Polymers of maleimide and cycloolefinic monomers as permanent dielectric materials

1. A polymer consisting of:

one or more distinct first repeating unit represented by formula (IA), each of said first repeating unit is derived from a monomer of formula (I):

wherein:

represents a position at which the bonding takes place with another repeat unit;

m is an integer 0, 1 or 2;

R 1 , R 2 , R 3 and R 4 are 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 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, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, —(CH 2 ) a —(O—(CH 2 ) b ) c —O—(C 1 -C 4 )alkyl, where a, b and c are integers from 1 to 4, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and halogen;

one or more distinct second repeating unit represented by formula (IIA), each of said second repeating unit is derived from a monomer of formula (II):

wherein:

R 5 , R 6 , R 7 and R 8 are each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl, and fluorinated or perfluorinated(C 1 -C 9 )alkyl; and

one or more distinct third repeating unit represented by formula (IIIA), each of said third repeating unit is derived from a monomer of formula (III):

wherein:

R 9 and R 10 are each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 12 )alkyl, (C 3 -C 8 )cycloalkyl, (C 6 -C 12 )aryl and (C 6 -C 12 )aryl(C 1 -C 12 )alkyl; and

R 11 is selected from linear or branched (C 1 -C 12 )alkyl, (C 3 -C 8 )cycloalkyl, (C 6 -C 12 )aryl and (C 6 -C 12 )aryl(C 1 -C 12 )alkyl.

2. The polymer according to claim 1 , wherein said polymer consisting of two or more distinct repeat units of formula (Ia).

3. The polymer according to claim 1 , wherein

m is 0; and

R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, linear or branched (C 1 -C 12 )alkyl, phenyl(C 1 -C 3 )alkyl and —(CH 2 ) a —(O—(CH 2 ) b ) c —O—(C 1 -C 4 )alkyl, where a is 1 or 2, b is 2 to 4 and c is 2 or 3.

4. The polymer according to claim 1 , wherein R 5 and R 6 are independently of each other selected from hydrogen and methyl; each R 7 and R 8 independently of one another selected from hydrogen, methyl, ethyl, n-propyl and n-butyl; R 9 and R 10 are independently of each other selected from hydrogen and methyl; and R 11 is selected from hexyl, cyclohexyl and phenyl.

5. The polymer according to claim 1 , wherein said one or more first repeating unit is derived from a monomer selected from the group consisting of:

5-hexylbicyclo[2.2.1]hept-2-ene;

5-octylbicyclo[2.2.1]hept-2-ene;

5-decylbicyclo[2.2.1]hept-2-ene;

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

1-(bicyclo[2.2.1]hept-5-en-2-yl)-2,5,8,11-tetraoxadodecane;

5-benzylbicyclo[2.2.1]hept-2-ene; and

5-phenethylbicyclo[2.2.1]hept-2-ene.

6. The polymer according to claim 1 , wherein said second repeating unit is derived from a monomer selected form the group consisting of:

maleic anhydride;

2-methyl-maleic anhydride (3-methylfuran-2,5-dione);

2,3-dimethyl-maleic anhydride (3,4-dimethylfuran-2,5-dione);

2-ethyl-maleic anhydride (3-ethylfuran-2,5-dione);

2,3-diethyl-maleic anhydride (3,4-diethylfuran-2,5-dione);

2-trifluoromethyl-maleic anhydride (3-trifluoromethylfuran-2,5-dione);

2,3-bis(trifluoromethyl)-maleic anhydride (3,4-bis(trifluoromethyl)furan-2,5-dione); and

2-methyl-3-trifluoromethyl-maleic anhydride (3-methyl-4-(trifluoromethyl)furan-2,5-dione).

7. The polymer according to claim 2 , wherein said third repeating unit is derived from a monomer selected form the group consisting of:

N-ethylmaleimide (1-ethyl-1H-pyrrole-2,5-dione);

N-butylmaleimide (1-butyl-1H-pyrrole-2,5-dione);

N-hexylmaleimide (1-hexyl-1H-pyrrole-2,5-dione);

N-octylmaleimide (1-octyl-1H-pyrrole-2,5-dione);

N-cyclopentylmaleimide (1-cyclopentyl-1H-pyrrole-2,5-dione);

N-cyclohexylmaleimide (1-cyclohexyl-1H-pyrrole-2,5-dione);

N-cycloheptylmaleimide (1-cycloheptyl-1H-pyrrole-2,5-dione);

N-phenylmaleimide (1-phenyl-1H-pyrrole-2,5-dione); and

N-benzylmaleimide (1-benzyl-1H-pyrrole-2,5-dione).

8. The polymer according to claim 1 , wherein said first repeat unit is derived from:

5-octylbicyclo[2.2.1]hept-2-ene;

5-decylbicyclo[2.2.1]hept-2-ene;

5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]kept-2-ene;

1-(bicyclo[2.2.1]hept-5-en-2-yl)-2,5,8,11-tetraoxadodecane; and

5-phenethylbicyclo[2.2.1]kept-2-ene;

said second repeat unit is derived from maleic anhydride;

and said third repeat unit is derived from:

N-hexylmaleimide (1-hexyl-1H-pyrrole-2,5-dione);

N-cyclohexylmaleimide (1-cyclohexyl-1H-pyrrole-2,5-dione); and

N-phenylmaleimide (1-phenyl-1H-pyrrole-2,5-dione).

