Photosensitive resin compositions
View Patent ↗A positive photosensitive resin composition comprising: (a) at least one polybenzoxazole precursor polymer having structure I or II; (b) at least one photosensitive compound selected from compounds described by structures III–V, (c) at least one solvent; and (d) optionally an adhesion promoter.
1. A positive photosensitive resin composition comprising:
(a) at least one polybenzoxazole precursor polymer having structure I or II;
wherein Ar 1 is selected from the group consisting of a tetravalent aromatic group, a tetravalent heterocyclic group, or mixtures thereof; Ar 2 is selected from the group consisting of a divalent aromatic, a divalent heterocyclic, a divalent alicyclic, or a divalent aliphatic group that may contain silicon or mixtures thereof; Ar 3 is selected from the group consisting of a divalent aromatic group or a divalent aliphatic group, a divalent heterocyclic group, or mixtures thereof; D is selected from the group consisting of one of the following moieties:
wherein R is selected from the group consisting of H, halogen, a C 1 –C 4 alkyl group, a C 1 –C 4 alkoxy group, or a C 5 –C 7 cycloalkyl group; k 1 can be any positive value of up to about 0.5, k 2 can be any value from about 1.5 to about 2, with the proviso that (k 1 +k 2 )=2, x is from about 10 to about 1000; y is from about 0 to about 900;
(b) at least one photosensitive compound selected from the group consisting of compounds described by structures III–V,
wherein R 1 , R 2 , R 4 , R 5 , R 6 and R 7 each independently are selected from the group consisting of a linear or branched C 1 –C 4 alkyl group, a phenyl or halide substituted C 1 –C 4 linear or branched alkyl group, a perfluorinated C 1 –C 4 linear or branched alkyl group, a C 5 –C 7 cycloalkyl group, a C 1 –C 4 alkyl or halide substituted C 5 –C 7 cycloalkyl group or alternatively R 1 and R 2 or any two of R 4 , R 5 , and R 6 may together form a 5–7 membered ring; each R 3 is independently selected from the group consisting of H, a linear or branched C 1 –C 4 alkyl group, a halide substituted C 1 –C 4 linear or branched alkyl group, a perfluorinated linear or branched C 1 –C 4 alkyl group, a C 5 –C 7 cycloalkyl group, a C 1 –C 4 alkyl or halide substituted C 5 –C 7 cycloalkyl group, an unsubstituted phenyl group or a phenyl or alkyl or halide substituted phenyl group; Q is selected from the group consisting of H or D with the proviso that at least one Q=D; D is as defined hereinbefore; a is an integer from 1 to 5; b and c are integers from 0 to 5 with the provisos (1) that for Structure III, if a=b=1 and both OQ are substituted para to the R 1 R 2 C substituent, then both R 1 and R 2 are not simultaneously methyl and (2) 1<=a+b<6; and the proviso that for Structure V, if a=b=c=1 and all OQ are para to the triphenyl methane carbon substituent, then at least one R 3 is not H;
(c) at least one solvent; and
(d) optionally an adhesion promoter.
2. A positive photosensitive composition according to claim 1 , wherein Ar 1 in Structure I and II is a moiety selected from the group consisting of
wherein X 1 is selected from the group consisting of —O—, —S—, —C(CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO— or —SiR 8 2 — and each R 8 is independently selected from the group consisting of a C 1 –C 7 linear or branched alkyl or C 5 –C 8 cycloalkyl group.
3. A positive photosensitive composition according to claim 1 , wherein Ar 1 in Structure I and II is
4. A positive photosensitive composition according to claim 1 , wherein Ar 2 in Structure I and II is a moiety selected from the group consisting of
wherein X 1 is selected from the group consisting of —O—, —S—, —C(CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO— and —SiR 8 2 —, X 2 is selected from the group consisting of —O—, —S—, —C(CF 3 ) 2 —, —CH 2 —, —SO 2 —, and —NHCO—, Z=H or a C 1 –C 8 linear, branched or cyclic alkyl group, p is an integer from 1 to 6, and each R 8 is independently selected from the group consisting of a C 1 –C 7 linear or branched alkyl and C 5 –C 8 cycloalkyl group.
5. A positive photosensitive composition according to claim 4 wherein Z is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl, and cyclooctyl.
6. A positive photosensitive composition according to claim 1 , wherein Ar 3 in Structures I and II is a moiety selected from the group consisting of
wherein X 2 is selected from the group consisting of —O—, —S—, —C(CF 3 ) 2 —, —CH 2 —, —SO 2 —, or —NHCO—.
7. A positive photosensitive composition according to claim 1 , wherein D in Structure II is selected from the group consisting of
8. A positive photosensitive composition according to claim 1 , wherein the polybenzoxazole precursor polymer has structure II.
9. A positive photosensitive composition according to claim 1 , wherein the amount of polybenzoxazole precursor polymer of Structures I or II in the photosensitive composition is from about 2.5 wt. % to about 45 wt. %.
10. A positive photosensitive composition according to claim 1 , wherein the amount of polybenzoxazole precursor polymer of Structures I or II in the photosensitive composition is from about 15 wt. % to about 40 wt. %.
11. A positive photosensitive composition according to claim 1 , wherein the amount of polybenzoxazole precursor polymer of Structures I or II in the photosensitive composition is from about 25 wt. % to about 35 wt. %.
