Fluorine free photopatternable phenol functional group containing polymer compositions

1. A terpolymer consisting of:

at least one repeating unit represented by formula (IA), said 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;

at least one of R 1 , R 2 , R 3 and R 4 is a group of the formula (A):

—R—CO—Ar—(Y) n   (A)

wherein:

R is a divalent radical selected from the group consisting of substituted or unsubstituted (C 1 -C 6 )alkylene, substituted or unsubstituted (C 3 -C 5 )cycloalkylene, substituted or unsubstituted (C 1 -C 6 )alkyleneAr, and Ar;

Ar is a divalent radical selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene and substituted or unsubstituted naphthalene;

Y is hydroxy or (C 1 -C 6 )acyloxy; and

n is an integer 1 to 9;

the remaining R 1 , R 2 , R 3 and R 4 are the same or different and independently of each other 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 1 a)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; and

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

wherein:

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

p is an integer 0, 1 or 2;

R 5 , R 6 , R 7 and R 8 are the same or different and independently of each other 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, hydroxyperfluoro(C 1 -C 6 )alkyl(C 1 -C 6 )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, halogen and (C 1 -C 6 )alkylCOOR 9 where R 9 is hydrogen or (C 1 -C 12 )alkyl.

2. The terpolymer according to claim 1 , wherein the group of formula (A) is selected from the group consisting of:

wherein:

d is an integer from 1 to 6;

e is an integer from 1 to 5;

f is an integer from 1 to 9;

g is an integer from 1 to 7;

X is selected from the group consisting of hydrogen, linear or branched (C 1 -C 6 )alkyl, hydroxy(C 1 -C 6 )alkyl and perfluoro(C 1 -C 6 )alkyl; and

Y is hydroxy or acetoxy.

3. The terpolymer according to claim 1 , wherein:

p is 0 or 1;

R 5 , R 6 , R 7 and R 8 independently represents hydrogen, linear or branched (C 1 -C 16 )alkyl, hydroxyperfluoro(C 1 -C 6 )alkyl(C 1 -C 6 )alkyl, (C 6 -C 10 )aryl(C 1 -C 3 )alkyl, perfluoro(C 6 -C 10 )aryl, —(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 6 -C 10 )aryloxy, (C 1 -C 6 )acyloxy or (C 1 -C 6 )alkylCOOH.

4. The terpolymer according to claim 3 , wherein

p is 0;

R 5 , R 6 , R 7 and R 8 are independently represents hydrogen, linear or branched (C 1 -C 12 )alkyl, hydroxyhexafluoropropylmethyl, phenyl(C 1 -C 3 )alkyl, —(CH 2 ) 2 CO 2 H, or —(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.

5. The terpolymer according to claim 1 , wherein said repeating unit of formula (IA) is derived from a monomer selected from the group consisting of:

4-(2-(bicyclo[2.2.1]hept-5-en-2-yl)acetyl)phenyl acetate;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one;

4-(2-(bicyclo[2.2.1]hept-5-en-2-yl)acetyl)-2-methoxyphenyl acetate;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxy-3-methoxyphenyl)ethan-1-one;

(4-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)phenyl)(4-hydroxyphenyl)methanone;

3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)propan-1-one;

3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxy-3-methoxyphenyl)propan-1-one;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4′-hydroxy-[1,1′-biphenyl]-4-yl)ethan-1-one;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4′-hydroxy-3′-methoxy-[1,1′-biphenyl]-4-yl)ethan-1-one;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(6-hydroxynaphthalen-2-yl)ethan-1-one; and

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(6-hydroxy-7-methoxynaphthalen-2-yl)ethan-1-one.

6. The terpolymer according to claim 1 , wherein said one or more repeating unit of formula (IIA) is derived from a monomer selected from the group consisting of:

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

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

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

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

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

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

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

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

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

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

7. The terpolymer according to claim 1 , which is selected from the group consisting of:

a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 2-(bicyclo[2.2.1]hept-5-en-2-ylmethyl)-1,1,1,3,3,3-hexafluoropropan-2-ol and 2-(bicyclo[2.2.1]hept-5-en-2-yl)acetic acid; and

a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene.