9. The polymer according to claim 1 , wherein said first repeat unit is derived from:

5-decylbicyclo[2.2.1]hept-2-ene;

5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene; and

5-phenethylbicyclo[2.2.1]hept-2-ene;

said second repeat unit is derived from maleic anhydride; and

said third repeat unit is derived from:

N-hexylmaleimide (1-hexyl-1H-pyrrole-2,5-dione);

N-cyclohexylmaleimide (1-cyclohexyl-1H-pyrrole-2,5-dione); and

N-phenylmaleimide (1-phenyl-1H-pyrrole-2,5-dione).

10. A layer forming composition comprising:

a polymer consisting of:

one or more distinct first repeating unit represented by formula (IA), each of said first repeating unit is derived from a monomer of formula (I):

wherein:

represents a position at which the bonding takes place with another repeat unit;

m is an integer 0, 1 or 2;

R 1 , R 2 , R 3 and R 4 are 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 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, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryl, (C 5 -C 10 )heteroaryl(C 1 -C 3 )alkyl, hydroxy, (C 1 -C 12 )alkoxy, (C 3 -C 12 )cycloalkoxy, (C 6 -C 12 )bicycloalkoxy, (C 7 -C 14 )tricycloalkoxy, —(CH 2 ) a —(O—(CH 2 ) b ) c —O—(C 1 -C 4 )alkyl, where a, b and c are integers from 1 to 4, (C 6 -C 10 )aryloxy(C 1 -C 3 )alkyl, (C 5 -C 10 )heteroaryloxy(C 1 -C 3 )alkyl, (C 6 -C 10 )aryloxy, (C 5 -C 10 )heteroaryloxy, and halogen;

one or more distinct second repeating unit represented by formula (IIA), each of said second repeating unit is derived from a monomer of formula (II):

wherein:

R 5 , R 6 , R 7 and R 8 are each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl, and fluorinated or perfluorinated(C 1 -C 9 )alkyl; and

one or more distinct third repeating unit represented by formula (IIIA), each of said third repeating unit is derived from a monomer of formula (III):

wherein:

R 9 and R 10 are each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 12 )alkyl, (C 3 -C 8 )cycloalkyl, (C 6 -C 12 )aryl and (C 6 -C 12 )aryl(C 1 -C 12 )alkyl; and

R 11 is selected from linear or branched (C 1 -C 12 )alkyl, (C 3 -C 8 )cycloalkyl, (C 6 -C 12 )aryl and (C 6 -C 12 )aryl(C 1 -C 12 )alkyl;

a photo active compound;

an epoxy resin; and

a solvent.

11. The composition according to claim 10 where said polymer consisting of two or more distinct repeat units of formula (Ia).

12. The composition according to claim 10 , wherein said first repeat unit of said polymer is derived from:

5-decylbicyclo[2.2.1]hept-2-ene;

5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene; and

5-phenethylbicyclo[2.2.1]hept-2-ene;

said second repeat unit is derived from maleic anhydride; and

said third repeat unit is derived from:

N-hexylmaleimide (1-hexyl-1H-pyrrole-2,5-dione);

N-cyclohexylmaleimide (1-cyclohexyl-1H-pyrrole-2,5-dione); and

N-phenylmaleimide (1-phenyl-1H-pyrrole-2,5-dione).

13. The composition according to claim 10 , 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 (VIIa) and (VIIb), respectively:

or a sulfonyl benzoquinone diazide group represented by structural formula (VIIc):

14. The composition according to claim 13 , wherein said photoactive compound is

wherein at least one of Q is a group of formula (VIIa) or (VIIb):

and the remaining Q is hydrogen.

15. The composition according to claim 10 , wherein said epoxy resin is selected from the group consisting of:

bisphenol A epichlorohydrin epoxy resin;

polypropylene glycol epichlorohydrin epoxy resin;

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

glycidyl ether of para-tertiary butyl phenol;

polyethylene glycol diglycidyl ether;

polypropylene glycol diglycidyl ether;

and a mixture in any combination thereof.

16. The composition according to claim 10 , wherein said solvent is selected from the group consisting of propyleneglycol monomethylether acetate, gamma-butyrolactone, N-methylpyrrolidone and a mixture in any combination thereof.

17. The composition according to claim 10 , wherein said solvent is propyleneglycol monomethylether acetate.

18. The composition according to claim 10 , wherein said composition further comprises one or more additives selected from the group consisting of:

adhesion promoters;

antioxidants;

surfactants;

thermal acid or thermal base generator; and

mixtures in any combination thereof.

19. A process for forming a cured product, comprising:

(i) applying the layer forming composition of claim 10 on a substrate to form a coating film;

(ii) exposing the coating film to light through a desired pattern mask;

(iii) dissolving and removing the exposed portions by developing with an alkaline developer to obtain the desired pattern; and

(iv) heating the obtained desired pattern.

20. A cured product obtained by curing the layer forming composition of claim 10 .