US2020283580A1PendingUtilityA1
Unsaturated cyclic anhydride end capped polyimides and polyamic acids and photosensitive compositions thereof
Est. expiryMar 5, 2039(~12.6 yrs left)· nominal 20-yr term from priority
Inventors:Pramod Kandanarachchi
C08G 73/1014C08L 79/08C08G 73/1067C08G 73/1032G03F 7/037C08G 73/1078C08G 73/1025C08G 73/1085G03F 7/029C08G 73/1039G03F 7/031C08G 73/105C08G 73/1042C08K 5/0025
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Claims
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.
Claims
exact text as granted — not AI-modifiedWhat is claimed is:
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;
X is one or more distinct tetravalent organic group;
Y is one or more distinct divalent organic group; and
R 1 and R 2 are the same or different and each independently of one another selected from the group consisting of linear or branched (C 1 -C 16 )alkenyl, hydroxy(C 1 -C 12 )alkenyl, perfluoro(C 1 -C 12 )alkenyl, and (C 6 -C 10 )aryl(C 1 -C 3 )alkenyl.
2 . The polyamic acid or polyimide according to claim 1 , wherein 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);
5,5′-(perfluoropentane-3,3-diyl)bis(isobenzofuran-1,3-dione);
5,5′-carbonylbis(isobenzofuran-1,3-dione) (BTDA);
5,5′-azanediylbis(isobenzofuran-1,3-dione);
[4,5′-biisobenzofuran]-1,1′,3,3′-tetraone (α-BPDA);
5,5′-oxybis(isobenzofuran-1,3-dione) (ODPA);
[5,5′-biisobenzofuran]-1,1′,3,3′-tetraone (BPDA); and
5-(2,5-dioxotetrahydrofuran-3-yl)-7-methyl-3a,4,5,7a-tetrahydroisobenzofuran-1,3-dione (D1901).
3 . The polyamic acid or polyimide according to claim 1 , wherein 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);
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);
4,4′-oxydianiline (4,4′-ODA);
4,4′-(1,3-phenylenebis(oxy))dianiline (APB);
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);
benzo[d]oxazole-2,6-diamine (BZX-6);
bicyclo[2.2.1]heptane-2,5-diyldimethanamine (NBDA);
a diamine of formula (MA)
where, n=2 to 6 (JD-230);
4,4′-(perfluoropropane-2,2-diyl)bis(2-aminophenol) (BAFA); and
4,4′-(propane-2,2-diyl)bis(2-aminophenol) (DABPA).
4 . The polyamic acid or polyimide according to claim 1 , 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 R 1 and R 2 are as defined in claim 1 .
5 . The polyimide according to claim 4 , wherein the compound of formula (II) is selected from the group consisting of:
itaconic anhydride (IA);
3-methyl-4-methylenedihydrofuran-2,5-dione;
3-(2-methylallyl)dihydrofuran-2,5-dione (MPSA); and
3-methyl-4-(2-methylallyl)dihydrofuran-2,5-dione.
6 . 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 itaconic anhydride (IA); 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 itaconic anhydride (IA); 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 itaconic anhydride (IA); 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′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2-(4-aminophenyl)benzo[d]oxazol-5-amine (BZXPh-5) and itaconic anhydride (IA).
7 . The polyamic acid or polyimide according to claim 1 having a weight average molecular weight (M w ) of at least 5,000 and is soluble in an organic solvent.
8 . The polyamic acid or polyimide according to claim 7 , 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.
9 . A composition comprising:
a) 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;
X is one or more distinct tetravalent organic group;
Y is one or more distinct divalent organic group; and
R 1 and R 2 are the same or different and each independently of one another selected from the group consisting of linear or branched (C 1 -C 16 )alkenyl, hydroxy(C 1 -C 12 )alkenyl, perfluoro(C 1 -C 12 )alkenyl, and (C 6 -C 10 )aryl(C 1 -C 3 )alkenyl;
b) a photo radical generator; and
c) a thermal radical generator.
10 . The composition according to claim 9 , wherein the polyamic acid or polyimide 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);
5,5′-(perfluoropentane-3,3-diyl)bis(isobenzofuran-1,3-dione);
5,5′-carbonylbis(isobenzofuran-1,3-dione) (BTDA);
5,5′-azanediylbis(isobenzofuran-1,3-dione);
[4,5′-biisobenzofuran]-1,1′,3,3′-tetraone (α-BPDA);
5,5′-oxybis(isobenzofuran-1,3-dione) (ODPA); and
[5,5′-biisobenzofuran]-1,1′,3,3′-tetraone (BPDA).