8. The terpolymer according to claim 1 , which is

a terpolymer of 2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one, 3-(bicyclo[2.2.1]hept-5-en-2-yl)propanoic acid and 5-((2-(2-methoxyethoxy)ethoxy)methyl)-bicyclo[2.2.1]hept-2-ene.

9. A layer forming polymer composition comprising:

a terpolymer consisting of:

at least one repeating unit represented by formula (IA), said 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;

at least one of R 1 , R 2 , R 3 and R 4 is a group of the formula (A):

—R—CO—Ar—(Y) n   (A)

wherein:

R is a divalent radical selected from the group consisting of substituted or unsubstituted (C 1 -C 6 )alkylene, substituted or unsubstituted (C 3 -C 8 )cycloalkylene, substituted or unsubstituted (C 1 -C 6 )alkyleneAr, and Ar;

Ar is a divalent radical selected from the group consisting of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene and substituted or unsubstituted naphthalene;

Y is hydroxy or (C 1 -C 6 )acyloxy; and

n is an integer 1 to 9;

the remaining R 1 , R 2 , R 3 and R 4 are the same or different and independently of each other 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 1 a)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; and

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

wherein:

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

p is an integer 0, 1 or 2;

R 5 , R 6 , R 7 and R 8 are the same or different and independently of each other 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, hydroxyperfluoro(C 1 -C 6 )alkyl(C 1 -C 6 )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, halogen and (C 1 -C 6 )alkylCOOR 9 where R 9 is hydrogen or (C 1 -C 12 )alkyl;

a photo active compound;

an epoxy resin; and

a solvent.

10. The composition according to claim 9 , wherein the group of formula (A) is selected from the group consisting of:

wherein:

d is an integer from 1 to 6;

e is an integer from 1 to 5;

f is an integer from 1 to 9;

g is an integer from 1 to 7;

X is selected from the group consisting of hydrogen, linear or branched (C 1 -C 6 )alkyl, hydroxy(C 1 -C 6 )alkyl and perfluoro(C 1 -C 6 )alkyl; and

Y is hydroxy or acetoxy.

11. The composition according to claim 10 , wherein said repeat unit of formula (IA) or formula (IIA) is derived from a monomer selected from the group consisting of:

4-(2-(bicyclo[2.2.1]hept-5-en-2-yl)acetyl)phenyl acetate;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)ethan-1-one;

4-(2-(bicyclo[2.2.1]hept-5-en-2-yl)acetyl)-2-methoxyphenyl acetate;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxy-3-methoxyphenyl)ethan-1-one;

3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxyphenyl)propan-1-one;

3-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4-hydroxy-3-methoxyphenyl)propan-1-one;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4′-hydroxy-[1,1′-biphenyl]-4-yl)ethan-1-one;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(4′-hydroxy-3′-methoxy-[1,1′-biphenyl]-4-yl)ethan-1-one;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(6-hydroxynaphthalen-2-yl)ethan-1-one;

2-(bicyclo[2.2.1]hept-5-en-2-yl)-1-(6-hydroxy-7-methoxynaphthalen-2-yl)ethan-1-one;

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

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

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

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

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

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

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

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

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

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

12. The composition according to claim 9 , 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 (IIIa) and (IIIb), respectively:

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

13. The composition according to claim 12 , 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.

14. The composition according to claim 9 , wherein said epoxy resin is selected from the group consisting of:

epoxy resin made from bisphenol A and epichlorohydrin;

epoxy resin made from polypropylene glycol and epichlorohydrin;

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.

15. The composition according to claim 9 , wherein said solvent is propyleneglycol monomethylether acetate, gamma-butyrolactone or N-methylpyrrolidone.

16. The composition according to claim 9 , 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.

17. A process for forming a cured product, comprising: (i) applying the layer forming polymer composition of claim 9 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.

18. A cured product obtained by curing the layer forming polymer composition of claim 9 .

19. An optoelectronic or microelectronic device comprising the cured product of claim 18 , which is having a dielectric constant of 3.2 or less at 1 MHz.