T is hydrogen, methyl, ethyl, n-butyl, or a mixture thereof; and n is about 10 to about 100.

22. The imageable element of claim 1 in which the substrate additionally comprises an interlayer.

23. A method for forming an image, the method comprising the steps of:

thermally imaging an imageable element comprising an imageable layer and forming an imaged imageable element comprising imaged and complementary unimaged regions in the imageable layer; and

developing the imaged imageable element with ink and fountain solution and removing the unimaged regions;

in which:

the imageable element comprises:

(a) a substrate comprising a support; and

(b) an imageable layer over the substrate;

in which:

the support is aluminum or an aluminum alloy;

the imageable layer comprises a polymerizable compound and a polymeric binder;

the polymeric binder comprises K units and L units, and

the imageable element comprises one or more adhesion promoting ingredients selected from the group consisting of:

i) titanium chelates;

ii) co-polymers that comprise L units and M units; and

iii) mixtures thereof;

the K units are selected from —[CH 2 C(R 1 )R 2 ]—, —[CH 2 CR 1 (CO 2 R 3 )]—, —[CH 2 CR 1 (CONR 3 2 )]—, —[CH(CONR 6 CO)CH]—, and mixtures thereof,

the L units are —[CH 2 C(R 1 )(CO 2 (CH 2 CH 2 O) n T)]—;

the M units are —[CH(R 4 )CH(CO 2 H)]—;

each R 1 is independently hydrogen, methyl, or a mixture thereof;

R 2 is hydrogen, methyl, phenyl, substituted phenyl, halogen, cyano, alkoxy of one to four carbon atoms, acyl of one to five carbon atoms, acyloxy of one to five carbon atoms, allyl, or a mixture thereof;

R 3 is alkyl of one to six carbon atoms, phenyl, or a mixture thereof;

R 4 is hydrogen, methyl, —CO 2 H, —CO2R 5 , or a mixture thereof;

R 5 is an alkyl group of one to six carbon atoms or a mixture of alkyl groups of one to six carbon atoms;

R 6 is hydrogen, hydroxyl, phenyl, substituted phenyl, alkyl of one to six carbon atoms, cyclohexyl, benzyl, or a mixture thereof;

n is about 5 to about 400; and

T is hydrogen, alkyl of one to eight carbon atoms, phenyl, or a mixture thereof,

provided that when said adhesion promoting ingredient includes a titanium chelate it is present in said imageable layer only.

24. The method of claim 23 in which the K units are selected from —[CH 2 C(R 1 )R 2 ]—, —[CH 2 CR 1 (CO 2 R 3 )]—, and mixtures thereof; R 2 is phenyl, cyano, or a mixture thereof; and R 3 is methyl.

25. The method of claim 24 in which the imageable layer comprises the adhesion promoting ingredient or mixture of adhesion promoting ingredients.

26. The method of claim 25 in which the one or more adhesion promoting ingredients are selected from the titanium chelates.

27. The method of claim 26 in which the adhesion promoting ingredient or mixture of adhesion promoting ingredients comprises titanium(triethanolamineaminato)iso-propoxide.

28. The method of claim 27 in which the one or more adhesion promoting ingredients comprises one or more co-polymers selected from the co-polymers that comprises L units and M units, the one or more co-polymer each comprise about 20 wt % to about 40 wt % of the L units and about 80 wt % to about 60 wt % of the M units, and the L units and M units together comprise about 100 wt % of each of the one or more co-polymers.

29. The method of claim 27 in which R 3 is methyl; T is hydrogen, methyl, ethyl, n-butyl, or a mixture thereof; and n is about 10 to about 100.

30. The method of claim 27 in which the adhesion promoting ingredient or mixture of adhesion promoting ingredients is in a separate layer between the substrate and the imageable layer.

31. The method of claim 29 in which the adhesion promoting ingredient or mixture of adhesion promoting ingredients are one or more co-polymers selected from the co-polymers that comprises L units and M units.

32. The method of claim 30 in which R 3 is methyl; T is hydrogen, methyl, ethyl, n-butyl, or a mixture thereof; and n is about 10 to about 100, each of the one or more co-polymers comprises about 20 wt % to about 40 wt % of the L units and about 80 wt % to about 60 wt % of the M units, and the L units and M units together comprise about 100 wt % of each of the one or more the co-polymers.