# US 7,407,731 B2 · Photosensitive resin compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,407,731 B2 - Document ID: US7407731B2 - Status: Granted - Kind: B2 - Application number: 11/386,471 - Filed: 2006-03-22 - Published: 2006-09-28 - Granted: 2008-08-05 - Earliest claimed: 2005-03-25 - Assignees: Fujifilm Electronic Materials U.S.A., Inc. - Inventors: Ahmad A. Naiini; David B. Powell; N. Jon Metivier; Donald F. Perry - Web page: https://patentgrep.com/patent/US7407731B2 ## CPC - G03F 7/023: Macromolecular quinonediazides; Macromolecular additives, e.g. binders {(G03F7/0226 takes precedence)} - G03F 7/022: Quinonediazides (G03F7/075 takes precedence) - G03F 7/0233: {characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides} - G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) - G03F 7/0382: {the macromolecular compound being present in a chemically amplified negative photoresist composition} - G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) - G03F 7/085: Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives (G03F7/075 takes precedence) - G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)} - G03F 7/0751: {used as adhesion-promoting additives or as means to improve adhesion} - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) ## Abstract A photosensitive resin composition comprising: (a) at least one polybenzoxazole precursor polymer; (b) at least one compound having Structure VI wherein, V is CH or N, Y is O or NR3 wherein R3 is H, CH3 or C2H5, R1 and R2 each independently are H, C1-C4 alkyl group, C1-C4 alkoxy group, cyclopentyl or cyclohexyl, or alternatively, R1 and R2 can be fused to produce a substituted or unsubstituted benzene ring; and (c) at least one solvent; wherein the amount of the compound of Structure VI present in the composition is effective to inhibit residue from forming when the composition is coated on a substrate and the coated substrate is subsequently processed to form an image on the substrate, and with the proviso that if the polybenzoxazole precursor polymer solely consists of polybenzoxazole precursor polymers that do not contain a photoactive moiety in the polymer, then (d) at least one photoactive compound is also present in the composition. The present invention also concerns a process for forming a relief pattern and electronic parts using the composition. ## Claims ### Claim 1 A photosensitive resin composition comprising: (a) at least one polybenzoxazole precursor polymer; (b) at least one compound having Structure VI wherein, V is selected from the group consisting of CH and N, Y is selected from the group consisting of O and NR3 wherein R3 is selected from the group consisting of H, CH3 and C2H5, R1 and R2 are each independently selected from the group consisting of H, C1-C4 alkyl group, C1-C4 alkoxy group, cyclopentyl and cyclohexyl, or R1 and R2 can be fused to produce a substituted or unsubstituted benzene ring; and (c) at least one solvent; wherein the amount of the compound of Structure VI present in the composition is an amount effective to inhibit residue from forming when the composition is coated on a substrate and the coated substrate is subsequently processed to form an image on the substrate, and with the proviso that if the polybenzoxazole precursor polymer solely consists of polybenzoxazole precursor polymers that do not contain a photoactive moiety in the polymer, then (d) at least one photoactive compound is also present in the composition. ### Claim 2 (depends on 1) A photosensitive composition according to claim 1 comprising a positive photosensitive resin composition wherein the polybenzoxazole precursor polymer comprises: at least one polybenzoxazole precursor polymer having Structure I or II or III or III* or IV or IV* or V, wherein Ar1 is selected from the group consisting of a tetravalent aromatic group, a tetravalent heterocyclic group, and mixtures thereof; Ar2 is selected from the group consisting of a divalent aromatic, a divalent heterocyclic, a divalent alicyclic, and a divalent aliphatic group that may contain silicon, Ar3 is selected from the group consisting of a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, and mixtures thereof; Ar4 is selected from the group consisting of Ar1(OH)2 and Ar2, x is from about 10 to about 1000; y is from 0 to about 900; 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 C1-C4 alkyl group, a C1-C4 alkoxy group, cyclopentyl, and cyclohexyl; k1 is any positive value of up to about 0.5, k2 is any value from about 1.5 to about 2, with the proviso that (k1+k2)=2, G is a monovalent organic group having a group selected from the group consisting of carbonyl, carbonyloxy and sulfonyl group, G* is a divalent organic group having at least one carbonyl or sulfonyl group, Ar7 is a bivalent to octavalent organic group with at least two carbon atoms, Ar8 is a bivalent to hexavalent organic group with at least two carbon atoms, and R4 is selected from the group consisting of hydrogen and an organic group with 1 to 10 carbons, m1 and m3 are integers in the range of 0 to 4 but m1 and m3 cannot be simultaneously 0 and m2 is an integer in the range of 0 to 2; with the proviso that if the polybenzoxazole precursor polymer solely consists of Structure I or III or V or a mixture containing any of these three Structures, then the photosensitive resin composition also comprises (d) at least one photoactive compound. ### Claim 3 (depends on 2) A positive photoresist composition according to claim 2 wherein the polybenzoxazole precursor polymer is at least one polybenzoxazole precursor polymer selected from the group consisting of those of Structures I, II, III, IV and V. ### Claim 4 (depends on 2) A positive photosensitive resin composition according to claim 2 wherein the component of Structure VI is selected from the group consisting of ### Claim 5 (depends on 3) A positive photosensitive resin composition according to claim 3 wherein the component of Structure VI is selected from the group consisting of ### Claim 6 (depends on 2) A positive photosensitive composition according to claim 2 additionally comprising an adhesion promoter. ### Claim 7 (depends on 6) A positive photosensitive composition according to claim 6 wherein the adhesion promoter is a compound of Structure XIV wherein each R14 is independently selected from the group consisting of a C1-C4 