Nadic anhydride polymers and photosensitive compositions derived therefrom

1. A copolymer consisting of a first repeat unit which is derived from a monomer selected from the group consisting of:

3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione (nadic anhydride); and

5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione; and a second repeat unit which is derived from a monomer selected from the group consisting of:

2-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethyl acetate (NBCH 2 GlyOAc);

2-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethanol (NBCH 2 GlyOH);

trioxanonanenorbornene (NBTON);

tetraoxadodecanenorbomnene (NBTODD);

5-(3-methoxybutoxy)methyl-2-norbornene (NB-3-MBM);

5-(3-methoxypropoxy)methyl-2-norbornene (NB-3-MPM);

5-(2-(2-ethoxyethoxy)ethyl)bicyclo[2.2.1]hept-2-ene;

5-(2-(2-(2-propoxyethoxy)ethoxy)ethoxy)bicyclo[2.2.1]hept-2-ene;

2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol (HFANB);

4-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)butan-2-ol (HFACH 2 NB);

5-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)pentan-2-ol (HFACH 2 CH 2 NB);

2-((bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol; and

2-((2-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethoxy)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol (GlyHFIPNB).

2. A terpolymer consisting of a first repeat unit which is derived from a monomer selected from the group consisting of:

3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione (nadic anhydride); and

5-methyl-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione;

and a second re eat unit which is derived from a monomer selected from the group consisting of:

2-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethyl acetate (NBCH 2 GlyOAc);

2-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethanol (NBCH 2 GlyOH);

trioxanonanenorbornene (NBTON);

tetraoxadodecanenorbornene (NBTODD);

5-(3-methoxybutoxy)methyl-2-norbornene (NB-3-MBM);

5-(3-methoxypropoxy)methyl-2-norbornene (NB3-MPM);

5-(2-(2-(2-propoxyethoxy)ethoxy)ethoxy)bicyclo[2.2.1]hept-2-ene;

2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol (HFANB);

4-(bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)butan-2-ol (HFACH 2 NB);

5-bicyclo[2.2.1]hept-5-en-2-yl)-1,1,1-trifluoro-2-(trifluoromethyl)pentan-2-ol (HFACH 2 CH 2 NB);

2-((bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol; and

2-((2-bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethoxy)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol (GlyHFIPNB); and

a third repeat unit which is derived from a monomer selected from the group consisting of:

bicyclo[2.2.1]hept-2-ene (NB);

5-methylbicyclo[2.2.1]hept-2-ene (MeNB);

5-ethylbicyclo[2.2.1]hept-2-ene (EtNB);

5-hexylbicyclo[2.2.1]hept-2-ene (HexNB);

5-octylbicyclo[2.2.1]hept-2-ene (OctNB);

5-decylbicyclo[2.2.1]hept-2-ene (DecNB);

5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene (HexenylNB);

bicyclo[2.2.1]hept-5-en-2-ylmethanamine;

tert-butyl (bicyclo[2.2.1]hept-5-en-2-ylmethyl)carbamate;

tert-butyl 4-((bicyclo[2.2.1]hept-5-en-2-ylmethyl)amino)-4-oxobutanoate;

(E)-4-((bicyclo[2.2.1]hept-5-en-2-ylmethyl)amino)-2,3-di methyl-4-oxobut-2-enoic acid;

N-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-2,3,4,5,7-pentahydroxyheptanamide;

N-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1-trifluoromethanesulfonamide;

1-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (MeDMMINB);

1-(3-(bicyclo[2.2.1]hept-5-en-2-yl)propyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (PrDMMINB);

1-(4-(bicyclo[2.2.1]hept-5-en-2-yl)butyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (BuDMMINB);

1-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)-3,4-dimethyl-1H-pyrrole-2,5-dione (HexDMMINB);

bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate (NBMeOAc);

2-((bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl)oxirane (MGENB);

2-(bicyclo[2.2.1]hept-5-en-2-yl)oxirane;

2-(6-(bicyclo[2.2.1]hept-5-en-2-yl)hexyl)oxirane; and

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

bicyclo[2.2.1]hept-5-ene-2-carboxylic acid;

