Photoimageable compositions containing thermal base generators

1. A photoimageable aqueous developable positive tone composition comprising:

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

wherein:

m is an integer 0, 1 or 2;

R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, halogen, linear or branched (C 1 -C 12 )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 6 )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, (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, —(CH 2 ) a —CO 2 R, a group of formula (A):

—(CH 2 ) b —(OCH 2 —CH 2 ) c —OR  (A);

and a group of formula (B):

wherein:

a is an integer from 0 to 4

b is an integer 0, 1, 2, 3 or 4;

c is an integer 0, 1, 2, 3 or 4; and

R is selected from the group consisting of hydrogen, linear or branched (C 1 -C 6 )alkyl, (C 5 -C 8 )cycloalkyl, (C 6 -C 10 )aryl and (C 7 -C 12 )aralkyl; and

a second repeating unit represented by formula (IIA) or (IIB), 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, fluorinated or perfluorinated (C 1 -C 9 )alkyl, (C 1 -C 12 )alkoxy(C 1 -C 12 )alkyl and (C 1 -C 12 )alkoxy(C 1 -C 12 )alkoxy(C 1 -C 12 )alkyl; and

wherein each of aforementioned groups, where valence is permissible, is optionally substituted with one or more groups selected from the group consisting of linear or branched (C 1 -C 6 )alkyl, (C 3 -C 7 )cycloalkyl, (C 1 -C 6 )perfluoroalkyl, (C 1 -C 6 )alkoxy, (C 3 -C 7 )cycloalkoxy, (C 1 -C 6 )perfluoroalkoxy, halogen, hydroxy, linear or branched hydroxy(C 1 -C 6 )alkyl, acetoxy, phenyl, hydroxyphenyl and acetoxyphenyl;

b) a thermal base generator selected from the group consisting of:

(i) a compound of formula (III):

(ii) a compound of formula (IV):

(iii) a compound of formula (V):

 and

(iv) a compound of formula (VI):

wherein

R 9 , R 10 and R 11 are the same or different and each independently of one another selected from the group consisting of hydrogen, linear or branched (C 1 -C 16 )alkyl, cyano(C 1 -C 16 )alkyl, cyano(C 1 -C 16 )alkoxy(C 1 -C 16 )alkyl, (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 1 -C 12 )alkoxy(C 1 -C 8 )alkyl, (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 (C 1 -C 6 )acyloxy;

R 12 is selected from the group consisting of (C 1 -C 6 )alkyloxycarbonyl, (C 6 -C 10 )aryl(C 1 -C 6 )alkyloxycarbonyl, (C 6 -C 10 )aryloxycarbonyl and cyano(C 1 -C 6 )alkyl;

R 13 , R 14 and R 17 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl, a linear, branched or cyclic (C 3 -C 12 )alkyl, a linear, branched or cyclic (C 3 -C 12 )heteroalkyl having from 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur, (C 6 -C 10 )aryl and (C 5 -C 10 )heteroaryl having from 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur;

R 15 and R 16 are the same or different and each independently of one another selected from the group consisting of hydrogen and (C 1 -C 6 )alkyl;

or where

R 16 taken together with the nitrogen atom to which it is attached to and one of R 13 or R 14 taken together with the nitrogen atom to which it is attached to and any intervening atoms form a cyclic heteroalkyl group;

R 17 taken together with the carbon atom to which it is attached to and one of R 13 or R 14 taken together with the nitrogen atom to which it is attached to and any intervening atoms form a cyclic heteroalkyl group;

one of R 13 or R 14 taken together with the nitrogen atom to which it is attached to and one of adjacent R 13 or R 14 taken together with the nitrogen atom to which it is attached to and any intervening atoms form a cyclic heteroalkyl group;

and

X Θ is selected from the group consisting of halide, sulfonate, methanesulfonate, trifluoromethanesulfonate and a carboxylate anion;

c) a photoactive compound; and

d) a carrier solvent.

2. The composition of claim 1 , wherein m is 0, R 1 is phenethyl, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are hydrogen.

3. The composition of claim 1 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:

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

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

4. The composition of claim 1 , wherein the polymer comprises one or more repeat units derived from the corresponding monomers selected from the group consisting of:

maleic anhydride; and

2-methyl-maleic anhydride.