11 . The composition according to claim 9 , wherein the polyamic acid or the polyimide 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);
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);
4,4′-oxydianiline (4,4′-ODA);
4,4′-(1,3-phenylenebis(oxy))dianiline (APB);
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);
benzo[d]oxazole-2,6-diamine (BZX-6);
bicyclo[2.2.1]heptane-2,5-diyldimethanamine (NBDA); and
a diamine of formula (III)
where, n=2 to 6 (JD-230).
12 . The composition according to claim 9 , 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 R 1 and R 2 are as defined in claim 9 .
13 . The composition according to claim 9 , 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 itaconic anhydride (IA); 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 itaconic anhydride (IA); 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 itaconic anhydride (IA); 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′-([1,1′-biphenyl]-4,4′-diylbis(oxy))bis(3-(trifluoromethyl)aniline) (6BF), 2-(4-aminophenyl)benzo[d]oxazol-5-amine (BZXPh-5) and itaconic anhydride (IA).
14 . The composition according to claim 9 , 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 ) c —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.
15 . The composition according to claim 9 , wherein the photo radical generator is selected from the group consisting of:
(1-hydroxycyclohexyl)(phenyl)methanone;
2,2-dimethoxy-1,2-diphenylethan-1-one;
(phenylphosphoryl)bis(mesitylmethanone);
(diphenylphosphoryl)(mesityl)methanone;
ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate;
(diphenylphosphoryl)(mesityl)methanone;
2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one;
2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one;
oxybis(ethane-2,1-diyl) bis(2-oxo-2-phenylacetate);
(E)-2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one;
methyl 2-oxo-2-phenylacetate;
benzophenone;
2-hydroxy-2-methyl-1-phenylpropan-1-one;
2-hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one;
2,2-dimethyl-1-phenylpropan-1-one;
and a mixture in any combination thereof.
16 . The composition according to claim 9 , wherein the thermal radical generator is selected from the group consisting of: benzoyl peroxide, dicumyl peroxide, m-chloroperbenzoic acid, methyl ethyl ketone peroxide, azobisisobutyronitrile (AIBN), (1-phenyl-3,3-dipropyltriazene), (1-(phenyldiazenyl)pyrrolidine), (1-(phenyldiazenyl)piperidine) and (1-(phenyldiazenyl)azepane).
17 . The composition according to claim 9 , further comprising one or more photosensitizers selected from the group consisting of:
1-chloro-4-methoxy-9H-thioxanthen-9-one;
1-chloro-4-ethoxy-9H-thioxanthen-9-one;
1-chloro-4-propoxy-9H-thioxanthen-9-one;
1-chloro-2-propoxy-9H-thioxanthen-9-one;
1-chloro-2-ethoxy-9H-thioxanthen-9-one;
1-chloro-2-methoxy-9H-thioxanthen-9-one;
1-chloro-4-methyl-9H-thioxanthen-9-one;
1-chloro-4-ethyl-9H-thioxanthen-9-one;
1-bromo-4-propoxy-9H-thioxanthen-9-one;
1-chloro-4-phenoxy-9H-thioxanthen-9-one;
2,4-diethyl-9H-thioxanthen-9-one; and
2-isopropyl-9H-thioxanthen-9-one.
18 . The composition according to claim 9 , further comprising one or more crosslinking agents selected from the group consisting of:
(2,4,6-trioxo-1,3,5-triazinane-1,3,5-triyl)tris(ethane-2,1-diyl) triacrylate (TAEICY);
(oxybis(methylene))bis(2-ethylpropane-2,1,3-triyl) tetraacrylate (BTMPTA);
2,2′-(((2-ethyl-2-((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxirane) (TMPTGE);
2,2-bis(((3-mercaptopropanoyl)oxy)methyl)propane-1,3-diyl bis(3-mercaptopropanoate) (PET3MP); and
2,2,2′,2′-tetrakis(3-mercaptopropanoyl)-3,3′(3-mercaptopropanoyl)-1,1′-dipropyl ether (DPEH3MP).
19 . A cured product comprising the composition of claim 9 .
20 . A microelectronic or optoelectronic device comprising one or more of a redistribution layer (RDL) structure, a chip-stack structure, a CMOS image sensor dam structure, where said structures comprising a composition according to claim 9 .Join the waitlist — get patent alerts
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