N-(2,2,2-trifluoroacetyl)bicyclo[2.2.1]hept-5-ene-2-carboxamide;

2-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid (NBCH 2 CO 2 H);

3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid (NBCH 2 CH 2 CO 2 H);

ethyl 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoate;

tert-butyl 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoate;

4-(bicyclo[2.2.1]hept-5-en-2-yl)butanoic acid (NBCH 2 CH 2 CH 2 CO 2 H);

2-(bicyclo[2.2.1]hept-5-en-2-yl)-N-(2-hydroxyphenyl)acetamide;

3-(bicyclo[2.2.1]hept-5-en-2-yl)-N-(2-hydroxy henyl)propanamide;

4-(bicyclo[2.2.1]hept-5-en-2-yl)phenol;

4-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-2-methoxyphenol.

3. The copolymer of claim 1 which is selected from the group consisting of:

a copolymer of nadic anhydride and trioxanonanenorbornene;

a copolymer of nadic anhydride and tetraoxadodecanenorbornene;

a copolymer of nadic anhydride and 5-(3-methoxypropoxy)methyl-2-norbornene;

a copolymer of nadic anhydride and 5-(3-methoxybutoxy)methyl-2-norbornene;

a copolymer of nadic anhydride and 5-(2-(2-ethoxyethoxy)ethyl)bicyclo[2.2.1]hept-2-ene;

a copolymer of nadic anhydride and 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,3,3,3-hexafluoropropan-2-ol.

4. The terpolymer of claim 2 which is selected from the group consisting of:

a terpolymer of nadic anhydride, trioxanonanenorbornene and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene;

a terpolymer of nadic anhydride, trioxanonanenorbornene and bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate;

a terpolymer of nadic anhydride, trioxanonanenorbornene and 2-((2-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethoxy)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol.

5. A composition consisting of:

(i) a copolymer according to claim 1 which is selected from the group consisting of:

a copolymer of nadic anhydride and trioxanonanenorbornene;

a copolymer of nadic anhydride and tetraoxadodecanenorbornene;

a copolymer of nadic anhydride and 5-(3-methoxypropoxy)methyl-2-norbornene;

a copolymer of nadic anhydride and 5-(3-methoxybutoxy)methyl-2-norbornene;

a copolymer of nadic anhydride and 5-(2-(2-ethoxyethoxy)ethyl)bicyclo[2.2.1]hept-2-ene; and

a copolymer of nadic anhydride and 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol;

(ii) a photo active compounds; and

(iii) a solvent.

6. A composition consisting of:

(i) a terpolymer according to claim 2 which is selected from the group consisting of:

a terpolymer of nadic anhydride, trioxanonanenorbornene and 5-(hex-5-en-1-yl)bicyclo[2.2.1]hept-2-ene;

a terpolymer of nadic anhydride, trioxanonanenorbornene and bicyclo[2.2.1]hept-5-en-2-ylmethyl acetate; and

a terpolymer of nadic anhydride, trioxanonanenorbornene and 2-((2-(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)ethoxy)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol;

(ii) a photo active compound; and

(iii) a solvent.

7. The composition according to claim 5 , wherein said photoactive compound comprises a 1,2-naphthoquinonediazide-5-sulfonyl moiety and/or a 1,2-naphthoquinonediazide-4-sulfonyl moiety as represented by structural formulae (IVa) and (IVb), respectively:

or a sulfonyl benzoquinone diazide group represented by structural formula (IVc).

8. The composition according to claim 7 , wherein said photoactive compound is

wherein at least one of Q is a group of formula (IVa) or (IVb):

and the remaining Q is hydrogen.

