Positive photosensitive resin compositions
View Patent ↗An end-capped polybenzoxazole precursor having acid labile functional groups, positive working photosensitive compositions thereof and use of the compositions for producing heat resistant relief images on substrates.
1. A photosensitive resin comprising:
an end- capped polybenzoxazole precursor polymer bearing acid labile functional groups having the structure I:
wherein k 1 is any number between 0.1 and 2, k 2 is any number between 0–1.9 provided that (k 1 +k 2 )=2; x is an integer from about 10 to about 1000, y is an integer from 0 to about 900 and (x+y)<1000; Ar 1 is selected from the group consisting of a tetravalent aromatic, a heterocyclic group, and mixture thereof; Ar 2 is selected from the group consisting of a divalent aromatic, heterocyclic, alicyclic and aliphatic group; Ar 3 is selected from the group consisting of a divalent aromatic, aliphatic and heterocyclic group; Ar 4 is selected from the group consisting of Ar 1 (OD) k 1 (OH) k 2 and Ar 2 ; D is selected from the group consisting of an acid sensitive group R 1 and a moiety (B—O—R 2 ) containing an acid sensitive group R 2 ; B is a divalent group which is not acid labile, R is an organic group having a carbonyl, carbonyloxy or sulfonyl group attached directly to the terminal NH of the polymer, and the —OR 1 group is not a carbonate group.
2. A photosensitive resin of claim 1 wherein R 1 in combination with the O atom attached to Ar 1 forms a group selected from the group consisting of acetal groups, ketal groups, ether groups, and silyl ethers groups.
3. A photosensitive resin of claim 1 wherein R 1 is selected from the group consisting of the groups
4. A photosensitive resin according to claim 1 wherein R 2 in combination with the portions of B forms a group selected from the group consisting of an acid sensitive acetal group and an acid sensitive ester group.
5. A photosensitive resin according to claim 1 wherein the group B—O—R 2 is selected from the group consisting of
6. A photosensitive resin of claim 1 wherein R 1 in combination with the O atom attached to Ar 1 forms an acetal group and R is an organic group having a carbonyl group attached directly to the terminal NH of the polymer.
7. A positive-working photosensitive composition comprising:
an end-capped polybenzoxazole precursor polymer of claim 1 ;
a photoacid generator;
a solvent; and
optionally, a photosensitizer.
8. A positive-working photosensitive composition of claim 7 wherein R 1 in combination with the O atom attached to Ar 1 forms a group selected from the group consisting of acetal groups, ketal groups, ether groups, and silyl ethers groups.
9. A positive-working photosensitive composition of claim 7 wherein R 1 is selected from the group consisting of the groups
10. A positive-working photosensitive composition according to claim 7 wherein R 2 in combination with the portions of B forms a group selected from the group consisting of an acid sensitive acetal group and an acid sensitive ester group.
11. A positive-working photosensitive composition according to claim 7 wherein the group B—O—R 2 is selected from the group consisting of
12. A positive-working photosensitive composition of claim 7 wherein R 1 in combination with the O atom attached to Ar 1 forms an acetal group and R is an organic group having a carbonyl group attached directly to the terminal NH of the polymer.
13. A positive-working photosensitive composition of claim 7 wherein the photoacid generator is selected from the group consisting of oxime sulfonates, sulfonium salts and iodonium salts.
14. A positive-working photosensitive composition of claim 12 wherein the photoacid generator is selected from the group consisting of oxime sulfonates and sulfonium salts.
15. A positive-working photosensitive composition of claim 7 additionally comprising an adhesion promoter.
16. A process for the preparation of a heat-resistant relief image comprising the steps of:
a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 7 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
17. A process for the preparation of a heat-resistant relief image comprising the steps of:
(a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 8 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
18. A process for the preparation of a heat-resistant relief image comprising the steps of:
(a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 9 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
19. A process for the preparation of a heat-resistant relief image comprising the steps of:
(a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 10 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
20. A process for the preparation of a heat-resistant relief image comprising the steps of:
(a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 11 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
21. A process for the preparation of a heat-resistant relief image comprising the steps of:
(a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 12 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
22. A process for the preparation of a heat-resistant relief image comprising the steps of:
(a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 13 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
23. A process for the preparation of a heat-resistant relief image comprising the steps of:
(a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 14 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
24. A process for the preparation of a heat-resistant relief image comprising the steps of:
(a) coating on a substrate, a heat resistant positive-working photosensitive composition of claim 15 , thereby forming a coated substrate;
(b) exposing said coated substrate to actinic radiation;
(c) post exposure baking said coated substrate at an elevated temperature;
(d) developing said coated substrate with an aqueous developer, thereby forming a developed substrate; and
(e) baking said developed substrate at an elevated temperature to convert the polybenzoxazole precursor to a polybenzoxazole.
25. A process for the preparation of a heat-resistant relief image of claim 16 wherein the substrate of step (a) is treated with an adhesion promoter before being coated with the positive-working photosensitive composition.
26. A process for the preparation of a heat-resistant relief image of claim 25 wherein the substrate is treated with an adhesion promoter selected from the group consisting of vinylalkoxysilanes, methacryloxalkoxysilanes, mercaptoalkoxysilanes, aminoalkoxysilanes, epoxyalkoxysilanes and glycidoxyalkoxysilanes.
27. A process for the preparation of a heat-resistant relief image of claim 26 wherein the substrate is treated with an adhesion promoter selected from the group consisting of gamma-aminopropyltrimethoxy-silane, gamma-glycidoxypropylmethyldimethoxysilane, gamma-glycidoxypropyl-methyldiethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, 3-methacryl-oxypropyldimethoxymethylsilane, and 3-methacryloxypropyltrimethoxysilane.
28. A substrate having a patterned image produced by the process of claim 16 .
29. A substrate having a patterned image produced by the process of claim 17 .
30. A substrate having a patterned image produced by the process of claim 18 .
31. A substrate having a patterned image produced by the process of claim 19 .
32. A substrate having a patterned image produced by the process of claim 20 .
33. A substrate having a patterned image produced by the process of claim 21 .
34. A substrate having a patterned image produced by the process of claim 22 .
35. A substrate having a patterned image produced by the process of claim 23 .
36. A substrate having a patterned image produced by the process of claim 24 .
37. A substrate having a patterned image produced by the process of claim 25 .
38. A substrate having a patterned image produced by the process of claim 26 .
39. A substrate having a patterned image produced by the process of claim 27 .
40. An article of commerce having incorporated therein a patterned image of claim 28 .
41. An article of commerce having incorporated therein a patterned image of claim 37 .
42. An article of commerce of claim 40 wherein the item of commerce is selected from the group consisting of memory devices, logic devices and plating stencils.
43. An article of commerce having incorporated therein a patterned image of claim 36 .