Photosensitive resin composition, photosensitive dry film, layered product, and pattern formation method
The coating formed from the photosensitive resin composition has excellent resolution and improved microprocessing properties, as well as satisfactory reliability in terms of adhesion and crack resistance, resolution, and flexibility. The photosensitive resin composition includes (A) a polymer including a silicone skeleton and (B) photo-acid generators, wherein the photo-acid generators (B) comprise (B1) a photo-acid generator which is an onium salt and (B2) a photo-acid generator which is not an onium salt.
1 . A photosensitive resin composition comprising of:
(A) a silicone skeleton-containing polymer;
(B) a photoacid generator,
(C) optionally, a crosslinker;
(D) optionally, a solvent; and
(E) optionally, a quencher;
wherein the silicone skeleton-containing polymer (A) consisting of:
repeat units having the formulae (a1), (a3), (a4), (b1), (b3) and (b4), and
optionally repeat units having the formulae (a2), and (b2):
wherein R 1 to R 4 are each independently a C 1 -C 8 monovalent hydrocarbon group, m is an integer of 1 to 600,
a 1 to a 4 and b 1 to b 4 are numbers in the range: 0<a 1 <1,0<a 2 <1,0<a 3 <1,0<a 4 <1,0<b 1 <1,0<b 2 <1,0<b 3 <1,0<b 4 1,0<a 1 +a 2 +a 3 +a 4 <1,0<b 1 +b 2 +b 3 +b 4 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 =1,
X 1 is a divalent group having the formula (X1), X 2 is a divalent group having the formula (X2), X 3 is a divalent group having the formula (X3), X 4 is a divalent group having the formula (X4),
wherein Z 1 is a single bond, methylene group, propane-2,2-diyl group, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or fluorene-9,9-diyl group, R 11 and R 12 are each independently hydrogen or methyl, R 13 and R 14 are each independently a C 1 -C 4 alkyl group or C 1 -C 4 alkoxy group, p 1 and p 2 are each independently an integer of 0 to 7, q 1 and q 2 are each independently an integer of 0 to 2,
wherein Z 2 is a single bond, methylene group, propane-2,2-diyl group, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl group or fluorene-9,9-diyl group, R 21 and R 22 are each independently hydrogen or methyl, R 23 and R 24 are each independently a C 1 -C 4 alkyl group or C 1 -C 4 alkoxy group, r 1 and r 2 are each independently an integer of 0 to 7, s 1 and s 2 are each independently an integer of 0 to 2,
wherein R 31 and R 32 are each independently hydrogen or methyl, t 1 and t 2 are each independently an integer of 0 to 7,
wherein R 41 and R 42 are each independently hydrogen or methyl, R 43 and R 44 are each independently a C 1 -C 8 monovalent hydrocarbon group, u 1 and u 2 are each independently an integer of 0 to 7, and v is an integer of 0 to 600,
wherein the photoacid generator (B) contains (B1) a photoacid generator in the form of an onium salt and (B2) a photoacid generator other than an onium salt.
2 . The photosensitive resin composition of claim 1 wherein the silicone skeleton-containing polymer (A) comprises repeat units having the formulae (a1) (a2), (a3), (a4), (b1), (b2), (b3) and (b4).
3 . The photosensitive resin composition of claim 1 , further comprising (C) a crosslinker.
4 . The photosensitive resin composition of claim 1 , further comprising (D) a solvent.
5 . The photosensitive resin composition of claim 1 , further comprising (E) a quencher.
6 . A photosensitive resin coating obtained from the photosensitive resin composition of claim 1 .
7 . A photosensitive dry film comprising a support film and the photosensitive resin coating of claim 6 thereon.
8 . A laminate comprising a substrate and the photosensitive resin coating of claim 6 thereon.
9 . A pattern forming process comprising the steps of:
(i) applying the photosensitive resin composition of claim 1 onto a substrate to form a photosensitive resin coating thereon,
(ii) exposing the photosensitive resin coating to radiation, and
(iii) developing the exposed photosensitive resin coating in a developer to form a pattern.
10 . A pattern forming process comprising the steps of:
(i′) applying the photosensitive dry film of claim 7 onto a substrate to form a photosensitive resin coating thereon,
(ii) exposing the photosensitive resin coating to radiation, and
(iii) developing the exposed photosensitive resin coating in a developer to form a pattern.
11 . The pattern forming process of claim 9 , further comprising step (iv) of post-curing the patterned photosensitive resin coating at a temperature of 100 to 250° C.
12 . The photosensitive resin composition of claim 1 , wherein the crosslinker is selected from the group consisting of melamine, guanamine, glycoluril and urea compounds, phenol compounds, epoxy compounds.
13 . The photosensitive resin composition of claim 1 , wherein the quencher is an amine compound.