9. The composition according to claim 5 , which further comprises one or more crosslinking agents selected from the group consisting of:

di-tert-butyl ((perfluoropropane-2,2-diyl)bis(6-hydroxy-2,1-phenylene))dicarbamate;

di-tert-butyl (propane-2,2-diylbis(6-hydroxy-2,1-phenylene))dicarbamate;

silicone modified epoxy resin;

2,2′-(((2-ethyl-2-((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxirane);

bisphenol A epichlorohydrin based epoxy resin;

polypropylene glycol epichlorohydrin based epoxy resin;

bis(4-(oxiran-2-ylmethoxy)phenyl)methane;

glycidyl ether of para-tertiary butyl phenol (Heloxy 65);

polyethylene glycol diglycidyl ether (PEGDGE);

polypropylene glycol diglycidyl ether (PPGDGE);

and a mixture in any combination thereof.

10. The composition according to claim 5 , wherein said photoactive compound is a photoacid generator selected from the group consisting of:

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tetrakis(perfluorophenyl)borate;

(2-(4-methoxynaphthalen-1-yl)-2-oxoethyl)dimethylsulfonium tetrakis(perfluorophenyl)borate;

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tris((trifluoromethyl)sulfonyl)methanide;

(4-ethylphenyl)(4-isopropylphenyl)iodonium tetrakis(perfluorophenyl)borate;

di-(p-t-butylphenyl)iodonium tris(trifluoromethanesulfonyl)methanide;

and a mixture in any combination thereof.

11. A semiconductor device comprising a laminated semiconductor element where said lamination consists of a composition according to claim 5 .

12. A microelectronic or optoelectronic device comprising one or more of a redistribution layer (RDL) structure, a chip-stack structure or a CMOS image sensor dam structure, where said structures further comprise a composition according to claim 5 .

13. A film comprising the composition of claim 5 .

14. A method of forming a film for the fabrication of a microelectronic or optoelectronic device comprising:

coating a suitable substrate with a composition according to claim 5 to form a film;

patterning the film with a mask by exposing to a suitable radiation;

developing the film after exposure to form a photo-pattern; and

curing the film by heating to a suitable temperature.

15. A cured product obtained by curing the composition of claim 5 .

16. An optoelectronic or microelectronic device comprising the cured product of claim 15 .

17. The composition according to claim 6 , wherein said photoactive compound comprises a 1,2-naphthoquinonediazide-5-sulfonyl moiety and/or a 1,2-naphthoquinonediazide-4-sulfonyl moiety as represented by structural formulae (IVa) and (IVb), respectively:

or a sulfonyl benzoquinone diazide group represented by structural formula (IVc).

18. The composition according to claim 17 , wherein said photoactive compound is or

wherein at least one of Q is a group of formula (IVa) or (IVb):

and the remaining Q is hydrogen.

19. The composition according to claim 6 , which further comprises one or more crosslinking agents selected from the group consisting of:

di-tert-butyl ((perfluoropropane-2,2-diyl)bis(6-hydroxy-2,1-phenylene))dicarbamate;

di-tert-butyl (propane-2,2-diylbis(6-hydroxy-2,1-phenylene))dicarbamate;

silicone modified epoxy resin;

2,2′-(((2-ethyl-2-((oxiran-2-ylmethoxy)methyl)propane-1,3-diyl)bis(oxy))bis(methylene))bis(oxirane);

bisphenol A epichlorohydrin based epoxy resin;

polypropylene glycol epichlorohydrin based epoxy resin;

bis(4-(oxiran-2-ylmethoxy)phenyl)methane;

glycidyl ether of para-tertiary butyl phenol (Heloxy 65);

polyethylene glycol diglycidyl ether (PEGDGE);

polypropylene glycol diglycidyl ether (PPGDGE);

and a mixture in any combination thereof.

20. The composition according to claim 6 , wherein said photoactive compound is a photoacid generator selected from the group consisting of:

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tetrakis(perfluorophenyl)borate;

(2-(4-methoxynaphthalen-1-yl)-2-oxoethyl)dimethylsulfonium tetrakis(perfluorophenyl)borate;

tris(4-((4-acetylphenyl)thio)phenyl)sulfonium tris((trifluoromethyl)sulfonyl)methanide;

(4-ethylphenyl)(4-isopropylphenyl)iodonium tetrakis(perfluorophenyl)borate;

di-(p-t-butylphenyl)iodonium tris(trifluoromethanesulfonyl)methanide;

and a mixture in any combination thereof.