5. The composition of claim 1 , wherein the polymer is selected from the group consisting of:

a copolymer containing repeating units derived from 5-phenethylbicyclo[2.2.1]hept-2-ene and repeat unit of formula (IIA) where R 5 , R 6 , R 7 and R 8 are hydrogen;

a copolymer containing repeating units derived from 5-phenethylbicyclo[2.2.1]hept-2-ene and repeat unit of formula (IIA) where R 5 , R 6 , R 7 are hydrogen and R 8 is methyl.

6. The composition of claim 1 , wherein the thermal base generator is of the formula (III):

wherein

R 12 is selected from the group consisting of tert-butoxycarbonyl, iso-butoxycarbonyl, iso-propoxycarbonyl, n-propoxycarbonyl, methoxycarbonyl, ethoxycarbonyl and cyanoethyl; and

R 9 , R 10 and R 11 are the same or different and each independently of one another selected from the group consisting of hydrogen, methyl, ethyl, phenyl and cyanoethoxymethyl.

7. The composition of claim 6 , wherein the thermal base generator is selected from the group consisting of:

1-(tert-butoxycarbonyl)imidazole;

1-(iso-butoxycarbonyl)imidazole;

1-(iso-propoxycarbonyl)imidazole;

1-(n-propoxycarbonyl)imidazole;

1-(methoxycarbonyl)imidazole;

1-(ethoxycarbonyl)imidazole;

1-(2-cyanoethyl)-2-ethyl-4-methyl-imidazole; and

1-(cyanoethyl)-2-phenyl-4,5-(dicyanoethoxymethyl)imidazole.

8. The composition of claim 6 , wherein the thermal base generator is selected from the group consisting of:

1-(tert-butoxycarbonyl)imidazole;

1-(2-cyanoethyl)-2-ethyl-4-methyl-imidazole; and

1-(cyanoethyl)-2-phenyl-4,5-(dicyanoethoxymethyl)imidazole.

9. The composition of claim 6 , wherein the thermal base generator is selected from the group consisting of:

1-(tert-butoxycarbonyl)imidazole; and

1-(2-cyanoethyl)-2-ethyl-4-methyl-imidazole.

10. The composition of claim 1 , wherein the thermal base generator is of the formula (IV):

wherein

R 16 taken together with the nitrogen atom to which it is attached to and R 13 taken together with the nitrogen atom to which it is attached to and the intervening carbon atom form a cyclic heteroalkyl group, and R 17 taken together with the carbon atom to which it is attached to and R 14 taken together with the nitrogen atom to which it is attached to and the intervening carbon atom form a cyclic heteroalkyl group;

R 15 is hydrogen; and

X Θ is selected from the group consisting of chloride, 2-(3-benzoylphenyl)propanoate, 2-(9-oxo-9H-xanthen-2-yl)acetate and 2-(9-oxo-9H-thioxanthen-2-yl)acetate.

11. The composition of claim 10 , wherein the thermal base generator is selected from the group consisting of:

1,8-diazabicyclo[5.4.0]undec-7-ene hydrochloride;

3,4,6,7,8,9-hexahydro-2H-pyrido[1,2-a]pyrimidine hydrochloride;

2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidine hydrochloride;

1,6-diazabicyclo[4.3.0]non-5-enium 2-(3-benzoylphenyl)propanoate;

1,6-diazabicyclo[4.3.0]non-5-enium 2-(9-oxo-9H-xanthen-2-yl)acetate;

1,8-diazabicyclo[5.4.0]undec-7-enium 2-(3-benzoylphenyl)propanoate;

1,8-diazabicyclo[5.4.0]undec-7-enium 2-(9-oxo-9H-xanthen-2-yl)acetate;

1,8-diazabicyclo[5.4.0]undec-7-enium 2-(9-oxo-9H-thioxanthen-2-yl)acetate; and

1,6-diazabicyclo[4.3.0]non-5-enium 2-(9-oxo-9H-thioxanthen-2-yl)acetate.

