Reactive end group containing polyimides and polyamic acids and photosensitive compositions thereof
Embodiments in accordance with the present invention encompass polyamic acid or polyimide polymers containing a reactive maleimide 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.
1. An end capped polyamic acid of the formula (IA) or an end capped polyimide of the formula (IB):
wherein:
m is an integer of at least 50;
n is an integer from 1 to 12, inclusive;
X is one or more distinct tetravalent organic group;
Y is one or more distinct divalent organic group, wherein Y is derived from one or more diamines selected from the group consisting of:
R 1 and R 2 are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 6 -C 10 )aryl and (C 6 -C 10 )aryl(C 1 -C 3 )alkyl provided that both R 1 and R 2 are not hydrogen; or
R 1 and R 2 taken together with the carbon atoms to which they are attached to form a 5 to 7 membered monocyclic ring or 6 to 12 membered bicyclic ring, said ring optionally containing one or more heteroatoms selected from O, N and S, and said rings optionally substituted with one or more groups selected from the group consisting of linear or branched (C 1 -C 8 )alkyl, (C 6 -C 10 )aryl, halogen, hydroxy, linear or branched (C 1 -C 8 )alkoxy and (C 6 -C 10 )aryloxy.
2. The polyamic acid or polyimide according to claim 1 , wherein X is selected from the group consisting of:
wherein
a is an integer from 0 to 4, inclusive;
is a single bond or a double bond;
each of R 3 is independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, trifluoromethyl, pentafluoroethyl, linear or branched perfluoro(C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, phenyl and phenoxy;
Z is a divalent group selected from the group consisting of: (CR 4 R 5 ) b , O(CR 4 R 5 ) b , (CR 4 R 5 ) b O, (OCR 4 R 5 ) d , (CR 4 R 5 O) d , (CR 4 R 5 ) b —O—(CR 4 R 5 ) c , (CR 4 R 5 ) b —O—(SiR 4 R 5 ) c , (CR 4 R 5 ) b —(CO)O—(CR 4 R 5 ) c , (CR 4 R 5 ) b —O(CO)—(CR 4 R 5 ) c , (CR 4 R 5 ) b —(CO)—(CR 4 R 5 ) c , (CR 4 R 5 ) b —(CO)NH—(CR 4 R 5 ) c , (CR 4 R 5 ) b —NH(CO)—(CR 4 R 5 ) c , (CR 4 R 5 ) b —NH—(CR 4 R 5 ) c , where b and c are integers which may be the same or different and each independently is 0 to 12, and d is an integer from 1 to 12, inclusive;
R 4 and R 5 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, trifluoromethyl, pentafluoroethyl, linear or branched perfluoro(C 3 -C 6 )alkyl, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, (C 2 -C 6 )acyl, (C 2 -C 6 )acyloxy, phenyl and phenoxy.
3. The polyamic acid or polyimide according to claim 1 , wherein X is derived from one or more dianhydrides selected from the group consisting of:
4. The polyamic acid or polyimide according to claim 1 , wherein Y is derived from one or more diamines selected from the group consisting of:
5. The polyamic acid or polyimide according to claim 1 , wherein the end cap is derived from a compound of formula (II):
wherein n, R 1 and R 2 are as defined in claim 1 .
6. The polyimide according to claim 5 , wherein the compound of formula (II) is selected from the group consisting of:
7. The polyimide according to claim 1 , which is selected from the group consisting of:
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2-(4-aminophenyl)benzo[d]oxazol-5-amine (BZXPh-5) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 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) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 4,4′-methylenebis(2,6-dimethylaniline) (DO3) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), bicyclo[2.2.1]heptane-2,5-diyldimethanamine (NBDA) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), a diamine of formula (III) (JD-230), 2-(4-aminophenyl)benzo[d]oxazol-5-amine (BZXPh-5) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-(1,3-phenylenebis(oxy))dianiline (APB), a diamine of formula (III) (JD-230) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 ); and
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-(((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy))dianiline (HFBAPP), 2,2′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-diamine (PFMB) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 ).
8. The polyamic acid or polyimide according to claim 1 having a weight average molecular weight (M w ) of at least 5,000.
9. The polyamic acid or polyimide according to claim 1 which is soluble in an organic solvent, wherein the organic solvent is 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 and 2-heptanone and mixtures in any combination thereof.