12. A positive photosensitive composition according to claim 1 , wherein the photosensitive compound (b) is selected from the group consisting of
13. A positive photosensitive composition according to claim 1 , wherein the photosensitive compound (b) is selected from the group consisting of
14. A positive photosensitive composition according to claim 1 , wherein the photosensitive compound (b) is
15. A positive photosensitive composition according to claim 1 , wherein the adhesion promoter is described by Structure IX
wherein each R 10 is independently selected from the group consisting of a C 1 –C 4 alkyl group and a C 5 –C 7 cycloalkyl group and each R 11 is independently selected from the group consisting of a C 1 –C 4 alkyl group, a C 1 –C 4 alkoxy group, a C 5 –C 7 cycloalkyl group and a C 5 –C 7 cycloalkoxy group; d is an integer from 0 to 3 and n is an integer from 1 to about 6. R 12 is selected from the group consisting of one of the following moieties:
wherein each R 13 and R 14 are independently selected from the group consisting of a C 1 –C 4 alkyl group and a C 5 –C 7 cycloalkyl group, and R 15 is selected from the group consisting of a C 1 –C 4 alkyl group and a C 5 –C 7 cycloalkyl group.
16. A positive photosensitive composition according to claim 15 , wherein the R 12 is selected from the group consisting of
17. A positive photosensitive composition according to claim 15 , wherein adhesion promoter is selected from the group consisting of
18. A positive photosensitive composition according to claim 1 , wherein the amount of adhesion promoter of in the photosensitive composition is from about 0.1 wt. % to about 10 wt. %.
19. A positive photosensitive composition according to claim 1 , wherein the amount of adhesion promoter in the photosensitive composition is from about 0.3 wt. % to about 5 wt. %.
20. A positive photosensitive composition according to claim 1 , wherein the amount of adhesion promoter in the photosensitive composition is from about 0.5 wt. % to about 2.5 wt. %.
21. A positive photosensitive composition of claim 1 , wherein the polybenzoxazole precursor polymer is a polymer of structure II and wherein the D in the polymer structure is selected from the group consisting of
and the photosensitive compound (b) is a compound having the structure V.
22. A positive photosensitive composition of claim 21 wherein an adhesion promoter is present in the composition.
23. A positive photosensitive composition of claim 22 wherein the adhesion promoter is described by Structure IX
wherein each R 10 is independently selected from the group consisting of a C 1 –C 4 alkyl group and a C 5 –C 7 cycloalkyl group and each R 11 is independently selected from the group consisting of a C 1 –C 4 alkyl group, a C 1 –C 4 alkoxy group, a C 5 –C 7 cycloalkyl group and a C 5 –C 7 cycloalkoxy group; d is an integer from 0 to 3 and n is an integer from 1 to about 6 and R 12 is selected from the group consisting of one of the following moieties:
wherein each R 13 and R 14 are independently selected from the group consisting of a C 1 –C 4 alkyl group and a C 5 –C 7 cycloalkyl group, and R 15 is selected from the group consisting of a C 1 –C 4 alkyl group and a C 5 –C 7 cycloalkyl group.
24. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 1 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
25. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 2 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
26. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 3 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
27. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 4 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
28. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 5 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
29. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 6 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
30. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 7 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
31. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 8 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
32. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 9 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
33. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 10 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
34. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 11 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
35. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 12 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
36. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 13 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
37. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 14 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
38. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 15 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
39. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 16 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
40. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 17 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
41. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 18 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
42. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 19 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
43. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 20 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
44. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 21 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
45. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 22 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
46. A process for forming a relief pattern on a substrate, the process comprises the steps of:
(a) coating on a suitable substrate, a positive-working photosensitive composition of claim 23 , thereby forming a coated substrate;
(b) prebaking the coated substrate;
(c) exposing the prebaked coated substrate to actinic radiation;
(d) developing the exposed coated substrate with an aqueous developer, thereby forming an uncured relief image on the coated substrate; and
(e) baking the developed coated substrate at an elevated temperature, thereby curing the relief image.
47. A process according to claim 24 , wherein the suitable substrate to be coated with the positive-working photosensitive composition in step (a) is a substrate that has been treated with an external adhesion promoter.
48. A process according to claim 47 wherein the external adhesion promoter is selected from the group consisting of vinylalkoxysilanes, methacryloxalkoxyysilanes, mercaptoalkoxysilanes, aminoalkoxysilanes, epoxyalkoxysilanes and glycidoxyalkoxysilanes.
49. A process according to claim 48 wherein the external adhesion promoter is selected from the group consisting of gamma-aminopropyltrimethoxy-silane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyl-methyldiethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, and 3-methacryloxypropyltrimethoxysilane.
50. A process according to claim 49 wherein the external adhesion promoter is gamma-Aminopropyltrimethoxysilane.
51. A substrate having a patterned image produced by the process of claim 24 .
52. A substrate having a patterned image produced by the process of claim 30 .
53. A substrate having a patterned image produced by the process of claim 35 .
54. A substrate having a patterned image produced by the process of claim 38 .
55. A substrate having a patterned image produced by the process of claim 44 .
56. A substrate having a patterned image produced by the process of claim 45 .
57. A substrate having a patterned image produced by the process of claim 46 .
58. A substrate having a patterned image produced by the process of claim 47 .