alkyl group and a C5-C7 cycloalkyl group, each R15 is independently selected from the group consisting of a C1-C4 alkyl group, a C1-C4 alkoxy group, a C5-C7 cycloalkyl group and a C5-C7 cycloalkoxy group, d is an integer from 0 to 3 and q is an integer from 1 to about 6, R16 is selected from the group consisting of one of the following moieties: wherein each R17 and R18 is independently selected from the group consisting of a C1-C4 alkyl group and a C5-C7 cycloalkyl group, and R19 is selected from the group consisting of a C1-C4 alkyl group or a C5-C7 cycloalkyl group. ### Claim 8 (depends on 3) A positive photosensitive composition according to claim 3 additionally comprising an adhesion promoter and wherein the adhesion promoter is a compound of Structure XIV wherein each R14 is independently selected from the group consisting of a C1-C4 alkyl group and a C5-C7 cycloalkyl group, each R15 is independently selected from the group consisting of a C1-C4 alkyl group, a C1-C4 alkoxy group, a C5-C7 cycloalkyl group and a C5-C7 cycloalkoxy group, d is an integer from 0 to 3 and q is an integer from 1 to about 6, R16 is selected from the group consisting of one of the following moieties: wherein each R17 and R18 is independently selected from the group consisting of a C1-C4 alkyl group and a C5-C7 cycloalkyl group, and R19 is selected from the group consisting of a C1-C4 alkyl group or a C5-C7 cycloalkyl group. ### Claim 9 (depends on 1) A photosensitive composition according to claim 1 comprising a negative working photoresist composition wherein the polybenzoxazole precursor comprises one or more polybenzoxazole precursor polymers of Structures I or III or III* III* wherein Ar1 is selected from the group consisting of a tetravalent aromatic group, a tetravalent heterocyclic group, and mixtures thereof; Ar2 is selected from the group consisting of a divalent aromatic, a divalent heterocyclic, a divalent alicyclic, and a divalent aliphatic group that may contain silicon, Ar3 is selected from the group consisting of a divalent aromatic group, a divalent aliphatic group, a divalent heterocyclic group, and mixtures thereof; G is a monovalent organic group having a group selected from the group consisting of carbonyl, carbonyloxy and sulfonyl groups, G* is a divalent organic group having at least one carbonyl or sulfonyl group, x is from about 10 to about 1000; and y is from 0 to about 900; and the composition additionally comprises (d) at least one photoactive compound which releases acid upon radiation, and (e) at least one latent crosslinker which contains at least two ˜N—(CH2OR29)a units where a selected from 1 or 2, and R29 is a linear or branched C1-C8 alkyl group. ### Claim 10 (depends on 9) A photoresist composition according to claim 9 comprising a negative working photoresist composition wherein the one or more polybenzoxazole precursor polymers is selected from polybenzoxazole precursor polymers of Structures I and III. ### Claim 11 (depends on 9) A negative photosensitive resin composition according to claim 9 wherein the component of Structure VI is selected from the group consisting of ### Claim 12 (depends on 10) A negative photosensitive resin composition according to claim 10 wherein the component of Structure VI is selected from the group consisting of ### Claim 13 (depends on 9) A negative photosensitive resin composition according to claim 9 wherein the latent crosslinker is selected from the group consisting of ### Claim 14 (depends on 10) A negative photosensitive resin composition according to claim 10 wherein the latent crosslinker is selected from the group consisting of ### Claim 15 (depends on 2) A process for forming a relief pattern using the positive photosensitive composition, the process comprising the steps of: (a) coating on a substrate, a positive-working photosensitive composition according to claim 2; (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. ### Claim 16 (depends on 3) A process for forming a relief pattern using the positive photosensitive composition, the process comprising the steps of: (a) coating on a substrate, a positive-working photosensitive composition according to claim 3; (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. ### Claim 17 (depends on 15) The process according to claim 15 wherein prior to step (a) the substrate is precoated with a solvent containing an adhesion promoter. ### Claim 18 (depends on 16) The process according to claim 16 wherein prior to step (a) the substrate is precoated with a solvent containing an adhesion promoter. ### Claim 19 (depends on 9) A process for forming a negative tone relief image, the process comprising the steps of: (a) providing a substrate, (b) coating on said substrate, a negative-working photosensitive composition according to claim 9; (c) exposing the coated substrate to actinic radiation; (d) post exposure baking the coated substrate at an elevated temperature; (e) developing the coated substrate with an aqueous developer, thereby forming a relief image; and (f) baking the substrate at an elevated temperature, thereby curing the relief image. ### Claim 20 (depends on 10) A process for forming a negative tone relief image, the process comprising the steps of: (a) providing a substrate, (b) coating on said substrate, a negative-working photosensitive composition according to claim 10; (c) exposing the coated substrate to actinic radiation; (d) post exposure baking the coated substrate at an elevated temperature; (e) developing the coated substrate with an aqueous developer, thereby forming a relief image; and (f) baking the substrate at an elevated temperature, thereby curing the relief image. ### Claim 21 (depends on 19) The process according to claim 19 wherein prior to step (b) the substrate is precoated with a solvent containing an adhesion promoter. ### Claim 22 (depends on 20) The process according to claim 20 wherein prior to step (b) the substrate is precoated with a solvent containing an adhesion promoter. ### Claim 23 (depends on 15) A relief image on a substrate formed by the process of claim 15. ### Claim 24 (depends on 16) A relief image on a substrate formed by the process of claim 16. ### Claim 25 (depends on 19) A relief image on a substrate formed by the process of claim 19. ### Claim 26 (depends on 20) A relief image on a substrate formed by the process of claim 20.