12. The composition of claim 1 , wherein the thermal base generator is of the formula (V):

wherein

R 16 taken together with the nitrogen atom to which it is attached to and one of R 13 or R 14 taken together with the nitrogen atom to which it is attached to and the intervening carbon atom form a cyclic heteroalkyl group, and one of R 13 or R 14 taken together with the nitrogen atom to which it is attached to and one of adjacent R 13 or R 14 taken together with the adjacent nitrogen atom to which it is attached to and the intervening carbon atom form a cyclic heteroalkyl group and the remaining R 13 and R 14 are the same or different and independently of each other selected from the group consisting of hydrogen, methyl, ethyl, n-propyl and iso-propyl;

R 15 is hydrogen; and

X Θ is selected from the group consisting of chloride, 2-(3-benzoylphenyl)propanoate, 2-(9-oxo-9H-xanthen-2-yl)acetate and 2-(9-oxo-9H-thioxanthen-2-yl)acetate.

13. The composition of claim 12 , wherein the thermal base generator is selected from the group consisting of:

1,6,8-triazabicyclo[5.4.0]undec-7-ene hydrochloride;

1,5,7-triaza-bicyclo[4.4.0]dec-5-ene hydrochloride;

1,5,7-triaza-7-methyl-bicyclo[4.4.0]dec-5-ene hydrochloride;

1,5,7-triaza-7-ethyl-bicyclo[4.4.0]dec-5-ene hydrochloride;

1,5,7-triaza-7-isopropyl-bicyclo[4.4.0]dec-5-ene hydrochloride;

1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyrimidine hydrochloride;

bis(dimethylamino)methaniminium chloride;

1,5,7-triaza-7-methyl-bicyclo[4.4.0]dec-5-enium 2-(3-benzoylphenyl)propanoate;

1,5,7-triaza-7-methyl-bicyclo[4.4.0]dec-5-enium 2-(9-oxo-9H-xanthen-2-yl)acetate;

1,5,7-triaza-bicyclo[4.4.0]dec-5-enium 2-(3-benzoylphenyl)propanoate;

1,5,7-triaza-bicyclo[4.4.0]dec-5-enium 2-(9-oxo-9H-xanthen-2-yl)acetate; and

1,5,7-triaza-7-methyl-bicyclo[4.4.0]dec-5-enium 2-(9-oxo-9H-thioxanthen-2-yl)acetate.

14. The composition of claim 1 , wherein the thermal base generator is of the formula (VI):

wherein

R 16 is hydrogen or (C 1 -C 6 )alkyl;

R 13 and R 14 are the same or different and each independently of one another is selected from hydrogen, a methyl or ethyl group, a linear, branched or cyclic (C 3 -C 12 )alkyl group; a linear, branched or cyclic (C 3 -C 12 )heteroalkyl group having from 1 to 4 heteroatoms independently selected from nitrogen, oxygen or sulfur; a (C 6 -C 10 )aryl group; a (C 5 -C 10 )heteroaryl group having from 1 to 4 heteroatoms independently selected from nitrogen, oxygen or sulfur; or where R 16 taken together with R 13 and R 14 and any intervening atoms form a cyclic heteroalkyl group and one of R 13 or R 14 taken together with one of R 13 or R 14 on the adjacent nitrogen atom and any intervening atoms form a cyclic heteroalkyl group and the remaining R 13 and R 14 are hydrogen;

R 15 is hydrogen or (C 1 -C 6 )alkyl; and

X Θ is halide, sulfonate, methanesulfonate, trifluoromethanesulfonate or a carboxylate anion.

15. The composition of claim 1 , wherein the photoactive compound comprises a 1,2-naphthoquinonediazide-5-sulfonyl moiety 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):

16. The composition of claim 15 , wherein the photoactive compound is selected from the group consisting of:

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

and the remaining Q is hydrogen.

17. The composition of claim 1 further comprises one or more additives selected from the group consisting of:

a crosslinking agent;

an antioxidant; and

an adhesion promoter.

18. The composition of claim 17 , wherein the crosslinking agent is selected from:

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

triglycidyl ether of poly(oxypropylene)epoxide ether of glycerol; and

2-((4-(tert-butyl)phenoxy)methyl)oxirane.

19. The composition of claim 17 , wherein the antioxidant is pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

20. The composition of claim 17 , wherein the adhesion promoter is selected from the group consisting of: