Polymers derived from norbornadiene and maleic anhydride and use thereof

1. A composition comprising:

a polymer comprising 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;

each of R 1 , R 2 , R 3 and R 4 is independently 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(C 1 -C 3 )alkyl, —CO 2 R, halogen and a group of formula (A):

where

R is (C 1 -C 6 )alkyl or tri((C 1 -C 6 )alkyl)silyl; and

R a is selected from the group consisting of —(CH 2 ) p —, —(CH 2 ) q —OCH 2 — and —(CH 2 ) q —(OCH 2 CH 2 ) r —OCH 2 —, where p is an integer from 0 to 6, q is an integer from 0 to 4 and r is an integer from 0 to 3;

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

wherein:

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

R 7 is selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl, fluorinated or perfluorinated(C 1 -C 9 )alkyl, and —(CH 2 ) a -(0-(CH 2 ) b ) c —O(C 1 -C 6 )alkyl, where a, b and c are integers from 1 to 4; and

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

wherein:

each of R 8 and R 9 is independently selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl and fluorinated or perfluorinated(C 1 -C 9 )alkyl;

R 10 is selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, (C 3 -C 9 )cycloalkyl, (C 3 -C 9 )cycloalkyl(C 1 -C 10 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 4 )alkyl, (C 1 -C 16 )alkylCO 2 R, (C 1 -C 16 )alkylCH 2 OR, (C 6 -C 10 )arylCO 2 R and (C 6 -C 10 )arylCH 2 OR;

where R is hydrogen, (C 1 -C 6 )alkyl or tri((C 1 -C 6 )alkyl)silyl;

and wherein molar amount of repeating unit of formula (IIIA) is at least 3 mole percent;

a photoactive compound;

a cross-linking agent; and

a carrier solvent.

2. The composition according to claim 1 , wherein said polymer further comprises one or more distinct fourth repeat unit of formula (IVA) derived from a monomer of formula (IV):

wherein:

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

m is an integer 0, 1 or 2;

each of R 11 , R 12 , R 13 and R 14 is independently 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, (C 1 -C 6 )acyloxy and halogen.

3. The composition according to claim 1 , wherein said polymer further comprises a repeat unit of formula (IB) derived from the monomer of formula (I):

wherein R 1 , R 2 , R 3 and R 4 are each as defined in claim 1 .

4. The composition according to claim 1 , wherein said polymer comprises one or more distinct repeating units of formula (IA) wherein, each of R 1 , R 2 , R 3 and R 4 is independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 1 -C 12 )alkyl and phenyl(C 1 -C 3 )alkyl.

5. The composition according to claim 1 , wherein said polymer comprises one or more distinct repeating units of formula (IIA) wherein, R 5 and R 6 are the same or different and independently of each other selected from hydrogen or methyl; and R 7 is selected from hydrogen, methyl, ethyl, n-propyl, iso-propyl or n-butyl.

6. The composition according to claim 1 , wherein said polymer comprises one or more distinct repeating units of formula (IIIA) wherein, R 8 and R 9 are the same or different and independently of each other selected from hydrogen or methyl; and R 10 is selected from hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, benzyl or phenethyl.

7. The composition according to claim 2 , wherein said polymer comprises one or more distinct repeating units of formula (IVA) wherein:

m is 0;

each of R 11 , R 12 , R 13 and R 14 is independently selected from the group consisting of hydrogen, methyl, ethyl, 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.

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

bicyclo[2.2.1]hepta-2,5-diene (norbornadiene);

2-methylbicyclo[2.2.1]hepta-2,5-diene;

2-butylbicyclo[2.2.1]hepta-2,5-diene;

2-hexylbicyclo[2.2.1]hepta-2,5-diene;

2-octylbicyclo[2.2.1]hepta-2,5-diene;

2-phenethylbicyclo[2.2.1]hepta-2,5-diene;

tert-butyl bicyclo[2.2.1]hepta-2,5-diene-2-carboxylate;

trimethylsilyl bicyclo[2.2.1]hepta-2,5-diene-2-carboxylate; and

bicyclo[2.2.1]hepta-2,5-dien-2-ylmethanol.

9. The composition according to claim 1 , wherein said polymer is having one or more distinct second repeating unit derived from a respective monomer selected from 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).

10. The composition according to claim 1 , wherein said polymer is having one or more distinct third repeating unit derived from a respective monomer selected from the group consisting of:

maleimide;

N-methylmaleimide;

N-butylmaleimide;

3-methylmaleimide (3-methylpyrrolidine-2,5-dione);

N-cyclohexylmaleimide;

N-phenylmaleimide;

N-benzylmaleimide; and

N-phenethylmaleimide.

11. The composition according to claim 2 , wherein said polymer is having one or more distinct fourth repeating unit derived from a respective monomer selected from the group consisting of:

norbornene;

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 (NBTON);

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]kept-2-ene.

12. The composition according to claim 1 , wherein said polymer is selected from the group consisting of:

a terpolymer of norbornadiene (NBD), maleic anhydride in which maleic anhydride repeating unit is ring opened with methanol and N-phenylmaleimide;

a terpolymer of norbornadiene (NBD), maleic anhydride in which maleic anhydride repeating unit is ring opened with methanol and maleimide;

a terpolymer of norbornadiene (NBD), maleic anhydride in which maleic anhydride repeating unit is ring opened with methanol and N-cyclohexyl-maleimide;

a tetrapolymer of norbornadiene (NBD), 5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene (NBTON), maleic anhydride in which maleic anhydride repeating unit is ring opened with methanol and N-phenylmaleimide;

a tetrapolymer of norbornadiene (NBD), maleic anhydride in which maleic anhydride repeating unit is ring opened with methanol, N-cyclohexylmaleimide and maleimide; and

a tetrapolymer of norbornadiene (NBD), maleic anhydride in which maleic anhydride repeating unit is ring opened with methanol, N-phenylmaleimide and maleimide.

13. The composition according to claim 1 , wherein said photoactive compound comprises one or more of a 1,2-naphthoquinonediazide-5-sulfonyl moiety, 1,2-naphthoquinonediazide-4-sulfonyl moiety as represented by structural formulae (Va) and (Vb), respectively:

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

14. The composition according to claim 13 , wherein said photoactive compound is selected from the group consisting of:

wherein at least one of Q is a group of formula (Va) or (Vb):

and the remaining Q is hydrogen.

15. The composition according to claim 1 , wherein said cross-linking agent is selected from the group consisting of:

and a mixture in any combination thereof.

16. The composition according to claim 1 , wherein said solvent is selected from the group consisting of propyleneglycol monomethylether acetate (PGMEA), N-methylpyrrolidone (NMP) and γ-butyrolactone (GBL) and a mixture in any combination thereof.

17. The composition according to claim 1 , wherein said composition further comprises one or more additives selected from the group consisting of:

a photo base generator;

a thermal base generator;

adhesion promoters;

antioxidants;

surfactants; and

mixtures in any combination thereof.

18. A process for forming a cured product, comprising: (i) applying the layer forming polymer composition of claim 1 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.

19. A cured product obtained by curing the composition of claim 1 .

20. A polymer comprising 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;

each of R 1 , R 2 , R 3 and R 4 is independently 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(C 1 -C 3 )alkyl, —CO 2 R, halogen and a group of the formula (A):

where R is (C 1 -C 6 )alkyl or tri((C 1 -C 6 )alkyl)silyl; and

R a is selected from the group consisting of —(CH 2 ) p —, —(CH 2 ) q —OCH 2 — and —(CH 2 ) q —(OCH 2 CH 2 ) r —OCH 2 —, where p is an integer from 0 to 6, q is an integer from 0 to 4 and r is an integer from 0 to 3;

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

wherein:

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

R 7 is selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl, fluorinated or perfluorinated(C 1 -C 9 )alkyl, and —(CH 2 ) a -(0-(CH 2 ) b ) c —O—(C 1 -C 6 )alkyl, where a, b and c are integers from 1 to 4; and

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

wherein:

each of R 8 and R 9 is independently selected from the group consisting of hydrogen, linear or branched (C 1 -C 9 )alkyl and fluorinated or perfluorinated(C 1 -C 9 )alkyl;

R 10 is selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, (C 3 -C 9 )cycloalkyl, (C 3 -C 9 )cycloalkyl(C 1 -C 10 )alkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 4 )alkyl, (C 1 -C 16 )alkylCO 2 R, (C 1 -C 16 )alkylCH 2 OR, (C 6 -C 10 )arylCO 2 R and (C 6 -C 10 )arylCH 2 OR; where R is hydrogen, (C 1 -C 6 )alkyl or tri((C 1 -C 6 )alkyl)silyl;

and wherein molar amount of repeating unit of formula (IIIA) is at least 3 mole percent.