10. A composition comprising:
a) an end capped polyamic acid of the formula (IA) or an end capped polyimide of the formula (TB):
wherein:
m is an integer of at least 50; (from 50 to 2000, inclusive);
n is an integer from 1 to 12, inclusive;
X is one or more distinct tetravalent organic group;
Y is one or more distinct divalent organic group, wherein Y is derived from one or more diamines selected from the group consisting of:
R 1 and R 2 are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxy(C 1 -C 12 )alkyl, perfluoro(C 1 -C 12 )alkyl, (C 6 -C 10 )aryl and (C 6 -C 10 )aryl(C 1 -C 3 )alkyl provided that both R 1 and R 2 are not hydrogen; or
R 1 and R 2 taken together with the carbon atoms to which they are attached to form a 5 to 7 membered monocyclic ring or 6 to 12 membered bicyclic ring, said ring optionally containing one or more heteroatoms selected from O, N and S, and said rings optionally substituted with one or more groups selected from the group consisting of linear or branched (C 1 -C 8 )alkyl, (C 6 -C 10 )aryl, halogen, hydroxy, linear or branched (C 1 -C 8 )alkoxy and (C 6 -C 10 )aryloxy; and
b) a photo radical generator.
11. The composition according to claim 10 , wherein the polyamic acid or polyimide is derived from one or more dianhydrides selected from the group consisting of:
12. The composition according to claim 10 , wherein the polyamic acid or the polyimide is derived from one or more diamines selected from the group consisting of:
13. The composition according to claim 10 , wherein at least one end of the main chain of the polyamic acid or the polyimide is end capped with a compound of formula (II):
wherein n, R 1 and R 2 are as defined in claim 10 .
14. The composition according to claim 10 , wherein the polyimide is selected from the group consisting of:
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2-(4-aminophenyl)benzo[d]oxazol-5-amine (BZXPh-5) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 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) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 4,4′-methylenebis(2,6-dimethylaniline) (DO3) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), bicyclo[2.2.1]heptane-2,5-diyldimethanamine (NBDA) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), a diamine of formula (III) (JD-230), 2-(4-aminophenyl)benzo[d]oxazol-5-amine (BZXPh-5) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 );
a polyimide formed from 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-(1,3-phenylenebis(oxy))dianiline (APB), a diamine of formula (III) (JD-230) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 ); and
a polyimide formed from 5,5′-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) (6FDA), 1H,3H-benzo[1,2-c:4,5-c′]difuran-1,3,5,7-tetraone (PMDA), 4,4′-(((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(oxy))dianiline (HFBAPP), 2,2′-bis(trifluoromethyl)[1,1′-biphenyl]-4,4′-diamine (PFMB) and 1-(2-aminoethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (DMMIEt-NH 2 ).
15. The composition according to claim 10 , wherein the photo radical generator is selected from the group consisting of:
a compound of formula (IV):
wherein
R 6 and R 7 are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 8 )alkyl and (C 6 -C 10 )aryl; or
R 6 and R 7 taken together with the nitrogen atom to which they are attached to form a 5 to 7 membered monocyclic ring or 6 to 12 membered bicyclic ring, said ring optionally containing one or more heteroatoms selected from 0 and N, and said ring optionally substituted with linear or branched (C 1 -C 8 )alkyl, (C 6 -C 10 )aryl, halogen, hydroxy, linear or branched (C 1 -C 8 )alkoxy and (C 6 -C 10 )aryloxy; and
R 8 , R 9 and R 10 are the same or different and each independently of one another is selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, hydroxy, halogen, linear or branched (C 1 -C 12 )alkoxy and (C 6 -C 10 )aryloxy; and
a compound of formula (V):
wherein
d is an integer from 0 to 3, inclusive;
R 11 is selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, hydroxy, halogen, linear or branched (C 1 -C 12 )alkoxy and (C 6 -C 10 )aryloxy;
R 12 is selected from the group consisting of linear or branched (C 1 -C 16 )alkyl, (C 3 -C 8 )cycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 6 -C 10 )aryl(C 1 -C 6 )alkylphosphinate, (C 6 -C 10 )heterocycle(C 1 -C 3 )alkyl, a group of formula C(O)—(OCH 2 CH 2 ) e —OC(O)C(O)(C 6 -C 10 )aryl, where e is an integer from 2 to 4, inclusive, C(O)C(O)O(C 1 -C 3 )alkyl and a group of formula (C):
wherein
R 13 is linear or branched (C 1 -C 16 )alkyl; and
R 14 is (C 6 -C 10 )aryl;
and where each of said alkyl, cycloalkyl, aryl and heterocycle may additionally be substituted with one or more groups selected from the group consisting of hydroxy, linear or branched (C 1 -C 6 )alkyl, linear or branched (C 1 -C 6 )alkoxy and linear or branched thio(C 1 -C 6 )alkyl.
16. The composition according to claim 10 , wherein the photo radical generator is selected from the group consisting of:
and a mixture in any combination thereof.
17. The composition according to claim 10 , further comprising one or more photo sensitizers, which is of the formula (VI):
wherein
R 15 and R 16 are the same or different and independently of each other selected from the group consisting of hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl and (C 6 -C 10 )-aryloxy.
18. The composition according to claim 17 , wherein the photosensitizer is selected from the group consisting of:
19. The composition according to claim 10 , further comprising one or more crosslinking agent selected from the group consisting of:
20. A cured product comprising the composition of claim 10 .