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US 12,643,981 B2Granted
Unsaturated cyclic anhydride end capped polyimides and polyamic acids and photosensitive compositions thereof
AssigneePromerus, LLC
InventorPramod Kandanarachchi
Life of this patent
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Abstract
Embodiments in accordance with the present invention encompass polyamic acid or polyimide polymers containing a reactive unsaturated cyclic anhydride end group as well as photosensitive compositions made therefrom which are useful for forming films that can be patterned to create structures for microelectronic devices, microelectronic packaging, microelectromechanical systems, optoelectronic devices and displays. In some embodiments the compositions of this invention are shown to feature excellent hitherto unachievable mechanical properties. The negative images formed therefrom exhibit improved thermo-mechanical properties, among other property enhancements.
Claims18
A process for forming an end capped polyimide of formula (IB):
- wherein:
- m is an integer of at least 50;
- X is derived from one or more dianhydrides selected from the group consisting of:
- 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA);
- 4-methyl-1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone;
- 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA);
- and
- 5,5′-(perfluoropentane-3,3-diyl)bis(isobenzofuran-1,3-dione);
- Y is derived from one or more diamines selected from the group consisting of:
- 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF);
- 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB);
- 4,4′-methylenebis(2,6-dimethylaniline) (DO3);
- 2-(4-aminophenyl)benzo[d]oxazol-5-amine (BZXPh-5);
- 2-(4-aminophenyl)benzo[d]oxazol-6-amine (BZXPh-6);
- benzo[d]oxazole-2,5-diamine (BZX-5);
- and
- benzo[d]oxazole-2,6-diamine (BZX-6);
- and
- R1 and R2 are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C1-C16)alkenyl, hydroxy(C1-C12)alkenyl, perfluoro(C1-C12)alkenyl, and (C6-C10)aryl(C1-C3)alkenyl;
- and with the proviso that R1 and R2 are not both hydrogen;
- comprising:
- reacting the one or more dianhydrides, the one or more diamines, and a compound of formula (II):
- in N-methyl-2-pyrrolidone at ambient temperature to form a polyamic acid solution;
- mixing the polyamic acid solution with cyclopentanone, acetic anhydride and pyridine, and heating the mixture at a temperature of about 90° C. for about four hours in nitrogen atmosphere;
- and
- cooling to obtain the polyimide of formula (IB), wherein the polyimide of formula (IB) is soluble in an organic solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), N,N-dimethylacetamide (DMAc), propylene glycol monomethyl ether acetate (PGMEA), dimethyl sulfoxide (DMSO), cyclopentanone, cyclohexanone, 2-butanone, 2-heptanone and mixtures in any combination thereof;
- and wherein the amount of compound of formula (II) used to form the end capped polyimide of formula (IB) is about 2.5 mole percent based on total moles of dianhydride, diamine and the compound of formula (II).
24 more elements
A process for forming a patterned film comprising:
- a) forming an organic solvent soluble end capped polyimide of formula (IB):
- wherein:
- m is an integer of at least 50;
- X is derived from one or more dianhydrides selected from the group consisting of:
- 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA);
- 4-methyl-1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone;
- 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA);
- and
- 5,5′-(perfluoropentane-3,3-diyl)bis(isobenzofuran-1,3-dione);
- Y is derived from one or more diamines selected from the group consisting of:
- 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF);
- 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB);
- 4,4′-methylenebis(2,6-dimethylaniline) (DO3);
- 2-(4-aminophenyl)benzo[d]oxazol-5-amine (BZXPh-5);
- 2-(4-aminophenyl)benzo[d]oxazol-6-amine (BZXPh-6);
- benzo[d]oxazole-2,5-diamine (BZX-5);
- and
- benzo[d]oxazole-2,6-diamine (BZX-6);
- and
- R1 and R2 are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C1-C16)alkenyl, hydroxy(C1-C12)alkenyl, perfluoro(C1-C12)alkenyl, and (C6-C10)aryl(C1-C3)alkenyl;
- and with the proviso that R1 and R2 are not both hydrogen;
- by reacting the one or more dianhydrides, the one or more diamines, and a compound of formula (II):
- in N-methyl-2-pyrrolidone at ambient temperature to form a polyamic acid solution;
- mixing the polyamic acid solution with cyclopentanone, acetic anhydride and pyridine, and heating the mixture at a temperature of about 90° C. for about four hours in nitrogen atmosphere;
- and
- cooling to obtain the polyimide of formula (IB), wherein the polyimide of formula (IB) is soluble in an organic solvent selected from the group consisting of N-methyl-2-pyrrolidone (NMP), γ-butyrolactone (GBL), N,N-dimethylacetamide (DMAc), propylene glycol monomethyl ether acetate (PGMEA), dimethyl sulfoxide (DMSO), cyclopentanone, cyclohexanone, 2-butanone, 2-heptanone and mixtures in any combination thereof;
- and wherein the amount of compound of formula (II) used to form the end capped polyimide of formula (IB) is about 2.5 mole percent based on total moles of dianhydride, diamine and compound of formula (II);
- and
- b) mixing a solution of the polyimide of formula (IB) with a photo radical generator and a thermal radical generator to form a composition;
- c) coating the composition on a substrate;
- and
- d) exposing the coated substrate to actinic radiation through a mask to form an exposed film;
- e) developing the exposed film in cyclopentanone;
- and
- f) curing the developed film at a temperature of about 170° C. to obtain the patterned film.
32 more elements
Dependencies are inferred from the claim text.